Light-induced degradation of dimethylmercury in different natural waters.

Photo-induced degradation of dimethylmercury (DMHg) is considered to be an important source for the generation of methylmercury (MMHg). However, studies on DMHg photodegradation are scarce, and it is even debatable about whether DMHg can be degraded in natural waters. Herein, we found that both DMHg and MMHg could be photodegraded in three natural waters collected from the Yellow River Delta, while in pure water only DMHg photodegradation occurred under visible light irradiation. The effects of different environmental factors on DMHg photodegradation were investigated, and the underlying mechanisms were elucidated by density functional theory calculations and a series of control experiments. Our findings revealed that the DMHg degradation rate was higher in the tidal creek water compared to Yellow River, Yan Lake, and purified water. NO3-, NO2-, and DOM could promote the photodegradation with DOM and NO3- showing particularly strong positive effects. Different light sources were employed, and UV light was found to be more effective in DMHg photodegradation. Moreover, MMHg was detected during the photodegradation of DMHg, confirming that the photochemical demethylation of DMHg is a source of MMHg in sunlit water. This work may provide a novel mechanistic insight into the DMHg photodegradation in natural waters and enrich the study of the global biogeochemical cycle of Hg.

Phthalate acid esters: A review of aquatic environmental occurrence and their interactions with plants.

The increasing use of phthalate acid esters (PAEs) in various applications has inevitably led to their widespread presence in the aquatic environment. This presents a considerable threat to plants. However, the interactions between PAEs and plants in the aquatic environment have not yet been comprehensively reviewed. In this review, the properties, occurrence, uptake, transformation, and toxic effects of PAEs on plants in the aquatic environment are summarized. PAEs have been prevalently detected in the aquatic environment, including surface water, groundwater, seawater, and sediment, with concentrations ranging from the ng/L or ng/kg to the mg/L or mg/kg range. PAEs in the aquatic environment can be uptake, translocated, and metabolized by plants. Exposure to PAEs induces multiple adverse effects in aquatic plants, including growth perturbation, structural damage, disruption of photosynthesis, oxidative damage, and potential genotoxicity. High-throughput omics techniques further reveal the underlying toxicity molecular mechanisms of how PAEs disrupt plants on the transcription, protein, and metabolism levels. Finally, this review proposes that future studies should evaluate the interactions between plants and PAEs with a focus on long-term exposure to environmental PAE concentrations, the effects of PAE alternatives, and human health risks via the intake of plant-based foods.

The hidden diet: Synthetic antioxidants in packaged food and their impact on human exposure and health.

Synthetic antioxidants (AOs) are commonly used in everyday items and industrial products to inhibit oxidative deterioration. However, the presence of AOs in food packaging and packaged foods has not been thoroughly documented. Moreover, studies on human exposure to AOs through skin contact with packaging or ingesting packaged foods are limited. In this study, we analyzed twenty-three AOs-including synthetic phenolic antioxidants (SPAs) and organophosphite antioxidants (OPAs)-along with six transformation products in various food samples and their packaging materials. We found AOs in food products at concentrations ranging from 1.30 × 103 to 1.77 × 105 ng/g, which exceeded the levels in both outer packaging (6.05 × 102-3.07 × 104 ng/g) and inner packaging (2.27 × 102-1.09 × 105 ng/g). The most common AOs detected in foodstuffs were tris(2,4-di-tert-butylphenyl) phosphate (AO168O), butylated hydroxytoluene (BHT), and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (AO1076), together constituting 95.7 % of the total AOs found. Our preliminary exposure assessment revealed that dietary exposure-estimated at a median of 2.55 × 104 ng/kg body weight/day for children and 1.24 × 104 ng/kg body weight/day for adults-is a more significant exposure route than dermal contact with packaging. Notably, four AOs were identified in food for the first time, with BHT making up 76.8 % and 67.6 % of the total BHT intake for children and adults, respectively. These findings suggest that food consumption is a significant source of BHT exposure. The estimated daily intakes of AOs via consumption of foodstuffs were compared with the recommended acceptable daily intake to assess the risks. This systematic investigation into AOs contributes to understanding potential exposure and health risks associated with AOs in packaged foods. It emphasizes the need for further evaluation of human exposure to these substances.

