Urinary bisphenol A concentrations and their implications for human exposure in several Asian countries

Bisphenol A (BPA) is an industrial chemical used in the manufacture of polycarbonate plastics and epoxy resins. Due to the potential of this compound to disrupt normal endocrinal functions, concerns over human exposure to BPA have been raised. Although several studies have reported human exposure to BPA in Western nations, little is known about exposure in Asian countries. In this study, we determined total urinary BPA concentrations (free plus conjugated) in 296 urine samples (male/female: 153/143) collected from the general population in seven Asian countries, China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam, using high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS). On the basis of urinary BPA concentrations, we estimated the total daily intake. The results indicated that BPA was detected in 94.3% of the samples analyzed, at concentrations ranging from <0.1 to 30.1 ng/mL. The geometric mean concentration of BPA for the entire sample set from seven countries was 1.20 ng/mL. The highest concentration of BPA was found in samples from Kuwait (median: 3.05 ng/mL, 2.45 μg/g creatinine), followed by Korea (2.17 ng/mL, 2.40 μg/g), India (1.71 ng/mL, 2.09 μg/g), Vietnam (1.18 ng/mL, 1.15 μg/g), China (1.10 ng/mL, 1.38 μg/g), Malaysia (1.06 ng/mL, 2.31 μg/g), and Japan (0.95 ng/mL, 0.58 μg/g). Among the five age groups studied (≤ 19, 20-29, 30-39, 40-49, and ≥ 50 years), the highest median concentration of BPA was found in urine samples from the age group of ≤ 19 years. There was no significant difference in BPA concentrations between genders (male and female) or domicile of residence (rural and urban). The estimated median daily intakes of BPA for the populations in Kuwait, Korea, India, China, Vietnam, Malaysia, and Japan were 5.19, 3.69, 2.90, 2.13, 2.01, 1.80, and 1.61 μg/day, respectively. The estimated daily intake of BPA in the seven Asian countries was significantly lower than the tolerable daily intake recommended by the U.S. Environmental Protection Agency. This is the first study to document the occurrence of and human exposure to BPA in several Asian countries.     

Occurrence of phthalate metabolites in human urine from several Asian countries

The occurrence of 14 phthalate metabolites was found in human urine samples collected from seven Asian countries: China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam. Phthalate metabolites were found in all samples, indicating widespread exposure of humans to phthalates in these Asian countries. The highest total (the sum of 14 phthalates) phthalate metabolite concentrations were found in samples collected from Kuwait (median: 1050 ng/mL), followed in decreasing order by samples from India (389 ng/mL), China (234 ng/mL), Vietnam (133 ng/mL), Japan (120 ng/mL), Korea (117 ng/mL), and Malaysia (94.9 ng/mL). The creatinine-adjusted median concentrations of total phthalates for urine samples from Kuwait, India, China, Vietnam, Japan, Korea, and Malaysia were 692, 506, 289, 119, 103, 104, and 169 μg/g creatinine, respectively. Monomethyl phthalate (mMP), monoethyl phthalate (mEP), mono (2-isobutyl phthalate) (miBP), mono-n-butyl phthalate (mBP), and metabolites of di-(2-ethylhexyl) phthalate (DEHP) were the dominant compounds, collectively accounting for >95% of the total concentrations in the samples from the seven countries. The profiles of urinary phthalate metabolite concentrations varied among the samples collected from the seven countries. Urine samples from Kuwait contained the highest concentrations of mEP (median: 391 ng/mL), mBP (94.1 ng/mL), and the metabolites of DEHP (202 ng/mL), whereas samples from China and Japan contained the highest concentrations of miBP (50.8 ng/mL) and mMP (17.5 ng/mL), respectively. mEP was the predominant metabolite in urine samples from India and Kuwait (accounting for 49% of the total), mBP and miBP were the predominant compounds in samples from China (52%), and DEHP metabolites were the predominant compounds in samples from Korea (46%) and Vietnam (52%). Based on the urinary concentrations of mEP, mBP, miBP, and DEHP metabolites of the samples from the seven Asian countries, we estimated daily intake rates of diethyl phthalate (DEP), dibutyl phthalate (DBP), and DEHP. The results indicated that people in the seven Asian countries are exposed to DEP, DBP, and DEHP at levels well below the reference doses (RfD) suggested as unsafe by the U.S. Environmental Protection Agency (EPA). The estimated exposure doses to DEHP in Kuwait, however, were above the RfD recommended by the EPA.     

