Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.     

Attempts to probe the ozone layer and the ultraviolet-B levels of the past

To get a proper perspective on the current status of atmospheric ozone, which protects the biosphere from ultraviolet-B (UV-B; 280-315 nm) radiation, it would be of value to know how ozone and UV-B radiation have varied in the past. The record of worldwide ozone monitoring goes back only a few decades, and the record of reliable UV-B measurements is even shorter. Here we review indirect methods to assess their status further back in time. These include variations in the Sun's emission and how these affect the atmosphere, changes in the Earth's orbit, geologic imprints of atmospheric ozone, effects of catastrophic events such as volcanic eruptions, biological proxies of UV-B radiation, the spectral signature of terrestrial ozone in old recordings of star spectra, and the modeling of UV-B irradiance from ozone data and meteorological recordings. Although reliable reconstructions do not yet extend far into the past, there is some hope for future progress.     

Techniques for the stabilization and assessment of treated copper-, chromium-, and arsenic-contaminated soil

Remediation mainly based on excavation and burial of the contaminated soil is impractical with regard to the large numbers of sites identified as being in need of remediation. Therefore, alternative methods are needed for brownfield remediation. This study was conducted to assess a chemical stabilization procedure of CCA-contaminated soil using iron (Fe)-containing blaster sand (BS) or oxygen-scarfing granulate (OSG). The stabilization technique was assessed with regard to the feasibility of mixing ameliorants at an industrial scale and the efficiency of the stabilization under different redox conditions. The stability was investigated under natural conditions in 1-m3 lysimeters in a field experiment, and the effect of redox conditions was assessed in a laboratory experiment (10 L). The treatments with high additions of ameliorant (8% and 17%) were more successful in both the laboratory and field experiments, even though there was enough Fe on a stochiometric basis even at the lowest addition rates (0.1% and 1%). The particle size of the Fe and the mixing influenced the stabilization efficiency. The development of anaerobic conditions, simulated by water saturation, increases the fraction of arsenic (AsIII) and, consequently, As mobility. The use of high concentrations of OSG under aerobic conditions increased the concentrations of nickel (Ni) and copper (Cu) in the pore water. However, under anaerobic conditions, it decreased the As leaching compared with the untreated soil, and Ni and Cu leaching was not critical. The final destination of the treated soil should govern the amendment choice, that is, an OSG concentration of approximately 10% may be suitable if the soil is to be landfilled under anaerobic conditions. Alternatively, the soil mixed with 1% BS could be kept under aerobic conditions in a landfill cover or in situ at a brownfield site. In addition, the treatment with BS appeared to produce better effects in the long term than treatment with OSG.     

Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.     

Recent advances in mercury speciation analysis with focus on spectrometric methods and enriched stable isotope applications

This paper discusses some recent advances in spectrometric methods and approaches for mercury speciation analysis of environmental samples with focus on isotope dilution techniques for determination of mercury species' concentrations in gaseous samples and reaction rates in soils and sediments. Such analytical data is important inter alia in fundamental research on mercury biogeochemistry and for risk assessments of mercury-contaminated soils and sediments and for designing effective remedial actions. The paper describes how the use of enriched stable isotope tracers in mercury speciation analysis can improve the traceability and accuracy of results, facilitate rational method developments, and be useful for studying biogeochemical processes, i.e. rate of reactions and fluxes, of mercury species. In particular the possibilities to study and correct for unwanted species transformation reactions during sample treatment and to study "natural" transformations of species in environmental samples, or micro- and mesocosm ecosystems, during incubations are highlighted. Important considerations to generate relevant data in isotope tracer experiments as well as reliability and quality assurance of mercury speciation analysis in general are also discussed.     

Microbial degradation and impact of Bracken toxin ptaquiloside on microbial communities in soil

The carcinogenic and toxic ptaquiloside (PTA) is a major secondary metabolite in Bracken fern (Pteridium aquilinum (L.) Kuhn) and was hypothesized to influence microbial communities in soil below Bracken stands. Soil and Bracken tissue were sampled at field sites in Denmark (DK) and New Zealand (NZ). PTA contents of 2.1 +/- 0.5 mg g(-1) and 37.0 +/- 8.7 mg g(-1) tissue were measured in Bracken fronds from DK and NZ, respectively. In the two soils the PTA levels were similar (0-5 microg g(-1) soil); a decrease with depth could be discerned in the deeper B and C horizons of the DK soil (weak acid sandy Spodosol), but not in the NZ soil (weak acid loamy Entisol). In the DK soil PTA turnover was predominantly due to microbial degradation (biodegradation); chemical hydrolysis was occurring mainly in the uppermost A horizon where pH was very low (3.4). Microbial activity (basal respiration) and growth ([3H]leucine incorporation assay) increased after PTA exposure, indicating that the Bracken toxin served as a C substrate for the organotrophic microorganisms. On the other hand, there was no apparent impact of PTA on community size as measured by substrate-induced respiration or composition as indicated by community-level physiological profiles. Our results demonstrate that PTA stimulates microbial activity and that microorganisms play a predominant role for rapid PTA degradation in Bracken-impacted soils.     

