Long-term pollution by chlordecone of tropical volcanic soils in the French West Indies: A simple leaching model accounts for current residue

Chlordecone was applied between 1972 and 1993 in banana fields of the French West Indies. This resulted in long-term pollution of soils and contamination of waters, aquatic biota, and crops. To assess pollution level and duration according to soil type, WISORCH, a leaching model based on first-order desorption kinetics, was developed and run. Its input parameters are soil organic carbon content (SOC) and SOC/water partitioning coefficient (K_oc). It accounts for current chlordecone soil contents and drainage water concentrations. The model was valid for andosol, which indicates that neither physico-chemical nor microbial degradation occurred. Dilution by previous deep tillages makes soil scrapping unrealistic. Lixiviation appeared the main way to reduce pollution. Besides the SOC and rainfall increases, K_oc increased from nitisol to ferralsol and then andosol while lixiviation efficiency decreased. Consequently, pollution is bound to last for several decades for nitisol, centuries for ferralsol, and half a millennium for andosol.     

Characterization of chlordecone-tolerant fungal populations isolated from long-term polluted tropical volcanic soil in the French West Indies

The insecticide chlordecone is a contaminant found in most of the banana plantations in the French West Indies. This study aims to search for fungal populations able to grow on it. An Andosol heavily contaminated with chlordecone, perfused for 1 year in a soil–charcoal system, was used to conduct enrichment cultures. A total of 103 fungal strains able to grow on chlordecone-mineral salt medium were isolated, purified, and deposited in the MIAE collection (Microorganismes d'Intérêt Agro-Environnemental, UMR Agroécologie, Institut National de la Recherche Agronomique, Dijon, France). Internal transcribed spacer sequencing revealed that all isolated strains belonged to the Ascomycota phylum and gathered in 11 genera: Metacordyceps, Cordyceps, Pochonia, Acremonium, Fusarium, Paecilomyces, Ophiocordyceps, Purpureocillium, Bionectria, Penicillium, and Aspergillus. Among predominant species, only one isolate, Fusarium oxysporum MIAE01197, was able to grow in a liquid culture medium that contained chlordecone as sole carbon source. Chlordecone increased F. oxysporum MIAE01197 growth rate, attesting for its tolerance to this organochlorine. Moreover, F. oxysporum MIAE01197 exhibited a higher EC₅₀ value than the reference strain F. oxysporum MIAE00047. This further suggests its adaptation to chlordecone tolerance up to 29.2 mg l^?1. Gas chromatography–mass spectrometry (GC-MS) analysis revealed that 40 % of chlordecone was dissipated in F. oxysporum MIAE01197 suspension culture. No chlordecone metabolite was detected by GC-MS. However, weak amount of ¹⁴CO₂ evolved from ¹⁴C₁₀-chlordecone and ¹⁴C₁₀-metabolites were observed. Sorption of ¹⁴C₁₀-chlordecone onto fungal biomass followed a linear relationship (r ²?=?0.99) suggesting that it may also account for chlordecone dissipation in F. oxysporum MIAE01197 culture.     

Partitioning and bioaccumulation of cadmium in artificial sediment systems: application of a stable isotope tracer technique

The utility of stable isotope tracers for investigating the relationship between cadmium (Cd) partitioning in artificial sediment-water systems and Cd accumulation in a benthic detritivore (Asellus racovitzai, Isopoda) was explored. In the laboratory, Cd isotopes were applied to synthetic sediment and isotope concentrations were measured in sediment, overlying water and exposed asellids over a 10-day period. Isotope ratios measured in sediment and water were compared to ratios measured in asellids to determine whether Cd partitioning could predict metal bioaccumulation. Two different parameters which might affect Cd partitioning between the sediment and overlying water compartments were investigated: the chemical form in which Cd was added to systems, and the organic matter content of the sediment. To test the effect of chemical form on Cd partitioning, three isotopes of cadmium were individually applied to formulated sediment in varying combinations of 113Cd(NO3)2, 112Cd-humic acid (HA) 114CdSO4. The results demonstrated that chemical form did not influence partitioning, as the Cd isotope that was applied to sediment in the nitrate form exhibited similar partitioning between sediment and overlying water as the isotope that was applied in the sulfate or HA form. However, Cd isotope concentrations in overlying water were strongly related to the pattern of isotope accumulation in asellids suggesting that overlying water concentrations determined Cd bioaccumulation. In contrast, when the organic matter content of sediment was increased through the addition of Sphagnum peat moss, total Cd concentrations in overlying water and tissue were low, and there was no relationship between Cd-isotope concentrations in tissue and water. These results indicate that Cd accumulation occurred primarily from water, and factors that increase metal partitioning to sediment, such as increased sediment organic matter content, decrease Cd accumulation in asellids. The stable isotope tracer method described herein appears to be a useful technique for investigating the relationship between metal partitioning and bioaccumulation in simple sediment systems, but could also be extended to more complex systems, and used with different metals that have multiple stable isotopes.     

