Toxicity and underlying lipidomic alterations generated by a mixture of water disinfection byproducts in human lung cells.

Complex mixtures of disinfection by-products (DBPs) are present in disinfected waters, but their mixture toxicity has been rarely described. Apart from ingestion, DBP exposure can occur through inhalation, which may lead to respiratory effects in highly exposed individuals. However, the underlying biological mechanisms have yet to be elucidated. This study aimed to investigate the toxicity of a mixture of 10 DBPs, including haloacetic acids and haloaromatics, on human alveolar A549 cells by assessing their cytotoxicity, genotoxicity, and impact on the cell lipidome. A DBP mixture up to 50 µM slightly reduced cell viability, induced the generation of reactive oxygen species (ROS) up to 3.5-fold, and increased the frequency of micronuclei formation. Exposure to 50 µM DBP mixture led to a significant accumulation of triacylglycerides and a decrease of diacylglycerides and phosphatidylcholines in A549 cells. Lipidomic profiling of extracellular vesicles (EVs) released in the culture medium revealed a marked increase in cholesterol esters, sphingomyelins, and other membrane lipids. Overall, these alterations in the lipidome of cells and EVs may indicate a disruption of lipid homeostasis, and thus, potentially contribute to the respiratory effects associated with DBP exposure.

Non-regulated haloaromatic water disinfection byproducts act as endocrine and lipid disrupters in human placental cells.

The disinfection of drinking water generates hundreds of disinfection byproducts (DBPs), including haloaromatic DBPs. These haloaromatic DBPs are suspected to be more toxic than haloaliphatic ones, and they are currently not regulated. This work investigates their toxicity and ability to interfere with estrogen synthesis in human placental JEG-3 cells, and their genotoxic potential in human alveolar A549 cells. Among the haloaromatic DBPs studied, halobenzoquinones (2,6-dichloro-1,4-benzoquinone (DCBQ) and 2,6-dibromo-1,4-benzoquinone (DBBQ)) showed the highest cytotoxicity (EC50: 18-26 µg/mL). They induced the generation of very high levels of reactive oxygen species (ROS) and up-regulated the expression of genes involved in estrogen synthesis (cyp19a1, hsd17b1). Increased ROS was linked to significant depletion of polyunsaturated lipid species from inner cell membranes. The other DBPs tested showed low or no significant cytotoxicity (EC50 ≥ 100 µg/mL), while 2,4,6-trichloro-phenol (TCP), 2,4,6-tribromo-phenol (TBP) and 3,5-dibromo-4-hydroxybenzaldehyde (DCHB) induced the formation of micronuclei at concentrations much higher than those typically found in water (100 µg/mL). This study reveals the different modes of action of haloaromatic DBPs, and highlights the toxic potential of halobenzoquinones, which had a significant impact on the expression of placenta steroid metabolism related genes and induce oxidative stress, implying potential adverse health effects.

Prioritization of organic contaminants in a reclaimed water irrigation system using wide-scope LC-HRMS screening.

A prioritization procedure was developed and implemented at the local level to identify the most relevant organic contaminants of emerging concern (CECs) in an agricultural area irrigated with reclaimed water. A wide-scope screening methodology based on UPLC-HRMS analysis was applied to holistically characterize the CEC footprint in water and its spatial and temporal variations. One hundred and fifty-eight CECs, including pharmaceuticals, industrial chemicals, and pesticides, among others, were identified with a confidence level of 2 in the water samples investigated. After water treatment in the reclamation plant and transport within the irrigation channel network, more than a hundred compounds were still detected at the location where water is abstracted for crop irrigation. Compound ecotoxicity and occurrence (semi-quantified concentrations or peak intensity) were the parameters used to prioritize CECs in the water used for irrigation. Results pointed at venlafaxine, O-desmethyl-venlafaxine, galaxolidone, theophylline/paraxanthine, oxybenzone, and N-phenyl-1-naphtylamine, among others, as CECs of concern in the investigated area. This study provides a simple and cost-effective approach to detecting site-specific priority pollutants that could otherwise be overlooked by national or European regulations. The prioritization tool provided contributes to rationally designing monitoring and attenuation programs and efficiently managing water resources, by ensuring the safety of reclaimed water applications.

