Bioretention Design Modifications Increase the Simulated Capture of Hydrophobic and Hydrophilic Trace Organic Compounds.

Stormwater rapidly moves trace organic contaminants (TrOCs) from the built environment to the aquatic environment. Bioretention cells reduce loadings of some TrOCs, but they struggle with hydrophilic compounds. Herein, we assessed the potential to enhance TrOC removal via changes in bioretention system design by simulating the fate of seven high-priority stormwater TrOCs (e.g., PFOA, 6PPD-quinone, PAHs) with log KOC values between -1.5 and 6.74 in a bioretention cell. We evaluated eight design and management interventions for three illustrative use cases representing a highway, a residential area, and an airport. We suggest two metrics of performance: mass advected to the sewer network, which poses an acute risk to aquatic ecosystems, and total mass advected from the system, which poses a longer-term risk for persistent compounds. The optimized designs for each use case reduced effluent loadings of all but the most polar compound (PFOA) to <5% of influent mass. Our results suggest that having the largest possible system area allowed bioretention systems to provide benefits during larger events, which improved performance for all compounds. To improve performance for the most hydrophilic TrOCs, an amendment like biochar was necessary; field-scale research is needed to confirm this result. Our results showed that changing the design of bioretention systems can allow them to effectively capture TrOCs with a wide range of physicochemical properties, protecting human health and aquatic species from chemical impacts.

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.

Textile Washing Conveys SVOCs from Indoors to Outdoors: Application and Evaluation of a Residential Multimedia Model.

Indoor environments have elevated concentrations of numerous semivolatile organic compounds (SVOCs). Textiles provide a large surface area for accumulating SVOCs, which can be transported to outdoors through washing. A multimedia model was developed to estimate advective transport rates (fluxes) of 14 SVOCs from indoors to outdoors by textile washing, ventilation, and dust removal/disposal. Most predicted concentrations were within 1 order of magnitude of measurements from a study of 26 Canadian homes. Median fluxes to outdoors [µg·(year·home)-1] spanned approximately 4 orders of magnitude across compounds, according to the variability in estimated aggregate emissions to indoor air. These fluxes ranged from 2 (2,4,4'-tribromodiphenyl ether, BDE-28) to 30 200 (diethyl phthalate, DEP) for textile washing, 12 (BDE-28) to 123 200 (DEP) for ventilation, and 0.1 (BDE-28) to 4200 (bis(2-ethylhexyl) phthalate, DEHP) for dust removal. Relative contributions of these pathways to the total flux to outdoors strongly depended on physical-chemical properties. Textile washing contributed 20% tris-(2-chloroisopropyl)phosphate (TCPP) to 62% tris(2-butoxyethyl)phosphate (TBOEP) on average. These results suggest that residential textile washing can be an important transport pathway to outdoors for SVOCs emitted to indoor air, with implications for human and ecological exposure. Interventions should try to balance the complex tradeoff of textile washing by minimizing exposures for both human occupants and aquatic ecosystems.

Trace Organic Contaminant Transfer and Transformation in Bioretention Cells: A Field Tracer Test with Benzotriazole.

Bioretention cells can effectively infiltrate stormwater runoff and partly remove conventional water contaminants. A field tracer injection experiment in a conventionally designed bioretention cell was used to investigate the fate of benzotriazole, a model trace organic contaminant, during and between runoff events. Moderate (29%) benzotriazole load reductions were measured during the 6 h long injection experiment. The detection of 1-methyl benzotriazole, hydroxy benzotriazole, and methoxy benzotriazole provided in situ evidence of some rapid benzotriazole microbial transformation during the tracer test and more importantly between the events. The detection of benzotriazole alanine and benzotriazole acetyl alanine also showed fast benzotriazole phytotransformation to amino acid conjugates during the tracer test and suggests further transformation of phytotransformation products between events. These data provide conclusive full-scale evidence of benzotriazole microbial and phytotransformation in bioretention cells. Non-target chemical analysis revealed the presence of a diverse range of trace organic contaminants in urban runoff and exiting the bioretention cell, including pesticides and industrial, household, and pharmaceutical compounds. We have demonstrated the in situ potential of urban green infrastructure such as bioretention cells to eliminate polar trace organic contaminants from stormwater. However, targeted design and operation strategies, for example, hydraulic control and the use of soil amendments, should be incorporated for improved bioretention cell performance for such compounds.

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.

Examining the Gas-Particle Partitioning of Organophosphate Esters: How Reliable Are Air Measurements?

