Abstract
The spatial distribution of Pt and Rh was assessed in Tagus estuary and their sources discussed. Both elements were analysed in superficial sediment samples (n = 72) by adsorptive cathodic stripping voltammetry. Concentrations varied within the following ranges: 0.18–5.1 ng Pt g−1 and 0.02–1.5 ng Rh g−1. Four distinct areas were established: “reference”; waste- and pluvial water discharge; motorway bridges and industrialised areas. The calculated reference median concentrations were 0.55 ng Pt g−1 and 0.27 ng Rh g−1. Linear relationships were found between Pt and Al, Fe and LOI, whereas Rh depicted scattered patterns. The highest concentrations were found nearby industrialised areas and a motorway bridge, corresponding to the enrichment of 10 and 6 times the background of Pt and Rh, respectively. The main sources of contamination to the Tagus estuary derived from historical and present industrial activities and from automotive catalytic converters. Large variations of Pt/Rh ratio (0.48–39) point to different sources, reactivity and dilution effects.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10661-019-7738-z/MediaObjects/10661_2019_7738_Fig1_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10661-019-7738-z/MediaObjects/10661_2019_7738_Fig2_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10661-019-7738-z/MediaObjects/10661_2019_7738_Fig3_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10661-019-7738-z/MediaObjects/10661_2019_7738_Fig4_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10661-019-7738-z/MediaObjects/10661_2019_7738_Fig5_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10661-019-7738-z/MediaObjects/10661_2019_7738_Fig6_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10661-019-7738-z/MediaObjects/10661_2019_7738_Fig7_HTML.png)
Similar content being viewed by others
References
Almécija, C., Sharma, M., Cobelo-García, A., Santos-Echeandía, J., & Caetano, M. (2015). Osmium and platinum decoupling in the environment: evidences in intertidal sediments (Tagus Estuary, SW Europe). Environmental Science and Technology, 49(11), 6545–6553. https://doi.org/10.1021/acs.est.5b00591.
Almécija, C., Cobelo-García, A., & Santos-Echeandía, J. (2016a). Improvement of the ultra-trace voltammetric determination of Rh in environmental samples using signal transformation. Talanta, 146, 737–743. https://doi.org/10.1016/j.talanta.2015.06.032.
Almécija, C., Cobelo-García, A., Santos-Echeandía, J., & Caetano, M. (2016b). Platinum in salt marsh sediments: behavior and plant uptake. Marine Chemistry, 185, 91–103. https://doi.org/10.1016/j.marchem.2016.05.009.
Birke, M., Rauch, U., Stummeyer, J., Lorenz, H., & Keilert, B. (2017). A review of platinum group element (PGE) geochemistry and a study of the changes of PGE contents in the topsoil of Berlin, Germany, between 1992 and 2013. Journal of Geochemical Exploration, 187, 72–96. https://doi.org/10.1016/j.gexplo.2017.09.005.
Brito, P., Prego, R., Mil-Homens, M., Caçador, I., & Caetano, M. (2018). Sources and distribution of yttrium and rare earth elements in surface sediments from Tagus estuary, Portugal. Science of The Total Environment, 621, 317–325. https://doi.org/10.1016/j.scitotenv.2017.11.245.
Cabeçadas, L. (1999). Phytoplankton production in the Tagus estuary (Portugal). Oceanologica Acta, 22(2), 205–214. https://doi.org/10.1016/S0399-1784(99)80046-2.
Cabrita, M. T., Catarino, F., & Vale, C. (1999). The effect of tidal range on the flushing of ammonium from intertidal sediments of the Tagus estuary, Portugal. Oceanologica Acta, 22(3), 291–302. https://doi.org/10.1016/S0399-1784(99)80053-X.
Caçador, I., Costa, J. L., Duarte, B., Silva, G., Medeiros, J. P., Azeda, C., Castro, N., Freitas, J., Pedro, S., Almeida, P. R., Cabral, H., & Costa, M. J. (2012). Macroinvertebrates and fishes as biomonitors of heavy metal concentration in the Seixal Bay (Tagus estuary): which species perform better? Ecological Indicators, 19, 184–190. https://doi.org/10.1016/j.ecolind.2011.09.007.