Human footprint on the water quality from the northern Antarctic Peninsula region.

This study assessed the human footprint on the chemical pollution of Antarctic waters by characterizing inorganic chemicals and selected organic anthropogenic contaminants of emerging concern (CECs) in inland freshwater and coastal seawater and the associated ecotoxicological risk. Nicotine and tolytriazole, present in 74% and 89% of the samples analyzed, respectively, were the most ubiquitous CECs in the investigated area. The most abundant CECs were citalopram, clarithromycin, and nicotine with concentrations reaching 292, 173, and 146 ng/L, respectively. The spatial distribution of CECs was not linked to any water characteristic or inorganic component. The contamination pattern by CECs in inland freshwater varied among locations, whereas it was very similar in coastal seawater. This suggests that concentrations in inland freshwater may be ruled by environmental processes (reemission from ice, atmospheric deposition, limited photo- and biodegradation processes, etc.) in addition to human activities. Following risk assessment, citalopram, clarithromycin, nicotine, venlafaxine, and hydrochlorothiazide should be considered of concern in this area, and hence, included in future monitoring of Antarctic waters and biota. This work provides evidence on the fact that current measures taken to protect the pristine environment of Antarctica from human activities are not effective to avoid CEC spread in its aquatic environment.

Genotoxicity and endocrine disruption potential of haloacetic acids in human placental and lung cells.

Chlorination of water results in the formation of haloacetic acids (HAAs) as major disinfection byproducts (DBPs). Previous studies have reported some HAAs species to act as cytotoxic, genotoxic, and carcinogenic. This work aimed at further exploring the toxicity potential of the most investigated HAAs (chloroacetic (CAA), bromoacetic (BAA), iodoacetic (IAA) acid) and HAAs species with high content of bromine (tribromoacetic acid (TBAA)), and iodine in their structures (chloroiodoacetic (CIAA) and diiodoacetic acid (DIAA)) to human cells. Novel knowledge was generated regarding cytotoxicity, oxidative stress, endocrine disrupting potential, and genotoxicity of these HAAs by using human placental and lung cells as in vitro models, not previously used for DBP assessment. IAA showed the highest cytotoxicity (EC50: 7.5 µM) and ability to generate ROS (up to 3-fold) in placental cells, followed by BAA (EC50: 20-25 µM and 2.1-fold). TBAA, CAA, DIAA, and CIAA showed no significant cytotoxicity (EC50 > 250 µM). All tested HAAs decreased the expression of the steroidogenic gene hsd17b1 up to 40 % in placental cells, and IAA and BAA (0.01-1 µM) slightly inhibited the aromatase activity. HAAs also induced the formation of micronuclei in A549 lung cells after 48 h of exposure. IAA and BAA showed a non-significant increase in micronuclei formation at low concentrations (1 µM), while BAA, CAA, CIAA and TBAA were genotoxic at exposure concentrations above 10 µM (100 µM in the case of DIAA). These results point to genotoxic and endocrine disruption effects associated with HAA exposure at low concentrations (0.01-1 µM), and the usefulness of the selected bioassays to provide fast and sensitive responses to HAA exposure, particularly in terms of genotoxicity and endocrine disruption effects. Further studies are needed to define thresholds that better protect public health.

Development of QuEChERS-based multiresidue analytical methods to determine pesticides in corn, grapes and alfalfa.

Analytical methods based on QuEChERS and liquid chromatography-tandem mass spectrometry were developed for the determination of 42 polar and semi-polar pesticides in three representative vegetable matrices, viz. corn, grapes and alfalfa. A 26-2 fractional factorial experimental design was used to cost-effectively optimize the extraction procedure. The optimal analytical approaches were validated in terms of linearity, sensitivity, trueness, and precision. Most of the target pesticides showed a relative recovery of 70-120 %. Moreover, limits of detection (between 0.01 ng/g and 20 ng/g) were below the maximum residue levels set for the target analytes in nearly all cases. Analysis of real samples showed the presence of five pesticides in grapes and alfalfa at concentrations between the method LOQs and 40 ng/g. To the authors' knowledge, these methods are the first ever described for the determination of 6, 13 and 24 of the 42 target pesticides measured in corn, grapes and alfalfa, respectively.

