Organophosphate Esters In Soil Research Articles

Characteristics and partitions of traditional and emerging organophosphate esters in soil and groundwater based on machine learning

Organophosphate esters (OPEs) pose hazards to both humans and the environment. This study applied target screening to analyze the concentrations and detection frequencies of OPEs in the soil and groundwater of representative contaminated sites in the Pearl River Delta. The clusters and correlation characteristics of OPEs in soil and groundwater were calculated by self-organizing map (SOM). The risk assessment and partitions of OPEs in industrial park soil and groundwater were conducted. The results revealed that 14 out of 23 types of OPEs were detected. The total concentrations (Σ23OPEs) ranged from 1.931 to 743.571 ng/L in the groundwater, and 0.218 to 79.578 ng/g in the soil, the former showed highly soluble OPEs with high detection frequencies and concentrations, whereas the latter exhibited the opposite trend. SOM analysis revealed that the distribution of OPEs in the soil differed significantly from that in the groundwater. In the industrial park, OPEs posed acceptable risks in both the soil and groundwater. The soil could be categorized into Zone I and II, and the groundwater into Zone I, II, and III, with corresponding management recommendations. Applying SOM to analyze the characteristics and partitions of OPEs may provide references for other new pollutants and contaminated sites.

Seasonal variations of organophosphate esters (OPEs) in atmospheric deposition, and their contribution to soil loading

Organophosphate esters (OPEs) are ubiquitous in surface soil, and atmospheric deposition is considered to be the major pollution source. However, the research on the environmental transport behaviors of OPEs between atmospheric deposition and soil is very limited. In this study, we investigated the contamination levels and seasonal variations of OPEs in atmospheric deposition samples (n = 33) collected from an area of South China every month between February 2021 and January 2022, and evaluated the contribution of OPEs in atmospheric deposition to soil. The concentrations of ∑21target-OPEs ranged from 3670 to 18,600 ng/g dry weight (dw), with a mean of 8200 ng/g dw (median: 7600 ng/g dw). ∑21target-OPEs concentrations in all atmospheric deposition samples exhibited significant seasonal differences (p < 0.05) with higher concentrations observed in winter and lower concentrations in summer. Tris(2,4-di-tert-butylphenyl) phosphate (TDTBPP) was the most dominant target OPE in atmospheric deposition (4870 ng/g dw), and its seasonal variation trend was consistent with ∑21OPEs (p < 0.05). Simultaneously, in order to further explore the effect of atmospheric deposition on the levels of OPEs in soil of the study region, input fluxes and accumulation increments were estimated. Ten OPEs (including seven target OPEs and three suspect OPEs) exhibited high input flux means and accumulation increments, indicating that these compounds are prone to accumulate in soil via atmospheric deposition. It is noteworthy that the non-target phosphonate analyte bis(2,4-di-tert-butylphenyl) dibutyl ethane-1,2-diylbis(phosphonate) (BDTBPDEDBP) was detected at highest median concentration (8960 ng/g dw) in atmospheric deposition. Correspondingly, the average input flux and accumulation increment of BDTBPDEDBP were higher than those of all target and suspect OPEs. Collectively, this study quantifies the environmental transport behavior of OPEs between atmospheric deposition and soil, and provides new evidences for the fact that atmospheric deposition is the important pollution source of OPEs in soil.

Distribution patterns and origins of organophosphate esters in soils from different climate systems on the Tibetan Plateau

