Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

Fate of autumn-applied metolachlor in a clay loam in the northern U.S. Corn Belt

Application of herbicides in autumn is of interest to land managers who seek to reduce the number of field operations during spring in the northern Corn Belt. A limited number of herbicides, however, posses the physical characteristics that are required to minimize loss from soil over winter. This study examined the fate of one of these herbicides, metolachlor, during three consecutive winters (1994-1995, 1995-1996, and 1996-1997) near Morris, MN. Metolachlor was applied to the top 5 cm of a clay loam that was packed into a 1.8-m long plastic pipe. The pipe was then set inside a larger diameter 1.8-m long plastic pipe that was buried vertically in the field. The gap between the pipes was insulated along the sides and sealed at the top; this configuration allowed collection of leachate and extraction of the smaller diameter pipe while the field soil was frozen. The experimental design was replicated thrice with sample date (date that the smaller diameter pipes were extracted from the field) as the main treatment. Pipes were extracted from the field at least twice during winter and sectioned into 2 cm or larger increments. The soil contained within these sections was then analyzed for metolachlor. Downward movement of metolachlor occurred in the soil profile during the autumn, but only in 1995. This movement was likely caused by exclusion during pore ice formation as the soil froze. At the time of complete soil thaw in spring, the majority of metolachlor was still detected in the zone of application (0-5 cm depth). Some metolachlor, however, was detected 1 to 3 cm below the zone of application in all three years. Downward movement during thaw was due primarily to infiltration of snowmelt and rain. Metolachlor was most vulnerable to degradation during spring, but some loss occurred in autumn prior to freeze-up. This study suggests that autumn-applied metolachlor moves little in a repacked clay loam profile during winter. Further studies are warranted in evaluating movement under a range of soil physical properties and management practices.     

Saturated and Unsaturated Water Flow in Inclined Porous Media

This paper considers the two-dimensional saturated and unsaturated flow of water through inclined porous media, namely a waste dump or hill slope. Since the partial differential equation governing this water flow transforms from being parabolic to elliptic as the water flow varies from unsaturated to saturated, an iterative, finite differencing scheme is used to develop a numerical solution. The model can be used to investigate the effects that hill slope angle, depth of soil cover and hilltop width have on water accumulation in the dump and the time required for saturation to occur at different areas in the dump domain. The accuracy and reliability of the computer based solution is tested for two different boundary conditions – (1) no flow on all boundaries (i.e., the internal redistribution of soil moisture to steady state) and (2) a constant rainfall flux on the dump surface. Numerical studies then show the effects of changing the hill slope angle, depth of layer, and dump geometry on the flow characteristics in the dump.     

A thermodynamically based method to quantify true sorption hysteresis

Sorption of organic chemicals to soils and sediments often shows true hysteresis (i.e., nonsingularity of the sorption-desorption isotherm not attributable to known experimental artifacts). Since true sorption hysteresis is fundamentally important to contaminant fate, a way to quantify it is desirable. Previously proposed indices of hysteresis are empirical and usually depend on the isotherm model. True sorption hysteresis to synthetic and natural organic solids has been attributed to irreversible alteration of the solid during the sorption-desorption cycle. Given this mechanism, we propose the Thermodynamic Index of Irreversibility (TII) for quantifying hysteresis in soils where natural organic matter dominates the sorption process. The TII is based on the difference in free energy between the real desorption state and the hypothetical fully reversible state. The index is 0 for completely reversible systems and approaches 1 as the process tends toward complete irreversibility. It does not require any assumptions about the physical properties or molecular composition of the solid, and it does not depend on a specific equilibrium model. A sensitivity analysis of measurement errors provides general recommendations for the setup of sorption-desorption experiments. The TII was applied to sorption of 1,4-dichlorobenzene (DCB) to two high-organic soils, Pahokee peat (PP) and Amherst soil (AS), and a low-rank coal reference material, Beulah-Zap lignite (BZL). Common artificial causes of hysteresis were eliminated. Hysteresis was significant in the peat and the coal. The TII was clearly concentration dependent for both solids; it decreased with concentration for the peat, but increased with concentration for the coal. The TII allows quantification of hysteresis as a function of sorbate-sorbent combination, concentration, time, and other variables.     

