Concentration levels and ecological risk assessment of typical organophosphate esters in representative surface waters of a megacity.

Organophosphate esters (OPEs) have been widely used as flame retardants and plasticizers in consumer and industrial products. They have been found to have numerous exposure hazards. Recently, several OPEs have been detected in surface waters around the world, which may pose potential ecological risks to freshwater organisms. In this study, the concentration, spatial variation, and ecological risk of 15 OPEs in the Beiyun and Yongding rivers were unprecedentedly investigated by the ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) and risk quotient (RQ) method. The result showed that triethyl phosphate (TEP), tri (2-chloroisopropyl) phosphate (TCPP) were the most abundant OPEs with average concentrations of 55.53 ng/L and 42.29 ng/L, respectively. The concentrations of OPEs in the Beiyun River are higher than in the Yongding River, and their levels were higher in densely populated and industrial areas. The risk assessment showed that there was insignificant from OPEs to freshwater organisms in these rivers (RQs <0.1). The risk was higher downstream than upstream, which was related to human-intensive industrial activities downstream in the Yongding River. The ecological risk of OPEs in surface waters worldwide was estimated by joint probability curves (JPCs), and the result showed that there was a moderate risk for tri (2-chloroethyl) phosphate (TCEP), a low risk for trimethyl phosphate (TMP), and insignificant for other OPEs. In addition, the QSAR-ICE-SSD model was used to calculate the hazardous concentration for 5% (HC5). This result validated the feasibility and accuracy of this model in predicting acute data of OPEs and reducing biological experiments on the toxicity of OPEs. These results revealed the ecological risk of OPEs and provided the scientific basis for environmental managers.

Exposure to organophosphate esters and maternal-child health.

Organophosphate esters (OPEs) are a class of chemicals now widely used as flame retardants and plasticizers after the phase-out of polybrominated diphenyl ethers (PBDEs). However, OPEs carry their own risk of developmental toxicity, which poses concern for recent birth cohorts as they have become ubiquitous in the environment. In this review, we summarize the literature evaluating the association between OPE exposure and maternal, perinatal, and child health outcomes. We included original articles investigating associations of OPE exposure with any health outcome on pregnant women, newborns, children, and adolescents. We found 48 articles on this topic. Of these, five addressed maternal health and pregnancy outcomes, 24 evaluated prenatal OPE exposure and child health, 18 evaluated childhood OPE exposure and child/adolescent health, and one article evaluated both prenatal and childhood OPE exposure. These studies suggest that OPE exposure is possibly associated with a wide range of adverse health outcomes, including pregnancy loss, altered gestational duration and smaller birthweight, maternal and neonatal thyroid dysfunction, child metabolic dysregulation and abnormal growth, impaired neurodevelopment, and changes in immune response. Many of the reported outcomes associated with OPE exposure varied by child sex. Findings also varied substantially by OPE metabolite and exposure time. The OPEs most frequently measured, detected, and found to be associated with health outcomes were triphenyl phosphate (TPHP, metabolized to DPHP) and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP, metabolized to BDCIPP). The extensive range of health outcomes associated with OPEs raises concern about their growing use in consumer products; however, these findings should be interpreted considering the limitations of these epidemiological studies, such as possible exposure misclassification, lack of generalizability, insufficient adjustment for covariates, and failure to consider chemical exposures as a mixture.

Association of co-exposure to organophosphate esters and per- and polyfluoroalkyl substances and mixture with cardiovascular-kidney-liver-metabolic biomarkers among Chinese adults.

