High-Resolution Mass Spectrometry for Human Exposomics: Expanding Chemical Space Coverage.

In the modern "omics" era, measurement of the human exposome is a critical missing link between genetic drivers and disease outcomes. High-resolution mass spectrometry (HRMS), routinely used in proteomics and metabolomics, has emerged as a leading technology to broadly profile chemical exposure agents and related biomolecules for accurate mass measurement, high sensitivity, rapid data acquisition, and increased resolution of chemical space. Non-targeted approaches are increasingly accessible, supporting a shift from conventional hypothesis-driven, quantitation-centric targeted analyses toward data-driven, hypothesis-generating chemical exposome-wide profiling. However, HRMS-based exposomics encounters unique challenges. New analytical and computational infrastructures are needed to expand the analysis coverage through streamlined, scalable, and harmonized workflows and data pipelines that permit longitudinal chemical exposome tracking, retrospective validation, and multi-omics integration for meaningful health-oriented inferences. In this article, we survey the literature on state-of-the-art HRMS-based technologies, review current analytical workflows and informatic pipelines, and provide an up-to-date reference on exposomic approaches for chemists, toxicologists, epidemiologists, care providers, and stakeholders in health sciences and medicine. We propose efforts to benchmark fit-for-purpose platforms for expanding coverage of chemical space, including gas/liquid chromatography-HRMS (GC-HRMS and LC-HRMS), and discuss opportunities, challenges, and strategies to advance the burgeoning field of the exposome.

Investigating the partitioning behavior of per- and polyfluoroalkyl substances (PFAS) during thermal landfill leachate evaporation.

Thermal landfill leachate evaporator systems can reduce the volume of leachate by up to 97%, while releasing water vapor and producing residuals (volume-reduced leachate and sludge) that are managed on-site. On-site thermal evaporators offer landfill operators leachate management autonomy without being subject to increasingly stringent wastewater treatment plant requirements. However, little is known about the partitioning of PFAS within these systems, nor the extent to which PFAS may be emitted into the environment via vapor. In this study, feed leachate, residual evaporated leachate, sludge, and condensed vapor were sampled at two active full-scale thermal landfill leachate evaporators and from a laboratory-scale leachate evaporation experiment. Samples were analyzed for 91 PFAS via ultra-high pressure liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS). Similar trends were observed from Evaporator 1, Evaporator 2, and the laboratory-scale evaporator; ∑PFAS were concentrated in the residual evaporated leachate during evaporation by a factor of 5.3 to 20. All condensed vapors sampled (n = 5) contained PFAS, predominantly 5:3 fluorotelomer carboxylic acid (5:3FTCA), (full-scale vapors 729 - 4087 ng/L PFAS; lab-scale vapor 61.0 ng/L PFAS). For Evaporators 1 and 2, an estimated 9 - 24% and 10%, respectively, of the PFAS mass entering the evaporators in leachate was released with vapor during the days of sample collection. '.

Per- and polyfluoroalkyl substances (PFAS) in construction and demolition debris (CDD): discerning sources and fate during waste management.

As regulatory frameworks for per- and polyfluoroalkyl substances (PFAS) evolve, the solid waste community seeks to manage PFAS risks effectively. Despite extensive research on PFAS in municipal solid waste (MSW) and wastewater sludge, there is limited information on a major global waste stream which seldom gleans regulatory oversight - construction and demolition debris (CDD). This study sampled a CDD processing facility to provide material-specific information on the PFAS profile within CDD. The bulk CDD accepted by this facility was separated into major categories, representatively sampled, then characterized for total available PFAS (∑92PFAS). As reprocessed CDD is ultimately recycled or landfilled, often unencapsulated or in unlined landfills, the PFAS leaching potential was also examined using two leaching procedures. Among the categories assessed for total PFAS, carpeting, carpet padding, and gypsum drywall showed elevated concentrations compared to other components, with most of the PFAS mass contributed by precursor species. However, materials with the highest total PFAS, such as carpeting, did not necessarily exhibit the highest leaching, and leachate was predominantly composed of terminal species rather than precursors. Extrapolating these findings with national CDD generation and management data inventories suggests that despite MSW having higher total available PFAS concentrations, the leachability of PFAS from landfilled CDD is comparable, raising legitimate concerns with CDD disposal practices, particularly in unlined CDD landfills.