Assessing the skin irritation and sensitizing potential of concentrates of water chlorinated in the presence of iodinated X-ray contrast media.

Chemical disinfection of water provides significant public health benefits. However, disinfectants like chlorine can react with naturally occurring materials in the water to form disinfection byproducts (DBPs). Natural levels of iodine have been reported to be too low in some source waters to account for the levels of iodinated DBPs detected. Iodinated X-ray contrast media (ICM) have been identified as a potential source of iodine. The toxicological impact of ICM present in source water at the time of disinfection has not been fully investigated. Iopamidol, iohexol, iopromide, and diatrizoate are among the ICM most frequently detected in water. In this study, source water containing one of these four ICM was chlorinated; non-chlorinated ICM-containing water samples served as controls. Reactions were conducted at an ICM concentration of 5 µM and a chlorine dose of 100 µM over 72 hr. Water concentrates (20,000-fold) were prepared by XAD-resin/ethyl acetate extraction and DMSO solvent exchange. We used the MatTek® reconstituted human epithelial skin irritation model to evaluate the water concentrates and also assessed the dermal irritation and sensitization potential of these concentrates using the LLNA:BrdU ELISA in BALB/c mice. None of the water concentrates tested (2500X) resulted in a skin irritant response in the MatTek® skin irritation model. Likewise, none of the concentrates (2500X, 1250X, 625X, 312.5X, 156.25X) produced a skin irritation response in mice: erythema was minimal; the maximum increase in ear thickness was less than 25%. Importantly, none of the concentrates produced a positive threshold response for allergic skin sensitization at any concentration tested in the LLNA:BrdU ELISA. We conclude that concentrates of water disinfected in the presence of four different ICM did not cause significant skin irritation or effects consistent with skin sensitization at the concentrations tested.

Antibiotics in the Basque coast (N Spain): Occurrence in waste and receiving waters, and risk assessment (2017-2020).

The study of the presence of antibiotics in the aquatic environment is a preliminary step to analyse their possible harmful effects on aquatic ecosystems. In order to monitor their occurrence in the aquatic environment, the European Commission established in 2015, 2018, and 2020 three Watch Lists of substances for Union-wide monitoring (Decisions (EU) 2015/495, 2018/840, and 2020/1161), where some antibiotics within the classes of macrolides, fluoroquinolones and penicillins were included. In the Basque coast, northern Spain, three macrolide antibiotics (erythromycin, clarithromycin, azithromycin) and ciprofloxacin were monitored quarterly from 2017 to 2020 (covering a period before and after the COVID19 outbreak), in water samples collected from two Waste Water Treatment Plants (WWTPs), and three control points associated with receiving waters (transitional and coastal water bodies). This work was undertaken for the Basque Water Agency (URA). The three macrolide antibiotics in water showed a frequency of quantification >65 % in the Basque coast, with higher concentrations in the WWTP emission stations than in receiving waters. Their frequency of quantification decreased from 2017 to 2020, as did the consumption of antibiotics in Spanish primary care since 2015. Ciprofloxacin showed higher frequencies of quantification in receiving waters than in wastewaters, but the highest concentrations were observed in the WWTP emission stations. Although consumption of fluoroquinolones (among which is ciprofloxacin) in primary care in the Basque Country has decreased in recent years, this trend was not observed in the waters sampled in the present study. On the other hand, concentrations of clarithromycin, azithromycin, and ciprofloxacin in receiving waters exceeded their respective Predicted No-Effect Concentrations, so they could pose an environmental risk. These substances are widely used in human and animal medicine, so, although only ciprofloxacin is included in the third Watch List, it would be advisable to continue monitoring macrolides in the Basque coast as well.

QuEChERS-based analytical methods developed for LC-MS/MS multiresidue determination of pesticides in representative crop fatty matrices: Olives and sunflower seeds.

