Azulene-Containing Bis(squaraine) Dyes: Design, Synthesis and Aggregation Behaviors.

The relationship among chemical structure, physicochemical property and aggregation behavior of organic functional material is an important research topic. Here, we designed and synthesized three bis(squaraine) dyes BSQ1, BSQ2 and BSQ3 through the combination of two kinds of unsymmetrical azulenyl squaraine monomers. Their physicochemical properties were investigated in both molecular and aggregate states. Generally, BSQ1 displayed different assembly behaviors from BSQ2 and BSQ3. Upon fabrication into nanoparticles, BSQ1 tend to form J-aggregates while BSQ2 and BSQ3 tend to form H-aggregates in aqueous medium. When in the form of thin films, three bis(squaraine) dyes all adopted J-aggregation packing modes while only BSQ1 presented the most significant rearrangement of aggregate structures as well as the improvement in the carrier mobilities upon thermal annealing. Our research highlights the discrepancy of aggregation behaviors originating from the molecular structure and surrounding circumstances, providing guidance for the molecular design and functional applications of squaraines.

Heterogeneous Photodegradation Behavior of Liquid Crystal Monomers in Dust: Quantitative Structure-Activity Relationship and Product Identification.

The heterogeneous photodegradation behavior of liquid crystal monomers (LCMs) in standard dust (standard reference material, SRM 2583) and environmental dust was investigated. The measured photodegradation ratios for 23 LCMs in SRM and environmental dust in 12 h were 11.1 ± 1.8 to 23.2 ± 1.1% and 8.7 ± 0.5 to 24.0 ± 2.8%, respectively. The degradation behavior of different LCM compounds varied depending on their structural properties. A quantitative structure-activity relationship model for predicting the degradation ratio of LCMs in SRM dust was established, which revealed that the molecular descriptors related to molecular polarizability, electronegativity, and molecular mass were closely associated with LCMs' photodegradation. The photodegradation products of the LCM compound 4'-propoxy-4-biphenylcarbonitrile (PBIPHCN) in dust, including •OH oxidation, C-O bond cleavage, and ring-opening products, were identified by nontarget analysis, and the corresponding degradation pathways were suggested. Some of the identified products, such as 4'-hydroxyethoxy-4-biphenylcarbonitrile, showed predicted toxicity (with an oral rat lethal dose of 50%) comparable to that of PBIPHCN. The half-lives of the studied LCMs in SRM dust were estimated at 32.2-82.5 h by fitting an exponential decay curve to the observed photodegradation data. The photodegradation mechanisms of LCMs in dust were revealed for the first time, enhancing the understanding of LCMs' environmental behavior and risks.

Stability and Biotransformation of 6:2 Fluorotelomer Sulfonic Acid, Sulfonamide Amine Oxide, and Sulfonamide Alkylbetaine in Aerobic Sludge.

The 6:2 fluorotelomer sulfonamide (6:2 FTSAm)-based compounds signify a prominent group of per- and polyfluoroalkyl substances (PFAS) widely used in contemporary aqueous film-forming foam (AFFF) formulations. Despite their widespread presence, the biotransformation behavior of these compounds in wastewater treatment plants remains uncertain. This study investigated the biotransformation of 6:2 FTSAm-based amine oxide (6:2 FTNO), alkylbetaine (6:2 FTAB), and 6:2 fluorotelomer sulfonic acid (6:2 FTSA) in aerobic sludge over a 100-day incubation period. The biotransformation of 6:2 fluorotelomer sulfonamide alkylamine (6:2 FTAA), a primary intermediate product of 6:2 FTNO, was indirectly assessed. Their stability was ranked based on the estimated half-lives (t1/2): 6:2 FTAB (no obvious products were detected) ≫ 6:2 FTSA (t1/2 ≈28.8 days) > 6:2 FTAA (t1/2 ≈11.5 days) > 6:2 FTNO (t1/2 ≈1.2 days). Seven transformation products of 6:2 FTSA and 15 products of 6:2 FTNO were identified through nontarget and suspect screening using high-resolution mass spectrometry. The transformation pathways of 6:2 FTNO and 6:2 FTSA in aerobic sludge were proposed. Interestingly, 6:2 FTSAm was hardly hydrolyzed to 6:2 FTSA and further biotransformed to perfluoroalkyl carboxylic acids (PFCAs). Furthermore, the novel pathways for the generation of perfluoroheptanoic acid (PFHpA) from 6:2 FTSA were revealed.

