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Pesticide applications in agriculture result in complex mixtures of Plant Protection Products (PPPs) in the environment. The ecotoxicological effects of these mixtures can occur at concentrations considered safe for individual chemicals, indicating potential risks underestimated by current regulatory assessments focused on individual active ingredients. To address this challenge, our study introduces a methodology for identifying priority PPPs for formulating mixtures, enabling further ecotoxicological testing in water and sediment compartments of edge-of-field surface water bodies, targeting pelagic and benthic organisms. This methodology was primarily based on the actual quantification of PPPs present in these compartments from selected case study sites (CSSs) in Europe and Argentina (11 and 4 for water and sediments, respectively). A conceptual framework was developed that discriminates and selects concerning PPPs based on their individual risk quotient and frequency of occurrence in each CSS, drawing upon two EU regulatory risk assessment approaches, i.e., the general approach under REACH for any environmental contaminant of concern - the European Chemicals Agency (ECHA) approach; and that specifically focusing on PPPs - the European Food Safety Authority (EFSA) approach. Irrespective of whether the focus is on water or sediments, the study revealed disparities in PPP rankings depending on the approach used to identify PPPs of concern, with the ECHA approach being more conservative than the EFSA approach. Despite this, the EFSA approach follows a more standardized assessment factor definition strategy, potentially allowing avoidance of risk overestimation, as well as resulting in a more balanced representation of different PPP classes for subsequent mixtures testing. Overall, the methodological development reported herein, along with the inconsistencies found when comparing different regulatory approaches to assess the risk of environmental contaminants, highlight the need for further discussion on the most appropriate directions towards the standardization of the regulatory risk assessment of PPP mixtures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier B.V. All rights reserved.)

In this study, the presence of 23 pharmaceutically active compounds (PhACs) including antibiotics, analgesics, anti-inflammatories, psychiatric and cardiovascular drugs, antifungals and metabolites was investigated in surface waters. A total of 89 samples were collected during 3 years (2020, 2021 and 2022) from a European representative river basin (Tagus, Spain). To elucidate PhAC potential sources, sampling points located in areas with low, median and high anthropogenic influence were selected. The analytical method based on solid phase extraction (SPE) followed by UHPLC-MS/MS analysis was validated meeting SANTE/2020/12830 and SANTE/12682/2019 performance criteria. PhACs were quantified above limits of quantification (LOQs) in 96 % of water samples, being the antihypertensives valsartan (648 ng/L, 87 % quantification frequency) and irbesartan (390 ng/L, 75 %) and the antidepressant o-desmethylvenlafaxine (495 ng/L, 76 %) the predominant pollutants. The rest of the target PhACs showed median concentrations between 4 and 172 ng/L with quantification frequencies ranging from 35 to 75 %. ∑PhAC concentrations did not show temporal or seasonal trends. However, valsartan and naproxen presented lower levels in drier (spring and summer) compared to the wetter. Source identification revealed a clear anthropogenic origin since concentrations obtained in highly populated areas were statistically higher (p < 0.01) than those quantified in sparsely populated ones. This finding was also confirmed by calculating PhACs mass flow rates, which ranged between 1.4 and 235 kg/y. Finally, data generated were used to estimate the potential risk to the aquatic ecosystem for three trophic levels (phototrophic, invertebrate and vertebrate organisms). Risk quotient ratios (RQs) were calculated for all PhACs at the median (P50) and worst-case (max) scenarios. Up to 7 PhACs (acetaminophen, carbamazepine, gemfibrozil, ibuprofen, irbesartan, ketoprofen and venlafaxine) showed high risk for the highest trophic level (fish) in >45 % of investigated locations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

