Bioavailability of phthalate congeners to earthworms (Eisenia fetida) in artificially contaminated soils

Bioavailability of phthalate congeners, dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate (DBP), di-(2-ethylhexyl) phthalate (DEHP), and dioctyl phthalate, to earthworms (Eisenia fetida) were studied when earthworms were exposed to two artificially contaminated agricultural and forest soils. Only DBP and DEHP were detected in earthworms. The uptake kinetics of DBP and DEHP in earthworms was fast within the initial 10 days followed by a nearly steady state for the subsequent 20 days. An equilibrium partitioning model could be used to describe the uptake kinetics of DBP and DEHP by earthworm in two types of soils (r = 0.709-0.864). The average biota-to-soil accumulation factors (BSAFs) of DBP and DEHP at 5 mg kg(-1) in soil were 0.27 +/- 0.07 and 0.17 +/- 0.03, respectively, in agricultural soil, while the BSAFs were 0.21 +/- 0.06 and 0.07 +/- 0.02, respectively, in forest soil. The concentrations of phthalates in earthworms increased with increasing concentrations of phthalates in soil. There was a significant correlation between logC(soil) and logC(worm), with r = 0.999-0.993, demonstrating a single linear partitioning of phthalates between soil and earthworms. The bioavailability of DBP and DEHP was assessed by Soxhlet, methanol, and methanol-water (1:1) extraction methods. Our results indicated that the extractable amounts of freshly added DBP and DEHP in soils by these extraction methods were significantly correlated with those in earthworms. It was observed that the extractable DBP and DEHP by the methanol and methanol-water (1:1) extraction methods decreased with their increasing residence time in soil. In contrast, the amount extracted by the Soxhlet extraction method did not show a similar decline. Therefore, Soxhlet extraction was a poor indicator of the bioavailability of DBP and DEHP to earthworms in soil, which could lead to overestimation of the risk of soil-associated DBP and DEHP. The extractable DBP and DEHP by methanol and methanol-water (1:1) significantly decreased over 440 days. Compared with the methanol-water (1:1) extraction method, the methanol extraction method was preferred for its ability to predict the bioavailability of DBP and DEHP in aged soils.     

Toxicity of nickel to a soil-dwelling springtail, Folsomia fimetaria (Collembola: Isotomidae).

Exposure of the collembolan Folsomia fimetaria L. to nickel via soil caused significant mortality and reduced growth and reproductive output. Nickel may be present in elevated concentrations due to anthropogenic discharge. Although collembolans are very numerous and important organisms in the soil ecosystem, the effect of nickel has not previously been studied on these organisms. The aim of this study was to investigate the toxic effects of high soil nickel concentrations on the collembolan F. fimetaria following a 3-week exposure in a loamy sand spiked with nickel up to 1000 mg Ni/kg. A 10% decrease in adult female numbers at 427 mg Ni/kg and at 645 mg Ni/kg for adult male numbers was observed for nickel-spiked soil. Juvenile numbers were reduced at 701 mg Ni/kg following a 3-week exposure. The corresponding EC50 values were 786 mg Ni/kg for females, 922 mg Ni/kg for males, and 859 mg Ni/kg for juveniles. The reproductive output seems to be the most sensitive parameter being reduced at soil nickel concentrations above 173 mg Ni/kg (EC10). Adult growth was not affected by soil nickel concentrations up to 1000 mg Ni/kg, but juvenile growth was reduced at concentrations above 480 mg Ni/kg (EC10).     

河南省市售食用植物油中邻苯二甲酸酯类塑化剂污染状况调查

目的 对2018年河南省市售食用植物油中的邻苯二甲酸酯类塑化剂污染状况进行调查，为食用植物油的监管重点提供依据。方法 在河南省抽取市售预包装食用植物油样品333份，根据气相色谱-质谱法测定样品中邻苯二甲酸二丁酯（DBP）和邻苯二甲酸二（2-乙基）己酯（DEHP）的含量。结果 总体来看，DBP检出率为44.4%，检出值范围为0.10～55.8 mg/kg，超标率为21.6%；DEHP检出率为50.2%，检出值范围为0.15～39.2 mg/kg，超标率为3.6%。从食品细类看，芝麻油中塑化剂（DBP或DEHP）污染最为严重，超标率为34.1%。从企业规模看，产自小微型企业的超标样品占超标样品总数的97.3%。从区域类型看，抽样地点为乡村的样品超标率为24.6%，高于城市（21.6%）3个百分点。结论 河南省市售食用植物油中DBP和DEHP污染情况严重，尤其是芝麻油，应加强监督管理，加大小微型企业食用植物油生产环节的监测，确保食品安全。     

