Voltammetric determination of inorganic arsenic in mildly acidified (pH 4.7) groundwaters from Mexico and India.

Routine monitoring of inorganic arsenic in groundwater using sensitive, reliable, easy-to-use and affordable analytical methods is integral to identifying sources, and delivering appropriate remediation solutions, to the widespread global issue of arsenic pollution. Voltammetry has many advantages over other analytical techniques, but the low electroactivity of arsenic(V) requires the use of either reducing agents or relatively strong acidic conditions, which both complicate the analytical procedures, and require more complex material handling by skilled operators. Here, we present the voltammetric determination of total inorganic arsenic in conditions of near-neutral pH using a new commercially available 25 µm diameter gold microwire (called the Gold Wirebond), which is described here for the first time. The method is based on the addition of low concentrations of permanganate (10 µM MnO4-) which fulfils two roles: (1) to ensure that all inorganic arsenic is present as arsenate by chemically oxidising arsenite to arsenate and, (2) to provide a source of manganese allowing the sensitive detection of arsenate by anodic stripping voltammetry at a gold electrode. Tests were carried out in synthetic solutions of various pH (ranging from 4.7 to 9) in presence/absence of chloride. The best response was obtained in 0.25 M chloride-containing acetate buffer resulting in analytical parameters (limit of detection of 0.28 µg L-1 for 10 s deposition time, linear range up to 20 µg L-1 and a sensitivity of 63.5 nA ppb-1. s-1) better than those obtained in acidic conditions. We used this new method to measure arsenic concentrations in contrasting groundwaters: the reducing, arsenite-rich groundwaters of India (West Bengal and Bihar regions) and the oxidising, arsenate-rich groundwaters of Mexico (Guanajuato region). Very good agreement was obtained in all groundwaters with arsenic concentrations measured by inductively coupled plasma-mass spectrometry (slope = +1.029, R2 = 0.99). The voltammetric method is sensitive, faster than other voltammetric techniques for detection of arsenic (typically 10 min per sample including triplicate measurements and 2 standard additions), easier to implement than previous methods (no acidic conditions, no chemical reduction required, reproducible sensor, can be used by non-voltammetric experts) and could enable cheaper groundwater surveying campaigns with in-the-field analysis for quick data reporting, even in remote communities.

Low-cost electrochemical detection of arsenic in the groundwater of Guanajuato state, central Mexico using an open-source potentiostat.

Arsenic is a carcinogenic groundwater contaminant that is toxic even at the parts-per-billion (ppb) level and its on-site determination remains challenging. Colorimetric test strips, though cheap and widely used, often fail to give reliable quantitative data. On the other hand, electrochemical detection is sensitive and accurate but considerably more expensive at the onset. Here, we present a study on arsenic detection in groundwater using a low-cost, open-source potentiostat based on Arduino technology. We tested different types of gold electrodes (screen-printed and microwire) with anodic stripping voltammetry (ASV), achieving low detection limits (0.7 µg L-1). In a study of arsenic contaminated groundwaters in Mexico, the microwire technique provides greater accuracy than test strips (reducing the median error from -50% to +2.9%) and greater precision (reducing uncertainties from ±25% to ±4.9%). Most importantly, the rate of false negatives versus the World Health Organisation's 10 µg L-1 limit was reduced from 50% to 0% (N = 13 samples). Arsenic determination using open-source potentiostats may offer a low-cost option for research groups and NGOs wishing to perform arsenic analysis in-house, yielding superior quantitative data than the more widely used colorimetric test strips.

A multi-criteria decision analysis of management alternatives for anaerobically digested kraft pulp mill sludge.

The Multi-Criteria Decision Analysis (MCDA) procedure was used to compare waste management options for kraft pulp mill sludge following its anaerobic digestion. Anaerobic digestion of sludge is advantageous because it produces biogas that may be used to generate electricity, heat and biofuels. However, adequate management of the digested sludge is essential. Landfill disposal is a non-sustainable waste management alternative. Kraft pulp mill digested sludge applied to land may pose risks to the environment and public health if the sludge has not been properly treated. This study is aimed to compare several recycling alternatives for anaerobically digested sludge from kraft pulp mills: land application, landfill disposal, composting, incineration, pyrolysis/gasification, and biofuel production by algae. The MCDA procedure considered nine criteria into three domains to compare digested sludge recycling alternatives in a kraft pulp mill: environmental (CO2 emission, exposure to pathogens, risk of pollution, material and energy recovery), economic (overall costs, value of products) and technical (maintenance and operation, feasibility of implementation). The most suitable management options for digested sludge from kraft pulp mills were found to be composting and incineration (when the latter was coupled with recycling ash to the cement industry). Landfill disposal was the worst option, presenting low performance in feasibility of implementation, risk of pollution, material and energy recovery.