Organophosphate esters (OPEs) have garnered significant attention for their extensive environmental presence and potential risk to biota, including humans. This study investigated the levels, influencing factors, sources and health risks of OPEs partitioning in atmospheric fine particulate matters (PM2.5) and total suspended particles (TSP) from Nanjing, China. The total concentrations of eleven OPEs (detection frequency > 50%) in PM2.5 and TSP were range of 57.0 − 404 pg/m3 and 37.7 − 354 pg/m3. OPEs tended to partition into fine particles for their higher adsorption capacity and octanol-air partition coefficient (KOA) of OPEs. Meteorological factors such as temperature and air pressure had opposite effects on halogenated and aryl OPEs, with high temperatures and low pressures causing halogenated OPEs to volatilize and partition into particles. Air mass trajectory analysis indicated differing sources for particulate matter and OPEs, with particulate matter originating mainly from Anhui, Jiangsu, Zhejiang, Henan, Jiangxi and Hubei provinces, and OPEs primarily from Jiangxi, Zhejiang and Shandong provinces. Correlation analysis and principal component analysis identified building constructions, traffic emissions and foam products, and indoor emissions as OPEs sources. The non-cancer risk assessment indicated no potential risk of concern, as the evaluation by hazard quotient was far below the acceptable risk.

Trace metals (TRs) and polycyclic aromatic hydrocarbons (PAHs) are major toxic components of fine particulate matter (PM 2.5 ) and related to various health adverse outcomes. The study aims to get a better understanding of the contents, sources and risks of PM 2.5 -bounded TRs and PAHs in Hefei, China, during the period of 2019–2021. We collected 504 samples and measured twelve TRs and sixteen priority PAHs by inductively coupled plasma mass spectrometry and high-performance liquid chromatography. The annual mass concentrations of PM 2.5 was fluctuated in the year of 2019–2021 at 50.95, 47.48 and 59.38 μg/m 3 , with seasonal variations in rank order of winter > spring > autumn > summer. The median concentrations of PM 2.5 -bounded ƩTRs and ƩPAHs were also fluctuated, 132.85, 80.93 and 120.27 ng/m 3 for ƩTRs, 2.57, 5.85 and 2.97 ng/m 3 for ƩPAHs, in the year of 2019, 2020 and 2021, respectively. Seasonal variations of ƩTRs and ƩPAHs show the highest concentration in winter. Positive matrix factorization was used for identified pollution emission sources, and TRs mainly originated from coal combustion, traffic emission and fugitive dust, while PAHs stemmed from biomass, diesel, gasoline and coal combustion. Health risk assessment indicated that adults were more vulnerable than children, the carcinogenic risk assessment of As and Cr manifested a certain degree of cancer risk (1.0 × 10 –6 < CR < 1.0 × 10 –4 ) in adults group, and health risks of TRs were higher than PAHs in Hefei. These findings suggest that PM 2.5 -bounded TRs and PAHs should be considered when making emission control strategies for air pollution, and winter, combustion sources and adults should achieve more policy attention to decrease exposure risks in Hefei.

The sorption mechanism and effects of pH of Na-montmorillonite dried by two different methods on estrone (E1) were investigated in this study. Freeze-dried and 110 ℃ oven-dried methods were used as the two different drying methods for Na-montmorillonite, and they were used for subsequent sorption isotherms and kinetic experiments. Results show that specific surface area and pore volume of freeze-dried Na-montmorillonite were higher than those of 110 ℃ oven-dried one. However, no significant variations of surface functional groups presented for the two Na-montmorillonites. According to the kinetic results, the two Na-montmorillonites both had rapid sorption rates, reaching sorption equilibrium in 45 min for freeze-dried one and in 20 min for 110 ℃ oven-dried one. Besides, the proposed first-order kinetics equation for the freeze-dried Na-montmorillonite and the pseudo-second-order rate equation for 110 ℃ oven-dried Na-montmorillonite were described. Moreover, the sorption isotherms indicate that freeze-dried Na-montmorillonite had significantly higher sorption affinity with E1 compared to oven-dried Na-montmorillonite. The effects of pH on the sorption of E1 by the two kinds of Na-montmorillonite were comparable. High or low pH value was not conducive to sorption of E1 by Na-montmorillonite, and the optimal pH value for adsorption is 6.

