Role of niche and micro-habitat preferences in per- and polyfluoroalkyl substances occurrence in the gills of tropical lake fish species.

The present study has investigated per- and poly-fluoroalkyl substances (PFAS) in the gill tissues of various fish species inhabiting different trophic levels within Eleyele Lake, a tropical freshwater lake in Nigeria. The mean concentrations of PFAS congeners were determined, and their trends and patterns were analyzed across different trophic species. The results revealed variations in congener abundance and species-specific patterns that was influenced by habitat and niche preferences. Multivariate associations using canonical-correlation analysis (CCA) revealed distinct trends in the relationships between gill concentrations of specific PFAS congeners and different trophic groups. The strongest congener relationships were observed in the pelagic omnivore (Oreochromic niloticus: ON) with positive associations for 4:2 FTS, 9CL-PF3ONS, PFTDA, MeFOSA and PFHxS. The differences in congener profiles for the two herbivorous fish (Sarotherodon melanotheron (SM) and Coptodon galilaeus (CG)) reflect possible divergence in microhabitat and niche preferences. Furthermore, the congener overlaps between the herbivore (CG), and benthic omnivore (Clarias gariepinus: ClG) indicate a possible niche and microhabitat overlap. Our study provides valuable insights into the congener dynamics of PFAS at Eleyele Lake. However, the dissimilarity and overlapping PFAS congener profile in fish gills reflects the interplay of species niche preference and microhabitat associations. The present study highlights the need for further research to assess ecological risks and develop effective PFAS management strategies.

Eco-toxicological and climate change effects of sludge thermal treatments: Pathways towards zero pollution and negative emissions.

The high moisture content and the potential presence of hazardous organic compounds (HOCs) and metals (HMs) in sewage sludge (SS) pose technical and regulatory challenges for its circular economy valorisation. Thermal treatments are expected to reduce the volume of SS while producing energy and eliminating HOCs. In this study, we integrate quantitative analysis of SS concentration of 12 HMs and 61 HOCs, including organophosphate flame retardants (OPFRs) and per- and poly-fluoroalkyl substances (PFAS), with life-cycle assessment to estimate removal efficiency of pollutants, climate change mitigation benefits and toxicological effects of existing and alternative SS treatments (involving pyrolysis, incineration, and/or anaerobic digestion). Conventional SS treatment leaves between 24 % and 40 % of OPFRs unabated, while almost no degradation occurs for PFAS. Thermal treatments can degrade more than 93% of target OPFRs and 95 % of target PFAS (with the rest released to effluents). The different treatments affect how HMs are emitted across environmental compartments. Conventional treatments also show higher climate change impacts than thermal treatments. Overall, thermal treatments can effectively reduce the HOCs emitted to the environment while delivering negative emissions (from about -56 to -111 kg CO2-eq per tonne of sludge, when pyrolysis is involved) and producing renewable energy from heat integration and valorization.

Edible Sea urchins Echinus esculentus from Norwegian waters- Effect of season on nutritional quality and chemical contaminants.

This study aimed to characterize Echinus esculentus gonads in terms of biometric parameters and nutritional quality at two sites in Mid-Norway at four different seasons. The chemical contamination of the gonads was also investigated for the first time through the evaluation of 28 macro- and trace elements and 32 components from the emerging and persistent group per- and polyfluoroalkyl substances (PFAS). The spawning period was determined in summer, given that the gonad index was the lowest in this season for both sites. Protein concentrations were constant (8%-10%). However, lipid contents (1%-3%) were noticed to be higher in gonads during autumn and winter. The gonads had high contents of PUFA mainly EPA and DHA, followed by SFA, and MUFA year around for both locations. E. esculentus gonads constitute a good source of fatty acids, macro, and trace elements. This species could also be a bioindicator for the monitoring of marine environments.

Exposure assessment of plastics, phthalate plasticizers and their transformation products in diverse bio-based fertilizers.

