Silvia Lacorte

Impact of pesticides used in agriculture and vineyards to surface and groundwater quality (North Spain).

An environmental monitoring program was carried out to determine the impact of eight pesticides on the surface and groundwater quality of agricultural areas within the Ebro, Duero and Miño river basins. Three triazines and their desethyl degradation products, metolachlor and metalaxyl, were monitored during 18 months in 63 sites. Solid-phase extraction (SPE) using OASIS HLB 60 mg cartridges and gas chromatography-mass spectrometry (GC-EI-MS) provided good analytical quality parameters and limits of quantification of 0.01 microg/L. Environmental data were assessed using descriptive statistical analysis and multivariate data analysis with principal component analysis (PCA) to elucidate the relevant contamination patterns and provide a description of their seasonal trends, according to the pesticide application timing. Duero was the site with the highest frequency of detection and highest concentration levels, followed by the Ebro and Miño basins. The frequency of detection of the studied compounds, considering all surface and groundwater samples, was atrazine>desethylatrazine>simazine>desethylsimazine>metolachlor>desethylterbuthylazine>terbuthylazine>metalaxyl. Over all results, and taking into consideration the European Union (EU) maximum residual limit of pesticides in groundwater, only 12% of the results exceeded the 0.1 microg/L limit. However, sporadic high levels up to 2.46 mug/L in groundwater and 0.63 microg/L in surface water were detected. PCA permitted to state that Duero and Ebro river basins were especially affected by a contamination pattern dominated by atrazine, the Ebro river basin being occasionally affected by a contamination pattern dominated by simazine. Only trace levels were rarely detected in the Miño river basin. Groundwater levels were higher than surface water levels for the studied pesticides.

Monitoring of priority pesticides and other organic pollutants in river water from Portugal by gas chromatography-mass spectrometry and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

Gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) were optimized and applied for the trace-level determination of 42 priority pesticides and 33 priority organic pollutants from European Union Directive EC 76/464. First, off-line solid-phase extraction of 200 ml of river water using an OASIS solid-phase extraction cartridge, followed by GC-MS was used. Next, selected samples that were positive to GC-MS were analyzed by LC-APCI-MS in order to detect further polar byproducts or to improve the determination of previously detected polar analytes. The transformation products of triazine pesticides like deethylatrazine (DEA) and deisopropylatrazine (DIA) and compounds such as diuron and several chlorophenols were positively identified by LC-APCI-MS. The present methodology has also been used for searching for new analytes not included in the EC 76/464 list, like Irgarol, DEA and DIA. In addition it was applied to target pollutants in 43 river water samples from Portugal during a pilot survey from April to July 1999. Atrazine followed by simazine and 2,4,6-trichlorophenol were the most ubiquitous compounds detected in this area. The levels detected of the different compounds were in the range of: 0.01-2.73 microg/l, 0.05-0.74 microg/l, 0.02-1.65 microg/l, 0.02-5.43 microg/l, 0.01-0.40 microg/l, 0.01-0.26 microg/l, 0.02-0.61 microg/l, 0.01-3.90 microg/l, 0.01-1.24 microg/l, 0.02-2.3 microg/l, 0.01-0.13 microg/l and 0.01-0.5 microg/l for atrazine, simazine, terbuthylazine, alachlor, metolachlor, Irgarol, propanil; tributhylphosphate, diuron, 2,4,6-trichlorophenol, deisopropylatrazine and deethylatrazine, respectively.

Determination and occurrence of phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs in an industrial sewage grid discharging to a Municipal Wastewater Treatment Plant

Industrial and urban discharges release organic contaminants which might affect the quality of receiving waters if not properly eliminated in Wastewater Treatment Plants (WWTP). This study is aimed to evaluate the source, transport and fate of contaminants of industrial origin in a sewage grid discharging to a WWTP and finally to the sea. The sampling network covered an industrial and urban area and wastewaters, influents and effluents of a WWTP were analyzed using a newly developed multiresidual method to capture a wide range contaminants (phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs). Alkylphenols and phthalates followed by PAHs were the main compounds detected at levels between 0.01 to 698 microg l(-1) in the sewage pipelines. At the WWTP influent they were detected at concentrations up to 345 microg l(-1). The contaminant load was eliminated in a 64-92% during the primary and secondary treatment of the plant. However, alkylphenols, phthalates bisphenol A and traces of PAHs were discharged with the effluent, producing a total net input of 825 g d(-1) to the sea. The study of wastewaters herein proposed can be used to better predict the loads into WWTP to improve treatment conditions according to specific sewage inputs and to assess the risks associated with the continuous discharge of contaminants to receiving plants.