Caetano, M., Prego, R., Vale, C., de Pablo, H., & Marmolejo-Rodríguez, J. (2009). Record of diagenesis of rare earth elements and other metals in a transitional sedimentary environment. Marine Chemistry, 116(1), 36–46. https://doi.org/10.1016/j.marchem.2009.09.003.
Canário, J., Vale, C., & Caetano, M. (2005). Distribution of monomethylmercury and mercury in surface sediments of the Tagus Estuary (Portugal). Marine pollution bulletin, 50(10), 1142–5. https://doi.org/10.1016/j.marpolbul.2005.06.052
Cesário, R., Hintelmann, H., O’Driscoll, N. J., Monteiro, C. E., Caetano, M., Nogueira, M., et al. (2017). Biogeochemical Cycle of Mercury and Methylmercury in Two Highly Contaminated Areas of Tagus Estuary (Portugal). Water, Air, & Soil Pollution, 228(7), 257. https://doi.org/10.1007/s11270-017-3442-1
Cobelo-García, A., Neira, P., Mil-Homens, M., & Caetano, M. (2011). Evaluation of the contamination of platinum in estuarine and coastal sediments (Tagus Estuary and Prodelta, Portugal). Marine Pollution Bulletin, 62(3), 646–650. https://doi.org/10.1016/j.marpolbul.2010.12.018.
Cobelo-García, A., López-Sánchez, D. E., Almécija, C., & Santos-Echeandía, J. (2013). Behavior of platinum during estuarine mixing (Pontevedra Ria, NW Iberian Peninsula). Marine Chemistry, 150, 11–18. https://doi.org/10.1016/j.marchem.2013.01.005.
Craft, C. B., Seneca, E. D., & Broome, S. W. (1991). Loss on ignition and kjeldahl digestion for estimating organic carbon and total nitrogen in estuarine marsh soils: calibration with dry combustion. Estuaries, 14(2), 175–179. https://doi.org/10.2307/1351691.
Dung, T. T. T., Cappuyns, V., Swennen, R., & Phung, N. K. (2013). From geochemical background determination to pollution assessment of heavy metals in sediments and soils. Reviews in Environmental Science and Bio/Technology, 12(4), 335–353. https://doi.org/10.1007/s11157-013-9315-1.
Ebrahimi, P., & Barbieri, M. (2019). Gadolinium as an Emerging Microcontaminant in Water Resources: Threats and Opportunities. Geosciences. https://doi.org/10.3390/geosciences9020093
Ek, K. H., Morrison, G. M., & Rauch, S. (2004). Environmental routes for platinum group elements to biological materials--a review. The Science of the total environment, 334–335, 21–38. https://doi.org/10.1016/j.scitotenv.2004.04.027.
Ely, J. C., Neal, C. R., Kulpa, C. F., Schneegurt, M. A., Seidler, J. A., & Jain, J. C. (2001). Implications of platinum-group element accumulation along U.S. roads from catalytic-converter attrition. Environmental Science & Technology, 35(19), 3816–3822. https://doi.org/10.1021/es001989s.
Essumang, D. K., Dodoo, D. K., & Adokoh, C. K. (2008). The impact of vehicular fallout on the Pra estuary of Ghana (a case study of the impact of platinum group metals (PGMs) on the marine ecosystem). Environmental Monitoring and Assessment, 145(1), 283–294. https://doi.org/10.1007/s10661-007-0037-0.
European Commission. (1991). Council Directive 91/542/EEC of 1 October 1991 amending Directive 88/77/EEC on the approximation of the laws of the Member States relating to the measures to be taken against the emission of gaseous pollutants from diesel engines for use in vehicles. http://eur-lex.europa.eu/eli/dir/1991/542/oj. Accessed 22 Jan 2018
Folk, R. L. (1954). The distinction between grain size and mineral composition in sedimentary-rock nomenclature. The Journal of Geology, 62(4), 344–359. https://doi.org/10.1086/626171.
