David Dumoulin

Arsenic behavior in river sediments under redox gradient: A review

The fate of arsenic - a redox sensitive metalloid - in surface sediments is closely linked to early diagenetic processes. The review presents the main redox mechanisms and final products of As that have been evidenced over the last years. Oxidation of organic matter and concomitant reduction of oxidants by bacterial activity result in redox transformations of As species. The evolution of the sediment reactivity will also induce secondary abiotic reactions like complexation/de-complexation, sorption, precipitation/dissolution and biotic reactions that could, for instance, lead to the detoxification of some As species. Overall, abiotic redox reactions that govern the speciation of As mostly involve manganese (hydr)-oxides and reduced sulfur species produced by the sulfate-reducing bacteria. Bacterial activity is also responsible for the inter-conversion between As(V) and As(III), as well as for the production of methylated arsenic species. In surficial sediments, sorption processes also control the fate of inorganic As(V), through the formation of inner sphere complexes with iron (hydr)-oxides, that are biologically reduced in buried sediment. Arsenic species can also be bound to organic matter, either directly to functional groups or indirectly through metal complexes. Finally, even if the role of reduced sulfur species in the cycling of arsenic in sediments has been evidenced, some of the transformations remain hypothetical and deserve further investigation.

Daily variations of Zn and Pb concentrations in the Deûle River in relation to the resuspension of heavily polluted sediments

Sediments in the Deûle River (northern France) are severely polluted by metals in the vicinity of several metallurgical plants. The aim of this paper is to identify the role played by the recurrent resuspension of these polluted sediments by boat traffic on the dissolved Pb and Zn concentrations in the river. For that purpose, several high-frequency on-line monitoring campaigns were performed. Our results clearly suggest that the resuspension of sedimentary particles into the overlying water significantly increased the dissolved electrolabile Pb and Zn contents. This increase does not persist for a long time because at night and during weekends and holidays, when the boat traffic strongly slows down, Pb and Zn concentrations drop again quickly. Our data also indicate that the biological processes (such as photosynthetic and respiration activities), diffusive and benthic fluxes, as well as dilution of pore water into the overlying water during sediment remobilization do not contribute significantly to the sharp increase of dissolved Pb and Zn concentrations in the river during the day. The good correlation between turbidity and electrolabile metal concentration allows us to discard slow AVS (Acid Volatile Sulfides) oxidation as well. Desorption of metals from sediment particles was clearly the most relevant process, responsible for the increase of dissolved Pb and Zn concentrations in the water column.

Development and application of a HPIC-ICP-MS method for the redox arsenic speciation in river sediment pore waters

A new sensitive chromatographic method has been developed for As speciation determination in anoxic pore waters. Starting from aliquots of 25 μL, the different As species As(III), As(V), MMAAV and DMAAV were separated in less than 4 min by HPIC-ICP-MS using the IonPac® AG7-AS7 anion-exchange column set and dilute HNO3 as mobile phase. The detection limits were below or equal to 0.25 μg L−1 for each As species, which makes the method efficient to determine As speciation in poorly-contaminated sediments. In addition, no precipitation of iron and manganese (hydr)-oxides was observed since the anoxic samples were systematically carefully manipulated under nitrogen atmosphere. Chlorides were eliminated by the chromatographic separation, thus making possible speciation analysis in estuarine or seawater samples. The use of internal standard was not necessary due to good signal stability (<10%) at m/z 75 over 4 h of analysis. An environmental application has also been successfully performed in the Marque River (Northern France). Inorganic As species were detected in pore waters at low concentrations [below 1 and 10 μg L−1, for As(V) and As(III) respectively]. Others As species, identified as thioarsenic species, were also detected.

Comparison of POCIS passive samplers vs. composite water sampling: A case study

The relevance of Polar Organic Chemical Integrative Samplers (POCIS) was evaluated for the assessment of concentrations of 46 pesticides and 19 pharmaceuticals in a small, peri-urban river with multi-origin inputs. Throughout the period of POCIS deployment, 24h-average water samples were collected automatically, and showed the rapid temporal evolution of concentrations of several micropollutants, as well as permitting the calculation of average concentrations in the water phase for comparison with those estimated from POCIS passive samplers. In the daily water samples, cyproconazol, epoxyconazol and imidacloprid showed high temporal variations with concentrations ranging from under the limit of detection up to several hundreds of ngL-1. Erythromycin, cyprofloxacin and iopromide also increased rapidly up to tens of ngL-1 within a few days. Conversely, atrazine, caffeine, diclofenac, and to a lesser extent carbamazepine and sucralose, were systematically present in the water samples and showed limited variation in concentrations. For most of the substances studied here, the passive samplers gave reliable average concentrations between the minimal and maximal daily concentrations during the time of deployment. For pesticides, a relatively good correlation was clearly established (R2=0.89) between the concentrations obtained by POCIS and those gained from average water samples. A slight underestimation of the concentration by POCIS can be attributed to inappropriate sampling rates extracted from the literature and for our system, and new values are proposed. Considering the all data set, 75% of the results indicate a relatively good agreement between the POCIS and the average water samples concentration (values of the ratio ranging between 0,33 and 3). Note further that this agreement between these concentrations remains valid considering different sampling rates extracted from the literature.

