Cetaceans face numerous anthropogenic chemical stressors in global oceans, yet there is a lack of studies that simultaneously assess their cumulative exposure to both legacy and emerging contaminants and their combined effects. To evaluate the susceptibility of fin whale (Balaenoptera physalus) to chemical pollution, this study employed for the first time a multidiagnostic molecular approach that integrates chemical exposomics and gene expression analysis in live-sampled skin and blubber biopsies from two distinct populations: the endangered Mediterranean subpopulation (Italy) and the vulnerable population from the Sea of Cortez (Mexico). Both marine regions are biodiversity hotspots characterized by different anthropogenic impacts, making them ideal for the assessment of heterogeneous contaminants exposure and their effects. Results revealed distinct exposure profiles in the two populations, with Mediterranean fin whales exhibiting higher concentrations of legacy pollutants such as polychlorinated biphenyls (PCBs), as well as plasticizers, perfluoroalkyl substances (PFAS), while both populations showed traces of pharmaceuticals and lifestyle-related chemicals (e.g., paracetamol, diclofenac, nicotine, UV filters) and other substances not previously reported in whales. Supported by 32 network correlations with gene expression relevant to transcriptional regulation, endocrine disruption, lipid homeostasis, and inflammation, our findings suggest that complex anthropogenic chemical exposures may compromise the health and reproductive viability of the endangered Mediterranean fin whales, affirming their importance as a global sentinel species, which reflects marine ecosystem integrity within the “One Health” framework.

Synthetic phenolic compounds are widely used in plastics and personal care products, leading to potential high human exposure. This study aimed to develop two multi-target analytical methods to quantify phenolic compounds in human serum, including free and conjugated synthetic phenolic antioxidants (SPAs), bisphenols, parabens, and UV filters. The two methods were applied to 30 human serum samples from young adults (15 females and 15 males) living in Stockholm, Sweden. An average recovery of 73 % (range 36-125 %) and good reproducibility (RSD <30 %) were established for 37 target analytes, and another four analytes were semi-quantified. Twenty-one target analytes were found above quantification levels. Notable, five SPAs, namely 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (AO2246), 4,4'-methylenebis(2,6-di-tert-butylphenol) (AO4426), 4-tert octylphenol (4-tOP), butylade hydroxyanisole (BHA), butylated hydroxytoluene (BHT) were quantified in >93 % of samples, and with median concentrations between 1.4 (BHA) and 520 ng/g (AO2246). Other compounds quantified in the samples were bisphenol B (quantification frequency 57 %) and methylparaben (quantification frequency 87 %), with median concentrations of 0.38 and 1.6 ng/g respectively. Additionally, two features were semi-quantified using suspect screening: Fenozan (an SPA metabolite, 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic acid) and benzophenone-4 (a UV filter, 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid). To the best of our knowledge, this is the first time AO4426, 3,5-di-tert-butyl-4-hydroxybenzoic acid (BHT-COOH), 2-tert-butylbenzene-1,4-diol (TBHQ), bisphenol B, and Fenozan have been found in human blood. The finding of SPAs in human blood indicates high human exposure and needs further investigation.

A combination of high-resolution mass spectrometry and computational molecular characterization techniques can structurally annotate up to 17% of organic compounds in fine particulate matter in highly polluted air sampled in the Maldives. Fine particulate-matter is an important component of air pollution that impacts health and climate, and which delivers anthropogenic contaminants to remote global regions. The complex composition of organic molecules in atmospheric particulates is poorly constrained, but has important implications for understanding pollutant sources, climate-aerosol interactions, and health risks of air pollution exposure. Here, comprehensive nontarget high-resolution mass spectrometry was combined with in silico structural prediction to achieve greater molecular-level insight for fine particulate samples (n = 40) collected at a remote receptor site in the Maldives during January to April 2018. Spectral database matching identified 0.5% of 60,030 molecular features observed, while a conservative computational workflow enabled structural annotation of 17% of organic structures among the remaining molecular dark matter. Compared to clean air from the southern Indian Ocean, molecular structures from highly-polluted regions were dominated by organic nitrogen compounds, many with computed physicochemical properties of high toxicological and climate relevance. We conclude that combining nontarget analysis with computational mass spectrometry can advance molecular-level understanding of the sources and impacts of polluted air.

