Organophosphate Triesters and Their Transformation Products in Sediments of Mangrove Wetlands in the Beibu Gulf, South China Sea.

As emerging pollutants, organophosphate esters (OPEs) have been reported in coastal environments worldwide. Nevertheless, information on the occurrence and ecological risks of OPEs, especially the related transformation products, in mangrove wetlands is scarce. For the first time, the coexistence and distribution of OP triesters and their transformation products in three mangrove wetlands in the Beibu Gulf were investigated using ultrasonication and solid-phase extraction, followed by UHPLC-MS/MS detection. The studied OPEs widely existed in all the sampling sites, with the total concentrations ranging from 6.43 ng/g dry weight (dw) to 39.96 ng/g dw and from 3.33 ng/g dw to 22.50 ng/g dw for the OP triesters and transformation products, respectively. Mangrove wetlands tend to retain more OPEs than the surrounding coastal environment. Pearson correlation analysis revealed that the TOC was not the sole factor in determining the OPEs' distribution, and degradation was not the main source of the transformation products in mangrove sediments in the Beibu Gulf. The ecological risks of selected OPEs for different organisms were also assessed, revealing a medium to high risk posed by OP diesters to organisms. The levels or coexistence of OPEs and their metabolites in mangroves need constant monitoring, and more toxicity data should be further studied to assess the effect on normal aquatic organisms.

Source Identification of Organophosphate Esters through the Profiles in Proglacial and Ocean Sediments from Ny-Ålesund, the Arctic.

Little is known about the sources and environmental behavior of organophosphate esters (OPEs) in the Arctic, especially their transformation products. The present study unprecedentedly investigated both 16 tri-OPEs and 8 di-OPEs in proglacial and ocean sediments from Ny-Ålesund, the Arctic. Mean concentrations of tri-OPEs and di-OPEs in proglacial sediments were 487 and 341 pg/g dry weight (dw), respectively, which were significantly lower than those in ocean sediments (1692 and 525 pg/g dw). Ocean sediments might be simultaneously influenced by long-range atmospheric transport (LRAT), oceanic transport, and human activities, whereas proglacial sediments, since they are isolated from human settlements, may be dominantly affected by LRAT. Such source difference was evidenced by the contamination profile of OPEs: chlorinated tri-OPEs with high environmental persistence and high LRAT were dominant in proglacial sediments (66%); however, weakly environmentally persistent and highly hydrophobic aryl tri-OPEs were dominant in ocean sediments (47%), which were plausibly from local emission sources due to their low LRAT potential. Di-OPEs in proglacial and ocean sediments were dominated by groups of parent tri-OPEs with strong photodegradability, such as alkyl (75%) and aryl (58%). A higher mean molar ratio of di-OPE/tri-OPE in the proglacial sediment (14) than that in the ocean sediment (2.2) may be related to its higher photodegradation than that of the ocean sediment.

Transplacental Behaviors of Organophosphate Tri- and Diesters Based on Paired Human Maternal and Cord Whole Blood: Efficiencies and Impact Factors.

Organophosphate tri- and diesters (tri-OPEs and di-OPEs) were quantified in 63 paired maternal and cord whole blood samples collected in Hubei, China, in which tri-o-cresyl phosphate (ToCP) was predominant. The transplacental transfer efficiencies (expressed as cord blood to maternal blood (C:M) concentration ratios) of aryl-tri-OPEs, such as ToCP (1.61) and triphenyl phosphate (TPHP) (1.06), were higher than those of alkyl-tri-OPEs (0.66-0.76). For the target tri-OPEs and some traditional organic compounds, the C:M ratios first increased with log Kow in the range of 1.63-5.23 and then decreased, showing a parabolic relationship. However, ToCP, with a log Kow of 6.34, deviated from this relationship and displayed the highest C:M ratio (1.61). Molecular docking indicated a very strong binding affinity between ToCP and transthyretin, suggesting that ToCP might be actively transported by transthyretin in the placenta. The di-OPE levels in the blood samples were significantly lower than the corresponding tri-OPE levels, and those in the cord blood were influenced not only by their transplacental behaviors but also by their low excretion rates and the metabolic characteristics of their parent compounds in the fetus. This study provides useful information for accurately assessing the health risks posed by tri-OPEs to pregnant women and fetuses.