An assessment of the toxicity of phthalate esters to freshwater benthos. 2. Sediment exposures

Seven phthalate esters were evaluated for their 10-d toxicity to the freshwater invertebrates Hyalella azteca and Chironomus tentans in sediment. The esters were diethyl phthalate (DEP), di-n-butyl phthalate (DBP), di-n-hexyl phthalate (DHP), di-(2-ethylhexyl) phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and a commercial mixture of C7, C9, and C11 isophthalate esters (711P). All seven esters were tested in a sediment containing 4.80% total organic carbon (TOC), and DBP alone was tested in two additional sediments with 2.45 and 14.1% TOC. Sediment spiking concentrations for DEP and DBP were based on LC50 (lethal concentration for 50% of the population) values from water-only toxicity tests, sediment organic carbon concentration, and equilibrium partitioning (EqP) theory. The five higher molecular weight phthalate esters (DHP, DEHP, DINP, DIDP, 711P), two of which were tested and found to be nontoxic in water-only tests (i.e., DHP and DEHP), were tested at single concentrations between 2,100 and 3,200 mg/kg dry weight. Preliminary spiking studies were performed to assess phthalate ester stability under test conditions. The five higher molecular weight phthalate esters in sediment had no effect on survival or growth of either C. tentans or H. azteca, consistent with predictions based on water-only tests and EqP theory. The 10-d LC50 values for DBP and H. azteca were >17,400, >29,500, and >71,900 mg/kg dry weight for the low, medium, and high TOC sediments, respectively. These values are more than 30x greater than predicted by EqP theory and may reflect the fact that H. azteca is an epibenthic species and not an obligative burrower. The 10-d LC50 values for DBP and C. tentans were 826, 1,664, and 4.730 mg/kg dry weight for the low, medium, and high TOC sediments, respectively. These values are within a factor of two of the values predicted by EqP theory. Pore-water 10-d LC50 values for DBP (dissolved fraction) and C. tentans in the three sediments were 0.65, 0.89, and 0.66 of the water-only LC50 value of 2.64 mg/L, thereby agreeing with EqP theory predictions to within a factor of 1.5. The LC50 value for DEP and C. tentans was >3,100 mg/kg dry weight, which is approximately 10x that predicted by EqP theory. It is postulated that test chemical loss and reduced organism exposure to pore water may have accounted for the observed discrepancies with EqP calculations for DEP     

Embryotoxic effects of di-2-ethylhexyl phthalate (DEHP) and di-n-butyl phthalate (DBP) in mice

Two major compounds of PVC plasticizers, di-2-ethylhexyl phthalate (DEHP) and di-n-butyl phthalate (DBP), were mixed with food at levels of 0.05, 0.1, 0.2, 0.4, and 1.0 wt% and given to pregnant mice of ICR-JCL strain throughout gestation. Treatment with 0.2, 0.4, and 1.0% DEHP and 1.0% DBP resulted in decreased maternal weight gain and increased resorption rate. All of the implanted ova died in utero at 0.4 and 1.0% level of DEHP. The malformation rate in term fetuses increased at 0.2% level of DEHP and 1.0% level of DBP, the difference from the control group being at the borderline level of significance. The major malformations observed in the treated groups were neural tube defects (exencephaly and spina bifida), suggesting that the phthalic acid esters could interfere with the closure of neuropores in developing embryos. Treatment with the compounds caused intrauterine growth retardation and delayed ossification with an apparently dose-related response pattern. These results indicate that DEHP and DBP at a high dose level could be embryotoxic and possibly teratogenic mice. The maximum no effect level of the PAEs on mouse fetuses was 70 mg/kg/day, which is far higher than the estimated human current intake from the environment.     