Determination of total arsenic using a novel Zn-ferrite binding gel for DGT techniques: Application to the redox speciation of arsenic in river sediments.

A new laboratory-made Zn-ferrite (ZnFe2O4) binding gel is fully tested using Diffusive Gradient in Thin films (DGT) probes to measure total As [including inorganic As(III) and As(V), as well as MonoMethyl Arsenic Acid (MMAA(V)) and DiMethyl Arsenic Acid (DMAA(V))] in river waters and sediment pore waters. The synthesis of the binding gel is easy, cheap and its insertion into the acrylamide gel is not problematic. An important series of triplicate tests have been carried out to validate the use of the Zn-ferrite binding gel in routine for several environmental matrixes studies, in order to test: (i) the effect of pH on the accumulation efficiency of inorganic As species; (ii) the reproducibility of the results; (iii) the accumulation efficiency of As species; (iv) the effects of the ionic strength and possible competitive anions; and (v) the uptake and the elution efficiency of As species after accumulation in the binding gel. All experimental conditions have been reproduced using two other existing binding gels for comparison: ferrihydrite and Metsorb® HMRP 50. We clearly demonstrate that the Zn-ferrite binding gel is at least as good as the two other binding gels, especially for pH values higher than 8. In addition, by taking into consideration the diffusion rates of As(III) and As(V) in the gel, combining the 3-mercaptopropyl [accumulating only As(III)] with the Zn-ferrite binding gels allows for performing speciation studies. An environmental study along the Marque River finally illustrates the ability of the new binding gel to be used for field studies.

Active biomonitoring for assessing effects of metal polluted sediment resuspension on gammarid amphipods during fluvial traffic

The resuspension of polluted sediments by boat traffic could release substantial amounts of metals to the water column, affecting at the same time their bioavailability. In order to characterize the impact of sediment resuspensions on biota, caged amphipods have been deployed on three different channelized watercourses in Northern France. Firstly, the biological responses of transplanted freshwater gammarid amphipods, Gammarus fossarum, described by trace metal accumulation, feeding and reproduction activities were quite similar for the three water courses despite the differences of metal contamination and navigability. Secondly, the concentrations of metals accumulated in gammarids never exceeded the contamination thresholds previously defined for Co, Cu, Cr and Zn. Values were in the same order of magnitude whatever the studied site despite: (i) large differences noticed in the sediment quality and (ii) some concentrations in the overlying waters exceeding the Environmental Quality Standards (EQS) defined by the Water Framework Directive. Conversely, Pb was highly bioaccumulated with values systematically exceeding the threshold value whatever the site. Therefore, the impact of navigation cannot be proved and the difference between the 3 monitoring periods is rather attributed to environmental variability, probably linked to the seasonality. Moreover, this study also confirms that organisms sampled from a local population in the vicinity of the three studied watercourses could be used as test organisms, leading to similar results than the ones obtained with reference gammarids initially used for developing all the biological responses. This would simplify and then promote the development of studies based on gammarid amphipod, G.xa0fossarum, as bioindicators.

Removal and Biodegradation of Phenanthrene, Fluoranthene and Pyrene by the Marine Algae Rhodomonas baltica Enriched from North Atlantic Coasts.

This study is focused on the removal, accumulation and degradation of three environmental ubiquitous polycyclic aromatic hydrocarbons (PAHs), phenanthrene (PHE), fluoranthene (FLA) and pyrene (PYR), by the marine alga Rhodomonas baltica enriched from the English Channel. After separation, purification and culture in several phases, R. baltica was exposed to PAH concentrations that are frequently encountered in the field in several anthropized environments. The results showed that R. baltica can grow under PAH stress, efficiently remove up to 70% of these compounds from the medium by 216xa0h of culture and selectively bioaccumulate PAHs by their hydrophobicity. Between PHE, FLA and PYR, phenanthrene was the compound with higher degradation rates throughout incubation. The equilibrium partitioning theoretical approach showed that physico-chemical partitioning, rather than active bioconcentration, was the major factor governing the bioaccumulation, outlying a potential application in decontamination processes for this species.

