Abstract
Forty-nine surface sediment samples from the Minho estuary sector between Tui and Caminha were analyzed for grain-size contents, Al, As, Cr, Cu, Hg, Li, Pb, Sn, and Zn concentrations. Selected heavy metal (Cu, Cr, Hg, and Zn) and metalloid (As and Sn) distributions were normalized against Al and Li with the main goal of compensating for natural grain-size variability and to separate natural from anthropogenic contributions, by using a combination of normalization techniques (definition of regional geochemical baselines (RGB) and determination of enrichment factors (EF)). Lead did not reveal a significant relationship with Al and Li. Aluminum explained more variance than Li for As, Cu, Hg, and Zn. Assuming the general non-impacted metal character of the Minho River estuary sediments, RGBs are defined for differentiating between natural and anthropogenic contributions. Based on RGB defined for each heavy metal/metalloid, the degree of enrichment is estimated through the determination of EF. Despite the relatively low total heavy metal and metalloid concentrations, the defined RGB identifies a set of samples characterized by presenting As, Cu, Cr, Hg, and Zn enrichments relatively to expected natural levels. Mercury is the element showing the highest level of enrichment relative to the baseline values being spread through all the study area. Tin present enrichments relatively to Al and or Li always lower than 1.5 suggesting natural contributions.
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Aloupi, M., & Angelidis, M. O. (2002). The significance of coarse sediments in metal pollution studies in the coastal zone. Water, Air, and Soil Pollution, 133(1), 121–131.
Balsinha, M., Santos, A. I., Alves, A. M., & Oliveira, A. (2009). Textural composition of sediments from Minho and Douro estuaries (Portugal) and its relation with hydrodynamics. Journal of Coastal Research, 56, 1330–1334.
Bettencourt, A., & Ramos, L. (Eds.). (2003). Estuários Portugueses. Lisbon: Instituto da Água.
Canário, J., Prego, R., Vale, C., & Branco, V. (2007). Distribution of mercury and monomethylmercury in sediments of Vigo Ria, NW Iberian Peninsula. Water, Air, and Soil Pollution, 182(1), 21–29.
Carro, A. M., Rubi, E., Bollain, M. H., Lorenzo, R. A., & Cela, R. (1994). Study of the distribution of methylmercury and total mercury in grain size fractions of freeze-dried estuarine sediment samples. Applied Organometallic Chemistry, 8(7–8), 665–676.
Cato, I. (1977). Recent sedimentological and geochemical conditions and pollution problems in two marine areas in Southwestern Sweden. Striae, 6, 150.
Cato, I. (1989). Normalization of heavy metal data by the gradient method. ICES, 288–108.
Fatela, F., Moreno, J., Moreno, F., Araújo, M. F., Valente, T., Antunes, C., Taborda, R., Andrade, C., & Drago, T. (2009). Environmental constraints of foraminiferal assemblages distribution across a brackish tidal marsh (Caminha, NW Portugal). Marine Micropaleontology, 70(1–2), 70–88.
Filgueiras, A., Lavilla, I., & Bendicho, C. (2004). Evaluation of distribution, mobility and binding behaviour of heavy metals in surficial sediments of Louro River (Galicia, Spain) using chemometric analysis: a case study. Science of the Total Environment, 330(1–3), 115–129.
Gouveia, A., Araújo, M. F., & Dias, J. M. A. (1993). Rare earth element distribution in sediments from the Minho river and estuary (Portugal)—a preliminary study. Chemical Geology, 107(3–4), 379–383.
Karageorgis, A., Sioulas, A., & Anagnostou, C. (2001). Use of surface sediments in Pagassitikos Gulf, Greece, to detect anthropogenic influence. Geo-Marine Letters, 21(4), 200–211.
Loring, D. H. (1991). Normalization of heavy-metal data from estuarine and coastal sediments. ICES Journal of Marine Science, 48, 101–115.
Loring, D. H., & Rantala, R. T. T. (1992). Manual for the geochemical analyses of marine sediments and suspended particulate matter. Earth-Science Reviews, 32, 235–283.
Loureiro, J., Machado, M., Macedo, M., Nunes, M., Botelho, O., Sousa, M., Almeida, M., & Martins, J. (1986). Monografias hidrológicas dos principais cursos de água de Portugal continental. Lisbon: Direcção-Geral dos Recursos e Aproveitamentos Hidráulicos. 569 pp.
Mil-Homens, M., Stevens, R. L., Cato, I., & Abrantes, F. (2007). Regional geochemical baselines for Portuguese shelf sediments. Environmental Pollution, 148(2), 418–427.
Neiva, A. M. R. (2002). Portuguese granites associated with Sn–W and Au mineralizations. Bulletin of the Geological Society of Finland, 74(1–2), 79–101.
Nordest (2011). Handbook for calculation of measurement uncertainty in environmental laboratories, Nordest TR 537, 3rd edn. Espoo: Nordest.
