A comparison of the low frequency electrical signatures of iron oxide versus calcite precipitation in granular zero valent iron columns

Geophysical methods have been proposed as technologies for non-invasively monitoring geochemical alteration in permeable reactive barriers (PRBs). We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in Fe0 columns using (a) Na2SO4, and (b) NaHCO3 plus CaCl2 mixture, solutions. At the influent interface where the reactions were most severe, a contrasting time-lapse electrical response was observed between the two columns. Solid phase analysis confirmed the formation of corrosion halos and increased mineralogical complexity in the corroded sections of the columns compared to the minimal/non-corroded sections. We attribute the contrasting time-lapse signatures to the differences in the electrical properties of the mineral phases formed within the two columns. While newly precipitated/transformed polarizable and semi-conductive iron oxides (mostly magnetite and green rust) increase the polarization and conductivity of the sulfate column, the decrease of both parameters in the bicarbonate column is attributed to the precipitation of non-polarizable and non-conductive calcite. Our results show that precipitate mineralogy is an important factor influencing the electrical properties of the corroded iron cores and must be considered if electrical geophysical methods are to be developed to monitor PRB barrier corrosion processes in situ.     

Calcite precipitation dominates the electrical signatures of zero valent iron columns under simulated field conditions

Calcium carbonate is a secondary mineral precipitate influencing zero valent iron (ZVI) barrier reactivity and hydraulic performance. We conducted column experiments to investigate electrical signatures resulting from concurrent CaCO₃ and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO₃ as a major mineral phase throughout the columns, with magnetite present primarily close to the influent based on XRD analysis. Electrical measurements revealed decreases in conductivity and polarization of both columns, suggesting that electrically insulating CaCO₃ dominates the electrical response despite the presence of electrically conductive iron oxides. SEM/EDX imaging suggests that the electrical signal reflects the geometrical arrangement of the mineral phases. CaCO₃ forms insulating films on ZVI/magnetite surfaces, restricting charge transfer between the pore electrolyte and ZVI particles, as well as across interconnected ZVI particles. As surface reactivity also depends on the ability of the surface to engage in redox reactions via charge transfer, electrical measurements may provide a minimally invasive technology for monitoring reactivity loss due to CaCO₃ precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.     

European risk assessment of LAS in agricultural soil revisited: species sensitivity distribution and risk estimates

Linear alkylbenzene sulphonate (LAS) is used at a rate of approximately 430,000 tons/y in Western Europe, mainly in laundry detergents. It is present in sewage sludge (70-5,600 mg/kg; 5-95th percentile) because of its high usage per capita, its sorption and precipitation in primary settlers, and its lack of degradation in anaerobic digesters. Immediately after amendment, calculated and measured concentrations are <1 to 60 mg LAS/kg soil. LAS biodegrades rapidly in soil with primary and ultimate half-lives of up to 7 and 30 days, respectively. Calculated residual concentrations after the averaging time (30 days) are 0.24-18 mg LAS/kg soil. The long-term ecotoxicity to soil microbiota is relatively low (EC10 >or=26 mg sludge-associated LAS/kg soil). An extensive review of the invertebrate and plant ecotoxicological data, combined with a probabilistic assessment approach, led to a PNEC value of 35 mg LAS/kg soil, i.e. the 5th percentile (HC5) of the species sensitivity distribution (lognormal distribution of the EC10 and NOEC values). Risk ratios were identified to fall within a range of 0.01 (median LAS concentration in sludge) to 0.1 (95th percentile) and always below 0.5 (maximum LAS concentration measured in sludge) according to various scenarios covering different factors such as local sewage influent concentration, water hardness, and sewage sludge stabilisation process. Based on the present information, it can be concluded that LAS does not represent an ecological risk in Western Europe when applied via normal sludge amendment to agricultural soil.     

Simulation of wind-driven dispersion of fire pollutants in a street canyon using FDS

Air quality in urban areas attracts great attention due to increasing pollutant emissions and their negative effects on human health and environment. Numerous studies, such as those by Mouilleau and Champassith (J Loss Prevent Proc 22(3): 316–323, 2009), Xie et al. (J Hydrodyn 21(1): 108–117, 2009), and Yassin (Environ Sci Pollut Res 20(6): 3975–3988, 2013) focus on the air pollutant dispersion with no buoyancy effect or weak buoyancy effect. A few studies, such as those by Hu et al. (J Hazard Mater 166(1): 394–406, 2009; J Hazard Mater 192(3): 940–948, 2011; J Civ Eng Manag (2013)) focus on the fire-induced dispersion of pollutants with heat buoyancy release rate in the range from 0.5 to 20 MW. However, the air pollution source might very often be concentrated and intensive, as a consequence of the hazardous materials fire. Namely, transportation of fuel through urban areas occurs regularly, because it is often impossible to find alternative supply routes. It is accompanied with the risk of fire accident occurrences. Accident prevention strategies require analysis of the worst scenarios in which fire products jeopardize the exposed population and environment. The aim of this article is to analyze the impact of wind flow on air pollution and human vulnerability to fire products in a street canyon. For simulation of the gasoline tanker truck fire as a result of a multivehicle accident, computational fluid dynamics large eddy simulation method has been used. Numerical results show that the fire products flow vertically upward, without touching the walls of the buildings in the absence of wind. However, when the wind velocity reaches the critical value, the products touch the walls of the buildings on both sides of the street canyon. The concentrations of carbon monoxide and soot decrease, whereas carbon dioxide concentration increases with the rise of height above the street canyon ground level. The longitudinal concentration of the pollutants inside the street increases with the rise of the wind velocity at the roof level of the street canyon.