Occurrence and ecological risk assessment of organic UV filters in coastal waters of the Iberian Peninsula.

This study aimed to assess the presence of 21 UVFs and metabolites in coastal regions of the Iberian Peninsula, to evaluate their environmental risk, and identify possible influential factors affecting their measured concentrations. Sampling was carried out in spring and summer to assess possible seasonal variations. UVFs were detected in 43 of the 46 sampling sites. Only 5 were found above LOD: BP4, OC, BP3 and metabolites BP1 and BP8. Samples collected in Mar Menor had the greatest variety of compounds per sample and the highest cumulative concentrations. The risk was characterized using Risk Quotients (RQ). BP1 showed a Low environmental Risk in 2 sites while for OC the RQ indicated a Moderate Risk in 22 points. The variables that contribute most to the variation are population density, sampling season, whether it was an open bay or not, and level of urbanization. The presence of WWTPs had a lower influence.

Effects of intensive agriculture and urbanization on water quality and pesticide risks in freshwater ecosystems of the Ecuadorian Amazon.

The Ecuadorian Amazon has experienced a significant land use change due to the demographic increase and the expansion of the agricultural frontier. Such changes in land use have been associated to water pollution problems, including the emission of untreated urban wastewater and pesticides. Here we provide the first report on the influence of urbanization and intensive agriculture expansion on water quality parameters, pesticide contamination and the ecological status of Amazonian freshwater ecosystems of Ecuador. We monitored 19 water quality parameters, 27 pesticides, and the macroinvertebrate community in 40 sampling locations of the Napo River basin (northern Ecuador), including a nature conservation reserve and sites in areas influenced by African palm oil production, corn production and urbanization. The ecological risks of pesticides were assessed using a probabilistic approach based on species sensitivity distributions. The results of our study show that urban areas and areas dominated by African palm oil production have a significant influence on water quality parameters, affecting macroinvertebrate communities and biomonitoring indices. Pesticide residues were detected in all sampling sites, with carbendazim, azoxystrobin, diazinon, propiconazole and imidacloprid showing the largest prevalence (>80% of the samples). We found a significant effect of land use on water pesticide contamination, with residues of organophosphate insecticides correlating with African palm oil production and some fungicides with urban areas. The pesticide risk assessment indicated organophosphate insecticides (ethion, chlorpyrifos, azinphos-methyl, profenofos and prothiophos) and imidacloprid as the compounds posing the largest ecotoxicological hazard, with pesticide mixtures potentially affecting up to 26-29% of aquatic species. Ecological risks of organophosphate insecticides were more likely to occur in rivers surrounded by African palm oil plantations, while imidacloprid risks were identified in corn crop areas as well as in natural areas. Future investigations are needed to clarify the sources of imidacloprid contamination and to assess its effects for Amazonian freshwater ecosystems.

Untargeted metabolomic analysis to explore the impact of soil amendments in a non-conventional wastewater treatment.

As non-conventional wastewater treatment, vegetation filters make the most of the natural attenuation processes that occur in soil to remove contaminants, while providing several environmental benefits. However, this practice may introduce contaminants of emerging concern (CECs) and their transformation products (TPs) into the environment. A potential improvement to the system was tested using column experiments containing soil (S) and soil amended with woodchips (SW) or biochar (SB) irrigated with synthetic wastewater that included 11 selected CECs. This study evaluated: i) known CECs attenuation and ii) unknown metabolites formation. Known CECs attenuation was assessed by total mass balance by considering both water and soil media. An untargeted metabolomic strategy was developed to assess the formation of unknown metabolites and to identify them in water samples. The results indicated that SB enhanced CECs attenuation and led to the formation of fewer metabolites. Sorption and biodegradation processes were favored by the bigger surface area of particles in SB column, especially for compounds with negative charges. Incorporating woodchips into soil shortened retention times in the column, which reduced attenuation phenomena and resulted in the formation of significantly more metabolites. Incomplete biodegradation reactions, fostered by shorter retention times in SW column could mainly explain these results.

Analytical method to monitor contaminants of emerging concern in water and soil samples from a non-conventional wastewater treatment system.

