Polybrominated diphenyl ethers, 2,2',4,4',5,5'-hexachlorobiphenyl (PCB-153), and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) concentrations in sera collected in 2009 from Texas children.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) have been measured in surplus serum collected in 2009 from a convenience sample of 300 Texas children (boys and girls) in the birth to 13 years of age range. Serum concentrations of traditional persistent organic pollutants such as 2,2',4,4',5,5'-hexachlorobiphenyl (PCB-153) and p,p'-DDE did not change consistently with age. By contrast, serum concentrations of tetra-, penta-, and hexa-BDEs were lowest in the youngest children (birth to two year old) and increased 3.0 to 7.9 times, depending on the analyte, for children in the >4 to 6 years of age group. From the apex concentration to the 10 to 13 years of age group, concentrations decreased significantly except for 2,2',4,4',5,5'-hexabromodiphenyl ether (PBDE-153), which also had a longer apex concentration of >4 to 8 years of age. This concentration trend for PBDE-153 is most likely due to a longer half-life of PBDE-153 than of other PBDE congeners. The observed PBDEs concentration patterns by age may be related, at least in part, to ingestion of residential dust containing PBDEs through hand-to-mouth behavior among toddlers, preschoolers, and kindergarteners. Further studies to characterize young children's exposure to PBDEs are warranted and, in particular, to determine the lifestyle factors that may contribute to such exposures.

Biomonitoring of Polybrominated Dioxins & Furans, Polychlorinated Dioxins & Furans, and Dioxin Like Polychlorinated Biphenyls in Vietnamese Female Electronic Waste Recyclers.

OBJECTIVE: E-waste is rising globally. This is a follow up to our study reporting metals/polybrominated diphenyl ethers (PBDE's)/polychlorinated biphenyls (PCBs) in female e-waste recyclers. Here we report polybrominated, polychlorinated dioxins/furans, and dioxin-like polychlorinated biphenyls in these same workers. METHODS: Female Vietnamese recyclers and non-recyclers recruited; blood samples collected. Polybrominated, polychlorinated dioxins/furans, and dioxin-like polychlorinated biphenyls levels compared in recyclers, non-recyclers, and National Health and Nutrition Examination Surveys (NHANES). RESULTS: Recyclers >non-recyclers: 12378-PBDD, 2378-TBDF, 12378-PCDF, 123478-HxCDF, 123678-HxCDF, 1234678-HpCDF, PCB-126. Non-recyclers >NHANES: 123478-HxCDF, 123678-HxCDF, 234678- HxCDF, PCB-126, PCB-169. NHANES >non-recyclers: 12378-PCDD, 123478-HxCDD, 123678-HxCDD, 123789-HxCDD, 1234678-HpCDD, 123789-HxCDF, 1234678-HpCDF, 1234789-HpCDF, OCDF, PCB-81, PCB-114, PCB-156, PCB-157, PCB-167, PCB-189. Recyclers >NHANES: S: 2378-TeCDF, 12378-PCDF, 23478-PCDF, 123478-HxCDF, 123678- HxCDF, 234678-HxCDF, PCB-126. NHANES >recyclers: 12378-PCDD, 123478-HxCDD, 123678-HxCDD, 123789-HxCDD, 1234678-HpCDD, OCDD, 123789-HxCDF, 1234678-HpCDF, 1234789-HpCDF, OCDF, PCB- 81, PCB-114, PCB-156, PCB-157, PCB-189. CONCLUSION: 12378 PCDD, 2378-TCDD, PCB 126 makeup most total dioxin equivalences (TEQs) in AQ5 these workers, indicating increased exposure; remediation indicated.

Polybrominated diphenyl ether levels in foodstuffs collected from three locations from the United States.

