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Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants of concern whose fate and transport in environmental media are incompletely understood. In the 1960s, PFAS were dumped in the House Street Disposal Site, an unlined landfill on the crest of a glacial end moraine near Rockford, Michigan, USA. In 2017, PFAS were discovered in groundwater and subsequently, a network of monitoring wells delineated a 2 mi (3 km) PFAS plume migrating downgradient toward the Rogue River. Today, the Michigan Department of Natural Resources (MDNR) operates fish-rearing ponds in the area where the plume intersects the groundwater-surface water interface (GSI). Each year, the MDNR fills these man-made ponds using water from a nearby creek. Springs in the ponds prevent them from draining completely at the end of fish-rearing each fall. We sampled surface water and modeled groundwater flow to investigate PFAS transport across the GSI. Numerical models constructed with and without the fishponds did not substantially change MODFLOW model calibration curves or predicted MODPATH flow lines, indicating that PFAS transport is dominated by the regional flow system with limited influence from semiannual changes to boundary conditions at the GSI. Surface water samples collected from five locations within and adjacent to the fishponds were analyzed using EPA Draft Method 1633. PFAS were detected at all locations with the highest total PFAS >60 ng/L in the fishponds. Mixing models based on total PFAS indicate that approximately 10 % of the fishpond water is sourced by groundwater. However, similar analyses with perfluoroalkyl carboxylic acids (PFCA) and perfluoroalkyl sulfonic acids (PFSA) imply that groundwater comprises as much as 30 % of water in the ponds, suggesting differential movement of individual PFAS across the groundwater-surface water interface. Additional investigation of PFAS within the pond sediments is needed to better understand partitioning and differential transport behavior across the GSI., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

African American women in the United States have a high risk of adverse pregnancy outcomes. DNA methylation is a potential mechanism by which exposure to BTEX (benzene, toluene, ethylbenzene, and xylenes) may cause adverse pregnancy outcomes. Data are from the Maternal Stress Study, which recruited African American women in the second trimester of pregnancy from February 2009 to June 2010. DNA methylation was measured in archived DNA from venous blood collected in the second trimester. Trimester-specific exposure to airshed BTEX was estimated using maternal self-reported addresses and geospatial models of ambient air pollution developed as part of the Geospatial Determinants of Health Outcomes Consortium. Among the 64 women with exposure and outcome data available, 46 differentially methylated regions (DMRs) were associated with BTEX exposure (FDR adjusted p -value < 0.05) using a DMR-based epigenome-wide association study approach. Overall, 89% of DMRs consistently exhibited hypomethylation with increasing BTEX exposure. Biological pathway analysis identified 11 enriched pathways, with the top 3 involving gamma-aminobutyric acid receptor signaling, oxytocin in brain signaling, and the gustation pathway. These findings highlight the potential impact of BTEX on DNA methylation in pregnant women.

