Tris(methylphenyl) Phosphate Research Articles

Toxicological Mechanisms and Potencies of Organophosphate Esters in KGN Human Ovarian Granulosa Cells as Revealed by High-throughput Transcriptomics.

Despite the growing number of studies reporting potential risks associated with exposure to organophosphate esters (OPEs), their molecular mechanisms of action remain poorly defined. We used the high-throughput TempO-Seq™ platform to investigate the effects of frequently detected OPEs on the expression of ∼3000 environmentally responsive genes in KGN human ovarian granulosa cells. Cells were exposed for 48 h to one of five OPEs (0.1 to 50 μM): tris(methylphenyl) phosphate (TMPP), isopropylated triphenyl phosphate (IPPP), tert-butylphenyl diphenyl phosphate (BPDP), triphenyl phosphate (TPHP), or tris(2-butoxyethyl) phosphate (TBOEP). The sequencing data indicate that four OPEs induced transcriptional changes, whereas TBOEP had no effect within the concentration range tested. Multiple pathway databases were used to predict alterations in biological processes based on differentially expressed genes. At lower concentrations, inhibition of the cholesterol biosynthetic pathway was the predominant effect of OPEs; this was likely a consequence of intracellular cholesterol accumulation. At higher concentrations, BPDP and TPHP had distinct effects, primarily affecting pathways involved in cell cycle progression and other stress responses. Benchmark concentration (BMC) modelling revealed that BPDP had the lowest transcriptomic point of departure. However, in vitro to in vivo extrapolation modeling indicated that TMPP was bioactive at lower concentrations than the other OPEs. We conclude that these new approach methodologies provide information on the mechanism(s) underlying the effects of data-poor compounds and assist in the derivation of protective points of departure for use in chemical read-across and decision-making.

Organophosphate Esters Disrupt Steroidogenesis in KGN Human Ovarian Granulosa Cells.

Organophosphate esters (OPEs) are used extensively as flame retardants and plasticizers and are found ubiquitously in the environment and human matrices. Previous studies suggested that exposure to some of these chemicals may disrupt the homeostasis of female sex hormones and have detrimental effects on female fertility. Here, we determined the effects of OPEs on the function of KGN ovarian granulosa cells. We hypothesized that OPEs alter the steroidogenic ability of these cells by dysregulating the expression of transcripts involved in steroid and cholesterol biosynthesis. KGN cells were exposed for 48 hours to 1 of 5 OPEs (1-50μM): triphenyl phosphate (TPHP), tris(methylphenyl) phosphate (TMPP), isopropylated triphenyl phosphate (IPPP), tert-butylphenyl diphenyl phosphate (BPDP), and tributoxyethyl phosphate (TBOEP), or to a polybrominated diphenyl ether flame retardant, 2,2',4,4' tetrabromodiphenyl ether (BDE-47), in the presence or absence of Bu2cAMP. OPEs increased the basal production of progesterone (P4) and 17β-estradiol (E2) and had either no effect or inhibited Bu2cAMP-stimulated P4 and E2 synthesis; exposure to BDE-47 had no effect. Quantitative real-time polymerase chain reaction (qRT-PCR) analyses revealed that OPEs (≥5μM) increased the basal expression of critical genes (STAR, CYP11A1, CYP19A1, HSD3B2, and NR5A1) involved in steroidogenesis; upon stimulation, the expression of all genes tested was downregulated. An overall inhibition in cholesterol biosynthesis was induced by OPEs, characterized by a downregulation in HMGCR and SREBF2 expression. TBOEP consistently showed the least effect. Therefore, OPEs perturbed steroidogenesis in KGN granulosa cells by targeting the expression of steroidogenic enzymes and cholesterol transporters; these effects may have an adverse impact on female reproduction.

The risk and impact of organophosphate esters on the development of female-specific cancers: Comparative analysis of patients with benign and malignant tumors

Environmental pollution has become a concern for public health. As endocrine disruptors, organophosphate esters (OPEs) causes many diseases via human exposure. However, there is limited research on the risk of OPE exposure to female-specific cancers. Blood measurements are biomarkers for chemical exposures by their definition. Thus, in the present study, 11 OPEs were analyzed in the plasma of patients with 4 female-specific tumors. 2-Ethylhexyl diphenyl phosphate (EHDPP) was detected at the highest levels in all groups. The Spearman correlation test results showed significantly positive correlations between some OPEs in each group, which indicated that those OPEs had similar sources and/or behaved similarly in the patients of each group. However, compared with different patient groups, obvious differences in the correlation results were noted, implying the differences in the metabolism of OPEs between different groups. The results of the correlation analysis showed that EHDPP concentration was associated with the risk of breast cancer (p < 0.05), while tri-n-butyl phosphate (TNBP), tris (methylphenyl) phosphate (TMPP), triphenyl phosphate (TPHP), and EHDPP concentrations were associated with the risk of cervical cancer (p < 0.05 or p < 0.01). These findings indicated that OPEs were associated with the risk of breast and cervical cancer.

