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Background Studies have shown regional and functional selectivity of cardiac postganglionic neurones indicating there might exist a similar heterogeneity in spinal segmental preganglionic neurones, which requires further investigation. Methods Right and left sympathetic chains were electrically stimulated from T6 to T1 in the innervated isolated rabbit heart preparation (n = 18). Sinus rate, left ventricular pressure, retrograde ventriculo-atrial conduction, monophasic action potential duration, effective refractory period, ventricular fibrillation threshold and electrical restitution were measured. Results Right sympathetic stimulation had a greater influence on heart rate (T1-T2: right; 59.9 ± 6.0%, left; 41.1 ± 5.6% P, Highlights • Direct evidence that the preganglionic sympathetic efferents show functionally distinct electrophysiological pathways in the rabbit heart • T1-T3 had a greater influence on heart rate and left ventricular pressure • T4-T6 of the left sympathetics had greater potential for arrhythmia generation

BackgroundThe intrinsic cardiac nervous system is a rich network of cardiac nerves that converge to form distinct ganglia and extend across the heart and is capable of influencing cardiac function.ObjectiveThe goals of this study were to provide a complete picture of the neurotransmitter/neuromodulator profile of the rabbit intrinsic cardiac nervous system and to determine the influence of spatially divergent ganglia on cardiac electrophysiology.MethodsNicotinic or electrical stimulation was applied at discrete sites of the intrinsic cardiac nerve plexus in the Langendorff-perfused rabbit heart. Functional effects on sinus rate and atrioventricular conduction were measured. Immunohistochemistry for choline acetyltransferase (ChAT), tyrosine hydroxylase, and/or neuronal nitric oxide synthase (nNOS) was performed using whole mount preparations.ResultsStimulation within all ganglia produced either bradycardia, tachycardia, or a biphasic brady-tachycardia. Electrical stimulation of the right atrial and right neuronal cluster regions produced the largest chronotropic responses. Significant prolongation of atrioventricular conduction was predominant at the pulmonary vein-caudal vein region. Neurons immunoreactive (IR) only for ChAT, tyrosine hydroxylase, or nNOS were consistently located within the limits of the hilum and at the roots of the right cranial and right pulmonary veins. ChAT-IR neurons were most abundant (1946 ± 668 neurons). Neurons IR only for nNOS were distributed within ganglia.ConclusionStimulation of intrinsic ganglia, shown to be of phenotypic complexity but predominantly of cholinergic nature, indicates that clusters of neurons are capable of independent selective effects on cardiac electrophysiology, therefore providing a potential therapeutic target for the prevention and treatment of cardiac disease.

Despite a theoretical link between plastic and plasticiser occurrence in the terrestrial environment, there are few empirical studies of the relationship between these contaminants in soils. We carried out a field study to assess the co-occurrence of plastic waste, and legacy and emerging plasticisers in UK soils (n = 19) from various land uses (woodlands, urban roadsides, urban parklands, landfill-associated). Surface plastics and soil microplastics were quantified and characterised using ATR-FTIR and μ-FTIR. Eight legacy (phthalate) and three emerging (adipate, citrate, trimellitate) plasticisers were quantified using GC–MS. Surface plastics were found at higher prevalence at landfill-associated and urban roadside sites, with levels significantly (2 orders of magnitude) greater than in woodlands. Microplastics were detected in landfill-associated (mean 12.3 particles g−1 dw), urban roadside (17.3 particles g−1 dw) and urban parkland (15.7 particles g−1 dw) soils, but not in woodland soils. The most commonly detected polymers were polyethene, polypropene and polystyrene. Mean ∑plasticiser concentration in urban roadside soils (3111 ng g−1 dw) was significantly higher than in woodlands (134 ng g−1 dw). No significant difference was found between landfill-associated (318 ng g−1 dw) and urban parkland (193 ng g−1 dw) soils and woodlands. Di-n-butyl phthalate (94.7% detection frequency) and the emerging plasticiser trioctyl trimellitate (89.5%) were the most commonly detected plasticisers, with diethylhexyl phthalate (493 ng g−1 dw) and di-iso-decyl phthalate (96.7 ng g−1 dw) present at the highest concentrations. ∑plasticiser concentrations were significantly correlated with surface plastic (R2 = 0.23), but not with soil microplastic concentrations. Whilst plastic litter seems a fundamental source of plasticisers in soils, mechanisms such as airborne transport from source areas may be as important. Based on the data from this study, phthalates remain the dominant plasticisers in soils, but emerging plasticisers are already widespread, as reflected by their presence in all land uses studied.

Fil: Arias, Andrés Hugo. IADO, Instituto Argentino de Oceanografía, CCT-CONICET, Bahía Blanca, Argentina Fil: Arias, Andrés Hugo. Departamento de Química, Universidad Nacional del Sur (UNS), Av. Alem 1253, 8000 Bahía Blanca, Argentina Fil: Oliva, Ana Laura. IADO, Instituto Argentino de Oceanografía, CCT-CONICET, Bahía Blanca, Argentina Fil: Ronda, Ana Carolina. IADO, Instituto Argentino de Oceanografía, CCT-CONICET, Bahía Blanca, Argentina Fil: Ronda, Ana Carolina. Departamento de Biología, Bioquímica y Farmacia, Universidad Nacional Del Sur (UNS)-CONICET, Bahía Blanca, Argentina Fil: Tombesi, Norma Beatriz. Departamento de Química, Universidad Nacional del Sur (UNS), Av. Alem 1253, 8000 Bahía Blanca, Argentina Fil: Macchi, Pablo Antonio. Universidad Nacional de Río Negro. Instituto de Investigaci ́on en Paleobiología y Geología. Río Negro, Argentina Fil: Solimano, Patricio José. Universidad Nacional de Río Negro. Centro de Investigaciones y Transferencia de Río Negro. Río Negro, Argentina Fil: Abrameto, Mariza Alejandra. Universidad Nacional de Río Negro. Río Negro, Argentina Fil: Migueles, Nathalia. Universidad Nacional de Río Negro. Río Negro, Argentina Organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) threaten the environment due to their wide environmental resistance. Environmental paradigms coexist along the Negro River (NR) in Argentina, South America, which flows to the sea below the latitude of 40o S; however, this is the first environmental assessment of OCPs and PAHs in water of the NR for more than 15 years. With 21 sampling sites covering a range of 600 km of river extension, we assessed 16 OCPs and 16 PAHs in suspended particulate material (SPM) with regard to their levels, seasonality, sources, and potential biological risk assessment. Using gas chromatography– mass spectrometry and gas chromatography coupled with electron capture detection, we found an overall mean value for Σ16 OCPs of 648.56 ng. g 1, d.w. Despite a ban spanning 25 years, an increasing trend of accumulation of hexachlorocyclohexanes (HCHs) and endosulfan was shown in the lower valley. The ɑ-HCH/ɤ- HCH and β-HCH/(ɑ + ɤ)-HCH ratios indicated a prevalent usage of technical HCH over lindane and recent HCH inputs. The most abundant compound, α-endosulfan, averaged 141.64 ng. g 1, d.w. and DDX (Σ 4,4′ -DDE, 4,4′ - DDD, and 4,4′ -DDT) averaged 99.98 ng. g 1, d.w. Winter OCP loads in the NR reflected the runoff of the heaviest pesticide application period. We estimated the total discharge of DDT into the Atlantic ocean was 96 g.day 1, added to 458 g of HCHs and 257 g of endosulfans (ɑ + β + epoxide) adsorbed by the SPM. PAHs occurred widely along the river (38.83 ± 43.52 μg. g 1) and the highest levels coincided with locations with marked anthropogenic-related activity, such as petroleum/gas exploitation facilities. Risk quotient analysis showed a lowrisk posed by OCPs, but a high risk of potential effects on biota posed by the PAHs, highlighting the need for mitigation measures. .

Background Bio-monitoring of polycyclic aromatic hydrocarbons (PAHs) contaminants in mother milk is essential to keep mothers and infants healthy against potential risks. The current study assesses the concentration of PAHs in mother milk through a meta-analytic and systematic review approach. Methods All the published studies up to December 2020 regarding the concentrations of various PAHs in mother milk were searched throughout major international databases such as PubMed, Scopus, and Web of Science. Moreover, the possible carcinogenic and mutagenic risks to infants were evaluated based on the BaP (benzo[a]pyrenee) equivalent dose. Results According to the results of 13 articles included among 936 retrieved studies, the lowest and highest concentration of PAHs was (0.125 ng/g) and (76.36 ng/g) related to benz(a)anthracenem and 1-methylnaphthalene, respectively. The highest (9.830 ng/g) and lowest (0.009 ng/g) concentration of PAHs was related to Mexico and Japan, respectively. Besides, carcinogenetic and mutagenic risk assessment of the PAHs indicated that risk pattern was different across countries. It can be concluded that the consumption of mother milk is safe and does not pose a risk due to the ingestion of PAHs to the health of infant consumers.

A soil that was historically contaminated with Aqueous Film Forming Foam (AFFF) was dry sieved into size fractions representative of those produced during soil washing. Batch sorption tests were then conducted to investigate the effect of soil parameters on in situ per- and polyfluoroalkyl substances (PFAS) sorption of these different size fractions: < 0.063 mm, 0.063 to 0.5 mm, 0.5 to 2 mm, 2 to 4 mm, 4 to 8 mm, and soil organic matter residues (SOMR). PFOS (513 ng/g), 6:2 FTS (132 ng/g) and PFHxS (58 ng/g) were the most dominant PFAS in the AFFF contaminated soil. Non-spiked, in situ Kd values for 19 PFAS ranged from 0.2 to 138 L/Kg (log Kd −0.8 to 2.14) for the bulk soil and were dependant on the head group and perfluorinated chain length (spanning C4 to C13). The Kd values increased with decreasing grain size and increasing organic carbon content (OC), which were correlated to each other. For example, the PFOS Kd value for silt and clay (< 0.063 mm, 17.1 L/Kg, log Kd 1.23) were approximately 30 times higher compared to the gravel fraction (4 to 8 mm, 0.6 L/Kg, log Kd −0.25). The highest PFOS Kd value (116.6 L/Kg, log Kd 2.07) was found for the SOMR fraction, which had the highest OC content. Koc values for PFOS ranged from 6.9 L/Kg (log Koc 0.84) for the gravel fraction to 1906 L/Kg (log Koc 3.28) for the silt and clay, indicating that the mineral composition of the different size fractions also influenced sorption. The results here emphasize the need to separate coarse-grained fractions and fine-grained fractions, and in particular the SOMR, to optimize the soil washing process. Higher Kd values for the smaller size fractions indicate that coarser soils are better suited for soil washing.