Single-well reactive tracer test and stable isotope analysis for determination of microbial activity in a fast hydrocarbon-contaminated aquifer

Single-well reactive tracer tests, such as the push-pull test are useful tools for characterising in-situ bioattenuation processes in contaminated aquifers. However, the analytical models that are used to interpret push-pull data may be over-simplified, and potentially overlook important processes responsible for the frequent discrepancy between predicted and observed results obtained from push-pull tests. In this study, the limitations underlying the push-pull test methodology were investigated and were supported with results from a push-pull test conducted in a sulphate-reducing aquifer contaminated by crude oil. Poor (<7%) mass recovery was achieved when the push-pull test was performed in a fast-flowing aquifer, preventing a quantifiable reaction rate to be determined. Breakthrough curve data were unexplainable using simplified analytical models, but exhibited trends analogous with tests conducted by others, when >20% mass recoveries were achieved. Push-pull test data collected from sulphate-reducing aquifers indicate that the assumption of a well-mixed batch reactor system is incorrect and that reaction rates obtained from push-pull tests in such systems may be affected by the extraction regime implemented. Evidence of microbial respiration of the reactive tracer was provided by stable sulphur isotope analysis, from which an isotope fractionation factor of +9.9 +/- 8.1 per thousand was estimated. The stable isotope data support the argument that reaction rates calculated using push-pull tests are not uniformly distributed in space and time and are likely to be influenced by heterogeneities in the flow field.     

Hg concentrations and stable isotope variations in tropical fish species of a gold-mining-impacted watershed in French Guiana

Environmental Science and Pollution Research - The aim of the study was to determine if gold-mining activities could impact the mercury (Hg) concentrations and isotopic signatures in freshwater...     

Feathers as a means of monitoring mercury in seabirds: Insights from stable isotope analysis

Mercury concentrations, together with nitrogen and carbon stable isotope signatures, were determined in body feather samples from northern fulmars Fulmarus glacialis and great skuas Catharacta skua, and in different flight feathers from great skuas. There were no significant relationships between trophic status, as defined using isotope analysis, and mercury concentration in the same feather type, in either species. Mercury concentrations in body feather samples were markedly different between fulmars and skuas, reflecting differences in diet, but there was no corresponding difference in trophic status as measured through nitrogen stable isotope signatures. We conclude that mercury concentrations and stable isotope values in feathers are uncoupled, mercury concentrations apparently reflecting the body pool of accumulated mercury at the time of feather growth whilst stable isotope values reflect the diet at the time of feather growth. There were significant positive correlations between the different flight feathers of great skuas for all three parameters measured. These were strongest between primary 10 and secondary 8, suggesting that these two feathers are replaced at the same time in the moult sequence in great skuas. Stable isotope analysis of different feathers may provide a means of investigating moult patterns in birds.     

