Geochemistry of highly acidic mine water following disposal into a natural lake with carbonate bedrock

Acid mine drainage (AMD) from the Zn-Pb(-Ag-Bi-Cu) deposit of Cerro de Pasco (Central Peru) and waste water from a Cu-extraction plant has been discharged since 1981 into Lake Yanamate, a natural lake with carbonate bedrock. The lake has developed a highly acidic pH of similar to 1. Mean lake water chemistry was characterized by 16,775 mg/L acidity as CaCO(3), 4330 mg/L Fe and 29,250 mg/L SO(4). Mean trace element concentrations were 86.8 mg/L Cu, 493 mg/L Zn, 2.9 mg/L Pb and 48 mg/L As, which did not differ greatly from the discharged AMD. Most elements showed increasing concentrations from the surface to the lake bottom at a maximal depth of 41 m (e.g. from 3581 to 5433 mg/L Fe and 25,609 to 35,959 mg/L SO(4)). The variations in the H and 0 isotope compositions and the element concentrations within the upper 10 m of the water column suggest mixing with recently discharged AMD, shallow groundwater and precipitation waters. Below 15 m a stagnant zone had developed. Gypsum (saturation index, SI similar to 0.25) and anglesite (SI similar to 0.1) were in equilibrium with lake water. Jarosite was oversaturated (SI similar to 1.7) in the upper part of the water column, resulting in downward settling and re-dissolution in the lower part of the water column (SI similar to -0.7). Accordingly, jarosite was only found in sediments from less than 7 m water depth. At the lake bottom, a layer of gel-like material (similar to 90 wt.% water) of pH similar to 1 with a total organic C content of up to 4.40 wet wt.% originated from the kerosene discharge of the Cu-extraction plant and had contaminant element concentrations similar to the lake water. Below the organic layer followed a layer of gypsum with pH 1.5, which overlaid the dissolving carbonate sediments of pH 5.3-7. In these two layers the contaminant elements were enriched compared to lake water in the sequence As < Pb approximate to Cu < Cd < Zn = Mn with increasing depth. This sequence of enrichment was explained by the following processes: (i) adsorption of As on Fe-hydroxides coating plant roots at low pH (up to 3326 mg/kg As), (ii) adsorption at increasing pH near the gypsum/calcite boundary (up to 1812 mg/kg Pb, 2531 mg/kg Cu. and 36 mg/kg Cd), and (iii) precipitation of carbonates (up to 5177 mg/kg Zn and 810 mg/kg Mn: all data corrected to a wet base). The infiltration rate was approximately equal to the discharge rate, thus gypsum and hydroxide precipitation had not resulted in complete clogging of the lake bedrocks. (C) 2010 Elsevier Ltd. All rights reserved.

High occurrence of hepatitis E virus in samples from wastewater treatment plants in Switzerland and comparison with other enteric viruses.

Hepatitis E virus (HEV) is responsible for many enterically transmitted viral hepatitides around the world. It is currently one of the waterborne diseases of global concern. In industrialized countries, HEV appears to be more common than previously thought, even if it is rarely virulent. In Switzerland, seroprevalence studies revealed that HEV is endemic, but no information was available on its environmental spread. The aim of this study was to investigate -using qPCR- the occurrence and concentration of HEV and three other viruses (norovirus genogroup II, human adenovirus-40 and porcine adenovirus) in influents and effluents of 31 wastewater treatment plants (WWTPs) in Switzerland. Low concentrations of HEV were detected in 40 out of 124 WWTP influent samples, showing that HEV is commonly present in this region. The frequency of HEV occurrence was higher in summer than in winter. No HEV was detected in WWTP effluent samples, which indicates a low risk of environmental contamination. HEV occurrence and concentrations were lower than those of norovirus and adenovirus. The autochthonous HEV genotype 3 was found in all positive samples, but a strain of the non-endemic and highly pathogenic HEV genotype I was isolated in one sample, highlighting the possibility of environmental circulation of this genotype. A porcine fecal marker (porcine adenovirus) was not detected in HEV positive samples, indicating that swine are not the direct source of HEV present in wastewater. Further investigations will be necessary to determine the reservoirs and the routes of dissemination of HEV.

Temporal variability of antibiotics fluxes in wastewater and contribution from hospitals.

