Modeling of Cs migration in soils using an 80-year soil archive: role of fertilizers and agricultural amendments

An 80-year soil archive, the 42-plot experimental design at the INRA in Versailles (France), is used here to study long-term contamination by ¹³⁷Cs atmospheric deposition and the fate of this radioisotope when associated with various agricultural practices: fallow land, KCl, NH₄(NO₃), superphosphate fertilizers, horse manure and lime amendments. The pertinence of a simple box model, where radiocaesium is supposed to move downward by convectional mechanisms, is checked using samples from control plots which had been neither amended, nor cultivated since 1928. This simple model presents the advantage of depending on only two parameters: α, a proportional factor allowing the historical atmospheric ¹³⁷Cs fluxes to be reconstructed locally, and k, an annual loss coefficient from the plow horizon. Another pseudo-unknown is however necessary to run the model: the shape of historical ¹³⁷Cs deposition, but this function can be easily computed by merging several curves previously established by other surveys. A loss of ∼1.5% per year from the plow horizon, combined with appropriate fluxes, provides good concordance between simulated and measured values. In the 0–25 cm horizon, the residence half time is found to be ∼18 yr (including both migration and radioactive decay). Migration rate constants are also calculated for some plots receiving continuous long-term agricultural treatments. Comparison with the control plots reveals significant influence of amendments on ¹³⁷Cs mobility in these soils developed from a unique genoform.     

Organochlorinated contaminants in decapod crustaceans from the coasts of Brittany and Normandy (France)

The contamination and distribution of organochlorinated compounds were considered in three crustacean species (edible crab, Cancer pagurus; spider crab, Maja brachydactyla; velvet swimming crab, Necora puber) from five sites along the coasts of Brittany and Normandy (Western and North-Western France). PCBs (16 single congeners), pp'-DDE and HCB were measured in hepatopancreas, gonads and muscle: in all, 175 samples were analysed. The spider crab was the only species found in the five sampling sites, thus enabling comparison between areas. Specimens from Antifer were much more contaminated (summation operator 16 PCBs in hepatopancreas=2000-4000 ng g(-1) dry weight) than those from other sites (50-1000 ng g(-1) d.w.). Among all the three species, the spider crab appeared more contaminated by PCBs than the edible crab, by a factor 2-3, probably in relation with specific differences in their life cycle. There was no difference due to the gender of the species. Within the different analysed tissues, contamination levels increased from muscle to gonads and hepatopancreas in relation with the fat content. A very similar PCB composition was observed in all samples, PCB fingerprints being characterised by the relative importance of the more persistent PCB congeners: CB153, 138, 180, 187, and 118. Finally, these results were compared to recent food regulations first of maximum marker PCB intake and secondly of maximum dioxin-like PCB intake. By considering the muscle, all samples were far below the regulatory limits; for hepatopancreas and gonads, however, some samples were unfit for human consumption.     

A high-resolution historical sediment record of nutrients,trace elements and organochlorines (DDT and PCB) deposition in a drinking water reservoir (Lake Brêt,Switzerland) points at local and regional pollutant sources

The ¹³⁷Cs and ²¹⁰Pb dating of a 61-cm long sediment core retrieved from a drinking water reservoir (Lake Brêt) located in Switzerland revealed a linear and relatively high sedimentation rate (～1 cm year^?1) over the last decades. The continuous centimeter scale measurement of physical (porewater and granulometry), organic (C_org, P, N, HI and OI indexes) and mineral (C_min and lithogenic trace elements) parameters therefore enables reconstructing the environmental history of the lake and anthropogenic pollutant input (trace metals, DDT and PCBs) at high resolution. A major change in the physical properties of the lowermost sediments occurred following the artificial rise of the dam in 1922. After ca. 1940, there was a long-term up-core increase in organic matter deposition attributed to enhance primary production and anoxic bottom water conditions due to excessive nutrient input from a watershed predominantly used for agriculture that also received domestic effluents of two wastewater-treatment plants. This pattern contrasts with the terrigenous element input (Eu, Sc, Mg, Ti, Al, and Fe) which doubled after the rising of the dam but continuously decreased during the last 60 years. By comparison, the trace metals (Cu, Pb and Hg) presented a slight enrichment factor (EF) only during the second part of the 20th century. Although maximum EF Pb (>2) occurred synchronously with the use of leaded gasoline in Switzerland (between ca. 1947 and 1985) the Hg and Cu profiles exhibited a relatively similar trend than Pb during the 20th century, therefore excluding the alkyl-lead added to petrol as the dominant (atmospheric) source of lead input to Lake Brêt. Conversely, the Cu profile that did not follow the decrease registered in Pb and Hg during the last 10 years, suggests an additional source of Cu probably linked to the impact of agricultural activities in the area. In absence of heavy industries in the catchment, the atmospheric deposition of DDT and PCBs via surface runoff followed the historical emissions of POPs in Switzerland. Such result highlights the regional contamination of freshwater resources by the large-scale emission of toxic industrial chemicals in the 1960s and 1970s as well as the efficiency of the regulatory measures subsequently taken.     