Identification and quantification of novel per- and polyfluoroalkyl substances (PFAS) contamination in a Great Lakes urban-dominated watershed.

Per- and polyfluoroalkyl substances (PFAS) are a large group of synthetic organic fluoro-compounds that are oil-, water-, and flame-resistant, making them useful in a wide range of commercial and consumer products, as well as resistant to environmental degradation. To assess the impact of urbanization and wastewater treatment processes, surface water and sediment samples were collected at 27 sites within the Great Lakes in the Lake Huron to Lake Erie corridor (HEC), an international waterway including the highly urbanized Detroit and Rouge Rivers. Samples were analyzed for 92 PFAS via UHPLC-MS/MS. Our previous data in the HEC found the highest amount of PFAS contamination at the Rouge River mouth. In addition to evaluating the input of the Rouge River into the HEC, we evaluated the transport of PFAS into the HEC from other major tributaries. PFAS were detected in both surface water and sediment at all sites in this study, with a total of 10 congeners quantified in all surface water samples and 16 congeners quantified in all sediment samples, indicating ubiquitous contamination. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were pervasive in the HEC as these two compounds were detected in all sites and matrices, often at concentrations above the US EPA's recommended lifetime interim updated health advisories. Surface water samples contained more perfluorohexanoic acid (PFHxA) than any other congener, with average aqueous PFHxA across all surface water samples exceeding the average concentration previously reported in the Great Lakes. Sediment samples were dominated by PFOS, but novel congeners, notably 3-Perfluoropentyl propanoic acid (FPePA), were also quantified in sediment. The Rouge River and other tributaries contribute significantly to the PFAS burden in the HEC including Lake Erie. Overall, our results indicate the need for expanding toxicological research and risk assessment focused on congeners such as PFHxA and PFAS mixtures, as well as regulation that is tighter at the onset of production and encompasses PFAS as a group at a national level.

Investigating the sources and fate of per- and polyfluoroalkyl substances (PFAS) in food waste compost.

Composting municipal food waste is a key strategy for beneficially reusing methane-producing waste that would otherwise occupy landfill space. However, land-applied compost can cycle per- and polyfluoroalkyl substances (PFAS) back into the food supply and the environment. We partnered with a pilot-scale windrow composting facility to investigate the sources and fate of 40 PFAS in food waste compost. A comparison of feedstock materials yielded concentrations of ∑PFAS under 1 ng g-1 in mulch and food waste and at 1380 ng g-1 in leachate from used compostable food contact materials. Concentrations of targeted ∑PFAS increased with compost maturity along the windrow (1.85-23.1 ng g-1) and in mature stockpiles of increasing curing age (12.6-84.3 ng g-1). Among 15 PFAS quantified in compost, short-chain perfluorocarboxylic acids (PFCAs) - C5 and C6 PFCAs in particular - led the increasing trend, suggesting biotransformation of precursor PFAS into these terminal PFAS through aerobic decomposition. Several precursor PFAS were also measured, including fluorotelomer carboxylic acids (FTCAs) and polyfluorinated phosphate diesters (PAPs). However, since most targeted analytical methods and proposed regulations prioritize terminal PFAS, testing fully matured compost would provide the most relevant snapshot of PFAS that could be land applied. In addition, removing co-disposed food contact materials from the FW feedstock onsite yielded only a 37 % reduction of PFAS loads in subsequent compost, likely due to PFAS leaching during co-disposal. Source-separation of food contact materials is currently the best management practice for meaningful reduction of PFAS in food waste composts intended for land application.

Assessing the suitability of leachability-based screening levels for per- and polyfluoroalkyl substances (PFAS) risk assessment.

