mgp waste method
DESCRIPTION
An overview of a simple laboratory data analysis procedure to characterize and differentiate tar waste from manufactured gas plants compared to petroleum products. Presented at the American Academy of Forensic Science 2005 annual meeting in New Orleans - at the environmental sciences session which I also coordinated and moderated.TRANSCRIPT
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
STATE OF NEW YORKDEPARTMENT OF HEALTH
Gas Handling and Measurement SystemGas Handling and Measurement System
STATE OF NEW YORKDEPARTMENT OF HEALTH
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
STATE OF NEW YORKDEPARTMENT OF HEALTH
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?
STATE OF NEW YORKDEPARTMENT OF HEALTH
Total Ion Chromatograms - Petroleum SamplesTotal Ion Chromatograms - Petroleum Samples
Natural Gas
Gasoline
Kerosene
Heating Oil
STATE OF NEW YORKDEPARTMENT OF HEALTH
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
STATE OF NEW YORKDEPARTMENT OF HEALTH
Alkanes (P)Alkanes (P)
43 57
71
85
STATE OF NEW YORKDEPARTMENT OF HEALTH
Cycloalkanes (C)Cycloalkanes (C)
41 5569 83 97, 98
111, 112
STATE OF NEW YORKDEPARTMENT OF HEALTH
Alkenes (O)Alkenes (O)
67, 6881, 82
96109
STATE OF NEW YORKDEPARTMENT OF HEALTH
Benzene/Alkylbenzenes (A)Benzene/Alkylbenzenes (A)
7891 105
119, 120
STATE OF NEW YORKDEPARTMENT OF HEALTH
Indane/Tetralins (T)Indane/Tetralins (T)
104
115
117, 118
131, 132
STATE OF NEW YORKDEPARTMENT OF HEALTH
Naphthalene / Naphthalene / Alkylnaphthalenes (N)Alkylnaphthalenes (N)
128
141, 142
STATE OF NEW YORKDEPARTMENT OF HEALTH
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
STATE OF NEW YORKDEPARTMENT OF HEALTH
TIC and Summed EICsTIC and Summed EICs
Total Ion Chromatogram
Summed EICs
STATE OF NEW YORKDEPARTMENT OF HEALTH
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.