RESUMEN
Among the numerous organochlorines (OCs) applied in the French West Indies (FWI), chlordecone (hydrated form C10Cl10O2H2; CLD) still causes major environmental pollution nowadays. A recent report revealed the unexpected presence in FWI environment of transformation products (TPs) of CLD not routinely monitored due to a lack of commercial standards. Here, we present a method for surface waters and groundwaters to analyze CLD, its main TPs (hydroCLDs, chlordecol (CLDOH), 10-monohydroCLDOH and polychloroindenes) and other OCs. We developed an SPME-GC-SIM/MS method with a PDMS-DVB fiber. Since CLDOH-d commonly used as internal standard (IS) proved unsuitable, we synthesized several IS candidates, and finally identified 10-monohydro-5-methyl-chlordecol as a satisfactory IS for CLDOH and 10-monohydroCLDOH avoiding the use of 13C-labelled analogue. LODs for CLD and its TPs varied from 0.3 to 10 ng/L, equal to or below LODs of the two laboratories, BRGM (the French geological survey) and LDA26 (one of the French Departmental Analytical Laboratories), requested in FWI pollution monitoring that used liquid-liquid extractions and advanced facilities (LLE-GC-MS/MS and LLE-LC-MS/MS methods, respectively). Then, we extended the multi-residue method to 30 OCs (CLD and its TPs, mirex, ß-HCH, lindane, dieldrin, aldrin, HCB, hexachlorobutadiene, TCE, PCE) and applied it to 30 surface and ground waters from FWI. While CLD, 8- and 10-monohydroCLD, CLDOH, 10-monohydroCLDOH, dieldrin, and ß-HCH were detected and quantified, pentachloroindene, another CLD TP, was sporadically found in trace levels. A comparison with BRGM and LDA26 confirmed the interest of the SPME method. Results suggested an underestimation of CLDOH and an overestimation of high CLD concentrations with one of the currently used routine protocol. In light of these findings, previous temporal monitoring of environmental waters in FWI were re-examined and revealed some atypical values, which may indeed be due to analytical bias. These discrepancies call for intensified efforts to reliably quantify CLD and its TPs.
RESUMEN
The infiltration of organic-rich surface waters towards groundwaters, is known to play a significant role in carbonate weathering and in contributing to the atmospheric continental carbon sink. This paper investigated biogeochemical interactions in karst critical zones, with strong surface water /groundwater interactions, and in particular the role of planktonic microorganisms and riverine bivalves through the analysis of particulate organic matter (OM) oxidation on carbonate weathering. In the large Val d'Orléans fluviokarst aquifer (France), a 20-year monthly dataset of Nitrates, Dissolved Oxygen (DO), dissolved inorganic and organic Carbon (DIC and DOC) fluxes was gathered. The surface water-groundwater comparison of geochemical trends showed that planktonic microorganisms had drastically decreased in surface waters, related to the proliferation of Corbicula bivalves spreading and a decrease in nutrients. This decrease in planktonic microorganisms was followed by a DO increase and an DIC decrease at the karst resurgence. The degradation of planktonic microorganisms consumes DO and produces NO3, dissolved inorganic carbon (DIC) and a proton that in turn, dissolves calcite and produces DIC. Without the input from planktonic microorganisms, the fluviokarst has lost 29 % of this nitrification and 12 % of the carbonate dissolution capacities. Thus, the oxidation of particulate organic matter of planktonic microorganisms, which is part of heterotrophic respiration, appears to be a significant source of the inorganic carbon flux in riverine ecosystems. This shows how weathering can remain active under waters saturated versus calcite and suggests that the oxidation of organic matter can be a more appropriate mechanism than autotrophic respiration to explain the relationship between global warming and DIC flux change in rivers. Through the consumption of plankton, the animal life in rivers thus influences the inorganic carbon in groundwaters, creating a negative feedback in the carbon cycle.
Asunto(s)
Bivalvos , Monitoreo del Ambiente , Animales , Carbonato de Calcio/análisis , Carbono/análisis , Carbonatos/análisis , Ecosistema , Plancton , Ríos/química , Agua/análisisRESUMEN
Groundwater pollution threatens human and ecosystem health in many regions around the globe. Fast flow to the groundwater through focused recharge is known to transmit short-lived pollutants into carbonate aquifers, endangering the quality of groundwaters where one quarter of the world's population lives. However, the large-scale impact of such focused recharge on groundwater quality remains poorly understood. Here, we apply a continental-scale model to quantify the risk of groundwater contamination by degradable pollutants through focused recharge in the carbonate rock regions of Europe, North Africa, and the Middle East. We show that focused recharge is the primary reason for widespread rapid transport of contaminants to the groundwater. Where it occurs, the concentration of pollutants in groundwater recharge that have not yet degraded increases from <1% to around 20 to 50% of their concentrations during infiltration. Assuming realistic application rates, our simulations show that degradable pollutants like glyphosate can exceed their permissible concentrations by 3 to 19 times when reaching the groundwater. Our results are supported by independent estimates of young water fractions at 78 carbonate rock springs over Europe and a dataset of observed glyphosate concentrations in the groundwater. They imply that in times of continuing and increasing industrial and agricultural productivity, focused recharge may result in an underestimated and widespread risk to usable groundwater volumes.
