Hlanganani Tutu

Selective extraction of triazine herbicides from food samples based on a combination of a liquid membrane and molecularly imprinted polymers.

A selective extraction technique based on the combination of liquid membrane (microporous membrane liquid-liquid extraction) and molecularly imprinted polymers (MIP) was applied to triazines herbicides in food samples. Simazine, atrazine and propazine were extracted from aqueous food samples through the hydrophobic porous membrane that was impregnated with toluene, which also formed part of the acceptor phase. In the acceptor phase, the compounds were re-extracted onto MIP particles. The extraction technique was optimised for the amount of molecularly imprinted polymers particles in the organic acceptor phase, extraction time, and type of organic acceptor solvent and desorption solvent. An extraction time of 90 min and 50mg of MIP were found to be optimum parameters. Toluene as the acceptor phase was found to give higher triazines binding onto MIP particles compared to hexane and combinations of diethyl ether and hexane. 90% methanol in water was found to be the best desorption solvent compared to acetonitrile, methanol and water. The selectivity of the technique was demonstrated by extracting spiked lettuce and apple extracts where clean chromatograms were obtained compared to liquid membrane extraction alone or to the microporous membrane liquid-liquid extraction - non-imprinted polymer combination. The MIP showed a certain degree of group specificity and the extraction efficiency in lettuce extract was 79% (0.72) for simazine, 98% (1.55) for atrazine and 86% (3.08) for propazine.

Critical parameters in a supported liquid membrane extraction technique for ionizable organic compounds with a stagnant acceptor phase

The reviews cover important critical parameters that are often optimized in a supported liquid membrane extraction technique in both flat sheet and hollow fibre designs for ionizable organic molecules. Understanding of these parameters can enable one to predict the behavior of the compound before hand and thus reduce the number of optimization experiments. Moreover, less number of experiments can be also generated using statistical techniques which are now becoming more commonly used. Supported liquid membrane extraction optimal parameters such as the conditions of the pH of the acceptor and donor phases should easily be fixed from the pKa values of the compounds. Other parameters, including the polarity of the compound can help to predict the partitioning into the membrane and the behavior of the compound. The influence of parameters such as temperature on the mass transfer in supported liquid membrane depends on the design of the module, experimental design and type of mass transfer controlling the extraction process.

Potential of combining of liquid membranes and molecularly imprinted polymers in extraction of 17β-estradiol from aqueous samples.

The potential of combination of liquid membranes (microporous membrane liquid-liquid extraction) and molecularly imprinted polymers (MIPs) was performed using 17beta-estradiol (E2) as model compound. The model compound was extracted from aqueous sample through a hydrophobic porous membrane that was impregnated with hexane/ethyl acetate (3:2), which also formed part of the acceptor phase. In the acceptor phase, the compound was bound onto MIP particles that were also part of the organic phase. The potential of such combination was optimised for the type and amount of MIP particles in the organic acceptor phase, the extraction time, and the type of organic acceptor solvent. Ultrasound assisted binding of E2 onto MIP particles was also investigated. MIPs prepared by precipitation polymerization were found to be superior to those prepared by bulk polymerization. Increase in the extraction time and the amount of MIP particles in the acceptor phase led to more E2 binding onto the MIP particles. Hexane/ethyl acetate (3:2) as an organic acceptor was found to give higher E2 binding onto MIP particles compared to toluene, diethyl ether, and hexane. Ultrasound was furthermore found to increase the binding of E2 onto MIP particles. The selectivity of the technique was demonstrated by extracting wastewater and where clean chromatograms were obtained compared to liquid membrane extractions (SLMs) alone.