Organophosphate esters (OPEs) are extensively applied in various materials as flame retardants and plasticizers, and have high biological toxicity. OPEs are detected worldwide, even in distant polar regions and the Tibetan Plateau (TP). However, few studies have been performed to evaluate the distribution patterns and origins of OPEs in different climate systems on the TP. This study investigated the distribution characteristics, possible sources, and ecological risks of OPEs in soils from the different climate systems on the TP and its surroundings. The total concentrations of OPEs in soil varied from 468 to 17,451 pg g−1 dry weight, with greater concentrations in southeast Tibet (monsoon zone), followed by Qinghai (transition zone) and, finally, southern Xingjiang (westerly zone). OPE composition profiles also differed among the three areas with tri-n-butyl phosphate dominant in the westerly zone and tris(2-butoxyethyl) phosphate dominant in the Indian monsoon zone. Correlations between different compounds and altitude, soil organic carbon, or longitude varied in different climate zones, indicating that OPE distribution originates from both long-range atmospheric transport and local emissions. Ecological risk assessment showed that tris(2-chloroethyl) phosphate and tri-phenyl phosphate exhibited medium risks in soil at several sites in southeast Tibet. Considering the sensitivity and vulnerability of TP ecosystems to anthropogenic pollutants, the ecological risks potentially caused by OPEs in this region should be further assessed.

Distribution and Risk Assessment of Organophosphate Esters in Agricultural Soils and Plants in the Coastal Areas of South China.

Organophosphate esters (OPEs) are frequently used as flame retardants and plasticizers in various commercial products. While initially considered as substitutes for brominated flame retardants, they have faced restrictions in some countries due to their toxic effects on organisms. We collected 37 soil and crop samples in 20 cities along the coast of South China, and OPEs were detected in all of them. Meanwhile, we studied the contamination and potential human health risks of OPEs. In soil samples, the combined concentrations of eight OPEs varied between 74.7 and 410 ng/g, averaging at 255 ng/g. Meanwhile, in plant samples, the collective concentrations of eight OPEs ranged from 202 to 751 ng/g, with an average concentration of 381 ng/g. TDCIPP, TCPP, TCEP, and ToCP were the main OPE compounds in both plant and soil samples. Within the study area, the contaminants showed different spatial distributions. Notably, higher OPEs were found in coastal agricultural soils in Guangdong Province and crops in the Guangxi Zhuang Autonomous Region. The results of an ecological risk assessment show that the farmland soil along the southern coast of China is at high or medium ecological risk. The average non-carcinogenic risk and the carcinogenic risk of OPEs in soil through ingestion and dermal exposure routes are within acceptable levels. Meanwhile, this study found that the dietary intake of OPEs through food is relatively low, but twice as high as other studies, requiring serious attention. The research findings suggest that the human risk assessment indicates potential adverse effects on human health due to OPEs in the soil-plant system along the coast of South China. This study provides a crucial foundation for managing safety risks in agricultural operations involving OPEs.

Occurrence, potential sources, and ecological risks of traditional and novel organophosphate esters in facility agriculture soils: A case study in Beijing, China

Although traditional organophosphate esters (OPEs) in soils have attracted widespread interest, there is little information on novel OPEs (NOPEs), especially in facility agriculture soils. In this work, we surveyed 11 traditional OPEs, four NOPEs, and four corresponding organophosphite antioxidant precursors (OPAs) for the NOPEs in soil samples collected from facility greenhouses and open fields. The median summed concentrations of traditional OPEs and NOPEs were 14.1 μg/kg (range: 5.38–115 μg/kg) and 702 μg/kg (range: 348–1952 μg/kg), respectively, in film-mulched soils from greenhouses. These concentrations were much higher than those in soils without mulch films, which suggests that OPEs in soils are associated with plastic mulch films. Tris(2,4-di-tert-butylphenyl) phosphate, which is a NOPE produced by oxidation of (2,4-di-tert-butylphenyl) phosphite, was the predominant congener in farmland soils, with concentrations several orders of magnitude greater than those of traditional OPEs. Comparisons of OPEs in different mulch films and the corresponding mulched soils revealed that degradable and black films caused more severe pollution than polyethylene and white films. Traditional OPEs, including tris(2-ethylhexyl) phosphate and tricresyl phosphate, exhibited moderate risks in farmland soils, especially in film-mulched soils. NOPEs, including trisnonylphenol phosphate, posed high ecological risks to the terrestrial ecosystem. Risk evaluations should be conducted for a broad range of NOPEs in the environment.

