Mercury speciation and dispersion from an active gold mine at the West Wits area, South Africa.

Total mercury (HgTOT), inorganic mercury (IHg), and methylmercury (MHg) were determined in dry season waters, sediments, and tailings from an active mine which has long history of gold exploitation. Although HgTOT in waters was generally low (0.03 to 19.60 ng L(-1)), the majority of the samples had proportions of MHg of at least 90 % of HgTOT which denotes a substantial methylation potential of the mine watersheds. Mercury was relatively high in tailing materials (up to 867 µg kg(-1)) and also in the mine sediments (up to 837 µg kg(-1)) especially in samples collected near tailing storage facilities and within a receiving water dam. Sediment profiles revealed mercury enrichment and enhanced methylation rate at deeper layers. The presence of IHg and decaying plants (organic matter) in the watersheds as well as the anoxic conditions of bulk sediments are believed to be some of the key factors favoring the mercury methylation at the site.

Removal of toxic elements from aqueous solution using bentonite modified with L-histidine.

This study proposes the use of bentonite modified with L-histidine for the removal of Cu, Co, Cr, Fe, Hg, Ni, U and Zn from aqueous solutions such as those impacted by acidic drainage. The surface areas of natural bentonite and bentonite-histidine were 73.8 and 61.2 m(2) g(-1), respectively. Elemental analysis showed an increase in the amount of carbon (0.258%) and nitrogen (0.066%) for the bentonite-histidine. At a fixed solid/solution ratio, the operating variables affecting the adsorption of metal ions from aqueous solution such as pH, initial concentration, contact time and temperature were studied in batch mode. The Freundlich isotherm model yielded a better fit than the Langmuir for the adsorption of Cu, Co, Ni and Zn, implying adsorption on a heterogeneous surface. Adsorption kinetics followed a pseudo-second-order model, suggesting chemisorption as the rate-limiting step. The apparent activation energy was greater than 40 kJ mol(-1) for Cu, Zn, Ni, Co and U, which is characteristic of a chemically controlled reaction. Thermodynamic constants ΔG and ΔH showed that the adsorption of metals was endothermic and spontaneous. Adsorption of heavy metals onto bentonite-histidine was efficient at low pH values, meaning that the adsorbent could be useful for remediating acid mine water.

Simple and efficient ion imprinted polymer for recovery of uranium from environmental samples.

Ion imprinted polymer material (IIP) was prepared by forming ternary complexes of uranyl imprint ion with 1-(prop-2-en-1-yl)-4-(pyridin-2-ylmethyl)piperazine and methacrylic acid followed by thermal copolymerization with ethylene glycol dimethacrylate as the cross-linking monomer in the presence of 1,1'-azobis(cyclohexanecarbonitrile) initiator and 2-methoxy ethanol porogenic solvent. HCl solution (5 mol/L) was used to leach out the uranyl template ion from the IIP particles. Similarly, the control polymer (CP) material was also prepared exactly under the same conditions as the IIP but without the uranyl ion template. Various parameters such as solution pH, initial concentration, aqueous phase volume, sorbent dosage, contact time and leaching solution volumes were investigated. SEM, IR and BET-surface area and pore size analysis were used for the characterization of IIP and CP materials. The extraction efficiency of the IIP and CP was compared using a batch and SPE mode of extraction. The optimal pH for quantitative removal is 4.0-8.0, sorbent amount is 20 mg, contact time is 20 min and the retention capacity is 120 mg of uranyl ion per g of IIP. The IIP prepared demonstrated superior selectivity towards coexisting cations and therefore it can be used for selective removal of uranium from complex matrices.

Multi-walled carbon nanotubes as adsorbents for the removal of parts per billion levels of hexavalent chromium from aqueous solution.

The adsorption capabilities for the removal of parts per billion levels (ppb) of hexavalent chromium by three adsorbents namely activated carbon, functionalized multi-walled carbon nanotubes (MWCNTs) and unfunctionalized multi-walled carbon nanotubes were investigated as a function of contact time, initial solution pH, initial Cr(VI) concentrations and the presence of competing anions. The unfunctionalized MWCNTs showed the highest adsorption capability with up to 98% of a 100 ppb Cr(VI) solution being adsorbed. Both functionalized and non-functionalized MWCNTs showed a superior adsorption capability to that of activated carbon. The removal of Cr(VI) was higher at lower pH. Furthermore, the uptake of Cr(VI) was hindered by the presence of the competing anions, Cl(-) and SO(4)(2-). Both Langmuir and Freundlich isotherms have been used to describe the Cr(VI) adsorption process. The major mechanisms for Cr(VI) removal have been identified as an ion exchange mechanism, intraparticle diffusion and electrostatic interactions. The adsorbed Cr(VI) could also be desorbed readily from the MWCNTs surface at high pH.

Performance optimization of a membrane assisted passive sampler for monitoring of ionizable organic compounds in water.

