Tracing Organophosphate Ester Pollutants in Hadal Trenches─Distribution, Possible Origins, and Transport Mechanisms.

Unraveling the mysterious pathways of pollutants to the deepest oceanic realms holds critical importance for assessing the integrity of remote marine ecosystems. This study tracks the transport of pollutants into the depths of the oceans, a key step in protecting the sanctity of these least explored ecosystems. By analyzing hadal trench samples from the Mariana, Mussau, and New Britain trenches, we found the widespread distribution of organophosphate ester (OPE) flame retardants but a complex transport pattern for the OPE in these regions. In the Mariana Trench seawater column, OPE concentrations range between 17.4 and 102 ng L-1, with peaks at depths of 500 and 4000 m, which may be linked to Equatorial Undercurrent and topographic Rossby waves, respectively. Sediments, particularly in Mariana (422 ng g-1 dw), showed high OPE affinity, likely due to organic matter serving as a transport medium, influenced by "solvent switching", "solvent depletion", and "filtering processes". Amphipods in the three trenches had consistent OPE levels (29.1-215 ng g-1 lipid weight), independent of the sediment pollution patterns. The OPEs in these amphipods appeared more linked to surface-dwelling organisms, suggesting the influence of "solvent depletion". This study highlights the need for an improved understanding of deep-sea pollutant sources and transport, urging the establishment of protective measures for these remote marine habitats.

Construction and application of artificial lipoproteins using adiposomes.

Lipoproteins are complex particles comprised of a neutral lipid core wrapped with a phospholipid monolayer membrane and apolipoproteins on the membrane, which is closely associated with metabolic diseases. To facilitate the elucidation of its formation and dynamics, as well as its applications, we developed an in vitro system in which adiposomes, consisting of a hydrophobic core encircled by a monolayer-phospholipid membrane, were engineered into artificial lipoproteins (ALPs) by recruiting one or more kinds of apolipoproteins, for example, apolipoprotein (Apo) A-I, ApoE, ApoA-IV, and ApoB. In vitro and in vivo studies demonstrated the stability and biological activity of ALPs derived from adiposomes, which resembles native lipoproteins. Of note, adiposomes bearing ApoE were internalized via clathrin-mediated endocytosis following LDLR binding and were delivered to lysosomes. On the other hand, adiposomes bearing ApoA-IV mimicked the existing form of endogenous ApoA-IV and exhibited significant improvement in glucose tolerance in mice. In addition, the construction process was simple, precise, reproducible, as well as easy to adjust for mass production. With this experimental system, different apolipoproteins can be recruited to build ALPs for some biological goals and potential applications in biomedicine.

Novel biomonitoring method for determining five classes of legacy and alternative flame retardants in human serum samples.

Flame retardants (FRs) are ubiquitous in environment and biota and may pose harm to human health. In recent years, concern regarding legacy and alternative FRs has been intensified due to their widespread production and increasing contamination in environmental and human matrices. In this study, we developed and validated a novel analytical method for simultaneous determination of legacy and alternative FRs, including polychlorinated naphthalenes (PCNs), short- and middle-chain chlorinated paraffins (SCCPs and MCCPs), novel brominated flame retardants (NBFRs), and organophosphate esters (OPEs) in human serum. Serum samples were prepared by liquid-liquid extraction using ethyl acetate, and purified with Oasis® HLB cartridge and Florisil-silica gel columns. Instrumental analyses were carried out using gas chromatography-triple quadrupole mass spectrometry, high-resolution gas chromatography coupled with high-resolution mass spectrometry, and gas chromatography coupled with quadrupole time-of-flight mass spectrometry, respectively. The proposed method was validated for linearity, sensitivity, precision, accuracy, and matrix effects. Method detection limits for NBFRs, OPEs, PCNs, SCCPs, and MCCPs were 4.6 × 10-4-8.6 × 10-2, 4.3 × 10-3-1.3, 1.1 × 10-5-1.0 × 10-4, 1.5, and 9.0 × 10-1 ng/mL, respectively. Matrix spike recoveries ranged from 73%-122%, 71%-124%, 75%-129%, 92%-126%, and 94%-126% for NBFRs, OPEs, PCNs, SCCPs, and MCCPs, respectively. The analytical method was applied for detection of real human serum. CPs were the dominant FRs in serum, indicating CPs were widely presented in human serum and should be pay more attention for their health risk.

First evidence and potential sources of novel brominated flame retardants and BDE 209 in the deepest ocean.

Organic anthropogenic pollutants reach even the deepest parts of the oceans, i.e., the hadal trenches. We here presented the concentrations, influencing factors, and potential sources of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in hadal sediments and amphipods from the Mariana, Mussau and New Britain trenches. Results showed that BDE 209 was the dominant PBDEs congener and DBDPE was the dominant NBFRs. No significant correlation was found between TOC contents and PBDEs or NBFRs levels in sediment. Lipid content and body length were the potential important factors affecting variation in pollutant concentrations in the carapace & muscle of amphipods, while the pollution levels of viscera were mainly affected by the sex and lipid content. PBDEs and NBFRs might reach trench surface seawater through long-range atmospheric transport and oceans currents but with little contribution from the Great Pacific Garbage Patch. Determination of carbon and nitrogen isotopes indicated that the pollutants were transported and accumulated in amphipods and sediment via different pathways. PBDEs and NBFRs in the hadal sediments were generally transported via the settling of sediment particles of either marine or terrigenous origin whereas in amphipods they accumulated via feeding on animal carrion through the food web. This is the first study reporting on BDE 209 and NBFR contaminations in hadal settings and provide new insight on influencing factors and sources of PBDEs and NBFRs in the deepest oceans.

