Monitoring of explosive residues in lake-bottom water using Polar Organic Chemical Integrative Sampler (POCIS) and chemcatcher: determination of transfer kinetics through Polyethersulfone (PES) membrane is crucial.

Between 1920 and 1967, approximatively 8200 tons of ammunition waste were dumped into some Swiss lakes. This study is part of the extensive historical and technical investigations performed since 1995 by Swiss authorities to provide a risk assessment. It aims to assess whether explosive monitoring by passive sampling is feasible in lake-bottom waters. Polar organic chemical integrative sampler (POCIS) and Chemcatcher were first calibrated in a channel system supplied with continuously refreshed lake water spiked with two nitroamines (HMX and RDX), one nitrate ester (PETN), and six nitroaromatics (including TNT). Exposure parameters were kept as close as possible to the ones expected at the bottom of two affected lakes. Sixteen POCIS and Chemcatcher were simultaneously deployed in the channel system and removed in duplicates at 8 different intervals over 21 days. Sorbents and polyethersulfone (PES) membranes were separately extracted and analyzed by UPLC-MS/MS. When possible, a three-compartment model was used to describe the uptake of compounds from water, over the PES membrane into the sorbent. Uptake of target compounds by sorbents was shown not to approach equilibrium during 21 days. However, nitroaromatics strongly accumulated in PES, thus delaying the transfer of these compounds to sorbents (lag-phase up to 9 days). Whereas sampling rate (RS) of nitroamines were in the range of 0.06-0.14 L day-1, RS of nitroaromatics were up to 10 times lower. As nitroaromatic accumulation in PES was integrative over 21 days, PES was used as receiving phase for these compounds. The samplers were then deployed at lake bottoms. To ensure that exposure conditions were similar between calibration and field experiments, low-density polyethylene strips spiked with performance reference compounds were co-deployed in both experiments and dissipation data were compared. Integrative concentrations of explosives measured in the lakes confirmed results obtained by previous studies based on grab sampling.

Effect of µM Fe addition, mild heat and solar UV on sulfate radical-mediated inactivation of bacteria, viruses, and micropollutant degradation in water.

In this work, solar disinfection (SODIS) was enhanced by moderate addition of Fe and sodium peroxydisulfate (PDS), under solar light. A systematic assessment of the activating factors was performed, firstly isolated, then in pairs and concluded in the combined Fe/heat/solar UV-PDS activation process. Solar light was the most effective (single) activator, and its combination with Fe and heat (double activation) yielded high level of synergies (up to S = 2.13). The triple activation was able to reduce the bacterial load up to 6-log in less than 1 h, similarly to the photo-Fenton process done in comparison (SODIS alone: >5 h). Fe-oxides were suitable activators of PDS under the same conditions while the presence of organic matter enhanced bacterial inactivation by the triple activated PDS process. The degradation of a (selected) mixture of micropollutants (i.e. drugs, pesticides) was also achieved in similar order of magnitude, and faster than the photo-Fenton process. Finally, the removal of a viral pathogen indicator (MS2 bacteriophage) was attained at minute-range residence times. The aforementioned facts indicate the suitability of the mild, combined process, as a potential SODIS enhancement, producing safe drinking water for sunny and especially for developing countries.

Analysis of antibiotic multi-resistant bacteria and resistance genes in the effluent of an intensive shrimp farm (Long An, Vietnam).

