Evaluation of pharmaceutical consumption between urban and suburban catchments in China by wastewater-based epidemiology.

Wastewater-based epidemiology (WBE) is amply used for estimating human consumption of chemicals, yet information on regional variation of pharmaceuticals and their environmental fate are scarce. Thus, this study aims to estimate the consumption of three cardiovascular, four non-steroidal anti-inflammatory pharmaceuticals (NSAIDs), and four psychoactive pharmaceuticals between urban and suburban catchments in China by WBE, and to explore their removal efficiencies and ecological risks. Eleven analytes were detected in both influent and effluent samples. The estimated consumptions ranged from

Periodic DFT calculations for the heterogeneous formation of 2-chlorothiophenoxy radical from 2-chlorothiophenol on Cu(111) surface in fly ash.

Copper plays a crucial role in the heterogenous dissociation of chlorothiophenols (CTPs) to form chlorothiophenoxy radicals (CTPRs), which is the initial and critical step in the formation of polychlorinated thianthrenes/dibenzothiophenes (PCTA/DTs). Here, first-principles calculations were performed to investigate the activity of Cu(111) surface towards the formation of adsorbed 2-CTPR from 2-CTP. The interaction between 2-CTP and Cu(111) surface was explored to find stable adsorption configurations. Besides, the decomposition routes of 2-CTP on the Cu(111) surface were further explored. Moreover, the effects of water on the formation of absorbed 2-CTPR on the Cu(111) surface were examined. Our results demonstrate that the flat adsorption of 2-CTP on the surface with adsorption energy in the range of -33.21 kcal/mol to -28.37 kcal/mol is more stable than the vertical adsorption with adsorption energy ranging from -23.53 kcal/mol to -13.38 kcal/mol. The Cu(111) surface catalyzes the conversion of 2-CTP into the adsorbed 2-CTPR with a modest energy barrier of 9.46 kcal/mol. Furthermore, water molecules exhibit stronger catalytic activity in this process with a decreased energy barrier of 5.87 kcal/mol through "water bridge" and hydrogen bonding. Specifically, the water accepts the hydrogen atom from 2-CTP and donates another hydrogen to the surface via "water bridge". This research provides a molecular-level understanding of the heterogeneous formation of PCTA/DTs by fly ash, suggesting novel approaches for control strategy and legislation of dioxin analogues.

Formation of Pre-PCTA/DT Intermediates from 2-Chlorothiophenol on Silica Clusters: A Quantum Mechanical Study.

Silica (SiO2), accounting for the main component of fly ash, plays a vital role in the heterogeneous formation of polychlorinated thianthrenes/dibenzothiophenes (PCTA/DTs) in high-temperature industrial processes. Silica clusters, as the basic units of silica, provide reasonable models to understand the general trends of complex surface reactions. Chlorothiophenols (CTPs) are the most crucial precursors for PCTA/DT formation. By employing density functional theory, this study examined the formation of 2-chlorothiophenolate from 2-CTP adsorbed on the dehydrated silica cluster ((SiO2)3) and the hydroxylated silica cluster ((SiO2)3O2H4). Additionally, this study investigated the formation of pre-PCTA/DTs, the crucial intermediates involved in PCTA/DT formation, from the coupling of two adsorbed 2-chlorothiophenolates via the Langmuir-Hinshelwood (L-H) mechanism and the coupling of adsorbed 2-chlorothiophenolate with gas-phase 2-CTP via the Eley-Rideal (E-R) mechanism on silica clusters. Moreover, the rate constants for the main elementary steps were calculated over the temperature range of 600-1200 K. Our study demonstrates that the 2-CTP is more likely to adsorb on the termination of the dehydrated silica cluster, which exhibits more effective catalysis in the formation of 2-chlorothiophenolate compared with the hydroxylated silica cluster. Moreover, the E-R mechanism mainly contributes to the formation of pre-PCTAs, whereas the L-H mechanism is prone to the formation of pre-PCDTs on dehydrated and hydroxylated silica clusters. Silica can act as a relatively mild catalyst in facilitating the heterogeneous formation of pre-PCTA/DTs from 2-CTP. This research provides new insights into the surface-mediated generation of PCTA/DTs, further providing theoretical foundations to reduce dioxin emission and establish dioxin control strategies.

