The impact of sulphide oxidation on dissolved metal (Cd, Zn, Cu, Cr, Co, Ni, U) inputs into the Lot–Garonne fluvial system (France) (original) (raw)
Related papers
Applied Geochemistry, 2004
Heavy metal (Zn, Cd, Cu and Pb) mass balances in the Lot-Garonne fluvial system have been established for 1999 and 2000. The mean annual discharges of these years are close to the mean discharge of the previous decade. The estimated annual dissolved and particulate fluxes in this model watershed integrate daily input from diffuse and point sources, diffusive fluxes at the water/sediment interface, changes in the dissolved-particulate partition and changes in sediment stock. Cadmium, Zn, Cu and Pb entering the Gironde estuary via the Garonne River (11–14 t a−1 of Cd; 1330–1450 t a−1 of Zn; 126–214 t a−1 of Cu and 127–155 t a−1 of Pb) are mainly transported in the particulate phase and the major part (i.e. ∼74 to 96% for Cd, ∼60% for Zn, ∼50 to 60% for Cu and ∼80% for Pb) is transported by the Lot River. The main anthropogenic heavy metal point source is located in a small upstream watershed (Riou-Mort River) accounting for at least 47% (Cd), ∼20% (Zn), ∼4% (Cu) and ∼7 to 9% (Pb) of the total heavy metal inputs into the Garonne River, although it contributes only 1% of the discharge. Mass balances for 1999 suggest that under mean annual hydrologic conditions on the basin scale, the heavy metal budget of the Lot-Garonne fluvial system is balanced and that the stocks of Cd [200 t; Environ. Tech. 16 (1995) 1145] and Zn in the Lot River sediment are constant under mean discharge conditions. Heavy metal input by molecular diffusion at the sediment surface represents an important component of dissolved metal inputs into the system (e.g. 30% for Cu). Except for Cu, these dissolved inputs are totally removed from solution by SPM. Based on the generally constant Zn/Cd (∼50) concentration ratio in sediment cores from the polluted Lot River reaches and the sediment stock of Cd [200 t; Environ. Tech. 16 (1995) 1145], the present day Zn stock in the Lot River sediments has been estimated at about 10,000 t. In addition to the mobilization of river-bed sediment and associated heavy metals by intense floods, local human activities, including river-bed dredging, may strongly modify the heavy metal budget of the river system. In 2000, the dredging-related remobilization of polluted Lot River sediment released 2–6 t Cd. This additional Cd point source was estimated to account for 15–43% of the gross inputs into the Gironde Estuary.
Applied Geochemistry, 2010
Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM-EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger postdepositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water-sediment interface of (i) dissolved SO 4 promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn-and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspensioninduced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ~6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.
Water, Air, and Soil Pollution, 2009
Using ICP-AES and ICP-MS, several metals were analyzed in water and suspended particulate matter (SPM) samples collected under normal turbidity conditions at various stations from Deûle river (in northern France) to assess the impact of a former smelting plant on the fate of particulate elements and on the water quality in this aquatic environment. Compared to their regional background, particulate Pb, Zn and Cd were found to be most enriched, suggesting anthropogenic inputs from bed sediments into the water column mainly due to physical disturbances induced by barges traffics. Conversely, no significant enrichments of particulate metals such as Cu, Cr and Ni were observed in Deûle SPM. Characterization of SPM with analyses of mineralogical and chemical compositions-using environmental scanning electron microscopy equipped with an energy dispersive X-ray spectrometer (ESEM/ EDS)-indicated the presence of micro-specimens attributed to anthropogenic minerals, mostly PbS and ZnS. The calculated enrichment index (or the geoaccumulation index, I geo ), enrichment factor (EF) and the partition coefficient (K d ) confirmed that SPM was strongly polluted in cadmium, lead and zinc, moderately polluted in copper and unpolluted in chromium and nickel. Based on the analytical data obtained for SPM from the BCR (European Community Bureau of Reference) sequential extraction scheme, it was concluded that: (i) the reducible phases were largely more important for the binding of Pb and Cd than that of Zn and Ni and in a lesser extent Cu and Cr; (ii) copper was found to be mostly associated with the sulphides/ organics fraction; (iii) chromium with a lithogenic origin was extracted in the largest percentage in the residual phase; and (iv) zinc was bound to the exchangeablecarbonate phase in the largest percentage in the particles analysed, followed by nickel and cadmium, suggesting that these metals might be easily remobilized if changes in environmental conditions would occur.
