Concurrent nitrate and Fe(III) reduction during anaerobic biodegradation of phenols in a sandstone aquifer

The biodegradation of phenols (5, 60, 600 mg l⁻¹) under anaerobic conditions (nitrate enriched and unamended) was studied in laboratory microcosms with sandstone material and groundwater from within an anaerobic ammonium plume in an aquifer. The aqueous phase was sampled and analyzed for phenols and selected redox sensitive parameters on a regular basis. An experiment with sandstone material from specific depth intervals from a vertical profile across the ammonium plume was also conducted. The miniature microcosms used in this experiment were sacrificed for sampling for phenols and selected redox sensitive parameters at the end of the experiment. The sandstone material was characterized with respect to oxidation and reduction potential and Fe(II) and Fe(III) speciation prior to use for all microcosms and at the end of the experiments for selected microcosms.The redox conditions in the anaerobic microcosms were mixed nitrate and Fe(III) reducing. Nitrate and Fe(III) were apparently the dominant electron acceptors at high and low nitrate concentrations, respectively. When biomass growth is taken into account, nitrate and Fe(III) reduction constituted sufficient electron acceptor capacity for the mineralization of the phenols observed to be degraded even at an initial phenols concentration of 60 mg l⁻¹ (high) in an unamended microcosm, whereas nitrate reduction alone is unlikely to have provided sufficient electron acceptor capacity for the observed degradation of the phenols in the unamended microcosm.For microcosm systems, with solid aquifer materials, dissolution of organic substances from the solid material may occur. A quantitative determination of the speciation (mineral types and quantity) of electron acceptors associated with the solids, at levels relevant for degradation of specific organic compounds in aquifers, cannot always be obtained. Hence, complete mass balances of electron acceptor consumption for specific organic compounds degradation are difficult to confine. For aquifer materials with low initial Fe(II) content, Fe(II) determinations on solids and in aqueous phase samples may provide valuable information on Fe(III) reduction. However, in microcosms with natural sediments and where electron acceptors are associated with the sediments, complete mass-balances for substrates and electron acceptors are not likely to be obtained.     

Synthesis and characterization of zwitterionic carbon dioxide fixing reagents

The synthesis of three amine-based carbon dioxide fixing reagents is presented. The reagents were designed so that they would be able to bind CO₂ reversibly through the formation of the well known carbamates that was stabilized through forming a zwitterion. CO₂ fixing experiments were performed with ¹³CO₂ labeling and medium pressure NMR. The experiments showed that two of the three reagents were able to form carbamates and thus bind CO₂. In addition we investigated this particular class of molecules for the possible formation of neutrally charged spiro compounds and we show that these did not form under the conditions studied.     

Forests under climate change and air pollution: gaps in understanding and future directions for research

Forests in Europe face significant changes in climate, which in interaction with air quality changes, may significantly affect forest productivity, stand composition and carbon sequestration in both vegetation and soils. Identified knowledge gaps and research needs include: (i) interaction between changes in air quality (trace gas concentrations), climate and other site factors on forest ecosystem response, (ii) significance of biotic processes in system response, (iii) tools for mechanistic and diagnostic understanding and upscaling, and (iv) the need for unifying modelling and empirical research for synthesis. This position paper highlights the above focuses, including the global dimension of air pollution as part of climate change and the need for knowledge transfer to enable reliable risk assessment. A new type of research site in forest ecosystems ("supersites") will be conducive to addressing these gaps by enabling integration of experimentation and modelling within the soil-plant-atmosphere interface, as well as further model development.     

Assessing chlorinated ethene degradation in a large scale contaminant plume by dual carbon-chlorine isotope analysis and quantitative PCR

The fate of chlorinated ethenes in a large contaminant plume originating from a tetrachloroethene (PCE) source in a sandy aquifer in Denmark was investigated using novel methods including compound-specific carbon and chlorine isotope analysis and quantitative real-time polymerase chain reaction (qPCR) methods targeting Dehaloccocoides sp. and vcrA genes. Redox conditions were characterized as well based on concentrations of dissolved redox sensitive compounds and sulfur isotopes in SO(4)(2-). In the first 400 m downgradient of the source, the plume was confined to the upper 20 m of the aquifer. Further downgradient it widened in vertical direction due to diverging groundwater flow reaching a depth of up to 50 m. As the plume dipped downward and moved away from the source, O(2) and NO(3)(-) decreased to below detection levels, while dissolved Fe(2+) and SO(4)(2-) increased above detectable concentrations, likely due to pyrite oxidation as confirmed by the depleted sulfur isotope signature of SO(4)(2-). In the same zone, PCE and trichloroethene (TCE) disappeared and cis-1,2-dichloroethene (cDCE) became the dominant chlorinated ethene. PCE and TCE were likely transformed by reductive dechlorination rather than abiotic reduction by pyrite as indicated by the formation of cDCE and stable carbon isotope data. TCE and cDCE showed carbon isotope trends typical for reductive dechlorination with an initial depletion of (13)C in the daughter products followed by an enrichment of (13)C as degradation proceeded. At 1000 m downgradient of the source, cDCE was the dominant chlorinated ethene and had reached the source δ(13)C value confirming that cDCE was not affected by abiotic or biotic degradation. Further downgradient (up to 1900 m), cDCE became enriched in (13)C by up to 8 ‰ demonstrating its further transformation while vinylchloride (VC) concentrations remained low (<1 μg/L) and ethene was not observed. The correlated shift of carbon and chlorine isotope ratios of cDCE by 8 and 3.9 ‰, respectively, the detection of Dehaloccocides sp genes, and strongly reducing conditions in this zone provide strong evidence for reductive dechlorination of cDCE. The significant enrichment of (13)C in VC indicates that VC was transformed further, although the mechanism could not be determined. The transformation of cDCE was the rate limiting step as no accumulation of VC occurred. In summary, the study demonstrates that carbon-chlorine isotope analysis and qPCR combined with traditional approaches can be used to gain detailed insight into the processes that control the fate of chlorinated ethenes in large scale plumes.     