Nonconventional wastewater treatments, such as vegetation filters (VFs), are propitious systems to attenuate contaminants of emerging concern (CECs) in small municipalities. The development of standardised multiresidue and multimatrix methods suitable for measuring a reliable number of CEC in environmental samples is crucial for monitoring infiltrating concentrations and for ensuring these systems' treatment capacity. The objective of this study is to develop and validate an analytical method for the simultaneous determination of CECs, including transformation products (TPs), with diverse physico-chemical properties, in environmental samples. The optimised method is based on sample clean-up and preconcentration by solid-phase extraction (SPE), followed by liquid chromatography electrospray ionization tandem mass spectrometry (LC-MS/MS). The method is able to detect and quantify 40 target CECs, including pharmaceuticals of different classes (analgesics, antibiotics, antihypertensives, lipid regulators, anticonvulsants, antidepressants, antiarrhythmics, beta-blockers, amongst others), hormones and lifestyle products with good reproducibility (variations below 23%), in different water matrices, and 28 CECs, in soil samples. Acceptable recoveries (65-120%) were obtained for most of the CECs in all the matrices. However in the soil samples, as complexity required a prior extraction treatment, the recovery of some analytes was affected, which reduced the number of target CECs. The achieved methodological quantification limits (0.05-5 ng/L and 0.04-1.1 ng/g levels for the water and the soil matrices, respectively) were reasonably low for most CECs. The proposed method was successfully applied to monitor CECs in a VF. The CECs detected at higher concentrations are some of the world's most widely used products (e.g. acetaminophen or caffeine and its main TP, paraxanthine). The results showed an almost 70% reduction in CEC concentrations during infiltration. The groundwater data indicated that the VF treatment operation did not affect the underlying aquifer (Cmax found in GW <1 µg/L).

Pharmaceutical and transformation products during unplanned water reuse: Insights into natural attenuation, plant uptake and human health impact under field conditions.

In urban and periurban areas, agricultural soils are often irrigated with surface water containing a complex mixture of contaminants due to wastewater treatment plant (WWTP) effluent discharges. The unplanned water reuse of these resources for crop irrigation can represent a pathway for contaminant propagation and a potential health risk due to their introduction in the food chain. The aim of this study is to provide data about the magnitude of attenuation processes and plant uptake, allowing for a reliable assessment of contaminant transfer among compartments and of the human health risk derived from unplanned water reuse activities. Target compounds are 25 pharmaceuticals, including transformation products (TPs). The field site is an agricultural parcel where maize is irrigated by a gravity-fed surface system supplied by the Jarama river, a water course strongly impacted by WWTP effluents. Throughout the 3-month irrigation period, irrigation water and water infiltrating through the vadose zone were sampled. The agricultural soil was collected before and after the irrigation campaign, and maize was sampled before harvesting. All selected compounds are detected in irrigation water (up to 12,867 ng L-1). Metformin, two metamizole TPs and valsartan occur with the highest concentrations. For most pharmaceuticals, results demonstrate a high natural attenuation during soil infiltration (>60%). However, leached concentrations of some compounds can be still at concern level (>400 ng L-1). A persistent behavior is observed for carbamazepine, carbamazepine epoxide and sulfamethoxazole. Pharmaceutical soil contents are in the order of ng g-1 and positively ionized compounds accumulate more effectively. Results also indicate the presence of a constant pool of drugs in soils. Only neutral and cationic pharmaceuticals are taken up in maize tissues, mainly in the roots. There is an insignificant threat to human health derived from maize consumption however, additional toxicity tests are recommended for 4AAA and acetaminophen.

Pharmaceuticals and other urban contaminants threaten Amazonian freshwater ecosystems.

Urban areas in the Brazilian Amazon have grown at an unprecedented rate during the last years. About 90% of the wastewater produced by these urban areas are discharged untreated into Amazonian freshwater ecosystems, constituting a potential environmental pathway for pharmaceuticals and other chemicals consumed by modern societies (e.g. psychostimulants, personal-care products, hormones). The distribution of these chemicals into the Amazon River and their potential risks for freshwater biodiversity have not been evaluated so far. Here, we show the results of the largest chemical monitoring campaign conducted in the Amazon region. We assessed exposure patterns for 43 pharmaceuticals and other urban contaminants in 40 sampling sites distributed along the Amazon River, three major tributaries (Negro, Tapajós and Tocantins Rivers), and four large cities of the Brazilian Amazon (Manaus, Santarém, Macapá, Belém). We assessed risks for freshwater biodiversity using species sensitivity distributions and mixture toxicity approaches. We found that urban areas constitute important hot-spots for chemical contamination, with mixtures containing up to 40 different compounds and exposure concentrations reaching the world's maxima for some of them. We show that chemical pollution can result in long-term effects for up to 50-80% of aquatic species next to urban areas. Moreover, we identified several ubiquitous compounds which can be used as tracers of anthropogenic pressure in the Amazon basin. We conclude that the chemical burden created by urbanization significantly contributes to a biodiversity loss in the region and should be further controlled.

Pharmaceuticals and trace metals in the surface water used for crop irrigation: Risk to health or natural attenuation?

