Luiz Felippe De Alencastro

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.

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.

Plastic pollution in Swiss surface waters: nature and concentrations, interaction with pollutants

Marine microplastic (,5 mm) water pollution has met growing public and scientific interest in the last few years. The situation in freshwater environments remains largely unknown, although it appears that they play an important role as part of the origin of marine pollution. Apart from the physical impacts on biota, chemical effects are to be expected as well, especially with smaller particles. This study aims at assessing plastic abundance in Lakes Geneva, Constance, Neuchaˆtel, Maggiore, Zurich and Brienz, and identifying the nature of the particles, potential ingestion by birds and fishes, and the associated pollutants. Lake surface transects and a few rivers were sampled using a floating manta net, and beach sediments were analysed. Plastics were sorted by type (fragments, pellets, cosmetic beads, lines, fibres, films, foams) and composition (polypropylene, polyethylene, polystyrene, etc.); fish and water birds were dissected to assess their potential exposure, and analyses were conducted on the hydrophobic micropollutants adsorbed to the microplastics as well as some potentially toxic additives they contained. Evidence of this pollution is shown for all lakes, microplastics of all types and diverse composition having been found in all samples. Birds and fish are prone to microplastic ingestion, and all the tested chemicals (both adsorbed micropollutants and contained additives) were found above the detection limit, and often the quantification limit. The sources and their respective contribution need to be confirmed and quantified, and the ecotoxicological effects need further investigation. Other questions remain open, including the transport and fate of plastic particles in the environment.

Urban stormwater contamination by polychlorinated biphenyls (PCBs) and its importance for urban water systems in Switzerland

Like other persistent organic pollutants (POPs), polychlorinated biphenyls (PCBs) are still present in the environment despite their almost worldwide prohibition. A study was conducted over 1 year in Switzerland to analyze the source and load of PCBs in urban stormwater and their importance in urban water systems. The mean PCB concentrations of 89 rain events were determined in five different strictly separate drainage systems (three in Lausanne and two in Geneva). The mean concentrations of PCBs in stormwater ranged from values below the detection limit (0.11-0.24 ng/l) to 403 ng/l. A model for the wet and dry deposition of PCBs based on these results estimates that their concentration in rainwater has remained practically constant (35 ng/l) over a period of 12 years. A mass balance of Swiss levels estimates a total input load of PCBs in the urban water systems at 110-125 kg/year. The contribution of stormwater is 75-94 kg/year in combined sewer systems and 23-34 kg in separate sewer systems. This mass balance illustrates that a major part of the PCB load in the environment or in WWTP sludges originates from urban stormwater. This result was confirmed by a fingerprint of PCB congeners in stormwater, which showed a pattern identical to that found in sewage sludge in combined sewer systems.

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.

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.

Trace determination of Tamoxifen and 5-Fluorouracil in hospital and urban wastewaters

Tamoxifen and 5-fluorouracil are widely used in cancer therapy. They are highly toxic (teratogenic, mutagenic, etc.), as are most of the anticancer drugs. Two methods were set up to analyse these drugs in wastewaters to evaluate the potential for environmental contamination by cytostatic agents. Liquid–liquid extraction followed by purification on OASIS® MCX cartridge and gas chromatography with mass spectrometry detection (GC-MS) was used for the analysis of tamoxifen. 5-Fluorouracil was extracted with an ENV+ (Isolute) cartridge (solid-phase extraction), derivatized with pentafluorobenzyl bromide (PFBBr) and detected by GC-MS. Both methods showed good recoveries (>70%), repeatability (RSD<10%) and limits of detection (LOD 6–15 ng/L). Wastewaters from a residential area, a hospital, and sewage-treatment plants (STPs) were analysed using the analytical methods developed in this study. Tamoxifen was detected in wastewaters of the hospital, residential area, and influent of STPs, but not in treated wastewaters. 5-Fluorouracil in all wastewaters was below the LOD of the analytical method.

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.

Application of multidimensional (heart-cut) gas chromatography to the analysis of complex mixtures of organic pollutants in environmental samples

Reference GR-CEL-ARTICLE-2003-001View record in Web of Science URL: http://www.sach.ch/doc/chimia/sept03/dealencastro.pdf Record created on 2005-07-15, modified on 2016-08-08

Multiresidue analysis of atrazine, diuron and their degradation products in sewage sludge by liquid chromatography tandem mass spectrometry

A multiresidue method has been developed to analyze atrazine (ATZ), diuron (DIU), and their major degradation products, desethylatrazine (DEA), desisopropylatrazine (DIA), and dichlorophenylmethylurea in sewage sludge. Liquid chromatography coupled to electrospray tandem mass spectrometry (LC–ESI-MS–MS) allowed, in the multiple-reaction monitoring mode, the simultaneous analysis of these pesticides in only one run after their extraction with ethyl acetate–dichloromethane 90:10 (v/v) and a cleanup on a Florisil column. Stable isotopically labeled ATZ and DIU were used as internal standards to overcome matrix effects during the pesticide quantification. Using fortified samples, the method gave rise to 86–115% as mean recovery values depending on the analyte. Limits of detection (LODs) and of quantification (LOQs) ranging from 0.3 (DIA) to 1.5 (DEA) μg kg−1 dw and from 0.4 (DIA) to 2.0 (DEA) μg kg−1 dw, respectively, were sufficient to achieve the monitoring of these molecules in sludge from wastewater treatment plants of the Ile-de-France region.