Multiple kinetic Langmuir modeling to predict the environmental behaviour of As(v) in soils

A soil with a relatively high Fe content (2.82% [w/w]) was loaded for up to one year with As(v) by equilibrating it with a solution containing 1000 mg l(-1) As(v) at a soil mass-to-solution ratio of 0.1 kg l(-1). The incorporation of As(v) into the soil and its distribution over the soil phases were monitored by sampling at strategic time intervals using an operationally defined five-step sequential extraction procedure (Wenzel et al., Anal. Chim. Acta, 2001, 436, 309) and subsequent As measurement. A multiple kinetic Langmuir model was developed to retrieve the dynamic parameters (adsorption and desorption rate constants, capacities and Langmuir equilibrium constants) for each of the soil phases by numerical fitting of the experimental adsorption data to the model. Under the equilibration conditions used the adsorption rate constants for all five operationally defined soil phases were very similar but the desorption rate constants decreased by a factor of ca. 150 from soil phase 1 (non-specifically sorbed As) to 5 (residual phases). This implies that As(v) incorporation "deeper" into the soil leads to stronger binding which is associated with the Langmuir equilibrium constants (adsorption rate constants/desorption rate constants). Equilibration of the soil with As(v) was complete in ca. 10 days with As(v) predominantly bound to soil phase 2 (specifically sorbed As) and soil phase 3 (amorphous and poorly crystalline hydrous oxides). X-Ray absorption spectroscopy techniques revealed that these binding characteristics may be related to adsorption of As(v) on Si- and/or Al-containing structures and natural hydrous iron oxide (HFO) surface sites, respectively. Since the model is independent of the initial As(v) concentration in the solution and the soil mass-to-solution ratio, the behaviour of the thus characterized soil-As(v) system can be predicted for a range of conditions. Simulations showed that in an accidental As(v) spill the soil studied would actively scavenge As(v) by instantaneous adsorption onto all soil phases followed by redistribution of As(v) from weaker binding sites to stronger ones over time.     

Fractionation of traffic-emitted Ce, La and Zr in road dusts

The introduction of catalytic converters has led to a new environmental problem since catalysts emit platinum group elements (PGEs) which are among the least distributed elements in nature. Along with PGEs the vehicle exhaust catalysts contain also a number of stabilizers, commonly oxides of rare earth elements and alkaline earth elements such as Ce, La and Zr. Since vehicular emission of these elements has received little attention so far this work attempts to offer insight into their distribution and fate in the environment by measuring their speciation in road dust samples collected along several highways in Germany and a city centre (Saarbrücken). Speciation of the elements (fractionation into associated mineralogical phases) was carried out via a conventional sequential extraction protocol and the complexing abilities of humic substances in the organic matter were investigated by selective extraction methods in combination with size segregation. For evaluation purposes soil samples spiked with catalytic converter material were analyzed, showing a much lower fraction of Ce, La and Zr mobilized in comparison to the road dust samples. It was found that the elements were effectively bound to humic substances in road dust with a preference for complexation with low molecular weight compounds (<1600 Da).     

Advanced REACH Tool (ART): calibration of the mechanistic model

The mechanistic model of the Advanced Reach Tool (ART) provides a relative ranking of exposure levels from different scenarios. The objectives of the calibration described in this paper are threefold: to study whether the mechanistic model scores are accurately ranked in relation to exposure measurements; to enable the mechanistic model to estimate actual exposure levels rather than relative scores; and to provide a method of quantifying model uncertainty. Stringent data quality guidelines were applied to the collated data. Linear mixed effects models were used to evaluate the association between relative ART model scores and measurements. A random scenario and company component of variance were introduced to reflect the model uncertainty. Stratified analyses were conducted for different forms of exposure (abrasive dust, dust, vapours and mists). In total more than 2000 good quality measurements were available for the calibration of the mechanistic model. The calibration showed that after calibration the mechanistic model of ART was able to estimate geometric mean (GM) exposure levels with 90% confidence for a given scenario to lie within a factor between two and six of the measured GM depending upon the form of exposure.     

Application of a checklist for quality assistance in environmental modelling to an energy model

Large, complex energy models present considerable challenges to develop and test. Uncertainty assessments of such models provide only partial guidance on the quality of the results. We have developed a model quality assistance checklist to aid in this purpose. The model checklist provides diagnostic output in the form of a set of pitfalls for the model application. The checklist is applied here to an energy model for the problem of assessing energy use and greenhouse gas emissions. Use of the checklist suggests that results on this issue are contingent on a number of assumptions that are highly value-laden. When these assumptions are held fixed, the model is deemed capable of producing moderately robust results of relevance to climate policy over the longer term. Checklist responses also indicate that a number of details critical to policy choices or outcomes on this issue are not captured in the model, and model results should therefore be supplemented with alternative analyses.     