Organophosphate esters (OPEs) in air have been found to be captured entirely on filters of typical active air samplers and thus designated as being in the particle phase. However, this particle fraction is unexpected, especially for more volatile tris(2-chloroethyl) phosphate (TCEP) and tris(chloroisopropyl) phosphate (TCIPP). We evaluated gas-particle partitioning in indoor and outdoor air for OPEs and polybrominated diphenyl ethers (PBDEs) using single-parameter models (Junge-Pankow, Harner-Bidleman) and poly-parameter linear free energy relationship (pp-LFER) models. We also used the pp-LFER to estimate filter-air partitioning in active air samplers. We found that all gas-particle partitioning models predicted that TCEP and TCIPP should be in the gas phase, contrary to measurements. The pp-LFER better accounted for OPE measurements than the single-parameter models, except for TCEP and TCIPP. Gas-particle partitioning of PBDEs was reasonably explained by all models. The pp-LFER for filter-air partitioning showed that gas-phase sorption to glass and especially quartz fiber filters used for active air samplers could account for up to 100% of filter capture and explain the high particle fractions reported for TCIPP, tris(1,3-dichloro-2-propyl) phosphate TDCIPP, and triphenyl phosphate TPhP, but not TCEP. The misclassification of gas-particle partitioning can result in erroneous estimates of the fraction of chemical subject to gas-phase reactions and atmospheric scavenging and, hence, atmospheric long-range transport.

Organophosphate Ester Transport, Fate, and Emissions in Toronto, Canada, Estimated Using an Updated Multimedia Urban Model.

Organophosphate esters (OPEs), used as flame retardants and plasticizers, occur at relatively high concentrations in urban air and surface waters. We tested the hypothesis that some OPEs could be considered persistent and mobile organic compounds (PMOCs), using the poly parameter linear free energy relationship-modified Multimedia Urban Model (ppLFER-MUM) in Toronto, Canada, as a case study. Modeled air emissions of ∑6OPEs of 3300 (190-190 000) kg yr-1 were 10-100 times higher than emissions of polychlorinated biphenyls (∑5PCBs) and polybrominated diphenyl ethers (∑5PBDEs). Model results suggested that measured ∑6OPE stream concentrations of ∼2000 ng L-1 originate from emissions to urban air transferred to water mostly via precipitation. Water transport removed 7-28% of total air inputs compared to 0.1-10% for PCBs and 2-10% for PBDEs. Chlorinated OPEs were efficiently transported via surface water due to their persistence and high solubility. Loadings of ∑6OPEs to Lake Ontario from wastewater treatment plants, streams, and atmospheric deposition were 70%, 18%, and 13%, respectively, of ∑6OPE loadings of 3100 (1200-45 000) kg yr-1. Our results support the hypothesis that three chlorinated OPEs, tris(2-chloroethyl)phosphate phosphate (TCEP), tris(chloroisopropyl)phosphate (TCiPP), and tris(1,3-dichloroisopropyl)phosphate (TDCiPP), fit the profile of PMOCs due to their mobility and persistence in surface waters.

Field study on the uptake pathways and their contributions to the accumulation of organophosphate esters, phthalates, and polycyclic aromatic hydrocarbons in upland rice.

Plant uptake of organic contaminants generally occurs through either root, gas-phase foliar, or particle-phase foliar uptake. Understanding these pathways is essential for food-system practitioners to reduce human exposures, and to clean contaminated-sites with phytoremediation. Herein, we conducted a field-based experiment using an improved specific exposure chamber to elucidate the uptake pathways of organophosphate esters, phthalates, and polycyclic aromatic compounds, and quantitatively assessed their contributions to organic contaminant accumulations in field-grown rice. For most target compounds, all three uptake pathways (root, foliar gas, and foliar particle uptakes) contributed substantially to the overall contaminant burden in rice. Compounds with lower octanol-water partition coefficients (Kow) were more readily translocated from roots to leaves, and compounds with higher octanol-air partition coefficients (Koa) tended to enter rice leaves mostly through particle deposition. Most compounds were mostly stored in the inner leaves (55.3-98.2 %), whereas the relatively volatile compounds were more readily absorbed by the waxy layer and then transferred to the inner leaves. Air particle desorption was a key process regulating foliar uptake of low-volatility compounds. The results can help us to better understand and predict the environmental fate of those contaminants, and develop more effective management strategies for reducing their human exposure through food ingestion.

Emissions and fate of organophosphate esters in outdoor urban environments.

