The Challenge and Its Solution When Determining Biogeochemically Reactive Inorganic Mercury (RHg): Getting the Analytical Method Right — Oak Academic Publishing
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The Challenge and Its Solution When Determining Biogeochemically Reactive Inorganic Mercury (RHg): Getting the Analytical Method Right
Cebam Analytical, Inc., Bothell, USA
,
Department of Environmental Sciences, J. Stefan Institute, Ljubljana, Slovenia
,
Chevron Energy Technology Company, Richmond, USA
,
Chevron Energy Technology Company, Richmond, USA
,
Department of Environmental Sciences, J. Stefan Institute, Ljubljana, Slovenia
,
Cebam Analytical, Inc., Bothell, USA
1 Cebam Analytical, Inc., Bothell, USA
2 Department of Environmental Sciences, J. Stefan Institute, Ljubljana, Slovenia
3 Chevron Energy Technology Company, Richmond, USA
4 Chevron Energy Technology Company, Richmond, USA
5 Department of Environmental Sciences, J. Stefan Institute, Ljubljana, Slovenia
Biogeochemially reactive inorganic mercury (RHg) is an important fraction of Hg. Researchers have attempted to measure RHg when characterizing Hg-impacted sites, conducting research and development of remediation practices, or evaluating remediation efficiency. In these uses, RHg will be the best choice for analysis in ways that total methyl, and other species of Hg cannot duplicate. The fraction has been inadequately measured using the Sn 2+ reduction method and operationally defined as “Sn 2+ reducible Hg 2+ ”, but the resulting data did not reflect well the nature of the fraction and caused researchers to lose interest, thus limiting the use of RHg in past years. In this work, the problems of using the Sn 2+ reduction method were discovered to be generating irreproducible and negatively biased results. Negative bias from 20 % to 99% was found in different types of waters. To obtain reliable results, an ethylation-based GC-CVAFS method was used to determine RHg. The performance of the method was evaluated by comparing it to the Sn 2+ reduction method. Biogeochemically meaningful results have been obtained in the application of the method to determine RHg in mercury mine-impacted waters from the Idrijca River in Slovenia .
T. W. Clarkson and L. Magos, “The Toxicology of Mercury and Its Chemical Compounds,” Critical Reviews in Toxicology, Vol. 36, No. 8, 2006, pp. 609-662. http://dx.doi.org/10.1080/10408440600845619
T. Barkay and I. Wagner-Dobler, “Microbial Transformations of Mercury: Potentials, Challenges, and Achievements in Controlling Mercury Toxicity in the Environment,” In: A. I. Laskin, J. W. Bennett and G. M. Gadd, Eds., Advances in Applied Microbiology, Vol. 57, Elsevier Academic Press Inc., San Diego, 2005, pp. 1-52.
M. Horvat, J. Snoj Tratnik and A. Miklavcic, “Mercury: Biomarkers of Exposure and Human Biomonitoring,” In: L. E. Knudsen and D. F. Merlo, Eds., Biomarkers and Human Biomonitoring, Issues in Toxicology, No. 9, RSC Publishing, Cambridge, 2012, pp. 381-417.
M. C. Newman, X. Y. Xu, A. Condon and L. Liang, “Floodplain Methylmercury Biomagnification Factor Higher than That of the Contiguous River (South River, Virginia USA),” Environmental Pollution, Vol. 159, No. 10, 2011, pp. 2840-2844. http://dx.doi.org/10.1016/j.envpol.2011.04.045
J. C. Wang, M. C. Newman, X. Y. Xu and L. Liang, “Higher and More Variable Methylmercury Biomagnification Factors for Floodplain Than the Contiguous River (South River, Virginia USA),” Ecotoxicology and Environmental Safety, 2013. http://dx.doi.org/10.1016/j.ecoenv.2012.04.023i
H. Hsu-Kim, K. H. Kucharzyk, T. Zhang and M. A. Deshusses, “Mechanisms Regulating Mercury Bioavailability for Methylating Microorganisms in the Aquatic Environment: A Critical Review,” Environmental Science & Technology, Vol. 47, No. 6, 2013, pp. 2441-2456. http://dx.doi.org/10.1021/es304370g
J. K. Schaefer, S. S. Rocks, W. Zheng, L. Y. Liang, B. H. Gu and F. M. M. Morel, “Active Transport, Substrate Specificity, and Methylation of Hg(II) in Anaerobic Bacteria,” Proceedings of the National Academy of Sciences, Vol. 108, No. 21, 2011, pp. 8714-8719. http://dx.doi.org/10.1073/pnas.1105781108
W. Zheng, L. Y. Liang and B. H. Gu, “Mercury Reduction and Oxidation by Reduced Natural Organic Matter in Anoxic Environments,” Environmental Science & Technology, Vol. 46, No. 1, 2012, pp. 292-299. http://dx.doi.org/10.1021/es203402p
M. E. Hines, J. Faganeli, I. Adatto and M. Horvat, “Microbial Mercury Transformations in Marine, Estuarine and Freshwater Sediment Downstream of the Idrija Mercury Mine,” Applied Geochemistry, Vol. 21, No. 11, 2006, pp. 1924-1939. http://dx.doi.org/10.1016/j.apgeochem.2006.08.008
N. S. Bloom, “Influence of Analytical Conditions on the Observed ‘Reactive Mercury’, Concentrations in Natural Fresh Waters,” In: J. Huckabee and C. J. Watras, Eds., Mercury as a Global Pollutant, Lewis Publishers, Ann Arbor, 1994.
