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Rationale: N2O isotopomers are a useful tool to study soil N cycling processes. The reliability of such measurements requires a consistent set of international N2O isotope reference materials to improve inter-laboratory and inter-instrument comparability and avoid reporting inaccurate results. All these are the more important given the role of N2O in anthropogenic climate change and the pressing need to develop our understanding of soil N cycling and N2O emission to mitigate such emissions. Cavity ring-down spectroscopy (CRDS) could potentially overcome resource requirements and technical challenges, making N2O isotopomer measurements more feasible and less expensive than previous approaches (e.g., gas chromatography [GC] and isotope ratio mass spectrometry [IRMS]). Methods: A combined laser spectrometer and small sample isotope module (CRDS & SSIM) method enabled N2O concentration, δ15Nbulk, δ15Nα, δ15Nβ and site preference (SP) measurements of sample volumes <20 mL, such as static chamber samples. Sample dilution and isotopic mixing as well as N2O concentration dependence were corrected numerically. A two-point calibration procedure normalised d values to the international isotope-ratio scales. The CRDS & SSIM repeatability was determined using a reference gas (Ref Gas). CRDS & SSIM concentration measurements were compared with those obtained by GC, and the isotope ratio measurements from two different mass spectrometers were compared. Results: The repeatability (mean ± 1s; n = 10) of the CRDS & SSIM measurements of the Ref Gas was 710.64 ppb (± 8.64), 2.82? (± 0.91), 5.41? (± 2.00), 0.23? (± 0.22) and 5.18? (± 2.18) for N2O concentration, δ15Nbulk, δ15Nα, δ15Nβ and SP, respectively. The CRDS & SSIM concentration measurements were strongly correlated with GC (r = 0.99), and they were more precise than those obtained using GC except when the N2O concentrations exceeded the specified operating range. Normalising CRDS & SSIM d values to the international isotope-ratio scales using isotopic N2O standards (AK1 and Mix1) produced accurate results when the samples were bracketed within the range of the d values of the standards. The CRDS & SSIM δ15Nbulk and SP precision was approximately one order of magnitude less than the typical IRMS precision. Conclusions: CRDS & SSIM is a promising approach that enables N2O concentrations and isotope ratios to be measured by CRDS for samples <20 mL. The CRDS & SSIM repeatability makes this approach suitable for N2O "isotopomer mapping" to distinguish dominant source pathways, such as nitrification and denitrification, and requires less extensive lab resources than the traditionally used GC/IRMS. Current study limitations highlighted potential improvements for future users of this approach to consider, such as automation and physical removal of interfering trace gases before sample analysis. [ABSTRACT FROM AUTHOR]

An increase in mean soil surface temperature has been observed over the last century, and it is predicted to further increase in the future. The effect of increased temperature on ecosystem carbon fluxes in a permanent temperate grassland was studied in a long-term (6 years) field experiment, using multiple temperature increments induced by IR lamps. Ecosystem respiration (R-eco) and net ecosystem exchange ( NEE) were measured and modeled by a modified Lloyd and Taylor model including a soil moisture component for R-eco (average R2 of 0.78) and inclusion of a photosynthetic component based on temperature and radiation for NEE ( R2 = 0.65). Modeled NEE values ranged between 2.3 and 5.3 kg CO2 m−2 year−1, depending on treatment. An increase of 2 or 3°C led to increased carbon losses, lowering the carbon storage potential by around 4 tonnes of C ha−1 year−1. The majority of significant NEE differences were found during night-time compared to daytime. This suggests that during daytime the increased respiration could be offset by an increase in photosynthetic uptake. This was also supported by differences in δ13C and δ18O, indicating prolonged increased photosynthetic activity associated with the higher temperature treatments. However, this increase in photosynthesis was insufficient to counteract the 24 h increase in respiration, explaining the higher CO2 emissions due to elevated temperature. [ABSTRACT FROM AUTHOR]

Multispecies pastures containing grasses, N-fixing legumes and forage herbs can maintain high herbage dry matter (DM) yield, while reducing the need for fertiliser N inputs thus potentially reducing harmful N losses such as nitrous oxide (N 2 O) emission and nitrate (NO 3 −) leaching to the wider environment. However, our understanding of these processes in grassland swards of contrasting composition is still very limited. A lysimeter experiment was carried out over 12 months to test the hypotheses that (1) cumulative and (2) seasonal N 2 O emission and N leaching would be highest from the Perennial Ryegrass only (PRG, 250 kg N ha-1 yr-1) treatment compared to three other treatments; Perennial Ryegrass and Low White Clover (PRG+LWC, 90 kg N ha-1 yr-1), Perennial Ryegrass and High White Clover (PRG+HWC, 0 kg N ha-1 yr-1) and Perennial Ryegrass, White Clover and Ribwort Plantain (PRG+WC+P, 45 kg N ha-1 yr-1) and (3) that the soil N cycling pathways (nitrification/denitrification) linked to these N losses would be different between treatments. Cumulative N 2 O emissions (2.74–3.25 kg N 2 O-N ha-1), leached N (10.91–13.70 kg N ha-1), DM yields (5083–5493 kg DM ha-1 yr-1) and N uptake (122–169 kg N ha-1 yr-1) were not significantly different between treatments. Nitrogen yield scaled N 2 O emissions were significantly lower from all other treatments compared to the high fertiliser N input PRG monoculture. A significant interaction between treatment and season showed that in Spring, N 2 O emission was significantly higher from PRG (1.39 kg N 2 O-N ha-1) and PRG+LWC (1.19 kg N 2 O-N ha-1) than PRG+HWC (0.81 kg N 2 O-N ha-1) and PRG+WC+P (0.85 kg N 2 O-N ha-1). This result was linked to a numerically lower fraction of nitrification (F N) for PRG+WC+P potentially indicating that biological nitrification inhibition associated with ribwort plantain could lessen N 2 O emissions. This study demonstrates some of the environmental benefits of grassland management systems that require less intensive chemical fertiliser N input. • N 2 O and leached N were 1.1–1.3 % and 4.4–5.5 % of N applied, respectively. • Nitrogen yield-scaled N 2 O emission were highest for perennial ryegrass monoculture. • Treatment × season interactions show opportune time and management to cut N loss. • Lower F N indicates nitrification inhibition associated with ribwort plantain. [ABSTRACT FROM AUTHOR]