In recent years, soil screening levels have been adopted by regulatory agencies for certain per- and polyfluoroalkyl substances (PFAS) to assess the risk of groundwater contamination through leaching. These soil screening levels, determined using an established equilibrium-based partitioning equation, have high variability among regulatory groups largely attributed to the diverse reported partitioning coefficients in the literature. This variability between reported partitioning coefficients, and subsequently soil screening levels, is due to the complex leaching behavior of PFAS not being predicted well by the standard equilibrium-based model. This has led one regulatory group to require batch leaching to assess risk rather than setting default soil screening levels based on partitioning equations. In this work, we conducted leaching experiments on five field-sampled soils impacted by aqueous film-forming foams (AFFF), following Leaching Environmental Assessment Framework (LEAF) Method 1316 and compared the results to expected leaching utilizing an equilibrium-based partitioning equation commonly employed by regulatory agencies to establish soil screening levels. Our analysis found among the six PFAS detected in the soils, which have regulatory leaching thresholds established, the partitioning values assumed by the U.S. EPA exhibited the highest accuracy in predicting leachate concentrations. These partitioning values predicted actual leaching within a ± 20 % margin of error for approximately 50 % of sample points, highlighting limitations in relying solely on equilibrium-based partitioning values as predictors of leaching behavior. This discrepancy between predicted and actual leaching has implications for site managers and regulatory entities overseeing PFAS-contaminated sites, suggesting that soil screening level determinations for PFAS might need to be revised to account for the unique transport characteristics of PFAS.

Lipidomics and plasma hormone analysis differentiate reproductive and pregnancy statuses in Florida manatees (Trichechus manatus latirostris).

Florida manatees (Trichechus manatus latirostris) are protected as a threatened species, and data are lacking regarding their reproductive physiology. This study aimed to (1) quantify plasma steroid hormones in Florida manatees from two field sites, Crystal River and Indian River Lagoon, at different gestational stages and to (2) identify individual lipids associated with pregnancy status. Ultra-high performance liquid chromatography-tandem mass spectrometric analysis was used to measure plasma steroid hormones and lipids. Pregnant female manatees were morphometrically distinct from male and non-pregnant female manatees, characterized by larger body weight and maximal girth. Progesterone concentrations in manatees were also elevated during early gestation versus late gestation. Cholesterol, an important metabolic lipid, and precursor for reproductive steroids, was not different between groups. Mass spectrometry quantified 949 lipids. Plasma concentrations of glycerophospholipids, glycerolipids, sphingolipids, acylcarnitines, and cholesteryl esters were associated with pregnancy status in the Florida manatee. Most of the lipid species associated with pregnancy were triacylglycerides, phosphatidylethanolamines, and ether-linked phosphatidylethanolamines, which may serve as energy sources for fetal development. This research contributes to improving knowledge of manatee reproductive physiology by providing data on plasma steroid hormones relative to reproductive status and by identifying plasma lipids that may be important for pregnancy. Elucidation of lipid species directly associated with pregnancy has the potential to serve as a diagnostic approach to identify pregnant individuals in fresh and archived samples. These biochemical and morphometric indicators of reproductive status advance the understanding of manatee physiology.

Characterization of per- and polyfluoroalkyl substances (PFAS) and other constituents in MSW landfill leachate from Puerto Rico.

Elevated per- and polyfluoroalkyl substance (PFAS) concentrations have been reported in municipal solid waste (MSW) landfill leachate with higher levels in wet and warmer subtropical climates. Information about landfill leachate characteristics is much more limited in tropical climates. In this study, 20 landfill leachate samples were collected from three MSW landfills on the tropical island of Puerto Rico and results were compared against landfills nationally and within Florida, USA. The samples collected in Puerto Rico underwent physical-chemical analysis, as well as a quantitative analysis of 92 PFAS. Samples described in this study include discrete leachate types, such as leachate, gas condensate, and leachate which has undergone on-site treatment (e.g., RO treatment, phytoremediation, lagoons). A total of 51 PFAS were detected above quantitation limits, including perfluorohexylphosphonic acid, a perfluoroalkyl acid (PFAA) which has not been reported previously in landfill leachate. ∑PFAS concentrations in this study (mean: 38,000 ng L-1), as well as concentrations of individual PFAS, are significantly higher than other reported MSW landfill leachate concentrations. The profiles of leachates collected from on-site treatment systems indicate possible transformation of precursor PFAS as a result of treatment processes - oxidizing conditions, for example, may facilitate aerobic transformation, increase the concentrations of PFAAs, and possibly increase the apparent ∑PFAS concentration. Extreme climate events, including rising temperatures and more frequent hurricanes, have placed additional strain on the solid waste management infrastructure on the island - adding complexity to an already challenging PFAS management issue. As concern grows over PFAS contamination in drinking water, these findings should inform solid waste and leachate management decisions in order to minimize PFAS emissions in island environments.

