Emissions of CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O from undisturbed,drained and mined peatlands in Estonia

The aim of this study is to estimate emissions of greenhouse gases CO₂, CH₄ and N₂O, and the effects of drainage and peat extraction on these processes, in Estonian transitional fens and ombrotrophic bogs. Closed-chamber-based sampling lasted from January to December 2009 in nine peatlands in Estonia, covering areas with different land-use practices: natural (four study sites), drained (six sites), abandoned peat mining (five sites) and active peat mining areas (five sites). Median values of soil CO₂ efflux were 1,509, 1,921, 2,845 and 1,741 kg CO₂-C ha^?1 year^?1 from natural, drained, abandoned and active mining areas, respectively. Emission of CH₄-C (median values) was 85.2, 23.7, 0.07 and 0.12 kg ha^?1 year^?1, and N₂O-N ?0.05, ?0.01, 0.18 and 0.19 kg ha^?1 year^?1, respectively. There were significantly higher emissions of CO₂ and N₂O from abandoned and active peat mining areas, whereas CH₄ emissions were significantly higher in natural and drained areas. Significant Spearman rank correlation was found between soil temperature and CO₂ flux at all sites, and CH₄ flux with high water level at natural and drained areas. Significant increase in CH₄ flux was detected for groundwater levels above 30 cm.     

Spatial Variation of Soil CO<Subscript>2</Subscript>, CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O Fluxes Across Topographical Positions in Tropical Forests of the Guiana Shield

The spatial variation of soil greenhouse gas fluxes (GHG; carbon dioxide—CO₂, methane—CH₄ and nitrous oxide—N₂O) remains poorly understood in highly complex ecosystems such as tropical forests. We used 240 individual flux measurements of these three GHGs from different soil types, at three topographical positions and in two extreme hydric conditions in the tropical forests of the Guiana Shield (French Guiana, South America) to (1) test the effect of topographical positions on GHG fluxes and (2) identify the soil characteristics driving flux variation in these nutrient-poor tropical soils. Surprisingly, none of the three GHG flux rates differed with topographical position. CO₂ effluxes covaried with soil pH, soil water content (SWC), available nitrogen and total phosphorus. The CH₄ fluxes were best explained by variation in SWC, with soils acting as a sink under drier conditions and as a source under wetter conditions. Unexpectedly, our study areas were generally sinks for N₂O and N₂O fluxes were partly explained by total phosphorus and available nitrogen concentrations. This first study describing the spatial variation of soil fluxes of the three main GHGs measured simultaneously in forests of the Guiana Shield lays the foundation for specific studies of the processes underlying the observed patterns.     

Study of Plasma Induced Chemistry by DC Discharges in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>/H<Subscript>2</Subscript>O Mixtures Above a Water Surface

The chemistry induced by atmospheric pressure DC discharges above a water surface in CO(2)/N(2)/H(2)O mixtures was investigated. The gaseous mixtures studied represent a model prebiotic atmosphere of the Earth. The most remarkable changes in the chemical composition of the treated gas were the decomposition of CO(2) and the production of CO. The concentration of CO increased logarithmically with the increasing input energy density and an increasing initial concentration of CO(2) in the gas. The highest achieved concentration of CO was 4.0 +/- 0.6 vol. %. The production of CO was crucial for the synthesis of organic species, since reactions of CO with some reactive species generated in the plasma, e. g. H* or N* radicals, were probably the starting point in this synthesis. The presence of organic species (including the tentative identification of some amino acids) was demonstrated by the analysis of solid and liquid samples by high-performance liquid chromatography, infrared absorption spectroscopy and proton-transfer-reaction mass spectrometry. Formation of organic species in a completely inorganic CO(2)/N(2)/H(2)O atmosphere is a significant finding for the theory of the origins of life.     

