Extreme hydrological regimes of a small urban river: impact on trace element partitioning, enrichment and fluxes.

The input of trace elements from a small urban river (Las River, Toulon, France) located on the northern Mediterranean coast was studied during both base flow and flood events. A 2-year monitoring period of water flow and suspended particulate matter (SPM) showed a typical Mediterranean hydrological regime: a strong increase in water flow and SPM during short flood periods. During the flood event, an up to 2-fold increase in dissolved trace element (DTM) concentrations and particulate trace element content in SPM (PTM) was observed compared to the baseline discharge. The enrichment factor of elements in the SPM ranges from low or moderate for Co, Ni and Cr (1.0-4.7) to extremely high for Cd (157). However, the enrichment factors decrease from base flow to flood, indicating a dilution effect with a large yield of weathering particles with higher particle size. The most significant total trace element loading occurred during flood, ranging from 78% for As and Ni to 91% for Pb, while PTM loading during flood ranged from 35% for As to 77% for Pb. The specific dissolved fluxes during the flood are significantly higher for Pb, Cu and Zn than in the surrounding rivers, indicating specificity in the catchment (lithology). This study shows the importance of monitoring the transport of pollutants through small urban rivers and their potential impact on the coastal region, especially when they enter small and closed bays, as a receiving pool.

Heavy ionic pollution disrupts assemblages of algae, macroinvertebrates and riparian vegetation.

Urban streams display consistent ecological symptoms that commonly express degraded biological, physical, and chemical conditions: the urban stream syndrome (USS). Changes linked to the USS result in consistent declines in the abundance and richness of algae, invertebrates, and riparian vegetation. In this paper, we assessed the impacts of extreme ionic pollution from an industrial effluent in an urban stream. We studied the community composition of benthic algae and benthic invertebrates and the indicator traits of riparian vegetation. The dominant pool of benthic algae, benthic invertebrates and riparian species were considered as euryece. However, ionic pollution impacted these three biotic compartments' communities, disrupting these tolerant species assemblages. Indeed, after the effluent, we observed the higher occurrence of conductivity-tolerant benthic taxa, like Nitzschia palea or Potamopyrgus antipodarum and plant species reflecting nitrogen and salt contents in soils. Providing insights into organisms' responses and resistance to heavy ionic pollution, this study sheds light on how industrial environmental perturbations could alter the ecology of freshwater aquatic biodiversity and riparian vegetation.

Characterization of the submarine disposal of a Bayer effluent (Gardanne alumina plant, southern France): I. Size distribution, chemical composition and settling rate of particles forming at the outfall.

The submarine discharge of the high pH clarified Bayer effluent of the Gardanne alumina plant (Marseille region, France) leads to the formation of concretions at the outfall 324 m underwater and to a plume of white particles. The bulk chemical composition of the concretions has been determined by SF-ICP-MS. Mg and Al are the major elements measured with concentrations of a few hundred mg g-1. Ca and S are also found at concentrations in the range of mg g-1. Among the measured trace elements there is a specific interest in As and V because of environmental concerns pointed out by regulation authorities. Their concentrations are of tens to thousands µg g-1, respectively. Concentrations of the other elements are in the range of a few ng g-1 to few hundreds µg g-1. In order to constrain the dispersion of particles in the environment and to understand how chemical elements can be scavenged from or released to seawater, the size distribution of particles composing the concretions has been measured by settling rate experiments and, for each size class of particles, their chemical composition has been determined. For example, As and V are mainly associated to particles with mean diameters between 15.6 and 63 µm and settling rates around 96 m d-1. Overall, all the main elements (Mg, Al, Ca, S) composing concretions are associated to this size class of particles which represents 53-60% of the total concretion mass.

Phthalates and organophosphate esters in surface water, sediments and zooplankton of the NW Mediterranean Sea: Exploring links with microplastic abundance and accumulation in the marine food web.

In this study, surface seawater, sediment and zooplankton samples were collected from three different sampling stations in Marseille Bay (NW Mediterranean Sea) and were analyzed for both microplastics and organic plastic additives including seven phthalates (PAEs) and nine organophosphate esters (OPEs). PAE concentrations ranged from 100 to 527 ng L-1 (mean 191 ± 123 ng L-1) in seawater, 12-610 ng g-1 dw (mean 194 ± 193 ng g-1 dw) in sediment and 0.9-47 µg g-1 dw (mean 7.2 ± 10 µg g-1 dw) in zooplankton, whereas OPE concentrations varied between 9 and 1013 ng L-1 (mean 243 ± 327 ng L-1) in seawater, 13-49 ng g-1 dw (mean 25 ± 11 ng g-1 dw) in sediment and 0.4-4.6 µg g-1 dw (mean 1.6 ± 1.0 µg g-1 dw) in zooplankton. Microplastic counts in seawater ranged from 0 to 0.3 items m-3 (mean 0.05 ± 0.05 items m-3). We observed high fluctuations in contaminant concentrations in zooplankton between different sampling events. However, the smallest zooplankton size class generally exhibited the highest PAE and OPE concentrations. Field-derived bioconcentration factors (BCFs) showed that certain compounds are prone to bioaccumulate in zooplankton, including some of the most widely used chlorinated OPEs, but with different intensity depending on the zooplankton size-class. The concentration of plastic additives in surface waters and the abundance of microplastic particles were not correlated, implying that they are not necessarily good indicators for each other in this compartment. This is the first comprehensive study on the occurrence and temporal variability of PAEs and OPEs in the coastal Mediterranean based on the parallel collection of water, sediment and differently sized zooplankton samples.

Evaluation of diffusive gradients in thin films (DGT) technique for speciation of trace metals in estuarine waters - A multimethodological approach.