Crowdsourcing citizens for statewide mapping of per- and polyfluoroalkyl substances (PFAS) in Florida drinking water.

Per- and polyfluoroalkyl substances (PFAS) are a class of persistent chemicals that have been associated with a diverse array of adverse environmental and human health related effects. In addition to a growing list of health concerns, PFAS are also ubiquitously used and pervasive in our natural and built environments, and they have an innate ability to be highly mobile once released into the environment with an unmatched ability to resist degradation. As such, PFAS have been detected in a wide variety of environmental matrices, including soil, water, and biota; however, the matrix that largely dictates human exposure to PFAS is drinking water, in large part due to their abundance in water sources and our reliance on drinking water. As Florida is heavily reliant upon water and its varying sources, the primary objective of this study was to survey the presence of PFAS in drinking water collected from taps from the state of Florida (United States). In this study, 448 drinking water samples were collected by networking with trained citizen scientists, with at least one sample collected from each of the 67 counties in Florida. Well water, tap water, and bottled water, all sourced from Florida, were extracted and analyzed (31 PFAS) using isotope dilution and ultra-high-performance liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS). Overall, when examining ∑PFAS: the minimum, maximum, median, and mean were ND, 219, 2.90, and 14.06 ng/L, respectively. The data herein allowed for a comparison of PFAS in drinking water geographically within the state of Florida, providing vital baseline concentrations for prospective monitoring and highlighting hotspots that require additional testing and mitigation. By incorporating citizen scientists into the study, we aimed to educate impacted communities regarding water quality issues and solutions.

Species-specific profiles of per- and polyfluoroalkyl substances (PFAS) in small coastal sharks along the South Atlantic Bight of the United States.

Per- and polyfluoroalkyl substances (PFAS) have gained widespread commercial use across the globe in various industrial and consumer products, such as textiles, firefighting foams, and surface coating materials. Studies have shown that PFAS exhibit a strong tendency to accumulate within aquatic food webs, primarily due to their high bioaccumulation potential and resistance to degradation. Despite such concerns, their impact on marine predators like sharks remains underexplored. This study aimed to investigate the presence of 34 PFAS in the plasma (n = 315) of four small coastal sharks inhabiting the South Atlantic Bight of the United States (U.S). Among the sharks studied, bonnetheads (Sphyrna tiburo) had the highest ∑PFAS concentration (3031 ± 1674 pg g - 1 plasma, n = 103), followed by the Atlantic sharpnose shark (Rhizoprionodon terraenovae, 2407 ± 969 pg g - 1, n = 101), blacknose shark (Carcharhinus acronotus, 1713 ± 662 pg g - 1, n = 83) and finetooth shark (Carcharhinus isodon, 1431 ± 891 pg g - 1, n = 28). Despite declines in the manufacturing of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), the long-chain (C8 - C13) perfluoroalkyl acids (PFAAs) were frequently detected, with PFOS, perfluorodecanoic acid (PFDA), and perfluorotridecanoic acid (PFTrDA) present as the most dominant PFAS. Furthermore, males exhibited significantly higher ∑PFAS concentrations than females in bonnetheads (p < 0.01), suggesting possible sex-specific PFAS accumulation or maternal offloading in some species. The results of this study underscore the urgency for more extensive biomonitoring of PFAS in aquatic/marine environments to obtain a comprehensive understanding of the impact and fate of these emerging pollutants on marine fauna.