Positive correlation between human exposure to organophosphate esters and gastrointestinal cancer in patients from Wuhan, China.

As kinds of endocrine disruptors, organophosphate esters (OPEs) pollution in the environment had received increasing attention recently. Food and water intake were two important exposure pathways for OPEs. However, the studies about the potential association between OPEs and gastrointestinal cancer were limited. This study investigated the possible association between OPEs and gastrointestinal cancer. All cancer patients were diagnosed with gastrointestinal cancer from a Grade 3A hospital in Wuhan, China, while the control group was non-cancer healthy persons. The results showed that 6 OPEs were found in the control samples, while 8 in the samples from patients with gastrointestinal cancer. The detection frequencies of OPEs in gastrointestinal cancer patients were significantly higher than those in the control group (p<0.05 or p<0.01), except for triethyl phosphate (TEP) and tris (methylphenyl) phosphate (TMPP) in the gastric cancer group. The concentrations of OPEs in the control group were significantly lower than those in the gastric cancer group and colorectal cancer group (p<0.01). In the control group and gastrointestinal cancer group, TEP was the dominant pollutant. Correlation analysis found that concentrations of TEP, tris(2-chloroisopropyl) phosphate (TCIPP), triphenyl phosphate (TPHP), TMPP, tris(2-ethylhexyl) phosphate (TEHP), and 2-ethylhexyl diphenyl phosphate (EHDPP) were associated with gastric cancer (p<0.01), and concentrations of TEP, TCIPP, TPHP, TMPP and TEHP were associated with colorectal cancer (p<0.01). A cluster analysis divided the 34 patients with gastric cancer and 40 patients with colorectal cancer in four groups. The results showed that the elderly male patients with gastric cancer were more sensitive to the exposure of EHDPP, while the TEP exposure was more sensitive to the relatively young gastrointestinal cancer patients. These findings indicated that OPEs might play a role in developing gastrointestinal cancer.

Traditional and emerging organophosphate esters (OPEs) in indoor dust of Nanjing, eastern China: Occurrence, human exposure, and risk assessment

Here, fifteen OPEs were investigated in n = 50 floor dust samples collected from six types of indoor spaces in Nanjing, eastern China, in the year 2018. Ten OPEs, including tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloro-isopropyl) phosphate (TDCIPP), tris(2-ethylhexyl) phosphate (TEHP), tris(2-butoxyethyl) phosphate (TBOEP), 2-ethylhexyl-diphenyl phosphate (EHDPP), triphenyl phosphate (TPHP), tris(methyl-phenyl) phosphate (TMPP), 4-biphenylyl diphenyl phosphate (4-BPDP) and tris(2-biphenylyl) phosphate (TBPP), were detected in at least one of the analyzed samples (>method limits of quantification). Regardless of indoor spaces, EHDPP (34% of Σ8OPEs, mean: 1.43 μg/g) and TDCIPP (19%, 0.81 μg/g) were the ascendant OPEs in indoor floor dust. 4-BPDP and TBPP were detectable in indoor floor dust samples, but at relatively low detection frequencies with 2% and 10%, respectively. Various indoor microenvironments exhibited different pollution characteristics of OPEs. Floor dust collected from electronic product maintenance centers contained the richest OPE contaminants with highest mean Σ8OPEs concentration of 7.92 μg/g. On the basis of measured Σ10OPEs concentrations in dust sample, we estimated daily intake via floor dust ingestion to be 1.37, 0.75 and 1.24 ng/kg BW/day for electronic engineers, undergraduates, and graduate students under mean-exposure scenario, respectively. Overall, our study reported the occurrence of 4-BPDP and TBPP in environmental samples for the first time, and demonstrated that indoor floor dust ingestion exposure does values were far less than reference dosage values of oral toxicity proposed by United States Environmental Protection Agency (USEPA) Integrated Risk Information System.