Congener-specific accumulation and trophic transfer of polychlorinated biphenyls in spider crab food webs revealed by stable isotope analysis

Polychlorobiphenyls (PCB) and stable isotopes (delta15N and delta13C) were analyzed in the spider crab (Maja brachydactyla) food web from the Iroise Sea (Western Brittany) and the Seine Bay (Eastern English Channel). PCB concentrations were all significantly higher in organisms from the Seine Bay than those from the Iroise Sea. PCB patterns were strongly related to the feeding mode of the species, and increased influence of higher chlorinated congeners was highlighted with trophic position of the organisms. PCB concentrations (lipid normalized) were significantly related to the isotopically derived trophic level (TL) in spider crab food webs. The highest trophic magnification factors (TMFs) were calculated for the congeners with 2,4,5-substitution, and were lower in the Seine Bay compared to the Iroise Sea. The confrontation of PCB and TL data also revealed biotransformation capacity of decapod crustaceans for specific congeners based on structure-activity relations.     

Responses of the European flounder (Platichthys flesus) to a mixture of PAHs and PCBs in experimental conditions

A multibiomarker approach was developed to evaluate the juvenile European flounder responses to a complex mixture of 9 polycyclic aromatic hydrocarbons (PAHs) and 12 polychlorinated biphenyls (PCBs). Exposure was performed through contaminated food pellets displaying: (1) PAH and PCB levels similar to those detected in the heavily polluted Seine estuary, respectively in sediments and in flatfish and (2) ten times these concentrations. Several biomarkers of the immune system (e.g., lysozyme concentration and gene expression of complement component C3 and TNF-receptor), DNA damage (e.g., Comet assay), energetic metabolism (e.g.,?activity of cytochrome C oxidase), detoxification process (e.g., cytochrome P450 1A1 expression level: CYP1A1; betaine homocysteine methyl transferase expression level: BHMT) were investigated after 14 and 29 days of contamination, followed by a 14-days recovery period. After 29 days of contamination, the detoxification activity (CYP1A1 expression level) was positively correlated with DNA damages; the increase of the BHMT expression level could also be related to the detoxification process. Furthermore, after the recovery period, some biomarkers were still upregulated (i.e., CYP1A1 and BHMT expression levels). The immune system was significantly modulated by the chemical stress at the two concentration levels, and the lysozyme appeared to be the most sensitive marker of the mixture impact.     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River, Romania

Background, aim and scope  

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River,Romania

Background, aim and scope

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.

Results and discussion

Sediment texture was uniform in the cores from both reservoirs. Laminated sediment structure, without any obvious discontinuities, was observed. Hg concentrations in the sediment core from the Valcea Reservoir were low and constant (0.01–0.08 mg/kg). In Babeni Reservoir sediments, Hg concentrations were very high in the deeper core section (up to 45 mg/kg in the longest core) and decreased to lower concentrations toward the top of the cores (1.3–2.4 mg/kg). This decrease probably reflects technological progress in control of emissions from the Hg-cell-based chlor-alkali industry. Two strong peaks could be distinguished in older sediments. The mean rate of sedimentation (5.9 cm/year) was calculated from the depth of the ¹³⁷Cs Chernobyl peak. This was in good agreement with the sedimentation rate estimated at this site from a bathymetric study. Assuming a constant sedimentation rate, the two Hg peaks would reflect two contamination events in 1987 and 1991, respectively. However, it is also possible that the two peaks belong to the same contamination event in 1987 but were separated by a sediment layer richer in sand and silt. This layer had a low Hg concentration, which can be interpreted as a mass deposition event related to a major flood bringing Hg-free sediments.

Conclusions

Whilst the chlor-alkali plant partly switched to a cleaner technology in 1999, no obvious decrease of Hg concentrations was observed in recent decade. Results from the sediment core reflected the historical trend of Hg release from the chlor-alkali plant, revealed important contamination episodes and confirmed a legacy of contamination of Hg in recent sediments even if the concentrations of Hg decreased toward the surface due to a more efficient emission control.