Phosphorus flame retardants in indoor dust and their relation to asthma and allergies of inhabitants.

Organophosphate esters are used as additives in flame retardants and plasticizers, and they are ubiquitous in the indoor environment. Phosphorus flame retardants (PFRs) are present in residential dust, but few epidemiological studies have assessed their impact on human health. We measured the levels of 11 PFRs in indoor floor dust and multi-surface dust in 182 single-family dwellings in Japan. We evaluated their correlations with asthma and allergies of the inhabitants. Tris(2-butoxyethyl) phosphate was detected in all samples (median value: 580 µg/g in floor dust, 111 µg/g in multi-surface dust). Tris(2-chloro-iso-propyl) phosphate (TCIPP) was detected at 8.69 µg/g in floor dust and 25.8 µg/g in multi-surface dust. After adjustment for potential confounders, significant associations were found between the prevalence of atopic dermatitis and the presence of TCIPP and tris(1,3-dichloro-2-propyl) phosphate in floor dust [per log10 -unit, odds ratio (OR): 2.43 and 1.84, respectively]. Tributyl phosphate was significantly associated with the prevalence of asthma (OR: 2.85 in floor dust, 5.34 in multi-surface dust) and allergic rhinitis (OR: 2.55 in multi-surface dust). PFR levels in Japan were high compared with values reported previously for Europe, Asia-Pacific, and the USA. Higher levels of PFRs in house dust were related to the inhabitants' health status.

Co-occurrence of organophosphate diesters and organophosphate triesters in daily household products: Potential emission and possible human health risk.

Eight paired organophosphate diesters (Di-OPs) and organophosphate triesters (Tri-OPs) were investigated in wipes from analytical instruments and 47 material samples related to household products, including textiles, electrical/electronic devices, building/ decoration materials and children's products. The total concentrations of Di-OPs ranged in 3577-95551 ng/m2 in the wipes and limit of detection-23002 ng/g in the materials. The Tri-OPs concentrations varied significantly in the ranges of 107218-1756892 ng/m2 and 2.13-503149 ng/g, respectively. Four industrial Di-OPs were detected in > 65% of the studied samples suggesting their direct application in the studied materials. Furthermore, we demonstrated for the first time that four non-industrial Di-OPs, e.g., bis(2-chloroethyl) phosphate, bis(1-chloro-2-propyl) phosphate, bis(1,3-dichloro-2-propyl) phosphate, and bis(butoxyethyl) phosphate, identified as degradation products of their respective Tri-OPs were also detected in these studied samples, which might act as important emission sources of Di-OPs in indoor environments. We estimated the burden of Di-OPs and Tri-OPs in a typical residential house and instrumental room, which both exhibited important contributions from furniture, building and decoration materials, and electrical/electronic devices. Limit health risk was posed to local people via air inhalation.

Insights into the occurrence, spatial distribution, and ecological implications of organophosphate triesters in surface sediments from polluted urban rivers across China.

Organophosphate triesters (tri-OPEs) are a kind of widespread contaminants in the world, particularly in China, which is a major producer and user of tri-OPEs. However, tri-OPE pollution in urban river sediments in China remains unclear. In current work, we carried out the first nationwide investigation to comprehensively monitor 10 conventional and five emerging tri-OPEs in sediments of 173 black-odorous urban rivers throughout China. Concentrations of 10 conventional and five emerging tri-OPEs were 3.8-1240 ng/g dw (mean: 253 ng/g dw) and 0.21-1107 ng/g dw (68 ng/g dw), respectively, and significantly differed among the cities sampled but generally decreased from Northeast and East China to Central and West China. These spatial patterns suggest that tri-OPE pollution was mainly from local sources and was controlled by the industrial and economic development levels in these four areas, as indicated by the significant correlations between tri-OPE concentrations and gross domestic production, gross industrial output, and daily wastewater treatment capacity. Although the tri-OPE composition varied spatially at different sites, which indicated different tri-OPE input patterns, it was commonly dominated by tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, and tris(1-chloro-2-propyl) phosphate (conventional tri-OPEs) and bisphenol A-bis(diphenyl phosphate) and isodecyl diphenyl phosphate (emerging tri-OPEs). A risk assessment indicated that tri-OPEs in most sampling sediments had a low to moderate risk to aquatic organisms.