Journal of Soils and Sediments, 2009
Background, aim, and scope Elevated levels of heavy metals in the aquatic and soil systems can be caused by the weathering of mineralized rocks. This enrichment is often considerably enlarged by historical and current mining and smelting activities. In Poland, the most contaminated river systems are those in the Silesia region. The metalliferous ore mining and smelting industries have been the main sources of heavy metal pollutions over the last 100-170 years. The previous and present studies have shown very high concentrations of heavy metals in the bottom sediments of the Mala Panew River, the most polluted tributary of the Oder River. The main objective of this work was to study temporary changes of selected metal (Zn, Pb, and Cd) concentrations in upper layer of bottom sediments at the measuring point near the outlet of the Mala Panew River into the Oder River, and to determine the vertical distribution of the metals in the sediment cores from the most polluted middle part of this river. The mobility of the metals and their potential bioavailability were assessed based on metal partitioning in the sediments and metal concentrations in pore waters. The presented data were compared with metal concentrations in aquatic sediments from similar historical mining and smelting sites in Poland and other countries. Methods The upper layer of bottom sediment samples from the same Mala Panew River measuring point were collected six times in the period 1997-2005, while five sediment cores were collected once from the middle course of Mala Panew River in 2006. Abiotic parameters such as pH and Eh have been determined in situ. Metal contents were determined in the <20 and <63 μm size fractions of sediments after digestion in a microwave oven with aqua regia or concentrated nitric acid. Metal mobility was assessed in the selected sediment cores by the chemical forms of metals (sequential extraction method) and their concentrations in pore waters were investigated. Results The concentrations of Cd, Pb, and Zn in the upper layer of sediments varied, depending on both the season and the year of sampling. Their mean concentrations (from six samplings) are [mg/kg]: Zn 1,846, Pb 229 and Cd 73. The metal concentrations in the sediment cores varied with the depth in the range of [mg/kg]: 0.18-559 for Cd, 26.2-3,309
Environmental Pollution, 2004
The Lot–Garonne fluvial system is known for its historic heavy metal pollution resulting from mining and smelting activities since the late 19th century. Here, we report 137Cs activities and heavy metal (Cd, Zn, Cu, Pb and V) concentration–depth profiles from sediment cores retrieved in 2001 from three reservoirs in the Lot River. High mean sedimentation rates of 2.4–2.8 cm a−1 are indicated by 137Cs dating. The reservoir sediments have recorded the heavy metal deposition and thus allow establishing a connection between the temporal evolution of the heavy metal pollution and historical changes in smelting and waste-treatment proceedings. Based on heavy metal concentrations in sediments upstream of the anthropogenic inputs and bottom-sediments of the furthest downstream core (interpreted as old soil or riverbed), concentrations of ∼17, ∼82, ∼0.33 and ∼28 mg kg−1 for Cu, Zn, Cd and Pb, respectively, are proposed as natural background values for the Lot fluvial system. The geoaccumulation index (Igeo [Müller, G., 1979. Schwermetalle in den Sedimenten des Rheins-Veränderungen seit. Umschav 79, 133–149.]) revealed that the Lot River sediments must be considered as “severely polluted” in Cd and Zn. Moreover, despite remediation efforts undertaken in the former smelting site, the Lot River is still “severely” (Igeo ∼ 4) and “moderately to severely” (Igeo > 2) impacted by Cd and Zn inputs, respectively.
Groundwater contributions to metal transport in a small river affected by mining and smelting waste
Water Research, 2007
Trace metal Point source Groundwater Pollution Remediation Smelting waste a b s t r a c t The Riou Mort watershed, strongly affected by former coal mining and Zn ore treatment, has been the major source of the historical polymetallic pollution of the Lot-Garonne-Gironde fluvial-estuarine system. Two decades after the end of ore treatment, the former industrial area still contributes important amounts of metals/metalloids from various, partly unidentified, sources to the downstream river system. This study presents the high spatial variability of metal/metalloid (Cd, Zn, As, Sb, U, V) concentrations in water and suspended particulate matter (SPM) from eight observation sites during a short, intense flood event. Despite important dilution effects, the observed concentration levels at the different sites suggested additional Cd and Zn inputs, probably from polluted groundwater.
Mobilization of heavy metals from Le An River sediment
Science of The Total Environment, 1999
The release of sediment-bound heavy metals can have a significant influence on river water quality. Generally speaking, variations of pH and oxygen are among the most important chemical factors that affect the mobility of Ž . sediment-bound metals. Recent research has indicated that sulfide, measured as acid-volatile sulfide AVS , is an important partitioning component of heavy metals. We determined the metal release potential of sediments from the Le An River which receives drainage from a major copper mining operation. We found that the in-situ Cu, Pb, Zn, Cd and As concentrations of the Le An River sediments below the mine are much higher than are the global background values, but that Ni was not elevated. There is potential for mobilization of bound metals to the overlying water, the order of metal release ratio in terms of pH dependencies is Zn ) Cu ) Cdf Pb. Sulfide is not a major binding component for metals in Le An River sediment. It is more likely that the iron and manganese oxides are the most important metal binding components in the sediments of the Le An River. ᮊ
Water Research, 1995
The geochemical and granulometric characteristics of sediments from three sites in the Lot River basin contaminated by heavy metals (cadmium, lead and zinc) were studied over a period of three years. Total heavy metal concentrations show little variation with time. However, a correlation between the heavy metal concentration and the fraction of sediment particles smaller than 20 #m in the Lot River at Capdenac-Gare, a moderately polluted site, shows the occurrence of yearly variations: concentrations are highest during the winter and spring, periods of high water discharge. Correlations between various componentg of the sediments and heavy metals indicate that the heavy metal content is probably not controlled by a single geochemical component but by several. Depending on the degree of contamination of the site [no pollution, moderate pollution or high pollution) and the heavy metal investigated, high metal concentrations may be associated to iron, manganese, organic and inorganic carbon, calcium, sulfide and small particles. Heavy metal transport in the Lot River, downstream from the confluence with the polluted Riou Mort, takes place mainly in particulate form. Zinc and Cd input is definitely related to the Riou Mort.
Environmental Chemistry, 2012
Environmental context. Exchange processes at the water-sediment interface can release metals to riverine waters, having negative effects on organisms in the water column. We investigate the geochemical processes and metal exchange between the surface sediment and the overlying water under metal contamination conditions. Results suggest that the sediment can be a significant source of metal pollution in aquatic systems, particularly during anoxic events.