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.

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.

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.

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.

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.

Up in the air: Polyfluoroalkyl phosphate esters (PAPs) in airborne dust captured by air conditioning (AC) filters.

Per- and polyfluoroalkyl substances (PFAS) are ubiquitously present in our indoor living environments. Dust is thought to accumulate PFAS released indoors and serve as an exposure pathway for humans. Here, we investigated whether spent air conditioning (AC) filters can be exploited as opportunistic samplers of airborne dust for assessing PFAS burden in indoor environments. Used AC filters from campus facilities (n = 19) and homes (n = 11) were analyzed for 92 PFAS via targeted ultra-high pressure liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS). While 27 PFAS were measured (in at least one filter), the predominant species were polyfluorinated dialkylated phosphate esters (diPAPs), with the sum of 6:2-, 8:2-, and 6:2/8:2diPAPs accounting for approximately 95 and 98 percent of ∑27PFAS in campus and household filters, respectively. Exploratory screening of a subset of the filters revealed the presence of additional species of mono-, di-, and tri-PAPs. Considering the constant human exposure to dust indoors and the potential of PAPs to degrade into terminal species with well-established toxicological risks, assessing dust for these precursor PFAS warrants further investigation with respect to both human health and PFAS loading to landfills from this under studied waste stream.

Assessment of per- and polyfluoroalkyl substances (PFAS) in the Indian River Lagoon and Atlantic coast of Brevard County, FL, reveals distinct spatial clusters.

Per- and polyfluoroalkyl substances (PFAS) constitute a class of highly stable and extensively manufactured anthropogenic chemicals that have been linked to a variety of adverse health effects in humans and wildlife. These compounds are ubiquitously distributed in the environment and have been measured in aquatic systems globally. However, there are limited data on longitudinal comprehensive assessments of PFAS profiles within sensitive aquatic ecosystems. Surface water samples were collected from the Indian River Lagoon (IRL) and the Atlantic coast within Brevard County (BC), FL in December of 2019 (n = 57) and again from corresponding locations in February of 2021 (n = 40). Samples were analyzed by ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) to determine the occurrence, concentration, and distribution of 92 PFAS. No significant difference in total PFAS concentrations were identified between samples collected in 2019 (87 ng/L) and those collected in 2021 (77 ng/L). However, comparisons of PFAS among four natural sub-regions within Brevard County revealed site- and regional-specific differences. The Banana River exhibited the greatest concentration of total PFAS, followed by the southern Indian River, the northern Indian River, and then the Atlantic coast. Six distinct PFAS profiles were identified with the novel application of multivariate statistical cluster analysis, which may be useful for identifying potential sources of PFAS. Elevated total PFAS and unique compound mixtures identified in the Banana River are most likely a result of industrial discharge and extensive historical use of aqueous film-forming foams (AFFF). The environmental persistence of PFAS threatens key ecosystem services and the ecological homeostasis of the Indian River Lagoon - the most biologically diverse estuary in North America. Brevard County offers a unique model site that may be used to investigate potential exposure and health implications for wildlife and adjacent coastal communities, which could be extrapolated to better understand and manage other critical coastal systems.

Ticks as novel sentinels to monitor environmental levels of per- and polyfluoroalkyl substances (PFAS).

Per- and polyfluoroalkyl substances (PFAS) are environmentally persistent, ubiquitous pollutants. It is important to continuously monitor the presence of PFAS contamination, utilizing both legacy and new sentinels. In this study, environmental PFAS levels were evaluated using ticks as a sentinel model due to their world-wide distribution, hematophagous nature, and ease of collection and sampling. Hematophagy in discrete blood meals, from a suite of vertebrates, allows ticks to sample dozens of species of consumers and bioaccumulation across communities. Four different species of ticks, across two states (NY, n = 28 in mid-April of 2020 and FL, n = 32 between 2015 and 2020) with two sampling sites in each state were analyzed for the presence of 53 PFAS. The total PFAS concentration in ticks was the lowest at Newburgh (NY), a site that has been undergoing remediation efforts, while the highest total PFAS concentrations were measured in ticks at the Sweetwater site, a wastewater treatment wetland. Detection of PFAS and the potential for variation between tick species and between locations are necessary to establish the utility of ticks as sentinels, in addition to assessing additional environmental factors, such as other wildlife, water, or soil.

Metabolomic Profiling of Biological Reference Materials using a Multiplatform High-Resolution Mass Spectrometric Approach.