In Vietnam, intensive shrimp farms heavily rely on a wide variety of antibiotics (ABs) to treat animals or prevent disease outbreak. Potential for the emergence of multi-resistant bacteria is high, with the concomitant contamination of adjacent natural aquatic habitats used for irrigation and drinking water, impairing in turn human health system. In the present study, quantification of AB multi-resistant bacteria was carried out in water and sediment samples from effluent channels connecting a shrimp farming area to the Vam Co River (Long An Province, Vietnam). Bacterial strains, e.g. Klebsiella pneumoniae and Aeromonas hydrophila, showing multi-resistance traits were isolated. Molecular biology analysis showed that these strains possessed from four to seven different AB resistance genes (ARGs) (e.g. sul1, sul2, qnrA, ermB, tetA, aac(6)lb, dfrA1, dfr12, dfrA5), conferring multidrug resistance capacity. Sequencing of plasmids present within these multi-resistant strains led to the identification of a total of forty-one resistance genes, targeting nine AB groups. qPCR analysis on the sul2 gene revealed the presence of high copy numbers in the effluent channel connecting to the Vam Co River. The results of the present study clearly indicated that multi-resistant bacteria present in intensive shrimp cultures may disseminate in the natural environment. This study offered a first insight in the impact of plasmid-born ARGs and the related pathogenic bacteria that could emerged due to inappropriate antibiotic utilization in South Vietnam.

Microbial communities associated with uranium in-situ recovery mining process are related to acid mine drainage assemblages.

A large fraction (47%) of the world's uranium is mined by a technique called "In Situ Recovery" (ISR). This mining technique involves the injection of a leaching fluid (acidic or alkaline) into a uranium-bearing aquifer and the pumping of the resulting solution through cation exchange columns for the recovery of dissolved uranium. The present study reports the in-depth alterations brought to autochthonous microbial communities during acidic ISR activities. Water samples were collected from a uranium roll-front deposit that is part of an ISR mine in operation (Tortkuduk, Kazakhstan). Water samples were obtained at a depth of ca 500 m below ground level from several zones of the Uyuk aquifer following the natural redox zonation inherited from the roll front deposit, including the native mineralized orebody and both upstream and downstream adjacent locations. Samples were collected equally from both the entrance and the exit of the uranium concentration plant. Next-generation sequencing data showed that the redox gradient shaped the community structures, within the anaerobic, reduced, and oligotrophic habitats of the native aquifer zones. Acid injection induced drastic changes in the structures of these communities, with a large decrease in both cell numbers and diversity. Communities present in the acidified (pH values < 2) mining areas exhibited similarities to those present in acid mine drainage, with the dominance of Sulfobacillus sp., Leptospirillum sp. and Acidithiobacillus sp., as well as the archaean Ferroplasma sp. Communities located up- and downstream of the mineralized zone under ISR and affected by acidic fluids were blended with additional facultative anaerobic and acidophilic microorganisms. These mixed biomes may be suitable communities for the natural attenuation of ISR mining-affected subsurface through the reduction of metals and sulfate. Assessing the effect of acidification on the microbial community is critical to evaluating the potential for natural attenuation or active bioremediation strategies.

Assessment of human exposure to pesticides by hair analysis: The case of vegetable-producing areas in Burkina Faso.

The present work assesses human exposure to pesticides in vegetable-producing areas in Burkina Faso, using hair as an indicator. The study design includes a comparison between operators who are occupationally exposed while working in the fields and a reference population (i.e. not occupationally exposed) to evaluate both occupational and indirect exposures. Hair samples from volunteers (n=101) were positive for 17 pesticides (38 analyzed). Acetamiprid, desethylatrazine, carbofuran, and deltamethrin were detected for the first time in field samples. With a maximum of 9 residues per sample, pesticide exposure was ubiquitous in both populations. Contamination by acetamiprid, cypermethrin, and lambda-cyhalothrin (used in vegetable production) prevailed in operator samples. For other pesticides, such as imidacloprid and deltamethrin, no significant difference was found. This indicates a potentially large environmental exposure (dietary intake or atmospheric contamination) or the prevalence of other contamination sources. The present findings are concerning, as detected levels are globally higher than those previously reported, and indicate exposure to endocrine disrupting chemicals and probable carcinogens. Hair was found to be a suitable matrix for biomonitoring human exposure to pesticides and assessing dominant factors (i.e. sex, age, and protective equipment) in subgroups, as well as identifying geographical contamination patterns.

Assessment of water resource contamination by pesticides in vegetable-producing areas in Burkina Faso.