Contamination Status of Novel Organophosphate Esters Derived from Organophosphite Antioxidants in Soil and the Effects on Soil Bacterial Communities.

The contamination status of novel organophosphate esters (NOPEs) and their precursors organophosphite antioxidants (OPAs) and hydroxylated/diester transformation products (OH-OPEs/di-OPEs) in soils across a large-scale area in China were investigated. The total concentrations of the three test NOPEs in soil were 82.4-716 ng g-1, which were considerably higher than those of traditional OPEs (4.50-430 ng g-1), OPAs (n.d.-30.8 ng g-1), OH-OPEs (n.d.-0.49 ng g-1), and di-OPEs (0.57-21.1 ng g-1). One NOPE compound, i.e., tris(2,4-di-tert-butylphenyl) phosphate (AO168 = O) contributed over 65% of the concentrations of the studied OPE-associated contaminants. A 30-day soil incubation experiment was performed to confirm the influence of AO168 = O on soil bacterial communities. Specific genera belonging to Proteobacteria, such as Lysobacter and Ensifer, were enriched in AO168 = O-contaminated soils. Moreover, the ecological function of methylotrophy was observed to be significantly enhanced (t-test, p < 0.01) in soil treated with AO168 = O, while nitrogen fixation was significantly inhibited (t-test, p < 0.01). These findings comprehensively revealed the contamination status of OPE-associated contaminants in the soil environment and provided the first evidence of the effects of NOPEs on soil microbial communities.

Nontarget Identification of Novel Organophosphorus Flame Retardants and Plasticizers in Indoor Air and Dust from Multiple Microenvironments in China.

The indoor environment is a typical source for organophosphorus flame retardants and plasticizers (OPFRs), yet the source characteristics of OPFRs in different microenvironments remain less clear. This study collected 109 indoor air samples and 34 paired indoor dust samples from 4 typical microenvironments within a university in Tianjin, China, including the dormitory, office, library, and information center. 29 target OPFRs were analyzed, and novel organophosphorus compounds (NOPs) were identified by fragment-based nontarget analysis. Target OPFRs exhibited the highest air and dust concentrations of 46.2-234 ng/m3 and 20.4-76.0 µg/g, respectively, in the information center, where chlorinated OPFRs were dominant. Triphenyl phosphate (TPHP) was the primary OPFR in office air, while tris(2-chloroethyl) phosphate dominated in the dust. TPHP was predominant in the library. Triethyl phosphate (TEP) was ubiquitous in the dormitory, and tris(2-butoxyethyl) phosphate was particularly high in the dust. 9 of 25 NOPs were identified for the first time, mainly from the information center and office, such as bis(chloropropyl) 2,3-dichloropropyl phosphate. Diphenyl phosphinic acid, two hydroxylated and methylated metabolites of tris(2,4-ditert-butylphenyl) phosphite (AO168), and a dimer phosphate were newly reported in the indoor environment. NOPs were widely associated with target OPFRs, and their human exposure risk and environmental behaviors warrant further study.

Urinary Metabolites of Polycyclic Aromatic Hydrocarbons of Rural Population in Northwestern China: Oxidative Stress and Health Risk Assessment.