Synthetic Antioxidants as Contaminants of Emerging Concern in Indoor Environments: Knowns and Unknowns.

Synthetic antioxidants, including synthetic phenolic antioxidants (SPAs), amine antioxidants (AAs), and organophosphite antioxidants (OPAs), are essential additives for preventing oxidative aging in various industrial and consumer products. Increasing attention has been paid to the environmental contamination caused by these chemicals, but our understanding of synthetic antioxidants is generally limited compared to other emerging contaminants such as plasticizers and flame retardants. Many people spend a significant portion (normally greater than 80%) of their time indoors, meaning that they experience widespread and persistent exposure to indoor contaminants. Thus, this Perspective focuses on the problem of synthetic antioxidants as indoor environmental contaminants. The wide application of antioxidants in commercial products and their demonstrated toxicity make them an important family of indoor contaminants of emerging concern. However, significant knowledge gaps still need to be bridged: novel synthetic antioxidants and their related transformation products need to be identified in indoor environments, different dust sampling strategies should be employed to evaluate human exposure to these contaminants, geographic scope and sampling scope of research on indoor contamination should be broadened, and the partition coefficients of synthetic antioxidants among different media need to be investigated.

Screening of Indoor Transformation Products of Organophosphates and Organophosphites with an in Silico Spectral Database.

Numerous transformation products are formed indoors, but they are outside the scope of current chemical databases. In this study, an in silico spectral database was established to screen previously unknown indoor transformation products of organophosphorus compounds (OPCs). An R package was developed that incorporated four indoor reactions to predict the transformation products of 712 seed OPCs. By further predicting MS2 fragments, an in silico spectral database was established consisting of 3509 OPCs and 28,812 MS2 fragments. With this database, 40 OPCs were tentatively detected in 23 indoor dust samples. This is the greatest number of OPCs reported to date indoors, among which two novel phosphonates were validated using standards. Twenty-four of the detected OPCs were predicted transformation products in which oxidation from organophosphites plays a major role. To confirm this, the in silico spectral database was expanded to include organophosphites for suspect screening in five types of preproduction plastics. A broad spectrum of 14 organophosphites was detected, with a particularly high abundance in polyvinyl chloride plastics and indoor end-user goods. This demonstrated the significant contribution of organophosphites to indoor organophosphates via oxidation, highlighting the strength of in silico spectral databases for the screening of unknown indoor transformation products.

Occurrence, Fate, Human Exposure, and Toxicity of Commercial Photoinitiators.

Photoinitiators (PIs) are a family of anthropogenic chemicals used in polymerization systems that generate active substances to initiate polymerization reactions under certain radiations. Although polymerization is considered a green method, its wide application in various commercial products, such as UV-curable inks, paints, and varnishes, has led to ubiquitous environmental issues caused by PIs. In this study, we present an overview of the current knowledge on the environmental occurrence, human exposure, and toxicity of PIs and provide suggestions for future research based on numerous available studies. The residual concentrations of PIs in commercial products, such as food packaging materials, are at microgram per gram levels. The migration of PIs from food packaging materials to foodstuffs has been confirmed by more than 100 reports of food contamination caused by PIs. Furthermore, more than 20 PIs have been detected in water, sediment, sewage sludge, and indoor dust collected from Asia, the United States, and Europe. Human internal exposure was also confirmed by the detection of PIs in serum. In addition, PIs were present in human breast milk, indicating that breastfeeding is an exposure pathway for infants. Among the most available studies, benzophenone is the dominant congener detected in the environment and humans. Toxicity studies of PIs reveal multiple toxic end points, such as carcinogenicity and endocrine-disrupting effects. Future investigations should focus on synergistic/antagonistic toxicity effects caused by PIs coexposure and metabolism/transformation pathways of newly identified PIs. Furthermore, future research should aim to develop "greener" PIs with high efficiency, low migration, and low toxicity.