Biodegradability of algal-derived organic matter in a large artificial lake by using stable isotope tracers

In order to understand the biodegradability of algal-derived organic matter, biodegradation experiments were conducted with ¹³C and ¹⁵N-labeled natural phytoplankton and periphytic algal populations in experimental conditions for 60 days. Qualitative changes in the dissolved organic matter were also determined using parallel factor analysis and the stable carbon isotopic composition of the hydrophobic dissolved organic matter through the experimental period. Although algal-derived organic matter is considered to be easily biodegradable, the initial amounts of total organic carbon newly produced by phytoplankton and periphytic algae remained approximately 16 and 44 % after 60 days, respectively, and about 22 and 43 % of newly produced particulate nitrogen remained. Further, the dissolved organic carbon derived from both algal populations increased significantly after 60 days. Although the dissolved organic matter gradually became refractory, the contributions of the algal-derived organic matter to the dissolved organic matter and hydrophobic dissolved organic matter increased. Our laboratory experimental results suggest that algal-derived organic matter produced by phytoplankton and periphytic algae could contribute significantly to the non-biodegradable organic matter through microbial transformations.     

Copper bioavailability and extractability as related to chemical properties of contaminated soils from a vine-growing area

Vineyard soils have been contaminated by Cu as a consequence of the long-term use of Cu salts as fungicides against mildew. This work aimed at identifying which soil parameters were the best related to Cu bioavailability, as assessed by measuring the concentrations of Cu in shoots and roots of tomato cropped (in lab conditions) over a range of 29 (24 calcareous and five acidic) Cu-contaminated topsoils from a vine-growing area (22-398 mg Cu kg(-1)). Copper concentrations in tomato shoots remained in the adequate range and were independent of soil properties and soil Cu content. Conversely, strong, positive correlations were found between root Cu concentration, total soil Cu, EDTA- or K-pyrophosphate-extractable Cu and organic C contents in the 24 calcareous soils, suggesting a prominent role of organic matter in the retention and bioavailability of Cu. Such relations were not observed when including the five acidic soils in the investigated population, suggesting a major pH effect. Root Cu concentration appeared as a much more sensitive indicator of soil Cu bioavailability than shoot Cu concentration. Simple extractions routinely used in soil testing procedures (total and EDTA-extractable Cu) were adequate indicators of Cu bioavailability for the investigated calcareous soils, but not when different soil types were considered (e.g. acidic versus calcareous soils).     

Trace metal and stable isotope measurements (delta13C and delta15N) in the harbour porpoise Phocoena phocoena relicta from the Black Sea

Stable carbon and nitrogen isotopes (delta13C and delta15N) and trace metals (Cd, Zn, Cu, Fe, Se, and Hg) were analysed in the tissues of 46 harbour porpoises (Phocoena phocoena relicta) caught in fishing nets along the Ukrainian coasts between 1997 and 1998. Mean delta13C values differed significantly between male and female harbour porpoises suggesting a trophic segregation between sexes with a more coastal distribution for females at least during their gestation and nursing periods. Hepatic Hg was correlated to delta13C measurements, reflecting a different exposure linked to coastal vs offshore feeding habitats. A geographical comparison with existing data from other regions showed general low levels of Hg, Cd, Cu and Zn in the tissues of harbour porpoises from the Black Sea compared to other Atlantic and North Sea areas.     

Estimation of contribution from non-point sources to perfluorinated surfactants in a river by using boron as a wastewater tracer

The contribution of non-point sources to perfluorinated surfactants (PFSs) in a river was evaluated by estimating their fluxes and by using boron (B) as a tracer. The utility of PFSs/B as an indicator for evaluating the impact of non-point sources was demonstrated. River water samples were collected from the Iruma River, upstream of the intake of drinking water treatment plants in Tokyo, during dry weather and wet weather, and 13 PFSs, dissolved organic carbon (DOC), total nitrogen (TN), and B were analyzed. Perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUA), and perfluorododecanoate (PFDoDA) were detected on all sampling dates. The concentrations and fluxes of perfluorocarboxylates (PFCAs, e.g. PFOA and PFNA) were higher during wet weather, but those of perfluoroalkyl sulfonates (PFASs, e.g. PFHxS and PFOS) were not. The wet/dry ratios of PFSs/B (ratios of PFSs/B during wet weather to those during dry weather) agreed well with those of PFS fluxes (ratios of PFS fluxes during wet weather to those during dry weather), indicating that PFSs/B is useful for evaluating the contribution from non-point sources to PFSs in rivers. The wet/dry ratios of PFOA and PFNA were higher than those of other PFSs, DOC, and TN, showing that non-point sources contributed greatly to PFOA and PFNA in the water. This is the first study to use B as a wastewater tracer to estimate the contribution of non-point sources to PFSs in a river.     

