不同职业人群血清PFOS和PFOA负荷水平检测

目的 了解浙江省温州市不同职业人群体内全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)的负荷水平.方法 选择制鞋厂职工为全氟化合物暴露组,面砖厂职工为全氟化合物非暴露组,采用液液萃取和高效液相色谱/质谱联用仪选择性监测离子法(PFOS:m/z=499,PFOA:m/z=413),测定目标人群血清中PFOS和PFOA的浓度.结果 制鞋厂工人血清中PFOS的几何均数(G)为10.79μg/L,高于面砖厂的4.93μg/L,差异有统计学意义(P＜0.01);而制鞋厂工人血清中PFOA的几何均数(G)为2.98μg/L,低于面砖厂的4.85μg/L,差异有统计学意义(P＜0.01);不同职业人群性别间PFOS和PFOA水平差异无统计学意义;制鞋厂人群＜3年和≥3年工龄组间2个物质水平差异亦无统计学意义.结论 无论有无职业性暴露,温州市2种职业人群血清中均可检出PFOS和PFOA.     

沈阳和重庆人群血清中全氟辛烷磺酸和全氟辛酸的污染水平比较研究

目的阐明沈阳和重庆两地一般人群血清中全氟辛烷磺酸(PFOS)和全氟辛酸(PFOA)污染水平,比较两地人群血清中PFOS和PFOA分布特征。方法采集沈阳和重庆地区无职业性PFOS和PFOA暴露人群血清,采用高压液相色谱-质谱仪联机系统测定血清中PFOS和PFOA含量。结果沈阳地区一般人群血清中PFOS和PFOA浓度中位数分别为22·40μg/L和4·32μg/L,重庆地区分别为7·40μg/L和1·00μg/L。沈阳地区人群血清中PFOS、PFOA浓度明显高于重庆地区(P<0·01)。两地区女性人群血清中PFOS和PFOA浓度均高于男性水平,沈阳地区人群血清中PFOS浓度男、女性别间差异显著(P<0·05)。重庆地区女性人群血清中PFOS、PFOA浓度与年龄呈正相关关系(rPFOS=0·298,rPFOA=0·271),50岁以上女性人群的相关程度大于13岁以下和13~50岁年龄组。结论沈阳和重庆两地人群血清中PFOS和PFOA污染水平具有显著的地区性差异和分布特征,血清中PFOS和PFOA水平与年龄存在相关性。     

人血清中全氟辛烷磺酰基化合物污染现状

目的 了解我国一般人群体内的全氟辛烷磺酰基化合物(PFOS)负荷水平。方法 采用液相色谱／质谱仪联机选择性监测离子法(m／z=499)，测定被调查血清中PFOS浓度。结果 男女血清中PFOS浓度几何均数分别为40．73和45．46μg／L，血清PFOS浓度与年龄无关。结论 我国一般人群体内也存在PFOS污染物，而且血清PFOS浓度高于美国人和日本人水平。     

高效液相色谱—质谱法测定皮革及皮革处理剂中全氟辛酸和全氟辛烷磺酸的浓度

建立液-液萃取、超声协同液液萃取和超声协同液液萃取合并固相萃取的方法对皮革处理剂液体、固体和皮革样品中全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)进行提取,并用高效液相色谱/质谱联用仪选择性监测离子法(PFOA:m/z=413;PFOS:m/z=499)进行样品测定.两种物质检测方法的检测限均为1 ng/ml,线性范...     