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.

Indoor dust is an important route of exposure for organophosphate esters (OPEs), which are associated with adverse health effects. In the present study, the pollution occurrence and potential health risks of 13 OPEs in indoor dust from urban homes, college dormitories, and rural homes in Nanjing were investigated. Most OPEs were detected in the tested samples. College dormitories dust samples showed significantly higher OPEs concentrations (132.31–1.61 × 103 ng/g), followed by that in urban homes (31.42–49.84 ng/g) and rural homes (51.19–309.75 ng/g). The Mann-Whitney U test found no significant difference in the total concentrations of OPEs except for some individual OPEs between urban and rural homes. Tris (2-chloroisopropyl) phosphate (TCPP) was the most abundant compound in all tested areas. Spearman correlation coefficients and principal component analysis indicated that OPEs might originate from different sources in three microenvironments. Estimated exposures for adults and children in all indoor dust were below the relevant reference doses. Additionally, TCPP was the primary contributors to the non-carcinogenic risk, ranging from 1.07 × 10−6 to 2.20 × 10−5. Tris (2,3-dibromopropyl) phosphate was the dominant carcinogenic risk contributor in indoor dust, with a range of 1.33 × 10−11 to 8.74 × 10−10. These results suggested that the health risk of OPEs was within acceptable limits in the tested areas.

[目的]建立了固相萃取-高效液相色谱法研究可溶性有机物对绿麦隆在小麦体内积累的影响.[方法]采用乙腈-水为提取溶剂,通过固相萃取Sep-pak C18柱分离和混合模式的GCC-SAX-PSA串联柱净化,反相高效液相色谱法定量分析了2种可溶性有机物(DOM)对绿麦隆在小麦体内积累的影响.[结果]该方法最小检出限为2×10-10g,最低检出质量分数为0.05 mg/kg,小麦叶片和根系中绿麦隆添加回收率为85.7％、92.4％,变异系数0.2％、2.8％.[结论]研究发现绿麦隆施药质量分数较低(5 mg/kg)时,可溶性有机物可以降低绿麦隆在小麦幼苗体内的含量,可降低其生物毒性;当施药质量分数较高(10、25 mg/kg)时,可溶性有机物使绿麦隆在小麦幼苗体内的含量增高,增大其生物毒性.来源于稻草的可溶性有机物对小麦幼苗吸收绿麦隆的影响强于来源于污泥的可溶性有机物,并且随可溶性有机物浓度的增高,影响增大.

A typical domestic waste incineration power plant was selected as the research objective, and the concentration of dioxins in ambient air, soil, groundwater and crops were monitored for assessing human exposure level. The concentration of dioxins in ambient air, soil and groundwater in the surrounding area of the power plant were 0. 236 pgTEQ/m3～ 0. 331 pgTEQ/m3, 1. 94 ngTEQ/kg ～ 2. 71 ngTEQ/kg and 0. 17 pgTEQ/L ～0. 26 pgTEQ/L, respectively. Dioxins emissions had less impact on the surrounding environment. Dioxin exposure dose estimation showed that dioxin exposure levels for adults and children living in the study area were0. 959 pgTEQ/ (kg·d) and 1. 59 pgTEQ/ (kg·d), respectively, which were below the tolerable intake level of4 pgTEQ/ (kg·d). Dioxin exposure dose through rice and flour were more than 90％ of the total, revealing that food was the dominant source of dioxin exposure.