Anaerobic Microbial Dechlorination of 6:2 Chlorinated Polyfluorooctane Ether Sulfonate and the Underlying Mechanisms.

The microbial transformation potential of 6:2 chlorinated polyfluorooctane ether sulfonate (6:2 Cl-PFESA) was explored in anaerobic microbial systems. Microbial communities from anaerobic wastewater sludge, an anaerobic digester, and anaerobic dechlorinating cultures enriched from aquifer materials reductively dechlorinated 6:2 Cl-PFESA to 6:2 hydrogen-substituted polyfluorooctane ether sulfonate (6:2 H-PFESA), which was identified as the sole metabolite by non-target analysis. Rapid and complete reductive dechlorination of 6:2 Cl-PFESA was achieved by the anaerobic dechlorinating cultures. The microbial community of the anaerobic dechlorinating cultures was impacted by 6:2 Cl-PFESA exposure. Organohalide-respiring bacteria originally present in the anaerobic dechlorinating cultures, including Geobacter, Dehalobacter, and Dehalococcoides, decreased in relative abundance over time. As the relative abundance of organohalide-respiring bacteria decreased, the rates of 6:2 Cl-PFESA dechlorination decreased, suggesting that the most likely mechanism for reductive dechlorination of 6:2 Cl-PFESA was co-metabolism rather than organohalide respiration. Reductive defluorination of 6:2 Cl-PFESA was not observed. Furthermore, 6:2 H-PFESA exhibited 5.5 times lower sorption affinity to the suspended biosolids than 6:2 Cl-PFESA, with the prospect of increased mobility in the environment. These results show the susceptibility of 6:2 Cl-PFESA to microbially mediated reductive dechlorination and the likely persistence of the product, 6:2 H-PFESA, in anaerobic environments.

Rat Metabolism Study Suggests 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic Acid as a Potential Urinary Biomarker of Human Exposure to Representative 3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate Antioxidants.

3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate antioxidants, a family of synthetic phenolic antioxidants (SPAs) widely used in polymers, have recently been identified in indoor and outdoor environments. However, limited information is available concerning human exposure to these novel contaminants. In the present study, seven 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants were analyzed in human urine samples of donors from the United States. None of the target SPAs were initially detected in the urine samples either before or after hydrolysis by ß-glucuronidase, prompting us to probe the major metabolites of these SPAs. We conducted rat metabolism studies with two representative congeners, tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (AO1010) and N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine (AO1024). Neither AO1010 nor AO1024 was detected in rat urine, while 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (fenozan acid) was identified as a urinary biomarker for these 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants. Surprisingly, fenozan acid was detected in 88% of the human urine samples before hydrolysis (geometric mean: 0.69 ng/mL) and 98% of the samples after hydrolysis (geometric mean: 10.2 ng/mL), indicating prevalent human exposure to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants. To our knowledge, this is the first study reporting the occurrence of fenozan acid in urine, where it can act as a potential biomarker of human exposure to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate antioxidants.

Printing ink related chemicals, including synthetic phenolic antioxidants, organophosphite antioxidants, and photoinitiators, in printing paper products and implications for human exposure.

Although synthetic antioxidants (AOs) and photoinitiators (PIs) are known to be used in printing inks, there are little data on residual concentrations in printing paper products. In the present study, twenty-five PIs, ten AOs, and six transformation products were analyzed in two types of printing paper products, magazines and paperboard food packaging materials, both of which are unavoidable everyday products in our life. Nine AOs and six transformation products can be detected in food packaging materials with total concentrations (geometric mean, GM) of 1.16 × 104 ng/dm2. Twenty-two PIs were detected in food packaging materials with total concentrations (GM) of 1.76 × 104 ng/dm2. These chemicals were also detected in magazines, albeit at low concentrations (GM of AOs: 466 ng/dm2, GM of PIs: 1.17 × 103 ng/dm2). Magazine front covers were found to have much higher concentrations of the target compounds than magazine inside pages. Tris(2,4-di-tert-butylphenyl) phosphate (AO168O), 2,6-di-tert-butyl-4-methylphenol (BHT), bisphenol A (BPA), and benzophenone (BP) were among the predominant chemicals in those printing paper products. Preliminary calculations suggest that dermal exposure to AOs (GM: 6.25 ng/day) and PIs (GM: 17.0 ng/day) via contact with printing paper products is a minor exposure pathway compared to food intake/dust ingestion and is exceedingly unlikely to cause adverse health effects.