Recommendations and perspectives

Although the Hg concentrations in Babeni Reservoir sediments were extremely high in the late eighties and they remain one order of magnitude higher in the surface sediments than in sediments from the upstream reservoir, little is known about the transfer of Hg to the biota and human population. Our initial measurements indicate the presence of monomethyl-Hg (MMHg) in pore water, but further studies are necessary to evaluate fluxes of MMHg at the sediment–water interface. Samples of fish and hair from various groups of the local population were recently collected to evaluate the potential hazard of Hg contamination to human health in the Rm Valcea region.

     

Historical record of mercury contamination in sediments from the Babeni Reservoir in the Olt River,Romania

Background, aim and scope

Mercury (Hg) is a ubiquitous and hazardous contaminant in the aquatic environment showing a strong biomagnification effect along the food chain. The most common transfer path of Hg to humans is contaminated fish consumption. In severely exposed humans, Hg poisoning may lead to damage in the central nervous system. Thus, it is important to examine current and past contamination levels of Hg in aquatic milieu. The Olt River is the largest Romanian tributary of the Danube River. The use of Hg as an electrode in a chlor-alkali plant contributed to the contamination of the aquatic environment in the Rm Valcea region. The purpose of this study was to compare the current state of Hg contamination with the past contamination using a historical record obtained from a dated sediment core from one of the Olt River reservoirs (Babeni) located downstream from the chlor-alkali plant. To our knowledge, no published data on Hg contamination in this region are available. The Babeni Reservoir was selected for this study because it is situated downstream from the chlor-alkali plant, whilst the other reservoirs only retain the pollutants coming from the upstream part of the watershed. Preliminary analyses (unpublished) showed high Hg concentrations in the surface sediment of the Babeni Reservoir. One core was taken in the upstream Valcea Reservoir to provide a local background level of Hg concentrations in sediments.

Results and discussion

Sediment texture was uniform in the cores from both reservoirs. Laminated sediment structure, without any obvious discontinuities, was observed. Hg concentrations in the sediment core from the Valcea Reservoir were low and constant (0.01–0.08 mg/kg). In Babeni Reservoir sediments, Hg concentrations were very high in the deeper core section (up to 45 mg/kg in the longest core) and decreased to lower concentrations toward the top of the cores (1.3–2.4 mg/kg). This decrease probably reflects technological progress in control of emissions from the Hg-cell-based chlor-alkali industry. Two strong peaks could be distinguished in older sediments. The mean rate of sedimentation (5.9 cm/year) was calculated from the depth of the ¹³⁷Cs Chernobyl peak. This was in good agreement with the sedimentation rate estimated at this site from a bathymetric study. Assuming a constant sedimentation rate, the two Hg peaks would reflect two contamination events in 1987 and 1991, respectively. However, it is also possible that the two peaks belong to the same contamination event in 1987 but were separated by a sediment layer richer in sand and silt. This layer had a low Hg concentration, which can be interpreted as a mass deposition event related to a major flood bringing Hg-free sediments.

Conclusions

Whilst the chlor-alkali plant partly switched to a cleaner technology in 1999, no obvious decrease of Hg concentrations was observed in recent decade. Results from the sediment core reflected the historical trend of Hg release from the chlor-alkali plant, revealed important contamination episodes and confirmed a legacy of contamination of Hg in recent sediments even if the concentrations of Hg decreased toward the surface due to a more efficient emission control.

Recommendations and perspectives

Although the Hg concentrations in Babeni Reservoir sediments were extremely high in the late eighties and they remain one order of magnitude higher in the surface sediments than in sediments from the upstream reservoir, little is known about the transfer of Hg to the biota and human population. Our initial measurements indicate the presence of monomethyl-Hg (MMHg) in pore water, but further studies are necessary to evaluate fluxes of MMHg at the sediment–water interface. Samples of fish and hair from various groups of the local population were recently collected to evaluate the potential hazard of Hg contamination to human health in the Rm Valcea region.

     

Mercury human exposure through fish consumption in a reservoir contaminated by a chlor-alkali plant: Babeni reservoir (Romania)

Purpose  

Chlor-alkali plants are one of the most important point sources of mercury to aquatic environment. The problem of Hg contamination has been studied in a region, Rm Valcea (Romania), impacted by the wastewater discharge of a chlor-alkali plant. The purpose of the present study is to evaluate the current status of mercury pollution in the Babeni reservoir (Olt River) and the exposure of local population via fish consumption to mercury originating from the chlor-alkali plant.