Fortunato, A., Oliveira, A., & Baptista, A. M. (1999). On the effect of tidal flats on the hydrodynamics of the Tagus estuary. Oceanologica Acta, 22(1), 31–44. https://doi.org/10.1016/S0399-1784(99)80030-9.
Freire, P., Taborda, R., & Silva, A. (2007). Sedimentary characterization of Tagus estuarine beaches (Portugal). Journal of Soils and Sediments, 7(5), 296–302. https://doi.org/10.1065/jss2007.08.243.
Gaudêncio, M. J., Guerra, M. T., & Glémarec, M. (1991). Recherches biosédimentaires sur la zone maritime de l’estuaire du Tage, Portugal: données préliminaire. In M. Elliott & J.-P. Ducrotoy (Eds.), Estuaries and Coasts: Spatial and Temporal Intercomparisons. ECSA 19 Symposium, Caen, (pp. 11–16).
Gil, O., & Vale, C. (1999). DDT concentrations in surficial sediments of three estuarine systems in Portugal. Aquatic Ecology, 33(3), 263–269. https://doi.org/10.1023/A:1009961901782.
Hatfield, W. R., Beshty, B. S., Lee, H. C., Heck, R. M., & Hsiung, T. M. (1987). Method for recovering platinum in a nitric acid plant. Google Patents.
Haus, N., Eybe, T., Zimmermann, S., & Sures, B. (2009). Is microwave digestion using TFM vessels a suitable preparation method for Pt determination in biological samples by adsorptive cathodic stripping voltammetry? Analytica chimica acta, 635(1), 53–57. https://doi.org/10.1016/j.aca.2008.12.043.
IMT. (2016). Relatório de Tráfego na Rede Nacional de Autoestradas - 4 o Trimestre. Lisboa, Portugal.
Jarvis, K. E., Parry, S. J., & Piper, J. M. (2001). Temporal and spatial studies of autocatalyst-derived platinum, rhodium, and palladium and selected vehicle-derived trace elements in the environment. Environmental Science & Technology, 35(6), 1031–1036. https://doi.org/10.1021/es0001512.
Kašpar, J., Fornasiero, P., & Hickey, N. (2003). Automotive catalytic converters: current status and some perspectives. Catalysis Today, 77(4), 419–449. https://doi.org/10.1016/S0920-5861(02)00384-X.
Laschka, D., & Nachtwey, M. (1997). Platinum in municipal sewage treatment plants. Chemosphere, 34(8), 1803–1812. https://doi.org/10.1016/S0045-6535(97)00036-2.
Lemaire, A., Dournel, P., & Deschrijver, P. (2014). Process for the manufacture of hydrogen peroxide. Google Patents.
Loring, D. H., & Rantala, R. T. T. (1992). Manual for the geochemical analyses of marine sediments and suspended particulate matter. Earth-Science Reviews, 32(4), 235–283. https://doi.org/10.1016/0012-8252(92)90001-A.
Marques da Costa, E. (2016). Sócio-Economia. In J. Rocha (Ed.), Atlas Digital da Área Metropolitana de Lisboa. Lisboa, Portugal: Centro de Estudos Geográficos. ISBN: 978-972-636-258-6
Mateus, M., & Neves, R. (2008). Evaluating light and nutrient limitation in the Tagus estuary using a process-oriented ecological model. Journal of Marine Engineering & Technology, 7(2), 43–54. https://doi.org/10.1080/20464177.2008.11020213.
Matys Grygar, T., & Popelka, J. (2016). Revisiting geochemical methods of distinguishing natural concentrations and pollution by risk elements in fluvial sediments. Journal of Geochemical Exploration, 170, 39–57. https://doi.org/10.1016/j.gexplo.2016.08.003.