Oilseed crops are greatly extended all over the world. Their high fat content can interfere during pesticide multiresidue analysis through liquid chromatography-tandem mass spectrometry (LC-MS/MS). This work aimed at overcoming this issue by developing and validating two QuEChERS-based methods for LC-MS/MS determination of 42 pesticides in two fatty food matrices: olives and sunflower seeds. Optimization of the extraction method was achieved following a 26-2 fractional factorial design in a highly cost-effective way. Validation of the multi-residue methods demonstrated improved limits of detection, below the established maximum residue levels (MRLs) for almost all compounds, good precision, and trueness, in compliance with SANTE guidelines. Application of these methods to the analysis of real samples from the Iberian Peninsula showed the presence of some pesticides of relevant environmental concern, including four compounds contained in the Pesticide Action Network International list of highly hazardous pesticides, found at levels between 0.03 ng/g and 104 ng/g.

High-throughput analysis of the steroid profile in placental cell cultures to evaluate endocrine disrupting effects of contaminant exposure.

Human placental JEG-3 cells conserve a high P450 aromatase activity and are therefore suitable to evaluate how contaminants may interfere with the routes involved in estrogen synthesis during pregnancy. This has been traditionally assessed by measuring aromatase activity through the amount of tritiated water (3H2O) formed during the aromatization of 1ß-3H-androst-4-ene-3,17-dione (3H-AD). This work presents a greener and safer analytical approach for this purpose, which consists of the determination of the trace amounts of the steroids (estradiol, estrone, testosterone, and androstenedione) present in the culture medium. Turbulent flow chromatography coupled to liquid chromatography-tandem mass spectrometry (TFC-HPLC-MS/MS) delivered the high selectivity and sensitivity (limits of detection between 2 and 5 pg/mL) required for these measurements. Moreover, its automation allows high-throughput of samples with minimum sample handling and achieves high precision in the analysis (relative standard deviation values <6%). As a proof of concept, the method was applied to evaluate the effect of monohaloacetic acid exposure on the steroid profile of JEG-3 cells. Iodoacetic acid showed an estrogenic effect (statistically significant increase of estradiol levels compared to unexposed cells) at the highest concentration level tested (0.5 µM) that deserves further evaluation.

Fungal degradation of selected medium to highly polar pesticides by Trametes versicolor: kinetics, biodegradation pathways, and ecotoxicity of treated waters.

The massive use of pesticides represents one of the main causes of environmental deterioration, as they have adverse effects on non-target organisms. Thus, the development of technologies capable of reducing their release into the environment is urgently needed. This study reports for the first time the white-rot fungus Trametes versicolor as an alternative towards the degradation of medium to highly polar pesticides such as the organophosphate malathion, and the neonicotinoids acetamiprid and imidacloprid. Specifically, T. versicolor could completely remove 1 mg/L of malathion in an Erlenmeyer flask within 48 h, while experiments of acetamiprid and imidacloprid (4 mg/L), conducted in air-pulse fluidized bioreactors, resulted in degradation percentages of 20% and 64.7%, respectively, after 7 days of operation. Enzymatic exploration studies revealed that the cytochrome P450 system, instead of the extracellular enzyme laccase, is involved in the degradation of acetamiprid and imidacloprid. The degradation pathways were proposed based on the main transformation products (TPs) formed in the solutions: seven in the case of malathion, and two and one in the case of imidacloprid and acetamiprid, respectively. Although the TPs identified were predicted to be less toxic than the investigated pesticides, the toxicity of the individual solutions slightly increased throughout the degradation process, according to the Microtox assay. However, the solution toxicity was always below the threshold established in the local regulation. Although additional research is needed to implement this treatment at a pilot plant scale, this work highlights the potential of T. versicolor to bio-remediate pesticide-contaminated waters.

Evaluation of an outdoor pilot-scale tubular photobioreactor for removal of selected pesticides from water.

This work assesses the capacity of a microalgae-based system to remove three highly to medium polar pesticides typically found in freshwater: acetamiprid, bentazone, and propanil. Degradation of the pesticides was firstly studied individually at batch lab-scale reactors and abiotic and heated-killed controls were employed to clarify their removal pathways. At lab-scale, propanil and acetamiprid were completely removed after 7 days whereas bentazone was not removed. Four and two transformation products (TPs) were generated in the biodegradation process for acetamiprid and propanil, respectively. Then, the simultaneous removal of the pesticides was assessed in an outdoor pilot photobioreactor, operated with a hydraulic residence time of 8 days. During the steady-state, high removal efficiencies were observed for propanil (99%) and acetamiprid (71%). The results from batch experiments suggest that removal is mainly caused by algal-mediated biodegradation. Acetamiprid TPs raised throughout the operational time in the photobioreactor, while no propanil TP was detected at the pilot-scale. This suggests complete mineralization of propanil or residual formation of its TPs at concentrations below the analytical method detection limit. Aiming at biomass valorization, diverse microalgae harvesting methods were investigated for biomass concentration, and the effect of residual pesticides on the biogas yield was determined by biochemical methane potential tests. Anaerobic digestion was not inhibited by the pesticides as verified by the digestion performance. The results highlight the potential of microalgae-based systems to couple nutrient removal, biomass production, micropollutant biodegradation, and biofuel production.

