Chemical contamination alters the interactions between bacteria and phytoplankton.

Bacteria and phytoplankton are key players in aquatic ecosystem functioning. Their interactions mediate carbon transfer through the trophic web. Chemical contamination can alter the function and diversity of phytoplankton and bacterioplankton, with important consequences for ecosystem functioning. The aim of the present study was to assess the impact of chemical contamination on the interactions between both biological compartments. Two contrasting marine coastal ecosystems, offshore waters and lagoon waters, were exposed to chemical contamination (artificial or produced from resuspension of contaminated sediment) in microcosms in four seasons characterized by distinct phytoplankton communities. Offshore waters were characterized by a complex phytoplankton-bacterioplankton network with a predominance of positive interactions between both compartments, especially with Haptophyta, Cryptophyta, and dinoflagellates. In contrast, for lagoon waters, the phytoplankton-bacterioplankton network was simpler with a prevalence of negative interactions with Ochrophyta, Cryptophyta, and flagellates. Contamination with an artificial mix of pesticides and trace metal elements resulted in a decrease in the number of interactions between phytoplankton and bacterioplankton, especially for offshore waters. Resuspension of contaminated sediment also altered the interactions between both compartments. The release of nutrients stored in the sediment allowed the growth of nutrient limited phytoplankton species with marked consequences for the interactions with bacterioplankton, with a predominance of positive interactions, whereas in lagoon waters, negative interactions were mostly observed. Overall, this study showed that chemical contamination and sediment resuspension resulted in significant effects on phytoplankton-bacterioplankton interactions that can alter the functioning of anthropogenic coastal ecosystems.

Study of passive sampler calibration (Chemcatcher®) for environmental monitoring of organotin compounds: Matrix effect, concentration levels and laboratory vs in situ calibration.

Application of Chemcatcher® to monitor organotin compounds [monobutyltin (MBT), dibutyltin (DBT) and tributlytin (TBT)] in sea water has been little developed. Prior to the measurement of the time-weighted average water concentrations (TWAC), a calibration step is required to determine sampling rates (Rs) which is usually assessed in a flow-through laboratory pilot where experimental conditions are well controlled. This paper investigates the effect of the water matrix (tap water vs real sea water from the harbor of Port Camargue in France) and organotin concentrations on the uptake rates of organotin compounds. Laboratory calibrations provided sampling rates in the range of 66-225 mL.day-1 in high concentration (usually used for laboratory calibrations) and in the range of 30-56 mL.day-1 at low concentrations (environmental range). When the tank is filled with real sea water, sampling rates were found to be in the range of 38-177 mL.day-1. In order to demonstrate the efficiency of Chemcatcher® in real conditions, in situ calibration was done in the harbor of Port Camargue. This calibration has been done in order to replicate environmental conditions: compounds concentrations, hydrodynamic and water matrix effects. To compare the impact of calibration procedures on TWAC determination, Chemcatcher® was deployed in the harbor of Port Camargue and spot sampling was performed to monitor the concentrations of organotins in water throughout the exposure period. Results obtained using the field Rs determined by in situ calibration were more reliable. In this case, TWAC is in agreement with spot sampling concentration.

Seasonal changes of chemical contamination in coastal waters during sediment resuspension.

The potential of remobilization of pollutants is a major problem for anthropogenic ecosystems, because even when the anthropogenic source of pollution is identified and removed, pollutants stored in sediments can be released into the water column and impact pelagic communities during sediment resuspension provoked by dredging, storms or bottom trawling. The objectives of the present study were to assess the changes observed in the chemical composition of the water column following resuspension of a polluted marine sediment and the consequences for the chemical composition of adjacent marine waters according to season. For that purpose, an experimental sediment resuspension protocol was performed on four distinct occasions, spring, summer, fall and winter, and the changes in nutrients, organic contaminants and inorganic contaminants were measured after mixing sediment elutriate with lagoon waters and offshore waters sampled nearby. Significant seasonal variations in the chemical composition of the contaminated sediments were observed, with a strong accumulation of PAHs in fall, whereas minimum PAH concentrations were observed during winter. In all seasons, sediment resuspension provoked a significant enrichment in nutrients, dissolved organic carbon, and trace metal elements like Ni, Cu, and Zn in offshore waters and lagoon waters, with enrichment factors that were season and site dependent. The most pronounced changes were observed for offshore waters, especially in spring and winter, whereas the chemical composition of lagoon waters was weakly impacted by the compounds supplied by sediment resuspension.