Occurrence of eight bisphenol analogues in indoor dust from the United States and several asian countries: implications for human exposure

Bisphenol A has been reported to be a ubiquitous contaminant in indoor dust, and human exposure to this compound is well documented. Information on the occurrence of and human exposure to other bisphenol analogues is limited. In this study, eight bisphenol analogues, namely 2,2-bis(4-hydroxyphenyl)propane (BPA), 4,4'-(hexafluoroisopropylidene)diphenol (BPAF), 4,4'-(1-phenylethylidene)bisphenol (BPAP), 2,2-bis(4-hydroxyphenyl)butane (BPB), 4,4'-dihydroxydiphenylmethane (BPF), 4,4'-(1,4-phenylenediisopropylidene)bisphenol (BPP), 4,4'- sulfonyldiphenol (BPS), and 4,4'-cyclohexylidenebisphenol (BPZ), were determined in indoor dust samples (n = 156) collected from the United States (U.S.), China, Japan, and Korea. Samples were extracted by solid-liquid extraction, purified by automated solid phase extraction methods, and determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The total concentrations of bisphenols (∑BPs; sum of eight bisphenols) in dust were in the range of 0.026-111 μg/g (geometric mean: 2.29 μg/g). BPA, BPS, and BPF were the three major bisphenols, accounting for >98% of the total concentrations. Other bisphenol analogues were rare or not detected, with the exception of BPAF, which was found in 76% of the 41 samples collected in Korea (geometric mean: 0.0039 μg/g). The indoor dust samples from Korea contained the highest concentrations of both individual and total bisphenols. BPA concentrations in dust were compared among three microenvironments (house, office, and laboratory). The estimated median daily intake (EDI) of ∑BPs through dust ingestion in the U.S., China, Japan, and Korea was 12.6, 4.61, 15.8, and 18.6 ng/kg body weight (bw)/day, respectively, for toddlers and 1.72, 0.78, 2.65, and 3.13 ng/kg bw/day, respectively, for adults. This is the first report on the occurrence of bisphenols, other than BPA, in indoor dust.     

Bisphenol s, a new bisphenol analogue, in paper products and currency bills and its association with bisphenol a residues

As the evidence of the toxic effects of bisphenol A (BPA) grows, its application in commercial products is gradually being replaced with other related compounds, such as bisphenol S (BPS). Nevertheless, very little is known about the occurrence of BPS in the environment. In this study, BPS was analyzed in 16 types of paper and paper products (n = 268), including thermal receipts, paper currencies, flyers, magazines, newspapers, food contact papers, airplane luggage tags, printing paper, kitchen rolls (i.e., paper towels), and toilet paper. All thermal receipt paper samples (n = 111) contained BPS at concentrations ranging from 0.0000138 to 22.0 mg/g (geometric mean: 0.181 mg/g). The overall mean concentrations of BPS in thermal receipt papers were similar to the concentrations reported earlier for BPA in the same set of samples. A significant negative correlation existed between BPS and BPA concentrations in thermal receipt paper samples (r = -0.55, p < 0.0001). BPS was detected in 87% of currency bill samples (n = 52) from 21 countries, at concentrations ranging from below the limit of quantification (LOQ) to 6.26 μg/g (geometric mean: 0.029 μg/g). BPS also was found in 14 other paper product types (n = 105), at concentrations ranging from 88%). To our knowledge, this is the first report on the occurrence of BPS in paper products and currency bills.     