Development and application of cross-linked polyethylenimine for trace metal and metalloid removal from mining and industrial wastewaters

Pollution of water bodies by trace metals is an established problem and several studies have been conducted to deal with it. South Africa is amongst those countries whose water systems are most affected as a result of intensive mining activities. This research was dedicated to the development of an insoluble chelating polymer for use as an adsorbent for abstraction of metal ions from mining and industrial wastewaters. Polyethylenimine (PEI), well known for its metal chelating potential, was cross-linked by epichlorohydrin (ECH) in order to convert it into a water-insoluble form for direct use as an adsorbent. The binding affinity of the cross-linked polyethylenimine (CPEI) to heavy metal ions was assessed as well as its ability to be regenerated for re-use. CPEI exhibited good complexation ability to metal ions with high affinity to Cr and most divalent metal ions. The observed order of complexation was: Cr > Zn> Fe > Ni > Mn > Pb. On the other hand, it showed very poor ability to bind oxo-anions such as SeO3 2− and AsO2 − which has been attributed to the unavailability of suitable functional groups to interact with these ions.

Radioactive disequilibrium and geochemical modelling as evidence of uranium leaching from gold tailings dumps in the Witwatersrand Basin

Gold tailings dams from the Witwatersrand Basin usually contain elevated amounts of heavy metals and radionuclides. Uranium, in the form of uraninite (UO2) and brannerite (UTi2O6), is normally associated with gold-bearing ores in the basin. As a result of acid mine drainage (AMD), uranium is released into groundwater and fluvial systems. Its transport, retardation and immobilisation depend strongly on the uranium species and prevailing geochemical conditions. This study was aimed at the quantitative assessment of the distribution of uranium based on measurement of its radioactivity and modelling of its geochemical speciation. Analyses of tailings, water and sediment in areas of previous mining were performed. The results indicate that there is active leaching of uranium from the tailings, transport of soluble uranium species through water systems, with subsequent deposition of insoluble uranium species in sediments of fluvial systems. Analysis of tailings material indicated that mobilisation and transportation of uranium from the tailings resulted in its decoupling from its progeny which remained largely unaffected by the weathering effects. Mobilisation occurs as uranium is oxidised to the U(VI) state which dominates aqueous chemistry, particularly via complexation with most ligands. The U(VI) is reduced to U(IV) which is immobile and is subsequently deposited in the wetland sediments downstream from the primary acid mine drainage. Geochemical modelling of uranium speciation revealed the two most influential hydrogeochemical facies in uranium mobility, namely a sulphate-dominated AMD system and a lime-neutralised carbonate-dominated system. In both cases, the uranium was shown to be soluble throughout a very wide pH regime, thus yielding important information for risk assessment considerations.

The Adsorption Properties of Agricultural and Forest Soils Towards Heavy Metal Ions (Ni, Cu, Zn, and Cd)

Adsorption of Cu, Cd, Ni, and Zn in single and multi-metal solutions by agricultural and forest soils was investigated in batch sorption experiments. The results showed significant differences in sorption capacities of the studied soils. The selectivity order was as follows: agricultural soil≫ top forest soil > bottom forest soil. The adsorption sequence Cu > Zn > Ni > Cd was established for the agricultural and bottom forest soil, while the order for the top forest soil was Cu > Ni > Zn > Cd. The experimental isotherms for the metal sorption were described satisfactorily by the Freundlich and Langmuir models. The competitive adsorption experiment indicated a reduction in the amount of metals adsorbed by the soils from the multi-metal solution compared to the single metal solution. Properties of the soils, such as pH, content of clay and organic matter, exchangeable bases and hydrolytic acidity, showed a significant influence on adsorption capacities of the studied soils.

Sulfonated cross-linked polyethylenimine for selective removal of mercury from aqueous solutions