Polycyclic aromatic hydrocarbon (PAH) exposure is suspected to be linked to oxidative damage. Herein, ten PAH human exposure biomarkers [hydroxylated PAH metabolites (OH-PAHs)] and five oxidative stress biomarkers (OSBs) were detected in urine samples collected from participants living in a rural area (n = 181) in Northwestern China. The median molar concentration of ΣOH-PAHs in urine was 47.0 pmol mL-1. The 2-hydroxynaphthalene (2-OHNap; median: 2.21 ng mL-1) was the dominant OH-PAH. The risk assessment of PAH exposure found that hazard index (HI) values were <1, indicating that the PAH exposure of rural people in Jingyuan would not generate significant cumulative risks. Smokers (median: 0.033) obtained higher HI values than nonsmokers (median: 0.015, p < 0.01), suggesting that smokers face a higher health risk from PAH exposure than nonsmokers. Pearson correlation and multivariate linear regression analysis revealed that ΣOH-PAH concentrations were significant factors in increasing the oxidative damage to deoxyribonucleic acid (DNA) (8-hydroxy-2'-deoxyguanosine, 8-OHdG), ribonucleic acid (RNA) (8-oxo-7,8-dihydroguanine, 8-oxoGua), and protein (o, o'-dityrosine, diY) (p < 0.05). Among all PAH metabolites, only 1-hydroxypyrene (1-OHPyr) could positively affect the expression of all five OSBs (p < 0.05), suggesting that urinary 1-OHPyr might be a reliable biomarker for PAH exposure and a useful indicator for assessing the impacts of PAH exposure on oxidative stress. This study is focused on the relation between PAH exposure and oxidative damage and lays a foundation for the study of the health effect mechanism of PAHs.

Fused Azulenyl Squaraine Derivatives Improve Phototheranostics in the Second Near-Infrared Window by Concentrating Excited State Energy on Non-Radiative Decay Pathways.

The second near-infrared (NIR-II) theranostics offer new opportunities for precise disease phototheranostic due to the enhanced tissue penetration and higher maximum permissible exposure of NIR-II light. However, traditional regimens lacking effective NIR-II absorption and uncontrollable excited-state energy decay pathways often result in insufficient theranostic outcomes. Herein a phototheranostic nano-agent (PS-1 NPs) based on azulenyl squaraine derivatives with a strong NIR-II absorption band centered at 1092 nm is reported, allowing almost all absorbed excitation energy to dissipate through non-radiative decay pathways, leading to high photothermal conversion efficiency (90.98 %) and strong photoacoustic response. Both in vitro and in vivo photoacoustic/photothermal therapy results demonstrate enhanced deep tissue cancer theranostic performance of PS-1 NPs. Even in the 5 mm deep-seated tumor model, PS-1 NPs demonstrated a satisfactory anti-tumor effect in photoacoustic imaging-guided photothermal therapy. Moreover, for the human extracted tooth root canal infection model, the synergistic outcomes of the photothermal effect of PS-1 NPs and 0.5 % NaClO solution resulted in therapeutic efficacy comparable to the clinical gold standard irrigation agent 5.25 % NaClO, opening up possibilities for the expansion of NIR-II theranostic agents in oral medicine.

First Insight into the Formation of In Vivo Transformation Products of 2-Ethylhexyl diphenyl phosphate in Zebrafish and Prediction of Their Potential Toxicities.

As a frequently detected organophosphorus flame retardant in the environment, 2-ethylhexyl diphenyl phosphate (EHDPHP) is vulnerable to biotransformation, while the transformation mechanisms and potential toxicities of its transformation products remain unclear. In the present study, in vivo transformation products of EHDPHP in exposed zebrafish for 21d were analyzed by suspect screening and identified by mass spectrometry. Fifteen metabolites were identified, including 10 phase I and 5 phase II products with monohydroxylated products being primary, among which 5-OH-EHDPHP was the most predominant. Two sulfation products and one terminal desaturation metabolite of EHDPHP were reported for the first time. A density functional calculation coupled with molecular docking disclosed that the specific conformation of EHDPHP docked in the protein pockets favored the primary formation of 5-OH-EHDPHP, which was fortified to be a more suitable biomarker of EHDPHP exposure. The in vitro tests suggested that EHDPHP transformation took place not only in liver but also in intestine, where gut microbes played an important role. Due to lack of standards, in silico toxicity prediction combined with molecular docking indicated that several metabolites potentially cause higher toxicities than EHDPHP. The results provide deep insight into the potential health risks due to specific in vivo transformation of EHDPHP.

