Relationship between ore deposits in river catchments and geochemistry of suspended particulate matter from six rivers in southwest France

Here we present original data on the geochemical composition of fluvial particulate matter transported by the rivers of the Adour/Garonne basin, which drains one-fifth of the French land surface. Suspended particulate matter from the six main rivers in the basin, sampled at 'normal' flow and during a flood, is compared in terms of: grain size; particulate organic carbon; Fe; Mn; and trace element concentrations (e.g. Zn, Cd, Pb, Cu, Mo, Sn, Ni, Co, Cr, V, As, Hg, U, Th, W, Au, Ag, Ta). Three of the six studied rivers (Garonne, Dordogne and Isle Rivers) are the main tributaries of the Gironde estuary (southwest France), known for Cd pollution. The Adour and Gaves Rivers enter the Adour Estuary and the Charente River reaches the ocean by the Charente Estuary. Our data show, that Cd (and Zn) are not the only trace elements of eco-toxicological relevance transported into the Gulf of Biscay by these six rivers. Potentially toxic elements (e.g. As, Sn, U, Cu, Ag) show elevated concentrations in river particulates entering the estuaries, compared to world average concentrations [Martin and Whitfield, 1983, The significance of the river input of chemical elements to the oceans. In: C.S. Wong, E. Boyle, K.W. Bruland, J.D. Burton, E.D. Goldberg (editors), Trace Metals in Sea Water, Plenum, New York: pp. 265-296]. Comparing SPM sampled during 'normal' discharge and flood, the basin shows a distinct trace element composition of SPM mostly related to ore deposits in the upper basins (Massif Central and Pyreneans). This geochemical signal is partly masked during floods due to changes in grain size, but also due to increased erosion of the lower parts of the basins. This study proves pumping/centrifugation to be the most appropriate sampling/separation technique (recovery, representativity, contamination) by comparing different methods of SPM recovery.     

Land inputs of trace metals, major elements, particulate organic carbon and suspended solids to an industrial coastal bay of the NE Atlantic

Rivers, streams and municipal and industrial effluents flowing into the Ferrol Ria (NW Spain) were analyzed for dissolved and particulate trace elements (Cd, Cu, Pb, Zn), particulate major elements (Al, Fe, Si), particulate organic carbon and nitrogen (POC and PON), and total suspended solids. Trace metal clean techniques were applied. Mean annual fluxes of these components were calculated. Dissolved trace metal concentrations in the major freshwater inputs were found to be within typical values for uncontaminated rivers: Cd: 0.020-0.035 nM; Cu: 11.7-19.2 nM; Pb: 0.40-0.71 nM and Zn: 18-54 nM. Two sources of suspended particulate matter (SPM) were observed: (i) a detrital SPM, which becomes more important at high river discharges, with metal concentrations tending to lithogenic values; (ii) an organic- and metal-rich SPM, which becomes dominant at low discharges. Municipal and industrial effluents in the northern shore, despite of constitute a minor freshwater contribution to the bay, were responsible for more than 50% of total inputs of Cu, Cd, Pb, Zn, POC and PON. The fluxes of trace metals obtained for the Ferrol Ria are in the range of other inhabited world semi-enclosed embayments.     

Composition of particulate and dissolved organic matter in a disturbed watershed of southeast Brazil (Piracicaba River basin)

The elemental and isotopic composition of particulate and dissolved organic matter was investigated in the Piracicaba River basin, S?o Paulo State, Brazil. Comparison of riverine organic matter from the Piracicaba River basin, a region where rivers and streams receive urban sewage and industrial effluents, with data reported for the pristine Amazon system revealed significant differences associated with anthropogenic impacts. One important difference was N enrichment in the particulate organic material of the Piracicaba basin rivers, due to (a) urban and industrial effluents, and (b) enhanced phytoplankton growth, which results from the combination of nutrient enrichment and damming of sections of the rivers. Radiocarbon concentrations were overall more depleted (older 14C age) in the Piracicaba basin rivers than in the Amazon, which may reflect the importance of soil erosion in the former. Analyses of stable and radioactive carbon isotopes and lignin-derived compounds indicated that coarse particulate organic material is composed of a mixture of soil particles and degraded organic matter from C3 and C4 vascular plants. Fine particulate organic material was composed mainly of soil particles and phytoplankton cell remains, the latter especially during low water. Ultrafiltered dissolved organic matter was the most degraded fraction according to its lignin oxidation products, and showed the greatest influence of C4 plant sources.     

