Lars Elsgaard

Anoxie transformations of radiolabeled hydrogen sulfide in marine and freshwater sediments

Abstract Radiolabeled hydrogen sulfide (H 35 S − ) was used to trace the anoxic sulfur transformations in marine and freshwater sediment slurries. Time course studies consistently showed a rapid 35 S 2 O 3 − formation and a progressive accumulation of 35 SO 4 − and thus indicated an anoxic sulfide oxidation to sulfate. Thiosulfate was partly turned over by oxidation or disproportionation and was found to be an intermediate in the 35 SO 4 − formation. The results demonstrate that oxidative and reductive sulfur cycling may occur simultaneously in marine and freshwater sediments. When added as exogenous oxidant, nitrate (NO 3 − ) stimulated the anoxic sulfide oxidation to sulfate. Ferric iron, added in the form of lepidocrocite (γ-FeOOH), caused the precipitation of iron sulfides and only partial sulfide oxidation to pyrite and elemental sulfur.

Measurement and modelling of CO2 flux from a drained fen peatland cultivated with reed canary grass and spring barley

Cultivation of bioenergy crops has been suggested as a promising option for reduction of greenhouse gas (GHG) emissions from arable organic soils (Histosols). Here, we report the annual net ecosystem exchange (NEE) fluxes of CO2 as measured with a dynamic closed chamber method at a drained fen peatland grown with reed canary grass (RCG) and spring barley (SB) in a plot experiment (n = 3 for each cropping system). The CO2 flux was partitioned into gross photosynthesis (GP) and ecosystem respiration (RE). For the data analysis, simple yet useful GP and RE models were developed which introduce plot‐scale ratio vegetation index as an active vegetation proxy. The GP model captures the effect of temperature and vegetation status, and the RE model estimates the proportion of foliar biomass dependent respiration (Rfb) in the total RE. Annual RE was 1887 ± 7 (mean ± standard error, n = 3) and 1288 ± 19 g CO2‐C m−2 in RCG and SB plots, respectively, with Rfb accounting for 32 and 22% respectively. Total estimated annual GP was −1818 ± 42 and −1329 ± 66 g CO2‐C m−2 in RCG and SB plots leading to a NEE of 69 ± 36 g CO2‐C m−2 yr−1 in RCG plots (i.e., a weak net source) and −41 ± 47 g CO2‐C m−2 yr−1 in SB plots (i.e., a weak net sink). Standard errors related to spatial variation were small (as shown above), but more significant uncertainties were related to the modelling approach for establishment of annual budgets. In conclusion, the bioenergy cropping system was not more favourable than the food cropping system when looking at the atmospheric CO2 emissions during cultivation. However, in a broader GHG life‐cycle perspective, the lower fertilizer N input and the higher biomass yield in bioenergy cropping systems could be beneficial.

The fate of sulfate in acidified pig slurry during storage and following application to cropped soil.

Acidification of slurry with sulfuric acid is a recent agricultural practice that may serve a double purpose: reducing ammonia emission and ensuring crop sulfur sufficiency. We investigated S transformations in untreated and acidified pig slurry stored for up to 11 mo at 2, 10, or 20 degrees C. Furthermore, the fertilizer efficiency of sulfuric acid in acidified slurry was investigated in a pot experiment with spring barley. The sulfate content from acidification with sulfuric acid was relatively stable and even after 11 mo of storage the majority was in the plant-available sulfate form. Microbial sulfate reduction during storage of acidified pig slurry was limited, presumably due to initial pH effects and a limitation in the availability of easily degradable organic matter. Sulfide accumulation was observed during storage but the sulfide levels in acidified slurry did not exceed those of the untreated slurry for several months after addition. The S fertilizer value of the acidified slurry was considerable as a result of the stable sulfate pool during storage. The high content of inorganic S in the acidified slurry may potentially lead to development of odorous volatile sulfur-containing compounds and investigations are needed into the relationship between odor development and the C and S composition of the slurry.