Organophosphate esters in soils of Beijing urban parks: Occurrence, potential sources, and probabilistic health risks

Organophosphate esters (OPEs) are an emerging contaminant widely distributed in the soil. OPEs have drawn increasing attention for their biological toxicity and possible threat to human health. This research investigated the pollution characteristics of two typical OPEs, organophosphate triesters (tri-OPEs) and organophosphate diesters (di-OPEs), in soils of 104 urban parks in Beijing. The median concentrations of Σ11tri-OPEs and Σ8di-OPEs were 157 and 17.9 ng/g dw, respectively. Tris(2-chloroisopropyl) phosphate and bis(2-ethylhexyl) phosphate were the dominant tri-OPE and di-OPE, respectively. Consumer materials (such as building insulation and decorative materials), traffic emissions, and reclaimed water irrigation may be critical sources of tri-OPEs in urban park soils. Di-OPEs mainly originated from the degradation of parent compounds and industrial applications. Machine learning models were employed to determine the influencing factors of OPEs and predict changes in their concentrations. The predicted OPEs concentrations in Beijing urban park soils in 2025 and 2030 are three times and five times those in 2018, respectively. According to probabilistic health risk assessment, non-carcinogenic and carcinogenic risks of OPEs can be negligible for children and adults. Our results could inform measures for preventing and controlling OPEs pollution in urban park soils.

Citric acid can enhance the uptake and accumulation of organophosphate esters (OPEs) in Suaeda salsa rhizosphere: Potential for phytoremediation.

Bioaccumulation of organophosphate esters (OPEs) by plants has been widely studied, but how root exudates influence their bioavailability to plants is poorly understood. Here, we examined whether root exudates could promote desorption of OPEs, thereby enhancing bioavailability and subsequent accumulation potential. Root exudate components exert great influences on the sorption/desorption isotherms of OPEs in soils, resulting in activating OPEs and enhanced bioavailability. Among root exudate components, citric acid was confirmed to play a crucial role in driving OPEs, with 77.7-90.3% attribution. Citric acid at rhizosphere levels (0.01-0.4mM) can successfully reduce OPEs sorption to soils by decreasing electrostatic interaction, ligand exchange, and hydrophobic force. Pot experiments indicated that the addition of citric acid can significantly increase OPEs dissolution and bioaccumulation from the rhizosphere soil to Suaeda salsa. A higher level of citric acid in rhizosphere soil resulted in a higher accumulation of OPEs in Suaeda salsa, which was partly attributed to the enhanced OPEs mobility, and the increased root lengths (13.4-29.0%) and tip numbers (60.2-120%), promoting OPEs uptake by roots. Our findings suggest the activation process of OPEs in soils by citric acid at rhizosphere levels and provide insights into designing LMWOAs-enhanced phytoremediation techniques in natural environment.

Bioaccumulation and emission of organophosphate esters in plants affecting the atmosphere's phosphorus cycle

The imbalance of atmospheric, terrestrial and aquatic phosphorus budgets remains a research conundrum and global concern. In this work, the uptake, distribution, bioaccumulation and emission of organophosphate esters (OPEs) by clove trees (Syzygium aromaticum), lemon trees (Citrus limon) and cape jasmine trees (Gardenia jasminoides var. fortuniana) was investigated as conduits for phosphorus transfer or sinks and sources. The objective was to assess the role OPEs in soils play as atmospheric phosphorus sources through plant bioaccumulation and emission. Results demonstrated OPEs in experimental soil plots ranging from 0.01 to 81.0 ng g−1 dry weight, were absorbed and transported through plants to the atmosphere. The total emission of OPEs varied greatly from 0.2 to 588.9 pg g−1 L−1 h−1, with a mean of 47.6 pg g−1 L−1 h−1. There was a negative linear relationship between the concentrations of total phosphorus and four OPEs, tri-iso-butyl phosphate, tri-n-butyl phosphate, tris (2-chloroisopropyl) phosphate and tripentyl phosphate. Trimethyl phosphate levels were positively correlated with total nitrogen, and the concentrations of tri-iso-butyl phosphate, tri-n-butyl phosphate, tris (2-chloroisopropyl) phosphate and tripentyl phosphate decreased along with available potassium in leaves after 72 h. There was a significantly positive linear relationship between higher emission concentrations of OPEs and the emission factor of OPEs concentration (F = 4.2, P = 0.002), with lower emissions of OPEs and the bioaccumulation of OPEs in leaves (F = 4.8, P = 0.004). OPEs releases to the atmosphere were enriched in aerosols, and participate in atmospheric chemical reactions like photolysis, thereby affecting the phosphorus balance and cycling in the atmosphere.

