Priority and emerging organic microcontaminants in three Mediterranean river basins: Occurrence, spatial distribution, and identification of river basin specific pollutants.

There is a worldwide growing use of chemicals by our developed, industrialized, and technological society. More than 100,000 chemical substances are thus commonly used both by industry and households. Depending on the amount produced, physical-chemical properties, and mode of use, many of them may reach the environment and, notably, the aquatic receiving systems. This may result in undesirable and harmful side-effects on both the human and the ecosystem's health. Mediterranean rivers are largely different from Northern and Central European rivers in terms of hydrological regime, climate conditions (e.g. air temperature, solar irradiation, precipitation), and socio-economics (e.g. land use, tourism, crop types, etc.), with all these factors leading to differences in the relative importance of the environmental stressors, in the classes and levels of the pollutants found and their environmental fate. Furthermore, water scarcity might be critical in affecting water pollution because of the lowered dilution capacity of chemicals. This work provides raw chemical data from different families of microcontaminants identified in three selected Mediterranean rivers (the Sava, Evrotas, and Adige) collected during two sampling campaigns conducted in 2014 and 2015 in three different matrices, namely, water, sediments, and biota (fish). More than 200 organic micropollutants were analyzed, including relevant groups like pharmaceuticals, personal care products, perfluorinated compounds, pesticides, pyrethroid insecticides, flame retardants, and persistent organic pollutants. Data obtained were summarized with some basic statistics for all compound families and matrices analyzed. Observed occurrence and spatial patterns were interpreted both in terms of compound physical-chemical properties and local environmental pressures. Finally, their spatial distribution was examined and their ecotoxicological risk in the water phase was assessed. This allowed locating, at each basin, the most polluted sites ("hot spots") and identifying the respective river basin specific pollutants (RBSPs), prioritizing them in terms of the potential ecotoxicological risk posed to the aquatic ecosystems.

Riverine anthropogenic litter load to the Mediterranean Sea near the metropolitan area of Barcelona, Spain.

Every year >4 million tonnes of plastic are estimated to enter the oceans and much of it comes from land-based sources through rivers and estuaries. To fill the lack of information related to plastic inputs from rivers, a harmonized approach based on visual observations for monitoring floating macro litter was followed in this work. We provide the results of one-year monitoring (October 2016-September 2017) in the Llobregat and El Besòs rivers, which are flowing through an industrialized and populated area nearby the city of Barcelona (Catalonia, NE Spain). Floating litter items categories were influenced by urban centres located along the rivers. Overall, similar litter composition was observed in both rivers with a prevalence of plastics, mainly related to the food and beverage sectors. Seasonal variability showed significant correlations with natural factors such as wind and rainfall. Approximately 0.4-0.6 tonnes of plastic per year were estimated to be loaded into the sea by these two Catalan rivers. This study contributes to enlarge our knowledge on anthropogenic riverine litter entering the NW Mediterranean Sea, providing a starting point for the development of further mitigation strategies.

Environmental risks associated with contaminants of legacy and emerging concern at European aquaculture areas.

The contamination of marine ecosystems by contaminants of emerging concern such as personal care products or per- and polyfluoroalkyl substances is of increasing concern. This work assessed the concentrations of selected contaminants of emerging concern in water and sediment of European aquaculture areas, to evaluate their co-variation with legacy contaminants (polycyclic aromatic hydrocarbons) and faecal biomarkers, and estimate the risks associated with their occurrence. The 9 study sites were selected in 7 European countries to be representative of the aquaculture activities of their region: 4 sites in the Atlantic Ocean and 5 in the Mediterranean Sea. Musks, UV filters, preservatives, per- and polyfluoroalkyl substances and polycyclic aromatic hydrocarbons were detected in at least one of the sites with regional differences. While personal care products appear to be the main component of the water contamination, polycyclic aromatic hydrocarbons were mostly found in sediments. As expected, generally higher levels of personal care products were found in sewage impacted sites, urbanised coasts and estuaries. The risk assessment for water and sediment revealed a potential risk for the local aquatic environment from contaminants of both legacy and emerging concern, with a significant contribution of the UV filter octocrylene. Despite marginal contributions of per- and polyfluoroalkyl substances to the total concentrations, PFOS (perfluorooctane sulfonate) aqueous concentrations combined to its low ecotoxicity thresholds produced significant hazard quotients indicating a potential risk to the ecosystems.

