液液萃取-气相色谱-质谱联用测定水中的邻苯二甲酸酯类化合物

本文建立了液液萃取-气相色谱-质谱法对地表水和生活饮用水中的三种邻苯二甲酸酯类化合物的检测方法。结果表明:目标物三种邻苯二甲酸酯类化合物在12 min内可以全部检出,且分离效果较好;在0~10.0 mg/L内,各组分标准曲线的线性相关系数均在0.995以上;方法检出限为:邻苯二甲酸二乙酯(DEP):2μg/L;邻苯二甲酸二丁酯(DBP):2μg/L;邻苯二甲酸二(2-乙基己基)酯(DEHP):2μg/L;相对标准偏差:邻苯二甲酸二乙酯(DEP):1.9%~4.5%;邻苯二甲酸二丁酯(DBP):1.3%~7.1%;邻苯二甲酸二(2-乙基己基)酯(DEHP):2.4%~3.3%。该方法操作易于操作,结果准确,适合用于地表水和生活饮用水中的邻苯二甲酸酯类化合物的检测。     

饮用水中邻苯二甲酸酯的调查及去除研究

采用固相萃取-高效液相色谱法调查了淮南市某自来水厂原水、各处理工艺单元出水中4种邻苯二甲酸酯(DMP、DEP、DBP、BBP)。结果表明,4种邻苯二甲酸酯在原水中均检出,质量浓度为0.010～0.142μg/L;DMP和DEP仅在部分水样中检出,在管网水中没有检出;DBP和BBP在各水样中均检出,质量浓度分别为1.702～2.897μg/L、0.248～0.676μg/L,说明现行常规净水处理工艺不能完全去除邻苯二甲酸酯,需要进行深度处理。研究采用臭氧氧化技术、活性炭吸附技术和臭氧-活性炭技术对该水厂原水中的2种邻苯二甲酸酯(DBP、BBP)去除情况进行验证。结果表明,臭氧氧化技术不能完全去除原水中的DBP和BBP,去除率为61%～65%;活性炭吸附技术能够完全去除原水中的DBP和BBP;臭氧-活性炭技术对原水中的DBP和BBP去除率达到100%。该技术可以作为水厂深度处理工艺去除DBP和BBP的主要单元。     

湘江水中邻苯二甲酸酯类环境激素的研究

采用分散液液微萃取-高效液相色谱法测定湘江株洲段水体中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二正丁酯(DBP)和邻苯二甲酸丁苄酯(BBP),利用正交实验优化了萃取条件,分析其污染水平分布,并进行生态风险评价。结果表明:4种邻苯二甲酸酯类物质普遍检出,∑PAEs的浓度范围为22.39～27.4μg/L,其中DBP为主要污染物。利用商值法对PAEs进行生态风险评价,各种物质均存在潜在生态风险。     

酞酸酯物质在皂河水体中的环境行为研究

分析皂河水体和沉积物中邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸丁基苄酯(BBP)、邻苯二甲酸二丁酯(DBP)四种物质的含量,用DMP进行吸附研究,探讨p H值和DMP初始浓度对吸附等温特性的影响。结果表明,皂河水体和沉积物中四种物质浓度范围分别为为0.004~3.44μg/L和1.1~6.12μg/g;在一定的浓度范围时,DMP在沉积物上的吸附速率先快后慢,吸附等温线以Langmuir方程拟合最佳。沉积物对DMP的吸附随着p H的增大而减小,初始浓度增大,平衡吸附量增大最后趋于稳定。     

气相色谱–质谱法测定玩具涂层中6种邻苯二甲酸酯增塑剂

建立了气相色谱–质谱法测定玩具涂层中邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁苄酯(BBP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二正辛酯(DNOP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)等6种邻苯二甲酸酯类增塑剂的分析方法,确定了适宜的微波辅助萃取条件为:以二氯甲烷为萃取剂,萃取温度60°C,萃取时间25 min。在试验选定的条件下,以该方法测定玩具涂层中6种邻苯二甲酸酯类增塑剂,以峰面积对质量浓度线性回归,线性范围在0.5~50 mg/L,则相关系数大于0.999,最低检出限为0.5~1.0 mg/L,加标回收率在83.5%~105.6%之间,相对标准偏差小于5.8%。该方法操作简便快速,准确度和灵敏度高,适合于玩具涂层中6种邻苯二甲酸酯类增塑剂含量的同时测定。     