Organophosphate esters (OPEs) in Chinese foodstuffs: Dietary intake estimation via a market basket method, and suspect screening using high-resolution mass spectrometry

Despite of the ubiquity of organophosphate esters (OPEs) in various environmental matrices, information regarding the dietary intakes of OPEs is currently limited. To better understand dietary exposure and intake, the present study investigated 11 OPE flame retardants (FRs) in 105 composite food samples divided into 9 food categories, collected in 2018 and based on the contents of a typical Chinese food market basket. Nine OPEs, including triethyl phosphate (TEP), tributyl phosphate (TNBP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), triphenyl phosphate (TPHP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-butoxyethyl) phosphate (TBOEP), tris(2-ethylhexyl) phosphate (TEHP) and tris(methyl-phenyl) phosphate (TMPP), were measurable above the method limits of quantifications (MLOQs) in at least one of the analyzed samples. Among the 9 food categories, sweets were contaminated most severely with a mean sum (Σ) OPE concentration of 10.34 ng/g wet weight (ww). Regardless the food categories, EHDPP and TEP were the predominant OPEs with mean concentrations of 1.12 and 0.95 ng/g ww, respectively. In addition, the levels of OPEs in “processed foods” were significantly (unpaired t-test, p < 0.01) higher than those in “non-processed foods”. Based on the measured OPE concentrations, we estimated daily per capita dietary intakes of ΣOPEs for Chinese adult population to be 44.3 ng/kg bw/day, that was mainly contributed by TCEP (14.3 ng/kg bw/day), TEP (12.7 ng/kg bw/day) and EHDPP (8.4 ng/kg bw/day). In addition to these 9 detected OPEs, further suspect screening in the combined extracts of foodstuffs by use of high-resolution spectrometry revealed a novel OP-FR, triphenyl phosphine oxide (TPPO). The highlight findings in this study were: 1) the amount of OPE via dietary intakes for the Chinese population is generally in the same order of magnitude as for other countries, i.e. the Swedish, Belgian and Australian adult population, and far less than the reference dosage value of each OPE (hazard index ≪ 1); 2) the total dietary intakes of OPEs were dominated by cereals, approximately accounting for 52.2%; and 3) the first reported detection of the novel OP-FR, TPPO, in foodstuff samples.

Measurement of legacy and emerging flame retardants in indoor dust from a rural village (Kopawa) in Nepal: Implication for source apportionment and health risk assessment

Under the Stockholm Convention, signatory countries are obliged to direct source inventories, find current sources, and provide ecological monitoring evidence to guarantee that the encompassing levels of persistent organic pollutants (POPs) are declining. However, such monitoring of different types of POPs are to a great degree constrained in most developing countries including Nepal and are primarily confined to suspected source area/ densely populated regions. In this study, 9 polybrominated diphenyl ethers (PBDEs), 2 dechlorane plus (DPs), 6 novel brominated flame retardants (NBFRs) and 8 organophosphate ester flame retardants (OPFRs) were investigated in indoor dust from a rural area (Kopawa) in Nepal in order to evaluate their occurrence/level, profile, spatial distribution and their sources. Additionally, health risk exposure was estimated to anticipate the possible health risk to the local population. The results showed that OPFRs was the most abundant FR measured in the dust. The concentration of ∑8OPFRs was about 2, 3 and 4 orders of magnitude higher than the ∑6NBFRs, ∑9PBDEs, and ∑2DPs, respectively. Tris (methylphenyl) phosphate (TMPP) and Tris (2-ethylhexyl) phosphate (TEHP) were the most abundant OPFRs analyzed in the dust; while decabromodiphenyl ethane (DBDPE) exceeded among NBFRs. Likewise, 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenylether (BDE-209) was the most identified chemical among PBDEs. The total organic carbon (TOC) content in dust was significantly and positively connected with octa-BDEs (Rho = 0.615, p < 0.01), BTBPE (Rho = 0.733, p < 0.01), TPHP (Rho = 0.621, p < 0.01), TEHP (Rho = 0.560, p < 0.01) and TMPPs (Rho = 0.550, p < 0.01), while black carbon (BC) was either weakly related or not related, suggesting little or no impact of BC in the distribution of FRs. Principal component analysis indicated the contribution from commercial penta-, octa- and deca-BDEs formulation, the adhesive substance, food packaging and paints, and degradation of BDE-209 as the essential sources of FRs. Health risk exposure estimates showed that dermal absorption via dust as the primary route of FRs intake. The estimated daily exposure of PBDEs, NBFRs and OPFRs were 2–10 orders of magnitude lower than their corresponding reference dose (RfD), suggesting insignificant risk. However, other routes such as inhalation and dietary intake might still be significant in the case of Kopawa which should be tested in future.