1,4-Dioxane released at the Gelman Site in Washtenaw County, Michigan, produced a series of contaminant plumes migrating up to 3 km through a heterogenous glacial aquifer system. An analysis of 1,4-dioxane concentrations in the Eastern Area of the Gelman Site between 2011 and 2017 documented a mass balance deficit of 2200 kg in excess of 2100 kg of 1,4-dioxane removed via remediation. Five mechanisms were evaluated to account for the mass deficiency: sorption, matrix diffusion, biodegradation, surface discharge, and bypass of the existing monitoring well network. The mass of 1,4-dioxane sorbed to aquifer and aquitard materials and the mass of 1,4-dioxane diffused into low permeability zones were estimated. However, decreasing aqueous concentrations across most of the contaminated area between 2011 and 2017 are expected to induce desorption and back diffusion during this period. Surface water discharge to a storm drain in the downgradient portion of the site was analyzed using concentration measurements and stream gage data. Results suggest that 1,4-dioxane mass entering the drain during the period between 2011 and 2017 was insufficient to account for the mass deficiency. Although available geochemical measurements indicate predominantly anaerobic aquifer conditions at the Gelman Site, biodegradation of 1,4-dioxane was estimated using first order decay rate constants from other sites where conditions may be more favorable. Results suggest that biodegradation could explain some but not all of the missing mass. Bypass of the downgradient monitoring well network is the most parsimonious explanation for the 1,4-dioxane mass deficit. This conclusion is supported by documented flow path complexity through the aquifer system and the sparse density of monitoring wells in the downgradient Eastern Area. These findings underscore the importance of characterizing aquifer heterogeneity when modeling and remediating persistent groundwater contaminants such as 1,4-dioxane., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Lawrence Lemke serves as a paid technical consultant to the City of Ann Arbor, Washtenaw County, Washtenaw County Health Department, Scio Township, and the Huron River Watershed Council, who collectively are parties to litigation concerning cleanup of the site described in this study., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Air pollution is associated with preterm birth (PTB), potentially via inflammation. We recently showed the mixture benzene, toluene, ethylbenzene, and xylene (BTEX) is associated with PTB. We examined if ambient BTEX exposure is associated with mid-pregnancy inflammation in a sample of 140 African-American women residing in Detroit, Michigan. The Geospatial Determinants of Health Outcomes Consortium study collected outdoor air pollution measurements in Detroit; these data were coupled with Michigan Air Sampling Network measurements to develop monthly BTEX concentration estimates at a spatial density of 300 m 2 . First trimester and mid-pregnancy BTEX exposure estimates were assigned to maternal address. Mid-pregnancy (mean 21.3 ± 3.7 weeks gestation) inflammatory biomarkers (high-sensitivity C-reactive protein, interleukin [IL]-6, IL-10, IL-1β, and tumor necrosis factor-α) were measured with enzyme immunoassays. After covariate adjustment, for every 1-unit increase in first trimester BTEX, there was an expected mean increase in log-transformed IL-1β of 0.05 ± 0.02 units (P = 0.014) and an expected mean increase in log-transformed tumor necrosis factor-α of 0.07 ± 0.02 units (P = 0.006). Similarly, for every 1-unit increase in mid-pregnancy BTEX, there was a mean increase in log IL-1β of 0.06 ± 0.03 units (P = 0.027). There was no association of either first trimester or mid-pregnancy BTEX with high-sensitivity C-reactive protein, IL-10, or IL-6 (all P > 0.05). Ambient BTEX exposure is associated with inflammation in mid-pregnancy in African-American women. Future studies examining if inflammation mediates associations between BTEX exposure and PTB are needed., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this study, we developed an analytical method for the determination of 1,4-dioxane in aqueous solutions using freeze-assisted liquid-liquid extraction, also known as frozen microextraction, and gas chromatography with triple quadrupole mass spectrometry with select reaction monitoring. The method is capable of quantifying 1,4-dioxane across a broad range of concentrations (1-10 000 μg/L) relevant to contaminated sites, with an instrument detection limit and method detection limit experimentally verified as 2.1 and 2.2 μg/L, respectively. In contrast to methods with similar detection limits that require 50 to 500 mL volume of sample, our method uses only 200 μL of sample. The method presented here facilitates field and laboratory applications where small sample volumes and high precision are required and could be extended to other strongly water-soluble GC-amenable analytes., (© 2021 Wiley-VCH GmbH.)

