Assessment of organochlorine pesticide residues in fish samples from the Okavango Delta, Botswana
- Authors: Mpofu, Christopher
- Date: 2011 , 2011-02-28
- Subjects: Pesticides , Organochlorine compounds , Freshwater fishes -- Effect of pesticides on -- Botswana -- Okavango River Delta , Water -- Pesticide content -- Botswana -- Okavango River Delta , Catfishes -- Botswana -- Okavango River Delta , Tigerfish -- Botswana -- Okavango River Delta , Redbreast tilapia -- Botswana -- Okavango River Delta
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4404 , http://hdl.handle.net/10962/d1006707 , Pesticides , Organochlorine compounds , Freshwater fishes -- Effect of pesticides on -- Botswana -- Okavango River Delta , Water -- Pesticide content -- Botswana -- Okavango River Delta , Catfishes -- Botswana -- Okavango River Delta , Tigerfish -- Botswana -- Okavango River Delta , Redbreast tilapia -- Botswana -- Okavango River Delta
- Description: This thesis presents an evaluation of the dispersive solid-phase extraction (d-SPE) method referred to as the quick, easy, cheap, effective, rugged and safe (QuEChERS) method for the determination of four organochlorine pesticide residues in fish samples. The pesticides investigated in this study were o, p′-DDT, p, p′-DDE, aldrin and dieldrin. The combined use of Gas Chromatography with an Electron Capture Detector (GC-ECD) and sensitive Time of Flight (TOF) mass detector facilitated the identification of the target analytes. In the absence of certified reference material, the overall analytical procedure was validated by systematic recovery experiments on spiked samples at three levels of 2, 5 and 10 ng/g. The targeted compounds were successfully extracted and their recovery ranged from 76 to 96% with relative standard deviations of less than 13%. The optimum QuEChERS conditions were 2g of fish powder, 10 ml acetonitrile and 1 min shaking time. The optimal conditions were applied to assess the levels of chlorinated pesticides in blunt-tooth catfish (Clarias ngamensis), tigerfish (Hydrocynus vittatus), Oreochromis andersonii and red-breasted tilapia (Tilapia rendalli) from the Okavango Delta, Botswana. Dieldrin, p, p′-DDE and aldrin were detected in all the analysed samples with a concentration range of 0.04 – 0.29, 0.07 – 0.33, 0.04 – 0.28 and 0.03 – 0.24 ng/g per dry weight in O. andersonii, C. ngamensis, T. rendalli and H. vittatus respectively. These concentrations were below the US-EPA 0.1 μg/g allowable limit in edible fish and the Australian Maximum Residue Limit (MRL) of 50 - 1000 ng/g in fresh fish. DDT was not detected in all the fish species investigated. The mean lipid content recorded in the fish samples were 1.24, 2.16, 2.18 and 4.21% for H. vittatus, T. rendalli, O. andersonni and C. ngamensis respectively. No systematic trend was observed between fish age and pesticide levels in fish. Acetylcholinesterase (AChE) activity assays were performed to assess the effects of organochlorine pesticides in Clarias ngamensis. The enzyme activity recorded in Clarias ngamensis from the Okavango Delta and the reference site was 12.31 μmol of acetylcholine iodide hydrolysed/min/g brain tissue. The enzyme activity remained the same indicating no enzyme inhibition. The conclusions drawn from this study are that the QuEChERS method is applicable for the determination of organochlorine pesticide residues in fish matrices. The fish from the Okavango Delta are safe for human consumption.