Effects of copper and butyltin compounds on the growth, photosynthetic activity and toxin production of two HAB dinoflagellates: The planktonic Alexandrium catenella and the benthic Ostreopsis cf. ovata.

Controlled laboratory experiments were conducted to test the effects of copper (Cu2+) and butyltins (BuT) on the growth, photosynthetic activity and toxin content of two HABs (Harmful Algal Blooms) dinoflagellates, the planktonic Alexandrium catenella and the benthic Ostreopsis cf. ovata. Microalgae were exposed to increasing concentrations of Cu2+ (10-4 to 31 nM) or BuT (0.084 to 84 nM) for seven days. When considering the growth, EC50 values were 0.16 (±0.09) nM and 0.03 (±0.02) nM of Cu2+ for A. catenella and O. cf. ovata, respectively. Regarding BuT, EC50 was 14.2 (±6) nM for O. cf. ovata, while A. catenella growth inhibition appeared at BuT concentrations ≥27 nM. Photosynthetic activity of the studied dinoflagellates decreased with increasing Cu and BuT concentrations. For O. cf. ovata, the response of this physiological parameter to contamination was less sensitive than the biomass. Cu exposure induced the formation of temporary cysts in both organisms that could resist adverse conditions. The ovatoxin-a and -b concentrations in O. cf. ovata cells increased significantly in the presence of Cu. Altogether, the results suggest a better tolerance of the planktonic A. catenella to Cu and BuT. This could result in a differentiated selection pressure exerted by these metals on phytoplankton species in highly polluted waters. The over-production of toxins in response to Cu stress could pose supplementary health and socio-economic threats in the contaminated marine ecosystems where HABs develop.

Comparison of index systems for rating water quality in intermittent rivers.

Water quality indexes (WQI) are a practical way to evaluate and compare the level of chemical contamination of different water bodies and to spatially and temporally compare levels of pollution. The purpose of this study was to check if these indexes are appropriate for intermittent rivers under arid and semi-arid climates. A literature review enabled the comparison of 25 water quality indexes to discern their capability to evaluate spatial (inter and intra catchment) and temporal (high and low water flow conditions) variations in water quality in three Mediterranean intermittent rivers: the River Vène (France) and the Oued Fez and the River Sebou (Morocco). Hierarchical cluster analysis identified groups of WQI with similar behavior and brought to light the 6 most distinguishing indexes. Whatever the hydrological conditions at the two sites, both the ME-MCATUHE and NCS indexes, which were developed for Morocco and Greece, and the CCMEWQI and BCWQI indexes, which were developed for non-arid or semi-arid zones, gave appropriate water quality evaluations.

The environmental legacy of historic Pb-Zn-Ag-Au mining in river basins of the southern edge of the Massif Central (France).

The main rivers (Aude, Orb, Herault) that discharge into the Gulf of Lions and the west bank tributaries of the Rhone River including the Gardon have former non-ferrous metal mines in their upper drainage basin. Using unpublished data and data from the literature, this study provides an integrated overview of the contamination of water and sediment along the continent-sea continuum and of its impacts on the biota and on human health. In the upper part of these basins, water and stream sediments are enriched in metal(-loids) compared to median European concentrations. Arsenic is the main contaminant in the rivers Aude and Gardon d'Anduze, Sb in the Orb and Gardon d'Alès, and Tl in the Herault river. A rapid reduction in dissolved and particulate concentrations was systematically observed along the river due to dilution and precipitation. The high concentrations of metal(-loid)s observed suggest that the former mining activity still represents a potential threat for the environment, but the lack of high temporal resolution monitoring, especially during Mediterranean floods, prevents accurate assessment of metal fluxes from these rivers to the Mediterranean Sea. Studies dedicated to the impacts on human health are too rare, given that studies have shown a higher rate of arsenic-specific cancer near Salsigne mine in the Aude River basin and cases of saturnism in children in the upper Herault River basin. These studies underline the need to take environmental health issues into consideration not only in these watersheds but around the entire Mediterranean basin, which harbors numerous metalliferous ores that have been mined for millennia.