The use of surface water impacted by wastewater treatment plant (WWTP) effluents for crop irrigation is a form of unplanned water reuse. Natural attenuation processes can buffer contamination spreading. However, this practice can promote the exposure of crops to contaminants of emerging concern, such as pharmaceuticals, trace metals (TMs) and metalloids, posing a risk to health. This research aimed to evaluate the presence of 50 pharmaceuticals, some transformation products, 7 TMs and a metalloid in the water-sediment-soil-plant system, and their potential to be bioaccumulated into edible parts of plants, as a result of the unplanned water reuse. The study site consists of an extensive agricultural land downstream Madrid city (Spain) where surface water, strongly impacted by WWTP effluents, is applied through gravity-based systems to cultivate mainly maize. Sampling campaigns were conducted to collect WWTP effluent, surface and irrigation water, river sediments, agricultural soils and maize fruits. Results demonstrate the ubiquitous presence of several pharmaceuticals. The concentration pattern in irrigation water did not resemble the pattern of contents in soils and plants. The pharmaceuticals included in the EU surface water watch lists were quantified in the lowest concentration range (macrolide antibiotics, ciprofloxacin) or were not detected (most of the hormones). Therefore, hormones do not represent an emerging risk in our scenario. The TMs and the metalloid in water and agricultural soils should not arise any concern. Whereas, their presence in the river sediments may have an adverse impact on aquatic ecosystems. Only acetaminophen, ibuprofen, carbamazepine, nicotine, Zn, Cu and Ni were quantified in corn grains. Calculated parameters to assess bioaccumulation and health risk indicate that neither pharmaceuticals nor TMs pose a threat to human health due to consumption of maize cultivated in the area. Results highlight the need to include different environmental matrices when assessing contaminant fate under real field-scale conditions.

Identification of contaminants of concern in the upper Tagus river basin (central Spain). Part 1: Screening, quantitative analysis and comparison of sampling methods.

Pesticides and point source contaminants (primarily pharmaceuticals) were monitored in 16 sampling sites of the upper Tagus river basin during spring, summer and autumn of 2016. A qualitative screening analysis was performed using a library of 430 compounds. Next, a novel method was implemented for the selection and quantification of contaminants with LC-MS/MS. The method is based on the frequency of detection in the screening, ecotoxicity data and the potential use in the watershed. Moreover, the efficacy of grab samples and passive samples (POCIS) in detecting compound-specific exposure patterns was compared during the summer sampling campaign. The screening method detected the presence of 268 compounds in the study area, out of which 52 were selected for the quantitative analysis (20 pesticides and 32 point source chemicals). Although very helpful in the prioritization exercise, the qualitative screening demonstrated some biases and the need for improvement by using more effective instruments for confirming positive results. Grab samples proved not to be fully suitable for contaminants with discontinuous exposure such as pesticides, which may be underestimated, but offer a sufficient basis for the characterization of contaminants coming from urban wastewaters. All selected chemicals showed a very high concentration variability due to differences among sampling sites, which are related to agricultural intensity and demographic pressure. Some insecticides (chlorpyrifos, dimethoate, imidacloprid), herbicides (diuron, metribuzine, simazine, terbuthylazine), and fungicides (carbendazim) were measured at concentrations exceeding 100 ng/L; while paracetamol, ibuprofen, some antibiotics (azithromycin, sulfamethoxazole, trimethoprim) and life-style compounds (caffeine, paraxanthine, nicotine) were found at very high concentrations (up to several µg/L). The results of this work represent the basis for the development of an ecological risk assessment for the aquatic ecosystem in the upper Tagus river basin and for the identification of basin-specific contaminant mixtures of environmental concern.

Effects of increased temperature, drought, and an insecticide on freshwater zooplankton communities.

In the present study we performed a microcosm experiment to assess the effects of the insecticide lufenuron on zooplankton communities exposed to increased temperature and drought in (semi-)arid regions. The experiment consisted of 3 environmental scenarios, assessed in 2 parts. Firstly, we assessed how water temperature (20 and 28 °C) affects the sensitivity and resilience of the zooplankton community to lufenuron. Secondly, we investigated the influence of drought on the structure of the zooplankton community at a high water temperature (28 °C) and evaluated its possible interaction with lufenuron. The results show that the community exposed to lufenuron at 28 °C had a faster lufenuron-related response and recovery than the community at 20 °C. The combined effects of lufenuron and temperature resulted in a synergistic effect on some taxa (Daphnia sp., Cyclopoida, and Copepoda nauplii). The tested zooplankton community had a high resilience to drought, although some particular taxa were severely affected after desiccation (Calanoida). Interactions between drought and lufenuron were not statistically significant. However, rewetting after desiccation contributed to lufenuron remobilization from sediments and resulted in a slight Cyclopoida population decline at high exposure concentrations. The study shows how environmental conditions related to global change in (semi-)arid regions may influence chemical fate and the vulnerability of zooplankton communities to chemical stress. Environ Toxicol Chem 2019;38:396-411. © 2018 SETAC.

