Ultratrace Speciation and Biogenesis of Methyltin Transport Species in Estuarine Waters

  • F. E. Brinckman
  • J. A. Jackson
  • W. R. Blair
  • G. J. Olson
  • W. P. Iverson
Part of the NATO Conference Series book series (NATOCS, volume 9)


Environmental tin, widely dispersed at low concentrations in waters, sediments, and biota, is shown to be a bioactive element susceptible to methylation and even hydridization by marine bacteria. The redox cycle of tin in natural waters is poorly understood and recent advances in tin-specific molecular characterization fail to speciate Sn(II) and Sn(IV) reliably. Nonetheless, such rapid developments in speciation methodology now permit growing numbers of studies of organotin distributions in aquatic systems, raising the question of the “natural” biogeochemical flux of methylstannanes in relation to increased anthropogenic organo-tin influx from industry and shipping. New methods for direct speciation of aquated or involatile organotins by liquid chromatography are compared with advances in purge-and-trap sampling of volatile or hydrophobic organotins speciated by gas chromatography. The work in our laboratory indicates that effective models for estuarine formation and transport may ultimately be developed, but that basic roadblocks to progress stem from inadequate descriptive aqueous organometallic chemistry and knowledge of critical kinetic parameters for the lifetimes of key organotin species in sea water, occurring at sub-nanomolar concentrations.