The fate and transport of mercury, methylmercury, and other trace metals in Chesapeake Bay tributaries

Six tributaries to the Chesapeake Bay were analyzed for suspended particulate matter, dissolved organic carbon, particulate organic carbon, mercury, methylmercury, lead, nickel, zinc, cadmium, chromium, and copper. This study examined the importance of flow regime, suspended particulate concentration, and watershed characteristics on the transport of mercury, methylmercury, and other trace metals. Total mercury concentrations were higher under high flow conditions which is consistent with the tendency of this metal to bind strongly to particulate matter. Methylmercury showed less flow rate dependence. Nickel, lead, and zinc concentrations responded strongly to flow rate on the Potomac River, while weaker correlations were found on the other rivers sampled. Cadmium, copper, and chromium concentrations were the least influenced by flow. Partition coefficients calculated in this study were similar to those of other estuaries and overall decreased in the order of Hg > Ni-MMHg > Cr-Pb-Zn > Cd > Cu. Watershed yield estimates and associated retention factors were calculated for the various rivers. These calculations showed that for most of the rivers, mercury was the most strongly retained within the watershed.     

Dredging-related mobilisation of trace metals: a case study in The Netherlands

Mobilisation of contaminants is an important issue in environmental risk assessment of dredging projects. This study has aimed at identifying the effects of dredging on mobilisation of trace metals (Zn, Cu, Cd and Pb). The intensities and time scales of trace metal mobilisation were investigated during an experimental dredging project conducted under field conditions. The loss of contaminated dredge spoil is mainly reflected by increasing levels of trace metals in the suspended matter, dissolved trace metal concentrations in the water column are not significantly influenced by the dredging activities. This indicates a strong binding mechanism of trace metals to the solid phase or a fast redistribution over sorptive phases in response to oxidation of e.g. trace metal sulphides. Given the differences in levels of reactive phases (Mn, Fe, sulphides and organic matter) between the riverine suspended matter and the sediments, changes in the levels of these parameters in the suspended matter upon dredging may give information on the processes influencing the behaviour of trace metals and on the potential loss of sediment during dredging operations. Therefore, we recommend to routinely measure these parameters in studies on contaminant behaviour related to dredging activities.     

Correlations, partitioning and bioaccumulation of heavy metals between different compartments of Lake Balaton

Correlations between trace metals in dissolved and particulate phases, zooplankton, mussels and sediments in Lake Balaton were investigated. The degree of correlation between the various metals was different in each of the investigated compartments. Particulate metal concentrations (microg g(-1)) were anti-correlated with suspended particulate matter (SPM) (mg l(-1)), indicating a dilution effect, while total metal concentrations in the water column (microg l(-1)) were highly correlated with SPM, implying a major influence of the turbidity on the total metal concentrations. Between compartments, not many significant correlations were recognized. Only Ba, Ca, Sr and Mg are correlated in the sediments and in the particulate phase, suggesting common sources for both compartments. Partitioning coefficients (Kd) of trace metals between dissolved and particulate phases are generally low, typical for natural water and fairly stable over the lake. Most of the trace metals (Zn, Co, Cd and Pb) exist in the particulate phase (for about 70% of the total metal load). Cu and Ni are exceptions, showing a more equal distribution. Bioconcentration factors (BCF) of zooplankton and mussels were comparable to those of other natural waters. A negative biomagnification from suspended particulate matter to zooplankton and from sediment to mussel was recognized for all trace metals, except a small enrichment of Zn in zooplankton and Cd in mussel. Four factors were recognized in SPM and in sediments but they did not contain the same group of metals. Cluster analysis showed that metal accumulations in the sediments were different between northern and southern shores and in SPM between western and eastern areas.     

