红海湾海域水产品中有机磷酸酯(OPEs)类阻燃剂污染分析及健康风险评估

为评估有机磷酸酯(organophosphate esters, OPEs)类阻燃剂污染引起的水产品质量安全风险,以广东汕尾红海湾海域近岸养殖和捕捞水产品为研究对象,采用气相色谱三重四级杆串联质谱法(Gas Chromatography-Tandem Mass Spectrometry, GC-MS/MS)对水产品中10种OPEs含量进行测定。结果表明:红海湾海域养殖水产品中∑10OPEs含量为(55.8±24.2)ng/g(干质量),显著高于捕捞水产品中的含量(20.5 ng/g±20.6 ng/g,干质量)(P<0.05);捕捞水产品中,底栖水产品中∑10OPEs含量(28.4 ng/g±22.6 ng/g,干质量)显著高于中上层水产品中的含量(7.4 ng/g±4.3 ng/g,干质量)(P<0.05);磷酸三(2-丁氧基乙基)酯[tris (2-butoxyethyl) phosphate, TBOEP]、磷酸三正丁酯(tri-n-butyl phosphate, TNBP)、磷酸三(2-氯异丙基)酯[tris (2-chloroisopropyl) phosphate, TCIPP]、磷酸三(2-氯乙基)酯[tris (2-chloroethyl) phosphate, TCEP]和磷酸三苯酯(triphenyl phosphate, TPHP)是红海湾海域水产品检出频率最高的OPEs化合物;养殖水产品和捕捞底栖水产品中主要OPEs污染物组成基本一致,含量最高的OPEs污染物依次为TCEP、TBOEP、TCIPP,而捕捞的中上层水产品中含量最高的OPEs污染物依次为TBOEP、TCIPP、TPHP,暴露评估显示,红海湾海域水产品中OPEs对不同年龄段男性和女性的非致癌风险和致癌风险均低于潜在风险阈值,健康风险可接受。研究表明,OPEs污染在养殖和捕捞水产品中普遍存在,所引起的健康风险水平尚在安全范围内,但随着OPEs消费量的持续增加,由其引起的水产品质量安全风险会越来越高,建议对水产品中OPEs污染情况进行持续跟踪调查。

Pollution characteristics and risk assessment of organophosphate esters in aquaculture farms and natural water bodies adjacent to the Huanghe River delta

To date,little attention has been paid to the effects of organophosphate esters(OPEs)pollution on aquacultural environment and aquatic product safety.Huanghe(Yellow)River delta area is one of the largest aquaculture centers in China,where ecological security protection is crucial in the national strategy of China.To explore the pollution characteristics,bioaccumulation,and health risks of OPEs in aquaculture farms in the Huanghe River delta and natural water bodies in the adjacent seas,five species of organisms from different farm types nearby the Huanghe River delta,and the corresponding culture water and sediments were sampled in this study.The total concentrations of Σ_(13)OPEs in water,sediments,and organisms were 51.53-272.18 ng/L,52.63-63.17 ng/g dry weight(dw),and 46.82-108.90 ng/g dw,respectively.Among the five types of culture ponds,the water samples from the swimming crab and hairy crab culture ponds exhibited higher OPEs,the concentration of OPEs in the sediments from the few ponds was relatively balanced,and the OPEs in the organism from the holothurian ponds was higher.Tris(1,3-dichloro-2-isopropyl pho sphate)(TDCP)was the main contaminant in water samples and tripropyl phosphate(TPrP)in sediments and organisms.However,trisphenyl phosphate(TPhP)showed the strongest bioaccumulation ability,followed by 2-ethylhexyl diphenyl phosphate(EHDPP)and TPrP.The bioaccumulation capacities of the five species were as follows:prawn>holothurian>hairy crab>swimming crab>carp.These five types of organisms,as main seafood in human consumption,were at low risk of negative impacts of pollution.However,the risk from the mixture of organophosphate flame retardants(OPFRs)still requires more attention due to the increasing consumption and production in the world.