Medium to highly polar pesticides in seawater: Analysis and fate in coastal areas of Catalonia (NE Spain).

Pollution has been less investigated in marine and coastal environments than in inland waters. The low levels at which pollutants are expected to be present in seawater calls for the use of reliable and high sensitivity analytical methodologies. In this context, this work presents the optimization and validation of an analytical method to determine 26 medium to highly polar pesticides in seawater based on solid phase extraction and liquid chromatography-tandem mass spectrometry detection. The developed methodology was linear, accurate (relative recoveries within 80-120% for most analytes), repeatable (relative standard deviations <18% for most analytes), and sensitive (limits of determination <1 ng/L for 89% of the compounds). The use of isotopically labeled compounds as surrogate standards compensated for low analyte recoveries and matrix effects. The method was applied to the analysis of seawater samples collected along the coastline of Catalonia (NE Spain). Overall, total pesticide loads were higher inside the marinas than outside. The booster biocides diuron and irgarol used in antifouling paintings and different triazine pesticides were the most abundant compounds. Irgarol was present above the maximum allowable concentration set in European regulations in 70% of the samples collected inside the marinas. A different pesticide pollution pattern, with MCPA and bentazone presenting the highest concentrations, was observed at the Ebro Delta area due to the impact of the agricultural activities carried out there. To the authors' knowledge, 4 out of the 26 target pesticides, namely, chlorfenvinphos, fenthion oxon, fenthion sulfone, and fenthion sulfoxide, have not been previously investigated in seawater.

Halogenated and organophosphorus flame retardants in European aquaculture samples.

This work monitors flame retardants in sediment, mussel and water samples from European fish farms. Polybrominated diphenyl ethers (PBDEs) were detected in 95% of the sediment and mussel samples with mean levels of 8.60±22.6ngg-1 dw in sediments and 0.07±0.18ngg-1 dw in mussels. BDE-209 was the main contributor for the sediments and BDE-47 was found in about 60% of the samples of both matrices. Pentabromoethylbenzene (PBEB) and hexabromobenzene (HBB) were detected in 42% of the sediments, but not in mussels. Decabromodiphenyl ethane (DBDPE) was found in about 55% of the samples of both matrices. The same happened for dechloranes in mussels, but they were detected in 92% of the sediments. Syn-DP and anti-DP were always the main contributors. Methoxylated PBDEs (MeO-PBDEs) were detected in all mussels and some sediments, mainly 6-MeO-BDE-47 and 2'-MeO-BDE-68. Organophosphorus flame retardants (OPFRs) were found in all matrices with concentrations of 0.04-92.8ngg-1 dw in sediment, 0.50-102ngg-1 dw in mussel and 0.43-867ngl-1 in water. Only OPFRs were analysed in water samples as halogenated flame retardants and MeO-PBDEs are highly unlikely to be detected in water due to their physicochemical properties. Flame retardants have no application in fish farming so results should reflect the impact of human activity on the farm locations. A large majority of the most contaminated samples were collected from sampling spots that were at urban shores or in enclosed water bodies not completely open to the sea.

Pharmaceuticals and pesticides in reclaimed water: Efficiency assessment of a microfiltration-reverse osmosis (MF-RO) pilot plant.

Water reuse is becoming a common practice in several areas in the world, particularly in those impacted by water scarcity driven by climate change and/or by rising human demand. Since conventional wastewater treatment plants (WWTPs) are not able to efficiently remove many organic contaminants and pathogens, more advanced water treatment processes should be applied to WWTP effluents for water reclamation purposes. In this work, a pilot plant based on microfiltration (MF) followed by reverse osmosis (RO) filtration was applied to the effluents of an urban WWTP. Both the WWTP and the pilot plant were investigated with regards to the removal of a group of relevant contaminants widely spread in the environment: 28 pharmaceuticals and 20 pesticides. The combined treatment by the MF-RO system was able to quantitatively remove the target micropollutants present in the WWTP effluents to values either in the low ng/L range or below limits of quantification. Monitoring of water quality of reclaimed water and water reclamation sources is equally necessary to design the most adequate treatment procedures aimed to water reuse for different needs.

Assessment of perfluoroalkyl substances in food items at global scale.

