Spectroscopy, Morphology, and Electrochemistry of Electrospun Polyamic Acid Nanofibers.

Polyamic acid (PAA) nanofibers produced by using the electrospinning method were fully characterized in terms of morphology and spectroscopy. A PAA nanofiber-modified screen-printed carbon electrode was applied to the detection of selected sulfonamides by following an electroanalytical protocol. The polyamic acid (PAA) nanofibers were characterized using Fourier transform infrared (FTIR) spectroscopy to study the integrity of polyamic acid functional groups as nanofibers by comparing them to chemically synthesized polyamic acid. A scanning electron microscope (SEM) was used to confirm the morphology of the produced nanofibers and 3D arrangement at the electrode interface. The Brunauer-Emmett-Teller (BET) method was used to determine the surface area of the nanofibers. Atomic force microscopy (AFM) was used to study the porosity and surface roughness of the nanofibers. Electrochemical evaluation based on diffusion-controlled kinetics was applied to determine the number of electrons transferred in the system, the surface concentration of the deposited PAA thin film (2.14 × 10-6 mol/cm2), and the diffusion coefficient (De) for the PAA nanofiber-modified screen-printed carbon electrode (9.43 × 10-7 cm-2/s). The reported LODs for sulfadiazine and sulfamethazine detection are consistent with requirements for trace-level monitoring by early warning diagnostic systems.

Particle Size-Controlled Growth of Carbon-Supported Platinum Nanoparticles (Pt/C) through Water-Assisted Polyol Synthesis.

A water-assisted control of Pt nanoparticle size during a surfactant-free, microwave-assisted polyol synthesis of the carbon-supported platinum nanoparticles (Pt/C) in a mixture of ethylene glycol and water using (NH4)2PtCl6 as the Pt precursor is demonstrated. The particle size was tuned between ∼2 and ∼6 nm by varying either the H2O volume percent or the Pt precursor concentration during synthesis. The electrochemical surface area (ECSA) and the oxygen-reduction reaction activity obtained for the Pt/C electrocatalyst show a catalytic performance competitive to that of the state-of-the-art commercial Pt/C electrocatalysts used for polymer electrolyte membrane fuel cell electrodes (ECSA: ∼70 m2/g; half-wave potential for oxygen reduction reaction: 0.83 V vs reversible hydrogen electrode). The synthesized Pt/C electrocatalysts show durability equivalent to or better than that of the commercial Pt/C. The durability was found to improve with increasing particle size, with the ECSA loss values being ∼70 and ∼55% for the particle sizes of 2.1 and 4.3 nm, respectively. The study may be used as a route to synthesize Pt/C electrocatalysts from a convenient and economic Pt precursor (NH4)2PtCl6 and avoiding the use of alkaline media.

The reach of human health risks associated with metals/metalloids in water and vegetables along a contaminated river catchment: South Africa and Mozambique.

BACKGROUND: Anthropogenic pollution was identified as an environmental problem of concern when, in 2008, dozens of crocodiles died in the Olifants River catchment near the border of South Africa and Mozambique. Given the close proximity of households to the river and their making use of river water, we aimed to determine to what extent water pollution has an impact on health of indigent communities in South Africa and Mozambique in the catchment area. METHODS: Water and vegetable samples were collected from the study areas. Biota samples were washed with double de-ionized Milli-Q water and freeze-dried. Heavy metal analyses in water and vegetables were done by means of Inductively Coupled Plasma Optical Emission Spectroscopy. Metal concentrations were applied in a human health risk assessment to estimate health risks. RESULTS: Mean concentrations of antimony, arsenic, cadmium, chromium, mercury, molybdenum, nickel and selenium in water samples from South Africa exceeded the World Health Organization guidelines for safe levels of intake. Only iron exceeded the recommended guidelines in water samples from Mozambique. Metals/metalloids were found in lower concentrations at Mozambique sites downstream of South African sites. In vegetables, uranium was between 10 and 20 times above safe guidelines in South Africa and between 3 and 6 times in Mozambique. Arsenic in water samples posed the highest cancer risk. CONCLUSIONS: Even with a reduction in the metal concentrations in river water from South Africa to Mozambique, the potential to cause adverse human health impacts from direct use of polluted river water is evident in both countries.

Aluminium (Al) fractionation and speciation; getting closer to describing the factors influencing Al(3+) in water impacted by acid mine drainage.

Acid mine drainage (AMD) severely impacts the water chemistry of a receiving resource, changing the occurrence, speciation and toxicity of metals such as Aluminium (Al). The toxicity of Al is determined by its speciation represented by the labile monomer Al fraction or Al(3+). The purpose of the study was to combine fractionation and Visual MINTEQ speciation to calculate the effect of AMD altered water chemistry on Al speciation and Al(3+) concentration. Water in rivers impacted by AMD presented with monomeric Al (Almon) concentrations between 0.35 and 15.37mgL(-)(1) which existed almost exclusively in the toxic labile form (98%). For the reference site, Almon was less than 2% (10µgL(-1)), suggesting significantly lower Al toxicity. Principal component analysis plots illustrated that labile Al was directly related to the total Al and iron concentrations and strongly influenced by parameters such as pH, electrical conductivity, sulphate and dissolved organic carbon. Visual MINTEQ modelling was used to determine the primary Al species distribution. The dominant form of Al in AMD impacted water was AlSO4(+), which increased proportionally with the sulphate and Al(3+) concentration. Heavily impacted areas, presented with an average of 1mgmL(-)(1) Al(3+), which poses a potential human health risk. A novel centrifugal ultrafiltration method was investigated as an alternative to determining Almon to simplify the speciation of Al. Monomeric and centrifugal ultrafiltrated (<10kD) Al fractions were significantly similar (p=0.74), suggesting that ultrafiltration may present a time, energy and cost saving alternative to organic extraction of Almon.

Photoelectrochemical determination of inorganic mercury in aqueous solutions.

An analytical method using an optical probe in a photoelectrochemical cell for the sensitive and selective determination of aqueous Hg(2+) is presented. A previously synthesized Hg(2+) selective chemosensor, proven to be Hg(2+) sensitive up to 2 microg L(-1), has been immobilized onto indium tin oxide (ITO) electrodes in a composite form with polyaniline. The coated ITO electrode was placed in a photoelectrochemical cell under closed circuit conditions in which the optical recognition of the chemosensor was converted to a measurable signal. A composite of the fluorescent chemosensor, Rhodamine 6G derivative (RS), and polyaniline (PANI) was immobilized on ITO glass plates and subjected to photovoltage measurements in the absence and presence of Hg(2+). The optical responses of the coated electrode were used to determine the sensitivity and selectivity of the immobilized sensor to Hg(2+) in the presence of background ions. The optical response of the PANI-dye coated electrode increased linearly with increasing Hg(2+) concentration in the range 10-150 microg L(-1), with a detection limit of 6 microg L(-1).