Use of Environmental Forensics In Drycleaning Investigations

Use of Environmental ForensicsIn Drycleaning InvestigationsRobert D. Morrison, Ph.D.DPRA, IncHawi, HIState Coalition for Remediation ofDrycleaners2009 Annual MeetingSan Antonio, TexasNovember 17-19, 2009

Forensic Issues in Drycleaner Investigations• Apportionment in comingled plumes• Date/age of a contaminant release• Optimizing forensic sampling locations• Forensic analytical program• Cost

Presentation OutlinePCEWhere to sample?What to sample (media)?Analytical decisionsIsolating the PCE sourceCase study – multiple sources

Degradation Pathways of Four ChlorinatedSolvents

Synonyms for PCEChemical namesCarbon bichlorideCarbon dichlorideEthylene tetrachloridePerchloroethyleneTetrachloroethyleneTrade names AnkilostinBlacosolve No. 2Dee-SolvDidakeneDowPer (Dow Chemical)*Isoform (Dow Chemical)MidsolvNemaPerclene (Du Pont, Diamond Shamrock)Perclene TG (Du Pont, Diamond Shamrock)PercosolvPer-ExPerklone (dry-cleaning)Perm-A-KleenPer Sec (Vulcan Materials)PhillsolvTetracapTetravecTetropilWecosol (Westinghouse)* Manufacturer names in italics.

PCE Applications (a)• Drycleaning (1960’s to 1980’s peak production years)• Metal cleaning/degreasing – especially for cleaningaluminum parts prior to the development ofTCA stabilized (1,4-dioxane) formulations• Removal of wax and resin residue• Cleaning of small, low-mass partsbecause the condensed solventcontact time is longer than forother solvents• Automotive brake cleaning

PCE Applications (b)• Rubber dissolution• Paint Removal• Sulfur Recovery• Printing Ink bleeding• Catalyst regeneration• Textile operations as a scouring agent• After 1966, primary use was in production of CFC-113and HFC- 134a

TCE in septictank cleaners

PCE Enriched via Solvent DistillationSIGHT GLASSFILTER BODYMUCK VALVEREGENERATIVE FILTERON A COOKER/STILLAUTOMATIC BUMPASSEMBLYPRESSURE GAUGETEMPERATURECONTROL BOXGAUGEPCE can be present in TCE, particularlyin degreasing grades because the twosolvents are produced by the sameprocess and are separated by fractionaldistillation. Other chlorinatedcompounds comprise 3 to 4 percent ofdegreasing-grade TCE.HANDLECOOKERSTILL BODYMOTORACCESS DOORWATERCLEAN OUTSEPARATORDOORThe boiling points of PCE and TCE are121.2 and 87.2°C, respectively. TCEdegreasers usually use hot watersomewhere below the boiling point of100°C. Because of this difference inboiling points, TCE volatilizes into theair and is lost from the degreaser at amuch more rapid rate than the PCE.

Major Manufacturers of PCECompanyApproximate Period of ManufactureDiamond Alkali/Diamond Shamrock 1950 ±1986Dow Chemical1923 ± presentE. I. Du Pont de Nemours 1933 ± 1986Ethyl Corporation 1967 ± 1983Frontier Chemical/Vulcan Materials1958 ± presentHooker Chemical/Occidental Chemical 1949 ± 1990Hooker-Detrex/Detrex Chemical 1947 ± 1971Pittsburgh Plate Glass/PPG Industries1949 ± presentStauffer Chemical 1955 ± 1985Westvaco Chlorine 1940 ± 1945

Feedstock used for PCE Productionfor Age Dating PCEThe primary production method for PCE prior tothe 1970s involved the chlorination of acetyleneto produce PCE/TCE. By 1978, acetyleneproduction ceased.Subsequent productionmethods used ethylene asa feedstock to produceethylene dichloride (1,2­DCA). In 1975, PCE productionwas 44% via propane chlorinolysis,35% via 1,2-DCA chlorination and3% by acetylene chlorination.

PCE/TCE Manufacturing Methods

The presence of 1,1,2,2-TeCA and/or 1,1,2-TCA withPCE suggests that the PCEwas manufactured priorto 1978.The presence of 1,2-DCAwith PCE (eliminate itspresence as a leadscavenger) indicates thatthe PCE was manufacturedpost 1978.