This study assessed the levels of 21 perfluoroalkyl substances (PFASs) in 283 food items (38 from Brazil, 35 from Saudi Arabia, 174 from Spain and 36 from Serbia) among the most widely consumed foodstuffs in these geographical areas. These countries were chosen as representatives of the diet in South America, Western Asia, Mediterranean countries and South-Eastern Europe. The analysis of foodstuffs was carried out by turbulent flow chromatography (TFC) combined with liquid chromatography with triple quadrupole mass spectrometry (LC-QqQ-MS) using electrospray ionization (ESI) in negative mode. The analytical method was validated for the analysis of different foodstuff classes (cereals, fish, fruit, milk, ready-to-eat foods, oil and meat). The analytical parameters of the method fulfill the requirements specified in the Commission Recommendation 2010/161/EU. Recovery rates were in the range between 70% and 120%. For all the selected matrices, the method limits of detection (MLOD) and the method limits of quantification (MLOQ) were in the range of 5 to 650 pg/g and 17 to 2000 pg/g, respectively. In general trends, the concentrations of PFASs were in the pg/g or pg/mL levels. The more frequently detected compounds were perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA). The prevalence of the eight-carbon chain compounds in biota indicates the high stability and bioaccumulation potential of these compounds. But, at the same time, the high frequency of the shorter chain compounds is also an indication of the use of replacement compounds in the new fluorinated materials. When comparing the compounds profile and their relative abundances in the samples from diverse origin, differences were identified. However, in absolute amounts of total PFASs no large differences were found between the studied countries. Fish and seafood were identified as the major PFASs contributors to the diet in all the countries. The total sum of PFASs in fresh fish and seafood was in the range from the MLOQ to 28ng/g ww. According to the FAO-WHO diets composition, the daily intake (DI) of PFASs was calculated for various age and gender groups in the different diets. The total PFASs food intake was estimated to be between 2300 and 3800 ng /person per day for the different diets. Finally, the risk intake (RI) was calculated for selected relevant compounds. The results have indicated that by far in no case the tolerable daily intake (TDI) (150, 1500, 50,000, 1,000,000, 150, 1500 ng/kg body weight, for perfluorohexanesulfonate (PFHxS), fluorotelomer alcohol (FTOH), perfluorobutanesulfonic acid (PFBS), perfluorobutanoic acid (PFBA), PFOS and PFOA, respectively) was exceeded.

Four-year advanced monitoring program of polar pesticides in groundwater of Catalonia (NE-Spain).

Pesticide contamination of groundwater is of paramount importance because it is the most sensitive and the largest body of freshwater in the European Union. In this paper, an isotopic dilution method based on on-line solid phase extraction-liquid chromatography (electrospray)-tandem mass spectrometry (SPE-LC(ESI)-MS/MS) was used for the analysis of 22 pesticides in groundwater. Results were evaluated from monitoring 112 wells and piezometers coming from 29 different aquifers located in 18 ground water bodies (GWBs), from Catalonia, Spain, for 4 years as part of the surveillance and operational monitoring programs conducted by the Catalan Water Agency. The analytical method developed allows the determination of the target pesticides (6 triazines, 4 phenylureas, 4 organophosphorous, 1 anilide, 2 chloroacetanilides, 1 thiocarbamate, and 4 acid herbicides) in groundwater with good sensitivity (limits of detection <5 ng/L), accuracy (relative recoveries between 85 and 116%, except for molinate), and repeatability (RSD<23%), and in a fully automated way. The most ubiquitous compounds were simazine, atrazine, desethylatrazine and diuron. Direct relation between frequency of detection of each target compound and Groundwater Ubiquity Score index (GUS index) is observed. Desethylatrazine and deisopropylatrazine, metabolites of atrazine and simazine, respectively, presented the highest mean concentrations. Compounds detected in less than 5% of the samples were cyanazine, molinate, fenitrothion and mecoprop. According to the Directive 2006/118/EC, 13 pesticides have individual values above the requested limits (desethylatrazine, atrazine and terbuthylazine lead the list) and 14 samples have total pesticide levels above 500 ng/L. The GWB with the highest levels of total pesticides is located in Lleida (NE-Spain), with 9 samples showing total pesticide levels above 500 ng/L. Several factors such as regulation of the use of pesticides, type of activities in the area, and irrigation were discussed in relation to the observed levels of pesticides.