Significant quantities of antibiotics are used in all parts of the globe to treat diseases with bacterial origins. After ingestion, antibiotics are excreted by the patient and transmitted in due course to the aquatic environment. This study examined temporal fluctuations (monthly time scale) in antibiotic sources (ambulatory sales and data from a hospital dispensary) for Lausanne, Switzerland. Source variability (i.e., antibiotic consumption, monthly data for 2006-2010) were examined in detail for nine antibiotics--azithromycin, ciprofloxacin, clarithromycin, clindamycin, metronidazole, norfloxacin, ofloxacin, sulfamethoxazole and trimethoprim, from which two main conclusions were reached. First, some substances--azithromycin, clarithromycin, ciprofloxacin--displayed high seasonality in their consumption, with the winter peak being up to three times higher than the summer minimum. This seasonality in consumption resulted in seasonality in Predicted Environmental Concentrations (PECs). In addition, the seasonality in PECs was also influenced by that in the base wastewater flow. Second, the contribution of hospitals to the total load of antibiotics reaching the Lausanne Wastewater Treatment Plant (WTP) fluctuated markedly on a monthly time scale, but with no seasonal pattern detected. That is, there was no connection between fluctuations in ambulatory and hospital consumption for the substances investigated.

Characterization of fecal indicator bacteria in sediments cores from the largest freshwater lake of Western Europe (Lake Geneva, Switzerland)

This study characterized the fecal indicator bacteria (FIB), including Escherichia coli (E. coli) and Enteroccocus (ENT), disseminated over time in the Bay of Vidy, which is the most contaminated area of Lake Geneva. Sediments were collected from a site located at similar to 500 m from the present waste water treatment plant (WWTP) outlet pipe, in front of the former WWTP outlet pipe, which was located at only 300 m from the coastal recreational area (before 2001). E. coil and ENT were enumerated in sediment suspension using the membrane filter method. The FIB characterization was performed for human Enterococcus faecalis (E. faecalis) and Enterococcus faecium (E. faecium) and human specific bacteroides by PCR using specific primers and a matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS). Bacterial cultures revealed that maximum values of 35.2 x 10(8) and 6.6 x 10(6) CFU g(-1) dry sediment for E. coil and ENT, respectively, were found in the sediments deposited following eutrophication of Lake Geneva in the 1970s. whereas the WWTP started operating in 1964. The same tendency was observed for the presence of human fecal pollution: the percentage of PCR amplification with primers ESP-1/ESP-2 for E. faecalis and E. faecium indicated that more than 90% of these bacteria were from human origin. Interestingly, the PCR assays for specific-human bacteroides HF183/HF134 were positive for DNA extracted from all isolated strains of sediment surrounding WWPT outlet pipe discharge. The MALDI-TOF MS confirmed the presence of general E. coli and predominance E. faecium in isolated strains. Our results demonstrated that human fecal bacteria highly increased in the sediments contaminated with WWTP effluent following the eutrophication of Lake Geneva. Additionally, other FIB cultivable strains from animals or adapted environmental strains were detected in the sediment of the bay. The approaches used in this research are valuable to assess the temporal distribution and the source of the human fecal pollution in aquatic environments. (C) 2011 Elsevier Inc. All rights reserved.

Practical considerations for conducting ecotoxicity test methods with manufactured nanomaterials: what have we learnt so far?

This review paper reports the consensus of a technical workshop hosted by the European network, NanoImpactNet (NIN). The workshop aimed to review the collective experience of working at the bench with manufactured nanomaterials (MNMs), and to recommend modifications to existing experimental methods and OECD protocols. Current procedures for cleaning glassware are appropriate for most MNMs, although interference with electrodes may occur. Maintaining exposure is more difficult with MNMs compared to conventional chemicals. A metal salt control is recommended for experiments with metallic MNMs that may release free metal ions. Dispersing agents should be avoided, but if they must be used, then natural or synthetic dispersing agents are possible, and dispersion controls essential. Time constraints and technology gaps indicate that full characterisation of test media during ecotoxicity tests is currently not practical. Details of electron microscopy, dark-field microscopy, a range of spectroscopic methods (EDX, XRD, XANES, EXAFS), light scattering techniques (DLS, SLS) and chromatography are discussed. The development of user-friendly software to predict particle behaviour in test media according to DLVO theory is in progress, and simple optical methods are available to estimate the settling behaviour of suspensions during experiments. However, for soil matrices such simple approaches may not be applicable. Alternatively, a Critical Body Residue approach may be taken in which body concentrations in organisms are related to effects, and toxicity thresholds derived. For microbial assays, the cell wall is a formidable barrier to MNMs and end points that rely on the test substance penetrating the cell may be insensitive. Instead assays based on the cell envelope should be developed for MNMs. In algal growth tests, the abiotic factors that promote particle aggregation in the media (e.g. ionic strength) are also important in providing nutrients, and manipulation of the media to control the dispersion may also inhibit growth. Controls to quantify shading effects, and precise details of lighting regimes, shaking or mixing should be reported in algal tests. Photosynthesis may be more sensitive than traditional growth end points for algae and plants. Tests with invertebrates should consider non-chemical toxicity from particle adherence to the organisms. The use of semi-static exposure methods with fish can reduce the logistical issues of waste water disposal and facilitate aspects of animal husbandry relevant to MMNs. There are concerns that the existing bioaccumulation tests are conceptually flawed for MNMs and that new test(s) are required. In vitro testing strategies, as exemplified by genotoxicity assays, can be modified for MNMs, but the risk of false negatives in some assays is highlighted. In conclusion, most protocols will require some modifications and recommendations are made to aid the researcher at the bench. [Authors]