Understanding the potential bioavailability of trace metals (TM) in marine systems is of prime importance to implement adapted regulations and efficiently protect our coastal and estuarine waters. In this study Diffusive Gradients in Thin films (DGT) technique with two different pore size was used to evaluate the potentially bioavailable fractions (DGT-labile) of Cd, Co, Cu, Ni, Pb and Zn at various depths of a highly stratified estuary (the Krka River estuary, Croatia) both in winter and summer. DGT-labile concentrations were compared to (1) total dissolved concentrations, (2) concentrations of labile species measured by anodic stripping voltammetry (ASV-labile) for Cu and (3) concentrations derived by chemical speciation modelling. High correlation between dissolved and DGT-labile concentrations was found for all metals, except for Zn where contamination problems prevented reliable conclusions. Percentages of DGT-labile fractions over total dissolved concentrations were (AVG ±â€¯SD): 92 ±â€¯3%, 64 ±â€¯2%, 23 ±â€¯5%, 61 ±â€¯3% and 57 ±â€¯6% for Cd, Pb, Cu, Ni and Co, respectively. No significant difference was found between trace metal concentrations measured with an open pore and restricted pore devices, implying the predominance of kinetically labile metal complexes smaller than 1 nm. For Cu, ASV-labile and DGT labile concentrations were highly correlated (0.97) with ASV-labile concentration being around 35% lower than that of the DGT-labile. Modelling of chemical speciation reliably predicted dynamic (free, inorganic and part of organic complexes) concentration of Cd, whereas dynamic concentrations of Cu and Pb were underestimated by 32% and 65%, respectively. In view of the relative simplicity of DGT devices, they are well suited for the monitoring effort of coastal waters, informing on potentially bioavailable concentrations of TM and thereby, helping to achieve good environmental status of coastal waters, as stipulated within the EU Water Framework Directive.

Effects of catchment area and nutrient deposition regime on phytoplankton functionality in alpine lakes.

High mountain lakes are a network of sentinels, sensitive to any events occurring within their waterbodies, their surrounding catchment and their airshed. In this paper, we investigate how catchments impact the taxonomic and functional composition of phytoplankton communities in high mountain lakes, and how this impact varies according to the atmospheric nutrient deposition regime. For two years, we sampled the post snow-melt and the late summer phytoplankton, with a set of biotic and abiotic parameters, in six French alpine lakes with differing catchments (size and vegetation cover) and contrasting nitrogen (N) and phosphorus (P) deposition regimes. Whatever the nutrient deposition regime, we found that the lakes with the smallest rocky catchments showed the lowest functional richness of phytoplankton communities. The lakes with larger vegetated catchments were characterized by the coexistence of phytoplankton taxa with more diverse strategies in the acquisition and utilization of nutrient resources. The nutrient deposition regime appeared to interact with catchment characteristics in determining which functional groups ultimately developed in lakes. Photoautotroph taxa dominated the phytoplankton assemblages under high NP deposition regime while mixotroph taxa were even more favored in lakes with large vegetated catchments under low NP deposition regime. Phytoplankton functional changes were likely related to the leaching of terrestrial organic matter from catchments evidenced by analyses of carbon (δ13C) and nitrogen (δ15N) stable isotope ratios in seston and zooplankton. Plankton δ15N values indicated greater water-soil interaction in lakes with larger vegetated catchments, while δ13C values indicated the effective mineralization of the organic matter in lakes. The role played by catchments should be considered when seeking to determine the vulnerability of high altitude lakes to future changes, as catchments' own properties will vary under changes related to climate and airborne contaminants.

Characterisation of the dynamics of organic contaminants (n-alkanes, PAHs and PCBs) in a coastal area.

The dynamics of three classes of organic contaminants, namely n-alkanes, polycyclic aromatic hydrocarbons and polychlorinated biphenyls, were evaluated from the settled suspended particulate matter (SPM) of two wastewater treatment plant outlets (O1 and O2) at the Marseille coast. We used a 1-m-high Plexiglas settling column filled with 7L of seawater to determine the particles' settling rates, size distribution, and the extent of organic contaminants. Six classes of SPM (50-200µm particles size) were obtained from 15 fractions of 500-mL successive filtering samples ranging from 30s to 5days, including those in the tube wall. The results of the experiment indicated that >68% of the particles settled within 15min, which highly correlated with the distribution of organic carbon and contaminant contents. Furthermore, we demonstrated that 9%-13% of the SPM, which contained 5%-11% of the organic contaminants, are non-settable even after 5days. Extrapolating such behaviour in situ using molecular diagnostic indices for organic contaminant source apportionment indicated that these non-settable contaminant particles are exported to the sea.

Evidencing the natural and anthropogenic processes controlling trace metals dynamic in a highly stratified estuary: The Krka River estuary (Adriatic, Croatia).

Distributions of trace metals (TM), organic carbon, SPM and physico-chemical parameters were studied in the highly stratified Krka River estuary in winter/summer periods. The non-conservative behaviour of Zn, Cd, Pb and Cu in the brackish layer (plume), easily spotted due to very low inputs by the river, was mainly caused by their inputs from the pleasure boats, nautical marinas and harbour (e.g. release from antifouling paints). Contrarily, Ni and Co followed near-conservative behaviour. The extremely low SPM discharged by the river, resulted in a predominant dissolved fraction (>80%) of all TM, except Pb. Vertical scavenging, coupled with the long residence time, caused accumulation and progressive upstream increase of TM and SPM in the bottom seawater. Decrease of distribution coefficient (KD) in the brackish layer for winter period was ascribed to the change of SPM nature (terrestrial vs. biogenic), whereas a variable and increased biogenic component of SPM caused scattered KDs in summer.