Fate of organophosphate esters from the Northwestern Pacific to the Southern Ocean:Occurrence,distribution,and fugacity model simulation

Eleven organophosphate esters(OPEs)in the air and seawater were investigated from the northwestern Pacific Ocean to the Southern Ocean during the 2018 Chinese 34th Antarctic Scientific Expedition.The concentration of total OPEs ranged from 164.82 to 3501.79 pg/m~3in air and from 4.54 to 70.09 ng/L in seawater.Two halogenated OPEs,tri(chloropropyl)phosphate(TCPP)and tri(2-chloroethyl)phosphate(TCEP),were generally more abundant than the non-halogenated OPEs.A levelⅢfugacity model was developed to simulate the transfer and fate of seven OPEs in the air and seawater regions of the central Ross Sea.The model results indicate that OPEs are transferred from the air to the seawater in the central Ross Sea in summer,during which the Ross Sea acts as a final OPE sink.Dry and wet deposition dominated the processes involving OPE transfer to seawater.The OPE degradation process was also found to be more pervasive in the atmosphere than in the seawater region.These findings highlights the importance of long-range transport of OPEs and their air–seawater interface behavior in the Antarctic.

典型有机磷酸酯在黄河入海口的分布与生物蓄积特征

以黄河入海口为研究区域,分别在地表水、沉积物、浮游生物以及12种水生生物中检测OPEs含量,结果发现共检出17种OPEs,其中氯代类检出丰度和检出频率最高,是主要的污染物成分,其次是烷基类和芳香类OPEs.同源性分析发现,在地表水与沉积物中氯代类的OPEs污染来源更为广泛.12种水生生物中较高营养级的野生鱼类(如鲢鱼、鲫鱼、梭鱼等)中∑OPEs含量高于低营养级的底栖生物(如日本沼虾等),表明OPEs在水生生物食物链上具有累积性特征,以及物种差异性特征.相比于鳃吸收,肠道摄食是野生鱼类OPEs污染的主要暴露途径.结果显示部分OPEs在黄河入海口的水生食物网中存在一定的生物蓄积和生物放大潜力.风险分析结果表明磷酸三(1,3-二氯异丙基)酯具有潜在的生态风险,需引起广泛关注.

固相萃取-液相色谱-串联质谱测定人体尿液中有机磷酸酯及其二酯和羟基代谢物

尿液中的有机磷酸酯二酯代谢物(di-OPEs)是现阶段识别和量化人体暴露于有机磷酸酯(OPEs)的首选生物标志物.目前鲜有研究同时对OPEs及其二酯代谢物、羟基代谢物(OH-OPEs)进行分析测定,且关注的目标化合物种类较少.本研究对尿液前处理过程中常用的净化浓缩方法进行了优化,建立了人体尿液样品中14种OPEs、7种di-OPEs和3种OH-OPEs的高效液相色谱-串联质谱分析方法(HPLC-MS/MS).取2 mL样品经β-葡萄糖醛酸酶/芳基硫酸酯酶酶解6 h后,加入2%甲酸/水调节pH,然后用STRATA-X-AW固相萃取柱进行净化,收集固相萃取过程中的2%甲酸/甲醇淋洗液和2%氨水/甲醇洗脱液氮吹浓缩后分别进行OPEs、OH-OPEs和di-OPEs的HPLC-MS/MS测定,OPEs和OHOPEs的质谱检测选用电喷雾正离子模式电离,di-OPEs选用负离子模式,在多重反应监测模式(MRM)下测定.尽管尿液样品中多数目标物质在检测时存在基质效应(均值24%-159%),但通过合适的同位素内标进行校正,可以抵消部分基质影响.在优化的条件下,24种目标物质在0.05-40 ng·mL^(−1)范围内线性关系良好(r>0.99),方法检出限(MDL)0.0008-0.32 ng·mL^(−1),加标回收率60%-131%,RSD为4%-22%.采用本方法对实际人体尿液样本进行分析,7种di-OPEs和3种OH-OPEs的总含量为0.07-7.04 ng·mL^(−1),中位含量为0.54 ng·mL^(−1),14种OPEs的总含量为<MDL-0.68 ng·mL^(−1),中位含量为0.05 ng·mL^(−1).两种具有直接工业生产应用的di-OPEs(磷酸二苯基酯DPHP和磷酸二丁酯DBP)检出率高于60%,其来源值得追溯.一种新型有机磷酸酯阻燃剂3-异丙基苯基二苯基磷酸酯(3IPPDPP)的检出率为66.7%,应该引起关注.