Synthetic Phenolic Antioxidants: A Review of Environmental Occurrence, Fate, Human Exposure, and Toxicity.

Synthetic phenolic antioxidants (SPAs) are widely used in various industrial and commercial products to retard oxidative reactions and lengthen product shelf life. In recent years, numerous studies have been conducted on the environmental occurrence, human exposure, and toxicity of SPAs. Here, we summarize the current understanding of these issues and provide recommendations for future research directions. SPAs have been detected in various environmental matrices including indoor dust, outdoor air particulates, sea sediment, and river water. Recent studies have also observed the occurrence of SPAs, such as 2,6-di-tert-butyl-4-methylphenol (BHT) and 2,4-di-tert-butyl-phenol (DBP), in humans (fat tissues, serum, urine, breast milk, and fingernails). In addition to these parent compounds, some transformation products have also been detected both in the environment and in humans. Human exposure pathways include food intake, dust ingestion, and use of personal care products. For breastfeeding infants, breast milk may be an important exposure pathway. Toxicity studies suggest some SPAs may cause hepatic toxicity, have endocrine disrupting effects, or even be carcinogenic. The toxicity effects of some transformation products are likely worse than those of the parent compound. For example, 2,6-di-tert-butyl-p-benzoquinone (BHT-Q) can cause DNA damage at low concentrations. Future studies should investigate the contamination and environmental behaviors of novel high molecular weight SPAs, toxicity effects of coexposure to several SPAs, and toxicity effects on infants. Future studies should also develop novel SPAs with low toxicity and low migration ability, decreasing the potential for environmental pollution.

Cadmium-binding proteins in human blood plasma.

Blood is the transmission medium for metal contaminants to and from bodily organs; as such, it can provide useful and reliable information about their bio-kinetics as they're distributed throughout the body. Metals can interact with endogenous proteins present in the blood, and these metal-protein complexes often dictate the fates of the introduced metals. The aim of this study was to investigate cadmium-binding protein characteristics in normal human plasma. Cadmium-binding plasma proteins in two different groups: normal human plasma (n = 29), and normal paired maternal and fetal umbilical cord plasmas (n = 3), were analyzed. In order to detect cadmium-binding plasma proteins present in low concentrations, blood plasma samples were first depleted of their two most abundant proteins - albumin and immunoglobulin G. Both the crude and depleted plasma samples were analyzed using column gel electrophoresis in conjunction with Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). One cadmium-binding protein was detected in 11 of 29 normal plasma samples and all three paired maternal and cord plasma samples. This protein was further identified as apolipoprotein A-I by high-resolution mass spectrometry. To the best of our knowledge, this is the first study to reveal cadmium-binding proteins in real human blood plasma, which is extremely critical to our understanding of cadmium transportation and accumulation in human blood.

Synthetic Phenolic Antioxidants in Personal Care Products in Toronto, Canada: Occurrence, Human Exposure, and Discharge via Greywater.