In this work, an analytical method was optimised and validated for the simultaneous extraction and enantioselective determination of chiral β-blockers, antidepressants and two of their metabolites in agricultural soils, compost and digested sludge. Sample treatment was based on ultrasound-assisted extraction and extract clean-up by dispersive solid-phase extraction. Analytical determination was carried out by liquid chromatography-tandem mass spectrometry using a chiral column. Enantiomeric resolutions were in the range from 0.71 to 1.36. Accuracy was in the range from 85 to 127% and precision, expressed as relative standard deviation, was lower than 17% for all the compounds. Method quantification limits were below 1.21–52.9 ng g−1 dry weight (dw) in soil, 0.76–35.8 ng g−1 dw in compost and 13.6–90.3 ng g−1 dw in digested sludge. Application to real samples revealed enantiomeric enrichment in the range especially in compost and digested sludge (enantiomeric fractions up to 1). Junta de Andalucía US-1254283 Ministerio de Universidades FPU20/00540

The ingestion of nanoplastics (NPs) by fish has led to concerns regarding fish health and food chain transfer, but analytical constraints have hindered quantitative data collection on their uptake and depuration. We used palladium-doped polystyrene nanoplastics (PS-Pd NPs, ~200 nm) to track particle fate in rainbow trout (Oncorhynchus mykiss) during a week-long dietary exposure and subsequent 7-day depuration period on a control diet (no added PS-Pd NPs). At Day 3 and 7 of the exposure, and after depuration, the mid intestine, hind intestine, liver, gallbladder, kidney, gill and carcass were sampled. All organs and the carcass were analysed for total Pd content by inductively couple plasma mass spectrometry. After 3 days of exposure, the mid (32.5 ± 8.3 ng g−1) and hind (42.3 ± 8.2 ng g−1) intestine had significantly higher total Pd concentrations compared to the liver and carcass (1.3 ± 0.4 and 3.4 ± 1.1 ng g−1, respectively). At Day 7, there was no time-related difference in any organ (or the carcass) total Pd concentrations compared to Day 3. When the total Pd content was expressed as a body distribution based on mass of tissue, the carcass contained the highest fraction with 72.5 ± 5.2 % at Day 7, which could raise concerns over transfer to higher trophic levels. The total number of particles that entered the fish over the 7 days was 94.5 ± 13.5 × 106 particles, representing 0.07 ± 0.01 % of the Pd the fish had been fed. Following depuration, there was no detectable Pd in any organ or the carcass, indicating clearance from the fish. These data indicate that these NPs are taken into the internal organs and carcass of fish, yet removal of the exposure results in substantial excretion to below the limit of detection., Science of The Total Environment, 854, ISSN:0048-9697, ISSN:1879-1026

Analytical methods based on QuEChERS and liquid chromatography-tandem mass spectrometry were developed for the determination of 42 polar and semi-polar pesticides in three representative vegetable matrices, viz. corn, grapes and alfalfa. A 26-2 fractional factorial experimental design was used to cost-effectively optimize the extraction procedure. The optimal analytical approaches were validated in terms of linearity, sensitivity, trueness, and precision. Most of the target pesticides showed a relative recovery of 70-120 %. Moreover, limits of detection (between 0.01 ng/g and 20 ng/g) were below the maximum residue levels set for the target analytes in nearly all cases. Analysis of real samples showed the presence of five pesticides in grapes and alfalfa at concentrations between the method LOQs and 40 ng/g. To the authors' knowledge, these methods are the first ever described for the determination of 6, 13 and 24 of the 42 target pesticides measured in corn, grapes and alfalfa, respectively., This work has been funded by the European Union through the European Agricultural Fund for Rural Development (FitoFarmGest Operational Group PDR2020-101-030926), the Spanish Ministry of Science and Innovation (grant CEX2018-00794-S, funded by MCIN//AEI/ 10.13039/501100011033) and the Government of Catalonia (2017 SGR 01404). BEKOlut is acknowledged for the gift of QuEChERS kits.

Oilseed crops are greatly extended all over the world. Their high fat content can interfere during pesticide multiresidue analysis through liquid chromatography-tandem mass spectrometry (LC-MS/MS). This work aimed at overcoming this issue by developing and validating two QuEChERS-based methods for LC-MS/MS determination of 42 pesticides in two fatty food matrices: olives and sunflower seeds. Optimization of the extraction method was achieved following a 26-2 fractional factorial design in a highly cost-effective way. Validation of the multi-residue methods demonstrated improved limits of detection, below the established maximum residue levels (MRLs) for almost all compounds, good precision, and trueness, in compliance with SANTE guidelines. Application of these methods to the analysis of real samples from the Iberian Peninsula showed the presence of some pesticides of relevant environmental concern, including four compounds contained in the Pesticide Action Network International list of highly hazardous pesticides, found at levels between 0.03 ng/g and 104 ng/g., This work has been funded by the European Union through the European Agricultural Fund for Rural Development (FitoFarmGest Operational Group PDR2020-101-030926), the Spanish Ministry of Science and Innovation (Project CEX2018-00794-S) and the Government of Catalonia (2017 SGR 01404). BEKOlut is acknowledged for the gift of QuEChERS kits.

This study is focused on the development of a multiclass analytical method for sensitive determination of steroid hormones (progestins, oestrogens, androgens and glucocorticoids) in fruits and vegetables. The herein considered analytes present a wide logP range, thus they tend to accumulate differently in edible parts. Therefore, a berry fruit (strawberry), a root vegetable (carrot), and a leafy vegetable (spinach) were chosen as probes to develop the extraction procedure. This, optimized by a chemometric approach (23 experimental design) on lyophilized samples (0.25 g, spike 100 ng g − 1), entails a rapid ultrasonic extraction (3 × 1 min cycles) with low consumption (3 × 2 mL) of MeOH, selected as extraction solvent by a preliminary screening. The clean-up step, necessary due to the complexity of the matrices, was performed by a simple solid-phase extraction procedure on the Supelclean™ LC-NH2 sorbent afore the selective quantification by HPLC–ESI-MS/MS (MRM mode). The final analytical method was successfully applied to multianalyte extraction at lower concentrations (10–50 ng g−1) with good recoveries and repeatability, and it was successfully extended to raspberry, radish and arugula, further supporting applicability to this kind of samples. The results from the analysis of fruits and vegetables purchased from local markets, where some steroids have been quantified at the low ng g−1 levels, are consistent with literature data about concentration of these emerging pollutants in edible plants, also according to their LogP values.

Breast milk is the ideal food for humans, the first 6 months of life. However, due to its lipid content, it may contain persistent organic compounds (POPs). Therefore, the Stockholm Convention established a comparative monitoring of POPs in breast milk in different regions of the world. Objectives: . As part of that project, our goal was to determine the presence and concentration of brominated and chlorinated POPs in breastmilk collected during 2019, from Mexican mothers residing in the agricultural state of Sinaloa. Methods: . Fifty healthy, primiparous women participated, whose milk samples were analyzed according to the WHO protocol, modified by UNEP. Results: . The sum of the concentration of brominated compounds was 13.92 ng/g fat and the highest value corresponded to BDE-47 (7.67 ng/g fat). Among the chlorinated, p.p’-DDE had the highest concentration (537.99 ng/g fat) and the total concentration of DDTs was 622.23 ng/g fat. Among the dioxins and furans, dioxin-like and non-dioxin-like, the highest concentration was found in the dioxin-like PCB 118 (661 ng/g fat). Hexachlorobenzene concentration was also high (6.14 ng/g lipid) in comparison to other chlorinated compounds. Medium and short-chain chlorinated paraffins have a sum concentration of 140 ng/g lipid. Aldrin, Endrin, and Endrin ketone, Mirex, Toxaphene group, endosulfan group, chlordecone, p,p’-dicofol, pentachlorophenol, its metabolite pentachloroanisole and hexachlorobutadiene were not detected. Conclusions: . POPs were detected in all samples analyzed; the individual concentrations of the great majority of POPs appear to be below the limits considered ''safe'' for adults, except for dioxin-like (DL) compounds PCDDs and PCDFs. It should be considered that the susceptibility to toxics is different in an individual newborn, compared to an adult, in such a way that the sum, or empowerment of POPs even at low concentrations can result in permanent damage to the product.