Di-n-butyl phthalate (DBP) exposure induces oxidative damage in testes of adult rats

Di-n-butyl phthalate (DBP) is a ubiquitous environmental pollutant, extensively used as a plasticizer in many products including plastics, cosmetics, and medical devices. Some studies have shown that DBP has potential testicular toxicity. However, the mechanism of action of DBP on male reproduction is not clear. The present study was designed to further investigate the potential male reproductive toxicity of DBP . Oxidative stress was assessed in rat testes as an underlying mechanism. Forty SD adult rats were randomly allotted to four groups, and DBP was administered to each group by oral gavage at doses of 0 (control), 100, 250, and 500?mg/kg/d for 2 consecutive weeks. The results indicated that the reproductive toxicity of DBP is dose-dependent. Body and testicular weight was significantly decreased in rats of DBP exposure at a dose of 500?mg/kg/d. Sperm count and motility were significantly decreased at doses of 250 and 500?mg/kg/d. The same two doses significantly inhibited the activities of superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), and glutathione (GSH) while the level of malondialdehyde (MDA) was significantly increased in testes of rats. Microscopy with hematoxylin and eosin (HE) staining showed that seminiferous tubules atrophy and seminiferous epithelial cells disintegrated and shed in rats of DBP exposure at doses of 500?mg/kg/d. In conclusion, DBP alters the testicular structure and function, at least partly, by inducing oxidative stress in testes of adult rats.     

正常儿童血清中邻苯二甲酸二丁酯和邻苯二甲酸-2-乙基己酯水平的测定

目的检测正常儿童血清中邻苯二甲酸二丁酯(DBP)和邻苯二甲酸-2-乙基己酯(DEHP)水平。方法选择上海市正常儿童作为研究对象,用气相色谱检测其血清中DBP、DEHP含量,作正常儿童血清DBP、DEHP浓度分布,以及DBP、DEHP不同年龄和性别水平分析。结果 310例血样中,110例可检出DBP,118可检出DEHP,全部样品中DBP的浓度范围为未检出～0.98ng/ml,P75为0.68ng/ml,95%上限为0.75ng/ml,男女检出率无差别,检出率在不同年龄组间存在差别。全部样品中DEHP的浓度范围为未检出～0.94ng/ml,P75为0.67ng/ml,95%上限为0.74ng/ml,男女检出率无差别,检出率在不同年龄组间存在差别,婴儿组的检出率明显低于其他组。结论正常儿童的血清DBP、DEHP浓度较低,DBP低于0.75ng/ml,DEHP低于0.74ng/ml。     

An assessment of the toxicity of phthalate esters to freshwater benthos. 1. Aqueous exposures

Tests were performed with the freshwater invertebrates Hyalella azteca, Chironomus tentans, and Lumbriculus variegatus to determine the acute toxicity of six phthalate esters, including dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBP), di-n-hexyl phthalate (DHP), and di-2-ethylhexyl phthalate (DEHP). It was possible to derive 10-d LC50 (lethal concentration for 50% of the population) values only for the four lower molecular weight esters (DMP, DEP, DBP, and BBP), for which toxicity increased with increasing octanol-water partition coefficient (Kow) and decreasing water solubility. The LC50 values for DMP, DEP, DBP, and BBP were 28.1, 4.21, 0.63, and 0.46 mg/L for H. azteca; 68.2, 31.0, 2.64, and > 1.76 mg/L for C. tentans; and 246, 102, 2.48, and 1.23 mg/L for L. variegatus, respectively. No significant survival reductions were observed when the three species were exposed to either DHP or DEHP at concentrations approximating their water solubilities.     

