A critical review on organophosphate esters in drinking water: Analysis, occurrence, sources, and human health risk assessment.

Organophosphate esters (OPEs) are ubiquitous in the environment. Copious studies assessed OPEs in various environmental media. However, there is limited summative information about OPEs in drinking water. This review provides comprehensive data for the analytical methods, occurrence, sources, and risk assessment of OPEs in drinking water. In general, liquid-liquid extraction and solid-phase extraction are the most common methods in the extraction of OPEs from drinking water, while gas chromatography and liquid chromatography are the most commonly used instrumental methods for detecting OPEs in drinking water. On the basis of these techniques, a variety of methods on OPEs pretreatment and determination have been developed to know the pollution situation of OPEs. Studies on the occurrence of OPEs in drinking water show that the total concentrations of OPEs vary seasonally and regionally, with tris(1-chloro-2-isopropyl) phosphate and tris(2-chloroethyl) phosphate dominant among different kinds of drinking water. Source identification studies show that there are three main sources of OPEs in drinking water: 1) source water contamination; 2) residual in drinking water treatment process; 3) leakage from device or pipeline. Besides, risk assessments indicate that individual and total OPEs pose no or negligible health risk to human, but this result may be significantly underestimated. Finally, the current knowledge gaps on the research of OPEs in drinking water are discussed and some suggestions are provided for future environmental research.

Organophosphate esters (OPEs) in plastic food packaging: non-target recognition, and migration behavior assessment.

Organophosphate esters (OPEs) are widely used as plasticizers in plastic food packaging; however, the migration of OPEs from plastic to food is largely unstudied. We do not even know the specific number of OPEs that exist in the plastic food packaging. Herein, an integrated target, suspect, and nontarget strategy for screening OPEs was optimized using ultrahigh-performance liquid chromatography-high-resolution mass spectrometry (UHPLC-HRMS). The strategy was used to analyze 106 samples of plastic food packaging collected in Nanjing city, China, in 2020. HRMS allowed full or tentative identification of 42 OPEs, of which seven were reported for the first time. Further, oxidation products of bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (AO626) in plastics were identified, implying that the oxidation of organophosphite antioxidants (OPAs) could be an important indirect source of OPEs in plastics. The migration of OPEs was examined with four simulated foods. Twenty-six out of 42 OPEs were detected in at least one of the four simulants, particularly isooctane, in which diverse OPEs were detected at elevated concentrations. Overall, the study supplements the list of OPEs that humans could ingest as well as provides essential information regarding the migration of OPEs from plastic food packaging to food.

Dietary intake assessment of known and unknown organophosphate esters (OPEs) in foodstuffs via high-resolution mass spectrometry.

We applied an integrated target, suspect, and non-target screening strategy to analyze known and unknown organophosphate esters (OPEs) in 107 foodstuffs collected from Nanjing City, China, in 2020. Twelve out of 19 target OPEs were detectable in at least one of the analyzed samples. Among the nine food categories, meat samples were contaminated the most severely with a mean ΣOPEs concentration of 68.5 ng/g wet weight (ww). In most food categories, tris(2,4-di-tert-butylphenyl) phosphate was the predominant OPE with a mean concentrations of 2.26 ng/g ww. In the food extract samples, suspect and non-target analysis identified other 6 suspect OPEs and 1 non-target OPE, of which two were fully identified as tri-m-cresyl phosphate, and trihexyl phosphate. Based on the measured OPE concentrations, we estimated the daily per capita dietary intakes of ΣOPEs for Nanjing residents to be 423 ng/kg bw/day, which is less than the reference dosage value of each OPE. Collectively, this study provides new information regarding the comprehensive identification of OPEs in foodstuffs, and revealed the importance of dietary risk assessment of this emerging class of contaminants.

Non-target screening and risk assessment of organophosphate esters (OPEs) in drinking water resource water, surface water, groundwater, and seawater.

