Pesticide Residues in Organic and Conventional Agricultural Soils across Europe: Measured and Predicted Concentrations.

During the growing season of 2021, 201 soil samples from conventionally and organically managed fields from 10 European countries and 8 cropping systems were taken, and 192 residues of synthetic pesticides were analyzed. Pesticide residues were found in 97% of the samples, and 88% of the samples contained mixtures of at least 2 substances. A maximum of 21 substances were found in conventionally managed fields, and a maximum of 12 were found in organically managed fields. The number and concentration of pesticide residues varied significantly between conventional and organic fields in 70 and 50% of the case study sites, respectively. Application records were available for a selected number of fields (n = 82), and these records were compared to the detected substances. Residues from 52% of the applied pesticides were detected in the soils. Only 21% of the pesticide residues detected in the soil samples were applied during the 2021 growing season. From the application data, predicted environmental concentrations of residues in soil were calculated and compared to the measured concentrations. These estimates turned out not to be accurate. The results of this study show that most European agricultural soils contain mixtures of pesticide residues and that current calculation methods may not reliably estimate their presence.

Immediate Impacts of Wildfires on Ground-dwelling macroinvertebrate Communities under Stones in Mediterranean Oak Forests.

Wildfires are considered a major disturbance to forest ecosystems in the Mediterranean countries of Southern Europe. Although ground-dwelling macroinvertebrates are crucial to many soil functions, there is a fundamental lack of understanding of how wildfires impact this community in the immediate term and of the role of stones in their survival. Hence, in the present study we assessed the immediate effects of wildfires in the ground-dwelling macroinvertebrate community found under stones by comparing communities in burnt and non-burnt Mediterranean oak forests. Our results revealed that stones allowed the survival of many taxa in the burnt area. However, abundance, richness, diversity, and equitability per stone were significantly lower at the burnt than unburnt sites. Furthermore, the results also showed that richness and abundance increased significantly with increasing stone depth and area, both at the burnt and unburnt sites. Significant changes at the trophic level were observed in the burnt area comparing to the unburnt, particularly a decline in predators. No significant differences were identified concerning habitat associations among taxa. Overall, this study stressed the role of stones as microhabitats and refuge for the ground-dwelling macroinvertebrate community during wildfires.

Wildfire effects on two freshwater producers: Combining in-situ and laboratory bioassays.

Mediterranean forests are highly susceptible to wildfires, which can cause several impacts not only within burnt areas but also on downstream aquatic ecosystems. The ashes' washout from burnt areas by surface runoff can be a diffuse source of toxic substances, such as metals, when reaching the nearby aquatic systems, and can be noxious to aquatic organisms. The present work aimed at assessing the ecotoxicological effects of post-fire contamination on two aquatic producers (the microalgae Raphidocelis subcapitata and the macrophyte Lemna minor) through in-situ bioassays, validating the obtained results with the outcomes of laboratory bioassays with surface water collected simultaneously. Four distinct sites were selected in a basin partially burnt (Ceira river basin; Coimbra district, Portugal) for bioassay deployment: one site upstream the burnt area in the Ceira river (RUS); three sites located under the influence of the burnt area, one immediately downstream of the burnt area in the Ceira river (RDS) and the other two in tributary streams within the burnt area (BS1 and BS2). The in-situ bioassays lasted for 13 days and began following the first post-fire major rain events. Results showed that the microalgae growth rate was able to distinguish the three sites within and downstream of the burnt area (BS1, BS2, RDS) from the site upstream (RUS). By contrast, the macrophytes growth rate only allowed to differentiate between the sites within the burnt area (BS1 and BS2) and those up- and downstream of the burnt area (RUS and RDS). The in-situ results for both species were corroborated with the results of the laboratory experiments, supporting the use of laboratory surrogates for a screening assessment of wildfire impacts in aquatic ecosystems. Direct causal relationships between the observed ecotoxicological effects on R. subcapitata and L. minor and the physical-chemical parameters of the water samples were difficult to establish, although the results suggest (i) a role of differential major and trace metal load in explaining species growth variation; (ii) interaction between metals and/or between metals and other field parameters are likely to modulate the biological responses to the challenges deriving from wildfire runoff.

Temperature modulates the interaction between fungicide pollution and disease: evidence from a Daphnia-microparasitic yeast model.