Evaluation des pratiques d'irrigation, de fertilisation et d'application de pesticides dans l'agriculture périurbaine de Dakar, Sénégal

RESUMEL'agriculture urbaine et périurbalne - nommée ci-après AU - est un thème fort de recherche transversale, au vu des nombreux enjeux économiques, sociaux et environnementaux. L'objectif de cette recherche était de contribuer à une meilleure connaissance des processus de transfert de polluants et du cycle des nutriments à l'échelle locale, afin de déterminer sous quelles conditions l'AU de Dakar peut être pratiquée sans porter atteinte à la santé et à l'environnement.Une approche basée sur l'étude des processus géochimiques dans ie sol jusqu'à la nappe a été choisie, à l'échelle de la parcelle cultivée et à une échelle un peu plus large de la zone périurbaine de Dakar pour déterminer les influences du type d'occupation du sol.L'évaluation des impacts de l'irrigation avec des eaux usées brutes et des eaux de nappe saumâtres sur la qualité des sols (chapitre 2) a montré que l'alcalinité et les teneurs en calcium élevées des eaux saumâtres induisent la précipitation de CaC03 dans l'horizon superficiel du sol. Na remplace consécutivement Ca sur le complexe argilo-humique du sol et les bicarbonates diminuent dans la solution du sol. Le carbone organique dissout (COD) augmente significativement dans la solution du sol et dans la nappe sous-jacente. Malgré l'alcalinité et les teneurs très élevées en calcium des eaux usées, il y a peu de précipitation de CaC03 dans l'horizon superficiel du sol et une faible augmentation du sodium échangeable ESP. La nitrification de l'ammonium des eaux usées (moy 190mg/L à Pikine) produit des protons, qui ne sont plus tamponnés par les bicarbonates exportés hors du profil. Il y a alors une nette baisse de pH des sols irrigués par des eaux usées non traitées. Les sols irrigués par des eaux usées et saumâtres stockent moins de C et Ν que les sols de référence.L'évaluation de l'influence de l'occupation des sols en zone périurbaine sur à la nappe phréatique peu profonde (chapitre 3) a permis de déterminer les traceurs représentatifs de l'occupation du sol, à savoir Br/CI, NO3/CI et δ180-Ν03 pour l'irrigation par des eaux usées, pH et δ15Ν-Ν03 pour l'irrigation par des eaux de nappe, et Rb+Cr et Κ pour les lixiviats de fosses septiques. Ce chapitre a mis en évidence des points importants de la dynamique de l'azote en zone périurbaine sous deux occupations du sol : (1) la dénitrification est un processus important dans l'agrosystème périurbain de Dakar en bas de dune, dans les gleysols où l'on trouve des conditions temporairement réduites et un substrat organique favorables aux microorganismes de la dénitrification. Les teneurs en nitrates sont presque nulles avec irrigation d'eau de nappe. (2) en bas de pente, mais avec irrigation quotidienne par les eaux usées, l'apport continu d'ammonium inhibe probablement la dénitrification, mais favorise la volatilisation. (3) la nitrification de l'ammonium dans la nappe lors de la lixiviation des fosses septiques se distingue de la nitrification de l'ammonium dans la zone non saturée dans la zone d'agriculture périurbaine par la composition isotopique de l'oxygène de l'eau. Une comparaison des flux d'azote entre l'agrosystème et les quartiers périurbains de Dakar (chapitre 4) ont révélé que ces derniers étaient du même ordre de grandeur par unité de surface, à savoir 2-4 tonnes Ν /ha/an.L'évaluation des flux de pesticides dans l'agrosystème et des risques induits pour les eaux souterraines (chapitre 5) a révélé un fiux total de pesticides de 60kg/ha/an, totalisant 15 matières actives. Seules deux de ces matières actives sont autorisées par le comité des pesticides sahélien. Les pesticides les plus utilisés par les producteurs sont l'organochloré dicofol, les organophosphorés methamidophos, dimethoate et fenithrotion ainsi que le cabamate methomyl. Les flux les plus importants sont de 9 à 7 kg/ha/an (methomyl, methamidophos, ethoprophos et dicofol). Les pesticides qui présentent un risque élevé de contamination des eaux souterraines et qui devraient être prioritaires pour un suivi analytique sont : le carbofuran, le dimethoate, l'ethoprophos et le methomyl.En conclusion, une meilleure gestion de la fertilisation est nécessaire dans la zone d'AU de Dakar, afin de (1) réduire les pertes gazeuses qui contribuent à l'effet de serre, (2) de ralentir la minéralisation du carbone et de l'azote organiques pour créer un stock de C et Ν dans ces sols, (3) de limiter le lessivage dans la nappe et enfin, 4) d'augmenter l'efficacité d'utilisation de Ν par les plantes. Une optimisation de l'irrigation