With increasing use of organophosphate esters (OPEs) largely due to the phasing out of various brominated flame retardants, much more attention has been paid to their occurrence, distribution and potential health risks. In this study, we investigated the occurrence and distribution characteristics associated to their potential health risks of selected 13 OPEs in outdoor dust with a comparison between urban and rural areas in Nanjing, China as well as seasonal variations. Ten out of 13 OPEs showed higher concentrations in urban dust than those in rural dust (p < 0.05). Six OPEs congeners exhibited significantly different concentrations with seasonal variations (p < 0.01) in rural dust. Halogenated OPEs were the dominant group in both urban (median: 56.8%) and rural (median: 45.9%) dust, and tris(2-chloroisopropyl) phosphate (TCPP) was found to be the most abundant OPE in both urban (median: 48.7%) and rural (median:26.4%) dust. Principal component analysis with multiple linear regression (PCA-MLR) and spearman correlations showed the different sources of OPEs in urban and rural dust. The non-carcinogenic (Hazard Index, HI < 1.62 × 10-5) and carcinogenic risks (CR < 2.28 × 10-9) of ΣOPEs were much lower than the theoretical threshold of risk, revealing a negligible risk to local residents from the exposure of OPEs in outdoor dust.

A method was established for the determination of chlorpyrifos metabolites employing QuEChERS method and ultra performance liquid chromatography-triple quadrupole-linear ion trap mass spectrometry (UPLC-QTRAP). The urine samples were extracted by acetonitrile and then cleaned up with PSA and GCB. The samples were separated with the gradient elution of acetonitrile-0.2% ammonia water on ZORBAX Eclipse Plus C-18 column. The analytes were detected by tandem mass spectrometry under negative ion mode with electrospray ionization (ESI) source and MRM-IDA-EPI mode. Under the optimized conditions, the calibration curve was linear in range of 1.0-100.0 mu g/L, and the limits of detection were 0.10-0.73 mu g/L. The average recoveries were 80.3%-90.1%, and RSDs were all within 10%. The developed method was simple, sensitive, accurate, and repeatable, and could avoid false positive result of samples effectively. The established method was successfully applied to determine the exposure level of chlorpyrifos metabolites in real samples of human health risk analysis. The results showed that the maximum concentration of chlorpyrifos metabolites was 54.6 mu g/L. This method provided technic support for simultaneous identification and quantification of chemicals in complex matrix.

Organophosphate esters (OPEs) are ubiquitous in the aquatic environment, which have been considered or suspected as carcinogens and neurotoxicants. In this study, the occurrence, spatial distribution, potential sources, partitioning character and potential risks of OPEs in the surface water and sediment collected from Taihu Lake were investigated. The concentrations of ∑12 OPEs varied from 1.0 × 102 to 1.7 × 103 ng/L for the surface water and from 8.1 to 4.2 × 102 ng/g dw for the sediment. Trimethyl phosphate (TEP) was the predominant congener in the surface water, while Tris(2-ethylhexyl) phosphate (TEHP) in the sediment. Positive correlations between OPEs indicated that they may have the same sources and/or similar environmental behavior. The pseudo-partitioning values of OPEs ranged from 0.59 to 6.5 × 104 L/kg. TEHP has the highest pseudo-partitioning coefficient, which indicated that TEHP inclined to be enriched in the sediment in Taihu Lake. Risk assessment (RQ) showed that individual OPEs in the surface water and sediment posed no/low risk to aquatic organisms, except 2-Ethylhexyl diphenyl phosphate (EHDPP) (moderate risk) in water.

