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Chemical availability of arsenic and heavy metals in sediments from abandoned cinnabar mine tailings

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Abstract

The understanding of the solid-phase speciation of arsenic in soils and sediments is important in the evaluations of its potential mobility and availability in the environment. The spoil heaps of abandoned mercury mines contain waste materials with high arsenic and heavy metals concentrations. The weathering of these tailings can cause their mobilization to the surroundings. In this work, the mobility and availability of arsenic and some heavy metals were evaluated in sediments from two heavily polluted mercury mining districts in Asturias (NW Spain). For this purpose, a slightly modified version of the Bureau Community of Reference sequential extraction scheme was applied to sediments. The total contents in the operationally defined fractions were analysed by inductively coupled plasma-atomic emission spectrometry. Extremely high total arsenic concentrations were found in all sediments ranging from 4,000 to 24,800 mg kg−1. High easily mobilizable arsenic contents were found in the first mining area, related to the solubilization of Ca-bearing phases, supported by extracts analyses, X-ray diffraction results and the positive correlation found among the As and Ca fractionations. Ni and Zn were the most mobile among heavy metals, being Cr the least mobile, suggesting an anthropogenic origin due to the metallurgical processes, transport or dispersion generated from neighbour spoil heaps. In the second mining area, the bulk of As was concentrated in the residual phase, as well as Cr, Cu, Fe, Pb, Ti, indicating a mineralogical origin and the low availability of these elements. The strong correlations established between As and Fe and Ti distributions support the hypothesis that As is mainly associated to structural mineral phases in these sediments.

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References

  • Appelo CAJ, Van der Weiden MJJ, Tournassat C, Charlet L (2002) Surface complexation of ferrous iron and carbonate on ferrihydrite, and the mobilisation of arsenic. Environ Sci Technol 36:3096–3103

    Article  Google Scholar 

  • Baig JA, Kazi TG, Arain MB, Shah AQ, Sarfraz RA, Afridi HI, Kandhro GA, Jamali MK, Khan S (2009) Arsenic fractionation in sediments of different origins using BCR sequential and single extraction methods. J Hazard Mater 167(1–3):745–751

    Article  Google Scholar 

  • Belazi AU, Davidson CM, Keating GE, Littlejohn D, McCartney M (1995) Determination and speciation of heavy metals in sediments from the Cumbrian coast, NW England, UK. J Anal Atomic Spectrom 10(3):233–240

    Article  Google Scholar 

  • Calderon V, Ryan A, Shrader D (2007) Analysis of environmental samples by ICP-OES following US EPA guidelines. Atom Spectrosc March, 17–18

  • Da Costa GM, Ribeiro-Herzog L (2011) Association between phosphorus and iron oxides in manganese ores. Am Mineral 96:68–73

    Article  Google Scholar 

  • Davidson CM, Duncan AL, Littlejohn D, Ure AM, Garden LM (1998) A critical evaluation of the three-stage BCR sequential extraction procedure to assess the potential mobility and toxicity of heavy metals in industrially-contaminated land. Anal Chim Acta 363(1):45–55

    Article  Google Scholar 

  • Davidson CM, Ferreira PCS, Ure AM (1999) Some sources of variability in application of the three-stage sequential extraction procedure recommended by BCR to industrially-contaminated soil. Fresenius J Anal Chem 363(5–6):446–451

    Article  Google Scholar 

  • Eggleton J, Thomas KV (2004) A review of factors affecting the release and bioavailability of contaminants during sediment disturbance events. Environ Int 30(7):973–980

    Article  Google Scholar 

  • Fernández E, Jiménez R, Lallena AM, Aguilar J (2004) Evaluation of the BCR sequential extraction procedure applied for two unpolluted Spanish soils. Environ Pollut 131(3):355–364

    Article  Google Scholar 

  • Fytianos K, Bovolenta S, Muntau H (1995) Assessment of metal mobility from sediment of lake Vegoritis. J Environ Sci Health A 30(6):1169–1190

    Article  Google Scholar 

  • Gao XL, Chen SY, Long AM (2008) Composition and sources of organic matter and its solvent extractable components in surface sediments of a bay under serious anthropogenic influences: daya Bay, China. Mar Pollut Bull 56(6):1066–1075