微波辅助萃取气质联用法测量PVC中的酞酸酯

采用微波辅助萃取气质(GC/MS)联用技术测量PVC中的PAEs检测方法,选择了邻苯二甲酸二正丁酯(DBP)、邻苯二甲酸苯甲基丁基二酯(BBP)、邻苯二甲酸二异辛酯(DEHP)、邻苯二甲酸二辛酯(DNOP)4种标物进行溶剂萃取、准确度、精密度以及方法检出限等多方面的研究。4种标物的方法检出限均在0.2~0.6μg/kg,精密度为3.16%~7.45%,回收率为91.3%~96.1%。该方法操作简便、准确,具有较好的实用性。     

高效液相色谱法测定4种邻苯二甲酸酯

本文建立了高效液相色谱法同时测定4种邻苯二甲酸酯类化合物[邻苯二甲酸二(2-乙基己酯)酯(DEHP)、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二丁酯(DBP)]的分析方法,优化了色谱条件中的梯度洗脱程序。方法的验证结果表明,4种邻苯二甲酸酯类物质在0.05～10mg·L~(-1)范围内线性关系良好,相关系数为0.9989～0.9997。方法重复性的相对标准偏差(RSD)为5.3%～8.1%。该方法操作简单、快速,灵敏度、精密度和重现性均较好。     

高效液相色谱法测定污水厂中邻苯二甲酸酯类污染物

建立了一种用高效液相色谱法(HPLC)测定污水中DMP、DEP、DBP和BBP 4种邻苯二甲酸酯的分析方法。HPLC分析条件:以C18色谱柱(4.6*250 mm,5μm)为分离柱,以乙腈-水(80∶20,v/v)为流动相,紫外检测器(检测波长238 nm),流速为1 mL/min。该方法操作简便、分析时间短,精密度与准确度良好,污水样加标回收率在88.59%~111.96%之间,相对标准偏差小于7.30%。污水厂水样测定结果表明,进水中4种PAEs污染较为严重,总浓度达到116.04μg/L,而出水总浓度降至6.29μg/L,污水处理工艺对4种邻苯二甲酸酯均具有较高的去除率。     

浊点萃取-高效液相色谱测定一次性塑料袋中邻苯二甲酸酯类化合物

建立了浊点萃取(CPE)和高效液相色谱法(HPLC)同时测定一次性塑料袋中三种邻苯二甲酸酯类化合物(PAEs)的方法。以非离子表面活性剂TritonX-114为萃取剂,考察了萃取剂的浓度、盐的浓度、加热温度及时间等因素对浊点萃取效果的影响。CPE的最佳条件:TritonX-114体积分数为0.4%、NaCl的质量浓度为100 g/L、平衡时间为75 min、平衡温度为60℃,离心时间为15 min;色谱条件:色谱柱为SepaxGP-C18,流动相为甲醇∶水体积比为85∶15,流速为1 mL/min,检测波长225 nm。在上述实验条件下,邻苯二甲酸甲酯(DMP)、邻苯二甲酸乙酯(DEP)、邻苯二甲酸丁酯(DBP)的质量浓度在0.529～52.88、0.617～61.74、0.534～53.42μg/mL范围内具有良好的线性关系,线性方程分别是Y=55 133X+44 140、Y=46 844X+123 163、Y=38 412X+5 835.3,相关系数分别为0.9996、0.999 8、0.999 9。结果表明一次性塑料袋中含有DEP、DBP,其含量分别是23.3、38.4μg/g。     

ASE-GC/MS法测定EVA塑料消费品中的7种PAEs

建立了乙烯-醋酸乙烯(EVA)塑料消费品中7种邻苯二甲酸酯(DBP、Di BP、BBP、DEHP、DNOP、DINP、DIDP)残留量的加速溶剂萃取-气相色谱/质谱(ASE-GC/MS)测定方法。采用含有DBP、Di BP、DEHP等3种邻苯二甲酸酯(PAEs)的EVA洞洞鞋阳性样品优化确定了PAEs的加速溶剂萃取最佳条件是以二氯甲烷为提取溶剂,在120℃下循环萃取2次,每次9 min,萃取液经固相萃取净化后采用GC/MS法进行定性和定量分析。本方法对EVA塑料消费品中Di BP、DBP、BBP、DEHP和DNOP的检出限均为0.05 mg/kg,DINP和DIDP的检出限均为0.2 mg/kg。样品的加标回收率和相对标准偏差分别为76%~101%和2.3%~13%。     