Evaluation of per- and polyfluoroalkyl substances (PFAS) in landfill liquids from Pennsylvania, Colorado, and Wisconsin.

PER: and polyfluoroalkyl substances (PFAS) have been measured in aqueous components within landfills. To date, the majority of these studies have been conducted in Florida. This current study aimed to evaluate PFAS concentrations in aqueous components (leachate, gas condensate, stormwater, and groundwater) from four landfills located outside of Florida, in Pennsylvania, Colorado, and Wisconsin (2 landfills). The Pennsylvania landfill also provided the opportunity to assess a leachate treatment system. Sample analyses were consistent across studies including the measurements of 26 PFAS and physical-chemical parameters. For the four target landfills, average PFAS concentrations were 6,900, 22,000, 280, and 260 ng L-1 in the leachate, gas condensate, stormwater, and groundwater, respectively. These results were not significantly different than those observed for landfills in Florida except for the significantly higher PFAS concentrations in gas condensate compared to leachate. For on-site treatment at the Pennsylvania landfill, results suggest that the membrane biological bioreactor (MBBR) system performed similarly as aeration-based leachate treatment systems at Florida landfills resulting in no significant decreases in ∑26PFAS. Overall, results suggest a general consistency across US regions in PFAS concentrations within different landfill liquid types, with the few differences observed likely influenced by landfill design and local climate. Results confirm that leachate exposed to open air (e.g., in trenches or in treatment systems) have lower proportions of perfluoroalkyl acid precursors relative to leachate collected in enclosed pipe systems. Results also confirm that landfills without bottom liner systems may have relatively higher PFAS levels in adjacent groundwater and that landfills in wetter climates tend to have higher PFAS concentrations in leachate.

Evaluation of per- and polyfluoroalkyl substances (PFAS) released from two Florida landfills based on mass balance analyses.

Per- and polyfluoroalkyl substances (PFAS) have been found at high levels within landfill environments. To assess PFAS distributions, this study aimed to evaluate PFAS mass flux leached from disposed solid waste and within landfill reservoirs by mass balance analyses for two full-scale operational Florida landfills. PFAS mass flux in different aqueous components within landfills were estimated based on PFAS concentrations and water flow rates. For PFAS concentration, 26 PFAS, including 18 perfluoroalkyl acids (PFAAs) and 8 PFAA-precursors, were measured in samples collected from the landfills or estimated based on previous studies. Flow rates of aqueous components (rainfall, evapotranspiration, runoff, stormwater, groundwater, leakage, gas condensate, and leachate) were evaluated through the Hydrologic Evaluation of Landfill Performance model, water balance, and Darcy's Law. Results showed that the average PFAS mass flux leached from the solid waste standardized by area was estimated as 36.8 g/ha-yr, which was approximately 1 % to 3 % of the total amount of PFAS within the solid waste. The majority of PFAS leached from the solid waste (95 % to 97 %) is captured by the leachate collection system, with other aqueous components representing much smaller fractions (stormwater system at 3 % to 5 %, and gas condensate and groundwater at < 1 %). Also, based on the results, we estimate that PFAS releases will likely occur at least over 40 years. Overall, these results can help prioritize components for waste management and PFAS treatment during the anticipated landfill release periods.

Assessing construction and demolition wood-derived biochar for in-situ per- and polyfluoroalkyl substance (PFAS) removal from landfill leachate.