Although synthetic phenolic antioxidants (SPAs) are widely used in various personal care products (PCPs), little is known about their levels, composition profiles, human exposure, or environmental emissions. In this study, the occurrence of SPAs was evaluated in 15 categories of 214 PCPs collected in Toronto, Canada. Nine SPAs were detected in the PCPs, of which only 2,6-di-tert-butyl-4-methylphenol (BHT, < method quantification limit (MQL)-827 900 ng/g, mean: 35 602 ng/g, median: 249 ng/g) was observed with a detection frequency of >50%. When the 214 PCPs were separated into products labeled as containing BHT and those labeled as not containing BHT, the BHT-labeled PCPs (mean: 369 253 ng//g, median: 382 560 ng/g) contained significantly higher concentrations of BHT than the BHT-unlabeled PCPs (mean: 4960 ng/g, median: 199 ng/g) did (p < 0.01). Five transformation products (TPs) of BHT were also detected in the PCPs at low concentrations (∑TPs: < MQL to 19 014 ng/g, mean: 730 ng/g, median: < MQL) and detection frequencies (12.6-37.4%). Preliminary calculations found that dermal absorption via PCP use may be an important exposure pathway for BHT (mean: 565 879 ng/day median: 2988 ng/day), although this is a negligible exposure pathway for other SPAs. In addition, the estimated discharges of BHT (mean: 7852 g/day, median: 88 g/day) via greywater after PCP use were calculated, which represents a nonignorable source of BHT loading into wastewater treatment plants in Toronto (contributing 10%). To our knowledge, this is the first evaluation of human exposure to and discharge of SPAs via PCP use.

Unexpectedly high concentrations of 2,4-di-tert-butylphenol in human urine.

Synthetic phenolic antioxidants (SPAs) have received increasing attention due to the reports of toxicity and environmental contamination. Nevertheless, limited information was available on human burdens of these SPAs, with the exception of 2,6-di-tert-butyl-4-methylphenol (BHT). In our study, BHT as well as six other SPAs were analyzed in human urine samples from United States donors. Three SPA congeners were detected in human urine: BHT, 2,4-di-tert-butylphenol (DBP), and 3-tert-butyl-4-hydroxyanisole (BHA). BHT, which is the congener received most concerns, was detected at low concentrations [geometric mean (GM): 0.06 ng/mL], whereas four of its metabolites were detected at relatively high concentrations (GM: 1.68 ng/mL). Surprisingly, DBP was detected at extremely high concentrations (GM: 18.3 ng/mL). The concentrations of DBP (GM: 25.8 ng/mL), BHT (0.853 ng/mL), and metabolites (GM: 10.5 ng/mL) increased significantly after the urine samples were hydrolyzed by ß-glucuronidase (p < 0.01), indicating the prevalence of the conjugated forms of SPAs and their metabolites in human urine. DBP, which has previously received little attention, was the predominant congener, contributing 88.2% and 63.6% to total target concentrations in the urine samples before and after ß-glucuronidase hydrolysis, respectively. Thus, previous studies have vastly underestimated the burdens of SPAs to humans. To our knowledge, this is the first study revealing the presence of DBP in human urine.

Synthetic phenolic antioxidants and transformation products in dust from different indoor environments in Toronto, Canada.

Synthetic phenolic antioxidants (SPAs) are a class of anthropogenic antioxidants that are widely used in a large variety of commercial products. Although several SPAs have been listed as targets for risk assessment by Environment and Climate Change Canada, little data are available on the occurrence of SPAs in the Canadian environment. In this study, eighty-three indoor dust samples were collected from offices and homes in Toronto. Eight SPAs were detected at concentrations ranging from 67.2 to 1.55e4 ng/g, with a geometric mean (GM) concentration of 1.49e3 ng/g, among which 2,6-di-tert-butyl-4-methylphenol (BHT) was the primary congener and had a GM concentration of 658 ng/g. Four BHT transformation products (TPs) were also detected in the indoor dust samples, with concentrations ranging from 40.4 to 1.27e4 ng/g and a GM concentration of 883 ng/g. No significant concentration difference was observed between the office and home dust samples for either the summed target SPA or TP concentrations (p > 0.05). The calculated estimated daily intakes of these chemical contaminants (0.004-10.0 ng/kg BW/day) suggest that they pose no immediate health risk to the Canadian population. To the best of our knowledge, this is the first report of the occurrence of these chemical contaminants and their transformation products in Canadian indoor environments, and furthermore the first detection of 4-tert-butyl-phenol in an environmental sample.

Identification of Photoinitiators, Including Novel Phosphine Oxides, and Their Transformation Products in Food Packaging Materials and Indoor Dust in Canada.