Temperature is expected to modulate the responses of organisms to stress. Here, we aimed to assess the influence of temperature on the interaction between parasitism and fungicide contamination. Specifically, using the cladoceran Daphnia as a model system, we explored the isolated and interactive effects of parasite challenge (yeast Metschnikowia bicuspidata) and exposure to fungicides (copper sulphate and tebuconazole) at two temperatures (17 and 20 °C), in a fully factorial design. Confirming a previous study, M. bicuspidata infection and copper exposure caused independent effects on Daphnia life history, whereas infection was permanently suppressed with tebuconazole exposure. Here, we show that higher temperature generally increased the virulence of the parasite, with the hosts developing signs of infection earlier, reproducing less and dying at an earlier age. These effects were consistent across copper concentrations, whereas the joint effects of temperature (which enhanced the difference between non-infected and infected hosts) and the anti-parasitic action of tebuconazole resulted in a more pronounced parasite × tebuconazole interaction at the higher temperature. Thus, besides independently influencing parasite and contaminant effects, the temperature can act as a modulator of interactions between pollution and disease.

Combined effect of copper sulfate and water temperature on key freshwater trophic levels - Approaching potential climatic change scenarios.

This work relied on the use microcosms to evaluate the individual and the combined effects of different levels of copper sulfate (0.0, 0.013, 0.064 and 0.318mg Cu L-1) - a fungicide commonly exceeding allowable thresholds in agricultural areas - and a range of water temperature increase scenarios (15, 20 and 25°C) on freshwater species belonging to different functional groups. Hence, the growth inhibition of primary producers (the microalgae Raphidocelis subcapitata and the macrophyte Lemna minor), as well as the survival and feeding behavior of a shredder species (the Trichoptera Schizopelex sp.) were evaluated. The results revealed that copper was toxic to primary producers growth, as well as shredders growth and survival, being the growth of L. minor particularly affected. Higher water temperatures had generally enhanced the growth of primary producers under non-contaminated (microalgae and macrophytes) or low-contaminated (macrophytes) conditions. Despite the tendency for a more pronounced toxicity of copper under increasing water temperatures, a significant interaction between the two factors was only observed for microalgae. Since the test organisms represent relevant functional groups for sustaining freshwater systems functions, the present results may raise some concerns on the impacts caused by possible future climate change scenarios in aquatic habitats chronically exposed to the frequent or intensive use of the fungicide copper sulfate.

Toxicity of two fungicides in Daphnia: is it always temperature-dependent?

The joint effect of increasing temperature and pollution on aquatic organisms is important to understand and predict, as a combination of stressors might be more noxious when compared to their individual effects. Our goal was to determine the sensitivity of a model organism (Daphnia spp.) to contaminants at increasing temperatures, allowing prior acclimation of the organisms to the different temperatures. Prior to exposure, two Daphnia genotypes (Daphnia longispina species complex) were acclimated to three temperatures (17, 20, and 23 °C). Afterwards, a crossed design was established using different exposure temperatures and a range of concentrations of two common fungicides (tebuconazole and copper). Daphnia life history parameters were analysed in each temperature × toxicant combination for 21 days. Temperature was the most influencing factor: Daphnia reproduced later and had lower fecundity at 17 °C than at 20 and 23 °C. Both copper and tebuconazole also significantly reduced the fecundity and survival of Daphnia at environmentally-relevant concentrations. Temperature-dependence was found for both toxicants, but the response pattern was endpoint- and genotype-specific. The combination of contaminant and high temperature often had severe effects on survival. However, unlike some literature on the subject, our results do not support the theory that increasing temperatures consistently foment increasing reproductive toxicity. The absence of a clear temperature-dependent toxicity pattern may result from the previous acclimation to the temperature regime. However, a proper framework is lacking to compare such studies and to avoid misleading conclusions for climate change scenarios.

Toxicity testing with the benthic diatom Navicula libonensis (Schoeman 1970): procedure optimisation and assessment of the species sensitivity to reference chemicals.

