June-Soo Park

Temporal changes in the levels of perfluorinated compounds in California women's serum over the past 50 years.

Serum samples collected from California women at different time periods: 1960s (n = 40), 1980s (n = 30), and 2009 (n = 35) were examined for the presence of 12 perfluorinated compounds (PFCs) using an online SPE-HPLC-MS/MS method. At each time period, perfluorooctane sulfonate (PFOS) was present at the highest concentration, followed by perfluorooctanoic acid (PFOA, except in the 1960s). We found the highest levels of PFOS (median = 42.1 ng/mL) and perfluorohexane sulfonate (PFHxS, median = 1.56 ng/mL) in the 1960s samples, possibly reflecting widespread use of precursor PFCs. PFOS showed a statistically significant drop from the 1960s to the 1980s (28.8 ng/mL ) and to 2009 (9.0 ng/mL ), the latter being in agreement with national data. For PFOA, there was an approximately 10-fold increase in median concentrations from the 1960s (0.27 ng/mL) to the 1980s (2.71 ng/mL), and a slight drop in the 2009 samples (2.08 ng/mL). For longer chain perfluorocarboxylic acids (PFCAs), there was a continuous build-up in serum from the 1960s to 2009. To our knowledge, this is the first study to investigate temporal changes of PFCs over the past 50 years.

High polybrominated diphenyl ether levels in California house cats: House dust a primary source?†

Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants that act as endocrine disruptors, affecting thyroid hormone homeostasis. As a follow-up to a recent study showing high PBDE levels in household cats and linking PBDE levels with cat hyperthyroidism, we measured PBDEs, polychlorinated biphenyls (PCBs), and organochlorinated pesticides (OCPs) in serum samples from 26 California household cats (16 hyperthyroid, 10 controls) using liquid-liquid extraction and high-resolution gas chromatography/high-resolution mass spectrometry. In the present pilot study, we found that PBDE levels in California house cats were extremely high (ΣPBDEs median = 2,904 ng/g lipid; range, 631-22,537 ng/g lipid). This is approximately 50 times higher than levels in California residents (ΣPBDEs geomean = 62 ± 8.9 ng/g lipid, National Health and Nutrition Examination Survey), who have among the highest human levels in the world. Polybrominated diphenyl ethers congener patterns (BDE-99 major congener, BDE-209 significant) differed markedly from patterns found in California residents (BDE-47 major) or wildlife but resembled patterns found in house dust. Polychlorinated biphenyls and OCPs in cats were highly correlated, consistent with a shared dietary source or pathway of exposure, but did not correlate with PBDEs. This suggests a different source or pathway of exposure for PBDEs, which was most likely house dust. The authors found no evidence that linked levels of PBDEs, PCBs, or OCPs with hyperthyroidism. This may be because of the small sample size, competing or confounding risk factors, or complicated causal mechanisms.

Polybrominated Diphenyl Ether (PBDE) Levels in Peregrine Falcon (Falco peregrinus) Eggs from California Correlate with Diet and Human Population Density

Peregrine falcons are now considered a conservation success story due in part to the phasing out of harmful contaminants that adversely affected reproduction. Recent studies have shown that peregrine eggs collected from California cities, however, have high levels of the higher-brominated polybrominated diphenyl ethers (SigmaPBDE(183-209)), a class of industrial flame retardants, in comparison to published data for other wildlife. Sources of these high PBDE levels and unusual PBDE profiles are unknown. Here we analyzed the stable carbon (delta(13)C), hydrogen (deltaD), and nitrogen (delta(15)N) isotope composition of peregrine eggs collected from urban and nonurban habitats. We found that delta(13)C values were significantly higher in urban versus nonurban eggs, suggesting that urban peregrines indirectly receive anthropogenic subsidies via their consumption of prey reliant on corn-based anthropogenic foods. delta(15)N and deltaD values were significantly lower in urban versus nonurban eggs, reflecting differences in dietary diversity and food/water sources available to peregrines in each habitat. These patterns suggest a link between an anthropogenic diet and high levels of SigmaPBDE(183-209) in California peregrines, and identify anthropogenic food as a potentially important PBDE exposure pathway for urban wildlife. If diet is an important PBDE exposure pathway for peregrines, continued high body burdens of SigmaPBDE(183-209) may be a potential risk to ongoing peregrine conservation efforts in California.

Polybrominated diphenyl ethers in residential dust: sources of variability.