Presence or Absence of mlr Genes and Nutrient Concentrations Co-Determine the Microcystin Biodegradation Efficiency of a Natural Bacterial Community.

The microcystin biodegradation potential of a natural bacterial community coexisting with a toxic cyanobacterial bloom was investigated in a water reservoir from central Spain. The biodegradation capacity was confirmed in all samples during the bloom and an increase of mlrA gene copies was found with increasing microcystin concentrations. Among the 24 microcystin degrading strains isolated from the bacterial community, only 28% showed presence of mlrA gene, strongly supporting the existence and abundance of alternative microcystin degradation pathways in nature. In vitro degradation assays with both mlr⁺ and mlr- bacterial genotypes (with presence and absence of the complete mlr gene cluster, respectively) were performed with four isolated strains (Sphingopyxis sp. IM-1, IM-2 and IM-3; Paucibacter toxinivorans IM-4) and two bacterial degraders from the culture collection (Sphingosinicella microcystinivorans Y2; Paucibacter toxinivorans 2C20). Differences in microcystin degradation efficiencies between genotypes were found under different total organic carbon and total nitrogen concentrations. While mlr⁺ strains significantly improved microcystin degradation rates when exposed to other carbon and nitrogen sources, mlr- strains showed lower degradation efficiencies. This suggests that the presence of alternative carbon and nitrogen sources possibly competes with microcystins and impairs putative non-mlr microcystin degradation pathways. Considering the abundance of the mlr- bacterial population and the increasing frequency of eutrophic conditions in aquatic systems, further research on the diversity of this population and the characterization and conditions affecting non-mlr degradation pathways deserves special attention.

Prospects and difficulties in TiO2 nanoparticles analysis in cosmetic and food products using asymmetrical flow field-flow fractionation hyphenated to inductively coupled plasma mass spectrometry.

In this work, we proposed an analytical approach based on asymmetrical flow field-flow fractionation combined to an inductively coupled plasma mass spectrometry (AsFlFFF-ICP-MS) for rutile titanium dioxide nanoparticles (TiO2NPs) characterization and quantification in cosmetic and food products. AsFlFFF-ICP-MS separation of TiO2NPs was performed using 0.2% (w/v) SDS, 6% (v/v) methanol at pH 8.7 as the carrier solution. Two problems were addressed during TiO2NPs analysis by AsFlFFF-ICP-MS: size distribution determination and element quantification of the NPs. Two approaches were used for size determination: size calibration using polystyrene latex standards of known sizes and transmission electron microscopy (TEM). A method based on focused sonication for preparing NPs dispersions followed by an on-line external calibration strategy based on AsFlFFF-ICP-MS, using rutile TiO2NPs as standards is presented here for the first time. The developed method suppressed non-specific interactions between NPs and membrane, and overcame possible erroneous results obtained when quantification is performed by using ionic Ti solutions. The applicability of the quantification method was tested on cosmetic products (moisturizing cream). Regarding validation, at the 95% confidence level, no significant differences were detected between titanium concentrations in the moisturizing cream prior sample mineralization (3865±139 mg Ti/kg sample), by FIA-ICP-MS analysis prior NPs extraction (3770±24 mg Ti/kg sample), and after using the optimized on-line calibration approach (3699±145 mg Ti/kg sample). Besides the high Ti content found in the studied food products (sugar glass and coffee cream), TiO2NPs were not detected.

Selenoproteins: the key factor in selenium essentiality. State of the art analytical techniques for selenoprotein studies.

Selenium is an essential element for human health. The benefits of selenium are many including protection against cancer, heart diseases and other cardiovascular and muscle disorders. Selenium is also helpful in controlling gastrointestinal disorders, enhancing immunity of the human body and reducing age-related diseases. The health-promoting properties of Se are due to vital functions of selenoproteins in which selenium is present as selenocysteine, the 21st amino acid. To date, dozens of selenoprotein families have been described though many have roles that have not been fully elucidated. Selenoproteins research has attracted tremendous interest from different scientific areas. Analytical chemists have not remained indifferent to the attractive features of these unique proteins. Different analytical techniques, such as multidimensional chromatography-inductively coupled plasma mass spectrometry (ICPMS), electrospray (tandem) mass spectrometry (ESI-MS/MS), matrix-assisted laser desorption ionization time-of flight (MALDI-TOF) and sodium dodecyl sulphate polyacrylamide gel electrophoresis-laser ablation inductively coupled plasma mass spectrometry (SDS-PAGE-LA-ICPMS), have been applied to the determination of selenoproteins and selenium-containing proteins. This review describes the best-characterized selenoproteins to date in addition to the major contributions of analytical chemistry to the field of selenoproteins. The article also highlights the challenges of combining elemental and molecular mass spectrometry for the determination of selenoproteins and selenium-containing proteins.