OBJECTIVES: The objectives of this study were to provide updated measurements of PBDEs in US food, to estimate possible difference in levels from differing geographical regions, and to provide an improved estimate of current dietary intake. METHODS: Thirty matched food samples for a total of 90 samples were collected from each of three cities (Los Angeles, California; Dallas, Texas; and Albany, New York) and were analyzed for 13 polybrominated diphenyl ether congeners (BDE 28, 47, 49, 66, 85, 99, 100, 138, 153, 154, 183, 203, and 209). Dietary intake of PBDEs was estimated by food type, age, and sex. RESULTS: In this pilot study, we did not note a statistically significant difference in total PBDE levels in food collected from the three locations. The median total PBDE levels (estimating non-detected values as half of the detection limit) in meat, dairy, eggs, and fish were 267 pg/g wet weight (ww) (range 102-3156 pg/g ww), 176 pg/g ww (range 41-954 pg/g ww), 637 pg/g ww (range 193-932 pg/g ww), and 243 pg/g ww (range 36-2161 pg/g ww). PBDE intake from food was estimated to range from 2.7 ng/kg/day for children 2 through 5 years of age to 0.8 ng/kg/day for women aged 60 years and older. This compares closely with our previous study where the intake estimate was 2.7 ng/kg/day for children 2 through 5 years of age and 0.9 ng/kg/day for women aged 60 years and older. CONCLUSION: We did not find a decrease of PBDEs in food since our previous studies which we expected to find due to the declining use of PBDEs in the USA. These findings could be consistent with food contamination from depot sources of PBDEs. A larger, more representative sampling of the US food supply is indicated based on our findings.

Bisphenol A (BPA) in U.S. food.

Bisphenol A (BPA) is a chemical used for lining metal cans and in polycarbonate plastics, such as baby bottles. In rodents, BPA is associated with early sexual maturation, altered behavior, and effects on prostate and mammary glands. In humans, BPA is associated with cardiovascular disease, diabetes, and male sexual dysfunction in exposed workers. Food is a major exposure source. We know of no studies reporting BPA in U.S. fresh food, canned food, and food in plastic packaging in peer reviewed journals. We measured BPA levels in 105 fresh and canned foods, foods sold in plastic packaging, and in cat and dog foods in cans and plastic packaging. We detected BPA in 63 of 105 samples, including fresh turkey, canned green beans, and canned infant formula. Ninety-three of these samples were triplicates which had similar detected levels. Detected levels ranged from 0.23 to 65.0 ng/g ww and were not associated with type of food or packaging but did vary with pH. BPA levels were higher for foods of pH 5 compared to more acidic and alkaline foods. Detected levels were comparable to those found by others. Further research is indicated to determine BPA levels in U.S. food in larger, representative sampling.

Retention of polybrominated diphenyl ethers and hydroxylated metabolites in paired human serum and milk in relation to CYP2B6 genotype.

Polybrominated diphenyl ethers (PBDEs) and their hydroxylated metabolites (OH-BDEs) are endocrine disrupting compounds prevalent in human serum and breast milk. Retention of PBDEs and OH-BDEs in humans may be affected by differences in PBDE metabolism due to variants in cytochrome P450 2B6 (CYP2B6). The objectives of this study are to assess the partitioning profiles of PBDEs and OH-BDEs in forty-eight paired human serum and milk samples, and to evaluate the relationship between variants in CYP2B6 genotype and PBDE and OH-BDE accumulation in humans. Results show that the geometric mean (GM) concentrations of PBDEs are similar in serum (GM = 43.4 ng/g lipid) and milk samples (GM = 52.9 ng/g lipid), while OH-BDEs are retained primarily in serum (GM = 2.31 ng/g lipid), compared to milk (GM = 0.045 ng/g lipid). Participants with CYP2B6*6 genotype had a greater relative retention of PBDEs in serum and milk, and significant relationships (p <  0.05) were also observed for PBDE-47, 5-OH-BDE-47 and 6-OH-BDE-47 concentrations relative to CYP2B6*5 and CYP2B6*6 genotypes. These results are the first to show that CYP2B6 genotype is significantly related to the relative retention of PBDEs in humans, which may have direct implications for variability in the susceptibility of individuals to the potential adverse effects of these contaminants.

Biomonitoring of Metals, Polybrominated Diphenyl Ethers, Polychlorinated Biphenyls, and Persistent Pesticides in Vietnamese Female Electronic Waste Recyclers.