Presence and release of phthalic esters and other endocrine disrupting compounds in drinking water

SummaryAn analytical method was developed to analyze 5 phthalate esters (dimethylphthalate, diethylphthalate, di-n-butylphthalate, butylbenzylphthalate, di(2-ethylhexyl)phthalate), nonylphenol, bisphenol A and BADGE (Bisphenol A diglycyleter) in distribution and bottled water. They are all industrial chemicals used in the manufacture of epoxy resins or paints, polycarbonate and polyethylene plastics (global production of phthalates over 4 Mton/year) or surfactants and have been classified as persistent, with high migration potential from plastic containers and with endocrine disrupting properties. The present paper reports a specific extraction protocol using solid phase extraction with Oasis 60 mg or C18 cartridges, followed by gas chromalography coupled to mass spectrometric detection using an appropriate surrogate and internal standard for process control. Quality parameters are reported, making special emphasis to limits of detection, reproducibility and blank analysis, which permitted to detect ng L−1 concentrations. In an application step, the method was used to determine target compounds in 7 distribution water and 9 mineral water bottled in polyethylene, polyethyleneter phthalate and glass containers which were analysed upon purchase and after 10 week storage at temperatures up to 30 °C. Distribution water coming from different aquifers which at some point are in contact with plastic or painted concrete reservoirs and pipes, contained dimethylphthalate, diethylphtalate, nonylphenol, buthylbenzylphthtalate and DEHP at concentrations ranging from 0.005 to 0.331 μgL−1, depending on the sampled crea whereas bottled water showed levels up to 1.7 μg L−1 of some of the studied compounds, attributed to 10 week storage conditions.

Organic compounds in paper-mill process waters and effluents

Paper-mill effluents are characterized by the presence of color and suspended solids, bad smell, high concentration of nutrients that cause eutrophication of receiving waters, and high toxicity overall. This study attempts to give an overview of organic compounds that contribute to the toxicity of paper-mill waters and effluents, their levels, toxicological characterization and the methodologies used for their analysis. Families included are natural products, such as resin and fatty acids (wood extractives), additives used during paper-making, such as biocides, surfactants and phenolic compounds and by-products generated during bleaching, such as dioxins and furans. Several extraction methods, such as liquid-liquid extraction (LLE) or solid phase extraction (SPE) followed by gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS) with atmospheric pressure chemical ionization (APCI) or electrospray (ESP) are described and method performance is discussed for each family of compounds. This study contributes to the characterization of the organic fraction of paper-mill effluents and highlights elimination strategies.

Rapid degradation of fenitrothion in estuarine waters.

The degradation of fenitrothion under real environmental conditions was studied. Fenitrothion was applied in the irrigation ditches of the Ebre Delta (Tarragona, Catalonia) at an estimated concentration of 200 (situation 1) and 20 μg/L (situation 2) in order to eliminate the american crab (Procamburus clarkii). The evolution of the levels of fenitrothion and the formation of transformation products (TPs) were recorded during the 4 days after application. The TPs formed were 3-methyl-4-nitrophenol, fenitrooxon, and 5-methyl isomer of fenitrothion. The concentration of fenitrothion decayed sharply in 2 h with 6% and 0.3% of the initial concentrations in situations 1 and 2, respectively, and reached a steady state within 10 h with a concentration of 4 and 0.01 μg/L, respectively, which was constant for the 4 days the experiment lasted

Pressurized liquid extraction followed by liquid chromatography–mass spectrometry for the determination of alkylphenolic compounds in river sediment

A new methodology based on pressurized liquid extraction (PLE) followed by LC-MS is presented for the simultaneous and unequivocal determination of alkylphenol ethoxylates (APEOs) and their degradation products, alkylphenols (APs) and alkylphenoxy carboxylates (APECs), in sediment samples. The protocol, applicable to a full range of APEO oligomers and degradation products, permits the sensitive and selective determination of APEOs (nEO = 1-15), APECs (nEO = 0-1) and APs at low ppb levels (LODs = 1-5 microg/kg) in sediment samples. Optimization of the operational parameters of PLE clearly demonstrates that significant thermal losses of APs occur during extraction at elevated temperatures. The loss of octylphenol (OP) at 100 degrees C was 61.2% and of nonylphenol (NP) 40.0%, whereas other compounds were completely recovered. Thus, to avoid losses due to the volatility of alkylphenols, a low extraction temperature should be applied. The conditions that gave the best results for all target compounds were as follows: extraction solvent mixture, methanol-acetone (1:1, v/v); temperature, 50 degrees C; pressure, 1500 p.s.i.; two static cycles. Using PLE and a subsequent clean-up with solid-phase extraction (SPE), the simultaneous extraction of APEOs, APs and APECs from sediment samples was achieved yielding recoveries >70% and producing low MS background noise. The developed methodology was applied on a routine basis to the analysis of alkylphenolic compounds in sediment samples. APEOs and their persistent degradation products were detected in significant concentrations in sediments from Portuguese rivers, especially at sites situated in the proximity of industrial plants (mainly the textile industry). The total concentration of alkylphenolic compounds (APEOs+APs+APECs) ranged from 155 to 2400 microg/kg. Of all the alkylphenolic compounds, NP comprised 40 to 50% with concentrations up to 1172 microg/kg.