Field-scale variation in microbial activity and soil properties in relation to mineralization and sorption of pesticides in a sandy soil.

Pesticides applied to agricultural soils are subject to environmental concerns because leaching to groundwater reservoirs and aquatic habitats may occur. Knowledge of field variation of pesticide-related parameters is required to evaluate the vulnerability of pesticide leaching. The mineralization and sorption of the pesticides glyphosate and metribuzin and the pesticide degradation product triazinamin in a field were measured and compared with the field-scale variation of geochemical and microbiological parameters. We focused on the soil parameters clay and organic carbon (C) content and on soil respiratory and enzymatic processes and microbial biomass. These parameters were measured in soil samples taken at two depths (Ap and Bs horizon) in 51 sampling points from a 4-ha agricultural fine sandy soil field. The results indicated that the spatial variation of the soil parameters, and in particular the content of organic C, had a major influence on the variability of the microbial parameters and on sorption and pesticide mineralization in the soil. For glyphosate, with a co-metabolic pathway for degradation, the mineralization was increased in soils with high microbial activity. The spatial variability, expressed as the CV, was about five times higher in the Bs horizon than in the Ap horizon, and the local-scale variation within 100 m(2) areas were two to three times lower than the field-scale variation within the entire field of about 4 ha.

Ethylene Removal at Low Temperatures under Biofilter and Batch Conditions

ABSTRACT Removal of the plant hormone ethylene (C2H4) is often required by horticultural storage facilities, which are operated at temperatures below 10°C. The aim of this study was to demonstrate an efficient, biological C2H4 removal under such low-temperature conditions. Peat-soil, acclimated to degradation of C2H4, was packed in a biofilter (687 cm3) and subjected to an airflow (∼73 ml min−1) with 2 ppm (μl liter−1) C2H4. The C2H4 removal efficiencies achieved at 20, 10, and 5°C, respectively, were 99.0, 98.8, and 98.4%. This corresponded to C2H4levels of 0.022 to 0.032 ppm in the biofilter outlet air. At 2°C, the average C2H4 removal efficiency dropped to 83%. The detailed temperature response of C2H4removal was tested under batch conditions by incubation of 1-g soil samples in a temperature gradient ranging from 0 to 29°C with increments of 1°C. The C2H4 removal rate was highest at 26°C (0.85 μg of C2H4 g [dry weight]−1 h−1), but remained at levels of 0.14 to 0.28 μg of C2H4 g (dry weight)−1 h−1 at 0 to 10°C. At 35 to 40°C, the C2H4 removal rate was negligible (0.02 to 0.06 μg of C2H4 g [dry weight]−1 h−1). TheQ10 (i.e., the ratio of rates 10°C apart) for C2H4 removal was 1.9 for the interval 0 to 10°C. In conclusion, the present results demonstrated microbial C2H4 removal, which proceeded at 0 to 2°C and produced a moderately psychrophilic temperature response.

Direct and Indirect Short-term Effects of Biochar on Physical Characteristics of an Arable Sandy Loam

Abstract Biochar addition to agricultural soil is reported in several studies to reduce climate gas emissions, boost carbon storage, and improve soil fertility and crop productivity. These effects may be partly related to soil physical changes resulting from biochar amendment, but knowledge of how biochar application mechanistically affects soil physical characteristics is limited. This study investigated the effect of biochar application on soil structural and functional properties, including specific surface area, water retention, and gas transport parameters. Intact soil cores were taken from a field experiment on an arable sandy loam that included four reference plots without biochar and four plots with 20 tons ha−1 biochar incorporated into the upper 20 cm 7 months before sampling. Water retention was measured at matric potentials ranging from wet (pF 1.0) to extremely dry conditions (pF ∼6.8), whereas gas transport parameters (air permeability, ka, and gas diffusivity, Dp/Do, where Dp is the gas diffusion coefficient in soil and Do is the gas diffusion coefficient in free air) were measured between pF 2.0 and 3.0. Water retention under dry conditions and measured specific surface area were not significantly greater in the biochar-amended soil than the reference soil probably because of the relatively low biochar application rate. Yet, the biochar-amended soil showed a significant decrease in soil bulk density and an accompanying increase in total porosity. Water retention and air-filled porosity (&egr;) were both markedly greater in the biochar-amended soil than in the reference soil between pF 1.0 and 3.0. Soil macroporosity (equivalent to >0.1 mm pore diameter) and the ratio of macroporosity to total porosity were also significantly greater in the biochar-amended soil. As a result, the level of the pore organization (PO, ka/&egr;) was greater in the biochar-amended soil. Across the tested matric potentials, biochar amendment caused average increases of 28 to 34% in &egr;, 53 to 161% in Dp/Do, and 69 to 223% in ka, with the most significant increases occurring around natural field capacity (pF 2.0). Overall, the results suggest that biochar application even at a relatively low rate can alter soil functional characteristics, especially under normal field moisture conditions.

