Environmental Earth Sciences

, 75:1438 | Cite as

Seasonal contamination of surface waters close to an abandoned Sn-W mine, northeast Portugal

  • Sérgio P. Lopes
  • M. Manuela Vinha G. SilvaEmail author
  • Elsa M. C. Gomes
  • Paula C. S. Carvalho
  • Ana M. R. Neiva
Original Article


The abandoned Ribeira mine consists of Sn-W quartz veins and is located in Trás-os-Montes, northeast Portugal. The mining activities took place on the northern side of the Viveiros stream valley that crosses the mining area. Viveiros is a tributary stream of the Sabor River, which is about 1 km downstream from the mining site. Tailings and rejected materials were deposited on northern hillside of the valley and are exposed to significant weathering and erosion. The Sn-W quartz veins intruded Silurian quartzites and shales and contain cassiterite, wolframite, sphalerite, scheelite, arsenopyrite, pyrite, chalcopyrite, columbite-(Mn) and bismuthinite. Water samples from the Viveiros stream, Sabor River and tailings seasonal drainages were collected. The water has a sodium bicarbonated to calcium sulphated facies, under maximum tailings influence. The sulphate content is low in these waters (up to 145 mg/L). The pH values are close to neutrality, and the maximum electrical conductivity is 303 μS/cm. The metal and semimetals contents in waters show a seasonal variation characterized by low values in the wet and cold season and high contents in the hot and dry season. The contents of Mn, Cu, Zn and Cd found on the tailings seasonal water drainages are higher than those found in the Viveiros stream and Sabor River in the same season. The highest contents of Cd are associated with the highest contents of Zn. These results point to arsenopyrite and sphalerite dissolution as the principal source of metals and semimetals in these waters. The principal component analysis shows a clear spatial and seasonal distinction between the water collected close to the mine influence in the summer period and the other waters. During this period, the Viveiros stream shows As, Cd and Pb contents (e.g. As 0.29; Cd 0.033 and Pb 0.55 mg/L) higher than those permitted by WHO (Guidelines for drinking-water quality, 4th edn (WEB version), 2011) and the Portuguese legislation. Lead, Cd and As are potential threats to the environment due to long-term loadings into the aquatic system. The differences found in the geochemistry of impacted mine water and in its contamination are well expressed if seasonality is considered.


Contamination Surface waters Abandoned Sn-W mine Seasonal Portugal 



The authors acknowledge the Geosciences Center for funding and the Department of Earth Sciences, Coimbra University for equipment facilities. We want to thank an anonymous referee whose comments greatly improved this paper.


