Geochemical signals and source contributions to heavy metal (Cd, Zn, Pb, Cu) fluxes into the Gironde Estuary via its major tributaries

Daily measurements of water discharges and suspended particulate matter (SPM) concentrations and monthly sampling for trace element analyses (Cd, Zn, Pb and Cu) were conducted from 1999 to 2002 on the Garonne, Dordogne and Isle Rivers, the three main tributaries of the Gironde Estuary, France. Dissolved and particulate Cd, Zn, Pb and Cu concentrations in the Isle River were generally higher than those in the Garonne River, despite the known historical polymetallic pollution affecting the Lot-Garonne River system. Even if the relatively high dissolved metal concentrations in the Isle River may be of importance for the local ecosystem, metal inputs into the estuarine and coastal zones are mainly controlled by fluvial transport via the Garonne River. Characteristic element concentration ratios (e.g., Zn/Pb) in SPM and stream sediments from the Dordogne and Isle Rivers suggest two different metal source areas with distinct geochemical signals. Low Zn/Pb ratios (<8) and low Cu/Pb ratios (<0.8) have been attributed to upstream source zones in the Massif Central, featuring various ore deposits and mining areas. High Zn/Pb ratios were assigned to downstream sources (e.g., vineyards), partly explaining high Zn and Cu concentrations and high Cu/Pb ratios (>0.8) in SPM. Although SPM derived from the upstream parts of the studied watersheds may greatly contribute to the observed fluvial metal transport (up to approximately 80% for Pb), the results suggest that intensive agriculture also considerably influences gross metal (e.g., Zn, Cu) fluxes into the Gironde Estuary. Relative contributions of upstream and downstream source zones may vary from one year to another reflecting hydrological variations and/or reservoir management. Monitoring fluxes and identifying distinct geochemical signals from source areas in heterogeneous watersheds may greatly improve understanding of contaminant transport to the coast.     

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.     

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.     

Chemical composition of suspended sediments in World Rivers: New insights from a new database

The aim of this paper is to present a new database on the chemical composition of suspended matter in World Rivers, together with the associated elemental fluxes. There is a lack of any recent attempt in the literature to update the pioneering work of Martin and Meybeck [Martin, J.-M., Meybeck, M., 1979. Elemental mass balance of material carried by major world rivers. Mar. Chem. 7, 173-206.] and Martin and Whitfield [Martin, J.-M., Whitfield, M., 1983. The significance of the river input of chemical elements to the ocean. Trace metals in sea water Wong, Boyle, Bruland, Burton, Goldberg (Eds) Plenum Publishing Corporation.] regarding the worldwide average major and trace element chemistry of riverine particulate matter.Apart from compiling a new database on particulate matter, this paper also aims to give a “snap-shot” of elemental fluxes for each continent. This approach should allow us to obtain new insights on weathering conditions in different environments and assess the influence of human activities on natural geochemical cycles. Finally, this study demonstrates the large uncertainties currently associated with estimating the flux of sediments transported by rivers.By comparing the riverine suspended sediment fluxes of some metals (Cd, Zn, Ni, Cu, Cr and Pb) given in this study with estimates of the anthropogenic fluxes of these metals to the atmosphere, soils and waters (natural ecosystems) [Nriagu, J.O., 1988. A silent epidemic of environmental poisoning. Environ. Pollut. 50, 139-161.], we can see that riverine fluxes are similar to anthropogenic fluxes. This casts light on the effect of human activities on the cycles of trace elements at the Earth's surface.     

Sampling frequency and accuracy of SPM flux estimates in two contrasted drainage basins

