Organophosphate ester (OPE) levels, profiles, sources, spatial distribution, and partitioning were firstly studied in the rivers of the Shandong Peninsula. A total of 53 water samples and 45 sediment samples were collected from the rivers and the sewage treatment plant in the peninsula to quantitate levels of 13 targeted OPEs. Total OPE concentrations ranged from 263 to 6676 ng L⁻¹ in the water, and 39.3–360 ng g⁻¹ in the sediment. TEP, TCPP, and TCEP together contributed more than 90% of total OPE content. TCEP and TCPP concentrations in the Xiaoqing River sediment were increased by approximately two and seven times from 2014 to 2019, respectively. Total OPE concentrations generally increased from upstream regions to the estuaries. The main OPE sources were municipal effluent in the Jiaozhou Bay (JZB) watershed and chemical industrial wastewater in the Laizhou Bay (LZB) watershed. TCPP, TEP, and TCEP were generally approaching equilibrium between sediment and overlying water, while TNBP, TIBP, and TBOEP effectively transferred from the overlying water to the sediment. The riverine OPE flux was 0.66 ton/year to JZB and 3.58 ton/year to the LZB. TCPP and TCEP in municipal effluent, and TEP in chemical industrial wastewater should be regulated to protect Shandong Peninsula waters.

Information about the co-occurrence of halogenated flame retardants (HFRs) and organophosphate esters (OPEs) in the environment of informal waste processing areas is still limited, especially in emerging and developing countries. In this study, OPEs and HFRs including polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and chlorinated flame retardants (CFRs) were determined in settled dust from Vietnamese e-waste recycling (WR) and vehicle processing (VP) workshops. Pollutant concentrations decreased in the order: OPEs (median 1500; range 230–410,000 ng/g) ≈ PBDEs (1200; 58–250,000) > NBFRs (140; not detected – 250,000) > CFRs (13; 0.39–2200). HFR and OPE levels in the WR workshops for e-waste and obsolete plastic were significantly higher than in the VP workshops. Decabromodiphenyl ether and decabromodiphenyl ethane are major HFRs, accounting for 60 ± 26% and 25 ± 29% of total HFRs, respectively. Triphenyl phosphate, tris(2-chloroisopropyl) phosphate, and tris(1,3-dichloroisopropyl) phosphate dominated the OPE profiles, accounting for 30 ± 25%, 25 ± 16%, and 24 ± 18% of total OPEs, respectively. The OPE profiles differed between WR and VP dust samples, implying different usage patterns of these substances in polymer materials for electric/electronic appliance and automotive industries. Human health risk related to dust-bound HFRs and OPEs in the study areas was low.

Organophosphate esters (OPEs) are ubiquitous contaminants in the environment, whereas their atmospheric processes and fate are poorly understood. The present study revealed the spatial heterogeneity and seasonal variations of traditional and novel OPEs in PM₂.₅ (particulate matter with diameters < 2.5 μm) across a megacity (including residential areas and potential source sites) in South China. Potential influencing factors on the contamination levels of OPEs were addressed. The total concentrations of 11 traditional OPEs ranging from 262 to 42,194 pg/m³ (median = 1872 pg/m³) were substantially higher than those of 10 novel OPEs (33.5–3835 pg/m³, median = 318 pg/m³). Significant spatial and temporal variations in the concentrations of most OPEs were observed. The overall district-specific contamination levels in this city showed dependence on the secondary industry sector for non-predominant OPEs and on the tertiary industry for predominant OPEs. The seasonal variations of the OPE concentrations suggest difference in their sources or influence of meteorological conditions. The correlations between the individual OPEs in PM₂.₅ are determined largely by either their applications or physicochemical properties (in particular vapor pressure). The correlations between OPE concentrations and each meteorological factor (temperature, relative humidity, wind speed, and surface solar radiation) were inconsistent (positive and negative). Wind speed had the greatest effect on the OPE levels; While most OPEs bound to PM₂.₅ were not efficiently scavenged by below-cloud rainfall. The results suggest that atmospheric half-life and Henry’s Law Constant of OPEs are also determining factors for the wind speed and rainfall influence, respectively. However, mechanisms underlying the influence of meteorological conditions on atmospheric OPEs still need further research.

