DEA: A Sleeping Remedial Giant?

Transcription

1 DEA: A Sleeping Remedial Giant? Konrad W. Quast, Ph.D. April 21, 2015 EXPLORE the Depths of our Experience

2 DEA Talk Outline General background Production & uses Chemical properties Analytical methods Toxicology Environmental regulatory framework Remedial options Conclusions EXPLORE the Depths of our Experience 2

3 Diethanolamine (DEA) General Background Alkanolamine CAS # IUPAC: 2,2'-Iminodiethanol Mild, ammonia-like odor Colorless crystals or a syrupy, white liquid (> 82 o F, 28 o C) Chemical Listings Not listed on USEPA s HPV Challenge Program Listed on OECD SIDS Program International EXPLORE the Depths of our Experience 3

4 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 EXPLORE the Depths of our Experience 4

5 IHS 2012 IARC 2012 EXPLORE the Depths of our Experience 5

6 Sour Natural Gas Treatment DEA & MEA in 95% of US sweeting operations 1 ~15-25 % of US natural gas is sour 2 ~30% of Canada s natural gas is sour 3 ~40% remaining reserves worldwide are sour EPA (1993) Report to Congress on Hydrogen Sulfide Emissions Associated with Extraction of Oil and Natural gas 3 Alberta Natural Gas Industry, Quarterly Update Winter 2011, Government of Alberta 4 IHS energy data, 2004 EXPLORE the Depths of our Experience 6

7 Estimated % Uses of DEA in USA (IARC 2012) EXPLORE the Depths of our Experience 7

8 Worldwide Sour Gas Fields Burgers et al. 2011, Worldwide development potential for sour gas EXPLORE the Depths of our Experience 8

9 Environmental Chemical Properties Miscible in water (infinite solubility) Highly mobile to/in groundwater Low vapor pressure ( 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 EXPLORE the Depths of our Experience 9

10 Analytical Methods Government of Alberta (2010) Gas chromatography (GC) 0.005mg/L water, 0.05mg/Kg soil High performance liquid chromatography (HPLC)? Ion chromatography (IC) 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 EXPLORE the Depths of our Experience 10

11 Analytical Methods Lack of analytical capability with large commercial laboratories 3 out of 5 had capability EPA 8015M 2 nd 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 / mg/l EXPLORE the Depths of our Experience 11

12 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 EXPLORE the Depths of our Experience 12

13 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: mg/l & soil: mg/kg) Due to unknown toxicology, Formation of NDELA Alberta Government (2010) 0.06mg/L EXPLORE the Depths of our Experience 13

14 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 EXPLORE the Depths of our Experience 14

15 Remedial Options Soils Excavation In-situ bioremediation Groundwater Pump & treat In-situ bioremediation Bioremediation identification Contaminant concentration changes Monitoring for biodegradation products EXPLORE the Depths of our Experience 15

16 Biodegradation Pathway Government of Alberta (2010). Soil and groundwater remediation guidelines for monoethanolamine and diethanolamine, , Available from Online ISBN EXPLORE the Depths of our Experience 16

17 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 EXPLORE the Depths of our Experience 17

18 Conclusions 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 EXPLORE the Depths of our Experience 18