The present paper is based on discharges and suspended particulate matter concentrations from a 9-years high-resolution database for the Garonne River (large plain river) covering contrasted hydrologic years, and a 12-months high frequency sampling for the Nivelle River (small mountainous river). Annual SPM fluxes in the Garonne River range from 0.6 x 10(6) t year(-1) (1997) to 3.9 x 10(6) t year(-1) (1996). In contrast, the Nivelle River transported 11 x 10(3) t year(-1) from December 1995 to December 1996. From the long-term observation of the Garonne River an empirical relation between SPM* (discharge-weighted mean annual SPM concentrations) and annual discharge was established. This relation allows estimating annual SPM fluxes for the Garonne River with less than 30% deviation from reference values for the whole range of mean annual discharge observed during the past decade. Specific (=area-normalized) annual SPM fluxes (YSPM) range from 11 to 74 t km(-2) year(-1) for the Garonne River. Comparison of these results with YSPM of the Nivelle River (69 t km(-2) year(-1) in 1996) suggests that interannual hydrological variations may have a greater impact on fluvial SPM transport than basin-specific parameters. By extracting individual SPM concentrations and corresponding discharge values from the database, different sampling frequencies were simulated and resulting SPM fluxes were then compared to reference fluxes derived from the complete database. If a deviation of simulated flux estimates from reference fluxes lower than +/-20% is accepted, the Garonne River (large plain river) must be sampled at least every 3 days (10 samples per month) and the Nivelle River every 7 h (approx. 100 samples per month). For the Garonne River this minimum sampling frequency is valid for all contrasted hydrologic years of the observation period. Below these minimum sampling frequencies, annual SPM flux estimates may greatly differ from reference fluxes (up to 200%) and there is high probability of systematic underestimation. Consequently, annual SPM flux estimates for the Garonne River derived from the empirical relation (SPM*-annual discharge) are likely to be more satisfactory (errors <30%) than estimates based on sampling frequencies lower than the minimum frequency. These findings underline the need of adapted sampling strategies for erosion assessment, reliable chemical (e.g. nutrients and pollutants) mass balances and characterisation of fluvial transport mechanisms in the world's contrasted watersheds.     

Geochemical studies in several rivers and estuaries used for oyster rearing

Base-line studies have been carried out on the trace metal content of bottom sediments and waters of five estuaries and their catchment drainage, representing both contaminated and relatively uncontaminated environments. Relationships have been established between the composition of water and sediments in tributary drainage and those in the estuary. In particular, regional contamination of the hinterland with one or more of the elements As, Cd, Cu, Pb, Zn and Sn from mining and smelting activity was reflected by enhancement in estuarine muds in relation to the proportion of the catchment affected and the degree of contamination. Preliminary observations on young oysters showed that in general metal accumulation reflected the geochemical status of the estuary. These investigations have confirmed the potential use of geochemical reconnaissance maps based on stream sediment analysis as a means of focussing attention on rivers and estuaries affected by regional metal pollution.     

The influence of contrasting suspended particulate matter transport regimes on the bias and precision of flux estimates

A large database (507 station-years) of daily suspended particulate matter (SPM) concentration and discharge data from 36 stations on river basins ranging from 600 km(2) to 600,000 km(2) in size (USA and Europe) was collected to assess the effects of SPM transport regime on bias and imprecision of flux estimates when using infrequent surveys and the discharge-weighted mean concentration method. By extracting individual SPM concentrations and corresponding discharge values from the database, sampling frequencies from 12 to 200 per year were simulated using Monte Carlo techniques. The resulting estimates of yearly SPM fluxes were compared to reference fluxes derived from the complete database. For each station and given frequency, bias was measured by the median of relative errors between estimated and reference fluxes, and imprecision by the difference between the upper and lower deciles of relative errors. Results show that the SPM transport regime of rivers affects the bias and imprecision of fluxes estimated by the discharge-weighted mean concentration method for given sampling frequencies (e.g. weekly, bimonthly, monthly). The percentage of annual SPM flux discharged in 2% of time (Ms(2)) is a robust indicator of SPM transport regime directly related to bias and imprecision. These errors are linked to the Ms(2) indicator for various sampling frequencies within a specific nomograph. For instance, based on a deviation of simulated flux estimates from reference fluxes lower than +/-20% and a bias lower than 1% or 2%, the required sampling intervals are less than 3 days for rivers with Ms(2) greater than 40% (basin size<10,000 km(2)), between 3 and 5 days for rivers with Ms(2) between 30 and 40% (basin size between 10,000 and 50,000 km(2)), between 5 and 12 days for Ms(2) from 20% to 30% (basin size between 50,000 and 200,000 km(2)), 12-20 days for Ms(2) in the 15-20% range (basin size between 200,000 and 500,000 km(2)).     

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.     