Periphytic communities are good indicators of river quality due to their general sensitivity to several pollutants. The primary objective of this study was to develop and optimize an ecotoxicological testing methodology using the freshwater benthic diatom Navicula libonensis. This species was selected due to its ubiquity and suitability for use under laboratory conditions. In the most suitable test medium (Chu10) the diatom demonstrated comparable sensitivity to potassium dichromate and 3,5-dichlorophenol using growth rate as the reference parameter, with median effect concentrations (ErC50) in the same order of magnitude (0.119 and 0.799 mg L(-1)) respectively. Yield-based estimates did not confirm this pattern and potassium dichromate was one order of magnitude more toxic than 3,5-dichlorophenol. The sensitivity of N. libonensis to the reference chemicals was higher than that published in the literature for several standard planktonic microalgae. This advantage, as well as the ability to grow the species in the laboratory, supports further efforts towards the standardisation of a toxicity testing protocol. In addition, the functional role of benthic diatoms in lotic ecosystems justifies their inclusion in risk assessment test batteries to better cover an environmental compartment that has so far been neglected.

Occurrence and distribution of pesticides and transformation products in ambient air in two European agricultural areas.

Pesticides present a significant risk for both humans and the environment. However, quantitative data for a broad range of airborne pesticides in agricultural areas are missing. During or after the application, pesticides can reach the atmosphere and partition between the particulate and gaseous phase. As part of the EU project SPRINT, weekly ambient air samples were collected from two agricultural areas in Portugal (vineyard) and the Netherlands (potatoes, onions, and sugarbeet) between April 2021 and June 2022 using high-volume air samplers. The samples were analysed for 329 pesticides, of which 99 were detected. The most frequently detected compounds included the fungicides folpet, fenpropidin and mandipropamid, the insecticide chlorpyrifos-methyl, the herbicide terbuthylazine, and the metabolite prothioconazole-desthio, which were found with detection frequencies between 40 and 57 %. Pesticide concentrations ranged between 0.003 ng/m3 and 10 ng/m3. Remarkably, 97 % of the samples contained at least one pesticide and in 95 % of the samples, pesticide mixtures were present. The calculated particle phase fractions correlated with the octanol-air partitioning coefficient for most of the investigated compounds. Furthermore, calculated daily inhalation rates for individual pesticides and pesticide mixtures were far below the Acceptable Daily Intake (ADI) with a margin of exposure (MOE) of >1000 for the highest calculated daily inhalation rate for a child. However, as this value only includes pesticide intake from food and drinking water and considering that 91 % of the detected pesticides are associated with potential adverse human health effects. These findings highlight the broad range of airborne pesticides in agricultural areas and the need for quantitative data to include the intake of mixtures of highly hazardous pesticides by inhalation in human risk assessment.

Potential effects of the discharge of wastewater treatment plant (WWTP) effluents in benthic communities: evidence from three distinct WWTP systems.

Wastewater treatment plant (WWTP) effluents can be sources of environmental contamination. In this study, we aimed to understand whether effluents of three different WWTPs may have ecological effects in riverine recipient ecosystems. To achieve this, we assessed benthic phytobenthos and macroinvertebrate communities at three different locations relative to the effluent discharge: immediately upstream, immediately downstream and 500-m downstream the effluent discharge. Two approaches were employed: the ecological status classification as defined in the Water Framework Directive (WFD) based on biological indicators; constrained multivariate analysis to disentangle the environmental drivers (physicochemical variables and contaminants, namely metals, polycyclic aromatic hydrocarbons, pharmaceuticals, and personal care products) of ecological changes across the study sites. The results showed inconsistencies between the WFD approach and the multivariate approach, as well as between the responses of macroinvertebrates and diatoms. The WWTP effluents impacted benthic communities in a single case: macroinvertebrates were negatively affected by one of the WWTP effluents, likely by the transported pharmaceuticals (other stressors are essentially homogeneous among sites). Given the findings and the scarcity of consistent evidence on ecological impacts that WWTP effluents may have in recipient ecosystems, further research is needed towards more sustainable regulation and linked environmental protection measures.

Identifying pesticides of high concern for ecosystem, plant, animal, and human health: A comprehensive field study across Europe and Argentina.

