A survey of bisphenol A and other bisphenol analogues in foodstuffs from nine cities in China

<div><p>Bisphenol A (BPA) is a high-production-volume chemical that is widely used in polycarbonate plastics and epoxy food-can coatings. Following several studies that have reported adverse effects of BPA over the past decade, other bisphenol analogues, such as bisphenol F (BPF), bisphenol S (BPS), bisphenol AF (BPAF), and bisphenol B (BPB), have been gradually developed as substitutes for BPA in several applications. Nevertheless, few studies have reported on the occurrence of compounds other than BPA in foodstuffs. In this study, 289 food samples (13 categories: cereals and cereal products, meat and meat products, fish and seafood, eggs, milk and milk products, bean products, fruits, vegetables, cookies/snacks, beverages, cooking oils, condiments, and others), collected from nine cities in China, were analysed for eight bisphenol analogues using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). BPA and BPF were found widely in foodstuffs at concentrations ranging from below the limit of quantitation (LOQ) to 299 ng g^–1 (mean = 4.94 ng g^–1) and from below the LOQ to 623 ng g^–1 (mean = 2.50 ng g^–1), fresh weight, respectively. The highest total concentrations of bisphenols (∑BPs: sum of eight bisphenols) were found in the category of vegetables that included canned products (mean = 27.0 ng g^–1), followed by fish and seafood (16.5 ng g^–1) and beverages (15.6 ng g^–1). ∑BP concentrations (mean = 2–3 ng g^–1) in milk and milk products, cooking oils, and eggs were low. Food samples sold in metallic cans contained higher mean ∑BP concentrations (56.9 ng g^–1) in comparison with those packaged in glass (0.43 ng g^–1), paper (11.9 ng g^–1), or plastic (6.40 ng g^–1). The daily dietary intakes of bisphenols were estimated, based on the mean concentrations measured and daily consumption rates of foods, to be 646 and 664 ng kg^–1 bw day^–1 for men and women, respectively.</p></div

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 (<i>r</i> > 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

Widespread Occurrence of Benzophenone-Type UV Light Filters in Personal Care Products from China and the United States: An Assessment of Human Exposure

Benzophenone-3 (BP-3) is a sunscreen agent used in a variety of personal care products (PCPs) for the protection of human skin and hair from damage by ultraviolet (UV) radiation. Concerns have been raised over exposure of humans to BP-3, owing to the estrogenic potential of this compound. Nevertheless, the levels and profiles of BP-3 in PCPs and sources of exposure of humans to this estrogenic compound are not well-known. In this study, concentrations of BP-3 were determined in seven categories of 231 PCPs collected from several cities in China (<i>n</i> = 117) and the United States (U.S.) (<i>n</i> = 114), using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). BP-3 was found in the majority (81%) of the samples analyzed, at concentrations as high as 0.148%. The highest BP-3 concentrations (geometric mean [GM]: 548; median: 530 ng/g) were found in skin lotions (including sunscreen lotions), followed by makeup products (284; 221 ng/g). PCPs collected from the U.S. contained higher concentrations of BP-3 than those collected from China. On the basis of the concentrations measured and daily usage rates of PCPs, we estimated the daily intake of BP-3 through dermal absorption from the use of PCPs. The GM and 95th percentile exposure doses to BP-3 were 0.978 and 25.5 μg/day, respectively, for adult women in China, which were 2 orders of magnitude lower than those found for adult women in the U.S. (24.4 and 5160 μg/day). Skin lotions and face creams contributed to the preponderance of daily BP-3 exposures (>80%)

Characteristic Profiles of Benzonphenone‑3 and its Derivatives in Urine of Children and Adults from the United States and China

Widespread exposure of humans to benzophenone-3 (BP-3) is a concern due to this compound’s potential to disrupt endocrine function. BP-3 can be metabolized by phase I and phase II reactions of the human cytochrome P450 system. Urinary measurements of BP-3 have been used as a biomarker of exposure. Nevertheless, metabolic transformation pathway and the transformation products of BP-3 in humans are still less known. In this study, 166 urine samples collected from children and adults in the U.S. and China were analyzed for free and total forms (free plus conjugated) of BP-3 as well as four of its metabolic derivatives, 4-OH–BP, 2,4-diOH–BP, 2,2′,4,4′-tetraOH–BP, and 2,2′-diOH–4-MeO–BP, using high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). BP-3 was found in almost all urine samples from the U.S. and China. Concentrations of BP-3 in urine from children (GM: 9.97 ng/mL) and adults (15.7 ng/mL) in the U.S. were significantly higher than those in children (0.622 ng/mL) and adults (0.977) from China. A significant positive relationship was found between the concentrations of urinary BP-3 and its derivatives. The profiles of BP derivatives in urine suggested that demethylation was a major route of BP-3 metabolism. The percentage of the free form of BP-3 in urine was used in the determination of efficacy of phase II metabolism among the different population groups studied. A significantly lower percentage of the free form of BP-3 was found in urine from the U.S. population than in the Chinese population