What's in the water? - Target and suspect screening of contaminants of emerging concern in raw water and drinking water from Europe and Asia.

There is growing worry that drinking water can be affected by contaminants of emerging concern (CECs), potentially threatening human health. In this study, a wide range of CECs (n = 177), including pharmaceuticals, pesticides, perfluoroalkyl substances (PFASs) and other compounds, were analysed in raw water and in drinking water collected from drinking water treatment plants (DWTPs) in Europe and Asia (n = 13). The impact of human activities was reflected in large numbers of compounds detected (n = 115) and high variation in concentrations in the raw water (range 15-7995 ng L-1 for ∑177CECs). The variation was less pronounced in drinking water, with total concentration ranging from 35 to 919 ng L-1. Treatment efficiency was on average 65 ± 28%, with wide variation between different DWTPs. The DWTP with the highest ∑CEC concentrations in raw water had the most efficient treatment procedure (average treatment efficiency 89%), whereas the DWTP with the lowest ∑177CEC concentration in the raw water had the lowest average treatment efficiency (2.3%). Suspect screening was performed for 500 compounds ranked high as chemicals of concern for drinking water, using a prioritisation tool (SusTool). Overall, 208 features of interest were discovered and three were confirmed with reference standards. There was co-variation between removal efficiency in DWTPs for the target compounds and the suspected features detected using suspect screening, implying that removal of known contaminants can be used to predict overall removal of potential CECs for drinking water production. Our results can be of high value for DWTPs around the globe in their planning for future treatment strategies to meet the increasing concern about human exposure to unknown CECs present in their drinking water.

The embodiment of wastewater data for the estimation of illicit drug consumption in Spain.

Data obtained from wastewater analysis can provide rapid and complementary insights in illicit drug consumption at community level. Within Europe, Spain is an important country of transit of both cocaine and cannabis. The quantity of seized drugs and prevalence of their use rank Spain at the top of Europe. Hence, the implementation of a wastewater monitoring program at national level would help to get better understanding of spatial differences and trends in use of illicit drugs. In this study, a national wastewater campaign was performed for the first time to get more insight on the consumption of illicit drugs within Spain. The 13 Spanish cities monitored cover approximately 6 million inhabitants (12.8% of the Spanish population). Untreated wastewater samples were analyzed for urinary biomarkers of amphetamine, methamphetamine, MDMA, cocaine, and cannabis. In addition, weekend samples were monitored for 17 new psychoactive substances. Cannabis and cocaine are the most consumed drugs in Spain, but geographical variations showed, for instance, comparatively higher levels of methamphetamine in Barcelona and amphetamine in Bilbao, with about 1-fold higher consumption of these two substances in such metropolitan areas. For amphetamine, an enantiomeric profiling was performed in order to assure the results were due to consumption and not to illegal dumping of production residues. Furthermore, different correction factors for the excretion of cannabis were used to compare consumption estimations. All wastewater results were compared with previously reported data, national seizure data and general population survey data, were a reasonable agreement was found. Daily and yearly drug consumption were extrapolated to the entire Spanish population with due precautions because of the uncertainty associated. These data was further used to estimate the retail drug market, where for instance cocaine illicit consumption alone was calculated to contribute to 0.2-0.5% of the Spanish gross domestic product (ca. 3000-6000 million Euro/year).

Boosting pharmaceutical removal through aeration in constructed wetlands.

