Soil N2O and CO2 emissions from cotton in Australia under varying irrigation management

Irrigation is known to stimulate soil microbial carbon and nitrogen turnover and potentially the emissions of nitrous oxide (N2O) and carbon dioxide (CO2). We conducted a study to evaluate the effect of three different irrigation intensities on soil N2O and CO2 fluxes and to determine if irrigation management can be used to mitigate N2O emissions from irrigated cotton on black vertisols in South-Eastern Queensland, Australia. Fluxes were measured over the entire 2009/2010 cotton growing season with a fully automated chamber system that measured emissions on a sub-daily basis. Irrigation intensity had a significant effect on CO2 emission. More frequent irrigation stimulated soil respiration and seasonal CO2 fluxes ranged from 2.7 to 4.1 Mg-C ha−1 for the treatments with the lowest and highest irrigation frequency, respectively. N2O emission happened episodic with highest emissions when heavy rainfall or irrigation coincided with elevated soil mineral N levels and seasonal emissions ranged from 0.80 to 1.07 kg N2O-N ha−1 for the different treatments. Emission factors (EF = proportion of N fertilizer emitted as N2O) over the cotton cropping season, uncorrected for background emissions, ranged from 0.40 to 0.53 % of total N applied for the different treatments. There was no significant effect of the different irrigation treatments on soil N2O fluxes because highest emission happened in all treatments following heavy rainfall caused by a series of summer thunderstorms which overrode the effect of the irrigation treatment. However, higher irrigation intensity increased the cotton yield and therefore reduced the N2O intensity (N2O emission per lint yield) of this cropping system. Our data suggest that there is only limited scope to reduce absolute N2O emissions by different irrigation intensities in irrigated cotton systems with summer dominated rainfall. However, the significant impact of the irrigation treatments on the N2O intensity clearly shows that irrigation can easily be used to optimize the N2O intensity of such a system.

A flexible Bayesian model for describing temporal variability of N2O emissions from an Australian pasture

Soil-based emissions of nitrous oxide (N2O), a well-known greenhouse gas, have been associated with changes in soil water-filled pore space (WFPS) and soil temperature in many previous studies. However, it is acknowledged that the environment-N2O relationship is complex and still relatively poorly unknown. In this article, we employed a Bayesian model selection approach (Reversible jump Markov chain Monte Carlo) to develop a data-informed model of the relationship between daily N2O emissions and daily WFPS and soil temperature measurements between March 2007 and February 2009 from a soil under pasture in Queensland, Australia, taking seasonal factors and time-lagged effects into account. The model indicates a very strong relationship between a hybrid seasonal structure and daily N2O emission, with the latter substantially increased in summer. Given the other variables in the model, daily soil WFPS, lagged by a week, had a negative influence on daily N2O; there was evidence of a nonlinear positive relationship between daily soil WFPS and daily N2O emission; and daily soil temperature tended to have a linear positive relationship with daily N2O emission when daily soil temperature was above a threshold of approximately 19°C. We suggest that this flexible Bayesian modeling approach could facilitate greater understanding of the shape of the covariate-N2O flux relation and detection of effect thresholds in the natural temporal variation of environmental variables on N2O emission.

Spatial prediction of N2O emissions in pasture : a Bayesian model averaging analysis

Nitrous oxide (N2O) is one of the greenhouse gases that can contribute to global warming. Spatial variability of N2O can lead to large uncertainties in prediction. However, previous studies have often ignored the spatial dependency to quantify the N2O - environmental factors relationships. Few researches have examined the impacts of various spatial correlation structures (e.g. independence, distance-based and neighbourhood based) on spatial prediction of N2O emissions. This study aimed to assess the impact of three spatial correlation structures on spatial predictions and calibrate the spatial prediction using Bayesian model averaging (BMA) based on replicated, irregular point-referenced data. The data were measured in 17 chambers randomly placed across a 271 m(2) field between October 2007 and September 2008 in the southeast of Australia. We used a Bayesian geostatistical model and a Bayesian spatial conditional autoregressive (CAR) model to investigate and accommodate spatial dependency, and to estimate the effects of environmental variables on N2O emissions across the study site. We compared these with a Bayesian regression model with independent errors. The three approaches resulted in different derived maps of spatial prediction of N2O emissions. We found that incorporating spatial dependency in the model not only substantially improved predictions of N2O emission from soil, but also better quantified uncertainties of soil parameters in the study. The hybrid model structure obtained by BMA improved the accuracy of spatial prediction of N2O emissions across this study region.