Nontarget Identification of Novel Per- and Polyfluoroalkyl Substances (PFAS) in Soils from an Oil Refinery in Southwestern China: A Combined Approach with TOP Assay.

Oil refinery activity can be an emission source of perfluoroalkyl and polyfluoroalkyl substances (PFAS) to the environment, while the contamination profiles in soils remain unknown. This study investigated 44 target PFAS in soil samples collected from an oil refinery in Southeastern China, identified novel PFAS, and characterized their behaviors by assessing their changes before and after employing advanced oxidation using a combination of nontarget analysis and a total oxidizable precursor (TOP) assay. Thirty-four target PFAS were detected in soil samples. Trifluoroacetic acid (TFA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were the dominant PFAS. Twenty-three novel PFAS of 14 classes were identified, including 8 precursors, 11 products, and 4 stable PFAS characterized by the TOP assay. Particularly, three per-/polyfluorinated alcohols were identified for the first time, and hexafluoroisopropanol (HFIP) quantified up to 657 ng/g dw is a novel precursor for TFA. Bistriflimide (NTf2) potentially associated with an oil refinery was also reported for the first time in the soil samples. This study highlighted the advantage of embedding the TOP assay in nontarget analysis to reveal not only the presence of unknown PFAS but also their roles in environmental processes. Overall, this approach provides an efficient way to uncover contamination profiles of PFAS especially in source-impacted areas.

Organophosphite Antioxidants and Novel Organophosphate Esters in Dust from China: Large-Scale Distribution and Heterogeneous Phototransformation.

A large-scale survey was conducted by measuring five organophosphite antioxidants (OPAs) and three novel organophosphate esters (NOPEs) in 139 dust samples across China. The median summed concentrations of OPAs and NOPEs in outdoor dust were 33.8 ng/g (range: 0.12-53,400 ng/g) and 7990 ng/g (2390-27,600 ng/g), respectively. The dust concentrations of OPAs associated with the increasing economic development and population density from western to eastern China, whereas the NOPE concentration in Northeast China (median, 11,900 ng/g; range, 4360-16,400 ng/g) was the highest. Geographically, the distribution of NOPEs was significantly associated with annual sunshine duration and precipitation at each sampling site. Results of laboratory experiments further revealed that the simulated sunlight irradiation promoted the heterogeneous phototransformation of OPAs in dust, and this process was accelerated with the existence of reactive oxygen species and enhanced relative humidity. Importantly, during this phototransformation, the hydroxylated, hydrolyzed, dealkylated, and methylated products, e.g., bis(2,4-di-tert-butylphenyl) methyl phosphate, were identified by nontargeted analysis, part of which were estimated to be more toxic than their parent compounds. The heterogeneous phototransformation pathway of OPAs was suggested accordingly. For the first time, the large-scale distribution of OPAs and NOPEs and the phototransformation of these "new chemicals" in dust were revealed.

Nontarget Identification of Novel Organophosphorus Flame Retardants and Plasticizers in Rainfall Runoffs and Agricultural Soils around a Plastic Recycling Industrial Park.