Although photopolymerization is generally considered a green technology, the contamination of foodstuffs by photoinitiators (PIs), an essential component of photopolymerization systems, has recently attracted notice. Despite this interest, little attention has been paid to PI contamination in the environment. To date, only one study, performed in China, has reported the occurrence of PIs in the environment. In the present study, the occurrence of 25 PI additives with discrete molecular structures was investigated in food packaging materials and indoor dust. The PIs studied here include benzophenones (BZPs), thioxanthones (TXs), amine co-initiators (ACIs), and novel phosphine oxides (POs). Twenty-four PIs were detected in food packaging materials. Total concentrations of PIs (∑PIs) ranged between 122 and 44 113 ng/g, with a geometric mean (GM) of 3375 ng/g. The photodegradation of PIs in food packaging materials was investigated for the first time, and the half-lives of PIs in these materials were found to range from 32 to 289 h. These 24 PIs were also detected in indoor dust samples (GM of ∑PIs = 1483 ng/g). The relative abundances of different PIs were found to vary between the packaging materials and the indoor dust, which is attributed in part to the different stabilities of different PIs under simulated sunlight. Using standards synthesized in our lab, four TX transformation products (GM: 34.8 ng/g) were also detected in indoor dust. The concentrations of the transformation products were higher than the concentrations of the parent chemicals in indoor dust. Thus, further studies exploring human exposure to TXs should include these transformation products to avoid underestimation. This is the first report of PIs and relevant transformation products in the indoor environment in North America.

Organophosphite Antioxidants in Indoor Dust Represent an Indirect Source of Organophosphate Esters.

Precise determination of organophosphate esters (OPEs) in the environment is crucial to estimating their potential toxicity effects on human health. Previous studies have mainly focused on OPEs from direct sources. This study explored a potential indirect source of OPEs: the oxidation of organophosphite antioxidants (OPAs). OPAs are frequently used to retard degradation in polymers through their oxidation to OPEs. In this work, five OPAs [tris(2-chloroethyl) phosphite, triphenyl phosphite, tris(2,4-di- tert-butylphenyl) phosphite, bis(2,4-di- tert-butylphenyl) pentaerythritol diphosphite, and trisnonylphenol phosphite] could be identified, with geometric mean (GM) concentrations from 2.46 to 70.4 ng/g, in indoor dust. Their oxidation products, triisodecyl phosphate (TiDeP), tris(2,4-di- tert-butylphenyl) phosphate (AO168═O), bis(2,4-di- tert-butylphenyl) pentaerythritol diphosphate (AO626═O2), and trisnonylphenol phosphate (TNPP), were found at significantly higher GM concentrations (30.5-3759 ng/g). Surprisingly, two novel oxidation products AO168═O (GM: 3759 ng/g) and TNPP (GM: 2185 ng/g) had higher concentrations than tris(2-chloroethyl) phosphate (GM: 1608 ng/g) and triphenyl phosphate (GM: 1827 ng/g), which are well-known OPEs. These four novel OPEs (TiDeP, TNPP, AO168═O, AO626═O2) contributed 54.1% to the total concentration of the eight OPEs. The present investigation demonstrates that oxidation of OPAs is an important indirect source of novel OPEs in indoor environments. This is the first detection of four OPAs and their newly identified OPE oxidation products in indoor dust.

Emerging aromatic secondary amine contaminants and related derivatives in various dust matrices in China.

Aromatic secondary amines (Ar-SAs), constituted of several analogues with varied substitutions in molecular structure, are among the most frequently used anthropogenic antioxidants. Despite the reported toxicity effects, little information is available on their environmental contamination, except for few particular congeners such as diphenylamine. In this study, the occurrence of two kinds of Ar-SAs, substituted diphenylamines (S-DPAs) and novel substituted p-phenylenediamines (S-PPDs), was investigated in dust samples collected from outdoor rubber playgrounds and residential houses. Seven S-DPAs (GM: 102 ng/g) and two S-PPDs (GM: 20.9 ng/g) were detected in indoor dust. Significantly higher concentrations of S-DPAs (GM: 422 ng/g) and S-PPDs (GM: 31.6 ng/g) were observed in playground dust (p < 0.05). Different dominant Ar-SA congeners were found for indoor dust (low molecular weight Ar-SAs) and playground dust (high molecular weight Ar-SAs), indicating varied sources of Ar-SAs for different dust matrices. Apart from these parent chemicals, three diphenylamine derivatives, including N-nitrosodiphenylamine, 2-nitrodiphenylamine, and 4-nitrodiphenylamine, were also confirmed in indoor dust (GM: 35.7 ng/g) and playground dust (GM: 7.88 ng/g). A preliminary estimated daily intake calculation via dust ingestion indicated no immediate health risk to Chinese population. To our knowledge, this is the first report on the occurrence of a wide range of Ar-SAs and related derivates in dust matrices.