This work evaluated the removal efficiency of 13 wastewater-borne pharmaceuticals in a pilot constructed wetland (CW) operated under different aeration strategies (no aeration, intermittent and continuous). Aeration improved the removal of conventional wastewater parameters and the targeted micropollutants, compared to the non-aerated treatment. Reduction of chemical oxygen demand (COD) and total nitrogen (TN) was slightly higher applying intermittent aeration than applying continuous aeration, the opposite was observed for the investigated pharmaceuticals. Seven targeted compounds were found in influent wastewater, and five of them (acetaminophen, diclofenac, ketoprofen, bezafibrate and gemfibrozil) were efficiently removed (> 83%) in the aerated systems. The overall risk of the investigated samples against aquatic ecosystems was moderate, decreasing in the order influent > no aeration > intermittent aeration > continuous aeration, based on the hazard quotient approach. Lorazepam, diclofenac and ketoprofen were the pharmaceuticals that could contribute the most to this potential environmental impact of the CW effluents after discharge. To the authors' knowledge this is the first sound study on the removal and fate of ketoprofen, bezafibrate, and lorazepam in aerated CWs, and provides additional evidence on the removal and fate of acetaminophen, diclofenac, gemfibrozil, and carbamazepine in this type of bioremediation systems at pilot plant scale.

Contaminants of emerging concern in the Basque coast (N Spain): Occurrence and risk assessment for a better monitoring and management decisions.

The study of the presence in the aquatic environment of certain substances considered as contaminants of emerging concern (CEC) is a preliminary step to the analysis of the possible harmful effects on aquatic ecosystems and the establishment of the corresponding environmental quality standards. In order to monitor the occurrence of CECs in the aquatic environment, the European Commission established in 2015 and 2018 two watch-list of substances for Union-wide monitoring in the field of water policy (Decision (EU) 2015/495 and Decision (EU) 2018/840). In the coast of the Basque Country, southeast of the Bay of Biscay, 19 of these watch list substances were monitored quarterly from May 2017 to March 2019. Water samples were collected at the effluent of three wastewater treatment plants and five control points associated with receiving waters (transitional and coastal water bodies). The most frequently quantified substances were azithromycin (91%), imidacloprid (82%), clarithromycin (80%), diclofenac (78%) and erythromycin (73%), with frequencies of quantification higher in wastewaters (83-100%) than in receiving waters (70-85%). In general, concentrations in wastewater were also higher than in receiving waters, indicating a dilution effect in the environment. In receiving waters, six out of the nineteen substances monitored exceeded their respective Predicted No-Effect Concentrations: azithromycin (34%), imidacloprid (9%), 17ß-estradiol (E2) (9%), clarithromycin (7%), ciprofloxacin (7%), and diclofenac (5%); and therefore, their levels could pose an environmental risk.

Drugs of abuse and their metabolites in river sediments: Analysis, occurrence in four Spanish river basins and environmental risk assessment.

The environmental impact produced by the presence of drugs of abuse in sediments has been scarcely studied to date, even though many of them may adsorb onto particulate matter due to their physical-chemical properties. This study presents an analytical method for the determination of 20 drugs of abuse and metabolites in sediments. The validated method was satisfactory in terms of linearity (r2 >0.99), recovery (90-135 %), repeatability (relative standard deviations <15 %), sensitivity (limits of quantification <2.1 ng/g d.w, except for cannabinoids), and matrix effects (ionization suppression <40 %). The method was applied to the analysis of 144 sediments collected in four Spanish river basins. Cocaine, methadone, and its metabolite 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) were the most ubiquitous compounds (detection frequencies>36 %), whereas cannabinol, Δ9-tetrahydrocannabinol (THC), and methadone were the most abundant compounds (up to 44, 37, and 33 ng/g d.w, respectively). The presence of EDDP, THC, and methadone in the sediments of 28 locations may pose a risk to sediment-dwelling organisms. To the author`s knowledge, this is the most extensive study conducted so far on the occurrence of drugs of abuse in sediments, and the first time that sediment-water distribution coefficients for EDDP, methadone, MDMA, and diazepam are reported from field observations.

Assessing population exposure to phthalate plasticizers in thirteen Spanish cities through the analysis of wastewater.