Cadmium transport in the Lot-Garonne River system (France) - temporal variability and a model for flux estimation

Fluvial cadmium (Cd) inputs into the Gironde estuary via the Lot-Garonne River system were evaluated using nine years of daily measurements of water discharge and total suspended sediment content (TSS) combined with monthly analyses of dissolved and particulate Cd concentrations. This study demonstrates that dissolved and particulate Cd concentrations in the Lot River have strongly decreased in the early 1990s. However, dissolved and particulate Cd concentrations in the Lot River are still higher than those in the Garonne River. In 1992-1998 mean annual Cd concentrations are more or less constant and thus, annual Cd fluxes mainly depend on hydrology. Daily total Cd fluxes range from 0.26 to 966 kg day(-1) in the Lot River and from 0.31 to 1360 kg day(-1) in the Garonne River, downstream their confluence. During dry years, Cd fluxes at La Réole are dominated by inputs from the upstream Garonne River, whereas during wet years they are controlled by inputs from the polluted Lot River watershed. The relation between particulate and dissolved Cd fluxes depends on TSS concentrations, which appear to be mainly controlled by the succession of floods and low waters reflecting short-term basin-scale climate variability. Cadmium concentrations, fluxes and the ratio between the particulate and dissolved Cd fluxes depends on the absolute value and instantaneous evolution (strong relative increase or decrease) of discharge. An empiric model permits deducing intervals of daily dissolved Cd fluxes from discharge, hydrological key situation and related intervals of 'typical' dissolved Cd concentrations. In 1992-1998 the Lot-Garonne River system shows close relations between annual dissolved and particulate Cd fluxes. These relations allow deducing annual particulate Cd fluxes using annual dissolved Cd fluxes obtained from the model. The validation a posteriori shows that our empiric model accurately reproduces the annual Cd fluxes estimated from the field data with uncertainty lower than 25% for dissolved fluxes and lower than 30% for the particulate fluxes. Consequently, the empiric model permits estimating annual dissolved and particulate Cd fluxes in the Lot-Garonne River system, from daily discharge data, without Cd analysis. Cadmium fluxes obtained from the model may be used as approximate values for gross fluvial Cd inputs into the Gironde estuary.     

The spatial and temporal trends of Cd, Cu, Hg, Pb and Zn in Seine River floodplain deposits (1994-2000)

Fresh floodplain deposits (FD), from 11 key stations, covering the Seine mainstem and its major tributaries (Yonne, Marne and Oise Rivers), were sampled from 1994 to 2000. Background levels for Cd, Cu, Hg, Pb, and Zn were established using prehistoric FD and actual bed sediments collected in small forested sub-basins in the most upstream part of the basin. Throughout the Seine River Basin, FD contain elevated concentrations of Cd, Cu, Hg, Pb and Zn compared to local background values (by factors>twofold). In the Seine River Basin, trace element concentrations display substantial downstream increases as a result of increasing population densities, particularly from Greater Paris (10 million inhabitants), and reach their maxima at the river mouth (Poses). These elevated levels make the Seine one of the most heavily impacted rivers in the world. On the other hand, floodplain-associated trace element levels have declined over the past 7 years. This mirrors results from contemporaneous suspended sediment surveys at the river mouth for the 1984-1999 period. Most of these temporal declines appear to reflect reductions in industrial and domestic solid wastes discharged from the main Parisian sewage plant (Seine Aval).     

Copper addition by organic matter degradation in the freshwater reaches of a turbid estuary

