Rob I. McCrindle

Composite nanofibers prepared from metallic iron nanoparticles and polyaniline: High performance for water treatment applications

Presented here is a simple preparation of metallic iron nanoparticles, supported on polyaniline nanofibers at room temperature. The preparation is based on polymerization of interconnected nanofibers by rapid mixing of the aniline monomer with Fe(III) chloride as the oxidant, followed by reductive deposition of Fe(0) nanoparticles, using the polymerization by-products as the Fe precursor. The morphology and other physico-chemical properties of the resulting composite were characterized by scanning and transmission electron microscopy, Brunauer-Emmett-Teller method, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and vibrating-sample magnetometry. The composite fibers were 80-150 nm in diameter and exhibited the expected ferromagnetic behavior. The composite rapidly and efficiently removed As(V), Cr(VI), and also Congo red dye, from aqueous solutions suggesting their usefulness for removal of toxic materials from wastewater. The composite fibers have high capacity for toxin removal: 42.37 mg/g of As(V), 434.78 mg/g of Cr(VI), and 243.9 mg/g of Congo red. The fibers are easily recovered from fluids by exploiting their ferromagnetic properties.

Multielement analysis of tea leaves by inductively coupled plasma optical emission spectrometry using slurry nebulisation

In order to evaluate the slurry nebulization method as an alternative method for the analysis of tea, the metal ion content of tea samples of different origins was determined. The concentrations of six elements, Al, Ba, Ca, Mg, Mn and Zn, were determined by introducing tea as a slurry into an inductively coupled plasma optical emission spectrometer (ICP-OES). Calibration was performed by using either aqueous standard solutions or by using the simplified generalized standard additions method (GSAM). The simplified GSAM is an expansion of the conventional standard additions method, based on the principle of varying both the sample mass and the amount of standard solution added. Initially the tea was ground for 3 h prior to slurry preparation. A carbonization procedure was included before the sample was ground. The grinding time was reduced to only 30 min. For comparison, tea was also digested by boiling in acid and being introduced into the plasma as an aqueous solution. The results obtained using slurry analysis were much higher than the results obtained from digested tea using aqueous standards for calibration. The metal content of the tea samples was found to be suitable for differentiating amongst the tea samples studied. The accuracy of the method was checked by analyzing a tea certified reference material. The Students t-test showed that values obtained using slurry nebulization were close to the certified values at a 95% confidence level. The simplified GSAM was applied to further confirm the accuracy of the slurry technique, and the values obtained using this method were comparable with those obtained using the slurry method with aqueous calibration. The slurry method can, therefore, be successfully applied to the analysis of tea leaves without the need to pre-dissolve them. This could avoid the use of hazardous chemicals, incomplete dissolution and loss of volatile analytes.

An investigation into the effect of various chemical and physical treatments of a South African phosphogypsum to render it suitable as a set retarder for cement

The work describes various physical and chemical treatments to eliminate the deleterious effects of impurities in phosphogypsum on the delayed setting time and impaired strength development behaviour of cement to which it was added as a set regulator. The physical treatments included washing, milling, and ultrasonic treatment of the material, while the chemical treatments dealt with acidic and basic additions to the phosphogypsum during the washing stage. It was found that chemical treatment with a milk of lime solution, which is often recommended in literature, was ineffective in reducing set retardation. Treatment with ammonium hydroxide or sulphuric acid was more effective in this regard. Intergrinding phosphogypsum with slaked lime improved its effectiveness in reducing set retardation, but the use of unslaked lime was less effective and also resulted in marked reductions in compressive strengths. A combined treatment of wet milling phosphogypsum with a lime slurry in a ball mall was derived from these experiments and is recommended for full-scale plant applications.

Polyaniline nanofibers as highly effective re-usable adsorbent for removal of reactive black 5 from aqueous solutions.

