bono,~, ami> particulat€ mutagenic °lctivitifs duriiig …

llBRARY - AlR RESoURCES 80Aao

MEASUREMENTS OF NCfrac12 BONO~ HCHO PAH IITROAREHFS AMIgt PARTICULATeuro MUTAGENIC deglCTIVITIFS DURIIIG n1E

CARBONACEOUS SPECIFS METHODS CalaquoPARIS(JI STUDY

Final Report

Contract No AS-150-32

ca11rornia Air Resources Board

February 1988

Principal Investigators

Dr Roger Atkinson Dr Arthur M Winer

Program Research Staff

Dr Janet Arey Ot Heinz W Biermann

Mr Travis Dinoff Mr William P Harger

Ms Patricia A McElroy Dr Ernesto C Tuazon Dr Barbara Zielinska

Statewide Air Pollution Research Center TD University of California 890 Riverside California 92521A755 1988

ABSTRACT

To allow for methods development and methods intercomparisons prior to the 1987 Southern California Air Quality Study the California Air Resources Board funded two methods intercomparison studies one in 1985 at Claremont concerning the measurement of nitrogenous species and a second at Citrus College Glendora during August 1986 dealing principally with measurement methods for organic and carbonaceous species In the Carbonaceous Species Methods Comparison Study (CSMCS at Citrus College Glendora the Statewide Air Pollution Research Center conducted measurements of the ambient concentrations or several inorganic and organic species Specifically the following measurements were made

bull Using long pathlength differential optical absorption spectroscopy (DOAS) we measured nitrogen dioxide (N02 nitrous acid (HONO) and formaldehyde (HCHO)

bull Using long pathlength Fourier infrared (FT-IR absorption specshytroscopy we measured nitric acid (HN03) amnonia (NH3) and HCH0

bull Ambient air samples were collected during 12-hr daytime and 12-hr nighttime periods onto Tenax solid adsorbent polyurethane foam plugs and Teflon-impregnated glass fiber filters and these samples were analyzed for mutagenicity and gas- and particle-associated polycyclic aromatic hydrocarbons (PAH) and nitroarenes

An extensive data set for the gas-phase concentrations of N02 HONO HN03 HCHO NH3 and the N03 radical was obtained (by DOAS andor FT-IR spectroscopy) during this study period Significant concentrations of these pollutants were observed with ambient concentrations of up to approximately 140 45 30 20 and 15 parts-per-billion (ppb) for N02 HONO HN03 HCHO and NH~ respectively A definitive measurement of the time-concentration profne of N03 radicals was made on only one night during this study with a peak N03 radical concentration of 70 parts-pershytrillion (ppt) being measured on fhe night of August 13 The presence of N03 radicals at levels lt40 ppt was observed on the evenings of August 13 19 and 20

Ambient particulate organic matter POM) was collected on a 12-hr daytime and nighttime sampling period (0800-2000 and 2000-0800 PDT and was tested for mutagenicity towards Salmonella typhimur ium strains TA98 (with and without added S9) TA98NR (-S9) and TA981 8-DNP6 (-S9) The mutagen densities obtained were consistent with those we nave measured previously in the South Coast Air Basin As also observed previously the mutagen densities and mutagenic activity of the POM measured in the presence and absence of S9 we3e essentially indistinguishable with average mutagen densities rev m-) of 33 and 35 towards strain TA98 with

3and without S9 respectively and a maximum of 61 rev m- (TA98 -S9

Ambient air was also sampled on filters and solid adsorbents to collect the gas- and particle associated PAH and nitroarenes for combined gas chromatography-mass spectrometry analysis The following PAH and nitroarenes were observed and quantified naphthalene 1- and 2-methylshynaphthalene biphenyl acenaphthene acenaphthylene fluorene phenanthrene anthracene dibenzothiophene fluoranthene pyrene benz(a)shyanthracene chrysenetriphenylene benzo(a)pyrene 1- and 2-nitronaphthashylene 3-nitrobiphenyl 2- 3- and 8-nitrofluoranthene and 1- and 2-nitroshypyrene

ii

- --- ------

( TABLE OF CONTENTS

Abstract

Acknowledgments V

Disclaimer vi

List of Figures vii

List of Tables xi

Glossary of Terms Abbreviations and Symbols xiv

I bull PROJECT SUMMARY I-1 II INTRODUCTION 11-1

III DESCRIPTION OF SITE III-1

IV-1 IVmiddot ~~~~Ni1~~ ~~~~cA~0iBs~~h~~~

1 ~~T~c~~~ A Introduction IV-1

B Experimental Methods IV-1

C Results and Discussion IV-4

V LONG PATHLENGTH FT-IR MEASUREMENTS OF HN03 NH V-13AND HCHO

A Introduction V-1

B Experimental V-1

1 Kilometer Pathlength FT-IR System V-1

2 Acquisition of Spectra V-2 3 calibration V-2 4 Treatment of Data V-9

C Results and Discussion V-11 Vl AMBIENT CONCENTRATIONS OF PAH AND NITRO-PAH VI-1

A Introduction VI-1

B Experimental VI-1

1 Sampling Media Cleaning Procedure Vl-1 2 Tenax-GC Cartridges Sampling and Analysis VI-1

3 High-Volume Filters Followed by PUF Plugs VI-2 Sampling and Analysis

4 Hi-Vols with TIGF Filters Sampling and Analysis VI-4

5 GCHS Analyses VI-7

6 Chemicals VI-9

111

TABLE OF CONTENTS (continued)

C Results 1 Volatile PAH Sampled on Tenax-GC Cartridges 2 PAH Sampled on PUF Plugs

3 Diurnal Variations in the Volatile PAH

4 Nitroarenes Sampled on PUF Plugs

5 PAH Sampled on TIGF Filters

6 Nitroarenes Sampled on TIGF Filters

VII AMBIENT MUTAGENICITY

A Introduction

B Experimental

C Results

VIII CONCLUSIONS IX REFERENCES

Appendix

A DOAS Measurements of Gaseous Nitrous Acid HONO Formaldehyde (HCHOand Nitrogen Dioxide (N02 at Citrus College Glendora from August 12-21 1986

B PAH Concentrations Measured on the Low- and High-Flow Tenax Sampling Cartridges

Page

Vl-10 VI-10 Vl-13 VI-16

Vl-21

Vl-28 VI-29 Vll-1

VIl-1

Vll-1

VIl-5 VIIl-1

IX-1

A-1

B-1

iv

l J

(

ACKNOWLEDGMENTS

Stimulating discussion and valuable exchanges or technical informashy

tion for which we express our appreciation took place at various times

during this program with Ors Douglas R Lawson John R Holmes Jack K

Suder and Charles D Unger members of the California Air Resources Board

research staff

We gratefully acknowledge Mr Chris Berglund Mr Frank Finazzo Mr

Michael Kienitz Mr William Long Mr Ervin Mateer Ms Li Li Parker and

Mr Phillip Pelzel for assistance in carrying out this research We thank

Ms Christy Laclaire for typing and assembling this report and Ms Diane

Skaggs and Ms Anne Greene for their assistance in the fiscal administrashy

tion of this project

Numerous individuals and organizations made valuable contributions to

this work and we wish to express our appreciation to the following Dr

James N Pitts Jr Director of SAPRC generously made available to the

program substantial equipment and instrument resources Ms Susanne

Hering provided valuable logistical support during the study

This report was submitted in fulfillment of Contract No A5-150-32 by

the Statewide Air Pollution Research Center University of California

Riverside under the partial sponsorship of the California Air Resources

Board Work on this program was completed as of November 13 1987

(

V

The statements and conclusions in this report are

those of the contractor and not necessarily those

of the california Air Resources Board The

mention of commercial products their source or

their use in connection with material reported

herein is not to be construed as either an actual

or implied endorsement of such products

vi

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page

Time-concentration profiles for formaldehyde nitric I-3 acid and anmonia measured by long pathlength FT-IR spectroscopy during the 1986 Citrus College study

Nitrous acid time-concentration profiles measured by 1-4 long pathlength DOAS system at Citrus College (Glendora) in August 1986

Diurnal variations in naphthalene concentration at 1-7 Citrus College in Glendora CA

Diurnal variation in the concentrations of 1-methyl- 1-7 naphthalene (1-Me) and 2-methylnaphthalene (2-Me) at Citrus College in Glendora CA

Citrus College campus showing location of August 1986 III-2 field study adjacent to football stadium bull- Field study site

Positions of the longpath FT-IR and DOAS systems and 11-3 UCR Hi-vols relative to the instruments of the other participants in the Carbonaceous Aerosol Study on the Citrus College campus August 1986

Schematic diagram of the longpath DOAS system lV-2

Time concentration profiles for nitrogen dioxide IV-9 measured by DOAS and chemiluminescence (NOi-NO) at Citrus College (Glendora) in August 198

Time concentration profiles for formaldehyde measured IV-10 by long pathlength DOAS and FT-IR spectrometers at Citrus College (Glendora) in August 1986

Nitrous acid time-concentration profiles measured by IV-11 long pathlength OOAS system at Citrus College (Glendora) in August 1986

Relative arrangement of the longpath FT-IR and V-3 DOAS systems

Schematic optical diagram of the longpath FT-IR V-4 spectrometer

Reference spectra of gaseous HNO~ (061 torr and V-5 NH3 (023 torr) at spectral resolution of 0125 cm- 1 pathlength of 25 cm total pressure with N2 of 740 torr The HN03 plot is offset by O 30 absorbance (base 10) unit for clarity Asterisks mark the absorption peaks used for analysis

vii

LIST OF FIGURES (continued)

Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page

Infrared absorption peaks of HN03 (lower trace) V-7 relative to atmosp~eric H2o absorptions (upper trace) in the 870-910 cm- region

Infrared absorption peaks of NH3 (lower trace) V-8 relative to atmospheric H2o and CO2 absorptions (upper

1trace in the 1080-1120 cm- region

Time-concentration profiles for formaldehyde nitric V-20 acid and anmonia measured by long pathlength FT-IR spectroscopy during the 1986 Citrus College study

Time-concentration plots of average HN03 (FT-IR) V-25 N02 DOAS) and 03 Dasibi monitor) at Citrus College for August 15-16 1986

Time-concentration plots of average HN03 (Fr-IR) V-27 N02 (DOAS) and o3 (Dasibi monitor) at Citrus College for August 18-19 1986

Schematic or modified Hi-vol sampler with PUF plugs Vl-3 underneath the filter to collect gas phase species and compounds blown-off the filter

HPLC trace (254 nm and gradient solvent program for Vl-5 separation of an ambient sample collected on PUF plug Semi-pre~rative Ultrasphere Si column (1 cm z 25 cm) 3 mL min- HPLC factions were combined as follows 3-7 8-11 112 113-15 16-23

HPLC trace (254 nm and gradient solvent program for Vl-8 separation of an ambient POM sample Semi-pre~rative Ultrasphere Si column (1 cm x 25 cm) 3 mL ain- HPLC fractions were combined as follows 2-5 6-7 18 9 110-13 114-18

GCMS-MID traces showing the molecular ions of VI-15 naphthalene mz 128) 1- and 2-methylnaphthalene (mz 142) and the dimethylnaphthalenes mz 156) for analyses of a Tenax-GC left) and PUF plug (right) sample collected simultaneously in Glendora CA on 813-1486 from 2000-0800 PDT The abundances of naphthalene and the alkylnaphthalenes collected on the PUF plug sample are similar and do not reflect the true ambient concentrations Note the ~uantitative naphthashylene concentration of -5~000 ng m- measured by the Tenax sample vs 2 ng - as measured by the PUF sample

viii


Figure Number Title Page

VI-5 Diurnal variations in naphthalene concentration at Citrus College in Glendora CA

VI-17

VI-6 Diurnal variation in the concentrations of 1-aethyl-naphthalene (1-Me) and 2-methylnaphthalene (2-Me) at Citrus College in Glendora CA

VI-17

Vl-7 GCMS-MID traces for the molecular ion of biphenyl and acenaphthene (mz 154) and the deuterated internal standard biphenyl-d 10 (mz 164) from the analyses of a daytime (top) and nighttime (bottom ambient air sample collected on Tenax-GC solid adsorbent at Citrus College Glendora CA

VI-18

Vl-8 GCMS-MID traces for the molecular ion of phenanthrene (PH) and anthracene (AN mz 178] and their corres-ponding deuterated species (mz 188) utilized as internal standards from the analyses of a daytime (top and nighttime (bottom) ambient air sample collected on PUF plugs at Citrus College Glendora CA

VI-19

VI-9 GCMS-MID traces for the molecular ion of fluoranthene (FL) pyrene PY) and acephenanthrylene AC) [mz 202] and the deuterated internal standards FL-d 10 and PY-d 10(mz 212 from the analyses of a daytime (top and nighttime (bottom ambient air sample collected on PUF plugs at Citrus College Glendora CA

Vl-20

Vl-10 GCMS-MID traces for the molecular ion (mz 173 and several characteristic fragment ions of 1- and 2-nitronaphthalene NN and an abundant fragment ion from the deuterated internal standard 1-NN-d7 showing the presence of 1-NN and 2-NN in an ambient air sample collected on PUF plugs at Citrus College Glendora CA

VI-22

VI-11 GCMS-MID traces showing the presence of methylnitro-naphthalenes in an ambient air sample collected on PUF plugs at Citrus College Glendora CA

Vl-23

VI-12 GCMS-MlD traces from the analysis of a standard mixture of the isomeric nitrobiphenyls and nitro-acenaphthenes showing their excellent resolution on the 30-m DB-5 capillary column utilized

Vl-24

ix


Figure Number Title

VI-13 GCMS-MID traces showing 3-nitrobiphenyl to be VI-25 present in an ambient air sample collected on PUF plugs at Citrus College Glendora CA The top trace repeats the molecular ion trace or the standard mixture (Figure VI-12) and it can be seen that the peak in the ambient sample (the molecular ion and two characteristic fragment ions shown) exactly bulltches 3-nitrobiphenyl in retention time

VI-14 GCMS-MID trace showing the molecular ion or the Vl-30 nitrofluoranthenes (NF) and nitropyrenes (NP) analyzed in an ambient POM sample collected at Citrus College Glendora August 20-21 1986 from 2000-0800 PDT

VII-1 12-Hour particulate mutagen densities at Citrus Vll-10 College Glendora CA August 12-21 1986

VII-2 Mutagen density TA98 -S9) vs the +S9 to -S9 VII-11 ratio for August 12-21 1986 Glendora CA

VIII-1 Plot or the average nighttimeaverage daytime VIII-3 concentration ratio for the volatile PAH against the OH radical reaction rate constant

VIII-2 Comparison or the daytime and nighttime ambient VIII-4 concentrations or 1-nitronaphthalene 1-NN) 2-nitronaphthalene 2-NN) and 3-nitrobiphenyl 3-NBPh) at El Camino Conmunity College Torrance CA Winer et al 1987) and Citrus College Glendora

X

(

LIST OF TABLES

Table Number Ill Page

1-1 Particulate Mutagen Densities Citrus College August 1986

1-5

IV-1 calculated Detection Limits tor 25-m Basepatb Multiple-Reflection Cell DOAS System Operated at 1 km Pathlength

lV-4

IV-2 Maximum o3 Levels and Observations or NO Radicals at Citrus College Glendora CA During ugust 13-20 1986

IV-5

IV-3 Hourly Average HONO Concentrations (ppb) Measured by the Long Pathlength DOAS System During the 1986 Citrus College Study

IV-6

IV-4 Hourly Average N02 Concentrations (ppb) Measured by the Long Pathlength DOAS System During the 1986 Citrus College Study

IV-7

IV-5 Hourly Average HCHO Concentrations (ppb) Measured by the Long Pathlength DOAS System During the 1986 Citrus College Study

IV-8

V-1 Simultaneous HN03 NH3 and HCHO Concentrations (ppb) in Glendora CA August 12-21 1986 by Long Path-length FT-IR Spectroscopy

V-12

V-2 Hourly Average HNOi Concentrations ppb) at Glendora CA August 12-20 986 Measured by Long Pathlength FT-IR Spectroscopy

V-21

V-3 Hourly Average NH3 Concentrations (ppb) at Glendora CA August 12-21 1986 Measured by Long Pathlength FT-IR Spectroscopy

V-22

V-4 Hourly Average HCHO Concentrations (ppb) at Glendora CA August 13-21 1986 Measured by Long Pathlength FT-IR Spectroscopy

V-23

VI-1 Concentrations ng m-3) of Volatile PAH Sampled onto Tenax-GC Solid Adsorbent at Citrus College Glendora CA in August 1986 (Day 0800-2000 PDT Night 2000-0800 PDT)

VI-11

1 VI-2 A Comparison of PAH Concentrations (ng m-3) Measured on Low Flow and High Flow Tenax-GC Solid Adsorbent at Citrus College Glendora CA Day 0800-2000 PDT Night 2000-0800 PDT)

VI-12

xi

LIST OF TABLES (continued)

Table Number Title

Vl-3 PAH Concentrations (ng m-3) Measured on PUF Plugs at Citrus College Glendora CA

VI-4 Nitro-PAH Measured on PUF Plugs at Citrus College Glendora CA

VI-5 Nitroarene Concentrations Measured on PUF Plugs at Citrus College Glendora CA

VI-6 PAH in NBS Standard Reference Material 1649 Washington DC Air Particulate Sample

VI-7 PAH Concentrations Measured on Particles Collected on TIGF Filters at Citrus College Glendora CA

VI-8 Concentration (pg m-3) of Nitrofluoranthenes and Nitropyrenes in Ambient POM at Citrus College Glendora CA

VII-1 Response of TA98NR and TA9818-DNP6 Relative to TA98 for Standard Nitroarenes

VII-2 Particulate Data for 12-Hour Collections at Citrus College August 1986

VII-3 Specific Activities of Particulate Extracts Collected at Citrus College August 1986

VII-4 Mutagen Loadings or Particulate Matter Collected at Citrus College August 1986

VII-5 Particulate Mutagen Densities Citrus College August 1986

Vll-6 The Effect of Extraction Solvent on Mutagenicity

VIlI-1 Ambient Atmospheric Concentrations (ng m-3) or Selected PAH and Nitroarenes at Torrance and Glendora CA

VIll-2 Mutagenic Densities (rev m-3) Towards TA98(-S9) at Citrus College Glendora Due to the Measured Ambient Concentrations of 2- 3- and 8-Nitrofluoranthene and 1- and 2-Nitropyrene (Using the Mutagenicity Data given in Table Vll-1 for the Mutagenic Activities or these Nitroarenes)

3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(


Table Number Title Page

A-1 Ambient Concentrations Determined by OOAS During A-2 Citrus College Study

B-1 Citrus College Glendora CA PAH Concentrations B-2 (Day 0800-2000 PDT Night 2000-0800 PDT) Measured on Low-Flow Tenax

B-2 Citrus College Glendora CA PAH Concentrations B-4 (Day 0800-2000 PDT Night 2000-0800 PDT) Measured on High-Flow Tenax

B-3 Citrus College Glendora CA PAH Concentrations B-6 Measured on Particles Collected on TIGF Filters

xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol

GLOSSARY OF TERMS ABBREVIATIONS AND snmoLS

California Air Resources Board

Atmosphere (pressure

Benzo(a)pyrene

Deuterated benzo(apyrene

Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter

Carbonaceous Species Methods Comparison Study

Dimethyl sulfoxide

Differential optical absorption spectroscopy

US Environmental Protection Agency

Electron volt

Degrees Fahrenheit

Deuterated fluoranthene

Feet

Fourier-transform infrared absorption spectroscopy

Gram

Gas chromatograph gas chromatography or gas chromatographic

Gas chromatography-mass spectrometry

Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID

GLOSSARY OF TERMS (continued)

Nitric acid

Water

Nitrous acid

High performance liquid chromatography

Hour

Hertz (cycle s-1)

Light intensity

Initial light intensity

Internal diameter

Thousand

Degrees Kelvin

Kilometer

Growth medium for overnight culture of Salmonella strains

Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride

Multiple ion detection technique used together with GC-MS

Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3


mole (6022 x 1023 molecules)

Mass spectrometer

Mass to charge ratio

Atmospheric mutagenicity concentration total activity divided by sampling volume (rev m-j)

Specific mutagenicity or the particulate matter total activity divided by particulate weight rev mg-)

Molecular weight

National Bureau of Standards Standard Reference Material 1648 urban dust collected in St Louis MO

National Bureau of Standards Standard Reference Material 1649 urban dust collected in Washington DC

Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate

Nitrated polycyclic aromatic hydrocarbons (PAH)

Nanometer (10-9 meter)

Nitric oxide

Nitrogen dioxide

Gaseous nitrate radical

Oxides of nitrogen NO+ N02)

Dinitrogen pentoxide

Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi

Open column chromatography

PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR


Liquid chromatography technique used for compound separation or purification

Polycyclic aromatic hydrocarbons

Pacific daylight time

Deuterated perylene

Picogram 10-12 gram

-log 10[H+] [Ir]= hydrogen ion concentration in mol 1-1

Perylene

Particulate organic matter

Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene

Revertants net response above background in the Salmonella mutagenicity test

Supernatant from a 9000 x g centrifugation of rat liver homogenate

Statewide Air Pollution Research Center

Southern California Edison

Standard cubic feet per minute

Semi-preparative scale column used for compound separation or purification by HPLC

Specific mutagenicity of the particulate extra~t slope of the Salmonella dose-response curve rev ~g-

Ames Salmonella typhimurium strain detects frameshift mutations Most sensitive strain for detecting ambient particulate mutagens

Nitroreductase-deficient isolate of strain TA98 less sensitive than TA98 to many mononitroarenes

xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w


Transacetylase-deficient isolate of strain TA98 less sensitive than TA98 to dinltropyrenes

Solid adsorbent used for the collection of volatile organics

Teflon impregnated glass fiber filters

The product of specific activity and total extract weight for a given collection period (rev)

University of California Riverside

Microgram (10-6 gram)

Microliter (10-6 liter)

Micrometer (10-6 meter)

Micromole (10-6 mole)

Ultravioletvisible

Watt

xviii

(

I bull PROJECT SUMMARY

The chemical processes leading to the production of ozone from the

reactive organic gases and oxides of nitrogen precursors are complex and

it is necessary to have measurements of the reactant and product species

in as detailed a manner as possible in order to provide a data base

suitable for input into airshed computer models These organic compounds

may be distributed between the gas and particle phases and hence measureshy

ments of their concentrations in both phases must be carried out In

order to allow for a methods development and methods intercomparison prior

to the 1987 Southern California Air Quality Study (SCAQS) the California

Air Resources Board (ARB) funded two methods intercomparison studies one

in 1985 at Claremont concerning the measurement of nitrogenous species

and a second at Citrus College GleQdora during August of 1986 dealing

principally with the intercomparison of measurement methods for organic

and carbonaceous species

In the Carbonaceous Species Methods Comparison Study (CSMCS) at

Citrus College Glendora the Statewide Air Pollution Research Center

(SAPRC) carried out the measurement of several inorganic and organic

species Specifically the following measurements were made

bull Using long pathlength differential optical absorption spectroscopy

(DOAS) we measured nitrogen dioxide (N02) nitrous acid (HONO) and

formaldehyde (HCHO

bull Using long pathlength Fourier infrared (FT-IR) absorption specshy

troscopy we measured nitric acid HN03) ammonia (NH3) and HCHO

bull Ambient air samples were collected during 12-hr daytime and 12-hr

nighttime periods onto Tenax solid adsorbent polyurethane foam (PUF)

plugs and Teflon-impregnated glass fiber (TIGF) filters and these samples

analyzed for mutagenicity and gas- and particle-associated polycyclic

aromatic hydrocarbons PAH) and nitroarenes

The DOAS and FT-IR systems utilized 25 m base-path multiple-reflecshy

tion optical systems aligned parallel to one another with the optical

beams being -24 m above the ground surface An extensive data set for

the gas-phase concentrations of N02 HONO HN03 HCHO (by both DOAS and

FT-IR spectroscopy NH3 and the N03 radical was obtained during this

study period The complete data set is tabulated in detail in Sections IV

1-1

and V of this report and Figures I-1 and I-2 show the HCHO HN03 and NH3 time-concentration profiles obtained by FT-IR spectroscopy (Figure I-1)

and the HONO time-concentration profile as monitored by DOAS (Figure I-2)

respectively These two figures and the data presented in Sections IV and

V show that significant concentrations of these pollutants were present

during this sampling period with ambient concentrations of up to

approximately 140 45 30 20 and 15 ppb for N02 BONO HN03 HCHO and

w3 respectively A definitiVe measurement of the presence of No3 radicals was made only on one night during this study (due to the

detection limit for this species) with a peak N03 radical concentration

of 70 ppt being measured on the night of August 13 The presence of N03 radicals at levels lt40 ppt was observed on the evenings of August 13 19

and 20

Ambient particulate organic matter (POM) was collected on a 12-hr

daytime and nighttime sampling period (0800-2000 and 2000-0800 PDT) and

was tested for mutagenicity towards Salmonella typhimurium strains TA98

with and without added S9) TA98NR (-S9) and TA9818-DNP6 (-S9) The

measured mutagen densities in revertants per m3 of air sampled are given

in Table I-1 These mutagen densities are consistent with those we have

measured previously in the South Coast Air Basin As also observed

previously the mutagen densities and mutagenic activity of the POM

measured in the presence and absence of S9 are essentially indistinguishshy

able with average mutagen densities (strain TA98) of 33 and 35 rev bull-3 with and without S9 respectively

Ambient air was also sampled on filters and solid adsorbents in order

to collect the gas- and particle associated PAH and PAH-derivatives for

combined gas chromatography-mass spectrometry analysis Three collection

systems were used to sample ambient air low and high-flow ( 1 and 10 L

min- 1 respectively) cartridges packed with Tenax-GC solid adsorbent to

sample the volatile PAH such as naphthalene and the methylnaphthalenes

Teflon-impregnated glass fiber (TIGF) filters backed up by polyurethane

foam (PUF plugs to sample the semi-volatile PAH and nitroarenes present

either in the gas phase or blown-off the filters during the collection

period and TIGF filters for the collection of POM containing the higher

molecular weight low-volatility PAH and nitroarenes The following PAH

I-2

(

AUC l 2bull21 l tll _a

Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)

Figure I-1 Time-concentration profiles for formaldehyde nitric acid and ammonia measured by long pathlength FT-IR spectroscopy during the 1986 Citrus College study

1-3

5----------------------

D 3 a

I a

2 t--4 I t-

1 ~ 0 f t t t t t I I I t t I I I I I I I I I I I I I I I I I I I I I I I I

13 14 15 16 17 18 19 20 21

DATE

Figure I-2 Nitrous acid time-concentration profiles measured by long pathlength DOAS system at Citrus College (Glendora) in August 1986

f

Table 1-1 Particulate Mutagen Densities Citrus College August 1986

Mutagen DensitJ ~rev m-31

Time of TA98 Day TA98 TA98 TA98NR 18-DNP6

Date (PDT +S9 -S9 -89 -S9

81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54

asampling volume -SJ low due to power failure

1-5

and nitroarenes were observed and quantified naphthalene 1- and 2-

methynaphthalene bipheny1 acenaphthene acenaphthylene fluorene

phenanthrene anthracene dibenzothiophene fluoranthene pyrene benz(a)shy

anthracene chrysenetriphenylene benzo(a)pyrene 1- and 2-nitronaphthashy

lene 3-nitrobiphenyl 2- 3- and 8-nitrofluoranthene and 1- and 2-nitroshy

pyrene The ambient concentrations of these PAH and nitroarenes are

presented in Section VI and as an example Figures 1-3 and I-4 show the

time-concentration profiles of naphthalene and 1- and 2-methylnaphthalene

respectively during this study period

This study site was also chosen by the ARB staff to be one of the

seven locations in California at which sampling was to be conducted to

obtain data concerning the ambient levels of mutagenicity and of PAH

(including PAH derivatives such as the nitro-PAH) to which populations

were exposed The Glendora site was chosen as the site impacted by

vehicle emissions The mutagenicity data and the concentrations of the

PAH and PAH-derivatives observed at this site are hence an integral part

of our ongoing study A Survey of Ambient Concentrations of Selected

Polycyclic Aromatic Hydrocarbons (PAH) at Various Locations in California

(ARB Contract No AS-185-32) and a full discussion of the data and the

conclusions to be drawn from the entire data set collected at the seven

sites throughout California will be presented in the final report to that

program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C

Figure I-3 Diurnal variations in naphthalene concentration at Citrus College in Glendora CA

METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)

Night lt2000-0800 hr)

I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I

Figure I-4 Diurnal variation in the concentrations of 1-methylshynaphthalene (1-Me) and 2-aethylnaphthalene (2-Me) at Citrus College in Glendora CA

1-7

11 INTRODUCTION


reactive organic gases and oxides or nitrogen precursors are exceedingly

complex and in order to provide a data base suitable for input into

airshed computer models it is necessary to have measurenents of the reacshytant and product species in as detailed a manner as possible Since these

organic compounds may be distributed between the gas anltI particle phases

measurements of both the gas- and particle-phase concentrations of organic

chemicals must be carried out In order to allow for a methods developshy

ment and methods intercomparison prior to the 1987 Southern California Air Quality Study (SCAQS) the California Air Resources Board (ARB) funded two

methods intercomparison studies one in 1985 at Clarsont concerning the

measurement of nitrogenous species and a second at Citrus College

Glendora during August of 1986 dealing principally with the intercomparishy

son or measurement methods for organic and carbonaceous species

In this Carbonaceous Species Methods Comparison Study at Citrus College Glendora the Statewide Air Pollution Researcplusmn Center (SAPRC) was

involved in the measurement of a number of inorganic and organic species

Specifically we measured the atmospheric concentrations of the following compounds


(DOAS we measured nitrogen dioxide (N02 nitrous acid (HONO) and formaldehyde (HCHO)

bull Using long pathlength Fourier infrared (FT-IR) absorption spectroscopy we measured nitric acid HN03) anmonia NH3) and HCHO


nighttime periods onto Tenax solid adsorbent polyllethane foam PUF

plugs and Teflon-impregnated glass fiber TIGF filters and these samples


aromatic hydrocarbOns (PAH) and nitroarenes

Furthermore the measurements of the ambient atmspheric concentrashy

tions of PAH and PAH-derivatives at Citrus College formed one part of a

further ambient measurement study funded by the ARB Contract No AS-185-

32 dealing with the ambient concentrations of PAH ant PAR-derivatives at

11-1

seven sites throughout California impacted by differing combustion

emission sources The Citrus College site served as the vehicle emissionshyimpacted site for this study

The description or the site at Citrus College Glendora and the

experimental procedures and data obtained from these measurement methods are detailed in the following sections

11-2

(

111 DESCRIPTION OF SITE

As noted earlier this monitoring program was conducted in conshy

junction with the ARB-funded carbonaceous Species Methods Comparison

Study As shown in Figure 111-1 the ARB selected a site adjacent to the

football stadium on the campus of Citrus College for this study The

orientation and relationship of the long pathlength n-IR and OOAS systems

to other investigators is shown in Figure 111-2 The SAPRC high-volume

(Hi-vol) samplers were located Just north of the mobile vans and trailers

of other investigators The optical spectrometers were elevated on

concrete blocks to achieve a 24 m (8 ft) height for the optical beams in

order to minimize the influences or dry deposition of nitric acid and

other nitrogenous species This requirement necessitated a major

restructuring or the FT~IR and DOAS instrument supports In order to

augment the 12 m 4 ft height initially designed into the optical axes

or both of the long pathlength mirror assemblies while at the same time

preventing extraneous vibrations the spectrometers mirror systems and

their housings wereset on massive concrete blocks

Six 4 ft x 4 ft x 10 ft concrete structures were rented from the

Pyramid Precast company which provided the necessary machinery to

position the blocks on premarked areas at the study site Three of these

blocks constituted the support platform for the FT-IR and DOAS assemblies

at each end of the optical path (see Figure 111-2) New 9 ft x 12 ft

sheds were procured and constructed on these platforms during the last

week of August and the first week of September Subsequent assembly and

testing of the spectrometers and optical systems was completed in time for

the scheduled start of the field study on September 11 1985

As shown in Figure 111-2 the two SAPRC 25 m basepath optical systems

were set up parallel to each other and to the scaffolding which supported

most of the samplers from other groups participating in the intercomparishy

son study The optical systems were aligned in a north-south orientation

to minimize scattered light problems at sunrise and sunset and positioned

due west of the scaffolding and various mobile vans and trailers f The study period began at 0800 PDT on Tuesday August 12 and conshy

tinued until 0800 PDT on August 21 The FT-IR and DOAS systems operated

essentially continuously during this period with FT-IR spectra being

III-1

X -------

---middotmiddot --- - - -_ ___ -middot-

~~o -middot-- -s -middot- - bull ---- bull ltmiddot bullbull bull bullmiddot bull ~W-bull-middotbull-

_ 8ft bull--

N middotbull--~ i -

- L ~

--- - tJ-C---7JIIVW-middot -~254 _ middot

bulla_~ ~ -- ~ __-- bull Ii middotmiddot-middot- (-----

~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~

middot~---middot ~--bullmiddotmiddot-~-==~ middotmiddotbull middot -~ L

-~ 1

Lf ltnCftr-f-1-~=~~~=~~~=====~----~-~--~--=------------------ middotmiddotmiddotmiddotmiddot --~ ______

middot~----middotmiddot middotbull- bull W Irps~ bullbull diams t ee bull~raquo

Figure III-1 Citrus College campus showing location of August 1986 field study adjacent to football stadium IC- Field study site

FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)

( Figure 111-2 Positions of the longpath FT-IR and DOAS systems and UCR

Hi-vols relative to the instruments or the other particishypants in the Carbonaceous Aerosol Study on the Citrus College campus August 1986

III-3

acquired every 12-15 minutes during the day and every 20 minutes at night

DOAS spectra were acquired approximately every 15 minutes day and night

The Hi-vol samplers and other associated experiments operated on the 12-hr time periods 0800-2000 PDT and 2000-0800 PDT

111-4

IV MEASUREMENTS OF HONO H()2 NO~ RADICALS AND HCHO BY DIFFERENTIAL OPTICAL ABSORPTION SPECTROSCOPY

A Introduction

The development of a long pathlength OOAS system by Perner and Platt

1979) and its application and extension by these workers and by SAPRC

researchers Platt et al 1980ab 1981 1982 1984 Harris et al 1982

Pitts et al 1984ab 1985a) has provided a technique capable of sensishy

tive specific and time-resolved measurements of the ambient concentrashy

tions of a number of important atmospheric species including nitrous

acid formaldehyde the nitrate radical and nitrogen dioxide

In this section we briefly describe the design and operation of the

25 m basepath DOAS system employed to measure ambient levels of N03 radicals HONO N02 and HCHO during the Carbonaceous Species Methods Comparison Study and the results obtained during this measurement

period A more detailed description of the experimental system is provided in an earlier report to the ARB (Winer et al 1987)

B Experimental Methods

The 25 m basepath optical system (Figure IV-1) was of the threeshy

mirror White design but with an added corner reflector at the in-focus

end which effectively doubled its maximum pathlength capability The

mirrors were fabricated from 30 cm dia x 5 cm thick Pyrex blanks and

coated with a custom dielectric coating for optimum reflectivity in the spectral regions of interest

The DOAS system measures the ambient concentrations of trace

components which have distinct vibronic structures by their light

absorption in the near-ultraviolet (uv) and visible spectral regions

White light from a 75 W high pressure Xenon lamp was imaged by a spherical

mirror into the plane of the nesting (in-focus) mirror of the White cell

and then propagated through the multiple reflection optics until it

emerged from the system and was imaged onto the entrance slit of the

monochromator SPEX 1870 05 m) The light intensity was monitored by a

photomultiplier EMI 9659Q) and the signal acquired and averaged by a DEC

MINC 1123 minicomputer

IV-1

II SLOTTED tr~-_---_ ~OtSK

-- middot - flHOrOIIIT_D--~-_----bull--~ TUE25bullMETER 8ASEMTH MULTIPLE - ~ REFLECTION OPTICS middot-1gt MATING

---middot-middot-middot--middot -middot-middot-middot-middot--middot-middot-middot-middot-middot-middot-middot-middot -ft~-middot-middot-middot-middot-middot-middot~a_~--- ~~-=--=-----=-middot--middot-middot _ middot-middot-middot-middot-middot-middot-middot-middot-middot L-

1 middot-middot-middot-- IGHT n_n~--middot-middot-middot-middotaN middot---middot~middot-middot-middot---=- _ ~I -middot==---=-middot -middot -middot-middot -middot-middot I I middotbull-bullWbull --middot --------~-middotmiddot= _--middot---middottail~middot-middot ---middot -

Figure IV-1 Schematic diagram or the longpath DOAS aystbull

(

With the DOAS a rotating slotted disk was used to allow rapid

scanning The slotted disk was formed by etching a set of exit slits (100

microm wide 10 m spacing) radially into a thin metal disk This disk was

rotated in the focal plane of the dispersed spectrua As each slit moved across the opening between the masks that block the two adjacent slits it

scanned a spectral range of -30-60 nm depending on the rotation frequency

of the slotted disk The orientation of the spectrometer grating

determined which specific spectral region was scanned As employed in its

final form in this program the slotted disk rotated at -4 Hz resulting in

a scan rate of -100 Hz well above the frequency distribution of

atmospheric turbulence (which otherwise would introduce unwanted structure

into the spectra)

As a slit became visible at the edge of the mask it was detected by

an infrared photodiode A trigger signal was sent to the computer which

continuously recorded digitized samples of the light intensity as the slit

scanned across the spectrum Since several tens of thousand such scans

were acquired and added in the computer memory within a few minutes this

improved the signal-to-noise ratio of the resulting spectrum The

rotational speed of the slotted disk was maintained constant to within

101j to preserve the spectral resolution while superimposing the scans

The computer was also used for spectral deconvolution and for the

calculation of optical densities

Since a single scan required only -10 msec atmospheric scintillation

effects had little effect on the signal Moreover since typically (2-8)

x 104 individual scans were recorded and signal-averaged over each several

minute measurement period even complete but momentary interruption of

the light beam had no appreciable effect on the final spectrum Except

under the haziest conditions stray light effects were negligible due to

the instruments narrow field of view -8 x 10-5 steradians] and in any

case stray light could be taken into account by means of appropriate

background spectra

The concentrations of atmospheric species were derived from Beers

Law However since the light intensity in the absence of any absorption

(1 0 ) cannot be obtained with this technique the differential optical

density was employed and thus only those compounds which have structured

absorption spectra could be measured Table IV-1 gives the characteristic

IV-3

absorption bands and detection limits for a number of atmospheric species

of interest based on a km pathlength It can be seen that the

detection limits range from 3 ppb for HCHO down to -10 ppt for the N03 radical For automatic scanning of spectra 32 or 40 reflections (corresshy

ponding to pathlengths of 800 and 1000 m respectively) were generally

employed and the corresponding detection limits for quantitative analyses

were then 06-07 ppb for HONO and 13-16 ppt for N03 radicals

Table IV-1 Calculated Detection Limits for 25-m Basepath MultipleshyReflection Cell DOAS System Operated at 1 km Pathlength

Detection Differential Limit (ppb)

Absorption Absorption for 1 km and4Coeffcien Wavelength 25 x 10- 0D

Compound (atn1 cm- ) (nm) (base 10)

N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30

C Results and Discussion

The SAPRC 25 m basepath DOAS system was set up at the Glendora site

in the specific orientation relative to other experiments conducted

during this field study as described in Section III

Essentially continuous DOAS measurements were conducted from August

13 until the morning of August 21 1986 Maximum ozone levels and peak

concentrations of N03 radicals during this study are sUD1Darized in Table

IV-2 Individual concentrations of HONO HCHO and N02 observed during

this period are given in tabular form in Appendix B and hourly average

data for these species are given in Tables IV-3 to IV-5 For the

majority of the time the pathlength was set to 800 m with a detection

IV-4

Table IV-2 Maximum o3 Levels and Observations or No3 Radicals at Citrus College Glendora CA During August 13-20 1986

Maximum 0~ N~Radical Date Concentrati n Peak centration

(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected

limit equivalent to an optical density of 3 x o-14 bull The data reduction

process was more automated than previously and thus the detection limit was raised from 2 x 10-4 to 3 x 10-4 OD to offset the tendency of the

software to interpret noise at the detection limit as a peak The

corresponding detection limits were N02 35 ppb HOHO 08 ppb and

HCHO 45 ppb

Because the HONO and HCHO bands are overlapped by N02 bands and N02 is more abundant in the Los Angeles basin the DOAS spectra must be first

analyzed for N02 to enable its features to be quantitatively removed prior

to determining HONO and HCHO concentrations Figure IV-2 shows the timeshy

concentration profile for N02 from 0000 PDT on August 13 to 0800 PDT on

August 21 The solid line shows the DOAS data while the dashed line

shows measurements made by our chemiluminescence oxides of nitrogen

analyzer The two curves track each other very well during the nighttime

and early morning hours In the afternoon the NOx analyzer consistently

read 10 to 30 ppb higher since the DOAS values at those times were as low

as 15-25 ppb this caused a discrepancy of a factor of two or more The

higher values measured by the chemiluminescence method are attributed to

IV-5

Table IV-3 Hourly Average HOIJO Concentrations (ppb)a Measured by the Long Pathlength DOAS System During the 1986 Citrus College Study

Time Period Date (hr) PDT 813 814 815 816 817 818 819 820 821

00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25

09-10 BD BD BD BD BD 12 BD 18

10-11 BD BD BD BD BD BD BD 1

11-12 BD BD BD BD BD BD BD BD

12-13 BD BD BD BD BD BD BD BD 13-14 BD BD BD BD BD BO BD BD 14-15 BD BD BD BD BD BD BD BD 15-16 BD BD BD BD BD BD BD BD 16-17 BD BD BD BD BD BD BD BD

17-18 BD BD BD BD BD BD BD BD 18-19 BD BD BD BD BD BD BD BD 19-20 BD BD BD 09 BD BD BD 09 20-21 BD 09 10 15 09 BD 10 13

21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7

Estimated errors t08 ppb or t30J whichever is largerBD = Below detection limit (08 ppb)

IV-6

(

Table IV-4 Hourly Average N02 Concentrations (ppb)a Measured by the Long Pathlength DOAS System During the 1986 Citrus College Study

Time Period Date hr) PDT 813 814 815 816 817 818 819 820 821

00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837

aEstimated errors plusmn35 ppb or plusmn15J whichever is larger

IV-7

Table IV-5 Hourly Average HCHO Concentrations (ppb)a Measured by the Long Pathlength DOAS System During the 1986 Citrus College Study


00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95

aEstimated errors plusmn45 ppb or plusmn30j whichever is larger

IV-8

---

~

BOAS iCIIIKlUIClllllcmtCI - - - 150

100 l ti

H

deg

f 50 ~ V~ VJlf1rr middotv f ~~ ~ ltI

01~ I I I I t I t I t t t t t I I t t I t I I I t t I I I t I I I t I t 17 18 19 2IJ 2114 15 16

DATE

Figure IV-2 Time concentration profiles for nitrogen dioxide measured by DOAS and chemiluminescence (N0

1-NO) at Citrus College (Glendora) in August 1986

0f I I I I I I I I I I I I I I I I I I I I It I I I It t t t t t t I 13 14 15 16 17 18 19 a 21

DATE

Figure IV-3 Time concentration profiles for formaldehyde measured by long pathlength DOAS and FT-IR spectrometers at Citrus College (Glendora) in August 1986

25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i

~ i I I Il I l) J~ fJ 1 1 1 1 1 1e1~ 1 - bull 1 bull I I I I I t t t t t t t t t 1 1 1 middot 1 1 1 1 I14 1S 16 17 18 19 28 2i

DATE

Figure IV-4 Nitrous acid time-concentration profiles measured by long pathlength DOAS system at Citrus College (Glendora) in August 1986

H

f--

the known interferences of HN03 and PAN in this detection method

consistent with the levels or HN03 and PAN in the afternoon periods being

approximately equivalent to this difference in the DOAS N02 and chemilshy

uminescence N0x-H0 readings

After the quantitative removal of the N02 features from the OOAS

spectra the data reduction procedure utilized a simultaneous leastshy

squares fit or HON0 and HCHO reference spectra to the residual ambient air

spectra Figure IV-3 shows the time concentration profile for HCHO as

determined by DOAS (solid line) For comparison the FT-IR data from

Section V are shown as the dashed line The agreement between the two

methods is very good with the discrepancies being within the error

limits However it appears that the OOAS results for the first four

nights are consistently higher than the FT-IR data by about 1-3 ppb This

could be due to an overestimation of HCH0 absorption features in the OOAS

spectra since the reported FT-IR HCH0 levels were at or below the DOAS

detection limit of 45 ppb (where the signal-to-noise ratio was near

unity)

Finally the H0N0 time-concentration profile for August 13-21 is

presented in Figure IV-4 No comparison data are available for HON0 for

this study However as discussed above the only source of a large

systematic error would be the literature value for the HON0 absorption

cross-sections used in the calculations During the Citrus College field

study nighttime HON0 levels were higher than observed in the 1985

Nitrogen Species Methods Comparison Study at Claremont where the maximum

HON0 concentrations were in the range 15 to 25 ppb For five of the

nights at Citrus College the HON0 concentrations were also in the same

range However for three nights H0N0 levels attained -35 ppb and

during the last night of the study H0N0 reached a maximum of Jamp5 ppb

There was however no correlation of the HON0 concentrations to the

nighttime N02 levels which were relatively constant at 60-75 ppb Since

the heterogeneous formation of H0N0 from N02 involves moisture correlashy

tions to other parameters such as relative humidity and particulate

loading may prove interesting

IV-12

(

V LONG PATHLENGTH FT-IR MEASUREMENTS OF HN03 NH3 AND HCHO

A Introduction

As discussed elsewhere in more detail (Winer et al 1987) the long

pathlength FT-IR system was employed to provide benchmark data for the

Nitrogen Species Methods Comparison Study held at Pomona College

(Claremont) in September 1985 Following this the FT-IR spectrometer

participated in our winter field study at El Camino CoDJDUnity College

(Torrance) Due to a need for a more detailed comparison of HN03 measurements by the FT-IR and tunable diode laser spectroscopic (TDLS)

methods than had been possible during the 1985 Claremont study the

longpath FT-IR system was subsequently set up in Glendora on the Citrus

College campus for more intensive measurements of HN03 and NH3 between

August 12-21 1986 In this study species coverage by the FT-IR method

was extended to include the measurement of formaldehyde (HCH0) Attempts

were also made to detect N2o5 in ambient air by thorough examination of

the spectra recorded in the late afternoon and evening hours Alllllonia

(NH3) was included among middot the species measured since in certain

localities it can profoundly affect the concentration of gaseous HN03 by

its reaction to form aerosol anmonium nitrate (Doyle et al 1979 Tuazon

et al 1980)

B Experimental

1 Kilometer Pathlength FT-IR System

Measurements of ambient air pollutants by infrared spectroscopy

were carried out using a recently constructed 25-m basepath open

multiple-reflection optical system interfaced to a Mattson Instruments

Inc Sirius 100 FT-IR spectrometer This spectr0111eter has a maximum

resolution capability of 0125 cm-1 and is equipped with a Motorola 68000-

based data system The long pathlength optics are of the three-mirror

White design (White 1942) with provisions for adding a corner reflector

at the in-focus end (Horn and Pimentel 1971) when desired to effectively

double the systems pathlength The mirrors in this new optical system

were fabricated from 30 cm diameter 6 cm thick Pyrex blanks and goldshy

coated for the best reflectivity (~99J) in the infrared The optimum

pathlength for monitoring was determined to be in the 1-1 5 km range

V-1

during routine operation although short-term use or optical patha greater

than 2 km were possible

As discussed in Section Ill the long pathlengtb FT-IR spectrometer

was operated alongside the long pathlength DOAS systell as shown in Figure

V-1 The optical layout of the FT-IR system is preaented in more detail

in Figure V-2 The sets or mirrors of the two spectrometers were arrayed

in opposite directions but aligned side by side in a compact arrangement

which made possible simultaneous analyses of virtually the same air

mass The FT-IR spectrometer was housed in an air conditioned shed while

the multiple reflection mirror assembly outside was shaded from direct

sunlight by protective shields While the spectrometer system had an

initial height of 1 2 m (above ground level) designed into the optical

axis this was raised to a total of 24 m (8 ft) the C0111110n sampling

height required for all analytical techniques being compared during this

field study Massive concrete blocks were employed as support structures

to attain this sampling height

2 Acquisition of Spectra

Spectra were recorded at a pathlength of 1150 meters and 0125 1cm- resolution unapodized) Sixty-four scans interferograms) were

added during a 45-min period and then transformed (calculation time of

-25 min) to a single beam spectrum Each spectrUII of 128 K points was 1truncated and the spectral region from 400 to 3000 cm- which contained

the absorption bands of HN03 NH3 and HCH0 used for analysis was retained

and archived

Four to five spectra per hour were collected This rate or data

collection permitted a real-time examination of the quality of spectra

being recorded and such checks were consistently made during daytime and

early evening hours 0800-2200 PDT) During the noncritical period of

2200-0600 hours when nitric acid was expected to be below the detection

limit the FT-IR spectrometer was programed to conduct automatic

monitoring

3 Calibration

Figure V-3 illustrates the absorption features or HNO3 and NH3 in

the region accessible to long pathlength FT-JR measurements Asterisks

mark the peaks which were employed to determine concentrations A more

V-2

________ _

~

25m BASEPATH FT-IR ANO OOAS SPECTROMETERS TOTAL OPTICAL PATHLENGTHS 1-2 km

_ __ ______ __I~~ jr~~f - ~ -------- ~RI -+-----------------~-~ ===-- I INTERFEROMETER DOAS I _ ___ __ ------- ) ~ II EJ ~ -- ~

bull 25m -

Figure V-1 Relative arrangement of the longpath FT-IR and DOAS systems

25-METER BASEMTH MllTIPIE MICROfJETER REFLECTION OPTICS

REFERENCE AOJUSALIGNtETMENT INFRARED DETECTOR LASER NTS SOURCE ~ middotmiddot- - -- --middot-=-=-a middot-middotrBi---81-- middot Gr~--- - diams-----middot--middot

flXEO CORNER CUBEli~--~ ~~----middot--7-~~~ middot middot-----~ ~~----middot--middot-- -=~ IS APERTURE I ~middot=middot fll~-=-===---_--- - middot-middot-middot===~~~~---middot-middot-middot-middot-middot~DI-bull n middot-middot-middot-middot-middot__~~~JJ -middot-middot-middot-middot-middot-middot-

middot-middot-middot-middot-middot-middot-middot~1 -middot-middot-middot-middot-middot-middot-middotmiddot ~

Figure V-2 Schematic optical diagram of the longpath FT-IR spectrometer

-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --

middot I t 1 1J I II I 1111 till middoti H IJ l l lJlll l I I

NH3

981 UIII 1188

WAVENUMBERS (cm- 1)

Figure V-3 Reference spectra of gaeous HN01 (061 torr) and NH3 (023 torr) at spectralresolution or 0125 cm- pathleftgth or 25 om total pressure with N2 or 740 torr The HN03 plot is offset by 030 absorbance (base 10) unit for clarity Asterisks mark the absorption peaks used for analysis

expanded plot or the HN03 spectrum in the range 870-910 cm- 1 is presented

in Figure V-11 to which is added a middotqualitative single beam spectrum or 1clean ambient air at a pathlength of 1150 m The Q-branch at 896 1 cm-

was the most appropriate one for quantitative measureaent because or its

favorable half-width and minimal interference by ataaspheric water vapor

We restricted our measurements to the heights of the sharp absorption (Qshy

branch) features only since measurements which include the broad undershy

lying envelope were more susceptible to unknown interferences The 8854 1cm- Q-branch was totally free of interferences but its relatively

narrower line shape was more susceptible to distortion by noise while the 1strongest Q-branch at 8789 cm- was severely overlapped by a strong water

line

Of the numerous sharp features of the NH3 spectna depicted in Figure

V-3 the lines at 11034 and 8679 cm-1 though not the strongest suffer

the least interference by H2o and CO2 absorption lines and were therefore

the ones chosen for analysis The line positions of NH3 relative to those

of atmospheric H20 (and CO2) in the 1080-1120 cm-1 region are shown in

Figure V-5 The calibration procedure for trn3 was straightforward

Spectra were recorded at O 125 cm- 1 resolution for several NH3 pressures

in the range 02-1 torr which were measured to within 10005 torr

accuracy with an MKS Baratron capacitance manometer The NH3 samples were

transferred to a 25-cm cell with KBr windows and pressurized with N2 gas

to atmospheric pressure No measurable decay of IH3 concentration was

observed within the 15-minute period during which repeat spectra were

recorded for each sample These data yielded absorptivities (base 10) at

23degC and 740 torr total pressure of 182 cm-1 atm-1 for the 11034 cm-1

peak and 97 cm-1 atm- 1 for the 8679 cm- 1 peak with uncertainties of t5J

(two standard deviations for both values

A similar calibration procedure was not possible for HN03 because of

its significant decay to the walls of the 25-cm cell We determined our

high resolution absorptivity values relative to the data of Graham and

Johnston (1978) who made an accurate determination of the absorptivity of

the HN03 4 ( 1325 cm- 1 fundamental band at -2 cm-1 resolution using two

independent methods for generating HN03 ( for more details see also Graham

1975) We assigned Graham and Johnstons ( 1978 absorptivity value

V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)

Figure V-4 Infrared absorption peaks of HN03 (lower trace) ~elative to atmosphericH 0 absorptions (upper traoe) in the 870-910 cmmiddot region2

02

W 015u z lt( llJ 1CD

ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)

Figure V-5 Infrared absorption peaks of NH1 (lower trace) relativ1 to atmospheric H20 and co absorptions (upper tracfi) in the 1080-1120 cm- region

2

1(peak-to-baseline) for the broad Jl P-branch at 1315 cm- to the same

feature in our 0125 cm- 1 resolution spectrum after S1100thing the latter

to -2 cm-1 resolution The absorptivity tor a Q-branch (eg 8961 cm- 1)

at O 125 cm-1 resolution was then determined from the intensity ratio of

the unsmoothed Q-branch to the smoothed P-branch

Smoothing removes the fine structure superimposed on the bandv4 envelope and in order to test the adequacy of tbe smoothing function