This study reports on the relationship between copper (Cu) behavior and organic matter (OM) transformation along the turbidity gradient in the freshwater reaches of the Gironde Estuary. During a one-year survey, surface water and suspended particulate matter (SPM) were sampled at least monthly at three sites along the Garonne Branch, representing the main fluvial branch of the Gironde Estuary. Additionally, a longitudinal high resolution profile was sampled along the Garonne Branch, covering the turbidity gradient from the river water endmember to the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of Cu in both the dissolved phases (< 0.2 μm, Cu_0.2 and < 0.02 μm, Cu_0.02) and particulate Cu (Cu_P) clearly suggested Cu_0.2 addition during summer, that increased the Cu_0.2 concentrations by a factor ~ 2, mainly manifested by an increase in the Cu_0.02 fraction. At the annual timescale (2004), this internal Cu reactivity increased Cu_0.02 fluxes in the Garonne Branch by ~ 20% (3.6 t year⁻¹), with the equivalent of ~ 2.9 t year⁻¹ derived from the Cu_P fraction and ~ 0.7 t year⁻¹ from the colloidal (0.02-0.2 μm) fraction, without involving and/or affecting the Cu_C18 (hydrophobic metal-organic complexes) fraction.Combining data on Cu speciation with the results obtained by several independent techniques (DOC and POC measurements, 3D-fluorescence, and TEM) suggested close relationships between Cu behavior and OM transformation/restructuration along the turbidity gradient in the Garonne Branch. The observed Cu_0.02 addition was related to increasing humification (humification index HIX increased from 9 to 12, network formation) and labile OM degradation (Iγ/Iα ratio decreased from 0.70 to 0.44), going along with decreasing DOC and POC concentrations. Mass-balances suggest that in the studied system, degradation of OM may account for the release of ~ 25 μmol potentially bioaccessible Cu_0.02 per mole of particulate organic carbon mineralized.     

Geochemical survey and metal bioaccumulation of three bivalve species (Crassostrea gigas, Cerastoderma edule and Ruditapes philippinarum) in the Nord Medoc salt marshes (Gironde estuary, France)

A 15-month experiment combining a geochemical survey of Cd, Cu, Zn and Hg with a bioaccumulation study for three filter-feeding bivalve species (oysters, Crassostrea gigas; cockles, Cerastoderma edule; and clams, Ruditapes philippinarum) was conducted in a breeding basin of the Nord Medoc salt marshes connected to the Gironde estuary, which is affected by historic polymetallic pollution. Regular manual surface measurements of temperature, salinity, pH and dissolved O(2) concentration and hourly multiprobe in situ measurements throughout several periods for 6-8 weeks were performed. The geochemical behavior of metals in water, suspended particulate matter and sediment and their ecotoxicological impact on the three bivalve species were evaluated by in situ exposure of juvenile oysters (water column) and adult cockles and clams (sediment surface). The physico-chemical parameters reflected seasonal variations and basin management. A distinct daily periodicity (except salinity) indicated intense photosynthesis and respiration. In summer, low dissolved O(2) saturations ( approximately 40-50%) occurred in the early morning at 30 cm above the sediment, whereas in depressions, the water column near the sediment surface was suboxic. Cadmium, Zn and Cu concentrations in suspended particulate matter exceeded typical estuarine values and were much higher than the homogeneously distributed concentrations in different depth ranges of the basin sediment. Particles collected in sediment traps showed intermediate metal concentrations close to sediment values. These results suggest trace metal recycling due to reductive dissolution under suboxic conditions at the sediment surface resulting in trace metal release to the water column and adsorption onto suspended particles. Dissolved Cd, Zn and Hg concentrations (e.g. 13-136 ng l(-1); 0.3-25.1 microg l(-1) and 0.5-2.0 ng l(-1), respectively) in the basin corresponded to the concentration range typically observed in the Gironde estuary, except for some maximum values attributed to metal recycling. In contrast, dissolved Cu concentrations (1.08-6.08 microg l(-1)) were mostly higher than typical estuarine values, probably due to recycled Cu complexation by dissolved organic matter. Growth, bioaccumulation rates and kinetics in the whole soft body of the bivalves were analyzed every 40 days. Although Cd bioaccumulation of oysters was lower in the basin than in the estuary during the same period (27,000 ng g(-1), dry weight and 40,000 ng g(-1), respectively) these values are largely above the new human consumption safety level (5000 ng g(-1), dw; European Community, 2002). For cockles and clams, Cd bioaccumulation was lower, reaching 1400 ng g(-1) and 950 ng g(-1), respectively. Similar results were obtained for Zn and Cu suggesting physiological differences between the species and/or differences in the exposure of the organisms due to physico-chemical conditions and metal distribution between dissolved and particulate phases. In contrast, Hg bioaccumulation was highest for cockles reaching bioconcentration factors of approximately 200,000, which even exceeded that of Cd in oysters (50,000) for the same exposition period. Nevertheless, Hg concentrations remained relatively low in the three bivalve species.     