基于改进QuEChERS测定植物油中邻苯二甲酸酯类化合物的气相色谱串联质谱质谱方法研究

目的 针对现有方法的不足,改进QuEChERS程序,采用气相色谱串联质谱质谱仪(GC-MS/MS)建立植物油中16种邻苯二甲酸酯类化合物(PAEs)的检测方法。方法 对前处理条件和仪器条件进行优化后,样品经乙腈超声提取,加入PSA+Silica净化,振荡离心后取上清液进行测定,外标法定量。结果 各种PAEs出峰良好,方法线性范围为0.02 mg/L～1.00 mg/L,相关系数均大于0.998,方法检出限为0.00021 mg/kg～0.014 mg/kg,定量限为0.00068 mg/kg～0.048 mg/kg, 3个加标浓度下的回收率为80.0%～103%,相对标准偏差(RSD%)为1.79%～6.96%,用本法检测了10个植物油样品,共有4种PAEs检出,分别是DBP、DEHP、DIBP和DNOP,本法和国标法检出值的相对偏差均小于10%。结论 该方法具有简便、高效、灵敏、快速等优点,能够很好地完成植物油中PAEs含量的检测。     

上海市女童血清中邻苯二甲酸二丁酯和邻苯二甲酸-2-乙基己酯水平与性早熟关系研究

目的通过对上海市性早熟女童血清中邻苯二甲酸二丁酯(DBP)和邻苯二甲酸-2-乙基己酯(DEHP)水平变化研究,探讨DBP、DEHP与性早熟女童发病的关系。方法运用气相色谱法测定110例性早熟女童和100例正常儿童血清中DBP和DEHP的含量,同时运用B型超声仪测定性早熟女童与正常儿童的子宫与卵巢体积,然后做性早熟女童血清中DBP和DEHP含量水平与子宫、卵巢体积之间的相关性分析。结果27.3%和22.7%的性早熟女童血清中分别检测出DBP和DEHP,而正常儿童仅4%和3%分别检测出DBP和DEHP。从血清中DBP和DEHP的含量构成比来看,性早熟女童血清中DBP和DEHP的含量构成比均高于正常儿童;性早熟女童子宫、卵巢体积均大于正常儿童子宫、卵巢体积(P<0.05,P<0.05);性早熟女童血清中DBP与子宫呈正相关(r=0.456,P<0.05),与卵巢也呈正相关(r=0.378,P<0.01),性早熟女童血清中DEHP与子宫呈正相关(r=0.382,P<0.05,),与卵巢呈正相关(r=0.689,P<0.01)。结论性早熟女童受DBP和DEHP污染的程度均比正常儿童严重得多,而且DBP和DEHP对子宫、卵巢的体积有影响。     

Occurrence of phthalate esters in the environment of The Netherlands

Overviews of levels of n-dibutylphthalate (DBP) and di(2-ethylhexyl)phthalate (DEHP) found in freshwater, marine water, sediment, and fish in the Netherlands are given. Sampling spanned a 9-month period (all seasons except winter) and allowed assessing whether phthalate levels are season dependent. Results obtained are compared to data reported for other Western European countries and a fugacity-based modeling approach is used to assess whether there is equilibrium among the various compartments. Highest levels of dissolved DBP and DEHP were found in freshwater samples, whereas these compounds were usually below the limit of detection (LOD) in marine water and sediment. Median levels were log-normally distributed; statistical analysis showed that sampling season is not a relevant determinant parameter. Similar results were obtained for the freshwater sediment compartment, with DEHP levels exceeding concentrations of DBP. DBP levels in fish were often below the LOD. Nevertheless, mean values around 1.8 microg kg(-1) wet fish were found for both DEHP and DBP. Fugacity calculations revealed that especially for DEHP there is no equilibrium among the compartments. DEHP emissions are directed to water, whereas the calculations reveal that sediments provide a sink for DEHP and there is net transport to air. Although it has been suggested that water is the primary compartment for DBP, fugacity plots suggest that air is the compartment to which emissions are directed dominantly. The data reported are in line with values found in Western Europe.     