OBJECTIVE: Electronic waste is increasing. It is frequently recycled in developing countries. This is the first study to report metals, polybrominated diphenyl-ethers (PBDEs), polychlorinated biphenyls (PCBs), 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane (p,p'-DDT), and p,p'-DDE concentrations in female e-waste workers. METHODS: Female Vietnamese recyclers and non-recyclers were studied. Metals and halogenated organics were measured in blood and urine, and compared with levels in women in the US National Health and Nutrition Examination Survey (NHANES). RESULTS: Recyclers had higher serum PBDE than nonrecyclers. PCB-138/158 and PCB-153 were higher in 18 to less than 38-year-old nonrecyclers. Median urinary arsenic in both cohorts was six to seven-fold higher than NHANES. Median lead in blood and urine was 40% to 60% higher in recyclers than nonrecyclers. Lead in nonrecyclers was four to six-fold higher than NHANES. Both cohorts had higher arsenic and mercury than NHANES. CONCLUSION: Occupational exposure to PBDEs and lead occurred in recyclers. Environmental exposure to arsenic, lead, and mercury occurred in both cohorts. Occupational and environmental remediation are recommended.

Polybrominated diphenyl ether (PBDE) levels in livers of U.S. human fetuses and newborns.

Polybrominated diphenyl ether (PBDE) brominated flame retardants have recently been found to contaminate humans in the United States and other countries. U.S. human breast milk and blood levels of PBDEs are presently the highest in the world. U.S. cord blood samples tested positive for PBDEs, but until now there have been no peer-reviewed published data concerning levels of PBDEs in human tissue prior to and immediately after birth. Liver tissues were obtained from 4 stillborn fetuses and 7 liveborn infants, ranging from 20.5 to 39 wk gestational age; only 2 of the liveborn infants lived longer than 4 h and none were formula-fed or nursed, so tissue levels reflect intrauterine PBDE intake only. All samples were contaminated with PBDEs. Levels varied from 4 to 98 ppb, lipid. The mean level was 23.1 and the median 15.2 ppb, lipid. PBDE levels did not increase with gestational age. These data document the transfer of PBDEs from maternal to fetal tissue. PBDE concentrations are somewhat lower than those reported in adult blood or breast milk. The health consequences of prenatal contamination are not clear at present.

Residential and biological exposure assessment of chemicals from a wood treatment plant.

This paper evaluates the results of contamination of residents and residential homes located in close proximity to a Wood Treatment Plant. The plant has produced treated wood products continuously since 1904. The principle chemicals used to treat the wood, which is primarily used for railroad ties (oblong objects laid perpendicular to the rails to act as a base for the tracks), are creosote and pentachlorophenol. For a number of years, the plant burned treated waste wood products containing creosote and pentachlorophenol. First the plant pressure impregnates the wood with creosote and pentachlorophenol, and then the wood is stacked on open ground to allow it to air dry. Chemicals from recently treated wood ties are allowed to evaporate into the air or drip onto the ground surrounding the stacked wood. Small drainage ditches carry the liquid wastes into larger water channels where eventually the waste streams are discharged into a river adjacent to the plant. The river serves as a source of drinking water for the nearby community. Prevailing wind patterns favor a drift of air emissions from the plant's boiler stack over the nearby community and its residents. Over the past few years, the town's residents have become increasingly concerned about their health status and have voiced concerns regarding multiple health problems (including cancer), possibly associated with plant discharges. The intention of this study is to examine a representative sample of the potentially affected residents and to evaluate their residential environment for the presence of dioxin and/or its congeners. Data obtained from EPA's Toxic Release Information (TRI) database revealed the plant routinely discharged creosote, pentachlorophenol, dioxin and dioxin-like compounds into the ambient air via fugitive air emissions and surface waste waters. Sampling of household dust and water sediment within and outside of residences within a 2-mile radius of the plant revealed the presence of significantly elevated levels of dioxins, principally octachlorodibenzo-p-dioxin (OCDD) and 1,2,3,4,6,7,8-hepta-CDD. Biomonitoring of 29 subjects identified the presence of significantly elevated chlorinated dioxins and furan levels (OCDD=1049 ppt for exposed and 374 ppt for controls and 1,2,3,4,6,7,8-hepta CDD=132 ppt for exposed and 45.1 ppt for controls). These levels are consistent with exposures to pentachlorophenol in this group of subjects. And they confirm the presence of unsafe levels of chlorinated dioxins in these persons.

Serum dioxin, testosterone, and subsequent risk of benign prostatic hyperplasia: a prospective cohort study of Air Force veterans.