Metal Exposure during Early Pregnancy and Risk of Gestational Diabetes Mellitus: Mixture Effect and Mediation by Phospholipid Fatty Acids.

Despite existing studies exploring the association between metal exposure and gestational diabetes mellitus (GDM), most of them have focused on a single metal or a small mixture of metals. Our prospective work investigated the joint and independent effects of early gestational exposure to 17 essential and nonessential metals on the GDM risk and potential mediation by plasma phospholipid fatty acids (PLFAs) based on a nested case-control study established with 335 GDM cases and 670 randomly matched healthy controls. The Bayesian kernel machine regression (BKMR) and quantile g-computation analyses demonstrated a joint effect from metal co-exposure on GDM risk. BKMR with hierarchical variable selection indicated that the group of essential metals was more strongly associated with GDM than the group of nonessential metals with group posterior inclusion probabilities (PIPs) of 0.979 and 0.672, respectively. Cu (0.988) and Ga (0.570) had the largest conditional PIPs within each group. We also observed significant mediation effects of selected unsaturated PLFAs on Cu-GDM and Ga-GDM associations. KEGG enrichment analysis further revealed significant enrichment in the biosynthesis of unsaturated PLFAs. C18:1 n-7 exhibited the largest proportion of mediation in both associations (23.8 and 22.9%). Collectively, our work demonstrated the joint effect of early gestational metal exposure on GDM risk and identified Cu and Ga as the key species to the joint effect. The findings lay a solid ground for further validation through multicenter investigations and mechanism exploration via laboratory studies.

The effects of the gas-liquid interface and gas phase on Cl/ClO radical interaction with water molecules.

In the marine boundary layer (MBL), chlorine (Cl) and chlorine monoxide (ClO) are powerful oxidants with high concentrations. The gas-liquid interface is also ubiquitous in the MBL as a favorable site for atmospheric reactions. Understanding the role of water in Cl/ClO radical chemistry is essential for predicting their behavior in the atmosphere and developing effective strategies for mitigating their harmful effects. However, the research studies on the system of Cl/ClO radicals on the surface of water droplets are still insufficient. In previous studies, we have found unique results related to the hydroxyl radical at the interface using ab initio molecular dynamics (AIMD). In this work, we have used AIMD to investigate interactions between Cl/ClO radicals and water molecules at the gas-liquid interface. Radical mobility, radial distribution functions, coordination, and population analyses were conducted to investigate the surface preference, bonding pattern, and track Cl/ClO radicals in the water droplets. In addition, density functional theory (DFT) analysis was conducted to compare the results at the gas-liquid interface with those in the gas phase. We found that Cl/ClO radicals tend to remain near the gas-liquid interface in water droplet systems and outside of water clusters in gas phase systems. The ClO radical can form O*-H and Cl-O bonds with water molecules; however, neither the O*-O hemibond nor the Cl-H bond was detected in all systems. Different dominant structures were obtained for ClO in the interface and gas phase. The ClO radical can be bonded to one water molecule from its oxygen side, (H2O)0-Cl-O*-(H2O)1 at the interface, or to two water molecules from the chlorine and oxygen sides, (H2O)1-Cl-O*-(H2O)1 in the gas phase. Meanwhile, the Cl radical can only form a dominant structure like Cl*-(H2O)1 at the gas-liquid interface by making a Cl*-O hemibond. Providing a thorough explanation of the Cl/ClO radical behavior at the gas-liquid interface, this study will improve our understanding of the MBL's oxidizing capacity and pollution causes.

Emerging and legacy per- and polyfluoroalkyl substances in house dust from South China: Contamination status and human exposure assessment.

