An Exploratory Investigation of Polar Organic Compounds in Waters from a Lead–Zinc Mine and Mill Complex
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Surface water samples were collected in 2006 from a lead mine–mill complex in Missouri to investigate possible organic compounds coming from the milling process. Water samples contained relatively high concentrations of dissolved organic carbon (DOC; greater than 20 mg/l) for surface waters but were colorless, implying a lack of naturally occurring aquatic humic or fulvic acids. Samples were extracted by three different types of solid-phase extraction and analyzed by electrospray ionization/mass spectrometry. Because large amounts of xanthate complexation reagents are used in the milling process, techniques were developed to extract and analyze for sodium isopropyl xanthate and sodium ethyl xanthate. Although these xanthate reagents were not found, trace amounts of the degradates, isopropyl xanthyl thiosulfonate and isopropyl xanthyl sulfonate, were found in most locations sampled, including the tailings pond downstream. Dioctyl sulfosuccinate, a surfactant and process filtering aid, was found at concentrations estimated at 350 μg/l at one mill outlet, but not downstream. Release of these organic compounds downstream from lead–zinc mine and milling areas has not previously been reported. A majority of the DOC remains unidentified.
KeywordsLead mine Tailings Organic compounds Xanthates Mass spectrometry
- Brumbaugh, W. G., May, T. W., Besser, J. M., Allert, A. L., & Schmitt, C. J. (2007). Assessment of elemental concentrations in streams of the New Lead Belt in southeastern Missouri, 2002–05. US Geological Survey Scientific Investigations Report 2007−5057. Washington, DC: US Geological Survey. 57 pp.Google Scholar
- Brumbaugh, W. G., Schmitt, C. J., & May, T. W. (2005). Concentrations of cadmium, lead, and zinc in fish from mining-influenced waters of Northeastern Oklahoma—Sampling of blood, carcass, and liver for aquatic biomonitoring. Archives of Environmental Contamination and Toxicology, 49, 76–88.CrossRefGoogle Scholar
- Cole, R. B. (1997). Electrospray ionization mass spectrometry—Fundamentals, instrumentation, and applications. New York: Wiley-Interscience.Google Scholar
- Doe Run Company (2003). Primary mining and smelting division, 2002 annual report to our community, Missouri. http://www.doerun.com/uploadfile/2002_Primary.pdf. Accessed May 2006.
- Goldhaber, M. B., Church, S. E., Doe, B. R., Aleinikoff, J. N., Brannon, J. C., Podosek, F. A., et al. (1995). Lead and sulfur isotope investigations of Paleozoic sedimentary rocks from the southern Midcontinent of the United States—Implications for paleohydrology and ore genesis of the southeastern Missouri lead belts. Economic Geology, 90(7), 1875–1910.CrossRefGoogle Scholar
- Imes, J. L. (2002). Geohydrological and biological investigations associated with a new lead–zinc exploration area near Winona, Missouri, and the Viburnum Trend of southeastern Missouri US Geological Survey Fact Sheet FS 0005-02. Washington, DC: US Geological Survey.Google Scholar
- Jennett, J. C., & Callier, A. J. (1977). Trace organic emissions from lead mining–milling operations. Journal of the Water Pollution Control Federation, 49, 469–488.Google Scholar
- Leenheer, J. A., Croue, J.-P., Benjamin, M., Korshin, G. V., Hwang, C. J., Bruchet, A., et al. (2000). Comprehensive isolation of natural organic matter for spectral characterization and reactivity testing. In S. Barrett, S. W. Krasner, & G. L. Amy (Eds.), Natural organic matter and disinfection by-products—Characterization and control in drinking water (American Chemical Society Symposium Series, Vol. 761, pp. 68–83). Washington, DC: American Chemical Society.CrossRefGoogle Scholar
