Nitric oxide emissions from agricultural soils

Nitric oxide (NO) plays a crucial role in photochemistry, particularly in the formation of tropospheric ozone. In soil the biogenic production of NO is primarily conducted by the microbial processes of nitrification and denitrification. The management of soils may, therefore, significantly impact on local atmospheric NO concentrations. The aim of this study was to investigate the influence of various agricultural practices on the magnitude of NO flux, specifically the role of tillage technique in an arable system and the comparative effect of organic wastes and inorganic fertilisers applied to a grassland system.Fluxes of NO from a sandy loam/silty clay loam soil cropped with spring barley, with and without the addition of NH4NO3 fertiliser (80 kg N ha'1), were measured using a static chamber method. The site was managed to compare the influence of 3 tillage regimes; conventional mouldboard ploughing, deep ploughing and direct drilling. There was a marked effect on the magnitude of NO fluxes fromboth the nitrogen and tillage treatment. Nitric oxide fluxes ranged between2-1deposition and emission from -2.6-49.5 jug NO-N m" h" (fertilised & ploughed) and -2.0-2.0 /xg NO-N m2 h"1 (unfertilised & direct drilled). Emissions of NO were significantly larger from the ploughed soils than from the direct drilled soils, primarily due to the increased water filled pore space stimulating denitrification and reducing NO emission. Of the fertiliser N added 0.002-0.011% was lost as NO.The flux of NO between ungrazed grassland (clay loam) and the atmosphere was measured following the application, at a target rate of 120 kg available N ha"1, of either cattle slurry, anaerobically digested sewage sludge, thermally dried sewage sludge pellets, mineral NPK fertiliser & Ficote 70® slow release fertiliser or no fertiliser addition. Nitric oxide emissions were stimulated by both organic wastes and NPK inorganic fertiliser, with cumulative fluxes markedly higher from the organic wastes, particularly from the sewage sludge pellets, which were 1.3-42.3 times larger than the other treatments. It was estimated that 0.0004-0.03% of the applied total N was released as NO.Complementary laboratory studies designed to investigate the influence of dominant environmental factors on NO emission from repacked soil cores under controlled conditions showed that NO emission was 2.2-23.5 times larger from soil amended with sewage sludge pellets. The magnitude of the flux was associated with a soil saprophytic fungus and incorporation of the pellets appeared to reduce the cumulative NO loss. In field and laboratory studies NO flux rate was strongly dependent on soil NH4+-N, soil NO3VN, soil water filled pore space and the pattern of precipitation, particularly around fertiliser application. The data suggest that NO was primarily produced by nitrification in the grassland soil and a combination of both denitrification and nitrification in the arable soil.The total flux from UK agricultural land was estimated as 0.007 Tg of NO-N. This is approximately 1.5% of the annual UK total NO-N production. Based on the evidence collected from the 2 field studies, therefore, the emission of NO from agricultural soils in the UK is not significant in terms of its contribution to the NO-N total. Flowever, agricultural soils may emit NO to the atmosphere and produce localised concentrations high enough (e.g. after fertiliser application) to generate harmful levels of tropospheric O3

Surface reactions of low energy electrons and ions with organometallic precursors for charged particle deposition processes