devrait limiter l'alcalinisation secondaire. Enfin, la mise en place d'une lutte intégrée ou biologique contre les ravageurs est indispensable afin de minimiser les risques pour les eaux souterraines et les mares permanentes.ABSTRACTUrban and periurban agriculture (UA) is an important issue in southern countries, because of its key role in their social and economical development and its environmental concern. The goal of this study was to contribute to a better understanding of pollutant transfer and nutrient cycling at the local scale, in order to implement the necessary improvements to guarantee the sustainability of this practice.An approach based on geochemical processes occurring in the vadose zone from the surface down to the groundwater level was chosen, at the scale of cultivated plots and at the regional scale of Dakar periurban areas, to determine the influence of land use.The assessment of irrigation with untreated domestic wastewater and brackish water on soil quality (chapter 2) showed: (1) that the high alkalinity and calcium contents of brackish water induce CaC03 precipitation in the top layer of the soil and therefore a replacement of Ca by Na on the clay- humic complexes, strongly marked during the dry season. Dissolved organic carbon (DOC) increased significantly in the soil solution and in the underlying groundwater. (2) in spite of the similarly high alkalinity and Ca contents of waste water, there is only little CaC03 precipitation and a low increase of the percentage of exchangeable sodium (ESP) in the soil top layer. The nitrification of the ammonium of wastewater (mean 190 mg/L in Pikine) produces protons, which are not any more buffered by bicarbonates exported out of the soil profile, which leads to a net decline of soil pH. Both soils irrigated with untreated wastewater and brackish water store less of C and Ν than soils irrigated with non saline groundwater.The assessment of the impact of land use on the shallow groundwater (chapter 3) allowed determining representative tracers of the land use. Low Br/CI ratio, high NO3/CI ratio and low δ1βΟ- nitrate indicated the influence of wastewater; high pH and high 515N-nitrates indicated the influence of brackish water together with high amendments of organic fertilizers; high Rb+Cr and Κ indicated the influence of poor sanitation facilities in periurban districts (septic tank leakage). This chapter also pointed out the following facts about the nitrogen dynamics : (1) denitrification is a key-process in the Dakar UA agrosystem in the gleysols irrigated with groundwater. The underlying groundwater is almost nitrate free. (2) in the Gleysols irrigated with waste water, ammonium inhibits denitrification but facilitate ammoniac volatilization. A comparison of nitrogen balance between the UA agrosystem and the periurban districts of Dakar (chapter 4) revealed similar flows per surface unit, namely 2-4 tons Ν / ha / year.The evaluation of pesticides use in the UA agrosystem and the risk assessment for the groundwater (chapter 5) revealed a total flow of pesticides of 60kg / ha / year, totalizing 15 active substances. Only two of these are authorized by the Sahelian Pesticides Committee. The most used pesticides are dicofol (organochlorinated), methamidophos, dimethoate and fenithrotion (organophosphate) as well as methomyl. (carbamate). The most important flows vary between 9 to 7 kg / ha / year. Pesticides with a high risk of groundwater contamination - according to SIRIS and EPRIP 2 indicators - are: carbofuran, dimethoate, ethoprophos and methomyl. These substances should be established as a priority for an analytical follow-up in the different environmental compartments.In conclusion, a better management of the fertilization is necessary in the Dakar UA, (1) to reduce the gaseous losses which contribute to greenhouse emissions (2) to slow down the mineralization of the organic carbon and the nitrogen, in order to enhance the C and Ν stock in these soils, (3) to limit the nitrate leaching in the groundwater and finally, 4) to increase the N-use efficiency of plants. An optimization of the irrigation scheme should limit the secondary sodisation if coupled with an increase the stable organic matter of the soil. An integrated or biologic crop pest strategy is urgently needed to minimize risks with respect to ground and surface water (ponds used for fishing).RESUME LARGE PUBLICL'agriculture mondiale connaît actuellement une crise majeure, affectée par les changements climatiques, la sécurité alimentaire et les dégradations de l'environnement. Elle n'a plus le rôle unique de produire, mais devient un élément