Introduction Heterogeneity of nephrotic diseases and a lack of validated biomarkers limits interventions and reduces the ability to examine outcomes. Urinary CD80 is a potential biomarker for minimal change disease (MCD) steroid-sensitive nephrotic syndrome (NS). We investigated and validated a CD80 enzyme-linked immunosorbent assay (ELISA) in urine in a large cohort with a variety of nephrotic diseases. Methods A commercial CD80 ELISA was enhanced and analytically validated for urine. Patients were from Mayo Clinic (307) and Nephrotic Syndrome Study Network Consortium (NEPTUNE; 104) as follows: minimal change disease (MCD, 56), focal segmental glomerulosclerosis (FSGS, 92), lupus nephritis (LN, 25), IgA nephropathy (IgAN, 20), membranous nephropathy (MN, 49), autosomal dominant polycystic kidney disease (ADPKD, 10), diabetic nephropathy (DN; 106), pyuria (19), and controls (34). Analysis was by Kruskal−Wallis test, generalized estimating equation (GEE) models, and receiver operating characteristic (AUC) curve. Results Urinary CD80/creatinine values were highest in MCD compared to other glomerular diseases and were increased in DN with proteinuria >2 compared to controls (control = 36 ng/g; MCD = 139 ng/g, P < 0.01; LN = 90 ng/g, P < 0.12; FSGS = 66 ng/g, P = 0.18; DN = 63, P = 0.03; MN = 69 ng/g, P = 0.33; ng/g, P = 0.07; IgA = 19 ng/g, P = 0.09; ADPKD = 42, P = 0.36; and pyuria 31, P = 0.20; GEE, median, P vs. control). In proteinuric patients, CD80 concentration appears to be independent of proteinuria levels, suggesting that it is unrelated to nonspecific passage across the glomeruli. CD80/creatinine values were higher in paired relapse versus remission cases of MCD and FSGS (P < 0.0001, GEE). Conclusion Using a validated ELISA, urinary CD80 levels discriminate MCD from other forms of NS (FSGS, DN, IgA, MN) and primary from secondary FSGS., Graphical abstract

A novel mixed matrix of MOF@COF hybrid was firstly formed by coating of hexahedral cage structure MOF with lightweight porous COF, and applied in dispersive solid-phase extraction of the phenoxy carboxylic acids (PCAs) from water and vegetable samples. Combined with liquid chromatography-tandem mass spectrometry, an excellent method with low limits of detection (0.69–1.79 ng·L−1/0.002–0.006 ng·g−1), good reproducibility (1.32%–7.02%/1.81%–6.71%), and excellent linearities (10–1000 ng·L−1, R ≥ 0.9955/0.04–50 ng·g−1, R ≥ 0.9966) was established. The adsorption mechanisms deduced that the π-π interaction, hydrophobic effects, hydrogen bond, and halogen bond may promote the excellent adsorption of the PCAs. Finally, the applicability of the method was verified by spiking four kinds of water and vegetable samples with PCAs, and satisfying recoveries were obtained (between 83.3% and 104.9%).

The current study aimed to gauge total mercury (THg) concentration and the environmental geochemical indices in tarmat contaminated sediments and test their presence in targeted coastal species. Layers of hard asphalt-like tarmats and sediment samples were collected from 34 sites along the coast of Qatar. The mean concentration of THg in tarmat-sediment mixture is 89 ± 20 ng·g−1. THg concentration varies significantly between the northern and eastern coasts. Geographically, sampling area were divided into four zones according to the relative closeness with low to serious potential ecological risk index (Er), moderate pollution load index (PLI), moderate Geoaccumulation index (Igeo), and no toxic risk (TRI) trending as Northern (Zones 4, 3) > North-Eastern (Zone 1) > Western (Zone 2) coasts. Three biota classes (Gastropoda, Bivalvia, and Crustacea) were sampled on the tarmat which the hermit crab (Clibanarius signatus) from Ras Rakan island obtained the highest THg (977 ng·g−1) and BSAF (29.70).

Parabens are widely used in the food, cosmetics and pharmaceutical industry and are widespread in the environment. As endocrine disruptors, parabens have adverse effects on living organisms. However, knowledge of the exposure of domestic animals to parabens is extremely scarce. Therefore, this study assessed the exposure level of dogs to three parabens commonly used in industry (i.e. methylparaben - MeP, ethylparaben - EtP and propylparaben - PrP) using fur sample analysis in liquid chromatography-tandem mass spectrometry. The presence of parabens has been noted in the samples collected from all dogs included in the study (n = 30). Mean concentrations of MeP, EtP and PrP in the fur of dogs were 176 (relative standard deviation – RSD = 127.48%) ng/g dry weight (dw), 48.4 (RSD = 163.64%) ng/g dw and 79.8 ng/g dw (RSD = 151.89%), respectively. The highest concentrations were found for MeP (up to 1023 ng/g dw). Concentrations of MeP and EtP in males were statistically higher than those in females (p < 0.05). Statistically significantly higher concentration levels of PrP in young animals (up to three years old) were also found. This is the first study concerning the use of fur samples to evaluate the exposure of domestic animals to parabens. The results indicate that an analysis of the fur may be a useful tool of paraben biomonitoring in dogs. The presence of parabens in the canine fur also suggests that these substances may play a role in veterinary toxicology. However, many aspects connected with this issue are not clear and require further study.

In this study, we evaluated the suitability of body feathers, preen oil and plasma for estimation of organohalogen compound (OHC) exposure in northern goshawk Accipiter gentilis nestlings (n = 37; 14 nests). In addition, body feathers received further examination concerning their potential to provide an integrated assessment of (1) OHC exposure, (2) its dietary sources (carbon sources and trophic position) and (3) adrenal gland response (corticosterone). While tetrabromobisphenol A was not detected in any sample, the presence of polychlorinated biphenyls, organochlorine pesticides, polybrominated diphenyl ethers and hexabromocyclododecane in body feathers (median: 23, 19, 1.6 and 3.5 ng g−1 respectively), plasma (median: 7.5, 6.2, 0.50 and 1.0 ng g−1 ww, respectively) and preen oil (median: 750, 600, 18 and 9.57 ng g−1 ww, respectively) suggests analytical suitability for biomonitoring of major OHCs in the three matrices. Furthermore, strong and significant associations (0.20 ≤ R2 ≤ 0.98; all P < 0.05) among the OHC concentrations in all three tissues showed that body feathers and preen oil reliably reflect circulating plasma OHC levels. Of the dietary proxies, δ13C (carbon source) was the most suitable predictor for variation in feather OHCs concentrations, while no significant relationships between body feather OHCs and δ15N (trophic position) were found. Finally, body feather corticosterone concentrations were not related to variation in OHC concentrations. This is the first study to evaluate feathers of a terrestrial bird of prey as an integrated non-destructive tool to jointly assess nestling ecophysiology and ecotoxicology.

We evaluated the distribution of eleven groups of pharmaceutically active compounds (PhACs) in surface waters and biota of different trophic levels, in five sites of two lowland urban rivers in Argentine. Twenty-nine out of 39 PhACs and two metabolites were detected in at least one water sample (2-9622 ng/L), eleven detected in biofilms (1-179 ng/g d.w.) and eight in the macrophyte Lemna gibba (4-112 ng/g d.w). The two more polluted sites had a similar distribution of the main groups of compounds. In surface waters, the largest concentrations were for the analgesic acetaminophen (9622 ng/L), the antibiotic sulfamethoxazole (326 ng/L), the antihypertensive valsartan (963 ng/L), the β-blocking agent atenolol (427 ng/L), the diuretic hydrochlorothiazide (445 ng/L) and the psychiatric drug carbamazepine (99 ng/L). The antibiotic ciprofloxacin exhibited the highest concentration in the biofilm (179 ng/g d.w.) and in the macrophyte L. gibba (112 ng/g d.w.) Several compounds were detected in the water but not in the biota (e.g., codeine and bezafibrate), and others (e.g., azithromycin and citalopram) were found in the biota but not in the surface water. Significant bioaccumulation factors (>1000 L/kg d.w.) were obtained for venlafaxine and ciprofloxacin in biofilm. Our results show that PhACs may accumulate in several biological compartments. Within an environmental compartment, similar PhACs profile and concentrations were found in different sites receiving urban pollution. Among different compartments, biofilms may be the most suitable biota matrix to monitor the immediate reception of PhACs in the biota. Our results indicate that the presence of PhACs in urban rivers and their accumulation in the biota could be incorporated as symptoms of the urban stream syndrome., This study has been partly supported by Catalan Institute for Water Research (ICRA), Instituto de Ecología y Desarrollo Sustentable (INEDES-CONICET), National Science and Technology Agency (PICT 2636/15 y 2694/16) and Departamento de Ciencias Básicas- Universidad Nacional de Luján. The authors are sincerely thankful to Jorge Viera, Felipe Pansechi and Juliana Pansechi for valuable help in sampling.

Veterinary pharmaceuticals, including antibiotics, are emerging contaminants of concern worldwide. Avian scavengers are exposed to pharmaceuticals through consumption of livestock carcasses used for feeding wildlife for conservation purposes at supplementary feeding stations. Here we tested the hypothesis that griffon vultures (Gyps fulvus) would be more exposed to antibiotics (i.e., quinolones) when feeding on livestock carcasses from intensive farming than when they rely on carcasses from extensive farming or wild animals. We sampled 657 adult griffon vultures captured between 2008 and 2012. In addition, we sampled tissues from domestic livestock supplied at feeding stations in the study area between 2009 and 2019; pig (n = 114), sheep (n = 28), cow (n = 1) and goat (n = 2). Samples were analysed by liquid chromatography with electrospray ionization mass spectrometry (LC-ESI-MS). Quinolones were detected in plasma from 12.9% of the griffon vultures analysed. Quinolone prevalence in griffon vultures varied significantly among feeding stations but was also affected by the total amount of carcasses supplemented, especially the mass of pig carcasses. These results aligned with a 21.1% quinolone prevalence in pig carcasses sampled at feeding stations, wherein enrofloxacin and ciprofloxacin levels of up to 3359 ng/g and 1550 ng/g, respectively, were found. Given enrofloxacin pharmacokinetics in pig tissues, 5.3% of the analysed pigs may have died no more than one day after treatment. Quinolone presence in vultures was negatively associated with blood lead levels, which mostly originates from lead ammunition and indicates a higher consumption of game animal carcasses. Carcass disposal for feeding avian scavengers must always assess and manage the risks posed by veterinary pharmaceuticals, especially when livestock provided may have died soon after treatment., Some of the carcass sampling was also undertaken in collaboration with TRAGSATEC through contract REF. TEC0004566 and with the Conselleria de Medi Ambient, Aigua, Urbanisme i Habitatge of the Generalitat Valenciana.