BACKGROUND: Organophosphate esters (OPEs) and Per- and polyfluoroalkyl substances (PFAS) are ubiquitous environmental contaminants with common exposure sources, leading to their widespread presence in human body. However, evidence on co-exposure to OPEs and PFAS and its impact on cardiovascular-kidney-liver-metabolic biomarkers remains limited. METHODS: In this cross-sectional study, 467 adults were enrolled from January to May 2022 during physical visits in Shijiazhuang, Hebei province. Eleven types of OPEs and twelves types of PFAS were detected, among which eight OPEs and six PFAS contaminants were detected in more than 60% of plasma samples. Seventeen biomarkers were assessed to comprehensively evaluate the cardiovascular-kidney-liver-metabolic function. Multiple linear regression, multipollutant models with sparse partial least squares, and Bayesian kernel machine regression (BKMR) models were applied to examine the associations of individual OPEs and PFAS and their mixtures with organ function and metabolism, respectively. RESULTS: Of the over 400 exposure-outcome associations tested when modelling, we observed robust results across three models that perfluorohexanoic acid (PFHxS) was significantly positively associated with alanine aminotransferase (ALT), aspartate aminotransferase (AST), total bilirubin (TBIL), and indirect bilirubin (IBIL). Perfluorononanoic acid was significantly associated with decreased AST/ALT and increased very-low-density lipoprotein cholesterol levels. Besides, perfluorodecanoic acid was correlated with increased high lipoprotein cholesterol and perfluoroundecanoic acid was consistently associated with lower glucose level. BKMR analysis showed that OPEs and PFAS mixtures were positively associated with IBIL and TBIL, among which PFHxS was the main toxic chemicals. CONCLUSIONS: Our findings suggest that exposure to OPEs and PFAS, especially PFHxS and PFNA, may disrupt organ function and metabolism in the general population, providing insight into the potential pathophysiological mechanisms of OPEs and PFAS co-exposure and chronic diseases.

Sex-specific effects of prenatal organophosphate ester (OPE) metabolite mixtures and adverse infant birth outcomes in the maternal and developmental risks from environmental and social stressors (MADRES) pregnancy cohort.

BACKGROUND: Organophosphate esters (OPEs) are used as flame retardants and plasticizers in various consumer products. Limited prior research suggests sex-specific effects of prenatal OPE exposures on fetal development. We evaluated overall and sex-specific associations between prenatal OPE exposures and gestational age (GA) at birth and birthweight for gestational age (BW for GA) z-scores among the predominately low-income, Hispanic MADRES cohort. METHODS: Nine OPE metabolite concentrations were measured in 421 maternal urine samples collected during a third trimester visit (GA = 31.5 ± 2.0 weeks). We examined associations between single urinary OPE metabolites and GA at birth and BW for GA z-scores using linear regression models and Generalized Additive Models (GAMs) and effects from OPE mixtures using Bayesian Kernel Machine Regression (BKMR). We also assessed sex-specific differences in single metabolite analyses by evaluating statistical interactions and stratifying by sex. RESULTS: We did not find significant associations between individual OPE metabolites and birth outcomes in the full infant sample; however, we found that higher bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) was associated with earlier GA at birth among male infants (p = 0.04), and a nonlinear, inverted U-shape association between the sum of dibutyl phosphate and di-isobutyl phosphate (DNBP + DIBP) and GA at birth among female infants (p = 0.03). In mixtures analysis, higher OPE metabolite mixture exposures was associated with lower GA at birth, which was primarily driven by female infants. No associations were observed between OPE mixtures and BW for GA z-scores. CONCLUSION: Higher BDCIPP and DNBP + DIBP concentrations were associated with earlier GA at birth among male and female infants, respectively. Higher exposure to OPE mixtures was associated with earlier GA at birth, particularly among female infants. However, we saw no associations between prenatal OPEs and BW for GA. Our results suggest sex-specific impacts of prenatal OPE exposures on GA at birth.

Penetration of Organophosphate Triesters and Diesters across the Blood-Cerebrospinal Fluid Barrier: Efficiencies, Impact Factors, and Mechanisms.

The penetration of organophosphate triesters (tri-OPEs) and diesters (di-OPEs) across the blood-brain barrier and their influencing factors remain unclear in humans. In this study, 21 tri-OPEs and 8 di-OPEs were measured in 288 paired serum and cerebrospinal fluid (CSF) samples collected in Jinan, China. Six tri-OPEs were frequently detected in both serum and CSF, with median concentrations ranging from 0.062 to 1.62 and 0.042-1.11 ng/mL, respectively. Their penetration efficiencies across the blood-CSF barrier (BCSFB) (RCSF/serum, CCSF/Cserum) were calculated at 0.667-2.80, and these efficiencies first increased and then decreased with their log Kow values. The reduced penetration efficiencies of triphenyl phosphate (TPHP) and 2-ethylhexyl diphenyl phosphate (EHDPP) may be attributed to their strong binding affinities for human serum albumin and p-glycoprotein due to their high hydrophobicity and aryl structure, as indicated by molecular docking. This suggests that active efflux transport may be involved in the penetration of TPHP and EHDPP in addition to passive diffusion similar to the other four tri-OPEs. Di-OPEs were found in few serum samples and even fewer CSF samples, indicating their limited BCSFB permeability. This may be due to their high polarity, low hydrophobicity, and ionic state in blood. This study has important implications for understanding the neurotoxicity of tri-OPEs and di-OPEs and the underlying mechanisms.