Bio-based fertilizers (BBFs) produced from organic waste have the potential to reduce societal dependence on limited and energy-intensive mineral fertilizers. BBFs, thereby, contribute to a circular economy for fertilizers. However, BBFs can contain plastic fragments and hazardous additives such as phthalate plasticizers, which could constitute a risk for agricultural soils and the environment. This study assessed the exposure associated with plastic and phthalates in BBFs from three types of organic wastes: agricultural and food industry waste (AgriFoodInduWaste), sewage sludge (SewSludge), and biowaste (i.e., garden, park, food and kitchen waste). The wastes were associated with various treatments like drying, anaerobic digestion, and vermicomposting. The number of microplastics (0.045-5 mm) increased from AgriFoodInduWaste-BBFs (15-258 particles g-1), to SewSludge-BBFs (59-1456 particles g-1) and then to Biowaste-BBFs (828-2912 particles g-1). Biowaste-BBFs mostly contained packaging plastics (e.g., polyethylene terephthalate), with the mass of plastic (>10 g kg-1) exceeding the EU threshold (3 g kg-1, plastics >2 mm). Other BBFs mostly contained small (< 1 mm) non-packaging plastics in amounts below the EU limit. The calculated numbers of microplastics entering agricultural soils via BBF application was high (107-1010 microplastics ha-1y-1), but the mass of plastic released from AgriFoodInduWaste-BBFs and SewSludge-BBFs was limited (< 1 and <7 kg ha-1y-1) compared to Biowaste-BBFs (95-156 kg ha-1y-1). The concentrations of di(2-ethylhexyl)phthalate (DEHP; < 2.5 mg kg-1) and phthalate transformation products (< 8 mg kg-1) were low (< benchmark of 50 mg kg-1 for DEHP), attributable to both the current phase-out of DEHP as well as phthalate degradation during waste treatment. The Biowaste-BBF exposed to vermicomposting indicated that worms accumulated phthalate transformation products (4 mg kg-1). These results are overall positive for the implementation of the studied AgriFoodInduWaste-BBFs and SewSludge-BBFs. However, the safe use of the studied Biowaste-BBFs requires reducing plastic use and improving sorting methods to minimize plastic contamination, in order to protect agricultural soils and reduce the environmental impact of Biowaste-BBFs.

Occurrence, bioaccumulation and trophic dynamics of per- and polyfluoroalkyl substances in two tropical freshwater lakes.

We have investigated the occurrence, distribution, and biomagnification of per- and polyfluoroalkyl substances (PFAS) in two tropical lakes (Asejire and Eleyele) of Southwestern Nigeria, with contrasting urban intensities. Over an 8-month period, we sampled sediment and fish species (Clarias gariepinus: CIG; Oreochromis niloticus: ON; Coptodon guineensis: CG; Sarotherodon melanotheron: SM) across trophic levels, and analyzed various PFAS congeners, in addition to a select group of toxicological responses. While herbivores (SM) and benthic omnivores (CIG) at Asejire exhibited elevated levels of PFBS and PFOS, the pelagic omnivores (ON) showed a dominance of PFOS, PFDA, PFHxDA and EtFOSE in the muscle. At the Eleyele urban lake, PFAS patterns was dominated by PFBS, EtFOSE, PFPeS, PFOcDA and PFOS in the herbivores (SM, CG), EtFOSE, PFOS and PFBS in the pelagic omnivore (ON) and benthic omnivore (ClG). The estimated biomagnification factor (BMF) analysis for both lakes indicated trophic level increase of PFOS, PFUnA and PFDA at the suburban lake, while PFOS and EtFOSE biomagnified at the urban lake. We detected the occurrence of diSAMPAP and 9CL-PF3ONS, novel compounds not commonly reported, in PFAS studies at both lakes. The studied toxicological responses varied across trophic groups in both lakes with probable modulations by environmental conditions, trophic structure, and relative PFAS exposures in the lakes. The present study documents, for the first time in Nigeria, or any other African country, the role of urbanization on contaminant load into the environment and their implications for contaminant dynamics within the ecosystem and for aquatic food safety.

Stabilization of PFAS-contaminated soil with sewage sludge- and wood-based biochar sorbents.

