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Acute Toxicity of the Agricultural Chemicals Endosulfan and Copper Sulfate to a Freshwater Shrimp, Palaemonetes Paludosus

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Acute Toxicity of the Agricultural Chemicals Endosulfan and Copper Sulfate to a Freshwater Shrimp, Palaemonetes Paludosus ACUTE TOXICITY OF THE AGRICULTURAL CHEMICALS ENDOSULFAN AND COPPER SULFATE TO A FRESHWATER SHRIMP, PALAEMONETES PALUDOSUS by Prajakta N. Kamthe A Thesis Submitted to the Faculty of The Charles E. Schmidt College of Science in Partial Fulfillment of the Requirements for the Degree of Master of Science Florida Atlantic University Boca Raton, Florida August 2002 Copyright by Prajakta N. Kamthe 2002 11 ACUTE TOXICITY OF THE AGRICULTURAL CHEMICALS ENDOSULFAN AND COPPER SULFATE TO A FRESHWATER SHRIMP, PALAEMONETES PALUDOSUS by Prajakta N. Kamthe This thesis was prepared under the direction of the candidate's thesis advisor, Dr. John Baldwin, Department of Biology, and has been approved by the members of her supervisory committee. It was submitted to the faculty of The Charles E. Schmidt College of Science and was accepted in partial fulfillment of the requirements for the degree of Master of Science. SUPERVISORY COMMITTEE: & ?;(?&?--:__ ~ Thesis Advisor w~ ~ 15rJ4 / [/?J · ector, Environmental Sciences Program 7 I 7 0 Z Vice Provost Date lll ACKNOWLEDGEMENTS I would like to thank my advisor Dr. John Baldwin and the members of my committee Dr. Craig Byrdwell and Dr. Bill Louda for all their help. Without them this study would not be possible. I would also like to thank my family and my friends for all their support and understanding. IV ABSTRACT Author: Prajakta N. Kamthe Title: Acute Toxicity of the Agricultural Chemicals Endosulfan and Copper Sulfate to a Freshwater Shrimp, Palaemonetes paludosus Institution: Florida Atlantic University Thesis Advisor: Dr. John Baldwin Degree: Master of Science Year: 2002 The toxicity of endosulfan, a restricted use pesticide, and copper sulfate, an anti-algal agent, ranks among the highest in all insecticides. Both chemicals, used in agriculture fields of southern Florida, are known to be highly toxic to aquatic invertebrates. Since Palaemonetes pugio, an extensively studied brackish water shrimp species, has proven to be excellent for toxicological analysis, a closely related freshwater shrimp species, Palaemonetes paludosus, was used as the test species in this study to determine the toxicity of endosulfan and copper sulfate in freshwater. A series of static renewal 96 h bioassays (renewed every 24 h) performed on juvenile P. paludosus resulted in the 96 h lethal concentration (LC50) estimates of 0.24 11g/L (0.24 ppb) for endosulfan and 0.79 mg/L (0.79 ppm)for copper sulfate. The results of this study, when compared to other studies, indicate that P. paludosus is more sensitive to endosulfan and copper sulfate than other similar aquatic invertebrate species and is therefore an excellent toxicological indicator. v TABLE OF CONTENTS Page LIST OFT ABLES ............. ............................................................................................... vii LIST OF FIGURES ..................................... ..................................................................... viii INTRODUCTION ............................................................................................................... 1 MATERIALS AND METHODS .. ............ .................. .. ............................................... ... ... 6 RESULTS ........................... .. ... ............................................................................................ 9 DISCUSSION ................................................................................................................... 11 REFERENCES .................................................................................................................. 18 Vl LIST OF TABLES Table Page 1. Comparison of acute toxicity estimates (LC50) for ... ..................................... .. ... .... 21 Palaemonetes paludosus and other aquatic species for 48 and 96 h exposure to endosulfan. 2. Comparisons of the LC50 values between different time endpoints .... ..................... 22 for endosulfan 3. Comparisons of the LC50 values between different time endpoints ................. ........ 22 for copper sulfate 4. Comparison of acute toxicity estimates (LC50) for ........... ....... ................................ 22 Palaemonetes paludosus and other aquatic species for 48 and 96 h exposure to copper sulfate using static renewal bioassays. Vll LIST OF FIGURES Figure Page l. Isomers of endosulfan and its degradation products ............ ..... .... ... .... ..... ... ..... ... .... 23 2. The 'ANA' area ... ............ ........ ................................................................................. 24 3. LC50 values of endosulfan toxicity at 24, 48, 72, and 96 hrs ... .. ................... .... .... ... 