This study proposes a comprehensive approach to investigate water resource contamination by pesticides under the specific climatic and hydrological conditions of the Sudano-Sahelian climate. Samples were collected from traditional wells, boreholes, and a lake in Burkina Faso. A multiresidue analysis was developed for 25 pesticides identified during field surveys. Polar organic chemical integrative samplers (POCIS) were used to confirm trends observed with grab samples. Uptake kinetics of POCIS were assessed by in situ calibration. The proposed use of nonlinear least squares regression proved to be a robust approach for estimating time-weighted average concentration in cases of nonlinear uptake. High sampling rates for triazines in a quasi-stagnant lake were attributed to warm water temperatures (30.8 ± 1.3 °C). The combination of sampling techniques during a 3-year monitoring period allowed for identifying potential interactions between resources, seasonal patterns, and origins of contaminants. Atrazine, azadirachtin, carbofuran, chlorpyrifos, cypermethrin, dieldrin, imidacloprid, and profenofos exceeded 0.1 µg L-1, indicating a potential risk for the consumers. Ecological risk assessment was performed using the Pesticide Tool Index for fish, cladocerans, and benthic invertebrates. Peak concentrations of cypermethrin and chlorpyrifos were systematically associated with hazard to the studied taxa.

Development of a modified QuEChERS method for multi-class pesticide analysis in human hair by GC-MS and UPLC-MS/MS.

The present study assessed the suitability of using QuEChERS procedure for the simultaneous determination and quantification of 37 multi-class pesticides in human hair. Matrix co-eluted material had a large influence on instrumental response sensitivity. Purification was needed although dSPE cleanup sorbent selection critically influenced analyte recovery. Optimized protocol using Z-Sep+ sorbent successfully achieved recovery of 28 pesticides with high sensitivity, precision, and accuracy. Limits of detection ranged from 0.2 to 86.6 pg mg-1 and from 0.5 to 6.3 pg mg-1 for GC and UPLC amenable substances respectively. Pyrethroid pesticides were the most influenced by matrix effects which explained the higher limits of quantification retained for these substances. On the contrary, high sensitivity was achieved for UPLC amenable substances (LOD < 1 pg mg-1 for atrazine, deisopropylatrazine, desethylatrazine, and imidacloprid). Suitability for monitoring pesticide exposure was assessed by application of the proposed protocol to samples collected on the field. Hairs of the volunteers were found positive to 8 pesticides with every sample containing at least one residue. Among these pesticides, only 3 were reported as used in local vegetable production, which suggested other sources of exposure. The developed method offers a sensitive, robust, and accessible tool for biomonitoring of human exposure.

Dietary risk assessment of pesticides from vegetables and drinking water in gardening areas in Burkina Faso.

Vegetables and water samples have been collected around the lake of Loumbila in Burkina Faso. Pesticides residues in food commodities were analyzed using a modified QuEChERS extraction method prior analysis on GC-MS and UPLC-MS/MS of 31 pesticides. Maximum Residue Limits (MRLs) were exceeded in 36% of the samples for seven pesticides: acetamiprid, carbofuran, chlorpyrifos, lambda-cyhalothrin, dieldrin, imidacloprid and profenofos. Exceedance of MRLs suggests a risk for the consumers and limits the opportunities of exportation. In order to define estimated daily intake, dietary surveys were conducted on 126 gardeners using a 24hours recall method. Single pesticide and cumulative exposure risks were assessed for children and adults. Risk was identified for: chlorpyrifos and lambda-cyhalothrin in acute and chronic exposure scenarios. Hazardous chronic exposure to the endocrine disruptor and probable carcinogen dieldrin was also detected. In the studied population, cumulative dietary exposure presented a risk (acute and chronic) for children and adults in respectively >17% and 4% of the cases when considering the worst case scenarios. Processing factor largely influenced the risk of occurrence suggesting that simple washing of vegetables with water considerably reduced the risk of hazardous exposure.

Accumulation of toxic metals and organic micro-pollutants in sediments from tropical urban rivers, Kinshasa, Democratic Republic of the Congo.