International audience; Marine sediment is a significant sink for the global pollutant mercury. In a rapidly changing Arctic region, mercury (Hg) bioaccumulation in the marine ecosystem remains a prominent environmental issue. Here, we report surface sediment (0-2 cm) concentrations of Hg and other toxic elements of interest (Cr, Ni, Zn, Cu, As, Cd, Pb) in the northern Barents Sea and Eurasian Basin. We observed average Hg concentrations of 65 ± 23 ng/g with the highest concentration of 116 ng/g in the Eurasian Basin. Our calculated enrichment factors suggest low anthropogenic enrichment for mercury, chromium, nickel, and copper. Mercury and trace element geographic patterns are best explained by the origin and transportation of fine grain sediment towards the Eurasian Basin, with scavenging by both particulate organic carbon and metal oxides as significant delivery mechanisms.

Single-use or disposable facemasks have been widely used by the public for personal protection against the spread of COVID-19. The majority of disposable facemasks are made of synthetic polymers such as polypropylene, polyethylene terephthalate (as polyester), and polystyrene, and could therefore be a source of human exposure to plasticizers that are incorporated into these polymers during production. Little is known, however, about the occurrence of plasticizers in facemasks. In this study, we determined the concentrations of nine phthalate diesters and six non-phthalate plasticizers in 66 facemasks purchased in the United States. Among phthalate diesters, dibutyl phthalate, di(2-ethylhexyl)phthalate, di-iso-butyl phthalate, and butyl benzyl phthalate were found in all facemask samples, at median concentrations of 486, 397, 254, and 92 ng/g, respectively. Among non-phthalate plasticizers, dibutyl sebacate (median: 3390 ng/g) and di(2-ethylhexyl)adipate (352 ng/g) were found at notable concentrations. Inhalation exposure to select phthalate and non-phthalate plasticizers from the use of facemasks was estimated to range from 0.1 to 3.1 and 3.5 to 151 ng/kg-bw/d, respectively. To our knowledge, this is the first study to report the occurrence of phthalate and non-phthalate plasticizers in facemasks collected from the United States.

Polycyclic musks (PMs) have drawn increased attention in recent years because of their persistence, bioaccumulation and toxicity. As two typical PMs contaminants, tonalide (AHTN) and galaxolide (HHCB) are widely detected in sediment worldwide. Acute and chronic toxicity data of AHTN and HHCB to freshwater and seawater organisms in water and sediments are collected and screened. The predicted no effect concentrations (PNECsediment) for AHTN and HHCB is derived according to the equilibrium partitioning method recommended by the EU technical guidance document (TGD) and the species sensitivity distribution (SSD) method based on the measured sediment toxicity data. The concentration levels of AHTN and HHCB are investigated and evaluated in freshwater and seawater sediments. Results show the difference between native and non-native freshwater species is not statistically significant. AHTN is more toxic to freshwater and seawater organisms than HHCB, and seawater organisms are more sensitive to 2 musks than freshwater organisms. The chronic PNECsediment values of AHTN and HHCB are 194.48 and 416.47 ng/g in freshwater sediment, 88.93 and 128.34 ng/g in seawater sediment respectively. The AHTN and HHCB linear correlation analysis exhibited a strong positive linear correlation in both domestic (R2=0.9054) and foreign (R2 = 0.9645) sediment. Preliminary risk assessment shows that the risks posed by AHTN and HHCB in sediment based on individual or combined concentrations of two musks are at medium to high levels in some regions. Further risk assessment results indicate that, for HHCB,1.72% of foreign freshwater sediment may pose an ecological risk to 5% species; for AHTN, 8.06% of foreign freshwater sediment and 1.02% of domestic freshwater sediment may pose an ecological risk to 5% species, and 5.86% of seawater sediment may pose an ecological risk to 5% species. The above results indicate that there are some negligible risks in domestic and foreign sediments posed by these two musks, we should continue to pay attention to the toxic effects and pollution level of both musks in environment.

This study presents an analytical procedure for measuring the 87Sr/86Sr isotopic ratio in olive oil and pomace using multicollector-inductively coupled mass spectrometry (MC-ICPMS). The developed method combines liquid-liquid extraction with an acid solution and degradation of organic residues in the extract by dry ashing and oxidation by H2O2 and HNO3. The method enabled 87Sr/86Sr ratios to be obtained in olive oil with Sr content as low as 0.2 ng g􀀀 1, with a precision of 54 ppm. The method’s validity was confirmed by an interlaboratory comparison using NIST SRM 2387, providing the first data on its elemental Sr (2380 ± 230 ng g􀀀 1; n = 10), and 87Sr/86Sr isotopic composition (0.70908 ± 0.00004; n = 14). The procedure was applied to olive oil and pomace samples, showing that they have an identical 87Sr/86Sr ratio, which was consistent with that determined in soils from the same orchards. The results thus revealed that Sr isotopic ratios of olive oil and pomace can both be used in geographical traceability studies of olive oil, which means that, instead of processing large volume of oil, characteristic 87Sr/86Sr signatures of olive oil can be more easily obtained by analyzing small quantities of pomace obtained by centrifuging the oil. &nbsp

Lumbini is a world heritage site located in the southern plains region of Nepal, and is regarded as a potential site for evaluating transboundary air pollution due to its proximity to the border with India. In this study, 82 aerosol samples were collected between April 2013 and July 2014 to investigate the levels of particulate-bound mercury (PBM) and the corresponding seasonality, sources, and influencing factors. The PBM concentration in total suspended particulate (TSP) matter ranged from 6.8 pg m−3 to 351.7 pg m−3 (mean of 99.7 ± 92.6 pg m−3), which exceeded the ranges reported for remote and rural sites worldwide. The Hg content (PBM/TSP) ranged from 68.2 ng g−1 to 1744.8 ng g−1 (mean of 446.9 ± 312.7 ng g−1), indicating anthropogenic enrichment. The PBM levels were higher in the dry season (i.e., winter and the pre-monsoon period) than in the wet season (i.e., the monsoon period). In addition, the δ202Hg signature indicated that waste/coal burning and traffic were the major sources of Hg in Lumbini during the pre-monsoon period. Meanwhile, precipitation occurring during photochemical processes in the atmosphere may have been responsible for the observed Δ199Hg values in the aerosol samples obtained during the monsoon period. The PBM concentration was influenced mostly by the resuspension of polluted dust during dry periods and crop residue burning during the post-monsoon period. The estimated PBM deposition flux at Lumbini was 15.7 μg m−2 yr−1. This study provides a reference dataset of atmospheric PBM over a year, which can be useful for understanding the geochemical cycling of Hg in this region of limited data.

In the present work, recycled polyethylene (LDPE) samples of agricultural, post-commercial, post-industrial and post-consumer origin were selected and analysed. The analysis comprised the determination of different contaminants such as metals, polycyclic aromatic hydrocarbons (PAHs), dioxin-like biphenyl polychlorides (PCBs), and polychlorinated-dibenzo-p-dioxins and furans (PCDD/Fs). A comparison with one sample of virgin plastic (unrecycled) was performed. The study aimed at stressing the importance of this type of analysis in recycled plastics. Indeed, such an examination will determine the material’s final destination, and the possible origin of the pollutants analysed is investigated. Black post-industrial and post-consumer samples presented the highest concentration of PCBs and PCDD/Fs, attaining a maximum value of 2.40 pg WHO-TEQ/g, while the least toxic sample (post-commercial) presented a toxicity of 0.38 pg WHO-TEQ/g. PAHs content was also much higher in black samples, reaching 514.41 ng/g, while the lowest concentrations were obtained for the post-commercial plastic sample, which did not exceed 38.98 ng/g. The higher PAHs concentrations in the black samples were related to the carbon black content of the black samples, which was 2.00% for black post-industrial sample and 1.51% for post-consumer sample. The PCDD/Fs congener profile observed in almost all samples was very similar to the profile found in the literature on urban air samples, indicating that the plastic is mainly influenced by the environment. The presence of some metals (mainly copper) showed a slight correlation with PCDD/Fs content. The pollutants analysed were found to be significantly reduced during the cleaning processes that are generally carried out in recycling companies. This work was supported by the Ministry of Science and Innovation (Spain) [grant number PID2019-105359RB-I00], and by the University of Alicante [grant number UAUSTI21-03].

Marine mammals are one of the groups of animals most affected by marine pollution including that by organic compounds which, besides bearing recognised harmful effects to adults, they may also affect foetuses through placental transfer. In this study we analysed samples of fin whale (Balaenoptera physalus) females and their foetuses collected in the western Iceland summer feeding grounds in 2018. Three different families of organic pollutants: organophosphate esters (OPEs); halogenated flame retardants (HFRs); and short chain chlorinated paraffins (SCCPs), were analysed and their placental transfer investigated. HFRs were detected in 87.5% of females and 100% of foetus samples with concentrations that ranged between nd-15.4 and 6.37–101 ng/g lipid weight (lw), respectively. OPEs were detected in all samples, both from females (85.8–567 ng/g lw) and foetuses (nq-1130 ng/g lw). SCCPs were detected in 87.5% of female samples and 100% of foetal samples with concentrations that ranged between nd-30.9 and nq-574 ng/g lw, respectively. For OPE compounds, a significant negative correlation was observed between the logarithm maternal transfer ratio and their log Kow, indicating that a high lipophilicity reduced placental transfer rate. Interestingly, the decabromodiphenyl ethane (DBDPE) was the compound with the highest log Kow but also the one that was transferred the most from mothers to foetuses, calling for in-depth research on this pollutant. These results constitute the first evidence of mother-calf transfer of plasticizers and flame retardants in fin whales. Further investigations are needed to determine their potential effects on this species and other groups of animals., During the conduct of this study, one of its authors, Gísli Arnór Víkingsson, sadly died unexpectedly. Serve this article as a last tribute to his memory. This study was supported by the Spanish Ministry of Science and innovation (grant CEX 2018-000794-S and project PID2020-119712GBI00) (MCIN/AEI/10.13039/501100011033), by the Ministry of Economic Affairs and Digital Transformation (project CGL2015-70468-R (MINECO, FEDER, UE)), and by the Generalitat de Catalunya (Consolidated Research Group 2017 SGR 1404 - Water and Soil Quality Unit 2017 SGR 1404).

