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Distribution and partitioning of mercury in a river catchment impacted by former mercury mining activity

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Abstract

Mercury distribution and partitioning was studied in the River Idrijca system, draining the area of the former Idrija mercury mine, Slovenia. Mercury dynamics were assessed by speciation analysis of mercury in water and river bed sediment samples during a 2-year study at locations on the River Idrijca and its major tributaries. Simultaneously, the influence of some major physico-chemical parameters that influence the fate of mercury in the aquatic environment was investigated. The distribution of mercury species in the River Idrijca catchment indicated contamination from mine tailings distributed in the town of Idrija and erosion of contaminated soils. The partitioning between dissolved and particulate mercury phases in river water was found to be mostly controlled by the variable content of suspended solids resulting from changing hydrological conditions and complexation with various ligands present in river water, among which dissolved organic carbon (DOC) seems to be the most important. Overall results indicate that mercury is transported downstream from the mining area mainly as finely suspended material including colloids rather than in the dissolved phase. This riverine transport occurs mostly during short, but extreme hydro-meteorological conditions when remobilization of mercury from the river bed sediments occurs. A significant part of the mercury particulate phase in water corresponds to cinnabar particles. During its transport, important Hg transformation mechanisms that increase the risk of mercury uptake by biota take place, evidenced by the increase in the relative contribution of reactive mercury (HgR), dissolved gaseous mercury (DGM) and monomethylmercury (MeHg) downstream from the Idrija mine. However, our data revealed relatively low methylation efficiency in this contaminated river system. We attribute this to the site specific physico-chemical conditions responsible for making inorganic mercury unavailable and limiting the capacity of methylating bacteria.

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References

  • Babiarz CL, Hoffmann SR, Shafer MM, Hurley JP, Andren AW, Armstrong DE (2000) A critical evaluation of tangential-flow ultrafiltration for trace metal studies in freshwater systems. 2. Total mercury and methylmercury. Environ Sci Technol 34:3428–3434

    Article  Google Scholar 

  • Barkay T, Wagner-Döbler I, Allen I, Laskin JWB, Geoffrey MG (2005) Microbial transformations of mercury: potentials, challenges, and achievements in controlling mercury toxicity in the environment. Adv Appl Microbiol 57:1–52

    Article  Google Scholar 

  • Berzas Nevado JJ, Rodríguez Martín-Doimeadios RC, Moreno MJ (2009) Mercury speciation in the Valdeazogues River-La Serena reservoir system: influence of Almadén (Spain) historic mining activities. Sci Total Environ 407:2372–2382

    Article  Google Scholar 

  • Biester H, Gosar M, Covelli S (2000) Mercury speciation in sediments affected by dumped mining residues in the drainage area of the Idrija mercury mine, Slovenia. Environ Sci Technol 34:3330–3336

    Article  Google Scholar 

  • Bonzongo JC, Lyons WB, Hines ME, Warwick JJ, Faganeli J, Horvat M, Lechler PJ, Miller JR (2002) Mercury in surface waters of three mine-dominated river systems: Idrija River, Slovenia; Carson River, Nevada; and Madeira River, Brazilian Amazon. Geochem Explor Environ Anal 2:111–119

    Article  Google Scholar 

  • Boszke L, Glosinska G, Siepak J (2002) Some aspects of speciation of mercury in a water environment. Pol J Environ Stud 11:285–295

    Google Scholar 

  • Boszke L, Kowalski A, Gosiska G, Szarek R, Siepak J (2003) Environmental factors affecting the speciation of mercury in the bottom sediments; an overview. Pol J Environ Stud 12:5–13

    Google Scholar 

  • Cardona-Marek T, Schaefer J, Ellickson K, Barkay T, Reinfelder JR (2007) Mercury speciation, reactivity, and bioavailability in a highly contaminated estuary, Berrys Creek, New Yersey Meadowlands. Environ Sci Technol 41:8268–8274

    Article  Google Scholar 

  • Dizdarevič T (2001) The influence of mercury production in Idrija mine on the environment in the Idrija region and over a broad area. RMZ—Mater Geoenviron 48:56–64