Sorption of chlorinated solvents and degradation products on natural clayey tills

The sorption of chlorinated solvents and degradation products on seven natural clayey till samples from three contaminated sites was investigated by laboratory batch experiments in order to obtain reliable sorption coefficients (K_d values). The sorption isotherms for all compounds were nearly linear, but fitted by Freundlich isotherms slightly better over the entire concentration range. For chloroethylenes, tetrachloroethylene (PCE) was most strongly sorbed to the clayey till samples (K_d = 0.84-2.45 L kg⁻¹), followed by trichloroethylene (TCE, K_d = 0.62-0.96 L kg⁻¹), cis-dichloroethylene (cis-DCE, K_d = 0.17-0.82 L kg⁻¹) and vinyl chloride (VC, K_d = 0.12-0.36 L kg⁻¹). For chloroethanes, 1,1,1-trichloroethane (1,1,1-TCA) was most strongly sorbed (K_d = 0.2-0.45 L kg⁻¹), followed by 1,1-dichloroethane (1,1-DCA, K_d = 0.16-0.24 L kg⁻¹) and chloroethane (CA, K_d = 0.12-0.18 L kg⁻¹). This is consistent with the order of hydrophobicity of the compounds. The octanol-water coefficient (log K_ow) correlated slightly better with log K_d values than log K_oc values indicating that the K_d values may be independent of the actual organic carbon content (f_oc). The estimated log K_oc or log K_d for chlorinated solvents and degradation products determined by regression of data in this study were significantly higher than values determined by previously published empirical relationships. The site specific K_d values as well as the new empirical relationship compared well with calculations on water and soil core concentration for cis-DCE and VC from the Rugårdsvej site. In conclusion, this study with a wide range of chlorinated ethenes and ethanes - in line with previous studies on PCE and TCE - suggest that sorption in clayey tills could be higher than typically expected.     

A Quantitative Analysis of Biodiversity and the Recreational Value of Potential National Parks in Denmark

Denmark has committed itself to the European 2010 target to halt the loss of biodiversity. Currently, Denmark is in the process of designating larger areas as national parks, and 7 areas (of a possible 32 larger nature areas) have been selected for pilot projects to test the feasibility of establishing national parks. In this article, we first evaluate the effectiveness of the a priori network of national parks proposed through expert and political consensus versus a network chosen specifically for biodiversity through quantitative analysis. Second, we analyze the potential synergy between preserving biodiversity in terms of species representation and recreational values in selecting a network of national parks. We use the actual distribution of 973 species within these 32 areas and 4 quantitative measures of recreational value. Our results show that the 7 pilot project areas are not significantly more effective in representing species than expected by chance and that considerably more efficient networks can be selected. Moreover, it is possible to select more-effective networks of areas that combine high representation of species with high ranking in terms of recreational values. Therefore, our findings suggest possible synergies between outdoor recreation and biodiversity conservation when selecting networks of national parks. Overall, this Danish case illustrates that data-driven analysis can not only provide valuable information to guide the decision-making process of designating national parks, but it can also be a means to identify solutions that simultaneously fulfill several goals (biodiversity preservation and recreational values).     

Health and Welfare in Danish Dairy Cattle in the Transition to Organic Production: Problems, Priorities and Perspectives

During the past few years,organic dairy farming has grown dramatically inDenmark. Consequently, an increasing number ofpeople are encountering this method ofproduction for the first time. Amongst these,many veterinarians have suddenly had to dealwith organic herds in their home district, and,meeting examples of poor animal welfare, theyhave recently started to express some concerns.Against this background, a so-called``Synthesis of Knowledge' project was initiatedto examine the health and welfare of dairycattle and the use of medication in thetransition to organic production. The aim ofthe project was to investigate associatedproblems from the point of view of the dairyherd. Based on qualitative research interviewswith vets and agricultural advisors, as well asfocus group interviews with farmers who hadrecently converted from conventional to organicfarming, an expert panel attempted to identifyproblem areas and possible solutions. Theproblems related to (a) the adjustment to newand unknown practices, (b) poor management ingeneral, and (c) inappropriate legislation fororganic farming.One problem area was the rearing of dairycalves, particularly with regard to theestablishment of post partumrelationships between cow and calf, grouphousing, and the grazing of young animals. A``natural life' was identified as beingfundamental to organic animal husbandry. Interms of animal welfare, this concept can beunderstood as a way of living in which the calfis allowed to express its natural behavior andsatisfy its natural needs. Essentially, theconditions needed for good calf welfare requirethe compatibility and interplay of elementsfrom ``nature' (the natural life; includingopportunities to satisfy natural needs) and``culture' (farmer management skills; exerciseof care). These elements should be balanced toensure animal welfare in organic herds.     