Test of some ecological concepts on the longitudinal distribution of zooplankton along a lowland water course

The distribution of zooplankton communities from the source to the mouth of a lowland water course, the Scheldt, was used to test some concepts on the longitudinal distribution of organisms along both estuarine (Remane’s diversity concept) and riverine reaches (River Continuum Concept (RCC), Riverine Ecosystem Synthesis (RES)). Substantial zooplankton densities were found in both April and June samples all along the water course, and not only in the lower reaches as suggested by the RCC. Based on the zooplankton communities, and using hierarchical classifications and Generalized Linear Model, several successive zones influenced by different physical and chemical variables and trophic conditions could be distinguished along the Scheldt, in agreement with the RES model: the non-tidal riverine, the tidal freshwater, the tidal salinity gradient, and the marine zones. Over the entire freshwater reach, rotifers were numerically dominant during both samplings; crustaceans became more abundant in June than in April, specifically in the downstream reaches. Highest total zooplankton abundance and diversity were found in the tidal freshwater reach, lowest in the brackish water reach, in accordance with Remane’s concept. An influence of the tributaries on zooplankton communities is suggested, directly by import or dilution of zooplankton communities or through changing environmental conditions.

Assessment of the treatment efficiency of an urban stormwater pond and its impact on the natural downstream watercourse

During the last few decades, stormwater ponds have become an alternative management practice in order to avoid flooding and to contain rainwater and runoff in urban areas where impervious land cover has increased. A second purpose of stormwater ponds is to improve the quality of runoff water that is usually contaminated with nitrogen, phosphorus, metals and organic micropollutants. Processes used are based on natural methods such as settlement and contribute to minimize the impact of these inputs to the natural aquatic system. This study aims to better understand the behavior of a wet stormwater pond, Heron Lake (33u202fha) located in the city of Villeneuve dAscq in northern France through various indicators [trace metals, PAHs, PCBs, caffeine (CAF), carbamazepine (CBZ), nutrients and pathogens]. For that purpose, water quality was monitored for 1 year, mainly at the entrance and at the outlet of the lake. Sampling have also been done in the downstream aquatic environment, the Marque River. Sediments were sampled in the lake to evaluate the pollution trapped during sedimentation. Our results of both water and sediment sampling highlight: (i) the wastewater input into the Heron Lake is estimated to be equivalent to that of roughly 3800 inhabitants; (ii) the removal rates observed at the outlet, relative to concentrations at the entrance channel, vary as follows for these dissolved species: 24% for NO3- and PO43-, 28% for CBZ, 35% for Cu, 63% for Pb, 78% for CAF, 84% for Zn and up to 93% for NH4+; (iii) there are high levels of sediment contamination with metals, PAHs and PCBs at the entrance channel; (iv) the eutrophication of this pond is attributed to persistent high nutrient concentrations in both water and sediment, and has contributed to the development of an invasive macrophyte, the Elodea nuttallii; and (v) there appears to be only a negligible impact of the discharge from the lake to the natural watercourse, contributing annual loads of <2 up to 6% of the total amount of Cu, Pb, Zn, CAF, CBZ and nutrients measured in the Marque River, and having a slight diluting effect on concentrations in the Marque River.

Are zooplankton communities structured by taxa ecological niches or by hydrological features

EcoLab, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France UMR 8187, LOG, Laboratoire dOcéanologie et de Géosciences, Univ. Lille, CNRS, Univ. Littoral Côte dOpale, 62930 Wimereux, France ECOBE (Ecosystem Management Research Group) Department of Biology, University of Antwerp, Universiteitsplein 1, 2610 Antwerpen, Belgium Agence de lEau Artois‐Picardie, 200 rue Marceline, 59500 Douai, France LASIR (Laboratoire de Spectrochimie Infrarouge et Raman)—UMR 8516, Université Lille 1‐Sciences et Technologies, Bâtiment C8, Cité Scientifique, 59655 Villeneuve dAscq Cedex, France Correspondence Maïwen Le Coz, Laboratoire EcoLab‐UMR 5245, Ecologie Fonctionnelle et Environnement, Université Paul Sabatier, Bât. 4R1, 118 route de Narbonne, 31062 Toulouse Cedex 9, France. Email: maiwenlc@gmail.com