全氟辛酸和全氟辛烷磺酸经大鼠离体皮肤吸收实验

[目的]探讨全氟辛酸（PFOA）和全氟辛烷磺酸（PFOS）是否能体外经皮吸收及其吸收特征。[方法]采用Franz扩散装置,以10μmol／L的PFOA和PFOS的混合溶液（1：1）作为供体液,用HPLC．MS测定两种化合物的单位面积SD大鼠离体皮肤的累积渗透量,分别计算其稳态渗透速率、渗透滞后时间和渗透系数。[结果]各透过时间点受体液中均可检测到PFOA和PFOS;PFOA和PFOS的12h累积渗透量分别为（4．97±1．80）、（1．76±1．06）μg/cm2,稳态渗透速率分别为（0．48±0．19）、（0．16±0．06）μg／cm2·h,渗透滞后时间分别为（0．31±0．18）、（0．50±0．06）h,渗透系数分别为（11．48±4．51）×10^-2、（3．17±1．22）×10^-2cm／h。[结论]PFOA和PFOS均能够经皮吸收,前者稳态渗透快于后者,渗透系数大于后者,渗透滞后时间明显小于后者。该研究确定了PFOA和PFOS的体外经皮吸收特征,为暴露量评定和危险性评价提供了有意义的基础研究数据。     

脐带血中全氟有机化合物及其典型异构体的分布研究

目的分析胎儿脐带血中全氟有机化合物(PFASs)及其典型异构体的浓度水平和地区差异。方法采用超高效液相色谱串联三重四级杆质谱法测定天津和广州地区胎儿脐带血中全氟有机化合物及其典型异构体的污染水平,分析不同地区间脐带血中PFASs的浓度水平差异以及全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)异构体所占比例差异。结果天津和广州地区污染水平最高的PFASs分别是total-PFOA和PFHx S,其中位数浓度分别为4.318和3.455 ng/ml。天津和广州地区分别检出了3种PFOA异构体和1种PFOA异构体,均检出5种PFOS异构体。天津地区(99.47%)n-PFOA占total-PFOA的比例显著高于广州地区(94.95%),差异有统计学意义(P0.01)。结论天津和广州地区脐带血中PFASs的污染水平和分布有较大差异;两地区间n-PFOS所占total-PFOS的比例相似。     

全氟化合物对儿童肺功能影响的病例对照研究

探讨全氟化合物对哮喘儿童和一般儿童肺功能影响的性别差异,为采取有效措施保护儿童心肺功能提供参考.方法 从台湾大学医院就诊的哮喘儿童选取132名,从台北地区7所公立中学随机选取168名一般健康儿童.采用Logistic回归和多重线性回归的方法分析血清全氟辛烷磺酸(perfluorooctanesulfonate,PFOS)和全氟辛酸(perfluo-rooctanoic acid,PFOA)水平对儿童肺功能的影响.结果 儿童哮喘的患病风险随着全氟化合物(perfluoroalkyl and polyfluoroalkyl substances,PFAAS)浓度的增加而呈现增高趋势,PFOS与PFOA暴露对儿童哮喘患病风险的优势比分别为1.32(95%CI=1.02~ 1.71)和2.80(95%CI=1.87~4.20).PFOS和PFOA暴露水平与哮喘男童的肺功能水平(FVC,FEV1和FEF25%-75%)呈负相关,男孩血清中PFOS和PFOA水平每增加1μg/L时,FEV1分别下降-0.062(95% CI=-0.106~-0.018)和-0.099(95%CI=-0.197-0.001)L.结论 PFAAs的暴露可以降低儿童肺功能水平,并且男童相较于女童更易感.     