Spatial Variation in 2-Methyl-4-chlorophenoxyacetic Acid Mineralization and Sorption in a Sandy Soil at Field Level

The phenoxyacetic acid herbicide MCPA (2-methyl-4-chlorophenoxyacetic acid) is frequently detected in groundwater beneath Danish agricultural fields. We investigated spatial variation in microbial MCPA mineralization potential in a flat agricultural field of fine sandy soil (USDA classification: Humic Dystrudept) located on the Yoldia plains of Northern Jutland, Denmark. Samples for determination of MCPA mineralization and sorption were collected from the Ap and Bs horizons at 51 sampling sites located in a 200 x 220 m grid. Spatial variation in sorption was low in both horizons (distribution coefficient, 0.36-4.16 L kg(-1)). Sorption correlated strongly with soil organic carbon content in both horizons (CV, 93 and 83%, respectively) and negatively with soil pH. [Ring-(14)C]-MCPA mineralized readily in the Ap horizon, with 49 to 62% of the (14)C-MCPA being converted to (14)CO(2) during the 67-d incubation period. With the subsoil, mineralization of (14)C-MCPA varied considerably between samples (0.5-72.8%). At neither depth was there correlation between (14)C-MCPA mineralization and sorption, soil pH, organic carbon content, clay content, number of colony-forming units (CFU), pseudomonad CFU, or any of the four microbial activity parameters measured. The presence of microbial genes encoding for the TfdA enzyme was quantified using real-time polymerase chain reaction. No correlation was found between MCPA mineralization potential and the natural background number of tfdA genes present in the soil samples. The degradation kinetics suggests that the high (14)C-MCPA mineralization rate detected in soil samples was linked to growth of the MCPA-degrading soil microbial community.

Temperature response of methane production in liquid manures and co-digestates.

Intensification of livestock production makes correct estimation of methanogenesis in liquid manure increasingly important for inventories of CH4 emissions. Such inventories currently rely on fixed methane conversion factors as knowledge gaps remain with respect to detailed temperature responses of CH4 emissions from liquid manure. Here, we describe the temperature response of CH4 production in liquid cattle slurry, pig slurry, and fresh and stored co-digested slurry from a thermophilic biogas plant. Subsamples of slurry were anoxically incubated at 20 temperatures from 5-52°C in a temperature gradient incubator and CH4 production was measured by gas chromatographic analysis of headspace gas after a 17-h incubation period. Methane production potentials at 5-37°C were described by the Arrhenius equation (modelling efficiencies, 79.2-98.1%), and the four materials showed a consistent activation energy (Ea) which averaged 81.0kJmol(-1) (95% confidence interval, 74.9-87.1kJmol(-1)) corresponding to a temperature sensitivity (Q10) of 3.4. In contrast, the frequency factor (A) differed among the slurry materials (30.1<ln A<33.3; mean, 31.3) reflecting that origin, age and composition of the manure affect this parameter. The Ea estimate, based on individual slurry materials, was intermediate when compared to published values of 63 and 112.7kJmol(-1) derived from composite data, but was similar to Ea estimated for CH4 production at microbial community level across aquatic ecosystems, wetlands and rice paddies (89.3kJmol(-1)). This supports that the derived temperature sensitivity parameters may be applicable to dynamic modelling of CH4 emissions from livestock manure.