有机磷酸酯在植物体内的吸收、积累、迁移与转化研究进展

有机磷酸酯(organophosphate esters,OPEs)在各类环境介质中被频繁检出,且对生态系统和人体健康存在潜在危害,其环境归趋已成为环境科学领域的热点问题.植物作为陆生食物链的重要环节,也是污染物的重要存储体之一,关于植物体吸收、积累OPEs及其在植物体内迁移转化的研究,对明确OPEs的环境行为、评价其生态风险以及科学使用和管理具有重要意义.本文就近年来关于OPEs在植物体内归趋的研究进行汇总,综述了植物吸收OPEs的主要方式、积累以及OPEs在植物体内的迁移与转化行为及其影响因素,并展望了未来研究趋势和发展方向. OPEs主要通过被动扩散被根系吸收;辛醇-水分配系数(octanol-water partition coefficient,K_(ow))是影响植物吸收、积累和迁移OPEs的关键因素,植物根系对lg K_(ow)值为3.5—9.5间的OPEs吸收速率更快;lg K_(ow)<3的OPEs更易通过植物木质部和韧皮部进行运输. OPEs在植物中的吸收、积累和迁移还受植物根系的蛋白质、脂质含量以及蒸腾能力等生理状况的差异影响. OPEs在植物体内会发生Ⅰ相和Ⅱ相代谢过程,磷酸三酯水解成对应的磷酸二酯是OPEs在植物中的主要转化途径,酸性磷酸酶是参与植物体内OPEs水解反应的关键性酶,细胞色素P450酶和谷胱甘肽S-转移酶也能有效促进OPEs在植物中的转化.

大气中有机磷酸酯的赋存状况及环境行为

有机磷酸酯(organophosphate esters,OPEs)作为阻燃剂和增塑剂添加在塑料、织物和建筑材料中,其产量逐年递增. OPEs曾经被认为是溴代阻燃剂(BFRs)的有效替代品;然而,最近的研究指出其在大气中的含量比BFRs高1—3个数量级,且某些OPEs化合物半衰期长,具有显著的毒性效应和长距离迁移潜力,因此,OPEs日益成为一类备受关注的全球性新型有机污染物,“更安全”的替代品的认知被质疑.本文总结了大气中OPEs的赋存状况、气-粒分配、长距离传输和光氧化等方面的研究.通过比较世界各地区大气OPEs的含量和组成特征发现,工业排放源、长距离传输和气象条件是影响大气中OPEs空间分布趋势的重要因素.尽管颗粒态对长距离传输、归趋和风险评价具有重要的科学意义,然而,气-粒分配模型研究和实际监测较为缺乏,模型结果和监测计算结果之间差异较大,推测模型的准确性可能受理化性质、气象条件以及采样技术的影响. OPEs在大气中光氧化降解的研究方兴未艾,仍需继续深入发掘多种环境因素的影响,推测降解路径和产物.因此,将来亟待发展适合OPEs的预测模型,开发新型的采样技术,揭示其光氧化降解路径和产物,以期更好地理解OPEs在大气中的环境赋存和行为规律,为环境质量管理提供理论支持.

气相色谱-质谱联用法同时测定可降解塑料中5种有机磷酸酯

本研究建立了一种可降解塑料制品中5种有机磷酸酯的气相色谱-质谱联用检测方法。样品经二氯甲烷溶解、甲醇反沉淀、气相色谱-质谱联用测定。结果可降解餐盒、地膜的加标回收率范围98.0%~119.8%,相对标准偏差(RSD)0.61%~6.73%(n=6),5种有机磷酸酯的检出限为1.0 mg/kg,定量限为2.5 mg/kg。用自制的添加5种磷酸酯的聚乳酸质控样品进行测试,回收率范围73.1%~89.9%,RSD均小于6.41%。采用该方法测定了11个可降解塑料制品,结果发现餐盒中均未检出5种磷酸酯类物质,地膜和购物袋中磷酸三苯酯(TPP)检出率较高,其余化合物未检出。该方法简单快速,灵敏度高,能够满足检测要求。本研究不仅可为可降解塑料制品企业在生产加工时提供参考,也可以为行业监管提供技术支撑。

