液相色谱-串联质谱法测定上光剂中全氟化合物

建立了针对上光剂中包括全氟己酸(PFHx A)、全氟辛酸(PFOA)、全氟壬酸(PFNA)、全氟癸酸(PFDA)、全氟十一酸(PFu DA)、全氟十二酸(PFDo A)、全氟丁烷磺酸(PFBS)、全氟己烷磺酸(PFHx S)、全氟辛烷磺酸(PFOS)、全氟癸烷磺酸(PFDS)在内的10种全氟化合物(PFCs)的液相色谱-串联质谱法(LC-MS/MS)测定分析方法。采用超声法提取测试目标化合物,提取液用混合型弱阴离子交换固相萃取柱净化,用液相色谱-串联质谱仪测定。结果表明,该方法的检测低限均为50μg/kg,相对标准偏差在10%以内,加标回收率85.5%~106.0%。该方法准确、快速,能满足上光剂中全氟化合物测定要求。     

液相色谱串联质谱法测定纺织品中PFOS和PFOA

针对国际对纺织品中全氟辛磺酸(PFOS)和全氟辛酸(PFOA)的限量要求,采用ASE-300快速溶剂萃取仪提取样品中PFOS和PFOA,经浓缩、净化、过膜、定容后用液相色谱串联质谱法测定,外标法定量。采用选择离子检测进行阳性确证,建立纺织品中PFOS和PFOA的检测方法。该方法的最低检出限、线性范围和方法回收率对PFOS为1.0μg/kg、3.0~300μg/kg和82.35%~105.60%;对PFOA为0.5μg/kg、1.5~200μg/kg和85.17%~107.78%。     

贵阳市市售食用油中全氟化合物污染水平研究

研究了贵阳市市售食用油中全氟有机化合物(PFCs)的污染水平。分别对贵阳市主要农贸市场14个品牌不同批次的食用油进行样品采集,采用液相色谱-串联质谱法(LC-MS/MS)对全氟己酸(PFHxA)、全氟庚酸(PFHpA)、全氟辛酸(PFOA)、全氟壬酸(PFNA)、全氟十二烷酸(PFDoA)、全氟十四烷酸(PFTA)及全氟辛烷磺酸盐(PFOS)7种PFCs进行了系统性分析。结果表明:贵阳市市售食用油中共检出2种PFCs,以全氟庚酸(PFHpA)为主;在大豆油中,PFHpA的平均含量为0.1186μg/kg,检出率为16.1%;在玉米油中,PFHpA的平均含量为6.9796μg/kg,检出率为14.3%;在色拉油中,PFHpA的平均含量为1.2127μg/kg,检出率为12.5%;在压榨菜籽油中,PFHpA的平均含量为8.9011μg/kg,检出率为25.0%;在花生油中,PFHpA的平均含量为0.4914μg/kg,检出率为7.1%,同时有2个花生油样品中检出全氟壬酸(PFNA),其平均含量为6.4918μg/kg;在所受检的浸出菜籽油和调和油样品中,未检出PFCs污染。通过对14个品牌不同批次的样品进行比较,发现贵阳市市售食用油中PFCs的污染存在较大差距,以压榨菜籽油和大豆油污染最严重,但其含量不会对贵阳市市民产生即时危害。     

广东省典型氟化工区周边蔬菜中3种全氟化合物及2种氯代多氟醚基磺酸的污染调查及膳食暴露评估

目的 调查分析广东省典型氟化工区周边种植的蔬菜中3种全氟化合物及2种氯代多氟醚基磺酸的污染现状及膳食暴露风险。方法 2019年在广东省3个氟化工区周边随机采集种植蔬菜及非氟化工区农贸市场市售样品共96份,采用同位素稀释超高效液相色谱-三重四级杆质谱法检测样品中全氟辛烷磺酸（PFOS）、全氟辛酸（PFOA）、全氟己烷磺酸（PFHxS）、6：2氯代多氟醚基磺酸（6：2 Cl-PFESA）和8：2氯代多氟醚基磺酸（8：2 Cl-PFESA）的浓度,并采用点评估法对食用蔬菜暴露5种化合物的健康风险进行评估。结果 所有样品均检出PFOS和PFOA,仅在2份叶类蔬菜检出氯代多氟醚基磺酸。样品中5种化合物的平均浓度之和（∑₃ PFASs+∑₂ Cl-PFESA）为0.792 ng/g fw （fresh weight,鲜质量）,其中氟化工区周边样品的平均浓度为农贸市场市售样品的2倍。在3类蔬菜样品中,叶类蔬菜5种化合物的平均浓度之和最高,为1.11 ng/g fw。暴露评估结果显示,通过食用氟化工区周边种植的蔬菜暴露PFOS、PFOA和PFHxS的范围为0.185~2.35 ng/kg·BW,其中PFOS和PFOA的危害指数（HI）大于1,2种氯代多氟醚基磺酸的暴露水平较低。结论 居民食用氟化工区周边种植的叶类和瓜果类蔬菜暴露PFOS和PFOA的水平已超过健康指导值,存在潜在健康风险。经蔬菜暴露2种氯代多氟醚基磺酸的健康风险较低,但仍需关注。     

