Triphenyl phosphate (TPhP) and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) are common organophosphate esters (OPEs), which are used as additives in various industries. These compounds have been widely detected in aquatic environment, raising concerns about their adverse effects on aquatic organisms. In order to protect aquatic ecosystems, a total of 7 species were selected for acute and chronic toxicity tests in this study. The results indicated that TPhP and TDCIPP exhibited varying degrees of toxicity to aquatic organisms. The 96-h LC50 values ranged from 1.088 mg/L to 1.574 mg/L for TPhP and from 2.027 mg/L to 17.855 mg/L for TDCIPP. The 28-d LC10 values ranged from 0.023 mg/L to 0.177 mg/L for TPhP and from 0.300 mg/L to 1.102 mg/L for TDCIPP. The tested toxicity data, combined with collected toxicity data, were used to investigate the predicted no-effect concentration in water (PNECwater) of TPhP and TDCIPP by species sensitivity distribution (SSD) method. The results revealed PNECwater values of 6.35 and 38.0 μg/L for TPhP and TDCIPP, respectively. Furthermore, the predicted no-effect concentrations in sediment (PNECsed) were derived as 110 μg/kg dry weight (dw) for TPhP and 424 μg/kg dw for TDCIPP using the equilibrium partitioning (EqP) approach. Based on the toxicity data and PNECs, the ecological risk of these two chemicals in surface waters and sediments worldwide over the last decade were evaluated. The results indicated that TDCIPP posed negligible risk in aquatic ecosystems. However, TPhP showed potential risk in sediments, as indicated by the hazard quotients (HQs) exceeding 0.1. The results of joint probability curves (JPC) indicated that the probabilities of exceeding hazardous concentration for 1 % of species for TPhP in water and sediment were 0.33 % and 5.2 %, respectively. Overall, these findings highlight the need for continued monitoring and assessment of the presence and potential impacts of TPhP and TDCIPP in aquatic ecosystems.

Recent studies have shown that instantaneous gas-particle equilibrium partitioning assumptions fail to predict SOA formation, even at high relative humidity (∼85%), and photochemical aging seems to be one driving factor. In this study, we probe the minimum aging time scale required to observe nonequilibrium partitioning of semivolatile organic compounds (SVOCs) between the gas and aerosol phase at ∼50% RH. Seed isoprene SOA is generated by photo-oxidation in the presence of effloresced ammonium sulfate seeds at <1 ppbv NOx, aged photochemically or in the dark for 0.3-6 h, and subsequently exposed to fresh isoprene SVOCs. Our results show that the equilibrium partitioning assumption is accurate for fresh isoprene SOA but breaks down after isoprene SOA has been aged for as short as 20 min even in the dark. Modeling results show that a semisolid SOA phase state is necessary to reproduce the observed particle size distribution evolution. The observed nonequilibrium partitioning behavior and inferred semisolid phase state are corroborated by offline mass spectrometric analysis on the bulk aerosol particles showing the formation of organosulfates and oligomers. The unexpected short time scale for the phase transition within isoprene SOA has important implications for the growth of atmospheric ultrafine particles to climate-relevant sizes.

