Grantee Research Project Results
1998 Progress Report: Ion-Pair/Supercritical Fluid Extraction and Derivatization for Polar Organic Pollutant Analysis
EPA Grant Number: R821195Title: Ion-Pair/Supercritical Fluid Extraction and Derivatization for Polar Organic Pollutant Analysis
Investigators: Field, Jennifer
Institution: Oregon State University
EPA Project Officer: Packard, Benjamin H
Project Period: September 1, 1995 through September 1, 1998
Project Period Covered by this Report: September 1, 1997 through September 1, 1998
Project Amount: $392,272
RFA: Exploratory Research - Chemistry and Physics of Water (1995) RFA Text | Recipients Lists
Research Category: Water , Land and Waste Management , Safer Chemicals
Objective:
The general goal of this project is to develop, validate, and demonstrate new methodologies for extracting and derivatizing polar organic chemicals in aqueous and solid matrices. In pursuit of this goal the following project objectives are outlined:
- To develop alternative methods for determining polar (acidic) contaminants in solid environmental matrices that couple supercritical fluid or subcritical (hot) water extraction together with derivatization reactions that minimize or eliminate organic solvents for the extraction and derivatization.
- To develop alternative extraction methods for polar organic contaminants in aqueous environmental matrices that couple preparative steps and minimizes organic solvent usage.
- To validate and demonstrate the alternative methodologies that couple the preparative steps such as extraction and derivatization using actual field samples including groundwater, surface water, soils/sediments, and sewage sludges.
Progress Summary:
An alternative method was developed for the determination of nonylphenol polyethoxy carboxylates (NPECs) in municipal and industrial sludges. These analytes are important because they are estrogenic towards fish. In addition, because NPECs biodegrade to nonylphenol, NPECs act as potential sources of NP in the environment. Although a growing body of data exists on the occurrence of NPECs in surface waters and effluents, very few reports exist that document the occurrence of NPECs in sludge. It is generally accepted that the sorption of NPECs to sludge is negligible. However, this view is attributed to the lack of analytical methods for the analysis of NPECs in sludge, To address this data gap, the objective of this portion of the project was to develop an environmentally-acceptable, simple, and rapid extraction method for the determination of NPECs in environmental samples, such as sewage sludge.Subcritical (hot) water with ethanol as modifier was developed as the extraction solvent for the determination of NPECs in sludge. Extraction conditions were evaluated and optimized to yield the maximum amount of native or incurred NPEC residues in samples of municipal sewage and industrial sludge. The optimal conditions consisted of extracting 0.25 g sludge with 30 % (v/v) ethanol in water at 75 oC for 20 min. The NPECs were recovered from the water/ethanol sludge extract using strong anion exchange Empore disks. The acid analytes were simultaneously eluted from the disk and derivatized to their methyl esters for analysis by chemical-ionization gas chromatography/mass spectrometry.
The method was demonstrated in the analysis of anaerobically-digested sewage sludge, a composted mixture of anaerobically-digested sewage sludge and yard waste, and secondary clarifier sludge from a paper mill. NPEC concentrations ranged from 27 to 113 mg/g with NP2EC as the most abundant oligomer. The ratio of ortho to para NP2EC and NP3EC isomers 1 for the two samples containing anaerobically-digested sewage sludge. The relatively higher percentage of ortho isomers in the samples containing anaerobically-digested sludge suggests that the sludge digestion process results in the enrichment of ortho isomers relative to para isomers since commercial mixtures of nonylphenol polyethoxylates contain only a minor amount (<10%) of ortho isomers. This relative enrichment could be due to lower rates of ortho-NPEC biodegradation. In contrast, the secondary clarifier sludge from the paper mill, which received only aerobic treatment, contained only para NPEC isomers.
The analytical method described is rapid, simple, and more environmentally friendly than conventional methods of analysis because the methods use small volumes (< 10 mL) of relatively benign solvents and eliminate the use of diazomethane, hazardous conventional derivatization reagent.
Journal Articles on this Report : 5 Displayed | Download in RIS Format
Other project views: | All 13 publications | 5 publications in selected types | All 5 journal articles |
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Field JA, Reed RL, Sawyer TE, Martinez M. Diuron and its metabolites in surface water and ground water by solid phase extraction and in-vial elution. Journal of Agricultural and Food Chemistry 1997;45(10):3897-3902. |
R821195 (1998) R821195 (Final) |
Exit |
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Field JA. Coupling chemical derivatization reactions with supercritical fluid extraction. Journal of Chromatography A 1997;785(1-2):239-249. |
R821195 (1998) R821195 (Final) |
Exit |
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Field JA, Monohan K, Reed R. Coupling supercritical CO2 and subcritical (hot) water for the determination of Dacthal and its acid metabolites in soil. Analytical Chemistry 1998;70(9):1956-1962. |
R821195 (1998) R821195 (Final) |
Exit |
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Moody CA, Field JA. Determination of perfluorocarboxylates in groundwater impacted by fire-fighting activity. Environmental Science & Technology 1999;33(16):2800-2806. |
R821195 (1998) R821195 (Final) |
Exit |
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Field JA, Reed RL. Subcritical (hot) water/ethanol extraction of nonylphenol polyethoxy carboxylates from industrial and municipal sludges. Environmental Science & Technology 1999;33(16):2782-2787. |
R821195 (1998) R821195 (Final) |
Exit |
Supplemental Keywords:
Scientific Discipline, Waste, Water, Contaminated Sediments, Physics, Environmental Chemistry, Chemistry, Engineering, Engineering, Chemistry, & Physics, solvent waste, sediment toxicity, contaminated sediment, alternative extraction, polar organic compounds, carbon dioxide, soil contaminants, super critical fluid extraction, ion pair, coupling derivatization reactionsProgress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.