    Article  Google Scholar 

  • García-Sánchez A, Alonso-Rojo P, Santos-Francés F (2010) Distribution and mobility of arsenic in soils of a mining area (Western Spain). Sci Total Environ 408(19):4194–4201

    Article  Google Scholar 

  • Gleyzes C, Tellier S, Astruc M (2002) Fractionation studies of trace elements in contaminated soils and sediments: a review of sequential extraction procedures. Trends Anal Chem 21(6–7):451–467

    Article  Google Scholar 

  • Glosinska G, Sobczynski T, Boszke L, Bierla K, Siepak J (2005) Fractionation of some heavy metals in bottom sediments from the middle Odra River (Germany/Poland). Polish J Environ Stud 14(3):305–317

    Google Scholar 

  • Gutiérrez-Claverol M, Luque-Cabal C (1994) Recursos del subsuelo de Asturias. Servicio de Publicaciones, Univ Oviedo, p 374

  • Harvey CF, Swartz CH, Badruzzaman ABM, Keon-Blute N, Yu W, Ali MA, Jay J, Beckie R, Niedan V, Brabander D, Oates PM, Ashfaque KN, Islam S, Hemond HF, Ahmed MF (2002) Arsenic mobility and groundwater extraction in Bangladesh. Science 298:1602–1606

    Article  Google Scholar 

  • Herrera V, De Gregori I, Pinochet H (2009a) Assessment of trace elements and mobility of arsenic and manganese in Lagoon sediments of the Huasco and Coposa salt flats, Chilean altiplano. J Chilean Chem Soc 54(4):454–459

    Google Scholar 

  • Herrera V, de Gregori I, Pinochet H (2009b) Assessment of trace elements and mobility of arsenic and manganese in lagoon sediments of the salars of Huasco and Coposa, Chilean Altiplano. J Chilean Chem Soc 54(3):282–288

    Google Scholar 

  • Hlavay J, Prohaska T, Weisz M, Wenzel WW, Stingeder GJ (2004) Determination of trace elements bound to soils and sediment fractions—(IUPAC technical report). Pure Appl Chem 76(2):415–442

    Article  Google Scholar 

  • Ho MD, Evans GJ (1997) Operational speciation of cadmium, copper, lead and zinc in the NIST Standard Reference Materials 2710 and 2711 (Montana Soil) by the BCR sequential extraction procedure and flame atomic absorption spectrometry. Anal Commun 34(11):363–364

    Article  Google Scholar 

  • Hoang TH, Bang S, Kim KW, Nguyen MH, Dang DM (2010) Arsenic in groundwater and sediment in the Mekong River delta, Vietnam. Environ Pollut 158(8):2648–2658

    Article  Google Scholar 

  • Klavins M, Briede A, Rodinov V, Kokorite I, Parele E, Klavina I (2000) Heavy metals in rivers of Latvia. Sci Total Environ 262(1–2):175–184

    Article  Google Scholar 

  • Larios R, Fernández-Martínez R, LeHecho I, Rucandio I (2012a) A methodological approach to evaluate arsenic speciation and bioaccumulation in different plant species from two highly polluted mining areas. Sci Total Environ 414:600–607

    Article  Google Scholar 

  • Larios R, Fernández-Martínez R, Silva V, Loredo J, Rucandio I (2012b) Arsenic contamination and speciation in surrounding waters of three old cinnabar mines. J Environ Monit 14:531–542

    Article  Google Scholar 

  • Licheng Z, Guijiu Z (1996) The species and geochemical characteristics of heavy metals in the sediments of Kangjiaxi River in the Shuikoushan Mine Area, China. Appl Geochem 11(1–2):217–222

    Article  Google Scholar 

  • Loredo J, Luque C, Iglesias JG (1988) Conditions of formation of mercury deposits from the Cantabrian Zone (Spain). Bull Minéral 111:393–400

    Google Scholar 

  • Loredo J, Ordóñez A, Baldo C, García-Iglesias J (2003a) Arsenic mobilization from waste piles of the El Terronal mine, Asturias, Spain. Geochem: Explor Environ, Anal 3(3):229–237