Simultaneous removal of phenanthrene and cadmium from contaminated soils by saponin, a plant-derived biosurfactant

Batch experiments were conducted to evaluate the performance of saponin, a plant-derived biosurfactant, for simultaneously removing phenanthrene and cadmium from the combined contaminated soils. Results showed that phenanthrene was desorbed from the contaminated soils by saponin with the partition of phenanthrene into surfactant micelle, meanwhile cadmium was effectively removed from the contaminated soils by the complexation of cadmium with the external carboxyl groups of saponin micelle. The efficiencies of saponin for the removal of phenanthrene and cadmium from the contaminated soils were greater than that of Triton X100 and citric acid, respectively. At concentration of 3750 mg/L, saponin has a removal rate of 87.7% and 76.2% of cadmium and phenanthrene, respectively, from the combined contaminated soil. The removals of cadmium and phenanthrene from the soils were not obviously constrained each other. Thus, saponin has the potential for the removal of heavy metal and PAHs from the combined contaminated soils.     

Quantifying nitrate sources in a large reservoir for drinking water by using stable isotopes and a Bayesian isotope mixing model

Drinking water reservoirs are threatened globally by anthropogenic nitrogen pollution. Hydrochemistry and isotopes were analyzed to identify spatial and temporal varieties of main nitrate sources in a large drinking water reservoir in East China. The results showed that NO₃^? was the main nitrogen form in both the dry and wet seasons, but dissolved organic nitrogen (DON) was increased in the wet season. The δ¹⁵N-NO₃^? values (+?1.3‰ to +?11.8‰) and δ¹⁸O-NO₃^? values (+?2.5‰ to +?13.5‰), combined with principal component analysis (PCA), indicated that chemical fertilizer was the main nitrate source during the dry season, while chemical fertilizer, soil N, and sewage/manure were the main nitrate sources during the wet season in the Qiandao Lake area. And, the nitrate isotopes showed the significant nitrification and assimilation in the Qiandao Lake area. A Bayesian isotopic mixing model (Stable Isotope Analysis in R) was applied to the spatial and seasonal trends in the proportional contribution of four NO₃^? sources (chemical fertilizer (CF), soil nitrogen (SN), sewage and manure (SM), and atmospheric deposition (AD)) in the Qiandao Lake area. It was revealed that CF was the most important nitrate source in the dry season, accounting for 53.4% with 19.2% of SM and 18.9% of SN, while the contribution of SN increased in the wet season, accounting for 31.6%, followed by CF (30.8%) and then SM (24.2%). The main nitrate sources in the urban area, rural area, and central lake area were CF and SN, accounting for 66.1% in the urban area, 71.7% in the rural area, and 68.2% in the central lake area. Measures should be made to improve chemical fertilizer use efficiency and to reduce nitrogen loss in the Qiandao Lake area.

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Arsenic hyperaccumulation by Pteris vittata from arsenic contaminated soils and the effect of liming and phosphate fertilisation

Pot experiments were carried out to investigate the potential of phytoremediation with the arsenic hyperaccumulator Pteris vittata in a range of soils contaminated with As and other heavy metals, and the influence of phosphate and lime additions on As hyperaccumulation by P. vittata. The fern was grown in 5 soils collected from Cornwall (England) containing 67-4550 mg As kg(-1) and different levels of metals. All soils showed a similar distribution pattern of As in different fractions in a sequential extraction, with more than 60% of the total As being associated with the fraction thought to represent amorphous and poorly-crystalline hydrous oxides of Fe and Al. The concentration of As in the fronds ranged from 84 to 3600 mg kg(-1), with 0.9-3.1% of the total soil As being taken up by P. vittata. In one soil which contained 5500 mg Cu kg(-1) and 1242 mg Zn kg(-1), P. vittata suffered from phytotoxicity and accumulated little As (0.002% of total). In a separate experiment, neither phosphate addition (50mg P kg(-1) soil) nor liming (4.6 g CaCO3 kg(-1) soil) was found to affect the As concentration in the fronds of P. vittata, even though phosphate addition increased the As concentration in the soil pore water. Between 4 and 7% of the total soil As was taken up by P. vittata in 4 cuttings in this experiment. The results indicate that P. vittata can hyperaccumulate As from naturally contaminated soils, but may be suitable for phytoremediation only in the moderately contaminated soils.     