The widespread and excessive use of pesticides in modern agricultural practices has caused pesticide contamination of the environment, animals, and humans, with confirmed serious health consequences. This study aimed to identify the 20 most critical substances based on an analysis of detection frequency (DF) and median concentrations (MC) across environmental and biological matrices. A sampling campaign was conducted across 10 case study sites in Europe and 1 in Argentina, each encompassing conventional and organic farming systems. We analysed 209 active substances in a total of 4609 samples. All substances ranked among the 20 most critical were detected in silicon wristbands worn by humans and animals and indoor dust from both farming systems. Five of them were detected in all environmental matrices. Overall, higher values of DF and MC, including in the blood plasma of animals and humans, were recorded in samples of conventional compared to organic farms. The differences between farming systems were greater in the environmental samples and less in animal and human samples. Ten substances were detected in animal blood plasma from conventional farms and eight in animal blood plasma from organic farms. Two of those, detected in both farming systems, are classified as hazardous for mammals (acute). Five substances detected in animal blood plasma from organic farms and seven detected in animal blood plasma from conventional farms are classified as hazardous for mammals (dietary). Three substances detected in human blood plasma are classified as carcinogens. Seven of the substances detected in human blood plasma are classified as endocrine disruptors. Six substances, of which five were detected in human blood plasma, are hazardous for reproduction/development. Efforts are needed to elucidate the unknown effects of mixtures, and it is crucial that such research also considers biocides and banned substances, which constitute a baseline of contamination that adds to the effect of substances used in agriculture.

Assessing pesticide residues occurrence and risks in water systems: A Pan-European and Argentina perspective.

Freshwater ecosystems face a particularly high risk of biodiversity loss compared to marine and terrestrial systems. The use of pesticides in agricultural fields is recognized as a relevant stressor for freshwater environments, exerting a negative impact worldwide on the overall status and health of the freshwater communities. In the present work, part of the Horizon 2020 funded SPRINT project, the occurrence of 193 pesticide residues was investigated in 64 small water bodies of distinct typology (creeks, streams, channels, ditches, rivers, lakes, ponds and reservoirs), located in regions with high agricultural activity in 10 European countries and in Argentina. Mixtures of pesticide residues were detected in all water bodies (20, median; 8-40 min-max). Total pesticide levels found ranged between 6.89 and 5860 ng/L, highlighting herbicides as the dominant type of pesticides. Glyphosate was the compound with the highest median concentration followed by 2,4-D and MCPA, and in a lower degree by dimethomorph, fluopicolide, prothioconazole and metolachlor(-S). Argentina was the site with the highest total pesticide concentration in water bodies followed by The Netherlands, Portugal and France. One or more pesticides exceeded the threshold values established in the European Water Framework Directive for surface water in 9 out of 11 case study sites (CSS), and the total pesticide concentration surpassed the reference value of 500 ng/L in 8 CSS. Although only 5 % (bifenthrin, dieldrin, fipronil sulfone, permethrin, and terbutryn) of the individual pesticides denoted high risk (RQ > 1), the ratios estimated for pesticide mixtures suggested potential environmental risk in the aquatic compartment studied.

Effects of aqueous extracts of wildfire ashes on tadpoles of Pelophylax perezi: Influence of plant coverage.

Wildfires have been pointed out as an important source of diffuse contamination to aquatic ecosystems, namely through the input of toxic compounds such as polycyclic aromatic hydrocarbons and metals. However, amphibians' responses to this disturbance have been largely ignored. Hence, this study intended to assess how ashes from Pinus sp. and Eucalyptus sp. plantation forests affect tadpoles of Pelophylax perezi. Tadpoles were exposed 14 days to serial concentrations (26.9 %-100 %) of aqueous extracts of ashes (AEA, with 10 g L-1 of ashes) containing Eucalypt (ELS) and Pine (PLS) ashes. The following endpoints were measured: mortality, malformations, developmental stage, body length and weight. Effects at sub-individual level were also monitored for oxidative stress, neurotoxicity, and energetic metabolism. Chemical characterization of the AEA of ELS showed higher concentrations of As, Cd, Co, Cr, Pb and V, while PLS showed higher concentrations of Cu, Mn, Ni and Zn. Concerning the lethal effects of AEAs on tadpoles, both extracts were able to induce mortality at high concentrations (76.9 and/or 100 % of AEA), although a high variability in the response was found. A significant mortality in tadpoles exposed to ELS was observed at the concentration of 76.9 %. For organisms exposed to PLS, though a mortality above 20 % was registered at the two highest tested concentrations, it was not significantly different from the control. No significant sub-lethal effects were observed in the ELS treatments. Contrasting, exposure to PLS induced a decrease in body length, weight, glutathione-S-transferase activity and an increase in oxygen consumption. Overall, the distinct effects of ELS and PLS suggest an influence of vegetation cover in ash toxicity. In conclusion, exposure to both ash extracts negatively affected sublethal responses of tadpoles of P. perezi. Future research is needed to assess how these effects at individual level may translate into effects at population level.