Cresyl diphenyl phosphate (CDP), as a kind of aryl substituted organophosphate esters (OPEs), is commonly used as emerging flame retardants and plasticizers detected in environmental media. Due to the accumulation of CDP in organisms, it is very important to discover the toxicological mechanism and metabolic process of CDP. Hence, liver microsomes of crucian carps (Carassius carassius) were prepared for in vitro metabolism kinetics assay to estimate metabolism rates of CDP. After 140 min incubation, the depletion of CDP accounted for 58.1%–77.1% (expect 0.5 and 2 μM) of the administrated concentrations. The depletion rates were best fitted to the Michaelis-Menten model (R² = 0.995), where maximum velocity (Vₘₐₓ) and Michaelis-Menten constant (Kₘ) were 12,700 ± 2120 pmol min⁻¹·mg⁻¹ protein and 1030 ± 212 μM, respectively. Moreover, the in vitro hepatic clearance (CLᵢₙₜ) of CDP was 12.3 μL min⁻¹·mg⁻¹ protein. Log Kₒw and bioconcentration factor (BCF) of aryl-OPEs were both higher than those of alkyl- and chlorinated-OPEs, indicating that CDP may easily accumulate in aquatic organisms. The results made clear that the metabolism rate of CDP was greater than those of other OPEs detected in liver microsomes in previous research. This paper was first of its kind to comprehensively investigate the in vitro metabolic kinetics of CDP in fish liver microsomes. The present study might provide useful information to understand the environmental fate and metabolic processes of these kinds of substances, and also provide a theoretical basis for the ecological risk assessment of emerging contaminants.

Organophosphate esters (OPEs) pose increasing concerns for their widespread distribution in soil environments and potential threat to human health. In this study, we investigated the occurrence and associated risks of seven OPEs in surface soils and the potential influence of human activities on soil OPE contamination in a heavily urbanized region of the Yangtze River Delta in Eastern China. All target OPEs were detected in the soil samples (100% of samples) reflecting their widespread distribution in the study region. The total OPE concentration (the sum of the seven OPEs) ranged from 162.7 to 986.0 ng/g on a dry weight basis, with a mean value of 469.3 ± 178.6 ng/g. Tris (2-butoxyethyl) phosphate was the main compound, accounting for 67–78% of the total OPE concentration. Ecological risk assessment showed that tris(2-chloroisopropyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(2-butoxyethyl) phosphate, and tris(2-ethylhexyl) phosphate posed a medium potential risk to terrestrial biota (0.1 < risk quotient <1). The human exposure estimation showed insignificant risks to local population. Redundancy analysis revealed that the individual and total OPE contaminations were positively correlated with human activity parameters. The total OPE concentrations were positively correlated to population density (R² = 0.38, P < 0.001), and urban land use percentage (R² = 0.39, P < 0.001), while negatively correlated to forest land use percentage (R² = 0.59, P < 0.001), suggesting a significant contribution of human disturbance to OPE pollution. These results can facilitate OPE contamination control and promote sustainable soil management in urbanized and industrialized regions.

We investigated the concentration, composition, and potential risk of organophosphate esters (OPEs) and phthalates (PAEs) in soils and vegetation from rural areas of Dalian, Northeast China. The residues of total OPEs and PAEs in soils were in the range of 33.1–136 ng/g dw (dry weight) and 465–5450 ng/g dw, while the values in plants were 140–2360 ng/g dw and 2440–21800 ng/g dw, respectively. The concentrations of both chemicals in the plant rhizosphere soils were significantly lower than those in the bulk soils, suggesting an enhanced degradation or uptake by plant. The contaminations in soils also varied for different land use types with the concentrations generally higher in paddy soils than those in maize soils. The OPE and PAE concentrations in plant leaves were slightly higher than those in their corresponding roots. The bioconcentration factors of OPEs & PAEs were significantly negatively correlated with their octanol-water partition coefficients. A hazard assessment suggested potential medium to high risks from tricresyl phosphate (TMPP) and di-n-butyl phthalate (DNBP) for the agricultural soils in Dalian of China. Although the ecological risks of OPEs and PAEs in the rhizosphere soils were lower than those in the bulk soils, the relevant risk could still endanger human health via oral intake of these plants. The daily dietary intakes of OPEs and PAEs via vegetable and rice consuming were estimated, and the result suggests a higher exposure risk via ingestion of leafy vegetable than rice.