Cities are drivers of the global economy, containing products and industries that emit many chemicals. Here, we use the Multimedia Urban Model (MUM) to estimate atmospheric emissions and fate of organophosphate esters (OPEs) from 19 global mega or major cities, finding that they collectively emitted ~81,000 kg yr-1 of ∑10OPEs in 2018. Typically, polar "mobile" compounds tend to partition to and be advected by water, while non-polar "bioaccumulative" chemicals do not. Depending on the built environment and climate of the city considered, the same compound behaves like either a mobile or a bioaccumulative chemical. Cities with large impervious surface areas, such as Kolkata, mobilize even bioaccumulative contaminants to aquatic ecosystems. By contrast, cities with large areas of vegetation fix and transform contaminants, reducing loadings to aquatic ecosystems. Our results therefore suggest that urban design choices could support policies aimed at reducing chemical releases to the broader environment without increasing exposure for urban residents.

Uptake, translocation, bioaccumulation, and bioavailability of organophosphate esters in rice paddy and maize fields.

Rice and maize are two main crops with different growth habits in Northeast China. To investigate the uptake, translocation, and accumulation of organophosphate esters (OPEs) in those two crops, we measured the OPE concentrations in their agricultural soil-crop systems during different growing seasons. OPE concentrations were higher in paddy (221 ± 62.0 ng/g) than in maize (149 ± 31.6 ng/g) soil, with higher OPE levels in the rhizosphere than in bulk soil for rice, and the opposite in maize. Two-step extractions were used to obtain the labile and stable adsorption components of OPEs. The stable-adsorbed OPEs were activated to be more bioavailable by root exudates as rice grew. OPEs in rice increased linearly with the growing period. The uptake and translocation processes of OPEs by crops were not well-explained by logKow alone, indicating other processes such as growth dilution are significant for understanding OPE levels in plant. The translocation factors of OPEs from nutritive to reproductive organs indicated that OPEs in rice seeds may follow the translocation from root to leaf and then transfer to grains. Two genera, Sphingomonas and Geobacter, associated with degradation of organophosphorus compounds were enriched in rhizosphere soils, indicating enhanced OPE degradation.

Identifying the contributions of root and foliage gaseous/particle uptakes to indoor plants for phthalates, OPFRs and PAHs.

Understanding the uptake pathways of organic chemicals in plants can help us use plants as biosentinels for human exposure, and as remediation tools for contaminated sites. Herein, we investigated the relative contributions of root and foliar (gas and particle) uptake pathways to indoor ornamental plants for phthalates (PAEs), organophosphorus flame retardants (OPFRs), and polycyclic aromatic hydrocarbons (PAHs). We looked at different kinds of indoor ornamental plants via pot and hydroponic control experiments, comparing the levels between their leaves and indoor air gaseous and particle phases, floor dust, and window film. Contributions of soil and foliage uptakes were calculated based on chemical concentrations in leaves of hydroponic and soil cultured plants and their mass uptake rates. Across all compounds, the contributions of root uptake to the chemicals in soil cultured plants ranged from 47.5 % to 88.5 %. We used binary first-order mass conservation equations to calculate the contributions of foliage uptake via gaseous and particle phases to the chemicals with similar Kow in plant leaves. Foliar uptake of PAEs occurred mainly via particle adsorption, for light PAHs via gaseous absorption, and for OPFRs via both particle and gaseous uptakes. Negative correlations between chemicals' foliage uptake ratios and their Kow and Koa values suggest that foliage uptake may be influenced by both chemical hydrophilicity and lipophilicity.

Bioretention Cells Provide a 10-Fold Reduction in 6PPD-Quinone Mass Loadings to Receiving Waters: Evidence from a Field Experiment and Modeling.

Road runoff to streams and rivers exposes aquatic organisms to complex mixtures of chemical contaminants. In particular, the tire-derived chemical 6PPD-quinone (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine-quinone) is acutely toxic to several species of salmonids, which are critical to fisheries, ecosystems, and Indigenous cultures. We therefore urgently require interventions that can reduce loadings of 6PPD-quinone to salmonid habitats. Herein, we conducted a spike and recovery experiment on a full-scale, mature bioretention cell to assess the efficacy of stormwater green infrastructure technologies in reducing 6PPD-quinone loadings to receiving waters. We then interpreted and extended the results of our experiment using an improved version of the "Bioretention Blues" contaminant transport and fate model. Overall, our results showed that stormwater bioretention systems can effectively mitigate >∼90% of 6PPD-quinone loadings to streams under most "typical" storm conditions (i.e., < 2-year return period). We therefore recommend that stormwater managers and other environmental stewards redirect stormwater away from receiving waters and into engineered green infrastructure systems such as bioretention cells.

