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Transcript of DEA: A Sleeping Remedial Giant? - esaa.org · DEA: A Sleeping Remedial Giant? • High probability...
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DEA: A Sleeping Remedial Giant?
Konrad W. Quast, Ph.D.April 21, 2015
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DEA Talk Outline
• General background
• Production & uses
• Chemical properties
• Analytical methods
• Toxicology
• Environmental regulatory framework
• Remedial options
• Conclusions
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Diethanolamine (DEA) General Background
• Alkanolamine
• CAS # 111-42-2
• IUPAC: 2,2'-Iminodiethanol
• Mild, ammonia-like odor
• Colorless crystals or a syrupy, white liquid(> 82oF, 28oC)
• Chemical Listings• Not listed on USEPA’s HPV Challenge Program
• Listed on OECD SIDS Program – International
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Production & Uses
• Commercial uses began in the 1930’s
• Sour gas treatment
• Personal care products
• Soaps and surfactants
• Corrosion inhibitor
• Stabilizer
• Drug Solvent
• Manufactured worldwide in at least 11 countries ????
• No known natural production routes
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IHS 2012
IARC 2012
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Sour Natural Gas Treatment
• DEA & MEA in 95% of US sweeting operations1
• ~15 - 25 % of US natural gas is sour2
• ~30% of Canada’s natural gas is sour3
• ~40% remaining reserves worldwide are sour4
1http://naturalgas.org/naturalgas/processing-ng/#sulphur
2EPA (1993) “Report to Congress on Hydrogen Sulfide Emissions Associated with Extraction of Oil
and Natural gas”
3Alberta Natural Gas Industry, Quarterly Update Winter 2011, Government of Alberta
4IHS energy data, 2004
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Estimated % Uses of DEA in USA (IARC 2012)
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Worldwide Sour Gas Fields
Burgers et al. 2011, Worldwide development potential for sour gas
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Environmental Chemical Properties
• Miscible in water (infinite solubility)
• Highly mobile to/in groundwater
• Low vapor pressure (0.00037 hPa 25 °C)
• Unlikely to volatilize from soils/water
• Low sorption coefficients
• Not readily sorbed to organic matter or soils
• May be sorbed to negatively charged clays
• Low persistence - biodegradeable
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• Government of Alberta (2010)
• Gas chromatography (GC) 0.005mg/L water, 0.05mg/Kg soil
• High performance liquid chromatography (HPLC) ?
• Ion chromatography (IC) 0.025 ppm water?
• Other techniques• Filter w/ 2% diphenylcarbazide 1.29ug
• Spectroscopy
• Tandem MS such as ESI-MS-MS
Witzaney, A.M. and Fedorak, P.M., (1996). A Review of the Characteristics, Analyses and Biodegradability of Sulfolane and the Alkanolamines used in Sour Gas Processing, Consulting report submitted to Shell Canada Limited, February 1996
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Analytical Methods
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• Lack of analytical capability with large commercial laboratories • 3 out of 5 had capability
• EPA 8015M 2nd Lowest MDL / RL (GC procedure)• Soil: 4.5 / 25 mg/Kg
• Groundwater: 10 / 25 mg/L
• LC/MS/MS Low MDL / RL but developmental• Clean Sand: 0.01 / 0.02 mg/Kg
• Clean Water 0.002 / 0.004 mg/L
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Analytical Methods
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Toxicology
• Inadequate evidence in humans for carcinogenicity
• Sufficient evidence in experimental animals for carcinogenicity in mice
• Can form N-nitrosodiethanolamine (NDELA) with nitrite
• Low groundwater/soil guidelines
• Allowed in food packaging and as an indirect food additive by US FDA
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Environmental Framework
• No soil or water promulgated standards
• US Environmental Protection Agency (USEPA)
• Alberta Environment (AENV) or Canadian Council of
Ministers of the Environment (CCME)
• Europe
• World Health Organization (WHO)
• Low groundwater/soil guidelines
• TCEQ (gw: 0.012 mg/L & soil: 0.024 mg/Kg)
• Due to unknown toxicology, Formation of NDELA
• Alberta Government (2010) 0.06mg/L
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DEA: A Sleeping Remedial Giant?
• High probability of environmental releases• High production
• Potentially >269,000 tonnes (>593,000,000 pounds) annually in 2015
• Wide spread use • Industrial
• Consumer
• High mobility in soils and water
• Potential Carcinogen
• Low clean up standards
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Remedial Options
• Soils
• Excavation
• In-situ bioremediation
• Groundwater
• Pump & treat
• In-situ bioremediation
• Bioremediation identification • Contaminant concentration changes
• Monitoring for biodegradation products
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Biodegradation Pathway
Government of Alberta (2010). Soil and groundwater remediation guidelines for monoethanolamine and diethanolamine,
08.07.2011, Available from http://environment.gov.ab.ca/info/ Online ISBN 978-0778-5900-6
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Bioremediation
• Microbial Insights, Inc.
• Bio-Trap® (Microbial Insights, Inc.)• In-situ passive microcosm sampler
• Active microbes, chemistry, stable isotopes
• CENSUS ® Quantitative Polymerase Chain Reaction (qPCR)
• Reverse Transcription-qPCR (mRNA)
• Stable Isotope Probing (SIP)
• Compound Specific Isotope Analysis (CSIA)
• Contaminant concentrations
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• DEA is a commonly used chemical in
industrial and consumer products
• Toxicology indicates potential for
carcinogenicity in humans
• Regulatory cleanup guidelines are low
relative to existing analytical capabilities
• High probability for bioremediation
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Conclusions