纺织化学品的重要限用法规评析(二)

<正>欧盟于2006年12月27日发布的2006/122/EC指令,只限制PFOS,化学品限量为50 mg/kg,对于PFOA只表示怀疑,并未提出限制。Oeko-Tex Standard 100的2009年修订版已将PFOS和PFOA列入考核项目中。PFOA比PFOS限量稍宽(都在纺织品上)。REACH法规需授权SVHC中,于第八批列入了全氟十一酸、全氟十二酸、全氟十三酸和全氟十四酸,在第九批中列入了全氟辛酸铵盐,但至今未见PFOS列入SVHC。Oeko-Tex Standard 100一般都会将欧盟法规涉     

纺织品中全氟辛烷磺酸及全氟辛酸的测定及其研究进展

全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)等化合物是应用广泛但对环境有持久污染的有机物.开展纺织品中PFOS和PFOA检测方法的研究是保护环境和人类健康,提升纺织产品质量的迫切要求.简述了PFOS和PFOA的各种检测方法和复杂样品的前处理技术,指出应研究有关纺织品中PFOS和PFOA快速、精确的测定方法,并尽快建立...     

北京市场食用油中全氟化合物污染调查及其膳食风险评估

研究了北京市市售植物性油脂中全氟化合物的污染水平,测定了4个超市中大豆油、花生油、芝麻油等6类植物油中18种全氟化合物,结果表明:北京市售植物性油脂中均存在一定浓度的全氟化合物污染,其中品牌油脂中共检出8种全氟化合物,以全氟辛酸(PFOA)、全氟壬酸(PFNA)和全氟己酸(PFHxA)为主,其中调和油中的PFNA最高浓度达到4.64μg/kg,而在油作坊采集的压榨油脂中共检出15种全氟化合物,浓度均较品牌油脂高,其安全问题值得关注。对植物性油脂中全氟化合物的膳食风险评估结果显示,北京市售植物性油脂产品中PFOS和PFOA的污染水平和膳食暴露均在可接受的范围内。     

一次性纸杯中全氟辛酸 及全氟辛烷磺酸的膳食暴露研究

为了评估不同人群通过一次性纸杯摄入全氟辛酸(PFOA)及全氟辛烷磺酸(PFOS)的风险,采用超高效液相色谱串联质谱法测定一次性纸杯中PFOA及PFOS向不同食品中的迁移量,结合调查所得一次性纸杯的消费数据,利用点评估方法计算PFOA及PFOS通过一次性纸杯向不同人群的急性及慢性暴露量,并评估其急慢性暴露风险。结果表明,20种一次性纸杯中,PFOA及PFOS向食品中的迁移量分别为ND~23.70×10-3 ng/cm2、ND~4.10×10-3 ng/cm2;PFOA及PFOS的急性人群暴露量分别为45.67×10-3~168.36×10-3 ng/(kg·d)和7.91×10-3~29.14×10-3 ng/(kg·d),慢性人群暴露量分别为0.16×10-3~4.05×10-3 ng/(kg·d)和0.02×10-3~0.51×10-3 ng/(kg·d),均远低于欧盟推荐的每日摄入耐受量。人群通过一次性纸杯摄入PFOA及PFOS的风险处于可接受的水平。     

采用高效液相色谱-电喷雾串联质谱法测定猪肉中的全氟化合物(PFOS、PFOA)

采用HPLC-ESI-MS/MS联用技术,建立了分析检测猪肉肌肉组织中全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)的方法.本方法以Waters sunfire C 18柱为液相分离柱,以乙腈-5mmol/L乙酸铵溶液梯度洗脱溶液,PFOS和PFOA在10min内即能达到良好分离,定性定量离子对分别为499.0/79....     