1employed measurements were carried out in which 2 cm-1 and 0125 cm-

resolution spectra were recorded alternately for an 11103 sample To take

into account the HN03 decay in the cell the 1315 cm-1 peak heights at 2

cm- 1 resolution were plotted against time as were those or the 0125 cm- 1

resolution spectra after having been smoothed to -2 m-1 resolution The

two curves were found to be indistinguishable indicating the accuracy or

the smoothing function applied The above procedure yielded a value of

52 plusmn 04 cm- 1 atm-1 for the absorptivity (base 10) of the HN03 peak at

896 1 cm- 1 (Q-branch height only) with the two standard deviation error

including that reported by Graham (1975) This value is in fact the same

as that we previously determined for this peak at 05 cm-1 resolution

(Tuazon et al 1980) Following the same method the absorptivity of the

8854 cm-1 Q-branch was found to be 61 plusmn 05 cm-1 ata- 1bull

The calibration procedure for HCHO was the sue as that for NH bull3Formaldehyde samples were pre-distilled from paraformaldehyde and

immediately used after collection in a liquid nitrogen cooled trap The

absorptivity value of the 2781 0 cm- 1 Q-branch an absorption peak well

isolated from H2o absorptions was determined to be 89 plusmn 05 cm- 1 atm-1

4 Treatment of Data

The quantitative analysis of species such as NH3 which possess

relatively narrow Q-branch features which are sufficiently resolved from

atmospheric H2o absorptions was normally straightforward The absorbance

(log 10 1 was derived directly from the single beaa spectrum and thus a

ratio plot against an actual background spectrum was not necessary Proshy

vided that the detector had a linear response 10

and I as determined from

a single beam spectrum had values on an arbitrary scale in which zero

corresponded to zero signal on the detector The appropriate differential

absorption coefficient such as those determined above and the absorption

pathlength had to be applied to the absorption intensity measured between

V-9

and I in order to convert to concentration units This procedure was10

followed for the 11034 and 8679 cm-1 lines of NH3 Estimates of the HN03 concentration could also be obtained from

single-beam spectra by employing the 8854 cmmiddot1 Q-branch However the

HN03 analysis was more reliably carried out using the 8961 cm-1 Q-branch

by ratioing the sample spectrum with a clean background spectrum a

procedure which improved the baseline and resulted in essentially complete

cancellation of a very weak H20 interference Background spectra were

chosen from those recorded at around midnight during low pollution days

since previous measurements (Spicer et al 1982) showed HN03 levels that

were much lower (lt1 ppb) than the FT-IR detection limit under these

conditions

The peak-to-peak noise level in the ratio spectrum was typically

00025 absorbance unit base 10) corresponding to a 250 1 signal to

peak-to-peak noise ratio for single spectral records The absorption

peaks used for the analyses were much wider than the frequency of random

noise such that peak heights as small as the noise level could be

detected above the noise itself Thus the detection sensitivities were

3-5 ppb for HN03 1-2 ppb for NH3 and 2-3 ppb for HCHO The lower

detection limit for each compound was realized when turbulence due to

temperature gradients andor wind were minimal for example during

nighttime hours)

The possible detection of N2o5 depended on how well its broad band

centered at 1246 cm- 1 ( 12) could be discerned from interfering H20

absorptions The H2o interferences were reduced by ratioing the sample

spectra against selected background spectra taken during those periods

(mid-morning to noon) when N2o5 was believed not to be present due to the

rapid photolysis of No3 radicals Although exact cancellation of the H2o absorptions was not possible the windows between these absorptions were

sufficient to define a baseline from which the presence of a broad absorpshy

tion contour could be distinguished From the literature value of 188

cm- 1 atmmiddot 1 for the absorptivity of the 1246 cm-1 peak (Graham 1975 Graham

and Johnston 1978) it was calculated that 5 ppb N2o5 at a pathlength of

1150 m would give a signal of -001 absorbance unit (base 10) approxishy

mately 4 times the peak-to-peak baseline noise of the ratio spectrum

V-10

The largest source of uncertainty in the analyses was the noise level

in the spectrum with other errors being generally negligible We

assigned to each peak height measurement the maxillum error which was

equal to the peak-to-peak noise level For HN03 this error was 4 ppb

The uncertainty arising from the error in the absorptivity (of the 8961

cm- 1 Q-branch in this case) increased with the concentration However

this contribution to the overall error limit was relatively small for the

range of HN03 concentrations encountered For example it increased the

t4 ppb error by only 10j when included in the error calculation for an

HN03 concentration of 25 ppb For NH concentrations i20 ppb the sum of uncertainties due to noise3

and error in the absorptivity of the 11034 cm-1 line was plusmn15 ppb At

higher concentrations the contribution from the absorptivity error became

relatively more important A detailed plot of this error contribution as

a function of concentration revealed that it is nearly linear in the

concentration range 20 to 100 ppb permitting the additional error to be

calculated from the empirical formula (0044( [NH3]-20) ppb Thus for the measurement of 60 ppb NH3 the total error can be calculated as [ 15 +

0 044 )( 60-20)] = plusmn33 ppb

For the range of HCH0 concentrations encountered in the 1986 Glendora

study the measurement errors were less than plusmn3 ppb


As discussed in Section II our measurements were conducted in

conjunction with the CARB-sponsored Carbonaceous Species Methods

Comparison Study which occurred from 0800 PDT August 12 to 0800 PDT

August 21 1986 ln contrast with the low level of air pollution during

the 1985 Claremont summer field study this August 1986 measurement period

at Citrus College was characterized by moderately high levels of photoshy

chemical activity Except for the second day of measurements the maximum

hourly average o3 concentrations exceeded 200 ppb each day

The FT-IR spectra obtained were analyzed for the simultaneous concenshy

trations of HN03 NH3 and HCH0 The detailed instantaneous data are

presented in Table V-1 and are plotted in Figure V-6 The hourly average concentrations are presented in Tables V-2 to V-4 Except for periods of

power disruption on August 14 and the loss of most of the daytime data on

V-11

Table V-1 Simultaneous HNOi NHr and HCHO Concentrations (ppb in Glendora CA Au ust 2-21 1986 by Long Pathlength FT-IR Spectroscopy (No entries tor HNO~ mean below detection limit Asterisks mark the times were gaps in the data occur

PDT HN03 NH3 PDT HN03 NH3 HCHO

81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(

Table V-1 (continued) - 2

PDT HN03 NH3 HCHO PDT HN03 IH3 HCHO

0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13


PDT HN03 NH3 HCHO PDT HN03 NH3 HCHO

bull1059 82 15 146 00Jl7 25 38bull1153 104 24 118 0107 28 361208 128 27 121 0126 25 341221 145 26 91 0116 3- 3 11240 16 1 211 137 0206 3 1 271253 16 1 33 133 0225 28 221309 157 29 130 0245 36 30bull1322 175 32 125 0305 32 39bull1507 201 27 94 0324 38 261520 223 30 153 03Jf11 32 281531 246 23 174 0404 33 391543 222 29 187 0Jf21 4Jl 351555 23 1 23 199 0443 39 361606 222 20 168 0503 112 311620 196 3 1 153 0523 52 291643 175 13219 0543 119 381655 182 22 127 0602 35 LO1711 188 17 133 0622 311 491723 18 1 12 126 0641 40 441735 17 1 16 124 0701 47 421746 163 2 1 135 0721 29 421801 159 20 109 0741 20 431818 138 1 6 108 0800 4 2 461830 128 22 109 0820 13 6 11842 130 22 128 OSJIO 13 741853 115 15 116 0859 1 7 16 731925 102 20 103 0919 3 1 1 1 881938 8 1 14 95 1016 62 07 1051951 84 22 84 1029 84 13 1072004 87 14 95 1043 99 12 1032017 56 18 85 1100 11 3 14 10 1 2030 53 20 83 1112 97 12 1082044 34 7623 1126 135 13 11 3 2057 38 1 7 72 1138 128 13 12 ll2110 2 1 20 77 1151 13 1 18 1282123 2 1 60 1203 145 14 1222136 21 60 1219 17 1 4 1282210 15 47 1231 160 1 9 1172229 17 55 1244 17 1 1 2 1102249 15 53 1256 21JJ 2 t 12309 15 49 1309 212 17 11 1 2328 26 42 1325 209 21 1222348 23 36 1341 196 30 104

1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(


PDT HN03 NH3 HCHO POT HN03 NH3 HCHO

1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17


PDT HN~ 183 HCHO PDT HN03 HCHOIH3

1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I

Figure V-6 Time-concentration profiles for formaldehyde nitric acid and ammonia measured by long pathlength FT-IR spectroscopy during the 1986 Citrus College study

V-20

(

Table V-2 Hourly Average HNO~ Concentrations (ppb) at Glendora CA August 12-20 986 Measured by Long Pathlength FT-IR Spectroscopy

Aug Aug Aug Aug Aug Aug Aug Aug Aug PDT 12 13 14 15 16 17 18 19 20

0700-0800 lt3 lt3 lt3 lt3 lt3 lt3 lt3 lt3 lt3 0800-0900 lt3 lt3 lt3 lt3 28 lt3 33 55 36 0900-1000 34 30 xa 37 44 lt3 59 108 59 1000-1100 7 1 67 X 83 90 X 110 170 102 1100-1200 13 1 105 X 123 142 X 140 20 1 165 1200-1300 159 133 148 171 158 X 196 187 225 1300-1400 182 150 X 201 180 X 17 1 226 212

1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12

1900-2000 33 49 95 40 78 X 3JI 37 47 2000-2100 lt3 42 53 lt3 45 X lt3 lt3 46 2100-2200 lt3 lt3 lt3 lt3 lt3 X lt3 lt3 lt3

ax - Designates no data due to power interruptions on August 14 and fault in archiving on August 17

V-21

Table V-3 Hourly Average N~ Concentrations (ppb) at Glendora CA August 12-2i 19 Measured by Long Pathlength FT-IR Spectroscop

Aug Aug Aug Aug Aug Aug Aug lug Aug Aug PDT 12 13 14 15 16 17 18 19 20 21

0000-0100 54 29 26 33 39 59 75 55 60

0100-0200 5 1 36 29 36 39 46 65 61 65 0200-0300 53 36 32 34 37 6 1 82 58 75 0300-0400 46 24 34 4 1 26 63 74 60 7 1 0400-0500 5 1 27 40 35 23 60 76 68 7 1 0500-0600 50 35 47 34 22 47 67 58 65 0600-0700 49 3 1 38 32 23 45 70 63 64 0700-0800 64 21 31 2 1 24 49 62 72 0800-0900 88 51 19 18 13 38 57 66 99 0900-1000 62 19 xb 1 1 11 54 7 1 67 100 1000-1100 39 16 X 12 X 99 63 90 1100-1200 34 19 X 14 19 X 132 73 89 1200-1300 39 26 27 6 24 X 82 50 79 1300-1400 44 3 1 X 23 26 X 64 62 63 1400-1500 39 35 X 3 1 30 I 44 611 60 1500-1600 37 38 26 26 29 X 58 52 62 1600-1700 32 43 23 23 29 x 55 46 50 1700-1800 3 1 38 17 2 1 24 X 54 54 55 1800-1900 5 4 1 19 20 23 I 65 62 75 1900-2000 59 40 18 23 29 X 56 74 97 2000-2100 44 36 1 9 33 115 X 7 1 90 74 2100-2200 48 53 20 3 1 4 X 85 69 7

2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84

8 Blank means outside the schedule bx - Designates no data due to power interruptions on August 14 and fault

in archiving on August 17

V-22

Table V-4 Hourly Average HCHO Concentrations (ppb) at Glendora CA August 13-211 1986 Measured by Long Patblength FT-IR Spectroscopy


0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102

0200-0300 52 42 28 47 67 76 69 86 9 1 0300-0400 40 40 3 1 43 74 76 7Iamp 87 92 0400-0500 42 47 36 46 74 78 8 85 84 0500-0600 so 39 34 40 75 74 70 92 98 0600-0700 43 4 1 45 38 63 62 96 105 10 1 0700-0800 75 63 43 59 7 1 85 130 117 0800-0900 92 101 65 97 94 97 145 195 0900-1000 124 xb 90 112 154 138 142 225 1000-1100 131 X 104 13 1 X 174 144 208 1100-1200 119 X 117 145 X 21 1 144 159 1200-1300 113 120 118 1 7 X 168 123 192 1300-1400 106 X 117 10 1 X 105 145 17 1 1400-1500 114 X 16 1 114 X 11 bull 1 149 159 1500-1600 119 159 15 1 148 X 157 106 122 1600-1700 133 146 132 142 X 152 75 80 1700-1800 12 1 127 90 132 X 116 8 1 76 1800-1900 100 114 88 11 o X 92 70 11 1 1900-2000 84 99 80 9 1 X 64 73 105 2000-2100 73 82 6 1 84 X 70 77 92 2100-2200 64 63 48 85 X 62 69 86 2200-2300 69 52 37 75 X 79 86 82 2300-2400 60 42 5 54 6 1 82 86 90

aBlank means outside the schedule bx - Designates no data due to power interruptions on August 14

( and fault in archiving on August 17

V-23

August 17 due to a fault in archiving the data onto agnetic tapes the

FT-IR system provided continuous coverage of HCHO and 1H3 concentrations

since they were always above the respective detection 11llits of -2-3 ppb

and -1-15 ppb HN~ was generally above the -3-Ji ppb detection

sensitivity between 0800 hr and 2000 hr each day throughout the study

period As for the 1985 Claremont and the 1986 Torrance studies N2o5 was

not observed above the estimated detection limit of 4 ppb

The FT-IR analysis of formaldehyde was easily carried out with the

use of single-beam spectra since the HCHO infrared spectrum has a Qshy

branch at 27810 cm-1 well isolated from other atmospheric absorptions

HCHO was included as one of the species to be measured by FT-IR (except

during the first day) because of the need for a standard against which

other HCHO methods employed at this study could be compared Our

contribution to this aspect of the carbonaceous species study was to

provide HCHO measurements by both DOAS and FT-IR spectroscopy either

method of which can serve as a benchmark standard l comparison or the

two sets of spectroscopic data for HCHO has been discussed in Section IV

and comparison with the results of the other HCHO methods is currently

being carried out by Dr Douglas Lawson of the CARB

The NH3 concentrations observed in Glendora (Table V-2) during the

first six days or the field study (September 12-17 were generally in the

range of 2-4 ppb These levels are similar to those aeasured during the

1985 Claremont study for the periods when there was no localized transport

of NH3 to the latter site from nearby agricultural sources NH3 levels

during the remaining days (August 18-21 were more variable and generally

about twice the above range of values (Figure V-6 he erratic pattern

found in the NH3 concentrations during these three days which is also

noticeable in the more well-defined HCHO and HN03 concentration profiles

(Figure V-6 could well be due to the prevailing wind conditions

The maximum instantaneous concentrations of HN~ attained 20 ppb or

higher during the eight days that the FT-IR measurements provided detailed

HN03 profiles (Figure V-6) with the highest concentration of 33 ppb being

observed on August 19 Comparison of our Dasibi ozone data with the FT-IR

measurements of HN03 showed a strong correspondence between the HN03 and

maxima This is illustrated in Figure V-7 for the pollution episodeso3 of August 15-16 where the hourly average HN03 concentrations (by FT-IR)

V-24

21

(

GLENDORAbull AUS 15-16 1986 a 3

a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16

Figure V-7 Time-concentration plots of average HN03 (FT-IR) N02 (DOAS) and o (Dasibi monitor) at Citrus College for August 15-1631986

V-25

are compared with the half-hourly average o3 concentrations The corresshy

pondence of the HN03 concentration profile with that of the o3 curve 1s

even more pronounced in the similar plot in Figure 1-8 for the August 18-19 episodes Figures V-7 and V-8 also include the hourly average H02 concentrations (DOAS data Section IV) which clearly show the expected

minimum at the times of the maximum o3 and HN03 concentrations However

the maximum levels of HN03 observed in the afternoon could not be correshy

lated with the maximum levels of NO2 that prevailed during the morning

hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a

liLENDORAbull AUG 11-1 1916

a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)

Figure V-8 Time-concentration plots of average HN0 (FT-IR N0 (DOAS)3 2and o3 (Dasibi monitor) at Citrus College tor August 18-19 1986

V-27

VI AMBIENT CONCENTRATIONS OF PAH AND NITRO-PAH

A Introduction

The PAH emitted from combustion sources exhibit a wide range of

volatility and are hence distributed in the atmosphere between the gas

and particle phases As we have shown previously (Arey et al 1987)

complementary sampling techniques are required to obtain a comprehensive

data set concerning the concentrations of volatile and non-volatile PAH

and their derivatives in the atmosphere Thus the volatile 2-ring PAH such as naphthalene which are present almost entirely in the gas-phase

can be quantitatively collected on Tenax GC solid adsorbent The nonshy

volatile 5-ring and larger PAH and 3- to 4-ring nitro-PAH are particle

associated and are collected totally on the Hi-vol filters The 3- and 4-

ring PAH of intermediate volatility and the 2-ring nitro-PAH can be

collected on PUF plugs as well as on the filters indicating that they are

either present mainly in the gas-phase or are blown-off the filter

during the collection period Thus three different collection media were

employed for the ambient air sampling at Citrus College Tenax-GC solid

adsorbent PUF plugs and Hi-vol filters The ambient air samples were

collected from August 12 to August 21 with 12-hr day (0800-2000 PDT) and

night (2000-0800 PDT) sampling intervals

B Experimental

1 Sampling Media Cleaning Procedure

Tenax-GC solid adsorbent was Soxhlet extracted in a cellulose

thimble for -5 hr in a 64 (vv) acetonehexane mixture After packing in

Pyrex tubes (using precleaned glass wool) the Tenax cartridges were

conditioned for -4 hr by heating at 275degC with nitrogen flowing through

them at -20 mL min- 1 The Teflon-impregnated glass fiber (TIGF) filters

and PUF plugs were cleaned by Soxhlet extraction for -16 hr in methylene

chloride followed by another 16 hr extraction with methanol

2 Tenax-GC Cartridges Sampling and Analysis

Two sizes of Tenax-GC cartridge were used for the collection of

gas-phase PAH at different flow rates Low-flow cartridges consisted of

10 cm x 4 nnn id Pyrex tubes packed with 0 1 g of Tenax GC solid

adsorbent with sampling flow rates of -1 L min-1 yielding an -06 m3

VI-1

volume of air for each 12-hr sampling period High-flow cartridges

consisted of 10 cm x 1 cm id Pyrex tubes packed with 06 g of Tenax-GC

and operated at flow rates of -10 L min-1 resulting in -6 m3 of air

sampled during a 12-hr period Each low-flow cartridge was equipped with

back-up Tenax cartridge placed in series downstream from the first

cartridge to check for breakthrough

After sampling the Tenax cartridges were stored in dry-ice transshy

ported to SAPRC and stored in a freezer prior to analysis

For analysis deuterated internal standards were added to the lowshy

and high-flow Tenax cartridges respectively as follows in microg)

naphthalene-d5 (18 16) biphenyl-d10 (07 10) phenanthrene-d 10 (06

06) The low- and high-flow cartridges were eluted with 2 mL and 10 mL respectively of diethyl ether which was then solvent exchanged to -02

mL of acetonitrile (using a micro-Snyder apparatus for the high-flow

cartridges)

PAH identifications and quantifications were made by combined gas

chromatographymass spectrometry (GCMS) with multiple ion detection

(MID) as described in detail below

3 High-Volume Filters Followed by PUF Plugs Sampling and Analysis

Two high-volume sampler systems consisting of a TIGF filter

follow by four PUF plugs (-9 cm diameter x 5 cm thickness) [see Figure VI-

1] were run at -23 SCFM for 12 hr intervals yielding ambient samples

collected from -1000 m3 of air

Prior to analysis the PUF plugs were combined into six samples

consisting of a single day sample and a single nighttime sample from the

early portion of the study single day and single night samples from the

latter part of the study and composite samples from four day and four

nights Specifically the samples were (11) August 13 0800-2000 hr

(2) August 13-14 2000-0800 hr (3) August 15 16 17 and 18 0800-2000

hr (4) August 15-16 16-17 17-18 18-19 2000-0800 hr (5 August 20

0800-2000 hr (6 August 20-21 2000-0800 hr

The samples from a single 12-hr day or night collection period (ie

samples 1 2 5 and 6) each consisted of eight PUF plugs (four from each

of the two Hi-vols used and these were combined and extracted together

The composite samples 3 and 4 were each analyzed in two parts ~UF

plugs 1-3 (see Figure VI-1) and to check for breakthrough of the more

VI-2

(

GLASS CYUNOER-1+-bull11middot middot

SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull

PLUG 3 middot middot middot bullPLUG Amiddot

MOTOR

EXHAUST

Figure VI-1 Schematic of modified Hi-vol sampler with PUF plugs underneath the filter to collect gas phase species and compounds blown-off the filter

Vl-3

volatile PAH PUF plugs 4 Prior to extraction the PUF plugs were

spiked with deuterated internal standards as follows single 12-hr

samples composite samples and fourth plugs respectively in microg)

naphthalene-da (327 992 248) biphenyl-d 10 (327 991 248)

phenanthrene-d 10 (330 1001 250) anthracene-d10 (369 1119 248

benz(aanthracene-d 12 (134 406 102) chrysene-d12 (278 843 211)

fluoranthene-d 10 (351 1064 266) pyrene-d10 345 1046 262

dibenzothiophene-da 102 308 077) 1-nitronaphthalene-d7 035 107

027) and 2-nitrofluoranthene-d9 (035 107 027) All samples were

Soxhlet extracted overnight (-16 hr) with methylene chloride concentrated

by rotary evaporation under vacuum to -4 mL filtered through 045 microm

Acrodiscs (Gelman Sci) and concentrated further under a stream of

nitrogen to -500 microL

The extracts were fractionated by HPLC using an Altex semi-prepashy

rative scale Ultrasphere Silica column (1 cm x 25 cm) Figure VI-2 shows

a typical HPLC profile of a PUF plug extract together with the mobile

phase program employed A fraction containing the PAH was collected from

4 min to 22 min and a nitroarene-containing fraction from 22 min to 34

min The fractions were concentrated by rotary evaporation then taken

just to dryness under a stream of nitrogen After dissolving in acetoshy

nitrile or CH2c12 the PAH and nitroarene fractions were analyzed by

GCMS-MID as described below

4 Hi-Vols with TIGF Filters Sampling and Analysis

Seven Hi-vol samplers each equipped with a 10 microm cut-off inlet

were employed for POM collection The samplers were run at -40 SCFM

yielding an ambient sample collected from -800 m3 of air for each Hi-vol

over a 12-hr sampling period Two Hi-vols were employed solely for the

collection of POM used for mutagenicity testing The TIGF filters from

the remaining five Hi-vols were combined into six samples corresponding to

the PUF plug samples described above ie samples 1 and 2 and samples

5 and 6 comprised the single day and night samples from August 13-14 and

August 20-21 respectively and samples 3 and 4 were the composite day

and night samples from August 15-16 16-17 17-18 and 18-19 The filter

extraction and work-up procedure was as shown in Scheme VI-1 Each sample

was spiked with deuterated internal standards as follows (single 12-hr

samples and composite samples respectively in pg) fluoranthene-d 10

VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p

I t I I I I I I Fraction

Hexane 1001 ctt2c12

- bull t bull ----middot-1001

CH CN3 ---middot4bullbull -~ middot-middotmiddot - _____ ____

1001 ---middot--middot-- - 0 10 20 30 40

Minutebull

Figure VI-2 HPLC trace (254 nm) and gradient solvent program for separation or an ambient s8JIIJ)le co11ycted on PUF plug Semi-preparative Ultrasphere Si column (1 cm x 25 cm) 3 mL min- HPLC factions were combined as follows 3-7 8-11 12 13-15 16-23

I

so 60

CJ c=JID c=J DD CJCJ I I I

SPIKED JlTH DEUTERATED STANDARDS LOJ FLOJ JlTH PUFs

SDXHLET SOXHLET BENZENEMeOH BENZENEHe H

l MUT AGENICITY TA98 ltplusmn $9)

TA98NR (-$9) TA9818-DNP 6 (-$9)

HYDROCARBONS HEXANE OPEN-COLUMN SlLlCA __Me_O_H_ POLAR COMPOUNDS

~ NORMAL-PHASE HPLC~

~-_______ HIGH HJI PAH

PAH I NITRO-AH 2o GCMS

Jeorl GCHS REVERSE PHASE HPLC

II NITROfLl~ANTHEN[SllirTROPYRENES

1 GCMS

Scheme VI-1 Outline of the chemical analysis procedure for a POM sample

Vl-6

(

(106 319) pyrene-d 10 (104 314) chrysene-d12 (527 158) benz(a)shy

anthracene-d12 (213 638) benzo(a)pyrene-d12 (281 844) perylene-d 12 (105 314) dibenz(ah)anthracene-d 14 (198 593) 1-nitronaphthaleneshy

d7 (054 161) 2-nitrofluoranthene-d9 (054 161) 1-nitropyrene-d9 O 50 1 bull 51) dini tropyrene-d8 mixture ( 1 98 5 94) The filters were

Soxhlet extracted overnight ( 16 hr) with benzenemethanol (41 vv) and

the extracts were concentrated by rotary evaporation and precleaned by

open-column silica chromatography using sequential elution with hexane

CH2c12 and methanol (MeOH) to segregate the aliphatic hydrocarbons (eluted

with hexane) and polar material (eluted with MeOH) The fraction of

interest (eluted with CH2c12) was further fractionated by HPLC on a semishy

preparative Altex Ultrasphere Silica column Figure VI-3 shows a typical

HPLC profile of the extract of an ambient POM sample together with the

mobile phase program employed The PAH-containing fraction was collected

from 4 min to 13 min and a nitroarene-containing fraction from 13 to 25

min The latter fraction contained the lower molecular weight nitroarenes

as well as nitrofluoranthenes and nitropyrenes (mw 247) and some higher

molecular weight PAH This fraction was divided into two parts 20 was

analyzed by GCMS-MID for PAH and lower molecular weight nitroarenes and

80 was fractionated further by reverse phase HPLC using an Altex semishy

preparative Ultrasphere ODS column and isocratic elution with methanol

water (82 vv) The fraction containing isomeric nitroarenes of mw 247

was then analyzed by GCMS-MID see below)

5 GCMS Analyses

Compound identifications and quantifications were made using

either a Finnigan 3200 quadrupole GCMS interfaced to a Teknivent data

system or a Hewlett Packard 5890 GC interfaced to a Hewlett Packard 5970

mass selective detector MSD) both operated in the electron impact mode

(70 eV) The GC separations were done either on a 60 m DB-5 fused silica

capillary column with a cool on-column injection system (J ampWScientific

Inc) or on a 30 m DB-5 fused silica capillary column with splitless

injection Both columns eluted directly into the MS ion source

Calibration curves for the GCMS-MID quantification of the PAH were

made for the molecular ion peaks of the PAH using the corresponding

deuterated species (or the deuterated species most closely matched in

volatility and retention characteristics) as an internal standard The

VI-7

I

I 3 4 5 I 9 11 u u 14 15 16 17 11t l 0I I I I I I I I I I I I Ibullrd 2

fncuou

Figure VI-3 HPLC trace (254 nm) and gradient solvent program for separation of an ambient POM sample Semi-pre~rative Ultrasphere Si column (1 cm x 25 cm) 3 mL min- HPLC fractions were combined as follows 12-5 16-7 18 19 110-13 114-18