超高效液相色谱-串联质谱法测定血清中26种有机磷酸酯类化合物

采用超高效液相色谱-串联质谱(UPLC-MS/MS)建立了血清中26种有机磷酸酯类化合物的检测方法。血清样本经乙腈沉淀蛋白后,通过HMR固相萃取小柱净化,净化液氮吹至近干,甲醇复溶后上机检测。以5mmol/L乙酸铵水溶液和甲醇为流动相,使用C_(18)色谱柱分离目标物,质谱采用电喷雾离子源(正离子模式),以多反应监测模式检测,稳定同位素内标法定量。结果表明,26种有机磷酸酯类化合物在相应质量浓度范围内线性关系良好(r^(2)>0.997),检出限为0.024~0.146 ng/mL,定量下限为0.079~0.483 ng/mL。血清样本的加标回收率为85.7%~115%,相对标准偏差为4.5%~12%。使用该方法检测实际血清样本,检出2种有机磷酸酯类化合物。该方法操作简便、灵敏度高、精密度好,适用于大批量血清样本中有机磷酸酯类化合物的痕量检测。

Short term temporal variability of selected organophosphate esters among healthy adults living in the National Capital Region of Canada

Organophosphate esters(OPEs)are used primarily as flame-retardants and plasticizers.OPEs are commonly detected in various environmental matrices,food and drinking water,and their metabolites are frequently found and quantified in urine.Potential adverse impacts on human health,including carcinogenicity,neurotoxicity,developmental and reproductive toxicity have been well documented.Urinary concentration of OPE metabolites can vary in the same individual,depending on the sampling time,thus introducing significant uncertainty in exposure assessment.The current study focusses on the assessment of short term temporal variability in adult men and women residing in Canada's Capital Region.Fifteen OPE metabolites were analyzed in 562 daily urine samples,collected every three days for five weeks from 11 volunteers.Sample extraction procedure was performed on an automated SPE and extracts analyzed using UPLC-MS/MS.In spot urine samples as well as first morning void(FMV),the detection frequency was greater than 50%for bis(2-chloroethyl)hydrogen phosphate(BCEP),bis(1-chloro-2-propyl)phosphate(BCIPP),bis(1,3-dichloro-2-propyl)phosphate(BDCIPP),diphenyl phosphate(DPHP)and bis(2,4-ditert-butylphenyl)hydrogen phosphate(B2,4DtBPP).Significant difference was observed in males and females for BCEP and BCIPP.Intra-class correlation coefficient(ICC)for creatinine corrected data for the spot urine samples ranged from 0.37 to 0.69.Good reproducibility was observed for creatinine corrected DPHP and BCIPP in both spot urine and FMV samples.More variation was observed between study participants in the spot urine samples when compared to the FMV samples.However,when considering diurnal difference there was a considerable inter-day variation in the FMV samples compared to the spot samples.The strength of the study is that the participants belonged to the same geographical location and working in the same facility,hence spatial variability did not influence the outcome of the results.

Developmental toxicity assessment of neonicotinoids and organophosphate esters with a human embryonic stem cell-and metabolism-based fast-screening model

In recent years,neonicotinoids(NEOs)and organophosphate esters(OPEs)have been widely used as substitutes for traditional pesticides and brominated fame-retardants,respectively.Previous studies have shown that those compounds can be frequently detected in environmental and human samples,are able to penetrate the placental barrier,and are toxic to animals.Thus,it is reasonable to speculate that NEOs and OPEs may have potential adverse effects in humans,especially during development.We employed a human embryonic stem cell differentiation-and liver S9 fraction metabolism-based fast screening model to assess the potential embryonic toxicity of those two types of chemicals.We show that four NEO and five OPE prototypes targeted mostly ectoderm specification,as neural ectoderm and neural crest genes were down-regulated,and surface ectoderm and placode markers up-regulated.Human liver S9 fraction's treatment could generally reduce the effects of the chemicals,except in a few specific instances,indicating the liver may detoxify NEOs and OPEs.Our findings suggest that NEOs and OPEs interfere with human early embryonic development.

