This study estimates the effect of environmental parameters on the mobility of four inorganic contaminants (As, Zn, Pb and Cd) in soils from three areas in the Ebro and Meuse River basins, within the context of global change. An experimental method, applicable to various soil systems, is used to measure the effect of four global-change-sensitive parameters (temperature, gas phase composition, pH and microbial activity). The aqueous phase of batch incubations was sampled regularly to monitor toxic element concentrations in water. Statistical processing enabled discrimination of the most relevant variations in dissolved concentrations measured at different incubation times and under different experimental conditions. Gas phase composition was identified as the most sensitive parameter for toxic element solubilization. This study confirms that total soil concentrations of inorganic pollutants are irrelevant when assessing the hazard for ecosystems or water resource quality. An experimental method applicable for different soil systems enables the determination of the effect of environmental parameters, potentially affected by global change, on the mobilization of inorganic pollutants.

As part of the Endis-Risks project, the current study describes the occurrence of the chlorotriazine pesticides atrazine, simazine and terbutylazine in water, sediment and suspended matter in the Scheldt estuary (B-Nl) from 2002 to 2005 (3 samplings a year, 8 sampling points). Atrazine was found at the highest concentrations, varying from 10 to 736 ng/l in water and from 5 up to 10 ng/g in suspended matter. Simazine and terbutylazine were detected at lower concentrations. Traces of the targeted pesticides were also detected in sediments, but these were below the limit of quantification. As part of an ecotoxicological assessment, we studied the potential effect of atrazine on molting of Neomysis integer (Crustacea:Mysidacea), a resident invertebrate of the Scheldt Estuary and a proposed test organism for the evaluation of endocrine disruption. Following chronic exposure (3 weeks), atrazine did not significantly affect mysid molting at environmentally relevant concentrations (up to 1 μg/l). The water of the Scheldt estuary and its associated suspended solids are contaminated with chlorotriazines at concentrations that do not affect mysid molting.

Application of riverbed sand for the adsorptive separation of cadmium(II) from aqueous solutions has been investigated. Removal increased from 26.8 to 56.4% by decreasing the initial concentration of cadmium from 7.5 x 10-5 to 1.0 x 10-5 M at pH 6.5, 25 °C temperature, agitation speed of 100 rpm, 100 μm particle size and 1.0 x 10-2 NaClO4 ionic strength. Process of separation is governed by first order rate kinetics. The value of rate constant of adsorption, kad, was found to be 2.30 x 10-2 per min at 25 °C. Values of coefficient of mass transfer, βL, were calculated and its value at 25 °C was found to be 1.92 x 10-2 cm/s. Values of Langmuir constant were calculated. Values of thermodynamic parameters ΔG0, ΔH0 and ΔS0 were also calculated and were recorded as -0.81 kcal/mol, -9.31 kcal/mol and -28.10 cal/mol at 25 °C. pH has been found to affect the removal of cadmium significantly and maximum removal, 58.4%, has been found at pH 8.5. Process can be used for treatment of cadmium(II) rich wastewaters.

The acid volatile sulphide (AVS) and simultaneously extracted metals (ΣSEM) method is increasingly used for risk assessment of toxic metals. In this study, we assessed spatial and temporal variations of AVS and ΣSEM in river sediments and floodplain soils, addressing influence of flow regime and flooding. Slow-flowing sites contained high organic matter and clay content, leading to anoxic conditions, and subsequent AVS formation and binding of metals. Seasonality affected these processes through temperature and oxygen concentration, leading to increased levels of AVS in summer at slow-flowing sites (max. 37 μmol g-1). In contrast, fast-flowing sites hardly contained AVS, so that seasonality had no influence on these sites. Floodplain soils showed an opposite AVS seasonality because of preferential inundation and concomitant AVS formation in winter (max. 3-30 μmol g-1). We conclude that in dynamic river systems, flow velocity is the key to understanding variability of AVS and ΣSEM. Flow velocity is the key to understanding variability of AVS and ΣSEM in river sediment.

The spatial pattern and magnitude of mass fluxes at the stream-aquifer interface have important implications for the fate and transport of contaminants in river basins. Integral pumping tests were performed to quantify average concentrations of chlorinated benzenes in an unconfined aquifer partially penetrated by a stream. Four pumping wells were operated simultaneously for a time period of 5 days and sampled for contaminant concentrations. Streambed temperatures were mapped at multiple depths along a 60 m long stream reach to identify the spatial patterns of groundwater discharge and to quantify water fluxes at the stream-aquifer interface. The combined interpretation of the results showed average potential contaminant mass fluxes from the aquifer to the stream of 272 μg m-2 d-1 MCB and 71 μg m-2 d-1 DCB, respectively. This methodology combines a large-scale assessment of aquifer contamination with a high-resolution survey of groundwater discharge zones to estimate contaminant mass fluxes between aquifer and stream. We provide a new methodology to quantify the potential contaminant mass flux from an aquifer to a stream.