The magnitude of fractionation during photorespiration and the effect on net photosynthetic 13C discrimination (Δ) were investigated for three Senecio species, S. squalidus, S. cineraria, and S. greyii. We determined the contributions of different processes during photosynthesis to Δ by comparing observations (Δobs) with discrimination predicted from gas-exchange measurements (Δpred). Photorespiration rates were manipulated by altering the O2 partial pressure (pO2) in the air surrounding the leaves. Contributions from 13C-depleted photorespiratory CO2 were largest at high pO2. The parameters for photorespiratory fractionation (f), net fractionation during carboxylation by Rubisco and phosphoenolpyruvate carboxylase (b), and mesophyll conductance (gi) were determined simultaneously for all measurements. Instead of using Δobs data to obtain gi and f successively, which requires that b is known, we treated b,f, and gi as unknowns. We propose this as an alternative approach to analyze measurements under field conditions when b and gi are not known or cannot be determined in separate experiments. Good agreement between modeled and observed Δ was achieved with f = 11.6‰ ± 1.5‰, b = 26.0‰ ± 0.3‰, and gi of 0.27 ± 0.01,0.25 ± 0.01, and 0.22 ± 0.01 mol m-1 s-1 for S. squalidus, S. cineraria, and S. greyii, respectively. We estimate that photorespiratory fractionation decreases Δ by about 1.2‰ on average under field conditions. In addition, diurnal changes in Δ are likely to reflect variations in photorespiration even at the canopy level. Our results emphasize that the effects of photorespiration must be taken into account when partitioning net CO2 exchange of ecosystems into gross fluxes of photosynthesis and respiration. [ABSTRACT FROM AUTHOR]

The effect of long‐term soil phosphorus (P) on in situ nitrous oxide (N2O) emissions from temperate grassland soil ecosystems is not well understood. Grasslands typically receive large nitrogen (N) inputs both from animal deposition and fertiliser application, with a large proportion of this N being lost to the environment. Understanding optimum nutrient stoichiometry by applying N fertilisers in a relative balance with P will help to reduce N losses by enabling maximum N‐uptake by plants and microbes. This study investigates the N2O response from soils of long‐term high and low P management receiving three forms of applied N at two different rates: a nitrate‐based fertiliser (KNO3) and an ammonium‐based fertiliser ([NH4]2SO4) (both at 40 Kg N ha−1), and a synthetic urine (750 Kg N ha−1). Low soil P significantly increased N2O emissions from KNO3 and (NH4)2SO4 fertilisers by over 50% and numerically increased N2O from urine by over 20%, which is suggested to be representative of the lack of significant effect of N fertilisation on N‐uptake observed in the low P soils. There was a significant positive effect of soil P on grass N‐uptake observed in the synthetic urine and KNO3 treatments, but not in the (NH4)2SO4 treatment. Low P soils had a significantly lower pH than high P soilss and responded differently to applied synthetic urine. There was also a significant effect of P level on potential nitrification which was nearly three times that of low P, but no significant difference between potential denitrification and P level. The results from this study highlight the importance of synergy between relative nutrient applications as a deficiency of one nutrient, such as P in this case, could be detrimental to the system as a whole. Optimising soil P can result in greater N uptake (over 12, 23 and 66% in (NH4)2SO4, KNO3 and synthetic urine treatments, respectively) and in reduced emissions by up to 50% representing a win‐win scenario for farmers. Highlights: P deficiency in grassland soils causes greater N2O emissions.Insufficent soil P inhibits N‐uptake, regardless of rate or form of N.Optimising soil P levels can reduce N2O emissions and improve overall NUE. [ABSTRACT FROM AUTHOR]

[Display omitted] • Assessing downstream impact of dairy diets on whole-farm emissions is crucial. • Process-based models may capture herd and interannual variation on emissions. • Pasture-based and confinement systems have different carbon footprints. • Process-based models capture dietary effects on-farm carbon and nitrogen cycling. Feed management decisions are crucial in mitigating greenhouse gas (GHG) and nitrogen (N) emissions from ruminant farming systems. However, assessing the downstream impact of diet on emissions in dairy production systems is complex, due to the multifunctional relationships between a variety of distinct but interconnected sources such as animals, housing, manure storage, and soil. Therefore, there is a need for an integral assessment of the direct and indirect GHG and N emissions that considers the underlying processes of carbon (C), N and their drivers within the system. Here we show the relevance of using a cascade of process-based (PB) models, such as Dutch Tier 3 and (Manure)-DNDC (Denitrification-Decomposition) models, for capturing the downstream influence of diet on whole-farm emissions in two contrasting case study dairy farms: a confinement system in Germany and a pasture-based system in New Zealand. Considerable variation was found in emissions on a per hectare and per head basis, and across different farm components and categories of animals. Moreover, the confinement system had a farm C emission of 1.01 kg CO 2 -eq kg−1 fat and protein corrected milk (FPCM), and a farm N emission of 0.0300 kg N kg−1 FPCM. In contrast, the pasture-based system had a lower farm C and N emission averaging 0.82 kg CO 2 -eq kg−1 FPCM and 0.006 kg N kg−1 FPCM, respectively over the 4-year period. The results demonstrate how inputs and outputs could be made compatible and exchangeable across the PB models for quantifying dietary effects on whole-farm GHG and N emissions. [ABSTRACT FROM AUTHOR]

