This study reports the results obtained from toxicological analyses of different types of baits referred to the laboratory of the Toxicology Area (Faculty of Veterinary Medicine, Cáceres, Spain) over a 17-year period (2002–2018). These baits were suspicious materials found in the environment of the region of Extremadura (Western Spain), where such malpractices are a problem to be addressed, as wide livestock farming and hunting activities are combined with a significant wealth of wildlife (especially birds of prey). A total of 246 baits, including 32 commercial chemical products to be used in baits, were analysed. Samples from 183 cases were received and classified according to the material used for their preparation and the toxic substance found. Overall, the most common bait consisted of meat preparations (56.3% of cases) intended to eliminate predators considered ‘annoying’ for livestock and hunting practices, such as carnivores and scavengers. It should be noted that contact baits (as fenthion-impregnated perches) were also detected (7.6%). Regarding the substances detected, anticholinesterase compounds (organophosphates and carbamates) were the most commonly used substances for the preparation of baits (detected in 85.3% of positive baits). Moreover, 8% of the positive baits presented more than one toxic substance in their composition. Due to the types of toxic compounds and the methods used to prepare the baits, this study shows that the malicious use of highly toxic substances in the environment to kill wildlife is a common and current issue and poses a serious risk to different species.

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.

The coastal megacity Shanghai is located in the center of the Yangtze River Delta, a dominant flame retardants (FRs) production region in China, especially for organophosphate esters (OPEs). This prompted us to investigate occurrence and seasonal changes of atmospheric OPEs in Shanghai, as well as to evaluate their sources, environmental behavior and fate as a case study for global coastal regions. Atmospheric gas and particle phase OPEs were weekly collected at two coastal sites - the emerging town Lingang New Area (LGNA), and the chemical-industry zone Jinshan Area (JSA) from July 2016–June 2017. Total atmospheric concentrations of the observed OPEs were significantly higher in JSA (median of 1800 pg m⁻³) than LGNA (median of 580 pg m⁻³). Tris(1-chloro-2-propyl) phosphate (TCPP) was the most abundant compound, and the proportion of three chlorinated OPEs were higher in the particle phase (55%) than in the gas phase (39%). The year-round median contribution of particle phase OPEs was 33%, which changed strongly with seasons, accounting for 10% in summer in contrast to 62% in winter. Gas and particle phase OPEs in JSA exhibited significant correlations with inverse of temperature, respectively, indicating the importance of local/secondary volatilization sources. The estimated fluxes of gaseous absorption were almost 2 orders of magnitude higher than those of particle phase deposition, which could act as sources of organic phosphorus to coastal and open ocean waters.

In many countries, including Morocco, groundwater contamination with pesticides such as globally banned organochlorides (e.g., dichlorodiphenyltrichloroethane (DDT)) and some accredited organophosphates and pyrethroids poses ecological and human health risks. To assess these risks, we herein monitored pesticides in Saïss plain groundwater (Morocco) during the summer of 2017 and the winter of 2018 using polar organic chemical integrative samplers. The two types of passive samplers were deployed in 22 traditional wells for 14–20 days and subjected to solid-phase extraction. The extracts were analyzed by gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry using a multiresidue method, and 27 pesticides were detected in total. In the summer campaign, 22 pesticides with individual concentrations ranging from <limit of quantitation (LOQ) to 243.1 ng L⁻¹ were identified, whereas 17 compounds with concentrations ranging from <LOQ to 53.8 ng L⁻¹ were detected in the winter campaign. In the summer period, the maximum individual concentrations of chlorothalonil, DDT, and α-hexachlorocyclohexane (α-HCH) equaled 111.7, 36.1, and 22.3 ng L⁻¹, respectively, with the respective values for the winter period equaling 18.14, 16.62, and 22.2 ng L⁻¹. Health risk assessment indicated that the carcinogenic α-HCH, β-HCH, DDT, and dichlorodiphenyldichloroethylene present in groundwater may also contaminate drinking water and thus pose a threat to human health, particularly to that of infants and children. Further analysis revealed that the Saïss aquifer presents a high ecological risk. Thus, the monitoring of pesticides in groundwater by passive sampling was effective and could be combined with human health and ecological risk assessment to develop ways of reducing human and environmental exposure to pesticides.