Nitrate and flooding induce N<Subscript>2</Subscript>O emissions from soybean nodules

Nitrous oxide (N₂O) is one of the three main biogenic greenhouse gases (GHGs) and agriculture represents close to 30 % of the total N₂O net emissions. In agricultural soils, N₂O is emitted by two main microbial processes, nitrification and denitrification, both of which can convert synthetic nitrogen fertilizer into N₂O. Legume-rhizobia symbiosis could be an effective and environmental-friendly alternative to nitrogen fertilization and hence, to mitigate soil N₂O emissions. However, legume crops also contribute to N₂O emissions. A better understanding of the environmental factors involved in the emission of N₂O from nodules would be instrumental for mitigating the release of this GHG gas. In this work, in vivo N₂O emissions from nodulated soybean roots in response to nitrate (0, 1, 2 and 4 mM) and flooding have been measured. To investigate the contribution of rhizobial denitrification in N₂O emission from nodules, plants were inoculated with B. japonicum USDA110 and napA and nosZ denitrification mutants. The results showed that nitrate was essential for N₂O emissions and its concentration enhanced N₂O fluxes showing a statistical linear correlation, being the highest N₂O fluxes obtained with 4 mM nitrate. When inoculated plants grown with 4 mM nitrate were subjected to flooding, a 150- and 830-fold induction of N₂O emission rates from USDA110 and nosZ nodulated roots, respectively, was observed compared to non-flooded plants, especially during long-term flooding. Under these conditions, N₂O emissions from detached nodules produced by the napA mutant were significantly lower (p?<?0.05) than those produced by the wild-type strain (382 versus 1120 nmol N₂O h^?1 g^?1 NFW, respectively). In contrast, nodules from plants inoculated with the nosZ mutant accumulated statistically higher levels of N₂O compared to wild-type nodules (2522 versus nmol 1120 N₂O h^?1 g^?1 NFW, p?<?0.05). These results demonstrate that flooding is an important environmental factor for N₂O emissions from soybean nodules and that B. japonicum denitrification is involved in such emission.     

Simulation of Effects of Soils,Climate and Management on N<Subscript>2</Subscript>O Emission from Grasslands

Nitrous oxide (N₂O) is a potent greenhouse gas with a high contribution from agricultural soils and emissions that depend on soil type, climate, crops and management practices. The N₂O emissions therefore need to be included as an integral part of environmental assessments of agricultural production systems. An algorithm for N₂O production and emission from agricultural soils was developed and included in the FASSET whole-farm model. The model simulated carbon and nitrogen (N) turnover on a daily basis. Both nitrification and denitrification was included in the model as sources for N₂O production, and the N₂O emissions depended on soil microbial and physical conditions. The model was tested on experimental data of N₂O emissions from grasslands in UK, Finland and Denmark, differing in climatic conditions, soil properties and management. The model simulated the general time course of N₂O emissions and captured the observed effects of fertiliser and manure management on emissions. Scenario analyses for grazed and cut grasslands were conducted to evaluate the effects of soil texture, climatic conditions, grassland management and N fertilisation on N₂O emissions. The soils varied from coarse sand to sandy loam and the climatic variation was taken to represent the climatic variation within Denmark. N fertiliser rates were varied from 0 to 500 kg N ha⁻¹. The simulated N₂O emissions showed a non-linear response to increasing N rates with increasing emission factors at higher N rates. The simulated emissions increased with increasing soil clay contents. N₂O emissions were slightly increased at higher temperatures, whereas increasing annual rainfall generally lead to decreasing emissions. Emissions were slightly higher from grazed grasslands compared with cut grasslands at similar rates of total N input (fertiliser and animal excreta). The results indicate higher emission factors and thus higher potentials for reducing N₂O emissions for intensively grazed grasslands on fine textured soils than for extensive cut-based grasslands on sandy soils.     

Responses of N<Subscript>2</Subscript>O Flux from Forest Soils to Land Use Change in Subtropical China

To evaluate the effect of land use change from a natural broadleaf evergreen forest to Moso bamboo plantations and their management practices on soil N₂O efflux in a subtropical region of China, N₂O efflux was measured during June 2008 and May 2009 using static closed chamber method. The observed mean N₂O fluxes were 0.230, 0.102 and 0.093 mg N₂O/m²/h from the intensively managed bamboo forest (IM), conventionally managed bamboo forest (CM), and broadleaf evergreen forest (BL), respectively, and calculated annual cumulative N₂O were 15.8, 8.7 and 7.2 kg N₂O/ha, respectively. Soil temperature had significant influence on N₂O flux. Whereas there was no correlation between N₂O flux and soil water content. Conversion of the natural subtropical broadleaf evergreen forest to Moso bamboo did not increase soil N₂O efflux, but intensive management practices such as regular tillage and fertiliser application, significantly increased soil N₂O emission from bamboo soil.     

