Behavior of Natural Polyelectrolytes in Water

Natural organic polyelectrolytes are highly active materials that are present in practically all natural water systems. They interact with both organic and inorganic pollutants and nutrients, influencing, and in many instances, controlling the toxicity, rate of movement, persistence and rate of degradation of the pollutants and nutrients in aquatic environments. Detailed knowledge of the chemistry of natural organic polyelectrolytes is therefore of primary importance in understanding the chemical changes that affect all of the components of natural water systems. Organic polyelectrolytes are partially eliminated from drinking water by coagulation and chlorination; however, the products of chlorination are not known. Both natural and synthetic organic compounds are present in all natural waters. Some of these compounds are toxic or mutagenic and it is therefore important that they be identified and quantified in surface and ground water and in precipitation. Objectives include (1) isolation of the various organic polyelectrolytes present in natural water systems from different environments; (2) determination of the physical and chemical properties of the most abundant organic polyelectrolytes; (3) elucidation of the mechanisms of interaction of pollutants with natural organic polyelectrolytes; (4) elucidation of the mechanism of interaction of natural organic polyelectrolytes with mineral surfaces; (5) development of nuclear magnetic resonance (NMR) spectroscopic methods for the characterization of humic substances; (6) determination and characterization of selected organic pollutants in ground water; (7) elucidation of the mechanisms of humification in natural systems; (8) identification of diagnostic NMR bands of different functional groups found in natural organic polyelectrolytes; (9) characterization of the nitrogen containing species in natural organic polyelectrolytes; and (10) identification of the carbohydrates in humic substances.

REPORTS PUBLISHED 1999-2004

Laird, D.A., Chappell, M.A., Martens, D.A., Wershaw, R.L., and Thompson, M., 2008, Distinguishing black carbon from biogenic humic substances in soil clay fractions: Geoderma v. 143, no. 1-2, p. 115-122. (on-line abstract of journal article)

Thorn, K.A., Thorne, P.G., Cox, L.G., 2004, Alkaline hydrolysis/polymerization of 2,4,6-trinitrotoluene: Characterization of products by ¹³C and ¹⁵N NMR: Environmental Science and Technology, v. 38, no. 7, p. 2224-2231. (on-line abstract)

Weiss, J.M., McKay, A.J., Derito, C., Watanabe, C., Thorn, K.A., and Madsen, E.L., 2004, Development and application of pyrolysis gas chromatogaphy/mass spectrometry for the analysis of bound trinitrotouene residues in soil: Environmental Science and Technology, v. 38, no. 7, p. 2167-2174. (on-line abstract)

Rutherford, D.W.; Wershaw, R.L.; Cox, L.G., 2004, Changes in composition and porosity occurring during the thermal degradation of wood and wood components: U.S. Geological Survey Scientific Investigation Report 2004-5292, 88 p. (on-line report)

Wershaw, R.L., 2004, Evaluation of conceptual models of natural organic matter (Humus) from a consideration of the chemical and biochemical processes of humification: U.S. Geological Survey Scientific Investigation Report 2004-5121, 44 p. (on-line report and on-line report in pdf format, 784 kb)

Bednar, A.J., Garbarino, J.R., Ferrer, I., Rutherford, D.W., Wershaw, R.L., Ranville, J.F., and Wildeman, T.R., 2003, Photodegradation of roxarsone in poultry litter leachates: The Science of the Total Environment, v. 302, p. 237-245. (on-line abstract)

Garbarino, J.R., Bednar, A.J., Rutherford, D.W., Beyer, R.S., and Wershaw, R.L., 2003, Environmental fate of Roxarsone in poultry litter. I. Degradation of Roxarsone during composting: Environmental Science and Technology, v. 37, no. 8, p. 1509-1514. (on-line abstract)

Leenheer, J.A., Wershaw, R.L., Brown, G.K., and Reddy, M.M., 2003, Characterization and diagenesis of strong-acid carboxyl groups in humic substances: Applied Geochemistry, v. 18, p. 471-482. (on-line abstract)

Qualls, R.G., Takiyama, A., and Wershaw, R.L., 2003, Formation and loss of humic substances during decomposition in a pine forest floor: Soil Science Society of America Journal, v. 67, no. 3, p. 899-909. (on-line abstract)

Rutherford, D.W., Bednar, A.J., Garbarino, J.R., Needham, R.,. Staver, K.W., and Wershaw , R.L., 2003, Environmental fate of Roxarsone in poultry litter. Part II. Mobility of arsenic in soils amended with poultry litter: Environmental Science and Technology, v. 37, no. 8, p. 1515-1520. (on-line abstract)

Wershaw, R.L., Rutherford, D.W., Leenheer, J.A., Kennedy, K.R., Cox, L.G., and Koci, D.R., 2003, Biogeochemical processes that produce dissolved organic matter from wheat straw: U.S. Geological Survey Water-Resources Investigation Report 03-4213. (on-line abstract or report)

Wershaw, R.L., Rutherford, D.W., Rostad, C.E., Garbarino, J.R., Ferrer, I., Kennedy, K.R., Momplaisir, G., Grange, A., 2003, Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylar-sonic acid: Talanta, v. 59, no. 6, p. 1219-1226. (on-line abstract)

Thorn, K.A., 2002, Reduction and incorporation of nitrate nitrogen into aquatic NOM upon UV irradiation examined by N-15 NMR: Division of Environmental Chemistry, 223rd American Chemical Society National Meeting, Orlando, Fla, April 7-11, 2002, v. 42, no. 1, p. 537-542.

