In late 2014, wastewater effluent samples were collected from eight treatment plants that discharge to San Francisco (SF) Bay in order to assess poly- and perfluoroalkyl substances (PFASs) currently ...released from municipal and industrial sources. In addition to direct measurement of twenty specific PFAS analytes, the total concentration of perfluoroalkyl acid (PFAA) precursors was also indirectly measured by adapting a previously developed oxidation assay. Effluent from six municipal treatment plants contained similar amounts of total PFASs, with highest median concentrations of PFHxA (24 ng/L), followed by PFOA (23 ng/L), PFBA (19 ng/L), and PFOS (15 ng/L). Compared to SF Bay municipal wastewater samples collected in 2009, the short chain perfluorinated carboxylates PFBA and PFHxA rose significantly in concentration. Effluent samples from two treatment plants contained much higher levels of PFASs: over two samplings, wastewater from one municipal plant contained an average of 420 ng/L PFOS and wastewater from an airport industrial treatment plant contained 560 ng/L PFOS, 390 ng/L 6:2 FtS, 570 ng/L PFPeA, and 500 ng/L PFHxA. The elevated levels observed in effluent samples from these two plants are likely related to aqueous film forming foam (AFFF) sources impacting their influent; PFASs attributable to both current use and discontinued AFFF formulations were observed. Indirectly measured PFAA precursor compounds accounted for 33%–63% of the total molar concentration of PFASs across all effluent samples and the PFAA precursors indicated by the oxidation assay were predominately short-chained. PFAS levels in SF Bay effluent samples reflect the manufacturing shifts towards shorter chained PFASs while also demonstrating significant impacts from localized usage of AFFF.
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•Impacts of AFFF usage can be seen in municipal and industrial wastewater effluent.•Short chain PFCAs significantly rose in concentration in wastewater since 2009.•PFOS concentrations ranged from 220 ng/L to 640 ng/L in AFFF-impacted wastewater.•PFAA precursors in final wastewater effluent are predominately short-chained.
The fate of per- and polyfluoroalkyl substances (PFASs) derived from aqueous film forming foam (AFFF) was investigated within a wastewater treatment plant (WWTP) receiving large AFFF inputs from a ...foam refractory testing event. Targeted analysis, the Total Oxidizable Precursor Assay (TOP Assay), and nontargeted analysis with quadrupole time-of-flight (QTOF) were used to characterize the samples. Over the duration of foam testing, approximately 10.8 kg of total PFASs was measured by TOP Assay in the influent, and 6.3 kg of total PFASs was measured in the effluent; 94 g of PFOS was released in the effluent, apparently from remobilization of historical sources. 1.7% of total PFASs measured in the influent were converted to short chain perfluoroalkyl carboxylates in the effluent. Ten PFAS classes previously reported, including 6:2 fluorotelomer thioether amido sulfonate (6:2 FtTAoS), and 5 PFAS classes newly reported were identified by QTOF. The trickling filter was the only unit operation that resulted in significant gains and losses of individual PFASs, including near complete loss of 6:2 FtTAoS due to transformation. Similar reaction pathways for 6:2 FtTAoS reported in previously published soil and activated sludge microcosm experiments were observed in this WWTP, although a higher yield of perfluoroheptanoic acid was observed.
Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants. Technical mixtures PentaBDE and OctaBDE were phased out in 2004 through voluntary and regulatory actions with DecaBDE remaining ...in limited use until 2013. Biomonitoring studies have shown widespread presence of PBDEs in the US and worldwide population. While some studies suggest that human serum concentrations are declining over time, it is unclear whether this trend will continue. Our objective was to examine temporal trends of PentaBDEs and their hydroxylated metabolites (OH-PBDEs) between 2008 and 2014 in populations of ethnically diverse, pregnant women residing in Northern California (n = 111). Serum samples were collected and analyzed by high resolution mass spectrometry for five PentaBDE congeners and two OH-PBDEs. We found widespread exposures in participants from all three time points (2008/09, 2011/12, 2014). Temporal patterns varied substantially by congener. BDE-47, -99 and the OH-PBDEs decreased between 2008/09-2011/12 but plateaued between 2011/12-2014. In contrast, BDE-100 decreased across all years, BDE-153 decreased in the latter years, and BDE-28 decreased initially and then increased. These findings indicate that while policies to remove PBDEs from the marketplace have successfully lead to declines in exposures to some PBDE congeners, human exposures to these legacy pollutants could plateau and remain ubiquitous in human populations.
•We measured PBDEs and OH-PBDEs in a demographically consistent population of pregnant women over six years.•Between 2008/09 and 2011/12, ∑PBDE5 concentrations decreased 45%, but plateaued between 2011/12 and 2014.•BDE-47 was found in 100% of pregnant women in all years studied.•The BDE-153 concentration decreased more between 2011/12 and 2014 than between the prior cohorts.
