MGP Waste Method

A Method to Characterize and A Method to Characterize and Differentiate VOCs from MGP Wastes Differentiate VOCs from MGP Wastes

and Petroleumand Petroleum

Bureau of Toxic Substance AssessmentWadsworth Center

NYS Department of Health

Todd R. Crawford, Michael Force,

Gerald McDonald and Kenneth M. Aldous

STATE OF NEW YORKDEPARTMENT OF HEALTH

Study ObjectivesStudy Objectives

• Analyze VOCs from MGP Waste• Determine if those VOCs are distinguishable from

Petroleum VOCs• Compare Total Ion Chromatograms (TICs) of

MGP Waste and Petroleum• Compare Extracted Ion Chromatograms (EICs) of

MGP Waste and Petroleum• Compare Proportions of Hydrocarbon Classes in

MGP Waste and Petroleum

STATE OF NEW YORKDEPARTMENT OF HEALTH

FindingsFindingsThere are no “Indicator” chemicals which

reliably indicate the presence of MGP waste

Total and Extracted Ion Chromatograms (“Fingerprints”) do not reliably indicate the presence of MGP waste

The proportion of Aromatic versus Aliphatic Hydrocarbons is an indicator of the presence of MGP waste

STATE OF NEW YORKDEPARTMENT OF HEALTH

MGP Soil Sample PreparationMGP Soil Sample Preparation

Samples from MGP sites collected in screw cap jars with PTFE-lined septa.

~100g transferred to clean, purged 2.5 Liter glass head-space vessel fitted with a PTFE-lined silicone septa and Swagelok® fitting.

Samples placed in incubator at 50oC for 24 hours. 500cc volume of headspace was directly sampled from the

vessel into a cleaned evacuated 6 Liter Summa® canister. The canister was filled to a volume of 12 Liters using zero

grade nitrogen and allowed to equilibrate 24 hours at room temperature.

STATE OF NEW YORKDEPARTMENT OF HEALTH

MGP Sample in Headspace VesselMGP Sample in Headspace Vessel

Vessel components

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Gas Handling and Measurement SystemGas Handling and Measurement System

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Analysis of Head-SpaceAnalysis of Head-Space

A volume of head-space transferred using cryoconcentration to quadrupole GC/MS.

Full scan GC/MS data collected following USEPA Method TO-15 protocol.

Total ion chromatogram (TIC) and extracted ion chromatograms (EICs) were obtained and integrated to give quantitative data.

STATE OF NEW YORKDEPARTMENT OF HEALTH

VOC Sampling and AnalysisVOC Sampling and AnalysisWhole Air Canister

Sampling Unit

GC/MS System with Cryoconcentration

Canister Autosampler

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MGP Waste VOC Headspace Total Ion Chromatogram Major VOCs identified and percent (%) contribution of the total area.

CompoundArea % of TIC

1 Benzene 14.96

2 Toluene 2.78

3 Ethylbenzene 11.97

4 m,p-Xylene 9.63

5 o-Xylene 4.97

6 Isopropylbenzene 1.12

7 Methylethylbenzene Isomer

7.51

8 1,2,4-Trimethylbenzene 1.34

9 Indane 2.57

10 Naphthalene 7.51

11 2-Methylnaphthalene 4.61

12 1-Methylnaphthalene 1.47

* Total Area 70.44

STATE OF NEW YORKDEPARTMENT OF HEALTH

VOCs in MGP WasteVOCs in MGP Waste

Markles Flat 418 N. Plain Str. #1 418 N. Plain Str. #2 Esty & WashingtonStr.

Gastown MW VW#2 Gowanus MW Newburgh TB-71

STATE OF NEW YORKDEPARTMENT OF HEALTH

VOCs in MGP Waste HeadspaceVOCs in MGP Waste Headspace

Most commonly see C2-benzenes (7/7) and naphthalene (7/7)

However, these compounds also are common components of gasoline…

Proportions of VOCs are not indicative of MGP waste

STATE OF NEW YORKDEPARTMENT OF HEALTH

Total Ion Chromatograms - One MGP SiteTotal Ion Chromatograms - One MGP Site

STATE OF NEW YORKDEPARTMENT OF HEALTH

Other MGP Waste SamplesOther MGP Waste Samples

STATE OF NEW YORKDEPARTMENT OF HEALTH

MGP Waste Sample?MGP Waste Sample?