- Full Text:
- Date Issued: 2011
- Authors: Mpofu, Christopher
- Date: 2011 , 2011-02-28
- Subjects: Pesticides , Organochlorine compounds , Freshwater fishes -- Effect of pesticides on -- Botswana -- Okavango River Delta , Water -- Pesticide content -- Botswana -- Okavango River Delta , Catfishes -- Botswana -- Okavango River Delta , Tigerfish -- Botswana -- Okavango River Delta , Redbreast tilapia -- Botswana -- Okavango River Delta
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4404 , http://hdl.handle.net/10962/d1006707 , Pesticides , Organochlorine compounds , Freshwater fishes -- Effect of pesticides on -- Botswana -- Okavango River Delta , Water -- Pesticide content -- Botswana -- Okavango River Delta , Catfishes -- Botswana -- Okavango River Delta , Tigerfish -- Botswana -- Okavango River Delta , Redbreast tilapia -- Botswana -- Okavango River Delta
- Description: This thesis presents an evaluation of the dispersive solid-phase extraction (d-SPE) method referred to as the quick, easy, cheap, effective, rugged and safe (QuEChERS) method for the determination of four organochlorine pesticide residues in fish samples. The pesticides investigated in this study were o, p′-DDT, p, p′-DDE, aldrin and dieldrin. The combined use of Gas Chromatography with an Electron Capture Detector (GC-ECD) and sensitive Time of Flight (TOF) mass detector facilitated the identification of the target analytes. In the absence of certified reference material, the overall analytical procedure was validated by systematic recovery experiments on spiked samples at three levels of 2, 5 and 10 ng/g. The targeted compounds were successfully extracted and their recovery ranged from 76 to 96% with relative standard deviations of less than 13%. The optimum QuEChERS conditions were 2g of fish powder, 10 ml acetonitrile and 1 min shaking time. The optimal conditions were applied to assess the levels of chlorinated pesticides in blunt-tooth catfish (Clarias ngamensis), tigerfish (Hydrocynus vittatus), Oreochromis andersonii and red-breasted tilapia (Tilapia rendalli) from the Okavango Delta, Botswana. Dieldrin, p, p′-DDE and aldrin were detected in all the analysed samples with a concentration range of 0.04 – 0.29, 0.07 – 0.33, 0.04 – 0.28 and 0.03 – 0.24 ng/g per dry weight in O. andersonii, C. ngamensis, T. rendalli and H. vittatus respectively. These concentrations were below the US-EPA 0.1 μg/g allowable limit in edible fish and the Australian Maximum Residue Limit (MRL) of 50 - 1000 ng/g in fresh fish. DDT was not detected in all the fish species investigated. The mean lipid content recorded in the fish samples were 1.24, 2.16, 2.18 and 4.21% for H. vittatus, T. rendalli, O. andersonni and C. ngamensis respectively. No systematic trend was observed between fish age and pesticide levels in fish. Acetylcholinesterase (AChE) activity assays were performed to assess the effects of organochlorine pesticides in Clarias ngamensis. The enzyme activity recorded in Clarias ngamensis from the Okavango Delta and the reference site was 12.31 μmol of acetylcholine iodide hydrolysed/min/g brain tissue. The enzyme activity remained the same indicating no enzyme inhibition. The conclusions drawn from this study are that the QuEChERS method is applicable for the determination of organochlorine pesticide residues in fish matrices. The fish from the Okavango Delta are safe for human consumption.