Estimated daily phthalate exposures in a population of mothers of male infants exhibiting reduced anogenital distance

Phthalate diesters have been shown to be developmental and reproductive toxicants in animal studies. A recent epidemiologic study showed certain phthalates to be significantly associated with reduced anogenital distance in human male infants, the first evidence of subtle developmental effects in human male infants exposed prenatally to phthalates. We used two previously published methods to estimate the daily phthalate exposures for the four phthalates whose urinary metabolites were statistically significantly associated with developmental effects in the 214 mother-infant pairs [di-n-butyl phthalate (DnBP) , diethyl phthalate (DEP) , butylbenzyl phthalate (BBzP) , diisobutyl phthalate (DiBP) ] and for another important phthalate [di-2-ethylhexyl phthalate (DEHP) ]. We estimated the median and 95th percentile of daily exposures to DBP to be 0.99 and 2.68 microg/kg/day, respectively ; for DEP, 6.64 and 112.3 microg/kg/day ; for BBzP, 0.50 and 2.47 microg/kg/day ; and for DEHP, 1.32 and 9.32 microg/kg/day. The U.S. Environmental Protection Agency (EPA) reference doses for these chemicals are 100 (DBP) , 800 (DEP) , 200 (BBzP) , and 20 (DEHP) microg/kg/day. The median and 95th percentile exposure estimates for the phthalates associated with reduced anogenital distance in the study population are substantially lower than current U.S. EPA reference doses for these chemicals and could be informative to any updates of the hazard assessments and risk assessments for these chemicals.     

人体生物样品中邻苯二甲酸酯类的含量

目的　研究和探讨环境内分泌干扰物邻苯二甲酸酯类在人体生物样品中的含量水平。方法　运用反相高效液相色谱分析法测定了人体生物样品 (6 0份血清、36份精液、11份脂肪 )中 3种邻苯二甲酸酯类物质 (phthalates) [邻苯二甲酸二乙酯 (DEP)、邻苯二甲酸二丁酯 (DBP)和邻苯二甲酸 2 乙基己酯 (DEHP) ]的含量水平 ,同时测定了血清中有关激素水平和精液常规指标 ,并运用SPSS分析软件中的非参数统计方法对测定结果进行了相关性分析。结果　上述 3种人体生物样品中均可检测到 phthalates,脂肪中的phthalates含量范围在ND～ 2 19mg/kg ,血清中为ND～ 37 91mg/L ,精液中为 0 0 8～ 1 32mg/L ;Spearman相关分析显示 ,女性血清中DBP与E2 呈正相关 (r =0 4 4 2 ) ,DEP与T呈负相关 (r =- 0 4 86 ) ;精液中phthalates与液化时间呈显著正相关关系 (P <0 0 1) ,DBP与精液量、活力分级中的c级精子活力呈显著负相关 ,与b级精子活力呈显著正相关 (P <0 0 5 ) ,DEHP与精液量、活力分级中的c级精子活力呈显著负相关 ,与精子畸形率、b级精子活力呈显著正相关 (P <0 0 5 )。结论　邻苯二甲酸酯类物质存在于人体组织中 ,并可影响人类的精液质量.     

Metabolic and peroxisome proliferation studies with di(2-ethylhexyl)phthalate in rats and monkeys

Male Fischer 344 rats and cynomolgus monkeys were treated with various doses of di(2-ethylhexyl)phthalate (DEHP) for at least 21 days. There was metabolic, biochemical, and morphological evidence for peroxisomal proliferation in rats that consumed diets containing 1000 ppm DEHP and above. These diets were estimated to provide average daily doses of about 100 mg/kg of DEHP. In contrast, peroxisomal proliferation was not observed in monkeys that received up to 500 mg/kg/day of DEHP by gavage. The results of this study suggest that rats do not provide a good model for predicting the results of DEHP exposure on peroxisomal proliferation in higher primates.     

Abnormalities of sexual development in male rats with in utero and lactational exposure to the antiandrogenic plasticizer Di(2-ethylhexyl) phthalate

