Multivariate regulation of soil CO2 and N2O pulse emissions from agricultural soils

Climate and land‐use models project increasing occurrence of high temperature and water deficit in both agricultural production systems and terrestrial ecosystems. Episodic soil wetting and subsequent drying may increase the occurrence and magnitude of pulsed biogeochemical activity, affecting carbon (C) and nitrogen (N) cycles and influencing greenhouse gas (GHG) emissions. In this study, we provide the first data to explore the responses of carbon dioxide (CO₂) and nitrous oxide (N₂O) fluxes to (i) temperature, (ii) soil water content as percent water holding capacity (%WHC), (iii) substrate availability throughout, and (iv) multiple soil drying and rewetting (DW) events. Each of these factors and their interactions exerted effects on GHG emissions over a range of four (CO₂) and six (N₂O) orders of magnitude. Maximal CO₂ and N₂O fluxes were observed in environments combining intermediate %WHC, elevated temperature, and sufficient substrate availability. Amendments of C and N and their interactions significantly affected CO₂ and N₂O fluxes and altered their temperature sensitivities (Q₁₀) over successive DW cycles. C amendments significantly enhanced CO₂ flux, reduced N₂O flux, and decreased the Q₁₀ of both. N amendments had no effect on CO₂ flux and increased N₂O flux, while significantly depressing the Q₁₀ for CO₂, and having no effect on the Q₁₀ for N₂O. The dynamics across DW cycles could be attributed to changes in soil microbial communities as the different responses to wetting events in specific group of microorganisms, to the altered substrate availabilities, or to both. The complex interactions among parameters influencing trace gas fluxes should be incorporated into next generation earth system models to improve estimation of GHG emissions.     

Greenhouse gas budget of a poplar bioenergy plantation in Belgium: CO2 uptake outweighs CH4 and N2O emissions

Biomass from short‐rotation coppice (SRC) of woody perennials is being increasingly used as a bioenergy source to replace fossil fuels, but accurate assessments of the long‐term greenhouse gas (GHG) balance of SRC are lacking. To evaluate its mitigation potential, we monitored the GHG balance of a poplar (Populus) SRC in Flanders, Belgium, over 7 years comprising three rotations (i.e., two 2 year rotations and one 3 year rotation). In the beginning—that is, during the establishment year and during each year immediately following coppicing—the SRC plantation was a net source of GHGs. Later on—that is, during each second or third year after coppicing—the site shifted to a net sink. From the sixth year onward, there was a net cumulative GHG uptake reaching ?35.8 Mg CO₂ eq/ha during the seventh year. Over the three rotations, the total CO₂ uptake was ?51.2 Mg CO₂/ha, while the emissions of CH₄ and N₂O amounted to 8.9 and 6.5 Mg CO₂ eq/ha, respectively. As the site was non‐fertilized, non‐irrigated, and only occasionally flooded, CO₂ fluxes dominated the GHG budget. Soil disturbance after land conversion and after coppicing were the main drivers for CO₂ losses. One single N₂O pulse shortly after SRC establishment contributed significantly to the N₂O release. The results prove the potential of SRC biomass plantations to reduce GHG emissions and demonstrate that, for the poplar plantation under study, the high CO₂ uptake outweighs the emissions of non‐CO₂ greenhouse gases.     

A test of a field‐based 15N–nitrous oxide pool dilution technique to measure gross N2O production in soil