Unravelling bioaccumulation, depletion and metabolism of organophosphate triesters in laying hens: Insight of in vivo biotransformation assisted by diester metabolites.

Organophosphate triesters (tri-OPEs) threaten human health through dietary exposure, but little is known about their feed-to-food transfer and in vivo behavior in farm animals. Herein 135 laying hens were fed with contaminated feed (control group, low-level group and high-level group) to elucidate the bioaccumulation, distribution, and metabolism of the six most commonly reported tri-OPEs. The storage (breast muscle), metabolism and mobilization (liver and blood) and non-invasive (feather) tissues were collected. The exposure-increase (D1∼14) and depuration-decrease (D15∼42) trends indicated that feed exposure caused tri-OPE accumulation in animal tissues. Tissue-specific and moiety-specific behavior was observed for tri-OPEs. The highest transfer factor (TF) and transfer rate (TR) were observed in liver (TF: 14.8%∼82.3%; TR: 4.40%∼24.5%), followed by feather, breast muscle, and blood. Tris(2-chloroisopropyl) phosphate (TCIPP) had the longest half-life in feather (72.2 days), while triphenyl phosphate (TPhP) showed the shortest half-life in liver (0.41 days). Tri-OPEs' major metabolites (organophosphate diesters, di-OPEs) were simultaneously studied, which exhibited dose-dependent and time-dependent variations following administration. In breast muscle, the inclusion of di-OPEs resulted in TF increases of 735%, 1108%, 798%, and 286% than considering TCIPP, tributyl phosphate, tris(2-butoxyethyl) phosphate and tris(2-ethylhexyl) phosphate alone. Feather was more of a proxy of birds' long-term exposure to tri-OPEs, while short-term exposure was better reflected by di-OPEs. Both experimental and in silico modeling methods validated aryl-functional group facilitated the initial accumulation and metabolism of TPhP in the avian liver compared to other moiety-substituted tri-OPEs.

Organophosphate tri-esters and di-esters in drinking water and surface water from the Pearl River Delta, South China: Implications for human exposure.

Some organophosphate di-esters (di-OPEs) have been found to be more toxic than their respective tri-esters. The environmental occurrence of di-OPEs remains largely unclear. A total of 106 water samples, including 56 drinking water (bottled, barreled, and tap water) and 50 surface water (lake and river) samples were collected and analyzed for 10 organophosphate tri-esters (tri-OPEs) and 7 di-OPEs. The concentrations (range (median)) of ∑7di-OPE were 2.8-22 (9.7), 1.1-5.8 (2.6), 3.7-250 (120), 13-410 (220), and 92-930 (210) ng/L in bottled water, barreled water, tap water, lake water, and river water, respectively. In all types of water samples, tris(1-chloro-2-propyl) phosphate was the dominant tri-OPE compound. Diphenyl phosphate was the predominant di-OPE compound in tap water and surface water, while di-n-butyl phosphate and bis(2-ethylhexyl) phosphate was the dominant compound in bottled water and barreled water, respectively. Source analysis suggested diverse sources of di-OPEs, including industrial applications, effluents of municipal wastewater treatment plants, degradation from tri-OPEs during production/usage and under natural environmental conditions. The non-carcinogenic and carcinogenic risks of OPEs were lower than the theoretical threshold of risk, indicating the human health risks to OPEs via drinking water consumption were negligible. More studies are needed to explore environmental behaviors of di-OPEs in the aquatic environment and to investigate ecological risks.

