Assessment of Phthalate Esters and Physiological Biomarkers in Bottlenose Dolphins (Tursiops truncatus) and Killer Whales (Orcinus orca).

There is growing concern about the potential adverse health effects of phthalates (PAEs) on human health and the environment due to their extensive use as plasticizers and additives in commercial and consumer products. In this study, we assessed PAE concentrations in serum samples from aquarium-based delphinids (Tursiops truncatus, n = 36; Orcinus orca, n = 42) from California, Florida, and Texas, USA. To better understand the physiological effects of phthalates on delphinids, we also explored potential correlations between phthalates and the biomarkers aldosterone, cortisol, corticosterone, hydrogen peroxide, and malondialdehyde while accounting for sex, age, and reproductive stage. All PAEs were detected in at least one of the individuals. ΣPAE ranges were 5.995-2743 ng·mL-1 in bottlenose dolphins and 5.372-88,675 ng·mL-1 in killer whales. Both species displayed higher mean concentrations of DEP and DEHP. PAEs were detected in newborn delphinids, indicating transference via placenta and/or lactation. Linear mixed model results indicated significant correlations between aldosterone, month, location, status, and ΣPAEs in killer whales, suggesting that aldosterone concentrations are likely affected by the cumulative effects of these variables. This study expands on the knowledge of delphinid physiological responses to PAEs and may influence management and conservation decisions on contamination discharge regulations near these species.

Assessment of per- and polyfluoroalkyl substances in Biscayne Bay surface waters and tap waters from South Florida.

Per- and polyfluoroalkyl substances (PFAS) are persistent anthropogenic pollutants present in many environmental media worldwide due to their extensive uses in many industrial and commercial products combined with their high thermal and chemical stabilities. Its ubiquitous presence in surface and drinking water supply and significant adverse health effects observed in wildlife and humans, associated with its bioaccumulation potential, pose big concerns. In this study, we have developed and validated a semi-automated solid phase extraction (SPE) followed by liquid chromatography-mass spectrometry (LC-MS/MS) for the determination of legacy and emerging short-chain PFAS substitutes in surface and tap water at low parts-per-trillion (ppt) levels in South Florida environments. Surface waters from Biscayne Bay and adjacent canals (n = 15) and tap waters from different counties (Miami-Dade, Broward, and Palm Beach County) (n = 21) were collected between October 2020 (wet season) and February 2021 (dry season). Total PFAS concentrations up to 242 ng L-1 (average of 168 ng L-1) were found in tap water from Grapeland Heights, which is the closest location to the Miami international airport that was sampled. The highest average total PFAS level of 106 ng L-1 was observed in surface water from the Biscayne Canal C-8 for the wet and dry season. In general, average total PFAS was higher in tap water (86.3 ng L-1) than in surface waters (46.3 ng L-1), whereas the most predominant and frequently detected PFAS were PFBA, PFBS, PFPeA, PFHxA, PFHxS, PFOA and PFOS. PFAS levels found could represent a high human health risk, and ecological risk based on PFOS levels above recommended thresholds are also noted. Such knowledge on PFAS occurrence, distribution and sources in South Florida will provide essential information for local and regional regulatory agencies related to water quality, further facilitating the development of guidelines and procedures for PFAS pollution control and reduction in Florida.

Assessment of Sucralose, Caffeine and Acetaminophen as Anthropogenic Tracers in Aquatic Systems Across Florida.

Sucralose is one of the most popular artificial sweeteners worldwide. Due to its high stability, persistence and low removal efficiency in wastewater treatment plants, sucralose has been used as an indicator of wastewater intrusion into aquatic systems. However, its stability has also been a reason for discussion whether sucralose's presence in surface water could indicate a recent anthropogenic input. Caffeine and acetaminophen have been considered as tracers in human impacted aquatic ecosystems and potentially good indicators of recent anthropogenic inputs into the environment due to their short half-lives in water. Here, a novel, high throughput and sensitive method based on online SPE-LC-HRMS for the determination of caffeine, sucralose and acetaminophen was developed and validated for both fresh and seawater samples and applied to environmental water samples to evaluate the efficiency of these compounds as tracers of aquatic pollution. Caffeine and sucralose were detected in > 70% of samples, while acetaminophen was only detected in 3% of samples above the MDL, demonstrating its limited environmental applicability.

An assessment of PCB and PBDE contamination in two tropical dolphin species from the Southeastern Brazilian coast.