Assessment of the natural attenuation of chlorinated ethenes in an anaerobic contaminated aquifer in the Bitterfeld/Wolfen area using stable isotope techniques, microcosm studies and molecular biomarkers

The in situ degradation of chlorinated ethenes was assessed in an anaerobic aquifer using stable isotope fractionation approaches, microcosm studies and taxon specific detection of specific dehalogenating groups of bacteria. The aquifer in the Bitterfeld/Wolfen region in Germany contained all chlorinated ethenes, benzene and toluene as contaminants. The concentrations and isotope composition of the chlorinated ethenes indicated biodegradation of the contaminants. Microcosm studies confirmed the presence of in situ microbial communities capable of the complete dechlorination of tetrachloroethene. Taxon specific investigation of the microbial communities indicated the presence of various potential dechlorinating organisms including Dehalococcoides, Desulfuromonas, Desulfitobacterium and Dehalobacter. The integrated approach, using metabolite spectra, molecular marker analysis and isotope studies, provided several lines of evidence for natural attenuation of the chlorinated ethenes.     

Improving the knowledge of pesticide and nitrate transfer processes using age-dating tools (CFC, SF6, H) in a volcanic island (Martinique, French West Indies)

Numerous successful examples of CFC and SF₆ groundwater dating applications were recently published. However the proposed CFC/SF₆ method needs various hydrodynamic parameters that are not always available. In order to predict groundwater-quality trends in areas where the hydrogeological context is poorly known, a dating method using tritium, CFC and SF₆ was successfully implemented in Martinique. Hydrogeological understanding is limited in this volcanic island where groundwater contamination by pesticides and nitrate has been recently proven in various areas. A negative correlation was observed between nitrate concentrations and groundwater ages while pesticide contamination showed a more complex schema. Consequently the presence of old groundwater clearly explained the absence or low pesticide and nitrate concentrations in some areas. However a possible degradation of the water quality is to be feared in the future. In view of the relatively long transfer times and the complexity of the remobilization processes of solutes, the expected effects of any modifications in the use of fertilizers, or of changes in pesticide-use legislation, would take a long time to become apparent.     

Synthesis, isolation and purification of C10-C13 polychloro-n-alkanes for use as standards in environmental analysis

Short chain (C10-C13) polychloro-n-alkanes (sPCAs) mixtures were synthesized by refluxing pure n-alkane (> 99%) with sulfuryl chloride (SO2Cl2) in the presence of UV-light (550 W). The free radical initiated reactions produced analogs containing approximately 4-9 chlorine atoms on each carbon chain. Purification of reaction products was achieved by adsorption chromatography on Florisil. The products were characterized by high-resolution gas chromatography/mass spectrometry (HRGC/MS) operated in the electron capture negative ionization (ECNI) and in electron ionization (EI) modes. Individual standards can now be combined to create standards whose profiles resemble that of environmental samples. Quantification of a known amount of the newly synthesized sPCAs mixture, using an industrial formulation as an external standard, resulted in an overestimation (approximately 28%) in its true value.     

Seasonal variations of cadmium and zinc in Arrhenatherum elatius, a perennial grass species from highly contaminated soils

There is interest in studying bioaccumulation in plants because they form the base of the food chain as well as their potential use in phytoextraction. From this viewpoint, our study deals with the seasonal variation, from January to July, of Cd and Zn bioaccumulation in three metallicolous populations of Arrhenatherum elatius, a perennial grass with a high biomass production. In heavily polluted soils, while Zn bioaccumulation is weak, A. elatius accumulates more Cd than reported gramineous plants, with concentration of up to 100 microg g(-1). Our results also showed seasonal variations of bioaccumulation, underlying the necessity for in situ studies to specify the date of sampling and also the phenology of the collected plant sample. In our experimental conditions, accumulation is lower in June, leading us to the hypothesis of restriction in heavy metals translocation from roots to aerial parts during seed production.