An ion imprinted polymer for the determination of Ni (II) ions from mine tailing samples
- Authors: Rammika, Modise
- Date: 2011
- Subjects: Imprinted polymers , Metal ions , Polymerization , Mineral industries -- Waste disposal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4323 , http://hdl.handle.net/10962/d1004981 , Imprinted polymers , Metal ions , Polymerization , Mineral industries -- Waste disposal
- Description: A Ni(II)-dimethylglyoxime ion imprinted polymer {Ni(II)-DMG IIP} was synthesized by the trapping method using the bulk polymerisation format. The structures of the imprinted and non-imprinted polymer were evaluated by infrared spectroscopy and the morphology was observed by scanning electron microscopy. The Ni(II)-DMG IIP was optimised for pH, mass, time and by the uniform design experimental method for the molar ratios of monomer to crosslinker to porogen and template to ligands as well as keeping these parameters constant and varying the quantities of initiator, 2,2'-azobisisobutyronitrile (AIBN). The optimum pH was 8.5, optimum mass was 50 mg, optimum time was 1 min and the optimum molar ratios of crosslinker to monomer, monomer to template and nickel(II) sulfate hexahydrate (NiSO₄.6H₂O) to 4-vinylpyridine to dimethylglyoxime were found to be 3.3:1.0, 0.6:1.0 and 1.0:0.6:3.6 respectively with 30 mg and 8 mL as the optimum amounts of initiator and porogen respectively. Through this optimisation, recovery of Ni(II) was increased from 98 to 100%. Selectivity of the ion imprinted polymer was evaluated by analysing, using an inductively coupled plasma-optical emission spectrometer, for Ni(II) ions that were spiked with varying concentrations of Co(II), Cu(II), Zn(II), Pd(II), Fe(II), Ca(II), Mg(II), Na(I) and K(I) in aqueous samples. Selectivity studies also confirmed that the ion imprinted polymer had very good selectivity characterised by % RSD of less than 5 %. Co(II) was the only ion found to slightly interfere with the determination of Ni(II). The limits of detection and quantification were found to be 3x10⁻⁴ μg/mL and 9x10⁻⁴ μg/mL respectively. The method was evaluated by a custom solution of ground water certified reference material (SEP-3) and sandy soil reference material (BCR-142R) and the concentrations of Ni(II) obtained were not significantly different to the certified ones. The Ni(II)-DMG IIP was then evaluated in aqueous and soil samples where recoveries of 93 to 100% and 98 to 99% respectively were obtained with enrichment factors ranging from 2 to 18 in aqueous and 27 to 40 in soil samples. Finally, the Ni(II)-DMG IIP was used to analyse mine tailings samples and Ni(II) recovery of 99% was obtained with an enrichment factor of 2.
- Full Text:
- Date Issued: 2011
- Authors: Rammika, Modise
- Date: 2011
- Subjects: Imprinted polymers , Metal ions , Polymerization , Mineral industries -- Waste disposal
- Language: English
- Type: Thesis , Masters , MSc
- Identifier: vital:4323 , http://hdl.handle.net/10962/d1004981 , Imprinted polymers , Metal ions , Polymerization , Mineral industries -- Waste disposal
- Description: A Ni(II)-dimethylglyoxime ion imprinted polymer {Ni(II)-DMG IIP} was synthesized by the trapping method using the bulk polymerisation format. The structures of the imprinted and non-imprinted polymer were evaluated by infrared spectroscopy and the morphology was observed by scanning electron microscopy. The Ni(II)-DMG IIP was optimised for pH, mass, time and by the uniform design experimental method for the molar ratios of monomer to crosslinker to porogen and template to ligands as well as keeping these parameters constant and varying the quantities of initiator, 2,2'-azobisisobutyronitrile (AIBN). The optimum pH was 8.5, optimum mass was 50 mg, optimum time was 1 min and the optimum molar ratios of crosslinker to monomer, monomer to template and nickel(II) sulfate hexahydrate (NiSO₄.6H₂O) to 4-vinylpyridine to dimethylglyoxime were found to be 3.3:1.0, 0.6:1.0 and 1.0:0.6:3.6 respectively with 30 mg and 8 mL as the optimum amounts of initiator and porogen respectively. Through this optimisation, recovery of Ni(II) was increased from 98 to 100%. Selectivity of the ion imprinted polymer was evaluated by analysing, using an inductively coupled plasma-optical emission spectrometer, for Ni(II) ions that were spiked with varying concentrations of Co(II), Cu(II), Zn(II), Pd(II), Fe(II), Ca(II), Mg(II), Na(I) and K(I) in aqueous samples. Selectivity studies also confirmed that the ion imprinted polymer had very good selectivity characterised by % RSD of less than 5 %. Co(II) was the only ion found to slightly interfere with the determination of Ni(II). The limits of detection and quantification were found to be 3x10⁻⁴ μg/mL and 9x10⁻⁴ μg/mL respectively. The method was evaluated by a custom solution of ground water certified reference material (SEP-3) and sandy soil reference material (BCR-142R) and the concentrations of Ni(II) obtained were not significantly different to the certified ones. The Ni(II)-DMG IIP was then evaluated in aqueous and soil samples where recoveries of 93 to 100% and 98 to 99% respectively were obtained with enrichment factors ranging from 2 to 18 in aqueous and 27 to 40 in soil samples. Finally, the Ni(II)-DMG IIP was used to analyse mine tailings samples and Ni(II) recovery of 99% was obtained with an enrichment factor of 2.