essentiel de la protection des ressources naturelles et du paysage. Les politiques agricoles basées sur les marchés mondiaux devront se réorienter vers une agriculture locale basée sur le développement durable.La production alimentaire située dans l'enceinte des villes, nommée agriculture urbaine ou périurbaine (AU ci-après) joue un rôle important dans le contexte actuel d'accroissement de la population et de la pauvreté urbaines. L'AU concerne en effet la majorité des mégapoies du monde, fait vivre plus de 200 millions de personnes dans les pays du Sud, fournit jusqu'à 80% de la demande urbaine en certains produits frais, fait barrière à l'extension urbaine et permet un recyclage de certains déchets urbains. L'AU a pour particularité d'être à cheval entre des politiques rurales et urbaines, d'où un délaissement ce cette activité au secteur informel. Ce qui a développé de nombreuses stratégies à risques, comme à Dakar, où les petits producteurs périurbains irriguent quotidiennement avec des eaux usées domestiques par manque d'accès à une eau de bonne qualité et pour raccourcir les cycles de production. L'extrême précarité foncière des acteurs de l'AU de Dakar les empêchent d'investir à long terme et induit des pratiques inadéquates d'irrigation, d'usage de pesticides et de fertilisation de ces sols sableux.L'objectif de cette recherche était de contribuer à une meilleure connaissance des processus de transfert de polluants et du cycle des nutriments à l'échelle des parcelles cultivées par des eaux usées et des eaux saumâtres, afin de déterminer sous quelles conditions l'AU de Dakar peut être pratiquée et surtout maintenue sans porter atteinte à la santé et à l'environnement. Pour cela, une approche basée sur l'étude des processus géochimiques dans le sol jusqu'à la nappe a été choisie, à l'échelle de la parcelle cultivée et à une échelle un peu plus large de la zone périurbaine de Dakar pour déterminer les influences du type d'occupation du sol.Les résultats principaux de cette étude ont montré que (1) il y a un processus de salinisation anthropique des sols (sodisation) lors d'irrigation avec des eaux de nappe saumâtres, un processus accentué en saison sèche et lors d'années à pluviométrie déficitaire. Bien que les eaux usées soient aussi salines que les eaux de nappe, la salinisation des sols irrigués' par des eaux usées est limitée par l'ammonium présent dans les eaux usées (moy 190mg NH4/L à Pikine) qui produit de l'acidité lors de la transformation en nitrates dans le sol (nitrification). (2) les sols irrigués par des eaux usées (EU) stockent moins de C et Ν que les sois de référence, ce qui montrent bien que l'azote des eaux usées n'est pas disponible pour les plantes, mais est lessivé dans la nappe (100 à 450 mg/L N03 sous irrigation par EU, alors que la limite de OMS est de 50mg/L). (3) l'utilisation des isotopes stables des nitrates et des éléments traces, notamment le bore et le brome, ont permis de distinguer l'influence de l'irrigation par des eaux usées, de l'irrigation par des eaux de nappe et des lixiviats de fosses septiques sur les propriétés de la nappe. (4) Le processus de la dénitrification (atténuation naturelle des concentrations en nitrates de la nappe par biotransformation en azote gazeux) est important dans les zones basses de l'agrosystème périurbain de Dakar, sous irrigation par eaux naturelles (ΝΟ3 < 50mg/L). Tandis que sous habitat sans assainissement adéquat, les nitrates atteignent 300 à 700 mg/L. (5) Le flux total de pesticides dans l'AU est énorme (60kg/ha/an) totalisant 15 pesticides, dont deux seulement sont autorisés. Les pesticides les plus utilisés sont des insecticides organophosphorés et organochlorés classés extrêmement dangereux à dangereux par l'OMS, appliqués à des doses de 2 à 9 kg/ha/an. Les pesticides qui ont montré un risque élevé de contamination des eaux souterraines avec les indicateurs SIRIS et EPRIP2 sont : le carbofuran, le dimethoate, l'ethoprophos et le methomyl.En conclusion, nous recommandons la reconstitution d'un horizon superficiel des sols riche en matière organique stable et structuré par production locale de compost. Cette mesure réduira les pertes gazeuses contribuant à l'effet de serre, augmentera le stock de Ν dans ces sols, alors utilisable par les plantes et permettra de diminuer l'irrigation car la capacité de rétention de l'eau dans le sol sera accru, ce qui limitera le lessivage des nitrates dans la nappe et l'alcalinisation secondaire. Enfin, la mise en place d'une lutte intégrée ou biologique contre les ravageurs est indispensable afin de minimiser les risques pour les eaux souterraines et lesmares permanentes.