The increasing contamination of fresh water resource by toxic metals and Persistence Organic Pollutants (POPs) is a major environmental concern globally. In the present investigation, surface sediments collected from three main rivers named, Makelele, Kalamu and Nsanga, draining through the city of Kinshasa, Democratic Republic of the Congo, were characterized for grain size, organic matter, toxic metals, POPs (including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs)), and polycyclic aromatic hydrocarbons (PAHs). Furthermore, enrichment factor (EF) and geoaccumulation index (Igeo) were performed to determine metal source and pollution status. The results highlighted high concentration of toxic metals in all sediment samples, reaching the values (mg kg-1) of 325 (Cu), 549 (Zn), 165 (Pb) and 1.5 (Cd). High values of PCBs and OCPs were detected in sediment samples, e.g. in Makelele river, PCB values ranged from 0.9 to 10.9 with total PCBs (∑7 PCBs × 4.3): 169.3 µg kg-1; OCPs from 21.6 to 146.8 with ∑OCPs: 270.6 µg kg-1. The PBDEs concentrations were higher in investigated rivers comparatively with values detected in many rivers from Sub-Saharan Africa. The ΣPAHs value ranged from 22.6 to 1011.9 µg kg-1. River contamination may be explained by local intense domestic activities, urban and agricultural runoff, industrial and hospital wastewaters discharge into the rivers without prior treatment. This research provides not only a first baseline information on the extent of contamination in this tropical ecosystem but also represents useful tools incorporated to evaluate sediment quality in the river receiving systems which can be applied to similar aquatic environments.

Spatial distribution and biological effects of trace metals (Cu, Zn, Pb, Cd) and organic micropollutants (PCBs, PAHs) in mussels Mytilus galloprovincialis along the Algerian west coast.

Native mussels Mytilus galloprovincialis are used as bioindicator organisms to assess the concentration levels and toxic effects of persistent chemicals, polychlorobiphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and heavy metals using biomarker responses, such as catalase (CAT), glutathione s-transferase (GST), and condition indices, for the Algerian coast. The results show that mussels of Oran Harbour are extremely polluted by PCBs and PAHs, i.e., 97.6 and 2892.1µg/kg d.w., respectively. Other sites present low levels of pollution. Furthermore, high concentrations of zinc, lead and cadmium are found in mussels from fishing, agricultural and estuarine sites, respectively, while low concentrations of copper are found in all of the sites studied. CAT activity is negatively correlated with Cd and Cu, and Zn is positively correlated with GST and CAT. Site classification tools reveal the potential toxicity of coastal areas exposed to anthropogenic pressure and a gradient of toxicity along the Algerian west coast.

Micropollutant degradation, bacterial inactivation and regrowth risk in wastewater effluents: Influence of the secondary (pre)treatment on the efficiency of Advanced Oxidation Processes.

In this work, disinfection by 5 Advanced Oxidation Processes was preceded by 3 different secondary treatment systems present in the wastewater treatment plant of Vidy, Lausanne (Switzerland). 5 AOPs after two biological treatment methods (conventional activated sludge and moving bed bioreactor) and a physiochemical process (coagulation-flocculation) were tested in laboratory scale. The dependence among AOPs efficiency and secondary (pre)treatment was estimated by following the bacterial concentration i) before secondary treatment, ii) after the different secondary treatment methods and iii) after the various AOPs. Disinfection and post-treatment bacterial regrowth were the evaluation indicators. The order of efficiency was Moving Bed Bioreactor > Activated Sludge > Coagulation-Flocculation > Primary Treatment. As far as the different AOPs are concerned, the disinfection kinetics were: UVC/H2O2 > UVC and solar photo-Fenton > Fenton or solar light. The contextualization and parallel study of microorganisms with the micropollutants of the effluents revealed that higher exposure times were necessary for complete degradation compared to microorganisms for the UV-based processes and inversed for the Fenton-related ones. Nevertheless, in the Fenton-related systems, the nominal 80% removal of micropollutants deriving from the Swiss legislation, often took place before the elimination of bacterial regrowth risk.