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 %)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Neonicotinoids (NNIs) are active substances used as insecticides mainly in plant protection products (PPPs) but also in veterinary applications. The increasing evidence of affecting non-targeted organisms led the European Commission to severely restrict or even ban outdoor uses. To evaluate their current use and their influence in the ecological status of freshwater ecosystem, a total of 19 river water samples were collected to determine the presence of 5 NNIs (acetamiprid, clothianidin, imidacloprid, thiamethoxam and thiacloprid) in the Tagus basin. At least one target analyte was quantified by HPLC-MS/MS analysis in 17 of the 19 water samples, with ∑NNIs ranging from 1) and for the mix of NNIs (RCRmix (PEC/PNEC) > 1). RCRmix(PEC/PNEC) and the sum of toxic units (STU) showed a risky situation for some locations with different organisms related to agriculture practices. This data arouses concern about NNis (legal or forbidden) use in Tagus basin, and manifest the need of monitoring their presence and effect on the aquatic ecosystem., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Presence of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and dechlorane plus (DP) were evaluated in indoor domestic air from four European countries (Belgium, Italy, Spain and Portugal). The main pollutants were hexachlorohexanes (sum of α-, β- and γ-HCH; ΣHCHs) and ΣPCBs (sum of PCB-28, 52, 101, 118, 138, 153 and 180), with median concentrations of 366 and 306 pg/m 3 , respectively. By decreasing order came hexachlorobenzene (HCB; 130 pg/m 3 ), ΣDDXs (sum of DDTs, DDEs and DDDs; 94.4 pg/m 3 ), ΣPBDEs (sum of BDE-17, 28, 47, 66, 99, 100, 153, 154, 183, 206, 207 and 209; 6.08 pg/m 3 ) and DP (0.30 pg/m 3 ). Lower ΣPCBs and ΣDDXs levels were found at Portuguese homes compared to Belgian, Italian and Spanish households. Italian samples presented also lower ΣHCHs concentrations while Spanish homes revealed higher HCB and BDE-209 indoor air concentrations than those obtained in the other countries. ΣHCHs, ΣDDXs and ΣPBDE levels mirrored lindane, dicofol and Penta-, DecaBDE use, respectively. The influence of building characteristics, surroundings and inhabitants habits on pollutant air concentrations was investigated. Data generated were used to conduct a human exposure assessment for toddlers and adults with median (P50) and upper (P95) concentrations. Results indicated that health risk posed by inhalation of ΣPCBs, ΣHCHs, ΣDDXs, HCB, ΣPBDEs and DP were 2 to 5 orders of magnitude lower than oral Reference Dose (RfD) values, and 90 (PCB-28) and 12 (γ-HCH) times lower than Minimal Risk Levels (MRLs) for toddlers at the worst case scenario., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

52 pollutants including organophosphate flame retardants and plasticizers (OPs), polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) were evaluated in household dust from Belgium, Italy and Spain. Pollutant pattern was dominated by ∑OPs (12.8 μg/g; median) followed in decreasing order by ∑PBDEs (229 ng/g), decabromodiphenyl ethane (DBDPE, 130 ng/g), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE, 1.35 ng/g), hexabromobenzene (HBB, 0.28 ng/g) and finally pentabromoethylbenzene (PBEB, 0.03 ng/g). Country differences and substitution of regulated chemicals by unregulated ones were explored. Results clearly reflected a decrease in c-penta and c-octaBDE commercial mixtures, which are mainly substituted by OPs, BTBPE and PBEB. On the other hand, c-decaBDE concentrations increased in Spanish case. However, positive correlations with its proposed substitute (DBDPE) and recent restricted policies make it possible to assume that this trend will change in the coming years. On the basis of the relationship between pollutants, house characteristics and inhabitant habits, potential sources were studied. Finally, data obtained were used to determine estimated daily intakes (EDI) via house dust ingestion and dermal absorption for toddlers and adults at central and upper percentiles. Calculated EDI levels even at worst case scenario were below available reference dose (RfD) values in all cases., (Copyright © 2019 Elsevier B.V. All rights reserved.)

65 house dust samples from three European countries (Belgium, Italy and Spain) were evaluated for the presence of 20 polyflouroalkyl substances (PFASs) including perfluoroalkane sulfonic acids (PFSAs), perfluoroalkyl carboxylic acid (PFCAs) and perfluoroalkane sulfonamides (PFOSAs). The three countries presented similar PFAS levels ranging from 3.13 to 155 ng/g (12.9 ng/g; median), but in all cases PFCAs concentrations (6.92, 15.2 and 8.68 ng/g; median for Belgium, Italy and Spain) were higher than those obtained for PFSAs (2.30, 1.76 and 2.68 ng/g). Interestingly, in comparison to previously published data exhibited an increase in perfluorobutanesulfonate (PFBS) concentrations in Belgian house dust. On the other hand, levels of perfluorooctanesulfonate (PFOS) decreased in Spanish case. Data were examined for relationships between PFAS house dust levels, building and outdoor surrounding characteristics and occupant habits. Main findings revealed a positive association between PFOS concentrations and the building edification age, which could highlight a decrease in the use of this chemical in Europe. Similarly, perfluorohexanesulfonate (PFHxS) levels correlated with the percentage of the floor covered by textiles. Homes located in industrial sites showed higher PFCA levels compared to urban or agricultural locations, revealing the industrial processes as a potential source of these chemicals in Europe. Data obtained were used to perform human exposure assessment for dust intake via oral ingestion. Estimated daily intakes, calculated for toddlers and adults at median and worst case scenarios, were below oral Reference Dose (RfD) and tolerable daily intakes (TDI). However, in perfluorooctanoic acid (PFOA) case, dust ingestion significance to total dietary exposure reached values of 51% for toddlers in the worst case scenario., (Copyright © 2019. Published by Elsevier B.V.)