25 4. Survival in relation to the concentration of insecticide- endosulfan ............ .... ...... 26 5. LC50 values of copper sulfate toxicity at 24, 48, 72, and 96 hrs ......................... ... .. 27 6. Survival in relation to the concentration of insecticide- copper sulfate ............ ..... 28 Vlll INTRODUCTION South Florida's sensitive wetland habitats receive a direct impact from one of the region's major economic activities, agriculture. Primary agriculture activities include extensive cultivation of sugarcane and rice in the Everglades Agricultural Area (EAA) south of Lake Okeechobee and the cultivation of citrus, watermelon, tomatoes, and green peppers in the Big Cypress region of south Florida. In all major agricultural operations, a large variety of chemicals are used to enhance production of crops, as well as to protect them from a variety of insects and diseases. These chemicals include fertilizers, herbicides, insecticides and fungicides. Irrigation and heavy seasonal rains common in south Florida promote the transfer of these xenobiotic chemicals into the surrounding aquatic habitats, resulting in exposure of the aquatic inhabitants to the toxicants. In general, insecticides are designed to target terrestrial arthropods; however, they may also affect non-target aquatic crustaceans, depending on their mode of action (Koeman et al., 1978; Raizada et al., 1981 ). One of the compounds commonly used in green pepper fields to control insects is Thiodan, which has endosulfan as an active ingredient. Endosulfan (6, 7, 8, 9, 10, 10-hexachloro-1, 5, Sa, 6, 9, 9a-hexahydro-6, 9-methano-2, 4, 3-benzodioxathiepin-3-oxide) (Fig. 1) was chosen for this study, as it is one of the most commonly used insecticides for agricultural crops in southern Florida (Baughman, 1986). It is used as an acaricide (kills insects and spiders) and miticide (kills ticks and mites) to control a variety of pests affecting fruits, vegetables, and ornamental plants (Berrill et al., 1998; Leight and Van Dolah, 1999). Since endosulfan is known to be highly toxic to freshwater aquatic invertebrates (Table 1) such as the crayfish Procambarus clarkii (Cebrian et al., 1992) and Daphnea magna, a cladoceran (Macek et al., 1976), it is classified as an EPA Class I Restricted Use Pesticide (EPA, Restricted use products report, 1995). Endosulfan is an organochlorine and a member of the cyclodiene class of insecticides (Fig. 1). It is made up of a mixture of two isomers, a and ~.both of which have similar insecticidal properties (Goebel et al., 1982). Technical endosulfan contains 70% a-endosulfan and 30% ~-endosulfan (Goebel eta!., 1982). Endosulfan and both its isomers work by inhibiting the Na+ - K+ ATPase (enzyme responsible for regulating the Na+- K+ channels along nervous system pathways) and the mitochondrial Mg2+ ATPase (enzyme responsible for regulating the ATP production in the mitochondria: Goebel et al., 1982). Exposure to this chemical initially results in: (i) increased excitation, restlessness, trembling, uncontrolled body and extremity movements, (ii) followed by general exhaustion, incapacity of translocation, arching of the body, and convulsive tremors, (iii) and ultimately lead to immobility, lethargic reaction to strong stimuli, collapse of the abdomen, and death (Goebel et al., 1982). In studies conducted on the fish species Oreochromis mossambicus and Clarias batrachus, endosulfan caused a reduction in the blood's affinity for oxygen, which generated anoxia and necrosis of the gill epithelium (Rangaswamy and Naidu, 1999; Berrill et al., 1998). Although no studies have been conducted on Palaemonetes paludosus (grass shrimp) concerning this topic, one can predict that a similar reaction may occur when shrimp are subjected to endosulfan, as crustaceans have similar mechanisms for oxygen intake as fish (Cochran and Burnett, 1996). 2 In an aquatic environment, endosulfan is degraded mostly by hydrolysis. Peterson and Batley (1993) state that of the two isomeric products, ~-endosulfan hydrolyzes faster than a-endosulfan. However, a-endosulfan is also removed efficiently by other mechanisms such as volatilization, isomerization, or biological hydrolysis. It is relatively more water- soluble than the ~-isomer, which is typically a more persistent compound. Thus, in an aqueous environment where many factors in addition to hydrolysis play a role in the degradation of endosulfan, a-endosulfan tends to degrade much faster than ~-endosulfan. In freshwater, with a pH of 7 .0, the half-life of a-endosulfan is approximately 5 days, while the half-life of ~-endosulfan is 15 days (Peterson and Batley, 1993). The degradation of endosulfan (a and~) yields the products endosulfan sulfate and endosulfan-diol (Peterson and Batley, 1993), each exhibiting different toxicity properties. Endosulfan sulfate, which is as toxic as its parent compound, has a half-life
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