Our study investigated a large variety of per- and polyfluoroalkyl substances (PFASs) in house dust collected from Guangzhou, South China during 2015-2018. The perfluorobutane sulfonic acid (PFBS) exhibited the highest median concentration (17.6 ng/g), followed by linear perfluorooctanoic acid (L-PFOA; 4.8 ng/g), linear perfluorooctane sulfonic acid (L-PFOS; 4.2 ng/g), 6:2 fluorotelomer phosphate diester (6:2 diPAP; 3.4 ng/g), perfluorodecanoic acid (PFDA; 1.2 ng/g) and perfluoroundecanoic acid (PFUdA; 1.2 ng/g), and 6:2 chlorinated perfluoroalkyl ether sulfonic acid (6:2 Cl-PFESA; 1.1 ng/g). Total concentrations of PFASs (median: 53 ng/g) were generally within the 25-50 percentile of the concentration range reported in global studies. However, our samples exhibited composition profiles different from those reported in many other regions. Analysis based on this and previous studies revealed that the compositions in house dust from East Asia, North America, and Europe exhibit a region-specific pattern. This may indicate region-specific market demands, application patterns, as well as associated human exposure risks. Exploration of dwelling characterizations suggested that renovation history appeared to be a significant factor influencing PFAS concentrations in house dust, although other factors may exist and play a role. Estimation of daily intakes via dust ingestion and dermal contact indicates low exposure risks from these two pathways. However, the PFAS chemical-specific biological effects, possible mixture effects, as well as additional exposure pathways, imply that the risk from indoor PFAS exposure should not be overlooked.

Halogenated organic pollutants in sediments and organisms from mangrove wetlands of the Jiulong River Estuary, South China.

Eighteen sediments and four biota species were collected from mangrove wetlands of the Jiulong River Estuary (JRE) in South China to investigate the distribution of dichlorodiphenyltrichloroethane (DDT), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), dechlorane plus (DP) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Concentrations of ΣDDTs, ΣPCBs, ΣPBDEs, DBDPE, DP, and BTBPE in mangrove sediments ranged from 21 to 84, 0.52-2.5, 9.0-66, 5.1-32, 0.05-0.14, and 0.03-0.25 ng/g dry weight, respectively. Levels of ΣDDTs, ΣPCBs, ΣPBDEs, DBDPE and DP in mangrove biota ranged from 950 to 30000, 56-400, 8.0-35, nd-20 and 0.44-3.1 ng/g lipid weight, respectively. DDTs were the predominant halogenated organic pollutants (HOPs) in mangrove sediments from the JRE, while PBDEs were the major HOPs in mangrove sediments from the Pearl River Estuary (PRE), suggesting that sediments in JRE and PRE had different sources of HOPs. The dominance of DDTs was found in both mangrove sediments and biota from the JRE, indicating that HOPs in JRE environment mainly come from agricultural sources. The biota-sediment accumulation factors for DDTs and PCBs were significantly higher than those of PBDEs, DBDPE and DP, suggesting high bioavailability of DDTs and PCBs in mangrove biota. Trophic magnification factors for DDTs, PCBs, PBDEs, and DP were 10.5, 3.00, 2.66 and 1.23, respectively, indicating their potential of biomagnification in mangrove food webs.

Positive fluid balance is associated with increased in-hospital mortality in patients with intracerebral hemorrhage.

Objective: This study aimed to investigate the association between fluid balance (FB) and in-hospital mortality in patients with intracerebral hemorrhage (ICH).Methods: Data were extracted from the online database Multi-parameter Intelligent Monitoring in Intensive Care III. Patients were divided into two groups according to the FB status at 48 hours after intensive care unit (ICU) admission: negative and positive 48-hour FB groups. The primary outcome was in-hospital mortality.Results: Data of 1407 patients were analyzed. Linear spline function in logistic models showed significant association between the volume of positive FB and in-hospital mortality (odds ratio (OR) 1.006; 95% CI: 1.002-1.010), while the association between the volume of negative FB and in-hospital mortality was non-significant. For interpretation, FB was further divided into four quartiles. Referred to Q1, the OR of in-hospital mortality stepwise increased from Q2 (OR, 1.11; 95% CI: 0.72-1.68) to Q4 (OR, 1.68; 95% CI: 1.13-2.48). A similar association was also found between FB and Glasgow coma scale at ICU discharge.Conclusions: In patients with ICH, increased volume of positive FB was associated with higher in-hospital mortality while the volume of negative FB was not. Whether maintaining a zero FB status is a beneficial strategy needs further investigation.