  1. Antunes IMHR, Neiva AMR, Silva MMVG (2002) The mineralized veins and the impact of old mine workings on the environment at Segura, central Portugal. Chem Geol 190:417–431CrossRefGoogle Scholar
  2. Appelo CAJ, Postma D (2005) Geochemistry. Groundwater and pollution. A.A. Balkema, Rotterdam, p 649CrossRefGoogle Scholar
  3. Atibu EK, Devarajan N, Thevenon F, Mwanamoki PM, Tshibanda JB, Mpiana PT, Prabakar K, Mubedi JI, Wildi W, Poté J (2013) Concentration of metals in surface water and sediment of Luilu and Musonoie Rivers, Kolwezi-Katanga, Democratic Republic of Congo. Appl Geochem 39:26–32CrossRefGoogle Scholar
  4. Bale CW, Chartrand P, Degtrev SA, Eriksson G, Hack K, Ben Mahfoud R, Melancon J, Pelton AD, Petersen S (2002) FactSage thermochemical software and databases. Calphad 26:189–228CrossRefGoogle Scholar
  5. Balistrieri LS, Seal RR II, Piatak NM, Paul B (2007) Assessing the concentration, speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine, Vermont, USA. Appl Geochem 22:930–952CrossRefGoogle Scholar
  6. Bilotta GS, Burnside NG, Cheek L, Dunbar MJ, Grove MK, Harrison C, Joyce C, Peacock C, Davy-Bowker J (2012) Developing environment-specific water quality guidelines for suspended particulate matter. Water Res 46:2324–2332CrossRefGoogle Scholar
  7. Carvalho PCS, Neiva AMR, Silva MMVG (2009) Geochemistry of soils, stream sediments and waters close to abandoned W–Au–Sb mines at Sarzedas, Castelo Branco, Central Portugal. Geochem: Explor Environ, Anal 9:341–352Google Scholar
  8. Carvalho PCS, Neiva AMR, Silva MMVG (2012) Assessment to the potential mobility and toxicity of metals and metalloids in soils contaminated by old Sb–Au and As–Au mines (NW Portugal). Environ Earth Sci 2012:1215–1230CrossRefGoogle Scholar
  9. Carvalho PCS, Neiva AMR, Silva MMVG, Ferreira da Silva EA (2014) Geochemical comparison of waters and stream sediments close to abandoned Sb–Au and As–Au mining areas, northern Portugal. Chem Erde 74(2):267–283CrossRefGoogle Scholar
  10. CCME (2007) Canadian water quality guidelines for the protection of aquatic life: summary table. In: Canadian Environmental Quality Guidelines, Canadian Council of Minister of the Environment. In: Accessed 08 Jan 2016
  11. Cidu R, Biddau R (2007) Transport of trace elements under different seasonal conditions: effects on the quality of river water in a Mediterranean area. Appl Geochem 22:2777–2794CrossRefGoogle Scholar
  12. Crosa G, Froebrich J, Nikolayenko V, Stefani F, Galli P, Calamari D (2006) Spatial and seasonal variations in the water quality of the Amu Darya River (Central Asia). Water Res 40:2237–2245CrossRefGoogle Scholar
  13. Custódio E, Llmas MR (1983) Hidrología Subterránia. Tomo I, 2ª ed., Barcelona, Ediciones Ómega, 1157 ppGoogle Scholar
  14. Decreto-lei no 236/98. Diário da República- 1ª série-A No. 176—01-08-1998Google Scholar
  15. Decreto-lei no 306/07. Diário da República, 1ª série- I SÉRIE-A No. 164—27-08-2007Google Scholar
  16. Desbarats AL, Parsons MB, Percival JB, Beauchemin Z, Kwong YTJ (2011) Geochemistry of mine waters draining a low-sulfide, gold-quartz vein deposit, Bralorne, British Columbia. Appl Geochem 26:1990–2003CrossRefGoogle Scholar
  17. Drahota P, Rohovec J, Filippi M, Mihaljevič M, Rychlovský P, Červený V, Pertold Z (2009) Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic. Sci Total Environ 407:3372–3384CrossRefGoogle Scholar
  18. EDM (2006) Recuperação da Área Mineira Abandonada de Mina da Ribeira: Avaliação de Incidências Ambientais. Internal ReportGoogle Scholar
  19. Ficklin WH, Plumlee GS, Smith KS, McHugh JB (1992) Geochemical classification of mine drainage and natural drainage in mineralized areas. In: Kharaka YK, Maest AS (eds) Water–rock interaction, vol 7. Balkema, Rotterdam, pp 81–384Google Scholar
  20. Gibbs RJ (1970) Mechanisms controlling world water chemistry. Science 170:1088–1090CrossRefGoogle Scholar
  21. Gomes MEP, Antunes IMHR, Silva PB, Neiva AMR, Pacheco FAL (2010) Geochemistry of waters associated with old mine workings at Fonte Santa (NE Portugal). J Geochem Explor 105:157–165CrossRefGoogle Scholar
  22. Gozzard E, Mayes WM, Potter HAB, Jarvis AP (2011) Seasonal and spatial variation of diffuse (non-point) source zinc pollution in a historically metal mined river catchment, UK. Environ Pollut 159:3113–3122CrossRefGoogle Scholar
  23. GSJ (2005) Atlas of Eh-pH diagrams. Intercomparison of thermodynamic databases. Geologica Survey of Japan, Open File Report No. 419. 285 ppGoogle Scholar
  24. Hiller E, Lalinská B, Chovan M, Jurkovic L, Klimko T, Jankulár M, Hovoric R, Šottník P, Flˇaková R, Zenišová 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 27:598–614CrossRefGoogle Scholar
  25. IPMA (2013) Instituto Português do Mar e da Atmosfera, Portugal. In: Accessed 11 June 2013