Increasing terrestrial run-off from melting glaciers and thawing permafrost to Arctic coastal areas is expected to facilitate re-mobilization of stored legacy persistent organic pollutants (POPs) and mercury (Hg), potentially increasing exposure to these contaminants for coastal benthic organisms. We quantified chlorinated POPs and Hg concentrations, lipid content and multiple dietary markers, in a littoral deposit-feeding amphipod Gammarus setosus and sediments during the melting period from April to August in Adventelva river estuary in Svalbard, a Norwegian Arctic Aarchipelago. There was an overall decrease in concentrations of ∑POPs from April to August (from 58 ± 23 to 13 ± 4 ng/g lipid weight; lw), Hg (from 5.6 ± 0.7 to 4.1 ± 0.5 ng/g dry weight; dw) and Methyl Hg (MeHg) (from 5 ± 1 to 0.8 ± 0.7 ng/g dw) in G. setosus. However, we observed a seasonal peak in penta- and hexachlorobenzene (PeCB and HCB) in May (2.44 ± 0.3 and 23.6 ± 1.7 ng/g lw). Sediment concentrations of POPs and Hg (dw) only partly correlated with the contaminant concentrations in G. setosus. Dietary markers, including fatty acids and carbon and nitrogen stable isotopes, indicated a diet of settled phytoplankton in May–July and a broader range of carbon sources after the spring bloom. Phytoplankton utilization and chlorobenzene concentrations in G. setosus exhibited similar seasonal patterns, suggesting a dietary uptake of chlorobenzenes that is delivered to the aquatic environment during spring snowmelt. The seasonal decrease in contaminant concentrations in G. setosus could be related to seasonal changes in dietary contaminant exposure and amphipod ecology. Furthermore, this decrease implies that terrestrial run-off is not a significant source of re-mobilized Hg and legacy POPs to littoral amphipods in the Adventelva river estuary during the melt season. publishedVersion

Brominated flame retardant chemicals, such as 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB) (CAS #: 183658–27-7) and bis(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH) (CAS #: 26040–51-7), have been detected in avian tissues and eggs from remote regions. Exposure to EHTBB and TBPH has been shown to cause oxidative stress and altered thyroid function in rodents and fish, yet no controlled studies have examined potential adverse effects of exposure in birds. Because flame retardants have been detected in wild raptors, we used American kestrels (Falco sparverius) as a model raptor to determine whether in ovo exposure to EHTBB or TBPH affected growth, hatching success, oxidative stress, or thyroid function. We exposed kestrel embryos to nominal concentrations (10, 50, or 100 ng g−1 egg weight) of EHTBB and TBPH via egg-injection on embryonic day 5. Embryonic exposure (~23 d) to EHTBB increased thyroid gland mass, reduced glandular colloid and total thyroxine (T4) in hatchling males and females, whereas deiodinase enzyme activity increased in males but decreased in females. Hatchlings exposed to TBPH in ovo exhibited reduced colloid and increased oxidative stress. Although exposure to EHTBB and TBPH caused several physiological effects (e.g., heart and brain mass), only exposure to 50 ng g−1 EHTBB appeared to reduce hatching success. Our results suggest these flame retardants may be hazardous for predatory birds. Future research should evaluate long-term survival and fitness consequences in birds exposed to these chemicals.

Although primary aromatic amines (AAs) are widely used in consumer products, little is known about their occurrence in indoor dust. A liquid chromatography – tandem mass spectrometry (LC-MS/MS) method was applied for the determination of 29 AAs and two tobacco smoke markers (nicotine and cotinine) in 256 house dust samples collected from 10 countries. Of the 29 AAs analyzed, p-anisidine, o-anisidine, 2,6-dimethylaniline (2,6-DMA), p-cresidine (p-CD), p-toluidine (p-TD), 4,4′-methylenedianiline (4,4′-MDA), ortho/meta-toluidine (o/m-TD), 4-chloroaniline (4-CA), 2,4-diaminotoluene (2,4-DAT), aniline, and 2-naphthylamine (2-NA) as well as nicotine and cotinine, were found prevalent in house dust samples. Sum median concentrations of AAs and tobacco smoke markers varied from 29.6 to 576 ng/g (overall median: 200 ng/g) and 10.8 to 2920 ng/g (415 ng/g), respectively. Among AAs, aniline was the abundant contaminant, found at median concentrations ranging from 19.6 ng/g (Colombia) to 334 ng/g (South Korea). Nicotine was detected in all indoor samples at median concentrations ranging from 9.92 ng/g (Colombia) to 2790 ng/g (India) ng/g. Concentrations of AAs in indoor dust were significantly correlated with those of nicotine. Estimated daily intake (EDI) of select AAs through the ingestion of house dust was in the range of 0.019–3.03 ng/kg-bw/day, which was five orders of magnitude below the tolerance limits.

Sediment samples from 25 locations in the Pensacola Bay System (PBS) watershed were analyzed for the presence of 51 per- and polyfluoroalkyl substances (PFAS) using ultra high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) and selected reaction monitoring. Results revealed quantifiable concentrations of PFAS in all sampling locations. More specifically, perfluorobutanoic acid (PFBA) was present in every sediment sample with a minimum and maximum concentration of 0.04 to 0.48 ng g−1 dry weight, respectively, across the 25 sites with an average of 0.1 ± 0.09 ng g−1. While PFOS, with an average of 0.11 ± 0.14 ng g−1 (range

Poly- and perfluoroalkyl substances (PFASs) are a large group of chemicals commonly used in various branches of industry, which may adversely affect the living organisms. The aim of this study were to evaluate exposure of dogs to six selected PFASs: five perfluoroalkyl carboxylic acids (perfluorobutanoic acid - PFBuA, perfluoropentanoic acid - PFPeA, perfluorohexanoic acid - PFHxA, perfluoroheptanoic acid - PFHpA, perfluorooctanoic acid – PFOA) and perfluorooctane sulfonic acid (PFOS) through the analysis of fur samples. To our knowledge this is the first study concerning the use of fur samples to evaluation of exposure of domestic animals to PFASs. Relationship between PFASs concentration and age, gender and body weight of animals was also evaluated. Fur samples were collected from 30 dogs living in Olsztyn (Poland). All PFASs studied were detected in the canine fur samples. The highest concentrations were observed in the case of PFOA and PFBuA, detected at concentrations in the range between 1.51 and 66.7 ng/g and 0.98–26.6 ng/g, respectively. During the present study generally no statistically significant differences dependent on gender, age and body weight of animals were found. This study confirms the suitability of fur samples for biomonitoring of exposure to PFASs in domestic animals, what may be important in veterinary toxicology. Minister of Science and Higher Education in the range of the program entitled “Regional Initiative of Excellence” for the years 2019–2022, project No. 010/RID/2018/19

The present study aimed to determine the serum organochlorine pesticides (OCPs) levels and risk of exposure among Saudi adults. Most OCPs are considered as endocrine-disrupting chemicals, and exposure can induce adverse health effects in both humans and wildlife. Serum OCP levels have not been documented in the Saudi population. Serum OCP concentrations were quantified using gas chromatography mass spectrometry (GC-MS/MS) in 302 serum samples collected from adult Saudis. All studied OCPs were detected in all participants. High concentrations of DDT and its metabolites (DDE and DDD) were detected in both males and females, with concentrations being significantly higher in males. High concentrations of 2,4-DDE, 4,4-DDE, and gamma-HCH were detected (18.31, 16.12, and 15.15 ng g−1 lipid and 5.9, 7.1, and 8.6 ng g−1 lipid for males and females, respectively). Alpha-HCH, Beta-HCH, 2,4-DDT, and 4,4-DDT were detected at concentrations lower than 2 ng g−1. Levels of OCPs varied according to age and body mass index (BMI). Serum concentrations of OCPs significantly differed between Saudi males and females and were influenced by age and BMI. This study is the first to document serum OCP concentrations in Saudi adults from Riyadh, KSA. Monitoring programs are suggested for evaluating serum OCP concentrations in the general population to track toxicity levels and serve as an indicator of possible adverse health effects. Keywords: Organochlorine pesticides, GC-MS/MS, Public health, Saudi Arabia

Exposure of e-waste workers to eight halogenated and five organophosphate ester flame retardant chemicals (FRs) was studied at a Canadian e-waste dismantling facility. FR concentrations were measured in air and dust samples collected at a central location and at four work benches over five-24 hour periods spanning two weeks. The highest concentrations in air from workbenches were of BDE-209 (median 156 ng m−3), followed by Tris(2-chloroethyl) phosphate (TCEP, median 59 ng m−3). Dust concentrations at the workbenches were higher than those measured at the central location, consistent with the release of contaminated dust during dismantling. Dust concentrations from the workbenches were also dominated by BDE-209 (median 96,300 ng g−1), followed by Triphenyl phosphate (TPhP, median 47,000 ng g−1). Most FRs were in coarse particles 5.6–18 μm diameter and ~30% were in respirable particles (