武汉市一般人群血清中全氟辛烷磺酸和全氟辛酸分布特征

目的 对武汉市一般人群体内全氟辛烷磺酸(perfluorooctane sulfonate,PFOS)和全氟辛酸(perfluorooctanoate,PFOA)负荷状况及分布特征进行研究,为武汉市制定控制PFOS和PFOA污染的法规政策提供科学依据。 方法 2014－2015年间采用分层随机抽样方法收集在武汉市居住5年以上的、无职业性暴露的成人及儿童的血液样本,采用高效液相色谱串联质谱法,测定血清中PFOS和PFOA含量。采用SPSS 22.0软件分析检测数据。 结果 武汉市人群血清中PFOS检出率为75.4%(儿童组)、83.3%(成人组),PFOA的检出率为80.5%(儿童组)、82.9%(成人组)。城市、农村地区儿童组、成人组男性和女性血清中PFOS和PFOA含量差异均无统计学意义(P>0.05)。城市地区女性血清中PFOS含量成人组( M=2.40 ng/ml,P₂₅=1.58 ng/ml,P₇₅=3.95 ng/ml)高于儿童组( M=2.00 ng/ml,P₂₅=0.23 ng/ml,P₇₅=3.20 ng/ml)(Z=-2.565,P=0.010),男性血清中PFOA含量成人组(M=1.80 ng/ml,P₂₅=0.25 ng/ml,P₇₅=5.82 ng/ml)低于儿童组(M=3.60 ng/ml,P₂₅=1.13 ng/ml,P₇₅=10.00 ng/ml)(Z=-2.158,P=0.031)。农村地区男性血清中PFOA含量成人组(M=1.29 ng/ml,P₂₅=0.05 ng/ml,P₇₅=3.60 ng/ml)低于儿童组(M=4.07 ng/ml,P₂₅=0.24 ng/ml,P₇₅=8.34 ng/ml)(Z=-2.820,P=0.005)。成人组女性血清中PFOS含量城市地区(M=2.40 ng/ml,P₂₅=1.58 ng/ml,P₇₅=3.95 ng/ml)高于农村地区(M=0.48 ng/ml,P₂₅=0.05 ng/ml,P₇₅=5.02 ng/ml)(Z=-4.316,P＜0.001),PFOA含量城市地区(M=3.30 ng/ml,P₂₅=0.85 ng/ml,P₇₅=6.85 ng/ml)高于农村地区(M=0.88 ng/ml,P₂₅=0.24 ng/ml,P₇₅=4.05 ng/ml)(Z=-3.639,P＜0.001)。武汉市人群血清中PFOS和PFOA含量之间存在正相关关系(P＜0.05)。 结论 地区、年龄、生理状态等因素的作用都可能造成人群体内PFOS和PFOA负荷的差异。 饮食摄入可能是武汉地区人群暴露于PFOS和PFOA共同途径。     

《生活饮用水卫生标准(GB5749-2022)》中全氟辛酸与全氟辛烷磺酸标准限值的制定研究

全氟化合物尤其是全氟辛酸(PFOA)与全氟辛烷磺酸(PFOS)在我国水环境中广泛检出。考虑到饮用水暴露途径的潜在健康风险, 我国新颁布的《生活饮用水卫生标准》(GB 5749-2022)中的水质参考指标增加了PFOA和PFOS指标, 限值分别为40和80 ng/L。本研究对确定该卫生标准限值的相关技术内容进行了分析和讨论, 包括PFOA与PFOS的环境存在水平和暴露状况、健康效应、安全基准值的推导和卫生标准限值的确定等, 并提出了未来饮用水标准制定方向的展望。     

贵阳市217例孕期妇女血清全氟辛酸、全氟辛烷磺酸负荷水平研究

目的了解贵阳市孕妇血清中全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)的负荷水平,为妇女孕期保健提供参考。方法选取到目标产前保健就诊点就诊的孕周为9~22周的217例孕妇为研究对象,采集孕妇肘部静脉血1~3 ml,用超高效液相色谱-串联质谱法(UPLC-MS/MS)对血清标本中PFOS和PFOA的含量进行检测。结果 PFOS和PFOA的检出率分别为86.18%、92.63%;平均浓度分别为(3.55±2.67)ng/ml、(8.27±1.49)ng/ml,血清中PFOS、PFOA两种物质的含量呈正相关(r=0.35,P0.001);该地区孕妇血清中PFOS和PFOA的含量与昆明、成都和重庆成人血清含量差异有统计学意义。结论该地孕期妇女血清中PFOS和PFOA均检出。与国内临近城市成人血清中的平均水平相比,其血清中PFOS和PFOA含量差异情况各异。     