Contribution of a medium-sized tropical river to the particulate heavy-metal load for the South Atlantic Ocean

The Paraíba do Sul River is a medium-sized river, 1145 km in length with a drainage basin of 55,400 km2. The riverine fluxes of particulate metals (Cu, Cr, Zn, Mn and Fe) were investigated over 24 months. Particulate matter samples were monthly collected from April 1994 to March 1996. The first 12-month period presented lower rainfall than the second, although both periods presented average precipitation lower than the regional average. The particulate matter flux in the second period (2,042,080 t) was 250% higher than the first period (821,489 t). The same trend was observed for the associated metals, which presented higher fluxes in the second period. This study highlights the strong dependence of the transported mass on the rainfall, and consequently with the river water discharge. The Paraiba do Sul River presents a low contribution to the world oceans, although the local contribution could be considered relevant.     

Retrieval of suspended particulate matter concentrations in the Danube River from Landsat ETM data

Alternations in river channel morphology result in a disturbed natural transport of suspended particulate matter (SPM). Suspended particulate matter serves as a transport medium for various pollutants, e.g. heavy metals. It is therefore important to understand how artificial obstructions alter the natural transport of suspended matter. Measurements of SPM in rivers are traditionally carried out during in situ sampling campaigns, which can provide only a limited view of the actual spatial distribution of suspended matter over large distances. Several authors have studied how space-borne remote sensing could be used for mapping of water quality in standing waters, but with only little attention paid to rivers. This paper describes the methodology how a Landsat ETM image was used to map the spatial patterns of SPM in the Slovak portion of the Danube River. Results of our investigation reveal that the Danube River in Slovakia exhibits gradual longitudinal decrease in concentrations of SPM. Based on a strong relationship between the Landsat near-infrared band (TM4) and field measurements, we developed a map of suspended particulate matter in the Danube River with a standard error (SE) of 2.92 mg/L. This study aims to show how archived satellite data and historical water quality data can be used for monitoring of SPM in large rivers. A methodology describing the minimum samples required for sufficiently accurate results is discussed in this paper also.     

Heavy metals in Lake Balaton: water column, suspended matter, sediment and biota

During the period 1999-2002, five sampling cruises have been carried out on Lake Balaton to assess trace metal distribution in the lake and to identify major sources. Eighteen elements, including Cr, Co, Ni, Cu, Zn, Cd, Pb (trace metals) and Al, Ba, Ca, Fe, K, Mg, Mn, Na, P, S, Sr (major metals), were determined in one or more of the lake's compartments. Lower trace metal concentrations in rainwater were observed in June and February 2000, while much higher levels were present in September 2001 (during a storm event) and in snow (February 2000). In the Northern and Western parts of the lake, especially at the inflow of river Zala and the locations of the yacht harbours, metal concentrations were higher in almost all compartments. Because the lake is very shallow, storm conditions also change significantly the metal distributions in the dissolved and particulate phases. The Kis-Balaton protection system located on Zala river functions very efficiently for retaining suspended particulate matter (SPM; 72% retention) and associated metals. Metal concentrations in surface sediments of the lake showed a high variability. After normalisation for the fine sediment fraction, only a few stations including Zala mouth appeared to be enriched in trace metals. In zooplankton, Zn seemed to be much more elevated compared to the other trace metals. Based on the molar ratios of the trace metals in the various compartments and input flows of the lake, several trends could be deduced. For example, molar ratios of the trace metals in the dissolved and solid (suspended particulate matter and sediments) phases in the lake are fairly similar to those in Zala River.     

Partitioning of trace metals between dissolved and particulate phases in a typical backwater system of Kerala,India

Concentrations of dissolved and particulate trace metals (Ni, Pb, Zn and Mn) and their partitioning behaviour between the dissolved and particulate phases in a typical backwater system of Kerala, viz. the southern upstream part of Cochin Estuarine System (South India), have been studied. Spatial and temporal variations of trace metals in the dissolved and particulate phases have been discussed with special reference to pH, dissolved oxygen, salinity and suspended particulate matter. The distribution and partitioning behaviour of trace metals in the water column were found influenced by the presence of a salinity barrier across the backwater system and also by the massive use of pesticides and chemical fertilizers in the vast area of agricultural land near the backwater system. Lack of proper flushing of the backwaters, which receive large amount of trace metals through the application of pesticides and agro‐chemicals, due to the presence of the salinity barrier has significantly affected the water quality of the area.     