Concentrations and Profiles of Bisphenol A and Other Bisphenol Analogues in Foodstuffs from the United States and Their Implications for Human Exposure

As the concern over the safety of bisphenol A (BPA) continues to grow, this compound is gradually being replaced, in industrial applications, with compounds such as bisphenol F (BPF) and bisphenol S (BPS). Occurrence of bisphenols, including BPA and BPS, has been reported in paper products and in environmental matrices. Information on the occurrence of bisphenols, other than BPA, in foodstuffs, however, is scarce. In this study, several bisphenol analogues, including BPA, BPF, and BPS, were analyzed in foodstuffs (<i>N</i> = 267) collected from Albany, NY, USA, using high-performance liquid chromatography–tandem mass spectrometry (HPLC-MS/MS). Foodstuffs were divided into nine categories of beverages, dairy products, fats and oils, fish and seafood, cereals, meat and meat products, fruits, vegetables, and “others”. Bisphenols were found in the majority (75%) of the food samples, and the total concentrations of bisphenols (ΣBPs: sum of eight bisphenols) were in the range of below the limit of quantification (LOQ) to 1130 ng/g fresh weight, with an overall mean value of 4.38 ng/g. The highest overall mean concentration of ΣBPs was found in the “others” category, which included condiments (preserved, ready-to-serve foods). A sample of mustard (dressing) and ginger, placed in the category of vegetables, contained the highest concentrations of 1130 ng/g for bisphenol F (BPF) and 237 ng/g for bisphenol P (BPP). Concentrations of BPs in beverages (mean = 0.341 ng/g) and fruits (0.698 ng/g) were low. The predominant bisphenol analogues found in foodstuffs were BPA and BPF, which accounted for 42 and 17% of the total BP concentrations, respectively. Canned foods contained higher concentrations of individual and total bisphenols in comparison to foods sold in glass, paper, or plastic containers. On the basis of measured concentrations and daily ingestion rates of foods, the daily dietary intakes of bisphenols (calculated from the mean concentration) were estimated to be 243, 142, 117, 63.6, and 58.6 ng/kg body weight (bw)/day for toddlers, infants, children, teenagers, and adults, respectively

Mass Loading and Removal of Select Illicit Drugs in Two Wastewater Treatment Plants in New York State and Estimation of Illicit Drug Usage in Communities through Wastewater Analysis

Sewage epidemiology is a rapidly expanding field that can provide information on illicit drug usage in communities, based on the measured concentrations in samples from wastewater treatment plants (WWTPs). In this study, select illicit drugs (six drugs and eight metabolites) were determined on a daily basis for a week in wastewater, suspended particulate matter (SPM), and sludge from two WWTPs in the Albany area in New York State. The WWTP that served a larger population (∼100 000, with a flow rate of 83 300 m³/d) showed 3.2 (methadone) to 51 (3,4-methylenedioxyamphetamine; MDA) times higher mass flows of illicit drugs than did the WWTP that served a smaller population (∼15 000, with a flow rate of 6850 m³/d). The consumption rate of target illicit drugs in the communities served by the two WWTPs was estimated to range from 1.67 to 3510 mg/d/1000 people. Between the dissolved and particulate phases, the fraction of methadone, 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), amphetamine, and MDA sorbed to SPM ranged from 34.3% to 41.1% of the total mass in the waste stream. The removal efficiencies of illicit drugs from the two WWTPs ranged from 4% (norcocaine) to 99% (cocaine); however, methamphetamine, methadone, and EDDP showed a negative removal in WWTPs. The environmental emission of illicit drugs from WWTP discharges was calculated to range from 0.38 (MDEA) to 67.5 (EDDP) mg/d/1000 people. Other markers such as caffeine, paraxanthine, nicotine, and cotinine were found to predict the concentrations of select illicit drugs in raw wastewater (<i>r</i>² = 0.20–0.79; <i>p</i> ≤ 0.029)

Novel Finding of Widespread Occurrence and Accumulation of Bisphenol A Diglycidyl Ethers (BADGEs) and Novolac Glycidyl Ethers (NOGEs) in Marine Mammals from the United States Coastal Waters

Bisphenol A diglycidyl ether (BADGE)- and bisphenol F diglycidyl ether (BFDGE)-based epoxy resins have a broad range of applications, including serving as inner coatings of food and beverage cans and as protective coatings in marine construction. Prior to this study, no studies had examined the occurrence and bioaccumulation of BADGEs or BFDGEs in aquatic organisms. In this study, BADGE, BFDGE, and nine of their derivatives were determined in 121 tissue (liver, kidney, blubber, and brain) samples from eight species of marine mammals collected from the U.S. coastal waters of Florida, California, Washington, and Alaska. BADGE·2HCl was the predominant compound found in the majority (78.5%) of the marine mammal tissues analyzed, at concentrations of up to 2950 ng/g (wet weight (wt)) found in the liver of a sea otter from Kachemak Bay, Alaska. The measured concentrations of BADGE·2HCl in marine mammals were on the order of hundreds of nanograms per gram tissue, which are some of the highest concentrations ever reported for this compound in biota. Males contained greater concentrations of BADGE·2HCl than did females. BADGE·2HCl also was found in the brain tissues of sea otters. Trace levels of BADGE·2HCl were found in the livers of polar bears from Alaska, which suggested that BADGEs are widely distributed in the oceanic environment