The Intercalation of CORM-2 with Pharmaceutical Clay Montmorillonite (MMT) Aids for Therapeutic Carbon Monoxide Release.

The pharmaceutical clay montmorillonite (MMT) is, for the first time, explored as a carbon monoxide-releasing material (CORMat). MMT consists of silicate double layered structure; its exfoliation feature intercalate the CORM-2 [RuCl(µ-Cl)(CO)3]2 inside the layers to suppress the toxicity of organometallic segment. The infrared spectroscopy (IR) confirmed the existence of ruthenium coordinated carbonyl ligand in MMT layers. The energy-dispersive X-ray spectroscopy (EDX) analysis showed that ruthenium element in this material was about 5%. The scanning electron microscopy (SEM) and transmission electron microscope (TEM) images showed that the layer-structure of MMT has been maintained after loading the ruthenium carbonyl segment. Moreover, the layers have been stretched out, which was confirmed by X-ray diffraction (XRD) analysis. Thermogravimetric (TG) curves with huge weight loss around 100-200 °C were attributed to the CO hot-release of ruthenium carbonyl as well as the loss of the adsorbed solvent molecules and the water molecules between the layers. The CO-liberating properties have been assessed through myoglobin assay. The horse myoglobin test showed that the material could be hydrolyzed to slowly release carbon monoxide in physiological environments. The half-life of CO release was much longer than that of CORM-3, and it has an excellent environmental tolerance and slow release effect.

Spatial Distribution and Congener Profiles of Polybrominated Diphenyl Ethers in Surface Sediment from Sanmen Bay and Xiamen Bay, Southeast China.

Coastal areas are influenced by anthropogenic input of a variety of organic pollutants, among which polybrominated diphenyl ethers (PBDEs) represent an important group. In the present study, we investigated the contamination status of PBDEs in surface sediment from two economically important Bays in Southeast China, Sanmen Bay (SMB; n = 29) and Xiamen Bay (XMB; n = 10). Concentrations of ∑PBDEs ranged from 2.2 to 78.5 ng/g dw (median 5.7 ng/g dw) in SMB and 7.9-276.0 ng/g dw (median 43.5 ng/g dw) in XMB, respectively. A nearshore-offshore decreasing trend was observed for both ∑PBDEs and BDE-209 concentrations, indicating strong urban influences. Although the current levels would not produce any significant impact on benthos and aquatic ecosystems of the studied regions, continuous monitoring is needed to understand the temporal trends of contamination in the important coastal waters and whether sediment-associated PBDEs constitute a potential source to aquatic ecosystems.

Polyhalogenated Carbazoles in Surface Sediment from Sanmen Bay, East China Sea: Spatial Distribution and Congener Profile.

Polyhalogenated carbazoles (PHCZs) have recently emerged as a group of halogenated pollutants with broad occurrences and bioaccumulation potential in aquatic systems. However, investigations on their occurrences in coastal waters remain very limited. In the present study we investigated PHCZs in surface sediment collected from 29 sites in Sanmen Bay, East China Sea. The results demonstrated a universal presence of PHCZs in sediment, with concentrations of ∑PHCZs (including all congeners) ranging from 7.7 to 17.5 ng/g dry weight (median: 11.3 ng/g dw). The PHCZ congener composition profile revealed a dominance of 3,6-dichlorocarbazole (36-CCZ) with comparable concentration with that of carbazole. Given that PHCZs are widely distributed in Sanmen Bay sediment and their concentrations rivaled other well-known persistent organic pollutants in the same area, this group of halogenated pollutants merits additional investigations of their potential risks to the studied aquatic system, as well as other important watersheds.