Single particle and inorganic characterization of rainwater collected above the North Sea

Suspended matter and the dissolved fraction of rainwater collected above the North Sea were characterized using electron probe X-ray microanalysis (EPXMA), inductively coupled plasma-optical emission spectrometry (ICP-OES) and ion chromatography (IC), respectively. Suspended particulate matter was dominated by aluminosilicates and organic particles. Fifteen particle types describe the composition of the North Sea rainwater suspended matter. Factor analysis, particle size distributions and manual EPXMA measurements illustrated the complex genesis of different particle types: terrigenous; biogenic (both marine and continental); and anthropogenic. It was demonstrated that at the beginning of a shower of rain the coarse particles that are present in the air under the cloud are washed out, while during the second phase rainout particles, formed in the cloud, become more important due to the absence of new coarse particles under the cloud. Above the sea, the total amount of suspended matter (TSM) is much smaller and more variable than above the land and also the decrease in particle diameter is less visible. Approximately 10% of the studied particles contained trace heavy metals. The dissolved compounds in the North Sea rainwater were also variable in time and space. In general, over a short period of time, the concentrations of all dissolved compounds seem to decrease during a shower, but this decrease is much larger above land than above sea. The concentrations of dissolved trace metals present in rainwater above the southern North Sea has decreased over the last 15 years.     

Solid state partitioning of trace metals in suspended particulate matter from a river system affected by smelting-waste drainage

The partitioning of particulate trace metals was investigated during one year of monthly sampling of suspended particulate matter (SPM) at eight sites along the Lot-Garonne fluvial system, known for its polymetallic pollution. The chemical partitioning in five operationally defined fractions (exchangeable/carbonate, Fe/Mn oxides, organic matter/sulfides, acid soluble, residual) was determined using a multiple single extraction approach. This approach showed that Cd, Zn, Pb and Cu were mainly associated with acid soluble phases (84-95%, 65-88%, 61-82% and 55-80% of the respective total metal content), and therefore showed a high mean potential of mobilization and bioavailability. In the Riou-Mort River, draining the smelting-wastes, Zn, Cd and Mn showed high mobility as they were little associated with the residual fraction (1-2%) and mainly bound to the 'exchangeable' fraction of SPM (60-80%), probably weakly adsorbed on amorphous freshly-precipitated sulfide and/or oxide phases. Upstream and downstream of the anthropogenic source of metallic pollution, Mn and Cd, and Zn to a lesser extent, remained highly reactive. The other trace metals were mainly associated with the residual fraction and thus less mobile. However, the multiple single extraction scheme revealed that the most reactive transport phases were non-selectively extracted by the conventional extractants used here. These selectivity problems could not have been observed if sequential extraction was used.     

Modeling copper partitioning in surface waters

Suspended particulate matter from the surface waters of the Susquehanna, Christina and Brandywine Rivers was collected by tangential flow filtration to study copper partitioning. Copper adsorption increased with an increase of suspended particles and decreased with low pH values or with an increase of dissolved organic matter. Effects of particulate organic matter on copper distribution between suspended particulate and solution phases were studied using modified aluminum oxide. An increase of particulate organic matter enhanced copper adsorption. Copper adsorption per mass of particulate organic carbon was similar for the different sources of suspended particles. A model, based on copper adsorption on particles and complexation with dissolved organic matter, was developed to assess copper partition coefficient as a function of the easily measurable water quality parameters: pH, alkalinity, dissolved organic carbon and particulate organic matter. The partitioning model was calibrated on pH edge data using suspended particles collected from the three rivers. The model was verified using partitioning data as a function of dissolved organic matter. The model adequately describes the system containing natural suspended solids collected from the surface waters.     

Heavy metal distribution,availability and fate in Sepetiba Bay,S.E. Brazil

The total flux, distribution and fate of Cu, Cr, Cd, Zn, Mn and Pb were studied in Sepetiba Bay, Rio de Janeiro, SE Brazil. Metal contamination in the bay is of the same order of magnitude as historically contaminated areas of Europe and North America, inspite of the recent (15–20 years) contamination of the area.The estimated metal fluxes to the bay in tons per year are: Cu, 2.7; Cr, 10.9; Cd, 0.9; Zn, 11.5; Mn, 20.4; and Pb, 4.5. For most metals, transport to the bay is mainly by suspended particulate matter; for Cd and Cr 90 and 47% of the total flux was in dissolved forms. Most metals transported by suspended particulate matter were in weakly bound forms.Analysis of bottom sediments showed two groups of metals in relation to their distribution and source in the bay. Manganese and Cu showed higher concentration along the southern parts of the bay, showing no correlation with the other metals, and probably being derived from natural sources. The other metals were present at higher concentrations along the depositional area of fluvial sediments, at the northern part of the bay, and are derived from industrial and urban sources.     