A novel 15N tracer approach for the quantification of N2 and N2O emissions from soil incubations in a completely automated laboratory set up

The microbial mediated production of nitrous oxide (N2O) and its reduction to dinitrogen (N2) via denitrification represents a loss of nitrogen (N) from fertilised agro-ecosystems to the atmosphere. Although denitrification has received great interest by biogeochemists in the last decades, the magnitude of N2lossesand related N2:N2O ratios from soils still are largely unknown due to methodical constraints. We present a novel 15N tracer approach, based on a previous developed tracer method to study denitrification in pure bacterial cultures which was modified for the use on soil incubations in a completely automated laboratory set up. The method uses a background air in the incubation vessels that is replaced with a helium-oxygen gas mixture with a 50-fold reduced N2 background (2 % v/v). This method allows for a direct and sensitive quantification of the N2 and N2O emissions from the soil with isotope-ratio mass spectrometry after 15N labelling of denitrification N substrates and minimises the sensitivity to the intrusion of atmospheric N2 at the same time. The incubation set up was used to determine the influence of different soil moisture levels on N2 and N2O emissions from a sub-tropical pasture soil in Queensland/Australia. The soil was labelled with an equivalent of 50 μg-N per gram dry soil by broadcast application of KNO3solution (4 at.% 15N) and incubated for 3 days at 80% and 100% water filled pore space (WFPS), respectively. The headspace of the incubation vessel was sampled automatically over 12hrs each day and 3 samples (0, 6, and 12 hrs after incubation start) of headspace gas analysed for N2 and N2O with an isotope-ratio mass spectrometer (DELTA V Plus, Thermo Fisher Scientific, Bremen, Germany(. In addition, the soil was analysed for 15N NO3- and NH4+ using the 15N diffusion method, which enabled us to obtain a complete N balance. The method proved to be highly sensitive for N2 and N2O emissions detecting N2O emissions ranging from 20 to 627 μN kg-1soil-1hr-1and N2 emissions ranging from 4.2 to 43 μN kg-1soil-1hr-1for the different treatments. The main end-product of denitrification was N2O for both water contents with N2 accounting for 9% and 13% of the total denitrification losses at 80% and 100%WFPS, respectively. Between 95-100% of the added 15N fertiliser could be recovered. Gross nitrification over the 3 days amounted to 8.6 μN g-1 soil-1 and 4.7 μN g-1 soil-1, denitrification to 4.1 μN g-1 soil-1 and 11.8 μN g-1 soil-1at 80% and 100%WFPS, respectively. The results confirm that the tested method allows for a direct and highly sensitive detection of N2 and N2O fluxes from soils and hence offers a sensitive tool to study denitrification and N turnover in terrestrial agro-ecosystems.

Soil N2O emissions under N2-fixing legumes and N-fertilised canola: A reappraisal of emissions factor calculations