Plastic recycling and reprocessing activities may release organophosphate ester (OPE) flame retardants and plasticizers into the surrounding environment. However, the relevant contamination profiles and impacts remain not well studied. This study investigated the occurrence of 28 OPEs and their metabolites (mOPEs) in rainfall runoffs and agricultural soils around one of the largest plastic recycling industrial parks in North China and identified novel organophosphorus compounds (NOPs) using high-resolution mass spectrometry-based nontarget analysis. Twenty and twenty-seven OPEs were detected in runoff water and soil samples, with total concentrations of 86.0-2491 ng/L and 2.53-199 ng/g dw, respectively. Thirteen NOPs were identified, of which eight were reported in the environment for the first time, including a chlorine-containing OPE, an organophosphorus heterocycle, a phosphite, three novel OPE metabolites, and two oligomers. Triphenylphosphine oxide and diphenylphosphinic acid occurred ubiquitously in runoffs and soils, with concentrations up to 390 ng/L and 40.2 ng/g dw, respectively. The downwind areas of the industrial park showed elevated levels of OPEs and NOPs. The contribution of hydroxylated mOPEs was higher in soils than in runoffs. These findings suggest that plastic recycling and reprocessing activities are significant sources of OPEs and NOPs and that biotransformation may further increase the ecological and human exposure risk.

Nontarget Screening and Fate of Emerging Per- and Polyfluoroalkyl Substances in Wastewater Treatment Plants in Tianjin, China.

Wastewater treatment plants (WWTPs) are typical point sources of per- and polyfluoroalkyl substances (PFAS) released into the environment. The suspect and nontarget screening based on gas chromatography or liquid chromatography-high resolution mass spectrometry were performed on atmosphere, wastewater, and sludge samples collected from two WWTPs in Tianjin to discover emerging PFAS and their fate in this study. A total of 40 PFAS (14 neutral and 26 ionic) and 64 PFAS were identified in the atmosphere and wastewater/sludge, respectively, among which 5 short-chain perfluoroalkyl sulfonamide derivatives, 4 ionic PFAS, and 15 aqueous film-forming foam-related cationic or zwitterionic PFAS have rarely or never been reported in WWTPs in China. Active air sampling is more conducive to the enrichment of emerging PFAS, while passive sampling is inclined to leave out some ultrashort-chain PFAS or unstable transformation intermediates. Moreover, most precursors and intermediates could be enriched in the atmosphere at night, while the PFAS associated with aerosols with high water content or particles enter the atmosphere easily during the day. Although most emerging PFAS could not be eliminated efficiently in conventional treatment units, deep bed filtration and advanced oxidation processes could partly remove some emerging precursors.

Degradation of Perfluorooctanoic Acid by Chlorine Radical Triggered Electrochemical Oxidation System.

Electrochemical oxidation (EO) has been shown to have the unique ability to degrade perfluorooctanoic acid (PFOA), although the radical chemistry involved in this degradation is unclear, particularly in the presence of chloride ions (Cl-). In this study, reaction kinetics, free radical quenching, electron spin resonance, and radical probes were used to examine the roles of ·OH and reactive chlorine species (RCS, including Cl·, Cl2•-, and ClO·) in the EO of PFOA. Using EO in the presence of NaCl, PFOA degradation rates of 89.4%-94.9% and defluorination rates of 38.7%-44.1% were achieved after 480 min with PFOA concentrations ranging from 2.4 to 240 µM. The degradation occurred via the synergistic effect of ·OH and Cl· rather than through direct anodic oxidation. The degradation products and density functional theory (DFT) calculations revealed that Cl· triggered the first step of the reaction, thus the initial direct electron transfer was not the rate-limiting step of PFOA degradation. The change in Gibbs free energy of the reaction caused by Cl· was 65.57 kJ mol-1, which was more than two times lower than that triggered by ·OH. However, ·OH was involved in the subsequent degradation of PFOA. The synergistic effect of Cl· and ·OH in PFOA degradation is demonstrated for the first time in this study, which is promising for the development of electrochemical technology to remove perfluorinated alkyl substances from the environment.

Ultra-High Sensitivity Terahertz Microstructured Fiber Biosensor for Diabetes Mellitus and Coronary Heart Disease Marker Detection.