Soils are both a major source and sink of nitrous oxide (N₂O), but the proportion of soil N₂O production released to the atmosphere (termed the N₂O yield) is poorly constrained due to the difficulty in measuring gross N₂O production. The quantification of gross N₂O fluxes would greatly improve our ability to predict N₂O dynamics across the soil‐atmosphere interface. We report a new approach, the ¹⁵N₂O pool dilution technique, to measure rates of gross N₂O production and consumption under laboratory and field conditions. In the laboratory, gross N₂O production and consumption compared well between the ¹⁵N₂O pool dilution and acetylene inhibition methods whereas the ¹⁵NO₃^? tracer method measured significantly higher rates. In the field, N₂O emissions were not significantly affected by increasing chamber headspace concentrations up to 100 ppb ¹⁵N₂O. The pool dilution model estimates of ¹⁴N₂O and ¹⁵N₂O concentrations as well as net N₂O fluxes fit observed data very well, suggesting that the technique yielded robust estimates of gross N₂O production. Estimated gross N₂O consumption rates were underestimated relative to rates calculated as the difference between gross and net N₂O production rates, possibly due to heterogeneous and/or inadequate tracer diffusion to deeper layers in the soil profile. Gross N₂O production rates were high, averaging 8.4 ± 3.2 mg N m^?2 day^?1, and were most strongly correlated to mineral nitrogen concentrations and denitrifying enzyme activity (R² = 0.73). Gross N₂O production rates varied spatially, with the highest rates in soils with the best drainage and the highest mineral N availability. Estimated and calculated N₂O consumption rates constrained the average N₂O yield from 0.70 to 0.84. Our results demonstrate that the ¹⁵N₂O pool dilution technique can provide well‐constrained estimates of N₂O yields and field rates of gross N₂O production correlated to soil characteristics, improving our understanding of terrestrial N₂O dynamics.     

N2O fluxes of a bio‐energy poplar plantation during a two years rotation period

Nitrous oxide emissions are of critical importance for the assumed climate neutrality of bio‐energy. In this study we report on the N₂O fluxes from a bio‐energy poplar plantation measured with eddy covariance for 2 years, after conversion of agricultural fields to few months after harvesting of the plantation. A pulse peak of N₂O was detected after the land use change and in the wake of the first heavy rainfall. The N₂O‐N emission during just a single week was 2.7 kg N₂O‐N ha^?1 which represented approximately 42% of the total N₂O‐N emitted during the 2 years of measurements. After this peak emission, N₂O fluxes were constantly rather low, not increasing after rainfall events any longer. Lowest emissions (and even N₂O sink) occurred mostly during the end of the second growing season with maximum canopy development, and water table deeper than 80 cm. Gross primary production (GPP) explained 68% of the monthly averaged variability in N₂O emission from August to December 2011. Probably N uptake by vegetation during the peak of the second growing season limited N₂O emission, which in fact increased again after the plantation was coppiced. For the majority of the measuring period, N₂O fluxes did not present a well‐defined diurnal pattern, with the exception of two periods: (1) from 19–22 August 2010 and (2) from September–November 2011. In both cases wind speed played a major role in controlling the diurnal pattern in these fluxes (explaining up to 80% of the diurnal variability in N₂O fluxes on 19–22 August 2010), whereas at the end of the second growing season (September–November 2011), GPP explained 73% of the diurnal pattern in N₂O fluxes.     

Climate change reduces the net sink of CH4 and N2O in a semiarid grassland

Atmospheric concentrations of methane (CH₄) and nitrous oxide (N₂O) have increased over the last 150 years because of human activity. Soils are important sources and sinks of both potent greenhouse gases where their production and consumption are largely regulated by biological processes. Climate change could alter these processes thereby affecting both rate and direction of their exchange with the atmosphere. We examined how a rise in atmospheric CO₂ and temperature affected CH₄ and N₂O fluxes in a well‐drained upland soil (volumetric water content ranging between 6% and 23%) in a semiarid grassland during five growing seasons. We hypothesized that responses of CH₄ and N₂O fluxes to elevated CO₂ and warming would be driven primarily by treatment effects on soil moisture. Previously we showed that elevated CO₂ increased and warming decreased soil moisture in this grassland. We therefore expected that elevated CO₂ and warming would have opposing effects on CH₄ and N₂O fluxes. Methane was taken up throughout the growing season in all 5 years. A bell‐shaped relationship was observed with soil moisture with highest CH₄ uptake at intermediate soil moisture. Both N₂O emission and uptake occurred at our site with some years showing cumulative N₂O emission and other years showing cumulative N₂O uptake. Nitrous oxide exchange switched from net uptake to net emission with increasing soil moisture. In contrast to our hypothesis, both elevated CO₂ and warming reduced the sink of CH₄ and N₂O expressed in CO₂ equivalents (across 5 years by 7% and 11% for elevated CO₂ and warming respectively) suggesting that soil moisture changes were not solely responsible for this reduction. We conclude that in a future climate this semiarid grassland may become a smaller sink for atmospheric CH₄ and N₂O expressed in CO₂‐equivalents.     