Polyaniline nanofibers (PANI NFs) with 50-80 nm in diameter were successfully prepared at room temperature (22 °C) using ferric chloride (FeCl3) as an oxidant via a simple rapid mixing polymerization method. The prepared PANI NFs were characterized by FE-SEM, HR-TEM, BET, ATR-FTIR and by Zeta potential measurement method. The adsorption of azo dye Reactive Black 5 (RB5) onto PANI NFs from aqueous solutions was investigated. Adsorption studies were carried out at different initial dye concentrations, initial solution pH and adsorbent doses. The kinetic data fitted well with the pseudo-second-order model while the equilibrium data were satisfactorily described by the Langmuir isotherm model. The Langmuir maximum adsorption capacity of RB5 at pH 6.0 was found to be 312.5, 389.1 and 434.7 mg/g at 25 °C, 35 °C and 45 °C, respectively. Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) changes indicated that the adsorption of RB5 onto PANI NFs was feasible, spontaneous, and endothermic. Moreover, desorption experiments revealed that the PANI NFs can be reused effectively for five consecutive adsorption-desorption cycles without any loss of its original capacity.

Determination of selected phthalate esters compounds in water and sediments by capillary gas chromatography and flame ionization detector

The presence of phthalate esters (PAEs) in the environment is not desirable and therefore, needs to be monitored. This study reports the first data on the concentration levels of PAEs in water and sediments of the Jukskei River catchment area, South Africa. The study was conducted during the summer and winter seasons of 2005. Liquid-liquid extraction (LLE) and Soxhlet extraction (SE) methods were optimized, evaluated and used to determine PAEs of interest in water (unfiltered and filtered) and sediments samples, respectively. Mean percentage recoveries in spiked doubly distilled water ranged from 100 ± 5.32 dimethyl phthalate (DMP) – 122 ± 0.46 di-2-ethylhexyl phthalate (DEHP) and 91.6 ± 1.93 diethyl phthalate (DEP) – 117 ± 4.80 dibutyl phthalate (DBP) in sediments. The concentration levels of PAEs studied in unfiltered environmental water samples were in the range of 0.04(± 0.00) (DMP) − 9.76(± 00.1) ng mL−1(DEHP) for PAEs and from 0.09 (± 0.01) (DMP) – 4.38 (± 0.06) ng mL−1(DEHP) for filtered environmental water samples. Concentration levels obtained in sediments were from 0.05 (0.00) (DMP) – 4910 (0.36) ng/gdw (DEHP). PAEs adsorbed on the sample bottle gave concentration levels of up to 0.10 (± 0.03) ng mL−1for some samples and no analyte was detected (ND) in some cases Generally, concentrations obtained were below the water quality guideline values of United States Environmental Protection Agency (USEPA).

Determination of amino acid contents of manketti seeds (Schinziophyton rautanenii) by pre-column derivatisation with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate and RP-HPLC

Defatted kernel flour from manketti seed kernels (Schinziophyton rautanenii) is an underutilised natural product. The plant grows in the wild, on sandy soils little used for agriculture in Southern Africa. The kernels are rich in protein and have a great potential for improving nutrition. The protein content and amino acid profile of manketti seed kernel were studied, using a new analytical method, in order to evaluate the nutritional value. The crude protein content of the press cake and defatted kernel flour was 29.0% and 67.5%, respectively. Leucine and arginine were found to be the most abundant essential and non-essential amino acids, respectively. The seed kernel contained 4.77 g leucine and 12.34 g arginine/100 g of defatted seed kernel flour. Methionine and proline were the least abundant essential and non-essential amino acids to with 0.23 g methionine and 0.36 g proline/100 g of defatted seed kernel flour, respectively. Validation of the pre-column derivatisation procedure with 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) for the determination of amino acids was carried out. The analytical parameters were determined: linearity (0.0025-0.20 mM), accuracy of the derivatisation procedure: 86.7-109.8%, precision (method: 0.72-5.04%, instrumental: 0.14-1.88% and derivatisation: 0.15-2.94% and 0.41-4.32% for intraday and interday, respectively). Limits of detection and quantification were 6.80-157 mg/100 g and 22.7-523 mg/100 g kernel flour, respectively.

