On-Chip Antifouling Gel-Integrated Microelectrode Arrays for In Situ High-Resolution Quantification of the Nickel Fraction Available for Bio-Uptake in Natural Waters.

We aimed to monitor in situ nickel (Ni(II)) concentrations in aquatic systems in the nanomolar range. To achieve this, we investigated whether an analytical protocol for the direct quantification of cobalt (Co(II)) using adsorptive cathodic sweep voltammetry (Ad-CSV) on antifouling gel-integrated microelectrode arrays (GIME) we recently developed is also suitable for direct Ni(II) quantification. The proposed protocol consists of the reduction of the complex formed between Ni(II) (or Ni(II) and Co(II)) and nioxime adsorbed on the surface of the GIME-sensing element. The GIME enables to (i) avoid fouling, (ii) control the metal complex mass transport and, when interrogated by Ad-CSV, (iii) selectively determine the dynamic (kinetically labile Ni-nioxime) fraction that is potentially bioavailable. The nioxime concentration and pH were optimized. A temperature correction factor was determined. The limit of detection established for 90 s of accumulation time was 0.43 ± 0.06 in freshwater and 0.34 ± 0.02 nM in seawater. The sensor was integrated in a submersible probe in which the nioxime-containing buffer and the sample were mixed automatically. In situ field measurements at high resolution were successfully achieved in Lake Geneva during a diurnal cycle. The determination of the kinetically labile Ni-nioxime fraction allows one to estimate the potential ecotoxicological impact of Ni(II) in Lake Geneva. Additional Ni fractions were measured by ICP-MS and coupled to the in situ Ad-CSV data to determine the temporal Ni(II) speciation.

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.

Speciation of Cu, Cd, Pb and Zn in a contaminated harbor and comparison to environmental quality standards.

The water column of harbors contains significant amounts of (priority) hazardous trace metals that may be released into coastal areas of high societal and economic interests where they may disturb their fragile equilibria. To deepen our understanding of the processes that influence the transport of the various metal fractions and allow for a more rigorous environmental risk assessment, it is important to spatially monitor the relevant chemical speciation of these metals. It is of particular interest to assess their so-called dynamic fraction, which comprises the dissolved chemical forms that are potentially bioavailable to living organisms. In this study this was achieved in the Genoa Harbor (NW Italy) for copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) by applying a multi-method approach. For the first time in this system the dynamic fractions of the target metals (CuDyn, CdDyn, PbDyn, ZnDyn) were observed in real-time on-board by voltammetry using innovative electrochemical sensing devices. Trace metals in the operationally defined dissolved <0.2 µm and <0.02 µm fractions were equally quantified through sampling/laboratory-based techniques. The obtained results showed a clear spatial trend for all studied metals from the enclosed contaminated part of the harbor towards the open part. The highest CuDyn and CdDyn fractions were found in the inner part of the harbor while the highest PbDyn fraction was found in the open part. The proportion of ZnDyn was negligible in the sampled area. Small and coarse colloids were involved in Cu, Cd and Zn partitioning while only coarse colloids played an important role in Pb partitioning. The determined concentrations were compared to the Environmental Quality Standards (EQS) established by the EU and those determined by the Australia and New Zealand to trigger for 99 and 95% species protection values. The results of this work allow us to highlight gaps in the EQS for which metal concentration thresholds are excessively high or non-existent and should urgently be revised. They also reflect the need to quantify the potentially bioavailable fraction of hazardous trace metals instead of just their total dissolved concentrations. The data support the establishment of environmental quality standards and guidelines based on realistic risk assessment to protect aquatic life and resources and ultimately human health.

Elutriate preparation affects embryo development test with Paracentrotus lividus: An in-depth study on the differences between two protocols and three different sediment/water mixing times.