Introducing nitrogen (N)-fixing legumes into cereal-based crop rotations reduces synthetic fertiliser-N use and may mitigate soil emissions of nitrous oxide (N2O). Current IPCC calculations assume 100% of legume biomass N as the anthropogenic N input and use 1% of this as an emission factor (EF)—the percentage of input N emitted as N2O. However, legumes also utilise soil inorganic N, so legume-fixed N is typically less than 100% of legume biomass N. In two field experiments, we measured soil N2O emissions from a black Vertosol in sub-tropical Australia for 12 months after sowing of chickpea (Cicer arietinum L.), canola (Brassica napus L.), faba bean (Vicia faba L.), and field pea (Pisum sativum L.). Cumulative N2O emissions from N-fertilised canola (624 g N2O-N ha−1) greatly exceeded those from chickpea (127 g N2O-N ha−1) in Experiment 1. Similarly, N2O emitted from canola (385 g N2O-N ha−1) in Experiment 2 was significantly greater than chickpea (166 g N2O-N ha−1), faba bean (166 g N2O-N ha−1) or field pea (135 g N2O-N ha−1). Highest losses from canola were recorded during the growing season, whereas 75% of the annual N2O losses from the legumes occurred post-harvest. Legume N2-fixation provided 37–43% (chickpea), 54% (field pea) and 64% (faba bean) of total plant biomass N. Using only fixed-N inputs, we calculated EFs for chickpea (0.13–0.31%), field pea (0.18%) and faba bean (0.04%) that were significantly less than N-fertilised canola (0.48–0.78%) (P < 0.05), suggesting legume-fixed N is a less emissive form of N input to the soil than fertiliser N. Inputs of legume-fixed N should be more accurately quantified to properly gauge the potential for legumes to mitigate soil N2O emissions. EF’s from legume crops need to be revised and should include a factor for the proportion of the legume’s N derived from the atmosphere.

Rice husk biochar and crop residue amendment in subtropical cropping soils: Effect on biomass production, nitrogen use efficiency and greenhouse gas emissions

We investigated the effect of maize residues and rice husk biochar on biomass production, fertiliser nitrogen recovery (FNR) and nitrous oxide (N2O) emissions for three different subtropical cropping soils. Maize residues at two rates (0 and 10 t ha−1) combined with three rates (0, 15 and 30 t ha-1) of rice husk biochar were added to three soil types in a pot trial with maize plants. Soil N2O emissions were monitored with static chambers for 91 days. Isotopic 15N-labelled urea was applied to the treatments without added crop residues to measure the FNR. Crop residue incorporation significantly reduced N uptake in all treatments but did not affect overall FNR. Rice husk biochar amendment had no effect on plant growth and N uptake but significantly reduced N2O and carbon dioxide (CO2) emissions in two of the three soils. The incorporation of crop residues had a contrasting effect on soil N2O emissions depending on the mineral N status of the soil. The study shows that effects of crop residues depend on soil properties at the time of application. Adding crop residues with a high C/N ratio to soil can immobilise N in the soil profile and hence reduce N uptake and/or total biomass production. Crop residue incorporation can either stimulate or reduce N2O emissions depending on the mineral N content of the soil. Crop residues pyrolysed to biochar can potentially stabilise native soil C (negative priming) and reduce N2O emissions from cropping soils thus providing climate change mitigation potential beyond the biochar C storage in soils. Incorporation of crop residues as an approach to recycle organic materials and reduce synthetic N fertiliser use in agricultural production requires a thorough evaluation, both in terms of biomass production and greenhouse gas emissions.

Establishing turf grass increases soil greenhouse gas emissions in peri-urban environments

Urbanization is becoming increasingly important in terms of climate change and ecosystem functionality worldwide. We are only beginning to understand how the processes of urbanization influence ecosystem dynamics and how peri-urban environments contribute to climate change. Brisbane in South East Queensland (SEQ) currently has the most extensive urban sprawl of all Australian cities. This leads to substantial land use changes in urban and peri-urban environments and the subsequent gaseous emissions from soils are to date neglected for IPCC climate change estimations. This research examines how land use change effects methane (CH4) and nitrous oxide (N2O) fluxes from peri-urban soils and consequently influences the Global Warming Potential (GWP) of rural ecosystems in agricultural use undergoing urbanization. Therefore, manual and fully automated static chamber measurements determined soil gas fluxes over a full year and an intensive sampling campaign of 80 days after land use change. Turf grass, as the major peri-urban land cover, increased the GWP by 415 kg CO2-e ha 1 over the first 80 days after conversion from a well-established pasture. This results principally from increased daily average N2O emissions of 0.5 g N2O ha-1 d-1 from the pasture to 18.3 g N2O ha-1 d-1 from the turf grass due to fertilizer application during conversion. Compared to the native dry sclerophyll eucalypt forest, turf grass establishment increases the GWP by another 30 kg CO2-e ha 1. The results presented in this study clearly indicate the substantial impact of urbanization on soil-atmosphere gas exchange in form of non-CO2 greenhouse gas emissions particularly after turf grass establishment.