LC-MS/MS analysis of bisphenol S and five other bisphenols in total diet food samples

ABSTRACT

It is already known that bisphenol S (BPS) has been used as a substitute for BPA in thermal papers in recent years. It is not clear, however, if BPS has also been used to replace BPA in can coatings as currently being speculated due to a lack of credible studies on migration of BPS from can coatings and occurrence data of BPS in foods. In this study, an LC-MS/MS method was developed for the analysis of BPS, along with several other bisphenols, and method detection limits for BPS varied from 0.0017 to 3.1 ng/g depending on the type of sample matrix and the amount of sample analysed. This method was used to analyse 159 different food composite samples from a recent Canadian total diet study. Bisphenol E (BPE), bisphenol B (BPB), and bisphenol AF (BPAF) were not detected in any of the 159 food composite samples, bisphenol F (BPF) was detected in only three samples (25–2360 ng/g), and bisphenol A (BPA) was detected in 10 samples (5.3–41 ng/g) which were all prepared from canned foods. BPS was not detected in any of the canned food composite samples but was detected in nine food composite samples prepared from meat and meat products (1.2–35 ng/g), indicating sources for BPS other than can coatings may be possible, which will be investigated in future studies.     

Determination of free and conjugated forms of bisphenol A in human urine and serum by liquid chromatography-tandem mass spectrometry

Exposure of humans to bisphenol A (BPA), a widely used industrial chemical, is well-known. In humans and animals, conjugation of BPA molecule with glucuronide or sulfate is considered as a mechanism for detoxification. Nevertheless, very few studies have directly measured free, conjugated (e.g., glucuronidated), and substituted (e.g., chlorinated) forms of BPA in human specimens. In this study, free, conjugated (BPA glucuronide or BPAG and BPA disulfate or BPADS), and substituted (chlorinated BPA; mono- [BPAMC], di-[BPADC], and trichloride [BPATrC]) forms of BPA were determined in human urine and serum samples, using solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) techniques. The instrumental calibration for each of the target compounds ranged from 0.01 to 100 ng/mL and showed excellent linearity (r > 0.99). The limits of quantification (LOQs) were 0.01 ng/mL for free BPA and 0.05 ng/mL for the conjugated and substituted BPA. Respective recoveries of the six target compounds spiked into water blanks and sample matrices (urine and serum), and passed through the entire analytical procedure, were 96 ± 14% and 105 ± 18% (mean ± SD) for urine samples and 87 ± 8% and 80 ± 13% for serum samples. The optimal recoveries of BPAG and BPADS in the analytical procedure indicted that no deconjugation occurred during the SPE procedure. The method was applied to measure six target chemicals in urine and serum samples collected from volunteers in Albany, New York. BPA and its derivatives were found in urine samples at concentrations ranging from < LOQ to a few tens of ng/mL. In serum, free and conjugated BPA were detected at sub ng/mL concentrations, whereas BPA chlorides were not detected. The urine and serum samples were also analyzed by enzymatic deconjugation and liquid-liquid extraction (LLE) for the determination of total BPA, and the results were compared with those measured by the SPE method. To our knowledge, this is the first report on the occurrence of BPAG and BPADS in human serum.     

Simultaneous determination of daidzein, equol, genistein and bisphenol A in human urine by a fast and simple method using SPE and GC-MS

Human diet contains weakly estrogenic compounds such as daidzein (DAI) and genistein (GEN), phytoestrogens present in soy and many vegetables as well as bisphenol A (BPA), a contaminant from packing materials and plastic containers for foods and beverages. In light of concerns about hormonally active agents, biomonitoring methods are needed to assess human exposure to such compounds. A method for simultaneous determination of DAI, its metabolite equol (EQ), GEN, and BPA by GC-MS analysis was established, validated and applied to measure concentrations in human urine. Sample preparation involves enzymatic conjugate cleavage, SPE and derivatization by silylation. For GC/MS analysis, deuterated DAI and GEN and( 13)C-BPA are used as internal standards. LOD are 4, 4, 5 and 3 ng/mL urine for DAI, EQ, GEN and BPA, respectively. Interassay variations were 9% for DAI, 15% for EQ, 18% for GEN and 10% for BPA. Simple workup and accuracy of the method are suited for biomonitoring. An analysis of urine samples from 15 adults consuming typical German food revealed dietary exposure to phytoestrogens in all samples: GEN concentrations ranged between 13 and 238 ng/mL, those for DAI ranged from 12 to 356 ng/mL. More than half of the individuals excreted also the more estrogenic metabolite EQ, at levels of 8-128 ng/mL. Higher concentrations (GEN: 820, DAI: 960 and EQ: 1740 ng/mL) were measured in a 24 h urine sample upon ingestion of soy protein (50 g with 12.9 mg DAI and 25.2 mg GEN). Only urine collected after some days on strict phytoestrogen-free diet had undetectable isoflavone levels. BPA was detected in 9 of 15 urine samples ranging from 3 to 11 ng/mL, and at 55 ng/mL in one sample. In conclusion, a reliable method to determine BPA and isoflavones in urine was established and applied in a pilot study: Biomonitoring results show much higher dietary exposure to phytoestrogens than to BPA in German adults.     