9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

National Bureau of Standards SRM 1647 certified PAH) with the addition of

biphenyl methylnaphthalenes dibenzothiophene and the deuterated internal

standards was utilized to make the calibration solutions

Identifications of the nitroarenes apart from the methylnitronaphshy

thalenes for which 14 isomers are possible) by GCMS-MID were made on the

basis of the presence in correct abundance of all of the major fragment

ions as well as retention time matching Authentic samples of all eight

of the ni trofluoranthene and nitropyrene isomers and all three of the

nitrobiphenyl isomers were available for retention time and fragment ion

abundance comparisons Quantifications for 1-nitronaphthalene 2-nitroshy

fluoranthene and 1-nitropyrene were made by comparison with deuterated

internal standards 2-Nitronaphthalene 3-nitrobiphenyl and 9-nitroshy

anthracene were quantified by external calibration of the molecular ion

peak to that of the 1-nitronaphthalene-d7 internal standard 2-Nitroshy

pyrene and 3- and 8-nitrofluoranthene were quantified by external calibrashy

tion using 1-nitropyrene-dg as the internal standard

6 Chemicals

The following chemicals were obtained from commercial sources

phenanthrene-d 10 biphenyl-ct10 anthracene-ct 10 pyrene-d 10 benzoa)shy

pyrene-d12 and perylene-d 12 (Cambridge Isotope Laboratories) fluorshy

anthene-d10 and dibenzothiophene-d8 (MSD Isotopes Inc) naphthalene-da

1-nitronaphthalene-d7 biphenyl 1- and 2-nitronaphthalene 2- 3- and 4-nitrobiphenyl and 9-nitroanthracene Aldrich Chemical Co 1- and 2-

methylnaphthalene (Chem Services) Standard Reference Material 1647

certified PAH (National Bureau of Standards) Commercially available 1-

nitropyrene Pfaltz and Bauer Inc was purified according to the method

described by Paputa-Peck et al 1983)

2-Nitrofluoranthene-dg and 1-nitropyrene-dg were synthesized as desshy

cribed by Zielinska et al (1986) and Pitts et al (1985a) 2-Nitropyrene

was provided by Dr D Schuetzle (Ford Motor Co Dearborn MI) and 4-

nitropyrene by Dr A Berg (University of Aarhus Denmark The 1- 2-

3- 7- and 8-nitrofluoranthenes were synthesized as described previously

(Ramdahl et al 1985 Zielinska et al 1986)

VI-9

C Results

1 Volatile PAH Sampled on Tenax-GC Cartridges

The most abundant PAH collected on the Tenaz-GC cartridges were

naphthalene and 1- and 2-methylnaphthalene GC~ analysis of Tenax

samples in the full scanning mode (rather than the MID mode used for

quantification) showed that not unexpectedly several alkylbenzenes were

also very abundant Table VI-1 sUJ11Darizes the ambient concentrations (ng

m-3) of the volatile PAH measured For reasons which will be detailed

below the naphthalene data from the low-flow cartridges have been

utilized while the data for the remaining PAH have been taken from the

values obtained from the high-flow cartridges

In Appendix B Table B-1 the microg quantities of each PAH measured on

the low-flow Tenax cartridges (for replicate GCMS-MID quantifications)

and the calculated total volumes for each sample are listed Replicate

injections gave reproducible values for naphthalene and 1- and 2-methylshy

naphthalene while the levels of biphenyl fluorene and phenanthrene were

too low for accurate quantification Also listed in Table B-1 are the

quantities of PAH observed on the back-up Tenax cartridges which were

also generally too low for accurate quantification Table B-2 lists the

microg quantities measured and volumes sampled for the high-flow cartridges

Since the volumes of air sampled on the high-flow cartridges was a factor

of 10 greater than the low-flow cartridges biphenyl fluorene and phenshy

anthrene could be accurately determined and in addition acenaphthylene

and acenaphthene were measured

Only traces of naphthalene were observed on the Tenax cartridges

which were back-up cartridges for the low-flow Tenax ie less than a

few percent of that measured on the primary cartridge Therefore

naphthalene was collected quantitatively on the low-flow Tenax Table VI-

2 compares the ambient naphthalene and 1- and 2-methylnaphthalene concenshy

trations calculated from the low-flow and high-flow Tenax cartridges The

high-flow values for naphthalene were consistently lower than those

obtained from the low-flow Tenax samples indicating that naphthalene was

not collected quantitatively at a collection rate of 10 L min- 1 at the

ambient temperatures encountered at Citrus College Hence the low-flow

Tenax values for naphthalene are given in Table VI-1

VI-10

- -

-Table VI-1 Concentrations (ng m-3) of Volatile PAH Sampled onto Tenax-GC Solid Adsorbent at Citrus College

-Glendora CA in August 1986 (Day 0800-2000 PDT Night 2000-0800 PDT)

ng m-3 a

1-Methyl- 2-Methyl-Naphtga- naphtha- naphtha- Acenaph- Acenaph- Phen-

Date lene lene0 lene0 Biphenyl0 thylene0 thene0 Fluorene0 anthrene0

e e e e -e81286 Day 2200 150d 250d - - - -812-1386 Night 5000 500 900 220 39 32 49 64

81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40

e e e e -e81586 Day 2800 18od 190d - - - -815-1686 Night 4100 380 730 66 10 21 35 42

~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e

AVERAGE DAYS 3100 130 240 2855 3 5 23 AVERAGE NIGHTS 4300 370 710 100 12 25 44 48

aAverage of replicate injections dvalue from low-flow Tenax bsampled at -1 L min- 1

1 8 High-flow Tenax sample lost

0sampled at -10 L min-

Table Vl-2 A Comparison of PAH Concentrations ng m-3) Measured on Low Flow and High Flow Tenax-GC Solid Adsorbent at Citrus College Glendora CA Day 0800-2000 PDT Night 2000-0800 PDT)

Naphthalene 1-Methylshy

naphthalene 2-Methylshy

naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow

_e _e _e81286 Day 2200 150 250 812-1386 Night 5000 2200 460 500 860 900 81386 Day 2400 1100 140 160 100 320 813-1486 Night 4800 1900 430 390 720 730 81486 Day 2500 820 100 130 150 260 814-1586 Night 3000 1600 340 330 680 640

_e _e _e81586 Day 2800 180 190 815-1686 Night 4100 2000 380 380 720 730 81686 Day 3200 690 130 98 60 200 816-1786 Night 3400 1800 350 350 660 700 81786 Day 2000 470 60 76 50 170 817-1886 Night 4300 1800 310 330 650 680 81886 Day 4100 670 110 120 120 260 818-1986 Night 4200 1600 270 280 540 570 81986 Day 4300 500 100 90 110 200 819-2086 Night 3800 1600 350 290 620 600 82086 Day 4100 810 180 150 180 320

_e _e _e820-2186 Night 6100 490 860

aAverage of replicate injections bSampled at -1 L min-1 cSampled at -10 L min- dcorrected by subtraction of average interference value as observed on

back-up Tenax eHigh flow Tenax sample lost

VI-12

( There is good agreement between the nighttime concentrations of the

1- and 2-methylnaphthalenes calculated from the low- and high-flow Tenax

samples For the daytime samples when the observed concentrations were

generally low the high-flow values tended to be somewhat higher than the

low-flow values and were judged to be more accurate It should be noted

that the low-flow values for 1-methylnaphthalene have been corrected for a

significant interference which was observed on the back-up Tenax

2 PAH Sampled on PUF Plugs

GCMS analysis of the HPLC fraction of the PUF plug extracts in

which the PAH elute (see Figure VI-2) showed this fraction to contain many

less abundant alkyl-PAH and dibenzothiophene as well as fluorene phenshy

anthrene anthracene fluoranthene and pyrene It must be remembered that

these PAH will be distributed between the gaseous and particle phases in

ambient air and that the quantities measured on the PUF plugs are the sum

of the PAH in the gas phase and the PAH initially present on the POM but

blown-off during the collection period

The ambient concentrations of five PAH and the sulfur heterocycle

dibenzothiophene measured on the PUF plugs are given in Table vI3 The

most abundant PAH collected on the PUF plugs was fluorene From the

composite samples in which the fourth PUF plugs were analyzed separately

it was obvious that fluorene (mw 166) and PAH of higher volatility were

not collected quantitatively on the PUF plugs since substantial amounts

were present on the fourth PUF (see Table VI-3) Consistent with fluorene

not being collected quantitatively on the PUF plugs the ambient concenshy

trations of fluorene listed in Table VI-1 from the Tenax cartridge quanshy

tifications are -2-5 fold higher than those listed in Table VI-3 The

ambient concentrations of phenanthrene measured on the PUF plugs and Tenax

cartridges agree to within better than a factor of two

Figure VI-4 shows the GCMS-MID traces of naphthalene and alkylshy

naphthalenes for the Tenax and PUF samples from the evening of 813-1486

From the Tenax sample trace it is clear that naphthalene was the most

abundant species (at a measured concentration of -5000 ng m-3)

Comparing the Tenax and PUF sample traces it is apparent that naphthalene

was retained on the PUF plugs only to a minor extent (with a measured

concentration of -2 ng m-3 Interestingly although not quantitatively

collected on the PUF plugs the presence of dimethylnaphthalenes in

ambient air is apparent from the PUF samples

Vl-13

Table VI-3 PAH Concentrations (ng m-3) Measured on PUF Plugs at Citrus College Glendora CA

Total Volwne Dibenzo- Phen- Anthra- Fluor-

m Fluorenea thiophene anthrene cene antheneb Pyreneb

Citrus College PUF Sample 1 469c 11 26 161 05 40 25 81386 0800-2000 PDT

Citrus College PUF Sample 2 938 175 33 232 19 62 55 813-11486 2000-0800 PDT

Citrus College PUF Sample 3 3751 54 23 03 4211 middot Day Composite 0800-2000 PDT 2 middot 81516171886

4th PUF Day Composite 3751 44 03d 15 004 003 002

lt Citrus College PUF Sample 14 3751 14 1 30 222 12 52 40 H I Night Composite 2000-0800 PDT 815-1616-1717-1818-1986~

4th PUF Night Composite 3751 11 6 005d 02 NDe 002 003

Citrus College PUF Sample 5 938 62 27 190 05 59 36 82086 0800-2000 PDT

Citrus College PUF Sample 6 938 208 45 318 18 68 49820-2186 2000-0800 PDT

Not quantitative a lower limit due to breakthroughSome present on the particles as well

~Only a single Hi-vol sample utilized second Hi-vol not operating correctlyBased on a single injection

eND = None detected

----_

nnoo iffOOTENAX SAMPLE GLENDORA CA PUF SAMPLE GLENDORA CA 813-1486 2000-0S00HR 813-1486 2000-0800HR

M12~ ~IOOOm3~05m3 nms

OIMETHYLNAPHTHALENESm1somtse

19H tzbullePS mz 156 mz 156OIMETHYLNAPHTHALENES

ti NLJlJl ssne-------------------------- iffstO-2-METHYLNAPHTHALENE

37222S1sem

1-METHYLNAPHTHALENE2itl501NtH 2-METHYLNAPHTHALENE

nm 1-METHYLNAPHTHALENE 12401$

mz 142 mz 142 ol JV Mib +bull

o1_____n(L_________

nmo- 19900-

NAPHTHALENE (5000ng m-3)HtzTS nms NAPHTHALENE

(2ng m-3) 171150 21SO

nm 1l4075

mz 128mr 128 bull ~middot bull j ft I j bull j ii j i i I i I I I j Ii Ii I I I I ij I I I I I I t I s o 1-i i I o t I f j u I s I o 4 s - gt diams et t o to I P s

1 JO u 12 IS 9 11 11 ubull

Figure VI-~ GCMS-MID traces showing the molecular ions of naphthalene (mz 128) 1- and 2-methylshynaphthalene (mz 112) and the dimethylnaphthalenes (mz 156) for analyses ot a Tenax-GC (left) and PUF plug (right) sample collected simultaneously in Glendora CA on 813-1486 from 2000-0800 PDT The abundances or naphthbulllene and the alkylnaphthaleneacollected on the PUF plug sample are similar and do not reflect the true ambient concentrations Note the quantitative n~phthalene concentration ot -5000 ng mmiddot3 measured by the Tenax sample vs 2 ng mmiddot as measured by the PUF sample


The ambient concentrations of naphthalene measured for 12-hr day

and night sampling intervals throughout the Citrus College study are shown

in Figure VI-5 It can be seen from these data that the naphthalene conshy

centrations were generally higher during the evening sampling intervals

and that there was a trend toward higher concentrations in the latter part

of the study

The daytime and nighttime concentrations of _ and 2-methylnaphthashy

lene are shown in Figure VI-6 As observed for naphthalene the nighttime

concentrations were generally higher The concentration of 2-methylshy

naphthalene was consistently higher than that of 1-methylnaphthalene The

concentration profiles of the methylnaphthalenes were remarkably similar

perhaps indicating a common source and similar atmospheric loss processes

Reaction with the hydroxyl radical is expected to be the major loss

process for both species with essentially identical atmospheric lifetimes

for 1- and 2-methylnaphthalene (Atkinson and Aschmann 1987a)

All of the volatile PAH were generally more abundant during the

nighttime than daytime sampling intervals (see Table VI-1 and VI-3

Meteorological factors such as inversion heights may certainly have played

a role in this observed trend at Citrus College bu it can be seen that

these diurnal variations are not solely due to meteorology by comparing

the diurnal profiles of species of differing reactiviy For example the

GCMS-MID traces for the molecular ion of biphenyl a11d acenaphthene (mz

154 for a typical daytime and nighttime Tenax sample are shown in Figure

VI-7 As seen from this figure acenaphthene [the ioore reactive of these

PAH (Atkinson and Aschmann 1987b] was generally significantly more

abundant in the nighttime samples presumably beig removed by rapid

reaction with the OH radical during daylight hours

GCMS-MID traces of daytime and nighttime PUF samples showing the

analyses of isomeric PAH of differing reactivity are shown in Figures VI-8

and VI-9 While phenanthrene was abundant on both ~~e day and nighttime

PUF plug samples the relative abundance of anthracen~ to phenanthrene was

consistently higher at night Figure VI-8) Similarly acephenanthrylene

an isomer of fluoranthene and pyrene expected to be more reactive than

these PAH towards ozone (Atkinson and Aschmann 1987b) was generally not

observed in the daytime PUF samples from Citrus College (Figure VI-9)

VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400

D Doy lt0800-2000 hr) IZI Night lt2000-0800 hr)

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

Diurnal variations in naphthalene concentration at Citrus College in Glendora CA

METHYLNAPHTHALENES

0 Day (0800-2000 hr)

Figure Vl-6 Diurnal variation in the concentrations of 1-methylshynaphthalene (1-Me) and 2-methylnaphthalene (2-Me at Citrus College in Glendora CA

Vl-17

21

GLENDORA CA 81786 0800-2000HR Ion ee38pound5 ~3SC5

DAY BIPHENYL TENAX2 0pound5middot 2 ecs

1 ecs 1 0pound5

bull - -u 0 C II Ion 16lt180 ampIIN

Tltne ( in In )

C Jecs 38pound5 ~ ~ BIPHENYL-d10([

2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115

GL ENOORA CA 817-1886 2000-0SOOHR Ion 15 00 ampmu

30es 38E5

BIPHENYLNIGHT 20pound5 20pound5TENAX

ACENAPHTHENE I 0pound5I 0E5

D u 0 C td II Ion 16 00 ainu C 30E5 30pound5 ~ ~ BlPHENYL - d10

2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt

Figure Vl-7 GCMS-KID traces for the molecular ion of biphenyl and acenaphthene (mz 154) and the deuterated internal standard biphenyl-d 10 mz 164) from the analyses of a daytime top) and nighttime (bottom) ambient air sample collected on Tenax-GC solid adsorbent at Citrus College Glendora CA

Vl-18

(

GLENDORA CA 81386 0800-2000HR Ion l iI ee awu

ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e

Ion 188 ee ampIIIU bull C

l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR

t 2pound6 l 0pound6 B 0E5 60ES 0ES

2 0ESbullu e C C l 2pound6z I[ 1 0pound6

80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165

I 2pound6 I 8pound6 88pound5 60ES bull 0pound5 28pound5

l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )

Figure Vl-8 GCMS-MID traces for the molecular ion of phenanthrene (PH) and anthracene (AN [mz 178] and their corresponding deuterated species (mz 188) utilized as internal standards from the analyses of a daytime (top) and nighttime (bottom) ambient air sample collected on PUF plugs at Citrus College Glendora CA(

VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF

Ion 212 ee alllU bull

19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210

GLENDORA CA 813-1486 2000-0SOOHR

4 ecs

30E5

20ES

t 0E5 D u 0 C

~

Ion 20200 amptrlU bull

0pound5FL 30pound5NIGHT PUF PY 2 0cs

1 BES

Ion 212ee anu C ~ 40pound5

SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt

Figure Vl-9 GCMS-MID traces for the molecular ion of fluoranthene FL) pyrene PY) and acephenanthrylene (AC) mz 202] and the deuterated internal standards FL-d10 and PY-d 10 (mz 212) from the analyses of a daytime (top and nighttime (bottom) ambient air sample collected on PUF plugs at Citrus College Glendora CA

Vl-20

(


The HPLC fraction of the PUF plug extracts eluting from 22 to 34

min (Figure VI-2) contained the volatile nitroarene species The most

abundant nitroarenes were 1- and 2-nitronaphthalene GCMS analysis in

the full scanning mode showed that this nitroarene-containing HPLC

fraction also contained alkylnitrophenols

Figure Vl-10 shows GCMS-MID traces from a typical analysis of a

Citrus College PUF plug extract for 1- and 2-nitronaphthalene (NN) As

seen from this figure identification was based on the presence of several

characteristic fragment ions as well as retention time matching with the

1-nitronaphthalene-d7 internal standard Figure VI-11 shows the presence

of several peaks at mz 187 which elute after 1- and 2-nitronaphthalene

These peaks were identified as methylnitronaphthalenes ( 14 isomers are

possible on the basis of the presence of characteristic [M-N02]+ and [Mshy

HN02J+ fragment ions as well as the mz 187 molecular ion

GCMS-MID traces of a standard mixture of the three nitrobiphenyl

isomers and two isomers of nitroacenaphthene are shown in Figure VI-12

5-Nitroacenaphthene has previously been reported in ambient air (Tokiwa et

al 1981) At Torrance CA during a wintertime high-NOx episode we did

not observe nitroacenaphthene but measured high concentrations of the

isomeric species 3-nitrobiphenyl (Arey et al 1987) In Figure Vl-13 the

[Mr ions of the standard mixture are shown together with the [M)+ ions

and characteristic fragment ion traces obtained from the analysis of a

Citrus College PUF plug sample As at Torrance CA the nitroarene isomer

of mw 199 observed at Citrus College was clearly 3-nitrobiphenyl

Table Vl-4 gives the microg quantities of 1- and 2-nitronaphthalene and

3-nitrobiphenyl collected on the PUF plugs at Citrus College From the

fourth PUF plugs of the composite samples it can be seen that 3-

nitrobiphenyl was quantitatively collected on the first three PUF plugs

Particularly during the daytime samples some breakthrough of 1- and 2-

nitronaphthalene occurred In addition to these nitroarene species

traces of 9-nitroanthracene were observed in most of the Citrus College

PUF plug samples but the levels present were too low to quantify

Vl-21

2-NN AtJBENT SAMPLE PUF PLUG 1-NN 813-14860800-2000 HR bullIOOOmJ

mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5

1-NN-d7 INTERNAL STANDARD

[11d-No-cof7

mz 122

RETENTION TIME (min)

Figure Vl-10 GCMS-MID traces for the molecular ion (mz 173) and several characteristic fragment ions of 1- and 2-nitroshynaphthalene NN) and an abundant fragaent ion from the deuterated internal standard 1-NN-d7 showing the presence of 1-NN and 2-NN in an ambient air saaple collected on PUF plugs at Citrus College Glendora Cl

Vl-22

~~

bull~

2-NN

1-NN

[M]+

AMBIENT SAMPLE PUF PLUG 813-14860800-2000 HR Nl000m3

mz 173

w u z METHYLNITR0NAPHTHALENES ~ j (M)+ ~ mz 187 -----~ NORM FACTOR~ 2

0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17


Figure VI-11 GCHS-HID traces showing the presence of methylnitronaphthalenes in an ambient air sample collected on PUF plugs at Citrus College Glendora CA

NITRO-PAH STANDARD MIXTURE 3-NI TROBIPHENYL

100 (Mt I

4-NITROBIPHENYL

mz 199

2-NITROBIPHENYL 11 11

I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t

5-NITROACENAPHTHE~ bull

3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141

0 t bullbullbull I It IS IS n II l9


Figure VI-12 GCHS-MID traces from the analysis of a standard mixture of the isomeric nitroshybiphenyls and nitroacenaphthenes showing their excellent resolution on the 30-m DB-5 capillary column utilized

r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0

3-NITROBIPHENYL 4-NITROBIPHENYL

5-NITROACENAPHTHENE 2-NITROBIPHENYL 3-NITROACENAPHTHENE

AMBIENT SAMPLE PUF PLUG 81386 0800- 2000 HR 500m3

m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19


Figure VI-13 GCMS-MID traces showing 3-nitrobiphenyl to be present in an ambient air sample collected on PUF plugs at Citrus College Glendora CA The top trace repeats the molecular ion trace of the standard mixture (Figure VI-12) and it can be seen that the peak in the ambient sample (the molecular ion and two characteristic fragment ions shown) exactly matches 3-nitrobiphenyl in retention time

--

Table VI-4 Nitro-PAH Measured on PUF Plugs at Citrus College Glendora CA

Replicate GCMS-MID Quantifications microg 1-Nitronaph- 2-Nitronaph- 3-Nitro-

thalene thalene biphenyl

Citrus College PUF Sample 1 81386 0800-2000 PDT

Citrus College PUF Sample 2 813-1486 2000-0800 PDT

Citrus College PUF Sample 3 Day Composite 0800-2000 PDT 815 16 17 1886

Sample 3 4th PUF Day Composite

Citrus College PUF Sample 4 Night Composite 2000-0800 PDT 815-1616-1717-1818-1986

Sample 4 4th PUF Night Composite



46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045

aRun at 23 SCFM b0n1y a single Hi-vol sample utilized cND = None detected

Table VI-5 swmnarizes the ambient concentrations of 1- and 2-nitroshy

naphthalene and 3-nitrobiphenyl As observed at Torrance CA the daytime

concentrations of 3-nitrobiphenyl were consistently higher than the nightshy

time concentrations reflecting the daytime atmospheric formation of this

species (Arey et al 1987) At Torrance both 1- and 2-nitronaphthalene

VI-26

(

(

were observed to be lower in the nighttime sample than the daytime sample

(Arey et al 1987) again reflecting their daytime formation by hydroxyl

radical-initiated reaction (Atkinson et al 1987) In contrast at Citrus

College 1-nitronaphthalene was consistently higher in the nighttime than

in the daytime samples The likely operation of a second atmospheric

formation mechanism for the nitronaphthalenes by reaction of naphthalene

with N2o5 during early evening hours will be discussed in Section VIII

Table VI-5 Nitroarene Concentrations Measured on POF Plugsa at Citrus College Glendora CA

pg -3

1-Nitroshy 2-Nitroshy 3-NitroshySample Site and Date naphthalene naphthalene biphenyl

PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT

PUF Sample 3 81516171886 Day Composite 0800-2000 PDT

PUF Sample 4 815-16 16-1717-1818-1986 Night Composite 2000-0800 PDT

PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27


As described in Section B above the extracts of the TIGF filters

were fractionated by HPLC HPLC fractions 2-5 (see Figure VI-3) were

collected as the PAH fraction with fractions 6-7 being chosen to include

the n i troarenes Through the use of deuterated internal standards it

became apparent that the higher molecular weight PAH such as dibenz(ah)shy

anthracene were eluting in HPLC fractions 6-7 The data reported here

for the PAH on filters will be for the lower molecular weight species

ie fluoranthene pyrene benz(a)anthracene chrysenetriphenylene and

benzo(a)pyrene Fractions 6-7 will be analyzed for the higher molecular

weight PAH and the full range of data for PAH on particles will be given

in our final report for our on-going CARB project (Contract No A5-185-

32) A survey of ambient concentrations of selected polycyclic aromatic

hydrocarbons (PAH) at various locations in California

Table VI-6 lists values for fluoranthane pyrene benz(a)anthracene

chrysenetriphenylene and benzo(a)pyrene in the NBS SRM 1649 an air

particulate sample collected in Washington DC The values recently

reported by the NBS (Wise et al 1986) for analyses by GC and HPLC with

fluorescence detection along with our values determined by GCMS-MID are

given The extraction and clean-up procedures we used for the SRM

particles were as described in Section B for the Citrus College POM sample

analyses As can be seen from Table VI-6 the agreement between our

values and those reported by NBS is generally excellent

The microg quantities of the five PAH measured in the Citrus College POM

samples for replicate GCMS-MID quantifications are given in Appendix B

Table B-3 The concentrations of these five PAH in ng m-3 (averaging the

replicate values) are given in Table VI-7 Two additional samples 7 and

8 repeat day and night composites are also listed in Tables B-3 and

VI-7 It was found that in taking the benzenemethanol extracts to a

constant weight a significant fraction of the deuterated internal stanshy

dards fluoranthene-d 10 pyrene-d 10 and even 2-nitrofluoranthene-d9 were

lost The use of internal standards should of course allow for correcshy

tion of such losses Since all of the filters from each day or night

comprising these composites had not been extracted we made replicate

composite samples and extracted these replicates with dichloromethane As

can be seen from Table VI-7 the composites and the repeat composites

VI-28

agree to within better than a factor of two In our current procedure for

POM analyses the benzenemethanol extract is not taken to dryness

6 Nitroarenes Sampled on TlGF Filters

The ambient concentrations of the nitrofluoranthenes and nitroshy

pyrenes measured for the six Citrus College POM samples are given in Table

VI-7 As we have observed previously (Pitts et al 1985c Ramdahl et al

1986 Arey et al 1987) 2-nitrofluoranthene was the most abundant

particle-associated nitroarene The GCMS-MID trace of the molecular ion

for the nitrofluoranthenes and nitropyrenes (mz 247) from the August 20-

21 1986 2000-0800 PDT sample is shown in Figure VI-14 This sample

represents the highest ambient concentration of 2-nitrofluoranthene that

we have observed to date being 2 ng m-3 of 2-nitrofluoranthene

VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -

GLENDORA CA 820-2186 NIGHT

23 24 25 26 27


Figure Vl-14 GCMS-MID trace showing the molecular ion of the nitrofluoranthenes (NF and nitropyrenes (NP analyzed in an ambient POM sample collected at Citrus College Glendora August 20-21 1986 from 2000-0800 PDT

Vl-30

( (

Table VI-6 PAH in NBS Standard Reference Material i649 Washington DC Air Particulate Sample

NBS Valuesa SAPRC Values for Replicate

PAH GC LC GCMS Analysis

Fluoranthene

Pyrene

Benz(a)anthracene

Chrysene triphenylene

Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31

Table VI-7 PAH Concentrations Measured on Particles Collected on TIGF Filters at Citrus College Glendora CA

mi m-3

Fluorshy Benz(a- Chrysene Benzo(ashySample Site and Date anthene Pyrene anthracene Triphenylene pyrene