J. D. Dean and R. P. Mason, “Estimation of Mercury Bioaccumulation Potential fromWastewater Treatment Plants in Receiving Waters: Phase II,” Final Report, 2009, 05-WEM-1COa, WERF, Co-published by IWA Publishing.
S. Rapsomanikis, O. F. X. Donard and J. H. Weber, “Speciation of Lead and Methyllead Ions in Water by Chromatography/Atomic Absorption Spectrometry after Ethylation with Sodium Tetraethylborate,” Analytical Chemistry, Vol. 58, No. 1, 1986, pp. 35-38. http://dx.doi.org/10.1021/ac00292a011
N. S. Bloom, “Determination of Pictogram Levels of Methylmercury by Aqueous Phase Ethylation, Followed by Cryogenic Gas Chromatography with Cold Vapor Atomic Fluorescence Detection,” Canadian Journal of Fisheries and Aquatic Sciences, Vol. 46, No. 7, 1989, pp. 1131-1140. http://dx.doi.org/10.1139/f89-147
L. Liang, M. Horvat and N. S. Bloom, “An Improved Speciation Method for Mercury by GC/CVAFS after Aqueous Phase Ethylation and Room Temperature Precollection,” Talanta, Vol. 41, No. 3, 1994, pp. 371-379. http://dx.doi.org/10.1016/0039-9140(94)80141-X
S. Zizek, R. Milaziz, R. Jacimivic, M. J. toman and M. Horvat, “Periphyton as a Bioindicator of Mercury Pollution in a Temperate Torrential River Ecosystem,” Chemosphere, Vol. 85, No. 5, 2011, pp. 883-891. http://dx.doi.org/10.1016/j.chemosphere.2011.06.110
W. R. Hatch and W. L. Ott, “Determination of Sub-Cold Vapour Atomic Absorption Spectrophotometry,” Analytical Chemistry, Vol. 40, No. 14, 1968, pp. 2085-2087. http://dx.doi.org/10.1021/ac50158a025
L. Liang, Bloom and M. Horvat, “Simultaneous Determination of Mercury Speciation in Biological Materials by GC/CVAFS after Ethylation and Room Temperature Precollection,” Clinical Chemistry, Vol. 40, No. 4, 1994, pp. 602-607.
L. Liang, C. Evens, S. Lazoff, J. S. Woods, E. Cernichiari, M. Horvat, M. D. Martin and T. DeRouen, “Determination of Methyl Mercury in Whole Blood by Ethylation-GC-CVAFS after Alkaline Digestion-Solvent Extraction,” Journal of Analytical Toxicology, Vol. 24, No. 5, 2000, pp. 328-332. http://dx.doi.org/10.1093/jat/24.5.328
US EPA Method 1669, “Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Levels,” Washington, DC, 1996.
US EPA 1631, “Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry,” Environmental Protection Agency, Washington, DC, 2002.
US EPA 1630, “Methyl Mercury in Water by Distillation, Aqueous Ethylation,” US Environmental Protection Agency, Washington, DC, 2001.
L. Liang and N. S. Bloom, “Determination of Total Mercury by Single-Stage Gold Amalgamation with Cold Vapor Atomic Spectrometry,” JAAS, Vol. 8, 1993, pp. 591-594.
M. Horvat, “Determination of Mercury and Its Compounds in Water, Sediment, Soil and Biological Samples,” In: N. Pirrone and K. R. Mahaffey, Eds., Dynamics of Mercury Pollution on Regional and Global Scales: Atmospheric Processes and Human Exposures around the World, Springer, New York, 2005, pp. 154-190. http://dx.doi.org/10.1007/0-387-24494-8_8
B. H. Gu, Y. R. Bian, C. L. Miller, W. M. Dong, X. Jiang and L. Y. Liang, “Mercury Reduction and Complexation by Natural Organic Matter in Anoxic Environments,” Proceedings of the National Academy of Sciences, Vol. 108, No. 4, 2011, pp. 1479-1483. http://dx.doi.org/10.1073/pnas.1008747108
W. M. Dong, L. Y. Liang, S. Brooks, G. Southworth and B. H. Gu, “Roles of Dissolved Organic Matter in the Speciation of Mercury and Methylmercury in an Contaminated Ecosystem in Oak Ridge,” Tennessee Environmental, Vol. 7, No. 1, 2010, pp. 94-102.