Determining Ecoregions for Environmental and GMO Monitoring Networks

A representative environmental monitoring network at the regional scale cannot use raster-based or random sampling designs, but requires a stratified sampling procedure integrating different information layers, and it has to occur in ecologically differing homogeneous regions (ecoregions). These we have determined using a set of spatial strata with ecological variables which we analysed with classification and regression trees (CART). We present a framework for environmental monitoring, that covers different scales, and we transfer the framework to a potential GMO (genetically modified organisms) monitoring network. We use ecoregion and other environmental strata together with existing environmental monitoring networks to determine GMO monitoring sites more precisely.     

Distribution of PAHs and trace metals in urban stormwater sediments: combination of density fractionation,mineralogy and microanalysis

Sediment management from stormwater infiltration basins represents a real environmental and economic issue for stakeholders due to the pollution load and important tonnages of these by-products. To reduce the sediment volumes to treat, organic and metal micropollutant-bearing phases should be identified. A combination of density fractionation procedure and microanalysis techniques was used to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) within variable density fractions for three urban stormwater basin sediments. The results confirm that PAHs are found in the lightest fractions (d?d??3) whereas trace metals are equally distributed within the light, intermediary, and highest fractions (d?d?d?d?>?2.8 g cm^?3) and are mostly in the 2.3?d??3 fraction. The characterization of the five fractions by global analyses and microanalysis techniques (XRD and MEB-EDX) allowed us to identify pollutant-bearing phases. PAHs are bound to the organic matter (OM) and trace metals to OM, clays, carbonates and dense particles. Moreover, the microanalysis study underlines that OM is the main constituent responsible for the aggregation, particularly for microaggregation. In terms of sediment management, it was shown that density fractionation is not suitable for trace metals but could be adapted to separate PAH-enriched phases.     

Distinct diversity of the czcA gene in two sedimentary horizons from a contaminated estuarine core

In estuarine ecosystems, trace metals are mainly associated with fine grain sediments which settle on mudflats. Over time, the layers of sediments accumulate and are then transformed by diagenetic processes, recording the history of the estuary’s chemical contamination. In such a specific environment, we investigated to what extent a chronic exposure to contaminants could affect metal-resistant sedimentary bacteria in subsurface sediments. The occurrence and diversity of cadmium resistance genes (cadA, czcA) was investigated in 5- and 33-year-old sediments from a highly contaminated estuary (Seine France). Primers were designed to detect a 252-bp fragment of the czcA gene, specifically targeting a transmembrane helice domain (TMH IV) involved in the proton substrate antiport of this efflux pump. Although the cadA gene was not detected, the highest diversity of the sequence of the czcA gene was observed in the 5-year-old sediment. According to the percentage of identity at the amino acid level, the closest CzcA relatives were identified among Proteobacteria (α, β, γ, and δ), Verrucomicrobia, Nitrospirae, and Bacteroidetes. The most abundant sequences were affiliated with Stenotrophomonas. In contrast, in the 33-year-old sediment, CzcA sequences were mainly related to Rhodanobacter thiooxydans and Stenotrophomonas, suggesting a shaping of the metal-resistant microbial communities over time by both diagenetic processes and trace metal contamination.     

Environmental effects of soil contamination by shale fuel oils

Estonia is currently one of the leading producers of shale oils in the world. Increased production, transportation and use of shale oils entail risks of environmental contamination. This paper studies the behaviour of two shale fuel oils (SFOs)—‘VKG D’ and ‘VKG sweet’—in different soil matrices under natural climatic conditions. Dynamics of SFOs’ hydrocarbons (C10–C40), 16 PAHs, and a number of soil heterotrophic bacteria in oil-spiked soils was investigated during the long-term (1 year) outdoor experiment. In parallel, toxicity of aqueous leachates of oil-spiked soils to aquatic organisms (crustaceans Daphnia magna and Thamnocephalus platyurus and marine bacteria Vibrio fischeri) and terrestrial plants (Sinapis alba and Hordeum vulgare) was evaluated. Our data showed that in temperate climate conditions, the degradation of SFOs in the oil-contaminated soils was very slow: after 1 year of treatment, the decrease of total hydrocarbons’ content in the soil did not exceed 25 %. In spite of the comparable chemical composition of the two studied SFOs, the VKG sweet posed higher hazard to the environment than the heavier fraction (VKG D) due to its higher mobility in the soil as well as higher toxicity to aquatic and terrestrial species. Our study demonstrated that the correlation between chemical parameters (such as total hydrocarbons or total PAHs) widely used for the evaluation of the soil pollution levels and corresponding toxicity to aquatic and terrestrial organisms was weak.