Priority and emerging flame retardants in rivers: Occurrence in water and sediment, Daphnia magna toxicity and risk assessment

The occurrence, partitioning and risk of eight polybrominated diphenyl ethers (PBDEs), nine new brominated (NBFRs) and ten organophosphorus flame retardants (OPFRs) were evaluated in three Spanish rivers suffering different anthropogenic pressures (Nalón, Arga and Besòs). OPFRs were ubiquitous contaminants in water (ΣOPFRs ranging from 0.0076 to 7.2μgL(-1)) and sediments (ΣOPFRs ranging 3.8 to 824μgkg(-1)). Brominated flame retardants were not detected in waters, whereas ΣPBDEs ranged from 88 to 812μgkg(-1) and decabromodiphenyl ethane (DBDPE) reached 435μgkg(-1) in sediments from the River Besòs, the most impacted river. The occurrence of flame retardants in river water and sediment was clearly associated with human activities, since the highest levels occurred near urban and industrial zones and after wastewater treatment plants discharge. Daphnia magna toxicity was carried out for OPFRs, the most ubiquitous flame retardants, considering individual compounds and mixtures. Toxicity of nine tested OPFRs differed largely among compounds, with EC50 values ranging over three magnitude orders (0.31-381mgL(-1)). Results evidenced that these compounds act by non-polar narcosis, since their toxicity was proportional to their lipophilicity (Kow). Furthermore, their joint toxicity was additive, which means that single and joint toxicity can be predicted knowing their concentration levels in water using quantitative structure activity relationships (QSARs) and predictive mixture models. Based on these results, a risk assessment considering joint effect was performed calculating and summing risk quotients (RQs) for the water and sediment samples. No significant risk to D. magna (ΣRQs <1) was observed for any of the monitored rivers.

Development of a multi-residue method for the determination of organic micropollutants in water, sediment and mussels using gas chromatography–tandem mass spectrometry

This study describes the development of a multiresidue method based on gas chromatography-electron ionization-tandem mass spectrometry (GC-EI-MS/MS) for the detection of sixteen polycyclic aromatic hydrocarbons (PAHs), five phthalate esters (PEs), seven polychlorinated biphenyls (PCBs), six polybrominated diphenyl ethers (PBDEs), six alkylphenols (APs), three organochlorined pesticides and their isomers or degradation products (OCPs) and bisphenol A in seawater, river water, wastewater treatment plant (WWTP) effluents, sediments and mussels. Solid phase extraction (SPE) was used for the extraction of target analytes in aqueous samples, and ultrasound assisted extraction for solid samples. GC-EI-MS/MS acquisition conditions in selected reaction monitoring (SRM) using two transitions per compound were optimized. In this way, quantification and unequivocal identification of organic micropollutants were performed in compliance with the Decision 2002/657/EC. Good linearity responses with coefficients of determination higher than 0.99 were obtained. Methodological detection limits (MDLs) in seawater ranged from 0.1 to 6 ng L(-1); in river water from 0.1 to 4.8 ng L(-1); in WWTP effluents from 1 to 75 ng L(-1); in sediments from 1 to 150 ng g(-1) and in mussels from 1 to 125 ng g(-1). MDLs and recovery yields were compared with other published methods and similarities or even improvements were achieved. The optimized method was applied to analyze five samples from each matrix collected in coastal areas, showing its potential use for marine pollution monitoring.

Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain).

The partitioning of alkylphenols in the dissolved and particulate matter of influents, effluents, accumulation onto sludge and the impact of sewage treatment plant upon receiving waters was studied along the Ter River basin (Catalonia, NE Spain). A solid-phase extraction or pressurized liquid extraction followed by liquid chromatography-mass spectrometry was developed and permitted to determine target compounds with high efficiency in waters, particulate material and sludge. Nonylphenol mono- and diethoxylate, nonylphenol and octylphenol partitioned preferably upon particulate matter and sludge, whereas long chain NPE(3-15)O prevailed in the dissolved phase and was released by effluents. Within the treatment process, a net accumulation of alkylphenols in sludge was found, producing up to 148g/t/month. The removal efficiency of alkylphenols was of 37-90% and depended on the treatment. Assessment on the fate of these contaminants within STPs is discussed in terms of flow rates, biological oxygen demand and tons of sludge produced.