Effect of advanced oxidation processes on the micropollutants and the effluent organic matter contained in municipal wastewater previously treated by three different secondary methods.

In this study, wastewater from the output of three different secondary treatment facilities (Activated Sludge, Moving Bed Bioreactor and Coagulation-Flocculation) present in the municipal wastewater treatment plant of Vidy, Lausanne (Switzerland), was further treated with various oxidation processes (UV, UV/H2O2, solar irradiation, Fenton, solar photo-Fenton), at laboratory scale. For this assessment, 6 organic micropollutants in agreement with the new environmental legislation requirements in Switzerland were selected (Carbamazepine, Clarithromycin, Diclofenac, Metoprolol, Benzotriazole, Mecoprop) and monitored throughout the treatment. Also, the overall removal of the organic load was assessed. After each secondary treatment, the efficiency of the AOPs increased in the following order: Coagulation-Flocculation < Activated Sludge < Moving Bed Bioreactor, in almost all cases. From the different combinations tested, municipal wastewater subjected to biological treatment followed by UV/H2O2 resulted in the highest elimination levels. Wastewater previously treated by physicochemical treatment demonstrated considerably inhibited micropollutant degradation rates. The degradation kinetics were determined, yielding: k (UV) < k (UV/H2O2) and k (Fenton) < k (solar irradiation) < k (photo-Fenton). Finally, the evolution of global pollution parameters (COD & TOC elimination) was followed and the degradation pathways for the effluent organic matter are discussed.

Divergent PCB organohalide-respiring consortia enriched from the efflux channel of a former Delor manufacturer in Eastern Europe.

Polychlorinated biphenyl (PCB) organohalide-respiring communities from the efflux channel of a former Delor manufacturer in Eastern Slovakia were assessed using metagenomic, statistical and cultivation-adapted approaches. Multivariate analysis of environmental factors together with terminal restriction fragment length polymorphisms of the bacterial communities in the primary sediments revealed both temporal and spatial heterogeneity in the distribution of microbial populations, which reflects the dynamic pattern of contamination and altered conditions for biodegradation activity along the channel. Anaerobic microcosms were developed from eight sediments sampled along the channel, where high concentrations of PCBs - from 6.6 to 136mg/kg dry weight, were measured. PCB dehalorespiring activity, congruent with changes in the microbial composition in all microcosms, was detected. After 10 months of cultivation, the divergently evolved consortia achieved up to 35.9 percent reduction of the total PCB concentration. Phylogenetic-analysis of the active Chloroflexi-related organohalide-respiring bacteria by partial sequencing of 16S rRNA genes in cDNA from microcosms with the highest PCB dechlorination activity revealed diverse and unique complexity of the populations. The predominant organohalide respirers were either affiliated with Dehalococcoides sp. and Dehalococcoides-like group (DLG) organisms or were composed of currently unknown distant clades of DLG bacteria. The present study should encourage researchers to explore the full potential of the indigenous PCB dechlorinating populations to develop effective bioremediation approaches that can perform the complete mineralization of PCBs in polluted environments.

An evaluation of surface micro- and mesoplastic pollution in pelagic ecosystems of the Western Mediterranean Sea.

This study examines the distribution, abundance and characteristics of surface micro- and mesoplastic debris in the Western Mediterranean Sea. 41 samples were collected in 2011 (summer) and 2012 (summer). Results, firstly, revealed that micro- (<5 mm) and mesoplastic debris were widely and uniformly distributed in this area with average concentrations of 130,000 parts/km(2) and 5700 parts/km(2), respectively. Importantly, a strong correlation between micro- and mesoplastic concentrations was identified. Secondly, a classification based on the shape and appearance of microplastics indicated the predominant presence of fragments (73%) followed by thin films (14%). Thirdly, the average mass ratio of microplastic to dry organic matter has been measured at 0.5, revealing a significant presence of microplastics in comparison to plankton. Finally, a correction method was applied in order to correct wind mixing effect on microplastics' vertical distribution. This data allows for a comprehensive view, for the first time, of the spatial distribution and nature of plastic debris in the Western Mediterranean Sea.