Removal of trace metals in the very low salinity region of the Tamar Estuary,England

Field observations have shown that the removal of a substantial proportion of the riverine influx of dissolved trace metals is a consistent feature of the very low salinity, high turbidity zone of the Tamar Estuary. Comparison of field data with the predictions of a simple sorptive equilibrium model indicates that the removal occurs through rapid uptake onto suspended particles comprising the estuarine turbidity maximum. The maintenance of relative depletion of exchangeable trace metals on this particle population is attributable to internal cycling of resuspendable particles within the estuary.     

How polluted is the Yangtze river? Water quality downstream from the Three Gorges Dam

The concentrations of major anions and cations, nitrogen and phosphorus, dissolved and particulate trace elements, and organic pollutants were determined for the middle and lower reaches of the Yangtze River (Changjiang) from below the Three Gorges Dam (TGD) to the mouth at Shanghai in November 2006. The concentration of dissolved inorganic phosphate (DIP) was constant at a low level of 6-8 microgP/L, but the concentration of nitrate (NO(3)(-)) approximately doubled downstream and was closely correlated with K(+). This translated to a daily load of well over 1000 t of dissolved inorganic nitrogen (DIN) at Datong. The average concentrations of dissolved Pb (0.078+/-0.023 microg/L), Cd (0.024+/-0.009 microg/L), Cr (0.57+/-0.09 microg/L), Cu (1.9+/-0.7 microg/L), and Ni (0.50+/-0.49 microg/L) were comparable with those in other major world rivers, while As (3.3+/-1.3 microg/L) and Zn (1.5+/-0.6 microg/L) were higher by factors of 5.5 and 2.5, respectively. The trace element contents of suspended particles of As (31+/-28 microg/g), Pb (83+/-34 microg/g), and Ni (52+/-16 microg/g) were close to maximum concentrations recommended for rivers by the European Community (EC). The average concentrations of Cd (2.6+/-1.6 microg/g), Cr (185+/-102 microg/g), Cu (115+/-106 microg/g), and Zn (500+/-300 microg/g) exceeded the EC standards by a factor of two, and Hg (4.4+/-4.7 microg/g) by a factor of 4 to 5. Locally occurring peak concentrations exceed these values up to fourfold, among them the notorious elements As, Hg, and Tl. All dissolved and particulate trace element concentrations were higher than estimates made twenty years ago [Zhang, J., Geochemistry of trace metals from Chinese river/estuary systems: an overview. Estuar Coast Shelf Sci 1995; 41: 631-658.]. The enormous loads of anthropogenic pollutants disposed to the river were diluted by the large water discharge of the Yangtze even during the lowest flow resulting in the relatively low concentration levels of trace elements and organic pollutants observed. We estimated loads of e.g. As, Pb and Ni to the East China Sea to be about 4600 kg As d(-1), 3000 kg Pb d(-1), and 2000 kg Ni d(-1). About 6000 t d(-1) of dissolved organic carbon (DOC) was delivered into the sea at the time of our cruise. We tested for 236 organic pollutants, and only the most infamous were found to be barely above detection limits. We estimated that the load of chlorinated compounds, aromatic hydrocarbons, phenols, and PAHs were between 500 and 3500 kg d(-1). We also detected eight herbicides entering the estuary with loads of 5-350 kg d(-1). The pollutant load, even when at low concentrations, are considerable and pose an increasing threat to the health of the East China Sea ecosystem.     