Increased emissions of N 2 O, a potent greenhouse gas (GHG), from agricultural soils is a major concern for the sustainability of grassland agriculture. Emissions of N 2 O are closely associated with the rates and forms of N fertilisers applied as well as prevailing weather and soil conditions. Evidence suggests that multispecies swards require less fertiliser N input, and may cycle N differently, thus reducing N loss to the environment. This study used a restricted simplex-centroid experimental design to investigate N 2 O emissions and soil N cycling following application of urea-N (40 kg N ha−1) to eight experimental swards (7.8 m2) with differing proportions of three plant functional groups (grass, legume, herb) represented by perennial ryegrass (PRG, Lolium perenne), white clover (WC, Trifolium repens) and ribwort plantain (PLAN, Plantago lanceolata), respectively. Swards were maintained under two contrasting soil moisture conditions to examine the balance between nitrification and denitrification. Two N 2 O peaks coincided with fertiliser application and heavy rainfall events; 13.4 and 17.7 g N 2 O-N ha−1 day−1 (ambient soil moisture) and 39.8 and 86.9 g N 2 O-N ha−1 day−1 (wet soil moisture). Overall, cumulative N 2 O emissions post-fertiliser application were higher under wet soil conditions. Increasing legume (WC) proportions from 0% to 60% in multispecies swards resulted in model predicted N 2 O emissions increasing from 22.3 to 96.2 g N 2 O-N ha−1 (ambient soil conditions) and from 59.0 to 219.3 g N 2 O-N ha−1 (wet soil conditions), after a uniform N application rate. Soil N dynamics support denitrification as the dominant source of N 2 O especially under wet soil conditions. Significant interactions of PRG or WC with PLAN on soil mineral N concentrations indicated that multispecies swards containing PLAN potentially inhibit nitrification and could be a useful mitigation strategy for N loss to the environment from grassland agriculture. Unlabelled Image • Measurement of N 2 O emissions and N cycling from varying sward compositions. • Post N application (40 kg N ha−1) N 2 O loss increased with white clover proportion. • N 2 O emissions from PRG were 2.5 fold higher in wet soil (WFPS > 60%) compared to ambient. • Soil N dynamics suggest denitrification as dominant N 2 O source when WFPS > 60%. • Plantago lanceolata (forage herb) potentially regulates N cycling pathways. [ABSTRACT FROM AUTHOR]

Grassland soils have been highlighted as a global soil carbon (C) sink, and have the potential to sequester additional C. Sequestration of C can occur through incorporation of soil organic carbon (SOC) within microaggregates and the silt and clay fractions. The distribution of SOC within macroaggregate fractions gives an insight into both SOC dynamics and its incorporation into the soil. Research to date on soil C has tended to focus on the topsoil (0–30 cm). While many studies have assessed the changes in aggregation and SOC dynamics after land use or management change, this paper assesses aggregation and SOC dynamics in the topsoil and subsoil of twenty-one temperate grassland sites covering four soil types (Haplic Luvisol, Haplic Stagnosol, Haplic Cambisol, Stagnic Cambisol). Results show that there are no differences in SOC between soil types in the surface 0–30 cm, except a decrease in the quantity of microaggregates within macroaggregates in Haplic Stagnosols. In the subsoil, the silt and clay fraction of clay-illuviated soils had a lower percentage of SOC. Soils with clay illuviation and reducing conditions had a decreased proportion of SOC in microaggregates and silt plus clay within small macroaggregates in the subsoil. This could be caused by a combination of (i) reduced incorporation of SOC into smaller fractions, because POM inputs could be limited due to soil saturation limiting root growth, and (ii) reduced mineralisation and subsequent incorporation of POM into microaggregates and silt plus clay within macroaggregates. These results enable elucidation of the mechanisms driving aggregate formation (and thus C sequestration in microaggregates and silt plus clay fractions) in topsoil and subsoil. This study shows that the dynamics of SOC in subsoil horizons is soil-type dependant and that differences between soil types cannot be elucidated when the sampling is limited to 30 cm. This suggests that the IPCC guidelines for SOC measurements should also include the sampling of subsoil horizons in order to get valuable information that allows discerning between soil types. [ABSTRACT FROM AUTHOR]

Most nitrogen (N) lost to the environment from grazed grassland is produced as a result of N excreted by livestock, released in the form of nitrous oxide (N2O) emissions, nitrate leaching and ammonia volatilisation. In addition to the N fertiliser applied, excreta deposited by grazing livestock constitute a heterogeneous excess of N, creating spatial hotspots of N losses. This study presents a yearlong N2O emissions map from a typical intensively managed temperate grassland, grazed periodically by a dairy herd. The excreta deposition mapping was undertaken using high-resolution RGB images captured with a remotely piloted aircraft system combined with N2O emissions measurements using closed statics chambers. The annual N2O emissions were estimated to be 3.36 ± 0.30 kg N2O–N ha−1 after a total N applied from fertiliser and excreta of 608 ± 40 kg N ha−1 yr−1. Emissions of N2O were 1.9, 3.6 and 4.4 times lower than that estimated using the default IPCC 2019, 2006 or country-specific emission factors, respectively. The spatial distribution and size of excreta deposits was non-uniform, and in each grazing period, an average of 15.1% of the field was covered by urine patches and 1.0% by dung deposits. Some areas of the field repeatedly received urine deposits, accounting for an estimated total of 2410 kg N ha−1. The method reported in this study can provide better estimates of how management practices can mitigate N2O emissions, to develop more efficient selective approaches to fertiliser application, targeted nitrification inhibitor application and improvements in the current N2O inventory estimation. [ABSTRACT FROM AUTHOR]