Environmental pollution promotes selection of microbial degradation pathways

Astonishing as it may seem, one organism's waste is often ideal food for another. Many waste products generated by human activities are routinely degraded by microorganisms under controlled conditions during waste-water treatment. Toxic pollutants resulting from inadvertent releases, such as oil spills, are also consumed by bacteria, the simplest organisms on Earth. Biodegradation of toxic or particularly persistent compounds, however, remains problematic. What has escaped the attention of many is that bacteria exposed to pollutants can adapt to them by mutating or acquiring degradative genes. These bacteria can proliferate in the environment as a result of the selection pressures created by pollutants. The positive outcome of selection pressure is that harmful compounds may eventually be broken down completely through biodegradation. The downside is that biodegradation may require extremely long periods of time. Although the adaptation process has been shown to be reproducible, it remains very difficult to predict.

Water as an essential nutrient: the physiological basis of hydration.

How much water we really need depends on water functions and the mechanisms of daily water balance regulation. The aim of this review is to describe the physiology of water balance and consequently to highlight the new recommendations with regard to water requirements. Water has numerous roles in the human body. It acts as a building material; as a solvent, reaction medium and reactant; as a carrier for nutrients and waste products; in thermoregulation; and as a lubricant and shock absorber. The regulation of water balance is very precise, as a loss of 1% of body water is usually compensated within 24 h. Both water intake and water losses are controlled to reach water balance. Minute changes in plasma osmolarity are the main factors that trigger these homeostatic mechanisms. Healthy adults regulate water balance with precision, but young infants and elderly people are at greater risk of dehydration. Dehydration can affect consciousness and can induce speech incoherence, extremity weakness, hypotonia of ocular globes, orthostatic hypotension and tachycardia. Human water requirements are not based on a minimal intake because it might lead to a water deficit due to numerous factors that modify water needs (climate, physical activity, diet and so on). Water needs are based on experimentally derived intake levels that are expected to meet the nutritional adequacy of a healthy population. The regulation of water balance is essential for the maintenance of health and life. On an average, a sedentary adult should drink 1.5 l of water per day, as water is the only liquid nutrient that is really essential for body hydration.

Effect of irrigation water and processing on the microbial quality of lettuces produced and sold on markets in Dakar (Senegal)

The aim of this survey is to assess the microbiological impact of irrigation water on lettuces produced on two urban agricultural sites and sold on markets; 6 and 7%, respectively, of lettuces coming from the sites of Pikine and Patte d'Oie were Salmonella spp. positive. Lettuces irrigated with shallow groundwater (''Ceanes'' water) were more contaminated (8% at both Pikine and Patte d'Oie sites) compared to those irrigated with wastewater (4% at Pikine) or well water (5% at Patte d'Oie). As for the lettuces in marketplaces, their contamination seems to depend on the type of treatment occurring before sale. Lettuces previously washed in the ``Ceanes'' were more contaminated than those rinsed with tap water at the marketplace. Salmonella spp. have been isolated from all marketplaces. However, the rates of contamination in markets surrounding Patte d'Oie are higher (9 and 11% at Grand Yoff and Dalifort) than those surrounding Pikine (4 and 2% at Zinc and Sham) or Rufisque, the control (2%). Our results confirm that the reuse of wastewater in irrigation is an alternative to animal manure. Its risk of microbial contamination can be significantly reduced by washing the vegetables with tap water before they are sold. Copyright (C) 2010 John Wiley & Sons, Ltd.

Low molecular weight carboxylic acids in oxidizing porphyry copper tailings

The distribution of low molecular weight carboxylic acids (LMWCA) was investigated in pore water profiles from two porphyry copper tailings impoundments in Chile (Piuquenes at La Andina and Cauquenes at El Teniente mine). The objectives of this study were (1) to determine the distribution of LMWCA, which are interpreted to be the metabolic byproducts of the autotroph microbial community in this low organic carbon system, and (2) to infer the potential role of these acids in cycling of Fe and other elements in the tailings impoundments. The speciation and mobility of iron, and potential for the release of H+ via hydrolysis of the ferric iron, are key factors in the formation of acid mine drainage in sulfidic mine wastes. In the low-pH oxidation zone of the Piuquenes tailings, Fe(III) is the dominant iron species and shows high mobility. LMWCA, which occur mainly between the oxidation front down to 300 cm below the tailings surface at both locations (e.g., max concentrations of 0.12 mmol/L formate, 0.17 mmol/L acetate, and 0.01 mmol/L pyruvate at Piuquenes and 0.14 mmol/L formate, 0.14 mmol/L acetate, and 0.006 mmol/L pyruvate at Cauquenes), are observed at the same location as high Fe concentrations (up to 71.2 mmol/L Fe(II) and 16.1 mmol/L Fe(III), respectively). In this zone, secondary Fe(111) hydroxides are depleted. Our data suggest that LMWCA may influence the mobility of iron in two ways. First, complexation of Fe(III), through formation of bidentate Fe(III)-LMWCA complexes (e.g., pyruvate, oxalate), may enhance the dissolution of Fe(III) (oxy)hydroxides or may prevent precipitation of Fe(III) (oxy)hydroxides. Soluble Fe(III) chelate complexes which may be mobilized downward and convert to Fe(II) by Fe(III) reducing bacteria. Second, monodentate LMWCA (e.g., acetate and formate) can be used by iron-reducing bacteria as electron donors (e.g., Acidophilum spp.), with ferric iron as the electron acceptor. These processes may, in part, explain the low abundances of secondary Fe(III) hydroxide precipitates below the oxidation front and the high concentrations of Fe(II) observed in the pore waters of some low-sulfide systems. The reduction of Fe(III) and the subsequent increase of iron mobility and potential acidity transfer (Fe(II) oxidation can result in the release of H+ in an oxic environment) should be taken in account in mine waste management strategies.