Sustainable and effective remediation technologies for the treatment of soil contaminated with per- and polyfluoroalkyl substances (PFAS) are greatly needed. This study investigated the effects of waste-based biochars on the leaching of PFAS from a sandy soil with a low total organic carbon content (TOC) of 0.57 ± 0.04 % impacted by PFAS from aqueous film forming foam (AFFF) dispersed at a former fire-fighting facility. Six different biochars (pyrolyzed at 700-900 °C) were tested, made from clean wood chips (CWC), waste timber (WT), activated waste timber (aWT), two digested sewage sludges (DSS-1 and DSS-2) and de-watered raw sewage sludge (DWSS). Up-flow column percolation tests (15 days and 16 pore volume replacements) with 1 % biochar indicated that the dominant congener in the soil, perfluorooctane sulphonic acid (PFOS) was retained best by the aWT biochar with a 99.9 % reduction in the leachate concentration, followed by sludge-based DWSS (98.9 %) and DSS-2 and DSS-1 (97.8 % and 91.6 %, respectively). The non-activated wood-based biochars (CWC and WT) on the other hand, reduced leaching by <42.4 %. Extrapolating this to field conditions, 90 % leaching of PFOS would occur after 15 y for unamended soil, and after 1200 y and 12,000 y, respectively, for soil amended with 1 % DWSS-amended and aWT biochar. The high effectiveness of aWT and the three sludge-based biochars in reducing PFAS leaching from the soil was attributed largely to high porosity in a pore size range (>1.5 nm) that can accommodate the large PFAS molecules (>1.02-2.20 nm) combined with a high affinity to the biochar matrix. Other factors like anionic exchange capacity could play a contributing role. Sorbent effectiveness was better for long-chain than for short-chain PFAS, due to weaker, apolar interactions between the biochar and the latter's shorter hydrophobic CF2-tails. The findings were the first to demonstrate that locally sourced activated wood-waste biochars and non-activated sewage sludge biochars could be suitable sorbents for the ex situ stabilization and in situ remediation of PFAS-contaminated soil, bringing this technology one step closer to full-scale field testing.

Running the gauntlet; flyway-wide patterns of pollutant exposure in blood of migratory shorebirds.

Shorebirds (order Charadriiformes) are among the world's most threatened avian taxa. Within the East Asian-Australasian Flyway (EAAF), a major threat to shorebirds' survival may be the gauntlet of pollution along the flyway. Metals, persistent organic pollutants (POPs), and per-/polyfluoroalkyl substances (PFASs) persist in the environment to the detriment of wildlife. In this study, we analysed element and PFAS concentrations in blood from 142 individuals across six species of Arctic-breeding migratory shorebirds with contrasting population trends, to discern species- and site-specific pollution differences, and determine how pollution correlated with population trends of EAAF shorebirds. Potential within-year pollution variations were investigated by blood-sampling birds at two sites, representing different points in the birds' annual migrations: staging in Taiwan on southward migrations and at non-breeding grounds in Western Australia (WA). Species' pollutant concentrations were compared to established population trends. Concentrations of potentially toxic elements were low in most individuals regardless of species. PFASs (range: <0.001-141 ng/g), Hg (<0.001-9910 ng/g) and Pb (<0.01-1210 ng/g) were higher in Taiwan than in WA (PFAS Taiwan median: 14.5 ng/g, WA median: 3.45 ng/g; Hg Taiwan: 338 ng/g, WA: 23.4 ng/g; Pb Taiwan: 36.8 ng/g, WA: 2.26 ng/g). Meanwhile As (range <0.001-8840 ng/g) and Se (290-47600 ng/g) were higher in WA than Taiwan (As Taiwan median: 500 ng/g, WA median: 1660 ng/g; Se Taiwan: 5490 ng/g, Se WA: 23700 ng/g). Nevertheless, pollutant concentrations in a subset of individuals may exceed sublethal effect thresholds (As, Se and PFASs). Finally, we found no consistent differences in pollution among species and demonstrated no correlation between pollution and population trends, suggesting pollution is likely not a major driver for population declines of EAAF shorebirds. However, ongoing and locally heavy environmental degradation and exposure to other contaminants not investigated here, such as POPs, warrants continued consideration when managing EAAF shorebird populations.

Occurrence of traffic related trace elements and organic micropollutants in tunnel wash water.