手机涂料及涂膜中邻苯二甲酸酯类有害物质的测定

涂料经溶剂提取或涂膜经索氏提取后,提出液中邻苯二甲酸酯类单体DEHP、DBP、BBP、DNOP可用DB-130.0m×φ0.25mm×0.5μm色谱柱同时分离,GC-FID或GC-MSD全扫描测定,DINP、DIDP宜采用GC-MSD选择离子扫描单独测定。采用GC-MSD测定时,方法的回收率不低于95%,DEHP、DBP、BBP、DNOP的最小检出限(LODs)均为0.04μg/mL,最低定量限(LOQ)均为0.35μg/mL。选择扫描时,DINP、DIDP的LODs、LOQ分别为0.4μg/mL、3.5μg/mL。实验结果表明:某些丙烯酸树脂涂料以及手机外壳涂层含有高含量生殖致癌物PAEs类单体,应为制定手机涂料中邻苯二甲酸酯类有害物质最高允许限量进行评价。     

SPE-GC/MS法快速检测水体中多组分内分泌干扰物

采用固相萃取-气相色谱/质谱法(SPE-GC/MS)研究了温州8个水体中邻苯二甲酸二甲酯、西玛津、莠去津、甲草胺、邻苯二甲酸二丁酯、双酚A、邻苯二甲酸二(2-乙基己基)酯七种内分泌干扰物的残留。水样用C18柱固相萃取进行富集、3mL10%的甲醇水溶液淋洗、10mL丙酮洗脱;并采用GC-MS法对七种内分泌干扰素进行分析。本实验建立的方法定性定量准确、可靠,适用于水体中多组分内分泌干扰物的快速检测,在所有测定的水样中,邻苯二甲酸二丁酯、双酚A、邻苯二甲酸二(2-乙基己基)酯是主要残留物,最高残留邻苯二甲酸二丁酯、双酚A、邻苯二甲酸二(2-乙基己基)酯分别为0.82、3.16、1.50ng/L。     

Studies on lipid biosynthesis and cholesterol content of liver and serum lipoproteins in rats fed various phthalate esters

The effect of various phthalate ester plasticizers on lipid metabolism in rats was studied in vivo and in vitro. Di-2-ethylhexyl phthalate (DEHP) and di-n-butyl phthalate (DBP) inhibited (30–70%) hepatic sterologenesis from¹⁴C-acetate and¹⁴C-mevalonate in liver minces from rats fed the phthalates at a level of 2.5 mmoles/100 g of chow diet for 21 days; inhibition of¹⁴C-acetate incorporation into phospholipids, triglycerides, and steryl esters was reduced (35–70%) by DEHP and DBP feeding. In addition, serum cholesterol was lowered ca. 14 mg/dl with dietary DEHP or DBP but not with dimethyl phthalate (DMP). Hepatic total cholesterol levels were reduced significantly (31%, P<0.001) by DMP but not by DBP or DEHP. In other studies with DEHP fed at the 0.5% level in chow diets (1.3 mmoles/100 g), the incorporation (esterification) of³H-oleate into di- and triglycerides was reduced ca. 40%. Furthermore, the addition of DEHP (2%, 5 mmoles/100 g) to a semisynthetic diet containing 10% fat (hydrogenated coconut oil) resulted in changes in serum lipoprotein composition. The percentage of serum cholesterol in LDL rose from 22% to 34% while that in HDL fell from 78% to 66%; these changes occurred without net changes in serum cholesterol levels. Possible mechanisms for the inhibitory effect of phthalates on hepatic lipid biosynthesis are discussed. These studies are in partial fulfillment of the requirements for a Doctorate degree in Medical Sciences, McMaster University, Hamilton, Ontario, Canada.     

PVC玩具和儿童用品中6种限用邻苯二甲酸酯类增塑剂的同时测定

提出了气相色谱-质谱联用同时测定PVC玩具和儿童用品中6种限用增塑剂的方法,以乙酸乙酯为溶剂,采用微波萃取法提取PVC玩具和儿童用品中6种限用邻苯二甲酸酯类增塑剂,以DHP为内标进行定量。该方法平均回收率为91.15%~98.72%,RSD为1.98%~4.47%,检测限(S/N=5)分别为0.5 mg/L(DBP、BBP、DEHP、DNOP)和10 mg/L(DINP、DIDP)。     