Method for the Determination of Iodide in Dried Blood Spots from Newborns by High Performance Liquid Chromatography Tandem Mass Spectrometry

Dried blood spots (DBS), collected for newborn screening programs in the United States, have been used to screen for congenital metabolic diseases in newborns for over 50 years. DBS provide an easy and inexpensive way to collect and store peripheral blood specimens and present an excellent resource for studies on the assessment of chemical exposures in newborns. In this study, a selective and sensitive method was developed for the analysis of iodide in DBS by high performance liquid chromatography electrospray tandem mass spectrometry. Accuracy, inter- and intraday precision, matrix effects, and detection limits of the method were determined. Further validation of the method was accomplished by concurrent analysis of whole blood and fortified blood spotted on a Whatman 903 filter card. A significant positive correlation was found between measured concentrations of iodide in venous whole blood and the same blood spotted as DBS. The method limit of detection was 0.15 ng/mL iodide. The method was further validated by the analysis of a whole blood sample certified for iodide levels (proficiency testing sample) by spotting on a filter card. Twenty DBS samples collected from newborns in New York State were analyzed to demonstrate the applicability of the method. The measured concentrations of iodide in whole blood of newborns from New York State ranged betwee

Simultaneous Analysis of Seven Biomarkers of Oxidative Damage to Lipids, Proteins, and DNA in Urine

The determination of oxidative stress biomarkers (OSBs) is useful for the assessment of health status and progress of diseases in humans. Whereas previous methods for the determination of OSBs in urine were focused on a single marker, in this study, we present a method for simultaneous determination of biomarkers of oxidative damage to lipids, proteins, and DNA. 2,4-Dinitrophenylhydrazine (DNPH) derivatization followed by solid phase extraction (SPE) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) allowed the determination of 8-hydroxy-2′-deoxyguanosine (8-OHdG), <i>o</i>-<i>o</i>′-dityrosine (diY), malondialdehyde (MDA), and four F₂-isoprostane isomers: 8-iso-prostaglandinF_2α (8-PGF_2α), 11β-prostaglandinF_2α (11-PGF_2α), 15­(<i>R</i>)-prostaglandinF_2α (15-PGF_2α), and 8-iso,15­(<i>R</i>)-prostaglandinF_2α (8,15-PGF_2α) in urine. Derivatization with DNPH and SPE was optimized to yield greater sensitivity and selectivity for the analysis of target chemicals. The limits of detection of target analytes in urine were below 30 pg mL^–1. The assay intra- and interday variability was below 16% of the relative standard deviation, and the recoveries of target chemicals spiked into synthetic urine were near 100%. The method was applied to the analysis of 21 real urine samples, and the analytes were found at a detection frequency of 85% for 8-PGF_2α and 15-PGF_2α, 71% for 11-PGF_2α, 81% for 8,15-PGF_2α, and 100% for diY, 8-OHdG, and MDA. This method offers simultaneous determination of multiple OSBs of different molecular origin in urine samples selectively with high accuracy and precision

Bisphenols, Benzophenones, and Bisphenol A Diglycidyl Ethers in Textiles and Infant Clothing

Little is known with regard to the occurrence of potentially toxic chemicals in textiles and clothes. In this study, 77 textiles and infant clothing pieces were analyzed for the determination of bisphenols including bisphenol A (BPA) and bisphenol S (BPS), benzophenones, bisphenol A diglycidyl ethers (BADGEs), and novolac glycidyl ethers (NOGEs). BPA and BPS occurred in 82% and 53% of the textile samples, respectively, and at mean concentrations of 366 and 15 ng/g, respectively. Benzophenone-3 (BP3) occurred in 70% of the samples at a mean concentration of 11.3 ng/g. Among 11 BADGEs and NOGEs analyzed, BFDGE was the predominant compound, with a mean concentration of 13.6 ng/g. Concentrations of target chemicals were assessed by fabric type, color, and uses. Socks contained the highest concentrations of BPA (mean: 1810 ng/g) with concentrations as high as 13 300 ng/g in a 97% polyester fabric marketed for infants. Calculated dermal exposure dose to BPA by infants via textiles was as high as 7280 pg/kg BW/d. This is the first study to report the occurrence of, and exposure to, BPA, BPS, BADGEs, and NOGEs in textiles and clothing