- Full Text:
- Date Issued: 2011
Evaluation of manufacturing processes for the production of atrazine
- Authors: Schaefer, Melissa Claire
- Date: 2002
- Subjects: Atrazine , Pesticides
- Language: English
- Type: Thesis , Masters , MTech (Chemistry)
- Identifier: vital:10960 , http://hdl.handle.net/10948/96 , Atrazine , Pesticides
- Description: This report describes the results of investigations carried out with the view to find an alternative for MIBK as solvent for the production of atrazine as currently practised by Dow AgroSciences in South Africa. The main motivating factors for the said investigation was: · to increase the yield of atrazine produced, · to reduce the amount of organics, consisting essentially of reaction solvent containing dissolved product, in the aqueous process effluent, and · to improve the properties of the solid (crystalline) product to enable easier product formulation. Synthetic reactions carried out in the absence of organic solvent, i.e. in essentially a 10% NaCl solution containing a surfactant, proved rather disappointing. Low yields of atrazine were obtained together with relatively large amounts of by-products such as propazine and simazine, irrespective of the nature of the surfactant. The reason for the low yield of atrazine and high yields of by-products were established in competing substitution reactions. In these reactions, IPA was reacted with an equimolar mixture of cyanuric chloride and mono-i (first reaction intermediate) in both aqueous medium and in toluene as reaction solvent. The results of these experiments indicated that in aqueous medium IPA reacts faster with mono-i than cyanuric chloride to give propazine as by-product. In toluene, however, the preferred reaction is with cyanuric chloride to give more mono-i as product. Toluene was investigated as an alternative organic solvent to MIBK in view of its desirable properties such as low solubility in water and ease of recovery and recycling. The synthesis of atrazine was optimised in terms of addition sequence and rates of amine reagents and base (HCl acceptor), both by means of benchscale reactions and reaction calorimetry. Reaction energy profiles indicated that both the reaction of secondary amine/NaOH and primary amine/NaOH were virtually instantaneous. This implies that the reaction can be performed under feed control conditions. Of particular importance in ensuring high yields of high purity product was accurate temperature control (since both reaction steps are highly exothermic) and mixing. The latter was important in view of the rapid reaction of amine/NaOH with cyanuric chloride, as well as the possible reaction of mono-i, the first reaction intermediate, with IPA in cases of local excesses of reagent. Under optimum conditions, a yield of atrazine > 97% could be achieved where the resultant product was well within stipulated product specifications. In view of the results obtained, the following recommendations regarding the synthesis of atrazine in toluene as reaction solvent can be made: · Use a reagent addition sequence that staggers the addition of amine and NaOH in such a manner that amine is added first for a short while, followed by the simultaneous addition of amine and NaOH, and ending with NaOH. Use two reaction vessels in series, one for the IPA addition reaction and one for the MEA addition reaction. In this manner the reaction can be run on a continuous basis since no lag time between amine additions is required. Also, smaller reactors may be used whilst maintaining high production rates. Smaller reactors will improve both temperature control and mixing of reagents.
- Full Text:
- Date Issued: 2002
- Authors: Schaefer, Melissa Claire
- Date: 2002
- Subjects: Atrazine , Pesticides
- Language: English
- Type: Thesis , Masters , MTech (Chemistry)
- Identifier: vital:10960 , http://hdl.handle.net/10948/96 , Atrazine , Pesticides
- Description: This report describes the results of investigations carried out with the view to find an alternative for MIBK as solvent for the production of atrazine as currently practised by Dow AgroSciences in South Africa. The main motivating factors for the said investigation was: · to increase the yield of atrazine produced, · to reduce the amount of organics, consisting essentially of reaction solvent containing dissolved product, in the aqueous process effluent, and · to improve the properties of the solid (crystalline) product to enable easier product formulation. Synthetic reactions carried out in the absence of organic solvent, i.e. in essentially a 10% NaCl solution containing a surfactant, proved rather disappointing. Low yields of atrazine were obtained together with relatively large amounts of by-products such as propazine and simazine, irrespective of the nature of the surfactant. The reason for the low yield of atrazine and high yields of by-products were established in competing substitution reactions. In these reactions, IPA was reacted with an equimolar mixture of cyanuric chloride and mono-i (first reaction intermediate) in both aqueous medium and in toluene as reaction solvent. The results of these experiments indicated that in aqueous medium IPA reacts faster with mono-i than cyanuric chloride to give propazine as by-product. In toluene, however, the preferred reaction is with cyanuric chloride to give more mono-i as product. Toluene was investigated as an alternative organic solvent to MIBK in view of its desirable properties such as low solubility in water and ease of recovery and recycling. The synthesis of atrazine was optimised in terms of addition sequence and rates of amine reagents and base (HCl acceptor), both by means of benchscale reactions and reaction calorimetry. Reaction energy profiles indicated that both the reaction of secondary amine/NaOH and primary amine/NaOH were virtually instantaneous. This implies that the reaction can be performed under feed control conditions. Of particular importance in ensuring high yields of high purity product was accurate temperature control (since both reaction steps are highly exothermic) and mixing. The latter was important in view of the rapid reaction of amine/NaOH with cyanuric chloride, as well as the possible reaction of mono-i, the first reaction intermediate, with IPA in cases of local excesses of reagent. Under optimum conditions, a yield of atrazine > 97% could be achieved where the resultant product was well within stipulated product specifications. In view of the results obtained, the following recommendations regarding the synthesis of atrazine in toluene as reaction solvent can be made: · Use a reagent addition sequence that staggers the addition of amine and NaOH in such a manner that amine is added first for a short while, followed by the simultaneous addition of amine and NaOH, and ending with NaOH. Use two reaction vessels in series, one for the IPA addition reaction and one for the MEA addition reaction. In this manner the reaction can be run on a continuous basis since no lag time between amine additions is required. Also, smaller reactors may be used whilst maintaining high production rates. Smaller reactors will improve both temperature control and mixing of reagents.