Real‐time monitoring of greenhouse gas emissions with tall chambers reveals diurnal N2O variation and increased emissions of CO2 and N2O from Miscanthus following compost addition

Miscanthus x giganteus's efficacy as an energy crop relies on maintaining low greenhouse gas (GHG) emissions. As demand for Miscanthus is expected to rise to meet bioenergy targets, fertilizers and composts may be employed to increase yields, but will also increase GHG emissions. Manipulation experiments are vital to investigate the consequences of any fertilizer additions, but there is currently no way to measure whole‐plant GHG fluxes from crops taller than 2.5 m, such as Miscanthus, at the experimental plot scale. We employed a unique combination of eddy covariance (EC), soil chambers and an entirely new automated chamber system, SkyBeam, to measure high frequency (ca. hourly) fluxes of carbon dioxide (CO₂), methane (CH₄) and nitrous oxide (N₂O) from a Miscanthus crop amended with green compost. Untreated controls were also monitored in a fully replicated experimental design. Net ecosystem exchange (NEE) of CO₂ was partitioned into soil respiration (R_s), gross primary productivity (GPP) and ecosystem respiration, and the crop was harvested to determine the effect of compost on crop productivity. Compost increased NEE emissions by 100% (p < .05), which was the result of a 20% increase of R_s (p < .06) and a 32% reduction in GPP (p < .05) and biomass of 37% (p < .06). Methane fluxes were small and unaffected by compost addition. N₂O emissions increased 34% under compost during an emission event; otherwise, fluxes were low and often negative, even under dry conditions. Diurnal variation in N₂O fluxes, with uptake during the day and emission at night was observed. These fluxes displayed a negative relationship with soil temperature and a hitherto undescribed diurnal temperature hysteresis. We conclude that compost addition negatively affected the productivity and environmental effects of Miscanthus cultivation during the first year following application.     

Exotic Spartina alterniflora invasion alters ecosystem–atmosphere exchange of CH4 and N2O and carbon sequestration in a coastal salt marsh in China

Coastal salt marshes are sensitive to global climate change and may play an important role in mitigating global warming. To evaluate the impacts of Spartina alterniflora invasion on global warming potential (GWP) in Chinese coastal areas, we measured CH₄ and N₂O fluxes and soil organic carbon sequestration rates along a transect of coastal wetlands in Jiangsu province, China, including open water; bare tidal flat; and invasive S. alterniflora, native Suaeda salsa, and Phragmites australis marshes. Annual CH₄ emissions were estimated as 2.81, 4.16, 4.88, 10.79, and 16.98 kg CH₄ ha^?1 for open water, bare tidal flat, and P. australis, S. salsa, and S. alterniflora marshes, respectively, indicating that S. alterniflora invasion increased CH₄ emissions by 57–505%. In contrast, negative N₂O fluxes were found to be significantly and negatively correlated (P < 0.001) with net ecosystem CO₂ exchange during the growing season in S. alterniflora and P. australis marshes. Annual N₂O emissions were 0.24, 0.38, and 0.56 kg N₂O ha^?1 in open water, bare tidal flat and S. salsa marsh, respectively, compared with ‐0.51 kg N₂O ha^?1 for S. alterniflora marsh and ?0.25 kg N₂O ha^?1 for P. australis marsh. The carbon sequestration rate of S. alterniflora marsh amounted to 3.16 Mg C ha^?1 yr^?1 in the top 100 cm soil profile, a value that was 2.63‐ to 8.78‐fold higher than in native plant marshes. The estimated GWP was 1.78, ?0.60, ?4.09, and ?1.14 Mg CO₂eq ha^?1 yr^?1 in open water, bare tidal flat, P. australis marsh and S. salsa marsh, respectively, but dropped to ?11.30 Mg CO₂eq ha^?1 yr^?1 in S. alterniflora marsh. Our results indicate that although S. alterniflora invasion stimulates CH₄ emissions, it can efficiently mitigate increases in atmospheric CO₂ and N₂O along the coast of China.     