We characterized the sources of variability for polybrominated diphenyl ethers (PBDEs) in residential dust and provided guidance for investigators who plan to use residential dust to assess exposure to PBDEs. We collected repeat dust samples from 292 households in the Northern California Childhood Leukemia Study during two sampling rounds (from 2001 to 2007 and during 2010) using household vacuum cleaners and measured 22 PBDEs using high resolution gas chromatography-high resolution mass spectrometry. Median concentrations for individual PBDEs ranged from <0.1-2500ng per g of dust. For each of eight representative PBDEs, we used a random-effects model to apportion total variance into regional variability (0-11%), intra-regional between-household variability (17-50%), within-household variability over time (38-74%), and within-sample variability (0-23%) and we used a mixed-effects model to identify determinants of PBDE levels. Regional differences in PBDE dust levels were associated with residential characteristics that differed by region, including the presence of furniture with exposed or crumbling foam and the recent installation of carpets in the residence. Intra-regional differences between households were associated with neighborhood urban density, racial and ethnic characteristics, and to a lesser extent, income. For some PBDEs, a decreasing time trend explained a modest fraction of the within-household variability; however, most of the within-household variability was unaccounted for by our mixed-effects models. Our findings indicate that it may be feasible to use residential dust for retrospective assessment of PBDE exposures in studies of childrens health (e.g., the Northern California Childhood Leukemia Study).

Detection of nonylphenol and persistent organic pollutants in fish from the North Pacific Central Gyre.

Despite scientific and public concern, research on food web contamination from chemicals in plastic is limited, and distinguishing plastic sources from prey remains a challenge. We analyzed juvenile yellowtail (Seriola lalandi) from the North Pacific Central Gyre for plastic ingestion and tissue concentrations of persistent organic pollutants and nonionic surfactants to investigate potential contamination from plastic exposure. Ingestion of synthetic debris occurred in ~10% of the sample population. PCBs and DDTs were 352±240 (mean±SD) and 1425±1118 ng/g lw, respectively. PBDEs were 9.08±10.6 ng/g lw, with BDEs-47, 99, and 209 representing 90% of PBDEs. Nonylphenol (NP) was detected in one-third of the yellowtail with a mean of 52.8±88.5 ng/g ww overall and 167±72.3 ng/g ww excluding non-detects. Because environmental NP is strongly associated with wastewater treatment effluents, long-range transport is unlikely, and NP was previously measured in gyre plastic, we concluded that plastic-mediated exposure best explained our findings of NP in yellowtail.

High Postnatal Exposures to Polybrominated Diphenyl Ethers (PBDEs) and Polychlorinated Biphenyls (PCBs) via Breast Milk in California: Does BDE-209 Transfer to Breast Milk?

Breast milk samples collected during 2003-2005 from 82 first-time mothers in 24 communities located throughout California contained levels of polybrominated diphenyl ethers (∑(tri-hexa (8))PBDEs; median = 53.3 ng/g lw, range = 9.60-1291) and polychlorinated biphenyls (∑(12)PCBs; median = 73.4 ng/g lw, range = 22.2-433) that are among the highest in the world. PBDE levels varied 100-fold. BDE-47 was the dominant PBDE congener, with levels exceeding the U.S.EPA Reference Dose (RfD) for neurodevelopmental toxicity (100 ng/kg/day) in most (60%) breast milk samples. In some samples, BDE-209 (2/82) and/or BDE-153 (5/82) were the dominant congeners, suggesting that BDE-209 can transfer to breast milk and/or break down in the mother and transfer to the nursing infant as the lower-brominated PBDEs associated with adverse effects. PBDE levels in California breast milk are approaching those of PCBs, and the trend PBDEs > PCBs may continue as PBDEs migrate from products to the indoor and outdoor environments.

Hydroxylated PCB metabolites (OH-PCBs) in archived serum from 1950-60s California mothers: a pilot study.

We are studying participants selected from the Child Health and Development Studies (CHDS), a longitudinal birth cohort of over 20,000 California pregnancies between 1959 and 1967, for associations between maternal body burden of organochlorine contaminants and thyroid function. We designed a pilot study using 30 samples selected among samples with high and low PCB concentrations to evaluate the feasibility of measuring OH-PCBs in the larger study population. GC-ECD and GC-NCI/MS were used to determine PCBs and OH-PCBs as methyl derivatives, respectively. Maternal serum levels of Sigma11PCBs and Sigma8OH-PCB metabolites varied from 0.74 to 7.99 ng/mL wet wt. with a median of 3.05 ng/mL, and from 0.12 to 0.98 ng/mL wet wt. with a median of 0.39 ng/mL, respectively. Average concentrations of Sigma8OH-PCB metabolites in the high PCB group were significantly higher than those in the low PCB group (p < 0.05). The levels of OH-PCB metabolites were dependent on PCB levels (r = 0.58, p < 0.05) but approximately an order of magnitude lower (p < 0.05). The average ratio of Sigma8OH-PCBs to Sigma11PCBs was 0.14 +/- 0.08. The primary metabolite was 4-OH-CB187 followed by 4-OH-CB107. Both of these metabolites interfere with the thyroid system in in vitro, animal, and human studies. OH-PCBs were detectable in all archived sera analyzed, supporting the feasibility to measure OH-PCB metabolites in the entire cohort.