By use of an integrated target, suspect, and non-target screening strategy, we investigated occurrence and spatial distribution of organophosphate esters (OPEs) in four types of water (drinking water resource water, surface water, groundwater, and seawater) collected from Jiangsu Province (China) in 2021 (n = 111). Eighteen out of 23 target OPEs were detectable at least once in these analyzed samples, and the total concentrations (Σ18OPEs) of OPEs in various water samples exhibited a descending order following as: groundwater (67026 ng/L) > surface water (35803 ng/L) > drinking water resource water (21055 ng/L) > seawater (17820 ng/L). The highest concentration detected in groundwater may be ascribed to pollution from surrounding factories. Among the target OPEs, triethyl phosphate (TEP), tris(chloroethyl) phosphate (TCEP), and tris (1-chloro-2-propyl) phosphate (TCIPP) were the most abundant congeners with the average concentrations of 407 ng/L, 143 ng/L, and 475 ng/L, respectively. Besides of 18 target OPEs, we further identified 17 suspect OPEs (3 of them were fully identified by authentic standards) on the basis of in-house suspect screening OPE database, and 2 non-target organophosphates (OPs) on the basis of feature fragments. One of these 2 non-target OPs was fully identified as bis(2-chloroethyl) 2-chloroethylphosphonate (B2CE2CEPP) by matching the retention time and MS/MS data with authentic standard, and the other one was preliminarily identified as 2,4,8,10-tetra-tert-butyl-6-methoxydibenzo[d,f][1,3,2]dioxaphosphepin-6-one (TTBMDBDOPPO). We also observed that B2CE2CEPP shared a similar structure with TCEP, suggesting that they may have similar toxicological characteristics and commercial sources. The ecological and human health risk assessments indicated that all OPEs posed a low or negligible ecological risk to aquatic organisms (algae, crustacean, and fish), and negligible risk to human health except for trimethyl phosphate (TMP) in drinking water resource water.

Comprehensively screening of citric acid ester (CAE) plasticizers in Chinese foodstuffs, and the food-based assessment of human exposure risk of CAEs.

An increasing number of studies on the toxicities of citric acid esters (CAEs)-a class of so-called "safe" alternative plasticizers-have highlighted the urgent need to understand their contamination profiles in foodstuffs and the corresponding potential risks to human health. This study determined the concentrations of 8 target CAEs in 105 foodstuff samples, grouped into 6 food categories, collected from Nanjing City, China, in 2020. All eight CAEs were detected in at least one of the analyzed samples and had detection frequencies (DFs) of 5-47%. The DFs and distribution profiles of the target CAEs varied among different food categories; for example, cereals had the highest DF (92%), while meat/fish contained the highest mean total concentration of CAEs (8.35 ng/g wet weight (ww)). Among the target CAEs, acetyl tributyl citrate (ATBC) had the highest DF (47%), and tributyl citrate (TBC) exhibited the highest mean concentration (1.24 ng/g ww). Based on the food ingestion route, the estimated total daily intake (EDI) values of the target CAEs for adults under average- and high-exposure scenarios were 38.3 ng/kg of body weight (bw) and 111 ng/kg bw, respectively, which were attributed to the high percentage contributions of TBC (50.6%) and ATBC (23.7%). In addition, a suspect and characteristic fragment-dependent screening strategy was applied to the foodstuff data, and a novel CAE, monoethyl citrate (MEC, CAS: 4552-00-5), with a DF of 34% was tentatively identified. Overall, this study provides novel and comprehensive information regarding the pollution status of CAEs in foodstuffs.

Traditional and emerging organophosphate esters (OPEs) in indoor dust of Nanjing, eastern China: Occurrence, human exposure, and risk assessment.

Here, fifteen OPEs were investigated in n = 50 floor dust samples collected from six types of indoor spaces in Nanjing, eastern China, in the year 2018. Ten OPEs, including tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloro-isopropyl) phosphate (TDCIPP), tris(2-ethylhexyl) phosphate (TEHP), tris(2-butoxyethyl) phosphate (TBOEP), 2-ethylhexyl-diphenyl phosphate (EHDPP), triphenyl phosphate (TPHP), tris(methyl-phenyl) phosphate (TMPP), 4-biphenylyl diphenyl phosphate (4-BPDP) and tris(2-biphenylyl) phosphate (TBPP), were detected in at least one of the analyzed samples (>method limits of quantification). Regardless of indoor spaces, EHDPP (34% of Σ8OPEs, mean: 1.43 µg/g) and TDCIPP (19%, 0.81 µg/g) were the ascendant OPEs in indoor floor dust. 4-BPDP and TBPP were detectable in indoor floor dust samples, but at relatively low detection frequencies with 2% and 10%, respectively. Various indoor microenvironments exhibited different pollution characteristics of OPEs. Floor dust collected from electronic product maintenance centers contained the richest OPE contaminants with highest mean Σ8OPEs concentration of 7.92 µg/g. On the basis of measured Σ10OPEs concentrations in dust sample, we estimated daily intake via floor dust ingestion to be 1.37, 0.75 and 1.24 ng/kg BW/day for electronic engineers, undergraduates, and graduate students under mean-exposure scenario, respectively. Overall, our study reported the occurrence of 4-BPDP and TBPP in environmental samples for the first time, and demonstrated that indoor floor dust ingestion exposure does values were far less than reference dosage values of oral toxicity proposed by United States Environmental Protection Agency (USEPA) Integrated Risk Information System.