Mihaljevič, M., Galušková, I., Strnad, L., & Majer, V. (2013). Distribution of platinum group elements in urban soils, comparison of historically different large cities Prague and Ostrava, Czech Republic. Journal of Geochemical Exploration, 124, 212–217. https://doi.org/10.1016/j.gexplo.2012.10.008.
Mil-Homens, M., Caetano, M., Costa, A. M., Lebreiro, S., Richter, T., de Stigter, H., Trancoso, M. A., & Brito, P. (2013). Temporal evolution of lead isotope ratios in sediments of the Central Portuguese Margin: a fingerprint of human activities. Marine Pollution Bulletin, 74(1), 274–284. https://doi.org/10.1016/j.marpolbul.2013.06.044.
Mil-Homens, M., Vicente, M., Grimalt, J. O., Micaelo, C., & Abrantes, F. (2016). Reconstruction of organochlorine compound inputs in the Tagus Prodelta. Science of The Total Environment, 540, 231–240. https://doi.org/10.1016/j.scitotenv.2015.07.009.
Miller, J., & Miller, J. (2010). Statistics and chemometrics for analytical chemistry (6th ed.). Pearson Education Limited. ISBN: 978-0-273-73042-2
Moldovan, M., Palacios, M. A., Gómez, M. M., Morrison, G., Rauch, S., McLeod, C., Ma, R., Caroli, S., Alimonti, A., Petrucci, F., Bocca, B., Schramel, P., Zischka, M., Pettersson, C., Wass, U., Luna, M., Saenz, J. C., & Santamarı́a, J. (2002). Environmental risk of particulate and soluble platinum group elements released from gasoline and diesel engine catalytic converters. Science of The Total Environment, 296(1), 199–208. https://doi.org/10.1016/S0048-9697(02)00087-6.
Monteiro, C. E., Cesário, R., O’Driscoll, N. J., Nogueira, M., Válega, M., Caetano, M., & Canário, J. (2016). Seasonal variation of methylmercury in sediment cores from the Tagus Estuary (Portugal). Marine Pollution Bulletin, 104(1), 162–170. https://doi.org/10.1016/j.marpolbul.2016.01.042.
Monteiro, C. E., Cobelo-Garcia, A., Caetano, M., & Correia dos Santos, M. M. (2017). Improved voltammetric method for simultaneous determination of Pt and Rh using second derivative signal transformation – application to environmental samples. Talanta, 175, 1–8. https://doi.org/10.1016/j.talanta.2017.06.067.
Nygren, O., Vaughan, G. T., Florence, T. M., Morrison, G. M., Warner, I. M., & Dale, L. S. (1990). Determination of platinum in blood by adsorptive voltammetry. Analytical chemistry, 62(15), 1637–1640. https://doi.org/10.1021/ac00214a020.
Paparatto, G., De, A. G., D’aloisio, R., & Buzzoni, R. (2010). Catalyst and its use in the synthesis of hydrogen peroxide. Google Patents.
Peucker-Ehrenbrink, B., & Jahn, B. (2001). Rhenium-osmium isotope systematics and platinum group element concentrations: loess and the upper continental crust. Geochemistry, Geophysics, Geosystems, 2(10), n/a–n/a. https://doi.org/10.1029/2001GC000172.
Prichard, H. M., & Fisher, P. C. (2012). Identification of platinum and palladium particles emitted from vehicles and dispersed into the surface environment. Environmental Science & Technology, 46(6), 3149–3154. https://doi.org/10.1021/es203666h.
Prichard, H. M., Jackson, M. T., & Sampson, J. (2008). Dispersal and accumulation of Pt, Pd and Rh derived from a roundabout in Sheffield (UK): from stream to tidal estuary. Science of The Total Environment, 401(1), 90–99. https://doi.org/10.1016/j.scitotenv.2008.03.037.
Prudêncio, M. I., Braga, M. A. S., & Gouveia, M. A. (1993). REE mobilization, fractionation and precipitation during weathering of basalts. Chemical Geology, 107(3), 251–254. https://doi.org/10.1016/0009-2541(93)90185-L.