In this paper,4 Na-montmorillonites were prepared by 4 pretreatment methods,including oven-drying at 100 ℃,calcination at 200℃and 300℃,and freeze-drying.Their physical and chemical properties were investigated.Meanwhile,the adsorption behaviors of the obtained Na-montmorillonites with regard to Cd2+was discussed. The purpose was to investigate the influence of different pretreatment methods on the physicochemical properties of Na-montmorillonite and its difference in the adsorption of Cd2+.Results showed that the dif-ferent pretreatment methods had a significant influence on the physical properties,such as the specific surface area,pore volume,and inter-layer spacing.However,the effects on chemical properties,such as surface functional groups and cation exchange capacity,were not obvi-ous. The adsorption could achieve equilibrium in 24 hours, while the adsorption kinetics indicated that the quasi- second- order kinetic equation was more suitable for describing the adsorption process, indicating ion-exchange adsorption. The adsorption isotherm was in accordance with the Langmuir isotherm model,partially proving single-layer adsorption.The maximum adsorption capacity of Na-montmo-rillonite could be achieved by calcination at 300℃,with an adsorption capacity of 11.1 mg·g-1.However,only 9.1 mg·g-1Cd2+could be ad-sorbed,as Na-montmorillonite from the oven-drying treatment at 100℃was employed.

Fourteen water samples collected from Nanjing reach of Yangtze River were analyzed using high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) to evaluate the contamination level,ecological risk and health risk of 12 sulfonamides.The results showed that eight sulfonamides were detected and the total concentrations ranged from 13.2 to 21.0 ng·L-1,median concentration was 16.4 ng ·L-1 and mean value was 16.2 ng· L-1.The highest concentration of the eight detected antibiotics was sulfamethoxazole (6.76-8.98 ng·L-1),followed by sulfadiazine (2.52-6.59 ng·L-1).Concentrations of sulfamethythiadiazole,sulfamonomethoxine,sulfamethoxypyridazine and sulfathiazole in sampling sites were all under limit of detection.In summary,levels of sulfonamides in Nanjing reach of Yangtze River were relatively low compared to the other domestic and foreign rivers and lakes.The risk assessment showed that risk quotients (RQs) of four selected sulfonamides were all less than 0.01.The combined risk quotients of 4 sulfonamides in water of Nanjing reach of Yangtze River were between 0.0029 and 0.0039,indicating that those compounds pose no significant risks to aquatic ecosystem altogether.Human health risk assessment showed that the RQs were less than 1 for the four selected sulfonamides,indicating that these compounds do not appear to pose an appreciable risk to human health from potential environmental exposure.

Hydroxylation polybrominated diphenyl ethers (OH-PBDEs) are a class of phenolic compounds that have been found to be an endocrine disruptor, and the in vitro metabolism of OH-PBDEs and effect on metabolism of synthetic estrogen were investigated using mouse liver microsome. The results showed that all of the four OH-PBDEs can be metabolized, and the metabolic rate followed the order: 6-OH-BDE-99＞6'-OH-BDE-99＞6-OH-BDE-137＞5'-OH-BDE-99, which indicated OH-PBDEs were more readily bio-transformed when the hydroxyl functional group (-OH) was in the ortho position with the ether bond and the Br atom. The four OH-PBDEs showed different effects on the metabolism of natural estrogens, including estrone (E1), 17β-estradiol (E2), estriol (E3). As a whole, the inhibition on metabolic rate of E1 and E2 gradually increased with the increasing concentrations of OHPBDE, but showed a promotion effect on metabolism of E3 and no significant effect on metabolism of synthetic estrogen 17α-ethynylestradiol (EE2). The quantification of the metabolite 2-hydroxyestradiol (2-OH-E2) showed that6-OH-BDE-99 promoted the 2-OH-E2 production, while 2-OH-E2 production was inhibited by the other three OHPBDEs as the experimental concentration increased, and these results revealed that it may be related to the different metabolic mechanisms mediated by enzymes.

有机磷酸酯类阻燃剂(organophosphate flame retardants,OPFRs)作为多溴联苯醚等溴代阻燃剂(brominated flame retardants,BFRs)的替代品被广泛应用,由此带来的环境影响广受关注.目前针对OPFRs的生物毒性研究仍相对有限,需要更全面调查其在多环境介质中的暴露状况、环境归趋、生物毒性效应等研究成果,在此基础上才能综合评价其可能引起的生态风险.因此,综述了OPFRs对水生生物、哺乳动物和人类等多种生物体的急性毒性、生殖与发育毒性、神经毒性、脏器毒性、基因毒性与致突变性和内分泌干扰性.OPFRs的多种生物毒性已得到证实,但相关致毒机制研究尚不完整深入.最后对OPFRs的进一步研究存在的问题进行分析,提出了研究展望,以期促进开展OPFRs的环境风险和人体健康风险研究.