Greenhouse Gas Fluxes in Tropical and Temperae Agriculture: The Need for a Full-Cost Accounting of Global Warming Potentials

Agriculture's contribution to radiative forcing is principally through its historical release of carbon in soil and vegetation to the atmosphere and through its contemporary release of nitrous oxide (N2O) and methane (CHM4). The sequestration of soil carbon in soils now depleted in soil organic matter is a well-known strategy for mitigating the buildup of CO2 in the atmosphere. Less well-recognized are other mitigation potentials. A full-cost accounting of the effects of agriculture on greenhouse gas emissions is necessary to quantify the relative importance of all mitigation options. Such an analysis shows nitrogen fertilizer, agricultural liming, fuel use, N2O emissions, and CH4 fluxes to have additional significant potential for mitigation. By evaluating all sources in terms of their global warming potential it becomes possible to directly evaluate greenhouse policy options for agriculture. A comparison of temperate and tropical systems illustrates some of these options.

The potential to mitigate global warming with no-tillage management is only realized when practised in the long term

No-tillage (NT) management has been promoted as a practice capable of offsetting greenhouse gas (GHG) emissions because of its ability to sequester carbon in soils. However, true mitigation is only possible if the overall impact of NT adoption reduces the net global warming potential (GWP) determined by fluxes of the three major biogenic GHGs (i.e. CO2, N2O, and CH4). We compiled all available data of soil-derived GHG emission comparisons between conventional tilled (CT) and NT systems for humid and dry temperate climates. Newly converted NT systems increase GWP relative to CT practices, in both humid and dry climate regimes, and longer-term adoption (>10 years) only significantly reduces GWP in humid climates. Mean cumulative GWP over a 20-year period is also reduced under continuous NT in dry areas, but with a high degree of uncertainty. Emissions of N2O drive much of the trend in net GWP, suggesting improved nitrogen management is essential to realize the full benefit from carbon storage in the soil for purposes of global warming mitigation. Our results indicate a strong time dependency in the GHG mitigation potential of NT agriculture, demonstrating that GHG mitigation by adoption of NT is much more variable and complex than previously considered, and policy plans to reduce global warming through this land management practice need further scrutiny to ensure success.

Influence of biochars on flux of N2O and CO2 from Ferrosol

Biochars produced by slow pyrolysis of greenwaste (GW), poultry litter (PL), papermill waste (PS), and biosolids (BS) were shown to reduce N₂O emissions from an acidic Ferrosol. Similar reductions were observed for the untreated GW feedstock. Soil was amended with biochar or feedstock giving application rates of 1 and 5%. Following an initial incubation, nitrogen (N) was added at 165 kg/ha as urea. Microcosms were again incubated before being brought to 100% water-filled porosity and held at this water content for a further 47 days. The flooding phase accounted for the majority (<80%) of total N₂O emissions. The control soil released 3165 mg N₂O-N/m², or 15.1% of the available N as N₂O. Amendment with 1 and 5% GW feedstock significantly reduced emissions to 1470 and 636 mg N₂O-N/m², respectively. This was equivalent to 8.6 and 3.8% of applied N. The GW biochar produced at 350°C was least effective in reducing emissions, resulting in 1625 and 1705 mg N₂O-N/m² for 1 and 5% amendments. Amendment with BS biochar at 5% had the greatest impact, reducing emissions to 518 mg N₂O-N/m², or 2.2% of the applied N over the incubation period. Metabolic activity as measured by CO₂ production could not explain the differences in N₂O emissions between controls and amendments, nor could NH₄⁺ or NO₃^– concentrations in biochar-amended soils. A decrease in NH₄⁺ and NO₃^– following GW feedstock application is likely to have been responsible for reducing N₂O emissions from this amendment. Reduction in N₂O emissions from the biochar-amended soils was attributed to increased adsorption of NO₃^–. Small reductions are possible due to improved aeration and porosity leading to lower levels of denitrification and N₂O emissions. Alternatively, increased pH was observed, which can drive denitrification through to dinitrogen during soil flooding.