Rauch, S., & Peucker-Ehrenbrink, B. (2015). In F. Zereini & C. L. S. Wiseman (Eds.), Sources of platinum group elements in the environment BT - platinum metals in the environment (pp. 3–17). Berlin: Springer Berlin Heidelberg. https://doi.org/10.1007/978-3-662-44559-4_1.
Rauch, S., Morrison, G. M., & Moldovan, M. (2002). Scanning laser ablation-ICP-MS tracking of platinum group elements in urban particles. Science of The Total Environment, 286(1), 243–251. https://doi.org/10.1016/S0048-9697(01)00988-3.
Rauch, S., Hemond, H. F., Barbante, C., Owari, M., Morrison, G. M., Peucker-Ehrenbrink, B., & Wass, U. (2005). Importance of automobile exhaust catalyst emissions for the deposition of platinum, palladium, and rhodium in the northern hemisphere. Environmental science & technology, 39(21), 8156–8162.
Rauch, S., Peucker-Ehrenbrink, B., Molina, L. T., Molina, M. J., Ramos, R., & Hemond, H. F. (2006). Platinum group elements in airborne particles in Mexico City. Environmental Science & Technology, 40(24), 7554–7560. https://doi.org/10.1021/es061470h.
Ravindra, K., Bencs, L., & Van Grieken, R. (2004). Platinum group elements in the environment and their health risk. The Science of the total environment, 318(1–3), 1–43. https://doi.org/10.1016/S0048-9697(03)00372-3.
Ruchter, N., & Sures, B. (2015). Distribution of platinum and other traffic related metals in sediments and clams (Corbicula sp.). Water Research, 70, 313–324. https://doi.org/10.1016/j.watres.2014.12.011.
Ruchter, N., Zimmermann, S., & Sures, B. (2015). Field studies on PGE in aquatic ecosystems. In Platinum Metals in the Environment (pp. 351–360). Springer.
Santos-Echeandía, J., Vale, C., Caetano, M., Pereira, P., & Prego, R. (2010). Effect of tidal flooding on metal distribution in pore waters of marsh sediments and its transport to water column (Tagus estuary, Portugal). Marine environmental research, 70(5), 358–367. https://doi.org/10.1016/j.marenvres.2010.07.003.
Schlitzer, R. (2017). Ocean Data View, odv.awi.de.
Sutherland, R. A., Pearson, G. D., Ottley, C. J., & Ziegler, A. D. (2015). Platinum-group elements in urban fluvial bed sediments—Hawaii. In Platinum Metals in the Environment (pp. 163–186). Springer.
Taborda, R., Freire, P., Silva, A., Andrade, C., & Freitas, M. (2009). Origin and evolution of Tagus estuarine beaches. Journal of Coastal Research, SI(56), 213–217.
Taylor, S. R., & McLennan, S. M. (1995). The geochemical evolution of the continental crust. Reviews of Geophysics, 33(2), 241–265. https://doi.org/10.1029/95RG00262.
Terashima, S., Katayama, H., & Itoh, S. (1993). Geochemical behavior of Pt and Pd in coastal marine sediments, southeastern margin of the Japan Sea. Applied Geochemistry, 8(3), 265–271. https://doi.org/10.1016/0883-2927(93)90041-E.
Troupin, C., Barth, A., Sirjacobs, D., Ouberdous, M., Brankart, J.-M., Brasseur, P., et al. (2012). Generation of analysis and consistent error fields using the Data Interpolating Variational Analysis (DIVA). Ocean Modelling, 52–53(Supplement C), 90–101. https://doi.org/10.1016/j.ocemod.2012.05.002.
Vale, C., & Sundby, B. (1987). Suspended sediment fluctuations in the Tagus estuary on semi-diurnal and fortnightly time scales. Estuarine, Coastal and Shelf Science, 25(5), 495–508. https://doi.org/10.1016/0272-7714(87)90110-7.
Vale, C., Canário, J., Caetano, M., Lavrado, J., & Brito, P. (2008). Estimation of the anthropogenic fraction of elements in surface sediments of the Tagus Estuary (Portugal). Marine Pollution Bulletin, 56(7), 1364–1367. https://doi.org/10.1016/j.marpolbul.2008.04.006.
