Total organic carbon concentrations in clastic cave sediments from Butler Cave, Virginia, USA: implications for contaminant fate and transport.

Clastic cave deposits are representative of sediments throughout the karst aquifer and thus are an abundant and accessible resource through which to study the chemistry of karst aquifer. Clastic cave sediments are attributed to depositional facies based on cave location, sorting, and particle size. These facies settings may influence different chemical parameters of the sediments, like concentrations of total organic carbon (TOC). The TOC concentrations in clastic cave sediments have not been well constrained nor has the role of clastic sediments in contaminant fate and transport through karst systems been well described. In this study, particle size, TOC, and total nitrogen were measured in sediments representing different facies in Butler Cave, Virginia, USA. TOC concentrations ranged from 0.08 - 0.87 weight percent and C:N molar ratio ranged from 3 - 15, indicating a possible terrestrial source of organic carbon in these sediments. The diamicton facies was sandier and but had similar TOC concentrations compared to the channel facies. TOC concentrations measured in Butler Cave were within the same range as those observed in above water, eogenetic clastic cave sediments from two caves in Puerto Rico. Estimated retardation factors calculated based on the TOC concentrations in the Butler Cave sediments indicate the range of TOC in this cave could be responsible for 39 - 987% increase in retardation of selected contaminants. This study highlights the importance of measuring the ranges of TOC in clastic cave sediments across different facies and their role in contaminant fate and transport.

Spatial-temporal targeted and non-targeted surveys to assess microbiological composition of drinking water in Puerto Rico following Hurricane Maria.

Loss of basic utilities, such as drinking water and electricity distribution, were sustained for months in the aftermath of Hurricane Maria's (HM) landfall in Puerto Rico (PR) in September 2017. The goal of this study was to assess if there was deterioration in biological quality of drinking water due to these disruptions. This study characterized the microbial composition of drinking water following HM across nine drinking water systems (DWSs) in PR and utilized an extended temporal sampling campaign to determine if changes in the drinking water microbiome were indicative of HM associated disturbance followed by recovery. In addition to monitoring water chemistry, the samples were subjected to culture independent targeted and non-targeted microbial analysis including quantitative PCR (qPCR) and genome-resolved metagenomics. The qPCR results showed that residual disinfectant was the major driver of bacterial concentrations in tap water with marked decrease in concentrations from early to late sampling timepoints. While Mycobacterium avium and Pseudomonas aeruginosa were not detected in any sampling locations and timepoints, genetic material from Leptospira and Legionella pneumophila were transiently detected in a few sampling locations. The majority of metagenome assembled genomes (MAGs) recovered from these samples were not associated with pathogens and were consistent with bacterial community members routinely detected in DWSs. Further, whole metagenome-level comparisons between drinking water samples collected in this study with samples from other full-scale DWS indicated no significant deviation from expected community membership of the drinking water microbiome. Overall, our results suggest that disruptions due to HM did not result in significant and sustained deterioration of biological quality of drinking water at our study sites.

Pilot-scale expanded assessment of inorganic and organic tapwater exposures and predicted effects in Puerto Rico, USA.

A pilot-scale expanded target assessment of mixtures of inorganic and organic contaminants in point-of-consumption drinking water (tapwater, TW) was conducted in Puerto Rico (PR) to continue to inform TW exposures and corresponding estimations of cumulative human-health risks across the US. In August 2018, a spatial synoptic pilot assessment of than 524 organic and 37 inorganic chemicals was conducted in 14 locations (7 home; 7 commercial) across PR. A follow-up 3-day temporal assessment of TW variability was conducted in December 2018 at two of the synoptic locations (1 home, 1 commercial) and included daily pre- and post-flush samples. Concentrations of regulated and unregulated TW contaminants were used to calculate cumulative in vitro bioactivity ratios and Hazard Indices (HI) based on existing human-health benchmarks. Synoptic results confirmed that human exposures to inorganic and organic contaminant mixtures, which are rarely monitored together in drinking water at the point of consumption, occurred across PR and consisted of elevated concentrations of inorganic contaminants (e.g., lead, copper), disinfection byproducts (DBP), and to a lesser extent per/polyfluoroalkyl substances (PFAS) and phthalates. Exceedances of human-health benchmarks in every synoptic TW sample support further investigation of the potential cumulative risk to vulnerable populations in PR and emphasize the importance of continued broad characterization of drinking-water exposures at the tap with analytical capabilities that better represent the complexity of both inorganic and organic contaminant mixtures known to occur in ambient source waters. Such health-based monitoring data are essential to support public engagement in source water sustainability and treatment and to inform consumer point-of-use treatment decision making in PR and throughout the US.