Occurrence, correlation, and partitioning of organophosphate esters in soil and tree bark from a megacity, Western China.

Concern over the influences of constant addition of emerging anthropogenic chemicals to the environment has become a public issue during the rapid urbanization. Here, we investigated the occurrence of organophosphate esters (OPEs) in soil and corresponding tree bark in a megacity, Western China. Our results showed levels of OPEs in tree bark (1250 ± 573ng/g dry weight (dw)) were 1-2 orders of magnitude higher than those in soil (40.4 ± 30.8ng/g dw). Rooster Mountain is a background mountain area, exhibiting significantly lower concentrations of OPEs in soil and tree bark than those in other sites with relatively high population density. This result highlights the effect of human activities on the distribution of OPEs in environmental matrices. Alkyl-OPEs were predominant compounds in soil, whereas halogenated- (Cl-) OPEs were characterized in tree bark. Furthermore, tris(2-chloroethyl) phosphate (TCEP) positively correlated with tris(2-chloroisopropyl) phosphate (TCIPP) in soil (r2 = 0.43, P < 0.05) while negatively correlated with TCIPP in tree bark (r2 = 0.31, P < 0.05). The ratios of logarithm concentrations of OPEs in tree bark to those in soil correlated well with logKOA values of OPEs from 6 to 10, indicating the equilibrium status was achieved between OPE partitioning in soil and in tree bark. Nevertheless, tris (2-butoxyethyl) phosphate (TBEP) and tris(2-ethylhexyl) phosphate (TEHP) with high values of logKOA deviated from this linear tendency, which was possibly due to the fact that they were subjected to the particle-bound deposition process, leading to partition into the soil.

A review of organophosphate esters in soil: Implications for the potential source, transfer, and transformation mechanism.

Organophosphate esters (OPEs) are widely used around the world as flame retardants and plasticizers with a growing production in the last 15 years due to the phase-out of polybrominated diphenyl ethers. Multiple papers reported the occurrences of OPEs in various environmental matrices and elevated concentrations of OPEs (0.1-10,000ng/g dry weight) were documented in different types of soils which were regarded as both the "sink" and "source" of OPEs. In this study, the source, transfer, and transformation mechanisms of OPEs are systematically reviewed from the perspective of the soil environment. The wet/dry deposition, air-soil exchange, sewage irrigation, sludge application, and indirect oxidization of organophosphate antioxidants are the possible sources of OPEs in soil. Meanwhile, the OPEs in the soil environment may also migrate into other environmental media via plant uptake, air-soil exchange, desorption, and infiltration to cause relevant ecological risk, which depends much on the chemical properties of these compounds. The trimethylphenyl phosphate (TMPP) (mixture of isomers) and triphenyl phosphate (TPHP), which have strong hydrophobicity, pose a higher ecological risk for the soil environment than other OPEs. Further, the hydrolysis, indirect photolysis, and biodegradation of OPEs in the soil environment may be affected by the soil pH, organic acid, dissolved metals and metal oxides, active oxygen species, and microorganisms significantly. Besides that, the human exposure risks of OPEs from the soil are limited compared to those via indoor dust and food ingestion pathways. Finally, this study identifies the knowledge gaps and generated the future perspectives of the OPEs in soil.