The whitemouth croaker (Micropogonias furnieri) is one of the most commercially important species along the Atlantic coast of South America. Moreover, some of its biological traits (long life span, inshore feeding, high trophic position) make this species a suitable sentinel of coastal pollution. Here, we investigated contamination by multiple legacy and emerging organic pollutants, such as brominated and chlorinated flame retardants, polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in whitemouth croakers from two estuaries (Guanabara and Sepetiba Bays) located in industrialized and urbanized areas in Rio de Janeiro State, Southeastern Brazil. Furthermore, we assessed how biological and ecological features could explain the observed contamination patterns. Regarding brominated flame retardants, concentrations of polybrominated diphenyl ethers (PBDEs) varied from 7.6 to 879.7 pg g -1 wet weight (w.w.), with high contribution of tetra-, penta-, hexa- and deca-BDEs. The sum of chlorinated flame retardants (dechlorane-related compounds, ΣDRC) ranged from -1 w.w., mostly represented by Dechlorane 603 and Dechlorane Plus (DP). Concentrations of PCDDs and PCDFs varied from -1 w.w., while the Toxic Equivalent (TEQ-PCDD/Fs) levels ranged from 0.1 to 0.2 pg g -1 w.w. Positive correlations between δ 15 N and concentrations of tri-, tetra- and penta-BDEs, as well as ΣDRC, DP and anti-DP isomers suggested that ecological factors (namely biomagnification along the food web) influence contamination of whitemouth croakers in the estuaries studied. Moreover, the sum of PBDEs (ΣPBDE), tri- and tetra-BDEs concentrations were negatively correlated with fish size, suggesting that depuration by fishes and/or habitat shift throughout the whitemouth croaker's life cycle might also influence concentrations. Overall, our study emphasized the need for further investigations to help understand the complex patterns of bioaccumulation and biomagnification that seem to exist in Southeastern Brazil., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The bioaccumulation behavior of perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) was examined in three horticultural crops and earthworms. Two species, spinach (Spinacia oleracea) and tomato (Solanum lycopersicum L.), were grown in field soil amended with a single application of biosolids (at agronomic rate for nitrogen), to represent the scenario using commercial biosolids as fertilizer, and the third crop, corn (Zea mays) was grown in spiked soil (~50mg PFOS/kg soil, ~5mg Deca-BDE/kg soil and a mixture of both, ~50mg PFOS and ~5mg Deca-BDE/kg soil) to represent a worst-case scenario. To examine the bioaccumulation in soil invertebrates, earthworms (Eisenia andrei) were exposed to the spiked soil where corn had been grown. PFASs and HFRs were detected in the three crops and earthworms. To evaluate the distribution of the compounds in the different plant tissues, transfer factors (TFs) were calculated, with TF values higher for PFASs than PBDEs in all crop plants: from 2 to 9-fold in spinach, 2 to 34-fold in tomato and 11 to 309-fold in corn. Bioaccumulation factor (BAF) values in earthworms were also higher for PFASs (4.06±2.23) than PBDEs (0.02±0.02)., (Copyright © 2016 Elsevier Inc. All rights reserved.)

In the present work, the bioaccumulation behavior of 49 target emerging organic compounds (20 perfluoroalkyl substances, PFASs, and 29 halogenated flame retardants, HFRs) was studied in soil invertebrates (Eisenia andrei). Multi species soil systems (MS·3) were used to assess the fate and the effects associated with the application of four biosolids in agricultural soil on terrestrial soil organisms. Biosolid amendment increased concentrations 1.5-14-fold for PFASs, 1.1-2.4-fold for polybrominated diphenyl ethers, PBDEs, and 1.1-3.6-fold for chlorinated flame retardants, CFRs. Perfluorooctanesulfonate, PFOS, (25%) and BDE-209 (60%) were the predominant PFAS and HFR compounds, respectively, in biosolids-amended soils. Total concentrations (ng/g dry weight) in earthworms from biosolid-amended soils ranged from 9.9 to 101 for PFASs, from 45 to 76 for PBDEs and 0.3-32 for CFRs. Bioaccumulation factors (BAFs) were calculated to evaluate the degree of exposure of pollutants in earthworms. The mean BAF ranged from 2.2 to 198 for PFASs, 0.6-17 for PBDEs and 0.5-20 for CFRs. The relationship of PFAS and PBDE BAFs in earthworms and their log Kow were compared: PFAS BAFs increased while PBDE BAFs declined with increasing log Kow values. The effect of the aging (21 days) on the bioavailability of the pollutants in amended soils was also assessed: the residence time affected differently to the compounds studied., (Copyright © 2016 Elsevier Inc. All rights reserved.)