BACKGROUND: Operation Ranch Hand veterans were involved in spraying herbicides, including Agent Orange, during the Vietnam War in 1962-1971; Agent Orange was contaminated with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). It has been hypothesized that dioxins may be partially responsible for an increase of male reproductive tract disorders such as testicular cancer, cryptorchidism, and hypospadias. OBJECTIVES: In this study, our objective was to assess the effect of serum TCDD concentration on the risk of development of benign prostatic hyperplasia (BPH) and on serum testosterone levels. METHODS: This study was a longitudinal, prospective cohort study made up of U.S. Air Force veterans involved in Operation Ranch Hand. Other Air Force veterans who did not spray herbicides were included as comparisons. BPH was determined by medical record review and by medical examinations conducted during the study. Data were available for 971 Ranch Hand and 1,266 comparison veterans. We investigated the relationship between BPH and serum TCDD level using the Cox proportional hazards models adjusted for testosterone levels, body mass index (BMI), and the percentage change in BMI per year. RESULTS: In univariate and multivariate analyses, the risk of BPH decreased with increasing serum TCDD in the comparison group. The multivariate risk ratio for BPH in the comparison group was 0.84 (95% confidence interval, 0.73-0.98). Excluding men with prostate cancer, inflammatory or other prostatic diseases did not substantially alter the association. Serum testosterone levels were inversely associated with serum TCDD levels in both Ranch Hand and comparison groups. CONCLUSIONS: TCDD exposure at general population levels is associated with a decreasing risk of BPH with higher exposure levels. TCDD exposure is also negatively associated with serum testosterone levels.

Polybrominated diphenyl ether (PBDE) levels in an expanded market basket survey of U.S. food and estimated PBDE dietary intake by age and sex.

OBJECTIVES: Our objectives in this study were to expand a previously reported U.S. market basket survey using a larger sample size and to estimate levels of PBDE intake from food for the U.S. general population by sex and age. METHODS: We measured concentrations of 13 polybrominated diphenyl ether (PBDE) congeners in food in 62 food samples. In addition, we estimated levels of PBDE intake from food for the U.S. general population by age (birth through > or = 60 years of age) and sex. RESULTS: In food samples, concentrations of total PBDEs varied from 7.9 pg/g (parts per trillion) in milk to 3,726 pg/g in canned sardines. Fish were highest in PBDEs (mean, 1,120 pg/g; median, 616 pg/g; range, 11.14-3,726 pg/g). This was followed by meat (mean, 383 pg/g; median, 190 pg/g; range, 39-1,426 pg/g) and dairy products (mean, 116 pg/g; median, 32.2 pg/g; range, 7.9-683 pg/g). However, using estimates for food consumption (excluding nursing infants), meat accounted for the highest U.S. dietary PBDE intake, followed by dairy and fish, with almost equal contributions. Adult females had lower dietary intake of PBDEs than did adult males, based on body weight. We estimated PBDE intake from food to be 307 ng/kg/day for nursing infants and from 2 ng/kg/day at 2-5 years of age for both males and females to 0.9 ng/kg/day in adult females. CONCLUSION: Dietary exposure alone does not appear to account for the very high body burdens measured. The indoor environment (dust, air) may play an important role in PBDE body burdens in addition to food.

Dioxin exposure and benign prostatic hyperplasia.

OBJECTIVE: Dioxins decrease prostate weight, reduce androgen responsiveness, and inhibit prostate morphogenesis in rats. We assessed the association of dioxins and benign prostatic hyperplasia (BPH) in participants in the National Health and Nutritional Examination Survey 1999-2000. METHODS: Forty-two participants were classified as having BPH and 99 were classified as controls. Dioxin exposure was expressed as dioxin toxic equivalents (TEQ). Age, body mass index, waist circumference, race/ethnicity, smoking, physical activity, and education were assessed as potential confounders. RESULTS: After age adjustment, men without BPH had 20.9% higher TEQs (95% confidence interval [CI] = 5.4-38.7%) as compared with men with BPH. On weighted, multivariate, logistic regression analyses, men with higher dioxin levels had lower odds of having BPH (odds ratio = 0.22, 95% CI = 0.08-0.62). CONCLUSIONS: Dioxin exposure in the general population may be associated with decreased odds of BPH. Our study findings need to be confirmed.