Stable lead isotopes ratios in major french rivers and estuaries

Lead isotopes ratios have been determined in suspended matter and water samples collected from major rivers and estuaries in France to assess their present level of Pb pollution.Most of the anthropogenic Pb found in the environment comes from Pb alkyls added to petrol. In France most petrol Pb comes from imported Pb ores which mainly have very characteristic Pb isotopes ratios (for example, a low ²⁰⁶Pb/²⁰⁷Pb ratio). Indeed, the ²⁰⁶Pb/²⁰⁷Pb ratio of aerosols sampled in France near a highway and a carpark was found to be very low (1.09-1.11). Despite not being so important with respect to atmospheric and water pollution, anthropogenic Pb produced by the iron, steel and copper production industries has also been considered and a slightly higher ²⁰⁶Pb/²⁰⁷Pb ratio (1.141) has been found from measurements made in the north of France near industrial plants.Conversely, higher ²⁰⁶Pb/²⁰⁷Pb ratios (1.197-1.206) were found in the pre-industrial sediments discharged by the rivers studied. These ratios are considered to be representative of local natural Pb during pre-industrial times.The measured Pb isotopes ratios in the suspended particulate matter compared with the two end-members show that the most polluted river is the Seine, followed by the Rhône and then the Garonne and the Loire. It is shown that anthropogenic Pb pollution is more easily detected when the solid discharge is low, such as in the Seine river. Conversely, a high particulate load can dilute the level of pollution by anthropogenic Pb and in this case Pb isotopes ratios are very similar to the natural level.As far as estuaries are concerned (the Seine estuary was not studied), variations of Pb isotopes ratios are generally observed and are attributed either to natural geochemical processes (Gironde estuary) or to man's influence (Loire and Rhône estuaries).     

Seasonal variations and annual fluxes of arsenic in the Garonne, Dordogne and Isle Rivers, France

Daily measurements of water discharges and suspended particulate matter (SPM) concentrations and monthly analyses for arsenic were conducted from 1999 to 2005 on the Garonne, Dordogne and Isle Rivers, the three main tributaries of the Gironde Estuary, France. Despite the known historical polymetallic pollution affecting the Lot-Garonne River system, the highest As concentration level was observed in the Isle River. This was explained by the geological context and various Au/As deposits in this watershed. In the three studied rivers, dissolved As concentrations showed important seasonal variations with maximum values in summer. The dissolved As concentrations were closely related to water temperature and their increase in spring/summer appeared to be induced by water temperatures above approximately 15 degrees C, independently from discharge. The reduction of As(V) to more soluble As(III) and/or destruction of solid As carrier phases by micro-organisms could explain this observation, suggesting that temperature-dependent biogeochemical processes play an important role in controlling As partition and speciation in fluvial systems. Water and SPM fluxes in the Garonne River mainly control arsenic inputs into the Gironde Estuary and the downstream coastal zones. Based on the present data, we propose an empirical model to roughly estimate the annual dissolved and particulate As fluxes in the Garonne, Dordogne and Isle Rivers from annual water and SPM fluxes. The comparison of observed As fluxes and those estimated from the empirical model suggests that resuspension of historical, polluted reservoir sediments during a major flood accounted for approximately 50% of the annual As fluxes in 2003.     

Short-term variability of dissolved trace element concentrations in the Marne and Seine rivers near Paris

The concentrations of dissolved trace elements (Li, B, Mn, Cu, As, Rb, Sr, Mo, Cd, Ba, Pb) in the Marne and Seine rivers in the Paris urban area were monitored over a 2-year period. The resulting data indicated moderate contamination of waters by the most toxic elements (Cu, As, Cd and Pb). The River Marne upstream and the River Seine downstream of the city of Paris displayed similar concentrations. However higher fluxes of trace elements were observed in the Seine than in the Marne due to their different discharges. Li, B, Rb, Sr and Ba concentrations were correlated with river discharge and concentrations were higher during high river flow. This was interpreted as a dilution by discharge from a major natural or anthropogenic source. Mn, Cu, Mo, Cd and Pb concentrations were not correlated with discharge. Dissolved Mn, Cu and Cd increased rapidly in summer, whereas the concentration of Mo decreased. These variations were attributed to redox processes. During summer when the dissolved oxygen concentrations decrease, Mn, Cu, Cd and Pb are released into solution whereas Mo is immobilised. Like metals, variations in arsenic contents were not linked with discharge. Its similarity with phosphate distribution suggests similar controls involving phytoplankton uptake and release from sediments through organic matter mineralization.