Chemical Name MW17S PBW-2 PBW-1 MW12D BD-17VOCsAcetone < 0.0500 < 0.0500 < 0.0500 < 0.0500 < 0.0500Benzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Bromobenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Bromochloromethane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Bromodichloromethane < 0.0020 < 0.0020 < 0.0020 < 0.0020 < 0.0020Bromoform 0.003 < 0.0010 0.016 < 0.0010 0.009Bromomethane < 0.0098 < 0.0098 < 0.0098 < 0.0098 < 0.00982-Butanone < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100n-Butylbenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050sec-Butylbenzene < 0.0050 < 0.0050 0.007 < 0.0050 < 0.0050tert-Butylbenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Carbon disulfide < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100Carbon tetrachloride < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Chlorobenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Chloroethane < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100Chloroform 0.0039 < 0.0002 0.034 < 0.0002 < 0.0002Chloromethane < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.01002-Chlorotoluene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00504-Chlorotoluene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Dibromochloromethane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Dibromomethane 0.043 < 0.0050 < 0.0050 0.086 < 0.00501,2-Dichlorobenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,3-Dichlorobenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,4-Dichlorobenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Dichlorodifluoromethane 0.0036 < 0.0100 0.074 < 0.0100 < 0.01001,1-Dichloroethane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,2-Dichloroethane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,1-Dichloroethene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050cis-1,2-Dichloroethene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050trans-1,2-Dichloroethene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,2-Dichloropropane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,3-Dichloropropane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00502,2-Dichloropropane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,1-Dichloropropene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050cis-1,3-Dichloropropene < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010trans-1,3-Dichloropropene < 0.0010 < 0.0010 < 0.0010 < 0.0010 < 0.0010Ethylbenzene 0.0050 0.045 < 0.0050 < 0.0050 < 0.0050Hexachlorobutadiene < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.01002-Hexanone < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Isopropylbenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050p-Isopropyltoluene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Methyl tert-butyl ether < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00504-Methyl-2-pentanone < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Methylene chloride < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050n-Propylbenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Styrene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,1,1,2-Tetrachloroethane 0.09 0.007 0.78 0.0019 0.0241,1,2,2-Tetrachloroethane 0.01 < 0.0050 0.4 0.002 0.002Tetrachloroethene 0.155 0.047 0.523 0.145 0.067Toluene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,2,3-Trichlorobenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,2,4-Trichlorobenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,1,1-Trichloroethane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,1,2-Trichloroethane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Trichloroethene 0.006 0.765 0.072 < 0.0050 0.015Trichlorofluoromethane < 0.0100 < 0.0100 < 0.0100 0.0271 < 0.01001,2,3-Trichloropropane < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,2,4-Trimethylbenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.00501,3,5-Trimethylbenzene < 0.0050 < 0.0050 < 0.0050 < 0.0050 < 0.0050Vinyl acetate < 0.0100 < 0.0100 < 0.0100 < 0.0100 < 0.0100Vinyl chloride < 0.0020 < 0.0020 < 0.0020 < 0.0020 < 0.0020Xylenes, Total < 0.0150 < 0.0150 < 0.0150 < 0.0150 < 0.0150

EPA Method 8270 – Substituted Phenols

Where/What to Sample?

Where to Sample?Knowledge of Drycleaning OperationUnderstand operational chronology, equipmentchronology, filter material, distillation still,equipment location, ancillary services, buildingmodifications/permits, sewer lines/connections,separator water connections, purchase/supplierrecords, equipment permits, insurance records.Visit Site Prior to SamplingIdentify piping, flooring, joints (wood, oakum,felt), sewer cleanouts, storm water, dumpsterlocations.

Knowledge of Equipment and Handling Practices

Traditional v. Forensic SamplingTraditional – Soil, soil gas, groundwaterForensic – Muck, sewer pipe, flooring, expansionjoints, filter material, asphalt/concrete pavingFlorida Drycleaning Solvent CleanupProgram on reported spills, leaks anddischarges of drycleaning solvent andsolvent-contaminated wastes at 334drycleaning facilities and 14 drycleaningwholesale supply facilities located inFlorida.