Agent Orange, dioxins, and other chemicals of concern in Vietnam: update 2006.

OBJECTIVE: The objective of this study was to find sites in Vietnam where there was human exposure from Agent Orange herbicide sprayed between 1962 and 1971, as determined by congener-specific measurement of dioxins, including 2,3,7,8-tetrachlorodibenzodioxin (TCDD), the dioxin that contaminated Agent Orange, in blood. METHODS: Blood was collected from residents of eight heavily sprayed regions in the south of Vietnam and analyzed for TCDD and in some cases the dioxin-like dibenzofurans and dioxin-like PCBs. RESULTS: Six of the eight newly studied sites did not show substantial or any elevated TCDD in blood. Marked elevation of TCDD in Vietnamese blood was found in one new location with a suggestion of slightly elevated TCDD in a second location. CONCLUSIONS: In newly studied locations in Vietnam, we found some persons with elevation of TCDD consistent with exposure to dioxin from Agent Orange. In our previous studies, we found PCBs, PCDDs, and PCDFs as well as pesticides in human milk, blood, or in food. Health effects from Agent Orange need to be differentiated from effects caused by chemicals other than TCDD from Agent Orange.

Polybrominated diphenyl ether flame retardants in the U.S. population: current levels, temporal trends, and comparison with dioxins, dibenzofurans, and polychlorinated biphenyls.

Brominated flame retardants have come into common use in the United States during the past 3 decades. This study reports levels of polybrominated diphenyl ether (PBDE) flame retardants in blood from the U.S. population at the present time and 30 years previously and also current human milk levels. This is also the first study to report measured congeners and dioxin toxic equivalents (TEQs) of dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls (PCBs) from archived, 1973, blood and compare them with current levels. The findings indicate there have been significant changes in levels of each class of these persistent organic pollutants (POPs) in U.S. human blood. Although dioxin, dibenzofuran, and PCB levels are markedly higher in the 1973 blood, the opposite is true for PBDEs. Furthermore, unlike dioxins, dibenzofurans, and PCBs, which increase with age, there was no significant correlation found in our study between PBDE levels and age. Current total PBDE levels in U.S. blood are the highest reported worldwide to date, with 2 pooled samples (N = 100 each) measuring 61.7 and 79.7 parts per billion (ppb) lipid, and in a series of 39 individual analyses, the range was 4.6 to 365.5 ppb with a median of 29 ppb and a mean of 52.6 ppb. The median for women in this study was 43.3 ppb, and for men it was 25.1 ppb. Although women have a higher level of PBDEs in blood than men, in our study, this is not statistically significant. Blood levels are similar to levels in U.S. human milk from 59 women, 6.2 to 418.8 ppb lipid. Levels of PBDE in pooled 2003 serum are far higher at 61.7 ppb than in 1973 archived pooled serum in which almost no PBDEs were quantified, although the estimated level using half the detection limit for nondetects was 0.77 ppb. Although no human health studies have been conducted on PBDEs, they are of concern because in vivo and in vitro animal studies show nervous system, reproductive, developmental, and endocrine effects, as well as cancer in high-dose studies.

Did TCDD exposure or service in Southeast Asia increase the risk of cancer in air force Vietnam veterans who did not spray agent orange?

OBJECTIVE: We sought to examine cancer incidence in 1482 Air Force veterans who served in Southeast Asia (SEA) and who were not occupationally exposed to herbicides. METHODS: Cancer incidence between 1982 and 2003 was determined by record review and Cox proportional hazards models were used to estimate risk ratios across serum 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and years served in SEA categories. RESULTS: All sites cancer risk increased with TCDD (relative risk = 1.6, 95% confidence interval = 1.2-2.2). The risk of prostate cancer increased with years of SEA service but not with TCDD. TCDD and years of SEA service interacted with all sites cancer; the risk was greatest in those with the highest TCDD levels and the longest time served in SEA. CONCLUSIONS: These results suggest nonoccupational exposures to TCDD or other factors while in SEA may contribute to cancer risk in these veterans.

Polybrominated diphenyl ethers (PBDEs) in U.S. computers and domestic carpet vacuuming: possible sources of human exposure.