Thorn, K.A., and Kennedy, K.R., 2002, ¹⁵N NMR Investigation of the covlaent binding and reduced TNT amines to soil humic acid, model compounds, and lignocellulose: Environmental Science and Technology, v. 36, no. 17, p. 3787-3796. (on-line abstract) or on-line pdf file - published by the American Chemical Society; not subject to U.S. copyright.)

Thorn, K.A., , Pennington, J.C., and Hayes, C.A., 2002, ¹⁵N NMR Investigation of the reduction and binding of TNT in aerobic bench scale reactor simulating windrow composting: Environmental Science and Technology, v. 36, no. 17, p. 3797-3805. (on-line abstract)

Thorn, K.A., , Pennington, J.C., Hayes, C.A., and Porter, B.E., 2002, Immobilization of 2,4- and 2,6-dinitrotoluene in compost investigated by N-15 NMR: Division of Environmental Chemistry, 224th American Chemical Society National Meeting, Boston, Mass., August 18-22, 2002, v. 42, no. 2, p. 127-135.

Wershaw, R.L., 2002, Establishment of a web-based NOM forum for the rapid publication and discussion of extended abstracts: Proceedings of the International Humic Substances Society Twentieth Anniversary Conference-Humic Substances: Nature's Most Versatile Materials, Boston, Northeastern University, p. 7.

Wershaw, R.L., and Kennedy, K.R., 2002, Characterization of wheat straw-derived DOM: Pro Proceedings of the International Humic Substances Society Twentieth Anniversary Conference—Humic Substances: Nature's Most Versatile Materials, Boston, Northeastern University, p. 87-89.

Osburn, C.L., Morris, D.P., Thorn, K.A., and Moellar, T.E., 2001, Chemical and optical changes in freshwater dissolved organic matter exposed to solar radiation: Biogeochemistry, v. 54, p. 251-278. (on-line abstract)

Thorn, K.A., , Pennington, J.C., and Hayes, C.A., 2001, Transformation of TNT in an aerobic compost: structure, and reactivity effects in the covalent binding of aromatic amines to organic matter: Division of Environmental Chemistry, 221st American Chemical Society National Meeting, San Diego, Calif., April 1-5, 2001, v. 42, no. 2, p. 127-135.

Wershaw, R. L. and Goljer, I., 2001, NMR characterization of the mobile components in intact green and senescent leaves as a means of studying the humification process, in Davies, G., and Ghabbour, E.A., eds., Humic substances: Structures, models, and functions: Cambridge, England, Royal Society of Chemistry, p. 31-38.

Wershaw, R. L. and Hayes, T. M., 2001, Solubilization of anthropogenic compounds by humic substances, in Clapp, C.E., Hayes, M.H.B., Senesi, N., Bloom, P.R., and Jardine, P.M., eds., Humic substances and chemical contaminants: Madison, Wisconsin., Soil Science Society of America, p. 165-176.

Thorn, K.A., and Mikita, M.A., 2000, Nitrite fixation by humic substances: 15N NMR evidence for potential intermediates in chemodenitrification: Soil Science Society America Journal, v. 64, no. 2, p. 568-582. (on-line abstract)

Wershaw, R.L., 2000, The study of humic substances-In search of a paradigm, in Davies, G. and Ghabbour, E.A., Humic substances: Versatile components of plants, soil, and water: Cambridge, England, Royal Society of Chemistry, p. 1-7.

Wershaw, R.L., Aiken, G.R., Leenheer, J.A., and Tregellas, 2000, Structural-group quantitation by CP/MAS ¹³C NMR measurements of dissolved organic matter from natural waters, in Davies, G. and Ghabbour, E.A., Humic substances: Versatile components of plants, soil, and water: Cambridge, England, Royal Society of Chemistry, p. 63-82.

Kile, D.E., Wershaw, R.L., and Chiou, C.T., 1999, Correlation of soil and sediment organic matter polarity to aqueous sorption of nonionic compounds: Environmental Science and Technology, v. 33, p. 2053-2056. (on-line abstract or on-line pdf file - published by the American Chemical Society; not subject to U.S. copyright.)

Thorn, K.A., and Aiken, G.R., 1999, Polar metabolites of crude oil, in Morganwalp, D.W., and Buxton, H.T., eds., U.S. Geological Survey Toxic Substances Hydrology Program - Proceedings of the Technical Meeting, Charleston, South Carolina, March 8-12, 1999--Volume 3 - Subsurface Contamination from Point Sources: U.S. Geological Survey Water-Resources Investigations Report 99-4018C, p. 231-236. (on-line abstract)

Wershaw, R.L., 1999, Molecular aggregation of humic substances: Soil Sci., v. 164, p. 803-813.(on-line abstract)

Wershaw, R.L., Leenheer, J.A, and Kennedy, K.R., 1999, Use of ¹³C NMR and FTIR for elucidation of degradation pathways during senescence and litter decomposition of Aspen leaves, in Davies, C. and Ghabbour, E.A., Understanding humic substances--Advanced methods, properties and applications: Cambridge, England, Royal Society of Chemistry, p. 19-30.

FOR ADDITIONAL INFORMATION ON THIS PROJECT, CONTACT:
Robert L. Wershaw
P.O. Box 25046, ms408, Denver Federal Center, Lakewood, CO
Email: rwershaw@usgs.gov

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