Polymeric materials are among the most promising, effective, and increasingly important adsorbents for the removal of toxic metals from wastewater. This study was dedicated to the development of an insoluble, modified chelating polymer for use as an adsorbent for abstraction of Hg from aqueous solutions. Cross-linked polyethylenimine (CPEI) was sulfonated by 3-chloropropanesulfonyl chloride for selective removal of Hg. The binding affinity of the sulfonated CPEI (SCPEI) to Hg was assessed as well as its ability to be regenerated for reuse. It exhibited high removal percentage for Hg up to 87% in synthetic solutions, with high selectivity even in the presence of competing ions: “Mn, Ni, Fe, Pb, Zn, and Cr.” The removal mechanism followed was observed to be adsorption and precipitation at pH 3 and 8, respectively. High adsorption capacities were also observed for wastewater to which the polymer was applied. The Freundlich isotherm was found to be the best fit describing the adsorption process of Hg onto the SCPEI. The pseudo second-order equation was found to better explain the adsorption kinetics, implying chemisorption. The thermodynamic study of the adsorption revealed high activation energies which confirmed the chemisorption as the mechanism of adsorption. The polymer exhibited up to 72% removal efficiency after regeneration, thus showing potential for re-use.

Phosphonated cross-linked polyethylenimine for selective removal of uranium ions from aqueous solutions

Among many remediation techniques for metal ion removal, polymeric adsorbents are efficient and widely applied. This has made them comparable with other remediation techniques in terms of technical and economic efficiency, feasibility as well as green technology. This study was dedicated to the development of an insoluble modified chelating polymer for use as an adsorbent for abstraction of uranium from wastewaters. Cross-linked polyethylenimine (CPEI) was phosphonated by phosphorous acid for selective removal of uranium ions. The binding affinity of the phosphonated cross-linked polyethylenimine (PCPEI) to uranium ions was assessed as well as its ability to be regenerated for reuse. It exhibited high removal percentage for uranium ions up to 99% with high selectivity even in the presence of competing ions (Mn, Ni, As). The Freundlich isotherm was found to be the best fit describing the adsorption process of uranyl ions onto the PCPEI. The pseudo-second-order equation was found to better explain the adsorption kinetics, implying chemisorption. The thermodynamic study of the adsorption revealed high activation energies which confirmed the chemisorption as the mechanism of adsorption.

Speciation of mercury in South African coals

Total mercury (HgTOT) concentrations were determined by inductively coupled plasma mass spectrometry (ICP MS) for South African Highveld coals. The distribution of Hg in coals was investigated using a four-stage sequential leaching protocol and isotope dilution/gas chromatography coupled to ICP MS (ID-GC-ICP MS). The results show that HgTOT ranged from 144 to 303 µg kg−1 with a mean of 199 ± 26 µg kg−1, while HgTOT leached from coals using different solvents ranged between 103 and 310 µg kg−1 (mean: 218 ± 60 µg kg−1). Hg leaching rates of 53–78% were achieved in crushed coals. Hg0, Hg2+, and CH3Hg+ were identified in all coals. CH3Hg+ in studied coals ranged between 0.1 and 0.4 (mean: 0.2) µg kg−1. GC ICP MS chromatograms also showed unknown Hg peaks which were identified as other organomercury species such as ethylmercury. Modes of occurrence of Hg in coals were variable with the organic-bound (37–40%) and the sulfide-bound (37–39%) being the dominant mercury forms. Increasing the HCl concentration in the used protocol increased the amount of Hg leached (16%) during this step.

Assessment of mobility of heavy metals in two soil types by use of column leaching experiments and chemometric evaluation of elution curves

The objectives of this study were to evaluate the mobility of heavy metals (HMs) in two types of soils (acidic forest soil and neutral agricultural soil) by leaching with calcium chloride solution in column experiments. The screening properties of neutral agricultural soil towards pollution by heavy metals (Ni, Cu, Zn and Cd) are approximately 10 times higher than those of acid forest soil. The neutral agricultural soil, polluted artificially by one pore volume (PV) of an HMs solution of concentration 200 mg L−1, can screen the leaching of these metals over several hundreds of years. The higher apparent desorption rate and per cent desorption of HMs (especially Cd) in acid forest soil indicated a higher potential of intensive migration of the metals across the profile and indicated potential risk of Cd pollution for this type of soil. The latest approach of artificial neural networks to describe transport of HMs in soil has been also evaluated. Using a simple three-layer perceptron topology with three hidden neurons, the experimental data could be simulated. The results suggested that the pH of soil is a major factor controlling the retention of the heavy metals in the soils.