Diabetes Mellitus (DM) and Coronary Heart Disease (CHD) are among top causes of patient health issues and fatalities in many countries. At present, terahertz biosensors have been widely used to detect chronic diseases because of their accurate detection, fast operation, flexible design and easy fabrication. In this paper, a Zeonex-based microstructured fiber (MSF) biosensor is proposed for detecting DM and CHD markers by adopting a terahertz time-domain spectroscopy system. A suspended hollow-core structure with a square core and a hexagonal cladding is used, which enhances the interaction of terahertz waves with targeted markers and reduces the loss. This work focuses on simulating the transmission performance of the proposed MSF sensor by using a finite element method and incorporating a perfectly matched layer as the absorption boundary. The simulation results show that this MSF biosensor exhibits an ultra-high relative sensitivity, especially up to 100.35% at 2.2THz, when detecting DM and CHD markers. Furthermore, for different concentrations of disease markers, the MSF exhibits significant differences in effective material loss, which can effectively improve clinical diagnostic accuracy and clearly distinguish the extent of the disease. This MSF biosensor is simple to fabricate by 3D printing and extrusion technologies, and is expected to provide a convenient and capable tool for rapid biomedical diagnosis.

In situ self-sacrificial synthesis of polypyrrole/biochar composites for efficiently removing short- and long-chain perfluoroalkyl acid from contaminated water.

Efficient removal of perfluoroalkyl acids (PFAAs), especially short-chain ones, from contaminated water is of great challenge and is urgently called for so as to safeguard the ecosystem and human health. Herein, polypyrrole (PPy) functionalized biochar (BC) composites were innovatively synthesized by an in situ self-sacrificial approach to allow efficient capture of PFAAs with different chain lengths. Compared with conventional PPy-based composites synthesized by direct polymerization using FeCl3 as an oxidizing agent, PPy/BC composites were fabricated utilizing freshly generated Fe3+ as an oxidizing agent from self-sacrificial Fe3O4 for pyrrole monomers in situ polymerizing on BC. As a result, with the support of BC and gradual release of Fe3+, PPy overcame its tendency to aggregate and became uniformly dispersed on BC, and meanwhile, PPy could well tailor the surface chemistry of BC to endow its positively charged surface. Consequently, the composites exhibited strong sorption capacities of 3.89 and 1.53 mmol/g for short-chain perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), 2.55 and 1.22 mmol/g for long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), respectively, which were superior to those of pristine BC, commercial activated carbon, and anion exchange resins reported. Additionally, they could effectively remove 17 different classes of per- and polyfluoroalkyl substances (PFAS) (removal >95%) from actual PFAS-contaminated water, and the spent sorbent could be well regenerated and reused at least 5 times. An integrated analysis indicated that such an outstanding PFAA sorption performance on PPy/BC composites could be mainly attributed to surface adsorption enhanced by electrostatic attractions (anion exchange interaction) with the traditional hydrophobic interaction and pore filling of less contribution, particularly for short-chain analogues. These results are expected to inform the design of BC with greater ability to remove PFAS from water and the new sorbent could help water facilities comply with PFAS regulations.

Factors influence the dignity of burns patients: A cross-sectional study.