Pesticides are useful products for agriculture and human life, but they are often released into surface waters and are hazardous to aquatic ecosystems. Pesticides monitoring in surface waters is challenging due to the great variety, ultratrace levels and nonpoint source pollution of pesticides; however, continuous passive sampling may be conducive to solving these problems. This work evaluated the performance of a newly developed passive sampler (hydrophilic-lipophilic balance sorbent-embedded cellulose acetate membrane, HECAM) for six types of currently used/present pesticides. The uptake kinetics and equilibrium partitioning of nineteen pesticides in different dissolved concentrations were studied by dynamic accumulation and equilibrium partitioning experiments, respectively. In the dynamic accumulation experiments, pesticides gradually accumulated in the HECAM and followed a first-order kinetic model. The same type of pesticides had roughly comparable accumulation concentrations. The estimated uptake rate constants ranged from 1.04 to 13.5 L g-1 d-1, and sampling rates ranged from 0.02 to 0.31 L d-1 for the pesticides in the HECAM (size of 2 cm × 3 cm). Pesticide accumulation concentrations in the HECAM increased linearly with increasing dissolved concentrations, which means that varying concentrations can also be monitored by the HECAM. In the equilibrium partitioning experiments, the pesticide partitioning behavior at varying dissolved concentrations can be described by the Freundlich model. The calculated equilibrium partition coefficients (log KD) for pesticides ranged from 3.32 to 4.54, and different pesticide types showed different changes with log Kow. Comparable results were found when estimating chemical equilibrium partition coefficients by the dynamic accumulation and equilibrium partitioning methods. Field deployment of the HECAM in river waters resulted in the detection of four pesticides, and the measured results were comparable to those of active sampling coupled with liquid-liquid extraction. These results suggest that the HECAM would be a promising strategy for simultaneously monitoring diverse pesticides in waters.

Traditional phase equilibrium models usually depend on simplified assumptions and empirical parameters, which are difficult to obtain during regular site investigations. As a result, they often under- or over-estimate soil vapor concentrations for assessing the risks of volatile organic compound (VOC)-contaminated sites. In this study, we develop several machine learning models to predict soil vapor concentrations using 2225 soil-soil vapor data pairs collected from seven contaminated sites in northern China. Compared to the classic dual equilibrium desorption model, the random forest (RF) model can provide more accurate predictions of soil vapor concentrations by at least 1-2 orders of magnitude. Among the employed covariates, soil concentration and organic carbon-water partition coefficient are two of the most significant explanatory covariates affecting soil vapor concentrations. Further examination of the developed RF model reveals the phase equilibrium behavior of VOCs in soil is that: the soil vapor concentration increases with soil concentration at different rates in the first two intervals but remains almost unchanged in the last interval; the solid-vapor partitioning interface may still exist at up to 15% mass water content in our simulations. These findings can help site investigators perform more accurate risk assessments at VOC-contaminated sites.

Conventional PAH analytical methods are time-consuming and expensive, limiting their utility in time sensitive events (i.e. oil spills and floods) or for widespread environmental monitoring. Unreliable and inefficient screening methods intended to prioritize samples for more extensive analyses exacerbate the issue. Antibody-based biosensor technology was implemented as a quantitative screening method to measure total PAH concentration in adult oysters (Crassostrea virginica) - a well-known bioindicator species with ecological and commercial significance. Individual oysters were analyzed throughout the historically polluted Elizabeth River watershed (Virginia, USA). Significant positive association was observed between biosensor and GC-MS measurements that persisted when the method was calibrated for different regulatory subsets of PAHs. Mapping of PAH concentrations in oysters throughout the watershed demonstrates the utility of this technology for environmental monitoring. Through a novel extension of equilibrium partitioning, biosensor technology shows promise as a cost-effective analysis to rapidly predict whole animal exposure to better assess human health risk as well as improve monitoring efforts.

Microbial volatile organic compounds (MVOCs) play an essential role in many environmental fields, such as indoor air quality. Long-term exposure to odorous and toxic MVOCs can negatively affect the health of occupants. Recently, the involvement of surface reservoirs in indoor chemistry has been realized, which signifies the importance of the phase partitioning of volatile organic pollutants. However, reliable partition coefficients of many MVOCs are currently lacking. Equilibrium partition coefficients, such as Henry\'s law constant, H, are crucial for understanding the environmental behavior of chemicals. This study aims to experimentally determine the H values and their temperature dependence for key MVOCs under temperature relevant to the indoor environment. The H values were determined with the inert gas-stripping (IGS) method and variable phase ratio headspace (VPR-HS) technique. A two-dimensional partitioning model was applied to predict the indoor phase distribution of MVOCs and potential exposure pathways to the residences. The findings show that the MVOCs are likely distributed between the gas and weakly polar (e.g., organic-rich) reservoirs indoors. Temperature and the volume of reservoirs can sensitively affect indoor partitioning. Our results give a more comprehensive view of indoor chemical partitioning and exposure.