Exposure to Novel Brominated Flame Retardants and Organophosphate Esters and Associations with Thyroid Cancer Risk: A Case-Control Study in Eastern China.

Novel brominated flame retardant (NBFR) and organophosphate ester (OPE) exposure may engender adverse effects on human health. However, present epidemiological information regarding the effects of such exposure is limited and controversial. In this case-control study, 481 serum samples were collected from patients with thyroid cancer (n = 242) and healthy controls (n = 239) in Shandong Province, eastern China. The levels of NBFRs and OPEs, thyroid hormones, and serum lipid parameters were measured in all the participants. Pentabromotoluene, 2,3-dibromopropyl 2,4,6 tribromophenyl ether, decabromodiphenylethane (DBDPE), tris (2-chloroethyl) phosphate (TCEP), and triphenyl phosphate (TPP) were widely detected (detection frequency > 60%) in all the participants. A significantly high risk association was found between exposure of NBFRs and OPEs (namely 1,2,3,4,5-pentabromobenzene, DBDPE, tri-n-propyl phosphate, tri[(2R)-1-chloro-2-propyl] phosphate, tris (1,3-dichloro-2-propyl) phosphate, and tris (2-butoxyethyl) phosphate) and thyroid cancer in both males and females. In the females of the control group, TCEP levels exhibited a significantly positive association with thyroid-stimulating hormone and a negative association with triiodothyronine (T3), free triiodothyronine (FT3), and free thyroxine (FT4) levels. Weighted quantile sum regression evaluated the mixed effects of the compounds on thyroid hormones levels and thyroid cancer. As a result, TPP accounted for the majority of the T3, thyroxine, and FT3 amounts. Our results suggest that NBFR and OPE exposure contributes to alterations in thyroid function, thereby increasing thyroid cancer risk.

Stormwater Bioretention Cells Are Not an Effective Treatment for Persistent and Mobile Organic Compounds (PMOCs).

Bioretention cells are a stormwater management technology intended to reduce the quantity of water entering receiving bodies. They are also used to reduce contaminant releases, but their performance is unclear for hydrophilic persistent and mobile organic compounds (PMOCs). We developed a novel eight-compartment one-dimensional (1D) multimedia model of a bioretention cell ("Bioretention Blues") and applied it to a spike and recovery experiment conducted on a system near Toronto, Canada, involving PMOC benzotriazole and four organophosphate esters (OPEs). Compounds with (log DOC) (organic carbon-water distribution coefficients) < ∼2.7 advected through the system, resulting in infiltration or underdrain flow. Compounds with log DOC > 3.8 were mostly sorbed to the soil, where subsequent fate depended on transformation. For compounds with 2.7 ≤ log DOC ≤ 3.8, sorption was sensitive to event size and compound-specific diffusion parameters, with more sorption expected for smaller rain events and for compounds with larger diffusion coefficients. Volatilization losses were minimal for all compounds tested. Direct uptake by vegetation also played a negligible role regardless of the compounds' physicochemical properties. Nonetheless, model simulations showed that vegetation could play a role by increasing transpiration, thereby increasing sorption to the bioretention soil and reducing PMOC release. Model results suggest design modifications to bioretention cells.

Microplastics in freshwater sediments: Analytical methods, temporal trends, and risk of associated organophosphate esters as exemplar plastics additives.

