steve greason, instructor lsp course no. 1203, 4 …visit: site-lab.com usa: 978-363-2299 eph...

Hydrocarbon Analysis using

Sitelab UVF for DENR UST Program

LSP Course No. 1203, 4 Edu Credits

Westford Regency Inn, Westford, MA

Tuesday, February, 2nd 2016 1:00 - 5:00 PM

Steve Greason, Instructor

Sitelab Corporation

West Newbury, MA (978) 363-2299

Field Screening Petroleum Hydrocarbons

Using Ultraviolet Fluorescence Technology

of 28 LSPA Training Course, Feb 2, 2016 ©Sitelab Corporation

What is Ultraviolet Fluorescence?

How Does it Work?


What Fluoresces �Gasoline

�Jet Fuel

�Kerosene

�Diesel Fuel

�Home Heating Oil, No 2. Fuel Oil

�Heavy Fuel Oil, No. 6 Fuel Oil

�Motor Oils

�Waste Oils

�Lubricating Oils

�Cutting Oils

�Transformer Oil

�Hydraulic Fluid

�Gas Condensates

�Drilling Muds & Drilling Fluids

�Crude Oils

�Bitumen, Tar Sands

�Creosote,

�Coal Tars, Coal Ash

Fluorescence does not detect straight chain aliphatic hydrocarbons:

�PCE, TCE, dry cleaning solvents

�Other SVOC chlorinated solvents

�Methanol or Hexane used with test kits

And What Doesn’t

Popular UVF Applications

• Soil excavation and cleanup

• Site Assessments

• Remediation & Treatment

• UST Fuel Sites

• Oil Refineries, Pipeline Spills

• Power Plants, MGP Sites

• Military Sites, Airports

• Natural Disasters, Oil Spills

• Oil & Gas Production


Aromatic Hydrocarbons

Aliphatic HydrocarbonsSaturated , Straight Chain Compounds (Alkenes)

Unsaturated , Ring Shaped Compounds (Arenes)

TPH by GC-FID

CH

CH

CH

CH

HC

HC Benzene

1-ring C6

GRO, VPH, BTEX, VOCs:

C6-C10, C5-C12 or C6-C12

BTEX: Benzene, Toluene, Ethylbenzene and Xylenes

Semi to Non-Volatile Compounds

Benzo [a] Pyrene

5 rings C20

Naphthalene

2-rings C10

Octadecane C18

H3C CH

3

Pentane C5

H3C CH

3

Volatile Compounds

Petroleum contaminants

are split into different

Carbon Ranges or Fractions:

DRO:

C10-C28

C12-C28

TPH, EPH, EDRO, ETPH, TRPH:

UV Fluorescence detects Aromatic

hydrocarbons over a wide range of

petroleum contaminants

ORO or RRO:

C20-C35

C25-C36

C28-C36

PAHs: Polynuclear or Polycyclic Aromatic Hydrocarbons

Regulators are concerned with 16 PAHs in C10-C22 range


Portable Analyzers Available

Manufactured for Sitelab Corporation by Turner Designs Hydrocarbon Instruments, Inc.


Evaluated by U.S. EPA in 2001

Sample test kits and calibration

kits are used for analysis

UVF-3100 Analyzer

Lab Certification with NJ DEP

Publication No.

EPA/600/R-01/080

Ranked highest compared to other

screening devices for TPH in soil.

Over 200 samples were tested.

EPA spent $800,000 on project.

Results were compared to split

samples sent to certified lab for

TPH analysis using 8015 by GC-FID.

Sitelab’s popular UVF-3100D

instrument is fitted with 3 sets of

optical filters which are sensitive

to different hydrocarbon ranges.

Can perform TPH Fingerprinting

Sitelab’s laboratory and use of

UVF certified from 2009 to 2015.

NC DENR

Regulators approve use of UVF for

TPH analysis in UST Guidelines.