Spatial and Vertical Distribution of Dechlorane Plus in Mangrove Sediments of the Pearl River Estuary, South China.

Thirty surface sediments and three sediment cores were collected from mangrove wetlands in the Pearl River Estuary of South China to investigate the spatial and vertical distribution of Dechlorane Plus (DP). DP concentrations in the mangrove surface sediments ranged from 0.0130 to 1.504 ng/g dry weight (dw). DP concentrations in sediments from Shenzhen were significantly greater than those from Guangzhou and Zhuhai. Anti-Cl11-DP, the dechlorinated product of anti-DP, was also detected in the mangrove sediments with concentrations ranged from not detected to 0.0198 ng/g dw. Significant positive relationship between anti-Cl11-DP and anti-DP levels was observed in the mangrove sediments, suggesting that photo and/or microbial degradation of anti-DP might occur in the sediments. The f anti values in the mangrove sediments were close to those in the technical DP products, suggesting that stereoselective enrichment of anti-DP may not exist in the mangrove sediments. DP concentrations in the mangrove sediment cores generally showed an increasing trend from the bottom to top layers. This is the first study to report the occurrence of DP and its degradation product in the mangrove wetlands.

DFT and AIMD insights into heterogeneous dissociation of 2-chlorothiophenol on CuO(111) surface: Impact of H2O and OH.

Copper oxides are vital catalysts in facilitating the formation of polychlorinated thianthrenes/dibenzothiophenes (PCTA/DTs) through heterogeneous reactions in high-temperature industrial processes. Chlorothiophenols (CTPs) are the most crucial precursors for PCTA/DT formation. The initial step in this process is the metal-catalyzed production of chlorothiophenoxy radicals (CTPRs) from CTPs via dissociation reactions. This work combines density functional theory (DFT) calculations with ab initio molecular dynamics (AIMD) simulations to explore the formation mechanism of the adsorbed 2-CTPR from 2-CTP, with the assistance of CuO(111). Our study demonstrates that flat adsorption configurations of 2-CTP on the CuO(111) surface are more stable than vertical configurations. The CuO(111) surface acts as a strong catalyst, facilitating the dissociation of 2-CTP into the adsorbed 2-CTPR. Surface oxygen vacancies enhance the adsorption of 2-CTP on the CuO(111) surface, while moderately suppressing the dissociation of 2-CTP. More importantly, water molecules and surface hydroxyl groups actively promote the dissociation of 2-CTP. Specifically, water directly participates in the reaction through "water bridge", enabling a barrier-free process. This research provides molecular-level insights into the heterogeneous generation of dioxins with the catalysis of metal oxides in fly ash from static and dynamic aspects, providing novel approaches for reducing dioxin emissions and establishing dioxin control strategies.

An effective tool for tracking steroids and their metabolites at the watershed level: Combining fugacity modeling and a chemical indicator.

Steroids have attracted concern worldwide because of their potential carcinogenicity and severe adverse effects on aquatic organisms. However, the contamination status of various steroids, particularly their metabolites, at the watershed level remains unknown. This was the first study to employ field investigations to elucidate the spatiotemporal patterns, riverine fluxes, and mass inventories, and conduct a risk assessment of 22 steroids and their metabolites. This study also developed an effective tool for predicting the target steroids and their metabolites in a typical watershed based on the fugacity model combined with a chemical indicator. Thirteen steroids in the river water and seven steroids in sediments were identified with total concentrations of 1.0-76 ng/L and

Prediction of persistent acute kidney injury in postoperative intensive care unit patients using integrated machine learning: a retrospective cohort study.