Several members of the phthalate ester family have antiandrogenic properties, yet little is known about how exposure to these ubiquitous environmental contaminants early in development may affect sexual development. We conducted experiments to determine effects of in utero and lactational exposure to the most prevalent phthalate ester, di(2-ethylhexyl) phthalate (DEHP), on male reproductive system development and sexual behavior. Sprague-Dawley rats were dosed with corn oil or DEHP (0, 375, 750, or 1,500 mg/kg/day, per os) from gestation day 3 through postnatal day (PND) 21. Dose-related effects on male offspring included reduced anogenital distance, areola and nipple retention, undescended testes, and permanently incomplete preputial separation. Testis, epididymis, glans penis, ventral prostate, dorsolateral prostate, anterior prostate, and seminal vesicle weights were reduced at PND 21, 63, and/or 105-112. Additional dose-related effects included a high incidence of anterior prostate agenesis, a lower incidence of partial or complete ventral prostate agenesis, occasional dorsolateral prostate and seminal vesicle agenesis, reduced sperm counts, and testicular, epididymal, and penile malformations. Many DEHP-exposed males were sexually inactive in the presence of receptive control females, but sexual inactivity did not correlate with abnormal male reproductive organs. These results suggest that in utero and lactational DEHP exposure also inhibited sexually dimorphic central nervous system development. No major abnormalities were found in any of eight control litters, but DEHP caused severe male reproductive system toxicity in five of eight litters at 375 mg/kg/day, seven of eight litters at 750 mg/kg/day, and five of five litters at 1,500 mg/kg/day. These results demonstrate that the male reproductive system is far more sensitive to DEHP early in development than when animals are exposed as juveniles or adults. The effects of DEHP on male reproductive organs and sexual behaviors and the lack of significant effects on time to vaginal opening and first estrus in their littermates demonstrate that DEHP (and/or its metabolites) affects development of the male reproductive system primarily by acting as an antiandrogen. The pattern of effects of in utero and lactational DEHP exposure differed from patterns caused by other phthalate esters, and the preponderance of anterior prostate agenesis appears to be unique among all chemicals. These results suggest that DEHP acts partly by mechanisms distinct from those of other antiandrogens.     

邻苯二甲酸二（２ 乙基己基）酯对小鼠肾脏损害及氧化应激机制的研究

摘要：目的　研究邻苯二甲酸二（２ 乙基己基） 酯（ＤＥＨＰ） 的肾脏毒性及氧化应激损伤作用机制;探讨
相关影响因素。方法　建立小鼠ＤＥＨＰ肾损伤模型：选择昆明４ 周龄小鼠６０ 只,体重（２０±２）ｇ,雌雄
各半,随机分为６ 组, 每组１０ 只。Ｏ 组为空白对照组,Ａ 组给予ＤＥＨＰ７５０ ｍｇ／ｋｇ,Ｂ 组给予ＤＥＨＰ
１５００ｍｇ／ｋｇ ,Ｃ 组给予３０００ ｍｇ／ｋｇＤＥＨＰ＋１０％ 维生素Ｃ,Ｄ 组给予ＤＥＨＰ３０００ ｍｇ／ｋｇ,Ｅ 组给予
３０００ｍｇ／ｋｇＤＥＨＰ＋０．５％ 尼古丁;经食饵和饮水连续自然给食染毒,于染毒第４周末处死。测量小鼠肾
脏和体质量的变化,检测不同ＤＥＨＰ染毒剂量组小鼠的血液、肾脏中谷胱甘肽过氧化物酶（ＧＰＸ）、过氧
化氢（Ｈ２Ｏ２）,丙二醛（ＭＤＡ）等变化。将实验数据进行单因素方差分析（ＡＮＯＶＡ）。结果　随着ＤＥＨＰ
染毒剂量的增加,小鼠体质量逐渐降低（犘＜０．０５）,高剂量组肾脏脏器系数呈现增加趋势。ＤＥＨＰ 高剂量
组ＨＥ 染色可见肾脏组织出现以明显充血和水肿为主的损伤,尼古丁干扰组最为严重。维生素Ｃ 呈现良好
的肾脏保护作用。氧化应激相关物质的改变：血液中的ＧＰＸ 活性由对照组的（４７１．３２±１２０．２４ ）Ｕ／ｍｌ降
低至Ｅ 组的（２０８．７５±５２．９２）Ｕ／ｍｌ （犘＜０．０５）,且有剂量 反应关系;肾脏中ＧＰＸ 活性降低（犘＜０．０５）,
同时肾组织中Ｈ２Ｏ２ 含量由（４０７．７４±３２８．８３）ｍｍｏｌ／ｍｇ蛋白增加到（１６７４．９８±３７６．０７）ｍｍｏｌ／ｍｇ蛋白
（犘＜０．０５）,血液中Ｈ２Ｏ２ 含量也随着ＤＥＨＰ 的剂量增加而增加（犘＜０．０５）;肾组织中ＭＤＡ 含量增加（犘
＜０．０５）;同时维生素Ｃ 的保护作用和尼古丁的协同作用也有体现。结论　ＤＥＨＰ 具有小鼠肾脏毒性,其
作用机制可能与氧化应激有关,抗氧化剂维生素Ｃ 对ＤＥＨＰ所致肾脏损伤具有抑制作用。
关键词：邻苯二甲酸二（２ 乙基己基）酯（ＤＥＨＰ）;肾脏毒性;氧化应激
中图分类号：Ｒ１２　　文献标识码：Ａ　　文章编号：１００９ ６６３９ （２０１４）０１ ０００８ ０５     