    Article  Google Scholar 

  • Loredo J, Pereira A, Ordóñez A (2003b) Untreated abandoned mercury mining works in a scenic area of Asturias (Spain). Environ Int 29(4):481–491

    Article  Google Scholar 

  • Loredo J, Álvarez R, Ordóñez A (2005) Release of toxic metals and metalloids from Los Rueldos mercury mine (Asturias, Spain). Sci Total Environ 340(1–3):247–260

    Article  Google Scholar 

  • Loredo J, Ordóñez A, Álvarez R (2006) Environmental impact of toxic metals and metalloids from the Muñón Cimero mercury-mining area (Asturias, Spain). J Hazard Mater 136(3):455–467

    Article  Google Scholar 

  • Loredo J, Petit-Domínguez MD, Ordoñez A, Galán MP, Fernández-Martínez R, Alvarez R, Rucandio MI (2010) Surface water monitoring in the mercury mining district of Asturias (Spain). J Hazard Mater 176(1–3):323–332

    Article  Google Scholar 

  • Luque Cabal C, Gutiérrez Claverol M (2006) La minería del mercurio en Asturias. Rasgos históricos. Eujoa, PhD Thesis. Oviedo (Spain), p 554

  • Martin T, Brockhoff C, Creed J, Group EMW (1994) Method 200.7: determination of metals and trace elements in water and wastes by inductively coupled plasma-atomic emission spectrometry. Revision 4.4 edn.

  • Mester Z, Cremisini C, Ghiara E, Morabito R (1998) Comparison of two sequential extraction procedures for metal fractionation in sediment samples. Anal Chim Acta 359(1–2):133–142

    Article  Google Scholar 

  • Morillo J, Usero J, Gracia I (2002) Partitioning of metals in sediments from the Odiel River (Spain). Environ Int 28(4):263–271

    Article  Google Scholar 

  • Morillo J, Usero J, Rojas R (2008) Fractionation of metals and As in sediments from a biosphere reserve (Odiel salt marshes) affected by acidic mine drainage. Environ Monit Assess 139(1–3):329–337

    Article  Google Scholar 

  • Naimo D, Adamo P, Imperato M, Stanzione D (2005) Mineralogy and geochemistry of a marine sequence, Gulf of Salerno, Italy. Quater Int 140–141:53–63

    Article  Google Scholar 

  • Nordstrom DK (2000) An overview of arsenic mass poisoning in Bangladesh and West Bengal, India. In: Young C (ed) Minor elements 2000: processing and environmental aspects of As, Sb, Se, Te, and Bi. Society for Mining, Metallurgy and Exploration, Littleton, CO, pp 21–30

  • Ordóñez A, Alvarez R, Charlesworth S, Miguel Ed, Loredo J (2011) Risk assessment of soils contaminated by mercury mining, Northern Spain. J Environ Monit 13:128–136

    Article  Google Scholar 

  • Pempkowiak J, Sikora A, Biernacka E (1999) Speciation of heavy metals in marine sediments vs their bioaccumulation by mussels. Chemosphere 39(2):313–321

    Article  Google Scholar 

  • Pérez-Cid B, Lavilla I, Bendicho C (1996) Analytical assessment of two sequential extraction schemes for metal partitioning in sewage sludges. Analyst 121(10):1479–1484

    Article  Google Scholar 

  • Quevauviller P (1998) Operationally defined extraction procedures for soil and sediment analysis I. Standardization. Trends Anal Chem 17(5):289–298

    Article  Google Scholar 

  • Quevauviller P, Ure A, Muntau H, Griepink B (1993) Improvement of analytical measurements within the BCR-program—single and sequential extraction procedures applied to soil and sediment analysis. Int J Environ Anal Chem 51(1–4):129–134

    Article  Google Scholar 

  • Rauret G, López-Sánchez JF, Sahuquillo A, Rubio R, Davidson C, Ure A, Quevauviller P (1999) Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials. J Environ Monit 1(1):57–61

    Article  Google Scholar 

  • Sadiq M (1997) Arsenic chemistry in soils: an overview of thermodynamic predictions and field observations. Water Air Soil Pollut 93(1–4):117–136

