Modelling of geochemical and isotopic changes in a column experiment for degradation of TCE by zero-valent iron

Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.     

Application and test of a simple tool for operational footprint evaluations

We present a user-friendly tool for footprint calculations of flux measurements in the surface layer. The calculations are based on the analytical footprint model by Kormann, R. and Meixner, F.X. [2001. An analytical footprint model for Non-neutral Stratification. Boundary-Layer Meteorology 99, 207-224]. The footprint density function of a flux sensor is determined using readily available data from standard eddy covariance measurements. This footprint density function is integrated over defined surface areas given as quadrangular polygons representing e.g. agricultural fields. We illustrate the use and performance of the tool by applying it to CO2 flux measurements with three eddy covariance system at the Swiss CarboEurope grassland site. Two flux towers were positioned in the centre of two neighbouring fields, respectively, that showed a very different CO2 flux during the study period. The third tower was located near the border of the two fields and was frequently influenced by both fields to a similar degree. The calculated footprint fractions were used to simulate the latter flux from the other two systems. The measured and simulated fluxes showed a good agreement and thus support the reliability of the footprint calculation. The presented simple footprint tool can be used as a routine quality check for flux monitoring stations influenced by surface areas with varying vegetation covers and/or land-use.     

Gesellschaftlicher Wandel und nachhaltige Entwicklung

Zusammenfassung   Hintergrund, Ziel und Themenbereich Um die Auswirkungen des gesellschaftlichen Wandels unter dem Kriterium der Nachhaltigkeit beurteilen zu k?nnen werden demographische, soziale und kulturelle Entwicklungen in den Blick genommen. Am Beispiel der Handlungsfelder ‚Bauen und Wohnen‘, ‚Infrastruktursysteme‘, ‚Verkehr und Mobilit?t‘ werden absehbare Entwicklungen aufgezeigt, und Handlungsspielr?ume und Instrumente für eine nachhaltige Gestaltung des gesellschaftlichen Wandels beschrieben. Schwerpunkte Demographischer Wandel, Sozio-kultureller Wandel, Auspr?gung des gesellschaftlichen Wandels in Schleswig-Holstein, Handlungsfelder ‚Bauen und Wohnen‘, ‚Infrastruktursysteme‘, ‚Mobilit?t und Verkehr‘, Umweltauswirkungen des gesellschaftlichen Wandels. Ergebnisse Weniger die absolute Zahl als vielmehr das von vielerlei Einflüssen gepr?gte Konsumverhalten der Menschen stellt unter Nachhaltigkeitsaspekten ein wichtiges Kriterium das. Ein wesentliches Kennzeichen des Wandels von der industriellen zur postindustriellen Gesellschaft ist eine Pluralisierung der Lebensstile und der damit verbundenen Konsummuster in nachhaltigkeitsrelevanten Handlungsfeldern. Diskussion Eine Vielzahl von Techniken steht zur Reduzierung des Umweltverbrauchs zur Verfügung. Dazu z?hlen z. B. w?rmeged?mmte H?user sowie strom- und wassersparende Haushaltsger?te, und verbrauchsarme Fahrzeuge mit geregeltem Katalysator. Ob diese Techniken eingesetzt werden, h?ngt dabei weniger von technischen als von kulturellen, politischen und ?konomischen Weichenstellungen ab. Schlussfolgerungen Der gesellschaftliche Wandel wird, wenn nicht gegengesteuert wird, massive Auswirkungen auf die Umwelt haben. Anders als man auf den ersten Blick vermuten k?nnte, wird es keine ‚Demographie-Rendite‘ geben. Auch die Nachhaltigkeitsbilanz der Postmaterialisten kann kaum positiver bewertet werden, als die der eher materiell eingestellten Menschen. Empfehlungen und Perspektiven Die Politik sollte die mit dem gesellschaftlichen Wandel verbundenen Probleme thematisieren, ihre Auswirkungen analysieren und zusammen mit den Akteuren einen umfassenden gesellschaftlichen Dialog- und Verst?ndigungsprozess initiieren. Dabei ist mit schnellen L?sungen nicht zu rechnen, denn die Komplexit?t der Thematik, die unterschiedlichen Interessenlagen und die Vielzahl der zu regelnden Sachverhalte erfordern einen langen Atem und Zeitr?ume, die über eine Legislaturperiode hinausgehen.      