Concentrations of persistent organic pollutants in California women’s serum and residential dust

BACKGROUND Humans are exposed to persistent organic pollutants (POPs) through various routes, including consumption of contaminated food and accidental ingestion of settled dust. OBJECTIVES We aimed to identify key routes of exposure to organochlorine pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in California women of reproductive age. METHODS Blood was collected from 48 mothers participating in the California Childhood Leukemia Study from 2006 to 2007 and analyzed for POPs using gas chromatography-mass spectrometry. Multivariable linear regression models of natural-log transformed serum concentrations were used to identify determinants of exposure from available questionnaire information on dietary habits, reproductive history, and demographic characteristics, as well as vacuum cleaner dust-POP levels. RESULTS After adjusting for blood lipid levels, age, body mass index, cumulative lactation, and sampling date, serum concentrations of multiple major PCBs were positively associated with fish consumption, but not dust-PCB levels. After adjusting for blood lipid levels, Hispanic ethnicity, country of origin, and household annual income, serum concentrations of multiple major PBDEs were positively associated with dust-PBDE levels. CONCLUSIONS Our findings suggest that the relative contribution of specific exposure routes to total POP intake varies by chemical class, with dust being a relatively important source of PBDEs and diet being a relatively important source of PCBs.

Unusual hepta- and octabrominated diphenyl ethers and nonabrominated diphenyl ether profile in California, USA, peregrine falcons (Falco peregrinus): more evidence for brominated diphenyl ether-209 debromination.

High (maximum of 4.1 ppm lipid weight) levels of BDE-209 and other higher brominated diphenyl ethers (BDEs) found in California, USA, peregrine falcon (Falco peregrinus) eggs (n = 95) provided an opportunity to examine homolog profiles of nona-, octa-, and hepta-BDEs as possible evidence for biological debromination of BDE-209. We found two congeners in eggs, an unidentified hepta-BDE (BDE-heptaUNK) and BDE-202 (octa-BDE) that are not present in commercial mixtures. In addition, BDE-208 (nona-BDE) was present at much higher (10-fold) proportions in eggs than in commercial mixtures. To examine whether these unusual homolog patterns arose from assimilation of environmentally degraded BDE commercial mixtures, we compared nona-hepta-BDE homolog profiles of peregrine falcon eggs with those of weathered BDEs present in various abiotic matrices (sludge, sediment, and dusts). We found the profiles differed significantly: BDE-207 was the major nona-BDE in eggs, whereas BDE-206 was the major nona-BDE in abiotic matrices. Thus, the evidence for the biological debromination of BDE-209 in peregrine falcons is twofold: Eggs have two congeners (BDE-202 and -heptaUNK) that are not reported for any commercial mixtures nor in the abiotic matrices examined thus far, and eggs have higher-brominated BDE homolog patterns that are different from those found in commercial mixtures or environmental matrices.

Polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs) in livers of harbor seals (Phoca vitulina) from San Francisco Bay, California and Gulf of Maine.

Bioaccumulation of endocrine disruptors in marine mammals positioned at the top of the food chain is of toxicological concern. Livers from four pups and ten adult harbor seals (Phoca vitulina) stranded in San Francisco Bay (SFB) and the Gulf of Maine (GOM) were analyzed for polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs). We used GC-ECD and GC-NCI/MS to investigate the presence of 28 PCBs and 8 OH-PCB metabolites, respectively. Sigma(28)PCB concentrations (di- to octa-CBs) ranged from 1.81 to 35.9 microg/g lipid with a median of 6.53 for the seal pups and 2.31 to 249 microg/g lipid with a median of 28.9 for the adult seals. Sigma(8)OH-PCB concentrations (penta- to hepta-OH-PCBs) ranged from 0.02 to 0.69 microg/g lipid with a median of 0.04 for the adult seals, i.e., at much lower concentrations than those for PCBs. Ratios of OH-PCBs to PCBs (0.24% on average) were comparable to those in beluga whale, but were lower than ratios in human livers. The OH-PCB profiles were slightly different between SFB and GOM seal livers, although similar PCB congener patterns were observed. Generally, 4-OH-CB107 was found predominantly in seal livers and was the only OH-PCB detectable in most of seal pup livers. This study provides information on OH-PCBs in seals, adding to the scarce exposure data for these chemicals.