The presence of pollutants in estuary and oceanic systems is a global problem and a serious concern to human and environmental health. Usually, environmental monitoring studies consider classical persistent organic pollutants (POPs). However, the lists of POPs keep continuously growing and new POPs and other emerging pollutants should be considered in new monitoring programs. So, this study aimed to investigate the distribution and profile of classical POPs (polychlorinated biphenyl (PCBs), organochlorine pesticides (OCPs), and polycyclic aromatic hydrocarbons (PAHs)), new POPs and emerging pollutants (polybrominated diphenyl ethers (PBDEs), perfluorinated compounds (PFCs), novel halogenated flame retardants (NFRs) and UV filters) in bivalve mollusc samples (both raft-cultivated and wild mussel, Mytilus galloprovincialis; cockle, Cerestoderma edule; and clam, Ruditapes descussatus) collected in nine Galician Rias during the period February 2012 to February 2013. A predominance of PAHs (6.8–317 ng/g dry weight (dw)) followed by PCBs (0.47–261 ng/g dw), UV filters (1.4–157 ng/g dw), PFCs (0.53–62 ng/g dw), OCPs (0.07–29 ng/g dw), PBDEs (0.31–6.6 ng/g dw) and NFRs (0.07–3.2 ng/g dw) was found in the studied bivalves, being the UV filter octocrylene the compound found at the highest concentration (141 ng/g dw in a cockle sample), while the PAHs chrysene and benzo(b)fluoranthene were the compounds with the highest average concentration (20 and 14 ng/g dw, respectively). Inter-species, temporal and geographical variations on pollutants concentration were assessed by multifactorial analysis of variance. Statistically significant differences among the type of mollusc were observed for levels of organochlorinated and organobrominated pollutants considered (PCBs, OCPs and PBDEs), which were detected at higher concentrations in wild mussel. On the other hand, the main PFCs and UV filters showed a higher detection frequency in cockle samples. Location played significant role for PAHs, PCBs and the main PBDEs, being the most polluted rias those more industrialized and populated, i.e. A Coruña, Ferrol and/or Vigo. Finally, sampling timepoint was also a significant factor for most of the families considered but with different profiles. Thus, PAHs and PCBs showed higher concentrations in both February 2012 and 2013 and lower in August 2012, while the main PBDEs were measured at higher concentrations in November 2012 and lower in February 2012; and the main NFRs, PFCs and UV filters were present at lower levels in February 2013 The authors acknowledge the financial support provided by Galician Government (Conselleria de Economía e Industria, Xunta de Galicia) in the framework of Projects 10MDS700006PR and ED431C2017/36 and by the Spanish Government through the Research Projects CTM2014-56628-C3-2-R, CTM2017-84763-C3-2-R and FEDER funds SI

Background: It is necessary to determine whether there are adverse health effects of prenatal exposure to long-term, low levels of mercury and selenium. However, there are limited that reports on the association between mercury levels by selenium levels and birth size. Therefore, we examined whether maternal mercury levels during pregnancy had any effect on infant birth size, and size, and whether selenium levels influenced this relationship. Objectives: To examine the association between mercury and selenium levels during pregnancy with infant birth size. Methods: The Japan Environment and Children's Study is a prospective birth cohort conducted between 2011 and 2014. Total mercury levels and total selenium levels in maternal blood during the second and third trimesters were measured using Inductively Coupled Plasma-Mass Spectrometry. Birth weight and small-for-gestational-age were confirmed by medical records. Small-for-gestational-age was defined as birth weight below the 10th percentile according to standard percentile for gender, parity, and gestational age. Multiple linear and logistic regression analyses were used to examine the association between maternal mercury exposure and birth weight or small-for-gestational-age adjusted for confounders (including maternal age and body mass index pregnancy). Results: Overall, 15,444 pregnant women were included in this study. Median (inter-quartile range) of blood mercury and selenium levels were 3.66 (2.59–5.18) ng/g and 170.0 (158.0–183.0) ng/g, respectively. Compared to infants of mothers with the highest blood selenium level, those of mothers with the lowest blood selenium level had neither a significant birth weight increase (9 g, 95% confidence interval: −6, 25) nor a significant odds ratio for small-for-gestational-age (0.903, 95% confidence interval: 0.748, 1.089). Compared to infants of mothers with the lowest blood mercury level, those of mothers with the highest blood mercury level had neither a significant birth weight reduction (−12 g, 95% confidence interval: −27, 4) nor a significant odds ratio for small-for-gestational-age (0.951, 95% confidence interval: 0.786, 1.150). Compared to infants of mothers with the lowest quartile of maternal blood mercury level, all infants of mothers with the highest quartile of maternal blood mercury level had a reduced birth head circumference of 0.073 cm (95% confidence interval: −0.134, −0.011). Conclusions: There was no association between maternal blood mercury levels and small-for-gestational-age and birth weight among 15,444 pregnant women. In a Japanese population, which has a relatively higher blood mercury level than reported in Western population, reduced birth size was not found to be associated with blood mercury levels, with the exception of birth head circumference. Keywords: Mercury, Selenium, Pregnancy, Birth weight, Small-for-gestational-age, The Japan Environment and Children's Study

Seasonal levels of organochlorine pesticides (OCPs) in yam, cassava, sweet potato and cocoyam samples collected from Esa-Oke Farm Settlement, Osun State, Nigeria were evaluated. Sampling regiment for three sites lasted four months each during the dry and wet seasons. The dried samples were extracted using Soxhlet extractor with dichloromethane (DCM) as the extraction solvent, while the identification and estimation of OCPs in the crop filtrates, after clean-up, were carried out with Gas Chromatography equipped with Time-of-Flight Mass Spectroscopy Detector (GC-TOFMS). Ten OCPs determined in the crops had the overall seasonal mean levels that ranged from 158 ng/g (dieldrin) to 544 ng/g (heptachlor) and the seasonal mean burden per OCP occurred in the order: heptachlor epoxide (518) > heptachlor (447) > p,p’-DDE (431) > dieldrin (349) > chlordane (327) > aldrin (321) > p,p’-DDD (313) > methoxychlor (303) > endosulfan I (287) > p,p’-DDT (284) for wet season while this order was not the same for dry season of the same crop with heptachlor epoxide (415) > p,p’-DDE (373) > aldrin (305) > heptachlor (307) > methoxychlor (288) > chlordane (274) > p,p’-DDT (263) > p,p’-DDD (263) > endosulfan I (260) > dieldrin (246). For all of the OCPs, the estimated daily intake (EDI) and health risk indices (HRI) were significantly higher than the recommended values. Thus, a regular large-scale consumption of crop products from the farm settlement could result in grave public health concern in the course of time., Food Crops, Organochlorine Pesticides, Health Risks, Farm settlement, Esa-Oke.

Polycyclic aromatic hydrocarbons (PAHs) are one of the important environmental pollutants that are mainly originated from industrial activities, vehicle emissions, biomass combustion, etc. Nowadays, the surrounding environment of the abandoned industrial area may still have potential health effects on the population, but current researches have paid less attention to this issue. Therefore, we report a comparative investigation focusing on the concentration, distribution, source identification, and risk assessment of PAHs in soils from surrounding areas of an abandoned industrial district and an ecological village in Zhejiang Province, China. Our findings are as follows: the levels of ∑16PAHs ranged from 150.2 to 83096 ng·g−1 with an average concentration of 7680.4 ng·g−1 in industrial area, whereas 49.4 to 778.2 ng·g−1 with an average concentration of 213.5 ng·g−1 in rural area. Although high molecular weight PAHs were both dominant contaminants in study areas, the composition profiles of 16 priority PAHs in soils from the two sampling sites had large differences. Source identification analysis verified that fossil fuel burning and vehicle emissions were the main sources of PAHs in industrial area, while the primary sources were biomass burning and vehicle emission in rural area. The incremental lifetime cancer risk results demonstrated that dermal contact was the most influential factor for all groups, and adults might face higher potential health risk than children in both industrial and rural areas. Moreover, the overall ecological risk of soil PAH pollution was low in rural area, but some individual samples were still high in the abandoned industrial area. Our research is of great significance for the management of the surrounding environment of abandoned industrial areas.

Water-soluble vitamins are essential dietary components with a multitude of important functions that require quantification from food sources to characterise the nutritional status of food. In this study, we have developed a hydrophilic interaction chromatography (HILIC) based method coupled to single-quadrupole mass spectrometry (MS) for the analysis of selected water-soluble vitamins. Due to their involvement in energy release from macronutrients, the quantification of thiamine (B ), riboflavin (B ), nicotinamide (B ) and pyridoxine (B ) offers significant value in food analysis. A commercially available vegetable soup was selected as the food matrix for this study and utilised to develop an efficient extraction procedure for the vitamins of interest. Vitamins were extracted using meta-phosphoric acid coupled with a reducing agent, DL-dithiothreitol (DTT) to produce the parent compound. The extracted vitamins were then analysed using an LC-MS system with electrospray - atmospheric pressure ionization (ES-API) source, operated in positive single ion monitoring (SIM) mode. The MS provided good linearity within the investigated range from 5 to 400 ng/mL with coefficient of determination (r ) ranging from 0.98 to 0.99. Retention times (0.65-9.04 min) were reproducible and no coelution between vitamins was observed. Limit of detection (LOD) varied from 2.4 to 9.0 ng/mL and limit of quantification (LOQ) was from 8 to 30 ng/mL, comparable to previously published studies. The extraction method provided good intra-day (%CV 1.56-6.56) and inter-day precision (%CV 8.07-10.97). Standard injections were used as part of quality control measures and provided excellent reproducibility (%CV 0.9-3.4). The overall runtime of this method was 19 min, including column reconditioning. Using this method, the quantity of thiamine (67 ± 7 ng/g), riboflavin (423 ± 39 ng/g), nicotinamide (856 ± 77 ng/g) and pyridoxine (133 ± 11 ng/g) was determined from a complex food matrix. In conclusion, we have developed a rapid and reliable, HILIC-single quad MS method utilising SIM for the low-level quantification of four B vitamins in a vegetable soup matrix in under 20 min. This method has shown excellent linearity, intra- and inter-day reproducibility and is directly applicable to other plant-based food matrices. [Abstract copyright: Copyright © 2021. Published by Elsevier B.V.]