- Full Text:
- Date Issued: 2011
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
Pressurized hot water extraction of nutraceuticals and organic pollutants from medicinal plants
- Authors: Mokgadi, Janes
- Date: 2011
- Subjects: Functional foods Medicinal plants -- Biotechnology Extraction (Chemistry) Goldenseal Botanical pesticides Sorbents Organic solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4338 , http://hdl.handle.net/10962/d1004999
- Description: This thesis explores the robustness and the versatility of pressurized hot water extraction (PHWE) for a variety of analytes and matrices. Applications discussed include: selective extraction of alkaloids in goldenseal followed by their degradation studies; in-cell clean-up of pesticides in medicinal plants employing custom made molecularly imprinted polymers (MIPs) sorbents; in-cell pre-concentration followed by desorption of aflatoxins in plants with MIPs; desorption of pesticides from electrospun nanofiber sorbents; and removal of templates from MIPs sorbents. It was demonstrated that selective extractions could be achieved by just changing the temperature of water while adjusting the pressure. For instance, the alkaloids in goldenseal (hydrastine and berberine), were extracted at 140 °C, 50 bars, 1 mL min⁻¹ in 15 min; organochlorine pesticides from medicinal plants were extracted at 260 °C, 80 bars, 1 mL min-1 in 10 min; while aflatoxins AFG2, AFG1, AFB2 and AFB1 were extracted at 180 °C, 60 bars and a flow rate of 0.5 mL min⁻¹ in 10 min. The selectivity of PHWE was further enhanced by combining it with selective MIPs sorbents at higher temperatutes. In-cell clean-up of interfering chlorophyll was successfully removed from the medicinal plants during pesticides analysis while clean-up of aflatoxins AFG2, AFG1, AFB2 and AFB1 was achieved in two extraction cells connected in series. Ultrasound was also combined with PHWE for extraction of hydrastine and berberine at 80 °C and 40 bars in 30 min. PHWE was further evaluated for removal of templates from quercetin, phthalocynine and chlorophyll MIPs. The templates were thoroughly washed off their MIPs within 70 min with PHWE compared to over 8 h for Soxhlet and ultrasound assisted extraction. Pesticides were also desorbed from electrospun nanofibers at 260 °C, 80 bars in 10 min employing only water at 0.5 mL min⁻¹. In the light of green chemistry, the decrease in the usage of organic solvents was 100%, resulting in no organic solvent waste.
- Full Text:
- Date Issued: 2011
- Authors: Mokgadi, Janes
- Date: 2011
- Subjects: Functional foods Medicinal plants -- Biotechnology Extraction (Chemistry) Goldenseal Botanical pesticides Sorbents Organic solvents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:4338 , http://hdl.handle.net/10962/d1004999
- Description: This thesis explores the robustness and the versatility of pressurized hot water extraction (PHWE) for a variety of analytes and matrices. Applications discussed include: selective extraction of alkaloids in goldenseal followed by their degradation studies; in-cell clean-up of pesticides in medicinal plants employing custom made molecularly imprinted polymers (MIPs) sorbents; in-cell pre-concentration followed by desorption of aflatoxins in plants with MIPs; desorption of pesticides from electrospun nanofiber sorbents; and removal of templates from MIPs sorbents. It was demonstrated that selective extractions could be achieved by just changing the temperature of water while adjusting the pressure. For instance, the alkaloids in goldenseal (hydrastine and berberine), were extracted at 140 °C, 50 bars, 1 mL min⁻¹ in 15 min; organochlorine pesticides from medicinal plants were extracted at 260 °C, 80 bars, 1 mL min-1 in 10 min; while aflatoxins AFG2, AFG1, AFB2 and AFB1 were extracted at 180 °C, 60 bars and a flow rate of 0.5 mL min⁻¹ in 10 min. The selectivity of PHWE was further enhanced by combining it with selective MIPs sorbents at higher temperatutes. In-cell clean-up of interfering chlorophyll was successfully removed from the medicinal plants during pesticides analysis while clean-up of aflatoxins AFG2, AFG1, AFB2 and AFB1 was achieved in two extraction cells connected in series. Ultrasound was also combined with PHWE for extraction of hydrastine and berberine at 80 °C and 40 bars in 30 min. PHWE was further evaluated for removal of templates from quercetin, phthalocynine and chlorophyll MIPs. The templates were thoroughly washed off their MIPs within 70 min with PHWE compared to over 8 h for Soxhlet and ultrasound assisted extraction. Pesticides were also desorbed from electrospun nanofibers at 260 °C, 80 bars in 10 min employing only water at 0.5 mL min⁻¹. In the light of green chemistry, the decrease in the usage of organic solvents was 100%, resulting in no organic solvent waste.
- Full Text:
- Date Issued: 2011
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