PFOS与PFOA的毒性效应及其在我国普通人群中的内暴露研究进展

全氟辛烷磺酸（PFOS）和全氟辛酸（PFOA）是应用广泛的人工合成化学物,在环境和人体内广泛存在,PFOS/PFOA毒性作用广泛且具有生物蓄积性,因为对人体健康有影响受到越来越多的关注。本文系统总结了PFOS/PFOA在哺乳动物体内的吸收、分布、代谢、排泄和毒性作用,以及目前国际上针对PFOS/PFOA提出的安全限量,并基于现有数据概述了我国普通人群PFOS/PFOA内暴露情况,以期为PFOS/PFOA的风险评估及风险管理提供科学基础。     

Temporal trends of perfluoroalkyl concentrations in American Red Cross adult blood donors, 2000-2010

Eleven perfluorinated alkyl acids (PFAAs) were analyzed in plasma from a total of 600 American Red Cross adult blood donors from six locations in 2010. The samples were extracted by protein precipitation and quantified by using liquid chromatography tandem mass spectrometry (HPLC/MS/MS). The anions of the three perfluorosulfonic acids measured were perfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS). The anions of the eight perfluorocarboxylic acids were perfluoropentanoate (PFPeA), perfluorohexanoate (PFHxA), perfluoroheptanoate (PFHpA), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), perfluorodecanoate (PFDA), perfluoroundecanoate (PFUnA), and perfluorododecanoate (PFDoA). Findings were compared to results from different donor samples analyzed at the same locations collected in 2000-2001 (N = 645 serum samples) and 2006 (N = 600 plasma samples). Most measurements in 2010 were less than the lower limit of quantitation for PFBS, PFPeA, PFHxA, and PFDoA. For the remaining analytes, the geometric mean concentrations (ng/mL) in 2000-2001, 2006, and 2010 were, respectively, PFHxS: (2.25, 1.52, 1.34); PFOS (34.9, 14.5, 8.3); PFHpA (0.13, 0.09, 0.05); PFOA (4.70, 3.44, 2.44); PFNA (0.57, 0.97, 0.83); PFDA (0.16, 0.34, 0.27), and PFUnA (0.10, 0.18, 0.14). The percentage decline (parentheses) in geometric mean concentrations from 2000-2001 to 2010 were PFHxS (40%), PFOS (76%), and PFOA (48%). The decline in PFOS suggested a population halving time of 4.3 years. This estimate is comparable to the geometric mean serum elimination half-life of 4.8 years reported in individuals. This similarity supports the conclusion that the dominant PFOS-related exposures to humans in the United States were greatly mitigated during the phase-out period.     

Perfluorooctanesulfonate and related fluorochemicals in human blood samples from China

Perfluorooctanesulfonylfluoride (POSF)-based compounds have been manufactured and used in a variety of industrial applications. These compounds degrade to perfluorooctanesulfonate (PFOS) which is regarded as a persistent end-stage metabolite and is found to accumulate in tissues of humans and wildlife. PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) have been found in human sera from the United States. In this study, concentrations of PFHxS, perfluorobutanesulfonate (PFBS), PFOS, perfluorohexanoic acid (PFHxA), PFOA, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUnDA), perfluorododecanoic acid (PFDoDA), and PFOSA were measured in 85 samples of whole human blood collected from nine cities (eight provinces) in China, including Shenyang (Liaoning), Beijing (Hebei), Zhengzhou (Henan), Jintan (Jiangsu), Wuhan (Hubei), Zhoushan (Zhejiang), Guiyang (Guizhou), Xiamen (Fujian), and Fuzhou (Fujian). Among the 10 perfluorinated compounds (PFCs) measured, PFOS was the predominant compound. The mean concentration of PFOS was greatest in samples collected from Shenyang (79.2 ng/mL) and least in samples from Jintan (3.72 ng/mL). PFHxS was the next most abundant perfluorochemical in the samples. No age-related differences in the concentrations of PFOA, PFOS, PFOSA, and PFHxS were observed. Gender-related differences were found,with males higher for PFOS and PFHxS, and females higher in PFUnDA. Concentrations of PFHxS were positively correlated with those of PFOS, while concentrations of PFNA, PFDA, and PFUnDA were positively correlated with those of PFOA. There were differences in the concentration profiles (percentage composition) of various PFCs in the samples among the nine cities.     