Water temperature governs organophosphate ester dynamics in the aquatic food chain of Poyang Lake

Organophosphate esters(OPEs)are increasingly recognized as pervasive environmental contaminants,primarily from their extensive application in flame retardants and plasticizers.Despite their widespread presence,the intricacies of OPE bioaccumulation within aquatic ecosystems remain poorly understood,particularly the environmental determinants influencing their distribution and the bioaccumulation dynamics across aquatic food chains.Here we show that water temperature plays a crucial role in modulating the dispersion of OPE in the aquatic environment of Poyang Lake.We quantified OPE concentrations across various matrices,uncovering levels ranging from 0.198 to 912.622 ng L^(-1) in water,0.013e493.36 ng per g dry weight(dw)in sediment,0.026e41.92 ng per g wet weight(ww)in plankton,0.13e2100.72 ng per g dw in benthic invertebrates,and 0.31e3956.49 ng per g dw in wild fish,highlighting a pronounced bioaccumulation gradient.Notably,the intestines emerged as the principal site for OPE absorption,displaying the highest concentrations among the seven tissues examined.Among the various OPEs,tris(chloroethyl)phosphate was distinguished by its significant bioaccumulation potential within the aquatic food web,suggesting a need for heightened scrutiny.The propensity for OPE accumulation was markedly higher in benthic invertebrates than wild fish,indicating a differential vulnerability within aquatic biota.This study lays a foundational basis for the risk assessment of OPEs as emerging contaminants and underscores the imperative to prioritize the examination of bioaccumulation effects,particularly in benthic invertebrates,to inform future environmental safeguarding strategies.

海洋环境中有机磷酸酯的含量、分布及来源研究进展

有机磷酸酯(Organophosphate Esters,OPEs)作为一种新兴有机污染物和潜在的持久性有机污染物,对其环境行为、生物毒性及风险评价等方面的研究已经成为环境科学领域的研究热点。海洋作为地球生态环境的重要组成部分,不仅是OPEs等众多污染物质最大的汇,还可以通过自身的物理、化学及生物过程将污染物质向全球输运。因此,对海洋环境中OPEs的探究关乎其全球循环和归趋。本文分析了目前已发表的全球海洋环境中OPEs的数据,系统总结了海洋环境中OPEs的分布及来源研究进展。结果表明,海洋上空大气中的OPEs含量一般在几百到几千皮克/米^(3),主要来源于陆地气团输运,且多数存在于颗粒相中,南北半球不存在明显差异;海水中OPEs的含量在零点几到几百纳克/升之间,近岸海域海水中的OPEs主要来源于河流输送,深远海区域海水中的OPEs则主要来源于洋流运动输送,海水中OPEs整体分布呈现近岸海域向深远海扩散的趋势;海洋沉积物中OPEs的平均浓度为几纳克/克(干重),海洋沉积物中的OPEs主要来源于工业、生活污水的排放;海洋生物体中OPEs的含量和组成差异较大,且与生物体内脂肪含量没有明显线性关系,海洋生物体主要通过自身呼吸、摄食、皮肤吸附及吸收等方式摄入海水和沉积物中的OPEs。

Convenient Self-Heating Instant Food Causes Significant Increasing Human Exposure to Organophosphate Esters

The self-heating lunch box(SHLB)is a kind of popular instant food in China,yet little is known about the associated chemical release risk during its heating process.In this study,we investigated organophosphate esters(OPEs)in original unheated food(UF),SHLB-heated processed food(HF)and potential OPE release from SHLB packaging materials.Significantly higher concentrations of OPEs were observed in HF(267±246 ng/g dry weight(dw))than in UF(163±211 ng/g dw)(p<0.001),suggesting an introduction of additional OPEs during heating processes.Tris(2-chloroethyl)phosphate,triethyl phosphate,and tris(2-chloroisopropyl)phosphate exhibited the highest absolute increased amounts,with 137,48.8,and 149%growth in HF than in UF,respectively.Migration testing revealed that packaging materials were rich in OPEs and can release considerable OPEs into food simulates(range,14.7-90.8 ng/g;mean,47.9±21.8).Influencing factors(temperature,contact time,oily food)on OPE migration from packaging materials to food were assessed.Higher temperature and longer contact time increased OPE contents in food simulates.Moreover,the presence of abundant OPEs in UF and significant correlations among different OPEs(p<0.05)suggested contamination happened during food processing and storage.With one SHLB meal a day,a 12-fold increase of OPE intake was observed for humans compared to those following a traditional dietary habit.In the high-exposure(95th percentile)scenario,hazard quotients of nine OPEs ranged from 0.00005 to 0.05.Our results suggested that the SHLB exposure pathway of OPEs should be particularly paid attention to in specific subpopulations that prefer this dietary habit.