Effects of elevated ozone concentration on CH4 and N2O emission from paddy soil under fully open‐air field conditions

We investigated the effects of elevated ozone concentration (E‐O₃) on CH₄ and N₂O emission from paddies with two rice cultivars: an inbred Indica cultivar Yangdao 6 (YD6) and a hybrid one II‐you 084 (IIY084), under fully open‐air field conditions in China. A mean 26.7% enhancement of ozone concentration above the ambient level (A‐O₃) significantly reduced CH₄ emission at tillering and flowering stages leading to a reduction of seasonal integral CH₄ emission by 29.6% on average across the two cultivars. The reduced CH₄ emission is associated with O₃‐induced reduction in the whole‐plant biomass (?13.2%), root biomass (?34.7%), and maximum tiller number (?10.3%), all of which curbed the carbon supply for belowground CH₄ production and its release from submerged soil to atmosphere. Although no significant difference was detected between the cultivars in the CH₄ emission response to E‐O₃, a larger decrease in CH₄ emission with IIY084 (?33.2%) than that with YD6 (?7.0%) was observed at tillering stage, which may be due to the larger reduction in tiller number in IIY084 by E‐O₃. Additionally, E‐O₃ reduced seasonal mean NO_x flux by 5.7% and 11.8% with IIY084 and YD6, respectively, but the effects were not significant statistically. We found that the relative response of CH₄ emission to E‐O₃ was not significantly different from those reported in open‐top chamber experiments. This study has thus confirmed that increasing ozone concentration would mitigate the global warming potential of CH₄ and suggested consideration of the feedback mechanism between ozone and its precursor emission into the projection of future ozone effects on terrestrial ecosystem.     

Four years of experimental climate change modifies the microbial drivers of N2O fluxes in an upland grassland ecosystem

Emissions of the trace gas nitrous oxide (N₂O) play an important role for the greenhouse effect and stratospheric ozone depletion, but the impacts of climate change on N₂O fluxes and the underlying microbial drivers remain unclear. The aim of this study was to determine the effects of sustained climate change on field N₂O fluxes and associated microbial enzymatic activities, microbial population abundance and community diversity in an extensively managed, upland grassland. We recorded N₂O fluxes, nitrification and denitrification, microbial population size involved in these processes and community structure of nitrite reducers (nirK) in a grassland exposed for 4 years to elevated atmospheric CO₂ (+200 ppm), elevated temperature (+3.5 °C) and reduction of summer precipitations (?20%) as part of a long‐term, multifactor climate change experiment. Our results showed that both warming and simultaneous application of warming, summer drought and elevated CO₂ had a positive effect on N₂O fluxes, nitrification, N₂O release by denitrification and the population size of N₂O reducers and NH₄ oxidizers. In situ N₂O fluxes showed a stronger correlation with microbial population size under warmed conditions compared with the control site. Specific lineages of nirK denitrifier communities responded significantly to temperature. In addition, nirK community composition showed significant changes in response to drought. Path analysis explained more than 85% of in situ N₂O fluxes variance by soil temperature, denitrification activity and specific denitrifying lineages. Overall, our study underlines that climate‐induced changes in grassland N₂O emissions reflect climate‐induced changes in microbial community structure, which in turn modify microbial processes.     