Focused electron beam induced deposition (FEBID) and focused ion beam induced deposition (FIBID) are maskless, resistless nanofabrication techniques that are capable of directly writing three-dimensional nanostructures onto surfaces with nonplanar topographies, making both techniques distinctly versatile. In FEBID and FIBID, tightly focused beams of electrons or ions create metal-containing nanostructures by decomposing organometallic precursors in low pressure environments. Deposit purity is often limited by incomplete precursor decomposition and ligand co-deposition; consequently, understanding the interactions of electrons and ions with surface-bound organometallic precursors is fundamental to improve the purity of nanostructures produced by these processes. Ultra-high vacuum (UHV) studies on low energy electron interactions with surface-adsorbed Pt(PF3)4, MeCpPtMe3, and Co(CO)3NO have been crucial to the present understanding that low energy electrons initiate decomposition reactions that lead to deposition in FEBID. Conversely, research aiming to understand deposition in FIBID has correlated parameters such as secondary electron yield and sputtering yield with deposit growth rate, which does not give insight into the chemistry that underlies ion-induced deposition. Thus, a study of low energy ion interactions with adsorbed organometallic molecules may be needed to understand the reactions that precede deposition in FIBID. The primary aim of this dissertation is to show that a low temperature, UHV surface science approach can be used to study the reactions of both low energy electrons and ions with organometallic precursors. In these experiments, X-ray photoelectron spectroscopy (XPS) and mass spectroscopy (MS) are used to study the interactions of low energy electrons and ions with nanometer-thick films of physisorbed precursors. Additionally, electron beam induced deposition (EBID) and ion beam induced deposition (IBID) performed in UHV chambers are used to bridge the gap between the well-controlled UHV experiments and deposition performed in high vacuum environments. First, a study of low energy electron and ion interactions with adsorbed (η5-Cp)Fe(CO)2Re(CO)5 showed markedly different electron- and ion-induced decomposition reactions. Further, low energy electron interactions with Ru(CO)4I2 in the gas phase and on surfaces were compared with EBID performed in a UHV chamber, elucidating the low energy electron-induced decomposition reactions that induce deposition for this molecule. These results were also compared to low energy argon ion interactions with adsorbed Ru(CO)4I2, showing different decomposition. Finally, the kinetics of low energy electron-induced decomposition of adsorbed Fe(CO)5 were studied and compared to ion-induced decomposition and IBID performed with Fe(CO)5 in a UHV chamber. It is hoped that these contributions will expand the current understanding of electron and ion interactions with organometallic molecules that underly deposition in FEBID and FIBID, as well as inform the design and selection of new precursors

Does liming grasslands increase biomass productivity without causing detrimental impacts on net greenhouse gas emissions?

Acknowledgements This work contributes to the SUPER-G project (funded under EU Horizon 2020 programme). We appreciate the support from the Estonian Research Council (PRG352) and the European Regional Development Fund (Centre of Excellence EcolChange, Estonia).We are grateful to Sarah Perryman for proving us with pictures from the Park Grass Experiment.Peer reviewedPublisher PD

Towards country-specific nitrous oxide emission factors for manures applied to arable and grassland soils in the UK

Nitrous oxide (N2O) emission factors (EFs) were calculated from measurements of emissions from livestock manures applied to UK arable crops and grassland as part of a wider research programme to reduce uncertainty in the UK national agricultural N2O inventory and to enhance regional inventory reporting through increased understanding of processes and factors controlling emissions. Field studies were undertaken between 2011 and 2013 at 3 arable and 3 grassland sites in the UK. Nitrous oxide emissions were measured following the autumn and spring application of different manures (pig slurry, cattle slurry, cattle farmyard manure (FYM), pig FYM, poultry layer manure, and broiler litter) at typical rates, using representative manure application and soil incorporation methods. In addition, ammonia emissions and nitrate leaching losses (1 site on a light sandy soil) were measured to calculate indirect N2O losses. IPCC comparable, direct N2O EFs ranged from −0.05 to 2.30% of total nitrogen applied, with the variability driven by a range of factors including differences in manure composition, application method, incorporation and climatic conditions. When data from the autumn applications were pooled, the mean N2O EF from poultry manure (1.52%) was found to be greater (P < 0.001) than from FYM (0.37%) and slurry (0.72%), with no difference found (P = 0.784) in the EF for bandspread compared with surface broadcast slurry application, and no effect (P = 0.328) of the nitrification inhibitor, Dicyandiamide (DCD). For the spring applications, the mean N2O EF for bandspread slurry (0.56%) was greater (P = 0.028) than from surface broadcast slurry (0.31%), but there were no differences (P = 0.212) in the mean N2O EFs from poultry manure (0.52%), slurry (0.44%), and FYM (0.22%). The study did confirm, however, that DCD reduced N2O emissions from slurries applied in the spring by 45%. EF data from this project have been used in the derivation of robust Tier 2 country specific EFs for inclusion in the UK national agriculture greenhouse gas inventory