北江典型流域沉积物中有机磷酸酯分布特征及生态风险

为探究北江典型流域沉积物中有机磷酸酯(OPEs)分布特征及生态风险,运用气相色谱—三重四级杆串联质谱检测了北江典型流域21个点位的沉积物中10种OPEs的残留量,分析了OPEs的可能来源,并以风险熵法评估其生态风险。结果显示,总OPEs(∑OPEs)为1.28~51.14 ng/g,磷酸三(2-丁氧基乙基)酯(TBOEP)、磷酸三(2-乙基己基)酯(TEHP)、磷酸三苯酯(TPHP)和磷酸三(2-氯异丙基)酯(TCPP)为主要组分。斯皮尔曼相关性分析和主成分分析结果表明,电子垃圾拆解厂可能是磷酸三(2-氯乙基)酯(TCEP)、TCPP、TPHP和磷酸三异丁酯(TiBP)的重要来源。生态风险评估结果表明,研究区域总体潜在生态风险较低,TPHP有2个中风险地区、1个高风险地区,乙基己基磷酸二苯酯(EHDPP)有5个中风险地区,其余地区沉积物中的OPEs均为低风险。研究结果为未来珠江流域水环境分类管理等提供了重要基础数据。

基于毒理学数据库整合有害结局路径(AOP)分析的有机磷酸酯毒性及机制研究

有机磷酸酯(organophosphate esters,OPEs)作为新型阻燃剂被广泛应用,然而其环境迁移导致的潜在毒性引起了广泛关注。已有研究表明,OPEs对神经系统和肝脏功能具有毒性。本研究系统回顾了近年来关于OPEs的毒理学研究,全面分析了OPEs诱导的神经、心脏、肝脏、内分泌干扰及生殖发育毒性通路,并构建了OPEs的有害结局路径(AOP)框架。研究结果表明,OPEs暴露可引起乙酰胆碱酯酶和多巴胺等神经发育关键酶活性的改变,进而导致神经递质系统紊乱。此外,OPEs诱导的氧化应激和线粒体功能障碍可导致细胞凋亡及肝脏代谢功能损伤。这些机制突出显示了发育期生物体对OPEs暴露的高度敏感性,长期暴露可能导致发育和代谢紊乱。本研究通过整合现有毒理学数据并构建AOP框架,为OPEs的毒性机制提供了新的见解,为未来新型OPEs的生态风险评估奠定了理论基础。

分散固相萃取-气相色谱-三重四级杆串联质谱法测定肉制品中15种有机磷酸酯

该研究基于分散固相萃取-气相色谱-三重四级杆串联质谱法建立了检测肉制品中15种有机磷酸酯的分析方法。试样中有机磷酸酯经乙腈提取,增强型基质去除吸附剂EMR-Lipid净化,HP-5MS色谱柱分离,采用GC-MS/MS动态多反应离子监测模式进行测定,基质匹配外标法定量。研究结果表明,15种有机磷酸酯的目标化合物在21 min内即可完成色谱分离和分析,并且目标物在0.01~100 ng/mL范围内线性关系良好,相关系数均大于0.999。在1.25、12.5、25 ng/g 3个不同质量浓度加标水平下的15种有机磷酸酯平均加标回收率为72.8%~123.8%,相对标准偏差(n=6)为1.6%~14.7%。方法检出限为0.25~0.40 ng/g,定量限为0.80~1.25 ng/g。将该方法应用到市售的70份肉制品样品中,结果显示,58份样品检测到7种有机磷酸酯,检出率82.8%,其中检出率较高的三种有机磷酸酯分别为磷酸三(2-氯-1-(氯甲基)乙基)酯、磷酸三(2-氯乙基)酯和磷酸三苯酯。该研究建立的方法具备操作简单、快速、净化效果好等优势,可用于肉制品中15种有机磷酸酯的快速检测。