GRO: Gasoline Range Organics

Product No. CAL-025, use with Slot B Optics

Correlates to Total VPH by GC/FID

EDRO: Extended Diesel Range Organics

Product No. CAL-042, use with Slot A Optics

Correlates to Total EPH by GC/FID

UVF-3100 Calibration Kits

PAHs: Poly Aromatic Hydrocarbons

Product No. CAL-060

Use with Slot A Optics for “Total PAHs”

Correlates to EPH C11-C22 Aromatics by GC

Or use with Slot D Optics for “Target PAHs”

Correlates to sum of 16 EPA PAHs by GC/MS

Each kit includes Certificate of Analysis

and MSDS. Standards made in methanol.

Calibration standards

also available in hexane

solvent for crude oil in

water applications.

0.999

29

AUG 24, 2015

NOV 24, 2015


3. Shake & Filter Extract1. Weigh 5 grams of Soil 2. Add 10 mL of Solvent

5. Pour into Glass Cuvette

for measurement

6. Place into UVF-3100.

Concentration (ppm) is

displayed in just a few

seconds.

4. Dilute Extract using 2nd

Test Tube and Micropipette

Test Procedure is Fast and Easy


Record and Report Test Results

UVF

Reading

“0.550”

“OVER”

“1.250”

“0.011”

“0.077”

Dilution

Tested

100X

100X

1,000X

100X

2X Extract

Final Concentration

Report as 55 ppm

Retest a bigger dilution

Report as 1,250 ppm

Low < 0.1 ppm Det limit

Report as ND <0.2 ppm

(2X x 0.1 ppm Det Limit)

Soil

ID

1

2

3

Quality Control

Tests to Perform

0.1 ppm EDRO Cal Std

5 ppm EDRO Cal Std

Methanol Blank

UVF

Reading

“0.109”

“5.122”

“0.001”

Comments

�Close to 0.1 ppm

�Close to 5.0 ppm

�Solvent clean, zero

5-point calibration curve and

sample results can be

downloaded to a computer

using UVF-3100 software


Case Studies Highlighting

UVF Accuracy & Performance


Samples take 5 minutes to

prepare and analyze. Test

results directly correlate to

the Mass DEP’s EPH aromatic

hydrocarbon fraction.

Sitelab’s PAH calibration kit

contains same compounds

used for Lab GC EPH analysis.

Lab EPH

C11-C22

Aromatics

UVF-3100

C11-C22

Aromatics

Wire Factory Site in Connecticut with No. 6 Fuel Oil

Paper Mill Site in Massachusetts with No. 6 Fuel Oil

4,600

4,800

11,000

14,000

14,000

21,000

5,300

5,250

9,100

11,800

14,400

23,600

Accuracy

Y = 0.97x

R2 = 0.92

Sitelab EPH C11-C22 Aromatics (ppm)

Lab

GC

EP

H C

11

-C2

2 A

rom

ati

cs (

pp

m)

-

5,000

10,000

15,000

20,000

25,000

- 5,000 10,000 15,000 20,000

Accuracy

Y = 1.33x

R2 = 0.98

Visible NAPL in Soil Boring

No. 6 FuelOil Sites

Sitelab Corporation

Visit: site-lab.com

USA: 978-363-2299

EPH C11-C22Aromatics

Using CAL-060 on UVF-3100 Slot A Optics


Lab EPH

C9-C18

Aliphatics

Lab EPH

C19-C36

Aliphatics

5,100

7,700

5,600

9,600

11,000

14,000

2,600

3,700

6,400

9,600

9,300

20,000

Soil 1

Soil 2

Soil 3

Soil 4

Soil 5

Soil 6

Results

in ppm

(mg/Kg)

vs. Lab PAHs

1,500

600

110

0.3

1,200

666

113

ND <1

Sitelab Corporation

Visit: site-lab.com

USA: 978-363-2299

Manufactured Gas Plant UVF Results

Sitelab Corporation

Visit: site-lab.com

USA: 978-363-2299

30

16

9

8

21

13

10

10

Power Plant

682

350

130

80

Petroleum Tank Farm

Wharf Site

Target PAHs

Examples testing Polycyclic Aromatic Hydrocarbons

Concentrations in ppm (mg/Kg)