Acute kidney injury (AKI) often occurs in patients in the intensive care unit (ICU). AKI duration is closely related to the prognosis of critically ill patients. Identifying the disease course length in AKI is critical for developing effective individualised treatment. To predict persistent AKI at an early stage based on a machine learning algorithm and integrated models. Overall, 955 patients admitted to the ICU after surgery complicated by AKI were retrospectively evaluated. The occurrence of persistent AKI was predicted using three machine learning methods: a support vector machine (SVM), decision tree, and extreme gradient boosting and with an integrated model. External validation was also performed. The incidence of persistent AKI was 39.4-45.1%. In the internal validation, SVM exhibited the highest area under the receiver operating characteristic curve (AUC) value, followed by the integrated model. In the external validation, the AUC values of the SVM and integrated models were 0.69 and 0.68, respectively, and the model calibration chart revealed that all models had good performance. Critically ill patients with AKI after surgery had high incidence of persistent AKI. Our machine learning model could effectively predict the occurrence of persistent AKI at an early stage.

Occurrence and ecological risks of brominated flame retardants and dechlorane plus in sediments from the Pearl River Estuary and Daya Bay, South China.

Considering the phasing-out of polybrominated diphenyl ethers (PBDEs), environmental concerns of PBDE alternatives and dechlorane plus (DP) are rising. Accordingly, this study investigates occurrence and ecological risks of PBDEs, PBDE alternatives and DPs in sediments of two littoral regions, the Pearl River Estuary (PRE) and Daya Bay (DYB), in southern China. Total PBDEs concentrations in surface sediments of the PRE and DYB were in the range (mean) of 0.30-28.7 (8.71) and 0.29-43.4 (6.05) ng/g dw, respectively. DP levels in surface sediments of the PRE (0.004-0.27 ng/g dw) were significantly higher than those in the DYB (0.005-0.24 ng/g dw) (p < 0.05). BDE 209 was the predominant component, followed by DBDPE, exhibiting regional variations in BFRs usage. Vertical profiles of BFRs and DP in the PRE and DYB sediment cores exhibited clear anthropogenic influences. Risk quotients suggest critical ecological risks of tetra-, penta- and deca-BDE congeners in all the surface sediments.

Legacy and alternative flame retardants in indoor dust from e-waste industrial parks and adjacent residential houses in South China: Variations, sources, and health implications.

Many studies have elucidated health concerns of informal e-waste recycling activities, yet few has evaluated the effectiveness of the regulations as well as the human exposure risks to adjacent residents. Herein, legacy polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDs), and alternative organophosphate esters (OPEs) were investigated in indoor dust collected from three e-waste industrial parks and five adjacent villages located in south China. The levels and composition patterns varied significantly between workshop and home dust. BDE209 showed much higher (p < 0.01) concentrations in workshop dust versus home dust, while relatively comparable levels were found for OPEs and HBCDs. Principal component analysis revealed that OPEs and PBDEs were mainly related to home and workshop dust, respectively. Results strongly indicated that e-waste dismantling activities still contribute to a high burden of BDE209 to surrounding residents, whilst the sources of OPEs may also originated from household products, especially for TCEP. The estimated daily intakes (EDIs) via dust ingestion and dermal absorption for occupational worker and nearby toddlers were below available reference dose (RfD) values even at worst case scenario. This study highlights the significance of deca-BDEs rather than alternative OPEs in e-waste generated in China, which could provide scientific suggestions for policy formulation.

Synthetical effect of microplastics and chiral drug amphetamine on a primary food source algae Chlorella pyrenoids.

The biological effects and fate of the chiral illicit drug amphetamine in the presence and absence of microplastics on freshwater algae (Chlorella pyrenoids), including acute toxicity, growth inhibition, photosynthetic pigment content, oxidative stress, lipid peroxidation, and enantioselective fate were assessed. An agglomeration and the shading effects of microplastics in algae suspension were also determined. Microplastics were observed to increase the toxicity of amphetamine to algae and reduce algae cell growth. Exposed Chlorella pyrenoids exhibited a reduced algae cell counts in an agglomeration test, wherein algae cells decreased between 18% and 56% among treatment groups exposed to 5-50 mg L-1 of microplastics. The agglomeration test suggested that microplastics might significantly increase the adverse effect on algae. Furthermore, our experiments demonstrated enantioselective degradation of amphetamine in algae, and demonstrated that the S-enantiomer was preferably degraded by algae cells. Adding microplastics to the algae suspension significantly reduced the enantioselectivity, with an EF value of 0.41 compared with amphetamine-alone group (0.34) after 21 d exposure. These results demonstrated the first evidence of microplastics acting as a vehicle to enhance amphetamine toxicity to Chlorella pyrenoids, as well as provided new insights into the co-effect of microplastics and organic contaminants on food source.