Indoor dust contains a multitude of industrial chemicals, and ingestion of dust is considered an important exposure route to organic contaminants. Some of these contaminants have been shown to interfere with the thyroid system, which may result in significant consequences on public health. The amphibian metamorphosis is a thyroid hormone-dependent process, which can be used as an in vivo model for studies on thyroid hormone-disrupting potency. Three contaminants of indoor dust were tested on metamorphosing Silurana (Xenopus) tropicalis tadpoles. The tested chemicals were Tris (1,3-dichloroisopropyl) phosphate (TDCiPP), tetrabromobisphenol-A (TBBPA) and propylparaben (PrP). Measurements reflecting general growth, development progress and thyroid epithelial cell height were performed on the exposed tadpoles as well as chemical analyses of the exposure water. It was shown that TDCiPP acts as a thyroid hormone-disrupting chemical in metamorphosing tadpoles by causing increased epithelial cell height in thyroid glands after exposure to a nominal concentration of 0.010 mg/L and in higher concentrations. TBBPA caused reductions in general growth of tadpoles at the nominal concentration 0.125 mg/L, and PrP caused acute toxicity at the nominal concentration 12.5 mg/L. However, no evident indications of specific thyroid-disrupting effects caused by TBBPA or PrP were observed.

Chlorinated paraffins (CPs) are high-production volume industrial chemicals consisting of n-alkanes (with 10 to 30 carbon atoms in the chain) with chlorine content from 30 to 70% of weight. In Europe, the use of short chain chlorinated paraffins (SCCPs) has been restricted by the Stockholm Convention on POPs due to their PBT (persistent, bioaccumulative and toxic) properties. Medium (MCCPs) and long chain (LCCPs) chlorinated paraffins are used as substitution products. In this work we studied the partitioning behavior of five different CP technical mixtures from the established categories (2 SCCPs, 1 MCCP, 1 LCCP and 1 CP technical mixture covering all categories) using passive dosing, by determining the partitioning coefficient of CP technical mixtures between silicone and water (Ksilicone-water) as well as between organic matter and water (Koc-water). We show that both silicone-water and organic carbon water partition coefficients overlap between different categories of CP technical mixtures. These results indicate that in-use MCCPs and LCCPs may be equally or more bioaccumulative than restricted SCCPs. For the tested mixtures, both chlorine content and carbon chain length showed a significant correlation with both Ksilicone-water and Koc-water.

The acaricide, dicofol, is a well-known pesticide and partly a substitute for dichlorodiphenyltrichloroethane (DDT). Only few reports on environmental occurrence and concentrations have been reported calling for improvements. Hence, an analytical method was further developed for dicofol and dichlorobenzophenone (DCBP) to enable assessments of their environmental occurrence. Concentrated sulfuric acid was used to remove lipids and to separate dicofol from DCBP. On-column injection was used as an alternative to splitless injection to protect dicofol from thermal decomposition. By the method presented herein, it is possible to quantify dicofol and DCBP in the same samples. Arctic cod (Gadus morhua) were spiked at two dose levels and the recoveries were determined. The mean recovery for dicofol was 65% at the low dose (1 ng) and 77% at the high dose (10 ng). The mean recovery for DCBP was 99% at the low dose (9.2 ng) and 146% at the high dose (46 ng). The method may be further improved by use of another lipid removal method, e.g., gel permeation chromatography. The method implies a step forward in dicofol environmental assessments.

Pet cats may be used as a biomarker for assessing exposures to organohalogen compounds (OHCs) adsorbed to household dust in home environments. This study explores two exposure routes of OHCs, ingestion of OHCs (i) via house dust and (ii) via cat food. House dust from 17 Swedish homes and serum from the participating families' pet cats were collected, and cat food was purchased matching the diet reported. Paired samples of cat serum, house dust, and cat food were analyzed for brominated flame retardants/natural products (polybrominated diphenyl ethers (PBDEs), decabromobiphenyl (BB-209), decabromodiphenyl ethane (DBDPE), 2,4,6-tribromophenol (2,4,6-TBP), OH-PBDEs) and organochlorines (polychlorinated biphenyls (PCBs), 1,1-bis(4,4'-dichlorodipheny1)-2,2,2-trichloroethane (4,4'-DDT), 1,1-bis(4,4'-dichlorodiphenyl)-2,2-dichloroethene (4,4'-DDE), hexachlorobenzene (HCB), pentachlorophenol (PCP)). Significant correlations were found between serum and dust samples from the living rooms for BDE-47 (p < 0.035), BDE-99 (p < 0.035), and BDE-153 (p < 0.039), from the adult's bedroom for BDE-99 < 0.019) and from all rooms for BDE-99 (p < 0.020) and BB-209 (p < 0.048). This is the first time a correlation between cat serum levels and household dust has been established, a finding that supports the hypothesis that dust is a significant exposure route for cats. Serum levels were also significantly correlated with concentrations found in cat food for 6-OH-BDE47 (p < 0.002), 2,4,6-TBP (p < 0.035), and BB-209 (p < 0.007). DBDPE was found in high concentrations in all dust (median 154 pmol/g) and food samples (median 0.7 pmol/ig lw) but was below detection in serum samples, suggesting low or no bioavailability for DBDPE in cats.