    Google Scholar 

  • Dong W, Liang L, Brooks S, Southworth G, Gu B (2010) Roles of dissolved organic matter in the speciation of mercury and methylmercury in a contaminated ecosystem in Oak Ridge, Tennessee. Environ Chem 7:94–102

    Article  Google Scholar 

  • Faganeli J, Horvat M, Covelli S, Fajon V, Logar M, Lipej L, Čermelj B (2003) Mercury and methylmercury in the Gulf of Trieste (Northern Adriatic Sea). Sci Total Environ 304:315–326

    Article  Google Scholar 

  • Foucher D, Ogrinc N, Hintelmann H (2009) Tracing mercury contamination from the Idrija mining region (Slovenia) to the Gulf of Trieste using Hg isotope ratio measurements. Environ Sci Technol 43:33–39

    Article  Google Scholar 

  • Ganguli PM, Mason RP, Abu-Saba KE, Anderson RS, Flegal AR (2000) Mercury speciation in drainage from the New Idria mercury mine, California. Environ Sci Technol 34:4773–4779

    Article  Google Scholar 

  • Gilmour C, Riedel GS, Ederington MC, Bell JT, Benoit JM, Gill GA, Stordal MC (1998) Methylmercury concentrations and production rates across a trophic gradient in the northern Everglades. Biogeochemistry 40:327–345

    Article  Google Scholar 

  • Gnamuš A, Byrne AR, Horvat M (2000) Mercury in the soil–plant–deer–predator food chain of a temperate forest in Slovenia. Environ Sci Technol 34:3337–3345

    Article  Google Scholar 

  • Gosar M, Pirc S, Bidovec M (1997) Mercury in the Idrijca River sediments as a reflection of mining and smelting activities of the Idrija mercury mine. J Geochem Explor 58:125–131

    Article  Google Scholar 

  • Gosar M, Šajn R, Biester H (2006) Binding of mercury in soils and attic dust in the Idrija mercury mine area (Slovenia). Sci Total Environ 369:150–162

    Article  Google Scholar 

  • Gray JE, Theodorakos PM, Bailey EA, Turner RR (2000) Distribution, speciation, and transport of mercury in stream-sediment, stream-water, and fish collected near abandoned mercury mines in southwestern Alaska, USA. Sci Total Environ 260:21–33

    Article  Google Scholar 

  • Hines ME, Horvat M, Faganeli J, Bonzongo JC, Barkay T, Major EB, Scott KJ, Bailey EA, Warwick JJ, Lyons WB (2000) Mercury biogeochemistry in the Idrija River, Slovenia, from above the mine into the Gulf of Trieste. Environ Res 83:129–139

    Article  Google Scholar 

  • Hines ME, Faganeli J, Adatto I, Horvat M (2006) Microbial mercury transformations in marine, estuarine and freshwater sediment downstream of the Idrija mercury mine, Slovenia. Appl Geochem 21:1924–1939

    Article  Google Scholar 

  • Hissler C, Probst JL (2006) Chlor-alkali industrial contamination and riverine transport of mercury: distribution and partitioning of mercury between water, suspended matter, and bottom sediment of the Thur River, France. Appl Geochem 21:1837–1854

    Article  Google Scholar 

  • Hissler C, Probst JL, Mortatti J (2006) Annual inorganic mercury speciation in river water disturbed by chlor-alkali effluents: role and competition of ligands (Cl, Br, DOC). Geochim Bras 20:133–147

    Google Scholar 

  • Horvat M, Zvonarič T, Stegnar P (1987) Determination of mercury in seawater by cold vapour atomic absorption spectroscopy. Acta Adria 28:59–63

    Google Scholar 

  • Horvat M, Lupšina V, Pihlar B (1991) Determination of total mercury in coal fly ash by gold amalgamation cold vapour atomic absorption spectrometry. Anal Chim Acta 24:71–79