Substantially polluted tunnel wash water (TWW) is produced during road tunnel maintenance. Previous literature has reported the presence of trace elements and polycyclic aromatic hydrocarbons (PAHs). However, it was hypothesized that other organic pollutants are present, and more knowledge is needed to prevent environmental harm. This study reveals for the first time the presence of four short- and 17 long-chained per- and polyfluoroalkyl substances (PFASs), three benzothiazoles (BTHs), six benzotriazoles (BTRs), four bisphenols, and four benzophenones in TWW from a Norwegian road tunnel over a period of three years. Concentrations of PAHs, PFASs, BTHs, and BTRs were higher than previously reported in e.g., road runoff and municipal wastewater. Trace elements and PAHs were largely particulate matter associated, while PFASs, BTHs, BTRs, bisphenols, and benzophenones were predominantly dissolved. 26 of the determined contaminants were classified as persistent, mobile, and toxic (PMT) and are of special concern. It was recommended that regulations for TWW quality should be expanded to include PMT contaminants (such as PFPeA, PFBS, BTR, and 4-OH-BzP) and markers of pollution (like 2-M-BTH, 2-OH-BTH, and 2-S-BTH from tire wear particles). These findings highlight the need to treat TWW before discharge into the environment, addressing both, particulate matter associated and dissolved contaminants.

Lead exposure is related to higher infection rate with the gapeworm in Norwegian house sparrows (Passer domesticus).

Anthropogenic pollution is identified as an important threat to bird and other wildlife populations. Many metals and toxic elements, along with poly- and perfluoroalkyl substances (PFASs) are known to induce immunomodulation and have previously been linked to increased pathogen prevalence and infectious disease severity. In this study, the house sparrow (Passer domesticus) was investigated at the coast of Helgeland in northern Norway. This population is commonly infected with the parasitic nematode "gapeworm" (Syngamus trachea), with a prevalence of 40-60 % during summer months. Gapeworm induces severe respiratory disease in birds and has been previously demonstrated to decrease survival and reproductive success in wild house sparrows. The aim of this study was to investigate whether a higher exposure to pollution with PFASs, metals and other elements influences gapeworm infection in wild house sparrows. We conducted PFASs and elemental analysis on whole blood from 52 house sparrows from Helgeland, including analyses of highly toxic metals such as lead (Pb), mercury (Hg) and arsenic (As). In addition, we studied gapeworm infection load by counting the parasite eggs in faeces from each individual. We also studied the expression of microRNA 155 (miR155) as a key regulator in the immune system. Elevated blood concentrations of Pb were found to be associated with an increased prevalence of gapeworm infection in the house sparrow. The expression of miR155 in the plasma of the house sparrow was only weakly associated with Pb. In contrast, we found relatively low PFASs concentrations in the house sparrow blood (∑ PFASs 0.00048-354 µg/L) and PFASs were not associated to miR155 nor infection rate. The current study highlights the potential threat posed by Pb as an immunotoxic pollutant in small songbirds.

Molecular formula assignment of dissolved organic matter by ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry using two non-targeted data processing approaches: A case study from recirculating aquaculture systems.

BACKGROUND: The accumulation of dissolved organic matter (DOM) poses an issue in the management of the water quality from recirculating aquaculture systems (RAS), but its characterization is often not detailed enough to understand the DOM transformations in RAS. In this study, we investigated the application of two distinct non-targeted data processing approaches using ultra-performance liquid chromatography (UPLC) with quadrupole time-of-flight mass spectrometry (QTOF-MS) and two software with different algorithmic designs: PetroOrg and Progenesis QI to accurately characterize the molecular composition of DOM in RAS by UPLC-QTOF-MS. RESULTS: The UPLC-QTOF-MS resolution in combination with PetroOrg and Progenesis QI software successfully assigned 912 and 106 unique elemental compositions, respectively, including compounds containing carbon, hydrogen, and oxygen (CHO) and nitrogen-containing CHO compounds (CHON), in the DOM samples from RAS. The results of these two distinct data processing approaches were consistent with the list of DOM formulas from RAS identified by higher resolution mass spectrometry techniques confirming their reliability. PetroOrg approach revealed only compositional information in the DOM samples from RAS, while Progenesis QI in addition to identifying new elemental compositions, increased their chemical space by giving information about their polarity and their possible key structures. DOM samples from RAS were found to be rich in unsaturated CHO compounds, with tentatively key structures of terpenoids with medium polarity indicating natural origins in their composition. The analysis also revealed probable structures of sucrose fatty acid esters and polyethylene glycol, indicating anthropogenic sources. SIGNIFICANCE AND NOVELTY: The combination of these two non-targeted data processing approaches significantly improves the characterization of the complex mixture of DOM from RAS by UPLC-QTOF-MS reporting for the first time accurate DOM results in terms of its composition, while proposing its key structures. The presented methods can also be used to analyze different DOM samples with other HRMS techniques and software.