Implications of short and long term (30 days) sorption on the desorption kinetic of trace metals (Cd, Zn, Co, Mn, Fe, Ag, Cs) associated with river suspended matter

The desorption kinetic of trace elements (Cd, Zn, Co, Mn, Fe, Ag, and Cs) associated with Loire river natural suspended particulate matter (SPM; 0.4-63 microm) was followed up on times varying from 0.5 h to 30 days, from SPM previously contaminated during 1 h, 24 h and 30 days. Long term sorption kinetics indicated that the difference between sorption occurring during the period 0-30 days (time investigated in this study) and the period 0-48 h (time often used for sorption experiments) ranges from few to 25% according to the element. Desorption kinetics show that, whatever the age of the complex formed during the sorption step, the release tends to equilibrium between complexed and dissolved elements equivalent to the equilibrium obtained for sorption after a given time. However, the time to get this equilibrium depends on the aging of the complex and on the element. All the above features indicate different types of complexes formation and strength of the binding according to the age of the complex and according to the element. Using a multi-compartmental model, simulating the transfer of metals between water and different types of particulate sites, the relationships between the parameters describing slow and rapid processes helped in explaining the "aging" effect observed.     

Characterisation of urban catchment suspended particulate matter (Auckland region, New Zealand); a comparison with non-urban SPM

Suspended particulate matter (SPM) is an important transport agent for metal contaminants in streams, particularly during high flow periods such as storm events. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal partitioning between the dissolved phase and SPM was determined, and SPM characterised in terms of its Si, Al, Fe, Mn, Zn, Cu, Pb, TOC, TON and PO(4) concentrations, as well as particle size, abundance, type and surface area. This data was compared to similar data from representative non-urban catchments in the Auckland region, the Kaipara River and Waikato River catchments, to identify any significant differences in the SPM and its potential trace metal adsorption capacity. Trace metal partitioning was assessed by way of a distribution coefficient: K(D)=[Me(SPM)]/[Me(DISS)]. Auckland urban SPM comprises quartz, feldspars and clay minerals, with Fe-oxides and minor Mn-oxides. No particles of anthropogenic origin, other than glass shards, were observed. No change in urban SPM particle size or SSA was observed with seasonal change in temperature, but the nature of the SPM was observed to change with flow regime. The abundance of finer particles, SSA and Al content of the SPM increased under moderate flow conditions; however, Si/Al ratios remained constant, confirming the importance of aluminosilicate detrital minerals in surface run-off. The SPM Fe content was observed to decrease with increased flow and was attributed to dilution of SPM Fe-oxide of groundwater origin. The Kaipara River SPM was found to be mineralogically, chemically and biologically similar to the urban SPM. However, major differences between urban catchment SPM and SPM from the much larger (non-urban) Waikato River were observed, and attributed to a higher abundance of diatoms. The Fe content of the Waikato River SPM was consistently lower (<5%), and the Si/Al ratio and Mn content was higher. Such differences observed between urban and non-urban SPM did not appear to affect the partitioning of Zn and Cu; however, Pb in the Kaipara and Waikato Rivers was found to be more associated with the dissolved phase. This is likely to reflect higher particulate Pb inputs to urban systems.     

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.     

Trace elements in stream bed sediments from agricultural catchments (Gascogne region, S-W France): Where do they come from?

The Gascogne region (SW of France) is cultivated for more than 75% of the area. 83 samples of stream bed sediments were collected in three main Gascogne river basins (Gers, Save and Touch, left tributaries of the Garonne river) to evaluate the impact of agricultural practices on trace elements behavior. Eight potential harmful elements (PHE) (Cr, Co, Ni, Cu, Zn, As, Cd and Pb), four reference elements for normalization (Sc, Cs, Al and Fe) and four major elements (Mn, Ca, Mg and P) were considered. The average trace element concentrations in the fine fractions (< 63 µm) are in the decreasing order: Zn > Cr > Ni > Pb > Cu > Co > As > Sc > Cs > Cd. Geochemical investigations and an original approach combining regression analysis and chemical sequential extraction allowed to select the most adequate reference material (regional molasse) and reference element (Cs) for normalization procedure. The enrichment factor (EF) is generally lower than 2.5, particularly for Cr, Ni, Cu, As, Zn; however, 23% of the sampling stations are more contaminated (2.5 < EF < 4.5), particularly for Cd, Pb and Co. The PHE in the Gascogne river sediments are mainly originated from natural weathering processes; nevertheless, anthropogenic contribution could represent up to 34% of the total sediment content. For lead, geochemical and isotopic methods gave very similar anthropogenic contributions (24% and 22%, respectively).The enrichment of Cu, Pb, Zn, Co, As, Ni, Cr was mainly related to global and local atmospheric deposition of industrial emissions and gasoline combustion, and was associated to forested catchments. All PHE's are controlled by clay and oxi-hydroxides minerals. Cd was the only PHE enriched downstream cultivated catchments and this enrichment was linked to Ca and P. This indicates a major origin of Cd from fertilizer inputs and a main control by carbonate minerals.     