First Detection of Photoinitiators and Metabolites in Human Sera from United States Donors.

Photoinitiators (PIs), including benzophenones (BZPs), thioxanthones (TXs), and amine co-initiators (ACIs), are commonly used in photopolymerization systems, and their contamination in foodstuffs and the environment is attracting attention. Although humans are likely exposed to PIs, no data on human burdens of these chemicals are available. In this study, 18 PIs were detected in 50 individual human serum samples with concentrations of ΣPIs (sum of the detected PIs) from 423 to 2870 pg/mL (geometric mean, GM: 836 pg/mL). ΣBZPs (231-1240 ng/g,; GM: 593 pg/mL) were the dominant components, while ΣTXs (21.0-1431 ng/g; GM: 145 pg/mL) and ΣACIs (11.3-976 ng/g; GM: 48.5 pg/mL) were much lower. Data analysis found significantly higher concentrations of most PIs in the male sera than in the female ( p < 0.05). ΣPIs (2921-4139 ng/g; GM: 3621 pg/mL) were also detected in five pooled serum samples, each from at least 1000 donors, indicating the prevalent human burdens of PIs in a large population. Human liver S9 biodegradations of representative PIs, 2-isopropylthioxanthone (2-ITX) and 2,4-diethylthioxanthone (DETX), were conducted. Hydroxylation, sulfoxide, and sulfone metabolites of DETX and 2-ITX were identified by high resolution mass spectrometry in human liver S9 incubation systems. With synthesized standards, the sulfoxide and sulfone metabolites were successfully detected in the human serum samples, which contributed substantially to total human burdens. The ubiquitous presence of PIs in human sera indicates significant human exposure to PIs, although photopolymerization reaction has been generally considered a green technology.

Unexpectedly High Concentrations of a Newly Identified Organophosphate Ester, Tris(2,4-di- tert-butylphenyl) Phosphate, in Indoor Dust from Canada.

Organophosphate esters (OPEs) represent a group of additives with significant levels of production and significant application to various household and industrial products. Given their potential adverse effects on human health, accurate analysis of novel OPEs in indoor dust is crucial. In this study, the novel tris(2,4-di- tert-butylphenyl) phosphate (AO168═O) and six well-known OPEs were investigated. The seven target OPEs were detected in 100% of the office and home dust samples, with ∑OPEs (sum of the OPE concentrations) ranging from 2.92 to 124 µg/g [geometric mean (GM) of 12.3 µg/g]. Surprisingly, the novel AO168═O (0.10-11.1 µg/g, GM of 1.97 µg/g) was among the highest-concentration congeners, contributing 1.36-65.5% to ∑OPEs (mean of 20.7%). AO168═O was the dominant congener in the home dust samples, indicating it is an important OPE congener overlooked previously. AO168═O was also detected in Standard Reference Material 2585 (indoor dust) at an elevated concentration of 10.9 µg/g, which was significantly higher than the concentrations of the other target OPEs (0.38-2.17 µg/g). Despite the high concentrations measured in this study, no industrial production or application could be identified for AO168═O. The precursor of AO168═O, tris(2,4-di- tert-butylphenyl) phosphite, was detected in 50% of the dust samples, with a GM concentration of 1.48 ng/g. This study demonstrates that human OPE exposure in indoor environments is greater than was previously reported. This is the first report of the occurrence of AO168═O, its precursor, and its hydrolysis products in the environment.