14

55

11

12

ND <3

6.0

ND <3

3.6

ND <3

ND <3

ND <3

ND <3

ND <3

ND <3

ND <3

ND <3

ND <3

Concentrations in ppm (mg/Kg)

Naphthalene

2-Methylnaphthalene

Phenanthrene

Acenaphthene

Acenaphthylene

Fluorene

Anthracene

Fluoranthene

Pyrene

Benzo[a]Anthracene

Chrysene

Benzo[b]Fluoranthene

Benzo[k]Fluoranthene

Benzo[a]Pyrene

Indeno[1,2,3)]Pyrene

Dibenzo[ah]Anthracene

Benzo[ghi]Perylene

Lab PAHs

= 102 ppm

Soil from

Wharf Site

Using CAL-060 on UVF-3100 Slot D Optics

Coal Tar, Sediment Site

Colorado

Coal Ash Site

North Carolina

vs. Lab PAHsUVF Results

Diesel & No. 6 Fuel Oil Site

Massachusetts


455

370

180

75

220

102

72

11


Heating Oil & Gasoline Site

Massachusetts

213

105

70

12

Sitelab PAHs

= 105 ppm

Sum of PAH

Compounds


UVF-3100

GRO Results

Lab GC

Total VPH

176

666

1,481

3,037

5,704

5,570

292

886

1,526

2,665

7,025

8,103

Mass DEP VPH Method reports

hydrocarbon fractions SEPARATELY:

C5-C8 Aliphatic Hydrocarbons

C8-C12 Aliphatic Hydrocarbons

C9-C10 Aromatic Hydrocarbons

+ Target BTEX Compounds & MtBE

260

1,500

1,500

2,300

6,000

8,000

Lab GC

EPA 8015-GRO

UVF Accuracy

vs. Lab GC GRO

R2 = 0.95

y = 1.27x

R2 = 0.98, y = 1.06x

Gasoline Station UST Site in Dracut, Massachusetts:

Concentrations in ppm units (mg/Kg)Gasoline Range

R2 = 0.90

y = 1.18x

UVF Accuracy

vs. Lab GC Total VPH

Lab GC Methods

GRO vs. Total VPH

EPA Method 8015 reports All

hydrocarbons in the C6-C10 range.

Organics & VPH

Mobile lab tested 113

samples during 2-day

site investigation. Data

used to delineate extent

of NAPL below ground.

UVF GRO (ppm)

Lab

VP

H (

pp

m)

Lab VPH (ppm)

Lab

GR

O (

pp

m)

UVF GRO (ppm)

Lab

GR

O (

pp

m)Samples collected from

six soil borings were

split and sent to a

certified lab. Results

correlate well to GRO

and VPH methods.

Using CAL-025 on UVF-3100 Slot B Optics


350

390

1,300

1,750

2,450

3,500

5,050

6,872

12,800

16,420

241

478

2,491

2,465

2,529

5,252

4,103

5,692

12,170

16,682

67

270

1,600

1,600

1,700

3,200

2,700

3,600

8,800

12,000

78

57

120

170

150

280

220

290

750

1,100

96

140

750

650

630

1,700

1,100

1,700

2,400

3,400

ND

11

21

45

49

72

83

102

220

182

Extended DieselRange Organics

Concentrations in ppm units (mg/Kg)

C9-C18

Aliphatics

C19-C36

Aliphatics

C11-C22

Aromatics

Sum of

17 PAHs

Lab GC

Total EPH

UVF-3100

EDRO

Contaminated Wharf Site, Massachusetts

UVF-3100 EDRO Performance vs. Total EPH Method

UVF Accuracy vs. Lab GC

R2 = 0.97, y = 0.95x Good!