BACKGROUND: There is a high incidence of burns in China and the sequelae of post-burn scar growth, disfigurement, and other body image disorders can cause serious psychological distress to burns patients, and negatively affecting the patient's dignity. However, there is limited knowledge relating to the dignity of burns patients. AIM: To investigate the factors that affect dignity in burns patients. DESIGN: Cross-sectional study. PARTICIPANTS AND RESEARCH CONTEXT: We recruited 323 burn patients from the burn unit of a tertiary care hospital. The Patient Dignity Scale, Burn Specific Health Scale-Brief, Hospital Anxiety and Depression Scale were used to assess burn patients' dignity, quality of life, anxiety, and depression, respectively. 18 sociodemographic variables were included in the questionnaire. ETHICAL CONSIDERATIONS: Before the data were collected, the study protocol was reviewed and approved by the Ethics Committee of the Guangzhou Red Cross Hospital of Jinan University (Reference: 2022-149-02) and all patients provided and signed informed consent forms. FINDINGS: This study included 323 burns patients; of these, 26 (8%) had a mild loss of dignity, 94 (29.1%) had a moderate loss of dignity, 125 (38.7%) had a severe loss of dignity, and 78 (24.1%) had a very severe loss of dignity. The main factors that influence the loss of dignity in burns patients, including the department in which the patient was treated after their burns, gender, the clinical stage of the burn, quality-of-life, depression, resident medical insurance, the cause of the burn, and the burn site. CONCLUSIONS: In most cases, the loss of dignity after burn injury is serious. Clinical health care professionals can provide personalized whole-life dignity care for patients by considering the factors that affect the dignity of burns patients, developing targeted dignity management programs, and implementing individualized interventions to maintain dignity, thus helping burns injury patients return to social life and work.

Per- and Polyfluoroalkyl Substances in Outdoor and Indoor Dust from Mainland China: Contributions of Unknown Precursors and Implications for Human Exposure.

Per- and polyfluoroalkyl substances (PFASs) were analyzed in outdoor (n = 101) and indoor dust (n = 43, 38 paired with outdoors) samples across mainland China. From 2013 to 2017, the median concentration of ∑PFASs in outdoor dust tripled from 63 to 164 ng/g with an elevated contribution of trifluoroacetic acid and 6:2 fluorotelomer alcohol. In 2017, the indoor dust levels of ∑PFASs were in the range 185-913 ng/g, which were generally higher than the outdoor dust levels (105-321 ng/g). Emerging PFASs were found at high median levels of 5.7-97 ng/g in both indoor and outdoor dust samples. As first revealed by the total oxidized precursors assay, unknown perfluoroalkyl acid (PFAA)-precursors contributed 37-67 mol % to the PFAS profiles in indoor dust samples. A great proportion of C8 PFAA-precursors were precursors for perfluorooctanesulfonic acid, while C6 and C4 PFAA-precursors were mostly fluorotelomer based. Furthermore, daily perfluorooctanoic acid (PFOA) equivalent intakes of PFAAs (C4-C12) mixtures via indoor dust were first estimated at 1.3-1.5 ng/kg b.w./d for toddlers at high scenarios, which exceeds the derived daily threshold of 0.63 ng/kg b.w./d. from the European Food Safety Authority (EFSA). On this basis, an underestimation of 56%-69% likely remains without considering potential risks due to the biotransformation of unknown PFAA-precursors.

Legacy and Emerging Poly- and Perfluoroalkyl Substances in Finless Porpoises from East China Sea: Temporal Trends and Tissue-Specific Accumulation.

Perfluoroalkyl sulfonates (PFSAs), perfluoroalkyl carboxylates (PFCAs), and emerging alternatives and precursors of these compounds were determined in tissues of finless porpoise (Neophocaena asiaeorientalis sunameri) collected from East China Sea in 2009-2010 and 2018-2019. The median hepatic concentrations of emerging poly- and perfluoroalkyl substances (PFASs), including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA), 2,3,3,3-tetrafluoro-2-propanoate (HFPO-DA), and 4,8-dioxa-3H-perfluorononanoate (ADONA) were 16.2, 2.16, < LOQ (limit of quantification) and < LOQ ng/g ww (wet weight), respectively. The concentrations of legacy substances, perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA), were 86.9 and 1.95 ng/g ww, respectively. The liver concentrations of 6:2 Cl-PFESA, HFPO-DA, and perfluorohexanesulfonate (PFHxS) increased with time between 2009-2010 and 2018-2019. Further, concentrations of PFOA showed a declining trend in finless porpoise, whereas PFOS and its precursor (i.e., perfluorooctane sulfonamide [FOSA]) showed an increasing trend with time between 2009-2010 and 2018-2019. Analysis of PFASs in nine different tissues/organs of finless porpoise (i.e., liver, heart, intestine, spleen, kidney, stomach, lung, muscle, and skin) revealed a similar distribution pattern between 6:2 Cl-PFESA and PFOS; however, the tissue distribution patterns differed between HFPO-DA and PFOA. The concentrations of PFAS alternatives in kidney were similar or lower than the prototype compounds PFOS and PFOA (i.e., 8:2 Cl-PFESA < 6:2 Cl-PFESA ≈ PFOS; HFPO-DA < PFOA), implying slow renal excretion of PFAS alternatives as that of legacy PFASs. The estimates of body burdens of PFASs in porpoises suggested comparable accumulation of PFAS alternatives and legacy PFSAs and PFCAs. This study provides novel information on temporal trends and tissue distribution of emerging PFASs in marine mammals in China.