In this study, urban stream sediment samples were collected in the Suzhou Industrial Park (SIP), one of the earliest national demonstration eco-industrial parks of China. PAHs were analyzed in these sediments, and concentrations of total PAHs were 180–81,000 ng g−1 (5700 ± 14,000 ng g−1). Medium molecular weight (4- ring) PAHs were predominant (42 ± 12%), followed by high molecular weight (5- and 6- ring) PAHs (31 ± 10%). No correlation was found between concentrations of PAHs and land uses of SIP in this study. Diagnostic ratios and a positive matrix factorization (PMF) model indicated that coal/biomass combustion might be the primary PAH source (61%), followed by non-combustion sources (21%) and vehicular emission (18%). According to the spatial analysis, PAHs in the sediments of SIP might be mainly associated with the coal/biomass combustion in the northeast industrial zone. Residential & commercial activities seem not to be the major causes of PAH contamination. Total PAH toxic equivalent concentrations, effect range low/effect range median values, and mean effects range–median quotient all showed that PAHs were present at a low toxicity risk level in most regions of the SIP. However, vigilance is required at some sampling sites with extremely high PAH concentrations or high mean effects range–median quotient.

A multi-residue analysis of six diacylhydrazine insecticides in water, sediment, and aquatic products was established by liquid chromatography triple quadrupole tandem mass spectrometry (LC-MS/MS). The water sample was extracted with acetonitrile by low-temperature enrichment liquid-liquid extraction technology. The sediment and aquatic products were prepared using QuEChERS technique. Method validation showed perfect linearity with correlation coefficients (R) more than 0.9992 for all insecticides, and the matrix effects were nearly negligible (−1.42% to −0.27%) for water, sediment and aquatic products. The recoveries were 80.0–99.7% at three spiked levels (0.02 ng·mL−1, 0.1 ng·mL−1, 0.5 ng·mL−1; 2.0, 10, and 50 ng·g−1) and the precisions (intra-day and inter-day precision) were lower than 5.28%, with the low LODs (3.8 ~ 9.6 pg·mL−1; 0.38–0.96 ng·g−1) and LOQs (12.7 ~ 32.0 pg·mL−1; 1.27–3.20 ng·g−1) for water, sediment, and aquatic products, indicating the good accuracy and precision of the proposed method. The applicability, efficiency, and sensitivity of this method have been proved in the analysis of six diacylhydrazine insecticides in water, sediment, and crucian carp in Rice- crucian carp - integrated planting system.

As a representative densely urbanized and industrialized city of China, Ningbo has experienced extremely rapid development, with a wide variety of chemical, electronic, pharmaceutical, and paper manufacturing industries. However, limited data and researches are available regarding the levels and profiles of perfluoroalkyl substances (PFASs) in surface soils of Ningbo. The present study was launched to address the knowledge gap through analyzing 27 sites in five functional regions for 9 PFASs types. Results showed that concentrations of the total PFASs (∑PFASs) ranged from 0.63 to 25.6 ng·g−1, with an average of 10.1 ng·g−1. The concentrations of ∑PFASs in different functional regions were in the order of landfill sites > industrial areas > farmlands > residential communities > animal farms. Correlation analyses between soil physicochemical properties and PFASs content revealed that concentrations of ∑PFASs were negatively correlated with soil pH but positively correlated with soil organic matter. Principal component analysis indicated that fluorochemical industrial discharge, daily life discharge, atmospheric precipitation, and electrochemical fluorination process dominated factor loadings. In addition, the ecological risk assessment based on the risk quotient demonstrated that although the risk of PFOA contamination in landfill sites was highest, there are no risk of PFOA and PFOS contamination in the surface soil environment, but needs more supervision for the neighborhood of landfill sites to avoid additional risk. This work provides new data on the different PFAS profiles in soils impacted by different contamination sources within a densely urbanized and industrialized area, and the results obtained should be useful for delineating priority sites for remediation and restauration of polluted soils.

Several bird species have adapted to foraging in landfills, although these sites are known to represent significant sources of emissions of toxic semi-volatile chemicals including the halogenated flame retardants (HFRs) (e.g., polybrominated diphenyl ethers (PBDEs) and emerging compounds). The objective of this study was to investigate the association between atmospheric exposure to PBDEs and selected emerging HFRs and their bioaccumulation in landfill-foraging birds. We determined HFR concentrations in liver of 58 GPS-tagged ring-billed gulls (Larus delawarensis) breeding in a colony near Montreal (Canada) as well as their atmospheric exposure determined using a miniature bird-borne passive air sampler. PBDE mixtures were the most abundant HFRs determined in passive air samplers (daily exposure rates of ∑9PentaBDE: 47.4 ± 6.5 pg/day; DecaBDE: 36.0 ± 6.3 pg/day, and ∑3OctaBDE: 3.4 ± 0.5 pg/day) and liver (∑9PentaBDE: 68.1 ± 8.9 ng/g ww; DecaBDE: 52.3 ± 8.1 ng/g ww, and ∑3OctaBDE: 12.8 ± 2.1 ng/g ww), and their concentrations increased with the presence probability of gulls in landfills. We found a spatial relationship between the local sources of atmospheric exposure to PBDEs and the sites associated with greatest PBDE concentrations in liver. Specifically, the atmospheric exposure index was correlated with the bioaccumulation index (Pearson r for ∑9PentaBDE: r = 0.63, p

In this work the presence of different pharmaceuticals at Doñana National Park (Spain) and their main entry sources (input source or entry points) have been stated over the 2011–2016 years period. Twenty-three selected pharmaceuticals (corresponding to eight therapeutic families) were evaluated in crayfish and water samples from Doñana National Park (Spain) (six sampling points selected in order to cover different possible pollution sources into and surrounding the Park). The multiresidue determination was carried out using enzymatic-microwave assisted extraction prior to high performance liquid chromatography mass spectrometry detection. Sulphonamides (sulfadiazine, sulfamerazine, sulfamethazine, and sulfamethoxazole); trimethoprim, an antibiotic that is frequently co-administered with sulfamethoxazole; amphenicols (chloramphenicol, florfenicol and thiamphenicol); fluoroquinolones (ciprofloxacin, enrofloxacin, flumequine, danofloxacin, gatifloxacin, norfloxacin, marbofloxacin and grepafloxacin); penicillins (amoxicillin); tetracyclines (chlortetracycline and oxytetracycline); non-steroidal anti-inflammatory drugs (salicylic acid and ibuprofen); beta-blocker drugs (atenolol); and antiepileptics (carbamazepine) were analysed. Ciprofloxacin, ibuprofen, salicylic acid, flumequine, and carbamazepine were detected and/or quantified at some of the selected sampling points. A clear ecotoxicological risk to the ecosystem was demonstrated from the occurrence of ciprofloxacin in samples obtained after the punctual and massive presence of people inside the Park. Furthermore, flumequine and carbamazepine have been detected in Procambarus clarkii specimens in concentrations around 30 ng g−1 and 14 ng g−1, respectively, and their occurrence in the specimens could indicate the persistence of the discharge sources. The main source of pharmaceuticals into the Park might be the livestock farming activities, and the influence of urban wastewaters from surrounding villages does not seem to be very important. Dirección General de Investigación y Gestión del Plan Nacional de I+D+i (Ministerio de Economía y Competitividad) CTM2012-38720- C03-01, CTM2015-67902-C02-01-P FEDER/ Ministerio de Ciencia e Innovación, Agencia Estatal de Investigación PGC2018-096608-B-C22

The scarcity of freshwater has led to a considerable increase of the reuse of reclaimed wastewater for irrigation of field crops [1,2]. This practice potentially exposes agricultural produce to a large variety of xenobiotic compounds including contaminants of emerging concern (CECs) which have been widely recognized to be present in wastewater [3]. Common approaches for the extraction of CECs from crops rely on solid-liquid extraction [4], assisted solvent extraction [5], ultra-sound solvent extraction [6] and recently QuEChERS (QUick, Easy, CHeap, Effective, Rugged and Safe) [[7], [8]–9]. Here, eight QuEChERS-based methodologies were compared for their suitability to determine 45 CECs in roots and leaves of soil-grown radish. The key points of the method development were: • The development of two single-step analytical methods specific for radish root and leaves, after testing eight different approaches using QuEChERS extraction for the quantitation of 45 CECs. The analytical methodology selected requires minimal time and solvent, making it cost-effective. • Methods validation were performed at five concentrations levels (2, 5, 10, 50 and 200 ng g−1), with low limits of quantification between 0.01 and 0.32 ng g−1. • The two optimized methodologies may be applied to identify large number of compounds of different families in radish crop. However, validation will be needed to quantify compounds different from the target compounds of this paper., This study has been financially supported through the Spanish national project TRAPPER (CICLIC, RTI2018-097158-B-C33). This work was supported by the Spanish Ministry of Science and Innovation (Project CEX2018-000794-S-19-2). Authors acknowledge SCIEX for providing the loan instrument LC/HRMS QTOF X500R. Cristina Labad (www.cristinalabad.com) was acknowledged for the graphical support.