Measurement report: Seasonality, distribution and sources of organophosphate esters in PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt; from an inland urban city in Southwest China

Abstract. Organophosphate esters (OPEs) are contaminants of emerging concern, and studies have concluded that urban areas are a significant source of OPEs. Samples were collected from six ground-based sites located in Chengdu, a typical rapidly developing metropolitan area in Southwest China, and were analyzed for seven OPEs in atmospheric PM2.5 (Σ7 OPEs). The concentrations of Σ7 OPEs in PM2.5 ranged from 5.83 to 6.91 ng m−3, with a mean of 6.6 ± 3.3 ng m−3, and the primary pollutants were tris-(2-butoxyethyl) phosphate (TBEP), tri-n-butyl phosphate (TnBP), tris-(2-chloroethyl) phosphate (TCEP) and tris-(2-chloroisopropyl) phosphate (TCPP), which together made up more than 80 % of the Σ7 OPEs. The concentrations of Σ7 OPEs were higher in autumn and winter than in summer. Nonparametric tests showed that there was no significant difference in Σ7 OPE concentrations among the six sampling sites, but the occurrence of unexpectedly high levels of individual OPEs at different sites in autumn might indicate noteworthy emissions. A very strong correlation (R2 = 0.98, p &lt; 0.01) between the OPEs in soil and in PM2.5 was observed. Backward trajectory analysis indicated that the OPEs in PM2.5 were mainly affected by local sources. Principal component analysis (PCA) revealed that the OPEs in PM2.5 were largely sourced from the plastics industry, interior decoration and traffic emission (34.5 %) and the chemical, mechanical and electrical industries (27.8 %), while the positive matrix factorization (PMF) model revealed that the main sources were the plastics industry and indoor source emissions, the food and cosmetics industry and industrial emissions. In contrast to coastal cities, sustained and stable high local emissions in the studied inland city were identified, which is particularly noteworthy. Chlorinated phosphates, especially TCPP and TCEP, had a high content, and their usage and source emissions should be controlled.

A pilot study of organophosphate esters in surface soils collected from Jinan City, China: implications for risk assessments.

Data monitoring is a prerequisite for the occurrence of organophosphate esters (OPEs) in the soil environment in light of their potential toxicity, bioaccumulation, and environmental persistence. In this study, we determined the concentrations and profiles of OPEs in surface soils collected from Jinan City, East China. The soil concentrations of ΣOPE (sum of all OPEs) were in the range of 2.55-581 ng/g dry weight (dw), with an average value of 106 ng/g dw. Industrial soils (mean: 433 ng/g dw) had significantly higher levels of ΣOPE compared with those in urban (42.1 ng/g dw) and farmland soils (7.89 ng/g dw) (p < 0.01), suggesting that industrial activity is an important source of OPEs to ambient soil environment. Tris(1-chloro-2-propyl) phosphate (TCIPP), triphenyl phosphate (TPHP), and tris(2-butoxyethyl) phosphate (TBOEP) were the most abundant OPEs in industrial soils, contributing 30%, 25%, and 20% of ΣOPE, respectively. Principal component analysis revealed that TCIPP, TPHP, and TBOEP in soils derived from respective industrial activities. As compared with other cities within China, the surface soil of Jinan City was mildly contaminated by OPEs, and its human exposure and eco-toxicological risks were found to be negligible. Our study provides current contamination status of OPEs in soils across the multiple functional regions of Jinan, which could be used to support the authorities to make relevant regulations.

Large-scale distribution of organophosphate esters (flame retardants and plasticizers) in soil from residential area across China: Implications for current level