Do the levels of industrial pollutants influence the distribution and abundance of dinoflagellate cysts in the recently-deposited sediment of a Mediterranean coastal ecosystem?

We studied the relationships between sediment industrial pollutants concentrations, sediment characteristics and the dinoflagellate cyst abundance within a coastal lagoon by investigating a total of 55 sampling stations within the Bizerte lagoon, a highly anthropized Mediterranean ecosystem. The sediment of Bizerte lagoon is characterized by a high dinocyst abundance, reaching a maximum value of 2742cysts·g-1 of dry sediment. The investigated cyst diversity was characterized by the presence of 22 dominant dinocyst morphotypes belonging to 11 genera. Two dinoflagellate species dominated the assemblage: Alexandrium pseudogonyaulax and Protoperidinium claudicans, representing 29 to 89% and 5 to 38% of the total cyst abundance, respectively, depending on the station. Seven morphotypes belonging to potentially toxic species were detected, including Alexandrium minutum, A. pseudogonyaulax, Alexandrium catenella/tamarense species complex, Lingulodinium polyedrum, Gonyaulax cf. spinifera complex, Prorocentrum micans and Protoceratium reticulatum. Pearson correlation values showed a positive correlation (α=0.05) between cyst abundance and both water content and fine silt sediment content. Clustering revealed that the highest abundance of cysts corresponds to stations presenting the higher amounts of heavy metals. The simultaneous autoregressive model (SAM) highlighted a significant correlation (α=0.05) between cyst accumulation and two main factors: sediment water content and sediment content for several heavy metals, including Hg, Cd, Cu, Ni and Cr. These results suggest that the degree of heavy metal pollution could influence cyst accumulation patterns.

Organotins' fate in lagoon sewage system: dealkylation and sludge sorption/desorption.

Organotin compounds (OTs) have been widely used for their biocidal properties and as stabilizers in various industrial applications. Due to their high toxicity, organotins are subject to many studies regarding their behavior in wastewater treatment plant and aquatic environment. However, few studies are available regarding their behavior in lagoon sewage system, although such treatment is commonly used for sewage treatment in low-population areas. The present study aimed at studying the fate of organotins (monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT)) in lagoon sewage system. Short-term experiments, carried out at lab scale, consisted in sampling sludge from aerobic stabilization ponds, and then quantifying sorption and desorption of the different organotin species, as well as their respective transformation, under defined operating conditions (e.g., tributyltin spike and dilution) simulating possible change in the surrounding environment of sludge in the lagoon. Results established that a very important percentage of the OTs was localized in the solid phase of the sludge (more than 98 %), whatever the operating conditions may be; however, transformation and locations of the three OT species differed according to the different conditions of sludge dilution, TBT spiking, and test duration. After dilution of lagoon sludge, TBT desorption from sludge was observed; it was supposed that dealkylation of TBT after desorption occurred rapidly and increased dissolved MBT and DBT in liquid phase; MBT sorbed subsequently on solid phase. The nature of the diluent (i.e., tap water or saline solution) appeared to slightly influence the sludge behavior. After TBT spiking, TBT was supposed to be rapidly sorbed but also transformed in DBT and MBT that would as well sorbed on the sludge, which explained the decrease of these species in the liquid phase. Tests aimed at studying long-term effect of TBT spiking demonstrated that the sorbed species could be remobilized and transformed after a dilution.