Trace metals and persistent organic pollutants in sediments from river-reservoir systems in Democratic Republic of Congo (DRC): Spatial distribution and potential ecotoxicological effects.

This paper discusses the occurrence and spatial distribution of metals and persistent organic pollutants (POPs: including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), Polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs) in sediments from a river-reservoir system. Surface sediments were sampled from thirteen sites of the Congo River Basin and Lake Ma Vallée, both situated in the vicinity of the capital city Kinshasa (Congo Democratic Republic). Sediment qualities were evaluated using toxicity test based on exposing Ostracods to the sediment samples. The highest metal concentrations were observed in sediments subjected to anthropogenic influences, urban runoff and domestic and industrial wastewaters, discharge into the Congo River basin. Ostracods exposed to the sediments resulted in 100% mortality rates after 6d of incubation, indicating the ultimate toxicity of these sediments as well as potential environmental risks. The POPs and PAHs levels in all sediment samples were low, with maximum concentration found in the sediments (area of pool Malebo): OCP value ranged from 0.02 to 2.50 with ∑OCPs: 3.3µgkg(-1); PCB ranged from 0.07 to 0.99 with Total PCBs (∑7×4.3): 15.31µgkg(-1); PAH value ranged from 0.12 to 9.39 with ∑PAHs: 63.89µgkg(-1). Our results indicate that the deterioration of urban river-reservoir water quality result mainly from urban stormwater runoff, untreated industrial effluents which discharge into the river-reservoirs, human activities and uncontrolled urbanization. This study represents useful tools incorporated to evaluate sediment quality in river-reservoir systems which can be applied to similar aquatic environments.

The Use of Passive Samplers to Reveal Industrial and Agricultural Pollution Trends in Swiss Rivers.

This study shows the efficiency of passive sampling to reveal industrial and agricultural pollution trends. Two practical applications for nonpolar and polar contaminants are presented. Low-density polyethylene (LDPE) samplers were deployed for one year in the Venoge River (VD) to monitor indicator PCBs (iPCBs, IUPAC nos. 28, 52, 101, 138, 153 and 180). The results showed that the impact of PCB emissions into the river is higher in summer than in other seasons due to the low flow rate of the river during this period. Polar organic chemical integrative samplers (POCIS) were deployed for 4 months in the Sion-Riddes canal (VS) to investigate herbicides (terbuthylazine, diuron and linuron). Desisopropylatrazine-d5 (DIA-d5) was tested as a performance reference compound (PRC) to estimate aqueous concentration. The results showed an increase of water contamination due to the studied agricultural area. The maximal contamination was observed in April and corresponds to the period of herbicide application on the crops.

Treatment of micropollutants in municipal wastewater: ozone or powdered activated carbon?

Many organic micropollutants present in wastewater, such as pharmaceuticals and pesticides, are poorly removed in conventional wastewater treatment plants (WWTPs). To reduce the release of these substances into the aquatic environment, advanced wastewater treatments are necessary. In this context, two large-scale pilot advanced treatments were tested in parallel over more than one year at the municipal WWTP of Lausanne, Switzerland. The treatments were: i) oxidation by ozone followed by sand filtration (SF) and ii) powdered activated carbon (PAC) adsorption followed by either ultrafiltration (UF) or sand filtration. More than 70 potentially problematic substances (pharmaceuticals, pesticides, endocrine disruptors, drug metabolites and other common chemicals) were regularly measured at different stages of treatment. Additionally, several ecotoxicological tests such as the Yeast Estrogen Screen, a combined algae bioassay and a fish early life stage test were performed to evaluate effluent toxicity. Both treatments significantly improved the effluent quality. Micropollutants were removed on average over 80% compared with raw wastewater, with an average ozone dose of 5.7 mg O3 l(-1) or a PAC dose between 10 and 20 mg l(-1). Depending on the chemical properties of the substances (presence of electron-rich moieties, charge and hydrophobicity), either ozone or PAC performed better. Both advanced treatments led to a clear reduction in toxicity of the effluents, with PAC-UF performing slightly better overall. As both treatments had, on average, relatively similar efficiency, further criteria relevant to their implementation were considered, including local constraints (e.g., safety, sludge disposal, disinfection), operational feasibility and cost. For sensitive receiving waters (drinking water resources or recreational waters), the PAC-UF treatment, despite its current higher cost, was considered to be the most suitable option, enabling good removal of most micropollutants and macropollutants without forming problematic by-products, the strongest decrease in toxicity and a total disinfection of the effluent.

