Monitoring fugitive emissions per EPA Draft Method 325 and ozone precursors via PAMS networks

Agilent technologies, Inc.

June 2015

Indoor air quality and

tracer gases used for

ventilation studies

Landfill gas monitoring

Biogenic

emissions

Odorous industrial emissions

Hydraulic

Fracturing

Air Monitoring Applications Include:

Atmospheric Research

In situ monitoring of underground

contamination

ambient air monitoring

Refinery Perimeter Monitoring per EPA Method 325 (Draft)

Passive Sampling with

VOC Analysis by

TD/GC/MS

Refinery Perimeter Monitoring New Regulation Requirements

Continuous monitoring of vapor phase organics (VOCs)

around the perimeter of oil refineries

• Planned implementation in mid-2015

• Operators will be given 3 years to comply

US EPA Methods 325 A and 325 B drafted for compliance

• Final comment period closes at end of October 2014

• Method 325 specifies 2-week passive sampling using sorbent

tubes. Pumped monitoring onto sorbent tubes may also be allowed.

• Analysis by TD/GC/MS (FID allowed, MS recommended)

Target Compounds Refinery Perimeter Monitoring

Target compounds include:

• Benzene

• Any of the 97 VOCs that EPA has classed as hazardous air

pollutants (HAPs)

• Other VOCs present in refinery air

• For example, light- and middle-distillate fuel

components

Why passive sampling using sorbent tubes?

• Well validated for ambient air – ISO 16017-2, ASTM D6196, EN

14662-4

• Robust – Variable ambient conditions (temperature, wind speed,

humidity, interferences) have minimal impact on uptake rate

• Low cost – Samplers are re-usable >50 times and are inexpensive

to buy and transport

• Versatile – Sorbent tubes can be used for

pumped or passive sampling and offer

quantitative sampling & release of

compounds over a wide volatility range.

For passive sampling a diffusion cap

is fitted to the sampling end of the

tube, while the other end is kept

sealed

Monitoring Industrial Air Using Passive Sorbent Tubes

Passive (diffusive) samplers

are deployed around the

perimeter of refineries and

other petrochemical plants

under weather proof hoods.

(Reproduced with permission from BP)

Method 325 (draft) specifies 12-

24 monitoring stations round

each refinery depending on

size.

Most US refineries will need 24

stations with at least one

passive air sampling tube at

each.

Further samplers are required

for replicates, blanks,

calibration, alternative sorbents

and additional shorter-term

monitoring for pinpointing

fugitive emissions

Perimeter Monitoring Method Requirements Proposed EPA Method 325

Long-term passive sampling of ambient and industrial air

2-week passive sampling of light hydrocarbons monitored around the perimeter

of a major petrochemical installation

Perimeter Monitoring for Volatile Emissions Recommended TD/GC/MS System Configuration

Hardware Components

MKI-TD100E TD100E Tag-ready Thermal Desorber, includes Electronic MFCs, recollection and backing pneumatics MKI-ISDPAC Internal Standard option for TD100 G3430-60011 Bulkhead connector kit G3442B 7890B for MS with SSL inlet G7042A 5977A Inert Turbo bundle, includes Data system and gas filters G1033A NIST library Required Consumables

122-506E 60 m x 0.25 mm x 0.5 um DB 5 column (for benzene and higher boilers) 122-1364 60 m x 0.25 x 1.4 um DB624 column for benzene and air toxics MKI-ULKIT Starter kit of Difflok caps for TD100 MKICCSLR Calibration solution loading rig

Accessories from Markes

2 x Method 325 cold traps Markes’ 325 bundle for US Sales comprising: TC-20 tube conditioner (compatible with tagged and untagged tubes) 2-days customer training check standards, CRS tubes and IS gas

Tube shelters for each refinery perimeter monitoring point

Field monitoring kits comprising:

Conditioned capped and tagged sorbent tubes

Diffusion caps

Convenient sampling tools

Tag read/write tools

Note: Continuous 14-day monitoring is required so 3 sets of samplers will

normally be needed: One in use in the field, one in the lab being analysed

and a third set ready for deployment

Perimeter Monitoring for Volatile Emissions Sampling equipment required

6/24/2015

Monitoring Refinery Perimeters for VOC Emissions

11

• Oil Refiners (~140 US Refinery Locations)

• Associated contract laboratories (environmental,

petrochemical services)

• Federal and state regulators

• Any other petrochemical operations faced with longer

term impact

Perimeter Monitoring for Volatile Emissions

Analytical system provides the following unique

advantages:

1. Quantitative sample re-collection for repeat analysis -

recommended for validation of analyte recovery

2. 100-tube capacity - optimises productivity

3. TubeTAG - RFID tube tags track tubes from field to lab and

record the history of each sampler. Recommended for

reliable audit trail and chain-of custody

4. Reliability - TD-100 system operates cryogen-free and

provides full compliance with key national and international

standard methods

Perimeter Monitoring for Volatile Emissions Key Performance Advantages

Agilent’s partners at Markes pioneered automatic

quantitative sample re-collection of TD samples

(SecureTD-Q)

Quantitative re-collection of TD samples offers the

following key capabilities

• Repeat analysis under the same conditions for

confirmation of data and method validation

• Repeat analysis using a different analytical system

• Sample archiving

Advantage #1: Recollection for Repeat Analysis A Breakthrough in Thermal Desorption

• Inert heated, low volume valve allows

quantitative recovery of high & low volatility

compounds plus reactive species

• It also isolates the TD system allowing

compliance with standard methods: leak testing,

backflush trap desorption, purge to vent, overlap

mode, etc.