Effects of wildfire ashes on aquatic invertebrates: First molecular approach on Chironomus riparius larvae.

The wildfire magnification in recent years has raised increasing concern about their adverse impacts on the environment. Wildfires are recognized as an important source of diffuse pollution for the nearby aquatic systems being potentially toxic to aquatic life. Albeit previous studies with wildfire runoff/ashes observed effects in aquatic organisms, to date, different severity origins of ashes and their impact at the sub-organismal level on aquatic biota have not been assessed. In this work, the molecular response of Chironomus riparius exposed to wildfire with low (LS) and high (HS) severity ashes from burnt Pine plantations was evaluated by employing an array of 42 genes related to crucial metabolic pathways by Real time-PCR. IV instar larvae were exposed for 72 h to aqueous extract of ashes (12.5 %, 25 %, 50 %, 75 % and 100 %) prepared from LS and HS ashes. Mn, Zn, and Pb were the metals found at highest concentration in both ash extracts, for HS notable Cd, Mn and Cr presence. From the 42 genes studied only 4 were not altered (22 genes modulated their response by LS and 38 genes in the case of HS) showing the opposite response at 100% with downregulated by LS and upregulated by HS. The 12.5 %, 25 %, 100 % HS and 25 % LS were the main modulators, confirmed by the integrative biomarkers response (IBR). Remarkable genotoxicity was generated by ashes even activating the apoptosis response, and endocrine disruption observed could modify the development. Moreover, detoxification and stress response were strongly activated, limiting the organism's future response to external aggressions. The employment of this novelty approach with molecular tools act as early alarm signal preventing greater damages. Overall, wildfire ashes showed to be a significant environmental disruptor to C. riparius even at lower concentration and the short exposure time employed, emphasizing the strong impact of wildfires on aquatic systems.

Do Freshwater and Marine Bivalves Differ in Their Response to Wildfire Ash? Effects on the Antioxidant Defense System and Metal Body Burden.

Wildfires constitute a source of contamination to both freshwater and marine ecosystems. This study aimed to compare the antioxidant defense response of the freshwater clam Corbicula fluminea and the marine cockle (Cerastoderma edule) to wildfire ash exposure and the concomitant metal body burden. Organisms were exposed to different concentrations (0%, 12.5%, 25%, 50%, and 100%) of aqueous extracts of Eucalypt ash (AEAs) from a moderate-to-high severity wildfire. The activity of various enzymes, as well as lipid peroxidation, protein content, and metal body burden, were determined after 96 h of exposure. A significant increase in the protein content of soft tissues was observed for C. edule at AEA concentrations ≥ 25%, unlike for C. fluminea. Similarly, significant effects on lipid peroxidation were observed for cockles, but not for clams. For both species, a significant effect in the total glutathione peroxidase activity was observed at AEA concentrations ≥ 25%. Relative to the control, AEAs-exposed clams showed higher Cd content, whereas AEAs-exposed cockles showed higher Cu content, thus exhibiting different responses to the exposure to wildfire ash. The susceptibility of bivalves to ashes, at environmentally relevant concentrations, raises concern about the effects of post-fire runoff to bivalve species.

Occurrence of pesticide residues in indoor dust of farmworker households across Europe and Argentina.

Pesticides are widely used as plant protection products (PPPs) in farming systems to preserve crops against pests, weeds, and fungal diseases. Indoor dust can act as a chemical repository revealing occurrence of pesticides in the indoor environment at the time of sampling and the (recent) past. This in turn provides information on the exposure of humans to pesticides in their homes. In the present study, part of the Horizon 2020 funded SPRINT project, the presence of 198 pesticide residues was assessed in 128 indoor dust samples from both conventional and organic farmworker households across Europe, and in Argentina. Mixtures of pesticide residues were found in all dust samples (25-121, min-max; 75, median). Concentrations varied in a wide range (<0.01 ng/g-206 µg/g), with glyphosate and its degradation product AMPA, permethrin, cypermethrin and piperonyl butoxide found in highest levels. Regarding the type of pesticides, insecticides showed significantly higher levels than herbicides and fungicides. Indoor dust samples related to organic farms showed a significantly lower number of residues, total and individual concentrations than those related to conventional farms. Some pesticides found in indoor dust were no longer approved ones (29 %), with acute/chronic hazards to human health (32 %) and with environmental toxicity (21 %).