C. L. Miller, G. Southworth, S. Brooks, L. Y. Liang and B. H. Gu, “Kinetic Controls on the Complexation between Mercury and Dissolved Organic Matter in a Contaminated Environment,” Environmental Science & Technology, 2009, Vol. 43, No. 22, 2009, pp. 8548-8553.
M. Horvat, N. S. Bloom and L. Liang, “A Comparison of Distillation with Other Current Isolation Methods for Determination of Methyl Mercury Compounds in Low Level Environmental Samples, Part 1: Sediment,” Analytica Chimica Acta, Vol. 281, No. 1, 1993, pp. 135-152. http://dx.doi.org/10.1016/0003-2670(93)85348-N
M. Horvat, L. Liang and N. S. Bloom, “A Comparison of Distillation with Other Current Isolation Methods for the Determination of Methyl Mercury Compounds in Low Level Environmental Samples, Part 2: Water,” Analytica Chimica Acta, Vol. 282, No. 1, 1993, pp. 153-168. http://dx.doi.org/10.1016/0003-2670(93)80364-Q
L. Liang, M. Berndt, T. K. Bavin and P. Pang, “Definition and Application of Alkylatable Mercury (AHg) for Estimation of Bioavailable Mercury,” 9th ICMGP, Guiyang, June 7-12, 2009, pp. S19-52.
L. Liang, D. Hwang, L. Young, E. A. Aultman and P. Pang, “The Use of Alkylatable Mercury for Risk Assessment and Remediation Evaluation of Hg Contaminated Water/Soil/Sediment,” 10th ICMGP, Halifax, Nova Scotia, July 24-29, 2011.
K. Matsunaga, S. Konishi and M. Nishimura, “Possible errors Caused Prior to Measurement of Mercury in Natural Waters with Special Reference to Seawater,” Environmental Science & Technology, Vol. 13, No. 1, 1979, pp. 63-70. http://dx.doi.org/10.1021/es60149a013
J. A. Dalziel and P. A. Yeats, “Reactive Mercury in the Central North Atlantic Ocean,” Marine Chemistry, Vol. 15, No. 4, 1985, pp. 357-365. http://dx.doi.org/10.1016/0304-4203(85)90046-5
N. S. Bloom and E. A. Crecelius, “Determination of Mercury in Seawater at Subnanogram per Liter Levels,” Marine Chemistry, Vol. 14, No. 1, 1983, pp. 59-64. http://dx.doi.org/10.1016/0304-4203(83)90069-5
G. A. Gill and W. F. Fitzgerald, “Picomolar Mercury Measurements in Seawater and Other Materials Using Stannous Chloride Reduction and Two Stage Gold Amalgamation with Gas Phase Detection,” Marine Chemistry, Vol. 20, No. 3, 1987, pp. 227-243. http://dx.doi.org/10.1016/0304-4203(87)90074-0
T. Kanduc, D. Kocman and N. Ogrinc, “Hydrogeochemical and Stable Isotope Characteristics of the River Idrijca (Slovenia), the Boundary Watershed between the Adriatic and Black Seas,” Marine Chemistry, Vol. 14, No. 3, 2008, pp. 239-262. http://dx.doi.org/10.1007/s10498-008-9035-2
M. E. Hines, M. Horvat, J. Faganeli, J. C. J. Bonzongo, T. Barkay, E. B. Major, K. J. Scott, E. A. Bailey, J. J. Warwick and W. B. Lyons, “Mercury Biogeochemistry in the Idrija River, Slovenia, from above the Mine into the Gulf of Trieste,” Environmental Research, Vol. 83, No. 2, 2000, pp. 129-139. http://dx.doi.org/10.1006/enrs.2000.4052
M. Horvat, S. Covelli, J. Faganeli, M. Logar, V. Mandic, R. Rajar, A. Sirca and D. Zagar, “Mercury in Contaminated Coastal Environments, a Case Study: The Gulf of Trieste,” Science of The Total Environment, Vol. 237-238, 1999, pp. 43-56. http://dx.doi.org/10.1016/S0048-9697(99)00123-0
M. Horvat, V. Jereb, V. Fajon, M. Logar, J. Kotnik, J. Faganeli, M. E. Hines and J.-C. Bonzongo, “Mercury Distribution in Water, Sediment and Soil in the Idrijca and Soca River Systems,” Geochemistry: Exploration, Environment, Analysis, Vol. 2, No. 3, 2002, pp. 287-296. http://dx.doi.org/10.1144/1467-787302-033
D. Kocman, T. Kanduc, N. Ogrinc and M. Horvat, “Distribution and Partitioning of Mercury in a River Catchment Impacted by Former Mercury Mining Activity,” Biogeochemistry, Vol. 104, No. 1-3, 2011, pp. 183-201. http://dx.doi.org/10.1007/s10533-010-9495-5