Temporal Variability of CO<Subscript>2</Subscript> and N<Subscript>2</Subscript>O Flux Spatial Patterns at a Mowed and a Grazed Grassland

Spatial patterns of ecosystem processes constitute significant sources of uncertainty in greenhouse gas flux estimations partly because the patterns are temporally dynamic. The aim of this study was to describe temporal variability in the spatial patterns of grassland CO₂ and N₂O flux under varying environmental conditions and to assess effects of the grassland management (grazing and mowing) on flux patterns. We made spatially explicit measurements of variables including soil respiration, aboveground biomass, N₂O flux, soil water content, and soil temperature during a 4-year study in the vegetation periods at grazed and mowed grasslands. Sampling was conducted in 80 × 60 m grids of 10 m resolution with 78 sampling points in both study plots. Soil respiration was monitored nine times, and N₂O flux was monitored twice during the study period. Altitude, soil organic carbon, and total soil nitrogen were used as background factors at each sampling position, while aboveground biomass, soil water content, and soil temperature were considered as covariates in the spatial analysis. Data were analyzed using variography and kriging. Altitude was autocorrelated over distances of 40–50 m in both plots and influenced spatial patterns of soil organic carbon, total soil nitrogen, and the covariates. Altitude was inversely related to soil water content and aboveground biomass and positively related to soil temperature. Autocorrelation lengths for soil respiration were similar on both plots (about 30 m), whereas autocorrelation lengths of N₂O flux differed between plots (39 m in the grazed plot vs. 18 m in the mowed plot). Grazing appeared to increase heterogeneity and linkage of the spatial patterns, whereas mowing had a homogenizing effect. Spatial patterns of soil water content, soil respiration, and aboveground biomass were temporally variable especially in the first 2 years of the experiment, whereas spatial patterns were more persistent (mostly significant correlation at p < 0.05 between location ranks) in the second 2 years, following a wet year. Increased persistence of spatial patterns after a wet year indicated the recovery potential of grasslands following drought and suggested that adequate water supply could have a homogenizing effect on CO₂ and N₂O fluxes.     

Denitrification and N<Subscript>2</Subscript>O emission from forested and cultivated alluvial clay soil

Restored forested wetlands reduce N loads in surface discharge through plant uptake and denitrification. While removal of reactive N reduces impact on receiving waters, it is unclear whether enhanced denitrification also enhances emissions of the greenhouse gas N₂O, thus compromising the water-quality benefits of restoration. This study compares denitrification rates and N₂O:N₂ emission ratios from Sharkey clay soil in a mature bottomland forest to those from an adjacent cultivated site in the Lower Mississippi Alluvial Valley. Potential denitrification of forested soil was 2.4 times of cultivated soil. Using intact soil cores, denitrification rates of forested soil were 5.2, 6.6 and 2.0 times those of cultivated soil at 70, 85 and 100% water-filled pore space (WFPS), respectively. When NO₃ was added, N₂O emissions from forested soil were 2.2 times those of cultivated soil at 70% WFPS. At 85 and 100% WFPS, N₂O emissions were not significantly different despite much greater denitrification rates in the forested soil because N₂O:N₂ emission ratios declined more rapidly in forested soil as WFPS increased. These findings suggest that restoration of forested wetlands to reduce NO₃ in surface discharge will not contribute significantly to the atmospheric burden of N₂O.     

Impacts of grazing intensity on denitrification and N<Subscript>2</Subscript>O production in a semi-arid grassland ecosystem