不同烹调油样品中邻苯二甲酸二丁酯与邻苯二甲酸二（2-乙基己基）酯的分析

[目的]了解不同烹调油样品中邻苯二甲酸二丁酯（di-n—butyl phthalate,DBP）与邻苯二甲酸二（2-乙基己基）酯[di（2-ethylhexyl）phthalate,DEHP]的污染情况。[方法]采用气相色谱-质谱联用仪的选择离子检测（SIR）方式,测定取自居民家中未加热食用油、烹调剩油和厨房抽油烟机内油盒中的烹调油烟冷凝物,食堂中未加热食用油、烹调剩油和烹调油烟冷凝物;小摊贩所用的未加热食用油及其锅内剩油;快餐店未加热过的固体起酥油及烹调剩油等样品中DBP与DEHP的含量。[结果]9户居民家庭厨房和食堂不同烹调油样品中DBP和DEHP均为阳性,且烹调油烟冷凝物中的含量明显高于未加热食用油和烹调剩油中的含量;DBP和DEHP含量：前者分别为2．29～597．01μg／g和38．96～4774．72μg／g;后者分别为3．22～42．81μg／g和15．61～112．64μg／g。小摊贩和快餐店不同烹调油样品中,仅1例炸面食剩油检出DBP和DEHP。[结论]大部分烹调油样品被DBP、DEHP污染,且烹调油烟冷凝物中的含量大大增加。     

室内降尘中邻苯二甲酸酯污染特征分析

目的 了解邻苯二甲酸酯在室内环境中的污染状况.方法 分别选取北京地区10户家庭住宅、10间办公室和10间学生宿舍进行室内降尘取样,采用高效液相色谱法测定降尘中的7种邻苯二甲酸酯类化合物,利用非参数检验进行统计分析.结果 室内降尘中主要存在邻苯二甲酸(2-乙基己基)酯(DEHP)、邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二环己酯(DCHP)污染,其中DEHP的含量范围为28～6073 mg/ks.是检出浓度最高的物质.对不同类型房间进行比较,发现家庭住宅邻苯二甲酸酯污染最严重,办公室次之,学生宿舍污染最小.Kumkal-Wallis H检验分析表明在这3种房间类型中,邻苯二甲酸丁基苄基酯(BBP)、DEHP和DCHP浓度差异有统计学意义(P<0.05).Spearman相关分析表明,DBP与BBP、DBP与DCHP之间均存在正相关关系(P<0.05),但相关关系并不密切(r<0.5).结论 家庭住宅中DEHP污染较为严重,应引起重视.

Abstract：

Objective To investigate the pollution of phthalate ester in indoor environment. Methods Settled dust samples from 10 households, 10 offices and 10 student dormitories in Beijing were collected. Seven kinds of phthalate esters in these samples were determined with solid phase extraction-high performance liquid chromatography (SPE-HPLC) .Dates were analyzed statistically by nonparametric tests. Results The main phthalate esters in dust were di (2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP) and dicyclohexyl phthalate (DCHP). Of phthalate esters, DEHP with the range of 28-6 073 mg/kg had the highest concentration in indoor dust. The total level of phthalate esters in households was the highest, offices followed, student dormitories was the last. The Kurskal-Wallis H test showed that the concentrations of BBP, DEHP and DCHP in dust were significantly different in 3 types of rooms (P<0.05). Spearman's correlation analysis showed that significantly positive correlations were found between DBP and both BBP and DCHP (r<0.5, P<0.05). Conclusion DEHP pollution in household environment is heavy. It should be taken into account.     

