Endosulfan is an insecticide-acaricide used in South Florida and is one of the remaining organochlorine insecticides registered under the Federal Insecticide Fungicide and Rodenticide Act by the U.S.EPA. The technical grade material consists of two isomers (alpha-, beta-) and the main environmental metabolite in water, sediment and tissue is endosulfan sulfate through oxidation. A comprehensive probabilistic aquatic ecological risk assessment was conducted to determine the potential risks of existing exposures to endosulfan and endosulfan sulfate in freshwaters of South Florida based on historical data (1992-2007). The assessment included hazard assessment (Tier 1) followed by probabilistic risk assessment (Tier 2). Tier 1 compared actual measured concentrations in surface freshwaters of 47 sites in South Florida from historical data to U.S.EPA numerical water quality criteria. Based on results of Tier 1, Tier 2 focused on the acute and chronic risks of endosulfan at nine sites by comparing distributions of surface water exposure concentrations of endosulfan [i.e., for total endosulfan (summation of concentrations of alpha- and beta-isomers plus the sulfate), alpha- plus beta-endosulfan, and endosulfan sulfate (alone)] with distributions of species effects from laboratory toxicity data. In Tier 2 the distribution of total endosulfan in fish tissue (whole body) from South Florida freshwaters was also used to determine the probability of exceeding a distribution of whole body residues of endosulfan producing mortality (critical lethal residues). Tier 1 showed the majority of endosulfan water quality violations in South Florida were at locations S-178 followed by S-177 in the C-111 system (southeastern boundary of Everglades National Park (ENP)). Nine surface water sampling sites were chosen for Tier 2. Tier 2 showed the highest potentially affected fraction of toxicity values (>10%) by the estimated 90th centile exposure concentration (total endosulfan) was at S-178. At all other freshwater sites there were <5% of the toxicity values exceeded. Potential chronic risk (9.2% for total endosulfan) was only found at S-178 and all other sites were <5%. Joint probability curves showed the higher probability of risk at S-178 than at S-177. The freshwater fish species which contain tissue concentrations of endosulfan (total) with the highest potential risk for lethal whole body tissue residues were marsh killifish, flagfish and mosquitofish. Based on existing surface water exposures and available aquatic toxicity data, there are potential risks of total endosulfan to freshwater organisms in South Florida. Although there are uncertainties, the presence of tissue concentrations of endosulfan in small demersal fish, is of ecological significance since these fish support higher trophic level species, such as wading birds.
Endosulfan sulfate is a persistent environmental metabolite of endosulfan, an organochlorine insecticide-acaricide presently registered by the United States Environmental Protection Agency. There is, however, limited acute fish toxicity data for endosulfan sulfate. This study determines the acute toxicity (LC₅₀s and LC₁₀s) of endosulfan sulfate to three inland Florida native fish species (mosquitofish [Gambusia affinis]; least killifish [Heterandria formosa]; and sailfin mollies [Poecilia latipinna]) as well as fathead minnows (Pimephales promelas). Ninety-six-h acute toxicity tests were conducted with each fish species under flow-through conditions. For all of the above-mentioned fish species, 96-h LC₅₀ estimates ranged from 2.1 to 3.5 μg/L endosulfan sulfate. The 96-h LC₁₀ estimates ranged from 0.8 to 2.1 μg/L endosulfan sulfate. Of all of the fish tested, the least killifish appeared to be the most sensitive to endosulfan sulfate exposure. The above-mentioned data were combined with previous acute toxicity data for endosulfan sulfate and freshwater fish for an effects analysis. The effects analysis estimated hazardous concentrations expected to exceed 5, 10, and 50% of the fish species' acute LC₅₀ or LC₁₀ values (HC₅, HC₁₀, and HC₅₀). The endosulfan sulfate freshwater-fish acute tests were also compared with the available freshwater-fish acute toxicity data for technical endosulfan. Technical endosulfan is a mixture of α- and β-endosulfan. The LC₅₀s had a wider range for technical endosulfan, and their distribution produced a lower HC₁₀ than for endosulfan sulfate. The number of freshwater-fish LC₅₀s for endosulfan sulfate is much smaller than the number available for technical endosulfan, reflecting priorities in examining the toxicity of the parent compounds of pesticides. The toxicity test results and effects analyses provided acute effect values for endosulfan sulfate and freshwater fish that might be applied in future screening level ecologic risk assessments. The effects analyses also discussed several deficiencies in conventional methods for setting water-quality criteria and determining ecologic effects from acute toxicity tests.
Endosulfan, the last remaining organochlorine pesticide, has been the subject of a number of international regulations and restriction/banning action plans worldwide. Occurrence of endosulfan residues in South Florida environments has been widely described in the literature for more than two decades. This work describes a selective, sensitive, and fast online solid-phase extraction (SPE) method coupled with liquid chromatography separation and tandem mass spectrometry (LC-MS/MS) for the determination of endosulfan isomers and endosulfan sulfate in water samples at low part per trillion levels with very little sample preparation. A negative atmospheric pressure chemical ionization source was carefully optimized to produce reproducible spectra of the target compounds with no adduct ion formation. Selected reaction monitoring transitions were monitored and quantitation was performed against a per-deuterated internal standard β-endosulfan (d4). The automated online SPE clean-up was performed using only 20 mL of untreated water sample prior to LC-MS/MS analysis. The method was capable of separating and quantifying endosulfan within a 24-min run using acetonitrile and water as mobile phases and presenting statistically calculated method detection limits of 3, 10, and 7 ng/L for endosulfan sulfate, α-endosulfan, and β-endosulfan, respectively. In addition, a QuEChERS method was successfully developed and applied for endosulfan determination in sediments/soils, floating and submerged algal mats, and small fish. Minimal matrix effects were observed in all matrices analyzed and recoveries for all analytes ranged from 50-144 %. The developed methodology was applied to monitor the occurrence and to assess the potential transport of endosulfan in the Loveland Slough watershed, an area adjacent to Everglades National Park showing long-term contamination with endosulfans.
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.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.