Pesticide residues with hazard classifications relevant to non-target species including humans are omnipresent in the environment and farmer residences.

Intensive and widespread use of pesticides raises serious environmental and human health concerns. The presence and levels of 209 pesticide residues (active substances and transformation products) in 625 environmental samples (201 soil, 193 crop, 20 outdoor air, 115 indoor dust, 58 surface water, and 38 sediment samples) have been studied. The samples were collected during the 2021 growing season, across 10 study sites, covering the main European crops, and conventional and organic farming systems. We profiled the pesticide residues found in the different matrices using existing hazard classifications towards non-target organisms and humans. Combining monitoring data and hazard information, we developed an indicator for the prioritization of pesticides, which can support policy decisions and sustainable pesticide use transitions. Eighty-six percent of the samples had at least one residue above the respective limit of detection. One hundred residues were found in soil, 112 in water, 99 in sediments, 78 in crops, 76 in outdoor air, and 197 in indoor dust. The number, levels, and profile of residues varied between farming systems. Our results show that non-approved compounds still represent a significant part of environmental cocktails and should be accounted for in monitoring programs and risk assessments. The hazard profiles analysis confirms the dominance of compounds of low-moderate hazard and underscores the high hazard of some approved compounds and recurring "no data available" situations. Overall, our results support the idea that risk should be assessed in a mixture context, taking environmentally relevant mixtures into consideration. We have uncovered uncertainties and data gaps that should be addressed, as well as the policy implications at the EU approval status level. Our newly introduced indicator can help identify research priority areas, and act as a reference for targeted scenarios set forth in the Farm to Fork pesticide reduction goals.

Acute and chronic toxicity of Betanal(®)Expert and its active ingredients on nontarget aquatic organisms from different trophic levels.

As a way to improve the efficacy to target organisms, new pesticide generation is based on technologically advanced coformulations of two or more active ingredients. One example is Betanal(®)Expert, a postemergence herbicide composed of an Advanced Micro Droplet coformulation of phenmedipham, desmedipham, and ethofumesate. Although its composed formulation brings an increase in the pesticide performance, it can also enhance its toxicity to nontarget species. Therefore, the present study intends to contribute with relevant information on ecotoxicological effects of Betanal(®)Expert and its active ingredients on a battery of bioassays using aquatic species from different trophic levels: bacteria (Vibrio fischeri), microalgae (Pseudokirchneriella subcapitata, Chlorella vulgaris, and Chlamydomonas pseudocostata), macrophyte (Lemna minor), and cladocerans (Daphnia magna and Daphnia longispina) species. Across the organisms tested and endpoints measured, different responses concerning the toxicity of the active ingredients were found: (i) phenmedipham was the most toxic to V. fischeri and L. minor; (ii) desmedipham was the most toxic to P. subcapitata, D. magna, and D. longispina; (iii) and ethofumesate was the most toxic to C. pseudocostata and C. vulgaris. Furthermore, for C. pseudocostata and daphnids, the toxicity observed for some active ingredients was higher than the toxicity of the commercial formulation. In fact, in an attempt to evaluate the contribution of each active ingredient to the overall toxicity of Betanal(®)Expert, it was observed that, in general, the toxicity values obtained for desmedipham and phenmedipham were close or even lower to the values determined for Betanal(®)Expert, indicating that the ethofumesate can act as an antagonist in the three-way coformulation. In spite of the most impaired species being the photosynthetic ones, this study also showed pernicious effects on nonphotosynthetic organisms with distinct target sites. Therefore, our results underline the importance of clarifying the mode of action and metabolic pathways of these compounds on nonphotosynthetic species.

Chemical characterization of riverine sediments affected by wastewater treatment plant effluent discharge.