Estuarine Water Antifouling Paint Flame Photometric Detector Calibration Slope Baltimore Harbor 
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  1. 1.
    Smith, J.D. and J.D. Barton, 1972: The occurrence and distribution of tin with particular reference to marine environments. Geochim. Cosmochim. Acta., 36, 621–629.CrossRefGoogle Scholar
  2. 2.
    Hellas, L.E., 1981: Ph.D. Dissertation, University of Maryland.Google Scholar
  3. 3.
    Helz, G.R., 1976: Trace element inventory for the northern Chesapeake Bay with emphasis on the influence of man. Geochim. Cosmochim. Acta., 40, 573–580.CrossRefGoogle Scholar
  4. 4.
    Craig, P.J., 1980: The feasibility of environmental methylation for tin - An assessment. Environ. Technol. Lett., 1, 225–234.CrossRefGoogle Scholar
  5. 5.
    Brinckman, F.E., 1981: Environmental organotin chemistry today: Experiences in the field and laboratory. J. Organometal. Chem. Library, 12, 343–376.Google Scholar
  6. 6.
    Huey, C., F.E. Brinckman, S. Grim and W.P. Iverson, 1974: The role of tin in bacterial methylation of mercury. In: “Proc. Internat. Conf. on Transport of Persistent Chemicals in Aquatic Ecosystems”, A.S.W. deFreitas, D.J. Kushner and S.U. Quadri, eds. National Research Council, Ottawa, 1173–1178.Google Scholar
  7. 7.
    Chau, Y.K., 1980: Biological methylation of tin compounds in the aquatic environment. 3rd Internat. Conf. Organo-metal. Coordinat. Chem. Germanium, Tin, Lead, Univ. Dortmund, West Germany, July, 1980. 30 pp.Google Scholar
  8. 8.
    Guard, H.E., A.B. Cobet and W.M. Coleman, 1981: Methylation of trimethyltin compounds by estuarine sediments. Science, 213, 770–771.Google Scholar
  9. 9.
    Hallas, L.E., J.C. Means and J.J. Cooney, 1982: Microbial transformations of tin by estuarine microorganisms. Science, 213, 1505–1506.Google Scholar
  10. 10.
    Braman, R.S. and M.A. Tompkins, 1979: Separation and determination of nanogram amounts of inorganic tin and methyltin compounds in the environment. Anal. Chem., 51, 12–19.CrossRefGoogle Scholar
  11. 11.
    Hodge, V.F., S.L. Seidel and E.D. Goldberg, 1979: Determination of tin(IV) and organotin compounds in natural waters, coastal sediments, and macro algae by atomic absorption spectrometry. Anal. Chem., 51, 1256–1259.CrossRefGoogle Scholar
  12. 12.
    Jackson, J.A., W.R. Blair, F.E. Brinckman and W.P. Iverson, 1982: Gas chromatographic speciation of methylstannanes in the Chesapeake Bay using purge and trap sampling with a tin-selective detector. Environ. Sci. Technol., 16, 110–119.CrossRefGoogle Scholar
  13. 13.
    Zuckerman, J.J., R.P. Reisdorf, H.V. Ellis and R.R. Wilkinson, 1978: Organotins in biology and the environment. In: “Organometals and Organometalloids: Occurence and fate in the environment”, F.E. Brinckman and J.M. Ballama, eds. American Chemical Society, Washington, D.C., 388–422.Google Scholar
  14. 14.
    Ridley, W.P., L.J. Dizikes and J.M. Wood, 1977: Biomethylation of toxic elements in the environment. Science, 197, 329–332.Google Scholar
  15. 15.
    Wood, J.M., H.J. Segall, W.P. Ridley, A. Cheh, W. Chudyk and J.S. Thayer, 1977: Metabolic cycles for toxic elements in the environment. In: “Proc. Internat. Conf. on Heavy Metals in the Environment”, T.C. Hutchinson, ed. University of Toronto, Toronto, 49–68.Google Scholar
  16. 16.
    Lantzy, R.J. and F.T. Mackenzie, 1979: Atmospheric trace metals: Global cycles and assessment of man’s impact. Geochim. Cosmochim. Acta., 43, 511–525.Google Scholar
  17. 17.
    Von Loon, J.C., 1979: Metal speciation by chromatography/atomic spectrometry. Anal. Chem., 51, 1139A–1150A.Google Scholar
  18. 18.
    Furr, A.K., A.W. Lawrence, S.S.C. Tong, M.C. Grandolfo, R.A. Hofstader, C.A. Bache, W.H. Gutenmann and D.J. Lisk, 1976: Multielement and chlorinated hydrocarbon analysis of municipal sewage sludges of American cities. Environ. Sci. Technol., 10, 683–687.Google Scholar
  19. 19.
    Brezonik, P.L., 1974: Analysis and speciation of trace metals in water supplies. In: “Aqueous-environmental Chemistry of Metals”, A.J. Rubin, ed. Ann Arbor Science, Ann Arbor, 167–191.Google Scholar
  20. 20.
    Nichols, M.: Virginia Inst. Marine Sci., personal communication.Google Scholar
  21. 21.
    Villa, O. and P.G. Johnson, 1974: Distribution of metals in Baltimore Harbor sediments. Annapolis Field Office Tech. Report 59, U.S. Environmental Protection Agency, Washington, D.C.Google Scholar