To recognize the occurrence and health risk of organophosphate esters (OPEs) in soil of residential areas, a nationwide survey was conducted covering 32 provincial-level administrative regions of China in 2018. Except for triamyl phosphate (TAP), twelve OPEs were detected in residential soil from 89 cities with a total concentration of 1.70–179 ng/g dw, indicating a relatively low contamination level of OPEs in residential soil of China (compared with point source soils and urban soils). Tris(1-chloro-2-propyl) phosphate (TCIPP) was the most abundant OPEs, followed by tris(2-butoxyethyl) phosphate (TBOEP), tris(2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPHP), which suggested that TCIPP has been a replacement of TCEP in recent years. An apparent geographical distribution of higher OPEs levels in the Bohai Rim, the Yangtze Delta and Shanxi province than other regions was found. According to the division of administrative levels, the most serious OPEs pollution occurred in prefecture-level city (20.2 ng/g dw), followed by provincial capital (17.9 ng/g dw) and county town (14.1 ng/g dw), which was affected by the usage of OPEs products and behaviors of local residents. The correlation analysis results showed that environmental parameters (total organic carbon (TOC), precipitation and temperature) were not the major factors determining OPEs contamination, while socioeconomic parameters were significantly correlated with OPEs concentration in undeveloped regions/cities with rare industrial source. Although the health risk assessment suggested a negligible risk to local residents (5.92 × 10−7-1.75 × 10−6 for non-carcinogenic risk and 4.82 × 10−12-2.10 × 10−11 for carcinogenic risk), the production and usage of TCIPP and TCEP should be paid more attention due to their relatively high risks. Our study was attempted to provide a nationwide baseline concentration of OPEs in soil of residential areas, which could be used to support further studies.

A nationwide survey of 19 organophosphate esters in soils from China: Spatial distribution and hazard assessment

Organophosphate esters (OPEs) are ubiquitous in the environment, but little is known about their distribution in soils. In this study, we measured 19 OPEs in soil samples collected nationwide in China for the first time. Concentrations of 19 OPEs (∑OPEs) in soils ranged from 4.50 to 430 ng/g dry weight (dw), with a median value of 36.6 ng/g dw. ∑OPE concentrations in soils were significantly higher in Northeastern (90.6, 19.1–180 ng/g dw; median, range) and Eastern/Southern China (57.4, 7.23–430 ng/g dw), areas with high population density and economic development, than those in Central (35.8, 4.80–417 ng/g dw) and Western China (29.7, 4.50–228 ng/g dw). High concentrations of ∑OPEs were found in soils collected from sites located in the most urbanized areas of China including Beijing (126 ng/g dw), Shanghai (388 ng/g dw), and Guangzhou (430 ng/g dw). Chlorinated (Cl-) OPEs were the predominant compounds, accounting for over 74.0% of ∑OPE concentrations in soils from China. In soil samples from Northeastern and Eastern/Southern China, Cl-OPEs accounted for 84.3% and 92.1% of ∑OPE concentrations, respectively. Cresyl diphenyl phosphate (CDPP) and isodecyl diphenyl phosphate (IDDP), which have been less studied thus far, were also found at measurable concentrations (0.15–0.40 ng/g dw) in soils. The Spearman's rank correlations among major aryl-OPEs in soils were significant (Rho = 0.582–0.747, p < 0.01), which suggested similar sources of environmental release of these compounds. Total organic carbon (TOC) content was not correlated with the concentrations of ∑OPE in soils (Rho = 0.036, p > 0.05). A hazard assessment for ten OPEs in soils suggested a notable risk from tris(2-ethylhexyl) phosphate (TEHP) and trimethylphenyl phosphate (TMPP). Further studies are needed to elucidate the fate of TMPP in soils.

Occurrence and Distribution of the Organophosphate Esters in Soils of Mixed-land Use Area in Chongqing City

Organophosphate esters (OPEs) in surface soil of four different functional areas in Chongqing were identified and quantified using ultra-high performance liquid chromatography-quadrupole-time of flight mass spectrometry (UPLC-Q-TOF-MS). The composition and characteristics of OPEs were discussed along with the relationships between soil organic matter (SOM) and OPEs through correlation analysis, and possible sources of OPEs were simultaneously investigated through principal component analysis (PCA). The results showed that the concentrations of ∑OPEs ranged from 10.7 to 108 ng·g-1 dry weight, with a mean concentration of 46.4 ng·g-1, which was at the low-level end of the global figure. The average concentration was 55.6 ng·g-1 in the industrial area, 55.5 ng·g-1 in the residential area, 41.8 ng·g-1 in the commercial area, and 34.1 ng·g-1 in the city park. Tris (1-chloro-2-propyl) phosphate (TCPP) and 2-ethylhexyl diphenyl phosphate (EHDPP) were dominant compounds, contributing up to 31.5% in the industrial area for TCPP and 23.4% and 24.7% in the commercial area and city park, respectively, for EHDPP. Significant relationships between concentrations of SOM and ∑OPEs (P<0.05) and tricresyl phosphate (TCP) (P<0.01), respectively, indicated that SOM was a factor affecting the concentration and distribution of the OPEs. The PCA suggested that there were multiple sources of OPEs in urban soil. Sewage irrigation, road runoff, indoor source pollution, and sludge reuse could be potential sources of soil OPEs.