- Leenheer, J. A., Ferrer, I., Furlong, E. T., & Rostad, C. E. (2002). Charge characteristics and fragmentation of polycarboxylic acids by electrospray ionization, multiple tandem mass spectrometry (ESI/MS/MS). Preprints of extended abstracts, 223rd National Meeting of American Chemical Society, Orlando, FL, USA, April 7–11, 2002, vol. 42(1), pp 365–369.Google Scholar
- Rostad, C. E., & Leenheer, J. A. (2002a). Molecular weight distributions of fractions of dissolved organic carbon by electrospray ionization/mass spectrometry, new analytical techniques for dissolved organic matter symposium. Preprints of extended abstracts, 223rd National Meeting of American Chemical Society, Orlando, Florida, April 7–11, 2002, vol. 42(1), pp 509–512.Google Scholar
- Rostad, C. E., & Leenheer, J. A. (2002b). Molecular weight distributions of Suwannee River fulvic acid by electrospray ionization/mass spectrometry, new analytical techniques for dissolved organic matter symposium. Preprints of extended abstracts, 223rd National Meeting of American Chemical Society, Orlando, Florida, April 7–11, 2002, vol. 42(1), pp 492–495.Google Scholar
- Rostad, C. E., & Leenheer, J. A. (2005). Factors that affect molecular weight distribution of fulvic acids as determined by electrospray ionization/mass spectrometry. Advanced Characterization of Natural Organic Matter Symposium, Division of Geochemistry, American Chemical Society, 230th National Meeting, Washington, DC, August 28–September 1.Google Scholar
- Schmitt, C. J., Brumbaugh, W. G., May, T. W., & Besser, J. M. (2007b). Concentrations of metals in aquatic invertebrates from the Ozark National Scenic Riverways, Missouri. US Geological Survey Open-File Report 2007-1435. Washington, DC: US Geological Survey. 23 pp.Google Scholar
- Schmitt, C. J., Wildhaber, M. L., Hunn, J. B., Nash, T., Tieger, M. N., & Steadman, B. L. (1993). Biomonitoring of lead-contaminated Missouri streams with an assay for erythrocyte d-aminolevulinic acid dehydratase activity in fish blood. Archives of Environmental Contamination and Toxicology, 25, 464–475.CrossRefGoogle Scholar
- Silvester, E., & Hao, F. P. (2002). Environmental fate of flotation collectors in mineral processing operations—Ethyl xanthate as an example. Green Processing 2002—Proceedings: International Conference on the Sustainable Processing of Minerals, Cairns, Queensland, Australia, pp 259–263.Google Scholar
- Suffet, I. H., & MacCarthy, P. (1989). Aquatic humic substances: Influence on fate, and treatment of pollutants (Advances in Chemistry Series, Vol. 219). Washington, DC: American Chemical Society.Google Scholar
- US Environmental Protection Agency. (1994). Technical resource document, extraction and beneficiation of ores and minerals, Volume 1: Lead–zinc, EPA 530-R-94-011, NTIS PB94-170248 (p. 127). Washington, DC: US Environmental Protection Agency.Google Scholar
- US Food and Drug Administration. (2007). Code of Federal Regulations. Title 21, Volume 3, Revised as of April 1, 2007. 21CFR177.2800, http://www.accessdata.fda.gov/scripts/cdrh/cfdocs/cfCFR/CFRSearch.cfm?fr=177.2800. Accessed 20 March 2008.
- US Geological Survey. (2004a). Columbia Environmental Research Center, semipermeable membrane device (SPMD), description and application. www.cerc.usgs.gov/pubs/center/pdfDocs/SPMD.pdf. Accessed May 2010.
- US Geological Survey. (2004b). Columbia Environmental Research Center, polar organic chemical integrative samplers (POCIS), description and application. www.cerc.usgs.gov/pubs/center/pdfDocs/POCIS.pdf. Accessed May 2010.
- Waters Corporation. (2003). Oasis application handbook. Milford: Waters Corporation. 195 pp.Google Scholar
- Wixson, B. G. (Ed.). (1977). The Missouri lead study—An interdisciplinary investigation of environmental pollution by lead and other heavy metals from industrial development in the New Lead Belt of southeastern Missouri. Final report to the National Science Foundation (Volume 1), University of Missouri–Rolla, MO.Google Scholar