Optimizing Sampling Locations

Sources of Muck

Knowledge of Operations

Surrogate Chemical Signature Associated with LeatherFinishing at a Dry CleanerProduct Description Ingredients Percentage by WeightLeather Spray Blue F2000Leather Spray Blood Red F2000Diisolbutyl ketone2,6-dimethyl-4-heptaone 28.5Butyl Cellosolve2-Butoxyethanol 4.8Titanium dioxide 2.2Dibutylphthlate 1.82-propoxethanol 1.4Diisolbutyl ketone2,6-dimethyl-4-heptaone 28.9Dibutyl phthlate 1.82-propoxyethanol 2.2Butyl cellosolve2-butoxyethanol 9.2Castor Oil exthoxylated 1.4Leather Spray Pure White F2000 Titanium Oxide 18.1Butyl cellosolve2-butoxyethanol 8.5Diisolbutyl ketone2,6-dimethyl-4-heptaone 25.1Leather Spray Orange F2000Diisolbutyl ketone2,6-dimethyl-4-heptaone 28.3N-butyl Alcohol 1-Butanol 1.2Disbutyl Phthlate 1.6Butyl cellosolve2-butoxyethanol 8.7Morrison, 2003. PCE contamination and the dry cleaning industry. Environmental Claims Journal. 15(1), 93-106.

Sediment/Muck in Cracks and Expansion JointsCracks/Multiple Pours

Muck from Expansion Joint Material(high probability sample)

Surrogate - Dry Cleaning FilterMaterial + PCE for Age DatingDiatomaceous Earth FilterActivated Carbon Filter

Case StudyExpansion Joint SamplingExpansion Joints

SEM of Paint Flakes and Rust

Sewer Videos – Sewer Sampling

Trial Graphic Depicting PCESources at a Dry Cleaner

Analytical DecisionsUnderstand the question - thendevelop the analytical program.

Forensic Techniques for PCE Investigationsat Dry CleanersAdditives (inhibitors, anti-oxidants, etc)Surrogate chemicals and materialsDegradation rate approach (half-life rates)Molar ratio approachIsotopic analysis (soil, groundwater, indoor air)

PCE StabilizersAcid InhibitorsAcetylenic alcoholsAcetylenic carbinolsAcetylenic estersAlcoholsAliphatic aminesAliphatic monohydric alcoholsAmidesAminesAzo aromatic compoundsEpoxidesHydroxyl aromatic compoundsKetonesNitroso compoundsPyridinesMetal InhibitorsAlcoholsAromatic hydrocarbonsCyclic trimersEstersLactoneOxazolesOximesSulfonesSulfoxideLight InhibitorsAminesCyanideHydroxyl aromatic compoundsNitrilesOrgano-metallic compoundsAntioxidantsAcetylene ethersPhenolsPyrroleThiocyanatesStabilizers and PCE (synoposis)Unlike TCE and TCA, PCE is relatively stable and requires only minor amounts of stabilizingadditives to prevent decomposition. Earlier stabilizers included amines and hydrocarbons; morerecent stabilizers include compounds such as morpholine derivatives. In the presence of water,unstabilized PCE will slowly hydrolyze to form trichloroacetic acid and hydrochloric acid.

Is TCE a PCE degradation product ?TCE – Some Similarities(yellow) /Differences (white)Acid InhibitorsAcetylenic alcoholsAlcoholsAliphatic aminesAliphatic monohydric alcoholsAlkaloidsAlky HalidesAminesAzinesAzirdinesAzo-aromatic compoundsEpoxidesEssential oilsHydroxyl-aromatic compoundsNitroso compoundsOlefinsOrganic Substitute NH 4 hydroxidesOxiranePhenolsPyridinesPyrroleQuatenary Ammonium compoundsTerpenesMetal InhibitorsAlcoholsAmidesAminesAromatic hydrocarbonsComplex ethers and oxidesCyanideCyclic EthanesCyclic trimersEpoxidesEstersEthersKetonesOlefinsPeroxidesPyridinesOxazolesOxazolinesOximesSulfonesSulfoxideThiopheneAntioxidantAmidesAminesAromatic carboxylic acidsAryl stibineBoranesButylhydroxyanisolePhenolsPyridinesPyrroleThiocyanatesLight InhibitorTCEAromatic benzene nucleiBoranesEthersGuanidineHydroxyl-aromatic compoundsOrgano-metallic compounds

TCE StabilizersMetal stabilizers used with TCE include1,2-butylene oxide and epichlorohydrin.Epichlorohydrin wasdiscontinued in the1980s due to its toxicity.Accumulate in still bottomTCEresidue “muck” up to35% greater than their original compositionin TCE.