某城区降雪中OPEs污染特征与风险评估

采用超高效液相色谱-质谱联用仪(UPLC-MS-MS)测定了某城区雪水中12种有机磷酸酯(OPEs)。结果表明:12种OPEs在所有采样点均有检出,总浓度范围为118.24~1580.26 ng/L,平均浓度为899.77 ng/L。烷基磷酸酯是检出的主要污染物,磷酸三(1-氯-2-丙基)酯(TCPP)和磷酸三丁氧乙酯(TBEP)是最主要的单体OPEs,分别占ΣOPEs的20.31%~63.52%和3.51%~62.10%。ΣOPEs的浓度水平与人类生产生活活动量密切相关,在科研单位1号和科研单位2号的实验室,以及火车站1号和火车站2号附近ΣOPEs的浓度较高,公园1号和公园2号的浓度较低。对雪水中OPEs进行源解析,发现建材涂料、塑料橡胶制品、交通运输、家居装潢和电子产品可能是该城区雪水中OPEs的主要来源。根据计算得到的雪水中OPEs的健康风险均低于理论风险阈值来看,研究区域雪水中OPEs的生态风险总体处于低水平,但是部分采样点雪水中2-乙基己基二苯基磷酸酯(EDHPP)具有中等生态风险。

Studies of n-Octanol/water Partition Coefficients (lgK_(ow)) for Organophosphate Compounds by Density Functional Theory

Optimized calculation of 35 dialkyl phenyl phosphate compounds （OPs） was carded out at the B3LYP/6-31G^＊ level in Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting n-octanol/water partition coefficients （lgKow） of OPs. The new model achieved in this work contains three variables, i.e., molecular volume （Vm）, dipole moment of the molecules （μ） and enthalpy （H^0）. For this model, R^2 = 0.9167 and SD = 0.31 at large t values. In addition, the variation inflation factors （VIF） of variables are all close to 1.0, suggesting high accuracy of the predicting model. And the results of cross-validation test （q^2 = 0.8993） and method validation also showed the model of this study exhibited optimum stability and better predictive power than that from semi-empirical method. The model achieved can be used to predict IgKow of congeneric compounds.

有机磷酸酯(OPEs)的环境污染特征、毒性和分析方法研究进展

随着溴系阻燃剂在世界范围内被禁止,其主要替代物有机磷酸酯(OPEs)在近年来的生产和使用量均呈现快速增长.但作为塑料添加剂,OPEs与材料间无化学键束缚,极易在产品生命周期中释放进入环境.目前,OPEs作为一类新兴污染物,已在全球各地的污水、自来水及其它各类环境介质和人体中广泛检出,包括极地地区,表现出长距离迁移能力,因此,其环境污染和毒性迅速受到国内外的广泛关注,但目前对其环境行为和潜在风险尚不完全清楚.本文对近15年来发表的相关文献进行了检索,综述了OPEs在各类环境介质和人体中的污染特征和现状、迁移转化行为、毒性和分析方法的研究进展.结果表明:OPEs在全球环境中普遍存在,可通过室内灰尘接触、呼吸、食物链传递等途径被生物体和人体吸收,并表现出内分泌干扰、神经毒性、生殖发育毒性等多种毒性效应;OPEs在生物体/人体中可被转化为低取代的二酯、单酯等代谢产物,但目前对其代谢转化途径尚不明确.鉴于OPEs生产使用历史悠久,用途广泛且用量巨大,污水处理去除效率有限,其环境行为过程和机理以及由此导致的潜在生态和健康风险值得引起持续关注.此外,OPEs种类繁多,化合物之间性质差异较大(lg K_(OW)=-0.65—9.49),目前报道中所采用的前处理及仪器分析方法均有所侧重,缺乏统一全面的标准分析方法,无法同步分析环境中可能存在的所有OPEs及其代谢转化产物,不同实验室间的数据可比对性也比较差,如何建立OPEs及其代谢产物的全分析方法也是目前研究亟待解决的问题.