Impact of Hurricane Maria on Drinking Water Quality in Puerto Rico.

This study performed a comprehensive assessment of the impact of Hurricane Maria (HM) on drinking water quality in Puerto Rico (PR) by integrating targeted chemical analysis of both inorganic (18 trace elements) and organic trace pollutants (200 micropollutants) with high-throughput quantitative toxicogenomics and in vitro biomarkers-based toxicity assays. Average concentrations of 14 detected trace elements and 20 organic micropollutants showed elevation after HM. Arsenic, sucralose, perfluorooctanoic acid (PFOA), atrazine-2-hydroxy, benzotriazole, acesulfame, and prometon were at significantly (p < 0.05) higher levels in the post-HM than in the pre-HM samples. Thirteen micropollutants, including four pesticides, were only detected in posthurricane samples. Spatial comparison showed higher pollutant and toxicity levels in the samples from northern PR (where eight Superfund sites are located) than in those from southern PR. Distinctive pathway-specific molecular toxicity fingerprints for water extracts before and after HM and at different locations revealed changes in toxicity nature that likely resulted from the impact of HM on drinking water composition. Correlation analysis and Maximum Cumulative Ratio assessment suggested that metals (i.e., arsenic) and PFOA were the top ranked pollutants that have the potential to cause increased risk after HM, providing a possible direction for future water resource management and epidemiological studies.

Identification of environmental chemicals targeting miscarriage genes and pathways using the comparative toxicogenomics database.

BACKGROUND: Miscarriage is a prevalent public health issue and many events occur before women are aware of their pregnancy, complicating research design. Thus, risk factors for miscarriage are critically understudied. Our goal was to identify environmental chemicals with a high number of interactions with miscarriage genes, based on known toxicogenomic responses. METHODS: We used miscarriage (MeSH: D000022) and chemical gene lists from the Comparative Toxicogenomics Database in human, mouse, and rat. We assessed enrichment for gene ontology biological processes among the miscarriage genes. We prioritized chemicals (n = 25) found at Superfund sites or in the blood or urine pregnant women. For chemical-disease gene sets of sufficient size (n = 13 chemicals, n = 20 comparisons), chi-squared enrichment tests and proportional reporting ratios (PRR) were calculated. We cross-validated enrichment results. RESULTS: Miscarriage was annotated with 121 genes and overrepresented in inflammatory response (q = 0.001), collagen metabolic process (q = 1 × 10-13), cell death (q = 0.02), and vasculature development (q = 0.005) pathways. The number of unique genes annotated to a chemical ranged from 2 (bromacil) to 5607 (atrazine). In humans, all chemicals tested were highly enriched for miscarriage gene overlap (all p < 0.001; parathion PRR = 7, cadmium PRR = 6.5, lead PRR = 3.9, arsenic PRR = 3.5, atrazine PRR = 2.8). In mice, highest enrichment (p < 0.001) was observed for naphthalene (PRR = 16.1), cadmium (PRR = 12.8), arsenic (PRR = 11.6), and carbon tetrachloride (PRR = 7.7). In rats, we observed highest enrichment (p < 0.001) for cadmium (PRR = 8.7), carbon tetrachloride (PRR = 8.3), and dieldrin (PRR = 5.3). Our findings were robust to 1000 permutations each of variable gene set sizes. CONCLUSION: We observed chemical gene sets (parathion, cadmium, naphthalene, carbon tetrachloride, arsenic, lead, dieldrin, and atrazine) were highly enriched for miscarriage genes. Exposures to chemicals linked to miscarriage, and thus linked to decreased probability of live birth, may limit the inclusion of fetuses susceptible to adverse birth outcomes in epidemiology studies. Our findings have critical public health implications for successful pregnancies and the interpretation of adverse impacts of environmental chemical exposures on pregnancy.

Effect of hydrogeological and anthropogenic factors on the spatial and temporal distribution of CVOCs in the karst system of northern Puerto Rico.

This study evaluates factors affecting the spatial and temporal distribution of chlorinated volatile organic contaminants (CVOCs) in the highly productive aquifers of the karst region in northern Puerto Rico (KR-NPR). Historical records from 1982 to 2016 are analyzed using spatial and statistical methods to evaluate hydrogeological and anthropogenic factors affecting the presence and concentrations of multiple CVOCs in the KR-NPR. Results show extensive spatial and temporal distributions of CVOCs, as single entities and as mixtures. It is found that at least one type of CVOC is present above detection limits in 64% of the samples and 77% of the sampling sites during the study period. CVOC distribution in the KR-NPR is contaminant-dependent, with some species being strongly influenced by the source of contamination and hydrogeological characteristics of the system. Persistent presence of CVOCs in the KR-NPR system, even after contaminated sites have been subjected to active remediation, reflect the high capacity of the system to store and slowly release contaminants over long periods of time. This study shows that karst aquifers are highly vulnerable to contamination and can serve as a long-term route of contaminants to potential points of exposure.