超高效液相色谱串联质谱法测定全蛋粉中的双酚A和双酚S

建立超高效液相色谱-串联质谱测定全蛋粉中双酚A和双酚S的检测方法。全蛋粉经水复溶后经乙腈提取,提取液使用分散系固相萃取-基质增强脂质去除产品进行除脂,使用Oasis PRiME HLB小柱进一步净化,使用超高效液相串联质谱测定,负离子多反应监测(MRM)模式测定,内标法定量。结果显示:双酚A在1~50 μg/kg范围内呈线性,相关系数为0.9991,加标回收率为98.8%~105.0%,日内和日间相对标准偏差分别为3.84%~8.58%和5.65%~8.74%,检出限为0.3 μg/kg,定量限为1.0 μg/kg;双酚S在0.4~20 μg/kg范围内呈线性,相关系数为0.9995,加标回收率为98.5%~102.5%,日内和日间相对标准偏差分别为3.01%~7.86%和3.18%~7.03%,检出限为0.1 μg/kg,定量限为0.3 μg/kg。实际样品测定结果分别为:双酚A 2.4~3.8 μg/kg;双酚S 0.48~0.82 μg/kg。本方法前处理简单、高灵敏度适用于全蛋粉中双酚A和双酚S的日常测定。     

Assessing the quantitative relationships between preschool children's exposures to bisphenol A by route and urinary biomonitoring

Limited published information exists on young children's exposures to bisphenol A (BPA) in the United States using urinary biomonitoring. In a previous project, we quantified the aggregate exposures of 257 preschool children to BPA in environmental and personal media over 48-h periods in 2000-2001 at homes and daycares in North Carolina and Ohio. In the present study for 81 Ohio preschool children ages 23-64 months, we quantified the children's urinary total BPA (free and conjugated) concentrations over these same 48-h periods in 2001. Then, we examined the quantitative relationships between the children's intakes doses of BPA through the dietary ingestion, nondietary ingestion, and inhalation routes and their excreted amounts of urinary BPA. BPA was detected in 100% of the urine samples. The estimated median intake doses of BPA for these 81 children were 109 ng/kg/day (dietary ingestion), 0.06 ng/kg/day (nondietary ingestion), and 0.27 ng/kg/day (inhalation); their estimated median excreted amount of urinary BPA was 114 ng/kg/day. Our multivariable regression model showed that dietary intake of BPA (p = 0.04) and creatinine concentration (p = 0.004) were significant predictors of urinary BPA excretion, collectively explaining 17% of the variability in excretion. Dietary ingestion of BPA accounted for >95% of the children's excreted amounts of urinary BPA.     

固相萃取-超高效液相色谱-串联质谱法测定饮用水中双酚A和双酚S

建立一种饮用水中痕量双酚A和双酚S的固相萃取-超高效液相色谱-串联质谱检测方法。水样中双酚A和双酚S经HLB固相萃取柱富集,甲醇洗脱并浓缩,再以1 mmol/L氟化铵-乙腈为流动相,经C18色谱柱分离,采用电喷雾离子源、质谱多反应监测模式分析。该方法对水样体积为500 mL时双酚A和双酚S检出限分别可达到1.0 ng/L和0.2 ng/L,在低、中、高3 个加标水平下两者的平均回收率分别为88.3%～114.8%和83.7%～98.2%,相对标准偏差分别为10.0%～16.2%和5.9%～12.3%。该方法灵敏度高、定性准确、操作简单高效,适用于饮用水中双酚A和双酚S的定性定量分析。     

Solid phase extraction of large volume of water and beverage samples to improve detection limits for GC-MS analysis of bisphenol A and four other bisphenols