Occurrence and distribution of organophosphate flame retardants in the typical soil profiles of the Tibetan Plateau, China.

The urbanization and development of Tibetan Plateau (TP) probably results in a significant contamination of organic pollutants, such as organophosphate flame retardants (OPFRs). However, there is a lack of monitoring and evaluation of their occurrence and risks in the soil of TP. We investigated the concentrations, vertical distributions, potential sources, and ecological risks of OPFRs in soil profiles from four regions of TP, China. The total concentrations of OPFRs in all soil samples ranged from 1.35 to 126 ng/g with a median of 12.6 ng/g. Relatively high concentrations were discovered in the top soils from Lhasa, suggesting a rising contamination around cities of TP due to anthropogenic disturbance. Tri-n-butyl phosphate (TNBP) was the dominant OPFRs followed by tris(2-chloroethyl) phosphate (TCEP). Vertical distribution of ΣOPFRs was discovered, especially at site Lhasa. Source apportionment based on principle component analysis and correlation analysis suggests that OPFRs in the TP soil mainly originate from atmospheric transport, while some OPFRs in the top soil may be also influenced by nearby sources. The vertical distributions of OPFRs in soil may be influenced by both soil and chemical properties, as well as their use. The ecological risk quotients (RQs) of 6 OPFRs in the TP soil were calculated, and most of their ecological risks were relatively low or negligible. However, for the worst-case scenario calculated by the 95th percentile concentrations, TNBP and tris(2-chloro-isopropyl) phosphate (TCIPP) at site Lhasa and cresyl diphenyl phosphate (CDP) at site Nagri had moderate risks. More attentions should be paid to the Tibetan Plateau in the future due to the rising ecological risks of OPFRs, especially to the areas around cities.

Ornamental houseplants as potential biosamplers for indoor pollution of organophosphorus flame retardants.

We investigated the occurrence, compositions, and partitioning behaviors of organophosphorus flame retardants (OPFRs) in indoor dust, air, and ornamental plants in Dalian, China, to evaluate the possibility of using houseplants as indoor biosamplers of OPFRs. The mean concentrations of OPFRs in the indoor air, dust, and plant samples were 14.9 ng/m3, 18,000 ng/g, and 345 ng/g, respectively. Tris(2-chloroisopropyl) phosphate (TCIPP) was the dominant congener in all kinds of samples. Significant correlation was found between the concentrations of tris(1,3-dichloroisopropyl) phosphate (TDCIPP) in indoor air and plants, suggesting that ornamental plant can be used as a sentinel for certain OPFRs in the indoor air. We developed a predictive model to assess the partitioning coefficients of OPFRs between indoor air and plant. The lipid content in leaf cuticle instead of leaf organic matter was used to improve the accuracy and reliability of this assessment. Using this model, we can estimate the OPFR concentrations in the indoor air based on their concentrations measured in the corresponding indoor plant. The estimated air concentrations were generally comparable with the measured concentrations, especially for those with octanol-air partition coefficient log Koa <11.6. Indoor plants can also provide a more holistic understanding of OPFR occurrence within a home due to the relatively long-term air-foliage partitioning. The results suggest that under certain conditions indoor ornamental plants have the potential to be used as the biosamplers of OPFRs in the indoor environment due to their convenience and low-cost.

Pet hair as a potential sentinel of human exposure: Investigating partitioning and exposures from OPEs and PAHs in indoor dust, air, and pet hair from China.

We investigated the levels, compositions, and partitioning behaviors of organophosphate esters (OPEs) and polycyclic aromatic hydrocarbons (PAHs) in indoor air, dust, and pet hair from North China, as well as their potential exposures for humans and pets. The mean OPE concentrations in the indoor air (n = 19), dust (n = 26), and pet hair (n = 29) samples were 52.1 ng/m3, 3510 ng/g, and 1440 ng/g; while the mean PAH concentrations were 369 ng/m3, 6000 ng/g, and 22.6 ng/g, respectively. The matrix-air partitioning of OPEs and PAHs may reach equilibrium for compounds with octanol-air partition coefficients (logKoa) between 7 and 11 for dust and logKoa < 12 for pet hair. Correlation analysis suggested that pet hair could be used as a sentinel for the exposure to certain PAHs, e.g., phenanthrene (PHE) or fluoranthene (FLA), via exposure to indoor air. This work suggests that pet hair may be a better sentinel than air and dust for human exposure to OPEs and PAHs across different indoor microenvironments. Estimated daily intakes (EDIs) to OPEs and PAHs via air inhalation, dust ingestion, and dermal absorption were calculated for children, adults, and pets. The median ΣEDIs for children, adults, and pets were 26.7, 5.40, and 55.0 ng/kg/day for ΣOPEs, and 68.8, 19.1, and 130 ng/kg/day for ΣPAHs, respectively. Air inhalation was the main exposure route to PAHs and OPEs with logKoa < 10, whereas dust ingestion was the main exposure route to those with logKoa > 10.