It has been estimated that over 28 million tonnes of plastics end up in water bodies annually. These plastics degrade into microplastics (MPs), which along with microbeads and MPs from other sources such as wastewater treatment plants continue to threaten the aquatic system. At such small sizes, and corresponding larger surface areas per unit mass/volume, MPs exhibit enhanced capacity for absorbing and desorbing toxic chemicals/additives. Therefore, MPs can serve as vectors through which additives as well as other persistent, bio-accumulative, and toxic chemicals can enter the food chain. Additives are a significant component of most plastic products with some identified as hazardous to health and the environment. One group of additives that has continued to attract interest is organophosphate esters (OPEs), which are used both as flame retardants and plasticizers. Some of these OPEs are suspected carcinogens and endocrine disruptors and have been reported to exert serious toxic effects on freshwater biota. Separate studies on the presence and fate in the freshwater environment of these additives and MPs have emerged recently. However, no studies exist that examine the extent to which plastics additives such as OPEs in sediments are sorbed to MPs as opposed to the sediment itself. This has potentially important implications for the bioavailability of such additives and studies to examine this are recommended. This paper reviews critically the current state-of-knowledge on MPs in freshwater sediments, methods for their analysis, as well as their occurrence, temporal trends, and risks to the freshwater aquatic environment. Moreover, to facilitate the study of additives associated with MPs that have been extracted from sediments, we consider the possible effect of MP isolation methods on the determination of concentrations of associated additives like OPEs.

Industrial Production of Organophosphate Flame Retardants (OPFRs): Big Knowledge Gaps Need to Be Filled?

Since the phase-out of traditional halogenated flame retardants (HFRs), interests of research are gradually being shifted to organophosphate flame retardants (OPFRs), and this can be reflected by the increasing number of publications on OPFRs year by year. Here, an extensive survey is conducted in an attempt to generate a list of OPFRs that are being produced in factories, and to investigate the annual production volume (APV). This survey suggests that at least n = 56 OPFR monomers and n = 62 OPFR mixtures are being currently produced in 367 factories around the world, and 201 out of them are in Mainland China. APV of OPFRs was estimated as 598,422 metric tons, and this number could be underestimated due to the limitation of available information. We also notice that current researches are confined to a limited number of OPFRs, especially for OP esters (OPEs), and other OPFRs with different structures from OPEs has been rarely studied. Based on all the collected datasets, we provide five recommendations for how to proceed with future research to more comprehensively understand the currently-produced OPFRs in the environment.

Presence of organophosphate flame retardants (OPEs) in different functional areas in residential homes in Beijing, China.

The production and application of organophosphate esters (OPEs) have dramatically increased in recent years due to their use as a replacement for brominated flame retardants. In this study, 13 OPEs (Σ13OPEs) were analyzed in indoor air samples from kitchens and living rooms in 14 residential homes in Beijing, China. The concentrations of Σ13OPEs in kitchen air samples (mean: 13 ng/m3) were significantly (p < 0.05) higher than in living room air samples (5.0 ng/m3). In addition, paired window surface organic film samples were collected and analyzed to investigate film-air partitioning, exhibiting a mean concentration of Σ13OPEs of 4100 ng/m2. The congener profiles showed that tris(2-chloroisopropyl) phosphate (TCPP) was the predominant compound in both window film samples (48%) and the corresponding indoor air sample (56%). The estimated daily intakes (EDI) of OPEs via indoor air inhalation were 2.8 and 1.4 ng/kg/day for infants and adults, respectively, both of which are below the reference dose values (RfDs). Overall, these findings indicate that OPEs in the indoor air environment of residential homes in Beijing are not likely to pose a health risk to the general population.

Rain Amplification of Persistent Organic Pollutants.

Scavenging of gas- and aerosol-phase organic pollutants by rain is an efficient wet deposition mechanism of organic pollutants. However, whereas snow has been identified as a key amplification mechanism of fugacities in cold environments, rain has received less attention in terms of amplification of organic pollutants. In this work, we provide new measurements of concentrations of perfluoroalkyl substances (PFAS), organophosphate esters (OPEs), and polycyclic aromatic hydrocarbons (PAHs) in rain from Antarctica, showing high scavenging ratios. Furthermore, a meta-analysis of previously published concentrations in air and rain was performed, with 46 works covering different climatic regions and a wide range of chemical classes, including PFAS, OPEs, PAHs, polychlorinated biphenyls and organochlorine compounds, polybromodiphenyl ethers, and dioxins. The rain-aerosol (KRP) and rain-gas (KRG) partition constants averaged 105.5 and 104.1, respectively, but showed large variability. The high field-derived values of KRG are consistent with adsorption onto the raindrops as a scavenging mechanism, in addition to gas-water absorption. The amplification of fugacities by rain deposition was up to 3 orders of magnitude for all chemical classes and was comparable to that due to snow. The amplification of concentrations and fugacities by rain underscores its relevance, explaining the occurrence of organic pollutants in environments across different climatic regions.

