Abstract
The main aim of this paper was to investigate the removal efficiency of antimony (Sb) and arsenic (As) from circum-neutral mine drainage in the former Sb mine in Poproč (Slovakia) using a simple field treatment system based on the adsorption onto iron fillings. The treatment system consisted of two batch reactors with a volume of 1 m3: the first was used for settling of spontaneously precipitated ochreous sediments and the second, filled with reactive iron material, was designed to remove Sb and As from mine water. This passively operated treatment system contained 150 kg of low-cost iron fillings and was able to treat approximately 360 l of mine drainage per hour. The average removal efficiency of Sb and As reached 84 and 89% during a period of 2.3 years of the system operation, respectively. On average, dissolved Sb and As concentrations in mine drainage decreased from 175 to 24.3 µg/l and from 452 to 50.6 µg/l, respectively. Based on the electron microprobe (EMP) analyses of corrosion products developed on the surfaces of iron fillings, average Sb and As contents were 0.28 and 0.73 wt%, respectively. The chemical analyses of precipitated HFOs in the settling reactor showed that these ochreous precipitates contained up to 19.3 g/kg Sb and 65.8 g/kg As, indicating their natural role in the removal of the two metalloids from circum-neutral mine drainage. The results of transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses confirmed the presence of ferrihydrite and goethite in ochreous sediments.
Similar content being viewed by others
References
Alloway BJ (2013) Heavy metals in soils, 3rd edn. Springer, Dordrecht
Anon (2015) Guideline of Ministry of Environment of the Slovak Republic No. 1/2015–7 for the elaboration of risk assessment analysis of contaminated sites. http://www.minzp.sk/files/sekcia-geologie-prirodnych-zdrojov/ar_smernica_final.pdf. Accessed 11 Nov 2017 (in Slovak)
Ashley PM, Craw D, Graham BP, Chappell DA (2003) Environmental mobility of antimony around mesothermal stibnite deposits, New South Wales, Australia and southern Zealand. J Geochem Explor 77:1–14. https://doi.org/10.1016/S0375-6742(02)00251-0
Asta MP, Cama J, Ayora C, Acero P, de Giudici G (2010) Arsenopyrite dissolution rates in O2-bearing solutions. Chem Geol 273:272–285. https://doi.org/10.1016/j.chemgeo.2010.03.002
Auxt A, Jurkovič Ľ, Šottník P, Bačik M, Sekula P, Sekula K, Peťková K, Brčeková J, Voleková B (2015) Environmental impact reconnoissance KS (012)/Poproč-Petrová Valley, SK/EZ/KS/353), Final report. Ministry of Environment of the Slovak Republic, Bratislava (in Slovak)
Bailey SE, Olin TJ, Brick RM, Adrian DD (1999) A review of potentially low-costs sorbents for heavy metals. Water Res 33:2469–2479. https://doi.org/10.1016/S0043-1354(98)00475-8
Bang S, Korfiatis GP, Meng X (2005a) Removal of arsenic from water by zero-valent iron. J Hazard Mater 121:61–67. https://doi.org/10.1016/j.jhazmat.2005.01.030
Bang S, Johnson MD, Korfiatis GP, Meng X (2005b) Chemical reactions between arsenic and zero-valent iron in water. Water Res 39:763–770. https://doi.org/10.1016/j.watres.2004.12.022
Bigham JM, Schwertmann U, Carlson L (1992) Mineralogy of precipitates formed by the biogeochemical oxidation of Fe(II) in mine drainage. In: Skinner HCW, Fitzpatrick RW (eds) Biomineralization processes of iron and manganese – modern and ancient environments. Catena Verlag, Berlin, pp 219–232