The influence of hydrogeological and anthropogenic variables on phthalate contamination in eogenetic karst groundwater systems.

This study investigates the occurrence of six phthalates and distribution of the three most-detected phthalates in the karst region of northern Puerto Rico (KRNPR) using data from historical records and current field measurements. Statistical data analyses, including ANOVA, Chi-Square, and logistic regression models are used to examine the major factors affecting the presence and concentrations of phthalates in the KRNPR. The most detected phthalates include DEHP, DBP, and DEP. At least one phthalate specie is detected above DL in 7% of the samples and 24% of the sampling sites. Concentrations of total phthalates average 5.08 ±â€¯1.37 µg L-1, and range from 0.093 to 58.4 µg L-1. The analysis shows extensive spatial and temporal presence of phthalates resulting from dispersed phthalate sources throughout the karst aquifers. Hydrogeological factors are significantly more important in predicting the presence and concentrations of phthalates in eogenetic karst aquifers than anthropogenic factors. Among the hydrogeological factors, time of detection and hydraulic conductivities larger than 300 m d-1 are the most influential factors. Persistent presence through time reflects continuous sources of phthalates entering the aquifers and a high capacity of the karst aquifers to store and slowly release contaminants for long periods of time. The influence of hydraulic conductivity reveals the importance of contaminant fate and transport mechanisms from contamination sources. This study improves the understanding of factors affecting the spatial variability and fate of phthalates in karst aquifers, and allows us to better predict their occurrence based on these factors.

BULK CHEMISTRY OF KARST SEDIMENT DEPOSITS.

Sediments are ubiquitous in karst systems and play a critical role in the fate and transport of contaminants. Sorbed contaminants may be stored on immobile sediments or rapidly dispersed on mobile sediments. Sediments may also influence remediation by either enhancing or interfering with the process. To better understand the potential effects of sediments on remediation, we conducted physical and chemical characterizations of 11 sediment samples from 7 cave and spring deposits from karst regions of Tennessee, Virginia, and West Virginia. The samples were analyzed for particle-size distribution using sieves and laser diffraction particle analysis. The sediment size fraction <2 mm (sand, silt, and clay) was analyzed for slurry pH and specific conductivity (SC) using electrodes and for bulk total carbon, organic carbon, nitrogen and sulfur on an ElementarTM Vario MAX Cube CNS. The same <2 mm fraction was subjected to a pseudo-total extraction using aqua regia with subsequent solution analysis by inductively coupled plasma-optical emission spectrometry (ICP-OES). Most of the samples were dominated by the <2 mm size fraction. Their slurry pHs ranged from 6.8 to 8.4 and their SCs ranged from 45 to 206 µS/cm with the exception of two high SC samples (726 and 8500 µS/cm). The fraction of organic carbon (Foc) in the sediments ranged from <0.1 to 2%. The sample from a saltpeter cave historically used for gunpowder production contained the highest concentrations of N and S (~3 g/kg) but lower total C than some of the spring samples. The pseudo-total extractions were analyzed for Al, Ca, Fe, Mg, and Mn. Of those elements, Mg was the most consistent across the locations (2.0-6.1 g/kg), and Ca was the most variable (1.4-52 g/kg). Given the importance of particle size and elemental concentrations in chemical reactions and remediation, more data of this type are needed to predict contaminant fate and transport and to plan successful remediation projects.

Hurricanes and the Environmental Justice Island: Irma and Maria in Puerto Rico.

This article presents an overview of our research team's disaster response to the massive destruction of Hurricanes, Irma and Maria, in September 2017, in light of the 120-year colonial legacy and long-term, widespread environmental contamination in Puerto Rico. Both local and federal governmental responses have been extremely inadequate, especially in light of the long-standing issues of environmental contamination throughout the island. Community organizations in Puerto Rico have been fighting for environmental justice for decades, often succeeding, and always confronting government unwillingness to address environmental protection. Hurricanes Irma and Maria afforded attention to Puerto Rico through international news coverage and awareness of its colonial status, rundown infrastructures (especially the electric grid), indebtedness, and environmental hazards. Since the hurricanes, the research teams of the Puerto Rico Test Site to Explore Contamination Threats (PROTECT), the Center for Research on Early Childhood Exposure and Development (CRECE), and Zika in Infants and Pregnancy (ZIP) have worked tirelessly to address the needs of our research participants, partnering clinics, as well as the local team to ensure safety and wellness. We have been able to continue our environmental public health work with pregnant women and children. In response to the historical problems and current crisis, we offer a "visionary rebuilding" approach for remediation of the hurricanes' effects, and for a deeper solution to the environmental and other social injustices Puerto Rico has long faced.