Greenhouse gas budget (CO2, CH4 and N2O) of intensively managed grassland following restoration

The first full greenhouse gas (GHG) flux budget of an intensively managed grassland in Switzerland (Chamau) is presented. The three major trace gases, carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) were measured with the eddy covariance (EC) technique. For CO₂ concentrations, an open‐path infrared gas analyzer was used, while N₂O and CH₄ concentrations were measured with a recently developed continuous‐wave quantum cascade laser absorption spectrometer (QCLAS). We investigated the magnitude of these trace gas emissions after grassland restoration, including ploughing, harrowing, sowing, and fertilization with inorganic and organic fertilizers in 2012. Large peaks of N₂O fluxes (20–50 nmol m^?2 s^?1 compared with a <5 nmol m^?2 s^?1 background) were observed during thawing of the soil after the winter period and after mineral fertilizer application followed by re‐sowing in the beginning of the summer season. Nitrous oxide (N₂O) fluxes were controlled by nitrogen input, plant productivity, soil water content and temperature. Management activities led to increased variations of N₂O fluxes up to 14 days after the management event as compared with background fluxes measured during periods without management (<5 nmol m^?2 s^?1). Fluxes of CO₂ remained small until full plant development in early summer 2012. In contrast, methane emissions showed only minor variations over time. The annual GHG flux budget was dominated by N₂O (48% contribution) and CO₂ emissions (44%). CH₄ flux contribution to the annual budget was only minor (8%). We conclude that recently developed multi‐species QCLAS in an EC system open new opportunities to determine the temporal variation of N₂O and CH₄ fluxes, which further allow to quantify annual emissions. With respect to grassland restoration, our study emphasizes the key role of N₂O and CO₂ losses after ploughing, changing a permanent grassland from a carbon sink to a significant carbon source.     

Soil N2O emissions with different reduced tillage methods during the establishment of Miscanthus in temperate grassland

An increase in renewable energy and the planting of perennial bioenergy crops is expected in order to meet global greenhouse gas (GHG) targets. Nitrous oxide (N₂O) is a potent greenhouse gas, and this paper addresses a knowledge gap concerning soil N₂O emissions over the possible “hot spot” of land use conversion from established pasture to the biofuel crop Miscanthus. The work aims to quantify the impacts of this land use change on N₂O fluxes using three different cultivation methods. Three replicates of four treatments were established: Miscanthus x giganteus (Mxg) planted without tillage; Mxg planted with light tillage; a novel seed‐based Miscanthus hybrid planted with light tillage under bio‐degradable mulch film; and a control of uncultivated established grass pasture with sheep grazing. Soil N₂O fluxes were recorded every 2 weeks using static chambers starting from preconversion in April 2016 and continuing until the end of October 2017. Monthly soil samples were also taken and analysed for nitrate and ammonium. There was no significant difference in N₂O emissions between the different cultivation methods. However, in comparison with the uncultivated pasture, N₂O emissions from the cultivated Miscanthus plots were 550%–819% higher in the first year (April to December 2016) and 469%–485% higher in the second year (January to October 2017). When added to an estimated carbon cost for production over a 10 year crop lifetime (including crop management, harvest, and transportation), the measured N₂O conversion cost of 4.13 Mg CO₂‐eq./ha represents a 44% increase in emission compared to the base case. This paper clearly shows the need to incorporate N₂O fluxes during Miscanthus establishment into assessments of GHG balances and life cycle analysis and provides vital knowledge needed for this process. This work therefore also helps to support policy decisions regarding the costs and benefits of land use change to Miscanthus.     

Gross nitrous oxide production drives net nitrous oxide fluxes across a salt marsh landscape

Sea level rise will change inundation regimes in salt marshes, altering redox dynamics that control nitrification – a potential source of the potent greenhouse gas, nitrous oxide (N₂O) – and denitrification, a major nitrogen (N) loss pathway in coastal ecosystems and both a source and sink of N₂O. Measurements of net N₂O fluxes alone yield little insight into the different effects of redox conditions on N₂O production and consumption. We used in situ measurements of gross N₂O fluxes across a salt marsh elevation gradient to determine how soil N₂O emissions in coastal ecosystems may respond to future sea level rise. Soil redox declined as marsh elevation decreased, with lower soil nitrate and higher ferrous iron in the low marsh compared to the mid and high marshes (P < 0.001 for both). In addition, soil oxygen concentrations were lower in the low and mid‐marshes relative to the high marsh (P < 0.001). Net N₂O fluxes differed significantly among marsh zones (P = 0.009), averaging 9.8 ± 5.4 μg N m^?2 h^?1, ?2.2 ± 0.9 μg N m^?2 h^?1, and 0.67 ± 0.57 μg N m^?2 h^?1 in the low, mid, and high marshes, respectively. Both net N₂O release and uptake were observed in the low and high marshes, but the mid‐marsh was consistently a net N₂O sink. Gross N₂O production was highest in the low marsh and lowest in the mid‐marsh (P = 0.02), whereas gross N₂O consumption did not differ among marsh zones. Thus, variability in gross N₂O production rates drove the differences in net N₂O flux among marsh zones. Our results suggest that future studies should focus on elucidating controls on the processes producing, rather than consuming, N₂O in salt marshes to improve our predictions of changes in net N₂O fluxes caused by future sea level rise.     