Paiva, P., Araújo, M. F., Dias, J. M. A. & Jouanneau, J.-M. (1993). Distribuição Elementar em Sedimentos do Rio Minho. In F. Noronha, M. Marques & P. Nogueira (Eds.), Proceedings of the 9th Week Geochemistry and the 2nd Congress of Geochemistry of Countries of Portuguese Language (pp. 561–566). Porto: Department of Mineralogy and Geology, Faculty of Sciences, University of Oporto.
Reis, P., Antunes, J. C., & Almeida, C. (2009). Metal levels in sediments from the Minho estuary salt marsh: a metal clean area? Environmental Monitoring and Assessment, 159(1), 191–205.
Rubio, B., Nombela, M., & Vilas, F. (2000). Geochemistry of major and trace elements in sediments of the Ria de Vigo (NW Spain): an assessment of metal pollution. Marine Pollution Bulletin, 40(11), 968–980.
Santos, S., Vilar, V., Alves, P., Boaventura, R. & Botelho, C. (2012). Water quality in Minho/Miño River (Portugal/Spain). Environmental Monitoring and Assessment. doi:10.1007/s10661-012-2789-4.
Schiff, K. C., & Weisberg, S. B. (1999). Iron as a reference element for determining trace metal enrichment in Southern California coastal shelf sediments. Marine Environmental Research, 48(2), 161–176.
Schlee, J. S. (1973). Atlantic continental shelf and slope of the United States—sediment texture of the northeastern part. US Geological Survey Professional Paper 529-L 64 pp.
Schropp, S. J., Lewis, F. G., Windom, H. L., Ryan, J. D., Calder, F. D., & Burney, L. C. (1990). Interpretation of metal concentrations in estuarine sediments of Florida using aluminum as a reference element. Estuaries, 13(3), 227–235.
Shepard, F. P. (1954). Nomenclature based on sand–silt–clay ratios. Journal of Sedimentary Petrology, 24(3), 151–158.
Sousa, R., Guilhermino, L., & Antunes, J. C. (2005). Molluscan fauna in the freshwater tidal area of the River Minho estuary, NW of Iberian Peninsula. Annales de Limnologie - International Journal of Limnology, 41(02), 141–147.
Stevenson, A. G. (2001). Metal concentrations in marine sediments around Scotland: a baseline for environmental studies. Continental Shelf Research, 21(8–10), 879–897.
SuperQ (2010). SuperQ version 3.0 reference manual, panalytical, 2nd edn. Panalytical, 020401 http://www.panalytical.com/index.cfm?sid=84. Accessed Nov 2010
Summers, J. K., Wade, T. L., Engle, V. D., & Malaeb, Z. A. (1996). Normalization of metal concentrations in estuarine sediments from the Gulf of Mexico. Estuaries, 19(3), 581–594.
Tam, N. F. Y., & Yao, M. W. Y. (1998). Normalisation and heavy metal contamination in mangrove sediments. Science of the Total Environment, 216(1–2), 33–39.
Teixeira, C., & Assunção, C. T. (1961). Sheet 1-C, Caminha, Geological chart of Portugal, 1:50.000. Lisbon: Serviços Geológicos de Portugal.
Valente, T., & Leal Gomes, C. (2001). Tipologia de impacte ambiental associado à actividade extractiva no Minho—Gestão de resíduos e soluções de reabilitação. Geonovas, 15, 87–97.
Windom, H. L., Schropp, S. J., Calder, F. D., Ryan, J. D., Smith, R. G., Burney, L. C., Lewis, F. G., & Rawlinson, C. H. (1989). Natural trace metal concentrations in estuarine and coastal marine sediments of the southeastern United States. Environmental Science and Technology, 23(3), 314–320.
Zhang, J., & Liu, C. L. (2002). Riverine composition and estuarine geochemistry of particulate metals in China—weathering features, anthropogenic impact and chemical fluxes. Estuarine, Coastal and Shelf Science, 54(6), 1051–1070.
Acknowledgments
This work was financially support by the Natura Miño-Minho Project (0234 NATURA MIÑO_MINHO_1_E, North Portugal-Galiza Spain Territorial Cooperation program (POCTEP) 2007–2013). Sediment samples were recovered on board of RV Leopard Atlantic so we would like to express our gratitude to its crew who made an efficient work. We also would like to thank Carlos Antunes for Aquamuseu laboratory facilities (storage and sampling of surface sediments during the Minho09 cruise). Special thanks to all UGM-LNEG collaborators (Ana Aranda, Andreia Rebotim, Catarina Cavaleiro, Célia Santos, Cremilde Monteiro, Daniel Ferreira, Fátima Abrantes, Henrique Duarte, Rúben Borges, Sandra Mateus, Teresa Rodrigues, Warley Soares), who participated in the Minho09 cruise and helped in laboratorial work. The manuscript benefited from helpful comments and suggestions by two anonymous reviewers.
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Mil-Homens, M., Costa, A.M., Fonseca, S. et al. Natural heavy metal and metalloid concentrations in sediments of the Minho River estuary (Portugal): baseline values for environmental studies. Environ Monit Assess 185, 5937–5950 (2013). https://doi.org/10.1007/s10661-012-2996-z
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DOI: https://doi.org/10.1007/s10661-012-2996-z