Tetrabromobisphenol A and hexabromocyclododecanes in sediments and biota from two typical mangrove wetlands of South China: Distribution, bioaccumulation and biomagnification.

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) were examined in sediments and biota species from two mangrove wetlands of the Pearl River Estuary (PRE) and the Jiulong River Estuary (JRE), South China, to investigate their distribution, bioaccumulation and biomagnification in mangrove food webs. Levels of TBBPA and ΣHBCD (sum of α-, ß- and γ-HBCDs) ranged from 0.003 to 0.31 and not detected (nd) to 1.11 ng/g dry weight in the sediments, and from 0.56 to 22.1 and nd to 56.3 ng/g lipid weight in the biota species, respectively. γ-HBCD was the major diastereoisomer in the PRE sediments, while α- and γ-HBCDs predominated in the JRE sediments. In contrast, α-HBCD was dominant in the biota. Mean enantiomeric fractions (EFs) of α-, ß- and γ-HBCDs in the sediments all followed the trend of JRE > racemic standard > PRE. A significant enrichment of (-)-α-HBCD was found in the biota (p = 0.04), with EFs in the range of 0.297-0.485. Bioaccumulations were seen for TBBPA and α-HBCD as their biota-sediment accumulation factors (BSAFs) were greater than 1. (-)-α-HBCD had significantly greater BSAFs than (+)-α-HBCD (p = 0.04), indicating the preferential bioaccumulation of (-)-α-HBCD. Biomagnification factors (BMFs) of TBBPA ranged from 0.83 to 1.51, which varied among feeding relationships and mangroves. Positive relationships were found between TBBPA concentrations and trophic levels of the biota species with trophic magnification factors of 2.17 for the PRE and 1.22 for the JRE, suggesting that TBBPA biomagnifies in the mangrove food webs. No biomagnifications were observed for ΣHBCD, α-HBCD and its enantiomers.

Polyhalogenated carbazoles in freshwater and estuarine sediment from China and the United States: A multi-regional study.

The present study represents a multi-regional investigation of polyhalogenated carbazoles (PHCZs) contamination in estuarine and freshwater systems from the United States and China. Although recent studies have suggested that PHCZs are persistent and bioaccumulative, available data are not sufficient to understand their large-scale spatial and temporal distributions in the environment. The present study investigated spatial distributions of PHCZs in surface sediment from multiple freshwater and estuarine systems located in China and the United States (U.S.) during the period of 2012-2017, as well as temporal distributions from vertical trends in selected sediment cores. The results demonstrated large variations of PHCZ contamination across regions, with median concentrations of ΣPHCZs in surface sediment ranging from 3.1 to 134 ng/g. Profiles of PHCZ congener composition also exhibited regional variations and estuarine-freshwater differences. These differences likely reflect the relative contributions of different natural and industrial sources among the locations. Vertical profiles of concentrations and compositions in one Chinese estuarine sediment core and two freshwater sediment cores from the U.S. all demonstrated clear anthropogenic influences to varying degrees. Toxic equivalents (TEQ) of PHCZs were estimated based on their dioxin-like activities, which ranged from <0.001 to 4.94 pg TEQ/g in all sites. The results suggest that PHCZs could add additional ecological risks to the benthos and other aquatic organisms. Our findings constitute an essential contribution to the knowledge body of PHCZ contamination in global aquatic systems and congener-specific contamination characterizations.