Artificial-lawn mats were used as sediment traps in floodplains to measure sediment input and composition during flood events. To estimate the natural variability, 10 traps were installed during two flood waves at three different morphological units in a meander loop of the River Elbe. The geochemical composition of deposited and suspended matter was compared. The sediment input showed weak correlations with concentration and composition of river water. It also correlated poorly with flood duration and level as well as distance of trap position from the main river. This is due to the high variability of the inundation, different morphological conditions and the variability of sources. The composition of the deposits and the suspended matter in the river water was comparable. Hence, for the investigated river reach, the expected pollution of the floodplain sediments can be derived from the pollution of the suspended matter in the river during the flood wave. The deposition of polluted sediments on floodplains is characterised by a high local variability.

Contaminated sediment in the river basin has become a source of pollution with increasing importance to the aquatic ecosystem downstream. To monitor the temporal changes of the sediment bound contaminants in the River Elbe and the River Dommel monthly toxicity tests were applied to layered sediment and river water samples over the course of 10 months. There is an indication that contaminated sediments upstream adversely affected sediments downstream, but this process did not cause a continuous increase of sediment toxicity. A clear decrease of toxic effects in water and upper layer sediment was observed at the River Elbe station in spring related to high water discharge and algal blooms. The less obvious variation of sediment toxicity in the River Dommel could be explained by stable hydrological conditions. Future monitoring programmes should promote a more frequent and intensive sampling regime during these particular events for ecotoxicological evaluation. Significant impacts of hydrological and biological factors on the ecotoxicological quality in two European rivers (Elbe and Dommel).

Global climate change may have large impacts on water supplies, drought or flood frequencies and magnitudes in local and regional hydrologic systems. Water authorities therefore rely on computer models for quantitative impact prediction. In this study we present kernel-based learning machine river flow models for the Upper Gallego catchment of the Ebro basin. Different learning machines were calibrated using daily gauge data. The models posed two major challenges: (1) estimation of the rainfall-runoff transfer function from the available time series is complicated by anthropogenic regulation and mountainous terrain and (2) the river flow model is weak when only climate data are used, but additional antecedent flow data seemed to lead to delayed peak flow estimation. These types of models, together with the presented downscaled climate scenarios, can be used for climate change impact assessment in the Gallego, which is important for the future management of the system. Future climate change and data-based rainfall-runoff predictions are presented for the Upper Gallego.

The sorption of hydrophobic organic pollutants on soils or sediments has been widely studied. However, more attention in the previous studies has been paid to sorption mechanism and effects of relevant environmental factors, few studies were reported on effects of heavy metals on the sorption of hydrophobic organic pollutants. In this paper, sorption of phthalate esters (diethyl phthalate, DEP, and di-n-butyl phthalate, DnBP) and copper on the Yellow River sediment was investigated with particular attention to the effects of copper on the phthalate sorption. The experimental results show that the sorption isotherms of phthalates could be reasonably described by the Freundlich equation. Higher sorption equilibrium constant was obtained for DnBP due to its greater hydrophobicity. The existence of copper would enhance the sorption of DnBP. Moreover, strong sorption of copper to sediment were found and attributed to abundant carbonates in the Yellow River sediment. After carbonates were removed, notable effects of copper on the phthalate sorption were observed due to the decrease of copper sorption and the increase of aqueous copper concentration. With 153 mg l-¹ copper added, the partition coefficient decreases by 52% for DEP and increases by 79% for DnBP. Primary factors that may influence interaction between the sorption of copper and DEP and DnBP were also investigated, such as complexation between copper and phthalate, and phthalate hydrophobicity. The complexation between phthalate esters and copper was substantiated by polarogram and fluorescence spectrograph, and the calculated mol ratio of complexation (copper : phthalate) was found to be 2:1.

Fluvial bed sediments are widely used for characterizing anthropogenic contaminant signals in urban watersheds. This study presents the first preliminary examination of sequentially extracted Pb from grain size fractionated bed sediments using the optimized (standardized) BCR procedure. Baseline sediment samples and samples from the vicinity of three storm-sewer outlets in Nuuanu Stream, Honolulu, Hawaii, were examined. The weighted average Pb liberated from four sequentially extracted phases was 144 ± 26 mg/kg (±SD). These Pb concentrations are high compared to 3 mg/kg leached by a 0.5 M HCl solution, and 13 mg/kg from a 4-acid total digestion of baseline sediments. Over a 1.8 km section of stream channel, land use variations and traffic density differences had little impact on the magnitude of Pb in specific phases for each of the six grain size fractions examined. Regardless of grain size or spatial location, Pb in the reducible phase exceeded that in oxidizable, residual and acid extractable phases. Weighted reducible Pb concentrations for three sewer outlet sites ranged from 69 to 92 mg/kg, and this phase typically accounted for 70-80% of all labile Pb. The <63 μm grain size class did not exhibit the highest Pb concentration, instead this was found in either the 125-250 μm or 500-1,000 μm fractions. Examining bed sediment phase associations of Pb over a smaller length dimension (i.e., 40 m) centered around one sewer outlet, indicated higher concentrations at the outlet (180 mg/kg) compared to upstream (132 mg/kg) or downstream (150 mg/kg). The differences were primarily associated with higher Pb concentrations in the reducible and oxidizable phases of the coarse sand fractions (500-2,000 μm) at the outlet. Overall, all data point to a significant anthropogenic signal for Pb in bed sediments in the urbanized section of Nuuanu Stream.