DATAMAN: A global database of nitrous oxide and ammonia emission factors for excreta deposited by livestock and land-applied manure

Nitrous oxide (N2 O), ammonia (NH3 ), and methane (CH4 ) emissions from the manure management chain of livestock production systems are important contributors to greenhouse gases (GHGs) and NH3 emitted by human activities. Several studies have evaluated manure-related emissions and associated key variables at regional, national, or continental scales. However, there have been few studies focusing on the drivers of these emissions using a global dataset. An international project was created (DATAMAN) to develop a global database on GHG and NH3 emissions from the manure management chain (housing, storage, and field) to identify key variables influencing emissions and ultimately to refine emission factors (EFs) for future national GHG inventories and NH3 emission reporting. This paper describes the "field" database that focuses on N2 O and NH3 EFs from land-applied manure and excreta deposited by grazing livestock. We collated relevant information (EFs, manure characteristics, soil properties, and climatic conditions) from published peer-reviewed research, conference papers, and existing databases. The database, containing 5,632 observations compiled from 184 studies, was relatively evenly split between N2 O and NH3 (56 and 44% of the EF values, respectively). The N2 O data were derived from studies conducted in 21 countries on five continents, with New Zealand, the United Kingdom, Kenya, and Brazil representing 86% of the data. The NH3 data originated from studies conducted in 17 countries on four continents, with the United Kingdom, Denmark, Canada, and The Netherlands representing 79% of the data. Wet temperate climates represented 90% of the total database. The DATAMAN field database is available at http://www.dataman.co.nz

Global Research Alliance N2O chamber methodology guidelines: Design considerations

Terrestrial ecosystems, both natural ecosystems and agroecosystems, generate greenhouse gases (GHGs). The chamber method is the most common method to quantify GHG fluxes from soil–plant systems and to better understand factors affecting their generation and mitigation. The objective of this study was to review and synthesize literature on chamber designs (non‐flow‐through, non‐steady‐state chamber) and associated factors that affect GHG nitrous oxide (N2O) flux measurement when using chamber methods. Chamber design requires consideration of many facets that include materials, insulation, sealing, venting, depth of placement, and the need to maintain plant growth and activity. Final designs should be tailored, and bench tested, in order to meet the nuances of the experimental objectives and the ecosystem under study while reducing potential artifacts. Good insulation, to prevent temperature fluctuations and pressure changes, and a high‐quality seal between base and chamber are essential. Elimination of pressure differentials between headspace and atmosphere through venting should be performed, and designs now exist to eliminate Venturi effects of earlier tube‐type vent designs. The use of fans within the chamber headspace increases measurement precision but may alter the flux. To establish best practice recommendations when using fans, further data are required, particularly in systems containing tall plants, to systematically evaluate the effects that fan speed, position, and mixing rate have on soil gas flux.Peer reviewe

Ammonia and nitrous oxide emission factors for excreta deposited by livestock and land-applied manure