Coastal areas are under continuous and increasing pressure from different human activities. A mixture of contaminants (e.g. hydrocarbons, pesticides, persistent organic pollutants (POPs), emerging contaminants, and others), originating mainly from populated, industrialised and agricultural areas, can reach the marine environment through different means such as wastewater discharge, soil runoffs, leaching from agriculture, and volatilisation/deposition. In this context, marine sediments have increasingly been considered repositories for a variety of pollutants that can accumulate and be stored for long periods, acting as a secondary source of contaminants during subsequent dredging operation or vessel manoeuvring. Chemical and ecotoxicological analyses of sediments are routinely conducted to evaluate the potential hazard/risk to the environment, either on bulk sediment or elutriate. In general, sediment elutriates are commonly prepared according to ASTM Guide even if alternative protocols are proposed by USACE for the various condition that they have to represent. The goal of the present study was to determine if the toxicological properties of ASTMprepared elutriates are comparable to those obtained from the USACE protocol. Sediment coming from 3 harbours (Olbia, Cagliari, and Toulon), as part of the "Se.D.Ri.Port" Interreg Project, were processed to obtain elutriates according to ASTM Guide and USACE Dredging Elutriate protocol and tested with the sea urchin Paracentrotus lividus embryo development test. Moreover, the significance of different stirring times of water/sediment mixture (1 h, 3 h, and 24 h) was tested with both the ASTM and USACE protocol. In addition to the biological analysis, for each sediment sample, heavy metals concentration, granulometry, and organic matter were determined. Even if for the ports of Toulon and Cagliari, the ASTM and USACE elutriates showed comparable results with P. lividus bioassay, for the port of Olbia the two protocols showed different criticalities. Preliminary results show that for the site Olbia elutriates prepared with the USACE protocol resulted in higher toxicity than elutriates obtained with ASTM (p < 0.001). In conclusion, differences in preparation protocols appear to be significant and can lead to different results in biological testing. To overcome this problem and to obtain more reliable evaluations of risk to the environment, standardisation and regulation must be the next goals in sediment management procedure.

On-field high-resolution quantification of the cobalt fraction available for bio-uptake in natural waters using antifouling gel-integrated microelectrode arrays.

We report the optimization, characterization, and validation of Adsorptive Square Wave Cathodic Stripping Voltammetry on antifouling gel-integrated microelectrode arrays for autonomous, direct monitoring of cobalt(II) metal species. Detection is accomplished by complexation with an added nioxime ligand. The limit of detection established for a 90 s accumulation time was 0.29 ± 0.01 nM in freshwater and 0.27 ± 0.06 nM in seawater. The microelectrode array was integrated in a submersible probe to automatically dose the complexing agent nioxime and realize an integrated sensing system. For the first time ever, the potentially bioavailable Co(II) fraction was determined in La Leyre River-Arcachon Bay continuum, enabling to evaluate the potential ecotoxicological impact of freshwater-carried Co(II) in the Arcachon Bay. The measured potentially bioavailable Co(II) concentrations were hazardous for aquatic biota along the continuum. The electrochemical Co(II) data were compared to ICP-MS data in various fractions to determine spatial Co(II) speciation.

Cd transfers during marine sediment resuspension over short and long-term period: Associated risk for coastal water quality.

Cadmium (Cd) is a highly toxic metal, regularly monitored uniformly for water quality across Europe, but scarcely for sediments. This study was designed to compare the kinetics of Cd remobilization and the amplitude of its transfers with different marine sediments. The results showed a highly reproducible transfer kinetics. Dissolved Cd was strongly and quickly removed from the dissolved phase (from 5 min up to 7 h). Then, the dissolved Cd concentration increased progressively to reach a maximal value after two weeks of mixing. The influence of the resuspension intensity representing light wind-induced resuspension up to dredging operations was observed after 2 weeks. The intensity of the sediment resuspension clearly impacted the amplitude of Cd remobilization, dissolved Cd ranging from a few ngL-1 to few hundreds of ngL-1, exceeding the maximal dissolved Cd concentration accepted by the European Union Water Framework Directive (WFD-2008/105 32/EC).

Integration of spatio-temporal variations of surface metabolomes and epibacterial communities highlights the importance of copper stress as a major factor shaping host-microbiota interactions within a Mediterranean seaweed holobiont.