N₂O production from denitrification in soils contributes to the enhanced greenhouse effect and the destruction of the stratospheric ozone. Ungulate grazing affects denitrification and the production of N₂O. The short-term effect of grazing on denitrification and N₂O production has been examined in several grassland ecosystems. However, the effects of long-term grazing have rarely been studied. We measured denitrification and N₂O production during the 2005 and 2006 growing seasons in a long-term (17 years) experiment that had five grazing intensities (GI; 0.00, 1.33, 2.67, 4.00 and 5.33 sheep ha⁻¹). We found that denitrification and N₂O production rates were seasonally variable during the measurement period, with higher values observed in summer and lower values found in spring and autumn. The grazed treatments resulted in decreased denitrification and N₂O production, primarily due to the reduced soil nitrate concentration and organic N content under the long-term grazing. This supported our hypothesis that long-term over-grazing suppresses denitrification and N₂O production. Although significant differences in denitrification and N₂O production were not found between the four GI, there was a general trend that cumulative denitrification and N₂O production decreased as grazing intensity increased, especially in 2006. Lower N losses via denitrification and N₂O production in the grazed plots, to some extent, may contribute to the mitigation of greenhouse gas emission and help to preserve soil N and ameliorate the negative impacts of grazing on plant growth, productivity, and ecological restoration processes in the temperate steppe in northern China.     

N<Subscript>2</Subscript>O and CH<Subscript>4</Subscript> emission from <Emphasis Type="Italic">Miscanthus</Emphasis> energy crop fields in the infertile Loess Plateau of China

Background

The greenhouse gas (GHG) mitigation is one of the most important environmental benefits of using bioenergy replacing fossil fuels. Nitrous oxide (N₂O) and methane (CH₄) are important GHGs and have drawn extra attention for their roles in global warming. Although there have been many works of soil emissions of N₂O and CH₄ from bioenergy crops in the field scale, GHG emissions in large area of marginal lands are rather sparse and how soil temperature and moisture affect the emission potential remains unknown. Therefore, we sought to estimate the regional GHG emission based on N₂O and CH₄ releases from the energy crop fields.

Results

Here we sampled the top soils from two Miscanthus fields and incubated them using a short-term laboratory microcosm approach under different conditions of typical soil temperatures and moistures. Based on the emission measurements of N₂O and CH₄, we developed a model to estimate annual regional GHG emission of Miscanthus production in the infertile Loess Plateau of China. The results showed that the N₂O emission potential was 0.27 kg N ha^?1 year^?1 and clearly lower than that of croplands and grasslands. The CH₄ uptake potential was 1.06 kg C ha^?1 year^?1 and was slightly higher than that of croplands. Integrated with our previous study on the emission of CO₂, the net greenhouse effect of three major GHGs (N₂O, CH₄ and CO₂) from Miscanthus fields was 4.08 t CO_2eq ha^?1 year^?1 in the Loess Plateau, which was lower than that of croplands, grasslands and shrub lands.

Conclusions

Our study revealed that Miscanthus production may hold a great potential for GHG mitigation in the vast infertile land in the Loess Plateau of China and could contribute to the sustainable energy utilization and have positive environmental impact on the region.

     

Mechanism leading to N<Subscript>2</Subscript>O production in wastewater treating biofilm systems

Wastewater treatment plants are known to be important point sources for nitrous oxide (N₂O) in the anthropogenic N cycle. Biofilm based treatment systems have gained increasing popularity in the treatment of wastewater, but the mechanisms and controls of N₂O formation are not fully understood. Here, we review functional groups of microorganism involved in nitrogen (N) transformations during wastewater treatment, with emphasis on potential mechanism of N₂O production in biofilms. Biofilms used in wastewater treatment typically harbour aerobic and anaerobic zones, mediating close interactions between different groups of N transforming organisms. Current models of mass transfer and biomass interactions in biofilms are discussed to illustrate the complex regulation of N₂O production. Ammonia oxidizing bacteria (AOB) are the prime source for N₂O in aerobic zones, while heterotrophic denitrifiers dominate N₂O production in anoxic zones. Nitrosative stress ensuing from accumulation of NO₂ ^? during partial nitrification or denitrification seems to be one of the most critical factors for enhanced N₂O formation. In AOB, N₂O production is coupled to nitrifier denitrification triggered by nitrosative stress, low O₂ tension or low pH. Chemical N₂O production from AOB intermediates (NH₂OH, HNO, NO) released during high NH₃ turnover seems to be limited to surface-near AOB clusters, since diffusive mass transport resistance for O₂ slows down NH₃ oxidation rates in deeper biofilm layers. The proportion of N₂O among gaseous intermediates (NO, N₂O, N₂) in heterotrophic denitrification increases when NO or nitrous acid (HNO₂) accumulates because of increasing NO₂ ^?, or when transient oxygen intrusion impairs complete denitrification. Limited electron donor availability due to mass transport limitation of organic substrates into anoxic biofilm zones is another important factor supporting high N₂O/N₂ ratios in heterotrophic denitrifiers. Biofilms accommodating Anammox bacteria release less N₂O, because Anammox bacteria have no known N₂O producing metabolism and reduce NO₂ ^? to N₂, thereby lowering nitrosative stress to AOB and heterotrophs.     