With regulations for per-and polyfluoroalkyl substances (PFAS) impending, the abundance of these chemicals of emerging concern in municipal solid waste (MSW) landfill leachate increasingly challenges landfill operators to seek on-site leachate pre-treatment options. This two-staged study explores the potential reuse of biochar derived from construction and demolition debris (CDD) wood as an in-situ PFAS sorbent for application within MSW landfill leachate collection systems. Batch leaching tests were first used to examine the feasibility of capturing PFAS from landfill leachate using two sources of CDD-wood-derived biochar. Then, columns were used to test the in-situ sorption capabilities of the same biochars under simulated landfill conditions. All leachates were characterized for pH, chemical oxygen demand, ammonia-nitrogen, and 92 PFAS. Seventeen PFAS were detected in the batch leaching experiment, and nine PFAS were detected in column leachates. In the batch leaching scenario, Biochar 1 achieved a maximum of 29% PFAS reduction compared to controls. Columns containing Biochar 1 generated leachates with PFAS concentrations 50% to 80% higher than those in control columns for the duration of the experiment. Columns containing Biochar 2 generated leachates with PFAS concentrations 44% less than controls in week 1 and similar concentrations in weeks 2, 3, and 4. In this study, PFAS removal from landfill leachate using biochar derived from CDD wood was not significant. Further research on biochar derived from CDD wood is needed before it can be recommended as an in-situ landfill leachate pre-treatment method.

Comparison of the PFAS and physical-chemical parameter fluctuations between an ash landfill and a MSW landfill.

Studies of per- and polyfluoroalkyl substances (PFAS) fluctuations at landfills have focused on municipal solid waste (MSW) leachate. Few studies exist that evaluate fluctuations (defined by the coefficient of variation, CV) in MSW incinerator ash (MSWA) landfill leachate and that evaluate PFAS fluctuations in stormwater, groundwater, and treated liquids on-site. In this study, aqueous landfill samples (leachate, treated leachate, stormwater, gas condensate, ambient groundwater, and effluent from a groundwater remediation system) were collected from a MSW and an MSWA landfill geographically located within close proximity (less than 40 km). The objective of this study was to compare the leachate compositions between these two landfill types and to evaluate temporal variations. Results indicated that the CV of total detected PFAS concentrations in leachate was higher for the MSW landfill (CV = 43 %) compared to the MSWA landfill (CV = 16 %). The total detected PFAS concentration in MSW leachate samples (mean: 9641 ng/L) was higher than in MSWA leachate samples (mean: 2621 ng/L) (p < 0.05). Within a landfill, PFAS concentrations were correlated (rs > 0.6, p < 0.05) with alkalinity, total organic carbon (TOC), and ammonia. Results from the on-site leachate treatment system at the MSW landfill indicated reductions in COD, TOC, and ammonia; however, the ∑26PFAS concentration increased 3 % after the treatment. Overall, results demonstrated that differences between landfill types and fluctuations in PFAS within landfills should be considered when designing landfill leachate collection and treatment systems to remove PFAS. The comparative analysis in this study can provide insights into optimizing leachate management for MSW and MSWA landfills.

Expanding Per- and Polyfluoroalkyl Substances Coverage in Nontargeted Analysis Using Data-Independent Analysis and IonDecon.

Per- and polyfluoroalkyl substances (PFAS) are widespread, persistent environmental contaminants that have been linked to various health issues. Comprehensive PFAS analysis often relies on ultra-high-performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC HRMS) and molecular fragmentation (MS/MS). However, the selection and fragmentation of ions for MS/MS analysis using data-dependent analysis results in only the topmost abundant ions being selected. To overcome these limitations, All Ions fragmentation (AIF) can be used alongside data-dependent analysis. In AIF, ions across the entire m/z range are simultaneously fragmented; hence, precursor-fragment relationships are lost, leading to a high false positive rate. We introduce IonDecon, which filters All Ions data to only those fragments correlating with precursor ions. This software can be used to deconvolute any All Ions files and generates an open source DDA formatted file, which can be used in any downstream nontargeted analysis workflow. In a neat solution, annotation of PFAS standards using IonDecon and All Ions had the exact same false positive rate as when using DDA; this suggests accurate annotation using All Ions and IonDecon. Furthermore, deconvoluted All Ions spectra retained the most abundant peaks also observed in DDA, while filtering out much of the artifact peaks. In complex samples, incorporating AIF and IonDecon into workflows can enhance the MS/MS coverage of PFAS (more than tripling the number of annotations in domestic sewage). Deconvolution in complex samples of All Ions data using IonDecon did retain some false fragments (fragments not observed when using ion selection, which were not isotopes or multimers), and therefore DDA and intelligent acquisition methods should still be acquired when possible alongside All Ions to decrease the false positive rate. Increased coverage of PFAS can inform on the development of regulations to address the entire PFAS problem, including both legacy and newly discovered PFAS.