Bowell RJ, Bruce I (1995) Geochemistry of iron ochres and mine waters from Levant Mine, Cornwall. Appl Geochem 10:237–250. https://doi.org/10.1016/0883-2927(94)00036-6
Casiot C, Ujevic M, Munoz M, Seidel JL, Elbaz-Poulichet F (2007) Antimony and arsenic mobility in a creek draining an antimony mine abandoned 85 years ago (upper Orb basin, France). Appl Geochem 22:788–798. https://doi.org/10.1016/j.apgeochem.2006.11.007
Chmielewská E, Tylus W, Drábik M, Majzlan J, Kravčak J, Williams C, Čaplovičová M, Čaplovič Ľ (2017) Structure investigation of nano-FeO(OH) modified clinoptilolite tuff for antimony removal. Microporous Mesoporous Mater 248:222–233. https://doi.org/10.1016/j.micromeso.2017.04.022
Corkhill CL, Vaughan DJ (2009) Arsenopyrite oxidation—a review. Appl Geochem 24:2342–2361. https://doi.org/10.1016/j.apgeochem.2009.09.008
Cornell RM, Schwertmann U (2003) The iron oxides—structure, properties, reactions, occurrences and uses, 2nd edn. Wiley-VCH, New York
Cundy AB, Hopkinson L, Whitby RLD (2008) Use of iron-based technologies in contaminated land and groundwater remediation: a review. Sci Total Environ 400:42–51. https://doi.org/10.1016/j.scitotenv.2008.07.002
DeMarco MJ, SenGupta AK, Greenleaf JE (2003) Arsenic removal using a polymeric/inorganic hybrid sorbent. Water Res 37:164–176. https://doi.org/10.1016/S0043-1354(02)00238-5
Dixit S, Hering JG (2003) Comparison of arsenic(V) and arsenic(III) sorption onto iron oxide minerals: implications for arsenic mobility. Environ Sci Technol 37:4182–4189. https://doi.org/10.1021/es030309t
Edwards AMC (1973) The variation of dissolved constituents with discharge in some Norfolk rivers. J Hydrol 18:219–242. https://doi.org/10.1016/0022-1694(73)90049-8
Fawcett SE, Jamieson HE, Nordstrom DK, McCleskey RB (2015) Arsenic and antimony geochemistry of mine wastes, associated waters and sediments at the Giant Mine, Yellowknife, Northwest Territories, Canada. Appl Geochem 62:3–17. https://doi.org/10.1016/j.apgeochem.2014.12.012
Filella M, Philippo S, Belzile N, Chen Y, Quentel F (2009) Natural attenuation processes applying to antimony: A study in the abandoned antimony mine in Goesdorf, Luxembourg. Sci Total Environ 407:6205–6216. https://doi.org/10.1016/j.scitotenv.2009.08.027
Flakova R, Zenisova Z, Sracek O, Krcmar D, Ondrejkova I, Chovan M, Lalinská B, Fendekova M (2012) The behavior of arsenic and antimony at Pezinok mining site, southwestern part of the Slovak Republic. Environ Earth Sci 66:1043–1057. https://doi.org/10.1007/s12665-011-1310-7
Fľaková R, Ženišová Z, Krčmář D, Ondrejková I, Sracek O (2017) Occurrence of antimony and arsenic at mining sites in Slovakia: Implications for their mobility. Carpath J Earth Environ Sci 12:41–48
Flores AN, Rubio LMD (2010) Arsenic and metal mobility from Au mine tailings in Rodalquilar (Almería, SE Spain). Environ Earth Sci 60:121–138. https://doi.org/10.1007/s12665-009-0174-6
Furukawa Y, Kim J-W, Watkins J, Wilkin RT (2002) Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron. Environ Sci Technol 36:5469–5475. https://doi.org/10.1021/es025533h
Gebel T (1997) Arsenic and antimony: comparative approach on mechanistic toxicology. Chem Biol Interact 107:131–144. https://doi.org/10.1016/S0009-2797(97)00087-2
Grecula P, Abonyi A, Abonyiová M, Antaš J, Bartalský B, Bartalský J, Dianiška I, Drzík E, Ďuďa R, Gargulák M, Gazdačko Ľ, Hudáček J, Kobulský J, Lörincz L, Macko J, Návesňák D, Németh Z, Novotný L, Radvanec M, Rojkovič I, Rozložník L, Rozložník O, Varček C, Zlocha J (1995) Mineral deposits of the Slovak Ore Mountains. Geokomplex, Bratislava (in Slovak)