The contribution of maize cropping in the Midwest USA to global warming: A regional estimate

Agricultural soils emit about 50% of the global flux of N2O attributable to human influence, mostly in response to nitrogen fertilizer use. Recent evidence that the relationship between N2O fluxes and N-fertilizer additions to cereal maize are non-linear provides an opportunity to estimate regional N2O fluxes based on estimates of N application rates rather than as a simple percentage of N inputs as used by the Intergovernmental Panel on Climate Change (IPCC). We combined a simple empirical model of N2O production with the SOCRATES soil carbon dynamics model to estimate N2O and other sources of Global Warming Potential (GWP) from cereal maize across 19,000 cropland polygons in the North Central Region (NCR) of the US over the period 1964–2005. Results indicate that the loading of greenhouse gases to the atmosphere from cereal maize production in the NCR was 1.7 Gt CO2e, with an average 268 t CO2e produced per tonne of grain. From 1970 until 2005, GHG emissions per unit product declined on average by 2.8 t CO2e ha−1 annum−1, coinciding with a stabilisation in N application rate and consistent increases in grain yield from the mid-1970’s. Nitrous oxide production from N fertilizer inputs represented 59% of these emissions, soil C decline (0–30 cm) represented 11% of total emissions, with the remaining 30% (517 Mt) from the combustion of fuel associated with farm operations. Of the 126 Mt of N fertilizer applied to cereal maize from 1964 to 2005, we estimate that 2.2 Mt N was emitted as N2O when using a non-linear response model, equivalent to 1.75% of the applied N.

Functionalised zinc oxide nanowire gas sensors : enhanced NO2 gas sensor response by chemical modification of nanowire surfaces

Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO2 produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO2 down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO2 compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO2 target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.

Hydrothermal technologies for the production of fuels and chemicals from biomass

Biomass and non-food crop residues are seen as relatively low cost and abundant renewable sources capable of making a large contribution to the world’s future energy and chemicals supply. Signifi cant quantities of ethanol are currently produced from biomass via biochemical processes, but thermochemical conversion processes offer greater potential to utilize the entire biomass source to produce a range of products. This chapter will review thermochemical gasifi cation and pyrolysis methods with a focus on hydrothermal liquefaction processes. Hydrothermal liquefaction is the most energetically advantageous thermochemical biomass conversion process. If the target is to produce sustainable liquid fuels and chemicals and reduce the impact of global warming as a result of carbon dioxide, nitrous oxide, and methane emissions (i.e., protect the natural environment), the use of “green” solvents, biocatalysts and heterogeneous catalysts must be the main R&D initiatives. As the biocrude produced from hydrothermal liquefaction is a complex mixture which is relatively viscous, corrosive, and unstable to oxidation (due to the presence of water and oxygenated compounds), additional upgrading processes are required to produce suitable biofuels and chemicals.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 2. -- A fourier-transform infrared spectroscopy study of methanol adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methanol adsorbed at 295 K on ZnO/SiO 2, on reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methanol on ZnO/SiO2 gave methoxy species on ZnO and SiO, in addition to both strongly and weakly physisorbed methanol on SiO2. The corresponding adsorption of methanol on reduced Cu/ZnO/SiO2 also gave methoxy species on Cu and a small amount of bridging formate. Reaction of methanol with a reoxidised Cu/ZnO/SiO2 catalyst resulted in an enhanced quantity of methoxy species on Cu. Heating adsorbed species on Cu/ZnO/SiO2 at 393 K led to the loss of methoxy groups on Cu and the concomitant formation of formate species on both ZnO and Cu. The comparable reaction on a reoxidised Cu/ZnO/SiO2 catalyst gave an increased amount of formate species on ZnO and this correlated with an increased quantity of methoxy groups lost from Cu. An explanation is given in terms of adsorption of formate and formaldehyde species at special sites located at the copper/zinc oxide interface.