Behaviour of butyltin compounds in the sediment pore waters of a contaminated marina (Port Camargue, South of France).

Despite the ban on tributyltin (TBT) in marine paints, harbour sediments are still highly contaminated by this antifouling agent. Concentrations of TBT and its dealkylated products dibutyltin (DBT) and monobutyltin (MBT) were determined in the pore waters of Port Camargue, a large marina located on the French Mediterranean coast. Pore waters were sampled in the field using peepers deployed in summer 2012 and 2013 and in winter 2012-2013. The winter surveys were characterized by the presence of sulphides in pore waters from a depth of 5 cm, which was not the case in winter. In summer 2013, TBT was shown to be released into pore waters below the sediment-water interface (SWI) at concentrations of up to 70 ngSn L(-1). This release was also observed in sediment anaerobic incubations and was attributed to the mineralization of the sedimentary organic matter, possible stabilization of TBT by complexation with sulphides, and lower debutylation rates in anoxic than in oxic conditions. In summer 2012, a comparatively lower concentration of TBT (around 20 ngSn L(-1) below the SWI) was measured and the presence of methyltin species was detected. We hypothesize that the differences between the two surveys reflect different microbial activity. In winter 2012-2013, marked by Fe-reducing conditions in the sediments, TBT was released into solution at the SWI at concentrations of up to 40 ngSn L(-1). Sediments are thus a continuing source of TBT for the overlying waters despite the ban on its use for boats in France.

Consequences of contaminant mixture on the dynamics and functional diversity of bacterioplankton in a southwestern Mediterranean coastal ecosystem.

Contamination of coastal environments is often due to a complex mixture of pollutants, sometimes in trace levels, that may have significant effects on diversity and function of organisms. The aim of this study was to evaluate the short-term dynamics of bacterioplankton exposed to natural and artificial mixtures of contaminants. Bacterial communities from a southwestern Mediterranean ecosystem, lagoon and the bay (offshore) of Bizerte were exposed to i) elutriate from resuspension of contaminated sediment, and ii) an artificial mixture of metals and herbicides mimicking the contamination observed during sediment resuspension. Elutriate incubation as well as artificial spiking induced strong enrichments in nutrients (up to 18 times), metals (up to six times) and herbicides (up to 20 times) relative to the in situ concentrations in the offshore station, whereas the increases in contaminants were less marked in the lagoon station. In the offshore waters, the artificial mixture of pollutants provoked a strong inhibition of bacterial abundance, production and respiration and significant modifications of the potential functional diversity of bacterioplankton with a strong decrease of the carbohydrate utilization. In contrast, incubation with elutriate resulted in a stimulation of bacterial activities and abundances, suggesting that the toxic effects of pollutants were modified by the increase in nutrient and DOM concentrations due to the sediment resuspension. The effects of elutriate and the artificial mixture of pollutants on bacterial dynamics and the functional diversity were less marked in the lagoon waters, than in offshore waters, suggesting a relative tolerance of lagoon bacteria against contaminants.

Study of photocatalytic degradation of tributyltin, dibutylin and monobutyltin in water and marine sediments.

This study reports on the first assessment of the treatment of sediments contaminated by organotin compounds using heterogeneous photocatalysis. Photocatalysis of organotins in water was carried out under realistic concentration conditions (µgL(-1)). Degradation compounds were analyzed by GC-ICP-MS; a quasi-complete degradation of tributyltin (TBT) in water (99.8%) was achieved after 30min of photocatalytic treatment. The degradation by photolysis was about (10%) in the same conditions. For the first time decontamination of highly polluted marine sediments (certified reference material and harbor sediments) by photocatalysis proves that the use of UV and the production of hydroxyl radicals are an efficient way to treat organotins adsorbed onto marine sediment despite the complexity of the matrix. In sediment, TBT degradation yield ranged from 32% to 37% after only 2h of irradiation (TiO2-UV) and the by-products: dibutyltin (DBT) and monobutyltin (MBT) were degraded very rapidly in comparison with TBT. It was shown that during photocatalysis of organotins in sediments, the hydroxyl radical attack and photolysis are the two ways for the degradation of adsorbed TBT.