Sitelab Corporation

Visit: site-lab.com

USA: 978-363-2299

1

2

3

4

5

6

7

8

9

10

Soil

#

Mass DEP EPH Method reports

hydrocarbon fractions SEPARATELY

as illustrated above

States using EPA Method 8015M

or similar TPH GC Methods report

SAME range of hydrocarbons but

not in fractions.

Samples collected from

ten borings were split

and sent to a certified

laboratory. Sitelab

EDRO correlates well to

TPH & EPH Methods.

Sitelab EDRO calibration kit is

specially formulated to account for

aliphatics not detectable by UVF.

Total Petroleum Hydrocarbons

GRO●VPH

Range

Extended Diesel

& Oil Range

C6 C10 C36

Using CAL-042 on UVF-3100 Slot A Optics


UVF-3100

EDRO Results

Lab GC TPH

TX 1005 Results

22 ppm

1,891 ppm

2,452 ppm

3,706 ppm

ND <33 ppm

1,860 ppm

2,180 ppm

2,350 ppm

Tank Battery

Storage Site

Texas 1005 Reports TPH in GRO, DRO and ORO Ranges:

C6-C12 Gasoline Range Hydrocarbons

C12-C28 Diesel Range Hydrocarbons

C28-C35 Oil Range Hydrocarbons

Total Petroleum Hydrocarbons (TPH)

2,782 ppm

5,190 ppm

1,900 ppm

4,590 ppm

Pipeline Spill

Site

356 ppm

3,920 ppm

314 ppm

4,590 ppm

+

=

Contractor uses their UVF-3100D analyzer to

help excavate and remediate soils contaminated

by produced water and crude oil. Laboratories

in Texas test TPH using the TX 1005 GC-FID

Method. This method is similar to U.S. EPA

Method 8015M, but reports the GRO, DRO and

ORO fractions separately.

Texas Crude Oil Sites

UVF equipment is set

up in a field trailer.

Customer tests soils

using Sitelab EDRO,

Product No. CAL-042. GRO DRO ORO

Chromatogram shows

TPH fractions. The

peaks are surrogates

used for quality control

C5 C12 C28 C35

Retention Time in Minutes

Re

spo

nse

/Vo

lta

ge

Tank Battery Spill, West Texas

Sitelab Corporation

Visit: site-lab.com

USA: 978-363-2299


TPH Fingerprinting Applications

Test for GRO and PAHs…Compare

Signatures to Other Contaminants


Sitelab Corporation

Visit: site-lab.com

USA: 978-363-2299

Oil company tests crude oils from different

well sites to determine the percentage of

oil content from two formations. The wells

tap into these zones at different depths.

Knowing what type of oil being pumped is

important.

CHESTER

FORMATIONMISSISSIPPI

FORMATION

% ?

CHESTER

Ref Oil

41 API

MISS.

Ref Oil

34 API

Well

1

Well

2

Well

3

Well

4

Oklahoma Crude Oil

% Content

Mississippi

23%

38%

64%

73%

Oils at 5 ppm

Chester

Well 1

Well 2

Well 3

Well 4

Mississippi

Total PAHs

0.45 ppm

0.76 ppm

0.96 ppm

1.32 ppm

1.43 ppm

1.80 ppm

% Content

Chester

77%

62%

36%

27%

Use UVF Data to Calculate % Content

Photo of Solvent Extracts at 10,000 ppm

Fluorescence Response at 100 ppmppm (or %)

0

10

20

30

40

50

60

CHESTER MISSISSIPPIWell

1

Well

2

Well

3

Well

4

UVF-3100D

GRO

Total

PAHs

Target

PAHs

Heavy

PAHs TD-500D


NAPL Plume at

Former Refinery Site

MW-30

Weathered fuel

oil and crude oil

MW-35 Outlier?