Appraising the Causal Role of Risk Factors in Coronary Artery Disease and Stroke: A Systematic Review of Mendelian Randomization Studies.

BACKGROUND Mendelian randomization (MR) offers a powerful approach to study potential causal associations between exposures and health outcomes by using genetic variants associated with an exposure as instrumental variables. In this systematic review, we aimed to summarize previous MR studies and to evaluate the evidence for causality for a broad range of exposures in relation to coronary artery disease and stroke. METHODS AND RESULTS MR studies investigating the association of any genetically predicted exposure with coronary artery disease or stroke were identified. Studies were classified into 4 categories built on the significance of the main MR analysis results and its concordance with sensitivity analyses, namely, robust, probable, suggestive, and insufficient. Studies reporting associations that did not perform any sensitivity analysis were classified as nonevaluable. We identified 2725 associations eligible for evaluation, examining 535 distinct exposures. Of them, 141 were classified as robust, 353 as probable, 110 as suggestive, and 926 had insufficient evidence. The most robust associations were observed for anthropometric traits, lipids, and lipoproteins and type 2 diabetes with coronary artery; disease and clinical measurements with coronary artery disease and stroke; and thrombotic factors with stroke. CONCLUSIONS Despite the large number of studies that have been conducted, only a limited number of associations were supported by robust evidence. Approximately half of the studies reporting associations presented an MR sensitivity analysis along with the main analysis that further supported the causality of associations. Future research should focus on more thorough assessments of sensitivity MR analyses and further assessments of mediation effects or nonlinearity of associations.

Per- and poly-fluoroalkyl substances in Tawny Owl (Strix aluco) feathers from Trøndelag, Norway.

Per- and polyfluoroalkyl substances (PFASs) are contaminants of global concern due to their ubiquitous occurrence in the environment, bioaccumulation and the adverse effects on organisms. Tawny Owls (Strix aluco) are documented to be exposed to increasing concentrations of perfluoroalkyl carboxylic acids (PFCAs), and have been suggested in literature as a key raptor monitoring species. Therefore, non-destructive biomonitoring efforts are of high interest. Thus far, the use of feathers for biomonitoring PFASs in Tawny Owls has not been investigated. In this study, 32 PFASs were analyzed in 49 Tawny Owl body feather samples collected from 2017 to 2020 in Trøndelag, Norway. There were 30 PFASs detected in at least one feather, with the sum concentrations ranging from 31 to 203 ng/g (w.w.). Perfluoroheptanoic acid (PFHpA) (median: 33 ng/g) and perfluorooctane sulfonamidoacetic acid (FOSAA) (median: 18 ng/g) were the two compounds with the highest concentrations. Perfluorooctane sulfonic acid (PFOS), which is banned for production and use in Norway since 2007, was found in all samples (median: 4.14 ng/g), indicating its high persistence. 8 PFASs were detected in at least 50 % of the samples: FOSAA (11-127 ng/g), PFHpA (<0.04-115 ng/g), perfluorobutanesulfonic acid (PFBS) (<0.28-21 ng/g), PFOS (0.23-13 ng/g), perfluorotridecanoic acid (PFTrDA) (0.24-5.15 ng/g), perfluorododecanoic acid (PFDoDA) (<0.28-4.45 ng/g), perfluoroundecanoic acid (PFUnDA) (<0.28-2.33 ng/g), and 1H,1H,2H,2H-perfluorooctanesulfonic acid (6:2 FTSA) (0.07-1.01 ng/g). No significant differences were found for the concentrations of PFASs between calendar years and locations, but a slight increase could be observed in the sum concentration of PFASs (Æ©32PFASs) over the sampling years. As Tawny Owls are residential owls that usually do not cover great distances, their feathers can be used as a potential alternative matrix for future biomonitoring studies. To our knowledge, this is the first study on the occurrence of 32 PFASs investigated in feathers of a Tawny Owl population.