Effects of Organophosphate Ester Flame Retardants on Endochondral Ossification in Ex Vivo Murine Limb Bud Cultures.

Phasing out the usage of polybrominated diphenyl ether (PBDE) flame retardants (FRs) in consumer products led to their widespread replacement with organophosphate ester (OPE) FRs, despite scarce safety data. PBDE exposures were associated with the suppression of endochondral ossification but little is known about the effects of OPEs on bones. Here, we used a novel ex vivo murine limb bud culture system to compare the effects of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) with those of several OPEs. Gestation day 13 embryos were collected from transgenic CD1 mice expressing fluorescent markers for the major stages of endochondral ossification: COL2A1-ECFP (chondrogenesis), COL10A1-mCherry (early osteogenesis), and COL1A1-YFP (late osteogenesis). Limbs were excised and cultured for 6 days in the presence of vehicle, BDE-47, or an OPE FR: triphenyl phosphate (TPHP), tert-butylphenyl diphenyl phosphate (BPDP), tris(methylphenyl) phosphate (TMPP), or isopropylated triphenyl phosphate (IPPP). BDE-47 (50 μM) decreased the extent of chondrogenesis in the digits and COL1A1-YFP expression in the radius and ulna relative to control. In comparison, concentrations of ≥1 μM of all 4 OPEs limited chondrogenesis; osteogenesis (both COL10A1-mCherry and COL1A1-YFP fluorescence) was markedly inhibited at concentrations ≥3 μM. The expression of Sox9, the master regulator of chondrogenesis, was altered by BDE-47, TPHP, and BPDP. BDE-47 exposure had minimal impact on the expression of Runx2 and Sp7, which drive osteogenesis, whereas TPHP and BPDP both suppressed the expression of these transcription factors. These data suggest that OPE FRs may be more detrimental to bone formation than their brominated predecessors.

Trophic transfer of organophosphorus flame retardants in a lake food web

Despite increasing use of organophosphorus flame retardants (OPFRs), their food web transfer behavior is not well known. In this study, concentrations of fourteen OPFRs were measured in 17 species from Taihu Lake, China, and their trophodynamics were assessed. Of the 14 OPFRs, nine were detected in at least 70% of the food web samples, including tris(ethyl) phosphate (TEP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(isobutyl) phosphate (TIBP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(n-butyl) phosphate (TNBP), tris(phenyl) phosphate (TPHP), tris(methylphenyl) phosphate (TMPP), and 2-ethylhexyl diphenyl phosphate (EHDPP). The total OPFR concentrations were 100 ± 23 ng/g ww in plankton, 17 ± 11 ng/g ww in invertebrates, and 9.8 ± 6.2 ng/g ww in fish. TIBP (93 ± 16 ng/g ww) was the dominant OPFR in plankton, whereas TCEP (2.4 ± 3.9 ng/g ww) and TPHP (3.3 ± 16 ng/g ww) were dominant in fish. While negative relationships between concentration and aquatic species trophic level were observed for all nine OPFRs, only those for TCIPP (p = 0.022), TDCIPP (p = 0.029), and TMPP (p = 0.021) were statistically significant, with trophic magnification factors (TMFs) of 0.55, 0.39, and 0.42, respectively. This study provides fundamental information for assessing ecological risks of OPFRs.

Organophosphate esters and phthalate esters in human hair from rural and urban areas, Chongqing, China: Concentrations, composition profiles and sources in comparison to street dust