Stabilizers used in Dry Cleaning PCEEarly PCE stabilizers included amines andpetroleum hydrocarbons; more recentstabilizers included morpholine stabilizers.Stabilizers used in dry cleaning grade PCEinclude 4-methyl morpholine, N-butyl glycidylether (best marker), cyclohexane oxide,diallylamine and 3-methoxy proprionitrile.

Manufacturers of PCE for Dry Cleaningand Associated StabilizersDow Chemical 4-methyl morpholineVulcan Diallylamine/tripropylene compoundsPPG Cyclohexene oxide, beta-thoxyproprinitrile,m-nethyl morpholine, 4-methylphenol

Distinguishing Drycleaner fromTransformer/Metal Cleaning PCE (a)PCE was used in transformers as a replacement for the more toxic class of dielectricfluids containing PCBs.PCE used as a dielectric fluid was subjected to extra refining including scrubbing anddistillation and was stabilized with n-methyl pyrrole (112 C) and pentaphen (p-tert amylphenol) (226 C).Drycleaning grades of PCE did not use n-methyl pyrrole or pentaphen. May use thepresence of these two stabilizers with PCE to distinguish PCE originating from adrycleaners from one originating from a transformer.Patent literature indicates that metal degreasing metal cleaningPCE used n-methyl pyrrole as an oxidant containing 0.022 to0.028% stabilizer andnot for dry cleaning.N-methyl pyrrole was also used to stabilize TCA and TCE;pentaphen used to stabilize TCE against oxidation.

Distinguishing Drycleaner fromTransformer/Metal Cleaning PCE (b)Stabilizers in DrycleaningGrade PCE4-methyl morpholinediallylaminetripropylene compoundscyclohexane oxide3-methyl proprionitrilen-butyl glycidyl etherStabilizers in PCE forTransformersp‐tert amyl phenol (pentaphen)n‐methyl pyrrole

Metal Cleaning v. Dry Cleaning (a)Metal Cleaning Traditionally contained a higher concentrationof additives than most dry cleaning grades. Classes include acidacceptors, antioxidants, and UV stabilizers. Antioxidants includeamine or phenolic compounds 50 – 200 ppm and acid acceptorsepoxide 0.2-0.7%. Early PCE formulations included alkylaminesand other hydrocarbons. Later stabilizers included morpholinederivatives, epoxides, esters and phenols.Dry Cleaning Traditionally contained a high concentration ofadditives, usually of a high purity and different types of additives.DOWPER-C-S contains a water soluble detergent, a corrosioninhibitor, an anti-static compound, “hand agent” compounds, anda fatty acid scavenger.

Metal Cleaning v. Dry Cleaning (b)Dry Cleaning PCE characterized by a high purity anddifferent types of additives than associated with metalcleaning. For example, DOWPER-C-S contains awater soluble detergent, a corrosion inhibitor, an antistaticcompound, “hand agent” compounds, and afatty acid scavenger.

Surrogate ApproachPCE from SewersSurfactants (a) amine alkylarenesulfonates(b) Sodium alkylarenesulfonates, (c) petroleumSulfonates, (d) ethoxylated phenols and (e)ethoxylated phosphate esters. Use MBAS for presence/absence as an inexpensive surrogate for detergents.Generic Indicators (a) high TDS values, (b)presence of trihalomethanes, (c) microbiological,(d) soil gas (methane, etc).

Co-mingled PCE-SeparateSources• PCE from two sources chemically identical• May be isotopically different• Carbon and Chlorine stable isotope ratios• 13 C/ 12 C and 37 Cl/ 35 Cl• May differentiate sources prior to comingling• Effects of biodegradation need to beconsideredClClCCClCL

-20.00-22.00-24.00TCE-26.00-28.00-30.00-32.00-34.00-28.00-27.00-26.00-25.00PCESource: Philp, P., 2003. Stable isotopes and biomarkers in Forensic chemistry. International Society of Environmental Forensics Workshop.May 19-20 th , 2003. Stresa, Italy.-24.00-23.00-22.00-21.00-20.00

Isotopic Analysis for Source Discrimination

Use of C and Cl Isotopes to DifferentiatePCE/TCE Sources

Degradation Rate Approach

Molar Ratio Approach

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