The occurrence and spatiotemporal distribution of 12 organophosphate esters (OPEs) were investigated in the sediments collected from Taihu Lake. Compared to the same lake in 2012 (3.4–14 ng/g dw), the concentrations of ∑12 OPEs in sediments ranged from 10.76 to 335.37 ng/g dw and from 8.06 to 425.39 ng/g dw in 2015 and in 2016, respectively, indicating that the OPEs levels in Taihu Lake have aggravated, recently. TEHP was the most abundant compound of the OPEs, which suggested that TEHP was the most widely used around Taihu Lake recently. The positive correlations between some of individual OPEs and the principal components analysis suggested the same potential sources for them. The strong positive correlation between ∑BPs and TOC content indicated that TOC content was one of the factors affected the distribution of ∑OPEs in the sediment. Risk quotient (RQ) for OPEs showed no high eco-toxicity risk in sediment for aquatic organisms.

Organophosphate esters (OPEs) are ubiquitous in the environment and pose a potential threat to ecosystem and human health. This study investigated the concentrations, distributions and risk of 12 OPEs in surface water and sediment from Luoma Lake, Fangting River and Yi River. Solid-phase extraction (SPE) method were used to extract OPEs from water samples, ultrasonic process and SPE method were used to extract OPEs from sediment samples, and the extracts were finally analyzed using the HPLC-MS/MS. The results revealed that the median and maximum concentrations of Sigma OPEs were 73.9 and 1066 ng/L in surface water, and were 28.7 and 35.9 ng/g in sediment, respectively. Tris(2-chloroethyl) phosphate (TCEP) and trimethyl phosphate (TMP) were the most abundant OPEs in the surface water with median concentrations of 24.3 and 16.4 ng/L in Luoma Lake, respectively. Triethyl phosphate (TEP) was the most abundant OPE in the sediment with amedian concentrations of 28.9 ng/g. However, tricresyl phosphate (TCrP) and ethylhexyl diphenyl phosphate (EHDPP) predominantly contributed to the ecological risk with respective median risk quotients 0.07 and 0.01 for surface water in Luoma Lake. TEP and TCrP were the most significant contributors to the ecological risk with respective median risk quotients of 6.4 x 10(-4) and 5.6 x 10(-4) for sediment. It was also found that inflowing Fangting River could be the major pollution source to Luoma Lake. The no-cancer and carcinogenic risks of OPEs were lower than the theoretical threshold of risk. The study found that the ecological and human health risks due to the exposure to OPEs were currently acceptable. In other words, the Luoma Lake was relatively safer to use as a drinking water source in urban areas in the context of OPEs pollution. (C) 2018 Elsevier B.V. All rights reserved.

The occurrence, distribution and bioaccumulation of six endocrine disrupting compounds (EDCs) were investigated in water, sediment and biota samples from Luoma Lake, a shallow Chinese freshwater lake. Total concentrations of ∑phenolic EDCs were much higher than ∑estrogens EDCs in both waters and sediments. There were not obvious differences on the concentrations of target compounds [except nonylphenol (NP)] in upstream, lake and downstream locations, these may be suggested that they were mainly affected by non-point discharges in this area. However, the high concentration of NP in water may be associated with the discharge of rural domestic wastewater without thorough treatment. Furthermore, concentrations of NP were about 2-3 order magnitude higher than those of OP in both water and sediment compartments. Relatively higher bioaccumulation factors (BAF) were obtained for DES and EE2. Ecological risk assessment revealed greater risk of NP in surface water, which may pose a serious threat to aquatic ecosystems. The estrogen equivalent concentration (EEQ) of male were higher than those in female, and occurred in the order of city >rural-urban>countryside.