Internal phthalate exposure over the last two decades--a retrospective human biomonitoring study

In a retrospective human biomonitoring study we analyzed 24h urine samples taken from the German Environmental Specimen Bank for Human Tissues (ESBHum), which were collected from 634 subjects (predominantly students, age range 20-29 years, 326 females, 308 males) in 9 years between 1988 and 2003 (each n >or= 60), for the concentrations of primary and/or secondary metabolites of di-n-butyl phthalate (DnBP), di-iso-butyl phthalate (DiBP), butylbenzyl phthalate (BBzP), di(2-ethylhexyl) phthalate (DEHP) and di-iso-nonyl phthalate (DiNP). Based on the urinary metabolite excretion we estimated daily intakes of the parent phthalates and investigated the chronological course of the phthalate exposure. In over 98% of the urine samples metabolites of all five phthalates were detectable indicating a ubiquitous exposure of the German population to all five phthalates throughout the last 20 years. The median daily intakes in the subsets between 1988 and 1993 were quite constant for DnBP (approx. 7 microg/kg bw/d) and DEHP (approx. 4 microg/kg bw/d). However, from 1996 the median levels of both phthalates decreased continuously until 2003 (DnBP 1.9 microg/kg bw/d; DEHP 2.4 microg/kg bw/d). By contrast, the daily intake values for DiBP were slightly increasing over the whole time frame investigated (median 1988: 1.1 microg/kg bw/d; median 2003: 1.4 microg/kg bw/d), approximating the levels for DnBP and DEHP. For BBzP we observed slightly decreasing values, even though the medians as of 1998 levelled off at around 0.2 microg/kg bw/d. Regarding daily DiNP exposure we found continuously increasing values, with the lowest median being 0.20 microg/kg bw/d for the subset of 1988 and the highest median for 2003 being twice as high. The trends observed in phthalate exposure may be associated with a change in production and usage pattern. Female subjects exhibited significantly higher daily intakes for the dibutyl phthalates (DnBP p=0.013; DiBP p=0.004). Compared to data from US National Health and Nutrition Examination Surveys (NHANES) exposure levels of the dibutyl phthalates were generally higher in our German study population, while levels of BBzP were somewhat lower. Overall, for a considerable 14% of the subjects we observed daily DnBP intakes above the tolerable daily intake (TDI) value deduced by the European Food Safety Authority (EFSA) (10 microg/kg bw/d). However, the frequency of exceedance decreased during the years and was beneath 2% in the 2003 subset. Even though transgressions of the exposure limit values of the EFSA and the US Environmental Protection Agency (US EPA) occurred only in a relatively small share of the subjects, one has to take into account the cumulative exposure to all phthalates investigated and possible dose-additive endocrine effects of these phthalates.     

邻苯二甲酸二丁酯对对羟基苯甲酸酯类雌激素活性效应的增强作用

目的评价对羟基苯甲酸丙酯(PP)、对羟基苯甲酸丁酯(BP)和邻苯二甲酸二丁酯(DPB)的单独和联合处理的雌激素活性效应。方法应用未成熟雌性Wistar大鼠连续3天皮下染毒的子宫增殖试验。通过重量及系数,判定PP、BP和DPB的单独处理和两两联合处理后的雌激素活性效应。结果实验中PP和BP雌激素活性最小可观察作用剂量(LOEL)分别为400mg/kg和200mg/kg,DPB在400~100mg/kg范围内没有发现雌激素活性。PP+BP等效应剂量配比联合处理中1LOEL和1/2LOEL具有子宫增殖作用,1/4LONEL未发现子宫增殖作用。PP和BP分别与子宫增殖试验中未见雌激素效应的DBP进行联合处理,在100mg/kgPP(1/4LOEL)+400mg/kgDBP,200mg/kgPP(1/2LOEL)+400mg/kgDBP和100mg/kgBP(1/2LOEL)+400mg/kgDBP联合处理下的子宫增殖试验出现雌激素活性。结论DBP具有增加PP和BP雌激素活性的效应,并且DBP对PP的雌激素活性的增强作用大于对BP的雌激素活性增强作用。