Novel Bayesian Method to Derive Final Adjusted Values of Physicochemical Properties: Application to 74 Compounds.

Accurate values of physicochemical properties are essential for screening semivolatile organic compounds for human and environmental hazard and risk. In silico approaches for estimation are widely used, but the accuracy of these and measured values can be difficult to ascertain. Final adjusted values (FAVs) harmonize literature-reported measurements to ensure consistency and minimize uncertainty. We propose a workflow, including a novel Bayesian approach, for estimating FAVs that combines measurements using direct and indirect methods and in silico values. The workflow was applied to 74 compounds across nine classes to generate recommended FAVs (FAVRs). Estimates generated by in silico methods (OPERA, COSMOtherm, EPI Suite, SPARC, and polyparameter linear free energy relationships (pp-LFER) models) differed by orders of magnitude for some properties and compounds and performed systematically worse for larger, more polar compounds. COSMOtherm and OPERA generally performed well with low bias although no single in silico method performed best across all compound classes and properties. Indirect measurement methods produced highly accurate and precise estimates compared with direct measurement methods. Our Bayesian method harmonized measured and in silico estimated physicochemical properties without introducing observable biases. We thus recommend use of the FAVRs presented here and that the proposed Bayesian workflow be used to generate FAVRs for SVOCs beyond those in this study.

Graphene-triphenyl phosphate (TPP) co-exposure in the marine environment: Interference with metabolism and immune regulation in mussel Mytilus galloprovincialis.

Both immune regulation and endocrine systems are great challenges to marine organisms, and effective protocols for determining these adverse outcome pathways are limited, especially in vivo. The increasing usage of graphene nanomaterials can lead to the frequent exposure to marine organisms. Triphenyl phosphate (TPP), an organophosphate flame retardant, is frequently detected in natural environments. In this study, the combined toxic effects of co-exposure to graphene and TPP was investigated in Mytilus galloprovincialis using computational toxicology and multi-omics technology. Noticeably, graphene could disturb the membrane stability and increase the tissue accumulation of TPP. The adsorption behavior of TPP on graphene could inhibit the surface activity of graphene. In the digestive gland, transcriptomics analysis revealed the down-regulated genes in graphene + TPP treatment, including glyceraldehyde-3-phosphate dehydrogenase (GAPDH), sorbitol dehydrogenase (SORD), glutathione s-transferase mu 3 (GSTM3) and 4-aminobutyrate aminotransferase (ABAT), were mainly associated with oxidative stress and energy metabolism. Moreover, metabolic responses indicated that graphene + TPP could cause disturbances in energy metabolism and osmotic regulation marked by differentially altered ATP, glucose and taurine in mussels. These data underline the need for further knowledge on the potential interactions of nanomaterials with existing contaminants in marine organisms.

Application of Hi-throat/Hi-volume SPE technique in analyzing occurrence, influencing factors and human health risk of organophosphate esters (OPEs) in drinking water of China.

Organophosphate esters (OPEs) are typical industrial additives widely applied in various industrial and household products, but they may pollute drinking water. In the present study, the occurrence of OPEs in drinking water was analyzed. For this purpose, 25 drinking water samples were collected from households in 25 cities in China. The concentrations of OPEs were accurately determined according to a high-throughput organic analysis testing combined with high-volume solid phase extraction (Hi-throat/Hi-volume SPE) technique. Through this technique, nine OPEs were detected, with spiked recoveries from 77% to 101%, and their total concentrations (ΣOPEs) ranging from 46.8 to 251 (average 126) ng L-1. The detection frequencies of the selected OPEs determined via Hi-throat/Hi-volume SPE were 88.0%-100%, which are much higher than those previously reported. The limit of detections of the OPEs was low at < 0.01 ng L-1, which could be mainly attributed to the high volume of accumulated drinking water (>20 L). OPEs in drinking water presented a decreasing trend from cities in coastal provinces to inland cities of China. Redundancy analysis showed that the concentrations of OPEs in drinking water were significantly influenced by economic-demographic influencing factors. The non-carcinogenic and lifetime carcinogenic risks (non-CR and CR) of the analyzed OPEs in drinking water were negligible for urban residents in China.