In this study, the occurrence of 12 organophosphorus flame retardants (OPFRs), 64 pesticides, 21 perfluoroalkyl substances (PFASs) and 34 pharmaceuticals and personal care products (PPCPs) in surface water, sediments and vegetation collected from seven locations along the South Riyadh and six locations along the Al-Jubail industrial city (Saudi Arabia) were reported. The median of the concentrations of ƩOPFRs, ƩPesticides, ƩPFASs and ƩPPCPs in water was 297, 231, 29.7 and 3794 ng L−1, respectively, in sediments 56.2, 40.4, 5.66 and 419 ng g−1 d.w., in crops for human consumption of 45.6, 42.0, 0.46 and 42.0 ng g−1, in farm crops of 13.4, 57.5, 3.2 and 637 ng g−1, and in natural vegetation of 51.7, 10.3, 1.88 and 1580 ng g−1. Predominant compounds in all matrices were tris-(1,3-dichloro-2-propyl)phosphate (TClPP), acetamiprid, imidacloprid, caffeine, bisphenol A (BPA), diclofenac and ibuprofen. Tris(2-butoxyethyl) phosphate (TBEP), tris-(2-ethylhexyl)phosphate (TPhP), perfluoroctanoic acid (PFOA), perfluoroalkyl sulfonate (PFOS) and paracetamol were also in many samples but at low concentrations. The contaminants' levels showed similar values in both cities. However, pesticide levels were significantly higher in surface water (p < 0.05) and lower in natural vegetation (p < 0.05) of Riyadh than those of Al-Jubail. The risk assessment for the aquatic biota showed that abamectin, diazinon (pesticides), bisphenol A and caffeine (PPCPs) had the highest risk levels. The cumulative risk assessment showed that the contaminant mixture in all water samples is of concern. As far as the risk to human health is concerned, individual contaminants did not show a significant hazard for the population. However, OPFRs and pesticide requires a closed monitoring since % of admissible daily intakes (ADIs) or reference doses (RfD) are high. This is one of the most comprehensive study covering environmental and human risk assessment of emerging contaminants carried out in Saudi Arabia., The financial support from the project number (RSP-2021/11) King Saud University, Riyadh, Saudi Arabia.

Coal ash spills occasionally occur due to the accidental failure of surface impoundments, and toxic metal-laden ash can pose a serious health threat to adjacent aquatic ecosystems. Here, we performed an investigation into longitudinal variations of mercury (Hg) contamination in the Dan River (North Carolina, United States) about 17 and 29 months after a February 2014 coal ash spill incident, in which the reported Hg concentrations in the spilled coal ash (210 ng/g) were 1–2 orders of magnitude higher than the river sediments (2–61 ng/g). We examined total Hg (THg) and methyl Hg (MeHg) in sediments from 0 to 65 km downstream of the spill, and found that most of the variations of THg and MeHg in surface sediments (0–16 cm) could be well accounted by the organic matter content and appeared to be not contaminated by Hg derived from coal ash. In examining MeHg bioaccumulation in invertebrates (aquatic and riparian) and fish in the Dan River and fish in a reservoir downstream of Dan River, we found no evidence of elevated MeHg bioaccumulation due to the 2014 coal ash spill. Thus, we concluded that Hg contamination from the coal ash spill is largely absent in the Dan River for both surface sediments and biota within the first three years of spill (until 2017), even though the majority of coal ash may be buried deeper in the sediment in the river channel and/or the downstream reservoir. Alternatively, the Hg associated with the coal ash is largely not bioavailable for extensive microbial Hg methylation. The findings provide useful insights into remediation strategies for this incident and other coal ash spills.

Diclofenac is a non-steroidal anti-inflammatory drug (NSAID) with a well-known toxicity for old world vultures that ingest the carrion of domestic animals treated with it. Diclofenac intoxication was directly related to the dramatic declines in the populations of three native South Asian Gyps vulture species two decades ago. In 2013, this NSAID was authorised for veterinary use in Spain, which has the largest vulture populations in Europe. One of these species is the cinereous vulture (Aegypius monachus), which is classified as “near threatened” by the International Union for Conservation of Nature (IUCN). This species has been reintroduced and monitored in Catalonia (NE Spain) since 2007, and in 2020 its current population consisted of 15 breeding pairs and a total number of 61 individuals. In September 2020, one fledgling was found dead in the nest. Post-mortem examination revealed severe generalised visceral and articular gout, which was confirmed histologically. Diclofenac was detected at average concentrations of 26.5 ng/g in the liver and 51.4 ng/g in kidney replicates (n = 3), respectively. These findings support a diagnosis of fatal gout caused by diclofenac intoxication. This is the first case of diclofenac poisoning in Spain (and in Europe), in addition to being the first report of diclofenac poisoning in cinereous vultures. This case report, therefore, supports the need to closely monitor vulture populations and carry out strict regulatory measures with which to prevent these poisonings., The programme to reintroduce the cinereous vulture into the Catalan pre-Pyrenees has been funded by “Obra Social la Caixa” (through a contract with the “Generalitat de Catalunya”), the “Red Eléctrica de España” and the “Fundación Biodiversidad” from the Spanish Ministry of Ecological Transition and Demographic Challenge (MITECO).

Persistent organic pollutants (POPs) accumulate in the food web of the Great Lakes ecosystem, causing concern that these chemicals play a role in the decline of avian species such as colonial-nesting waterbirds. In this study, samples from four life stages of the common tern (Sterna hirundo), a threatened species in New York State, were collected post-mortem in the Buffalo-Niagara region (United States). Brains (n = 26) and livers (n =27) were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and the insecticide p,p’-dichlorodiphenyltrichloroethane (DDT) and its two metabolites p,p’-dichlorodiphenyldichloroethylene (DDE) and p,p’-dichlorodiphenyldichloroethane (DDD). Detectable concentrations of PCBs and PBDEs were observed in all samples; concentrations of total PCBs ranged from 5.59 to 2,490 ng/g wet weight (ww), total PBDEs ranged from 1.09 to 494 ng/g ww, and DDE metabolites ranged from 0.56 to 637 ng/g ww. Analysis of the primary food source for terns in the Buffalo-Niagara region, emerald shiners (Notropis atherinoides), revealed that all three classes of POPs had similar contaminant profiles in the fish to those in the brains and livers of tern samples. Overall, small chicks contained greater concentrations of pollutants than medium chicks and juveniles, likely from maternal loading to eggs. These results underline the persistence of these legacy contaminants in the Great Lakes, despite their banning, and their biomagnification in threatened species through food web interactions.

Background Epidemiologic literature on the relation of organochlorine pesticides (OCPs) with semen quality among adult men has been inconclusive, and no studies have prospectively explored the association between peripubertal serum OCPs and semen parameters in young men. Objective To evaluate prospective associations of peripubertal serum concentrations of hexachlorobenzene (HCB), β-hexachlorocylohexane (β-HCH), and p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) with semen parameters among young Russian men. Methods This prospective cohort study included 152 young men who enrolled in the Russian Children’s Study (2003–2005) at age 8–9 years and were followed annually until young adulthood. HCB, β-HCH, and p,p′-DDE concentrations were measured at the CDC by mass spectrometry in serum collected at enrollment. Between 18 and 23 years, semen samples (n = 298) were provided for analysis of volume, concentration, and progressive motility; we also calculated total sperm count and total progressive motile count. Linear mixed models were used to examine the longitudinal associations of quartiles of serum HCB, β-HCH and p,p′-DDE with semen parameters, adjusting for total serum lipids, body mass index, smoking, abstinence time and baseline dietary macronutrient intake. Results Lipid-adjusted medians (IQR) for serum HCB, βHCH and p,p-DDE, respectively, were 150 ng/g lipid (102–243), 172 ng/g lipid (120–257) and 275 ng/g lipid (190–465). In adjusted models, we observed lower ejaculated volume with higher serum concentrations of HCB and βHCH, along with reduced progressive motility with higher concentrations of βHCH and p,p-DDE. Men in the highest quartile of serum HCB had a mean (95% Confidence Interval, CI) ejaculated volume of 2.25 mL (1.89, 2.60), as compared to those in the lowest quartile with a mean (95% CI) of 2.97 mL (2.46, 3.49) (p = 0.03). Also, men in the highest quartile of serum p,p-DDE had a mean (95% CI) progressive motility of 51.1% (48.6, 53.7), as compared to those in the lowest quartile with a mean (95% CI) of 55.1% (51.7, 58.5) (p = 0.07). Conclusion In this longitudinal Russian cohort study, peripubertal serum concentrations of selected OCPs were associated with lower ejaculated volume and progressive motility highlighting the importance of the peripubertal window when evaluating chemical exposures in relation to semen quality.

The variably serpentinized mantle peridotites of the Late Neoproterozoic Ess ophiolite (Western Saudi Arabia) are highly altered along shear zones and thrust planes to form erosion-resistant listvenites. The listvenites are distinguished petrographically and geochemically into three types: carbonate, silica-carbonate and silica (birbirite) listvenites. Geochemical analyses are consistent with expectations from petrography: carbonate listvenite is low in SiO2 content but high in MgO, Fe2O3, and CaO relative to silica-carbonate and birbirite, which is remarkably high in SiO2 at the expense of all other components. The total REE contents are low in silica-carbonate and carbonate listvenites but highly enriched in birbirite, with a large positive Eu anomaly. The host serpentinites have all the characteristics typically associated with highly depleted mantle harzburgite protoliths in supra-subduction fore-arc settings: bulk compositions are low in Al2O3 and CaO with high Mg# [molar Mg/(Mg + Fe)], relict Cr-spinel has high Cr# [molar Cr/(Cr + Al)] and low TiO2, and relict olivine has high Mg# and NiO content. The Cr-spinel relics are also found in the listvenites; those in serpentinite and carbonate listvenites have significantly higher Mg# than those in silica-carbonate and birbirite, suggesting re-equilibration of Cr-spinel in the later phases of listvenitization. The varieties of listvenite capture successive stages of fluid-mediated replacement reactions. The carbonate listvenite appears to have developed syn-contemporaneously with serpentinization, whereas silica-carbonate listvenite and birbirite formed later. The listvenite formation resulted in leaching and removal of some components accompanied by deposition of others in the solid products, notably CO3, SiO2, REE (especially Eu), Au, Zn, As, Sb and K. Our data show that listvenitization concentrated gold at sub-economic to economic grades; measured gold concentrations in the host serpentinite are 0.5–1.7 ng/g, versus 4–2569 ng/g in carbonate listvenite, 43–3117 ng/g in silica-carbonate listvenite and 5–281 ng/g in birbirite. The listvenite deposits in the Jabal Ess area merit further exploration for gold.