Perfluorinated chemicals in blood of residents in Wenzhou, China

Perfluorinated compounds (PFCs) are persistent organic pollutants ubiquitously distributed in the environment and human populations. Here we report PFC concentrations in the residents of Wenzhou City, which is characterized as the ‘Footwear Capital’ of China. Specifically, fifty serum samples collected from workers in a leather factory, fifty-five umbilical cord serum samples and fifteen serum samples from infertile men were analyzed. PFOS was one of the most frequently detected PFCs and showed the highest level. The mean serum levels of PFOS and PFOA of workers and infertile males were higher than the cord serum. PFOS concentration in cord serum increased with increase in age of the mother. Gender differences were significant both in worker serum samples and umbilical cord samples with higher levels found in males/male fetuses. Our findings suggested that PFOS, PFOA and PFHxS were widely distributed in Wenzhou residents, but occupational exposure was not the main source for workers.     

Historical comparison of perfluorooctanesulfonate, perfluorooctanoate, and other fluorochemicals in human blood

The purpose of this investigation was to determine whether there has been a change in the human blood concentration of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and five other fluorochemicals since 1974. Blood samples were collected in 1974 (serum) and 1989 (plasma) from volunteer participants of a large community health study. The study included a total of 356 samples (178 from each time period). These samples were analyzed by high-pressure liquid chromatography/tandem mass spectrometry methods. The median 1974 and 1989 fluorochemical concentrations, respectively, were as follows: PFOS, 29.5 ng/mL vs. 34.7 ng/mL; PFOA, 2.3 ng/mL vs. 5.6 ng/mL; perfluorohexanesulfonate (PFHS), 1.6 ng/mL vs. 2.4 ng/mL; and N-ethyl perfluorooctanesulfonamidoacetate (PFOSAA), less than the lower limit of quantitation (LLOQ; 1.6 ng/mL, vs. 3.4 ng/mL). For N-methyl perfluorooctanesulfonamidoacetate (M570), perfluorooctanesulfonamide, and perfluorooctanesulfonamidoacetate, median serum concentrations in both years were less than the LLOQ values (1.0, 1.0, and 2.5 ng/mL, respectively). Statistical analysis of 58 paired samples indicated that serum concentrations of PFOS, PFOSAA, PFOA, PFHS, and M570 were significantly (p < 0.001) higher in 1989 than in 1974. The data from 1989 were then compared with geometric mean fluorochemical concentrations of serum samples collected in 2001 from 108 American Red Cross adult blood donors from the same region. Except for M570, there were no statistically significant (p < 0.05) geometric mean fluorochemical concentration differences between the 1989 and 2001 samples. In conclusion, based on this study population, PFOS and other serum fluorochemical concentrations have increased between 1974 and 1989. Comparison with other regional data collected in 2001 did not suggest a continued increase in concentrations since 1989.     

Perfluorooctane sulphonate (PFOS) and perfluorooctanoic acid (PFOA) in human breast milk: results of a pilot study

Perfluorinated compounds (PFC) are a large group of chemicals produced for several decades and widely used for many industrial and consumer applications. Because of their global occurrence in different environmental media, their persistence and their potential to bioaccumulate in organisms they are of toxicological and public concern. In the present study, perfluorooctane sulphonate (PFOS) and perfluorooctanoic acid (PFOA) were quantified in 70 breast milk samples. Samples were obtained from Leipzig, Germany (38 archived samples), Munich, Germany (19 fresh samples) and Gyor, Hungary (13 frozen samples). PFOS could be quantified in all 70 samples. The concentration in samples from Germany ranged between 28 and 309 ng/l (median: 119 ng/l). Samples from Hungary showed significantly higher PFOS concentrations (median 330 ng/l, range 96-639 ng/l). In only 11 of 70 samples (16%) PFOA reached the LOQ (200 ng/l); values ranged from 201 to 460 ng/l. If only those samples with PFOA values above the LOQ were considered, we found a significant correlation between the PFOS and PFOA concentrations (r=0.75, p=0.008). Based on the results of the German sample, we estimated an intake of 0.10 microg PFOS/day (using median) or 0.27 PFOS microg/day (using maximum value) via breast milk for an infant of 5 kg bodyweight. Our data suggest that fully breastfed infants are unlikely to exceed the recommended tolerable daily intake of PFC. However, more target-oriented studies are needed to identify the amount and time-trend of PFOS and PFOA in maternal blood during pregnancy, after delivery, as well as in the growing infant and in its diet (e.g., breast milk and formula).     

