The nature of gas production patterns associated with methanol degradation in natural aquifer sediments: A microcosm study.

With growing global use of methanol as a fuel additive and extensive use in other industrial processes, there is the potential for unintended release and spills into soils and aquifers. In these subsurface systems it is likely that methanol will be readily biodegraded; however, degradation may lead to the production of by-products, most importantly methane possibly resulting in explosion hazards and volatile fatty acids (VFAs) causing aesthetic issues for groundwater. In this study, the formation of these potentially harmful by-products due to methanol biodegradation was investigated in natural sand and silt sediments using microcosms inoculated with neat methanol (100%) ranging in concentration from 100 to 100,000 ppm. To assess the rate of degradation and by-product formation, water and headspace samples were collected and analyzed for methanol, volatile fatty acids (VFAs, including acetic, butyric, and propionic acid), cation (metal) concentrations (Al, Ca, Fe, K, Mg, Mn and Na), microbial community structure and activity, headspace pressure, gas composition (CH4, CO2, O2 and N2), and compound specific isotopes. Methanol was completely biodegraded in sand and silt up to concentrations of 1000 ppm and 10,000 ppm, respectively. Degradation was initially aerobic, consuming oxygen (O2) and producing carbon dioxide (CO2). When O2 was depleted, the microcosms became anaerobic and a lag in methanol degradation occurred (ranging from 41 to 87 days). Following this lag, methanol was preferentially degraded to acetate, coupled with CO2 reduction. Microcosms with high methanol concentrations (10,000 ppm) were driven further down the redox ladder and exhibited fermentation, leading to concurrent acetate and methane (CH4) generation. In all cases acetate was an intermediate product, further degraded to the final products of CH4 and CO2. Carbonates present in the microcosm sediments helped buffer VFA acidification and replenished CO2. Methane generation in the anaerobic microcosms was short-lived, but temporarily reached high rates up to 13 mg kg-1 day-1. Under the conditions of these experiments, methanol degradation occurred rapidly, after initial lag periods, which were a function of methanol concentration and sediment type. Our experiment also showed that methanol degradation and associated methane production can occur in a stepwise fashion.

Long-term monitoring of waste-rock weathering at the Antamina mine, Peru.

The weathering of mine waste rock can cause release of metal-laden and acidic drainage that requires long-term and costly environmental management. To identify and quantify the geochemical processes and physical transport mechanisms controlling drainage quality, we monitored the weathering of five large-scale (20,000 t) instrumented waste-rock piles of variable and mixed-composition at the Antamina mine, Peru, in a decade-long monitoring program. Fine-grained, sulfidic waste rock with low-carbonate content exhibited high sulfide oxidation rates (>1 g S kg-1 waste rock yr-1) and within 7 years produced acidic (pH < 3) drainage with high Cu and Zn concentrations in the g L-1 range. In contrast, drainage from coarse, carbonate-rich waste rock remained neutral for >10 years and had significantly lower metal loads. Efficient metal retention (>99%) caused by sorption and secondary mineral formation of e.g., gypsum, Fe-(oxy)hydroxides, and Cu/Zn-hydroxysulfates enforced strong (temporary) controls on drainage quality. Furthermore, reactive waste-rock fractions, as small as 10% of total mass, dominated the overall drainage chemistry from the waste-rock piles through internal mixing. This study demonstrates that a reliable prediction of the timing and quality of waste-rock drainage on practice-relevant spatiotemporal scales requires a quantitative understanding of the prevailing in-situ porewater conditions, secondary mineralogy, and spatial distribution of reactive waste-rock fractions in composite piles.