Our proof-of-concept study develops a suspect screening workflow to identify and prioritize potentially ubiquitous chemical exposures in matched maternal/cord blood samples, a critical period of ...development for future health risks. We applied liquid chromatography–quadrupole time-of-flight tandem mass spectrometry (LC-QTOF/MS) to perform suspect screening for ∼3500 industrial chemicals on pilot data from 30 paired maternal and cord serum samples (n = 60). We matched 662 suspect features in positive ionization mode and 788 in negative ionization mode (557 unique formulas overall) to compounds in our database, and selected 208 of these for fragmentation analysis based on detection frequency, correlation in feature intensity between maternal and cord samples, and peak area differences by demographic characteristics. We tentatively identified 73 suspects through fragmentation spectra matching and confirmed 17 chemical features (15 unique compounds) using analytical standards. We tentatively identified 55 compounds not previously reported in the literature, the majority which have limited to no information about their sources or uses. Examples include (i) 1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)-3-dodecylpyrrolidine-2,5-dione (known high production volume chemical) (ii) methyl perfluoroundecanoate and 2-perfluorooctyl ethanoic acid (two PFAS compounds); and (iii) Sumilizer GA 80 (plasticizer). Thus, our workflow demonstrates an approach to evaluating the chemical exposome to identify and prioritize chemical exposures during a critical period of development.
Prenatal polybrominated diphenyl ether (PBDE) exposures are a public health concern due to their persistence and potential for reproductive and developmental harm. However, we have little information ...about the extent of fetal exposures during critical developmental periods and the variation in exposures for groups that may be more highly exposed, such as communities of color and lower socioeconomic status (SES). To characterize maternal-fetal PBDE exposures among potentially vulnerable groups, PBDE levels were examined in the largest sample of matched maternal serum, placenta, and fetal liver tissues during mid-gestation among a geographically, racially/ethnically, and socially diverse population of pregnant women from Northern California and the Central Valley (n = 180; 2014-16). Maternal-fetal PBDE levels were compared to population characteristics using censored Kendall's tau correlation and linear regression. PBDEs were commonly detected in all biomatrices. Before lipid adjustment, wet-weight levels of all four PBDE congeners were highest in the fetal liver (p < 0.001), whereas median PBDE levels were significantly higher in maternal serum than in the fetal liver or placenta after lipid-adjustment (p < 0.001). We also found evidence of racial/ethnic disparities in PBDE exposures (Non-Hispanic Black > Latina/Hispanic > Non-Hispanic White > Asian/Pacific Islander/Other; p < 0.01), with higher levels of BDE-100 and BDE-153 among non-Hispanic Black women compared to the referent group (Latina/Hispanic women). In addition, participants living in Fresno/South Central Valley had 34% (95% CI: - 2.4 to 84%, p = 0.07) higher wet-weight levels of BDE-47 than residents living in the San Francisco Bay Area. PBDEs are widely detected and differentially distributed in maternal-fetal compartments. Non-Hispanic Black pregnant women and women from Southern Central Valley geographical populations may be more highly exposed to PBDEs. Further research is needed to identify sources that may be contributing to differential exposures and associated health risks among these vulnerable populations.
DDT Exposure in Utero and Breast Cancer Cohn, Barbara A; La Merrill, Michele; Krigbaum, Nickilou Y ...
The journal of clinical endocrinology and metabolism,
2015-August, Letnik:
100, Številka:
8
Journal Article
Recenzirano
Odprti dostop
Context:
Currently no direct evidence links in utero dichlorodiphenyltrichloroethane (DDT) exposure to human breast cancer. However, in utero exposure to another xenoestrogen, diethylstilbestrol, ...predicts an increased breast cancer risk. If this finding extends to DDT, it could have far-reaching consequences. Many women were heavily exposed in utero during widespread DDT use in the 1960s. They are now reaching the age of heightened breast cancer risk. DDT exposure persists and use continues in Africa and Asia without clear knowledge of the consequences for the next generation.
Hypothesis:
In utero exposure to DDT is associated with an increased risk of breast cancer.
Design:
This was a case-control study nested in a prospective 54-year follow-up of 9300 daughters in the Child Health and Development Studies pregnancy cohort (n = 118 breast cancer cases, diagnosed by age 52 y and 354 controls matched on birth year).
Setting and Participants:
Kaiser Foundation Health Plan members who received obstetric care in Alameda County, California, from 1959 to 1967, and their adult daughters participated in the study.
Main Outcome Measure:
Daughters' breast cancer diagnosed by age 52 years as of 2012 was measured.