Human hair and street dust from rural and urban areas in Chongqing were collected to analyze Organophosphate esters (OPEs) and phthalate esters (PAEs). Concentrations of OPEs in urban hair were significantly higher than those in rural hair, whereas PAEs concentrations in rural hair were significantly higher than those in urban hair. Different composition patterns of OPEs were observed in rural and urban hair, where tris (2-chloroisopropyl) phosphate (TCIPP), tris (butyl) phosphate (TNBP) and triphenyl phosphate (TPHP) were the dominating analogues in rural hair, accounting for 62.1% of the OPEs burden, and tris (methylphenyl) phosphate (TMPP) exhibited a high contribution in urban hair, responsible for 51.3% of total OPEs, which differed from the composition profiles in corresponding street dust. Analogous composition patterns of PAEs were found in hair of both areas. Di-(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DNBP), diisobutyl phthalate (DIBP) and diethyl phthalate (DEP) were the most abundant analogues in hair samples, while DEHP was the predominant analogue in dust samples. No clear tendency was obtained between the increasing ages and the concentrations of both compounds. Most OPEs and PAEs congeners showed significantly positive correlation with one another in rural hair. On the contrary, different correlation patterns were observed in urban hair for OPEs and PAEs, indicating multiple or additional sources existed in urban areas. Significant correlations of OPEs and PAEs were found between hair and corresponding street dust samples, but poor correlations of OPEs and PAEs were observed between rural hair and rural indoor dust, suggesting that street dust may be a predominant exogenous source for human exposure to OPEs and PAEs in this area.

Occurrence and distribution of organophosphate flame retardants (OPFRs) in soil and outdoor settled dust from a multi-waste recycling area in China

Distribution of 12 organophosphate flame retardants (OPFRs) was determined in soil and outdoor settled dust samples collected from a multi-waste (electronic, plastic, and rubber wastes and abandoned household-appliances and vehicles) recycling area, that encompassed different modes of operation i.e. open (ORS) and semi-closed recycling (SCRS). Among the twelve OPFRs analyzed, eleven were detected at a frequency of 75%–100% in all soil and dust samples. In soil samples, ΣOPFR concentrations were significantly higher at ORS (122–2100ng/g) than at SCRS (58.5–316ng/g) and nearby farmlands (37.7–156ng/g). The ΣOPFR concentrations in dust samples were higher than those in soil samples with spatial distribution similar to that observed for soil, decreasing from ORS (1390–42,700ng/g) to SCRS (914–7940ng/g). Tris(2-chloroisopropyl) phosphate (TCIPP) was the major OPFRs in both soil (<MDL–1370ng/g) and dust (39.9–16,300ng/g) samples. Chlorinated OPFRs [TCIPP, tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and tris(2-chloroethyl) phosphate (TCEP)] and aryl-OPFRs [triphenyl phosphate (TPHP), tris(methylphenyl) phosphate (TMPP)] exhibited spatial difference between ORS and SCRS. Principle component analysis (PCA) of OPFR concentrations revealed that TCIPP, TDCIPP, TPHP, TMPP originated from similar sources. TMPP was assessed to pose eco-toxicological risk (risk quotient values: RQs) in the soil ecosystem. The median estimated daily intake (EDI) of OPFRs via soil and outdoor settled dust ingestion (based on average ingestion rate) was 3.14×10−1ng/kgbw/day for adults at ORS. Our results suggest that waste recycling is an important source of chlorinated- and aryl-OPFRs in the environment.

Dermal uptake and percutaneous penetration of organophosphate esters in a human skin ex vivo model

Organophosphate esters (OPEs) are used as flame retardants, plasticizers, and as hydraulic fluids. They are present in indoor environments in high concentrations compared with other flame retardants, and human exposure is ubiquitous. In this study we provide data for estimating dermal uptake for eight OPEs and ranking in OPEs risk assessment. Dermal uptake and percutaneous penetration of the OPEs were studied in a Franz diffusion cell system using human skin dosed with a mixture of OPEs in an ethanol:toluene (4:1) solution. Large variation in penetration profiles was observed between the OPEs. The chlorinated OPEs tris(2-chloroisopropyl) phosphate (TCIPP), and in particular tris(2-chloroethyl) phosphate (TCEP), penetrated the skin quite rapidly while tris(1,3-dichlor-2-propyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP) tended to build up in the skin tissue and only smaller amounts permeated through the skin. For tris(isobutyl) phosphate (TIBP), tris(n-butyl) phosphate (TNBP), and tris(methylphenyl) phosphate (TMPP) the mass balance was not stable over time indicating possible degradation during the experimental period of 72 h. The rates at which OPEs permeated through the skin decreased in the order TCEP > TCIPP ≥ TBOEP > TIBP ≥ TNBP > TDCIPP > TPHP > TMPP. Generally, the permeation coefficient, kp, decreased with increasing log Kow, whereas lag time and skin deposition increased with log Kow. The present data indicate that dermal uptake is a non-negligible human exposure pathway for the majority of the studied OPEs.

Current State, Distribution, and Sources of Phthalate Esters and Organophosphate Esters in Soils of the Three Gorges Reservoir Region, China.