Solid phase extraction (SPE) of large volumes of water and beverage products was investigated for the GC-MS analysis of bisphenol A (BPA), bisphenol AF (BPAF), bisphenol F (BPF), bisphenol E (BPE), and bisphenol B (BPB). While absolute recoveries of the method were improved for water and some beverage products (e.g. diet cola, iced tea), breakthrough may also have occurred during SPE of 200 mL of other beverages (e.g. BPF in cola). Improvements in method detection limits were observed with the analysis of large sample volumes for all bisphenols at ppt (pg/g) to sub-ppt levels. This improvement was found to be proportional to sample volumes for water and beverage products with less interferences and noise levels around the analytes. Matrix effects and interferences were observed during SPE of larger volumes (100 and 200 mL) of the beverage products, and affected the accurate analysis of BPF. This improved method was used to analyse bisphenols in various beverage samples, and only BPA was detected, with levels ranging from 0.022 to 0.030 ng/g for products in PET bottles, and 0.085 to 0.32 ng/g for products in cans.     

Concentrations of bisphenol A in the composite food samples from the 2008 Canadian total diet study in Quebec City and dietary intake estimates

A total of 154 food composite samples from the 2008 total diet study in Quebec City were analysed for bisphenol A (BPA), and BPA was detected in less than half (36%, or 55 samples) of the samples tested. High concentrations of BPA were found mostly in the composite samples containing canned foods, with the highest BPA level being observed in canned fish (106 ng g(-1)), followed by canned corn (83.7 ng g(-1)), canned soups (22.2-44.4 ng g(-1)), canned baked beans (23.5 ng g(-1)), canned peas (16.8 ng g(-1)), canned evaporated milk (15.3 ng g(-1)), and canned luncheon meats (10.5 ng g(-1)). BPA levels in baby food composite samples were low, with 2.75 ng g(-1) in canned liquid infant formula, and 0.84-2.46 ng g(-1) in jarred baby foods. BPA was also detected in some foods that are not canned or in jars, such as yeast (8.52 ng g(-1)), baking powder (0.64 ng g(-1)), some cheeses (0.68-2.24 ng g(-1)), breads and some cereals (0.40-1.73 ng g(-1)), and fast foods (1.1-10.9 ng g(-1)). Dietary intakes of BPA were low for all age-sex groups, with 0.17-0.33 μg kg(-1) body weight day(-1) for infants, 0.082-0.23 μg kg(-1) body weight day(-1) for children aged from 1 to 19 years, and 0.052-0.081 μg kg(-1) body weight day(-1) for adults, well below the established regulatory limits. BPA intakes from 19 of the 55 samples account for more than 95% of the total dietary intakes, and most of the 19 samples were either canned or in jars. Intakes of BPA from non-canned foods are low.     

Widespread occurrence of bisphenol A in paper and paper products: implications for human exposure

Bisphenol A (BPA) is used in a variety of consumer products, including some paper products, particularly thermal receipt papers, for which it is used as a color developer. Nevertheless, little is known about the magnitude of BPA contamination or human exposure to BPA as a result of contact with paper and paper products. In this study, concentrations of BPA were determined in 15 types of paper products (n = 202), including thermal receipts, flyers, magazines, tickets, mailing envelopes, newspapers, food contact papers, food cartons, airplane boarding passes, luggage tags, printing papers, business cards, napkins, paper towels, and toilet paper, collected from several cities in the USA. Thermal receipt papers also were collected from Japan, Korea, and Vietnam. BPA was found in 94% of thermal receipt papers (n = 103) at concentrations ranging from below the limit of quantitation (LOQ, 1 ng/g) to 13.9 mg/g (geometric mean: 0.211 mg/g). The majority (81%) of other paper products (n = 99) contained BPA at concentrations ranging from below the LOQ to 14.4 μg/g (geometric mean: 0.016 μg/g). Whereas thermal receipt papers contained the highest concentrations of BPA (milligram-per-gram), some paper products, including napkins and toilet paper, made from recycled papers contained microgram-per-gram concentrations of BPA. Contamination during the paper recycling process is a source of BPA in paper products. Daily intake (DI) of BPA through dermal absorption was estimated based on the measured BPA concentrations and handling frequency of paper products. The daily intake of BPA (calculated from median concentrations) through dermal absorption from handling of papers was 17.5 and 1300 ng/day for the general population and occupationally exposed individuals, respectively; these values are minor compared with exposure through diet. Among paper products, thermal receipt papers contributed to the majority (>98%) of the exposures.     