Filter Sample 1 023 046 o 15 050 021 81386 0800-2000 PDT

Filter Sample 12 024 032 020 073 0)18 813-1486 2000-0800 PDT

Filter Sample 3 022 021 010 030 012 Day Composite 0800-2000 PDT 81516171886

lt Filter Sample 4 0 16a 026a 006 027 o 15 H I Night Composite 2000-0800 PDT

I) N 815-1616-1717-1818-1986

Filter Sample 5 029 032 0 11 043 017 82086 0800-2000 PDT

Filter Sample 6 020 022 o 12 037 o 18 820-1286 2000-0800 PDT

Filter Sample 7b 030 032 o 13 055 o 17 Repeat Day Composite 81516171886

Filter Sample 8b 024 028 o 17 062 027 Repeat Night Composite 315-1616-1717-1818-1986

asingle injection bExtracted in CH2c12

middot-

Table VI-8 Concentration (pg m-3) of Nitrofluoranthenes and Nitropyrenes in Ambient POM at Citrus College Glendora CA

2-Nitroshy 3-Nitroshy 8-Nitroshy 1-Nitroshy 2-NitroshySample fluoranthene fluoranthene fluoranthene pyrene pyrene

Filter Sample 1 81386 0800-2000 PDT

Filter Sample 2 813-1486 2000-0800 PDT

Filter Sample 13 Day Compositeb 81516171886

lt H I Filter Sample I~ w

VJ Night Composite 815-1616-1717-1818-1986



8 N0 = None detected bExtracted with CH2c12bull

200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction

For the past several years the mutagenicity of ambient P0M has been

recognized as a characteristic of polluted urban atmospheres Further-

more although airborne particulate matter contains many carcinogenic PAH

its mutagenic activity does not resemble that of the PAH which require

mammalian metabolic activation (S9) as a requisite for expression of their

mutagenicity in the Ames Salmonella test Instead ambient P0M is

directly active ie expressing mutagenicity without the addition of

S9 and thus showing that other classes of organic chemicals which are

direct-acting mutagens are also present in ambient air

As an integral part of the CSMCS carried out at Citrus College

Glendora we measured the mutagenicity of collected 12-hour particulate

samples both with and without mammalian metabolic activation on

Salmonella strain TA98 Additionally we obtained mutagenicity data on

strains TA98NR and TA9818-DNP6

B Experimental

Sample Preparation for Mutagenicity Testing As noted in Section

II I POM samples were collected on a 12-hr basis throughout the study

period from 0800-2000 and 2000-0800 PDT The collected particulate

matter from two Hi-vols fitted with 10 microm cut-off inlets was weighed and

the filters Soxhlet extracted for 16-hr using a benzenemethanol (8020

azeotrope The solvent was removed under vacuum and the extracts were

taken to dryness under a stream of dry nitrogen Prior to mutagenicity

testing the sample extracts were stored in the dark at -75degC On the day

of the test each extract was taken up in DMS0 using a 20-minute

sonication and serial dilutions in DMS0 were made from this stock

solution

Tester Strains Ames Salmonella strain TA98 was used because of its

sensitivity to atmospheric particulate mutagens such as the nitroarenes

(Rosenkranz and Mermelstein 1983 and each particulate extract was tested

on this strain both in the presence and the absence of manmalian metabolic ( activation (S9 Each sample was also tested on strains TA98NR and

TA9818-DNP6 in the absence of S9 as a possible indication of nitroarene

VII-1

mutagenicity TA98NR and TA9818-DNP6 are isolates of TA98 which are

deficient in a nitroreductase Rosenkranz and Speck 1975 McCoy et al

1981 and a transacetylase enzyme (McCoy et al 1983 Orr et al 1985

Saito et al 1985 respectively The deficiency or these enzymes which

are required in the activation of many nitroarenes to penultimate

mutagens renders these strains less sensitive than TA98 to many mutagenic

nitroarenes Thus when a complex mixture exhibits less activity on

TA98NR or TA9818-DNP6 relative to TA98 it may be an indication of the

contribution of ni troarenes to the mutagenic activity of that sample

Table VII-1 shows the response of TA98NR and TA9818-DNP6 relative to

TA98 for several mutagenic atmospheric nitroarenes

The strains were cultured in 40 mL of L-broth for 12 hours at 37degC

with shaking The culture density was estimated by its absorbance at 550

nm and each strain was diluted with fresh medium to an absorbance

previously calculated to yield the standard culture density of 109 colony

forming units per mL (approximately 028 absorbance units) After

dilution the cultures were maintained in an ice bath for the duration of

the test The titer of each culture was determined by dilution and

plating on histidine-supplemented medium E The standard genotypic

markers which were routinely checked were crystal violet sensitivity UV

sensitivity and ampicillin resistance Three standard positive-control

mutagens were tested on each strain 1) 2-nitrofluorene a positive

control mutagen which we have used for the past ten years to check the

response of TA98 was also used to check the reduced response of TA98NR

relative to TA98 2 18-dinitropyrene was used to check the reduced

response of TA9818-DNP6 relative to TA98 and TA98NR for nitroarenes

which require the Salmonella transacetylase for activation and 3)

quercetin was used to check the equivalent response of these strains to

non-nitroarene mutagens Additionally benzo(apyrene was tested on

TA98(+S9) to check the response of this strain to indirect mutagens

Our testing protocol consistently results in somewhat higher

mutagenicities than other laboratories which we attribute primarily to

the use of L-broth instead of Oxoid broth to culture the tester strains

L-broth has about twice the amount of histidine as does Oxoid and its use

results in larger amounts of histidine on the test plate Because it is

the limiting growth factor a higher amount of histidine results in a

VII-2

( ( Table VII-1 Response of TA98NR and TA9818-DNP6 Relative to TA98

for Standard Nitroarenes

Ratios of Response (-S9)

TA98NR TA9818-DNP6 to to

Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021

higher number of cells on the test plate and hence a higher number of

revertants (Maron and Ames 1983) The use of L-broth also results in a

somewhat denser background lawn of unreverted Salmonella but colony

morphology and visibility are unaffected

S9 Mix Arochlor 1254-induced rat liver S9 was prepared by Litton

Bionetics Inc according to the method of Ames et al (1975) and containshy

ed 26 mg mL- 1 protein (manufacturers analysis) NADP was purchased from

Boehringer Mannheim and glucose-6-phosphate was purchased from Sigma

Chemical Company

The S9 mix was prepared by the standard protocol (Ames et al 1975

Maron and Ames 1983) with 001 ml S9 per plate c2i vv mix) This S9

concentration was chosen since we have previously found a 2i vv mix to be

optimal in activating ambient particulate extracts collected in southern

California Frequently the use of S9 in testing ambient POM results in a

net decrease in activity as deactivation of direct mutagens overrides the

presumed activation of indirect mutagens such as the PAH Many

nitroarenes are also subject to this S9 suppression of activity

VI-3

Testing Protocol The standard Ames Salmonella plate incorporation

mutagenicity test was performed according to the method of Ames and coshy

workers (Ames et al 1975 Maron and Ames 1983) with some modifications to

improve its accuracy and precision (Belser et al 1981) Because of the

large number of plates required for the complete set of samples the

extracts were assayed in two tests 1) TA98 with and without S9 and 2)

TA98NR and TA9818-DNP6 without S9 By dividing the tests by strain the

variation in response within one sample set was minimized Each extract

was tested in triplicate at eight doses chosen to logarithmically span the

region of linear response observed in the past for ambient P0M In

anticipation of lower activities on TA98NR and TA981 8-DNP6 the doses

chosen for these strains were twice as great as those for TA98 Hence

each sample was tested at 3 6 11 21 38 70 135 and 250 microg plate- 1 on

TA98 and at 6 12 22 42 76 140 270 and 500 microg plate-1 on TA98NR and

TA9818-DNP6

Each test was performed in a single afternoon by means of a procedure

designed to improve intraday precision Belser et al 1981) Darkroom

conditions were employed throughout to prevent any photodecomposi tion of

the samples which might occur under laboratory fluorescent 1 ights The

plates were incubated at 37degC for 63 hours and counted with a Biotran

automatic colony counter (New Brunswick Scientific) directly interfaced to

a microcomputer ( Apple II) The extract potencies or specific activishy

ties were obtained by 1 inear regression analysis of the dose-response

data in the region of linear response The slope of the dose-response 1curve is the specific activity in revertants microg- The ratios of the

specific activities on strains TA98NR and TA9818-DNP6 relative to TA98

were then calculated

From the specific activities the extract weights and the weights of

the particulate matter collected the potencies of the particulate matter

or mutagen loadings in revertants per mg of particulate matter collected

were calculated Finally from the specific activities the extract

weights and the volumes of sampled air the airborne mutagenicity conshy

centrations or mutagen densities in revertants per m3 of sampled air

were calculated

VII-4

( C Results

The complete data set including the sample collection data is given

in Tables VII-2 to VII-5 The concurrent General Motors Laboratories

mutagen density data (J Siak T L Chan and G T Wolff private

connnunication) are included in Table VII-5 for comparison As we have

observed before in southern California the sampled POM was principally

directly active the average direct activity (TA98 -S9 was 345 rev m-3

as compared to 332 rev m-3 with metabolic activation TA98 +S9 Figure

VII-1 shows the mutagen density with and without S9 observed during this

study The values are intermediate in the range of mutagen densities we

have observed before in southern California and followed a general trend

towards higher values at the end of the study Figure VII-2 shows the

TA98 +S9 to TA98 -S9) ratio together with the TA98 (-S9) mutagen

density which are anticorrelated Thus sampling periods with higher

direct mutagenicity tended to be those which exhibited less promutagenshy

icity and greater direct activity This observation is consistent in a

qualitative manner with the presence in ambient POM of nitroarenes

The final nighttime sampling period during this study 820-2186

2000-0800 PDT) was unusual because of the high levels of volatile and nonshy

volatile nitroarenes present in the atmosphere For example the 2-nitroshy

fluoranthene concentration was a factor of ~5 greater than on the previous

day and the 1-nitronaphthalene concentration increased by over a factor of

two Concurrent observations of the presence of the nitrate radical

indicated that chemistry could have been occurring on this nightN2o5 Our measured mutagen density however declined by a factor of two

inconsistent with these other observations Moreover in contrast to our

results researchers at General Motors Laboratories using CH2c12 as an

extraction solvent observed a significant increase in mutagenicity (TA98

-S9) from the daytime 82086 0800-2000 PDT) sample to the nighttime

(820-2186 2000-0800 PDT) sample in their tests Since we had used a

benzene-methanol azeotrope as the extraction solvent system we decided to

retest the POM collected during these final two sampling periods using

dichloromethane as the extraction solvent

VII-5

Table Vll-2 Particulate Data for 12-Hour Collections at Citrus College August 1986

Particulate Time of Weight Extract J

Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24

aFlow rates for the two samples 1Hi-vols 18 and 11) were 40 scfm for a total sampling volume of 1631 m

b16-hr Soxhlet extraction with benzenemethanol (8020) csampling volume -5J low due to power failure

VII-6

~- -Table VII-3 Specific Activities of Particulate Extracts Collected at Citrus College August 1986

Ratios 18S~ecific Activity rev ~g- of Res~onse -S2)

TA98 Time of TA98 TA98NR 18-DNP6

Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019

aslope of the dose-response curve in the region of linear response The number in parentheses is the standard error expressed as a percentage of the specific activity

-

Table VII-4 Mutagen Loadings of Particulate Hatter Collected at Citrus College August 1986

Mutagen Loading (rev mg-12 Time of TA98

Day TA98 TA98 TA98NR 18-DNP6 Date (PDT) +S9 -S9 -S9 -S9

81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8

Table VII-5 Particulate Mutagen Densities Citrus College August 1986

Mutagen DensitX rev m-32a


Date PDT) +S9 -S9 -S9 -S9

81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54

aFlow rates for the two samples ~Hi-vols 8 and 11) were 40 SCFM for a total sampling volume of 1631 m

bsampling volume -5 low due to power failure 0 oata in parenthesis from General Motors Laboratories see text)

l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-

MUTAGEN DENSITY TA98 +S9 a TA98 -S9

~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt

= = gt B ~ Igt ~ gtgt

gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt

i E = ~ f ~ ~ ~ ~ sectgtgt gt ie~ ~-~~n~~~~~~~u~m~~~~~ D ND ND ND ND ND NIN D NIN

D-DAY lt0800-2000gt N-NIGHT lt2000-0800)

Figure VII-1 12-Hour particulate mutagen densities at Citrus College Glendora CA August 12-21 1986

Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A

I z I w q I CJ 20 I42 I I) I ~

10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08

ra~n~~~~~~~v~~~~~~~ D N I N D N D N D N D N D N D N I N

D-DAY lt0800-2000) MUTAGEN DENSITY N-NIGHT lt2000-0800) 0 TA98 +S9 to -S9 RATIO

Figure VII-2 Mutagen density (TA98 -S9) vs the +S9 to -S9 ratio for August 12-21 1986 Glendora CA

(

VII-11

For this second mutagenicity test using CH2c12-extraction POM

collected on TGF filters in Hi-vol samplers modified to allow PUF plugs

to be placed downstream from the filters was employed These modified Hishy

vol samplers were operated at a flow rate or 23 SCFM instead of the

conventional 40 SCFM) to ensure that the flow controller remained

operative One filter from the daytime (82086 0800-2000 PDT) and one

filter from the nighttime 820-2186 2000-0800 PDT) collection period

were Soxhlet extracted for 16 hours with CH2c12 and tested on TA98 -S9)

The results or this collection and mutagenicity test are given in

Table VII-6 together with the data for our previous test of the benzene-methanol extracts As can be seen from the TSP data the modified

samplers collected more particulate matter than the standard Hi-vol as

expected since these Hi-vols were not equipped with a size-selective

inlet This was not expected to have greatly affected the mutagenicity

results however because very little mutagenicity is present on particles

larger than -10 micro

Table VII-6 The Effect of Extraction Solvent on Kutagenicity

Benzene-Methanol Extracts

CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110

J Extractable 26 24 12 14

Specific Activity rev microg- 1 20 16 25 55

Mutagen Loading (rev mg- 1) 530 390 300 760

Mutagen Density (rev m-3) 61 28 47 83

VII-12

The more polar benzene-methanol solvent system extracted much more

material than did CH2c12 bull Despite the larger amount of polar material

present in the benzene-methanol samples the mutagen density for the

nighttime sample is three-fold lower than for the corresponding CH2c12-

extracted sample In contrast the mutagen density for the benzeneshy

methanol daytime sample is somewhat higher than for the corresponding

CH2c12-extracted sample Apparently the polar material in the benzeneshy

methanol extract of the nighttime sample inhibited the mutagenicity of

this extract probably through toxic or bacteriostatic action In

contrast the mutagenici ty of the polar compounds in the daytime sample

overcame any inhibitory effect

These observations illustrate the inherent compromises in choosing a

solvent system for extracting ambient POM The benzene-methanol solvent

system was chosen precisely because it extracts more polar material than

does CH2c12 and does not generate the artifactual mutagenicity associated

with the use of acetonitrile Indeed because inhibitory compounds may be

of the same polarity as mutagens every solvent system must result in an

underestimation of the mutagenicity of ambient POM This underscores the

need for identification and quantification of ambient mutagens Once

identified and tested for mutagenicity in their pure form the known

mutagens in a sample can be quantified and an accurate sum of their

mutagenicities can be obtained

(

VII-13

t

VIII CONCLUSIONS

The objectives of SAPRCs involvement in the ARB-funded CSMCS study

held at Citrus College Glendora CA during the period August 12-21

1986 were met Using long pathlength differential optical absorption and

Fourier transform infrared absorption spectroscopic techniques the

ambient concentrations of N02 HONO HCHO HN03 NH3 and the N03 radical

were monitored in an essentially continuous mode throughout this study

period Since these data were obtained using absolute in-situ spectroshy

scopic methods they have served as benchmark data for the evaluation of

other more portable measurement methods for the determination of HCHO

and HN03 concentrations during the SCAQS carried out in 1987

Based upon the experimental methods used and ambient air concentshy

ration data obtained in our recent study at El Camino Conmtunity College

Torrance we were able to employ a complementary set of sampling techshy

niques to provide a comprehensive data set concerning the ambient atmosshy

pheric concentrations of both volatile and non-volatile PAH and nitroshy

arenes during this study at Citrus College Ambient atmospheric concenshy

tration data were obtained for the following PAH naphthalene 1- and 2-

methylnaphthalene biphenyl acenaphthene acenaphthylene fluorene


anthracene chrysenetriphenylene and benzo(a)pyrene and the following

nitroarenes 1- and 2-nitronaphthalene 3-nitrobiphenyl 2- 3- and 8-nitrofluoranthene and 1- and 2-nitropyrene The ambient concentrations of

the PAH cover a very large range (gt1000) with the most volatile PAH naphshy

thalene being the most abundant Indeed the naphthalene concentration

exceeded 1 ppb during the 12-hr nighttime period 2000-0800 PDT on August

20-21 and averaged 0 7 ppb (3700 ng m-3) over the entire study period

The next most abundant PAH were the 1- and 2-methylnaphthalenes with 2-

methylnaphthalene being about twice as abundant as 1-methylnaphthalene

The ambient concentrations of the PAH exhibited diurnal variations

with the concentrations generally being higher during the nighttime

sampling periods than during the daytime periods This diurnal variation

can most readily be seen for the volatile PAH which were sampled onto the

high and low flow Tenax cartridges and for which individual 12-hr analyses

were carried out This diurnal variation could in general be due to

VIII-1

differing daynight emission rates meteorology (with lower inversion

heights and hence higher concentrations during the nighttime periods

andor differing atmospheric removal rates due to chemical reactions The

observation (Table VI-1 that the magnitude of the diurnal variation

depended on the specific PAH with the largest variations being for the

most chemically reactive PAH indicates that part of this variation was

due to chemical removal of the PAH during daytime hours

The 2-3 ring PAH monitored using the Tenax cartridge system all react

with the OH radical during daylight hours (Atkinson 1986 Atkinson and

Aschmann 1987b) with expected lifetimes due to this OH radical reaction

of approximately 3 days for biphenyl and fluorene and 2-12 hrs for the

other PAH The PAH naphthalene 1- and 2-methylnaphthalene acenaphthene

acenaphthylene and phenanthrene also react to a lesser extent with N2o5bull

In addition acenaphthene and acenaphthylene also react with N03 radicals

(Atkinson and Aschmann 1987b) bull These andor radical removalN2o5 N03 processes were likely to be of minor significance during this study since

the N03 radical (and hence N2o5) concentrations were low In addition

acenaphthylene reacts with Atkinson and Aschmann 1987b) with thiso3 removal process again being most important during daytime Interestingly

the ratio (average nighttime concentrationaverage daytime concentration)

correlates well with the OH radical reaction rate constant (which varies

from 7 x 10-12 cm3 molecule- 1 s-1 for biphenyl to 1 1 x 10-10 cm3 moleshy1cule-1 s- for acenaphthylene (Atkinson 1986 Atkinson and Aschmann

1987b) as shown by the plot in Figure VIII-1 This good correlation

confirms our expectation that daytime reaction with the OH radical is an

important atmospheric removal process for the PAH present in the gas

phase

The nitroarenes also exhibit a diurnal concentration profile as

shown in Figure VIII-2 which gives our earlier data from Torrance CA

(Winer et al 1987) as well as from Citrus College Again this observed

diurnal variation in the nitroarene concentrations can be due to differing

emission rates differing formation rates from their parent PAH during

transport through the atmosphere meteorology or differing removal rates

during daytime and nighttime periods Our data for the PAH (Figure VIII-1)

show that meteorology at Citrus College had a relatively minor effect of

the order of 20J (estimated from the intercept representing no OH radical

VIII-2

(

z CJ I-ltC ~ I-z w uz CJ u w X I-I-c lJ z w lJ ltC ~ w gtltC

z CJ 6 I-ltC ~ I- 5z w uz 4 CJ u w X 3 I--gt-ltC A 2 w lJ ltC 1 ~ w gtltC 0

0 2 4 6 8 10 12 14

10 11 x OH RADICAL RATE CONSTANT (cM 3 Molecule-ls -l)

Figure VIII-1 Plot of the average nighttimeaverage daytime concenshytration ratio for the volatile PAH against the OH radical reaction rate constant

VIII-3

DAY NIGHT

TORRANCE CA 6

ng -3HIGH NlJx L_HIGH HON 224-2587 ~ _____i~=-i---1CJ_____1 I

ng -3

s13-14861 ~ _0

ng -31GLENDORA CA HIGH 03 ~~SITpound (1 FR ~EVENING N2 05

ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh

Figure VIII-2 Comparison of the daytime and nighttime ambient concenshytrations of 1-nitronaphthalene 1-NN) 2-nitronaphthalene (2-NN) and 3-nitrobiphenyl (3-NBPh) at El Camino CoIIIDUJlity College Torrance CA Winer et al 1987) and Citrus College Glendora

VllI-4

( reaction) on the daynight concentration ratio Further it is expected

(Atkinson et al 1987) that the atmospheric OH radical reactions of the

nitroarenes will be relatively slow Hence since 3-nitrobiphenyl is not

expected to be emitted and the daytimenighttime emission rates of the

nitronaphthalenes are not likely to vary significantly the observed difshy

ferences in the daynight concentration profiles for 1- and 2-nitronaphshy

thalene and 3-nitrobiphenyl strongly suggest differing formation rates

In particular our observation that the daytime concentrations of 3-nitroshy

biphenyl are always higher than the nighttime concentration ( in total

contrast to the situation for the PAH) shows that 3-nitrobiphenyl must be

made in the atmosphere during daytime hours Indeed we have shown from

laboratory studies (Atkinson et al 1987) that the daytime OH radical

reaction with biphenyl (the only significant atmospheric chemical removal

process for biphenyl) forms 3-nitrobiphenyl in approximately 5j yield

1- and 2-Nitronaphthalene are also formed from the reaction of OH radicals

with naphthalene (Atkinson et al 1987) but these nitroarenes can also be

formed from the nighttime reaction of naphthalene with N2o5 (Atkinson et

al 1987)

In our previous study in Torrance CA (Winer et al 1987) N03 radicals were not present during nighttime hours and hence the N2o5 forshy

mation route to the 1- and 2-nitronaphthalenes was not operative and the

daytime concentrations of the 1- and 2-nitronaphthalenes and 3-nitroshy

biphenyl were higher than during the nighttime as expected from a daytime

formation pathway via OH radical reaction from their parent PAH In

contrast at Citrus College N03 radicals were observed on several

evenings and both daytime and nighttime formation of 1- and 2-nitronaphshy

thalene was hence possible (note that 3-nitrobiphenyl could only be formed

during the daytime) Indeed while the daytime 3-nitrobiphenyl concenshy

trations were higher than the nighttime concentrations the 1- and 2-

nitronaphthalene concentrations were as high or higher during the

nights Even more interesting is the observation that during daytime the

1- and 2-nitronaphthalene concentrations were comparable consistent with

the similar formation yields from the daytime OH radical-initiated reacshy

tions with naphthalene (Atkinson et al 1987) During nighttime however

the 1-nitronaphthalene concentrations were significantly higher than the

2-nitronaphthalene concentrations consistent with nighttime formation

VII I-5

from N2o5 reaction with naphthalene for which the 1- and 2-nitronaphthashy

lene yields are 15J and 7J respectively (Atkinson et al 1987

The ambient nitroarene concentrations also vary widely from compound

to compound and as with the PAH the most volatile nitroarenes are again

the most abundant Indeed as shown in Table VIII-1 the ambient atmosshy

pheric concentrations of 1- and 2-nitronaphthalene and 3-nitrobiphenyl

(measured at both Torrance (Winer et al 1987) and Citrus College are

comparable to the ambient concentrations of fluoranthene and (not shown)

pyrene and are generally an order of magnitude higher than the concenshy

trations of 2-nitrofluoranthene the most abundant particle-associated

nitroarene

As noted in previous sections of this report the PAH themselves are

not directly mutagenic in the Ames assay without microsomal activation

The ambient atmospheric concentrations of the particle-associated nitroshy

arenes (which are direct-acting mutagens when combined with their

mutagenic activities (Table VII-1) allow the ambient mutagenic densities

resulting from the nitrofluoranthenes and nitropyrenes (by far the most

abundant particle-associated nitroarenes to be calculated Table Vlll-2

gives the overall direct-acting mutagenic densities towards strain TA98

(-S9 calculated from our measured ambient concentrations of 2- 3- and

8-nitrofluoranthene and 1- and 2-nitropyrene for the six time-periods for

which data were obtained The mutagenic densities (rev m-3) calculated

from the measured ambient concentrations of these nitrofluoranthenes and

nitropyrenes ranged from approximately 1-9 rev m-3_ 2-Nitrofluoranthene

itself accounted for from 50-90J of this overall mutagenic density contrishy

buted by the nitroarenes of molecular weight 247

These calculated nitrofluoranthene and nitropyrene mutagen densities

account for typically 10J of the measured ambient mutagenicity It is

difficult to cite a definite numerical contribution of the nitrofluorshy

anthenes and nitropyrenes to ambient mutagenicity due to potential

problems in the Ames assay as discussed in Section VII above This 10J

figure for the contribution of the particle-associated nitroarenes to

ambient mutagenicity is consistent with the values given by Arey et al

(1988) and shows that the majority ie typically 90j of the mutagenishy

city of ambient POM is presently unaccounted for Ihis as yet unaccountshy

ed for direct-acting mutagenicity could be associated with other PAH-

VIII-6

( derivatives formed in the atmosphere during transport from source to

receptor or from other classes of organics Further work to attempt to

determine the identity of these other mutagens and their sources (direct

emissions versus atmospheric formation) is clearly necessary

Table VIII-1 Ambient Atmospheric Concentrations (ng m-3) of Selected PAH and Nitroarenes at Torrance and Glendora CA

Concentration (ng m-3)

Location 1-Nitroshy 2-Nitro- 3-Nitro- Fluor- 2-Nitroshyand Date naphthalene naphthalene biphenyl anthene fluoranthene

Torrance CA 22586 0600-1800 hra

Torrance CA 224-2586 1800-0600 hra

Glendora CA 82186 0800-2000 hrb

Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20

aTimes in PST bTimes in PDT

(

VIII-7

Table VIII-2 Mutagenic Densities (rev m-3) Towards TA98(-S9) at Citrus College Glendora Due to the Measured Ambient Concentrashytions of 2- 3- and 8-Nitrofluoranthene and 1- and 2-Nitropyrene (Using the Mutagenicity Data given in Table VII-1 for the Mutagenic Activities of these Nitroarenes)

Date and Time Sample (PDT

1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr

4 815-16 16-17 17-18 18-1986 Night Composite 2000-0800 hr

5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES

Arey J Zielinska B Atkinson R and Winer A M (1987) Polycyclic aromatic hydrocarbons and nitroarene concentrations in ambient air during a wintertime high-NOx episode in the Los Angeles basin Atmos Environ 21 1437-1~44

Arey J Zielinska B Harger W P Atkinson R Winer A M (1988) The contribution of nitrofluoranthenes and nitropyrenes to the mutagenic activity of ambient particulate organic matter collected in southern California Mutat Res in press

Ames B N Mccann J and Yamasaki E (1975) Methods for detecting carcinogens and mutagens with the Salmonellamammalian-microsome mutagenicity test Mutat Res 31 347-364

Atkinson R (1986 Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with organic compounds under atmospheric conditions Chem Rev 86 69-201

Atkinson R and Aschmann S M (1987a) Kinetics of the gas-phase reacshytions of alkylnaphthalenes with 0~ N2o5 and OH radicals at 298 plusmn 2 K Atmos Environ gj 2323-232

Atkinson R and Aschmann S M 1987b) Kinetics of the gas-phase reactions of acenaphthene and acenaphthylene and structurally related aromatic compounds with OH and N03 radicals N2o5 and o3 at 296 plusmn 2 K Int J Chem Kinet in press

