First quantitative constraints on chlorine 36 dry deposition velocities on grassland: Comparing measurements and modelling results.

Once released into the atmosphere, radionuclide dry deposition represents a major transfer process. It can be accurately characterized by its deposition velocity. However, this parameter is poorly constrained for most radionuclides, including chlorine 36. Chlorine 36 is a radionuclide of cosmogenic and anthropogenic origin. It may be discharged into the environment as gases and/or particles during the decommissioning of nuclear plants and the recycling of nuclear fuels. In this study, chlorine 36 deposition velocities are, for the first time, experimentally determined on grass downwind from the Orano La-Hague plant. The atmospheric chlorine 36 measurements were on average 50 nBq.m-3 for the gaseous fraction and 19 nBq.m3 for the particulate fraction. To measure the chlorine 36 transferred from the atmosphere to the grass, a method was devised for extracting the chlorides contained in solid matrices. With this method, chlorides were extracted with a mean efficiency of 83%. Chlorine 36 concentrations in the grass were on average 4 µBq.g-1, suggesting fast uptake of atmospheric chlorine 36. The yielded 36Cl dry deposition velocities varied with the season and were between 1 × 10-3 and 6 × 10-3 m s-1. The chlorine 36 depositions were modelled by adapting the existing deposition models and based on meteorological and micro-meteorological data. The dry deposition velocities calculated by the model showed less than one order of magnitude of difference with those determined experimentally. The deposition fluxes calculated by the model showed that the atmospheric depositions were predominantly gaseous chlorine 36 (>97%). However, on remote sites, the particulate fraction could be larger and have a greater influence on dry deposition. As chlorine 36 is a highly soluble and bioavailable element, these results will enable a better study of its behaviour in the environment and a more accurate evaluation of its dosimetric impact.

Solid/liquid ratios of trace elements and radionuclides during a Nuclear Power Plant liquid discharge in the Seine River: Field measurements vs geochemical modeling.

This study focuses on the determination of field solid/liquid ratios (Rd) values of trace element (TE) and radionuclide (RN) in the Seine River (France) during a concerted low radioactivity level liquid regulatory discharge performed by a Nuclear Power Plant (NPP) and their confrontation with Kd values calculated from geochemical modeling. This research focuses on how field Rd measurements of TE and RN can be representative of Kd values and how Kd models should be improved. For this purpose 5 sampling points of the Seine River during a NPP's liquid discharge were investigated: upstream from the discharge in order to assess the natural background values in the area of effluent discharge, the total river water mixing distance (with transect sampling), and 2 points downstream from this last area. The main parameters required determining field Rd of TE and RN and their geochemical modeling (Kd) were acquired. Filtered waters were analyzed for alkalinity, anions, cations, dissolved organic carbon (DOC), TE, and RN concentrations. Suspended particulate matter (SPM) was analyzed for particulate organic carbon (POC), TE and RN concentrations and mineralogical composition. Field Rd and Kd values are in good agreement for stable Cd, Cu, Ni, Pb and Zn and for 7Be. Conversely, measured field Rd for stable Ag, Ba, Sr, Co and Cs are systematically higher than modeled Kd values. Even if only the lowest possible values were obtained for 137Cs and 60Co Rd measurements, these estimated limits are higher than calculated Kd for 137Cs and in good agreement for 60Co. Finally, only two RN exhibit field Rd lower than calculated Kd: 234Th and 210Pb. Comparison of field Rd vs. modeled Kd values for TE and RN allows the identification, for each element, of the main involved adsorption phases and geochemical mechanisms controlling their fate and partitioning in river systems.

Chlorination and dechlorination rates in a forest soil - A combined modelling and experimental approach.

Much of the total pool of chlorine (Cl) in soil consists of naturally produced organic chlorine (Clorg). The chlorination of bulk organic matter at substantial rates has been experimentally confirmed in various soil types. The subsequent fates of Clorg are important for ecosystem Cl cycling and residence times. As most previous research into dechlorination in soils has examined either single substances or specific groups of compounds, we lack information about overall bulk dechlorination rates. Here we assessed bulk organic matter chlorination and dechlorination rates in coniferous forest soil based on a radiotracer experiment conducted under various environmental conditions (additional water, labile organic matter, and ammonium nitrate). Experiment results were used to develop a model to estimate specific chlorination (i.e., fraction of Cl(-) transformed to Clorg per time unit) and specific dechlorination (i.e., fraction of Clorg transformed to Cl(-) per time unit) rates. The results indicate that chlorination and dechlorination occurred simultaneously under all tested environmental conditions. Specific chlorination rates ranged from 0.0005 to 0.01 d(-1) and were hampered by nitrogen fertilization but were otherwise similar among the treatments. Specific dechlorination rates were 0.01-0.03d(-1) and were similar among all treatments. This study finds that soil Clorg levels result from a dynamic equilibrium between the chlorination and rapid dechlorination of some Clorg compounds, while another Clorg pool is dechlorinated more slowly. Altogether, this study demonstrates a highly active Cl cycling in soils.