Dioxin screening in fish product by pattern recognition of biomarkers

Two alternative, cost- and time-effective dioxin screening methods relying on two categories of potential lipid biomarkers were investigated. A dioxin range varying from 1.1 to 47.1 pg PCDD/F TEQ-WHO/g lipid using 64 fish meal samples was used for model calibration. The methods were based on multivariate models using either (1) fatty acid composition monitored by GC-FID or (2) fluorescence landscape signals analysed using the PARAFAC model and in both cases predicting dioxin content as pgPCDD/F TEQ-WHO/g lipid. In both cases, Partial Least Squares (PLS) regression was performed for predicting the dioxin content of a sample. The GC-FID data analyses was based on automatic peak alignment and integration, enabling extraction of the area of 140 peaks from the gas chromatograms, as opposed to the 31 fatty acids usually considered for fish oil characterisation. In addition to classic PLS employing the whole dataset for calibration, a two-step local PLS modeling approach was performed based upon an initial selection of k number of calibration samples providing the best match to the prediction sample using a so-called k Nearest Neighbors (kNN) approach, then followed by PLS calibration on these kNN selected samples for dioxin prediction. Fluorescence spectroscopy offers a promising non-invasive and ultra-rapid technique, with less than two minutes analysis time. However, fluorescence spectroscopy using the pattern recognition "kNN-PLS" yielded a correlation of 0.76 (r2) and a high root mean square error of prediction of 11.4 pg PCDD/F TEQ-WHO/g lipid. The predictions were improved when the PLS calibration was performed on all the sample with a root mean square error of prediction of 7.0 pg PCDD/F TEQ-WHO/g lipid. Unfortunately, these results failed to demonstrate the potential of fluorophore monitoring as a screening method. In contrast, the overall best screening performance was obtained with the fatty acid profile, when the kNN-PLS combination employed for pattern recognition (kNN) all the areas of the 140 detected peaks and the PLS regression used the areas of 46 selected peaks. This "kNN-PLS" prediction with three latent variables and based upon the 12 nearest neighbors selected out of the 64 x 2 fatty acid profiles (duplicate analyses), yielded a correlation of 0.85 (r2) and a root mean square error of prediction of 2.1 pg PCDD/F TEQ-WHO/g lipid and resulted in a total analysis time of one and half hour per sample.     

A preliminary assessment of the potential environmental and human health impact of unsymmetrical dimethylhydrazine as a result of space activities

A preliminary assessment of the potential environmental and human health impact of UDMH as a result of space activities has been carried out applying a theoretical approach in comparison with selected experimental data. The theoretical framework includes QSAR, ADME and PASS modelling as well as studies on the possible atmospheric dispersion of UDMH as calculated applying the OML-Multi model. The possible impact on the environment and the human health has been elucidated and it has been concluded that UDMH especially inside the fall region of burned-out rocket stages constitute a significant threat to both environmental and human health, the latter as a results of the carcinogenic, mutagenic, convulsant, teratogenic and embryotoxic characteristics of UDMH in addition to the general toxic characteristics of the compound.     

Goals and remedial strategies for water quality and wildlife management in a coastal lagoon--a case-study of Ringkøbing Fjord, Denmark

The aim of this work is (1) to discuss approaches and tools to set management goals using operational indicators for coastal management (i.e., indicators that are easy to measure, understand and predict) and validated predictive models and (2) to discuss remedial strategies for sustainable coastal management regarding water quality and the abundance of fish, waterfowl and large aquatic plants. These approaches are exemplified using data from Ringkøbing Fjord, Denmark, which has undergone two major regime shifts during the last decades. This work discusses the changes taken place during the period from 1980 to 2004 (when there are good empirical data). For Ringkøbing Fjord, which is a very shallow, well-oxygenated lagoon dominated by resuspension processes, we have targeted on the following operational indicators, which are meant to reflect seasonal median values for the entire defined coastal area (the ecosystem scale) and not conditions at individual sites or data from shorter time periods: Secchi depth (as a standard measure of water clarity) and chlorophyll-a concentrations (as a key measure of algal biomass). The operational indicators are regulated by a set of standard abiotic factors, such as salinity, suspended particulate matter (SPM), nutrient concentrations (N and P), coastal morphometry and water exchange. Such relationships are quantified using well-tested, general quantitative models, which illustrate how these indicators are interrelated and how they reflect fundamental aspects of coastal ecosystems. We demonstrate that the regime shift in the lagoon can be modelled and quantitatively explained and is related to changes in salinity and nutrient inflow. A very important threshold is linked to increased salinities in the lagoon. For example, when the mean annual salinity is higher than about 9.5‰, large numbers of saltwater species of clams can survive and influence the structure and function of the ecosystem in profound ways. The model also illustrates the dynamic response to changes in nutrient loading. We have presented several management strategies with the goal of keeping the Secchi depth at 2 m, which would stimulate the growth of higher aquatic plants, which are fundamental for fish production and bird abundance in the lagoon. Given the fact that the Secchi depth depends on many variable factors (temperature, TP-inflow from land, salinity, changes in biomasses of macrophytes and clams, which are accounted for in these simulations), our results indicate that in practice it will likely be very difficult to reach that goal. However, it would be realistic to maintain a Secchi depth of 1.5 m if the variability in salinity is minimized and the mean salinity is kept at about 10.2‰.     

Low cost measurements of nitrogen and sulphur dry deposition velocities at a semi-alpine site: gradient measurements and a comparison with deposition model estimates

The conditional time averaged gradient method was used to measure air-surface exchange of nitrogen and sulphur compounds at a semi-alpine site in Southern Norway. Dry deposition velocities were then obtained from the bi-weekly concentration gradient measurements. Annual deposition velocities were found to be 1.4, 11.8 and 4.0 mm s(-1) for NH3, HNO3 and SO2, respectively, if all data were included, and to be 10.8, 11.8 and 13.0 mm s(-1), respectively, if only positive values were included. Measured deposition velocities were compared to two sets of values estimated from a big-leaf dry deposition module applying to two different land types (short grass and forbs, and tundra), driven by measured micrometeorological parameters. The deposition module gives reasonable values for this site throughout the year, but does not reproduce the large variability as shown in the measured data. No apparent seasonal variations were found from either measurements or module estimates due to the very low productivity of the studied area.