Polybrominated diphenyl ethers (PBDEs), a type of brominated flame retardant chemically and toxicologically similar to polychlorinated biphenyls (PCBs), are a class of emerging environmental and human contaminants. They have recently been detected in U.S. milk, blood, and food at the highest levels in the world. This pilot study was undertaken with the aim of determining levels of PBDE in the U.S. indoor environment, to assess the potential exposure to PBDEs from computer surfaces and carpets. Food of animal origin is the usual source of polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofurans (PCDF), and PCBs in humans, but there may also be environmental sources for intake of PBDEs. It was also our aim to characterize the PBDE congener profile in these indoor environmental samples. Four computer wipe samples and 9 domestic vacuum-sweeping samples were analyzed for 13 PBDE congeners, PBDEs 17 (2,2',4), 28 (2,4,4'?), 47 (2,2',4,4'?), 66 (2,3',4,4'?), 77 (3,3',4,4'?), 85 (2,2',3,4,4'?), 99 (2,2'4,4',5), 100 (2,2',4,4',6), 138 (2,2',3,4,4',5'?), 153 (2,2',4,4',5,5'?), 154 (2,2',4,4',5,6'?), 183 (2,2',3,4,4',5',6), and 209 (2,2',3,3',4,4',5,5',6,6'?). All samples tested positive for PBDEs. PBDE 209 was the dominant congener in all 4 computer wipe samples and in 7 out of the 9 vacuum dust samples. The congener profiles observed in this study varied considerably, a finding that has been observed previously. However these congener profiles differ from the pattern seen in U.S. human milk, human blood and in food, where PBDEs 47 and 99 predominate.

Exposure assessment of adult intake of bisphenol A (BPA) with emphasis on canned food dietary exposures.

Bisphenol A (BPA) is a high-volume, synthetic compound found in epoxy resins and plastics used in food packaging. Food is believed to be a major source of BPA intake. In this study, we measured the concentration of BPA in convenience samplings of foodstuffs purchased in Dallas, Texas. Sampling entailed collection of 204 samples of fresh, frozen, and canned foods in two rounds in 2010. BPA was positive in 73% of the canned food samples, while it was found in only 7% of non-canned foods at low concentrations. The results of this food sampling program were used to calculate adult dietary intakes of BPA. A pathway approach combined food intakes, a "canned fraction" parameter which described what portion of total intake of that food came from canned products, and measured food concentrations. Dietary intakes were calculated as 12.6 ng/kg-day, of which 12.4 ng/kg-day was from canned foods. Canned vegetable intakes alone were 11.9 ng/kg-day. This dietary intake was compared to total intakes of BPA estimated from urine measurements of the National Health and Nutrition Examination Survey (NHANES). Total adult central tendency intakes ranged from 30 to 70 ng/kg-day for NHANES cycles between 2005 and 2010. Three possibilities were explored to explain the difference between these two approaches for intake estimation. Not all foods which may have been canned, particularly canned beverages such as soft drinks, were sampled in our food sampling program. Second, non-food pathways of exposure may be important for adults, including thermal paper exposures, and dust and air exposures. Finally, our canned food concentrations may not be adequately representative of canned foods in the United States; they were found to be generally lower compared to canned food concentrations measured in six other worldwide food surveys including three in North America. Our finding that canned food concentrations greatly exceeded non-canned concentrations was consistent with other studies, and underscores the importance of canned foods in the overall exposure of adults of BPA.

"One-shot" analysis of polybrominated diphenyl ethers and their hydroxylated and methoxylated analogs in human breast milk and serum using gas chromatography-tandem mass spectrometry.