Nitrous oxide dynamics in managed northern forest soil profiles: is production offset by consumption?

This study investigates soil N₂O dynamics in forest soils representing early (3-years) and late (>50 years) post-harvest succession in Atlantic Canada over a 9-month snow-free period in order to develop a better understanding of the role of managed forests as sources and sinks of N₂O. We couple measurement of surface flux with detailed measurements of subsurface N₂O concentrations at four mineral soil depths (0, 5, 20 and 35 cm) at 40 plots located within four sites. Median surface fluxes were similar at all sites regardless of the management stage (−5 to +19 ugN₂O–N/m²/day), with all sites behaving as net sinks and sources of N₂O over the measurement period. Subsurface mineral soil N₂O concentrations at early (3-year) post-harvest succession sites, which ranged from median values of 362 ppbv at 0 cm to 1783 ppbv at 35 cm depth, were significantly higher than late post-harvest succession sites where median concentrations ranged from 329 ppbv at 0 cm to 460 ppbv at 35 cm depth. Examination of relationships between subsurface gas storage and surface flux magnitudes, suggested although recently harvested forest soils may be producing N₂O at a greater rate than mature forest soils, observed patterns are consistent with a strong sink for this gas that prevents its conservative transport through the soil profile, and ultimate emission to the atmosphere through the majority of the measurement period.     

Evaluation of photoacoustic infrared spectroscopy for simultaneous measurement of N2O and CO2 gas concentrations and fluxes at the soil surface

Simultaneous measurement of N₂O and CO₂ flux at the soil surface with photoacoustic infrared spectroscopy (PAS) is gaining popularity due to portability, low maintenance, and ease‐of‐operation. However, the ability of PAS to measure N₂O with accuracy and precision similar to gas chromatography (GC) is uncertain due to overlap in N₂O, CO₂, and H₂O absorbance spectra combined with the large range in analyte concentrations. We tested the ability of six PAS units to simultaneously measure N₂O and CO₂ gas concentrations and fluxes with accuracy and precision similar to two GC units. We also evaluated H₂O vapor and CO₂ interferences with N₂O measurement. The accuracy and precision of standard gas concentration measurements with PAS and GC were similar. High water vapor (~26 600 ppm) and CO₂ concentrations (~4500 ppm) did not interfere with N₂O measurement across the concentration range typically observed in static flux chambers at the soil surface (~0.5–3.0 ppm N₂O). On average, N₂O fluxes measured with the six PAS were 4.7% higher than one GC and 9.9% lower than the second GC.     

Environmental factors controlling temporal and spatial variability in the soil‐atmosphere exchange of CO2, CH4 and N2O from an Australian subtropical rainforest