Development of a multiresidue method for analysis of pesticides in sediments based on isotope dilution and liquid chromatography-electrospray-tandem mass spectrometry.

Because of the complexity of the sediment matrix, selective methods are necessary to identify and quantify different kinds of pesticides at a time. In this context, a multiresidue method based on isotope dilution and final analysis by liquid chromatography-electrospray-tandem mass spectrometry (LC-ESI-MS/MS) was developed for the determination of 26 pesticides and transformation products in sediment. The method developed comprises pressurized liquid extraction (PLE) and further purification of the extract by solid phase extraction (SPE) prior to analysis. In the process of method optimization various SPE cartridges as well as PLE and SPE elution solvents were evaluated. Due to the relatively high volatility of some compounds (e.g., propanil), special attention was paid to the evaporation step. Experiments comparing different pressures and times during solvent evaporation were performed with the aim to improve the recovery of these compounds. Matrix effects were also studied even though they were corrected through the use of 23 deuterated compounds as surrogate standards for quantification. The analytical method developed showed good validation parameters in terms of linearity, sensitivity (limits of detection in the pgg(-1) or low ngg(-1) range and limits of determination below 80ngg(-1)), accuracy (relative recoveries between 92 and 118%, except for malaoxon (66.5%)), and repeatability (relative standard deviations between 1.5 and 17%, for all compounds except the acidic herbicides). Its main advantage is the simultaneous analysis of pesticides with a large variety of physical-chemical properties, as well as its improved accuracy due to the use of the isotope dilution method. Application of the method to the analysis of 5 real samples from 4 different Spanish rivers revealed the presence of 5 of the 26 target compounds, being chlorpyrifos, diuron and diazinon the most ubiquitous, as expected, due to their high bioaccumulation and low mobility features.

Occurrence and behavior of pesticides in wastewater treatment plants and their environmental impact.

Reports on pesticides elimination during wastewater treatment are rare since these substances are typically considered of agricultural rather than of urban origin. In this context, the aim of this work was to evaluate the presence, removal and environmental relevance of 22 selected pesticides in three different wastewater treatment plants (WWTPs), paying attention not only to their occurrence and elimination but also to the toxicity of each pesticide against three aquatic micro organisms (algae, daphnia and fish) through the calculation of the so-named Environmental Relevance of Pesticides from Wastewater treatment plants Index (ERPWI). For this purpose, an analytical method based on isotope dilution on-line solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was optimized, allowing the determination of the 22 target pesticides in wastewater with satisfactory sensitivity (limits of detection below 30 ng/L), accuracy and precision. Concerning the results, total pesticide levels were in most instances below 1 µg/L but removal in the WWTPs was variable and often poor, with concentrations in the effluent sometimes higher than in the corresponding influent. Possible explanations for these poor or negative removal rates are, among many others considered (e.g. sampling, sample preservation, method biases, atmospheric deposition), deconjugation of metabolites and/or transformation products of the pesticides, hydrolysis, and desorption from particulate matter during wastewater treatment. The most significant pesticides in terms of concentration and frequency of detection were diazinon and diuron. These two pesticides, followed by atrazine, simazine and malathion, were also the most relevant from the environmental point of view, according to the calculated ERPWI.

Are pesticide residues associated to rice production affecting oyster production in Delta del Ebro, NE Spain?

Pesticide usage in Delta del Ebro (NE Spain) during the rice growing season has been associated with oyster episodes of mortality that occur early in summer. However, there are no studies that have directly evaluated pesticide levels and effects in oysters (Crassotrea gigas) cultured in Ebro's Bays. In this study pesticide levels in water, metal body burdens and up to 12 different biochemical markers were monitored in gills and digestive glands of oysters transplanted from May to June in 2008 and 2009. Biochemical responses evidenced clear differences in oysters from 2008 and 2009. Oysters transplanted in 2009 showed their antioxidant defenses unaffected from May to June and consequently increased levels of tissue damage measured as lipid peroxidation and DNA strand breaks and of mortality rates. Conversely oysters transplanted in 2008 increase their antioxidant defenses from May to June, had low levels of lipid peroxidation and DNA damage and low mortality rates. Some pesticides in water such as bentazone and propanil together with high temperatures and salinity levels were related with tissue damage in oyster transplanted in 2008 but the observed large differences between years indicate that abiotic factors alone could not explain the high mortalities observed in 2009. An analysis of recent reported studies pointed out in the direction that in addition to abiotic factors the use of oysters sensitive to diseases may explain the observed responses.