Guo X, Wu Z, He M, Meng X, Jin X, Qiu N, Zhang J (2014) Adsorption of antimony onto iron oxyhydroxides: adsorption behavior and surface structure. J Hazard Mater 276:339–345. https://doi.org/10.1016/j.jhazmat.2014.05.025
Gzyl G, Banks D (2007) Verification of the “first flush” phenomenon in mine water from coal mines in the Upper Silesian Coal Basin, Poland. J Contam Hydrol 92:66–86. https://doi.org/10.1016/j.jconhyd.2006.12.001
Herath I, Vithanage M, Bundschuh J (2017) Antimony as a global dilemma: Geochemistry, mobility, fate and transport. Environ Pollut 223:545–559. https://doi.org/10.1016/j.envpol.2017.01.057
Heviánková S, Bestová I, Kyncl M (2014) The application of wood ash as a reagent in acid mine drainage treatment. Miner Eng 56:109–111. https://doi.org/10.1016/j.mineng.2013.10.032
Hiller E, Lalinská B, Chovan M, Jurkovič Ľ, Klimko T, Jankulár M, Hovorič R, Šottník P, Fľaková R, Ženišová Z, Ondrejková I (2012) Arsenic and antimony contamination of waters, stream sediments and soils in the vicinity of abandoned antimony mines in the Western Carpathians, Slovakia. Appl Geochem 27:598–614. https://doi.org/10.1016/j.apgeochem.2011.12.005
Ilavský J, Barloková D, Munka K (2015) Antimony removal from water by adsorption to iron-based sorption materials. Water Air Soil Pollut 226:2238. https://doi.org/10.1007/s11270-014-2238-9
Jain CK, Ali I (2000) Arsenic: occurrence, toxicity and speciation techniques. Water Res 34:4304–4312. https://doi.org/10.1016/S0043-1354(00)00182-2
Jambor JL (2003) Mine-waste mineralogy and mineralogical perspectives of acid – base accounting. In: Jambor JL, Blowes DW, Ritchie AIM (eds) Environmental aspects of mine wastes, vol 31. Mineralogical Association of Canada, Quebec, pp 117–145
Kaartinen T, Laine-Ylijoki J, Ahoranta S, Korhonen T, Neitola R (2017) Arsenic removal from mine waters with sorption techniques. Mine Water Environ 36:199–208. https://doi.org/10.1007/s10230-017-0450-8
Kaličiaková E, Pacindová N, Repčiak M, Seliga J, Volko P (1996) Poproč – heaps, dumps, tailings ponds – the environment, Final report. State Geological Institute of Dionýz Štúr, Bratislava (in Slovak)
Klimko T, Heviánková S, Šottník P, Jurkovič Ľ, Lacková E, Vozár J (2014) Experimental removal of antimony from mine waters (abandoned Sb deposit Poproč, eastern Slovakia). Acta Geol Slov 6:203–213. (in Slovak with English abstract and summary)
Kolbe F, Weiss H, Morgenstern P, Wennrich R, Lorenz W, Schurk K, Stanjek H, Daus B (2011) Sorption of aqueous antimony and arsenic species onto akaganeite. J Colloid Interface Sci 357:460–465. https://doi.org/10.1016/j.jcis.2011.01.095
Lackovic JA, Nikolaidis NP, Dobbs GM (2000) Inorganic arsenic removal by zero-valent iron. Environ Eng Sci 17:29–39. https://doi.org/10.1089/ees.2000.17.29
Lalinská-Voleková B, Majzlan J, Klimko T, Chovan M, Kučerová G, Michňová J, Hovorič R, Göttlicher J, Steininger R (2012) Mineralogy of weathering products of Fe–As–Sb mine wastes and soils at several Sb deposits in Slovakia. Can Mineral 50:1207–1226. https://doi.org/10.3749/canmin.50.2.481
Leuz A-K, Mönch H, Johnson CA (2006) Sorption of Sb(III) and Sb(V) to goethite: influence on Sb(III) oxidation and mobilization. Environ Sci Technol 40:7277–7282. https://doi.org/10.1021/es061284b