Sorption of Phthalates on Molecularly Imprinted Polymers

Porous beads of styrene divinylbenzene copolymer, S-co-DVB, imprinted with dimethyl phthalate, DMP, were obtained. Two solvents were applied for the formation of pores: n-hexane and n-octane. The sorbents were prepared by membrane emulsification of monomer mixtures containing DMP followed by suspension polymerization. The average diameters of the synthesized beads were 40 µm for beads obtained from mixtures with n-octane, and 30 µm for preparations with n-hexane as solvent. It was shown that almost all monodispersive sorbents were obtained; their SPAN parameter was as small as 0.7–0.9. Sorption properties of evaluated samples varied in relation to the kind of applied reaction mixture. Generally, imprinted materials showed higher sorption capacity towards DMP than their off-template analogues. For the sorbent obtained in the presence of n-octane and with 3 wt.% of DMP, sorption of dimethyl phthalate took the highest value - 89 mg/g. The sorbents imprinted with DMP were checked for sorption of diethyl phthalate, DEP, and dibuthyl phthalate, DBP also. It was shown that sorbability of synthesized materials towards other phthalates was much smaller than for DMP and was not related to the presence of dimethyl phthalate foot prints.     

Emissivity values for poly(vinyl chloride) with varying plasticizer compositions

The emissivity of plasticized poly(vinly chloride) (PVC) containing varying compositions and amounts of plasticizer was investigated. The four plasticizers examined were dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP) (Phthalic acid type), and dioctyl adipate (DOA) (adipic acid type). The emmissivity of plasticized PVC film increased almost equally with the difference in the compositions between DOP and DOA. It was also clear that the emissivity of the plasticized PVC film decreased gradually with the molecular sequence length of DBP, DOP, and DIDP.     

Effect of plasticizers on mechanical,electrical, permanence,and thermal properties of poly(vinyl chloride)

Effects of three different plasticizers and their blends with dioctyl phthalate (DOP) on thermal stability, flammability, mechanical, electrical, and permanence properties of poly(vinyl chloride) (PVC) compound were studied. Various plasticizers used were DOP, butyl benzyl phthalate (BBP), isodecyl diphenyl phosphate (IDDP), and polybutylene adipate (PBA) at concentrations of up to 40 phr level. Studies showed that processability and softness were improved by addition of BBP. An increase in the content of IDDP increased the electrical and flammability properties, whereas compositions with PBA exhibited the best permanence properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3278–3284, 2003     

Diffusivities of Dialkyl Phthalates in Plasticized Poly(vinyl butyral): Impact on Binder Thermolysis

Hot-stage/Fourier transform infrared microspectroscopy (FTIR-M) was used to determine the diffusivities of a series of dialkyl phthalates in poly(vinyl butyral) (PVB) spin-coated films. The diffusivities ranged from 10⁻¹² to 10⁻¹⁰ cm²/s for the isotherms investigated (60° to 150°C). In their respective temperature regimes, dimethyl phthalate and diethyl phthalate exhibited nonlinear diffusion behavior, while dibutyl phthalate (DBP) and dioctyl phthalate (DOP) exhibited Fickian behavior in PVB. The activation energies for DBP and DOP diffusion in the PVB-based films were calculated to be 76.3 and 114.7 kJ/mol, respectively. The diffusitivity of DBP was used to compare the relative importance of diffusion and capillary migration in the thermolysis of PVB-DBP binders from ceramic greenware. Comparison of the calculated DBP loss due to diffusion alone could not account for the observed removal rates. A characteristic diffusion length is calculated from the experimental observations.     

Electrical properties of poly(vinyl chloride) compositions

A sample of poly(vinyl chloride) (PVC) and a polar plasticizer consisting of dioctyl phthalate (DOP) and dibutyl phthalate (DBP) was prepared and found to possess inconvenient electrical properties (permittivity, dielectric loss, and conductivity). Different samples of PVC compositions were formulated from the PVC–DOP–DBP system and also variable proportions of a copolymer of 1-octadecene-maleic anhydride or its hexadecylester. Lead stearate as a heat stabilizer and kaolin as a filler were added. The effect of copolymer structure on the electrical properties of the PVC–DOP–DBP system was studied to obtain a plasticized PVC of good electrical insulation character. © 1993 John Wiley & Sons, Inc.     

PVC制品中增塑剂DEHP含量的测定

建立了荧光光度法间接测定聚氯乙烯(PVC)制品中邻苯二甲酸二(2-乙基己酯)(DEHP)含量的方法。PVC制品中的DEHP经超声提取后,碱性水解生成邻苯二甲酸钠,将其置于pH值为7.6的磷酸盐缓冲溶液中,同Fenton反应产生的羟基自由基(?OH)反应,生成具有荧光的羟基邻苯二甲酸钠,测定其荧光强度可求出DEHP的含量。DEHP浓度在4.28×10-2～2.14mg/ml范围内与荧光强度呈线性关系,相关系数为0.9954。本测定方法操作简便,具有较高的灵敏度和准确度。