Contamination characteristics, equilibrium partitioning and risk assessment of phthalate esters (PAEs) were investigated in seawater, sediment and biological samples collected from the Xiangshan Bay area during an annual investigation between January and November 2019. PAE concentrations detected in the mariculture environment in surface seawater, sediment, and biological samples were 172-3365 ng/L, 190-2430 μg/kg (dry weight [dw]), and 820-4926 μg/kg (dw), respectively. The dominant congeners in different media included di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and di(2-ethylhexyl) phthalate (DEHP). The inner bay and the bay mouth were the gathering area of PAEs and heavily influenced by the mariculture activities, river inputs, and anthropogenic activities. The bioaccumulation of PAEs demonstrated benthic feeding fishes with relatively high trophic levels concentrated high levels of phthalates. The mobility of PAEs in sediment-seawater showed that the transfer tendency of low-molecular weight species was from the sediment to the water, which was in contrast with those of high-molecular weight PAEs. DEHP, DiBP and DnBP had various degrees of ecological risks in the aquatic environment, whereas only the DiBP posed potential risks in sediments. The current assessment of carcinogenic and noncarcinogenic risks posed by fish consumption were within acceptable limits for humans.

While the equilibrium partitioning (EqP) method has been demonstrated to effectively predict the adverse effects of nonionic organic chemicals in sediment on benthic organisms by sediment toxicity tests, only a limited number of studies have been performed both in water-only and whole-sediment toxicity tests using the same species and verified the validity of EqP-based toxicity assessment. To further examine the validity of the EqP method for application in a wide range of hydrophobicity, we conducted sorption/desorption experiments and both water-only and sediment toxicity tests using a popular aquatic crustacean species, Daphnia magna (48 h), and benthic species Hyalella azteca (96 h) for six typical polycyclic aromatic hydrocarbons (PAHs) with three to five rings and an amine derivative: anthracene, phenanthrene, fluoranthene, pyrene, benzo[a]pyrene, dibenzo[a,h]anthracene, and 1-aminopyrene. The linear sorption coefficient was determined and ranged from 2.7 × 102 (phenanthrene) and 1.2 × 104 L/kg (benzo[a]pyrene) highly depending on the hydrophobicity while the aqueous concentrations were stable after 24 h in the desorption test. As result of acute toxicity tests in the water-only exposure system, anthracene and dibenz[a,h]anthracene were found to be nontoxic to both species, while median effect/lethal concentrations (EC50/LC50) were determined as ranging from 0.66 (benzo[a]pyrene) to 330 μg/L (phenanthrene), and from 11 (1-aminopyrene) to 180 μg/L (phenanthrene) for D. magna and H. azteca, respectively. Among these compounds, three PAHs with three, four, and five rings each, and 1-aminopyrene were subjected to sediment-water toxicity tests. In the sediment-water tests, the LC50 of phenanthrene and pyrene was three to six times higher than that of the water-only tests for H. azteca while the EC50 was 1.1 to 2.0 times higher for D. magna. In contrast, the EC50/LC50 of benzo[a]pyrene (BaP) in the sediment-water toxicity test was more than 5 times higher than that in the water-only test for both H. azteca and D. magna. The EC50/LC50 values of 1-aminopyrene were similar in both the sediment-water and the water-only toxicity tests, ranging narrowly from 21 to 28 μg/L and 8.8 to 11 μg/L for D. magna and H. azteca, respectively. The EC50/LC50 based on the body residue (ER50/LR50) was investigated for two of the representative PAHs, pyrene, and BaP. The ER50/LR50 of pyrene in both species was 2.3 and 11 times higher in the water-only toxicity test for D. magna and H. azteca, respectively, while those of BaP in the sediment-water toxicity test were not calculated for the sediment-water toxicity tests, and the highest body concentration in the sediment-water tests was lower than the ER50/LR50 in the water-only toxicity test. Although the experimental results were comparable with the predicted sediment toxicity values based on the EqP method for the selected PAHs in this study, there is a risk of phenanthrene and pyrene being slightly underestimated (1.4-1.9 fold for phenanthrene and 3.7-6.1 fold for pyrene) by the EqP method for H. azteca. These results reaffirm that the bioavailability of poorly water-soluble chemicals is important for sediment toxicity and that the exposure pathway should be further investigated to avoid under- and overestimation via the EqP method.