Nitrous oxide (N2O) emissions are subject to intra- and interannual variation due to changes in weather and management. This creates significant uncertainties when quantifying estimates of annual N2O emissions from grazed grasslands. Despite these uncertainties, the majority of studies are short-term in nature (<1 year) and as a consequence, there is a lack of data on interannual variation in N2O emissions. The objectives of this study were to (i) quantify annual N2O emissions and (ii) assess the causes of interannual variation in emissions from grazed perennial ryegrass/white clover grassland. Nitrous oxide emissions were measured from fertilized and grazed perennial ryegrass/white clover grassland (WC) and from perennial ryegrass plots that were not grazed and did not receive N input (GB), over 4 years from 2008 to 2012 in Ireland (52°51'N, 08°21'W). The annual N2O-N emissions (kg ha-1; mean ± SE) ranged from 4.4 ± 0.2 to 34.4 ± 5.5 from WC and from 1.7 ± 0.8 to 6.3 ± 1.2 from GB. Interannual variation in N2O emissions was attributed to differences in annual rainfall, monthly (December) soil temperatures and variation in N input. Such substantial interannual variation in N2O emissions highlights the need for long-term studies of emissions from managed pastoral systems. [ABSTRACT FROM AUTHOR]

The effectiveness of chemical amendment of pig slurry to ameliorate phosphorus (P) losses in runoff is well studied, but research mainly has concentrated only on the runoff pathway. The aims of this study were to investigate changes to leachate nutrient losses, soil properties and greenhouse gas (GHG) emissions due to the chemical amendment of pig slurry spread at 19 kg total phosphorus (TP), 90 kg total nitrogen (TN), and 180 kg total carbon (TC) ha−1. The amendments examined were: (1) commercial grade liquid alum (8% Al2O3) applied at a rate of 0.88:1 [Al:TP], (2) commercial-grade liquid ferric chloride (38% FeCl3) applied at a rate of 0.89:1 [Fe:TP] and (3) commercial-grade liquid poly-aluminium chloride (PAC) (10% Al2O3) applied at a rate of 0.72:1 [Al:TP]. Columns filled with sieved soil were incubated for 8 mo at 10 °C and were leached with 160 mL (19 mm) distilled water wk−1. All amendments reduced the Morgan's phosphorus and water extractable P content of the soil to that of the soil-only treatment, indicating that they have the ability to reduce P loss in leachate following slurry application. There were no significant differences between treatments for nitrogen (N) or carbon (C) in leachate or soil, indicating no deleterious impact on reactive N emissions or soil C cycling. Chemical amendment posed no significant change to GHG emissions from pig slurry, and in the cases of alum and PAC, reduced cumulative N2O and CO2 losses. Chemical amendment of land applied pig slurry can reduce P in runoff without any negative impact on nutrient leaching and GHG emissions. Future work must be conducted to ascertain if more significant reductions in GHG emissions are possible with chemical amendments. [Copyright &y& Elsevier]

Abstract: Laboratory denitrifying bioreactors, which use an organic carbon (C) rich media to enhance microbial reduction of nitrate (NO3 −) to nitrogen (N) gases, are used worldwide to protect surface and groundwater. To highlight potential adverse effects of denitrifying bioreactors, NO3 − removal rates (gNO3-Nm−3 d−1 removed), NO3 − removal efficiencies (% removed minus production of other N species) and release of greenhouse gases and solutes (ammonium (NH4 +), phosphorus (P) and organic carbon (C)) were compared in this study using different media: lodgepole pine woodchips (LPW), cardboard, lodgepole pine needles (LPN), barley straw (BBS) and a soil control. Results showed that NO3 − removals were consistently >99% for all media for initial leaching and steady-state periods. When pollution swapping was considered, this ranged from 67% for LPW to 95% for cardboard. Sustained P releases over the threshold for the occurrence of eutrophication were measured in all media. Greenhouse gas emissions were dominated by carbon dioxide (CO2) and methane (CH4) fluxes with little nitrous oxide (N2O) release due to the anaerobic conditions prevalent within the bioreactors. Comparisons of different media, under steady-state conditions, showed that C fluxes were highest for cardboard and BBS bioreactors. Carbon fluxes from cardboard bioreactors ranged from 11.6gCm−2 d−1 to 13.9gCm−2 d−1, whilst BBS emissions ranged from 3.9gCm−2 d−1 to 4.4gCm−2 d−1. These C emissions were correlated with the total surface area exposed within the media. Such investigations highlight the need to consider pollution swapping during the initial leaching period and should improve design criteria for field-scale bioreactors used to mitigate shallow groundwater NO3 −. [Copyright &y& Elsevier]

• Urea hydrolysis induced rapid changes in organic labile and recalcitrant N pools. • Gross mineralisation and immobilisation rates declined as soil moisture increased. • Recovery of 15N was higher in the recalcitrant N pool at lower soil moisture. • Labile N pool size and turnover was higher under increasing soil moisture. Ruminant urine patches in grazed grasslands significantly change the chemical and biological properties of the affected soils due to the predominance of urea within ruminant urine and the high rates deposited onto pastures. The net result is the loss of reactive N (N r) but little is known about the gross N transformation rates leading to N r losses or the long-term fate of urine-N in pasture soils. Using data from a previous incubation study, that simulated ruminant urine application by applying 15N-urea, we investigated the effects of differing soil moisture regimes on gross soil N transformation rates, including urea hydrolysis and ammonia (NH 3) formation. Gross transformation rates were quantified using a 15N tracing tool ' Ntrace Basi c ' that was extended with a urea submodel. The new model (Ntrace Urea) matched the measured data well (NH 4 +, NO 3 − concentrations and their respective 15N enrichments over time). Soil moisture affected urea hydrolysis dynamics and was postulated to regulate the magnitude of the NH 3 dynamics due to constraints on gas diffusion under wetter (−1 kPa) soil conditions. Under drier soil conditions (−10 kPa) sorption and release of NH 4 +, the movement of NH 4 + into and out of the soil labile N pool, the movement of NO 3 − into and out of the soil recalcitrant N pool, and the mineralisation of the recalcitrant N pool were all enhanced relative to −1 kPa, as were the gross N transformation rates in general due to the high urea N rate applied. This study shows that the time required for soils to re-establish equilibrium following urea deposition is substantial, and provides an explanation for the long-term 15N recoveries observed under ruminant urine patches in soils. The results highlight future research directions including the need to understand the potential role of NH 3 in contributing to the recalcitrant N pool. [ABSTRACT FROM AUTHOR]