Detroit, Michigan, currently has the highest preterm birth (PTB) rate of large cities in the United States. Disproportionate exposure to ambient air pollutants, including particulate matter ≤2.5 μm (PM 2.5 ), PM ≤ 10 μm (PM 10 ), nitrogen dioxide (NO 2 ) and benzene, toluene, ethylbenzene, and xylenes (BTEX) may contribute to PTB. Our objective was to examine the association of airshed pollutants with PTB in Detroit, MI. The Geospatial Determinants of Health Outcomes Consortium (GeoDHOC) study collected air pollution measurements at 68 sites in Detroit in September 2008 and June 2009. GeoDHOC data were coupled with 2008-2010 Michigan Air Sampling Network measurements in Detroit to develop monthly ambient air pollution estimates at a spatial density of 300 m 2 . Using delivery records from two urban hospitals, we established a retrospective birth cohort of births by Detroit women occurring from June 2008 to May 2010. Estimates of air pollutant exposure throughout pregnancy were assigned to maternal address at delivery. Our analytic sample size included 7961 births; 891 (11.2%) were PTB. After covariate adjustment, PM 10 (P = 0.003) and BTEX (P < 0.001), but not PM 2.5 (P = 0.376) or NO 2 (P = 0.582), were statistically significantly associated with PTB. In adjusted models, for every 5-unit increase in PM 10 there was a 1.21 times higher odds of PTB (95% CI 1.07, 1.38) and for every 5-unit increase in BTEX there was a 1.54 times higher odds of PTB (95% CI 1.25, 1.89). Consistent with previous studies, higher PM 10 was associated with PTB. We also found novel evidence that higher airshed BTEX is associated with PTB. Future studies confirming these associations and examining direct measures of exposure are needed., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Forty eight potential outliers in air pollution measurements taken simultaneously in Detroit, Michigan, USA and Windsor, Ontario, Canada in 2008 and 2009 were identified using four independent methods: box plots, variogram clouds, difference maps, and the Local Moran's I statistic. These methods were subsequently used in combination to reduce and select a final set of 13 outliers for nitrogen dioxide (NO 2 ), volatile organic compounds (VOCs), total benzene, toluene, ethyl benzene, and xylene (BTEX), and particulate matter in two size fractions (PM 2.5 and PM 10 ). The selected outliers were excluded from the measurement datasets and used to revise air pollution models. In addition, a set of temporally-scaled air pollution models was generated using time series measurements from community air quality monitors, with and without the selected outliers. The influence of outlier exclusion on associations with asthma exacerbation rates aggregated at a postal zone scale in both cities was evaluated. Results demonstrate that the inclusion or exclusion of outliers influences the strength of observed associations between intraurban air quality and asthma exacerbation in both cities. The box plot, variogram cloud, and difference map methods largely determined the final list of outliers, due to the high degree of conformity among their results. The Moran's I approach was not useful for outlier identification in the datasets studied. Removing outliers changed the spatial distribution of modeled concentration values and derivative exposure estimates averaged over postal zones. Overall, associations between air pollution and acute asthma exacerbation rates were weaker with outliers removed, but improved with the addition of temporal information. Decreases in statistically significant associations between air pollution and asthma resulted, in part, from smaller pollutant concentration ranges used for linear regression. Nevertheless, the practice of identifying outliers through congruence among multiple methods strengthens confidence in the analysis of outlier presence and influence in environmental datasets., (Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.)

The Geospatial Determinants of Health Outcomes Consortium (GeoDHOC) study investigated ambient air quality across the international border between Detroit, Michigan, USA and Windsor, Ontario, Canada and its association with acute asthma events in 5- to 89-year-old residents of these cities. NO2, SO2, and volatile organic compounds (VOCs) were measured at 100 sites, and particulate matter (PM) and polycyclic aromatic hydrocarbons (PAHs) at 50 sites during two 2-week sampling periods in 2008 and 2009. Acute asthma event rates across neighborhoods in each city were calculated using emergency room visits and hospitalizations and standardized to the overall age and gender distribution of the population in the two cities combined. Results demonstrate that intra-urban air quality variations are related to adverse respiratory events in both cities. Annual 2008 asthma rates exhibited statistically significant positive correlations with total VOCs and total benzene, toluene, ethylbenzene and xylene (BTEX) at 5-digit zip code scale spatial resolution in Detroit. In Windsor, NO2, VOCs, and PM10 concentrations correlated positively with 2008 asthma rates at a similar 3-digit postal forward sortation area scale. The study is limited by its coarse temporal resolution (comparing relatively short term air quality measurements to annual asthma health data) and interpretation of findings is complicated by contrasts in population demographics and health-care delivery systems in Detroit and Windsor.