免疫亲和柱净化-高效液相色谱法检测两种饮料中双酚A含量

建立了免疫亲和柱净化-高效液相色谱荧光检测法(IAC-HPLC-FL)检测豆奶及橙汁饮料中的双酚A含量。采用甲醇提取、离心、磷酸缓冲溶液稀释后,经免疫亲和柱纯化,用1 mL甲醇-水(80:20,体积/体积)洗脱,应用高效液相色谱法检测。以C₁₈柱为分离色谱柱,甲醇-水(60:40,v/v)溶液为流动相洗脱,流速0.4 mL/min,柱温30℃,进样量10 μL,荧光检测器检测,激发波长228 nm,发射波长310 nm。结果表明:在1.0~300.0 ng/mL的浓度范围内,双酚A的浓度与峰面积呈良好的线性关系(相关系数R2=0.9998),检出限定为1 ng/mL。平均回收率为82.5%~104.6%,相对标准差为2.3%~6.4%。分别选取玻璃瓶装和塑料瓶装的豆奶和橙汁饮料进行双酚A含量检测,玻璃瓶装的豆奶和橙汁饮料中双酚A含量均小于检出限1 ng/mL,而某款塑料瓶装的豆奶和橙汁饮料检测出极其微量的双酚A,其双酚A含量分别为1.44、1.57 ng/mL,处于可接受水平。该方法简单快速、灵敏度高、重复性好,能够有效地分离和检测饮料中的双酚A,适用于豆奶和橙汁等饮料中的双酚A的测定。     

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.     

Migration of bisphenol A and benzophenones from paper and paperboard products used in contact with food

Migration of bisphenol A (BPA) and benzophenones, i.e., benzophenone (BZ), 4-(dimethylamino)benzophenone (DMAB), Michler's ketone (MK) and 4,4'-bis(diethylamino)benzophenone (DEAB), from 21 paper and paperboard products (15 recycled paperboard boxes and 6 virgin paper products) used in contact with food was examined. Migration levels of compounds from recycled paperboard were compared under various food-simulating conditions. BPA showed the highest migration into 20% ethanol and benzophenones into 95% ethanol. No compounds migrated from virgin paper products, but compounds did migrate into food simulants from recycled paperboard food boxes. BPA migrated into 20% ethanol from all recycled paperboard food boxes between 1.0 and 18.7 ng/mL. Into 95% ethanol, migration of BZ was observed in 8 samples (1.0-18.9 ng/mL), DMAB in 12 samples (1.2-3.7 ng/mL), MK in 13 samples (1.9-9.0 ng/mL), and DEAB in 13 samples (1.0-10.6 ng/mL). The highest migration level was 27.2 ng/mL and most of the migration levels were below 10 ng/mL. These values are sufficiently low compared with the TDI and NOAEL levels. Moreover, the amount of food in daily meals that comes into contact with paperboard products is relatively small. Consequently, it was concluded that there was no safety concern regarding the tested compounds in recycled paperboard food boxes.     

UPLC-MS/MS测定婴幼儿配方乳粉中双酚A和壬基酚

建立一种测定婴幼儿配方乳粉中双酚A和壬基酚的超高效液相色谱串联质谱准确定性定量方法。向配方乳粉样品中加水溶解,乙腈提取,使用在线捕集技术消除流动相中的本底影响,以甲醇-0.1%氨水溶液作为流动相在C₁₈色谱柱上进行梯度洗脱,用超高效液相色谱仪进行分离后,通过电喷雾负离子模式电离,多反应检测模式进行检测分析,内标法准确定量。结果表明:在1~2000 ng/mL范围内呈良好的线性关系,相关系数大于0.999。本方法BPA和NP检出限均低至0.1 μg/kg,在不同婴幼儿配方乳粉中添加1、10、100 μg/kg三水平加标,测定结果平均回收率在89.5%~102.8%之间,相对标准偏差为1.3%~4.8%,该方法具有较高的灵敏度和准确度。对市售200份婴幼儿配方乳粉进行测定,检出BPA含量为0.1~30.0 μg/kg,检出NP含量为1.1~105 μg/kg,适合婴幼儿配方乳粉中双酚A和壬基酚的定量测定。     