PCBs and PBDEs were determined in two dolphin species, Sotalia guianensis and Steno bredanensis, from an upwelling system off the Central-northern coast of Rio de Janeiro, Brazil. PCB levels varied from 0.040 to 0.75 µg g(-1) lw in muscles and from 0.022 to 1.32 µg g(-1)lw in liver samples from S. guianensis. In S. bredanensis, values varied from 0.085 to 11.3 µg g(-1) lw in muscles and from 0.024 to 18.6 µg g(-1) lw in livers. PCB-138, -153 and -180 were the major PCB congeners detected in both species, while BDE-47 was the predominant PBDE congener found in both species. Higher concentrations in S. bredanensis were possibly related to the different feeding habits for both delphinid species. These results contribute to extend the database on organic contamination in cetaceans from the southern hemisphere, understanding their distribution and environmental fate in Southeastern Brazil.

Fast determination of hydroxylated polychlorinated biphenyls in human plasma by online solid phase extraction coupled to liquid chromatography-tandem mass spectrometry.

Hydroxylated polychlorinated biphenyls (OH-PCBs) have been shown to be strongly retained in human blood causing endocrine-related toxicity, particularly on the thyroid system. Traditionally, analytical methods for the determination of OH-PCBs require labor-intensive and long-time consuming sample preparation with several extraction, evaporation and cleanup procedures steps and, in some cases, derivatization prior to the analysis by gas or liquid chromatography-mass spectrometry (GC-MS or LC-MS). The present study developed and validated a novel, sensitive and high throughput online solid phase extraction (SPE) method coupled to LC-tandem mass spectrometry (MS/MS) for the separation and quantitation of relevant congeners of OH-PCBs in human plasma. The developed method presented limits of quantification (LOQ) ranging from 0.02 to 0.5 ng mL(-1) and extraction recoveries from 71 to 134% for all congeners, requiring small amount of sample (only 100 µL) and minimal sample preparation. In order to evaluate the applicability of the method, preliminary tests (N = 93) were conducted in plasma from individuals occupationally exposed to very high levels of PCBs in a German cohort. Penta-through hepta-chlorinated OH-PCBs were the predominant congeners in human plasma with concentrations up to 44.5 ng mL(-1), while lower chlorinated OH-PCBs were occasionally detected. In addition, a new PCB 28 metabolite has been synthesized and identified for the first time in human plasma and associations between OH-PCBs and their parent compounds in the studied cohort were also assessed.

Occurrence and distribution of endosulfan in water, sediment, and fish tissue: an ecological assessment of protected lands in south Florida.

Over the past 30 years, endosulfan, one of the last polychlorinated pesticides still in use, has received considerable attention and has been the subject of a number of international regulations and restriction action plans worldwide. This study aimed to monitor the presence and to assess the potential transport of endosulfan within the protected areas of Everglades National Park, Biscayne National Park, and Big Cypress National Preserve, South Florida, USA. Endosulfan sulfate was the major metabolite detected in all matrices in areas along the C-111 and C-111E canals, which drain the Homestead agricultural area and discharge to either Florida or Biscayne Bays, both of which are critical wildlife habitats. Endosulfan concentrations of up to 158 ng L(-1) and 57 ng g(-1) were observed in surface water and sediments, respectively, which exceeded the U.S. EPA's chronic water quality criteria (56 ng L(-1)). Elevated levels of up to 371 ng g(-1) of endosulfan sulfate were detected in whole fish tissue.

Assessment of organochlorine pesticide residues in Atlantic Rain Forest fragments, Rio de Janeiro, Brazil.

A superficial water quality survey in a watershed of the Paraíba do Sul River, the main water supply for the most populated cities of southeastern Brazil, was held in order to assess the impact of the expansion of agricultural activity in the near border of the Atlantic Rain Forest. The aim of this study was to investigate the presence of priority organochlorine pollutants in soils and superficial waters of Atlantic rainforest fragments in Teresópolis, Rio de Janeiro State. Soil sample preparations were compared by using ultrasound, microwave assisted extraction and Soxhlet extraction. Recoveries of matrix spiked samples ranged from 70 to 130%. Analysis of a certified soil material showed recoveries ranging from 71 to 234%. Although low concentrations of organochlorine residues were found in water and soil samples, this area is of environmental importance and concern, thus demanding a monitoring program of its compartments.