Phthalate esters (PAEs) and organophosphate esters (OPEs) were identified and quantified in surface soils from farmland and riparian areas of the Three Gorges Reservoir (TGR), western China. Generally, the mean values of PAEs and OPEs were 618 and 266ng/g dry weight (dw) in farmland soil and 560 and 499ng/g dw in riparian soil, respectively. The occurrence of OPEs should be regarded as a risk factor in the TGR region. Analogous spatial distribution patterns for PAEs were observed with higher concentrations observed at site WZ in both types of soil, which might relate to the anthropogenic activities. The hydrodynamic conditions might be important factors contributing to the slightly different spatial distribution of OPEs. The concentrations of OPEs in riparian soil exceed those in farmland soil at all sampling sites, which could partly be ascribed to the complete operation of the TGR. Dibutyl phthalate (DnBP) was the most dominated PAEs congener in both types of soil. Of particular note is the elevated contribution of tris(methylphenyl) phosphate (TMPP), followed by 2-ethylhexyl diphenyl phosphate (EHDPP), accounting for more than 90% of the total OPEs, and the shipping or/and the local human activity might be considered as the major contributor. The slight differences in PAEs composition of principal components might largely attribute to the variety of emission sources in two types of soil. The different cluster patterns between two types of soil indicated that the anthropogenic activities as well as the full operation of TGR, may play a role.

Organophosphate ester flame retardants in Nepalese soil: Spatial distribution, source apportionment and air-soil exchange assessment

Despite soil being the major terrestrial environmental reservoir and one of the significant sinks for many hydrophobic organic compounds including organophosphate ester flame retardants (OPFRs), limited information is available about concentration and fate of OPFRs contamination in urban soil in general and especially in case of Nepal. This study investigates the environmental concentration, spatial distribution and source apportionment of eight OPFRs in surface soil (n = 28) from four major cities of Nepal with special interest on air-soil exchange. Overall, significantly high concentrations of ∑8OPFR were measured in soil ranging from 25–27,900 ng/g dw (median 248 ng/g dw). In terms of compositional pattern, tris(methyl phenyl) phosphate (TMPP) was the most abundant phosphorus chemical in soil, followed by tris(2-chloroisopropyl) phosphate (TCIPP), and accounted for 35–49% and 8–25% of ∑8OPFRs, respectively. The high level of these OPFRs was attributed to local sources as opposed to transboundary influence from remote areas. A Spearman's rank correlation analysis exhibited weak correlation of ∑8OPFRs with TOC (Rho = 0.117, p < 0.05) and BC (Rho = 0.007, p < 0.05), suggesting little or no influence of TOC and BC on the concentration of ∑8OPFRs. The fugacity fraction (ff) results indicated a strong influence of soil contamination on atmospheric level of OPFRs via volatilization.

Brominated and organophosphorus flame retardants in body wipes and house dust, and an estimation of house dust hand-loadings in Dutch toddlers

Children generally have higher Flame Retardant (FR) concentrations in serum compared to other age groups. Toddler behavior enhances direct contact with house dust since their frequent presence proximate to the floor, and their mouthing behavior. This study aimed to thoroughly investigate FR levels in body wipes of toddlers 8–18 months old) and in indoor dust using a noninvasive sampling technique. In this cross-sectional study, body wipes from hands, mouth and back, and indoor household dust samples were collected in twenty-one families and analyzed for one brominated- and seven organophosphorus FRs (polybrominated diphenyl ether 209 (BDE209), tris(2-chloroisopropyl) phosphate (TCIPP), tris(chloroethyl) phosphate (TCEP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(phenyl) phosphate (TPHP), tris(methylphenyl) phosphate (TMPP), resorcinol bis(diphenyl phosphate) and bisphenol A bis(diphenyl phosphate)). Accelerated solvent extraction was used for extraction and the extract was measured with liquid chromatography combined with mass spectrometry. Non-parametric correlation analyses were performed to assess associations. All FRs were detected in body- and indoor dust samples (median range: 1.0ng/hand wipe (BDE209) to 65ng/hand wipe (TCIPP)) and were mostly correlated with each other. We estimated that approximately 260mg dust (range 50–880mg) accumulated on toddler's hands per day. Hand-to-mouth frequency was negatively associated with FR levels in wipes (τ = −0.38, p = 0.04). With increasing age FR concentrations (BDE209, TCEP, TDCIPP, TPHP and TMPP) on hands decreased significantly (p = 0.01–0.03). Girls had significantly less FRs (TCEP, TCIPP, TPHP and TMPP) on the hands (p = 0.01–0.03) than boys. This is to the best of the authors’ knowledge the first study in Europe that measured brominated- as well as organophosphorus FRs in several types of body wipes from toddlers and that estimated the amount of house dust that accumulates on toddler's hands.