Trace elements in the sediments of a large Mediterranean marina (Port Camargue, France): levels and contamination history.

The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497 µg g(-1) of Cu, 475 µg g(-1) of Zn, 0.82 µg g(-1) of Hg, 94 µg g(-1) of Pb and over 10,000 ngSn g(-1) of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.

Spatial and temporal trends in water quality in a Mediterranean temporary river impacted by sewage effluents.

This paper analyzes how changes in hydrological conditions can affect the water quality of a temporary river that receives direct inputs of sewage effluents. Data from 12 spatial surveys of the Vène river were examined. Physico-chemical parameters, major ion, and nutrient concentrations were measured. Analyses of variance (ANOVA) and multivariate analyses were performed. ANOVA revealed significant spatial differences for conductivity and major ion but no significant spatial differences for nutrient concentrations even if higher average concentrations were observed at stations located downstream from sewage effluent discharge points. Significant temporal differences were observed among all the parameters. Karstic springs had a marked dilution effect on the direct disposal of sewage effluents. During high-flow periods, nutrient concentrations were high to moderate whereas nutrient concentrations ranged from moderate to bad at stations located downstream from the direct inputs of sewage effluents during low-flow periods. Principal component analysis showed that water quality parameters that explained the water quality of the Vène river were highly dependent on hydrological conditions. Cluster analysis showed that when the karstic springs were flowing, water quality was homogeneous all along the river, whereas when karstic springs were dry, water quality at the monitoring stations was more fragmented. These results underline the importance of considering hydrological conditions when monitoring the water quality of temporary rivers. In view of the pollution observed in the Vène river, "good water chemical status" can probably only be achieved by improving the management of sewage effluents during low-flow periods.

A contribution to the understanding of micro-pollutant sorption mechanisms in wastewater biological processes: case of the tributyltin.

Micro-pollutant fluxes distribution throughout the physical separation and biological units of wastewater treatment plants (WWTPs) are very dependent ofsorption phenomena. The understanding and the control of the sorption stage is thus essential for the optimization of micro-pollutant removal in WWTPs, and particularly in biological treatments where these mechanisms influence the bioavailability towards micro-organisms. If the influence of the micro-pollutant physicochemical characteristics (e.g. Kow, pKa) on their ability to sorb on biological media (i.e. sludge) has been demonstrated, it appears that some other parameters, like the biosorbent characteristics, have to been taken into account. The aim of this study is thus to correlate the capacities of sorption of an environmentally relevant substance (tributyltin), with a thorough characterization of different types of sludge. The characterization of three biological media (raw, sonicated and flocculated activated sludges) is proposed according to various characterization parameters related to biochemical composition, aggregate size, rheological behaviour etc. The results show first that, whatever the sludge characteristics may be, the sorption mechanisms are very rapid and that an equilibrium state is reached after a few minutes. The influence of the sludge characteristics, notably the floc size and the chemical oxygen demand partition between solid and colloidal fraction, on sorption efficiency is demonstrated. A Langmuir modelling allows giving the maximum sorption capacity, as well as the binding energy for the three studied sludges, according to their physicochemical characteristics.

Organotins in a medium-size Mediterranean basin (the Herault River).

This study reports the first assessment of organotin pollution in the Hérault watershed, a medium size Mediterranean basin. Organotin compounds were analyzed in surface waters, wells supplying drinking water and sewage treatment plants (STPs). In surface and ground waters, a background contamination by total organotin compounds has been identified in the range of 0.51 +/- 0.02-71 +/- 2 ng(Sn) L(-1), which is of the same order of magnitude as those observed in other European areas. Organotins were systematically present in STP influents and sludge. Total or partial elimination of organotin compounds from treated wastewater was observed. STP effluents appeared nevertheless to be a non-negligible source of contamination not only of rivers but also of aquifers tapped for drinking water supply. Tributyltin concentration was higher than the maximum allowable concentration proposed by the European Commission in some surface waters and wells supplying drinking water. This could compromise the water resource and have serious and irreversible consequences for the aquatic eco-system. As it was the case for the ban of antifouling paints, a regulatory regime in decreasing point-source emissions of these harmful compounds used in household products might be applied.