Perfluorinated Alkyl Acids in Blood Serum from Primiparous Women in Sweden: Serial Sampling during Pregnancy and Nursing, And Temporal Trends 1996-2010

We investigated temporal trends of blood serum levels of 13 perfluorinated alkyl acids (PFAAs) and perfluorooctane sulfonamide (FOSA) in primiparous women (N = 413) from Uppsala County, Sweden, sampled 3 weeks after delivery 1996-2010. Levels of the short-chain perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS) increased 11%/y and 8.3%/y, respectively, and levels of the long-chain perfluorononanoate (PFNA) and perfluorodecanoate (PFDA) increased 4.3%/y and 3.8%/y, respectively. Concomitantly, levels of FOSA (22%/y), perfluorooctane sulfonate (PFOS, 8.4%/y), perfluorodecane sulfonate (PFDS, 10%/y), and perfluorooctanoate (PFOA, 3.1%/y) decreased. Thus, one or several sources of exposure to the latter compounds have been reduced or eliminated, whereas exposure to the former compounds has recently increased. We explored if maternal levels of PFOS, PFOA, and PFNA during the early nursing period are representative for the fetal development period, using serial maternal serum samples, including cord blood (N = 19). PFAA levels in maternal serum sampled during pregnancy and the nursing period as well as in cord blood were strongly correlated. Strongest correlations between cord blood levels and maternal levels were observed for maternal serum sampled shortly before or after the delivery (r = 0.70-0.89 for PFOS and PFOA). A similar pattern was observed for PFNA, although the correlations were less strong due to levels close to the method detection limit in cord blood.     

Perfluorooctanesulfonate and related fluorochemicals in human blood from several countries

Perfluorooctanesulfonyl fluoride based compounds have been used in a wide variety of consumer products, such as carpets, upholstery, and textiles. These compounds degrade to perfluorooctanesulfonate (PFOS), a persistent metabolite that accumulates in tissues of humans and wildlife. Previous studies have reported the occurrence of PFOS, perfluorohexanesulfonate (PFHxS), perfluorooctanoate (PFOA), and perfluorooctanesulfonamide (PFOSA) in human sera collected from the United States. In this study, concentrations of PFOS, PFHxS, PFOA, and PFOSA were measured in 473 human blood/serum/plasma samples collected from the United States, Colombia, Brazil, Belgium, Italy, Poland, India, Malaysia, and Korea. Among the four perfluorochemicals measured, PFOS was the predominant compound found in blood. Concentrations of PFOS were the highest in the samples collected from the United States and Poland (>30 ng/mL); moderate in Korea, Belgium, Malaysia, Brazil, Italy, and Colombia (3 to 29 ng/mL); and lowest in India (<3 ng/mL). PFOA was the next most abundant perfluorochemical in blood samples, although the frequency of occurrence of this compound was relatively low. No age- or gender-related differences in the concentrations of PFOS and PFOA were found in serum samples. The degree of association between the concentrations of four perfluorochemicals varied, depending on the origin of the samples. These results suggested the existence of sources with varying levels and compositions of perfluorochemicals, and differences in exposure patterns to these chemicals, in various countries. In addition to the four target fluorochemicals measured, qualitative analysis of selected blood samples showed the presence of other perfluorochemicals such as perfluorodecanesulfonate (PFDS), perfluoroheptanoic acid (PFHpA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorododecanoic acid (PFDoA), and perfluoroundecanoic acid (PFUnDA) in serum samples, at concentrations approximately 5- to 10-fold lower than the concentration of PFOS. Further studies should focus on identifying sources and pathways of human exposure to perfluorochemicals.     

超高效液相色谱-串联质谱法测定食品包装材料中全氟辛酸及其盐类物质

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)结合加速溶剂萃取测定食品包装材料中全氟辛酸及其盐类物质(PFOA)的方法.采用甲醇作为溶剂,加速溶剂提取法提取食品包装材料中的PFOA,提取液经0.2 μm有机滤膜过滤后,以甲醇、水为流动相,梯度洗脱,经UPLC分离后用多级反应监测(MRM)方式测定.用两个子离子的...     

Exposure of an adult population to perfluorinated substances using duplicate diet portions and biomonitoring data

Because dietary intake is supposed to be an important route of human exposure we quantified the dietary intake of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorohexane sulfonate (PFHxS), perfluorohexanoate (PFHxA), and perfluorooctane sulfonamide (PFOSA) using 214 duplicate diet samples. The study was carried out with a study population of 15 female and 16 male healthy subjects aged 16-45 years. The participants collected daily duplicate diet samples over seven consecutive days in 2005. Duplicate samples were homogenized and their ultrasonic extracts were cleaned up by SPE and subjected to HPLC-ESI-MS/MS. In addition, individual intakes were estimated based on blood levels of PFOS and PFOA using a pharmacokinetic model. Blood samples were collected once during the sampling period. The median (90th percentile) daily dietary intake of PFOS and PFOA was 1.4 ng/kg b.w. (3.8 ng/kg b.w.) and 2.9 ng/kg b.w. (8.4 ng/kg b.w.), respectively. PFHxS and PFHxA could be detected only in some samples above detection limit with median (maximum) daily intakes of 2.0 ng/kg b.w. (4.0 ng/kg b.w.) and 4.3 ng/kg b.w. (9.2 ng/kg b.w.), respectively. Because PFOSA could not be detected above the limit of detection of 0.2 ng/g f.w. this indirect route of exposure seems to be of less significance. Overall, the results of this study demonstrate that the German population is exposed to PFOS and PFOA, but the median dietary intake did not reach the recommended tolerable daily intake by far. Biomonitoring data predict an exposure in a comparable range. We suppose that, normally, food intake is the main source of exposure of the general population to PFOS and PFOA.     