The presence of polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-BDE) and methoxylated (MeO-BDE) analogs in humans is an area of high interest to scientists and the public due to their neurotoxic and endocrine disrupting effects. Consequently, there is a rise in the investigation of the occurrence of these three classes of compounds together in environmental matrices and in humans in order to understand their bioaccumulation patterns. Analysis of PBDEs, OH-BDEs, and MeO-BDEs using liquid chromatography-mass spectrometry (LC-MS) can be accomplished simultaneously, but detection limits for PBDEs and MeO-BDEs in LC-MS is insufficient for trace level quantification. Therefore, fractionation steps of the phenolic (OH-BDEs) and neutral (PBDEs and MeO-BDEs) compounds during sample preparation are typically performed so that different analytical techniques can be used to achieve the needed sensitivities. However, this approach involves multiple injections, ultimately increasing analysis time. In this study, an analytical method was developed for a "one-shot" analysis of 12 PBDEs, 12 OH-BDEs, and 13 MeO-BDEs using gas chromatography with tandem mass spectrometry (GC-MS/MS). This overall method includes simultaneous extraction of all analytes via pressurized liquid extraction followed by lipid removal steps to reduce matrix interferences. The OH-BDEs were derivatized using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (TBDMS-MTFA), producing OH-TBDMS derivatives that can be analyzed together with PBDEs and MeO-BDEs by GC-MS/MS in "one shot" within a 25-min run time. The overall recoveries were generally higher than 65%, and the limits of detection ranged from 2 to 14 pg in both breast milk and serum matrices. The applicability of the method was successfully validated on four paired human breast milk and serum samples. The mean concentrations of total PBDEs, OH-BDEs, and MeO-BDEs in breast milk were 59, 2.2, and 0.57 ng g(-1) lipid, respectively. In serum, the mean total concentrations were 79, 38, and 0.96 ng g(-1) lipid, respectively, exhibiting different distribution profiles from the levels detected in breast milk. This "one-shot" GC-MS/MS method will prove useful and cost-effective in large-scale studies needed to further understand the partitioning behavior, and ultimately the adverse health effects, of these important classes of brominated flame retardants in humans.

Serum 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) levels and thyroid function in Air Force veterans of the Vietnam War.

PURPOSE: We assessed potential health effects of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) concentration in serum on thyroid function in US Air Force veterans involved in Operation Ranch Hand, the unit responsible for the aerial spraying of herbicides, including TCDD-contaminated Agent Orange, during the Vietnam War from 1962 to 1971. Other Air Force veterans who were not involved with spraying herbicides were included as Comparisons. METHODS: We analyzed thyroxine (total T4), thyroid stimulating hormone (TSH), triiodothyronin percent uptake (T3% uptake), the free thyroxine index (FTI), and thyroid diseases against serum TCDD levels. Data was available for 1,009 Ranch Hand and 1,429 Comparison veterans compliant to any of five examinations in 1982, 1985, 1987, 1992, and 1997. Each veteran was assigned to one of four exposure categories based on serum TCDD levels, named Comparison, Ranch Hand Background, Ranch Hand Low Elevated, and Ranch Hand High Elevated. RESULTS: Cross-sectional analyses found statistically significantly increased TSH means at the 1985 and 1987 examinations in the High category and a significant increasing trend across the three Ranch Hand TCDD categories in 1982, 1985, 1987 and 1992. A repeated-measures analysis found significantly increased TSH means in the High TCDD category. We found no significant relation between the occurrence of thyroid disease and TCDD category. CONCLUSIONS: These findings suggest that TCDD affects thyroid hormone metabolism and function in Ranch Hand veterans. Further follow-up will be necessary to understand the relation, if any, between thyroid disease and TCDD levels.

Exposure assessment to dioxins from the use of tampons and diapers.

Over the past several years there has been concern over exposure to dioxins through the use of tampons and other sanitary products. This article describes attempts to estimate dioxin exposures from tampons and infant diapers; we then compare exposure estimates to dietary dioxin exposures. We analyzed four brands of tampons and four brands of infant diapers obtained from commercial establishments in San Francisco, California, for dioxin concentrations. We estimated exposures to dioxins on the basis of a screening level analysis that assumed all dioxins present were completely absorbed. We also estimated exposures by using a more refined analysis that incorporates partition coefficients to estimate bioavailability. None of the products contained 2,3,7,8-tetrachlorodibenzo-p-dioxin, the most potent dioxin, although other dioxins were present at detectable concentrations in all samples. We observed minimal differences in the concentrations of dioxins between 100% cotton and cotton/pulp products. The refined exposure analysis indicates that exposures to dioxins from tampons are approximately 13,000-240,000 times less than dietary exposures. The refined exposure analysis showed that exposure to dioxins from the diet is more than 30,000-2,200,000 times the exposure through diapers in nursing infants. Although dioxins are found in trace amounts in both cotton and pulp sanitary products, exposure to dioxins through tampons and diapers does not significantly contribute to dioxin exposures in the United States.