A thin-walled silicone rubber hollow fibre membrane has been developed as a passive sampler. The inside of the tube is filled with an aqueous solution at an appropriate pH. The tube is sealed at both ends and then immersed in a water sample. In order for the ionizable permeating compounds to be trapped in the aqueous receiving phase, the pH is adjusted such that the compounds are ionized and trapped. The major advantages are its simplicity, low cost and high selectivity, since only ionizable organic compounds are trapped. Additionally, the sampler uses no organic solvent. By adjusting the pH of the acceptor phase, it is possible to control the extraction process and whether the sampler is used in the kinetic or equilibrium regime. Since it is very selective, no further clean-up of the extract is required. The membrane assisted passive sampler has been tested for extraction of chlorophenols under laboratory conditions. The extraction process was found to be linear over a 72 h sampling period. Selectivity of the passive sampler in river water was demonstrated and the extraction process was independent of sample concentration, even at lower concentration levels of analytes. However, the sample matrix in some river water samples led to incomplete trapping, thereby reducing the amount trapped in the acceptor phase. Detection limits (three times signal to noise ratio) were dependant on sample matrix and type of detection system and ranged from 0.05 microg L(-1) to about 1 microg L(-1) with a UV photodiode detector in water samples from one river and 1.0 microg L(-1) to 20 microg L(-1) in another but with an ordinary UV detector. The enrichment factors in river water were 28 for 2-chlorophenol and 44 for 2,4-dichlorophenol over a 72 h sampling period. 4-chlorophenol was poorly extracted and its enrichment factor was 3.

Acid mine drainage arising from gold mining activity in Johannesburg, South Africa and environs.

The Witwatersrand region of South Africa is famous for its gold production and a major conurbation, centred on Johannesburg, has developed as a result of mining activity. A study was undertaken of surface and ground water in a drainage system in this area. Soils were also analysed from a site within the mining district. This study revealed that the ground water within the mining district is heavily contaminated and acidified as a result of oxidation of pyrite (FeS2) contained within mine tailings dumps, and has elevated concentrations of heavy metals. Where the water table is close to surface, the upper 20 cm of soil profiles are severely contaminated by heavy metals due to capillary rise and evaporation of the ground water. The polluted ground water is discharging into streams in the area and contributes up to 20% of stream discharge, causing a lowering of pH of the stream water. Much of the metal load is precipitated in the stream: Fe and Mn precipitate as a consequence of oxidation, while other heavy metals are being removed by co-precipitation. The oxidation of iron has created a redox buffer which controls the pH of the stream water. The rate of oxidation and of dilution is slow and the deleterious effect of the addition of contaminated water persists for more than 10 km beyond the source.

Protonation constant of monoaza-12-crown-4 ether and stability constants with selected metal ions in aqueous solution in the presence of an excess of sodium ion: a potentiometric and differential pulse polarographic study at fixed ligand to metal ratio and varied pH.

The ligand monoaza-12-crown-4 ether (A12C4) was studied in aqueous solution at 298 K and an ionic strength of 0.5 mol dm(-3) in the presence of an excess of sodium ion (0.5 mol dm(-3) NaNO(3)). The protonation constant of A12C4, determined by glass electrode potentiometry (GEP) in the same background electrolyte, was found to be logK=9.36+/-0.03. Polarographic experimental and calculated complex formation curves (ECFC and CCFC) for labile metal-ligand systems, studied at a fixed total ligand (L(T)) to total metal (M(T)) concentration ratio and varied pH, were used for the modelling of the metal species formed and the refinement of their stability constants. The metal-ligand model and formation constants are optimised by solving mass-balance equations written for the assumed model and by fitting the CCFC to the ECFC. The CCFC can be generated for any metal-ligand model, including polynuclear metal species, for any L(T):M(T) ratio, and for more than one ligand competing in the complex formation reaction. Three lead complexes with the ligand A12C4, viz. PbL(2+), PbL(OH)(+) and PbL(OH)(2), were found and their overall stability constants from differential pulse polarography (DPP), as logbeta, were estimated to be 3.75+/-0.03, 9.30+/-0.05 and 12.70+/-0.05, respectively. Two copper complexes CuL(2+) and CuL(OH)(2) are reported and their stability constants (from DPP) were estimated to be 6.00+/-0.05 and 21.77+/-0.1, respectively. Two cadmium complexes CdL(2+) and CdL(OH)(+) are reported. The stability constant for CdL(2+) was estimated from DPP and GEP as 2.80+/-0.05 and 2.68+/-0.03 (the latter value was obtained from a few potentiometric experimental points), respectively, and the stability constant for CdL(OH)(+) from DPP was estimated to be 7.88+/-0.05. GEP could not be used for the stability constants determination of other metal complexes studied because of precipitation occurring prior the completion of a complex formation reaction.

Direct zinc determination in commercial sulphuric acid by dpasv. Comparison of rotating disc and stationary graphite electrodes.

A striking gas technique employed made a direct Zn determination possible at extremely low pH in commercial acid solutions when a stationary impregnated graphite-based mercury film electrode was used. The original Zn(II) concentrations were determined quantitatively by differential pulse anodic stripping voltammetry on 0.5M and 1M sulphuric acid solutions by standard addition and were found to be 2 x 10(-8)M and 4.1 x 10(-8)M, respectively. The influence of mercury ion concentration, pulse amplitude, potential step and pulse repetition time on analytical data was studied and optimized. A rotating disc graphite electrode was also used as a working electrode and was found unreliable for this purpose as hydrogen bubbles were not removed effectively and blocked the working electrode surface.

The influence of pH on cadmium toxicity to the green alga Stichococcus bacillaris and on the cadmium forms present in the culture medium.

Cadmium toxicity to the green alga Stichococcus bacillaris was investigated in media of pH 3-9. A significant decrease of cadmium toxicity occurred in both the acidic and alkaline ranges of pH. In media of pH 3 and 9, cadmium did not affect the dry mass content substantially. Maximum toxicity of cadmium was noticed at pH 6-7. Voltametric investigations showed a significant effect of pH on electrochemically measured cadmium content in the culture media. Hydrolysis of the medium components and formation of cadmium complexes with OH(-) ions caused a considerable decrease in amounts of electrochemically measured cadmium in the alkaline range of pH.