Manure application to land and deposition of urine and dung by grazing animals are major sources of ammonia (NH3 ) and nitrous oxide (N2 O) emissions. Using data on NH3 and N2 O emissions following land-applied manures and excreta deposited during grazing, emission factors (EFs) disaggregated by climate zone were developed, and the effects of mitigation strategies were evaluated. The NH3 data represent emissions from cattle and swine manures in temperate wet climates, and the N2 O data include cattle, sheep, and swine manure emissions in temperate wet/dry and tropical wet/dry climates. The NH3 EFs for broadcast cattle solid manure and slurry were 0.03 and 0.24 kg NH3 -N kg-1 total N (TN), respectively, whereas the NH3 EF of broadcast swine slurry was 0.29. Emissions from both cattle and swine slurry were reduced between 46 and 62% with low-emissions application methods. Land application of cattle and swine manure in wet climates had EFs of 0.005 and 0.011 kg N2 O-N kg-1 TN, respectively, whereas in dry climates the EF for cattle manure was 0.0031. The N2 O EFs for cattle urine and dung in wet climates were 0.0095 and 0.002 kg N2 O-N kg-1 TN, respectively, which were three times greater than for dry climates. The N2 O EFs for sheep urine and dung in wet climates were 0.0043 and 0.0005, respectively. The use of nitrification inhibitors reduced emissions in swine manure, cattle urine/dung, and sheep urine by 45-63%. These enhanced EFs can improve national inventories; however, more data from poorly represented regions (e.g., Asia, Africa, South America) are needed

Challenges of accounting nitrous oxide emissions from agricultural crop residues

Crop residues are important inputs of carbon (C) and nitrogen (N) to soils and thus directly and indirectly affect nitrous oxide (N2O) emissions. As the current inventory methodology considers N inputs by crop residues as the sole determining factor for N2O emissions, it fails to consider other underlying factors and processes. There is compelling evidence that emissions vary greatly between residues with different biochemical and physical characteristics, with the concentrations of mineralizable N and decomposable C in the residue biomass both enhancing the soil N2O production potential. High concentrations of these components are associated with immature residues (e.g., cover crops, grass, legumes, and vegetables) as opposed to mature residues (e.g., straw). A more accurate estimation of the short-term (months) effects of the crop residues on N2O could involve distinguishing mature and immature crop residues with distinctly different emission factors. The medium-term (years) and long-term (decades) effects relate to the effects of residue management on soil N fertility and soil physical and chemical properties, considering that these are affected by local climatic and soil conditions as well as land use and management. More targeted mitigation efforts for N2O emissions, after addition of crop residues to the soil, are urgently needed and require an improved methodology for emission accounting. This work needs to be underpinned by research to (1) develop and validate N2O emission factors for mature and immature crop residues, (2) assess emissions from belowground residues of terminated crops, (3) improve activity data on management of different residue types, in particular immature residues, and (4) evaluate long-term effects of residue addition on N2O emissions

Challenges of accounting nitrous oxide emissions from agricultural crop residues

Crop residues are important inputs of carbon (C) and nitrogen (N) to soils and thus directly and indirectly affect nitrous oxide (N$_2$O) emissions. As the current inventory methodology considers N inputs by crop residues as the sole determining factor for N$_2$O emissions, it fails to consider other underlying factors and processes. There is compelling evidence that emissions vary greatly between residues with different biochemical and physical characteristics, with the concentrations of mineralizable N and decomposable C in the residue biomass both enhancing the soil N$_2$O production potential. High concentrations of these components are associated with immature residues (e.g., cover crops, grass, legumes, and vegetables) as opposed to mature residues (e.g., straw). A more accurate estimation of the short-term (months) effects of the crop residues on N$_2$O could involve distinguishing mature and immature crop residues with distinctly different emission factors. The medium-term (years) and long-term (decades) effects relate to the effects of residue management on soil N fertility and soil physical and chemical properties, considering that these are affected by local climatic and soil conditions as well as land use and management. More targeted mitigation efforts for N$_2$O emissions, after addition of crop residues to the soil, are urgently needed and require an improved methodology for emission accounting. This work needs to be underpinned by research to (1) develop and validate N$_2$O emission factors for mature and immature crop residues, (2) assess emissions from belowground residues of terminated crops, (3) improve activity data on management of different residue types, in particular immature residues, and (4) evaluate long-term effects of residue addition on N$_2$O emissions