The number of metabolomics studies have increased dramatically in recent years, spanning from basic/mechanistic research to the identification and validation of clinical biomarkers. Developments in analyte separation techniques and the growth of databases are largely responsible for the rapid growth of metabolomics, although broad differences in analytical workflows can result in difficulty when comparing data across studies. The establishment of baseline metabolomics data for human reference materials using complementary/orthogonal data acquisition strategies can help to alleviate some of these challenges. To this end, we report nontargeted semiquantitative metabolomics data for 22 commercially available materials including plasma (healthy, diabetic, hypertriglyceridemic, African-American), serum (female, male, pregnant, among others), feces (meconium, vegan, omnivore), urine (smokers' and nonsmokers'), breast milk, saliva, and vaginal fluid, using ultrahigh-performance liquid chromatography-tandem mass spectrometry in positive and negative electrospray ionization, as well as gas chromatography-electron ionization-mass spectrometry. Significant differences were observed in the metabolomic fingerprints between all sample types. Post hoc comparisons between relevant sample types support the relevance of these materials and the validity of nontargeted strategies in global metabolomics. As the number and variety of reference materials continues to increase, it is imperative that their adoption is matched. The results of this study may inform future biomedical research by highlighting several metabolites across matrixes and treatments/states that could serve as clinical biomarkers or important biochemical pathway intermediates. Furthermore, our work can serve as a metric for systems suitability, quality assurance, and quality control across the community via the dissemination of high-quality and publicly available annotated metabolomics data.

Evaluation of Different Extraction Methods for the Analysis of Per- and Polyfluoroalkyl Substances in Dried Blood Spots from the Florida Manatee (Trichechus manatus).

Per- and polyfluoroalkyl substances (PFAS) are environmental contaminants linked to adverse health effects in humans and wildlife. Marine mammals, particularly manatees, have shown potential as sentinels for evaluating the presence and effects of anthropogenic chemicals. However, traditional blood collection techniques with marine mammals can be challenging, highlighting the need for improved strategies. In the present study, four different methods for the extraction of PFAS from dried blood spots were evaluated. Environ Toxicol Chem 2021;40:2726-2732. © 2021 SETAC.

Primary Thyroid Lymphoma: An Analysis of the National Cancer Database.

Introduction Primary thyroid lymphoma (PTL) is a rare malignancy, representing only 1% to 5% of thyroid malignancies and 2.5% to 7% of all extranodal lymphomas. Most cases of PTL are of B-cell origin, and 98% of all PTL cases are non-Hodgkin's lymphoma. Case series and case reports represent the majority of the available studies on PTL, with a paucity of large retrospective population studies available for this disease. This is the first National Cancer Database (NCDB) study completed on PTL and the only large retrospective study to examine the use of chemotherapy and immunotherapy in the treatment of this specific population. Methods The NCDB for non-Hodgkin's lymphoma was utilized to identify 3,466 patients diagnosed with PTL between 2004 and 2015. The database was used to examine demographic information including age, race, gender, histology, stage, and treatment modality. Bivariate Kaplan-Meier analysis with log-rank tests was used to analyze overall survival. Multivariate analysis was performed with Cox proportional hazards regression models to obtain hazard ratios to assess the association of patient characteristics and treatment methods with survival. Results The median all-cause survival for PTL was 11.6 years (95% confidence interval [CI]: 11.1 to 12.1 years). The majority of PTL patients were female (68%) and white (93%), with a mean age of 65.8 years. Histologically, 59.5% of cases were diffuse large B-cell lymphoma (DLBCL), 18.3% marginal zone lymphoma, 8% follicular lymphoma, and 1.9% Burkitt lymphoma. Regarding treatment, 40.6% received beam radiation, and 54% underwent surgical resection. Single-agent chemotherapy was used in only 3.5% of patients, where 60.7% received multiagent chemotherapy. Additionally, immunotherapy was used in 16.2% of patients. There was a significantly increased risk of mortality associated with increasing age, DLBCL histology, and higher disease stage. Multivariate analysis of treatment methods revealed that lobectomy (hazard ratio [HR]: 0.58, 95% CI: 0.47-0.73) and total or subtotal thyroidectomy (HR: 0.58, 95% CI: 0.47-0.71) had significantly improved survival rates over no surgical management (p < 0.001). Beam radiation (HR 0.67, 95% CI: 0.58-0.79) had a significant survival benefit over treatment regimens that did not include radiation therapy (p < 0.001). Multiagent (HR: 0.40, 95% CI: 0.33-0.49) and single-agent chemotherapy (HR: 0.43, 95% CI: 0.30-0.63) had significant improvement over treatment regimens that did not include chemotherapy (p < 0.001). Immunotherapy had a survival benefit (HR 0.87) although this was not found to be statistically significant (95% CI: 0.68-1.11). Other factors associated with decreased risk of mortality include treatment at academic medical centers (HR: 0.846) and integrated cancer centers (HR: 0.76) as compared to community centers (p < 0.05). Conclusion This is the largest study to date of PTL and the first to analyze the NCDB database. Patient characteristics, treatment modalities, and overall survival in PTL were examined to further characterize this rare disease. Beam radiation, chemotherapy, and surgical resection all reveal significant survival benefit, with multiagent chemotherapy having the greatest advantage.