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.     

Characterisation of bed sediments and suspension of the river Po (Italy) during normal and high flow conditions

Grain-size distribution, major elements, nutrients and trace metals were determined in bed sediments and suspension collected at 10 representative sites along the river Po under normal and high flow conditions. Grain-size distribution and major element composition of suspension highlighted the presence of two distinct particle populations in the upper-middle Po (coarser particles, lower carbonate content) and in the lower Po (finer particles, higher carbonate content). This change partly reflects the geological differences between the two parts of the basin, and also the presence of a hydroelectric power plant at Isola Serafini (Piacenza). With respect to environmental quality issues, bed sediments and suspension provide similar results. A moderate nutrient pollution is found in all but the uppermost parts of the river basin, while the most significant inputs of trace metals appear to originate from the urban areas of Turin and Milan. Calculation of sediment enrichment factors identifies Cd, Cu, Hg and Zn as the most impacted elements by human activities. On the other hand, the high levels of Ni and Cr throughout the river seem to derive mainly from the presence of basic rocks in the upper and middle parts of the basin. Both nutrient and trace metal particulate concentrations substantially decrease under high flow conditions possibly due to "flushing" of contaminated bed sediments and resuspension of coarser material. Under normal flow conditions, water hydrochemistry and concentrations of some elements (As, Ca, Cr, Cu, K, Mg, Mn, Na, Ni, and Pb) in the dissolved phase (<0.45 microm) were also determined. Calculation of trace metals partition coefficients shows that the relative importance of the particulate and water phases varies in response to water hydrochemistry and suspended solid content, but that most elements achieve a conditional equilibrium in the lower stretches of the river Po. These results are the first of this kind reported for the whole river course and highlight the factors and mechanisms controlling the origin, mobility and fate of nutrients and trace metals in the river Po.     

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.     

Concentration of mercury, methylmercury, cadmium, lead, arsenic, and selenium in the rain and stream water of two contrasting watersheds in western Maryland.

Weekly wet deposition and throughfall rain samples were collected in the Blacklick Run (BLK) and Herrington Creek Tributary (HCRT), two streams in western Maryland (MD). Samples were analyzed for total mercury (Hg), methylmercury (MMHg). arsenic (As), selenium (Se), cadmium (Cd), and Icad (Pb). Hg concentrations generally fell between 50 and 100 pM. comparable to concentrations in wet deposition measured at other MD sites. While Hg concentrations decreased with rainfall amount, a similar washout trend was not seen for MMHg. Cd, Pb, As, and Se concentrations were comparable overall to those measured in the region. Concentrations of Hg, Cd, and Pb in throughfall were similar between sites and equivalent or higher than wet deposition concentrations. As and Se concentrations were similar in throughfall at the two sites, though throughfall at BLK seemed to be punctuated with slightly higher concentrations of these two metals. Concentrations of Hg, MMHg, Cd, Pb, As, Se, and SPM were measured in monthly stream collections and compared with concentrations found in other MD rivers. In addition to the monthly collections, four storm events were sampled. These measurements demonstrate the importance of storm events in trace metal transport, especially for Hg, Pb and MMHg. For these metals, a strong correlation between metal and suspended particulate concentration was evident. Retention efficiencies of the watersheds for the metals were calculated for each watershed. Of all the metals, Hg is the most and As is the least strongly retained in the watershed.