Atkinson R Arey J Zielinska B and Aschmann S M (1987) Kinetics and products of the gas-phase reactions of OH radicals and N2o5 with naphthalene and biphenyl Environ Sci Technol 21 101ij-1022

Belser W L Jr Shaffer S D Bliss R D Hynds P M Yamamoto L Pitts J N Jr and Winer J A (1981 A standardized proceshydure for quantification of the Ames Salmonellamannnalian-microsome mutagenicity test Environ Mutagen J 123-139

Doyle GD Tuazon E C Graham R A Mischke T M Winer A M and Pitts J N Jr 1979 Simultaneous concentrations of ammonia and nitric acid in a polluted atmosphere and their equilibrium relationship to particulate ammonium nitrate Environ Sci Technol ll 1416-1419

Gibson T L 1983) Sources of direct-acting nitroarene mutagens in airborne particulate matter Mutat Res 122 115-121

Graham R A (1975) The photochemistry of N03 and the kinetics of the N2o5-o3 system PhD Thesis UC-Berkeley 176 pp

Graham R A and Johnston H S (1978 The photochemistry of N03 and the kinetics of the N2o5-o3 system J Phys Chem 82 254-268

IX-1

Harris G W Carter W P L Winer A M Pitts J N Jr Platt U and Perner D (1982) Observations of nitrous acid in the Los Angeles atmosphere and implications for predictions of ozone-precusor relationships Environ Sci Technol ~ 414--19

Horn D and Pimentel G C (1971) 25 km Low-temperature multipleshyreflection cell Applied Optics 10 1892-1898

Maron D M and Ames B N (1983) Revised methods for the Salmonella mutagenicity test Mutat Res ill 173-215

McCoy E C Rosenkranz H S and Mermelstein R (1981) Evidence for the existence of a family of bacterial nitroreductases capable of activating nitrated polycyclics to mutagens Environ Mutagen l 421-427

McCoy E C Anders M and Rosenkranz H S (1983) The basis of the insensitivity of Salmonella typhimurium strain TA9818-DNP6 to the mutagenic action of nitroarenes Mutat Res 121 17-23

Orr JC Bryant D W McCalla DR and Quilliam MA 1985) Dinitropyrene-resistant Salmonella typhimurium are deficient in acetyl-CoA acetyltransferase Chem-Biol Interactions 54 281-288

Paputa-Peck H C Marano R S Schuetzle D Riley T L Hampton C V Prater T J Skewes L M Jensen T E Ruehle PH Bosch L C and Duncan W P (1983) Determination of nitrated polynuclear aromatic hydrocarbons in particulate extracts by capillary column gas chromatography with nitrogen selective detection Anal Chem 55 1946-1954

Perner D and Platt U (1979) Detection of nitrous acid in the atmosshyphere by differential optical absorption Geophys Res Lett 6 917-920

Pitts J N Jr Biermann H W Atkinson R and Viner A M (1984a) Atmospheric implications of simultaneous nighttime measurements of N03 radicals and HONO Geophys Res Lett 11 557-560

Pitts J N Jr Biermann H W Winer A M and Tuazon E C (1984b) Spectroscopic identification and measurement of gaseous nitrous acid in dilute auto exhaust Atmos Environ 18 847-854

Pitts J N Jr Sweetman J A Zielinska B Winer A M and Atkinson R (1985a) Determination of 2-nitrofluoranthene and 2-nitropyrene in ambient particulate organic matter evidence for atmospheric reactions Atmos Environ 12 1601-1608

Pitts J N Jr Wallington T J Biermann H W and Winer A M 1985b) Identification and measurement of nitrous acid in an indoor environment Atmos Environ 19 763-767

IX-2

Pitts J N Jr Sweetman J A Zielinska B Winer A M and Atkinson R (1985c) Determination of 2-nitrofluoranthene and 2-nitropyrene in ambient particulate organic matter Evidence for atmospheric reactions Atmos Environ 12 1601-1608

Platt U Perner D Harris G W Winer AH and Pitts J N Jr (1980a Observations of nitrous acid in an urban atmosphere by differential optical absorption Nature 285 312-314

Platt U Perner D Winer AH Harris G W and Pitts J N Jr (1980b) Detection of N03 in the polluted troposphere by differenshytial optical absorption Geophys Res Lett 1 89-92

-Platt U Perner D Schroder J Kessler C and Toennissen A 1981 The diurnal variation of N03bull J Geophys Res 86 11965-11970

Platt U Perner D and Kessler C 1982) The importance of N03 for the atmospheric NOx cycle from experimental observations Proceedshyings of the 2nd Symposium on the Non-Urban Troposphere Williamsburg Virginia

Platt U F Winer A M Biermann H W Atkinson R and Pitts J N Jr 1984 Measurement of nitrate radical concentrations in continental air Environ Sci Technol 18 365-369

Ramdahl T Sweetman J A Zielinska B Atkinson R Winer A M and Pitts J N Jr 1985) Analysis of mononitro-isomers of fluoranthene and pyrene by high resolution capillary gas chromashytographymass spectrometry J High Resolut Chromat Chromat Communsect 849-852

Ramdahl T Zielinska B Arey J Atkinson R Winer A M and Pitts J N Jr 1986) Ubiquitous occurrence of 2-nitrofluoranthene and 2-nitropyrene in air Nature 321 425-427

Rosenkranz H S and Speck W T 1975) Mutagenicity of metroshynidazole activation by mammalian liver microsomes Biochem Biophys Res Commun 66 520-525

Rosenkranz H S and Mermelstein R (1983 Mutagenicity and genotoxshyicity of nitroarenes all nitro-containing chemicals were not created equal Mutat Res 114 217-267

Saito K Shinohara A Kamataki T and Kato R (1985 Metabolic activation of mutagenic N-hydroxylarylamines by 0-acetyltransferase in Salmonella typhimurium TA98 Arch Biochem Biophys 239 286-295

Spicer C W Howes JE Jr Bishop T A Arnold L H and Stevens R K (1982) Nitric acid measurement methods an intershycomparison Atmos Environ 16 1487-1500

IX-3

Tokiwa H Nakagawa R Morita K and Ohnishi Y (1981) Mutagenicity of nitro derivatives induced by exposure of aromatic compounds to nitrogen dioxide Mutat Res 85 195-205

Tuazon E C Winer A M Graham R A and Pitts J N Jr (1980) Atmospheric measurements of trace pollutants by kilometer pathlength FT-IR spectroscopy Adv Environ Sci Technol 10 259-300

White J U (1942) Long optical paths of large aperture J Opt Soc Amer~ 285-288

Winer A M Atkinson R Arey J Biermann H W Harger W P Tuazon E C and Zielinska B (1987) The role of nitrogenous pollutants in the formation of atmospheric mutagens and acid deposition Final Report to California Air Resources Board Contract No A4-081-32 March

Wise S A Bennes B A Chesler S N Hilpert L R Vogt CR and May W E (1986) Characterization of the polycyclic aromatic hydrocarbons from two standard reference material air particulate samples Anal Chem 58 3067-3077

Zielinska B Arey J Atkinson R Ramdahl T Winer A M and Pitts J N Jr (1986) Reaction of dinitrogen pentoxide with fluoranthene J Am Chem Soc 108 4126-4132

IX-4

( APPENDIX A

DOAS Measurements of Gaseous Nitrous Acid (HONO)

Formaldehyde (HCHO) and Nitrogen Dioxide (N02)

at Citrus College Glendora

from August 12-21 1986

(

A-1

( ( Table A-1 Ambient Concentrations Determined by

DOAS During Citrus College Study

Concentration (~~b)Scan Period

Date PDT HONO HCHO N02

13-AUG-86 0014-0033 2 1 79 650 0033-0047 18 67 63701 08-01 22 19 78 623 01 22-01 36 20 10 642 01 56-02 10 23 68 596 02 10-02 24 22 64 609 0245-0259 24 64 558 0259-0313 24 78 568 0334-0348 28 53 524 0348-0402 19 65 557 0422-0437 bull 9 55 547 0437-0451 32 56 476 0511-0525 3 1 73 49 1 0525-0539 37 53 460 06 00-06 14 4 1 66 44 1 06 14-06 28 30 74 499 0649-0703 35 59 463 0703-0717 3 1 78 523 0737-0751 20 100 657 0751-0806 15 108 742 0811-0831 1 bull 1 110 730 0831-0846 13 97 7630846-0901 2 125 873 0901-0916 09 107 9170916-0931 08 126 917 0931-0946 NDa 122 9750946-1001 ND 140 9381001-10 16 ND 130 89310 16-1031 ND 142 832 1031-1046 ND 119 78o 1046-1101 ND 11 6 725 1101-1116 ND 114 662 11 16-1 1 31 ND 122 5771131-1146 ND 113 5351146-1201 ND 115 4931201-1216 ND 110 438 12 16-12 31 ND 13 1 437 1231-1246 ND 133 412 1246-1301 ND 113 440 1301-1316 ND 11 8 487 1316-1331 ND 100 438 1331-1346 ND 149 402 1346-1401 ND 13 1 355 (

(continued)

A-2

Table A-1 continued) - 2

Concentration ~eeb2 Scan Period


13-AUG-86 1546-1601 ND 158 37 1 1601-1616 ND 140 38 1 1616-1631 ND 144 384 1631-1646 ND 157 3581646-1701 ND 154 432 1701-1716 ND 160 369 1716-1731 ND 148 ll 1 bull 1 1731-1746 ND 137 431 1746-1753 ND 132 474 1800-18 17 ND 107 528 1817-1832 ND 11 o 5391832-1847 ND 95 527 1910-1921 ND 94 614 1942-1953 ND 96 622 20 15-2026 ND 9 1 679 2050-2101 08 9 1 730 21 22-21 33 ND 68 761 2237-2249 18 85 7372321-2335 22 68 714 2335-2349 bull 9 66 682

14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3

( Table A-1 continued) - 3 Concentration (ppb)

Scan Period Date PDT HONO HCHO N02

14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338

ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND 12 13 12 13 14 1 6

125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4


Concentration t22bScan Period


15-AUG-86 0314-0328 19 53 427 0328-0342 20 54 420 04 02-04 16 20 57 42 1 04 16-04 30 2 1 59 398 0451-0505 24 53 38905 05-05 19 26 56 396 0539-0553 19 62 416 0553-0607 19 65 435 0628-0642 23 47 3980642-0656 19 8 1 467 0717-0731 17 72 512 0731-0745 18 78 518 0755-0809 12 86 5720810-0825 12 86 611 0825-0840 13 80 600 0840-0855 4 96 636 0855-09 10 1 104 6530925-0940 ND 98 665 0940-0955 ND 102 629 09 55-10 10 ND 116 63710 10-10 25 09 108 5831025-1040 ND 120 608 1040-1058 ND 122 619 1058-11 13 ND 135 5751113-1129 ND 132 574 11 29-11 4 3 ND 120 5191143-1158 ND 134 474 11 58-12 13 ND 128 39 712 13-12 28 ND 122 3931228-1243 ND 129 3991243-1258 ND 129 36 1 1258-13 18 ND 129 31313 18-13 34 ND 135 283 1334-1349 ND 113 316 1349-1404 ND 141 3431404-1419 ND 189 302 1419-1434 ND 158 248 1434-1449 ND 144 216 1449-1504 ND 159 24 7 1504-15 19 ND 168 299 15 19-15 34 ND 150 3591534-1554 ND 137 458 1555-1613 ND 120 436 1613-1628 ND 114 454 1628-1643 ND 104 472

(continued)

A-5

(

fTable A-1 (continued) - 5

Concentration ieeb)Scan Period


15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6


Concentration ~QQbScan Period


16-AUG-86 0917-0932 08 107 707 0932-0947 ND 126 710 0947-1002 09 126 629 1002-10 17 ND 87 619 1017-1032 ND 99 615 1032-1047 ND 13 1 598 1047-1101 ND 125 590 1101-1116 ND 126 543 1116-1131 ND 135 526 1131-1146 ND 13 1 416 1146-1201 ND 113 384 1201-1218 ND 96 337 12 18-1233 ND 117 308 1233-1248 ND 129 242 1248-1303 ND 8 1 193 1303-1318 ND 101 143 13 18-1333 ND 119 160 1333-1348 ND 96 13 1 1348-1403 ND 84 128 1403-1418 ND 140 14 1 14 18-14 34 ND 104 118 1434-1449 ND 102 132 1449-1504 ND 104 137 1504-1519 ND 11 6 118 15 19-1534 ND 11 7 154 1534-1549 ND 11 3 154 1549-1604 ND 114 144 1604-1619 ND 102 163 16 19-16 34 ND 11 7 194 1634-1652 ND 137 214 1652-1707 ND 126 236 1709-1727 ND 113 282 1727-1742 ND 11 3 355 1742-1757 ND 96 37 1 1757-18 12 ND 108 367 18 12-1827 ND 10 1 389 1827-1843 ND 92 38 1 1859-19 15 ND 68 520 1935-1946 ND 83 642 2008-2019 14 8 1 754 2040-2051 15 84 779 21 12-21 23 17 78 833 21 43-21 54 17 86 81 1 22 14-2226 20 68 650 2248-2302 20 63 730

(continued)

A-7

( Table A-1 continued) - 7 -

Concentration ~22bScan Period

Date PDT HONO HCHO I02

16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662

17-AUG-86 0000-0005 24 62 662 0025-0039 27 8 1 582 0040-0054 32 104 middot601 14-01 28 37 89 628 01 28-01 42 36 87 -30203-0217 38 83 6o8 02 17-02 31 40 8o 604 0252-0305 37 93 5390305-0320 26 84 478 0340-0354 30 90 ~-50354-0408 19 92 2370429-0443 25 65 26 7 0443-0457 24 66 30405 18-05 32 15 66 219 0532-0546 17 84 2370606-0620 1 6 69 18 7 0620-0634 17 60 190 0655-0709 1 5 8o 2~2 0709-0723 12 92 28 1 0745-0800 ND 86 a208 10-0825 ND 83 2i50825-0840 ND 10 1 25 10840-0855 ND 102 3360855-0909 ND 13 1 3680909-0924 ND 14 1 1159 0924-0939 ND 161 504 0939-0954 ND 138 5230954-1009 ND 147 5661009-1024 ND 125 ta 0 1024-1039 ND 162 122 1039-1054 ND 17 3 39 71245-1300 ND 143 a 1 1300-1315 ND 134 160 13 15-1330 ND 134 s31330-1345 ND 126 152 1345-1400 ND 129 1761400-1415 ND 125 160 14 15-14 30 ND 122 132 1430-1445 ND 120 1i 3 1445-1500 ND 119 i06 1500-1515 ND 114 1_ 7 (

(contin~d)

A-8

Table A-1 (continued) - 8

Concentration QQb)Scan Period


17-AUG-86 1515-1530 ND 153 153 1530-1545 ND 144 223 1545-1600 ND 146 215 1600-1617 ND 146 223 1617-1632 ND 137 225 1632-1647 ND 110 224 16 47-17 02 ND 77 202 1702-17 17 ND 80 210 17 17- 17 32 ND 8 1 244 1732-1747 ND 72 268 1747-1802 ND 86 337 1802-18 17 ND 60 405 18 17-1832 ND 75 514 1832-1847 ND 53 51 1 1847-1902 ND 98 589 1902-1917 ND 11 635 1943-1954 ND 87 789 20 15-2026 12 83 818 2047-2058 ND 72 774 21 19-21 30 12 54 698 2151-2202 10 68 706 2223-2234 10 72 695 2255-2306 ND 12 657 2330-2341 1 11 697 2341-2355 13 62 762

18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9

( tTable A-1 (continued) - 9

Concentration (ppb)Scan Period


18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320

10 ND ND ND 09 09 ND ND ND ND ND ND ND ND

125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538

ND ND ND ND ND ND ND ND ND

107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723

ND ND ND ND ND ND ND

168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10


Concentration QQbScan Period


18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644

19-AUG-86 0000-0002 15 84 644 0002-0016 15 72 619 0037-0051 17 77 564 0051-01 05 18 77 492 01 25-01 39 20 84 466 01 39-01 54 15 78 444 02 14-02 28 12 86 271 0228-0242 12 77 251 0303-0317 12 78 267 0317-0331 09 83 185 0352-0406 ND 63 237 0406-0420 ND 89 194 0441-0455 ND 80 183 0455-0509 ND 7 1 152 0530-0544 ND 84 148 0544-0558 10 96 276 06 18-0632 1 5 11 9 403 0632-0647 1 5 92 416 0707-0721 18 123 561 0721-0735 1 6 114 656 0757-0811 10 11 o 585 0811-0826 ND 113 499 0826-0841 ND 11 1 438 0841-0856 ND 11 4 428 0856-0911 ND 125 41 5 0911-0927 ND 126 469 0927-0942 ND 131 574 0942-0957 ND 13 1 527 0957-1013 ND 116 380 10 13-10 28 ND 128 343 1028-1043 ND 120 500 1043-1058 ND 123 416 1058-1113 ND 147 462 1113-1128 ND 137 373 1128-1143 ND 114 254 1143-1158 ND 120 239

(continued)

A-11

I (

Table A-1 (continued - 11 ~



19-AUG-86 1158-1213 ND 134 2501213-1228 ND 13 1 3381229-1244 ND 125 2361244-1259 ND 119 170 1259-1314 ND 98 13713 14-13 29 ND 144 2551329-1344 ND 150 244 1344-1359 ND 195 405 13 59-14 14 ND 189 3151414-1429 ND 156 2551429-1444 ND 119 2791444-1459 ND 123 263 14 59-15 14 ND 116 304 1514-1529 ND 117 314 1529-1544 ND 93 3051544-1559 ND 8 1 274 15 59-16 14 ND 75 2551614-1629 ND 69 2591629-1644 ND 56 267 1644-1659 ND 8o 3451704-1719 ND 63 3851719-1734 ND 74 434 1734-1749 ND 74 434 1749-1804 ND 48 485 1804-1820 ND 69 561 1820-1835 ND 56 6151835-1850 ND 59 628 1850-1905 ND 50 652 1905-1920 ND 60 746 1942-1953 ND 54 89520 14-2025 09 54 8262046-2057 10 68 86621 18-21 29 09 59 808 21 50-2201 ND 53 76 1 2222-2233 19 8 1 767 2254-2305 2 1 99 688 2326-2340 25 99 680 2340-2354 20 92 605

20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12


Concentration Q~b)Scan Period


20-AUG-86 0241-0255 13 93 193 0255-0309 1 7 96 182 0330-0344 18 104 205 0344-0358 17 1 4 216 0414-0433 2 1 10 1 209 0432-0447 16 99 208 0503-0521 18 105 259 05 56-06 10 22 108 403 06 10-06 24 2 1 92 1140 0645-0659 20 89 454 0659-0713 3 1 128 527 0734-0749 23 132 645 0749-0804 19 131 719 0804-0820 23 149 994 0820-0835 25 167 1162 0836-0851 28 209 1420 0851-0906 20 183 138 1 0906-0921 2 1 183 1365 0921-0936 18 17 1 129 0936-0951 1 7 197 165 1 0951-1006 1 4 188 1737 1006-1021 12 17 4 1663 1021-1036 1 3 162 1415 1036-1051 08 138 97 1 1051-1106 ND 159 777 1106-1121 ND 134 749 1136-1151 ND 132 462 1151-1206 ND 127 41 7 1206-1221 ND 162 531 1221-1236 ND 159 449 1236-1251 ND 207 436 1251-1306 ND 152 329 1306-1321 ND 168 304 1321-1336 ND 154 262 1336-1351 ND 140 217 1351-1406 ND 137 186 1406-1421 ND 156 176 1421-1436 ND 149 168 1436-1451 ND 140 159 1451-1506 ND 125 162 1506-1521 ND 11 6 22 1 1521-1536 ND 105 345 1536-1551 ND 122 370 1551-1606 ND 122 327 1606-1621 ND 98 288

(continued)

A-13

( Table A-1 (continued) - 13

Scan Period Concentration ~QQb)


20-AUG-86 1621-1636 ND 95 309 1636-1651 ND 87 293 1651-1706 ND 68 258 1706-1721 ND 68 325 1721-1736 ND 75 404 1736-1751 ND 87 409 1751-1806 ND 87 436 1806-1821 ND 92 570 1821-1836 ND 84 598 1836-1851 ND 96 675 1851-1856 ND 110 754 1916-1927 ND 77 836 1948-1959 09 87 911 2020-2031 10 74 890 2052-2103 15 77 903 2123-2135 12 74 857 2155-2206 2 1 74 854 2228-2242 1 74 736 2242-2256 10 62 78 1 2316-2330 1 8 102 846 2330-2344 20 98 848

21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818

aND = below detection limit 08 ppb for HONO 45 ppb for HCHO 35 ppb for N02

A-14

( APPENDIX 8

PAH Concentrations Measured on the Low- and High-Flow

Tenax Sampling Cartridges

f (

B-1

- --frac34_

Table B-1 Citrus College Glendora CA PAH Concentrations (Day 0800-2000 PDT Night 2000-0800 PDT) Measured on Low-Flow Tenax

a

Total 2-Methyl- 1-Methyl Volre Na~hthaleneb na~hthalene na12hthalene Acenaph- Phen-

Date m Back-up Back-up Back-up Biphenyl thene Fluorene anthrene

81286 Day 0662 1 51 trace 0 18 C- 022 (0 11) 004 -C 004 trace 141 II 0 15 020 (009) 003 006 001

812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -

Table B-1 (continued) - 2

a fa

Date

Total Volre

m Na12hthaleneb

Back-up

2-Methyl-na(2hthalene

Back-up

1-Methyl na~hthalene

Back-up Biphenyl Acenaph-thene Fluorene

Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002

avalues given are for replicate injections bNot corrected for small amount on back-up Tenax cNone detected

_-

Table B-2 Citrus College Glendora CA PAH Concentrations (Day 0800-2000 PDT Night 2000-0800 PDT) Measured on High-Flow Tenax

a

Total Volfle Naphtha- 2-Methyl- 1-Methyl- Acenaph- Acenaph- Phen-

Date m lene naphthalene naphthalene Biphenyl thylene thene Fluorene anthrene

812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a

Total VolW1e Naphtha- 2-Methyl- 1-Methyl- Acenaph- Acenaph- Phen-


817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020

~Values given are for replicate injections Peak area too small for quantification

-- -

Table B-3 Citrus College Glendora CA PAH Concentrations Measured on Particles Collected on TIGF Filters

a Total

Fluor- Benza)- Chrysene Benzoa)- Volre anthene Pyrene anthracene Triphenylene pyrene m

Filter Sample 1 81386 0800-2000 hrb

090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078

Filter Sample 3 Day composite 81516171886

276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-

Filter Sample 4 Night Composite 815-1616-1717-1818-1986

NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078

Filter Sample 7 Repeat Dry Composite 81516171886

150 162

155 176

064 066

276 288

o83 095 5158

Filter Sample 118 Repeat Night Composite 315-1616-1717-1818-19

134 142

152 165

093 096

348 348

161 143 5627

~Values given are for replicate GCMS analyses Times in PDT

0 NQ = Too low to quantify

-~

-middot~

__

$0272 bullIOI

REPORT DOCUMENTATION 1_1_111POfff NO

PAGE 1 ARBR-88366

nttbull - Sutltlttbull 5 ~ oteMeasurements of N02 HONO N03 HCHO PAH Nitroarenes and F b 1988Particulate Mutagenic Activities During the Carbonaceous Specie~s-_-e_ruary-=--------~ Methods Comparison Study

L ~ OtentlcA _ Ne1-~middotmiddottltoger Atkinson Arthbullir M Winer ~_ Addw 10 _ Unit Na

Statewide Air Pollution Research Center University of California 11 Contnct(C Of Glafll(Q)

Riverside California 92521 ltegtARB AS-150-32

12 ~sonnc Orpftlnaon _ end AddfN8 lJ Type et R9-t amp _ 0Dwred

Air Resources Board Final Report State of California 7986-73087 P 0 Box 2815 14

Sacramento California 95812

---------middotmiddot--middot-middotmiddot middotbullmiddot------------ middot la Ab9Cnct (Ufflit 200 __

In the Carbonaceous Soecies Mthoos Catparison Study in August 1986 at Citrus COllege Glendora CA the ambient concentrations of N~ HONO and HCHO were measured by long pathlength a1rrerent1a1 optical absorption spectroscopy (DOAS) Ambient concentrations of HNO]t NH3 and HCHO were measured by long patblength Fourier infrared (FT-IR) absorption spectroscopy Signiticant concentrations of these pollutants were observed with mixing rat1s ot up to approximately 140 45 30~ 20 and 15 parts-per-billion (ppb) for N02 HONO ~bull HCHO and NH3 respectively being determined

In addition allbient air samples were collected during 12-hr daytime and 12-hr nightshytime periods onto Tenax solid adsorbent polyurethane foam (PUF) plugs and Teflon-impregshynated glass fiber (TIGF) filters and these samples 1were analyzed for mutagenicity and gas- and particle-associat~d polycyclic aromatic hydrocarbons (PAH) and nitroarenes The mutagen densities obtained were consistent with those measured previously in the South Coast Air Basin The following PAH and nitroarenes were observed and quantified naphthalene 1- and 2-methylnaphthalene biphenyl acenaphthene acenaphthylene fluorene phenanthrene anthracene dibenzothiophene fluoranthene pyrene benz ( a )anthracene chrysenetriphenylene benzo(a)pyrene 1- and 2-nitronaphthalene 3-nitrobiphenyl 2- 3-and 8-nitrofluoranthene and 1- and 2-nitropyrene

17 Oocufflfllt Molya a o-nocor-a Nitrous Acid Polycyclic Aromatic Hydrocarbons Formaldehyde Nitroarenes ~itrogen Dioxide Mutagenicity Ammonia

ld-lfle0oen-poundnded -

Long pathlength spectroscopy ~1utagenic activity of particulate ambient concentrations

( COSATImiddot FleidGrouci

lL Ave1ao1titv S12tament 19 Scunty Clau bullbull Reoort

~elease unliI11ted iILABLE =-~OM nATIOrJAL LNCLAS sIFIED ---middot] IC~L FORMA~IO sirc 285 PORT CQfAL - iJ 20 SCUncy Clau n P111bull1

LNCUSiS IIED $1995 SN ANSI-ZJ918l SH lftSfnlCTIOft9 Oft Ifbull~_ 01OHAL lOttM Z72 (4-7)

-- --- __ ----

ABSTRACT

To allow for methods development and methods intercomparisons prior to the 1987 Southern California Air Quality Study the California Air Resources Board funded two methods intercomparison studies one in 1985 at Claremont concerning the measurement of nitrogenous species and a second at Citrus College Glendora during August 1986 dealing principally with measurement methods for organic and carbonaceous species In the Carbonaceous Species Methods Comparison Study (CSMCS at Citrus College Glendora the Statewide Air Pollution Research Center conducted measurements of the ambient concentrations or several inorganic and organic species Specifically the following measurements were made

bull Using long pathlength differential optical absorption spectroscopy (DOAS) we measured nitrogen dioxide (N02 nitrous acid (HONO) and formaldehyde (HCHO)

bull Using long pathlength Fourier infrared (FT-IR absorption specshytroscopy we measured nitric acid (HN03) amnonia (NH3) and HCH0

bull Ambient air samples were collected during 12-hr daytime and 12-hr nighttime periods onto Tenax solid adsorbent polyurethane foam plugs and Teflon-impregnated glass fiber filters and these samples were analyzed for mutagenicity and gas- and particle-associated polycyclic aromatic hydrocarbons (PAH) and nitroarenes