First Evidence of Prenatal Exposure to Emerging Poly- and Perfluoroalkyl Substances Associated with E-Waste Dismantling: Chemical Structure-Based Placental Transfer and Health Risks.

Limited information is available about prenatal exposure to per- and polyfluoroalkyl substances (PFAS) in electronic waste (e-waste) recycling sites. In this study, we determined 21 emerging PFAS and 13 legacy PFAS in 94 paired maternal and cord serum samples collected from an e-waste dismantling site in Southern China. We found 6:2 fluorotelomer sulfonate (6:2 FTSA), 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), and perfluorooctanephosphonate (PFOPA) as the major emerging PFAS, regardless of matrices, at median concentrations of 2.40, 1.78, and 0.69 ng/mL, respectively, in maternal serum samples, and 2.30, 0.73, and 0.72 ng/mL, respectively, in cord serum samples. Our results provide evidence that e-waste dismantling activities contribute to human exposure to 6:2 FTSA, 6:2 Cl-PFESA, and PFOPA. The trans-placental transfer efficiencies of emerging PFAS (0.42-0.94) were higher than that of perfluorooctanesulfonic acid (0.37) and were structure-dependent. The substitution of fluorine with chlorine or hydrogen and/or hydrophilic functional groups may alter trans-placental transfer efficiencies. Multiple linear regression analysis indicated significant associations between maternal serum concentrations of emerging PFAS and maternal clinical parameters, especially liver function and erythrocyte-related biomarkers. This study provides new insights into prenatal exposure to multiple PFAS in e-waste dismantling areas and the prevalence of emerging PFAS in people living near the sites.

Identification of Novel Organophosphate Esters in Hydroponic Lettuces (Lactuca sativa L.): Biotransformation and Acropetal Translocation.

The absorption, translocation, and biotransformation behaviors of organophosphate esters (OPEs) and diesters (OPdEs) in a hydroponic system were investigated. The lateral root was found as the main accumulation and biotransformation place of OPEs and OPdEs in lettuce. The nontarget analysis using high-resolution mass spectrometry revealed five hydroxylated metabolites and five conjugating metabolites in the OPE exposure group, among which methylation, acetylation, and palmitoyl conjugating OPEs were reported as metabolites for the first time. Particularly, methylation on phosphate can be a significant process for plant metabolism, and methyl diphenyl phosphate (MDPP) accounted for the majority of metabolites. The translocation factor values of most identified OPE metabolites are negatively associated with their predicted logarithmic octanol-water partitioning coefficient (log Kow) values (0.75-2.45), indicating that hydrophilicity is a dominant factor in the translocation of OPE metabolites in lettuce. In contrast, palmitoyl conjugation may lead to an enhanced acropetal translocation and those with log Kow values < 0 may have limited translocation potential. Additionally, OPE diesters produced from the biotransformation of OPEs in lettuce showed a higher acropetal translocation potential than those exposed directly. These results further emphasize the necessity to consider biotransformation as an utmost important factor in the accumulation and acropetal translocation potential of OPEs in plants.