Assessment of chemical process hazards in early design stages

A new method called SREST-layer-assessment method with automated software tool is presented that in a hierarchical approach reveals the degree of non-ideality of chemical processes with regard to SHE (safety, health and environment) aspects at different layers: the properties of the chemical substances involved (substance assessment layer (SAL)), possible interactions between the substances (reactivity assessment layer (RAL)), possible hazard scenarios resulting from the combination of substances and operating conditions in the various equipments involved (equipment assessment layer (EAL)), and the safety technologies that are required to run a process safely and in accordance with legal regulations (safety-technology assessment layer (STAL)). In RAL, EAL and STAL the main focus is put on process safety. A case study is used to show the principles of the method. It is demonstrated how the method can be used as a systematic tool to support chemical engineers and chemists in evaluating chemical process safety in early process development stages.     

Closing remarks: novel approaches to complex societal change and sustainability

This paper summarizes some personal impressions of the 7th conference of the International Complex Systems Society, co-organized with “Future Earth”, held in Stockholm on August 24–26, 2017. The main point is that it is urgent and important to consider the sustainability conundrum as long-term, society-driven one, and to place societal dynamics at the core of how we, as a global society, came to this point, how ongoing dynamics are driving us towards a tipping point, and which role the Information and Communication Technology revolution plays in that process. A much wider involvement of the social sciences is essential. This also requires major changes in our thinking about sustainability—we need to develop an approach in which change is the natural state of affairs and societies attempt to impose stability on the dynamics involved. We need to focus on learning from the past, about the present, but above all for the future. And we need to shift from an entity-focused approach to a relational one, which pays more attention to contexts and networks. Other issues raised by such a shift in our thinking are about the role of science, the adoption of complex systems approaches and a few others that the paper points to.     

Test of aerobic TCE degradation by willows (Salix viminalis) and willows inoculated with TCE-cometabolizing strains of Burkholderia cepacia

Environmental Science and Pollution Research - Trichloroethylene (TCE) is a widespread soil and groundwater pollutant and clean-up is often problematic and expensive. Phytoremediation may be a...     

Phosphine by bio-corrosion of phosphide-rich iron

Phosphine is a toxic agent and part of the phosphorus cycle. A hitherto unknown formation mechanism for phosphine in the environment was investigated. When iron samples containing iron phosphide were incubated in corrosive aquatic media affected by microbial metabolites, phosphine was liberated and measured by gas chromatography. Iron liberates phosphine especially in anoxic aquatic media under the influence of sulfide and an acidic pH. A phosphine-forming mechanism is suggested: Phosphate, an impurity of iron containing minerals, is reduced abioticly to iron phosphide. When iron is exposed to the environment (e.g. as outdoor equipment, scrap, contamination in iron milled food or as iron meteorites) and corrodes, the iron phosphide present in the iron is suspended in the medium and can hydrolyze to phosphine. Phosphine can accumulate to measurable quantities in anoxic microbial media, accelerating corrosion and preserving the phosphine formed from oxidation.     

Estimation of the impact of prevailing weather conditions on the occurrence of oil-contaminated dead birds on the German North Sea coast

Chronic oil pollution by illegal oil dumping in the North Sea is difficult to quantify. Beached, oil-contaminated sea birds, however, may be used as an indirect indicator. Reconstructing the drift of oil slicks and sea bird corpses in the southern North Sea for the period 1992-2003 by means of a two-dimensional numerical transport model driven by re-analysed weather data, we show with an example of two common sea bird species that the variability observed within the number of corpses registered during beached bird surveys for the German coast primarily reflects the inter-annual variability of prevailing weather conditions. This should be taken into account when interpreting the data. We propose normalisation of beached bird survey data based on numerical drift simulations to improve the recognition of trends in the level of chronic oil pollution.