Is fish a major source of fluorinated surfactants and repellents in humans living on the Baltic Coast?

Concentrations of 19 perfluorochemicals have been quantified in human blood and in some marine food resources from the region of the Gulf of Gda?sk at the Baltic Sea south coast in Poland. We indicate that in addition to PFOS and PFOA, a further 8 perfluorochemicals bioaccumulate in the human body. Food chain is an important route of exposure for all 10 perfluoroalkyl compounds detected in nonoccupationally exposed humans. Individuals who declared to have a high fish intake in their diet (mainly Baltic fish) on average contained the highest load of all 10 fluorochemicals when compared with the other human subpopulations. Baltic seafood has been found to highly influence human body burden of PFHxS, PFOS, PFOSA, PFHxA, PFHpA, PFNA, PFDA, PFUnDA, and PFDoDA, and to a lesser extent PFOA.     

Occurrence of selected perfluorinated alkyl acids in lunch meals served at school canteens in Italy and their relevance for children’s intake

Ready-to-eat servings may be more contaminated with perfluorinated alkyl acids (PFAAs) than the corresponding unprocessed foods due to the presence of PFAAs in and transfer from food contact materials (FCM) and cookware. Therefore, the presence of selected PFAAs in meals served weekly at lunch time in six Italian school canteens was assessed. Five towns were selected representing different areas with local water and food supply. Daily lunch menus were sampled and pooled to form a composite. Analyses were carried out on the weekly composite from each canteen. UPLC-MS/MS quantification limits were in the 6.0–12 pg g^–1 range for the selected PFAAs (PFHxA, PFOA, PFNA, PFDA, PFUnDA, PFHxS, branched and non-branched PFOS). Non-branched PFOS was quantified in four out of six composites, with levels ranging from 14 to 25 pg g^–1, while PFOA and PFDA were determined in two out of six in the range 6.5–8.2 pg g^–1. Theoretical estimates and analytical results in the same order of magnitude indicate a negligible contribution from food processing and serving to meal contamination. When composite analytical data are transposed into dietary estimates, it is shown that Italian school-age children have intakes in the range of 0.3–1.1 and 0.5–1.4 ng kg^–1 bw day^–1 for PFOA and PFOS respectively, well below the corresponding tolerable daily intakes (TDIs).     

Health risks in infants associated with exposure to perfluorinated compounds in human breast milk from Zhoushan, China

Recent studies have reported the ubiquitous distribution of perfluorinated compounds (PFCs), especially perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA), in wildlife and human whole blood or serum. In 2003 a solid phase extraction method was developed, which allowed the measurement of PFCs in human breast milk. In the present study, PFCs in samples of human breast milk from 19 individuals from Zhoushan, China, were analyzed by modifying a previously established method, based on weak-anion exchange extraction. PFOS and PFOA were the two dominant chemicals detected in all the milk samples. Concentrations of PFOS and PFOA ranged from 45 to 360 ng/L and 47 to 210 ng/L, respectively. The maximum concentrations of other PFCs were 100 ng/L for perfluorohexanesulfonate (PFHxS), 62 ng/L for perfluorononanoate (PFNA), 15 ng/L for perfluorodecanoate (PFDA) and 56 ng/L for perfluoroundecanoate (PFUnDA). Statistically significant correlations between various PFCs suggested a common exposure source to humans. No statistically significant correlation was found between concentrations of either PFOS or PFOA and maternal age, weight, or infant weight. Rate of consumption of fish was found to be positively correlated with PFNA, PFDA, and PFUnDA concentrations. Daily intake of PFOS for the child via breast milk with greater PFOS concentrations exceeded the predicted conservative reference dose in 1 of 19 samples, indicating that there may be a small potential risk of PFOS for the infants in Zhoushan via the consumption of breast milk.