Determination of bisphenol A in canned fish by sol–gel immunoaffinity chromatography,HPLC and fluorescence detection

The paper presents a highly selective analysis method for the determination of bisphenol A (BPA) in canned fish. The procedure consists of sample clean-up by sol–gel immunoaffinity chromatography followed by high performance liquid chromatography and fluorescence detection. BPA concentrations were determined in nineteen tuna, sardine and mackerel cans by analysing the solid and the liquid parts of the contents separately. In different tested matrices limits of detection (S/N=3) ranged from 0.2 ng/g (sardines) to 1.8 ng/ml (oil) and limits of quantification (S/N=6) from 0.4 ng/g to 3.8 ng/ml, respectively. In the solid part (fish) very low BPA levels (2–4 ng/g) were found in mackerels, the highest level (59 ng/g) in tuna. In oil significantly higher BPA concentrations were found than in brine. In all samples BPA concentrations were significantly lower than the Specific Migration Level of 0.6 mg/kg for BPA migration into food established by the EU Commission in 2004.     

高效液相色谱-三重四极杆串联质谱法研究塑料接触材料中酚类化合物向奶油中的迁移

建立奶油中14 种酚类化合物高效液相色谱-三重四极杆串联质谱的同时测定方法，研究裱花蛋糕塑料接触材料中酚类化合物在真实样品奶油中的迁移情况。塑料样品经奶油浸泡，乙腈-甲醇提取，T3色谱柱分离，以负离子-多反应监测模式进行测定，基质外标法定量；分析双酚A（bisphenol A，BPA）和4-壬基酚（4-nonylphenol，4-NP）在奶油样品中的迁移规律，用于14 种酚类化合物在奶油中迁移量的测定研究。结果表明，14 种酚类化合物的检出限为0.15～0.75 μg/kg，定量限为0.5～2.5 μg/kg，线性关系良好，相关系数均大于0.99；酚类物质在动物和植物奶油中的加标回收率分别为78.2%～117.1%、79.4%～114.6%，相对标准偏差分别为1.07%～12.1%、1.12%～12.5%；塑料接触材料中BPA和4-NP在奶油中的迁移量随着温度的升高和时间的延长逐渐增大。采用本方法对市售塑料蛋糕装饰摆件等在动物奶油中的迁移量等进行测定，迁出化合物BPA和双酚S迁移量最高值分别为4.61、0.94 μg/kg；4-NP迁移量最高值为125.1 μg/kg，检出样品数量最多。酚类化合物迁移到食品中的风险性应引起关注。     

Asian Mussel Watch Program: contamination status of polybrominated diphenyl ethers and organochlorines in coastal waters of Asian countries

Mussel samples were used in this study to measure the levels of polybrominated diphenyl ethers (PBDEs) and organochlorines (OCs) in the coastal waters of Asian countries like Cambodia, China, Hong Kong, India, Indonesia, Japan, Korea, Malaysia, the Philippines, and Vietnam. PBDEs were detected in all the samples analyzed, and the concentrations ranged from 0.66 to 440 ng/g lipid wt. Apparently higher concentrations of PBDEs were found in mussels from the coastal waters of Korea, Hong Kong, China, and the Philippines, which suggests that significant sources of these chemicals exist in and around this region. With regard to the composition of PBDE congeners, BDE-47, BDE-99, and BDE-100 were the dominant congeners in most of the samples. Among the OCs analyzed, concentrations of DDTs were the highest followed by PCBs > CHLs > HCHs > HCB. Total concentrations of DDTs, PCBs, CHLs, and HCHs in mussel samples ranged from 21 to 58 000, 3.8 to 2000, 0.93 to 900, and 0.90 to 230 ng/g lipid wt., respectively. High levels of DDTs were found in mussels from Hong Kong, Vietnam, and China; PCBs were found in Japan, Hong Kong, and industrialized/urbanized locations in Korea, Indonesia, the Philippines, and India; CHLs were found in Japan and Hong Kong; HCHs were found in India and China. These countries seem to play a role as probable emission sources of corresponding contaminants in Asia and, in turn, may influence their global distribution.