Evaluation of the OECD POV and LRTP screening tool for estimating the long-range transport of organophosphate esters.

Scientists and decision makers need accurate, accessible and fast tools to assess and prioritize the persistence (POV) and environmental long-range transport potential (LRTP) of chemicals. Here we evaluated the Organisation for Economic Co-operation and Development (OECD) POV and LRTP Screening Tool ("the Tool") with respect to the POV and LRTP estimates that the Tool provides for organophosphate esters (OPEs). We found that the use of default parameter values could significantly underestimate POV and LRTP values of OPEs and, potentially, other Persistent Mobile Organic Compounds (PMOCs), by not accounting for episodic atmospheric transport and poleward river-based transport in the northern hemisphere. Specifically, sensitivity and Monte Carlo uncertainty analyses indicate that non-chlorinated OPEs could be subject to LRTP when uncertainties in gas-particle partitioning and its implications for atmospheric degradation are considered, and chlorinated OPEs when river-based transport is considered. Further, the analyses showed strong dependence of results on the accuracy of the environmental half-lives used as input parameters. We suggest that the Tool could be modified to include an optional "Arctic (PMOC) LRTP setting" that incorporates episodic atmospheric and river-based transport as well as decreased environmental half-lives due to cold temperatures.

Projected declines in global DHA availability for human consumption as a result of global warming.

Docosahexaenoic acid (DHA) is an essential, omega-3, long-chain polyunsaturated fatty acid that is a key component of cell membranes and plays a vital role in vertebrate brain function. The capacity to synthesize DHA is limited in mammals, despite its critical role in neurological development and health. For humans, DHA is most commonly obtained by eating fish. Global warming is predicted to reduce the de novo synthesis of DHA by algae, at the base of aquatic food chains, and which is expected to reduce DHA transferred to fish. We estimated the global quantity of DHA (total and per capita) currently available from commercial (wild caught and aquaculture) and recreational fisheries. The potential decrease in the amount of DHA available from fish for human consumption was modeled using the predicted effect of established global warming scenarios on algal DHA production and ensuing transfer to fish. We conclude that an increase in water temperature could result, depending on the climate scenario and location, in a ~ 10 to 58% loss of globally available DHA by 2100, potentially limiting the availability of this critical nutrient to humans. Inland waters show the greatest potential for climate-warming-induced decreases in DHA available for human consumption. The projected decrease in DHA availability as a result of global warming would disproportionately affect vulnerable populations (e.g., fetuses, infants), especially in inland Africa (due to low reported per capita DHA availability). We estimated, in the worst-case scenario, that DHA availability could decline to levels where 96% of the global population may not have access to sufficient DHA.

Characteristics and risk assessment of organophosphorus flame retardants in urban road dust of Dalian, Northeast China.

We investigated the occurrence, distribution, and potential sources of 10 organophosphorus flame retardants (OPFRs) in road dust from the urban area of Dalian, China, as well as their associated human exposures and health risks. The total concentration of Σ10OPFRs ranged from 300 to 7480 ng/g with a median of 1600 ng/g. Relatively high concentrations were observed mainly near prosperous business districts or dense residential areas. Tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and triphenylphosphine oxide (TPPO) were detected in all dust samples. TCIPP was the dominant congener, followed by TPPO. It was found that traffic flow can obviously influence the concentration of OPFRs in road dust, suggesting vehicles may be the major sources of OPFRs in road dust, presumably from materials used in their interiors. Correlations between certain OPFRs and population density indicate a significant influence by anthropogenic activities on OPFR levels. The average daily doses (ADD) of Σ10OPFRs via ingestion, inhalation and dermal absorption from road dust were evaluated as 0.26 and 0.087 ng/(kg-bw·d) for children and adults respectively, with dust ingestion as the main exposure pathway of OPFRs. Although the exposure risk of OPFRs via road dust was relatively low in Dalian, further studies on the exposure of OPFRs are still necessary due to combined effects with other exposure pathways.