Assessment of contaminants, health and survival of migratory shorebirds in natural versus artificial wetlands - The potential of wastewater treatment plants as alternative habitats.

The rapid destruction of natural wetland habitats over past decades has been partially offset by an increase in artificial wetlands. However, these also include wastewater treatment plants, which may pose a pollution risk to the wildlife using them. We studied two long-distance Arctic-breeding migratory shorebird species, curlew sandpiper (Calidris ferruginea, n = 69) and red-necked stint (Calidris ruficollis, n = 103), while on their Australian non-breeding grounds using an artificial wetland at a wastewater treatment plant (WTP) and a natural coastal wetland. We compared pollutant exposure (elements and per- and poly-fluoroalkyl substances/PFASs), disease (avian influenza), physiological status (oxidative stress) of the birds at the two locations from 2011 to 2020, and population survival from 1978 to 2019. Our results indicated no significant differences in blood pellet pollutant concentrations between the habitats except mercury (WTP median: 224 ng/g, range: 19-873 ng/g; natural wetland: 160 ng/g, 22-998 ng/g) and PFASs (total PFASs WTP median: 85.1 ng/g, range: <0.01-836 ng/g; natural wetland: 8.02 ng/g, <0.01-85.3 ng/g) which were higher at the WTP, and selenium which was lower at the WTP (WTP median: 5000 ng/g, range: 1950-34,400 ng/g; natural wetland: 19,200 ng/g, 4130-65,200 ng/g). We also measured higher blood o,o'-dityrosine (an indicator of protein damage) at the WTP. No significant differences were found for adult survival, but survival of immature birds at the WTP appeared to be lower which could be due to higher dispersal to other wetlands. Interestingly, we found active avian influenza infections were higher in the natural habitat, while seropositivity was higher in the WTP, seemingly not directly related to pollutant exposure. Overall, we found limited differences in pollutant exposure, health and survival of the shorebirds in the two habitats. Our findings suggest that appropriately managed wastewater treatment wetlands could provide a suitable alternative habitat to these migratory species, which may aid in curbing the decline of shorebird populations from widespread habitat loss.

Impact of the antidepressant Bupropion on the Dynamic Energy Budget of Daphnia magna.

Psychiatric drugs are considered among the emerging contaminants of concern in ecological risk assessment, due to their potential to disrupt homeostasis in aquatic organisms. Bupropion is an antidepressant that acts by selective reuptake inhibition of norepinephrine and dopamine. Little is known about this compound's effects on aquatic organisms, despite being detected in significant concentrations in both water and biota close to waste-water treatment plants and densely populated areas. Dynamic Energy Budget (DEB) models are flexible mechanistic tools that can be applied to understand toxic effects and extrapolate individual responses to higher biological levels and under untested environmental conditions. In this work, we used the stdDEB-TKTD (an application of the DEB theory to ecotoxicology) approach to investigate the possible physiological mode of action of Bupropion on the model organism Daphnia magna. Next, Dynamic Energy Budget Individual-Based Models (DEB-IBM) were used to extrapolate the results to the population level and to predict the combined effects of Bupropion exposure and food availability on the daphnids. Our results revealed an increasing negative effect of this antidepressant on the reproduction and survival of the animals with increasing concentration (0.004, 0.058, 0.58 and 58 µM). At the population level, we found that even the lowest used doses of Bupropion could reduce the population density and its reproductive output. The impacts are predicted to be stronger under limited food conditions.

Occurrence and tissue distribution of 33 legacy and novel per- and polyfluoroalkyl substances (PFASs) in Baikal seals (Phoca sibirica).