Livestock excreta deposition on concrete farmyards has been identified as an important source of ammonia (NH 3) emissions from agriculture. The objective of this study was to quantify the effect of urine application rate and four cleaning strategies on NH 3 emissions from excreta deposited on a concrete yard. Three experiments were conducted on a concrete yard over a three week period in August 2016. Experiment 1 consisted of 1 kg dung applied with either (i) 0.67 l urine (1:0.67), (ii) 1 l urine (1:1) or (iii) 2 l urine (1:2). In experiments 2 and 3 the treatments were (i) non cleaned control, (ii) cleaned after 1 h and (iii) cleaned after 3 h. The cleaning method in experiment 2 and 3 was pressure washing and scraping, respectively. Ammonia emissions were measured using wind-tunnels for 72 h. Cumulative NH 3 emissions increased linearly with increasing urine N rate and emission factors ranged from 46% to 67% of urine urea-N applied and from 22% to 29% of total N applied. In experiment 2 and 3 the greatest reduction in cumulative NH 3 emissions was obtained from pressure washing at 1 h which reduced emissions compared to the non-cleaned control by 91%. Pressure washing at 3 h reduced emissions by 80% while scraping after 1 h and 3 h reduced emissions by 78% and 54%, respectively. Farmers should be encouraged to clean their animal handling yards as soon as possible after use in order to maximise reductions in NH 3 emissions from this source. Image 1 • Three experiments measuring NH 3 using wind tunnels from a concrete farmyard. • NH 3 emissions increased linearly with increasing cow urine application rate. • Pressure washing was more effective at reducing NH 3 emissions than scraping. • Interval between excreta deposition and farmyard cleaning is important for NH 3 reduction. [ABSTRACT FROM AUTHOR]

The nitrogen (N) cycle represents one of the most well-studied systems, yet the taxonomic diversity of the organisms that contribute to it is mostly unknown, or linked to poorly characterized microbial groups. While new information has allowed functional groups to be refined, they still rely on a priori knowledge of enzymes involved and the assumption of functional conservation, with little connection to the role the transformations, plays for specific organisms. Here, we use soil microcosms to test the impact of N deposition on prokaryotic communities. By combining chemical, genomic and transcriptomic analysis, we are able to identify and link changes in community structure to specific organisms catalysing given chemical reactions. Urea deposition led to a decrease in prokaryotic richness, and a shift in community composition. This was driven by replacement of stable native populations, which utilize energy from N-linked redox reactions for physiological maintenance, with fast responding populations that use this energy for growth. This model can be used to predict response to N disturbances and allows us to identify putative life strategies of different functional and taxonomic groups, thus providing insights into how they persist in ecosystems by niche differentiation. [ABSTRACT FROM AUTHOR]

Soil plays a key role in the global carbon (C) cycle. Most current assessments of SOC stocks and the guidelines given by Intergovernmental Panel on Climate Change (IPCC) focus on the top 30 cm of soil. Our research shows that, when considering only total quantities, most of the SOC stocks are found in this top layer. However, not all forms of SOC are equally valuable as long-term stable stores of carbon: the majority of SOC is available for mineralisation and can potentially be re-emitted to the atmosphere. SOC associated with micro-aggregates and silt plus clay fractions is more stable and therefore represents a long-term carbon store. Our research shows that most of this stable carbon is located at depths below 30 cm (42% of subsoil SOC is located in microaggregates and silt and clay, compared to 16% in the topsoil), specifically in soils that are subject to clay illuviation. This has implications for land management decisions in temperate grassland regions, defining the trade-offs between primary productivity and C emissions in clay-illuviated soils, as a result of drainage. Therefore, climate smart land management should consider the balance between SOC stabilisation in topsoils for productivity versus sequestration in subsoils for climate mitigation. [ABSTRACT FROM AUTHOR]

According to the available guidelines, good practices for calculating nitrous oxide (N 2 O) emission factors (EFs) for livestock excreta and manure application include that sampling duration should be of at least one year after the nitrogen (N) application or deposition. However, the available experimental data suggest that in many cases most emissions are concentrated in the first months following N application. Therefore resources could be better deployed by measuring more intensively during a shorter period. This study aimed to assess the contribution of the N 2 O flux in the period directly after N application to the annual net emission. We used a database of 100 year-long plot experiments from different excreted-N sources (dung, urine, farmyard manure and slurry) used to derive EFs for the UK and Ireland. We explored different shorter potential measurement periods that could be used as proxies for cumulative annual emissions. The analysis showed that the majority of emissions occur in the first months after application, especially in experiments that i) had urine as the N source, ii) had spring N application, iii) were conducted on fine-textured soils, or iv) showed high annual emissions magnitude. Experiments that showed a smaller percentage of emissions in the first months also had a low magnitude of annual net emissions (below 370 gN 2 O–N ha−1 year−1), so the impact of measuring during a shorter period would not greatly influence the calculated EF. Accurate EF estimations were obtained by measuring for at least 60 days for urine (underestimation: 7.1%), 120 days for dung and slurry (4.7 and 5.1%) and 180 days for FYM (1.4%). At least in temperate climates, these results are promising in terms of being able to estimate annual N 2 O fluxes accurately by collecting data for less than 12 months, with significant resource-saving when conducting experiments towards developing country-specific EFs. • Sampling period to calculate country-specific N 2 O emission factors was revised. • We analyzed data from 100 year-long IPCC compliant manure and excreta experiments. • A high proportion of annual emissions occurred in the months directly after N application. • Accurate EFs were measured at 60–180 days, with significant resource saving. [ABSTRACT FROM AUTHOR]