Trichloropropyl phosphate (TCPP) is a halogenated organophosphate ester that is widely used as flame retardants and plasticizers. In this study, gender-specific accumulation and responses in mussel Mytilus galloprovincialis to TCPP exposure were focused and highlighted. After TCPP (100 nmol L⁻¹) exposure for 42 days, male mussels showed similar average bioaccumulation (37.14 ± 6.09 nmol g⁻¹ fat weight (fw)) of TCPP with that in female mussels (32.28 ± 4.49 nmol g⁻¹ fw). Proteomic analysis identified 219 differentially expressed proteins (DEPs) between male and female mussels in control group. There were 52 and 54 DEPs induced by TCPP in male and female mussels, respectively. Interestingly, gender-specific DEPs included 37 and 41 DEPs induced by TCPP in male and female mussels, respectively. The proteomic differences between male and female mussels were related to protein synthesis and degradation, energy metabolism, and functions of cytoskeleton and motor proteins. TCPP influenced protein synthesis, energy metabolism, cytoskeleton functions, immunity, and reproduction in both male and female mussels. Protein-protein interaction (PPI) networks indicated that protein synthesis and energy metabolism were the main biological processes influenced by TCPP. However, DEPs involved in these processes and their interaction patterns were quite different between male and female mussels. Basically, twelve ribosome DEPs which directly or indirectly interacted were found in protein synthesis in TCPP-exposed male mussels, while only 3 ribosome DEPs (not interacted) in TCPP-exposed female mussels. In energy metabolism, only 4 DEPs (with the relatively simple interaction pattern) mainly resided in fatty acid metabolism, butanoate/propanoate metabolism and glucose metabolism were discovered in TCPP-exposed male mussels, and more DEPs (with multiple interactions) functioned in TCA cycle and pyruvate/glyoxylate/dicarboxylate metabolism were found in TCCP-exposed female mussels. Taken together, TCPP induced gender-specific toxicological effects in mussels, which may shed new lights on further understanding the toxicological mechanisms of TCPP in aquatic organisms.

As emerging pollutants, the occurrence and risks of organophosphate esters (OPEs) in mariculture farms should be concerned; however, information is limited. Beibu Gulf is one of the essential mariculture zones in China. This study aimed to investigate the occurrence of OPEs in mariculture farms of the Beibu Gulf, their phase distribution and bioaccumulation among sediment, organisms (shrimp, crab, and oyster), water, and feed. Human exposure to OPEs through seafood consumption was also assessed. The total concentrations of the 11 target OPEs (∑₁₁OPEs) in the water samples ranged 32.9–227 ng L⁻¹. It was significantly higher in water from the culture ponds (mean 122 ng L⁻¹) than in water from the estuaries and nearshore areas (mean 51.1 ng L⁻¹) (nonparametric test, p < 0.05). ∑₁₁OPEs in the feeds averaged 46.0 (range 21.7–84.5) ng g⁻¹ dw, which is similar to the level in the organism samples (mean 55.5, range 21.3–138 ng g⁻¹ dw) and 4.4 times higher than that in the sediment (mean 10.9, range 35–22.1 ng g⁻¹ dw). The ∑₁₁OPEs released from the feeds to the culture ponds was estimated to be 49 μg m⁻² per three-month period. In the aquaculture ponds, the sediment-water distribution coefficient (log KOC), and the bioaccumulation factors from the water (log BWAFs) or the feed (log BFAFs) to the organisms, depend linearly on the hydrophobicity (log KOW) of OPEs. The log BWAFs and log BFAFs increased with increasing log KOW within the log KOW range of 1–7. The human exposure to OPEs through consumption of shrimp, crab, and oysters from the mariculture farms does not pose a health risk at present.

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

Semivolatile organic compounds (SVOCs) in air can react with hydroxyl radicals (OH), nitrate radicals (NO₃) and ozone (O₃). Two questions regarding SVOC reactivity with OH, NO₃ and O₃ in the gas and particle phases remain to be addressed: according to the existing measurements in the literature, which are the most reactive SVOCs in air, and how can the SVOC reactivity in the gas and particle phases be predicted? In the present study, a literature review of the second-order rate constant (k) was carried out to determine the SVOC reactivity with OH, NO₃ and O₃ in the gas and particle phases in ambient and indoor air at room temperature. Measured k values were available in the literature for 90 polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphates, dioxins, di(2-ethylhexyl)phthalate (DEHP) and pesticides including pyrifenox, carbamates and terbuthylazine. PAHs and organophosphates were found to be more reactive than dioxins and PCBs. Based on the obtained data, quantitative structure-activity relationship (QSAR) models were developed to predict the k value using quantum chemical, molecular, physical property and environmental descriptors. Eight linear and nonlinear statistical models were employed, including regression models, bagging, random forest and gradient boosting. QSAR models were developed for SVOC/OH reactions in the gas and particle phases and SVOC/O₃ reactions in the particle phase. Models for SVOC/NO₃ and SVOC/O₃ reactions in the gas phase could not be developed due to the lack of measured k values for model training. The least absolute shrinkage and selection operator (LASSO) regression and random forest models were identified as the most effective models for SVOC reactivity prediction according to a comparison of model performance metrics.