BACKGROUND: Although considered as holobionts, macroalgae and their surface microbiota share intimate interactions that are still poorly understood. Little is known on the effect of environmental parameters on the close relationships between the host and its surface-associated microbiota, and even more in a context of coastal pollutions. Therefore, the main objective of this study was to decipher the impact of local environmental parameters, especially trace metal concentrations, on an algal holobiont dynamics using the Phaeophyta Taonia atomaria as a model. Through a multidisciplinary multi-omics approach combining metabarcoding and untargeted LC-MS-based metabolomics, the epibacterial communities and the surface metabolome of T. atomaria were monitored along a spatio-temporal gradient in the bay of Toulon (Northwestern Mediterranean coast) and its surrounding. Indeed, this geographical area displays a well-described trace metal gradient particularly relevant to investigate the effect of such pollutants on marine organisms. RESULTS: Epibacterial communities of T. atomaria exhibited a high specificity whatever the five environmentally contrasted collecting sites investigated on the NW Mediterranean coast. By integrating metabarcoding and metabolomics analyses, the holobiont dynamics varied as a whole. During the occurrence period of T. atomaria, epibacterial densities and α-diversity increased while the relative proportion of core communities decreased. Pioneer bacterial colonizers constituted a large part of the specific and core taxa, and their decrease might be linked to biofilm maturation through time. Then, the temporal increase of the Roseobacter was proposed to result from the higher temperature conditions, but also the increased production of dimethylsulfoniopropionate (DMSP) at the algal surface which could constitute of the source of carbon and sulfur for the catabolism pathways of these taxa. Finally, as a major result of this study, copper concentration constituted a key factor shaping the holobiont system. Thus, the higher expression of carotenoids suggested an oxidative stress which might result from an adaptation of the algal surface metabolome to high copper levels. In turn, this change in the surface metabolome composition could result in the selection of particular epibacterial taxa. CONCLUSION: We showed that associated epibacterial communities were highly specific to the algal host and that the holobiont dynamics varied as a whole. While temperature increase was confirmed to be one of the main parameters associated to Taonia dynamics, the originality of this study was highlighting copper-stress as a major driver of seaweed-epibacterial interactions. In a context of global change, this study brought new insights on the dynamics of a Mediterranean algal holobiont submitted to heavy anthropic pressures. Video abstract.

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.

Have decades of abiotic studies in sediments been misinterpreted?

Sterilization techniques are largely employed to distinguish biotic and abiotic processes in biogeochemical studies as they inhibit microbial activity. Since one century, chemical sterilizers, supposed to preserve original environmental samples, have taken precedence over physical sterilization techniques considered too destructive. Sodium azide (NaN3) is nowadays the most commonly used inorganic chemical sterilizer. It is sufficiently purified to study trace metals, as well. Nevertheless, its (in)activity in physico-chemical processes was never ascertained. Through the investigation of sediment resuspension in seawater, the present work unequivocally demonstrated that NaN3 can impact carbon and trace metals' transfers by altering the redox balance and pH. Unlike decades of blind practice, NaN3 should be used with great care to track abiotic processes from organic matter rich and reductive matrices.

Impacts of copper and lead exposure on prokaryotic communities from contaminated contrasted coastal seawaters: the influence of previous metal exposure.

Our understanding of environmental factors controlling prokaryotic community is largely hampered by the large environmental variability across spatial scales (e.g. trace metal contamination, nutrient enrichment and physicochemical variations) and the broad diversity of bacterial pre-exposure to environmental factors. In this article, we investigated the specific influence of copper (Cu) and lead (Pb) on prokaryotic communities from the uncontaminated site, using mesocosm experiments. In addition, we studied how pre-exposure (i.e. life history) affects communities, with reference to previous metal exposure on the response of three prokaryotic communities to similar Cu exposition. This study showed a stronger influence of Cu contamination than Pb contamination on prokaryotic diversity and structure. We identified 12 and 34 bacterial families and genera, respectively, contributing to the significant differences observed in community structure between control and spiked conditions. Taken altogether, our results point toward a combination of direct negative responses to Cu contamination and indirect responses mediated by interaction with phytoplankton. These identified responses were largely conditioned by the previous exposure of community to contaminants.

Kinetic processes of copper and lead remobilization during sediment resuspension of marine polluted sediments.

Contaminated sediments could act as a source of contamination to the surrounding environments by several processes (e.g., diffusive flux, sediment resuspension). This study aimed at highlighting the mechanisms of copper and lead mobilization from resuspended particles to the aqueous phase using laboratory experiments and a kinetic model. Three sediments, differed by their compositions and metal partition from Toulon Bay (SE France) were used. In addition, three solid/liquid ratios (0.1, 1 and 10 g L-1) allowed simulating at best natural and anthropogenic scenarios (e.g., storm, nautical traffic, dredging). We monitored metal concentrations, physicochemical parameters (pH, Eh, [O2]) and organic matter concentration along with their optical properties. Experimental results showed successive reactions over short and long terms (hour and day scale, respectively) that controlled Cu and Pb exchanges between particles and the aqueous phase over 4 weeks. The quick Cu removal was attributed to the implications of newly formed oxides while the long-term Cu release in the dissolved fraction from the more refractory solid pool is more likely related to organic complexation. In fact, we observed a transformation of the dissolved organic matter: an increase in molecular weight and in humic fluorescence properties. However, the Pb removal toward the end of the experiment could be explained by a migration toward the exchangeable sites of higher energy, which could correspond to the particulate organic matter or a combination with organic-coating carrier phases. Both kinetic rate and system response times (τi) were coherent despite the variability of parameters intrinsic to sediments (e.g., sediment composition and initial metal repartition) but also extrinsic parameters (solid/liquid ratios). Such a coherence would imply the universality of the obtained constants to be used in a more predictive approach to assess the potential of metal mobility using metal repartition in contaminated sediments when combined with hydrological and sedimentological models.