Denitrification in pasture soils is mediated by microbial and physicochemical processes leading to nitrogen loss through the emission of N2O and N2. It is known that N2O reduction to N2 is impaired by low soil pH yet controversy remains as inconsistent use of soil pH measurement methods by researchers, and differences in analytical methods between studies, undermine direct comparison of results. In addition, the link between denitrification and N2O emissions in response to carbon (C) mineralization and pH in different pasture soils is still not well described. We hypothesized that potential denitrification rate and aerobic respiration rate would be positively associated with soils. This relationship was predicted to be more robust when a high resolution analysis is performed as opposed to a single time point comparison. We tested this by characterizing 13 different temperate pasture soils from northern and southern hemispheres sites (Ireland and New Zealand) using a fully automated-high-resolution GC detection system that allowed us to detect a wide range of gas emissions simultaneously. We also compared the impact of using different extractants for determining pH on our conclusions. In all pH measurements, soil pH was strongly and negatively associated with both N2O production index (IN2O) and N2O/(N2O+N2) product ratio. Furthermore, emission kinetics across all soils revealed that the denitrification rates under anoxic conditions (NO+N2O+N2 μmol N/h/vial) were significantly associated with C mineralization (CO2 μmol/h/vial) measured both under oxic (r2 = 0.62, p = 0.0015) and anoxic (r2 = 0.89, p<0.0001) conditions. [ABSTRACT FROM AUTHOR]

Land application of cattle slurry can result in incidental and chronic phosphorus (P) loss to waterbodies, leading to eutrophication. Chemical amendment of slurry has been proposed as a management practice, allowing slurry nutrients to remain available to plants whilst mitigating P losses in runoff. The effectiveness of amendments is well understood but their impacts on other loss pathways (so-called ‘pollution swapping’ potential) and therefore the feasibility of using such amendments has not been examined to date. The aim of this laboratory scale study was to determine how the chemical amendment of slurry affects losses of NH3, CH4, N2O, and CO2. Alum, FeCl2, Polyaluminium chloride (PAC)- and biochar reduced NH3 emissions by 92, 54, 65 and 77% compared to the slurry control, while lime increased emissions by 114%. Cumulative N2O emissions of cattle slurry increased when amended with alum and FeCl2 by 202% and 154% compared to the slurry only treatment. Lime, PAC and biochar resulted in a reduction of 44, 29 and 63% in cumulative N2O loss compared to the slurry only treatment. Addition of amendments to slurry did not significantly affect soil CO2 release during the study while CH4 emissions followed a similar trend for all of the amended slurries applied, with an initial increase in losses followed by a rapid decrease for the duration of the study. All of the amendments examined reduced the initial peak in CH4 emissions compared to the slurry only treatment. There was no significant effect of slurry amendments on global warming potential (GWP) caused by slurry land application, with the exception of biochar. After considering pollution swapping in conjunction with amendment effectiveness, the amendments recommended for further field study are PAC, alum and lime. This study has also shown that biochar has potential to reduce GHG losses arising from slurry application. [ABSTRACT FROM AUTHOR]

Quantifying nitrous oxide (N 2 O) emissions from grazed pastures can be problematic due to the presence of hotspots and hot moments of N 2 O from animal excreta and synthetic fertilisers. In this study, we quantified field scale N 2 O emissions from a temperate grassland under a rotational grazing management using eddy covariance (EC) and static chamber techniques. Measurements of N 2 O by static chambers were made for four out of nine grazing events for a control, calcium ammonium nitrate (CAN), synthetic urine (SU) + CAN and dung + CAN treatments. Static chamber N 2 O flux measurements were upscaled to the field scale (F CH FIELD) using site specific emission factors (EF) for CAN, SU+CAN and dung + CAN. Mean N 2 O EFs were greatest from the CAN treatment while dung + CAN and SU + CAN emitted similar N 2 O-N emissions. Cumulative N 2 O-N emissions over the study period measured by F CH FIELD measurements were lower than gap-filled EC measurements. Emission factors of N 2 O from grazing calculated by F CH FIELD and gap-filled were 0.72% and 0.96%, respectively. N 2 O-N emissions were derived mainly from animal excreta (dung and urine) contributing 50% while N 2 O-N losses from CAN and background accounted for 36% and 14%, respectively. The study highlights the advantage of using both the EC and static chamber techniques in tandem to better quantify both total N 2 O-N losses from grazed pastures while also constraining the contribution of individual N sources. The EC technique was most accurate in quantifying N 2 O emissions, showing a range of uncertainty that was seven times lower relative to that attributed to static chamber measurements, due to the small chamber sample size per treatment and highly variable N 2 O flux measurements over space and time. • N 2 O emissions were measured using EC and static chambers (SC) from a grazed pasture. • The magnitude of mean N 2 O-N EFs measured by SC were CAN > dung + CAN > SU + CAN. • EFs of CAN, dung + CAN and SU + CAN were used to upscale SC N 2 O fluxes (F CH FIELD). • N 2 O-N EFs by EC and F CH FIELD were 0.72% and 0.96%, > IPCC default value 0.6%. • EC showed lower uncertainties in cumulative N 2 O emissions compared to F CH FIELD. [ABSTRACT FROM AUTHOR]