Li J, Bao H, Xiong X, Sun Y, Guan X (2015) Effective Sb(V) immobilization from water by zero-valent iron with weak magnetic field. Sep Purif Technol 151:276–283. https://doi.org/10.1016/j.seppur.2015.07.056
Li S, Wang W, Liang F, Zhang W-X (2017) Heavy metal removal using nanoscale zero-valent iron (nZVI): theory and application. J Hazard Mater 322:163–171. https://doi.org/10.1016/j.jhazmat.2016.01.032
Lintnerová O, Šucha V, Streško V (1999) Mineralogy and geochemistry of acid mine Fe-precipitates from the main Slovak mining regions. Geol Carpath 50:395–404
Majzlan J, Lalinská B, Chovan M, Jurkovič Ľ, Milovská S, Göttlicher J (2007) The formation, structure, and ageing of As-rich hydrous ferric oxide at the abandoned Sb deposit Pezinok (Slovakia). Geochim Cosmochim Acta 71:4206–4220. https://doi.org/10.1016/j.gca.2007.06.053
Manning BA, Hunt ML, Amrhein C, Yarmoff JA (2002) Arsenic(III) and arsenic(V) reactions with zerovalent iron corrosion products. Environ Sci Technol 36:5455–5461. https://doi.org/10.1021/es0206846
Masson M, Schäfer J, Blanc G, Dabrin A, Castelle S, Lavaux G (2009) Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France. Appl Geochem 24:1747–1756. https://doi.org/10.1016/j.apgeochem.2009.05.004
Milham L, Craw D (2009) Antimony mobilization through two contrasting gold ore processing systems, New Zealand. Min Water Environ 28:136–145. https://doi.org/10.1007/s10230-009-0071-y
Mohan D, Pittman JCU (2007) Arsenic removal from water/wastewater using adsorbents—a critical review. J Hazard Mater 142:1–53. https://doi.org/10.1016/j.jhazmat.2007.01.006
Nikolaidis NP, Dobbs GM, Lackovic JA (2003) Arsenic removal by zero-valent iron: field, laboratory and modeling studies. Water Res 37:1417–1425. https://doi.org/10.1016/S0043-1354(02)00483-9
Nordstrom DK (2011) Mine waters: acidic to circumneutral. Elements 7:393–398. https://doi.org/10.2113/gselements.7.6.393
Parkhurst DL, Appelo CAJ (1999) PHREEQC-2, A hydrogeochemical computer program. U.S. Geological Survey Water Resources Investigation, pp Report, 99–4259
Qi P, Pichler T (2017) Competitive adsorption of As(III), As(V), Sb(III) and Sb(V) onto ferrihydrite in multi-component systems: implications for mobility and distribution. J Hazard Mater 330:142–148. https://doi.org/10.1016/j.jhazmat.2017.02.016
Ritchie VJ, Ilgen AG, Mueller SH, Trainor TP, Goldfarb RJ (2013) Mobility and chemical fate of antimony and arsenic in historic mining environments of the Kantishna Hills district. Denali National Park Preserve Alaska Chem Geol 335:172–188. https://doi.org/10.1016/j.chemgeo.2012.10.016
Rozložník O (1980) Questions of genesis and prospecting of stibnite deposits in Poproč and Zlatá Idka. In: Ilavský J (ed) Antimony ores of Czechoslovakia. State Geological Institute of Dionýz Štúr, Bratislava, pp 141–146 (in Slovak)
Schwertmann U, Taylor RM (1989)) Iron Oxides. In: Dixon JB, Weed SB (eds) Minerals in soil environments. SSSA Book Series 1, 2nd edn. Soil Science Society of America, Madison, pp 380–438
Sharifi R, Moore F, Keshavarzi B (2016) Mobility and chemical fate of arsenic and antimony in water and sediments of Sarouq River catchment, Takab geothermal field, northwest Iran. J Environ Manag 170:136–144. https://doi.org/10.1016/j.jenvman.2016.01.018
Shim MJ, Choi BY, Lee G, Hwang YH, Yang J-S, O’Loughlin EJ, Kwon MJ (2015) Water quality changes in acid mine drainage streams in Gangneung, Korea, 10 years after treatment with limestone. J Geochem Explor 159:234–242. https://doi.org/10.1016/j.gexplo.2015.09.015