An extensive data set for the gas-phase concentrations of N02 HONO HN03 HCHO NH3 and the N03 radical was obtained (by DOAS andor FT-IR spectroscopy) during this study period Significant concentrations of these pollutants were observed with ambient concentrations of up to approximately 140 45 30 20 and 15 parts-per-billion (ppb) for N02 HONO HN03 HCHO and NH~ respectively A definitive measurement of the time-concentration profne of N03 radicals was made on only one night during this study with a peak N03 radical concentration of 70 parts-pershytrillion (ppt) being measured on fhe night of August 13 The presence of N03 radicals at levels lt40 ppt was observed on the evenings of August 13 19 and 20

Ambient particulate organic matter POM) was collected on a 12-hr daytime and nighttime sampling period (0800-2000 and 2000-0800 PDT and was tested for mutagenicity towards Salmonella typhimur ium strains TA98 (with and without added S9) TA98NR (-S9) and TA981 8-DNP6 (-S9) The mutagen densities obtained were consistent with those we nave measured previously in the South Coast Air Basin As also observed previously the mutagen densities and mutagenic activity of the POM measured in the presence and absence of S9 we3e essentially indistinguishable with average mutagen densities rev m-) of 33 and 35 towards strain TA98 with

3and without S9 respectively and a maximum of 61 rev m- (TA98 -S9

Ambient air was also sampled on filters and solid adsorbents to collect the gas- and particle associated PAH and nitroarenes for combined gas chromatography-mass spectrometry analysis The following PAH and nitroarenes were observed and quantified naphthalene 1- and 2-methylshynaphthalene biphenyl acenaphthene acenaphthylene fluorene phenanthrene anthracene dibenzothiophene fluoranthene pyrene benz(a)shyanthracene chrysenetriphenylene benzo(a)pyrene 1- and 2-nitronaphthashylene 3-nitrobiphenyl 2- 3- and 8-nitrofluoranthene and 1- and 2-nitroshypyrene

ii

- --- ------

( TABLE OF CONTENTS

Abstract

Acknowledgments V

Disclaimer vi

List of Figures vii

List of Tables xi









A Introduction V-1

B Experimental V-1




A Introduction VI-1

B Experimental VI-1





6 Chemicals VI-9

111








A Introduction

B Experimental

C Results


Appendix



Page

Vl-10 VI-10 Vl-13 VI-16

Vl-21

Vl-28 VI-29 Vll-1

VIl-1

Vll-1

VIl-5 VIIl-1

IX-1

A-1

B-1

iv

l J

(

ACKNOWLEDGMENTS





research staff
















(

V








vi

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page














vii


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----

- --- ------

( TABLE OF CONTENTS

Abstract

Acknowledgments V

Disclaimer vi

List of Figures vii

List of Tables xi









A Introduction V-1

B Experimental V-1




A Introduction VI-1

B Experimental VI-1





6 Chemicals VI-9

111








A Introduction

B Experimental

C Results


Appendix



Page

Vl-10 VI-10 Vl-13 VI-16

Vl-21

Vl-28 VI-29 Vll-1

VIl-1

Vll-1

VIl-5 VIIl-1

IX-1

A-1

B-1

iv

l J

(

ACKNOWLEDGMENTS





research staff
















(

V








vi

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page














vii


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----

( TABLE OF CONTENTS

Abstract

Acknowledgments V

Disclaimer vi

List of Figures vii

List of Tables xi









A Introduction V-1

B Experimental V-1




A Introduction VI-1

B Experimental VI-1





6 Chemicals VI-9

111








A Introduction

B Experimental

C Results


Appendix



Page

Vl-10 VI-10 Vl-13 VI-16

Vl-21

Vl-28 VI-29 Vll-1

VIl-1

Vll-1

VIl-5 VIIl-1

IX-1

A-1

B-1

iv

l J

(

ACKNOWLEDGMENTS





research staff
















(

V








vi

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page














vii


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----








A Introduction

B Experimental

C Results


Appendix



Page

Vl-10 VI-10 Vl-13 VI-16

Vl-21

Vl-28 VI-29 Vll-1

VIl-1

Vll-1

VIl-5 VIIl-1

IX-1

A-1

B-1

iv

l J

(

ACKNOWLEDGMENTS





research staff
















(

V








vi

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page














vii


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----

l J

(

ACKNOWLEDGMENTS





research staff
















(

V








vi

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page














vii


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----








vi

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page














vii


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----

(

Figure Number

1-1

1-2

I-3

I-4

111-1

111-2

lV-1

IV-2

IV-3

IV-4

V-1

V-3

(

LIST OF FIGURES

ill Page














vii


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----


Figure Number

V-5

V-6

V-7

V-8

Vl-1

Vl-2

Vl-3

Vl-4

Title Page











viii




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















-- --- __ ----




VI-17


VI-17


VI-18


VI-19


Vl-20


VI-22


Vl-23


Vl-24

ix


Figure Number Title







X

(

LIST OF TABLES



1-5


lV-4


IV-5


IV-6


IV-7


IV-8


V-12


V-21


V-22


V-23


VI-11


VI-12

xi


Table Number Title















3 VI-14

VI-26

VI-27

Vl-31

Vl-32

Vl-33

VII-3

VII-6

VII-7

VII-8

VII-9

Vll-12

VlII-7

Vlll-8

xii

(







xiii

(

ARB

CH2Cl2

CH~

CH30H

CSMCS

DMSO

DOAS

EPA

FL-d 1O

ft

FT-IR

GC-HS

GF filters

HCHO

( HCOOH

Hi-vol




Benzo(a)pyrene


Degrees Centigrade

Dichloromethane

Acetonitrile

Methanol

Centimeter


Dimethyl sulfoxide



Electron volt

Degrees Fahrenheit


Feet


Gram



Glass fiber filters

Formaldehyde

Formic acid

High volume sampler

xiv

I

HN03

fi2Q HONO

HPLC

hr

Hz

K

km

L-broth or LB-broth

m

M

MeOH

MgC12

MID

min

min- 1

mL

DID


Nitric acid

Water

Nitrous acid


Hour

Hertz (cycle s-1)

Light intensity


Internal diameter

Thousand

Degrees Kelvin

Kilometer


Meter

Cubic meter

Molar

Methanol

Milligram

Magnesium chloride


Minute

Per minute

Milliliter

Millimeter

xv

(

mol

MS

mz

Mutagen density

Mutagen loading

NBS SRM 1648

NBS SRM 1649

NF

amp

NH3

NH11No3

Nitroarenes

nm

NO

N02

N03

NOX

~Q5

NP

OD

OH

Q3



Mass spectrometer




Molecular weight



Nitrofluoranthene

Nanogram (10-9 gram

Ammonia

Ammonium nitrate



Nitric oxide

Nitrogen dioxide




Nitropyrene

Optical density

Hydroxyl radical

Ozone

xvi


PAH

PDT

PER-d 12

2amp

2fl

PER

POM

~

~

PUF

PY-d 10

rev

S9

SAPRC

SCE

SCFM

Semi-prep column

Specific activity

TA98

TA98NR





Deuterated perylene

Picogram 10-12 gram


Perylene


Part per billion

Part per trillion

Polyurethane foam

Deuterated pyrene










xvii

(

TA981 8-DNP6

Tenax-GC

TIGF filters

Total activity

UCR

l

l

uvvis

w











Ultravioletvisible

Watt

xviii

(






















formaldehyde (HCHO














1-1










and 20






















I-2

(


Q IOtD S-25

21 ~ a 0 J

z 1S 0 H t-lt 11 Q t-

~ u s ~ u bull 1

20AUG 12 13 14 15 16 17 18

TIME CPOT)


1-3

5----------------------

D 3 a

I a

2 t--4 I t-


13 14 15 16 17 18 19 20 21

DATE


f





81286 0800-2000 42a 398 -a 9-~ 812-1386 2000-0800 31 30 15 65 81386 0800-2000 27 22 78 33 813-1486 2000-0800 411 44 25 10

81486 0800-2000 33 35 15 68

814-1586 2000-0800 15 11 65 35 81586 0800-2000 28 27 11 5 1

815-1686 2000-0800 31 41 21 10

81686 0800-2000 28 29 12 49 816-1786 2000-0800 40 40 19 83 81786 0800-2000 27 27 11 45 817-1886 2000-0800 40 43 22 95 81886 0800-2000 42 53 23 76 818-1986 2000-0800 15 13 74 29 81986 0800-2000 33 35 12 53 819-2086 2000-0800 38 43 18 85 82086 0800-2000 55 61 21 10

820-2186 2000-0800 28 28 13 54


1-5






















program

I-6

800

M 6QQI

pound

0)

C 40 I I I I I

NAPHTHALENE 8000

Doy (0800-2000 hr)

~ Night (2000-0800 hr)

lt) I

C 0) C


METHYLNAPHTHALENES

12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986

1000 0 Doy lt0800-2000 hr)


I I

I I 0 I

0

I I I I I I I 12 13 14 15 16 17 18 19 20 21

August 1986

I I


1-7

11 INTRODUCTION




























11-1





11-2

(



































III-1

X -------



_ 8ft bull--

N middotbull--~ i -

- L ~



~ ~~-= I I

e-4 e-4

I __~~~ H

~s-~ ~~~~~ - u ---~


-~ 1




FOOTIALL STADIUM

FENCE

+ N

ARB HQ TRAILER

l FORD ]

I APPEL ]

[uNt~

l EPA I [ SCpound

I ARB

I ARB

]

]

]

25m I IshyC J A

c

-z

C Cl)



III-3




111-4


A Introduction



























IV-1






(











into the spectra)



















background spectra






IV-3











N02 27 365 23 HONO 11 354 06 N03 Radical 480 662 001

so2 15 300 04

HCHO 2 1 339 30












IV-4



(ppm) (ppt)

813 0185 72

814 027 lt~O

815 026 wa 816 024 HD

817 027 HD

818 028 ND

819 030 lt40

820 027 lt40

aND = Not detected





HCHO 45 ppb












IV-5



00-01 19 20 15 24 32 1 7 17 20 24

01-02 22 23 1 6 33 36 20 18 2 1 24

02-03 23 23 8 29 38 17 12 1 6 29

03-04 25 20 20 29 27 21 BDb 17 30

04-05 24 26 23 33 23 25 BD 1 8 35 05-06 35 26 2 1 35 17 19 09 20 39 06-07 33 26 2 1 33 16 13 15 2 1 46

07-08 22 20 14 24 09 13 13 24 31

08-09 12 1 1 13 12 BD 1 bull BD 25






21-22 09 13 1 4 bull 7 1 10 BD 1 7

22-23 16 13 16 20 09 15 20 13 23-24 2 15 1 9 2 1 1 15 23 1 7


IV-6

(



00-01 641 669 545 563 644 72 1 562 543 694 01-02 615 616 518 509 633 744 459 434 555 02-03 573 609 489 520 563 75 1 277 228 606

03-04 542 640 427 503 362 695 218 204 639 04-05 52 1 617 392 467 273 659 182 214 62 1

05-06 469 616 414 461 234 4JI 1 189 338 610

06-07 475 633 429 431 22 1 513 402 452 609 07-08 644 638 554 494 211 58 1 616 636 724 08-09 777 744 619 700 264 530 47 6 140 1

09-10 936 768 650 683 483 828 495 1185 10-11 81 1 665 609 607 449 919 412 130 3 11-12 57 1 508 530 47 1 333 906 325 507 12-13 433 385 385 278 23 1 544 204 445 13-14 422 332 311 144 168 202 263 257 14-15 359 244 260 131 128 17 8 278 169 15-16 368 284 438 142 177 250 298 299 16-17 388 396 462 195 219 352 283 294 17-18 424 411 516 332 260 477 427 37 6 18-19 536 477 573 455 496 524 60 1 618 19-20 62 1 596 703 626 743 52 1 852 887 20-21 712 765 67 1 77 5 787 729 854 898 21-22 753 774 606 813 703 773 777 855 22-23 74 1 735 601 704 672 69 1 719 776

23-24 708 61 1 605 669 706 657 660 837


IV-7



00-01 73 58 56 57 103 57 76 92 110 01-02 69 58 60 13 89 69 8 1 100 88

02-03 64 52 60 54 88 7 8 8 1 94 99 03-04 62 55 55 64 89 86 10 105 10 1

04-05 58 55 55 63 7 1 74 81 102 96 05-06 63 54 61 67 73 75 85 107 108 06-07 64 67 62 6 1 72 73 105 9 1 116 07-08 97 74 83 73 88 89 112 13 1 139 08-09 110 1 2 89 87 97 96 113 199 09-10 124 130 102 112 144 13 1 128 184 10-11 127 140 117 11 1 154 143 123 16 1 11-12 116 135 130 126 163 178 129 131 12-13 122 128 127 107 148 138 12 1 168 13-14 124 11 -3 129 100 131 102 148 151 14-15 138 100 16 1 112 122 79 146 14 4 15-16 153 147 12 1 114 139 137 101 117 16-17 149 135 109 120 120 132 70 92 17-18 143 127 95 108 79 114 66 11 18-19 102 11 1 83 79 71 78 59 9-3 19-20 95 100 74 79 84 53 56 84 20-21 9 1 85 57 83 75 58 64 76 21-22 74 73 5 1 83 63 77 55 74 22-23 8 1 63 5 1 65 72 72 92 70 23-24 70 5-9 54 6 1 7 1 84 9-7 95


IV-8

---

~


100 l ti

H

deg



DATE




DATE


25 I

DOAS nbullIR - - -

20 + I

0 15 + I a ) bull

( fta JI

a

10

1-4 lt

sect I

0

5

1I b

l lt

--~

~

5-----------------------

4

a 3 a a

0 2

i


DATE


H

f--

















unity)

















IV-12

(


A Introduction

















et al 1980)

B Experimental














V-1






















and archived







monitoring

3 Calibration




V-2

________ _

~



bull 25m -







-

- 871

068

~ I 050

w ~ ltt co

848 ---1 rr HN03

0 838 0 Cl) CD lt( 8 21

ltI

_J I I Vt

8 18 --


NH3

981 UIII 1188

WAVENUMBERS (cm- 1)










line
























V-6

_~ middot-

035

031

w0 025 z lt(CD 021

ltI a 0 015

() coltt a11

015

888 891 910870

WAVENUMBERS (cm- 1)


02


ltI

0 00 0 015()

al lt(

middot -aas

1121191 1181 1111

WAVENUMBERS (cm- 1)


2
























4 Treatment of Data












V-9











conditions










nighttime hours)













V-10

















0 044 )( 60-20)] = plusmn33 ppb
















V-11



81286 1816 1amp6 II 1 1828 1amp 0 5-9

0758 0811 0825

1318 74

181amp8 19()1 1920

54 1amp 8 35

56 63 62

0837 103 1934 28 50 0851 2 1 81 1947 26 6 1 0905 21 69 2000 26 60 0917 26 67 2014 o 0930 39 6 1 2106 Jl5 0944 39 53 2118 116 0957 45 6 1 2132 51 1010 44 49 2144 5 1 1021amp 53 33 2201 117 1037 89 39 2215 116 1052 97 29 1119 1136

118 144

26 39

81386

1149 145 42 0027 57 48 1202 152 35 0043 5 1 5 1 1221 153 34 0059 53 43 1234 163 37 0114 50 54 1250 163 46 0130 52 5 1 1305 177 47 0146 50 5 1 1320 158 47 0201 55 54 1339 195 50 0217 55 46 1353 200 29 0233 55 59 1406 206 35 0249 5 1 53 1419 216 43 0304 116 40 1433 237 42 0320 113 36 1447 222 39 0336 II 2 43 1503 215 35 0351 52 40 1517 216 28 0407 Jl7 39 1532 189 47 0423 117 45 1546 187 38 0439 ll6 40 1608 139 34 0454 67 46 1622 124 30 0510 5 1 45 1635 105 34 0526 119 55 1651 116 3 0541 114 55 1705 58 32 0557 53 42 1718 57 32 0612 116 44 1732 67 29 0628 50 39 1745 59 3 1 0644 115 43 1802 59 34 0659 54 52

V-12

(



0715 66 62 1926 54 s 790731 59 70 1939 52 1 810746 74 97 1952 45 36 910802 6 1 90 442005 34 750818 58 90 2018 34 37 790833 49 79 2034 5 1 37 7 10849 48 103 2113 24 37 620904 17 22 107 2133 59 670920 17 18 125 21146 64 630936 38 18 126 2206 68 590951 43 19 134 2226 43 761007 11 5 17 135 2245 39 691035 76 1 J4 125 2305 46 741048 80 18 137 2324 42 501101 87 17 126 2344 38 65111JJ 87 22 122 1128 118 18 127 814861145 107 19 11 3 1158 125 18 106 0004 37 481211 126 19 11 4 0023 26 551229 129 30 120 0043 27 621248 140 30 middot10 9 0102 29 591309 155 30 97 0122 36 501331 139 28 106 0142 37 431344 159 36 119 0201 47 471357 148 32 10 1 0221 35 371410 155 36 123 0211 34 421423 134 35 116 0300 30 451440 166 38 11 2 0320 26 421453 169 3 1 11 1 0339 19 361506 179 31 113 0359 24 401522 197 39 12 1 0419 27 451535 18 1 40 103 0438 30 501548 173 39 124 0458 25 491601 165 41 153 0518 29 451614 185 45 139 0537 40 341630 130 48 130 0557 4 1 331643 139 39 127 0616 34 341655 129 39 121 0636 28 381706 134 37 131 0656 25 601718 135 13139 0716 24 621734 130 35 109 0735 2 1 571747 104 42 126 0755 15 741800 106 40 98 0815 26 82(

1813 97 4 1 116 0834 18 1091827 83 4 1 90 0854 26 1 5 1221850 6o 4 10 1 0914 26 14 1251913 43 38 83 1033 5 7 128

V-13




1353 202 2Ji 13181586 1410 250 27 13 1 1425 226 35 17 80008 25 4 1 1440 222 29 1760027 28 34 i453 216 3-3 164

V-14

(



1505 214 31 162 0418 36 421518 196 27 151 0438 33 491530 214 25 143 0458 36 471542 205 25 158 0517 38 32160JI 171 23 129 0537 3ll 431616 162 23 138 0557 27 4ll1629 162 28 122 0616 26 401641 115 21 135 0636 38 3 11653 109 19 138 0656 3-3 441707 108 20 125 0715 28 501720 105 14 9 1 0735 18 571732 94 6 1 2 1 0755 09 3 791744 90 23 79 0815 30 16 981757 9 ll 27 9 1 0834 2 1 15 1001830 82 16 77 0854 4 1 06 971842 67 22 90 0914 38 1 1 1121854 68 8 106 0933 38 1 1 1121907 68 19 88 1015 81 15 1221919 43 2 1 81 1028 87 09 1261938 29 28 8 1 1048 103 09 1441950 26 23 68 1100 116 18 1492003 22 27 12 1118 138 l8 14 92015 27 74 1131 137 23 16 12027 36 55 1143 155 15 1262106 36 5 11 1155 158 20 1382125 29 60 1207 156 22 1242145 29 34 1219 160 22 1232205 27 34 1231 144 29 1132224 3 1 27 1243 155 22 1182244 30 44 1255 177 24 1032323 32 57 1308 175 23 10 1 2313 4 8 44 1320 17 1 28 96 1332 192 23 9681686 1344 166 3 1 11 4 1356 197 28 990003 31 55 1409 194 28 1090022 3 1 40 1421 208 32 1050042 36 43 1433 203 28 1090101 32 49 1445 203 3 1 1170121 40 49 1457 211 35 1420111 35 49 1509 208 3 1 14 10200 36 45 1522 205 33 1380220 32 5 1 1534 205 26 1670240 32 48 1546 205 26 143 0259 42 40 1558 228 26 1550319 3 1 47 1610 198 35 1380339 5 1 37 1623 205 3 1 1520359 38 49 1635 19 1 31 139

V-15



1647 1659 1711 1724 1736 1748 1800 1812 1902 1917 1924 1942

209 216 199 209 196 169 187 13 1 103 79 67 82

22 29 23 2 1 27 24 26 23 23 28 27 3 1

144 127 116 135 147 134 126 12 1 92 93 91 89

0644 0704 0723 0743 0803 0823 0843 0902 0922 09112

bull1002

20 22 34 17 22 38 112 53 54 55 56

62 10 63 7JI 85 83

104 11 7 131 185 189

1954 2006 2024 2036 2049 2144 2152 2212 2232

68 53 54 5 1 26

32 47 48 38 50 45 39 36 38

89 91 82 81 95 76 90 80 77

bull2235 2253 2306 2317 2337 2356

81886

59 II 2 35 JI 6 33 40

60 62 53 60 63 64

2251 2311 2331 2350

36 37 43 38

68 53 47 59

0016 0036 0056 0115

50 59 83 38

69 55 72 8 1

81786 0135 0155

39 52

69 87

0010 0030 0049 0109 0129 0148 0208 0228 0248 0307 0327 0347 0406 0426 0446 0506 0525 0545 0605 0621

37 40 4 1 32 5 1 34 34 37 40 29 2 27 26 18 25 2 1 18 26 2 1 28

56 69 62 74 79 62 66 69 63 89 75 58 82 78 63 79 83 7 1 52 69

0214 0234 0254 0313 0333 0353 0412 0432 0452 0511 0531 0550 0610 0630 0649 0709 0729 0748 0808 0828 0847

28 27 3 37

59 53 75 65 62 60 56 58 67 46 48 43 44 42 47 62 4 1 46 43 46 75

72 79 74 11 79 73 75 8 1 77 79 80 65 56 60 64 93 79 84 89 99 92

V-16

(



0907 56 82 150 2009 22 1 480926 55 7 1 158 2021 68 670946 56 57 105 2035 79 861004 99 84 153 2047 87 8 11017 112 94 170 2059 82 7 11029 103 97 153 2111 94 541057 123 115 215 2124 90 581111 128 143 220 2206 69 721123 131 145 205 2226 76 781140 150 128 224 2246 95 851156 155 11 5 188 2305 85 801207 207 98 222 2325 77 851220 192 90 193 2345 71 781233 207 62 152 1245 154 ss 124 819861256 239 104 136 1308 207 10 1 146 00011 5970 103 0024 59

9 69

11320 177 1333 154 50 93 0044 105 761345 159 47 91 0103 69 771357 137 38 82 0123 53 621409 16 7 43 106 0143 69 561421 167 4 1 89 0202 751433 185 46 132 0222 96

67 601445 185 42 116 0242 80 751451 157 46 117 0301 67 791509 224 62 14l~ 0321 53 6 11521 195 47 145 0341 851534 277 62 15 1 0400 102 79 841546 262 6 1 19 1 Oll20 7 1 8 11558 262 58 163 0439 6 1 771610 212 53 151 0459 89 831622 213 48 14 1 0519 78 6 111635 16 1 56 146 0538 42 651647 172 6 1 179 0558 73 791700 164 54 124 0618 64 901712 163 57 118 0637 64 1001724 150 44 123 0657 85 11 1 1737 152 6 1 104 0717 58 121750 130 5JI 119 0737 26 59 1431802 128 55 108 0757 26 6o 1461814 13 1 50 96 0816 49 63 1421826 99 69 97 0836 60 6 1 1491839 57 66 100 0855 67 79 142~ 1852 54 8 1 69 0915 84 68 1271932 28 53 7 1 0935 115 65 1551944 28 43 47 1006 162 66 1381956 25 11 8 58 1018 16 1 57 134

V-17



1030 173 60 143 2017 8127 811043 173 64 152 2029 110 771057 18 1 70 153 2042 95 701109 219 69 186 2054 12 771121 175 69 159 2106 71 631133 195 69 115 2118 77 721148 206 87 134 2130 10 7 1 1200 229 64 115 2142 65 781213 182 54 137 2155 60 591225 216 55 142 2207 67 681237 223 49 138 2219 72 931249 125 39 92 2231 75 991305 134 32 87 2243 10 871317 166 58 108 2314 69 8 11329 224 66 122 2334 58 861346 292 190 607 1 2353 9 11355 33 1 8 1 238 1405 272 78 213 820861415 273 65 165 1426 234 64 133 0013 50 841436 223 6 1 130 0032 58 961448 212 58 127 0052 57 851501 200 5 1 119 0112 56 841512 185 57 106 0131 69 821522 172 5 1 133 0151 58 881532 166 45 109 0210 64 881542 125 64 94 0230 57 901554 116 47 0250 8290 541604 107 42 68 0309 58 7 11614 83 47 76 0329 60 961624 75 43 82 0348 6 1 921634 71 49 67 0408 60 891645 76 44 8 1 0428 69 801655 62 52 70 0447 78 841705 48 5 1 76 0507 59 881720 65 53 8 0527 56 861733 68 5 1 83 0546 58 1011747 74 5 1 88 0606 6 1 1001759 72 7 1 74 0625 63 1101811 47 5 1 76 0645 65 1031823 37 60 62 0705 64 1041835 50 68 67 0724 71 1071847 50 58 72 0744 72 1301902 46 81 76 0803 23 95 1391914 40 70 66 0823 37 115 1801927 33 69 72 0843 38 93 2391939 34 7 1 71 0902 50 83 2222007 33 85 56 18991 0923 98

V-18

(



0942 64 112 252 1849 42 8 1 12 1 1001 65 100 251 1900 58 9-3 98 1013 92 94 235 1910 57 1011 124 1025 104 99 233 1920 41 98 117 1038 100 75 169 1930 34 103 11 bull1 1050 121 88 18S 1940 46 98 9 1 1104 141 89 169 2023 58 66 9 1 1117 145 88 176 2035 43 61 104 1129 175 96 147 2050 33 89 84 1141 183 89 164 2110 37 63 87 1153 175 8 134 2129 1 2 5-9 76 1208 187 95 174 2149 83 97 1220 234 87 189 2209 99 84 1232 220 71 205 2228 82 78 1244 249 75 214 2248 56 83 1300 245 63 177 2307 108 85 1311 217 65 193 2327 9 1 86 1321 20 1 63 179 2347 67 97 1331 196 66 154 1341 220 62 147 82186 1352 210 59 175 1402 200 55 184 0006 middot 5 1 105 1414 200 50 168 0026 62 98 1424 218 49 167 0046 65 106 1434 190 63 167 0106 60 118 1444 180 64 161 0125 55 92 1454 158 79 11 1 0145 75 10 1 1507 154 10 13 0204 83 94 1517 14 8 63 123 0224 75 93 1530 143 63 119 0244 72 86 1540 143 5 1 119 0303 67 93 1550 150 6 1 128 0323 6 1 79 1600 157 59 104 0343 8 1 108 1610 128 5 1 99 0402 79 85 1621 85 54 88 0422 68 84 1631 79 50 80 0442 70 84 1643 73 46 7 1 0501 68 85 1656 50 43 52 0521 7 1 105 1706 57 50 64 0541 58 96 1716 63 57 76 0601 66 101 1727 65 52 68 0620 6 1 105 1737 60 54 84 0640 65 90 1747 63 57 80 0700 63 16 1757 67 60 90 0717 6 1 130 1807 9 1 59 102 0730 70 11L3 1817 90 76 113 1828 75 64 113 1839 7 1 87 14