Exposure to novel brominated and organophosphate flame retardants and associations with type 2 diabetes in East China: A case-control study.

The alternative flame retardants, novel brominated flame retardants (NBFRs) and organophosphate flame retardants (OPFRs) are ubiquitous in the environment and biota and may induce endocrine disruption effects. Associations between traditional endocrine-disrupting chemicals and type 2 diabetes have been extensively reported in epidemiological studies. However, the effects of NBFRs and OPFRs in humans have not been reported to date. This paper reports a case-control study of 344 participants aged 25-80 years from Shandong Province, East China, where potential associations between serum NBFR and OPFR concentrations and type 2 diabetes are assessed for the first time. After adjusting for covariates (i.e., age, sex, body mass index, smoking status, alcohol consumption, triglycerides, and total cholesterol), serum concentrations of pentabromotoluene, 2,3-dibromopropyl 2,4,6-tribromophenyl ether, tri-n-propyl phosphate, triphenyl phosphate, and tris (2-ethylhexyl) phosphate were significantly positively associated with type 2 diabetes. In the control group, decabromodiphenyl ethane and triphenyl phosphate were significantly positively associated with fasting plasma glucose, triglycerides, and high-density lipoprotein cholesterol. In the quantile g-computation model, significant positive mixture effect was found between the flame retardants mixtures and high-density lipoprotein cholesterol levels, and decabromodiphenyl ethane contributed the largest positive weights to the mixture effect. Overall, these findings suggest that exposure to NBFRs and OPFRs may promote type 2 diabetes.

Exposure to Novel Brominated Flame Retardants and Organophosphate Esters and Associations with Thyroid Cancer Risk: A Case-Control Study in Eastern China.

Novel brominated flame retardant (NBFR) and organophosphate ester (OPE) exposure may engender adverse effects on human health. However, present epidemiological information regarding the effects of such exposure is limited and controversial. In this case-control study, 481 serum samples were collected from patients with thyroid cancer (n = 242) and healthy controls (n = 239) in Shandong Province, eastern China. The levels of NBFRs and OPEs, thyroid hormones, and serum lipid parameters were measured in all the participants. Pentabromotoluene, 2,3-dibromopropyl 2,4,6 tribromophenyl ether, decabromodiphenylethane (DBDPE), tris (2-chloroethyl) phosphate (TCEP), and triphenyl phosphate (TPP) were widely detected (detection frequency > 60%) in all the participants. A significantly high risk association was found between exposure of NBFRs and OPEs (namely 1,2,3,4,5-pentabromobenzene, DBDPE, tri-n-propyl phosphate, tri[(2R)-1-chloro-2-propyl] phosphate, tris (1,3-dichloro-2-propyl) phosphate, and tris (2-butoxyethyl) phosphate) and thyroid cancer in both males and females. In the females of the control group, TCEP levels exhibited a significantly positive association with thyroid-stimulating hormone and a negative association with triiodothyronine (T3), free triiodothyronine (FT3), and free thyroxine (FT4) levels. Weighted quantile sum regression evaluated the mixed effects of the compounds on thyroid hormones levels and thyroid cancer. As a result, TPP accounted for the majority of the T3, thyroxine, and FT3 amounts. Our results suggest that NBFR and OPE exposure contributes to alterations in thyroid function, thereby increasing thyroid cancer risk.

Parent and Halogenated Polycyclic Aromatic Hydrocarbons in the Serum of Coal-Fired Power Plant Workers: Levels, Sex Differences, Accumulation Trends, and Risks.

Workers in coal-fired power plants are at a high risk of exposure to polycyclic aromatic hydrocarbons (PAHs) and their halogenated derivatives (HPAHs), yet no studies have investigated such exposure of HPAHs. In this study, 12 PAHs and 8 chlorinated PAHs, but no brominated PAHs, were detected in >80% of serum samples from workers of a coal-fired power plant in eastern China. Serum HPAH concentrations were higher in plant workers (16-273 ng/g lipid) than in people without occupational exposure (12-51 ng/g lipid), and serum PAH and HPAH concentrations both in male and female workers were positively correlated with the occupational exposure duration, with an estimated doubling time of 11-17 years. Correlations were found between concentrations of ∑8HPAHs and ∑12PAHs but not between 7-chlorobenz[a]anthracene (7-ClBaA) and 1-chloropyrene (1-ClPyr) and their respective parent PAHs. In males, total concentrations of PAHs and HPAHs were positively correlated with pulmonary hypofunction and hypertension but not with abnormal electrocardiogram. The benzo[a]pyrene equivalents ratio of ∑8HPAHs/∑12PAHs was 0.3 ± 0.1. Among the HPAHs in the serum, 9-chlorophenanthrene, 7-ClBaA, and 1-ClPyr showed high health risks. This study is the first report on HPAH exposure in coal-fired power plant workers and provides new evidence on the health risks of PAHs and HPAHs in humans.