- Full Text:
- Date Issued: 2002
The effect of the pesticide, endosulfan, on hepatic cytochrome P-450, liver and gill ultrastructure, and selected haematological parameters of Oreochromis Mossambicus (Peters, 1852) (Pisces : Cichlidae)
- Authors: Quick, Arthur Joseph Rex
- Date: 1986
- Subjects: Pesticides , Mozambique tilapia , Cichlids
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5195 , http://hdl.handle.net/10962/d1001971 , Pesticides , Mozambique tilapia , Cichlids
- Description: Two possible ways in which fish may acclimate to prolonged exposure· to sublethal levels of endosulfan were investigated: induction of the hepatic monooxygenase system and changes in haematology. These studies also involved an examination of the ultrastructure of liver and gill tissue. Endosulfan caused none of the characteristic phenobarbital-type inductive effects on the liver of Oreochromis mossambicus. There was no increase in cytochrome P-450 levels, microsomal protein or hepatosomatic index. The reasons for the lack of induction are discussed. The effect of endosulfan on the following haematological parameters was determined: haemoglobin, erythrocyte count, microhaematocrit, mean erythrocyte volume and mean erythrocyte haemoglobin concentration. The only effect was an increase in erythrocyte count. The value of changes in haematological parameters as indicators of pollutioninduced anemia in the field is discussed. No changes in gill ultrastructure were noted although electron micrographs of liver tissue showed lesions in hepatocytes. The diagnostic value of pollution-induced pathological changes on cell ultrastructure are discussed. Recommendations are made with regard to future large scale application of pesticides on or near large water bodies
- Full Text:
- Date Issued: 1986
- Authors: Quick, Arthur Joseph Rex
- Date: 1986
- Subjects: Pesticides , Mozambique tilapia , Cichlids
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:5195 , http://hdl.handle.net/10962/d1001971 , Pesticides , Mozambique tilapia , Cichlids
- Description: Two possible ways in which fish may acclimate to prolonged exposure· to sublethal levels of endosulfan were investigated: induction of the hepatic monooxygenase system and changes in haematology. These studies also involved an examination of the ultrastructure of liver and gill tissue. Endosulfan caused none of the characteristic phenobarbital-type inductive effects on the liver of Oreochromis mossambicus. There was no increase in cytochrome P-450 levels, microsomal protein or hepatosomatic index. The reasons for the lack of induction are discussed. The effect of endosulfan on the following haematological parameters was determined: haemoglobin, erythrocyte count, microhaematocrit, mean erythrocyte volume and mean erythrocyte haemoglobin concentration. The only effect was an increase in erythrocyte count. The value of changes in haematological parameters as indicators of pollutioninduced anemia in the field is discussed. No changes in gill ultrastructure were noted although electron micrographs of liver tissue showed lesions in hepatocytes. The diagnostic value of pollution-induced pathological changes on cell ultrastructure are discussed. Recommendations are made with regard to future large scale application of pesticides on or near large water bodies
- Full Text:
- Date Issued: 1986
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