The influence of time, sex and geographic factors on levels of perfluorooctane sulfonate and perfluorooctanoate in human serum over the last 25 years

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are important perfluorochemicals (PFCs) in various applications. Recently, it has been shown that these chemicals are widespread in the environment, wildlife and humans. But the kinds of factors that affect their levels in serum are unclear, and it is also not clear whether exposure to them is increasing or not. To investigate the impacts of time, geographical location and sex on the levels of these chemicals, we measured PFOS and PFOA concentrations in human sera samples collected both historically and recently in Miyagi, Akita and Kyoto Prefectures in Japan. The PFOS and PFOA levels in sera [Geometric Mean (Geometric Standard Deviation)] (microg/L) in 2003 ranged from 3.5 (2.9) in Miyagi to 28.1 (1.5) in Kyoto for PFOS and from 2.8 (1.5) to 12.4 (1.4) for PFOA. Historical samples collected from females demonstrated that PFOS and PFOA concentrations have increased by factors of 3 and 14, respectively, over the past 25 yr. There are large sex differences in PFOS and PFOA concentrations in serum at all locations. Furthermore, there are predominant regional differences for both PFOS and PFOA concentrations. In Kyoto the concentrations of PFOA in dwellers who had lived in the Kinki area for more than 2 yr were significantly higher than in people who had recently moved into the area, in both sexes. This finding suggests that there are sources of PFOA in the Kinki area that have raised the PFOA serum levels of its inhabitants. Further studies are needed to elucidate these sources in the Kinki area of Japan.     

Biomonitoring of perfluorinated compounds in children and adults exposed to perfluorooctanoate-contaminated drinking water

OBJECTIVE: 40,000 residents in Arnsberg, Germany, had been exposed to drinking water contaminated with perfluorinated compounds (PFCs). Internal exposure of the residents of Arnsberg to six PFCs was assessed in comparison with reference areas. DESIGN AND PARTICIPANTS: One hundred seventy children (5-6 years of age), 317 mothers (23-49 years), and 204 men (18-69 years) took part in the cross-sectional study. MEASUREMENTS: Individual consumption of drinking water and personal characteristics were assessed by questionnaire and interview. Perfluorooctanoate (PFOA), perfluorooctanesulfonate (PFOS), perfluorohexanoate, perfluorohexanesulfonate (PFHxS), perfluoropentanoate, and perfluorobutanesulfonate (PFBS) in blood plasma and PFOA/PFOS in drinking water samples were measured by solid-phase extraction, high-performance liquid chromatrography, and tandem mass spectrometry detection. RESULTS: Of the various PFCs, PFOA was the main compound found in drinking water (500-640 ng/L). PFOA levels in blood plasma of residents living in Arnsberg were 4.5-8.3 times higher than those for the reference population (arithmetic means Arnsberg/controls: children 24.6/5.2 microg/L, mothers 26.7/3.2 microg/L, men 28.5/6.4 microg/L). Consumption of tap water at home was a significant predictor of PFOA blood concentrations in Arnsberg. PFHxS concentrations were significantly increased in Arnsberg compared with controls (p < 0.05). PFBS was detected in 33% of the children, 4% of the women, and 13% of the men in Arnsberg compared with 5%, 0.7%, and 3%, respectively, in the reference areas (p < 0.05). Regression analysis showed that age and male sex were significant predictors of PFOS, PFOA, and PFHxS; associations of other regressors (diet, body mass index) varied among PFCs. CONCLUSIONS: PFC concentrations in blood plasma of children and adults exposed to PFC-contaminated drinking water were increased 4- to 8-fold compared with controls.     