V-19

11

AUS 12bull21 1116 J

tOtD~

~25

- 41J a a-~ 31 H lt 21 0 z ~ z 0 u

I 21 J a a-

AUG 13 15 16 17 21 TIME CPOT)

z 15 0 H t-lt 11 0 t-

ffiu s z 0 u bull I


V-20

(




1400-1500 220 156 X 227 203 X 172 239 190 1500-1600 196 181 223 203 209 X 239 156 149 1600-1700 119 149 193 143 204 X 192 78 89 1700-1800 6 1 124 174 99 195 X 149 65 62

1800-1900 49 80 133 7-9 126 X 89 48 12



V-21



0000-0100 54 29 26 33 39 59 75 55 60


2200-2300 48 49 16 30 37 X 8 70 80 2300-2400 52 4 1 22 37 39 39 75 63 84



V-22



0000-0100 48 56 37 45 63 65 77 89 104

0100-0200 s 1 49 33 48 7 77 611 85 102




V-23




































V-24

21

(


a a a a0 aD

DD D15 D D

D D

II a Da D D

8 u

I

5 D Da D D

258 0 OZONE

H02 o 0 0 a 288 0a

oO 0~ 158

~ I- 118z UJ

~ 0 SI u

bull 12 AOO 15

0

0

oo 0 0

0

I 0

0

0

0

8

TnE CPOT)

12 8 AUG 16


V-25







hours

V-26

bull bull

21

(

IS

ll

s

251bull 88 211 J

158

111

SI

a


a D D

aa D a aa D

DDD

a D D

D DD D

DDa D

0

0 O 0

O OZONE o 0 N02 0

00

0 0 ~

0 00~ 0 0 0

0 0

12 12 Al6 18 AOO 19

TDpound CPOT)


V-27


A Introduction


















B Experimental














VI-1














cartridges)
















0800-2000 hr (6 August 20-21 2000-0800 hr






VI-2

(


SPRING SPRING

~ PLUG 1 middot -

middot PLUG 2 bull


MOTOR

EXHAUST


Vl-3





































VI-4

bull bull bull

_ -~~

1 II~~

lt H I

u

4 6 7 8 9 10 11 12 14 15 16 17 18 19 20 21 22 23 I 3 t 5

I I I t I I I p


Hexane 1001 ctt2c12



1001 ---middot--middot-- - 0 10 20 30 40

Minutebull


I

so 60





TA98NR (-$9) TA9818-DNP 6 (-$9)







1 GCMS


Vl-6

(






















5 GCMS Analyses













VI-7

I


fncuou


9euna 1~

00 100

~ 10 20 JO 50 -~--

VI-8

















6 Chemicals
















VI-9

C Results



































VI-10

- -



ng m-3 a




81386 Day 2400 160 320 95 -3 4 30 26 8 13-1486 Night 4800 390 730 170 12 22 37 51

81486 Day 2500 130 260 70 -3 4 30 20 814-1586 Night 3000 330 640 100 23 17 34 40


~ 81686 Day 3200 98 200 52 -3 -4 23 16 H

I 816-1786 Night 3400 350 700 98 -3 24 40 37 81786 Day 2000 76 170 36 -3 -5 27 20 817-1886 Night 4300 330 680 54 4 30 47 51

81886 Day 4100 120 260 43 -3 5 31 26 818-1986 Night 4200 280 570 67 -3 28 43 46 81986 Day 4300 90 200 36 -3 4 23 21

819-2086 Night 3800 290 600 60 -3 28 44 50 82086 Day 4100 150 320 53 -3 6 33 29

-e e -e -e820-2186 Night 6100 490d 860d e








naphthalene

Date Low

Flowb HighFlowe

Low Flowd

High Flow

Low Flow

High Flow



_e _e _e820-2186 Night 6100 490 860



VI-12






































Vl-13














eND = None detected

----_






37222S1sem




o1_____n(L_________

nmo- 19900-


(2ng m-3) 171150 21SO

nm 1l4075


1 JO u 12 IS 9 11 11 ubull








of the study






























VI-16

I I I I I I

I I

0


( NAPHTHALENE

12 13 14 15 16 17 18 19 20 August 1986(

8000

6000

M I

C 4000 0) C

2000

Figure VI-5

1000

800

MI

600 pound

CJ)

C 400


12-13 13-14 14-15 15-16 16-17 17-18 18-19 19-20 20-21

August 1986


METHYLNAPHTHALENES

0 Day (0800-2000 hr)


Vl-17

21



1 ecs 1 0pound5


Tltne ( in In )


2 0CS 2ec5

10ES 1 0pound5

e ~

95 10e 10 5 110 115


30es 38E5




2ecs ([

20pound5

I 8pound5I 0pound5

e 9 18 I I

Tlinbull ltintn gt


Vl-18

(


ampBES

48E5 DAY PUF

PHENANTHRENE sec5

2ec5 2BES

bullu C

e


l ampecs ampecs

15 S 168 165 Ttae (min)

GLENDORA CA 813-1486 2000 -0800HR



80E5

60E5

0E5

20E5

Ion t 78 ee ainu

NIGHT PUF

Ion 18880 unu

PH-d10

e 15 e 155 t6 e

PHENANTHRENE

ANTHRACENE

AN-d 10

165


l 2 E6

l 8pound6 8BC5

6 8pound5

8pound5

20pound5

Tl 111e ( 1111 n )


VI-19

GLENDORA CA 81386 0800- 2000 HR

28pound5

I 5pound5

18pound5

5 8pound4

bullu 0 C

C

l 20pound5

l 5pound5

10pound5

s0c

0

lon 282N alllU

FL OAY PUF


19 0 19 5

FL-d I0

20e

Tlllle (tlltn gt

28pound5

1 5pound5

18pound5

58pound4

PY-d10 20pound5

15pound5

18pound5

50pound

205 210


4 ecs

30E5

20ES

t 0E5 D u 0 C

~



1 BES


SJ I[

30ES

2eEs

I BES

e

4 0pound5

30pound5

20pound5

I BES

19 e 195 288 285 Tltlle t 111 In gt


Vl-20

(


































Vl-21


mz 173

[M-NO]+

mz 143

w u z ~ 0 z ) CD ~

0 w N-J ~ ~ cr 0 z

[M-N02f

mz 127

[M-HN02t

mz 126

fflZ 11 5


[11d-No-cof7

mz 122



Vl-22

~~

bull~

2-NN

1-NN

[M]+


mz 173


0 w N-J

lt lt(

I ~ N w

H

~ 1mz 141 cC- d _ ~

mz 140

n H 115 17




100 (Mt I

4-NITROBIPHENYL

mz 199


I - 0 ~ 100 j (M-N02J+

u Imz 153 z ~ z ) 0 ~100 W I(M-HN02t


3-NITROACENAPHTHENE

f mz 152 l ~ ~ o L JL -~ fl ~A

100 [M-NO-CO]+

mz 141




r 1r=t bull11

~

~

1 STANDARD MIXTURE

(MtI

0-100 ~ 0-w u z ~ 1[M]+z gt 0




m 100 ltl

w gt-lt

H lt( I

N - i [M-N02t V w

0 108

[M-HN02J+ I

bull 1 r - v- ~ ---( ~~~- r 1 p 11 u IS 15 1T 18 19



--












46gb

938

3751

3751

938

938

106 112

230 259

748 804

1 47 127

11 65 1186

052 057

244 259

5 16 556

085 056 083 060

149 039 157 045

809 292 843 335

073 008 1 04 NDc

751 119 731 1 28

009 001 022 ND

241 079 245 087

264 041 326 045







VI-26

(

(









pg -3


PUF Sample 1 81386 0800-2000 PDT

PUF Sample 2 813-1486 2000-0800 PDT



PUF Sample 5 82086 0800-2000 PDT

PUF Sample 6 820-2186 2000-0800 PDT

2320

2610

2430

3280

2680

5710

1790

1630

2440

2020

2590

3140

1240

450

840

330

880

460

(at 4 PUF plugs

VI-27





































VI-28













VI-29

2-NF180

90 mz 247

80

70

60

50

40

30

20

2-NP10 8-NF

0 -


23 24 25 26 27



Vl-30

( (




Fluoranthene

Pyrene

Benz(a)anthracene


Benzo(a)pyrene

73 plusmn 02

12 plusmn 02

24 plusmn 01

46 plusmn 02

30 plusmn 03

71 plusmn 05

60 plusmn 02

24plusmn01

35 t o 1 17 t 01

24 plusmn 02

71 70

62 61

23 2 1

4 o 39

23 22

awise et al (1986)

VI-31


mi m-3






I) N 815-1616-1717-1818-1986






middot-











200

480

220

950

410

2000

NDa

ND

15

18

Traces

Traces

3

7

3

4

25

4

20

31

8

10

12

14

17

50

7

21

13

42

~

~

(


A Introduction















B Experimental











solution






VII-1





































VII-2





Compound TA98 TA98

2-Nitrofluoranthene

3-Nitrofluoranthene

8-Nitrofluoranthene

1-Nitropyrene

2-Nitropyrene

18-Dinitropyrene

024

049

033

0 13

010

10

017

013

030

057

o 14

0021









Chemical Company









VI-3















TA9818-DNP6


















were calculated

VII-4

( C Results
































VII-5



Date Day (PDT)

2 Filters (mg)

TSP (lg m-3)a

Weight (mg)

Extrait-able

81286 0800-2000 2004 130c 4839 24

812-1386 2000-0800 1156 71 5028 43

81386 0800-2000 2088 130 5761 28

813-1486 2000-0800 1344 82 5954 44

81486 0800-2000 2333 140 6484 28

814-1586 2000-0800 1068 65 3142 29

81586 0800-2000 1855 110 5581 30

815-1686 2000-0800 1073 66 3361 31 81686 0800-2000 1526 94 5366 35 816-1786 2000-0800 960 59 4665 49

81786 0800-2000 1347 83 5203 39 817-1886 2000-0800 924 57 28 10 30

81886 0800-2000 2107 130 4287 20

818-1986 2000-0800 937 57 1881 20

81986 0800-2000 1695 100 4108 24

819-2086 2000-0800 972 60 3661 38 82086 0800-2000 1884 120 4969 26

820-2186 2000-0800 117 1 72 2846 24



VII-6




Date Day

(PDT) TA98 +S9

TA98 -S9

TA98NR -S9

18-DNP6 -S9

to TA98

to TA98

81286 0800-2000 14 ( 18) 13 (35) 058 (2 10 031 58) 045 024

812-1386 2000-0800 10 (20) 097 (22) 050 (30) 021 ( 7 1) 052 022

81386 0800-2000 077 (11) 063 (32) 022 (55) 0093 (85) 035 o 15

813-1486 2000-0800 12 26) 12 ( 13) o68 lt14) 027 (59) 057 023

81486 0800-2000 082 ( 1 1) 087 (40) 038 (32) o 17 (88) 044 020

814-1586 2000-0800 078 40) 057 (21) 034 25) o 18 ( 6 1) 060 032 ltH H 81586 0800-2000 o 82 (2 1) 080 (23) 031 39) o 15 (93) 039 o 19 I 815-1686 2000-0800 15 (07) 20 (31) 10 (22) 047 (49) 050 024

81686 0800-2000 084 (24) 087 (34) 035 (60) o 15 (13) 040 017 816-1786 2000-0800 14 (20) 14 (29) 066 (27) 029 (28) 047 021 81786 0800-2000 086 20) 084 (31) 035 (40) o 14 14) 042 o 17 817-1886 2000-0800 23 ( 18) 25 (LO) 13 (30) 055 (31) 052 022 81886 0800-2000 16 ( 18) 20 (33) 087 (40) 029 (52) 044 o 15 818-1986 2000-0800 1 3 (30) 1 1 (27) 064 (28) 025 (60) 058 023 81986 0800-2000 13 ( 1 7) 14 (54) 048 ( 3 1) 021 (7 1) 034 o 15

819-2086 2000-0800 17 (32) 19 ( 1 8) 081 (21) 038 (63) 043 020

82086 0800-2000 18 (26) 20 (70) 069 (33) 034 (26) 035 017

820-2186 2000-0800 16 (24) 16 (33) 073 (92) 031 (42) 046 019


-




81286 0800-2000 340 300 140 75

812-1386 2000-0800 430 420 220 91

81386 0800-2000 210 170 61 26

813-1486 2000-0800 530 530 300 120

81486 0800-2000 230 240 110 47

814-1586 2000-0800 230 170 100 53 81586 0800-2000 250 240 93 45

815-1686 2000-0800 470 630 310 150

81686 0800-2000 300 310 120 53 816-1786 2000-0800 680 680 320 140

81786 0800-2000 330 320 140 54

817-1886 2000-0800 700 760 400 170

81886 0800-2000 330 410 180 59 818-1986 2000-0800 260 220 130 50

81986 0800-2000 320 340 120 51

819-2086 2000-0800 640 720 310 140

82086 0800-2000 470 530 180 90 820-2186 2000-0800 390 390 180 75

VII-8





81286 0800-2000 42b 39b 22) 0 17b 92b

812-1386 2000-0800 31 30 23) 15 65 81386 0800-2000 27 22 19) 78 33 813-1486 2000-0800 44 44 11) 25 10

81486 0800-2000 33 35 21) 15 68

814-1586 2000-0800 15 11 9) 65 35 81586 0800-2000 28 27 15) 11 5 1

815-1686 2000-0800 31 41 13) 21 10

8ti6J86 0800-2000 28 29 14) 12 49

816-1786 2000-0800 40 40 27) 19 83 81786 0800-2000 27 27 13) 11 45 817-1886 2000-0800 40 43 22) 22 95 81886 0800-2000 42 53 17) 23 76

818-1986 2000-0800 15 13 18) 74 29 81986 0800-2000 33 35 (12) 12 53 819-2086 2000-0800 38 43 16) 18 85 82086 0800-2000 55 61 24) 21 10

820-2186 2000-0800 28 28 38) 13 54



l

VII-9

Ibull60

Ibullso

M I

pound gt a i

Ibull40

Ibull30

20

-


~ ]

gt

=

=

~

~

gt

~

~

=

~

l=

~

gt= ~

~

s

gt ~E = ~

~

~

gt

gt

gt

~

= ~ = Cl gt


gt gt ~ ~~ =

5

~

~

=

~

~

l =

~

t

~

= ~ ~~ - euro~I ~ ~

I ~

E

gt




Vll-10

70 0

60

r I

(I) I I C

I I

gt QI L

50 ~ I

I I I I

I I gt- 40 I I () z ~ w 30A


10 b

I

Ia I

u--d

14

13 0 4212 ~ (1 () I11 0 +gt (110 ()

+ (X) (109 42

08




(

VII-11


















CH2Cl Extraceuros

Date 82086 820-2186 82086 820-2186

Time Period (PDT)

Day Night 0800-2000 2000-0800

Day Night 0800-2000 2000-0800

Flow Rate SCFM) 400 400 230 230

TSP microg m-3) 120 72 160 110





VII-12























(

VII-13

t

VIII CONCLUSIONS


































VIII-1
























phase










VIII-2

(



0 2 4 6 8 10 12 14



VIII-3

DAY NIGHT

TORRANCE CA 6


ng -3

s13-14861 ~ _0


ng -31 820-21861 ~ -- I

1~ 2-~ 3-Nlflh 1~ 2~ 3--NJIPh


VllI-4


















al 1987)


















VII I-5











nitroarene


























VIII-6









Torrance CA 224-2586 1800-0600 hra


Glendora CA 820-2186 2000-0800 hrb

30 29 60 80 03

23 1 bull 1 06 97 03

27 26 09 59 04

57 3 1 05 68 20


(

VIII-7



1 81386 0800-2000 hr

2 813-1486 2000-0800 hr

3 81516171886 Day composite 0800-2000 hr


5 82086 0800-2000 hr

6 820-2186 2000-0800 hr

14

27

11

52

2 1

94

VIII-8

( IX REFERENCES













IX-1













IX-2













IX-3







IX-4

( APPENDIX A





(

A-1






(continued)

A-2





14-AUG-86 0010-0024 1 6 74 673 0024-0038 1 9 54 6580058-01 12 20 6 678 01 12-01 26 2 1 59 642 0147-0201 24 58 605 0201-02 15 23 59 617 0236-0250 25 52 596 0250-0304 20 ND 631 0325-0339 20 64 636 0339-0353 20 49 652 04 13-04 27 3 1 6 1 605 0427-0441 23 55 625 0502-0516 25 ND 609 05 16-05 30 25 70 628 0551-0605 27 ND 60906 05-06 19 29 48 609 0640-0654 25 79 651 0654-0708 25 54 600 0728-0742 2 1 80 615 0742-0756 15 76 688 08 18-0833 13 110 707 0833-0848 09 134 774 0848-0903 ND 112 818 09 03-09 18 ND 121 792

(continued)

A-3



14-AUG-86 0918-0933 ND 142 686 0948-1003 1003-1018 1033-1048 1048-1103 1103-1118 1118-1133 1133-1148 12 18-1233 1233-1248 1248-1303 1303-1318 13 18-13 33 1333-1348 1348~1403 1403-1414 1506-1521 1521-1536 1536-1551 1608-1623 1623-1638 1638-1653 1709-1724 1724-1743 1743-1800 18 00-18 15 18 15-1835 19 18-19 38 1959-20 10 2031-2042 21 02-21 14 21 28-21 43 2222-2236 2236-2250 2310-2324 2324-2338


125 136 140 144 133 136 134 133 116 127 144 88

10 1 116 78

138 164 147 134 150 125 138 129 11 1 10 1 117 104 96 83 8 1 72 63 6o 60 57

799 732 657 637 478 559 502 278 447 502 375 332 290 288 230 262 262 307 404 397 396 396 400 446 458 468 567 622 805 797 772 744 726 622 574

15-AUG-86 0000-0014 00 14-0028 0048-01 02 01 02-01 16 01 36-01 50 01 50-0204 0225-0239 0239-0253

16 15 15 1 7 18 1 2 19 19

56 53 57 54 63 59 59 62

546 557 539 530 512 519 489 478 (

continued)

A-4





(continued)

A-5

(




15-AUG-86 1858-19 14 1930-1946 2059-21 14 21 30-21 53 22 15-22 33 2303-2322 2322-2336 2352-2400

ND ND 1 2 14 1 5 20 15 2 1

11 75 45 53 47 62 66 48

599 728 633 600 598 611 603 606

(

16-AUG-86 0000-0002 00 16-00 22 0034-0049 0049-0104 01 04-01 19 01 19-01 34 01 34-01 49 01 49-0204 0204-0219 02 19-0234 0234-0249 0249-0304 0304-0319 03 19-03 34 0334-0349 0349-0404 04 04-04 19 04 19-04 34 0434-0448 0448-0503 05 03-05 18 05 18-05 33 0533-0548 0548-0603 06 03-06 18 06 18-06 37 0637-0654 0654-0711 0711-0728 0728-0747 0747-0802 0802-0817 08 17-0832 0832-0847 0847-0902 09 02-09 17

2 1 20 23 27 29 36 33 34 27 30 28 3 1 28 32 29 26 30 36 35 35 35 35 35 35 29 33 36 32 29 22 13 16 09 12 09 ND

48 7 1 54 54 69 84 78 66 59 47 45 63 77 62 60 56 7 1 47 72 66 7 1 56 72 69 ND 72 62 57 69 83 77 7 1 8 1 95

104 92

606 567 567 552 54 1 485 504 490 537 526 516 504 526 475 495 519 465 460 472 454 469 450 460 468 469 449 385 394 45 1 519 596 705 736 71 654 68 1 f

lt

(continued)

A-6





(continued)

A-7




16-AUG-86 2302-2316 20 50 68 1 2337-2351 2 1 66 6672351-2400 24 62 662


(contin~d)

A-8





18-AUG-86 0018-0030 14 57 75 1 0030-0044 19 57 696 01 05-01 19 18 60 760 01 19-01 33 1 7 68 760 0153-0207 2 1 69 735 0207-0221 2 1 72 757 0242-0256 15 80 752 02 56-03 10 17 78 727 0331-0345 23 89 695 0345-0359 19 86 674 0420-0434 25 89 659 0434-0448 28 5 1 674 0508-0522 20 87 534 0522-0537 23 95 51 1 0558-0611 15 59 383 0611-0625 1 5 69 460 0646-0700 12 75 535 07 00-07 14 17 7 1 553 0736-0750 13 86 55 1

(continued)

A-9




18-AUG-86 0751-0806 0806-0821 0821-0836

13 12 12

89 8 1 95

583 524 438

0836-0851 0851-0906 0906-0921

ND 14 19

102 120 155

49 1 72 1

1064 0921-0936 1005-1020 1020-1035 1035-1050 1050-1105 11 05-11 20 11 20-11 35 1135-1150 1150-1205 1205-1220 1220-1235 1235-1250 1250-1305 1305-1320


125 120 150 152 164 171 198 179 165 149 144 114 134 11 1

728 831 877

102 1 1010 1004 960 820 756 710 607 368 359 26 1

1320-1335 1335-1350 1350-1406 1406-1421 1421-1436 1436-1451 1451-1506 1506-1521 1521-1538


107 98 7 1 69 75 89 92

110 143

166 162 148 160 147 206 232 245 212

1538-1553 1553-1608 1608-1623 1623-1638 1638-1653 1653-1708 1708-1723


168 150 134 123 132 123 104

279 306 245 324 477 428 428

1723-1738 1738-1753 1753-1808 1808-1823 1823-1838 1838-1853

ND ND ND ND ND ND

11 9 114 113 104 69 57

492 506 54 1 508 529 520

(

1853-1909 1931-1942 2005-2011

ND ND ND

50 54 53

539 504 573

(continued)

A-10




18-AUG-86 2032-2043 ND 57 802 21 04-21 15 10 69 633 2136-2147 09 80 825 22 10-22 24 18 78 741 2224-2238 16 7 1 700 2259-2313 15 72 683 23 13-23 27 15 83 684 2348-2400 15 84 644


(continued)

A-11

I (





20-AUG-86 0015-0029 18 95 5850029-0043 2 1 89 53801 04-01 18 2 1 98 472 01 18-01 32 27 108 546 01 53-0207 17 95 367

(0207-0221 22 96 335

(continued)

A-12





(continued)

A-13





21-AUG-86 0005-0019 22 89 787 0019-0033 24 11 0 788 0054-01 08 24 110 634 01 08-01 22 24 105 562 0143-0157 24 8 1 549 0157-0211 26 87 574 0232-0246 3 1 105 643 0246-0300 27 99 566 0320-0334 29 96 554 0334-0348 34 108 756 0409-0423 26 87 683 0423-0437 33 75 622 04 58-05 12 36 113 620 05 12-05 26 36 11 1 598 0547-0601 4 1 107 616 06 01-06 15 42 105 61 1 0636-0650 50 116 606 0650-0704 40 128 616 0724-0738 3 1 14 7 71 1 0738-0753 26 134 818


A-14

( APPENDIX 8



f (

B-1

- --frac34_


a




812-1386 Night 0559 286 270

trace 004

050 046

trace (002)

037 033

(014) (013)

001 006

- 004 006

001 002

81386 Day 0524 131 121

trace 001

007 004

--

017 o 16

(O 10) (0 10)

001 002

- 003 005

trace

813-1486 Night 0545 265 253

--

040 039

--

033 032

(011) (010)

006 005

- 003 006

001 002

81486 Day 0662 167 161

trace -

011 009

--018 018

(009) (008)

002 002

- 003 006

trace 001

814-1586 Night 0662 200 195

trace tt

045 045

- 034 033

011) (010)

004 003

- 003 006

001 002

81586 Day 0607 171 169

trace II

012 o 11

--

021 021

011) (0 10)

002 002

- 003 006

trace 001

815-1686 Night 0517 2 16 206

--

037 037

- 029 028

(009) (009)

trace 002

- 003 006

trace 001

81686 Day 0469 153 144

trace II

003 003

- I

015 014

(011) (010)

trace 001

- 003 005

trace

(continued)

~ -


a fa

Date

Total Volre

m Na12hthaleneb

Back-up


Back-up



Phen-anthrene

816-1786 Night 0572 201 190

trace 039 036

- 031 029

(011) (009)

002 002

- 004 006

trace 001

81786 Day 0662 137 126

trace 004 003

- o 16 o 14

(009) (008)

trace 001

- 003 006

trace

817-1886 Night 0628 276 260

trace 042 040

- 031 029

(010) (008)

trace 002

- 004 006

002 002

ol I

uJ

81886

818-1986

Day

Night

0517

0586

220 199

249 238

trace

trace

007 005

032 031

-

(trace)

o 15 o 14

026 025

(0 10) (009)

(010) (010)

trace 001

001 002

-

-

003 005

004 006

trace

001 002

81986 Day 0593 255 258

trace 002

007 006

(trace) 016 016

(011) (010)

trace 001

- 003 006

trace 001

819-2086 Night 0524 205 193

- 033 032

- 028 027

(011) (011)

trace 002

004 006

001 002

82086 Day 0490 204 195

trace 002

010 008

- 017 o 17

(008) (008)

trace 001

- 003 006

trace 001

820-2186 Night o455 275 278

- 039 039

- 030 030

(007) (007)

001 002

- 004 006

001 002


_-


a



812-1386 Night 676 1499 1lL57

583 635

324 346

151 151

026 027

022 021

033 033

043 043

81386 Day 676 797 209 107 064 -b 002 020 017 756 2 18 1 bull 11 064 002 004 021 018

813-1486 Night 683 1283 475 253 116 008 o 15 025 034 1266 521 274 119 009 o 15 026 035

81486 Day 683 570 173 090 048 - 002 020 014 545 179 092 048 002 004 021 014

814-1586 Night 683 11 22 423 2 19 071 o 15 011 023 021 1079 lf56 232 072 o 16 012 0211 028

815-1686 Night 683 13 76 1340

lf75 520

250 266

Olf5 045

006 007

o 14 o 15

023 025

028 030

81686 Day 669 466 463

132 140

064 067

034 035

-002

-003

015 016

010 011

816-1786 Night 683 1260 457 229 066 - o 16 027 025 1239 501 251 068 002 o 17 028 026

817186 Day 634 299 102 047 023 - - 017 012 296 108 o49 023 002 003 017 013

(continued)

~~

~


a



817-1886 Night 676 12 16 1228

440 483

2 17 236

036 037

002 004

020 020

030 033

034 035

81886 Day 642 430 431

1 61 1 74

o 78 081

027 028

-002

002 004

o 19 021

o 16 o 17

tI I

IJ1

818-1986

81986

Night

Day

676

676

1071 1034

343 338

367 408

127 137

183 202

060 062

044 046

024 025

-002

-002

0 18 020

002 004

028 030

015 o 16

030 032

O 14 o 15

819-2086 Night 676 1084 1036

389 4 19

189 198

040 o41

-002

018 020

028 031

033 034

82086 Day 676 552 541

2 11 227

100 106

036 036

-002

003 005

022 023

o 19 020


-- -


a Total



090 095

186 188

058 068

186 222

080 092 4078

Filter Sample 2 813-1486 2000-0800 hr

093 104

127 135

079 o85

283 3 12

189 206 4078


276 291

276 280

125 135

367 4 14

164 138 13050

bI I

0-


NQC 2 11

NQ 334

073 o83

334 362

188 2 13 13050

Filter Sample 115 82086 0800-2000 hr

124 110

122 138

040 047

172 177

071 080 4078

Filter Sample 6 820-2186 2000-0800 hr

087 095

099 100

058 055

162 168

077 o84 4078


150 162

155 176

064 066

276 288

o83 095 5158


134 142

152 165

093 096

348 348

161 143 5627



-~

-middot~

__

$0272 bullIOI


PAGE 1 ARBR-88366


















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