Occurrence and spatio-seasonal distribution of organophosphate tri- and di-esters in surface water from Dongting Lake and their potential biological risk.

In this study, 24 surface water samples were collected from Dongting Lake, China, in the wet and dry seasons, then the concentrations, composition profiles and spatio-seasonal variations of nine organophosphate triesters (OPEs) and five organophosphate diesters (Di-OPs) were determined. Significantly higher total OPE concentrations (∑OPEs) were observed in the wet season (49.5-148 ng L-1) than in the dry season (5.00-45.7 ng L-1) suggesting higher input via tributaries discharge as well as wet deposition in the studied region. Whereas lower levels of TnBP and (triphenyl phosphate (TPHP) in wet season reflected their possible degradation under solar irradiation. Comparable levels of total Di-OPs (∑Di-OPs) were found in the wet season (3.41-13.9 ng L-1) and dry season (1.01-12.3 ng L-1). Tri(2-chloroethyl) phosphate and tris(2-chloroisopropyl) phosphate were the main OPE components, while diphenyl phosphate, di-n-butyl phosphate and bis(1,3-dichloro-2-propyl) phosphate were the main Di-OP components. High levels of OPEs and Di-OPs were found in Datong Lake suggesting possible local emissions potentially related to fishery activity in the land-locked lake. Samples at river mouths to the lake also have higher levels of target OPEs and Di-OPs, the results disclosed obvious discharges from tributaries in Hunan Province. Negligible non-carcinogenic and carcinogenic risks were determined based on the measured concentrations in source waters. A limited ecological risk aquatic organisms in the Dongting Lake was identified, with most risk from TPHP.

Be Aware of Organophosphate Diesters as Direct Sources in Addition to Organophosphate Ester Metabolites in Food Supplies.

The substantial application of organophosphate triesters (tri-OPEs) may lead to a concentration escalation of their major metabolites, organophosphate diesters (di-OPEs) in animal-derived and plant-derived animal protein supplement feeds (APFs). APFs are major food for raised animals and may bring OPEs into the food supply. In the present study, the concentrations of Σ8di-OPEs in animal-derived and plant-derived APFs were in the range of 1.98-182 ng/g dw (average: 39.2 ng/g dw). Meat meal had the highest average concentrations of di-OPEs (52.1 ng/g dw), followed by blood meal (49.9 ng/g), feather meal (23.3 ng/g dw), and plant-derived feeds (18.3 ng/g dw). The concentrations of di-OPEs were at the same order of magnitude as those of tri-OPEs in APFs. Bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) was the major contributor in blood meal, feather meal, and plant-derived APFs, while dimethyl phosphate dominated in meat meal. The ratios of di-OPEs/tri-OPEs (Rdi/tri) displayed large variability, ranging from 0 for the bis(2-chloroethyl) phosphate-tris(2-chloroethyl) phosphate pair to 175 for the BDCIPP-tris(1,3-dichloroisopropyl) phosphate pair, which indicated that the metabolism capacities and environmental sources for di-OPEs are diverse in APFs. Different Rdi/tri between APFs and similar food matrices implied that di-OPEs may have different environmental sources. The similar Rdi/tri values for some of the di-/tri-OPE pairs among APFs and dust samples indicated that dust may be a direct exogenous source of OPE exposure in some APF matrices. Future studies should simultaneously focus on tri- and di-OPEs, together of which may reflect the actual exposure to OPEs through the food supply.

Organophosphate di- and tri-esters in indoor and outdoor dust from China and its implications for human exposure.