Vaz, N., Mateus, M., & Dias, J. M. (2011). Semidiurnal and spring-neap variations in the Tagus Estuary : application of a process-oriented hydro-biogeochemical model. Journal of Coastal Research, SI(64), 1619–1623.
Vyas, N., Turner, A., & Sewell, G. (2014). Platinum-based anticancer drugs in waste waters of a major UK hospital and predicted concentrations in recipient surface waters. Science of The Total Environment, 493, 324–329. https://doi.org/10.1016/j.scitotenv.2014.05.127.
Wei, C., & Morrison, G. M. (1994). Platinum in road dusts and urban river sediments. Science of The Total Environment, 146–147(Supplement C), 169–174. https://doi.org/10.1016/0048-9697(94)90234-8.
Wiseman, C. L. S., & Zereini, F. (2009). Airborne particulate matter, platinum group elements and human health: a review of recent evidence. The Science of the total environment, 407(8), 2493–2500. https://doi.org/10.1016/j.scitotenv.2008.12.057.
Wiseman, C. L. S., Zereini, F., & Püttmann, W. (2013). Traffic-related trace element fate and uptake by plants cultivated in roadside soils in Toronto, Canada. Science of The Total Environment, 442, 86–95. https://doi.org/10.1016/j.scitotenv.2012.10.051.
Wiseman, C. L. S., Hassan Pour, Z., & Zereini, F. (2016). Platinum group element and cerium concentrations in roadside environments in Toronto, Canada. Chemosphere, 145, 61–67. https://doi.org/10.1016/j.chemosphere.2015.11.056.
Zereini, F., & Wiseman, C. L. S. (2015). In F. Zereini & C. L. S. Wiseman (Eds.), Platinum Metals in the Environment. Berlin: Springer Berlin Heidelberg. https://doi.org/10.1007/978-3-662-44559-4.
Zereini, F., Alt, F., Messerschmidt, J., von Bohlen, A., Liebl, K., & Püttmann, W. (2004). Concentration and distribution of platinum group elements (Pt, Pd, Rh) in airborne particulate matter in Frankfurt am Main, Germany. Environmental Science & Technology, 38(6), 1686–1692. https://doi.org/10.1021/es030127z.
Zereini, F., Wiseman, C., & Püttmann, W. (2007). Changes in palladium, platinum, and rhodium concentrations, and their spatial distribution in soils along a major highway in Germany from 1994 to 2004. Environmental Science & Technology, 41(2), 451–456. https://doi.org/10.1021/es061453s.
Zhong, L., Yan, W., Li, J., Tu, X., Liu, B., & Xia, Z. (2012). Pt and Pd in sediments from the Pearl River Estuary, South China: background levels, distribution, and source. Environmental Science and Pollution Research, 19(4), 1305–1314. https://doi.org/10.1007/s11356-011-0653-7.
Acknowledgements
Carlos E. Monteiro (CEM) acknowledges the Portuguese Foundation for Science and Technology (FCT) for the grant funding of his PhD (SFRH/BD/111087/2015). The authors would like to gratefully acknowledge also the support of FCT projects UID/QUI/001002013 and PTDC/QEQ-EPR/1249/2014 ‘Recovery versus environmental impacts of Rare Earth Elements derived from human activities’ (REEuse); the COST Action TD1407, Network on Technology-Critical Elements (NOTICE), from environmental processes to human health threats, by means of a short-term scientific mission support to CEM; and the support of Rute Cesário in part of the field work and ICP-MS analysis.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 1098 kb)
Rights and permissions
About this article
Cite this article
Monteiro, C.E., Correia dos Santos, M., Cobelo-García, A. et al. Platinum and rhodium in Tagus estuary, SW Europe: sources and spatial distribution. Environ Monit Assess 191, 579 (2019). https://doi.org/10.1007/s10661-019-7738-z
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s10661-019-7738-z