, Volume 104, Issue 1–3, pp 183–201 | Cite as

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

  • David Kocman
  • Tjaša Kanduč
  • Nives Ogrinc
  • Milena Horvat


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.


Idrija Mercury River system Sediment Speciation Water 



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.


  1. 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 34:3428–3434CrossRefGoogle Scholar
  2. 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 57:1–52CrossRefGoogle Scholar
  3. 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 407:2372–2382CrossRefGoogle Scholar
  4. 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 34:3330–3336CrossRefGoogle Scholar
  5. 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 2:111–119CrossRefGoogle Scholar
  6. Boszke L, Glosinska G, Siepak J (2002) Some aspects of speciation of mercury in a water environment. Pol J Environ Stud 11:285–295Google Scholar
  7. 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 12:5–13Google Scholar
  8. 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 41:8268–8274CrossRefGoogle Scholar
  9. 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 48:56–64Google Scholar
  10. 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 7:94–102CrossRefGoogle Scholar
  11. 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 304:315–326CrossRefGoogle Scholar
  12. 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 43:33–39CrossRefGoogle Scholar
  13. 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 34:4773–4779CrossRefGoogle Scholar
  14. 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 40:327–345CrossRefGoogle Scholar
  15. 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 34:3337–3345CrossRefGoogle Scholar
  16. 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 58:125–131CrossRefGoogle Scholar
  17. 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 369:150–162CrossRefGoogle Scholar
  18. 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 260:21–33CrossRefGoogle Scholar
  19. 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 83:129–139CrossRefGoogle Scholar
  20. 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 21:1924–1939CrossRefGoogle Scholar
  21. 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 21:1837–1854CrossRefGoogle Scholar
  22. 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 20:133–147Google Scholar
  23. Horvat M, Zvonarič T, Stegnar P (1987) Determination of mercury in seawater by cold vapour atomic absorption spectroscopy. Acta Adria 28:59–63Google Scholar
  24. 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 24:71–79CrossRefGoogle Scholar
  25. 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 282:153–168CrossRefGoogle Scholar
  26. 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 237–238:43–56CrossRefGoogle Scholar
  27. 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 2:287–296CrossRefGoogle Scholar
  28. 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 37:93–108CrossRefGoogle Scholar
  29. 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 14:239–262CrossRefGoogle Scholar
  30. 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 270:9–20CrossRefGoogle Scholar
  31. 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 17:261–274CrossRefGoogle Scholar
  32. Kobal AB, Prezelj M, Horvat M, Krsnik M, Gibičar D, Osredkar J (2008) Glutathione level after long-term occupational elemental mercury exposure. Environ Res 107:115–123CrossRefGoogle Scholar
  33. Kocman D, Horvat M, Kotnik J (2004) Mercury fractionation in contaminated soils from the Idrija mercury mine region. J Environ Monit 6:696–703CrossRefGoogle Scholar
  34. Kotnik J, Horvat M, Dizdarevič T (2005) Current and past mercury distribution in air over the Idrija Hg mine region, Slovenia. Atmos Environ 39:7570–7579CrossRefGoogle Scholar
  35. 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 107:13–30CrossRefGoogle Scholar
  36. 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 37:3316–3322CrossRefGoogle Scholar
  37. 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 41:371–379CrossRefGoogle Scholar
  38. 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 43:1883–1888CrossRefGoogle Scholar
  39. Morel FMM, Kraepiel AML, Amyot M (1998) The chemical cycle and bioaccumulation of mercury. Annu Rev Ecol Syst 29:543–566CrossRefGoogle Scholar
  40. 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 37:2226–2235CrossRefGoogle Scholar
  41. Peckenham JM, Kahl JS, Mower B (2003) Background mercury concentrations in river water in Maine, U.S.A. Environ Monit Assess 89:129–152CrossRefGoogle Scholar
  42. 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 23:2055–2064CrossRefGoogle Scholar
  43. Rajar R, Žagar D, Širca A, Horvat M (2000) Three-dimensional modelling of mercury cycling in the Gulf of Trieste. Sci Total Environ 260:109–123CrossRefGoogle Scholar
  44. Ravichandran M (2004) Interactions between mercury and dissolved organic matter—a review. Chemosphere 55:319–331CrossRefGoogle Scholar
  45. 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 63:1277–1292CrossRefGoogle Scholar
  46. 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 56:667–680CrossRefGoogle Scholar
  47. Shu T (1998) Spatial and temporal variation in DOC in the Yichun River, China. Water Res 32:2205–2210CrossRefGoogle Scholar
  48. Ullrich SM, Tanton TW, Abdrashitova SA (2001) Mercury in the aquatic environment: a review of factors affecting methylation. Crit Rev Environ Sci Technol 31:241–293CrossRefGoogle Scholar
  49. U.S.EPA (1992) Water quality standards, establishment of numeric criteria for priority toxic pollutants, state’s compliance, final ruleGoogle Scholar
  50. Yamamoto M (1996) Stimulation of elemental mercury oxidation in the presence of chloride ion in aquatic environments. Chemosphere 32:1217–1224CrossRefGoogle Scholar
  51. 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 368:149–163CrossRefGoogle Scholar
  52. Žibret G, Gosar M (2006) Calculation of the mercury accumulation in the Idrijca River alluvial plain sediments. Sci Total Environ 368:291–297CrossRefGoogle Scholar
  53. 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 377:407–415CrossRefGoogle Scholar
  54. Žižek S, Guevara SR, Horvat M (2008) Validation of methodology for determination of the mercury methylation potential in sediments using radiotracers. Anal Bioanal Chem 390:2115–2122CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2010

Authors and Affiliations

  • David Kocman
    • 1
  • Tjaša Kanduč
    • 1
  • Nives Ogrinc
    • 1
  • Milena Horvat
    • 1
  1. 1.Department of Environmental SciencesJožef Stefan InstituteLjubljanaSlovenia

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