Organophosphate (OP) esters are emerging environmental contaminants, but little is known about their occurrence in dust. In this study, 19 OP triesters and their 11 diester degradation products were measured in indoor dust and outdoor dust collected from China. ∑OP triester concentrations in indoor dust (median: 2380 ng/g dry weight [dw]) were an order of magnitude higher than those in outdoor dust (446 ng/g dw). The median concentrations of ∑OP diesters in indoor and outdoor dust were 260 and 96.8 ng/g dw, respectively. Dust samples collected from eastern and southern China contained higher concentrations of ∑OP di- and tri-esters than those from the other regions. Dust from the most urbanized areas in China including Beijing, Shanghai, and Guangzhou exhibited the highest concentrations of ∑OP di- (>1000 ng/g dw) and triesters (>4000 ng/g dw). We also found notable concentrations of emerging aryl-OP triesters in dust (3.85-10.6 ng/g dw). Significant correlations existed between the concentrations of bis(2-ethylhexyl) phosphate (BEHP) and tris(2-ethylhexyl) phosphate (TEHP) (rho = 0.672-0.691, p < 0.01), as well as DPHP and triphenyl phosphate (TPHP) (rho = 0.537-0.766, p < 0.01) in dust samples, indicating that OP diesters originated from the degradation of triesters. High molar concentration ratios of DEP to triethyl phosphate (TEP) and DPHP to TPHP/ethylhexyl diphenyl phosphate (EHDPP) suggested that these OP triesters degrade readily. Significant correlations were found between the concentrations of ∑OP di- (R2 = 0.390, p < 0.05) and tri-esters (R2 = 0.475, p < 0.01) in paired indoor-outdoor dust samples, which suggested that indoor dust was the source of OP esters to the outdoor environment. The estimated daily intake (EDI) of ∑OP diesters through dust ingestion was 0.21 ng/kg bw/d for adults and 2.59 ng/kg bw/d for children. The exposure levels of OP diesters, DEP and DPHP, were comparable to those of their parent triester compounds.

Developmental circulatory failure caused by metabolites of organophosphorus flame retardants in zebrafish, Danio rerio.

Organophosphate triesters are used worldwide as additives in flame retardants and plasticizer as a replacement of polybrominated diphenyl ethers. Increasing evidence on human exposure to and environmental contamination with organophosphorus flame retardants (OPFRs) requires an adequate toxicity assessment for this class of chemicals. While developmental toxicity of several OPFRs has been reported, developmental effects of OPFR metabolites have still to be understood. The present study aimed at characterizing developmental effects of OPFR metabolites using zebrafish embryos (Danio rerio). Triphenyl phosphate (TPHP) and two of its metabolites, 3-hydroxylphenyl diphenyl phosphate and 4-hydroxylphenyl diphenyl phosphate, were most potent for inducing pericardial edema and reduction in blood flow in trunk vessels. Other TPHP metabolites, such as diphenyl phosphate and 4-hydroxylphenyl phenyl phosphate, showed no substantial increase in circulatory failure at concentrations up to 30 µM. Tris (1,3-dichloro-2-propyl) phosphate showed circulatory failure at 30 µM, but its metabolite bis(1,3-dichloro-2-propyl) phosphate did not. Neither tris(2-chloroethyl) phosphate nor its metabolite bis(2-chloroethyl) phosphate, induced circulatory failure. The circulatory failure appeared to be enhanced with the increase in the octanol-water partition coefficients of OPFRs and their metabolites, suggesting that developmental circulatory failure posed by these chemicals could be estimated by their bioaccumulative potential. The present study demonstrated developmental circulatory failure of hydroxylated TPHP metabolites, which was almost equipotent to TPHP. Diester OPFR metabolites showed no major developmental toxicity at the concentrations used in this study. The current results establish the foundation for further understanding the similarities and differences in the toxic mechanisms between OPFRs and their metabolites.

Co-occurrence and distribution of organophosphate tri- and di-esters in indoor dust from different indoor environments in Guangzhou and their potential human health risk.