    Article  Google Scholar 

  • Horvat M, Liang L, Bloom NS (1993) Comparison of distillation with other current isolation methods for the determination of methyl mercury compounds in low level environmental samples. Part II. Water Anal Chim Acta 282:153–168

    Article  Google Scholar 

  • Horvat M, Covelli S, Faganeli J, Logar M, Mandič V, Rajar R, Širca A, Žagar D (1999) Mercury in contaminated coastal environments; a case study: the Gulf of Trieste. Sci Total Environ 237–238:43–56

    Article  Google Scholar 

  • Horvat M, Jereb V, Fajon V, Logar M, Kotnik J, Faganeli J, Hines ME, Bonzongo JC (2002) Mercury distribution in water, sediment and soil in the Idrijca and Soča River systems. Geochem Explor Environ Anal 2:287–296

    Article  Google Scholar 

  • Horvat M, Kotnik J, Logar M, Fajon V, Zvonarič T, Pirrone N (2003) Speciation of mercury in surface and deep-sea waters in the Mediterranean Sea. Atmos Environ 37:93–108

    Article  Google Scholar 

  • Kanduč T, Kocman D, Ogrinc N (2008) Hydrogeochemical and stable isotope characteristics of the River Idrijca (Slovenia), the boundary watershed between the Adriatic and Black Seas. Aquat Geochem 14:239–262

    Article  Google Scholar 

  • Kim CS, Rytuba JJ, Brown GE (2004) EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides: II. Effects of chloride and sulfate. J Colloid Interf Sci 270:9–20

    Article  Google Scholar 

  • Kobal AB, Horvat M, Prezelj M, Sešek-Briški A, Krsnik M, Dizdarevič T, Mazej D, Falnoga I, Stibilj V, Arnerič N, Kobal D, Osredkar J (2004) The impact of long-term past exposure to elemental mercury on antioxidative capacity and lipid peroxidation in mercury miners. J Trace Elem Med Bio 17:261–274

    Article  Google Scholar 

  • Kobal AB, Prezelj M, Horvat M, Krsnik M, Gibičar D, Osredkar J (2008) Glutathione level after long-term occupational elemental mercury exposure. Environ Res 107:115–123

    Article  Google Scholar 

  • Kocman D, Horvat M, Kotnik J (2004) Mercury fractionation in contaminated soils from the Idrija mercury mine region. J Environ Monit 6:696–703

    Article  Google Scholar 

  • Kotnik J, Horvat M, Dizdarevič T (2005) Current and past mercury distribution in air over the Idrija Hg mine region, Slovenia. Atmos Environ 39:7570–7579

    Article  Google Scholar 

  • Kotnik J, Horvat M, Tessier E, Ogrinc N, Monperrus M, Amouroux D, Fajon V, Gibičar D, Žižek S, Sprovieri F, Pirrone N (2007) Mercury speciation in surface and deep waters of the Mediterranean Sea. Mar Chem 107:13–30

    Article  Google Scholar 

  • Lamborg CH, Tseng CM, Fitzgerald WF, Balcom PH, Hammerschmidt CR (2003) Determination of the mercury complexation characteristics of dissolved organic matter in natural waters with reducible Hg titrations. Environ Sci Technol 37:3316–3322

    Article  Google Scholar 

  • Liang L, Horvat M, Bloom NS (1994) An improved method for speciation of mercury by aqueous phase ethylation, room temperature precollection, GC separation and CVAFS detection. Talanta 41:371–379

    Article  Google Scholar 

  • Liang L, Horvat M, Cernichiari E, Gelein B, Balogh S (1996) Simple solvent extraction technique for elimination of matrix interferences in the determination of methylmercury in environmental and biological samples by ethylation-gas chromatography-cold vapor atomic fluorescence spectrometry. Talanta 43:1883–1888

    Article  Google Scholar 

  • Morel FMM, Kraepiel AML, Amyot M (1998) The chemical cycle and bioaccumulation of mercury. Annu Rev Ecol Syst 29:543–566