The temporal variations in CO₂, CH₄ and N₂O fluxes were measured over two consecutive years from February 2007 to March 2009 from a subtropical rainforest in south‐eastern Queensland, Australia, using an automated sampling system. A concurrent study using an additional 30 manual chambers examined the spatial variability of emissions distributed across three nearby remnant rainforest sites with similar vegetation and climatic conditions. Interannual variation in fluxes of all gases over the 2 years was minimal, despite large discrepancies in rainfall, whereas a pronounced seasonal variation could only be observed for CO₂ fluxes. High infiltration, drainage and subsequent high soil aeration under the rainforest limited N₂O loss while promoting substantial CH₄ uptake. The average annual N₂O loss of 0.5 ± 0.1 kg N₂O‐N ha^?1 over the 2‐year measurement period was at the lower end of reported fluxes from rainforest soils. The rainforest soil functioned as a sink for atmospheric CH₄ throughout the entire 2‐year period, despite periods of substantial rainfall. A clear linear correlation between soil moisture and CH₄ uptake was found. Rates of uptake ranged from greater than 15 g CH₄‐C ha^?1 day^?1 during extended dry periods to less than 2–5 g CH₄‐C ha^?1 day^?1 when soil water content was high. The calculated annual CH₄ uptake at the site was 3.65 kg CH₄‐C ha^?1 yr^?1. This is amongst the highest reported for rainforest systems, reiterating the ability of aerated subtropical rainforests to act as substantial sinks of CH₄. The spatial study showed N₂O fluxes almost eight times higher, and CH₄ uptake reduced by over one‐third, as clay content of the rainforest soil increased from 12% to more than 23%. This demonstrates that for some rainforest ecosystems, soil texture and related water infiltration and drainage capacity constraints may play a more important role in controlling fluxes than either vegetation or seasonal variability.     

Nonlinear nitrous oxide (N2O) response to nitrogen fertilizer in on‐farm corn crops of the US Midwest

Row‐crop agriculture is a major source of nitrous oxide (N₂O) globally, and results from recent field experiments suggest that significant decreases in N₂O emissions may be possible by decreasing nitrogen (N) fertilizer inputs without affecting economic return from grain yield. We tested this hypothesis on five commercially farmed fields in Michigan, USA planted with corn in 2007 and 2008. Six rates of N fertilizer (0–225 kg N ha^?1) were broadcast and incorporated before planting, as per local practice. Across all sites and years, increases in N₂O flux were best described by a nonlinear, exponentially increasing response to increasing N rate. N₂O emission factors per unit of N applied ranged from 0.6% to 1.5% and increased with increasing N application across all sites and years, especially at N rates above those required for maximum crop yield. At the two N fertilizer rates above those recommended for maximum economic return (135 kg N ha^?1), average N₂O fluxes were 43% (18 g N₂O–N ha^?1 day^?1) and 115% (26 g N₂O–N ha^?1 day^?1) higher than were fluxes at the recommended rate, respectively. The maximum return to nitrogen rate of 154 kg N ha^?1 yielded an average 8.3 Mg grain ha^?1. Our study shows the potential to lower agricultural N₂O fluxes within a range of N fertilization that does not affect economic return from grain yield.     

Weakened growth of cropland‐N2O emissions in China associated with nationwide policy interventions

China has experienced rapid agricultural development over recent decades, accompanied by increased fertilizer consumption in croplands; yet, the trend and drivers of the associated nitrous oxide (N₂O) emissions remain uncertain. The primary sources of this uncertainty are the coarse spatial variation of activity data and the incomplete model representation of N₂O emissions in response to agricultural management. Here, we provide new data‐driven estimates of cropland‐N₂O emissions across China in 1990–2014, compiled using a global cropland‐N₂O flux observation dataset, nationwide survey‐based reconstruction of N‐fertilization and irrigation, and an updated nonlinear model. In addition, we have evaluated the drivers behind changing cropland‐N₂O patterns using an index decomposition analysis approach. We find that China's annual cropland‐N₂O emissions increased on average by 11.2 Gg N/year² (p < .001) from 1990 to 2003, after which emissions plateaued until 2014 (2.8 Gg N/year², p = .02), consistent with the output from an ensemble of process‐based terrestrial biosphere models. The slowdown of the increase in cropland‐N₂O emissions after 2003 was pervasive across two thirds of China's sowing areas. This change was mainly driven by the nationwide reduction in N‐fertilizer applied per area, partially due to the prevalence of nationwide technological adoptions. This reduction has almost offset the N₂O emissions induced by policy‐driven expansion of sowing areas, particularly in the Northeast Plain and the lower Yangtze River Basin. Our results underline the importance of high‐resolution activity data and adoption of nonlinear model of N₂O emission for capturing cropland‐N₂O emission changes. Improving the representation of policy interventions is also recommended for future projections.     