Monitoring the levels of brominated and organophosphate flame retardants in passenger cars: Utilisation of car air filters as active samplers.

Filters in residential and office air conditioning (A/C) systems have been used as sampling devices for monitoring different pollutants. However, cabin air filters (CAFs) in the A/C system of passenger cars have not been utilised for this purpose. In this study, we collected 22 used CAFs from passenger cars in Hanoi, Vietnam to analyse for 8 polybrominated diphenyl ethers (PBDEs) and 10 organophosphate esters (OPEs). All the analytes were detected in more than 50% of samples with the exception of BDE153 and BDE154. The average concentrations of ∑10OPEs and ∑8BDEs in the captured dust were 2600 and 40 ng/g, respectively with Tris (1-chloro-2-propyl) phosphate (TCIPP) and BDE209 as the dominant congener in OPE and BDE groups, respectively. CAFs are a potential tool to qualitatively assess the levels of semi-volatile chemicals in suspended dust in cars as a screening step for exposure assessment of those chemicals.

Presence and human exposure assessment of organophosphate flame retardants (OPEs) in indoor dust and air in Beijing, China.

In this study, levels of 14 organophosphate flame retardants (OPEs) were measured in 101 indoor dust samples collected from dormitories, residential homes, and offices in Beijing, China. In addition, paired air samples were also analyzed to evaluate any correlation between OPE levels in air and that in corresponding dust samples. The Σ14OPEs levels substantially varied between individual samples. Thereinto, significantly higher OPE levels were found in dust samples from office (mean value: 14 µg g-1), comparing to that in dust samples from residential homes (mean value: 5.9 µg g-1) and dormitories (mean value: 6.9 µg g-1). Congener profiles of OPEs in dust samples from different microenvironments indicated that tris (2-chloroethyl) phosphate (TCEP) was the dominant OPE in the office samples, followed by tris (2-chloroisopropyl) phosphate (TCPP). In contrast, TCPP was the dominant OPE in the residential home and dormitory samples, followed by TCEP. The mean concentration (range) of Σ14OPEs in the 15 air samples was 5.2 (1.0-20) ng m-3, and TCPP was the dominated congener in these samples. The concentration of TCEP and TCPP in air was positively correlated with that in corresponding indoor dust, and OPEs with highly saturated vapor pressures have higher fractions in the air than that in the dust. The estimated daily intakes through dust ingestion, dermal absorption, and inhalation indicated that the exposure to OPEs in indoor environments do not result in significant health risk for the general population in Beijing.

Carbohydrates and Charges on Oligo(phenylenethynylenes): Towards the Design of Cancer Bullets.

Two new tetralkylammonium-OPEs, bearing one or two positively charged groups directly linked to the aromatic residues and two ß-d-glucopyranose terminations, were synthesized. Their peculiar structural features, joining the biologically relevant sugar moieties, flat aromatic cores and positive charges, make these luminescent dyes soluble in aqueous media and able to strongly interact with DNA. As a result of UV/Vis spectral variations, DNA melting temperature measures, viscometric titrations and induced CD, we propose a partial insertion of the OPEs aromatic core into the helix, stabilized by glucose H-bonding with the groups accessible from the grooves. This interaction leads to the quenching of the OPE luminescence due to guanine reduction. The biocompatibility of the monocationic OPE with healthy and cancer cells, and the reduction of proliferation in HEp-2 cancer cells induced by the dicationic one, make this class of compounds promising for future biological applications.

Organophosphorus esters (OPEs) in PM2.5 in urban and e-waste recycling regions in southern China: concentrations, sources, and emissions.