Hydrothermal Stability of Adenine Under Controlled Fugacities of N<Subscript>2</Subscript>, CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>

An experimental study has been carried out on the stability of adenine (one of the five nucleic acid bases) under hydrothermal conditions. The experiments were performed in sealed autoclaves at 300 degrees C under fugacities of CO(2), N(2) and H(2) supposedly representative of those in marine hydrothermal systems on the early Earth. The composition of the gas phase was obtained from the degradation of oxalic acid, sodium nitrite and ammonium chloride, and the oxidation of metallic iron. The results of the experiments indicate that after 200 h, adenine is still present in detectable concentration in the aqueous phase. In fact, the concentration of adenine does not seem to be decreasing after approximately 24 h, which suggests that an equilibrium state may have been established with the inorganic constituents of the hydrothermal fluid. Such a conclusion is corroborated by independent thermodynamic calculations.     

Simulation and optical spectroscopy of a DC discharge in a CH<Subscript>4</Subscript>/H<Subscript>2</Subscript>/N<Subscript>2</Subscript> mixture during deposition of nanostructured carbon films

Two-dimensional numerical simulations of a dc discharge in a CH₄/H₂/N₂ mixture in the regime of deposition of nanostructured carbon films are carried out with account of the cathode electron beam effects. The distributions of the gas temperature and species number densities are calculated, and the main plasmachemical kinetic processes governing the distribution of methyl radicals above the substrate are analyzed. It is shown that the number density of methyl radicals above the substrate is several orders of magnitude higher than the number densities of other hydrocarbon radicals, which indicates that the former play a dominant role in the growth of nanostructured carbon films. The model is verified by comparing the measured optical emission profiles of the H(n ≡ 3), C ₂ ^* , CH*, and CN* species and the calculated number densities of excited species, as well as the measured and calculated values of the discharge voltage and heat fluxes onto the electrodes and reactor walls. The key role of ion–electron recombination and dissociative excitation of H₂, C₂H₂, CH₄, and HCN molecules in the generation of emitting species (first of all, in the cold regions adjacent to the electrodes) is revealed.     

TCNE-modified graphene as an adsorbent for N<Subscript>2</Subscript>O molecule: a DFT study

Adsorption behavior of nitrous oxide (N₂O) on pristine graphene (PG) and tetracyanoethylene (TCNE) modified PG surfaces is investigated using density functional theory. A number of initial adsorbate geometries are considered on both surfaces and the most stable ones are chosen upon calculation of the adsorption energies (E_ads). N₂O is found to adsorb in a weakly exoergic process (E_ads?～??3.18 kJ mol^?1) at the equilibrium distance of 3.52 Å on the PG surface. N₂O adsorption can be greatly enhanced with the presence of a TCNE molecule (E_ads?=??87.00 kJ mol^?1). Mulliken charge analysis confirms that adsorption of N₂O is not accompanied by distinct charge transfer from the surfaces to the molecule (? 0.001 │e│ for each case). Moreover, on the basis of calculated changes in the HOMO/LUMO energy gap, it is found that electronic properties of PG and TCNE modified PG are not sensitive toward adsorption of N₂O, indicating that both surfaces are not good enough to introduce as an N₂O detector. However, the considerable amount of E_ads in TCNE modified PG can be a guide to the design of graphene-based adsorbents for N₂O capture.     