Former naphtha

tank location

Examples

at 10 ppm

MW-22

MW-30

MW-35

GRO

Response

1.52 ppm

0.73 ppm

0.32 ppm

DRO

Response

1.80 ppm

12.5 ppm

0.18 ppm

DRO/GRO

Ratios

1.2

17

0.6

MW-22

Contains

mostly

gasoline

NAPL samples collected from 35 monitoring wells


�U.S. EPA post-dredge site in Hammond, Indiana, located near Lake Michigan.

�Client collected 100 sediment samples by boat using push cores. GPS used to locate samples.

�Sitelab’s test equipment was setup in back of

U-Haul truck on-site during 4-day site investigation.

�Data used by client to determine which areas would require further attention as part of cap monitoring plan.

Field Screening PAHs in Sediments:

West Branch Grand Calumet River

Dredge Site of 28 LSPA Training Course, Feb 2, 2016 ©Sitelab Corporation

Sediment Contamination in River

Fingerprinting Map showing

Total PAH to Heavy PAH Signatures

“Hot Spots”

Fresher, less

weathered

crude oil

Older, more

weathered

crude oil

Map showing Target PAH Concentrations

from 100 Sample Locations

Field Trailer

& Dredging

Facility

Field Trailer

& Dredging

Facility

Sediments collected over a

1-mile stretch of river

“Hot Spots”


LAF-038

LAF-040LAF-070

LAF-073LAF- 071

Examples showing PAH Concentrations and Ratios Exhibited:

Sample ID

LAF 038

LAF 040

LAF 070

LAF 071

LAF 073

Total PAHs

75,900 ppm

5,940 ppm

19,840 ppm

17,000 ppm

42,600 ppm

Target PAHs

6,240 ppm

590 ppm

1,860 ppm

1,420 ppm

4,000 ppm

Heavy PAHs

2,260 ppm

696 ppm

500 ppm

426 ppm

1,700 ppm

Total PAH to

Target PAHs:

12x

10x

11x

12x

11x

Total PAH to

Heavy PAHs:

34x

9x

40x

40x

25x

Close up of “Hot Spots”


Costs & Benefits using UVF?

Section of Grand Calumet River

Showing Two “Hot Spot” Locations

�400 test results in 4 days.

� Cost $9,500.

�Contamination identified as crude oil using fingerprinting data.


“Hot Spots”

Challenges and Limitations

using UVF Technology


Soil

Sample 1

Soil

Sample 2

15,150 ppm

15,430 ppm

7,160 ppm

7,800 ppm

Customer EDRO Results

Sitelab’s EDRO Results

Using EPA 8015M: C9-C40

46,000 ppm 13,000 ppm

Nigeria Crude Oil Nigerian Lab GC-FID 15,000 ppm 6,829 ppm

American Lab GC-FID

Using EPA 8015M: C10-C36

American Lab GC-FID 24,800 ppm 10,200 ppm

Lower/better results! Remember, labs don’t always get it right.

Results high! Samples retested!

American Lab GC

Sample 1 = 24,800 ppm

TPH Range: C9 to C40

Chromatograms Can

Look Different Too

Nigerian Lab GC

Sample 1 = 15,000 ppm

TPH Range:

C10 to C36

Safic Technologies, Ltd. - Port Harcourt

For QA/QC, sample extracts were sent

to Sitelab for EDRO analysis and results

were the same.

Samples were split and sent to a

Nigerian lab and a highly reputable lab

in the United States for confirmation.

After testing the samples a second time,

the American lab got better results.

Labs from different countries report TPH

in different carbon ranges.

Sitelab Corporation

Visit: site-lab.com

USA: 978-363-2299

Soils from

Pipeline Spill


6

4,760

6,270

7,800

9,760

16,380

8

1,100

4,200

6,500

3,900

6,000

1

680

700

950

1,175

1,800

7

5,440

6,970

8,747

10,938

18,180

8

5,500

9,200

13,200

10,900

18,000

UVF-3100

EDRO

Results

Jet Fuel Contaminated Soils, Westover Air Force Base

Concentrations in ppm units (mg/Kg)

