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.     

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.     

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.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic Bromeliad species as biomonitor and measuring total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

Risk assessment of contaminated sediments in river basins--theoretical considerations and pragmatic approach

In order to ensure chemical quality of river basins, measures as required in the Water Framework Directive will also have to address contaminated sediments with subsequent monitoring of their successful application. Financial resources need to be allocated as part of a river basin plan to those contaminated sites that pose the biggest risk to the river basin. In order to differentiate between areas with elevated contaminant levels ("areas of concern") and those sites from which contaminated sediments can become resuspended and transported with the river, affecting the water phase and downstream sites in the catchment ("areas of risk"), the dynamics of sediment and suspended matter need to come into focus. Hydrological data have to be combined with concentration of suspended matter and its contaminant concentration to allow assessment of particle bound contaminant load. Each of these kinds of data, however, are subject to uncertainties--e.g. due to natural variability, heterogeneity of the matrix, challenges during sampling and chemical analyses of the suspended matter. Considering these uncertainties throughout the traceability chains of data collection, use of different lines of evidence and tools like fuzzy logic will increase the confidence of potentially costly management decisions.