Taihu Lake area is one of the densest metropolitan areas in the world including diverse industrial activity. In the present study, the snail (Bellamya aeruginosa) and sediment were collected from the Taihu Lake area to investigate the contamination status, congener pattern, spatial distribution, and bioaccumulation effect of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). The samples underwent liquid extraction, lipid removal by sulfuric acid, and acidic silica gel column, and subsequently analyzed by gas chromatography-electron capture detector (GC-ECD) and gas chromatography-mass spectrometry (GC-MS). Concentration of S22PCBs ranged between 90 and 680 ng g(-1) lipid weight in the snails and between 0.018 and 0.82 ng g(-1) dry weight in the sediments. Concentration of S24PBDEs varied from 25 to 200 ng g(-1) lipid weight in the snails and from 0.62 to 67 ng g(-1) dry weight in the sediments. The levels of PCBs and PBDEs observed were in the medium to low range compared with other studies in the world. CB-153 was the predominant PCB congener in both snails and sediments whereas BDE-209 showed a low bioavailability in the snails, even if it contributed up to 70% of S24PBDEs in the sediments. The spatial distribution showed that the highest concentration of PCBs and PBDEs were detected in samples from Zhushan Lake. East Taihu Lake and Dianshan Lake showed lower concentration of PCBs and PBDEs than the other sampling sites. Biota-sediment accumulation was found between snails and sediments of most of PCB and PBDE congeners except for the highly brominated BDEs (i.e., BDE-209). Therefore, sediment is suggested to be an appropriate matrix to monitor BDE-209 while aquatic species such as the snail could be good for monitoring of PCBs and lower brominated BDE congeners. No significant correlation (Spearman correlation test, two-tailed) of CB-153 (r = 0.54, p = 0.27) or BDE-47 (r = 0.60, p = 0.21) was found between snails and sediments.

The recently described solid solution ( Co,Ni,Mn)(3)Sb4O6F6 has proved stable and efficient as a catalyst for electrocatalytic water oxidation. The end component Co3Sb4O6F6 was found to be most efficient, maintaining a current density of j = 10 mA cm(-2) at an overpotential of 443 mV with good capability. At this current density, O-2 and H-2 were produced in the ratio 1 : 2 without loss of faradaic current against a Pt-cathode. A morphological change in the crystallite surface was observed after 0.5 h, however, even after 64.5 h, the overall shape and size of the small crystallites were unaffected and the electrolyte contained only 0.02 at% Co. It was also possible to conclude from in situ EXAFS measurements that the coordination around Co did not change. The oxofluorides express both hydrophilic and hydrophobic surface sites, incorporate a flexible metalloid element and offer the possibility of a mechanism that differs from other inorganic catalytic pathways previously described.

The environmental and human health concerns for organohalogen contaminants (OHCs) extend beyond the 23 persistent organic pollutants (POPs) regulated by the Stockholm Convention. The current, intense industrial production and use of chemicals in China and their bioaccumulation makes Chinese wildlife highly suitable for the assessment of legacy, novel and emerging environmental pollutants. In the present study, six species of amphibians, fish and birds were sampled from paddy fields in the Yangtze River Delta (YRD) were screened for OHCs. Some extensive contamination was found, both regarding number and concentrations of the analytes, among the species assessed. High concentrations of chlorinated paraffins were found in the snake, Short-tailed mamushi (range of 200-340 mu g g(-1) lw), Peregrine falcon (8-59 mu g g(-1) lw) and Asiatic toad (97 mu g g(-1) lw). Novel contaminants and patterns were observed; octaCBs to decaCB made up 20% of the total polychlorinated biphenyls (PCBs) content in the samples and new OHCs, substituted with 5-8 chlorines, were found but are not yet structurally confirmed. In addition, Dechlorane 602 (DDC-DBF) and numerous other OHCs (DDTs, hexachlorocyclohexanes (HCHs), polybrominated diphenyl ethers (PBDEs), hexbromocyclododecane (HBCDD), chlordane, heptachlor, endosulfan and Mirex) were found in all species analyzed. These data show extensive chemical contamination of wildlife in the YRD with a suite of OHCs with both known and unknown toxicities, calling for further indepth studies.