The environmental load of organophosphate ester (OPE) flame retardants has caused a series of problems due to their extensive use. The soil matrix, as an ultimate sink for organic pollution, plays a vital part in the fate of OPEs in the environment. In this study, the spatial occurrence, composition profile and health risk of 13 OPE species in farmland soils from four provinces of China were characterized. Excluding tris(2,3-dibromopropyl) phosphate (TDBPP) and ethylhexyl diphenyl phosphate (EHDPP), the remaining eleven OPEs had a high detection frequency (DF) ranging from 60% to 100%. The range of total OPE (ΣOPE) concentrations were 62.3–394 ng/g dry weight (dw), with a median of 228 ng/g dw. Among these OPEs, tris(2-ethylhexyl) phosphate (TEHP) with a median of 143 ng/g dw) was the predominant species, followed by tricresyl phosphate (TCP; median of 20.1 ng/g dw) and tris(2-chloroethyl) phosphate (TCEP; median of 17.9 ng/g dw). In terms of geographical distribution, significantly lower OPEs levels were found in samples from Heilongjiang (159 ± 47.0 ng/g dw) than in those of Guangxi (264 ± 66.0 ng/g dw), Henan (252 ± 74.5 ng/g dw) and Hubei (242 ± 52.8 ng/g dw) provinces. Principal component analysis and Spearman’s correlations were used to reveal potential sources of OPEs in the different provincial regions. Health risk exposure to OPEs in farmland soils was at an acceptable level (<1.20 × 10⁻⁵ for non-carcinogenic risk to children as the most sensitive age group; and <6.47 × 10⁻¹⁰ for carcinogenic risk to adults as the most sensitive age group) at the present detected concentrations. However, TCEP and TEHP, the predominant risk contributors, should be paid more attention.

In this study, water and sediment samples from the Jiaozhou Bay and surrounding rivers were collected to analyze the seasonal occurrence and allocation of 12 organophosphate esters (OPEs) and the associated ecological risk. The higher contamination of OPEs in the adjacent rivers indicated the impact of terrestrial input. Tris(1-chloropropan-2-yl) phosphate (TCIPP) was the predominant OPE in the four environmental sample groups investigated. The spatial distribution of OPEs in seawater varied greatly seasonally and was mainly affected by terrestrial input, with OPEs being redistributed under the influence of tidal currents. The partition coefficients (log Kₒc) of the OPEs were calculated, and their strong correlation with the log Kₒw (octanol-water) values suggested that the water-sediment allocation was significantly affected by hydrophobicity. The homologous relationships among the 7 OPEs with detection frequencies greater than 40% were identified by principal component analysis (PCA). The partial least squares regression (PLSR) model explicated that ∑OPEs cycling dynamics and principal controlling factors were dissimilar in the bay versus surrounding rivers. The risk quotient (RQ) faced by typical organisms in seawater and river water indicated that short-term OPEs exposure was safe for green algae, daphnia and fish. The organisms in rivers faced the higher ecological risk of OPEs in spring than in summer and winter. Therefore, the terrestrial transport of OPEs in spring should be controlled.

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.