Effects of biochar on air and water permeability and colloid and phosphorus leaching in soils from a natural calcium carbonate gradient.

Application of biochar to agricultural fields to improve soil quality has increased in popularity in recent years, but limited attention is generally paid to existing field conditions before biochar application. This study examined the short-term physicochemical effects of biochar amendment in an agricultural field in Denmark with a calcium carbonate (CaCO) gradient. The field comprised four reference plots and four plots to which biochar (birch wood pyrolyzed at 500°C) was applied at a rate of 20 t ha. Five undisturbed soil columns (10 cm diam., 8 cm height) were sampled from each plot 7 mo after biochar application, and a series of leaching experiments was conducted. The leachate was analyzed for tritium (used as a tracer), colloids, and phosphorus concentration. The results revealed that the presence of CaCO has resulted in marked changes in soil structure (bulk density) and soil chemical properties (e.g., pH and ionic strength), which significantly affected air and water transport and colloid and phosphorous leaching. In denser soils (bulk density, 1.57-1.69 g cm) preferential flow dominated the transport and caused an enhanced movement of air and water, whereas in less dense soils (bulk density, 1.38-1.52 g cm) matrix flow predominated the transport. Compared with reference soils, biochar-amended soils showed slightly lower air permeability and a shorter travel time for 5% of the applied tracer (tritium) to leach through the soil columns. Colloid and phosphorus leaching was observed to be time dependent in soils with low CaCO. Biochar-amended soils showed higher colloid and P release than reference soils. Field-scale variations in total colloid and P leaching reflected clear effects of changes in pH and ionic strength due to the presence of CaCO. There was a linear relationship between colloid and P concentrations in the leachate, suggesting that colloid-facilitated P leaching was the dominant P transport mechanism.

Biodegradation of linear alkylbenzene sulfonates in sulfate-leached soil mesocosms

Aromatic sulfonates (R-SO(3)(-)) can be used as sulfur sources by sulfate-starved bacteria in laboratory cultures and the corresponding phenols are excreted from the cells. The present study was conducted to demonstrate whether such desulfonation reactions also occur in sulfate-leached agricultural soil, where desulfonation of organic sulfur compounds may have agronomic importance as a S source for plants. Xenobiotic linear alkylbenzene sulfonates (LAS) were added to nominal concentrations of 0, 10 and 100 mgkg(-1) dry weight in a sandy soil that was depleted in sulfate by leaching the soil with water (sulfate depletion, approximately 75%). The soil was incubated at 20 degrees C in duplicate 3-dm(3) mesocosms for 8 weeks. Primary degradation of LAS was rapid with half-lives of 1-4 days. Sulfophenylcarboxylates were identified and quantified as intermediates, whereas linear alkylphenols (the expected primary desulfonation products) were not detected by high-pressure liquid chromatography coupled with both fluorescence and electrospray ionization-mass spectrometry. Thus, LAS was used by the bacteria as a source of energy and carbon, rather than as a source of sulfur. Measurements of soil pH, fluorescein diacetate (FDA) hydrolysis and arylsulfatase activity showed that stable microbial conditions prevailed in the soil mesocosms. FDA hydrolysis (a measure of total microbial activity) was transiently inhibited at the highest LAS concentrations. Arylsulfatase activity (i.e., hydrolysis of aromatic sulfate esters) was not significantly affected by the soil incubation, although arylsulfatases may be upregulated in sulfate-starved bacteria. However, an increased production of arylsulfatase may be difficult to detect due to the background of extracellular arylsulfatases stabilised in the soil. Therefore, the present data does not exclude a regulatory response to sulfate depletion by the soil microorganisms. However, the importance of desulfonation reactions in natural environments still needs to be demonstrated.