  22. 22.
    Harris, R., M. Nichols and G. Thompson, 1979: heavy metal inventory of suspended sediment and fluid mud in Chesapeake Bay. Special Sci. Report 99, Virginia Inst. Marine Sci., Gloucester Point, Virginia.Google Scholar
  23. 23.
    Sigleo, A.C., G.R. Helz and W.H. Zoller, 1980: Organic-rich colloidal material in estuaries and its alteration by chlorination. Environ. Sci. Technol., 14, 673–679.Google Scholar
  24. 24.
    Beck, R.A. and J.J. Brink, 1978: Production of cobalamins during activated sewage sludge treatment. Environ. Sci. Technol., 12, 435–438.Google Scholar
  25. 25.
    Dodd, D. and M.D. Johnson, 1973: The organic compounds of cobalt(III). Organometal. Chem. Rev., 52, 1–232.Google Scholar
  26. 26.
    Thayer, J.S. and F.E. Brinckman, 1982: The biological methylation of metals and metalloids. In: “Advances in Organometallic Chemistry”, F.G.A. Stone and R. West, eds. Vol. 20, Academic Press, Inc., New York, 313–356.Google Scholar
  27. 27.
    Daniels, S.L., 1980: Mechanisms involved in sorption of microorganisms to solid surfaces. In: “Adsorption of Microorganisms to Surfaces”, G. Bitton and K.C. Marshall, eds. Wiley-Interscience, New York, 7–58.Google Scholar
  28. 28.
    Piotrowicz, S.R., B.J. Ray, G.L. Hoffman and R.A. Duce, 1972: Trace metal enrichment in the sea-surface microlayer. J. Geophys. Res., 77, 5243–5254.Google Scholar
  29. 29.
    Smith, P.J., 1978: Toxicological data on organotin compounds. Internat. Tin Res. Inst., London, 16 pp.Google Scholar
  30. 30.
    Jernelöv, A. and A. Martin, 1975: Ecological implications of metal metabolism by microorganisms. Ann. Rev. Microbiol., 29, 61–77.Google Scholar
  31. 31.
    Spangler, W.J., J.L. Spigarelli, J.M. Rose, R.S. Flippen and H.H. Miller, 1973: Degradation of methylmercury by bacteria isolated from environmental samples. Appl. Microbiol., 25, 488–493.Google Scholar
  32. 32.
    Jewett, K.L., F.E. Brinckman and J.M. Bellama, 1978: Influence of environmental parameters on transmethylation between aquated metal ions. In: “Organometals and Organometalloids: Occurrence and Fate in the Environment”, F.E. Brinckman and J.M. Bellama, eds. American Chem. Soc., Washington, D.C., 158–187.Google Scholar
  33. 33.
    Goldberg, E.D., 1965: In: “Chemical Oceanography”, J.P. Riley and G. Skirrow, eds. Academic Press, London; E.D. Goldberg, 1963: In: “The Sea”, M.N. Hills, ed. Wiley-Interscience, New York.Google Scholar
  34. 34.
    Cheng, C.N. and D.D. Focht, 1979: Production of arsine and methylarsines in soil and in culture. Appl. Environ. Microbiol., 38, 494–498.Google Scholar
  35. 35.
    Nelson, J.D. and R.R. Colwell, 1975: The ecology of mercury-resistant bacteria in the Chesapeake Bay. Microbiol. Ecol., 1, 191–218.Google Scholar
  36. 36.
    Brinckman, F.E. and W.P. Iverson, 1975: Chemical and bacterial cycling of heavy metals in the estuarine system. In: “Marine Chemistry in the Coastal Environment”, T.M. Church, ed. American Chem. Soc., Washington, D.C., 319–342.Google Scholar
  37. 37.
    Brinckman, F.E., G.E. Parris, W.R. Blair, K.L. Jewett, W.P. Iverson and J.M. Bellama, 1977: Questions concerning environmental mobility of arsenic: Needs for a chemical data base and means for speciation of trace organo-arsenicals. Environ. Health Perspectives, 19, 11–24.Google Scholar
  38. 38.
    Parris, G.E. and F.E. Brinckman, unpublished results.Google Scholar
  39. 39.
    Ahmad, I., Y.K. Chau, P.T.S. Wong, A.J. Carty and L. Taylor, 1980: Chemical alkylation of lead(II) salts to tetraalkyllead(IV) in aqueous solution. Nature, 287, 715–717.Google Scholar
  40. 40.
    Parris, G.E. and F.E. Brinckman, 1975: Reactions which relate to the environmental mobility of arsenic and antimony. I. Quaternization of trimethylarsine and trimethylstibine. J. Org. Chem., 40, 3801–3803.CrossRefGoogle Scholar
  41. 41.
    Akagi, H. and E. Takabatake, 1973: Photochemical formation of methylmercuric compounds from mercuric acetate. Chemosphere, 2, 131–133.Google Scholar
  42. 42.
    Jewett, K.L., 1978: Ph.D. Dissertation, University of Maryland.Google Scholar
  43. 43.
    Clinton, N.A. and J.K. Kochi, 1973: Alkylation as a route to reduction of copper(II) by tetraalkyllead. J. Organo-metal Chem., 56, 243–254.Google Scholar
  44. 44.
    Lovelock, J.E., 1975: Natural halocarbons in the air and in the sea. Nature, 256, 193–194.Google Scholar