Occurrence, Removal, and Environmental Emission of Organophosphate Flame Retardants/Plasticizers in a Wastewater Treatment Plant in New York State.

The occurrence and fate of 14 triester organophosphate flame retardants (OPFRs) and plasticizers and their two diester metabolites were investigated in a wastewater treatment plant (WWTP) in the Albany area of New York State. All target OPFRs were found in wastewater, with average concentrations that ranged from 20.1 ng/L for tris(methylphenyl) phosphate (TMPP) to 30 100 ng/L for tris(2-butoxyethyl)phosphate (TBOEP) in influents and from 7.68 ng/L for TMPP to 12 600 ng/L for TBOEP in final effluents. TBOEP was the dominant compound in influents (max: 69 500 ng/L) followed in decreasing order by tris(1-chloro-2-propyl)phosphate (TCIPP; max: 14 500 ng/L), bis(1,3-dichloro-2-propyl)phosphate (BDCIPP; max: 4550 ng/L), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP; max: 3150 ng/L) and tris(2-chloroethyl)phosphate (TCEP; max: 8450 ng/L). The fraction of TMPP sorbed to suspended particulate matter (SPM) was 56.4% of the total mass in wastewater, which was the highest among the target chemicals analyzed. The average concentrations of OPFRs in sludge were between 4.14 ng/g dw for tripropyl phosphate (TPP) and 7290 ng/g dw for TBOEP; for ash, they were between 2.17 ng/g dw for TMPP and 427 ng/g dw for triphenyl phosphate (TPhP). The mass loadings of OPFRs into the WWTP ranged from 0.02 mg/day/person for TPP to 28.7 mg/day/person for TBOEP, whereas the emission from the WWTP ranged from 0.01 mg/day/person for 2-ethylhexyl diphenyl phosphate (EHDPP) to 5.12 mg/day/person for TCIPP. The removal efficiencies for OPFRs were slightly above 60% for TMPP, TBOEP, and tris(2-ethylhexyl)phosphate (TEHP) whereas those for other OPFRs were <40% (TPhP and BDCIPP) to negative values, suggesting incomplete removal in WWTPs.

Brominated, chlorinated and phosphate organic contaminants in house dust from Portugal

House dust is an important matrix to evaluate the human exposure to a large number of contaminants including organochlorine compounds and flame retardants. In this study, we measured the levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), polychlorinated biphenyls (PCBs) and several organophosphorus flames retardants (PFRs) in 28 house dust samples collected between 2010 and 2011 in two Portuguese cities, Aveiro and Coimbra. Among the measured compounds, PFRs, particularly tris(2-ethylhexyl) phosphate (TEHP), triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP) and tris(methylphenyl) phosphate (TMPP), were the dominant group (median: 3200ngg−1). PBDE levels were the second highest (median: 340ngg−1) with great predominance of BDE 209 (median 270ngg−1), followed by HBCDDs (median: 150ngg−1), DBDPE (54ngg−1), PCBs (median: 6.3ngg−1) and BTBPE (median: 1.2ngg−1). Estimated daily intakes (EDIs) via dust ingestion showed a higher intake of PFRs (median: 4.6ngkg-bw−1day); however for all contaminants the EDIs were much lower than the established reference dose (RfD) values. Therefore, the studied population is exposed to non-hazardous levels of the target compounds when considering the exposure through house dust ingestion.

Organophosphate esters in dust samples collected from Danish homes and daycare centers