Soil lead pollution is a recalcitrant problem in urban areas resulting from a combination of historical residential, industrial, and transportation practices. The emergence of urban gardening movements in postindustrial cities necessitates accurate assessment of soil lead levels to ensure safe gardening. In this study, we examined small-scale spatial variability of soil lead within a 15 × 30 m urban garden plot established on two adjacent residential lots located in Detroit, Michigan, USA. Eighty samples collected using a variably spaced sampling grid were analyzed for total, fine fraction (less than 250 μm), and bioaccessible soil lead. Measured concentrations varied at sampling scales of 1-10 m and a hot spot exceeding 400 ppm total soil lead was identified in the northwest portion of the site. An interpolated map of total lead was treated as an exhaustive data set, and random sampling was simulated to generate Monte Carlo distributions and evaluate alternative sampling strategies intended to estimate the average soil lead concentration or detect hot spots. Increasing the number of individual samples decreases the probability of overlooking the hot spot (type II error). However, the practice of compositing and averaging samples decreased the probability of overestimating the mean concentration (type I error) at the expense of increasing the chance for type II error. The results reported here suggest a need to reconsider U.S. Environmental Protection Agency sampling objectives and consequent guidelines for reclaimed city lots where soil lead distributions are expected to be nonuniform., (© 2013 Society for Risk Analysis.)

A pilot-scale demonstration of surfactant-enhanced aquifer remediation (SEAR) was conducted to recover dense nonaqueous phase liquid (DNAPL) tetrachloroethene (PCE) from a sandy glacial outwash aquifer underlying a former dry cleaning facility at the Bachman Road site in Oscoda, MI. Part one of this two-part paper describes site characterization efforts and a comprehensive approach to SEAR test design, effectively integrating laboratory and modeling studies. Aquifer coring and drive point sampling suggested the presence of PCE-DNAPL in a zone beneath an occupied building. A narrow PCE plume emanating from the vicinity of this building discharges into Lake Huron. The shallow unconfined aquifer, characterized by relatively homogeneous fine-medium sand deposits, an underlying clay layer, and the absence of significant PCE transformation products, was judged suitable for the demonstration of SEAR. Tween 80 was selected for application based upon its favorable solubilization performance in batch and two-dimensional sand tank treatability studies, biodegradation potential, and regulatory acceptance. Three-dimensional flow and transport models were employed to develop a robust design for surfactant delivery and recovery. Physical and fiscal constraints led to an unusual hydraulic design, in which surfactant was flushed across the regional groundwater gradient, facilitating the delivery of concentrations of Tween 80 exceeding 1% (wt) throughout the treatment zone. The potential influence of small-scale heterogeneity on PCE-DNAPL distribution and SEAR performance was assessed through numerical simulations incorporating geostatistical permeability fields based upon available core data. For the examined conditions simulated PCE recoveries ranged from 94to 99%. The effluent treatment system design consisted of low-profile air strippers coupled with carbon adsorption to trap off-gas PCE and discharge of treated aqueous effluent to a local wastewater treatment plant. The systematic and comprehensive design methodology described herein may serve as a template for application at other DNAPL sites.

Two different deterministic and two alternative stochastic (i.e., geostatistical) approaches to modeling the distribution of hydraulic conductivity (K) in a nonuniform (sigma2ln(K)) = 0.29) glacial sand aquifer were used to explore the influence of conceptual model selection on simulations of three-dimensional tracer movement. The deterministic K models employed included a homogeneous effective K and a perfectly stratified 14 layer model. Stochastic K models were constructed using sequential Gaussian simulation and sequential i ndicator simulation conditioned to available K values estimated from measured grain size distributions. Standard simulation software packages MODFLOW, MT3DMS, and MODPATH were used to model three-dimensional ground water flow and transport in a field tracer test, where a pulse of bromide was injected through an array of three fully screened wells and extracted through a single fully screened well approximately 8 m away. Agreement between observed and simulated transport behavior was assessed through direct comparison of breakthrough curves (BTCs) and selected breakthrough metrics at the extraction well and at 26 individual multilevel sample ports distributed irregularly between the injection and extraction wells. Results indicate that conceptual models incorporating formation variability are better able to capture observed breakthrough behavior. Root mean square (RMS) error of the deterministic models bracketed the ensemble mean RMS error of stochastic models for simulated concentration vs. time series, but not for individual BTC characteristic metrics. The spatial variability models evaluated here may be better suited to simulating breakthrough behavior measured in wells screened over large intervals than at arbitrarily distributed observation points within a nonuniform aquifer domain.