Phthalates are widely used plasticizers that produce endocrine-disrupting disorders. Quantifying exposure is crucial to perform risk assessments and to develop proper health measures. Herein, a wastewater-based epidemiology approach has been applied to estimate human exposure to six of the mostly used phthalates within the Spanish population. Wastewater samples were collected over four weekdays from seventeen wastewater treatment plants serving thirteen cities and ca. 6 million people (12.8 % of the Spanish population). Phthalate metabolite loads in wastewater were transformed into metabolite concentrations in urine and into daily exposure levels to the parent phthalates. Considering all the sampled sites, population-weighted overall means of the estimated concentrations in urine varied between 0.7 ng/mL and 520 ng/mL. Very high levels, compared to human biomonitoring data, were estimated for monomethyl phthalate, metabolite of dimethyl phthalate. This, together with literature data pointing to other sources of this metabolite in sewage led to its exclusion for exposure assessments. For the remaining metabolites, estimated concentrations were closer to those found in urine. Their 4-days average exposure levels ranged from 2 to 1347 µg/(day∙inh), exceeding in some sites the daily exposure thresholds set for di-i-butyl phthalate and di-n-buthyl phthalate by the European Food Safety Authority.

Investigative monitoring of pesticide and nitrogen pollution sources in a complex multi-stressed catchment: The lower Llobregat River basin case study (Barcelona, Spain).

The management of the anthropogenic water cycle must ensure the preservation of the quality and quantity of water resources and their careful allocation to the different uses. Protection of water resources requires the control of pollution sources that may deteriorate them. This is a challenging task in multi-stressed catchments. This work presents an approach that combines pesticide occurrence patterns and stable isotope analyses of nitrogen (δ15N-NO3-, δ15N-NH4+), oxygen (δ18O-NO3-), and boron (δ11B) to discriminate the origin of pesticides and nitrogen-pollution to tackle this challenge. The approach has been applied to a Mediterranean sub-catchment subject to a variety of natural and anthropogenic pressures. Combining the results from both analytical approaches in selected locations of the basin, the urban/industrial activity was identified as the main pressure on the quality of the surface water resources, and to a large extent also on the groundwater resources, although agriculture may play also an important role, mainly in terms of nitrate and ammonium pollution. Total pesticide concentrations in surface waters were one order of magnitude higher than in groundwaters and believed to originate mainly from soil and/or sediments desorption processes and urban and industrial use, as they were mainly associated with treated wastewaters. These findings were supported by the stable isotope results that pointed to an organic origin of nitrate in surface waters and most groundwater samples. Ammonium pollution observed in some aquifer locations is probably generated by nitrate reduction. Overall, no significant attenuation processes could be inferred for nitrate pollution. The approach presented here exemplifies the investigative monitoring envisioned in the Water Framework Directive.

Evaluation of the occurrence and fate of pesticides in a typical Mediterranean delta ecosystem (Ebro River Delta) and risk assessment for aquatic organisms.

Delta ecosystems are areas of high ecologic and economic values, where wildlife commonly shares the territory with intensive agricultural activities, particularly, rice cultivation and seafood production. This work aimed at evaluating the occurrence of a wide spectrum of pesticides and transformation products in the water of irrigation and drainage channels of the Ebro River Delta (NE Spain) during the main rice-growing season, when pesticide application is at its peak. Furthermore, the impact that these contaminants may have on local ecosystems and seafood production activities was assessed. A total of 35 pesticides, mainly associated with rice cultivation, out of the 66 analyzed were detected. Bentazone, propanil, MCPA, acetamiprid, and triallate were found at the µg/L level. Cybutryne, despite being banned in the European Union, was measured for the first time in the area and at concentrations above its environmental quality standard (11-49 ng/L). Sixteen additional banned pesticides were also detected at trace levels, likely due to their desorption from soil and sediment particles. Despite its dilution when discharged into the bay, this study demonstrates that the agricultural use of pesticides may have important effects on water quality and may cause a serious hazard for aquatic non-target organisms, although other factors such as temperature and salinity may play also a relevant role. Bentazone, cybutryne, dicofol, imidacloprid, MCPA, and propanil may pose a moderate to high risk for aquatic organisms at the concentration levels measured during the rice-growing season. The co-occurrence of pesticides may result in a high risk for aquatic organisms in all sampling locations. The finding of the EU Watch List insecticides imidacloprid and acetamiprid at concentrations above their maximum acceptable method detection limit calls for control of their use and revision of their legal status.