In this study, seven bisphenol analogues were measured in water and sediment samples from Taihu Lake, and potential risk was evaluated. The results showed that BPF, BPS and BPA were the predominant components in water samples from Lake Taihu. In sediment, BPA was always predominant, followed by BPF and BPS, and there was a significant positive correlation between BPs and TOC content. In addition, the high concentration levels of BPF, BPS and BPA were distributed in the tributaries of Lake Taihu(S4-S10). The risk assessment of the target BPs showed that the combined risk quotients posed a low eco-toxicity to aquatic ecosystem, and there was no appreciable risk to human health from potential environmental exposure of drinking water.

To evaluate passenger health risks associated with inhalation exposure to carbonyl compounds mainly emitted from decoration materials of vehicles, we tested the carbonyl concentrations in interior air of 20 family cars, 6 metro lines, and 5 buses in the city of Nanjing. To assess non-carcinogenic health risks, we compared the data to the health guidelines of China, US Environmental Protection Agency (EPA), and Office of Environmental Health Hazard Assessment (OEHHA), respectively. To assess carcinogenic risks, we followed a standard approach proposed by the OEHHA to calculate lifetime cancer risks (LCR) of formaldehyde and acetaldehyde for various age groups. The results showed that there are formaldehyde, acetaldehyde, and acrolein concentrations in 40, 35, and 50% of family car samples exceeded the reference concentrations (RfCs) provided by Chinese guidelines (GB/T 27630-2011 and GB/T 18883-2002). Whereas, in the tested public transports, concentrations of the three carbonyls were all below the Chinese RfCs. Fifty and 90% of family cars had formaldehyde and acrolein concentrations exceeding the guidelines of OEHHA. Only one public transport sample (one bus) possesses formaldehyde and acetaldehyde concentrations above the chronic inhalation reference exposure limits (RELs). Furthermore, the assessments of carcinogenic risk of formaldehyde and acetaldehyde showed that lifetime cancer risks were higher than the limits of EPA for some family cars and public transports. In the study, buses and metros appear to be relatively clean environments, with total carbonyl concentrations that do not exceed 126 μg/m3. In family cars, carbonyl levels showed significant variations from 6.1 to 811 μg/m3 that was greatly influenced by direct emissions from materials inside the vehicles. Public transports seemed to be the first choice for resident trips as compared to family cars.

Oxytetracycline (OTC) commonly undergoes direct photolysis as the main elimination pathway in surface waters. The photolysis of OTC was studied as a function of initial concentration, pH and temperature. The experiments were performed in the absence of oxygen to avoid oxygen induced indirect photolysis. The photolysis rate decreased when increasing the initial OTC concentration, and was accelerated as raising the temperature. pH was the key factor controlling the photolysis rate. By measuring the UV-vis absorption spectra of OTC under various pH conditions and fitting them with global analysis, four OTC species H3L+, H2L +/-, HL-, and L2- (L represents OTC) were decomposed, meanwhile, the acid dissociation constant of OTC and the molar absorption coefficient of each species were resolved. Because apparent photolysis rate constants under varied light source conditions are often incomparable, therefore the direct photolysis quantum yield of OTC species were calculated by a mathematical approach which based on the molar absorption coefficients, the species composition and apparent kinetic rates of OTC under experimental pH conditions. The result shows the photolysis quantum yield of OTC followed the order L2- > (HL +/-)-L-2 > HL- > H3L+. The direct photolysis rates of OTC were tightly correlated to the energy dissipation processes at the excited states, e.g., the excited states inter-/intramolecular proton transfer (ESIPT), and the molecular conformation transfer induced internal energy transmission between ground state and excited state. Fluorescence emission was not an important energy dissipation process. The results of this study provide the useful parameters for predicting the environmental fate of OTC in surface waters. And the approach for calculating the photolysis quantum yield is also available for other antibiotics with multiple pKa values. (C) 2016 Published by Elsevier B.V.