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Total Ion Chromatograms - Petroleum SamplesTotal Ion Chromatograms - Petroleum Samples

Natural Gas

Gasoline

Kerosene

Heating Oil

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Hydrocarbon Group Hydrocarbon Group Representative Fragmentation IonsRepresentative Fragmentation Ions

Hydrocarbon Group Fragmentation Ions (m/z)

Alkanes (P) 43, 57, 71, 85

Cycloalkanes (C) 41, 55, 69, 83, 97, 98, 111, 112

Alkenes (O) 67, 68, 81, 82, 96, 109, 121

Benzene/Alkylbenzenes (A) 78, 91, 105, 119, 120, 134, 148

Indane/Tetralins (T) 104, 115, 117, 118, 131, 132, 145

Naphthalene/Alkylnaphthalenes (N) 128, 141, 142, 155

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Alkanes (P)Alkanes (P)

43 57

71

85

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Cycloalkanes (C)Cycloalkanes (C)

41 5569 83 97, 98

111, 112

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Alkenes (O)Alkenes (O)

67, 6881, 82

96109

STATE OF NEW YORKDEPARTMENT OF HEALTH

Benzene/Alkylbenzenes (A)Benzene/Alkylbenzenes (A)

7891 105

119, 120

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Indane/Tetralins (T)Indane/Tetralins (T)

104

115

117, 118

131, 132

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Naphthalene / Naphthalene / Alkylnaphthalenes (N)Alkylnaphthalenes (N)

128

141, 142

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Extracted Ion Profiles – MGP SampleExtracted Ion Profiles – MGP Sample

Naphthalene

Indane

Alkylbenzenes

Alkenes

Cycloalkanes

Alkanes

STATE OF NEW YORKDEPARTMENT OF HEALTH

Extracted Ion Profiles – MGP Sample?Extracted Ion Profiles – MGP Sample?

Naphthalene

Indane

Alkylbenzenes

Alkenes

Cycloalkanes

Alkanes

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TIC and Summed EICsTIC and Summed EICs

Total Ion Chromatogram

Summed EICs

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Plot of Hydrocarbon Group Distribution

0%

5%

10%

15%

20%

25%

30%

35%

40%

[P] 33% 21% 23% 20% 0% 1% 3% 2%

[C] 21% 19% 27% 19% 1% 2% 6% 4%

[O] 1% 3% 7% 6% 1% 1% 2% 1%

[A] 3% 14% 12% 19% 31% 38% 33% 27%

[T] 0% 1% 2% 6% 12% 9% 12% 18%

[N] 0% 0% 0% 1% 4% 1% 4% 6%

Natural Gas Auto. Gasoline Kerosene Heating Oil Markles FlatEsty &

Washington Street

418 N. Plain St (1)

418 N. Plain St (2)

STATE OF NEW YORKDEPARTMENT OF HEALTH

Plot of Aromatic and Aliphatic Fractions

0%

10%

20%

30%

40%

50%

60%

Markles Flat Esty &Washington

Street

418 N. Plain St(2)

418 N. Plain St(1)

Newburgh Gowanus Gastown ConEd SB24 ConEd MW6

STATE OF NEW YORKDEPARTMENT OF HEALTH

Plot of Aromatic and Aliphatic Fractions

0%

5%

10%

15%

20%

25%

30%

35%

40%

Natural Gas Auto. Gasoline Kerosene Heating Oil

STATE OF NEW YORKDEPARTMENT OF HEALTH

ConclusionsConclusions

The proportions of aromatic and aliphatic material in headspace may be used to differentiate MGP waste from some common petroleum materials.

The study did not consider weathered petroleum products, which may have different distributions of aromatic and aliphatic materials.

STATE OF NEW YORKDEPARTMENT OF HEALTH

ConclusionsConclusions

The study considered a very small number of MGP waste samples from a small number of sites - additional research is needed.

The study considered a very small number of petroleum products - additional standards and analysis are needed.