Asunto(s)
Monitoreo del Ambiente , Glicina/análogos & derivados , Agua Subterránea/química , Modelos Estadísticos , Contaminantes Químicos del Agua/aislamiento & purificación , África del Norte , Simulación por Computador , Europa (Continente) , Glicina/aislamiento & purificación , Humanos , Medio Oriente , Movimientos del Agua , Abastecimiento de Agua , GlifosatoRESUMEN
An amendment to this paper has been published and can be accessed via a link at the top of the paper.
RESUMEN
Karst aquifers provide drinking water for 10% of the world's population, support agriculture, groundwater-dependent activities, and ecosystems. These aquifers are characterised by complex groundwater-flow systems, hence, they are extremely vulnerable and protecting them requires an in-depth understanding of the systems. Poor data accessibility has limited advances in karst research and realistic representation of karst processes in large-scale hydrological studies. In this study, we present World Karst Spring hydrograph (WoKaS) database, a community-wide effort to improve data accessibility. WoKaS is the first global karst springs discharge database with over 400 spring observations collected from articles, hydrological databases and researchers. The dataset's coverage compares to the global distribution of carbonate rocks with some bias towards the latitudes of more developed countries. WoKaS database will ensure easy access to a large-sample of good quality datasets suitable for a wide range of applications: comparative studies, trend analysis and model evaluation. This database will largely contribute to research advancement in karst hydrology, supports karst groundwater management, and promotes international and interdisciplinary collaborations.
RESUMEN
Chlordecone, applied on soils until 1993 to control banana weevil, has polluted water resources in the French West Indies for more than 40 years. At the watershed scale, chlordecone applications were not homogenous, generating a spatial heterogeneity of the pollution. The roles of climate, hydrology, soil, agronomy, and geology on watershed functioning generate a temporal heterogeneity of the pollution. This study questions the interactions between practices and the environment that induce such variability. We analyzed hydrological and water pollution datasets from a 2-year monitoring program on the Galion watershed in Martinique (French West Indies). We conjointly analyzed (i) weekly chlordecone (CLD) concentration monitored on 3 river sampling sites, (ii) aquifer piezometric dynamics and pollutions, and (iii) agricultural practices on polluted soils. Our results showed that chlordecone pollution in surface waters are characterized by annual trends and infra-annual variations. Aquifers showed CLD concentration 10 times higher than surface water, with CLD concentration peaks during recharge events. We showed strong interactions between rainfall events and practices on CLD pollution requiring a systemic management approach, in particular during post-cyclonic periods. Small sub-watershed with high CLD pollution appeared to be a substantial contributor to CLD mass transfers to the marine environment via rivers and should therefore receive priority management. We suggest increasing stable organic matter return to soil as well as external input of organic matter to reduce CLD transfers to water. We identified hydrological conditions-notably drying periods-and tillage as the most influential factors on CLD leaching. In particular, tillage acts on 3 processes that increases CLD leaching: organic matter degradation, modification of water paths in soil, and allophane clay degradation.
Asunto(s)
Clordecona , Insecticidas , Contaminantes del Suelo , Clordecona/análisis , Insecticidas/análisis , Martinica , Suelo , Contaminantes del Suelo/análisis , Contaminación del Agua , Indias OccidentalesRESUMEN
The aim of this article is to determine how the nematicide cadusafos [S,S-di-sec-butyl O-ethyl phosphorodithioate] contaminates water and soils at two scales, subcatchment and catchment. The study site was a small banana (Musa spp.)-growing catchment on the tropical volcanic island of Guadeloupe in the Caribbean. Two application campaigns were conducted, one in 2003 on 40% of the catchment and one in 2006 on 12%. The study involved monitoring for 100 d the surface water and groundwater flows and the cadusafos concentrations in the soil and in surface and groundwaters in a 2400 m(2) subcatchment and a 17.8 ha catchment. The results show that at the subcatchment scale the high retention in the A horizon of the soil limits the transport of cadusafos by runoff, whereas the lower retention of the molecule in the B horizon favors percolation toward the shallow groundwater. Comparing the losses of cadusafos at the subcatchment and at the catchment scales revealed that the nematicide re-infiltrated in the hydrographic network. Two successive phases of stream water contamination were observed, corresponding to two distinct contamination mechanisms: an event-dominated contamination phase (of <30 d) when transport was linked to overland flow during precipitation shortly after application, and a stabilized contamination phase when transport originated mainly from the drainage of the shallow aquifer. Lastly, comparing the losses of the two phases during 2003 and 2006 showed that shallow groundwater, which is promoted in such permeable soils under abundant tropical rainfalls, seems to be the main contributor to stream contamination.