Novel In Vitro Intestinal Microbiome Model to Study Lipidomic and Metabolomic Adaptations Due to Exposure to Glyphosate, Perfluorooctanoic Acid, and Docusate Sodium.

Cell and animal models have been used to provide insights with regard to physiological changes in intestinal flora due to exposure to drugs and environmental contaminants. Here, a novel in vitro model known as simulator of the human intestinal microbial ecosystem (SHIME) was used to assess the effects of three chemicals of emerging concern, namely glyphosate, perfluorooctanoic acid (PFOA), and docusate sodium (dioctyl sulfosuccinate, DOSS), on the lipidomic and metabolomic profiles of the gut microenvironment in both the proximal and distal colonic compartments. Nontargeted analyses by ultra-high performance liquid chromatography-tandem mass spectrometry and gas chromatography-electron ionization-mass spectrometry revealed minor differences in the lipidomic and metabolomic signatures of the proximal and distal colon following treatment with either glyphosate or PFOA at acceptable human daily intake levels or average daily exposures. However, global dysregulation of lipids and metabolites was observed due to DOSS treatment at conventional prescription doses when indicated as a stool softener. Our findings suggest that the current guidelines for glyphosate and PFOA exposure may be adequate at the level of the lower gut microbiome in healthy adults, but the probable yet uncharacterized off-target effects, safety, and efficacy of long-term DOSS treatment warrants further investigation. Indeed, we highlight the SHIME system as a novel in vitro approach which can be used as a screening tool to assess the impact of drugs and/or chemicals on the gut microbiome, while implementing state-of-the-art and data-driven mass spectrometric workflows to identify toxic lipidomic and metabolomic signatures.

PFAS surveillance in abiotic matrices within vital aquatic habitats throughout Florida.

Per- and polyfluoroalkyl substances (PFAS) are a group of manufactured chemicals that are resistant to degradation and thus persistent in the environment. The presence, uptake, and accumulation of PFAS is dependent upon the physiochemical properties of the PFAS and matrix, as well as the environmental conditions since the time of release. The objective of this study was to measure the extent of PFAS contamination in surface water and sediment from nine vulnerable aquatic systems throughout Florida. PFAS were detected at all sampling locations with sediment exhibiting greater PFAS concentrations when compared to surface water. At most locations, elevated concentrations of PFAS were identified around areas of increased human activity, such as airports, military bases, and wastewater effluents. The results from the present study highlight the ubiquitous presence of PFAS in vital Florida waterways and filled an important gap in understanding the distribution of PFAS in dynamic, yet vulnerable, aquatic environments.

Emerging polycyclic aromatic hydrocarbon (PAH) and trace metal leachability from reclaimed asphalt pavement (RAP).

The environmental risks associated with the storage, reuse, and disposal of unencapsulated reclaimed asphalt pavement (RAP) has been previously examined, but because of a lack of standardized column testing protocols and recent interest on emerging constituents with higher toxicity, questions surrounding leaching risks from RAP continue. To address these concerns, RAP from six, discrete stockpiles in Florida was collected and leach tested following the most up-to-date, standard column leaching protocol - United States Environmental Protection Agency (US EPA) Leaching Environmental Assessment Framework (LEAF) Method 1314. Sixteen EPA priority polycyclic aromatic hydrocarbons (PAHs), 23 emerging PAHs, identified through relevance in literature, and heavy metals were investigated. Column testing showed minimal leaching of PAHs; only eight compounds, three priority PAHs and five emerging PAHs, were released at quantifiable concentrations, and where applicable, were below US EPA Regional Screening Levels (RSL). Though emerging PAHs were identified more frequently, in most cases, priority compounds dominated contributions to overall PAH concentration and benzo(a)pyrene (BaP) equivalent toxicity. Except for arsenic, molybdenum, and vanadium in two samples, metals were found below limits of detection (LOD) or below risk thresholds. Arsenic and molybdenum concentrations diminished over time with increased exposure to liquid, but elevated vanadium concentrations persisted in one sample. Further batch testing linked vanadium to the aggregate component of the sample, unlikely to be encountered in typical RAP sources. As demonstrated by generally low constituent mobility observed during testing, the leaching risks associated with the beneficial reuse of RAP are limited, and under typical reuse conditions, factors of dilution and attenuation would likely reduce leached concentrations below relevant risk-based thresholds at a point of compliance. When considering emerging PAHs with higher toxicities, analyses indicated minimal impact to overall leachate toxicity, further suggesting that with proper management, this heavily recycled waste stream is unlikely to pose leaching risk.