Floating Aquatic Macrophytes Can Substantially Offset Open Water CO<Subscript>2</Subscript> Emissions from Tropical Floodplain Lake Ecosystems

Tropical floodplain lake ecosystems are recognized as important sources of carbon (C) from the water to the atmosphere. They receive large amounts of organic matter and nutrients from the watershed, leading to intense net heterotrophy and carbon dioxide (CO₂) emission from open waters. However, the role of extensive stands of floating macrophytes colonizing floodplains areas is still neglected in assessments of net ecosystem exchange of CO₂ (NEE). We assessed rates of air-lake CO₂ flux using static chambers in both open waters and waters covered by the widespread floating aquatic macrophyte (water hyacinth; Eichornia sp.) in two tropical floodplain lakes in Pantanal, Brazil during different hydrological seasons. In both lakes, areas colonized by floating macrophytes were a net CO₂ sink during all seasons. In contrast, open waters emitted CO₂, with higher emissions during the rising and high water periods. Our results indicate that the lake NEE can be substantially overestimated (fivefold or more in the studied lakes) if the carbon fixation by macrophytes is not considered. The contribution of these plants can lead to neutral or negative NEE (that is, net uptake of CO₂) on a yearly basis. This highlights the importance of floating aquatic macrophytes for the C balance in shallow lakes and extensive floodplain areas.     

Quantifying the contribution of land use to N<Subscript>2</Subscript>O,NO and CO<Subscript>2</Subscript> fluxes in a montane forest ecosystem of Kenya

Increasing demand for food and fibre by the growing human population is driving significant land use (LU) change from forest into intensively managed land systems in tropical areas. But empirical evidence on the extent to which such changes affect the soil-atmosphere exchange of trace gases is still scarce, especially in Africa. We investigated the effect of LU on soil trace gas production in the Mau Forest Complex region, Kenya. Intact soil cores were taken from natural forest, commercial and smallholder tea plantations, eucalyptus plantations and grazing lands, and were incubated in the lab under different soil moisture conditions. Soil fluxes of nitrous oxide (N₂O), nitric oxide (NO) and carbon dioxide (CO₂) were quantified, and we approximated annual estimates of soil N₂O and NO fluxes using soil moisture values measured in situ. Forest and eucalyptus plantations yielded annual fluxes of 0.3–1.3 kg N₂O–N ha^?1 a^?1 and 1.5–5.2 kg NO–N ha^?1 a^?1. Soils of commercial tea plantations, which are highly fertilized, showed higher fluxes (0.9 kg N₂O–N ha^?1 a^?1 and 4.3 kg NO–N ha^?1 a^?1) than smallholder tea plantations (0.1 kg N₂O–N ha^?1 a^?1 and 2.1 kg NO–N ha^?1 a^?1) or grazing land (0.1 kg N₂O–N ha^?1 a^?1 and 1.1 kg NO–N ha^?1 a^?1). High soil NO fluxes were probably the consequence of long-term N fertilization and associated soil acidification, likely promoting chemodenitrification. Our experimental approach can be implemented in understudied regions, with the potential to increase the amount of information on production and consumption of trace gases from soils.     

Microbial N Turnover and N-Oxide (N<Subscript>2</Subscript>O/NO/NO<Subscript>2</Subscript>) Fluxes in Semi-arid Grassland of Inner Mongolia

Gross rates of N mineralization and nitrification, and soil–atmosphere fluxes of N₂O, NO and NO₂ were measured at differently grazed and ungrazed steppe grassland sites in the Xilin river catchment, Inner Mongolia, P. R. China, during the 2004 and 2005 growing season. The experimental sites were a plot ungrazed since 1979 (UG79), a plot ungrazed since 1999 (UG99), a plot moderately grazed in winter (WG), and an overgrazed plot (OG), all in close vicinity to each other. Gross rates of N mineralization and nitrification determined at in situ soil moisture and soil temperature conditions were in a range of 0.5–4.1 mg N kg⁻¹ soil dry weight day⁻¹. In 2005, gross N turnover rates were significantly higher at the UG79 plot than at the UG99 plot, which in turn had significantly higher gross N turnover rates than the WG and OG plots. The WG and the OG plot were not significantly different in gross ammonification and in gross nitrification rates. Site differences in SOC content, bulk density and texture could explain only less than 15% of the observed site differences in gross N turnover rates. N₂O and NO _x flux rates were very low during both growing seasons. No significant differences in N trace gas fluxes were found between plots. Mean values of N₂O fluxes varied between 0.39 and 1.60 μg N₂O-N m⁻² h⁻¹, equivalent to 0.03–0.14 kg N₂O-N ha⁻¹ y⁻¹, and were considerably lower than previously reported for the same region. NO _x flux rates ranged between 0.16 and 0.48 μg NO _x -N m⁻² h⁻¹, equivalent to 0.01–0.04 kg NO _x -N ha⁻¹ y⁻¹, respectively. N₂O fluxes were significantly correlated with soil temperature and soil moisture. The correlations, however, explained only less than 20% of the flux variance.     