From 1859 to 1948, the Dover Gas Light plant produced combustible gas for industrial, commercial, and residential applications using pine resin, coking coal, oil, and wood, and finally, a coal-gas process. Waste coal tar was discharged into the St. Jones River in Dover, Delaware (USA), via a ditch and culvert and, following plant closure in the 1940s, through groundwater flow from structures buried on the site. By the end of the 20th century, polycyclic aromatic hydrocarbon (PAH) contamination of the sediments in the St. Jones River was suspected to have occurred, and state and federal agencies initiated environmental assessments of the newly designated Superfund site. The current study investigated the spatial distributions of total PAHs in St. Jones River sediments adjacent to the site and evaluated their bioavailability. In 2017, 34 sediment cores were collected, sectioned, and analyzed using an on-site fluorometric screening technology indicating total PAH sediment concentrations ranging from 0.1 to 15 000 mg/kg (wet). A subset of cores involving 20 samples of various depths was selected and further analyzed by conventional GC/MS analysis for 16 parent PAHs. In addition, a 34-day in situ deployment of polyethylene passive samplers was performed to measure vertical bioavailability profiles of parent PAHs in sediments at three locations and overlying waters at four stations. Freely dissolved concentrations (C free ) of total PAHs were estimated based on equilibrium partitioning (EqP) of the GC/MS results and the passive sampling findings. C free values were used to calculate acute and chronic toxic units ranging from 1.4 to 56, based on EqP and 1.3 to 15 based on passive sampling. For six samples where comparative data were available, EqP calculations overestimated bioavailability by < 2- to 54-fold. Combining rapid field measurements with more accurate analyses of sediment concentrations and bioavailability in a tiered framework supported a time-efficient and cost-effective site investigation. Integr Environ Assess Manag 2021;17:1215-1228. © Published 2021. This article is a U.S. Government work and is in the public domain in the USA.

A promising concept for sampling contaminants of emerging concern (CECs) using a home-made Simple Teabag Equilibrium Passive Sampler (STEPS) containing hydrophilic divinylbenzene (h-DVB) sorbent is presented and evaluated for application in estuarine systems. The uptake of a multi-class mixture of CECs with a broad polarity range (Log P ranging from -0.1 to 9.9) was investigated in static exposure batch experiments. Sampling rates (Rs) and equilibrium partitioning coefficients (Ksw) were determined for up to 74 CECs. Fast uptake (Rs = 0.3-12 L d-1) was noticed and the STEPS attained equilibrium partitioning after 1 to 2 weeks of exposure, with Log Ksw ranging from 4.1 to 6.5 L kg-1. Field application of this novel h-DVB containing STEPS, followed by ultra-high performance liquid chromatography coupled to high-resolution Orbitrap mass spectrometry, revealed the presence of up to 40 steroidal hormones, (alkyl)phenols, phthalates, pharmaceuticals, personal care products, and pesticides in the Belgian Part of the North Sea. The measured trace concentrations (from 0.003 ng L-1 to 1.9 μg L-1) and good precision (average RSD < 30%, n = 3) demonstrate the STEPS as fit-for-purpose for micropollutant analysis in the marine environment.