Environmental assessment of ester-based lubricants after application

GOAL, SCOPE AND BACKGROUND: Lubricants based on renewable resources are an environmentally friendly alternative to petrochemical products due to their better ecotoxicological performance and their excellent biodegradability. To improve the technical performance of lubricants, and to reduce friction and wear, the use of additives is nowadays obligatory. The collaborative research center SFB 442 aims at developing environmentally acceptable lubricants that facilitate the avoidance of these additives by transferring their function to suitable coatings. For a complete assessment of the ecological performance of these newly developed lubricants, the whole life cycle including production, application as well as disposal and fate in the environment is studied. In the following study the focus was on the application and its influence on the environmental behavior of the lubricant. The application of lubricants leads, among other things, to the intake of metals due to abrasion from tools, work pieces or mechanical components. Previous examinations indicated a possible influence of metals on the toxicity of eluates prepared from used lubricants (Erlenkaemper et al. 2005). To clarify if the apparent toxicity of used lubricants solely results from the intake of metals, the extractability of these metals from the oil matrix is determined. By combining chemical analyses with bioassays, the bioavailability of metals that are present in the extract is estimated. To further investigate the relevance of metals on toxicity, toxic units (TU) were calculated and related to the results of the bioassays. Interactions between the metals were investigated with aqueous mixtures of metal chlorides and calculations based on the concept of concentration addition and independent action. METHODS: A lubricant mixture was applied to a tribological test bench that simulates real conditions of use and extremely short time load, respectively. Samples were taken at particular times, water soluble fractions (WSF) of these fluids were prepared and dilution series were investigated in several bioassays. Concentration of metals and total organic carbon (TOC) were determined in the eluates. TUs were calculated according to Sprague (1970) and mixture toxicity was calculated according to the concept of concentration addition (Loewe and Muischnek 1926) and independent action (Bliss 1939). RESULTS: Analyses of the metal content of the lubricant and the eluates clearly revealed the availability of the metals in the aqueous extracts. Especially copper, zinc, nickel and chromium were found and their concentrations increased during the time of use. The water extractable fraction, e.g., of copper, rose from 8.8% to 45.3% of the total content in the lubricant after 33.5 hours of use. Tests performed with the algal growth inhibition assay and the luminescence inhibition assay revealed the uptake or absorption by the organisms and, thus, the bioavailability of the metals. The calculation of TUs partly indicated a possible influence of the metals on ecotoxicity of the eluates. Copper reached concentrations equal to or higher than the EC50 value of copper chloride in the growth inhibition assays with algae and Ps. putida as well in the immobilization assay with daphnids. TUs for copper are also larger than 1 for the algal growth inhibition assay. The EL50 values indicated that the luminescence inhibition assay was the most sensitive test system, with values between 4.7% and 9.6%. While the toxicity towards algae and V. fischeri in the growth inhibition assay decreased until both organisms were no longer influenced by the exposure, the EL50 values for the D. magna immobilization assay and the Ps. putida growth inhibition assay decreased with the progressing use of the lubricant. The tested metal salt mixtures showed that Ps. putida, algae and daphnids are the most sensitive organisms with EC50 values below 1 mg/l. DISCUSSION: Although the intake of metals mainly occurred via abrasion of particles, the results revealed the availability of these metals in water. The availability varied for each of the four metals. For both the algal growth inhibition assay and the luminescence inhibition assay, an uptake or absorption of the metals could be demonstrated. The calculated TUs indicated an effect in some bioassays that was not verified in the test itself. The influence of copper on V. fischeri, for example, was not confirmed while the EL50 values for the daphnid bioassay decreased, meaning that the eluates became more toxic with progressing use of the lubricant. The calculations of mixture toxicity based on the concept of concentration addition demonstrated good correlations with the tested metal mixtures, but also a different sensitivity of the organisms. CONCLUSIONS: The results presented here reveal the availability of those metals in water that were taken in during the use of the lubricant in a tribological test bench and, thus, have the possibility of interacting with the organisms. The availability of the metals in the bioassays was proven by chemical analyses. The calculation of TUs and the corresponding EL50 values, however, indicate different availabilities of the metals. The results of the metal salt mixtures show good correlations with calculations of mixture toxicity based on concentration addition. Moreover, the varying sensitivity of the organisms when exposed to eluates or metal mixtures indicates a different bioavailability of the metals and/or the presence of other compounds that exert toxic action. RECOMMENDATIONS AND PERSPECTIVES: For further investigations, the organic oil matrix and its influence on the toxicity have to be taken into account. The toxicity of the eluates may not only be due to metals; additional effects could arise from changes in the lubricant itself.     

Risk assessment of toxins derived from Bacillus thuringiensis—synergism,efficacy, and selectivity

Background, aim, and scope  

This review deals with publications concerning the mode of action of Bt proteins and their potential synergism with extrinsic factors. The aim was to assess the impact of those factors especially regarding selectivity and efficacy of Bt toxins and to discuss possible gaps in current risk assessment of genetically engineered plants expressing Bt toxins.     

Seasonality of PCDD/Fs in the ambient air of Malopolska Region,southern Poland

Background, aim, and scope  

The aim of the study was to identify the impact of polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emission sources on ambient air concentrations in the Malopolska Region, southern Poland. Three sites were selected: the city center of Krakow (Aleje), an industrial area (Nova Huta), and a rural site (Zakopane). In order to investigate the annual variations of PCDD/F sources, summer and winter time samples were taken.     