Skousen J, Zipper CE, Rose A, Ziemkiewicz PF, Nairn R, McDonald LM, Kleinmann RL (2017) Review of passive systems for acid mine drainage treatment. Mine Water Environ 36:133–153. https://doi.org/10.1007/s10230-016-0417-1
Sprague DD, Michel FA, Vermaire JC (2016) The effects of migration on ca. 100-year-old arsenic-rich mine tailings in Cobalt, Ontario, Canada. Environ Earth Sci 75:405. https://doi.org/10.1007/s12665-015-4898-1
Sracek O, Mihaljevič M, Kříbek B, Majer V, Filip J, Vaněk A, Penížek V, Ettler V, Mapani B (2014) Geochemistry of mine tailings and behavior of arsenic at Kombat, northeastern Namibia. Environ Monit Assess 186:4891–4903. https://doi.org/10.1007/s10661-014-3746-1
Su C, Puls RW (2001) Arsenate and arsenite removal by zerovalent iron: kinetics, redox transformation, and implications for in situ groundwater remediation. Environ Sci Technol 35:1487–1492. https://doi.org/10.1021/es001607i
Su C, Puls RW (2003) In situ remediation of arsenic in simulated groundwater using zerovalent iron: laboratory column tests on combined effects of phosphate and silicate. Environ Sci Technol 37:2582–2587. https://doi.org/10.1021/es026351q
Ungureanu G, Santos S, Boaventura R, Botelho C (2015) Arsenic and antimony in water and wastewater: overview of removal techniques with special reference to latest advances in adsorption. J Environ Manag 151:326–342. https://doi.org/10.1016/j.jenvman.2014.12.051
Vasquez Y, Escobar MC, Neculita CM, Arbeli Z, Roldan F (2016) Biochemical passive reactors for treatment of acid mine drainage: effect of hydraulic retention time on changes in efficiency, composition of reactive mixture, and microbial activity. Chemosphere 153:244–253. https://doi.org/10.1016/j.chemosphere.2016.03.052
Woo ES, Kim JJ, Kim YH, Jeong GC, Jang YD, Dick WA (2013) Mineralogical and geochemical characterization of precipitates on stream receiving acid mine water. Korea Environ Earth Sci 69:2199–2209. https://doi.org/10.1007/s12665-012-2048-6
Xi J, He M, Zhang G (2014) Antimony adsorption on kaolinite in the presence of competitive anions. Environ Earth Sci 71:2989–2997. https://doi.org/10.1007/s12665-013-2673-8
Young PL (1997) The longevity of minewater pollution: a basis for decision-making. Sci Total Environ 194–195:457–466. https://doi.org/10.1016/S0048-9697(96)05383-1
Ženišová Z, Fľaková R, Jašová I, Cicmanová S (2009) Antimony and arsenic in waters influenced by mining activities in selected parts of Slovakia. Podzemná voda 15:100–117. (in Slovak with English abstract and summary)
Zhang R, Sun H, Yin J (2008) Arsenic and chromate removal from water by iron chips—effects of anions. Front Environ Sci Eng China 2:203–208. https://doi.org/10.1007/s11783-008-0036-6
Acknowledgements
We acknowledge the project APVV-0344-11 and the Ministry of Environment of the Slovak Republic that financially supported the research presented in this paper. We wish to thank Dr. Andrew Cundy for editing of the English in the manuscript. We would also like to thank the two anonymous reviewers for their valuable and helpful comments and suggestions.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Sekula, P., Hiller, E., Šottník, P. et al. Removal of antimony and arsenic from circum-neutral mine drainage in Poproč, Slovakia: a field treatment system using low-cost iron-based material. Environ Earth Sci 77, 518 (2018). https://doi.org/10.1007/s12665-018-7700-3
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s12665-018-7700-3