  26. Kappler A, Amstaetter K, Borch T, Larese-Casanova P, Jiang J, Bauer I, Paul A (2011) Arsenic redox transformation by humic substances and Fe minerals. Appl Geochem 26:S317CrossRefGoogle Scholar
  27. Ko M-S, Kim J-Y, Lee J-S, Ko J-I, Kim K-W (2013) Arsenic immobilization in water and soil using acid mine drainage sludge. Appl Geochem 35:1–6CrossRefGoogle Scholar
  28. Liu CP, Luo CL, Gao Y, Li FB, Lin LW, Wu CA, Li XD (2010) Arsenic contamination and potential health risk implications at an abandoned tungsten mine, southern China. Environ Pollut 158:820–826CrossRefGoogle Scholar
  29. Lopes SP (2008) Contaminação ambiental da antiga exploração mineira da mina da Ribeira na região do Nordeste transmontano. Coimbra University, 110 p. (unpublished M.Sc. thesis)Google Scholar
  30. Moncur MC, Ptacek CJ, Hayashi M, Blowes DB, Birks SJ (2014) Seasonal cycling and mass-loading of dissolved metals and sulphate discharging from an abandoned mine site in northern Canada. Appl Geochem 41:176–188CrossRefGoogle Scholar
  31. Mudhoo A, Sharma SK, Garg VK, Tseng C-H (2011) Arsenic: an overview of applications, health, and environmental concerns and removal processes. Crit Rev Environ Sci Technol 41(5):435–519CrossRefGoogle Scholar
  32. Mukherjee A, Bhattacharya P, Fryar AE (2011) Arsenic and other toxic elements in surface and groundwater systems. Appl Geochem 26:415–420CrossRefGoogle Scholar
  33. Neiva AMR, Carvalho PCS, Antunes IMHR, Silva MMVG, Santos AC, Pinto MMSC, Cunha PP (2014) Contaminated water, stream sediments and soils close to the abandoned Pinhal do Souto uranium mine, central Portugal. J Geochem Explor 136:102–117CrossRefGoogle Scholar
  34. Nordstrom DK (2011) Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters. Appl Geochem 26:1777–1791CrossRefGoogle Scholar
  35. Nordstrom DK, Wilde FD (2005) Reduction-oxidation potential (electrode method) (version 1.2). In: National field manual for the collection of water-quality data, vol 9. US Geological Survey Techniques of Water-Resources Investigations, pp 1–22Google Scholar
  36. Ontario Guidelines (2011) Soil, groundwater and sediment standards for use under Part XV.1 of the Environmental Protection Act. Ministry of The Environment. April 15, 2011Google Scholar
  37. Parkhurst DL, Appelo CAJ (1999) User’s guide to PHREEQC (version 2): a computer program for speciation, batchreaction, one-dimensional transport, and inverse geochemical calculations. US Geol. Surv. Water-Resour. Invest. Rep., pp 99–4259Google Scholar
  38. Pereira E (2006) Carta Geológica de Portugal—Noticia Explicativa da Folha 2, 1:200 000. Lisboa, INETIGoogle Scholar
  39. Pinto MMSC, Silva MMVG, Neiva AMR (2004) Pollution of water and stream sediments associated with the Vale de Abrutiga uranium mine, central Portugal. Mine Water Environ 23:66–75CrossRefGoogle Scholar
  40. Plumlee G, Smith K, Montour M, Ficklin W, Mosier E (1999) Geological controls on the composition of natural waters and mine waters draining diverse mineral-deposit types. In: The environmental geochemistry of mineral deposits. Part B: case studies and research topics. vol. 6B, Chapter 19. Reviews in Economic Geology. Society of Economic Geologists, Inc., Chelsea, MI, pp 373–432Google Scholar
  41. Siegel FR (2002) Environmental geochemistry of potentially toxic metals. Springer, Berlin, p 218CrossRefGoogle Scholar
  42. Silva MMVG, Lopes SP, Gomes EC (2014) Geochemistry and behaviour of REE in stream sediments close to an old Sn-W mine, Ribeira, northeast Portugal. Chem Erde 74:545–555CrossRefGoogle Scholar
  43. Smedley PL, Kinniburgh DG (2002) A review of the source, behaviour and distribution of arsenic in natural waters. Appl Geochem 17:517–568CrossRefGoogle Scholar
  44. SNIRH (2013) Serviço Nacional de Informação de Recursos Hídricos, Portugal. In Accessed 11 June 2013
  45. Thadeu D (1965) Minas da Ribeira, Trabalhos de Reconhecimento. Serviços de Fomento MineiroGoogle Scholar
  46. Thadeu D (1986) Tungsten deposits of Portugal. In: Beus AA (eds) Geology of tungsten, 18, International Geological Correlation Programme, Unesco, pp 115–125Google Scholar
  47. Vörösmarty CJ, McIntyre PB, Gessner MO, Dudgeon D, Prusevich A, Green P, Glidden S, Bunn SE, Sullivan CA, Liermann CR, Davies PM (2010) Global threats to human water security and river biodiversity. Nature 467:555–561CrossRefGoogle Scholar
  48. WHO (World Health Organization) (2011) Guidelines for drinking-water quality, 4th edition (WEB version)Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Sérgio P. Lopes
    • 1
  • M. Manuela Vinha G. Silva
    • 2
    • 3
    Email author
  • Elsa M. C. Gomes
    • 2
    • 3
  • Paula C. S. Carvalho
    • 4
  • Ana M. R. Neiva
    • 3
    • 4
  1. 1.Mota-Engil, Engenharia e Construção, S.A.PortoPortugal
  2. 2.CEMUCUniversity of CoimbraCoimbraPortugal
  3. 3.Department of Earth SciencesUniversity of CoimbraCoimbraPortugal
  4. 4.GeoBioTecUniversity of AveiroAveiroPortugal

Personalised recommendations