Formation of diclofenac and sulfamethoxazole reversible transformation products in aquifer material under denitrifying conditions: batch experiments.

Soil-aquifer processes have proven to work as a natural treatment for the attenuation of numerous contaminants during artificial recharge of groundwater. Nowadays, significant scientific effort is being devoted to understanding the fate of pharmaceuticals in subsurface environments, and to verify if such semipersistent organic micropollutants could also be efficiently removed from water. In this context we carried out a series of batch experiments involving aquifer material, selected drugs (initial concentration of 1 µg/L and 1 mg/L), and denitrifying conditions. Diclofenac and sulfamethoxazole exhibited an unreported and peculiar behavior. Their concentrations consistently dropped in the middle of the tests but recovered toward the end, which suggest a complex effect of denitrifying conditions on aromatic amines. The transformation products Nitro-Diclofenac and 4-Nitro-Sulfamethoxazole were detected in the biotic experiments, while nitrite was present in the water. Their concentrations developed almost opposite to those of their respective parent compounds. We conjecture that this temporal and reversible effect of denitrifying conditions on the studied aromatic amines could have significant environmental implications, and could explain at least partially the wide range of removals in subsurface environments reported in literature for DCF and SMX, as well as some apparent discrepancies on SMX behavior.

Analysis of the occurrence and risk assessment of polar pesticides in the Llobregat River Basin (NE Spain).

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L(-1), respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L(-1), were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.

Microcosm experiments to control anaerobic redox conditions when studying the fate of organic micropollutants in aquifer material.

The natural processes occurring in subsurface environments have proven to effectively remove a number of organic pollutants from water. The predominant redox conditions revealed to be one of the controlling factors. However, in the case of organic micropollutants the knowledge on this potential redox-dependent behavior is still limited. Motivated by managed aquifer recharge practices microcosm experiments involving aquifer material, settings potentially feasible in field applications, and organic micropollutants at environmental concentrations were carried out. Different anaerobic redox conditions were promoted and sustained in each set of microcosms by adding adequate quantities of electron donors and acceptors. Whereas denitrification and sulfate-reducing conditions are easily achieved and maintained, Fe- and Mn-reduction are strongly constrained by the slower dissolution of the solid phases commonly present in aquifers. The thorough description and numerical modeling of the evolution of the experiments, including major and trace solutes and dissolution/precipitation of solid phases, have been proven necessary to the understanding of the processes and closing the mass balance. As an example of micropollutant results, the ubiquitous beta-blocker atenolol is completely removed in the experiments, the removal occurring faster under more advanced redox conditions. This suggests that aquifers constitute a potentially efficient alternative water treatment for atenolol, especially if adequate redox conditions are promoted during recharge and long enough residence times are ensured.

Wastewater reuse in Mediterranean semi-arid areas: The impact of discharges of tertiary treated sewage on the load of polar micro pollutants in the Llobregat river (NE Spain).

The presence of sewage-borne micro contaminants in environmental waters is directly related to the discharge of treated effluents from wastewater treatment plants (WWTP) and the flow rate of the receiving river waters. Mediterranean rivers, in particular, are characterized by important fluctuations in the flow rates and heavy pollution pressures resulting from extensive urban, industrial and agricultural activities. This translates into contamination levels in these rivers often higher than those in other larger European basins. The present work provides an overview of the occurrence of five groups of organic contaminants (131 compounds) namely pharmaceuticals, illicit drugs, polar pesticides, estrogens, alkylphenols and related ethoxylates in WWTP tertiary treatment effluents. Data gathered during a period of water reuse carried out in the lower stretch of the Llobregat river (NE Spain), in the surroundings of the town of Barcelona as a consequence of the severe drought that took place along the years 2007-2008 are presented as illustrative example. In general, measured concentrations of the target compounds were in the low to mid ngL(-1) range. The total concentration of each compound class downstream to the discharge point was similar or slightly higher than that found upstream. Regarding the loads calculated for each compound, the relative contribution from the river upstream and the tertiary effluent were highly compound depending with no apparent trend. However, estimation of the overall bulk loads for each compound class determined in the Llobregat river showed the following rank order: pharmaceuticals>alkylphenols>pesticides>illicit drugs≫estrogens.