Per- and polyfluoroalkyl substances (PFASs) are bioaccumulative and associated with adverse effects in both wildlife and humans. The occurrence of 33 PFASs was assessed in the plasma, liver, blubber, and brain of 18 Baikal seals (Phoca sibirica) (16 pups and 2 adult females) from Lake Baikal, Russia (in 2011). Of the 33 congeners analysed for: perfluorooctanosulfonic acid (PFOS), 7 long chain perfluoroalkyl carboxylic acids (C8-C14 PFCAs) and 1 branched PFCA (perfluoro-3,7-dimethyloctanoic acid; P37DMOA) were most frequently detected. The PFASs in plasma and liver with the highest median concentrations were legacy congeners: perfluoroundecanoic acid (PFUnA; plasma: 11.2 ng/g w.w.; liver: 7.36 ng/g w.w.), PFOS (plasma: 8.67 ng/g w.w.; liver: 9.86 ng/g w.w.), perfluorodecanoic acid (PFDA; plasma: 5.13 ng/g w.w.; liver: 6.69 ng/g w.w.), perfluorononanoic acid (PFNA; plasma: 4.65 ng/g w.w.; liver: 5.83 ng/g w.w.) and perfluorotridecanoic acid (PFTriDA; plasma: 4.29 ng/g w.w.; liver: 2.55 ng/g w.w.). PFASs were detected in the brain of Baikal seals, indicating that PFASs cross through the blood-brain barrier. In blubber, the majority of PFASs were detected in low abundance and concentrations. In contrast to legacy PFASs, novel congeners (e.g., Gen X) were either detected infrequently or not found in Baikal seals. The worldwide occurrence of PFASs in pinnipeds was compared and lower median concentrations of PFOS were observed in Baikal seals relative to other pinnipeds. Conversely, similar concentrations of long chain PFCAs were found in Baikal seals compared to other pinnipeds. Furthermore, human exposure was assessed by estimating weekly intakes (EWI) of PFASs through Baikal seal consumption. Although PFASs concentrations were comparatively low relative to other pinnipeds, consumption of Baikal seal could exceed current regulatory guidelines.

Identification of Poly(ethylene terephthalate) Nanoplastics in Commercially Bottled Drinking Water Using Surface-Enhanced Raman Spectroscopy.

Micro/nanoplastics have emerged as global contaminants of serious concern to human and ecosystem health. However, identification and visualization of microplastics and particularly nanoplastics have remained elusive due to the lack of feasible and reliable analytical approaches, particularly for trace nanoplastics. Here, an efficient surface-enhanced Raman spectroscopy (SERS)-active substrate with triangular cavity arrays is reported. The fabricated substrate exhibited high SERS performance for standard polystyrene (PS) nanoplastic detection with size down to 50 nm and a detection limit of 0.001% (1.5 × 1011 particles/mL). Poly(ethylene terephthalate) (PET) nanoplastics collected from commercially bottled drinking water were detected with an average mean size of ∼88.2 nm. Furthermore, the concentration of the collected sample was estimated to be about 108 particles/mL by nanoparticle tracking analysis (NTA), and the annual nanoplastic consumption of human beings through bottled drinking water was also estimated to be about 1014 particles, assuming water consumption of 2 L/day for adults. The facile and highly sensitive SERS substrate provides more possibilities for detecting trace nanoplastics in an aquatic environment with high sensitivity and reliability.

The decomposition and emission factors of a wide range of PFAS in diverse, contaminated organic waste fractions undergoing dry pyrolysis.

Current treatment options for organic waste contaminated with per- and polyfluoroalkyl substances (PFAS) are generally limited to incineration, composting or landfilling, all resulting in emissions. Dry pyrolysis is a promising emerging alternative to these practices, but there is uncertainty related to the fate of PFAS during this process. The present work first developed a robust method for the determination of PFAS in complex matrices, such as sewage sludge and biochar. Then, a mass balance was established for 56 different PFAS during full-scale pyrolysis (2-10 kg biochar hr-1, 500-800 °C) of sewage sludges, food waste reject, garden waste and waste timber. PFAS were found in all wastes (56-3651 ng g-1), but pyrolysis resulted in a ≥ 96.9% removal. Residual PFAS (0.1-3.4 ng g-1) were detected in biochars obtained at temperatures up to 750 °C and were dominated by long chain PFAS. Emitted PFAS loads ranged from 0.01 to 3.1 mg tonne-1 of biochar produced and were dominated by short chain PFAS. Emissions made up < 3% of total PFAS-mass in the wastes. Remaining uncertainties are mainly related to the presence of thermal degradation products in flue gas and condensation oils.