Improved regional groundwater flow modeling using drainage features: a case study of the central northern karst aquifer system of Puerto Rico (USA).

In northern Puerto Rico (USA), subsurface conduit networks with unknown characteristics, and surface features such as springs, rivers, lagoons and wetlands, drain the coastal karst aquifers. In this study, drain lines connecting sinkholes and springs are used to improve the developed regional model by simulating the drainage effects of conduit networks. Implemented in an equivalent porous media (EPM) approach, the model with drains is able to roughly reproduce the spring discharge hydrographs in response to rainfall. Hydraulic conductivities are found to be scale dependent and significantly increase with higher test radius, indicating scale dependency of the EPM approach. Similar to other karst regions in the world, hydraulic gradients are steeper where the transmissivity is lower approaching the coastline. This study enhances current understanding of the complex flow patterns in karst aquifers and suggests that using a drainage feature improves modeling results where available data on conduit characteristics are minimal.

Patterns of temporal scaling of groundwater level fluctuation.

We studied the fractal scaling behavior of groundwater level fluctuation for various types of aquifers in Puerto Rico using the methods of (1) detrended fluctuation analysis (DFA) to examine the monofractality and (2) wavelet transform maximum modulus (WTMM) to analyze the multifractality. The DFA results show that fractals exist in groundwater fluctuations of all the aquifers with scaling patterns that are anti-persistent (1 < ß < 1.5; 1.32 ± 0.12, 18 wells) or persistent (ß > 1.5; 1.62 ± 0.07, 4 wells). The multi-fractal analysis confirmed the need to characterize these highly complex processes with multifractality, which originated from the stochastic distribution of the irregularly-shaped fluctuations. The singularity spectra of the fluctuation processes in each well were site specific. We found a general elevational effect with smaller fractal scaling coefficients in the shallower wells, except for the Northern Karst Aquifer Upper System. High spatial variability of fractal scaling of groundwater level fluctuations in the karst aquifer is due to the coupled effects of anthropogenic perturbations, precipitation, elevation and particularly the high heterogeneous hydrogeological conditions.

Urinary phthalate metabolite concentrations among pregnant women in Northern Puerto Rico: distribution, temporal variability, and predictors.

BACKGROUND: Phthalate contamination exists in the North Coast karst aquifer system in Puerto Rico. In light of potential health impacts associated with phthalate exposure, targeted action for elimination of exposure sources may be warranted, especially for sensitive populations such as pregnant women. However, information on exposure to phthalates from a variety of sources in Puerto Rico is lacking. The objective of this study was to determine concentrations and predictors of urinary phthalate biomarkers measured at multiple times during pregnancy among women living in the Northern karst area of Puerto Rico. METHODS: We recruited 139 pregnant women in Northern Puerto Rico and collected urine samples and questionnaire data at three separate visits (18 ± 2 weeks, 22 ± 2 weeks, and 26 ± 2 weeks of gestation). Urine samples were analyzed for eleven phthalate metabolites: mono-2-ethylhexyl phthalate (MEHP), mono-2-ethyl-5-hydroxyhexyl phthalate, mono-2-ethyl-5-oxohexyl phthalate, mono-2-ethyl-5-carboxypentyl phthalate, mono-ethyl phthalate (MEP), mono-n-butyl phthalate, mono-benzyl phthalate, mono-isobutyl phthalate, mono-3-carboxypropyl phthalate (MCPP), mono carboxyisononyl phthalate (MCNP), and mono carboxyisooctyl phthalate (MCOP). RESULTS: Detectable concentrations of phthalate metabolites among pregnant women living in Puerto Rico was prevalent, and metabolite concentrations tended to be higher than or similar to those measured in women of reproductive age from the general US population. Intraclass correlation coefficients ranged from very weak (MCNP; 0.05) to moderate (MEP; 0.44) reproducibility among all phthalate metabolites. We observed significant or suggestive positive associations between urinary phthalate metabolite concentrations and water usage/storage habits (MEP, MCNP, MCOP), use of personal care products (MEP), and consumption of certain food items (MCPP, MCNP, and MCOP). CONCLUSIONS: To our knowledge this is the first study to report concentrations, temporal variability, and predictors of phthalate biomarkers among pregnant women in Puerto Rico. Preliminary results suggest several potentially important exposure sources to phthalates in this population and future analysis from this ongoing prospective cohort will help to inform targeted approaches to reduce exposure.