Associations between Novel and Legacy Per- and Polyfluoroalkyl Substances in Human Serum and Thyroid Cancer: A Case and Healthy Population in Shandong Province, East China.

Per- and polyfluoroalkyl substances (PFASs) are widely detected in the environment and may cause adverse human health effects after exposure. Studies on the effect of PFASs on some health end points, including cancer, are still limited and show inconsistent results. In this research, 319 participants were recruited from Shandong Province, East China, consisting of patients with thyroid cancer and healthy controls. Seven novel and legacy PFASs were frequently detected (detection rate > 75%) in the serum samples of the participants. The concentrations of perfluorooctanoic acid (PFOA) were the highest in the case and control groups. Males showed significantly higher concentrations of PFASs than females. Exposure to PFASs was inversely associated with the risk of thyroid cancer. In the control group, we identified significant positive associations between PFASs and free thyroxine (FT4) as well as between PFOA and thyroid stimulating hormone (TSH) in females. A significant negative association between perfluorononanoic acid (PFNA) and triiodothyronine (T3) was observed in males. Our results suggest that exposure to certain PFASs could interfere with thyroid function. To our knowledge, this is the first case-control study demonstrating associations between novel and legacy PFASs in human and thyroid cancer.

Exposure to novel and legacy per- and polyfluoroalkyl substances (PFASs) and associations with type 2 diabetes: A case-control study in East China.

Associations between per- and polyfluoroalkyl substances (PFASs) and the incidence of type 2 diabetes are controversial in epidemiological studies. In addition, limited data are available for assessing the health effects of novel PFAS alternatives. Our study evaluated the effects of PFAS exposure on type 2 diabetes by estimating the associations of PFASs in human serum with the risk of type 2 diabetes and levels of glycemic biomarkers and lipid fractions. The case-control study consisted of 304 participants from Shandong Province, East China, half of which were diagnosed with type 2 diabetes. Logistic regression showed that most PFASs were inversely associated with the risk of type 2 diabetes after adjusting for age, sex, and body mass index. However, concentrations of perfluorooctanoic acid (PFOA) in the control group were positively associated with fasting plasma glucose levels (ß = 0.04, 95% confidence interval (CI): 0.0003, 0.08), which may promote the development of type 2 diabetes. Furthermore, each log-unit increase in the concentrations of perfluorononanoic acid (PFNA), perfluoroundecanoic acid (PFUnDA), and 6:2 chlorinated polyfluoroalkyl ether sulfonic acid (Cl-PFESA) were associated with a total cholesterol increase (i.e., 17.49% (95% CI: 0.93%, 34.90%), 17.49% (95% CI: 4.71%, 31.83%), and 17.49% (95% CI: 4.71%, 31.83%), respectively). Positive associations were also observed between PFNA, PFUnDA, perfluorooctane sulfonate (PFOS), and 6:2 Cl-PFESA and low-density lipoprotein cholesterol. However, no associations between PFASs and hemoglobin A1c, triglycerides, or high-density lipoprotein cholesterol reached statistical significance, nor associations between PFAS mixtures and outcomes of interest. In conclusion, the significant correlations between serum PFASs and glycemic biomarkers and lipid fractions indicated that PFAS exposure may be a potential diabetogenic factor. To the best of our knowledge, this is the first study to assess the associations between novel Cl-PFESAs and type 2 diabetes, although the inverse associations observed require clarification in future studies.

Occurrence and distribution of organophosphate esters in the air and soils of Ny-Ålesund and London Island, Svalbard, Arctic.

The levels of eight organophosphate esters (OPEs) were analyzed in air and soil samples collected at Ny-Ålesund and London Island, Svalbard during the Chinese Scientific Research Expedition to the Arctic during 2014-2015. The concentrations of total OPEs (∑OPEs) ranged from 357 pg/m3 to 852 pg/m3 in the air and from 1.33 ng/g to 17.5 ng/g dry weight (dw) in the soils. Non-Cl OPEs accounted for 56 ± 13% and 62 ± 16% of ∑OPEs for the air and soil, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant compound in the air, with an average concentration of 180 ± 122 pg/m3. Triphenyl phosphate, tri(1-chloro-2-propyl) phosphate, and TCEP were the most abundant OPEs in the soils, with mean values of 1.77, 2.13, and 1.02 ng/g dw, respectively. Compared with the levels of polybrominated diphenyl ethers found in Arctic regions in previous studies, OPEs showed significantly higher concentrations, thereby indicating the large production and wide usage of OPEs globally. In addition, the fugacity fraction results indicated that net deposition from air to soil was dominated in the area. Overall, the occurrence and distribution of OPEs in the air and soils in the Arctic region indicated that OPEs can undergo long-range atmospheric transport and accumulate in remote regions.