Organophosphate esters (OPEs) are novel ubiquitous contaminants that are attracting growing concern, but their emissions into the environment are still poorly understood. In this study, 12 OPEs were measured in fine particulate matter (PM2.5) at 20 industrial sites in an urban region and four e-waste recycling facilities in a rural region in southern China. There was no significant difference in the concentrations of ∑OPEs between the urban region (519-62,747 pg/m3, median = 2854 pg/m3) and the rural e-waste region (775-13,823 pg/m3, 3321 pg/m3). High OPE concentrations in urban PM2.5 were generally associated with the electrical, electronic, plastic, and chemical industries. There were no significant correlations between most OPEs in these two regions, suggesting different emission mechanisms. The average emissions of ∑OPEs estimated using a simplified dispersion model were 73.0 kg/yr from the urban industrial point sources and 33.2 kg/yr from the e-waste recycling facilities. The estimated emission inventory from industrial activities in the whole city (3228-4452 kg/yr) was approximately 30-fold higher than that from the e-waste recycling (133 kg/yr) facilities because urban region has a much larger industrial scale. To the best of our knowledge, this is the first effort to model the emissions of OPEs from industrial and e-waste recycling activities to the atmosphere.

Carbo-biphenyls and Carbo-terphenyls: Oligo(phenylene ethynylene) Ring Carbo-mers.

Ring carbo-mers of oligo(phenylene ethynylene)s (OPEn, n=0-2), made of C2 -catenated C18 carbo-benzene rings, have been synthesized and characterized by NMR and UV-vis spectroscopy, crystallography and voltammetry. Analyses of crystal and DFT-optimized structures show that the C18 rings preserve their individual aromatic character according to structural and magnetic criteria (NICS indices). Carbo-terphenyls (n=2) are reversibly reduced at ca. -0.42 V/SCE, i.e. 0.41 V more readily than the corresponding carbo-benzene (-0.83 V/SCE), thus revealing efficient inter-ring π-conjugation. An accurate linear fit of E1/2red1 vs. the DFT LUMO energy suggests a notably higher value (-0.30 V/SCE) for a carbo-quaterphenyl congener (n=3). Increase with n of the effective π-conjugation is also evidenced by a red shift of two of the three main visible light absorption bands, all being assigned to TDDFT-calculated excited states, one of them restricting to a HOMO→LUMO main one-electron transition.

Prenatal exposures to organophosphate ester metabolites and early motor development in the MADRES cohort.

Organophosphate esters (OPEs) are increasingly considered neurotoxicants which may impact gross and fine motor development. We evaluated associations between prenatal OPE exposures and infant motor development. Third trimester urinary concentrations of nine OPE metabolites were measured in 329 mother-infant dyads participating in the Maternal And Developmental Risks from Environmental and Social Stressors (MADRES) cohort. Child gross and fine motor development at 6, 9, 12, and 18-months were assessed with the Ages and Stages Questionnaire-3 (ASQ-3) and operationalized in models using dichotomous instrument-specific cutoffs for typical motor development. Five OPE metabolites with >60% detection were specific-gravity-adjusted, natural log-transformed, and modeled continuously, while four metabolites with <60% detection were modeled dichotomously (detected/not-detected). We fit mixed effects logistic regression between OPE metabolites and fine/gross motor development and assessed sex-specific effects using a statistical interaction term and sex-stratified models. Among children, 31% and 23% had gross and fine motor scores, respectively, below the ASQ-3 at-risk cutoffs at least once across infancy. A doubling in prenatal diphenyl phosphate (DPHP) exposure was associated with 26% increased odds of potential fine motor delays (ORfine = 1.26, 95% CI: 1.02, 1.57, p = 0.04). We also observed significant interactions by infant sex for associations of detected dipropyl phosphate (DPRP) with gross motor development (pinteraction = 0.048) and detected bis(1-chloro-2-propyl) phosphate (BCIPP) with fine motor development (pinteraction = 0.02). Females had greater odds of potential motor delays for both detected DPRP (females vs males ORgross (95% CI) = 1.48 (0.71, 3.09), p = 0.30 vs 0.27 (0.06, 1.29), p = 0.10) and detected BCIPP (females vs males ORfine (95% CI) = 2.72 (1.27, 5.85), p = 0.01 vs 0.76 (0.31, 1.90), p = 0.56). There were no other significant associations between other metabolites and motor development, despite similar patterns. We found evidence of adverse effects of prenatal OPE exposures on infant motor development with greater adverse effects among female infants with some OPE metabolites.