Results:
Maternal o,p′-DDT predicted daughters' breast cancer (odds ratio fourth quartile vs first = 3.7, 95% confidence interval 1.5–9.0). Mothers' lipids, weight, race, age, and breast cancer history did not explain the findings.
Conclusions:
This prospective human study links measured DDT exposure in utero to risk of breast cancer. Experimental studies are essential to confirm results and discover causal mechanisms. Findings support classification of DDT as an endocrine disruptor, a predictor of breast cancer, and a marker of high risk.
To assess the efficacy of the bans in reducing PBDE levels, we recruited 67 California first time mothers (sampled during 2009–2012) and collected cord blood at birth (n = 31), breast milk (n = 66) ...and maternal blood (n = 65) at 3–8 weeks postpartum. Using the same sample extraction procedures and analytical instrumentation method (GC-HRMS), we compared PBDE as well as PCB levels in these breast milk samples to those from our previous study (n = 82, sampled during 2003–2005) and found that the sum of PBDEs over the ∼7 year course declined by 39% (GeoMean = 67.8 ng/g lipid in 2003–2005; 41.5 ng/g lipid in 2009–2012) and that the sum of PCBs declined by 36% (GeoMean = 71.6 ng/g lipid in 2003–2005; 45.7 ng/g lipid in 2009–2012). This supports our earlier finding of a PBDE decline (39%) in blood. We also found that the PBDE concentrations and congener profiles were similar in breast milk and their matched maternal/cord blood: BDE-47 was the dominant congener, followed by BDE-153, -99, and -100. Similar levels and congener profiles of PBDEs in these matrices suggest that they are at equilibrium. Therefore, we propose that maternal serum levels may be used to predict an infant's daily dose of PBDE exposure from breastfeeding when breast milk levels are not available. In addition, our study confirmed that breastfeeding babies are still exposed to high levels of PBDEs, even though PBDE levels are decreasing.
PBDE levels (mean and standard error, ng/g lipid) decreased in CA breast milk in 2009–2012 (red bars) compared to 2003–2005 levels (blue bars). *** = p < 0.05, p values were determined from one tailed t test. Display omitted
•We found significant declines in PBDE and PCB levels between 2003–2005 and 2009–2012 in breast milk of California women.•We found highly correlated levels and identical congener profiles in breast milk, maternal, and cord blood.•We confirmed that PBDE levels are decreasing in California after PBDE ban.•Almost 30% of breastfed babies would be exposed to BDE-47 above the USEPA RfD.
Exposure to environmental chemicals during pregnancy adversely affects maternal and infant health, and identifying socio-demographic differences in exposures can inform contributions to health ...inequities.
We recruited 294 demographically diverse pregnant participants in San Francisco from the Mission Bay/Moffit Long (MB/ML) hospitals, which serve a primarily higher income population, and Zuckerberg San Francisco General Hospital (ZSFGH), which serves a lower income population. We collected maternal and cord sera, which we screened for 2420 unique formulas and their isomers using high-resolution mass spectrometry using LC-QTOF/MS. We assessed differences in chemical abundances across socioeconomic and demographic groups using linear regression adjusting for false discovery rate.
Our participants were racially diverse (31% Latinx, 16% Asian/Pacific Islander, 5% Black, 5% other or multi-race, and 43% white). A substantial portion experienced financial strain (28%) and food insecurity (20%) during pregnancy. We observed significant abundance differences in maternal (9 chemicals) and cord sera (39 chemicals) between participants who delivered at the MB/ML hospitals versus ZSFGH. Of the 39 chemical features differentially detected in cord blood, 18 were present in pesticides, one per- or poly-fluoroalkyl substance (PFAS), 21 in plasticizers, 24 in cosmetics, and 17 in pharmaceuticals; 4 chemical features had unknown sources. A chemical feature annotated as 2,4-dichlorophenol had higher abundances among Latinx compared to white participants, those delivering at ZSFGH compared to MB/ML, those with food insecurity, and those with financial strain. Post-hoc QTOF analyses indicated the chemical feature was either 2,4-dichlorophenol or 2,5-dichlorophenol, both of which have potential endocrine-disrupting effects.
Chemical exposures differed between delivery hospitals, likely due to underlying social conditions faced by populations served. Differential exposures to 2,4-dichlorophenol or 2,5-dichlorophenol may contribute to disparities in adverse outcomes.
•Non-targeted chemical analysis among pregnant women and their newborns can help characterize the prenatal exposome.•Participants with higher socioeconomic status tended to have higher PFAS abundances.•Participants with lower socioeconomic status had higher 2,4-dichlorophenol or 2,5-dichlorophenol abundances.•Differences in chemical abundances were largest when comparing participants delivering at a safety net versus academic hospitals
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