Aquatic Vegetation, an Understudied Depot for PFAS.

Per- and polyfluoroalkyl substances (PFAS) are a class of manufactured chemicals that have been extensively utilized worldwide. We hypothesize that the presence, uptake, and accumulation of PFAS in aquatic vegetation (AV) is dependent upon several factors, such as the physiochemical properties of PFAS and proximity to potential sources. In this study, AV was collected from eight locations in Florida to investigate the PFAS presence, accumulation, and spatiotemporal distribution. PFAS were detected in AV at all sampling locations, with a range from 0.18 to 55 ng/g sum (∑)PFAS. Individual PFAS and their concentrations varied by sampling location, time, and AV species. A total of 12 PFAS were identified, with the greatest concentrations measured in macroalgae. The average bioconcentration factor (BCF) among all samples was 1225, indicating high PFAS accumulation in AV from surface water. The highest concentrations, across all AV types, were recorded in the Indian River Lagoon (IRL), a location with a history of elevated PFAS burdens. The present study represents the first investigation of PFAS in naturally existing estuarine AV, filling an important gap on PFAS partitioning within the environment, as well as providing insights into exposure pathways for aquatic herbivores. Examining the presence, fate, and transport of these persistent chemicals in Florida's waterways is critical for understanding their effect on environmental, wildlife, and human health.

Assessment of lipids and adrenal hormones in the Florida manatee (Trichechus manatus latirostris) from different habitats.

Florida manatees (Trichechus manatus latirostris), a federally protected species, are classified as threatened due to anthropogenic stressors. Manatees inhabit sites that are impacted by human activities that can negatively affect stress physiology and metabolism. Samples collected from healthy manatees (pregnant females, non-pregnant females, and males) at Crystal River and Indian River Lagoon in Florida, were assessed for adrenal hormones, proteins, glucose, and lipid content in plasma. The objective was to determine if healthy manatees sampled between 2010-2014 from the Indian River Lagoon exhibited evidence of stress compared to healthy manatees sampled between 2012-2019 from Crystal River. Plasma cortisol concentrations were not different in male and non-pregnant female manatees between sites but were elevated in pregnant manatees. Plasma aldosterone concentrations were elevated in Indian River Lagoon manatees relative to those at Crystal River, possibly due to differences in salinity and available freshwater between the two environments. Site differences were noted for plasma protein and glucose concentrations in manatees; additionally, differences between the sexes were also observed in glucose concentrations. Fifteen lipid subclasses, including oxidized lysophosphatidylcholines, oxidized phosphatidylcholines, oxidized triacylglycerols, were elevated in manatees from the Indian River Lagoon relative to manatees from Crystal River. Evidence of a stress response in healthy Indian River Lagoon manatees was lacking compared to Crystal River manatees. Differences in metabolites related to energy (glucose, protein, and lipids) may be related to site-specific variables, such as salinity and food availability/quality. This study generates novel data on plasma lipid profiles and provides cortisol, aldosterone, glucose, and protein values from healthy Florida manatees in two disparate sites that can be referenced in future studies. These data contribute to an improved understanding of manatee physiology to better inform population management.