Influence of grain size, organic carbon and organic matter residue content on the sorption of per- and polyfluoroalkyl substances in aqueous film forming foam contaminated soils - Implications for remediation using soil washing.

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.

Association between Polymorphisms of Hemochromatosis (HFE), Blood Lead (Pb) Levels, and DNA Oxidative Damage in Battery Workers.

Occupational exposure to lead (Pb) continues to be a serious public health concern and may pose an elevated risk of genetic oxidative damage. In Brazil, car battery manufacturing and recycling factories represent a great source of Pb contamination, and there are no guidelines on how to properly protect workers from exposure or to dispose the process wastes. Previous studies have shown that Pb body burden is associated with genetic polymorphisms, which consequently may influence the toxicity of the metal. The aim of this study was to assess the impact of Pb exposure on DNA oxidative damage, as well as the modulation of hemochromatosis (HFE) polymorphisms on Pb body burden, and the toxicity of Pb, through the analysis of 8-hydroxy-2'-deoxyguanosine (8-OHdG), in subjects occupationally exposed to the metal. Male Pb-exposed workers (n = 236) from car battery manufacturing and recycling factories in Brazil participated in the study. Blood and plasma lead levels (BLL and PLL, respectively) were determined by ICP-MS and urinary 8-OHdG levels were measured by LC-MS/MS, and genotyping of HFE SNPs (rs1799945, C → G; and 1800562, G → A) was performed by TaqMan assays. Our data showed that carriers of at least one variant allele for HFE rs1799945 (CG + GG) tended to have higher PLL than those with the non-variant genotype (ß = 0.34; p = 0.043); further, PLL was significantly correlated with the levels of urinary 8-OHdG (ß = 0.19; p = 0.0060), while workers that carry the variant genotype for HFE rs1800562 (A-allele) showed a prominent increase in 8-OHdG, as a function of PLL (ß = 0.78; p = 0.046). Taken together, our data suggest that HFE polymorphisms may modulate the Pb body burden and, consequently, the oxidative DNA damage induced by the metal.

Analysis, occurrence and removal efficiencies of organophosphate flame retardants (OPFRs) in sludge undergoing anaerobic digestion followed by diverse thermal treatments.

Organophosphate flame retardants (OPFRs) are a complex group of contaminants to deal with in sewage sludge, as currently there is a lack of robust analytical methods to measure them and management strategies to remove them. To facilitate quantifications of the occurrence of OPFRs in sludge and to establish their removal efficiencies (REs%) during thermal treatments, a simple, reliable, and rapid sample preparation methodology was developed for the determination of 21 OPFRs in diverse sludge, ash and biochar matrices. Matrix-solid phase dispersion (MSPD) tailored to ultra-performance liquid chromatography (UPLC) coupled to tandem mass spectrometry (MS/MS) was applied. Under optimal conditions, 0.5 g of freeze-dried sample were dispersed in 2 g of Bondesil C18, and 1.5 g of deactivated florisil were used as clean-up sorbent. The target analytes were extracted with 5 mL of acetone. The obtained extract was ready for analysis within 20 min without the need of any further treatment. The proposed methodology was assessed, providing absolute recoveries (Abs%) ranging from 50.4 to 112 % with good method repeatability (RSDs <17.9 %). Method limits of quantification ranged from 0.10 to 14.0 ng g-1 dry weight (d.w.). The optimized methodology was applied to raw-, digested-, combusted and pyrolyzed sludge samples collected from different waste treatment plants located in Norway, where 16 out of 21 OPFRs were detected in digested sludge samples up to 2186 ng g-1 (d.w.; sum concentration of OPFRs). Diverse thermal treatments of combustion and dry pyrolysis were assessed for the removal of OPFRs from sludge. Combustion at 300 °C reduced the concentrations of OPFRs by 98 % (in the ashes formed), whereas pyrolysis at temperatures >500 °C effectively removed the OPFRs in the produced biochar. Thermal treatments, in particularly dry pyrolysis, showed potential for achieving zero pollution management and recycling of OPFR contaminated sludge.