Effect of bacterial mineralization of phytoplankton-derived phytodetritus on the release of arsenic, cobalt and manganese from muddy sediments in the Southern North Sea. A microcosm study.

Muddy sediments of the Belgian Continental Zone (BCZ) are contaminated by metals such as Co, As, Cd, Pb, and Ni. Previous studies have suggested that mineralization of phytodetritus accumulating each year on sediments might cause secondary contaminations of the overlying seawater (metal effluxes). The aim of the present research was to investigate these effluxes using a microcosm approach. Muddy sediments were placed in microcosms (diameter: 15 cm) and overlaid by phytodetritus (a mix of Phaeocystis globosa with the diatom Skeletonema costatum). The final suspension was 130.6 mg L(-1) (dw) and the final chlorophyll a content was 750 ± 35 µg L(-1) (mean ± SD). Natural seawater was used for controls. Microcosms were then incubated in the dark at 15°C during 7 days. Metals were monitored in overlying waters and microbial communities were followed using bacterial and nanoflagellate DAPI counts, thymidine incorporation, community level physiological profiling (CLPP) and fluorescein diacetate analysis (FDA). Benthic effluxes observed in sediments exposed to phytodetritus were always more elevated than those observed in controls. Large effluxes were observed for Mn, Co and As, reaching 1084 nmol m(-2)day(-1) (As), 512 nmol m(-2)day(-1) (Co), and 755 µmol m(-2)day(-1) (Mn). A clear link was established between heterotrophic microbial activity and metal effluxes. The onset of mineralization was very fast and started within 2h of deposition as revealed by CLPP. An increased bacterial production was observed after two days (8.7 mg Cm(-2)day(-2)) and the bacterial biomass appeared controlled by heterotrophic nanoflagellates. Calculations suggest that during phytoplankton blooms the microbial activity alone may release substantial amounts of dissolved arsenic in areas of the BCZ covered by muddy sediments.

Evidence of highly dynamic geochemical behaviour of zinc in the Deûle river (northern France).

The monitoring of dissolved zinc in the Deûle river was undertaken at three different periods of the years 2008 and 2009. Electrolabile concentrations of Zn were estimated every 2 hours for several weeks by using an ATMS (Automatic Trace metal Monitoring System) based on voltammetric measurements using a solid Ag-Hg rotating disc working electrode. Complementary measurements were carried out with DGT (Diffusive Gradient in Thin films) pistons deployed directly in the river for 24 hours. Water samples filtrated at 0.45 µm were also analysed by HR-ICP-MS to estimate the total dissolved concentrations of zinc and other trace metals. High frequency monitoring of zinc over several weeks in the Deûle river indicated that the concentration could change significantly over short time periods. Resuspension of polluted sediment and biological activities are two main factors that control the behaviour of zinc in the Deûle river. Furthermore, in May 2009, daily cycles of the electrolabile zinc fraction have been observed at relatively constant total dissolved concentration. It is assumed that this particular behaviour of zinc is based on an exchange between colloids and/or nonelectrolabile forms and free cation and inorganic complexes at a daily time scale.

Potential risks of metal toxicity in contaminated sediments of Deûle river in northern France.

The aim of this paper was to evaluate the potential sediment cumulative damage and toxicity due to metal contamination in a polluted zone of Deûle river (in northern France) from nearby two smelters. Metal-enrichment factors and geoaccumulation indices measured with sediment depth revealed that--compared to background levels either in local reference soils or in world rivers sediments/suspended particulate matter--Cd contributed to the highest pollution levels, followed by Zn, Pb and to a much lesser extent Cu and Ni. A comparison of the vertical distribution of AVS (acid volatile sulfides), SEM (simultaneously extracted metals), TMC (total metal concentrations), TOC (total organic carbon) and interstitial water-metal concentrations in the sediment allowed us to highlight the extent of toxicity caused by Cd, Pb, Zn, Ni and Cu and to raise the possibility of their association with certain geochemical phases. To assess the actual environmental impacts of these metals in Deûle river, numerical sediment quality guidelines were further used in the present work. Sedimentary Pb, Zn, and Cd contents largely exceeded PEC (probable effect concentration) values reported as consensus-based sediment quality guidelines for freshwater ecosystems. As for risks of toxicity from pore waters, metal concentrations reached their maxima at the surficial layers of the sediment (1-3 cm) and IWCTU (Interstitial Water Criteria Toxicity Unit) observed for Pb and to a lesser extent Cd, violated the corresponding water quality data recommended by USEPA.

Automatic trace metal monitoring station use for early warning and short term events in polluted rivers: application to streams loaded by mining tailing.

An automatic trace metal monitoring station (ATMS) system was implemented to study seasonal and short time changes in selected metal concentrations in two river courses influenced by mine drainage. High frequency monitoring over periods of months revealed daily variations of zinc, iron and copper, and also proved the use of ATMS as an early warning system in such polluted environments. Complementary measurements with ICP-MS (inductively coupled plasma-mass spectrometry), ionic chromatography, and thermodynamic equilibrium calculations also gave some new insights into the geochemical behaviour of the metals in these two rivers.