UVF is Higher

UVF-3100

GRO

Results

Lab GC

Total VPH

Results

Lab GC

Total EPH

Results

Lab GC

VPH+EPH

= TPH

Sitelab UVF

GRO+EDRO

= TPH

ND

4,400

5,000

6,700

7,000

12,000

C10 C12C6 C36

EDROGRO

UVF detects higher GRO vs. VPH due to C10 break point

Jet Fuels are abundant with

naphtha aliphatics (the “Hump”)

which are not detectable by UVF

Jet Fuel Chromatogram Showing C10 to C12 “Hump”

UVF is Lower But TPH is Accurate

Total VPH C5-C12

Total EPH C10-C36

Jet Fuel

TPH SitesConsultant uses Sitelab to

test soils collected from

borings to delineate a large

plume of jet fuel below

ground.

TPH is used to calculate the

total mass of NAPL. Split

samples were sent to a lab

for analysis using the

VPH/EPH method.

Sitelab’s UVF-3100 analyzer has

optical filters sensitive to GRO and

EDRO range hydrocarbons

Soil 1

Soil 2

Soil 3

Soil 4

Soil 5

Soil 6


PAHs in Asphalt

ESITC – France

New regulations across Europe are

requiring laboratory analysis for PAH

content in asphalt. Scientists are

using the TD-500D analyzer to

monitor PAH levels in new and

reclaimed/recycled asphalt.

In this study, samples were ground

down to different particle sizes and

sent to four certified laboratories for

comparison. In France, they use EPA

Method 8270 for PAH analysis.

Ecole Supérieure d'Ingénieurs des

Travaux de la Construction de Cachan

10 mm

600

340

555

246

0.5 mm

270

424

367

282

Sample 1

LAB 1: ESITC

LAB 2

LAB 3

LAB 4

290

172

215

109

129

212

195

141

Sample 2

LAB 1: ESITC

LAB 2

LAB 3

LAB 4

2 mm

349

426

356

220

182

243

162

84

356

2,033

1,685

1,310

729

747

1,347

1,231

958

Sample 3

LAB 1: ESITC

LAB 2

LAB 3

LAB 4

1,531

1,773

1,967

1,139

Sample 1 Sample 2 Sample 3

Laboratory PAH results testing

different particle sized sub-samples

TD-500D

PAH results

228

1,177

Photo showing asphalt samples used for TD-500D evaluation (granular size 2 mm)

The TD-500D is

highly sensitive to

PAHs in asphalt

Samples are

extracted in

methanol solvent

Concentrations above are in ppm units (mg/Kg)

PAH Calibration

Kit CAL-061 used

for analysis


Proficiency Evaluation Study Testing

Water Samples vs. 83 LaboratoriesLab GC-GRO Methods UsedGasoline

Concentration

3.47 mg/L

UVF-3100

GRO Result

3.33 mg/L 3.60 mg/L1.34 mg/L

to

6.11 mg/L

Acceptance

LimitLaboratory

Mean Result EPA 8015

EPA 8015B

EPA 8015M

EPA 8020

EPA 8260B

California LUFT

Iowa OA-1

Maine 4.2.17

NWTPH-GX

Lab GC-DRO Methods UsedDiesel Fuel

Concentration

3.62 ppm

UVF-3100

EDRO Result

3.78 mg/L 2.60 mg/L0.90 mg/L

to

4.66 mg/L

Acceptance

LimitLaboratory

Mean Result California LUFT

Connecticut ETPH

Maine 4.2.25

NWTPH-DX

Oklahoma DRO

EPA 8015

EPA 8015B

EPA 8015M

Florida PRO

Iowa OA-2

Laboratories must pass these “blind” tests to be certified thru the

National Environmental Laboratory Accreditation Program (NELAP) or

similar programs several times a year. This study conducted by ERA, Inc.

Pretty Easy

To Pass!


Visit: site-lab.com

Call: 978-363-2299

End of Presentation

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steve greason, instructor lsp course no. 1203, 4 …visit: site-lab.com usa: 978-363-2299 eph...

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