Heated valve

To GC

Time

Inte

nsity

During stage 1 trapped analytes are

desorbed from the heated sample

tube and transferred to the

electrically-cooled focusing trap

Principles of Operation Recollection for Repeat Analysis, Stage 1

Heated valve

To GC

Time

Inte

nsity

• Repeat analysis of recollected samples

facilitates validating analyte recovery through

the TD flow path

• A change to the overall VOC profile indicates

any bias

During stage 2, the trap heats

rapidly to transfer/inject analytes

into the GC column. Split effluent is

quantitatively re-collected on a

clean tube ready for repeat analysis

Principles of Operation Recollection for Repeat Analysis, Stage 2

With a compact arrangement of up to 10 trays, each housing up to 10 tagged or untagged

tubes, TD-100 can accommodate up to 100 sorbent tubes

This can comprise:

- 100 sample tubes, or…

- 50 sample tubes and 50 re-collection tubes

With 40 minute GC cycle times a fully loaded TD-100 can operate unattended all weekend

Another unique advantage of TD-100 is the patented

tube capping arrangement… Tubes are kept capped

and sealed at all times while on the TD-100 – before,

during and after operation. This prevents analyte losses

and ingress of lab air contaminants, without

complicating mechanical operation

Advantage #2: TD-100 has capacity for 100 tubes

DiffLok caps remain on sorbent

tubes throughout automatic

thermal desorption

All tubes are labelled with a unique ID number

in barcode and alphanumeric format, standard.

- They can also be RFID-tagged

Tags allow history to be tracked throughout

tube life: sorbent type, date of packing, number

of analytical cycles, etc.

Tags can also be programmed with sample-

specific data, such as, sampling start

time/date, sampling end time/date, and

sampling location

Tag read/write functions standard feature of the

TD-100

Advantage #3: TubeTAGTM Unique Innovation for TD

Note: tube tagging is optional not mandatory on TD-100

1. Tag permanently attached to tube & programmed

with tube-related information using TAGSCRIBE

2. Tagged tube sent

to field. Sample

details written to tag

via TAGSCRIBE

3. Tagged tube returned to lab and data

retrieved using automated tag r/w on TD

instrument

4. Tube analysed on TD system.

Tag(s) automatically updated with

relevant info. Tagged tube ready for

re-use

RFID tagging offers

enhanced traceability

for optimum chain-

of-custody

TubeTAGTM Theory of Operation

Tube Information

Sample location

Sorbent packing

# analytical cycles

Tube status

Access to

sample info

in the field

Sample Information

Access to tube &

sample info via

TD-100 in lab

Sample start info Sample end info “TubeTAG is a genuine breakthrough in TD technology. It allows users to monitor the history of each individual tube and track samples from field to lab.”

Information Stored on TubeTAG

Use of tagged tubes enhances automated re-

collection for repeat analysis

When tagged tubes are used, sample information is

automatically transferred to the tag of the re-

collection tube creating an audit trail

Automated TD re-collection using a single TD autosampler is proprietary.

Patents: GB 2395785 & US 6,446,515 B2

On-board TAG Read/Write and Recollection

TD-100 Thermal Desorber

• With barcode technology it is difficult to guarantee continued legibility as

tubes are subjected to high desorption temperatures and ambient

weather conditions. If you can’t read the barcode, you cannot read the

data!

• Who creates and maintains the tube database? The environmental lab?

The field monitoring contractor? The site owners? If you can’t rely on a

well maintained database, barcodes can’t be used to track tube history or

sample information.

− With tags, the information stays with the tube and can be accessed at any

time via TAGScribe or TD-100

• Barcodes are difficult / impossible to read automatically during TD-GCMS

analysis. This means bar codes can’t be used to track a sample through a

sequence of re-collections and repeat analysis

Advantages of TubeTAG versus bar codes

PAMS Program: Monitoring Ozone Precursors

Agilent technologies, Inc.

June 2015

Online sampling applications

Ambient Air

Zero Air

Standard

Gas

A three sample channel system can be used to alternate between

sample, standard and blank gases facilitating automatic calibration

and unattended operation of the system.

Where to monitor?

Ozone precursor (O3P) stations are carefully located according to

meteorology, topography, and relative proximity to emissions sources of

VOC and NOx.