In this study, 45 indoor dust samples and four particulate samples from air-conditioner filters were collected from four different indoor environments in Guangzhou, China, and the concentration and composition of organophosphate tri-esters (OPEs) and organophosphate di-esters (Di-OPs) were determined. Eight of the 10 target OPEs were detected in indoor dust at different detection frequencies (DFs), with tris(2-chloroisopropyl) phosphate and tris(2-chloroethyl) phosphate being the main components. Seven target Di-OPs were detected at different DFs, with diphenyl phosphate being the dominant compound. The total OPEs (∑8 OPEs) and total Di-OPs (∑7 Di-OPs) concentrations varied from 726 to 39,312 ng/g and 68.8-14,766 ng/g, respectively. The ∑8 OPEs concentrations in instrumental houses were significantly higher (p < 0.001) than in three other indoor environments. The varying strengths of the correlation between Di-OPs and their respective parent OPEs was suggestive of their emission sources (e.g., direct application, impurities in OPE formulas, and OPE degradation). The hazard index (HI) values of individual OPEs in residential house were lower than 1, the results suggested a limited human health risk from individual OPEs. However, the total HI value (∑HIs) of OPEs was approximately 1 based on a high exposure scenario and suggested a low risk for toddlers.

Occurrence and distribution of organophosphate triesters and diesters in sludge from sewage treatment plants of Beijing, China.

The occurrence and distribution of 14 organophosphate (OP) triesters and 5 diesters were investigated in sludge from eight sewage treatment plants (STPs) in Beijing, China, during 2008-2014. Tri(2-ethylhexyl) phosphate (TEHP) and tri-m-cresyl phosphate (TCrP) were the predominant triesters with the average concentration of 233-137 µg/kg, respectively. Also, the polar and hydrophilic trimethyl phosphate (TMP) and triethyl phosphate (TEP) were detected in 19% and 74% of sludge samples, respectively. Three of five diesters were detected in sludge samples, and di(2-ethylhexyl) phosphate (DEHP) revealed the highest average concentration of 96.0 µg/kg, followed by diphenyl phosphate (DPhP, 18.0 µg/kg). The levels of OP triesters in sludge varied with the compositions of the sewage and treatment capacity of STPs, as well as the adjacent sources. In comparison with that in the former years, relatively higher concentration of total OP triesters in sludge was observed in 2014, which is consistent with the rapid growth in consumption of these chemicals in China. Finally, environmental risk assessment indicated potential harmful effects of OP triesters on soil microorganisms after sludge landfill or fertilization.

Consumer products are important reservoirs and sources of organophosphate tri-esters and di-esters: Characteristics, mass inventory, and implication for waste management.

Numerous studies documented the occurrence of organophosphate tri-esters (tri-OPEs) and di-esters (di-OPEs) in the environment. Little information is available on their occurrence in waste consumer products, reservoirs and sources of these chemicals. This study collected and analyzed 92 waste consumer products manufactured from diverse polymers, including polyurethane foam (PUF), polystyrene (PS), acrylonitrile butadiene styrene (ABS), polypropylene (PP), and polyethylene (PE) to obtain information on the occurrence and profiles of 16 tri-OPEs and 10 di-OPEs. Total concentrations of di-OPEs (18-370,000 ng/ g, median 1,700 ng/g) were one order of magnitude lower than those of tri-OPEs (94-4,500,000 ng/g, median 5,400 ng/g). The concentrations of both tri- and di-OPEs in products made of PUF, PS, and ABS were orders of magnitude higher than those made of PP and PE. The compositional patterns of OPEs varied among different polymer types but were generally dominated by bisphenol A bis(diphenyl phosphate), triphenyl phosphate, tris(1-chloro-2-propyl) phosphate, di-phenyl phosphate (DPHP), and bis (2-ethylhexyl) phosphate. Two industrially applied di-OPEs (di-n-butyl phosphate and DPHP) exhibited higher levels than their respective tri-OPEs, contrary to their production volumes. Some non-industrially applied chlorinated di-OPEs were also detected, with concentrations up to 97,000 ng/g. These findings suggest that degradation of tri-OPEs during the manufacturing and use of products is an important source of di-OPEs. The mass inventories of tri-OPEs and di-OPEs in consumer products were estimated at 3,100 and 750 tons/year, respectively. This study highlights the importance of consumer products as emission sources of a broad suite of OPEs.