During three sampling periods in 2014, systematic investigations were conducted into contamination profiles of ten organophosphate flame retardants (OPFRs) in both suspended particulate phase and water phase in the Yellow River (Henan Area). This research shows that OPFRs exist at lower concentrations in the suspended phase than in the water phase. The median concentration of 10 OPFRs (∑₁₀OPFRs) in the suspended particulate phase was 62.5 ng/g (fluctuating from ND to 6.17 × 10³ ng/g, dw), while their median concentration in the water phase was 109 ng/L (fluctuating from 35.6 to 469 ng/L). Among the selected 10 OPFRs, triethylphosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(2-chloroethyl) phosphate (TCEP) were the predominant compounds in the water phase (occupying 91.6% of the ∑₁₀OPFRs), while TCPP, TCEP, and tri-o-tolyl phosphate (o-TCP) were the most common in the suspended particulate phase, accounting for 90.1% of the ∑₁₀OPFRs. Across the three sampling periods, there was no significant seasonable variation for OPFRs either in the water phase or in the suspended particulate phase, except for TCEP and TCPP in the water phase. Compared with research findings relating to concentrations of OPFRs around China and abroad, the OPFRs of the Yellow River (Henan Area) in the water phase were at a moderate level. Suspended particles (SS) had a very important impact on the transportation of OPFRs in the studied area, with about 83.9% of ∑₁₀OPFRs inflow attributed to SS inflow and about 81.7% of ∑₁₀OPFRs outflow attributed to SS outflow. The total annual inflow and outflow of OPFRs were 7.72 × 10⁴ kg and 6.62 × 10⁴ kg in the studied area, respectively.

A pilot study was initiated in 2018 under the Global Atmospheric Passive Sampling (GAPS) Network named GAPS-Megacities. This study included 20 megacities/major cities across the globe with the goal of better understanding and comparing ambient air levels of persistent organic pollutants and other chemicals of emerging concern, to which humans residing in large cities are exposed. The first results from the initial period of sampling are reported for 19 cities for several classes of flame retardants (FRs) including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and halogenated flame retardants (HFRs) including new flame retardants (NFRs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDD). The two cities, New York (USA) and London (UK) stood out with ∼3.5 to 30 times higher total FR concentrations as compared to other major cities, with total concentrations of OPEs of 15,100 and 14,100 pg/m³, respectively. Atmospheric concentrations of OPEs significantly dominated the FR profile at all sites, with total concentrations in air that were 2–5 orders of magnitude higher compared to other targeted chemical classes. A moderately strong and significant correlation (r = 0.625, p < 0.001) was observed for Gross Domestic Product index of the cities with total OPEs levels. Although large differences in FR levels were observed between some cities, when averaged across the five United Nations regions, the FR classes were more evenly distributed and varied by less than a factor of five. Results for Toronto, which is a ‘reference city’ for this study, agreed well with a more in-depth investigation of the level of FRs over different seasons and across eight sites representing different urban source sectors (e.g. traffic, industrial, residential and background). Future sampling periods under this project will investigate trace metals and other contaminant classes, linkages to toxicology, non-targeted analysis, and eventually temporal trends. The study provides a unique urban platform for evaluating global exposome.

The levels of eight organophosphate esters (OPEs) were analyzed in air and soil samples collected at Ny-Ålesund and London Island, Svalbard during the Chinese Scientific Research Expedition to the Arctic during 2014–2015. The concentrations of total OPEs (∑OPEs) ranged from 357 pg/m³ to 852 pg/m³ in the air and from 1.33 ng/g to 17.5 ng/g dry weight (dw) in the soils. Non-Cl OPEs accounted for 56 ± 13% and 62 ± 16% of ∑OPEs for the air and soil, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant compound in the air, with an average concentration of 180 ± 122 pg/m³. Triphenyl phosphate, tri(1-chloro-2-propyl) phosphate, and TCEP were the most abundant OPEs in the soils, with mean values of 1.77, 2.13, and 1.02 ng/g dw, respectively. Compared with the levels of polybrominated diphenyl ethers found in Arctic regions in previous studies, OPEs showed significantly higher concentrations, thereby indicating the large production and wide usage of OPEs globally. In addition, the fugacity fraction results indicated that net deposition from air to soil was dominated in the area. Overall, the occurrence and distribution of OPEs in the air and soils in the Arctic region indicated that OPEs can undergo long-range atmospheric transport and accumulate in remote regions.