Bioenergy from crops is expected to make a considerable contribution to climate change mitigation. However, bioenergy is not necessarily carbon neutral because emissions of CO2, N2O and CH4 during crop production may reduce or completely counterbalance CO2 savings of the substituted fossil fuels. These greenhouse gases ( GHGs) need to be included into the carbon footprint calculation of different bioenergy crops under a range of soil conditions and management practices. This review compiles existing knowledge on agronomic and environmental constraints and GHG balances of the major European bioenergy crops, although it focuses on dedicated perennial crops such as M iscanthus and short rotation coppice species. Such second-generation crops account for only 3% of the current European bioenergy production, but field data suggest they emit 40% to >99% less N2O than conventional annual crops. This is a result of lower fertilizer requirements as well as a higher N-use efficiency, due to effective N-recycling. Perennial energy crops have the potential to sequester additional carbon in soil biomass if established on former cropland (0.44 Mg soil C ha−1 yr−1 for poplar and willow and 0.66 Mg soil C ha−1 yr−1 for M iscanthus). However, there was no positive or even negative effects on the C balance if energy crops are established on former grassland. Increased bioenergy production may also result in direct and indirect land-use changes with potential high C losses when native vegetation is converted to annual crops. Although dedicated perennial energy crops have a high potential to improve the GHG balance of bioenergy production, several agronomic and economic constraints still have to be overcome. [ABSTRACT FROM AUTHOR]

The effects of slurry application method and weather conditions after application on ammonia volatilisation are well documented, however, the effect on slurry N recovery in herbage is less evident due to large variability of results. The objective of this field experiment was to determine the recovery of cattle slurry NH4-N in herbage and soil in the year of application as affected by application method (trailing shoe versus broadcast) and season of application (spring versus summer), using 15N as a tracer. In 2007 and 2008, 15N enriched slurry was applied on grassland plots. N recovery in herbage and soil during the year of application was determined. Both spring and trailing shoe application resulted in significantly higher herbage DM yields, N uptake and an increased recovery of 15NH4-N in herbage. Additionally, the recovery of slurry 15NH4-N in the soil at the end of the growing season was increased. Spring and trailing shoe application reduced the losses of slurry 15NH4-N by on average 14 and 18 percentage points, respectively, which corresponded closely to ammonia volatilisation as predicted by the ALFAM model. It was concluded that slurry N recovery in temperate pasture systems can be increased by adjusting the slurry application method or timing. [ABSTRACT FROM AUTHOR]

Soil N 2 O emission potential is commonly investigated under idealized denitrifying conditions (e.g. nitrate-N supplied and anaerobic soil), with pH commonly identified as a major determinant of N 2 O emission potential. However, under urine patch conditions in grazed pastures soils a more complex series of abiotic and biotic factors may influence emissions due to the complex N transformations that occur following urea hydrolysis. These transformations may decouple native and/or expected controls of N 2 O emissions encountered under classic denitrifying conditions. Here, we tracked O 2 , CO 2 , NO, N 2 O and N 2 emissions from urine amended soils (i.e. simulating a urine patch) to determine putative controls of N 2 O emissions within 13 different pasture soils from northern (Ireland) and southern hemispheres (New Zealand). Incubations were performed under aerobic conditions±artificial urine (13.3 mg N vial−1) equivalent to field ruminant urine deposition rates of 1000 kg N ha−1. Results revealed that pH was not an important regulator of the emission ratio (N 2 O/(NO + N 2 O + N 2)) in urine amended soils. Within urine affected soils, a new set of variables emerged as regulators of N 2 O emissions, likely due to the unique environment created within this system. We show that urine results in decoupling of the initial soil pH control of the emission ratio allowing other regulators such as nitrite to dominate. In addition, we observed that the emission ratio of N 2 O increased linearly with the rate of N- gas loss (NO + N 2 O + N 2 μmol N h−1), O 2 consumption was positively associated with ammonia oxidising bacteria (AOB) and that the production of NO and N 2 O were also enhanced under urine conditions. • Kinetic profiles reveal urine amended soils as significant sources of NO and N 2 O. • No relationship between soil pH and emission ratio of N 2 O following urine addition. • Ammonia oxidising bacterial (AOB) abundance positively correlated with oxic respiration. • NO 2 − was correlated with N 2 O emission ratio. [ABSTRACT FROM AUTHOR]

Perennial species with the C4 pathway hold promise for biomass-based energy sources. We have explored the extent that CO2 uptake of such species may be limited by light in a temperate climate. One energetic cost of the C4 pathway is the leakiness (Φ) of bundle sheath tissues, whereby a variable proportion of the CO2. concentrated in bundle sheath cells, retrodiffuses back to the mesophyll. In this study, we scale Φ from leaf to canopy level of a Miscanthus crop (Miscanthus X giganteus hybrid) under field conditions and model the likely limitations to CO2 fixation. At the leaf level, measurements of photosynthesis coupled to online carbon isotope discrimination showed that leaves within a 3.3-m canopy (leaf area index = 8.3) show a progressive increase in both carbon isotope discrimination and Φ as light decreases. A similar increase was observed at the ecosystem scale when we used eddy covariance net ecosystem CO2 fluxes, together with isotopic profiles, to partition photosynthetic and respiratory isotopic flux densities (isofluxes) and derive canopy carbon isotope discrimination as an integrated proxy for Φ at the canopy level. Modeled values of canopy CO2 fixation using leaf-level measurements of Φ suggest that around 32% of potential photosynthetic carbon gain is lost due to light limitation, whereas using 4 determined independently from isofluxes at the canopy level the reduction in canopy CO2 uptake is estimated at 14%. Based on these results, we identify 4' as an important limitation to CO2 uptake of crops with the C4 pathway. [ABSTRACT FROM AUTHOR]