This study was aimed at assessing the contribution of wastewater treatment effluents to the contamination profile of the sediments of receiving waterways. Three wastewater treatment plants (WWTP) were addressed, encompassing different population equivalent sizes, urbanization degrees and treatment methods translating differences in expected contamination patterns. Within each WWTP system, the assessment targeted the effluent and sediment samples collected upstream and downstream the effluent discharge point; contaminants belonging to several concerning chemical classes (metals and metalloids; pesticides; pharmaceuticals and personal care products, PPCPs; and polycyclic aromatic hydrocarbons, PAHs) were quantified both in effluent and sediment samples. Clear associations between contaminants present in the effluent and corresponding sediment samples were not always verified. In fact, a noticeable difference between the number or abundance of contaminants detected in effluents and in sediments, suggesting that effluents are not always the most likely source (e.g. PAHs). However, sediment contaminants that were likely sourced by the effluents were also identified (e.g. PPCPs). Sediment analysis offers an important historical view of contamination, especially in flowing recipient ecosystems where any characterization over the water matrix is ephemeral and linking exclusively to the moment of sampling. Hence, sediments should be considered for the establishment of WWTP operational benchmarks regulating the emission of contaminants, which is currently focused mostly on effluent composition thus potentially over/underestimating the longer-term impact of effluent discharge in the recipient waterways.

Effects of Pine and Eucalypt ashes on bacterial isolates from the skin microbiome of the fire salamander (Salamandra salamandra).

Environmental contamination influences the diversity of the resident skin microbial community of amphibians, ultimately affecting the individual's immune system. Wildfires are expected to impact the skin microbiome, since post-fire runoff typically transports hazardous substances, that can affect terrestrial and aquatic ecosystems. The present study is the first to assess the effects of Eucalypt and Pine wildfire ash on cultivable bacterial isolates from the skin microbiome of amphibians, in particular the fire salamander (Salamandra salamandra), a common species in fire-prone Mediterranean ecosystems. To achieve this goal, samples of skin bacteria of adult individuals of S. salamandra were collected at a site without influence of wildfires. The bacterial isolates were tested against the pathogenic agent Aeromonas salmonicida for assessing their antimicrobial activity, before exposing them to a series of dilutions of aqueous extracts of Eucalypt and Pine ashes (AAEs) from high severity wildfires. From the 80 bacterial isolates collected, 48 (mostly Pseudomonas spp.) showed antimicrobial activity. Exposure of bacteria with antimicrobial activity to the Eucalypt and Pine AAEs at concentrations of 0, 6.25, 12.5, 25, 50, 75, and 100%, revealed that bacterial growth could be significantly inhibited, stimulated or unaffected by ash. Growth inhibition was found for Pine and Eucalypt AAEs at concentrations as low as 6.25% and 12.5%, respectively, but were more expressive at concentrations equal or above 50%. Eucalypt AAEs had a higher negative impact on bacterial growth than Pine AAEs, likely due to differences in metal concentrations between ash types. These findings raise concern about the future of amphibians in fire-prone regions since the foreseen increase in fire frequency and severity owing to climate changes are likely to alter the skin microbiome of amphibians, weaken the immune system and consequently increasing the incidence of infections or diseases, further contributing to the decline of the populations.

A review on polycyclic aromatic hydrocarbons distribution in freshwater ecosystems and their toxicity to benthic fauna.

Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds, found ubiquitously in all environmental compartments. PAHs are considered hazardous pollutants, being of concern to both the environmental and human health. In the aquatic environment, PAHs tend to accumulate in the sediment due to their high hydrophobicity, and thus sediments can be considered their ultimate sink. Concurrently, sediments comprise important habitats for benthic species. This raises concern over the toxic effects of PAHs to benthic communities. Despite PAHs have been the subject of several reviews, their toxicity to freshwater benthic species has not been comprehensively discussed. This review aimed to provide an overview on PAHs distribution in freshwater environments and on their toxicity to benthic fauna species. The distribution of PAHs between sediments and the overlying water column, given by the sediment-water partition coefficient, revealed that PAHs concentrations were 2 to 4 orders of magnitude higher in sediments than in water. The sediment-water partition coefficient was positively correlated to PAHs hydrophobicity. Toxicity of PAHs to benthic fauna was addressed through Species Sensitivity Distributions. The derived hazardous concentration for 5% of the species (HC5) decreased as follows: NAP (376 µg L-1) > PHE > PYR > FLT > ANT (0.854 µg L-1), varying by 3 orders of magnitude. The hazardous concentrations (HC5) to benthic species were inversely correlated to the hydrophobicity of the individual PAHs. These findings are pertinent for environmental risk assessment of these compounds. This review also identified future challenges regarding the environmental toxicity of PAHs to freshwater benthic communities, namely the need for updating the PAHs priority list and the importance of comprehensively and more realistically assess the toxicity of PAHs in combination with other stressors, both chemical and climate-related.