Long-term monitoring emphasizes impacts of the dredging on dissolved Cu and Pb contamination along with ultraplankton distribution and structure in Toulon Bay (NW Mediterranean Sea, France).

A long-term monitoring during dredging and non-dredging periods was performed. Total and dissolved Cu and Pb concentrations, DGT-labile Pb, ultraphytoplankton abundance and structure were monitored at four sites: dredging site, dumping site (inside/outside of a geotextile bag) and reference site. During the reference period (non-dredging), an increasing contamination in Pb, Cu and a progressive shift from Synechococcus to photosynthetic picoeukaryotes dominance was observed from reference to dumping site. Pb concentrations were significantly higher during dredging period, pointing out sediment resuspension as Pb major source of contamination. Unlike Pb, Cu concentrations were not statistically different during the two periods. Dredging period did not impact on ultraphytoplankton abundance and structure but influence heterotrophic prokaryotes abundance. Sediment resuspension is therefore a major driver of chemical and biological qualities in Toulon Bay. Furthermore, although the geotextile bag reduces particulate transport of the dredged sediment, the transport in the dissolved phase remains a major problem.

Improved voltammetric methodology for chromium redox speciation in estuarine waters.

Chromium is a toxic element naturally present in natural waters whose chemical speciation regulates its cycling, mobility and bioavailability. We present here: 1- an improved analytical method for chromium speciation (Cr(VI) vs Cr(III)) in estuarine samples by catalytic adsorptive cathodic stripping voltammetric (cat-AdCSV) and 2- a study highlighting a significant change of redox speciation during summer and winter. Initial measurements first revealed that surface-active substances (SAS) present in estuarine samples strongly influenced the analytical determination of Cr by partially masking the Cr peak through an increase of the background current. We found that the application of a low negative accumulation potential (-1.65 V) resulted in much better voltammograms compared to those obtained using the usual accumulation potential of -1.0 V. Using humic acid (HA) as a model SAS of natural origin, we show that this negative potential clearly prevents adsorption of SAS on the Hg-electrode surface, which in turns benefits the adsorption of the in-situ formed Cr(III)-DTPA complex and the resulting signal. The optimised method was applied to determine chromium redox speciation and distribution along the 23 km long salinity gradient, well oxygenated, Krka River estuary (Croatia). Cr(VI) was found to be the dominant redox species in both summer and winter, with Cr(III) contribution being lower in summer (up to ∼30%, average of ∼5%) than in winter (up to ∼50%, average of ∼30%). In summer, lower concentrations of Cr(VI) were found in the freshwater end-member (2.5 nM) than in the seawater end-member (4-5 nM), while the opposite trend was found in winter. Hexavalent chromium exhibited a non-conservative behaviour along the salinity gradient for both seasons. Chromium predominantly exists in dissolved phase, and contribution of particles reactive Cr(III) was minor.

Quantitative model of carbon and nitrogen isotope composition to highlight phosphorus cycling and sources in coastal sediments (Toulon Bay, France).

Nutrient loadings from either point or non-point sources to the environment are related to the growing global population. Subsequent negative impacts of nutrient loading to aquatic environments requires a better understanding of the biogeochemical cycling and better tools to track their sources. This study examines the carbon (C), nitrogen (N) and phosphorus (P) discharge and cycling in a Mediterranean coastal area from rivers to marine sediments and assesses the anthropogenic contributions. Carbon and N concentrations and isotope compositions in rivers particles, surface sediments, and sediment cores were investigated to build up a quantitative multiple-end-member mixing model for C and N isotopes. This model predicts the contribution of four natural and one anthropogenic sources to the sediments and highlighted the anthropogenic fraction of P based on the relationship with anthropogenic δ15N. Although P is a monoisotopic element and total P concentration has been the sole index to study P loading, this study suggests an alternative approach to differentiate anthropogenic and non-anthropogenic (diagenetic) P, revealed point and non-point sources of P, and the corresponding P loading. Also, the diagenetic P background has been calculated for the 50-cm sediment layer of the whole Bay.