Metal pollution trajectories and mixture risk assessed by combining dated cores and subsurface sediments along a major European river (Rhône River, France).

In European rivers, research and monitoring programmes have targeted metal pollution from bed and floodplain sediments since the mid-20th century by using various sampling and analysis protocols. We propose to characterise metal contamination trajectories since the 1960s based on the joint use of a large amount of data from dated cores and subsurface sediments along the Rhône River (ca. 512 km, Switzerland-France). For the reconstruction of spatio-temporal trends, enrichment factors (EF) and geo-accumulation (Igeo) approaches were compared. The latter index was preferred due to the recurrent lack of grain-size and lithogenic elements in the dataset. Local geochemical backgrounds were established near (1) the Subalps and (2) the Massif Central to consider the geological variability of the watershed. A high contamination (Igeo = 3-5) was found for Cd, Cu and Zn from upstream to downstream over the period 1980-2000. This pattern is consistent with long-term emissions from major cities and the nearby industrial areas of the Upper Rhône (Geneva, Arve Valley), and Middle Rhône (Lyon, Chemical Corridor, Gier Valley). Hotspots due to Cu and Zn leaching from vineyards, mining, and highway runoff were also identified, while Pb was especially driven by industrial sources. The recovery time of pollution in sediment varied according to the metals and was shorter upstream of Lyon (15-20 years) than downstream (30-40 years). More widely, it was faster on the Rhône than along other European rivers (e.g. Seine and Rhine). Finally, the ecotoxicological mixture risk of metal with Persistent Organic Pollutants (POPs) for sediment-dwelling organisms showed a medium "cocktail risk" dominated by metals upstream of Lyon, although it is enhanced due to POPs downstream, and southward to the delta and the Mediterranean Sea. Overall, this study demonstrates the heterogeneity of the contamination trends along large fluvial corridors such as the Rhône River.

A Bayesian network approach for the identification of relationships between drivers of chlordecone bioaccumulation in plants.

Plants were sampled from four different types of chlordecone-contaminated land in Guadeloupe (West Indies). The objective was to investigate the importance of biological and agri-environmental parameters in the ability of plants to bioaccumulate chlordecone. Among the plant traits studied, only the growth habit significantly affected chlordecone transfer, since prostrate plants concentrated more chlordecone than erect plants. In addition, intensification of land use has led to a significant increase in the amount of chlordecone absorbed by plants. The use of Bayesian networks uncovers some hypothesis and identifies paths for reflection and possible studies to identify and quantify relationships that explain our data. Graphical abstract.

Past and recent state of sediment contamination by persistent organic pollutants (POPs) in the Rhône River: Overview of ecotoxicological implications.

Twenty-one sediment samples were taken from five dated sediment cores collected along the Rhône River from 2008 to 2011. A total of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 7 polychlorinated biphenyls (PCBs), 8 polybrominated diphenyl ethers (PBDEs), 3 polybrominated biphenyls (PBBs), 3 hexabromocyclododecanes (HBCD) and 31 organochlorine pesticides (OCPs) were investigated to provide information on deposition dynamics in time and space, but also regarding the ecotoxicological risks associated with these contaminants. Median concentrations of total PBDEs are nine times lower than the levels of total PCBs along the entire studied stretch of the Rhône River. The results show that total PBDEs concentrations range from 0.06 to 239 µg·kg-1 DW with a median value of 3.81 µg·kg-1 DW and a maximum concentration measured in the years 2000s. These maximum concentrations are identical to those measured for total PCBs at the end of the 1990s, but show a different pattern of distribution. Abnormal dichlorodiphenyltrichloroethane (DDT) levels were also detected in the downstream section of the river, with a peak concentration of 147.5 µg·kg-1 DW measured at the GEC site from 2005 onwards. Analyses of the enantiomeric fractions reveal a fresh input resulting from a technical formulation. Sediments from the core sampled at the most downstream site (GEC) are found to be highly toxic to organisms living nearby, particularly because of the total PCDD/Fs, DDE and DDT levels. In addition, based on available sediment quality guidelines, there may be a potential bioaccumulation risk for humans not only for these three compounds of concern but also for total PCBs and 7 out of the 8 analysed PBDEs.

Growth parameters influencing uptake of chlordecone by Miscanthus species.

Because of its high persistence in soils, t1/2=30years, chlordecone (CLD) was classified as a persistent organic pollutant (POP) by the Stockholm Convention in 2009.The distribution of CLD over time has been heterogeneous, ranging from banana plantations to watersheds, and contaminating all environmental compartments. The aims of this study were to (i) evaluate the potential of Miscanthus species to extract chlordecone from contaminated soils, (ii) identify the growth parameters that influence the transfer of CLD from the soil to aboveground plant parts. CLD uptake was investigated in two species of Miscanthus, C4 plants adapted to tropical climates. M. sinensis and M.×giganteus were transplanted in a soil spiked with [14C]CLD at environmental concentrations (1mgkg-1) under controlled conditions. Root-shoot transfer of CLD was compared in the two species after two growing periods (2 then 6months) after transplantation. CLD was found in all plant organs, roots, rhizomes, stems, leaves, and even flower spikes. The highest concentration of CLD was in the roots, 5398±1636 (M.×giganteus) and 14842±3210ngg-1 DW (M. sinensis), whereas the concentration in shoots was lower, 152±28 (M.×giganteus) and 266±70ngg-1 DW (M. sinensis) in soil contaminated at 1mgkg-1. CLD translocation led to an acropetal gradient from the bottom to the top of the plants. CLD concentrations were also monitored over two complete growing periods (10months) in M. sinensis grown in 8.05mgkg-1 CLD contaminated soils. Concentrations decreased in M. sinensis shoots after the second growth period due to the increase in organic matters in the vicinity of the roots. Results showed that, owing to their respective biomass production, the two species were equally efficient at phytoextraction of CLD.

Chlordecone Transfer and Distribution in Maize Shoots.

Chlordecone (CLD) is a persistent organic pollutant (POP) that was mainly used as an insecticide against banana weevils in the French West Indies (1972-1993). Transfer of CLD via the food chain is now the major mechanism for exposure of the population to CLD. The uptake and the transfer of CLD were investigated in shoots of maize, a C4 model plant growing under tropical climates, to estimate the exposure of livestock via feed. Maize plants were grown on soils contaminated with [(14)C]CLD under controlled conditions. The greatest part of the radioactivity was associated with roots, nearly 95%, but CLD was detected in whole shoots, concentrations in old leaves being higher than those in young ones. CLD was thus transferred from the base toward the plant top, forming an acropetal gradient of contaminant. In contrast, results evidenced the existence of a basipetal gradient of CLD concentration within leaves whose extremities accumulated larger amounts of CLD because of evapotranspiration localization. Extractable residues accounted for two-thirds of total residues both in roots and in shoots. This study highlighted the fact that the distribution of CLD contamination within grasses resulted from a conjunction between the age and evapotranspiration rate of tissues. CLD accumulation in fodder may be the main route of exposure for livestock.