Characterisation of coal slurries for introduction into ICP OES for multi-element determinations

The characterisation and stability of coal slurries for introduction into an inductively coupled plasma optical emission spectrometer (ICP OES) and the application of slurries in the analysis of coal was investigated. The importance of rheology and the stability of the coal slurries on the analytical results produced by ICP OES was demonstrated. The homogeneity and stability of various coal slurries were characterised by sedimentation tests, scanning electron microscopy (SEM), zeta potential and viscosity measurements. The porosities and surface areas of different South African coals and a mechanism for the adsorption of the dispersants onto the coals were determined using low-temperature nitrogen physisorption studies. The possibility of partially solubulising the coal in N,N-dimethylformamide (DMF) was investigated. SEM indicated that DMF solubulised coal fines and that 0.1% (m/v) Triton X-100 with 10% (v/v) DMF resulted in well dispersed slurries relative to other dispersants (glycerol, PEI and water). Slurry analysis of coarse and ground coal in 0.1% (m/v) Triton X-100, showed that higher emission intensities and better precision was obtained when using ground coal. This was confirmed by lower RSDs (less than 5% for most of the elements analysed) relative to the unground, coarse coal. Glycerol slurries gave higher RSDs (higher than 5% for most of the elements) most of the time, thus negatively influencing the precision of measurement. Physisorption studies indicated that ground coal had up to ten times higher surface areas than coarse coal. The higher surface areas for fine ground coals suggested why they were better dispersed and thus better transported into the plasma, resulting in higher emission signals. Zeta potentials indicated that for all dispersants, the coal particles were well repelled from each other, although SEM pictures indicated better dispersion for 0.1% (m/v) Triton X-100 with 10% (v/v) DMF. It was demonstrated that higher intensities and higher precision could be obtained with well dispersed and stable coal slurries.

Adaptation and detoxification mechanisms of Vetiver grass (Chrysopogon zizanioides) growing on gold mine tailings

Vetiver grass (Chrysopogon zizanioides) was investigated for its potential use in the rehabilitation of gold mine tailings, its ability to extract and accumulate toxic metals from the tailings and its metal tolerant strategies. Vetiver grass was grown on gold mine tailings soil, in a hothouse, and monitored for sixteen weeks. The mine tailings were highly acidic and had high electrical conductivity. Vetiver grass was able to grow and adapt well on gold mine tailings. The results showed that Vetiver grass accumulated large amounts of metals in the roots and restricted their translocation to the shoots. This was confirmed by the bioconcentration factor of Zn, Cu, and Ni of >1 and the translocation factor of <1 for all the metals. This study revealed the defense mechanisms employed by Vetiver grass against metal stress that include: chelation of toxic metals by phenolics, glutathione S-tranferase, and low molecular weight thiols; sequestration and accumulation of metals within the cell wall that was revealed by the scanning electron microscopy that showed closure of stomata and thickened cell wall and was confirmed by high content of cell wall bound phenolics. Metal induced reactive oxygen species are reduced or eliminated by catalase, superoxide dismutase and peroxidase dismutase.

Degradation of galvanised iron roofing material in Tanzania by atmospheric corrosion

Abstract Galvanised iron is popular in many applications, particular as a roofing material. However, just like other materials, especially metallic ones, it is prone to degradation by corrosion. In this particular study, the degradation of galvanised roof sheets was investigated at a coastal, urban and rural site in Tanzania, Africa. Samples were exposed to various outdoor environments over a period of 3 years. In addition, some accelerated laboratory investigations were conducted in different simulated air pollution environments in an artificial corrosion chamber constructed for this purpose to supplement the outdoor exposure tests. It was found that the combination of the tropical climate and increasing air pollution due to industrial development in the capital Dar-es-Salaam resulted in substantial atmospheric corrosion of the roof sheets, which eventually leads to failure and the necessity for replacement. The rural site had the lowest degree of atmospheric corrosion as expected. A combination of different corrosion products was identified as a result of the atmospheric corrosion by Raman and EDX analyses. The information gained from this investigation could be utilised to construct more durable structures requiring less frequent replacement and maintenance in future.

Characterization of the Cultivation Region of Ethiopian Coffee by Elemental Analysis

ABSTRACT Forty-nine green coffee (Coffea arabica L.) bean samples, representing the Harar, Jimma, Kaffa, Wollega, Sidama, and Yirgachefe varieties from east, west, and south Ethiopia were analyzed for Mg, P, S, Ca, Mn, Fe, Cu, Ba, Si, and K using inductively coupled plasma-optical emission spectroscopy. Principal component analysis was used to group the samples based on their elemental compositions. Application of linear discriminant analysis provided models with an accuracy of 92% for region of production and 79% for variety. The elements P, Mn, S, Cu, and Fe were the most discriminating elements. These results show that initial screening may be performed to characterize possible fraudulently labelled products with verification by the existing paper-based traceability system and sensory evaluation.