    Google Scholar 

  • Saria L, Shimaoka T, Miyawaki K (2006) Leaching of heavy metals in acid mine drainage. Waste Manage Res 24(2):134–140

    Article  Google Scholar 

  • Slavek J, Pickering WF (1981) A study of the sorptive properties of surface sediments in a landfill project region. Water Res 15(7):867–874

    Article  Google Scholar 

  • Smith E, Naidu R, Alston AM (1998) Arsenic in the soil environment: a review. Adv Agron 64:149–195

    Article  Google Scholar 

  • Svete P, Milacic R, Pihlar B (2001) Partitioning of Zn, Pb and Cd in river sediments from a lead and zinc mining area using the BCR three-step sequential extraction procedure. J Environ Monit 3(6):586–590

    Article  Google Scholar 

  • Szakova J, Tlustos P, Balik J, Pavlikova D, Vanek V (1999) The sequential analytical procedure as a tool for evaluation of As, Cd and Zn mobility in soil. Fresenius J Anal Chem 363(5–6):594–595

    Google Scholar 

  • Tack FMG, Verloo MG (1995) Chemical speciation and fractionation in soil and sediment heavy-metal analysis—a review. Int J Environ Anal Chem 59(2–4):225–238

    Article  Google Scholar 

  • Tessier A, Campbell PGC, Bisson M (1979) Sequential extraction procedure for the speciation of particulate trace metals. Anal Chem 51(7):844–851

    Article  Google Scholar 

  • Ure AM, Davidson CM (1995) Chemical speciation in the environment. Blackie Academic & Professional, Glasgow, p 408

    Google Scholar 

  • USEPA (2007) Method 9056A: determination of inorganic anions by ion chromatography, Rev. 1. http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/9056a.pdf

  • Usero J, Gamero M, Morillo J, Gracia I (1998) Comparative study of three sequential extraction procedures for metals in marine sediments. Environ Int 24(4):487–496

    Article  Google Scholar 

  • Van Herreweghe S, Swennen R, Vandecasteele C, Cappuyns V (2003) Solid phase speciation of arsenic by sequential extraction in standard reference materials and industrially contaminated soil samples. Environ Pollut 122(3):323–342

    Article  Google Scholar 

  • Varejão EVV, Bellato CR, Fontes MPF, Mello JWV (2011) Arsenic and trace metals in river water and sediments from the southeast portion of the Iron Quadrangle, Brazil. Environ Monit Assess 172:631–642

    Google Scholar 

  • Yuan CG, Shi JB, He B, Liu JF, Liang LN, Jiang GB (2004) Speciation of heavy metals in marine sediments from the East China Sea by ICP-MS with sequential extraction. Environ Int 30(6):769–783

    Article  Google Scholar 

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Acknowledgments

Authors are indebted to Jorge Loredo Group for the sampling and inconditional help, in particular to Rodrigo Alvarez for his valuable comments and SEM analysis, and to Pilar Galán, Mª Belén Gómez, Fernando García, Amor Calderón, Candelas Alonso, Luis Vicente Gómez for their analytical assistance. CIEMAT is greatly appreciated to support this work by a FPI grant for Raquel Larios Ardila. Authors thank the Spanish Ministry of Science and Innovation (previously others) for the financial support (national project CGL-2006-08192).

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Authors and Affiliations

  1. Unidad de Espectroscopía, División de Química, Departamento de Tecnología, CIEMAT, Av. Complutense, 40, Madrid, Spain

    Raquel Larios, Rodolfo Fernández-Martínez & Isabel Rucandio

  2. Dpto. de Explotación y Prospección de Minas, Universidad de Oviedo, Escuela de Minas. C/Independencia, 13, Oviedo, Spain

    Verónica Silva

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  1. Raquel Larios
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  2. Rodolfo Fernández-Martínez
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  3. Verónica Silva
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  4. Isabel Rucandio
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Correspondence to Isabel Rucandio.

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Larios, R., Fernández-Martínez, R., Silva, V. et al. Chemical availability of arsenic and heavy metals in sediments from abandoned cinnabar mine tailings. Environ Earth Sci 68, 535–546 (2013). https://doi.org/10.1007/s12665-012-1757-1

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  • DOI: https://doi.org/10.1007/s12665-012-1757-1

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