Each O3P network generally consists of four different monitoring sites

(Types 1, 2, 3, and 4) designed to fulfill unique data collection objectives.

Type 1

Type 2

Type 3 Type 4

Quantitative Retention of

Acetylene from 1500 mL of

Air without Liquid Cryogen

Plot of peak area against volume

sampled for acetylene

(courtesy Ecole des Mines de Douai)

Key:

Blue (3 am)

Red (12 noon)

Green (5.30 pm)

Ethane

Ethene

Acetylene

Propane Propene

2-methylpropene

Butane

1-Butene

Pentane

Sequence of Analyses of Ozone

Precursors in Suburban Air Using a

Single Column Splitless analysis of 500 mL of ambient air

Performance of the system

Click to edit Master title style

Deans Switch Switch

effluent to

Second

Column

Deans

Switch

7890A GC

FID1 FID2

Column 1 Column 2

Capillary Flow Technology

UNITY -

Air Server

Column 1

Mid point pressure

17 psi

Sample in

38 psi

Polydimethylsiloxane

(Pre-column)

PLOT AL2O3/Na2SO4

(Column 2)

Deactivated silica (Column 1)

FID 1 FID 2

Dual-column, dual-FID, System for Optimum

Ozone Precursor Analysis

Column 2

Mid point pressure

17 psi

Sample in

38 psi

Polydimethylsiloxane

(Pre-column)

PLOT AL2O3/Na2SO4

(Column 2)

Deactivated silica (Column 1)

FID 1 FID 2

Dual-column, dual-FID, System for Optimum

Ozone Precursor Analysis

Application: Monitoring of C2-C10 hydrocarbons (ozone precursors) in ambient air (TD-GC dual FID)

• Target compounds:

- C2 to C10 Hydrocarbons (Ozone

Precursors)

- ‘Ozone Precursors’ focusing trap

used at -30ºC, flow path at 120⁰C

• Performance in field operation:

- Detection limits: <0.05 ppb

- Retention time stability: <0.2% RSD

across all compounds

- Standard reproducibility: 0.2-5%

RSD

- Excellent peak shape for splitless

injection

DB-1 Column showing

retention of C7 to C9

PLOT Column

showing retention of

C2 to C6 compounds

Repeat Analyses of Ozone Precursor Gas

Standard by UNITY-Air Server - GC-FID (Dual

column)

Volume of standard Range of RSD’s

250 mL 0.2 to 5.5

375 mL 0.3 to 2.9

500 mL 0.2 to 4.3

625 mL 0.3 to 3.5

750 mL 0.3 to 3.2

C2–C3 hydrocarbons:

Detection: 0.05 ppb; quantification: 0.1 ppb

C4+ hydrocarbons:

Detection: 0.03 ppb; quantification: 0.06 ppb

Retention time stability

Compound Retention time RSD %

n= 30

Benzene 0.0090%

2,2,4-trimetylpentane

0.0122%

n-Heptane 0.0119%

Octane 0.0123%

Toluene 0.0127%

Ethylbenzene 0.0121%

m+p-Xylene 0.0131%

o-Xylene 0.0133%

1,3,5-Trimethylbenzene 0.0119%

1,2,4-Trimethylbenzene 0.0108%

1,2,3-Trimethylbenzene 0.0104%

Compound Retention time

RSD % n=15 Compound

Retention time

RSD % n=15

Ethane 0.0413% Cis-2-Butene 0.1360%

Ethene 0.1375% 2-Methylbutane 0.1339%

Propane 0.1695% Pentane 0.1217%

Propene 0.2976% 1,3-Butadiene 0.1558%

2-

Methylpropane 0.1776% Trans-2-pentene 0.1013%

n-Butane 0.1600% Pent-1-ene 0.1145%

Acetylene

(Ethyne) 0.3204% 2-Methylpentane 0.1008%

Trans-2-

butene 0.1644% Isoprene 0.0972%

But-1-ene 0.1552% n-Hexane 0.1313%

• Retention time stability of the

polydimethylsiloxane column all

compounds < 0.2 %

• Retention time stability of the PLOT

column all compounds < 0.3 %

Application: Ultra Volatile Greenhouse Gases

from Ambient Air (UNITY-Air Server™)

Extracted ion 69

Extracted ion 119

Extracted ion 127

Extracted ion 30

CF4

C2F6

C2F6

SF6

N2O

• Target compounds:

‒ CF4 (Carbon Tetrafluoride)

‒ C2F6 (Hexafluoroethane)

‒ SF6 (Sulphur Hexafluoride)

‒ N2O (Nitrous Oxide)

• ‘Greenhouse Gas’ focusing trap at -30ºC and

flow path at 120⁰C.

• Performance in field operation:

‒ Detection limits: 0.05 - 0.2 ppt for SF6 &

C2F6, 50 ppt (CF4) and 200 ppt (N2O)

‒ Retention time stability: <0.1% RSD

across all compounds

‒ Standard reproducibility: 0.8-5% RSD

‒ Excellent peak shape for splitless

injection

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