Assessing the Cr(VI) reduction efficiency of a permeable reactive barrier using Cr isotope measurements and 2D reactive transport modeling

In Thun, Switzerland, a permeable reactive barrier (PRB) for Cr(VI) reduction by gray cast iron was installed in May 2008. The PRB is composed of a double array of vertical piles containing iron shavings and gravel. The aquifer in Thun is almost saturated with dissolved oxygen and the groundwater flow velocities are ca. 10-15m/day. Two years after PRB installation Cr(VI) concentrations still permanently exceed the Swiss threshold value for contaminated sites downstream of the barrier at selected localities. Groundwater δ(53/52)Cr(SRM979) measurements were used to track Cr(VI) reduction induced by the PRB. δ(53/52)Cr(SRM979) values of two samples downstream of the PRB showed a clear fractionation towards more positive values compared to four samples from the hotspot, which is clear evidence of Cr(VI) reduction induced by the PRB. Another downstream sample did not show a shift to more positive δ(53/52)Cr(SRM979) values. Because this latter location correlates with the highest downstream Cr(VI) concentration it is proposed that a part of the Cr(VI) plume is bypassing the barrier. Using a Rayleigh fractionation model a minimum present-day overall Cr(VI) reduction efficiency of ca. 15% was estimated. A series of 2D model simulations, including the fractionation of Cr isotopes, confirm that only a PRB bypass of parts of the Cr(VI) plume can lead to the observed values. Additionally, the simulations revealed that the proposed bypass occurs due to an insufficient permeability of the individual PRB piles. It is concluded that with this type of PRB a complete and long-lasting Cr(VI) reduction is extremely difficult to achieve for Cr(VI) contaminations located in nearly oxygen and calcium carbonate saturated aquifer in a regime of high groundwater velocities. Additional remediation action would limit the environmental impact and allow to reach target concentrations.     

Approach for detecting mutagenicity of biodegraded and ozonated pharmaceuticals, metabolites and transformation products from a drinking water perspective

Many pharmaceuticals and related metabolites are not efficiently removed in sewage treatment plants and enter into surface water. There, they might be subject of drinking water abstraction and treatment by ozonation. In this study, a systematic approach for producing and effect-based testing of transformation products (TPs) during the drinking water ozonation process is proposed. For this, two pharmaceutical parent substances, three metabolites and one environmental degradation product were investigated with respect to their biodegradability and fate during drinking water ozonation. The Ames test (TA98, TA100) was used for the identification of mutagenic activity present in the solutions after testing inherent biodegradability and/or after ozonation of the samples. Suspicious results were complemented with the umu test. Due to the low substrate concentration required for ozonation, all ozonated samples were concentrated via solid phase extraction (SPE) before performing the Ames test. With the exception of piracetam, all substances were only incompletely biodegradable, suggesting the formation of stable TPs. Metformin, piracetam and guanylurea could not be removed completely by the ozonation process. We received some evidence that technical TPs are formed by ozonation of metformin and piracetam, whereas all tested metabolites were not detectable by analytical means after ozonation. In the case of guanylurea, one ozonation TP was identified by LC/MS. None of the experiments showed an increase of mutagenic effects in the Ames test. However, the SPE concentration procedure might lead to false-positive results due to the generation of mutagenic artefacts or might lead to false-negative results by missing adequate recovery efficiency. Thus, these investigations should always be accompanied by process blank controls that are carried out along the whole ozonation and SPE procedure. The study presented here is a first attempt to investigate the significance of transformation products by a systematic approach. However, the adequacy and sensitivity of the methodology need to be further investigated. The approach of combining biodegradation and ozonation with effect-based assays is a promising tool for the early detection of potential hazards from TPs as drinking water contaminants. It can support the strategy for the evaluation of substances and metabolites in drinking water. A multitude of possible factors which influence the results have to be carefully considered, among them the selectivity and sensibility of the mutagenicity test applied, the extraction method for concentrating the relevant compounds and the biocompatibility of the solvent. Therefore, the results have to be carefully interpreted, and possible false-negative and false-positive results should be considered.     

Recently planted vegetation strips reduce Giardia runoff reaching waterways

Current methods for tracking pathogens across farmland and into surrounding waterways via runoff are limited and typically have been developed using artificially created landscapes. No studies have investigated how Giardia in farm runoff moves across the landscape, despite high prevalence rates in dairy cattle (Bos taurus) worldwide. Here, we report the development of a field-based tracking method specific for Giardia movement in runoff and use this technique to compare the pathogen reduction capability of recently planted vegetation strips with bare soil strips cleared of vegetation. Such scenarios represent typical events in schemes to plant vegetation barriers aimed at reducing waterway contamination. A significant treatment effect was identified, with 26% fewer Giardia detected in runoff collected from the planted strip (P = 0.006). These results highlight the immediate benefit of pathogen removal to be gained from vegetation planting. The successful discrimination of treatment effects by this new technique will enable the assessment of different vegetation types on runoff reduction and the effects of plant development over time.