Chirality in Distorted Square Planar Pd(O,N)2 Compounds

Salicylidenimine palladium(II) complexes trans‐Pd(O,N)₂ adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N‐substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)₂ unit. In complexes 1 , 2 , 3 , 4 , 5 , 6 with enantiomerically pure N‐substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)₂ complexes with bridging N‐substituents in trans‐arrangement are inherently chiral. For dimers 7 , 8 , 9 , 10 , 11 different chirality patterns for the Pd(O,N)₂ square are observed. The crystals contain racemates of enantiomers. In complex 12 two independent molecules form a tight pair. The (R_C) configuration of the ligand induces the same Δ chirality in the Pd(O,N)₂ units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes 13 and 14 atrop isomerism induces specific configurations in the Pd(O,N)₂ bowl systems. The square chirality is largest for complex 15 [(Diop)Rh(PPh₃)Cl)], a catalyst for enantioselective hydrogenation. In the lattice of 15 two diastereomers with the same (R_C,R_C) configuration in the ligand Diop but opposite Δ and Λ square configurations co‐crystallize, a rare phenomenon in stereochemistry. Chirality 25:663–667, 2013. © 2013 Wiley Periodicals, Inc.     

Bi-directional soil/atmosphere N2O exchange over two mown grassland systems with contrasting management practices

Nitrous oxide (N₂O) fluxes from soil under mown grassland were monitored using static chambers over three growing seasons in intensively and extensively managed systems in Central Switzerland. Emissions were largest following the application of mineral (NH₄NO₃) fertilizer, but there were also substantial emissions following cattle slurry application, after grass cuts and during the thawing of frozen soil. Continuous flux sampling, using automatic chambers, showed marked diurnal patterns in N₂O fluxes during emission peaks, with highest values in the afternoon. Net uptake fluxes of N₂O and subambient N₂O concentrations in soil open pore space were frequently measured on both fields. Flux integration over 2.5 years yields a cumulated emission of +4.7 kgN₂O‐N ha^?1 for the intensively managed field, equivalent to an average emission factor of 1.1%, and a small net sink activity of ?0.4 kg N₂O‐N ha^?1 for the unfertilized system. The data suggest the existence of a consumption mechanism for N₂O in dry, areated soil conditions, which cannot be explained by conventional anaerobic denitrification. The effect of fertilization on greenhouse gas budgets of grassland at the ecosystem level is discussed.     

Contribution of plants to N 2 O emissions in soil-winter wheat ecosystem: pot and field experiments

Outdoor pot and field experiments were conducted to assess the role of growing plants in agricultural ecosystem N₂O emissions. N₂O emissions from plants were quantified as the difference in soil-crop system N₂O emissions before and immediately after cutting plants during the main growth stages in 2001–02 and 2002–03 winter wheat seasons. Emissions of N₂O from plants depended on biomass within the same plant developmental status. Field results indicated that the seasonal contribution of N₂O emissions from plants to ecosystem fluxes averaged 25%, ranging from 10% at wheat tillering to 62% at the heading stage. The fluxes of N₂O emissions from plants varied between 0.3 and 3.9 mg N₂O-N m⁻² day⁻¹ and its seasonal amount was equivalent to 0.23% of plant N released as N₂O. A N₂O emission coefficient (N₂O_E, mg N₂O-N g⁻¹ C day⁻¹), defined as N₂O-N emission in milligrams from per gram carbon of plant dry matter within a day, was represented by a 5-fold variation ranging from 0.021 to 0.004 mg N₂O-N g C⁻¹ day⁻¹. A linear relationship (y=0.4611x+0.0015, r ²=0.9352, p < 0.001) between N₂O_E (y) and plant dark respiration rate (x, mg CO₂-C g C⁻¹ day⁻¹) suggested that in the absence of photosynthesis, some N₂O production in plant N assimilation was associated with plant respiration. Although this study could not show whether N₂O was produced or transferred by winter wheat plants, these results indicated an important role for higher plant in N₂O exchange. Identifying its potential contribution is critical for understanding agricultural ecosystem N₂O sources.