    Article  Google Scholar 

  • O’Driscoll NJ, Beauchamp S, Siciliano SD, Rencz AN, Lean DRS (2003) Continuous analysis of dissolved gaseous mercury (DGM) and mercury flux in two freshwater lakes in Kejimkujik Park, Nova Scotia: evaluating mercury flux models with quantitative data. Environ Sci Technol 37:2226–2235

    Article  Google Scholar 

  • Peckenham JM, Kahl JS, Mower B (2003) Background mercury concentrations in river water in Maine, U.S.A. Environ Monit Assess 89:129–152

    Article  Google Scholar 

  • Ping L, Feng X, Shang L, Qiu G, Meng B, Liang P, Zhang H (2008) Mercury pollution from artisanal mercury mining in Tongren, Guizhou, China. Appl Geochem 23:2055–2064

    Article  Google Scholar 

  • Rajar R, Žagar D, Širca A, Horvat M (2000) Three-dimensional modelling of mercury cycling in the Gulf of Trieste. Sci Total Environ 260:109–123

    Article  Google Scholar 

  • Ravichandran M (2004) Interactions between mercury and dissolved organic matter—a review. Chemosphere 55:319–331

    Article  Google Scholar 

  • Roy S, Gaillardet J, Allègre CJ (1999) Geochemistry of dissolved and suspended loads of the Seine River, France: anthropogenic impact, carbonate and silicate weathering. Geochim Cosmochim Acta 63:1277–1292

    Article  Google Scholar 

  • Schuster E (1991) The behavior of mercury in the soil with special emphasis on complexation and adsorption processes—a review of the literature. Water Air Soil Pollut 56:667–680

    Article  Google Scholar 

  • Shu T (1998) Spatial and temporal variation in DOC in the Yichun River, China. Water Res 32:2205–2210

    Article  Google Scholar 

  • Ullrich SM, Tanton TW, Abdrashitova SA (2001) Mercury in the aquatic environment: a review of factors affecting methylation. Crit Rev Environ Sci Technol 31:241–293

    Article  Google Scholar 

  • U.S.EPA (1992) Water quality standards, establishment of numeric criteria for priority toxic pollutants, state’s compliance, final rule

  • Yamamoto M (1996) Stimulation of elemental mercury oxidation in the presence of chloride ion in aquatic environments. Chemosphere 32:1217–1224

    Article  Google Scholar 

  • Žagar D, Knap A, Warwick JJ, Rajar R, Horvat M, Četina M (2006) Modelling of mercury transport and transformation processes in the Idrijca and Soča river system. Sci Total Environ 368:149–163

    Article  Google Scholar 

  • Žibret G, Gosar M (2006) Calculation of the mercury accumulation in the Idrijca River alluvial plain sediments. Sci Total Environ 368:291–297

    Article  Google Scholar 

  • Žižek S, Horvat M, Gibičar D, Fajon V, Toman MJ (2007) Bioaccumulation of mercury in benthic communities of a river ecosystem affected by mercury mining. Sci Total Environ 377:407–415

    Article  Google Scholar 

  • Žižek S, Guevara SR, Horvat M (2008) Validation of methodology for determination of the mercury methylation potential in sediments using radiotracers. Anal Bioanal Chem 390:2115–2122

    Article  Google Scholar 

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Acknowledgements

The authors acknowledge financial support from the state budget by the Slovenian Research Agency (L1-0367) and the research group “Cycling of nutrients and contaminants in the environment, mass balances and modeling environmental processes and risk analysis” (P1-0143). The measurements of cations, anions and DOC were performed at University of Michigan, Ann Arbor, USA. For that, special thanks are given to Dr. Lyn Walter. Authors also thank Dr. A. Byrne for linguistic corrections. Dr. J. Kotnik and Dr. S. Žižek are acknowledged for their help with mercury analysis.

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Kocman, D., Kanduč, T., Ogrinc, N. et al. Distribution and partitioning of mercury in a river catchment impacted by former mercury mining activity. Biogeochemistry 104, 183–201 (2011). https://doi.org/10.1007/s10533-010-9495-5

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