Simultaneous accelerated solvent extraction and purification for the determination of 13 organophosphate esters in soils by gas chromatography-tandem mass spectrometry.

Through the optimization of extraction, purification, and determination parameters, a reliable and convenient analytical method for the simultaneous determination of 13 organophosphate esters in soils was developed. The method is based on one-step extraction and purification by accelerated solvent extraction and analysis by gas chromatography-ion trap tandem mass spectrometry. Under the optimal conditions, the method detection limits and method quantitation limits ranged from 0.10 to 0.22ng/g and from 0.33 to 0.72ng/g, respectively. The recoveries obtained were in the range of 81.7-107%, and the relative standard deviations were less than 12%. As compared to other methods, this proposed method was simple and time and solvent saving. The developed method was successfully applied to analyze organophosphate esters in soil samples collected from Liaohe estuarine wetland, China. Thirteen organophosphate esters were detected in all of the soil samples which indicated that Liaohe estuarine wetland has polluted by organophosphate esters.

Occurrence of Organophosphate Esters in Soils of the Three Gorges Reservoir

Organophosphate esters (OPEs) were first identified and quantified in farmland and riparian soil in the Three Gorges Reservoir (TGR) of western China. The mean concentrations of OPEs were 272 ng·g-1 dry weight (dw) in farmland soil and 498 ng·g-1 dw in riparian soil. These values lie at the middle of the range of worldwide values. Hydrodynamic conditions might be important factors contributing to the slightly different spatial distribution of the OPEs. The concentrations of the OPEs in riparian soil exceed those in farmland soil, which could partly be ascribed to the operation of the Three Gorges Dam (TGD). Of particular note is the elevated contribution of TCP, followed by EHDPP, accounting for more than 90% of the total OPEs, and the degradation of TBEP by microorganisms in the soil could be related to the low occurrence of TBEP. Significant correlation between the OPE concentrations in farmland and riparian soil were obtained, indicating that the OPEs in farmland and riparian soil originated from the same source. A principal component analysis (PCA) showed that the OPEs in farmland soil might come largely from construction and decoration materials, and the OPEs in riparian soil may be derived from a combination of construction materials and vehicular traffic emissions.

Current State, Distribution, and Sources of Phthalate Esters and Organophosphate Esters in Soils of the Three Gorges Reservoir Region, China.

Phthalate esters (PAEs) and organophosphate esters (OPEs) were identified and quantified in surface soils from farmland and riparian areas of the Three Gorges Reservoir (TGR), western China. Generally, the mean values of PAEs and OPEs were 618 and 266ng/g dry weight (dw) in farmland soil and 560 and 499ng/g dw in riparian soil, respectively. The occurrence of OPEs should be regarded as a risk factor in the TGR region. Analogous spatial distribution patterns for PAEs were observed with higher concentrations observed at site WZ in both types of soil, which might relate to the anthropogenic activities. The hydrodynamic conditions might be important factors contributing to the slightly different spatial distribution of OPEs. The concentrations of OPEs in riparian soil exceed those in farmland soil at all sampling sites, which could partly be ascribed to the complete operation of the TGR. Dibutyl phthalate (DnBP) was the most dominated PAEs congener in both types of soil. Of particular note is the elevated contribution of tris(methylphenyl) phosphate (TMPP), followed by 2-ethylhexyl diphenyl phosphate (EHDPP), accounting for more than 90% of the total OPEs, and the shipping or/and the local human activity might be considered as the major contributor. The slight differences in PAEs composition of principal components might largely attribute to the variety of emission sources in two types of soil. The different cluster patterns between two types of soil indicated that the anthropogenic activities as well as the full operation of TGR, may play a role.