Perfluorooctane sulfonate (PFOS) and related perfluorinated compounds in human maternal and cord blood samples: assessment of PFOS exposure in a susceptible population during pregnancy

Fluorinated organic compounds (FOCs), such as perfluorooctane sulfonate (PFOS), perfluoro-octanoate (PFOA), and perfluorooctane sulfonylamide (PFOSA), are widely used in the manufacture of plastic, electronics, textile, and construction material in the apparel, leather, and upholstery industries. FOCs have been detected in human blood samples. Studies have indicated that FOCs may be detrimental to rodent development possibly by affecting thyroid hormone levels. In the present study, we determined the concentrations of FOCs in maternal and cord blood samples. Pregnant women 17-37 years of age were enrolled as subjects. FOCs in 15 pairs of maternal and cord blood samples were analyzed by liquid chromatography-electrospray mass spectrometry coupled with online extraction. The limits of quantification of PFOS, PFOA, and PFOSA in human plasma or serum were 0.5, 0.5, and 1.0 ng/mL, respectively. The method enables the precise determination of FOCs and can be applied to the detection of FOCs in human blood samples for monitoring human exposure. PFOS concentrations in maternal samples ranged from 4.9 to 17.6 ng/mL, whereas those in fetal samples ranged from 1.6 to 5.3 ng/mL. In contrast, PFOSA was not detected in fetal or maternal samples, whereas PFOA was detected only in maternal samples (range, < 0.5 to 2.3 ng/mL, 4 of 15). Our results revealed a high correlation between PFOS concentrations in maternal and cord blood (r2 = 0.876). However, we did not find any significant correlations between PFOS concentration in maternal and cord blood samples and age bracket, birth weight, or levels of thyroid-stimulating hormone or free thyroxine. Our study revealed that human fetuses in Japan may be exposed to relatively high levels of FOCs. Further investigation is required to determine the postnatal effects of fetal exposure to FOCs. Key words: cord blood, fluorinated organic compounds, human, PFOA, PFOS, PFOSA, pregnancy.     

Serum levels of perfluoroalkyl compounds in human maternal and umbilical cord blood samples

Perfluoroalkyl compounds (PFCs) are end-stage metabolic products from industrial flourochemicals used in the manufacture of plastics, textiles, and electronics that are widely distributed in the environment. The objective of the present study was to quantify exposure to perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorodecanoic acid (PFDeA), perfluorohexane sulfonate (PFHxS), perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA) in serum samples collected from pregnant women and the umbilical cord at delivery. Pregnant women (n=101) presenting for second trimester ultrasound were recruited and PFC residue levels were quantified in maternal serum at 24-28 weeks of pregnancy, at delivery, and in umbilical cord blood (UCB; n=105) by liquid chromatography-mass spectrometry. Paired t-test and multiple regression analysis were performed to determine the relationship between the concentrations of each analyte at different sample collection time points. PFOA and PFOS were detectable in all serum samples analyzed including the UCB. PFOS serum levels (mean±S.D.) were significantly higher (p<0.001) in second trimester maternal serum (18.1±10.9 ng/mL) than maternal serum levels at delivery (16.2±10.4 ng/mL), which were higher than the levels found in UCB (7.3±5.8 ng/mL; p<0.001). PFHxS was quantifiable in 46/101 (45.5%) maternal and 21/105 (20%) UCB samples with a mean concentration of 4.05±12.3 and 5.05±12.9 ng/mL, respectively. There was no association between serum PFCs at any time point studied and birth weight. Taken together our data demonstrate that although there is widespread exposure to PFCs during development, these exposures do not affect birth weight.