Nitrogen fertiliser application represents the largest anthropogenic source of nitrous oxide (N2O) emissions, and the magnitude of these emissions is dependent on the type of fertilisers applied in the agroecosystems. Despite N-P-K compound fertilisers being commonly used in agricultural soils, a lack of information exists regarding their effects on N2O emissions. This study aims at examining the effects of different commonly used N-P-K compound fertiliser formulations with contrasting nitrate to ammonium ratios (0.05 to 0.88) on N2O emissions, yield, and nitrogen use efficiency (NUE) in temperate grassland and to compare these variables with common straight N fertilisers. Compound fertilisers with varying NPK inclusion rates (18-6-12, 10-10-20, 24-2.2-4.5, and 27-2.5-5), and calcium ammonium nitrate (CAN) and urea + N-(n-butyl) thiophosphoric triamide (NBPT) were applied at 80 kg N ha−1 to experimental plots in managed grassland on two occasions in a growing season. Fluxes of N2O during the experiment period, yield and NUE following two harvests were measured. The cumulative N2O emission from urea + NBPT, 18-6-12, 10-10-20, and 24-2.2-4.5 treatments were significantly reduced by 44%, 43%, 37%, and 31% compared with CAN treatment under conducive soil moisture condition. Under the same soil condition, 18-6-12 and 10-10-20 treatments showed higher yield, N uptake, and NUE although did not significantly differ from the other fertiliser treatments. Our results suggest that ammonium-based compound fertilisers have a potential to reduce N2O emissions while maintaining yields. Further long-term study is needed to capture the full magnitude of variations in N2O emissions, including ammonia (NH3) volatilization from nitrate and ammonium-based compound fertiliser applications from multiple soil types and under different climatic conditions. [ABSTRACT FROM AUTHOR]

• N 2 O emissions were measured at six site-years in Irish grassland. • 90 N 2 O-EF were observed from three N fertilisers and five rates. • Average direct N 2 O-EF for CAN (1.62 %)>urea + NBPT (0.6 %)>urea (0.46 %). • The urea EF was most sensitive to increasing N rate. • The EF increased significantly with increasing rate in 3 (CAN), 5 (urea) and 2 (urea + NBPT) site-years. The present study evaluated the impact of three nitrogen (N) fertiliser formulations, applied at five N rates, on nitrous oxide (N 2 O) fluxes and annual direct N 2 O-N emission factors (EF) in temperate grassland. Closed static chambers were used to measure direct N 2 O fluxes at three geographically dispersed locations in Ireland over a two-year period, generating a total of 90 EFs across the six site-years and treatments. The three fertiliser formulations tested were calcium ammonium nitrate (CAN), urea, and urea amended with the urease inhibitor N -(n -butyl) thiophosphoric triamide (NBPT) at 100, 200, 300, 400 and 500 kg N ha−1 yr−1. All treatments were applied in five equal split applications ranging from 20 to 100 kg N ha−1 split-1 over the growing season. The N 2 O-N EFs for CAN ranged from 0.39 − 4.68 with a mean of 1.62 (cv. 81 %), for urea from 0.04 – 1.7 with a mean of 0.46 (cv. 77 %) and for urea + NBPT from 0.18 – 1.7 with a mean of 0.60 (cv. 59 %). A significant positive relationship was found between the N rate and the annual N 2 O-N EFs in three (CAN), five (urea) and two (urea + NBPT) of six the site-years. For the remainder of the site-years EF was unaffected by N rate. These results indicate that fertiliser N choice and rate can be management factors that enable farmers to alter N 2 O losses in temperate grassland. Notably, the response of EF to increasing N rate was not consistent across the fertilisers, with the EF from urea being the most sensitive to the increasing N rate, urea + NBPT the least sensitive and CAN being intermediate. The accuracy of national greenhouse gas accounting could be improved by including N fertiliser formulation and its rate of application. Further research is also needed to understand the inconsistency in EF response to N rate across sites. [ABSTRACT FROM AUTHOR]

Ruminant urine patches on grazed grassland are a significant source of agricultural nitrous oxide (N2O) emissions. Of the many biotic and abiotic N2O production mechanisms initiated following urine-urea deposition, codenitrification resulting in the formation of hybrid N2O, is one of the least understood. Codenitrification forms hybrid N2O via biotic N-nitrosation, co-metabolising organic and inorganic N compounds (N substrates) to produce N2O. The objective of this study was to assess the relative significance of different N substrates on codenitrification and to determine the contributions of fungi and bacteria to codenitrification. 15N-labelled ammonium, hydroxylamine (NH2OH) and two amino acids (phenylalanine or glycine) were applied, separately, to sieved soil mesocosms eight days after a simulated urine event, in the absence or presence of bacterial and fungal inhibitors. Soil chemical variables and N2O fluxes were monitored and the codenitrified N2O fluxes determined. Fungal inhibition decreased N2O fluxes by ca. 40% for both amino acid treatments, while bacterial inhibition only decreased the N2O flux of the glycine treatment, by 14%. Hydroxylamine (NH2OH) generated the highest N2O fluxes which declined with either fungal or bacterial inhibition alone, while combined inhibition resulted in a 60% decrease in the N2O flux. All the N substrates examined participated to some extent in codenitrification. Trends for codenitrification under the NH2OH substrate treatment followed those of total N2O fluxes (85.7% of total N2O flux). Codenitrification fluxes under non-NH2OH substrate treatments (0.7–1.2% of total N2O flux) were two orders of magnitude lower, and significant decreases in these treatments only occurred with fungal inhibition in the amino acid substrate treatments. These results demonstrate that in situ studies are required to better understand the dynamics of codenitrification substrates in grazed pasture soils and the associated role that fungi have with respect to codenitrification. [ABSTRACT FROM AUTHOR]