Concentration and spatial distribution of organophosphate esters in the soil-sediment profile of Kathmandu Valley, Nepal: Implication for risk assessment

Despite the fact that soil and sediments, which act as a sink or potential source of organic pollutants, have been polluted with organophosphate esters (OPEs) around the globe, extremely constrained data is accessible on environmental concentration and fate of OPEs in solid matrices in whole of the South Asia particularly if there should be an occurrence in Nepal. In this study, surface soil (N=19) and sediments samples (N=20) were analyzed for eight different OPE in Kathmandu Valley during October 2014. The concentration of ∑8OPE measured in sediments samples was 12 times higher than soil and ranged 983–7460ng/g dw (median 2210ng/g dw) and 65–27,500ng/g dw (186ng/g dw), respectively. TMPP was most abundant in soil followed by TCIPP, TEHP and EHDPHP and ranged 17–25,300ng/g dw (41.3ng/g dw), 11.2–911ng/g dw (31.7ng/g dw), 8.52–858ng/g dw (26.1ng/g dw) and 10.2–114ng/g dw (25.6ng/g dw), respectively. TEHP was most prevalent in sediments followed by TMPP and EHDPHP and were in the range of 657–3020ng/g dw (median 1140ng/g dw), 267–2630ng/g dw (median 815g/g dw), 34–418ng/g (median 131ng/g dw), respectively. The sources of the high level of OPEs in soil was related to the end point use of consumer materials, traffic emission, and close proximity to commercial and industrial areas; while domestic sewage discharges and effluents from carpet industry were identified as the possible entry of OPE in sediments. Total organic carbon (TOC) and black carbon (BC) content in soil were moderately and positively correlated with ∑8OPE indicating more or less influence of soil organic carbon. The health risk assessment suggested dermal absorption of OPEs via soil is the primary pathway of human exposure to the general population. The significantly high-risk quotient (RQ) estimated for ∑8OPEs especially TMPP and TPHP suggested significant potential adverse risk for aquatic organisms.

Application of Twisselmann Extraction, SPME, and GC-MS To Assess Input Sources for Organophosphate Esters into Soil

Although the ubiquitous distribution of organophosphate esters (OPEs) in the environment has been documented very thoroughly, data on their occurrence in soil is so far sparse. In this study, an analytical method was developed to determine six OPEs in soil. The method consists of a combination of Twisselmann extraction and solid-phase microextraction (SPME), followed by gas chromatography-mass spectrometry (GC-MS). To develop the method, spiked soil was extracted using a Twisselmann extractor after freeze-drying. The extract was evaporated to dryness, redissolved, and filtered. A volume of 7 mL was then analyzed by SPME, followed by GC-MS. The effects of different parameters on analyte recoveries during sample preparation, e.g., solvent for Twisselmann extraction, solvent for redissolving the extract, addition of copper, and filtration of the extract, were systematically investigated. Under optimum conditions, 10 g soil samples were extracted using toluene, and the extract was redissolved in methanol/water (1:14) and filtered. It was not necessary to add copper. For TnBP, TBEP, TCPP, and TCEP, recoveries ranged from 77.0% to 89.6%. Those for TPP and TDCP were much lower, at 31.5% and 42.0%, respectively (addition level 22.9-45.8 ng g(-1)). The variability of recoveries under these conditions was between 0.3 and 16.2% (n = 3). Limits of detection (LOD) were 0.002-3 ng g(-1). When ultrasonication was used in place of Twisselmann extraction in the developed method, recoveries were three to four times lower (27.4% to 30.6%), but the variability of recoveries was below 3% (n = 3). The method was applied to quantify OPEs in soil collected from the university campus in Osnabrueck (Germany). Average concentrations (n = 6) in soil samples ranged from 1.23 ng g(-1) to 4.96 ng g(-1) (dry weight) for TCPP, TPP, and TCEP. The results demonstrate for the first time that atmospheric deposition leads to soil contamination by OPEs.