Sorption of 17β-estradiol to pig slurry separates and soil in the soil-slurry environment

Contamination of freshwater by estrogens from manure applied to agricultural land is of grave concern because of the potentially harmful effects on aquatic life and human health. Recent developments in liquid manure (slurry) management include partial removal of particulate slurry dry matter (PSDM) by separation technologies, which may also remove parts of the estrogens and enhance infiltration of the slurry on field application and hence the interaction between estrogens and the soil matrix. This study investigated how 17β-estradiol (E2), a natural estrogen commonly found in pig manure, sorbs to agricultural soils, to different size fractions of pig slurry separates, and to soils amended with each size fraction to simulate conditions in the soil-slurry environment. A crude fiber fraction (SS1) was prepared by sieving (<500 μm) the solids removed by an on-farm separation process. Three other size fractions (SS2 > SS3 > SS4) were prepared from the liquid fraction of the separated slurry by sedimentation and centrifugation. Sorption experiments were conducted in 0.01 mol L(-1) CaCl(2) and in natural pig urine matrix. Sorption in 0.01 mol L(-1) CaCl(2) was higher than that in pig urine for all solids used. Sorption of E2 to soil increased with its organic carbon content for both liquid phases. The solid-liquid partition coefficients of slurry separates were 10 to 30 times higher than those of soils, but the organoic carbon normalized partition coefficient values, reflecting sorption per unit organic carbon, were lower for slurry separates. Mixing slurry separates with soil increased the sorption of E2 to the solid phase significantly in the order: SS1 < SS3 < SS2 for both liquid phases. In contrast, SS4 reduced the sorption of E2 to the solid phase by increasing the sorption to suspended or dissolved organic matter. The study suggested that potentially 50 to 75% of E2 in slurry can be removed from the liquid fraction of slurry by physical separation.     

The use of biomass production and allometric models to estimate carbon sequestration of <Emphasis Type="Italic">Jatropha curcas</Emphasis> L. plantations in western Burkina Faso

The topic of carbon sequestration in plants has received much attention recently due to concerns about global climate change, which is being exacerbated by deforestation. In the early days of the global bioenergy boom, the private sector and non-government organizations enthusiastically promoted the planting of Jatropha curcas L. as a key candidate shrub species for the production of bioenergy in West Africa. This study investigates the aboveground biomass production and carbon sequestration potential of J. curcas, which is already widely cultivated for the production of oil seeds, biodiesel and biokerosene. The specific objective is to use a destructive method to develop allometric prediction equations of the aboveground biomass production of J. curcas plantations. 38 J. curcas shrubs were harvested and weighed in order to estimate biomass production. These data were used to develop allometric equations for the estimation of wood, leaf and total aboveground biomass production. The best-fit models found for estimating shrub component biomass and total aboveground biomass production were of the power form. All of the regression equations relating the prediction of leaf biomass, wood biomass and total aboveground biomass with J. curcas diameter at 20 cm above the ground (D) were statistically significant (p < 0.001) and also presented the highest goodness of fit (high R ²). The aboveground biomass carbon content was estimated using the ash method. Carbon content in leaves and wood was, respectively, 48 and 54 %. The current established allometric equations can be helpful to provide a rapid estimation of the aboveground biomass and C stock for J. curcas biofuel projects in semi-arid conditions.     

A remediation performance model for enhanced metabolic reductive dechlorination of chloroethenes in fractured clay till

A numerical model of metabolic reductive dechlorination is used to describe the performance of enhanced bioremediation in fractured clay till. The model is developed to simulate field observations of a full scale bioremediation scheme in a fractured clay till and thereby to assess remediation efficiency and timeframe. A relatively simple approach is used to link the fermentation of the electron donor soybean oil to the sequential dechlorination of trichloroethene (TCE) while considering redox conditions and the heterogeneous clay till system (clay till matrix, fractures and sand stringers). The model is tested on lab batch experiments and applied to describe sediment core samples from a TCE-contaminated site. Model simulations compare favorably to field observations and demonstrate that dechlorination may be limited to narrow bioactive zones in the clay matrix around fractures and sand stringers. Field scale simulations show that the injected donor is expected to be depleted after 5 years, and that without donor re-injection contaminant rebound will occur in the high permeability zones and the mass removal will stall at 18%. Long remediation timeframes, if dechlorination is limited to narrow bioactive zones, and the need for additional donor injections to maintain dechlorination activity may limit the efficiency of ERD in low-permeability media. Future work should address the dynamics of the bioactive zones, which is essential to understand for predictions of long term mass removal.