Geochemical evolution of active porphyry copper tailings impoundments : from alkaline deposition towards acidification

J. Smuda: Geochemical evolution of active porphyry copper tailings impoundments Thesis abstract Mine waste is the largest volume of materials handled in the world. The oxidation of sulfidic mine waste may result in the release of acid mine drainage (AMD) rich in heavy metals and arsenic to the environment, one of the major problems the mining industry is facing today. To control and reduce this environmental impact, it is crucial to identify the main geochemical and hydrological processes influencing contaminant liberation, transport, and retention. This thesis presents the results of a geochemical, mineralogical and stable isotope study (δ2H, δ18O, δ34S) from two active porphyry copper tailings impoundments in Mediterranean (Carén tailings impoundment, El Teniente mine, Central Chile) and hyper-arid climate (Talabre tailings impoundment, Chuquicamata, Northern Chile) from the deposition in alkaline environment (pH 10.5) towards acidification after several years of exposure. The major hydrological results were the identification of vertical contaminant and water transport in the uppermost, not water-saturated zone, triggered by capillary rise due to evaporation, and infiltration downwards due to new tailings deposition, and of horizontal transport in the groundwater zone. At the surface of the sedimented tailings, evaporation of pore water led to the precipitation of Na-Ca-Mg sulfates (e.g., gypsum, tenorite), in hyper-arid climate also halite. At the Carén tailings impoundment, renewed deposition in a 4-week interval inhibited a pH decrease below neutral values and the formation of an efflorescent salt crust. At the Talabre tailings impoundment, deposition breaks of several years resulted in the formation of acidic oxidation zones in the timeframe of less than 4 years. This process enabled the transport of liberated Cu, Zn, and Fe via capillary rise to the surface, where these metals precipitated as heavy-metal sulfates (e.g., devilline, krohnkite) and chlorides (eriochalcite, atacamite). Renewed depositing may dissolve efflorescent salts and transport liberated elements towards the groundwater zone. This zone was found to be highly dynamic due to infiltration and mixing with water from different sources, like groundwater, catchment water, and infiltration from superficial waters. There, Cu was found to be partially mobile due to complexation with Cl (in Cl-rich groundwater, Talabre) and dissolved organic matter (in zones with infiltration of catchment water rich in dissolved organic matter, Carén). A laboratory study on the isotopic fractionation of sulfur and oxygen of sulfate in different minerals groups (water-soluble sulfates, low- and high-crystalline Fe(III) oxyhydroxides) contributed to the use of stable isotopes as tracer of geochemical and transport processes for environmental studies. The results highlight that a detailed geochemical, stable isotope and mineralogical study permits the identification of contamination processes and pathways already during the deposition of mine tailings. This knowledge allows the early planning of adequate actions to reduce and control the environmental impact during tailings deposition and after the closing of the impoundment. J. Smuda: Geochemical evolution of active porphyry copper tailings impoundments Résumé de these Les déchets miniers constituent les plus grands volumes de matériel gérés dans le monde. L'oxydation des déchets miniers sulfuriques peut conduire à la libération de drainages miniers acides (DMA) riches en métaux et arsenic dans l'environnement, ce qui est l'un des principaux problèmes de l'industrie minière aujourd'hui. Pour contrôler et réduire ces impacts sur l'environnement, il est crucial d'identifier les principaux processus géochimiques et hydrologiques influençant la libération, le transport et la rétention des contaminants. Cette thèse présente les résultats d'une étude géochimique, minéralogique et des isotopes stables (δ2H, δ18O, δ34S) sur des déchets miniers de 2 sites de dépôt actifs en climat méditerranéen (Dépôt de déchets de Carén, mine de El Teniente, Centre du Chili) et en climat hyper-aride (Dépôt de déchets de Talabre, mine de Chuquicamata, Nord du Chili). L'objectif était d'étudier l'évolution des déchets de la déposition en milieu alcalin (pH = 10.5) vers l'acidification après plusieurs années d'exposition. Le principal résultat hydrologique a été l'identification de 2 types de transport : un transport vertical de l'eau et des contaminants dans la zone non saturée en surface, induit par la montée capillaire due à l'évaporation et par l'infiltration subséquente de la déposition de sédiments frais ; et un transport horizontal dans la zone des eaux souterraines. À la surface des déchets, l'évaporation de l'eau interstitielle conduit à la précipitation de sulfates de Na-Ca-Mg (ex. gypse, ténorite) et halite en climat hyper-aride. Dans le site de Carén, une nouvelle déposition de déchets frais à 4 semaines intervalle a empêché la baise du pH en deçà des valeurs neutres et la formation d'une croûte de sels efflorescentes en surface. Dans le site de Talabre, les fentes de dessiccation des dépôts ont entraîné la formation d'une zone d'oxydation à pH acide en moins de 4 ans. Ce processus a permis la libération et le transport par capillarité de Cu, Zn, Fe vers la surface, où ces éléments précipitent sous forme de sulfates de métaux lourds (ex., dévilline, krohnkite) de chlorures (ex. ériochalcite, atacamite). Une nouvelle déposition de sédiments frais pourrait dissoudre ces sels et les transporter vers la zone des eaux souterraines. Cette dernière zone était très dynamique en raison du mélange d'eaux provenant de différentes sources, comme les eaux souterraines, l'eau de captage et l'infiltration des eaux superficielles. Egalement dans cette zone, le cuivre était partiellement mobile à cause de la formation de complexe avec le chlore (dans les zone riche en Cl, Talabre) et avec la matière organique dissoute (dans les zones où s'infiltre l'eau de captage riche en matière organique, Carén). Une étude en laboratoire sur le fractionnement des isotopes stables de sulfure et d'oxygène des sulfates dans différents groupes de minéraux (sulfates hydrosolubles, sulfures de oxy-hydroxyde de Fe(III) faiblement ou fortement cristallins) a permis d'apporter une contribution à leur utilisation comme traceurs dans l'étude des processus géochimiques et de transport lors d'études environnementales. Les résultats montrent qu'une étude détaillée de la géochimie, des isotopes stables et de la minéralogie permet d'identifier les processus et les voies de contamination déjà pendant la période de dépôt des déchets miniers. Cette connaissance permet de planifier, dès le début de l'exploitation, des mesures adéquates pour réduire et contrôler l'impact sur l'environnement pendant la période de dépôts de déchets miniers et après la fermeture du site.