Headspace single-drop microextration for the detection of organotin compounds.

The performance of single-drop microextraction (SDME), coupled with gas chromatography/mass spectrometry, was assessed for the determination of tributyltin compounds in water and solid samples. Experimental parameters impacting the performance of SDME, such as microextraction solvent and sampling and stirring time, were investigated. Analytical results obtained by SDME were compared with those generated by conventional solid phase microextraction (SPME) and liquid-liquid extraction (LLE) for the determination of TBT in PACS-2 sediment certified reference material (CRM).

Effects of gamma-sterilization on butyltin homogeneity and content in sediments: a GC-ICP-MS study.

A GC-ICP-MS method based on extraction and alkylation of butyltins with sodium tetraethylborate was used to quantitatively assess the fate of these analytes in solutions and sediments following exposure to gamma-irradiation. The effects of a 2.5 Mrad sterilization dose on three butyltin species in both methanolic calibration solutions and in sediment matrices were investigated. Although significant losses of tributyltin (TBT, 90%), dibutyltin (DBT, 100%) and monobutyltin (MBT, 80%) were detected in standard solutions prepared in methanol following gamma-irradiation, no species inter-conversion occurred. Some degradation of TBT (38%) and DBT (32%) but no significant change in MBT content was found using a spiked sediment CRM HISS-1. Conversion DBT to MBT in spiked HISS-1 was deduced. Much smaller degradation of TBT (16% loss) and 10% loss of DBT by conversion to MBT (14% gain) was registered using a sediment blend of PACS-2 and HISS-1 (SOPH). Despite some initial losses of TBT and DBT due to irradiation, better than 2% RSD in both TBT and DBT concentrations measured in twelve different bottles of blended sediment SOPH were obtained, indicating the material may be considered homogeneous for these analytes. Results from a long-term five-year stability study of PACS-2 show that all three butyltins are stable during storage at 4 degrees C followed with 2.5 Mrad minimum dose of gamma-irradiation sterilization treatment.

Improvement of measurement precision of SPME-GC/MS determination of tributyltin using isotope dilution calibration.

A unique approach was developed to improve the precision of quantification of tributyltin (TBT) in sedimentsby solid phase microextraction (SPME) using isotope dilution GC/MS. The precision of the analytical technique was initially evaluated using standard calibration solutions. In selective ion monitoring (SIM) mode, the relative standard deviation (RSD) obtained for TBT based on peak area response was 18% (n = 11). When an internal standard, tripropyltin (TPrT), was used, the RSD decreased to 12%. A significant improvement in the precision using SPME was noted when a 117Sn-enriched TBT spike was employed; the RSD decreased 4-fold to 3%. Detection limits of 0.2 and 20 ng(Sn) L(-1) were achieved with SPME sampling and liquid-liquid extraction, respectively. Six analyses were performed for determination of TBT in PACS-2 sediment Certified Reference Material using both standard additions and isotope dilution procedures. For the latter, a 117Sn-enriched TBT spike was used. A concentration of 0.88 +/- 0.03 microg g(-1) (RSD 3.4%) obtained using standard additions was in good agreement with the certified value of 0.98 +/- 0.13 microg g(-1) as tin. Concentrations found using isotope dilution were 0.895 +/- 0.015 microg g(-1) (RSD 1.73%) as tin and 0.874 +/- 0.014 microg g(-1) (RSD 1.66%) as tin using a liquid-liquid extraction and SPME sampling, respectively. A 2-fold improvement in the precision of TBT concentration measurement using isotope dilution was clearly achieved, demonstrating its superiority in providing more accurate and precise results as compared to the method of standard additions. The isotope dilution technique eliminated the problem of poor reproducibility, which typically plagues SPME.