  45. 45.
    Dulka, J.J. and T.H. Risby, 1976: Ultratrace metals in some environmental and biological systems. Anal. Chem., 48, 640A–653A.Google Scholar
  46. 46.
    Michael, L.C., M.D. Erickson, S.P. Parks and E.D. Pellizzari, 1980: Volatile environmental pollutants in biological matrices with a headspace purge technique. Anal. Chem., 52, 1836–1841.Google Scholar
  47. 47.
    Aue, W.A. and C.G. Flinn, 1977: A photometric tin detector for gas chromatography. J. Chromatogr., 142, 145–154.Google Scholar
  48. 48.
    Snyder, L.R. and J.J. Kirkland, 1979: “Introduction to Modern Liquid Chromatography”, 2nd Ed., Wiley & Sons, New York.Google Scholar
  49. 49.
    Jewett, K.L. and F.E. Brinckman, 1981: Speciation of trace di- and triorganotins in water by ion exchange H PLCGFAA. J. Chrmoatogr. Sci., 19, 583–593.Google Scholar
  50. 50.
    Brinckman, F.E., W.R. Blair, K.L. Jewett and W.P. Iverson, 1977: Application of a liquid chromatograph coupled with a flameless atomic absorption detector for speciation of trace organometallic compounds. J. Chromatogr. Sci., 15, 493–503.Google Scholar
  51. 51.
    Parris, G.E., W.R. Blair and F.E. Brinckman, 1977: Chemical and physical considerations in the use of atomic absorption detectors coupled with a gas chromatograph for determination of trace organometallic gases. Anal. Chem., 49, 378–386.Google Scholar
  52. 52.
    Pourbaix, M., 1966: “Atlas of Electrochemical Equilibria”. Pergamon Press, New York.Google Scholar
  53. 53.
    Sillén, L.G., 1961: The physical chemistry of sea water. In: “Oceanography”, M. Sears, ed. Amer. Assoc, Adv. Sci., Washington, D.C.Google Scholar
  54. 54.
    Johnson, D.L., 1972: Bacterial reduction of arsenate in sea water. Nature, 240, 44–45.Google Scholar
  55. 55.
    Andreae, M.O., 1979: Arsenic speciation in sea water and interstitial waters: The influence of biological-chemical interactions on the chemistry of a trace element. Limnol. Oceanogr., 24, 440–452.Google Scholar
  56. 56.
    Tallman, D.E. and A.U. Shaikh, 1980: Redox stability of inorganic arsenic(III) and arsenic(V) in aqueous solution. Anal. Chem., 52, 196–199.Google Scholar
  57. 57.
    Schaeffer, G.W. and M. Emilius, 1954: The preparation of stannane. J. Amer. Chem. Soc., 76, 1203–1204.Google Scholar
  58. 58.
    Jolly, W.L. and J.E. Drake, 1963: Hydrides of germanium, tin, arsenic, and antimony. Inorg. Synth., 7, 34–44.Google Scholar
  59. 59.
    Evans, W.H., F.J. Jackson and D. Deller, 1979: Evaluation of a method for determination of total antimony, arsenic, and tin in foodstuffs using measurement by atomic-absorption spectrophotometry with atomization in a silica tube using the hydride generation technique. Analyst, 104, 16–34.Google Scholar
  60. 60.
    Hallas, L.E. and J.J. Cooney, 1981: Tin and tin-resistant microorganisms in Chesapeake Bay. Appl. Environ. Microbiol., 41, 466–471.Google Scholar
  61. 61.
    Young, D.R., G.V. Alexander and D. McDermott-Ehrlich, 1979: Vessel related contamination of Southern California harbors by copper and other trace metals. Mar. Pollut. Bull., 10, 50–56.Google Scholar
  62. 62.
    Berk, S.G. and R.R. Colwell, 1981: Transfer of mercury through a marine microbial food web. J. Exp. Mar. Biol. Ecol., 52, 157–172.CrossRefGoogle Scholar
  63. 63.
    Blair, W.R., C.J. Olson, F.E. Brinckman and W.P. Iverson, 1982: Uptake and fate of tributyltin cation in estuarine bacteria. Microbial. Ecol., submitted.Google Scholar
  64. 64.
    Craig, P.J., 1980: Metal cycles and biological methylation. In: “The Handbook of Environmental Chemistry”, Vol. 1, Part A., O. Hutzinger, ed. Springer-Verlag, New York, 169–227.Google Scholar
  65. 65.
    Williams, R.J.P., 1980: On first looking into nature’s chemistry. Part I. The role of small molecules and ions: The transport of the elements. Chem. Soc. Rev., 9, 281–364.CrossRefGoogle Scholar
  66. 66.
    Jensen, F.R. and B. Rickborn, 1968: “Electrophilic Substitution of Organomercurials”, McGraw-Hill Book Co., New York.Google Scholar

Copyright information

© Springer Science+Business Media New York 1983

Authors and Affiliations

  • F. E. Brinckman
    • 1
  • J. A. Jackson
    • 1
  • W. R. Blair
    • 1
  • G. J. Olson
    • 1
  • W. P. Iverson
    • 1
  1. 1.Chemical and Biodegradation Processes GroupNational Bureau of StandardsUSA

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