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 (137)Cs and (210)Pb 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.

Plant uptake of pesticides and human health: dynamic modeling of residues in wheat and ingestion intake.

Human intake of pesticide residues from consumption of processed food plays an important role for evaluating current agricultural practice. We take advantage of latest developments in crop-specific plant uptake modeling and propose an innovative dynamic model to estimate pesticide residues in the wheat-environment system, dynamiCROP. We used this model to analyze uptake and translocation of pesticides in wheat after foliar spray application and subsequent intake fractions by humans. Based on the evolution of residues in edible parts of harvested wheat we predict that between 22 mg and 2.1 g per kg applied pesticide are taken in by humans via consumption of processed wheat products. Model results were compared with experimentally derived concentrations in wheat ears and with estimated intake via inhalation and ingestion caused by indirect emissions, i.e. the amount lost to the environment during pesticide application. Modeled and measured concentrations in wheat fitted very well and deviate from less than a factor 1.5 for chlorothalonil to a maximum factor 3 for tebuconazole. Main aspects influencing pesticide fate behavior are degradation half-life in plant and time between pesticide application and crop harvest, leading to variations in harvest fraction of at least three orders of magnitude. Food processing may further reduce residues by approximately 63%. Intake fractions from residues in sprayed wheat were up to four orders of magnitude higher than intake fractions estimated from indirect emissions, thereby demonstrating the importance of exposure from consumption of food crops after direct pesticide treatment.

Occurrence and fate of micropollutants in the Vidy Bay of Lake Geneva, Switzerland. Part II: micropollutant removal between wastewater and raw drinking water.

The occurrence and removal of 58 pharmaceuticals, endocrine disruptors, corrosion inhibitors, biocides, and pesticides, were assessed in the wastewater treatment plant (WWTP) of the city of Lausanne, Switzerland, as well as in the effluent-receiving water body, the Vidy Bay of Lake Geneva. An analytical screening method to simultaneously measure all of the 58 micropollutants was developed based on ultra performance liquid chromatography coupled to a tandem mass spectrometer (UPLC-MS/MS). The selection of pharmaceuticals was primarily based on a prioritization study, which designated them as environmentally relevant for the Lake Geneva region. Except for the endocrine disruptor 17alpha-ethinylestradiol, all substances were detected in 24-h composite samples of wastewater entering the WWTP or in the treated effluent. Of these compounds, 40% were also detected in raw drinking water, pumped from the lake 3 km downstream of the WWTP. The contributions of dilution and degradation to micropollutant elimination between the WWTP outlet and the raw drinking water intake were established in different model scenarios using hypothetical residence times of the wastewater in Vidy Bay of 1, 4, or 90 d. Concentration decrease due to processes other than dilution was observed for diclofenac, beta-blockers, several antibiotics, corrosion inhibitors, and pesticides. Measured environmental concentrations (MECs) of pharmaceuticals were compared to the predicted environmental concentrations (PECs) determined in the prioritization study and agreed within one order of magnitude, but MECs were typically greater than the corresponding PECs. Predicted no-effect concentrations of the analgesic paracetamol, and the two antibiotics ciprofloxacin and sulfamethoxazole, were exceeded in raw drinking water samples and therefore present a potential risk to the ecosystem.