Effects of Herbivory,Fire and N<Subscript>2</Subscript>-fixation on Nutrient Limitation in a Humid African Savanna

The quantities and spatial distribution of nutrients in savanna ecosystems are affected by many factors, of which fire, herbivory and symbiotic N₂-fixation are particularly important. We measured soil nitrogen (N) pools and the relative abundance of N and phosphorus (P) in herbaceous vegetation in five vegetation types in a humid savanna in Tanzania. We also performed a factorial fertilization experiment to investigate which nutrients most limit herbaceous production. N pools in the top 10 cm of soil were low at sites where fires were frequent, and higher in areas with woody legume encroachment, or high herbivore excretion. Biomass production was co-limited by N and P at sites that were frequently burnt or heavily grazed by native herbivores. In contrast, aboveground production was limited by N in areas receiving large amounts of excreta from livestock. N₂-fixation by woody legumes did not lead to P-limitation, but did increase the availability of N relative to P. We conclude that the effects of fire, herbivory and N₂-fixation upon soil N pools and N:P-stoichiometry in savanna ecosystems are, to a large extent, predictable. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Author Contributions  P.C., H.O.V. and P.E. designed the study and wrote the paper. P.C. and T.K. performed the research and analyzed the data.     

Reduced Snow Cover Increases Wintertime Nitrous Oxide (N<Subscript>2</Subscript>O) Emissions from an Agricultural Soil in the Upper U.S. Midwest

Throughout most of the northern hemisphere, snow cover decreased in almost every winter month from 1967 to 2012. Because snow is an effective insulator, snow cover loss has likely enhanced soil freezing and the frequency of soil freeze–thaw cycles, which can disrupt soil nitrogen dynamics including the production of nitrous oxide (N₂O). We used replicated automated gas flux chambers deployed in an annual cropping system in the upper Midwest US for three winters (December–March, 2011–2013) to examine the effects of snow removal and additions on N₂O fluxes. Diminished snow cover resulted in increased N₂O emissions each year; over the entire experiment, cumulative emissions in plots with snow removed were 69% higher than in ambient snow control plots and 95% higher than in plots that received additional snow (P < 0.001). Higher emissions coincided with a greater number of freeze–thaw cycles that broke up soil macroaggregates (250–8000 µm) and significantly increased soil inorganic nitrogen pools. We conclude that winters with less snow cover can be expected to accelerate N₂O fluxes from agricultural soils subject to wintertime freezing.     

Theoretical investigation of reactivities of amines in the <Emphasis Type="Italic">N</Emphasis>-nitrosation reactions by N<Subscript>2</Subscript>O<Subscript>3</Subscript>

N-nitrosamine is a class of carcinogenic, mutagenic, and teratogenic compounds, which can be produced from N-nitrosation of amine by nitrosating agents. N-nitrosation of 19 amines (eight acyclic amines, five heterocyclic amines, and six amines with unsaturated groups) by N₂O₃ was investigated at the CBS-QB3 level of theory. The results indicate that generally the heterocyclic amines have the highest reactivities among the three kinds of amines, whereas the reactivities of the amines with unsaturated and electron-withdrawing groups are relatively low. Frontier molecular orbital analysis indicates that the energy gap between the HOMO of an amine and the LUMO of N₂O₃ has a close connection with the reactivity of an amine. A structure-reactivity relationship of amines in the N-nitrosation reactions by N₂O₃ was established using the stepwise multivariate linear regression. The results indicate that the reactivity of an amine has a definite relationship (R_adj² = 0.947) with the heterolytic bond dissociation energy of R₁R₂N-H bond, energy of HOMO, NBO occupancy of the natural lone pair orbital of N atom, the NBO charge of the N atom, and the pyramidalization angle of an amine. This work will be helpful to gain more insight into the N-nitrosation reactions.