Geological structure, recharge processes and underground drainage of a glacierised karst aquifer system, Tsanfleuron-Sanetsch, Swiss Alps

The relationships between stratigraphic and tectonic setting, recharge processes and underground drainage of the glacierised karst aquifer system `Tsanfleuron-Sanetsch' in the Swiss Alps have been studied by means of various methods, particularly tracer tests (19 injections). The area belongs to the Helvetic nappes and consists of Jurassic to Palaeogene sedimentary rocks. Strata are folded and form a regional anticlinorium. Cretaceous Urgonian limestone constitutes the main karst aquifer, overlain by a retreating glacier in its upper part. Polished limestone surfaces are exposed between the glacier front and the end moraine of 1855/1860 (Little Ice Age); typical alpine karrenfields can be observed further below. Results show that (1) large parts of the area are drained by the Glarey spring, which is used as a drinking water source, while marginal parts belong to the catchments of other springs; (2) groundwater flow towards the Glarey spring occurs in the main aquifer, parallel to stratification, while flow towards another spring crosses the entire stratigraphic sequence, consisting of about 800 m of marl and limestone, along deep faults that were probably enlarged by mass movements; (3) the variability of glacial meltwater production influences the shape of the tracer breakthrough curves and, consequently, flow and transport in the aquifer.

Determination of 241Pu in nuclear waste slurries: a comparative study using LSC and ICP-MS.

(241)Pu was determined in slurry samples from a nuclear reactor decommissioning project at the Paul Scherrer Institute (Switzerland). To validate the results, the (241)Pu activities of five samples were determined by LSC (TriCarb and Quantulus) and ICP-MS, with each instrument at a different laboratory. In lack of certified reference materials for (241)Pu, the methods were further validated using the (241)Pu information values of two reference sediments (IAEA-300 and IAEA-384). Excellent agreement with the results was found between LSC and ICP-MS in the nuclear waste slurries and the reference sediments.