Organophosphates are used in a wide range of materials and consumer products and are ubiquitous in indoor environments. Certain organophosphates have been associated with various adverse health effects. The present paper reports mass fractions of organophosphates in dust samples collected from 500 bedrooms and 151 daycare centers of children living in Odense, Denmark. The identified compounds include: tris(isobutyl) phosphate (TIBP), tri-n-butyl phosphate (TNBP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(2-butoxyethyl) phosphate (TBOEP), triphenylphosphate (TPHP), 2-ethylhexyl-diphenyl phosphate (EHDPP), tris(2-ethylhexyl) phosphate (TEHP) and tris(methylphenyl) phosphate (TMPP). Both the number of organophosphates with median values above the limit of detection and the median values were higher for samples from daycare centers than for samples from homes. Organophosphates with median mass fractions above the limit of detection were: TCEP from homes (6.9 μg g−1), and TCEP (16 μg g−1), TCIPP (5.6 μg g−1), TDCIPP (7.1 μg g−1), TBOEP (26 μg g−1), TPHP (2.0 μg g−1) and EHDPP (2.1 μg g−1) from daycare centers. When present, TBOEP was typically the most abundant of the identified OPs. The sum of the organophosphate dust mass fractions measured in this study was roughly in the mid-range of summed mass fractions reported for dust samples collected in other countries. On a global scale, the geographical distribution of organophosphates in indoor dust is quite variable, with higher concentrations in industrialized countries. This trend differs from that for phthalate esters, whose geographic distribution is more homogeneous. Exposure to organophosphates via dust ingestion is relatively low, although there is considerable uncertainly in this assessment.

Can activated sludge treatments and advanced oxidation processes remove organophosphorus flame retardants?

This study aims to determine the occurrence of 10 OPFRs (including chlorinated, nonchlorinated alkyl and aryl compounds) in influent, effluent wastewaters and partitioning into sludge of 5 wastewater treatment plants (WWTP) in Catalonia (Spain). All target OPFRs were detected in the WWTPs influents, and the total concentration ranged from 3.67µgL−1 to 150µgL−1. During activated sludge treatment, most OPFRs were accumulated in the sludge at concentrations from 35.3 to 9980ngg−1dw. Chlorinated compounds tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(2,3-dichloropropyl) phosphate (TDCPP) were not removed by the conventional activated sludge treatment and they were released by the effluents at approximately the same inlet concentration. On the contrary, aryl compounds tris(methylphenyl) phosphate (TMPP) and 2-ethylhexyl diphenyl phosphate (EHDP) together with alkyl tris(2-ethylhexyl) phosphate (TEHP) were not detected in any of the effluents. Advanced oxidation processes (UV/H2O2 and O3) were applied to investigate the degradability of recalcitrant OPFRs in WWTP effluents. Those detected in the effluent sample (TCEP, TCIPP, TDCPP, tributyl phosphate (TNBP), tri-iso-butyl phosphate (TIBP) and tris(2-butoxyethyl) phosphate (TBOEP)) had very low direct UV-C photolysis rates. TBOEP, TNBP and TIBP were degraded by UV/H2O2 and O3. Chlorinated compounds TCEP, TDCPP and TCIPP were the most recalcitrant OPFR to the advanced oxidation processes applied. The study provides information on the partitioning and degradability pathways of OPFR within conventional activated sludge WWTPs.

Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alternatives for PBDEs

Three oligomeric organophosphorus flame retardants (o-PFRs), eight monomeric PFRs (m-PFRs), tetrabromobisphenol A (TBBPA), and polybrominated diphenyl ethers (PBDEs) were identified and quantified in surface soils and river sediments around the e-waste recycling area in Bui Dau, northern Vietnam. Around the e-waste recycling workshops, 1,3-phenylene bis(diphenyl phosphate) (PBDPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), triphenyl phosphate (TPHP), TBBPA, and PBDEs were dominant among the investigated flame retardants (FRs). The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs were 6.6–14000ng/g-dry, <2–1500ng/g-dry, 11–3300ng/g-dry, <5–2900ng/g-dry, and 67–9200ng/g-dry in surface soils, and 4.4–78ng/g-dry, <2–20ng/g-dry, 7.3–38ng/g-dry, 6.0–44ng/g-dry and 100–350ng/g-dry in river sediments. Near the open burning site of e-waste, tris(methylphenyl) phosphate (TMPP), (2-ethylhexyl)diphenyl phosphate (EHDPP), TPHP, and the total PBDEs were abundantly with respective concentrations of <2–190ng/g-dry, <2–69ng/g-dry, <3–51ng/g-dry and 1.7–67ng/g-dry in surface soils. Open storage and burning of e-waste have been determined to be important factors contributing to the emissions of FRs. The environmental occurrence of emerging FRs, especially o-PFRs, indicates that the alternation of FRs addition in electronic products is shifting in response to domestic and international regulations of PBDEs. The emissions of alternatives from open storage and burning of e-waste might become greater than those of PBDEs in the following years. The presence and environmental effects of alternatives should be regarded as a risk factor along with e-waste recycling.