Biochar application as a tool to decrease soil nitrogen losses (NH3 volatilization,N2O emissions,and N leaching) from croplands: Options and mitigation strength in a global perspective

Biochar application to croplands has been proposed as a potential strategy to decrease losses of soil‐reactive nitrogen (N) to the air and water. However, the extent and spatial variability of biochar function at the global level are still unclear. Using Random Forest regression modelling of machine learning based on data compiled from the literature, we mapped the impacts of different biochar types (derived from wood, straw, or manure), and their interactions with biochar application rates, soil properties, and environmental factors, on soil N losses (NH₃ volatilization, N₂O emissions, and N leaching) and crop productivity. The results show that a suitable distribution of biochar across global croplands (i.e., one application of <40 t ha^?1 wood biochar for poorly buffered soils, such as those characterized by soil pH<5, organic carbon<1%, or clay>30%; and one application of <80 t ha^?1 wood biochar, <40 t ha^?1 straw biochar, or <10 t ha^?1 manure biochar for other soils) could achieve an increase in global crop yields by 222–766 Tg yr^?1 (4%–16% increase), a mitigation of cropland N₂O emissions by 0.19–0.88 Tg N yr^?1 (6%–30% decrease), a decline of cropland N leaching by 3.9–9.2 Tg N yr^?1 (12%–29% decrease), but also a fluctuation of cropland NH₃ volatilization by ?1.9–4.7 Tg N yr^?1 (?12%–31% change). The decreased sum of the three major reactive N losses amount to 1.7–9.4 Tg N yr^?1, which corresponds to 3%–14% of the global cropland total N loss. Biochar generally has a larger potential for decreasing soil N losses but with less benefits to crop production in temperate regions than in tropical regions.     

Crystal Structures of the Human G3BP1 NTF2-Like Domain Visualize FxFG Nup Repeat Specificity

Ras GTPase Activating Protein SH3 Domain Binding Protein (G3BP) is a potential anti-cancer drug target implicated in several cellular functions. We have used protein crystallography to solve crystal structures of the human G3BP1 NTF2-like domain both alone and in complex with an FxFG Nup repeat peptide. Despite high structural similarity, the FxFG binding site is located between two alpha helices in the G3BP1 NTF2-like domain and not at the dimer interface as observed for nuclear transport factor 2. ITC studies showed specificity towards the FxFG motif but not FG and GLFG motifs. The unliganded form of the G3BP1 NTF2-like domain was solved in two crystal forms to resolutions of 1.6 and 3.3 Å in space groups P2₁2₁2₁ and P6₃22 based on two different constructs, residues 1–139 and 11–139, respectively. Crystal packing of the N-terminal residues against a symmetry related molecule in the P2₁2₁2₁ crystal form might indicate a novel ligand binding site that, however, remains to be validated. The crystal structures give insight into the nuclear transportation mechanisms of G3BP and provide a basis for future structure based drug design.     

Nitrous oxide emissions from inland waters: Are IPCC estimates too high?

Nitrous oxide (N₂O) emissions from inland waters remain a major source of uncertainty in global greenhouse gas budgets. N₂O emissions are typically estimated using emission factors (EFs), defined as the proportion of the terrestrial nitrogen (N) load to a water body that is emitted as N₂O to the atmosphere. The Intergovernmental Panel on Climate Change (IPCC) has proposed EFs of 0.25% and 0.75%, though studies have suggested that both these values are either too high or too low. In this work, we develop a mechanistic modeling approach to explicitly predict N₂O production and emissions via nitrification and denitrification in rivers, reservoirs and estuaries. In particular, we introduce a water residence time dependence, which kinetically limits the extent of denitrification and nitrification in water bodies. We revise existing spatially explicit estimates of N loads to inland waters to predict both lumped watershed and half‐degree grid cell emissions and EFs worldwide, as well as the proportions of these emissions that originate from denitrification and nitrification. We estimate global inland water N₂O emissions of 10.6–19.8 Gmol N year^?1 (148–277 Gg N year^?1), with reservoirs producing most N₂O per unit area. Our results indicate that IPCC EFs are likely overestimated by up to an order of magnitude, and that achieving the magnitude of the IPCC's EFs is kinetically improbable in most river systems. Denitrification represents the major pathway of N₂O production in river systems, whereas nitrification dominates production in reservoirs and estuaries.     

Characterization of G3BPs: Tissue specific expression,chromosomal localisation and rasGAP120 binding studies

The G3BP (ras‐GTPase‐Activating Protein SH3‐Domain‐Binding Protein) family of proteins has been implicated in both signal transduction and RNA‐metabolism. We have previously identified human G3BP‐1, G3BP‐2, and mouse G3BP‐2. Here, we report the cloning of mouse G3BP‐1, the discovery of two alternatively spliced isoforms of mouse, and human G3BP‐2 (G3BP‐2a and G3BP‐2b), and the chromosomal localisation of human G3BP‐1 and G3BP‐2, which map to 5q14.2‐5q33.3 and 4q12‐4q24 respectively. We mapped the rasGAP¹²⁰ interactive region of the G3BP‐2 isoforms and show that both G3BP‐2a and G3BP‐2b use an N‐terminal NTF2‐like domain for rasGAP¹²⁰ binding rather than several available proline‐rich (PxxP) motifs found in members of the G3BPs. Furthermore, we have characterized the protein expression of both G3BP‐1 and G3BP‐2a/b in adult mouse tissues, and show them to be both tissue and isoform specific. J. Cell. Biochem. 84: 173–187, 2002. © 2001 Wiley‐Liss, Inc.     

Soil GHG fluxes are altered by N deposition: New data indicate lower N stimulation of the N2O flux and greater stimulation of the calculated C pools

The effects of nitrogen (N) deposition on soil organic carbon (C) and greenhouse gas (GHG) emissions in terrestrial ecosystems are the main drivers affecting GHG budgets under global climate change. Although many studies have been conducted on this topic, we still have little understanding of how N deposition affects soil C pools and GHG budgets at the global scale. We synthesized a comprehensive dataset of 275 sites from multiple terrestrial ecosystems around the world and quantified the responses of the global soil C pool and GHG fluxes induced by N enrichment. The results showed that the soil organic C concentration and the soil CO₂, CH₄ and N₂O emissions increased by an average of 3.7%, 0.3%, 24.3% and 91.3% under N enrichment, respectively, and that the soil CH₄ uptake decreased by 6.0%. Furthermore, the percentage increase in N₂O emissions (91.3%) was two times lower than that (215%) reported by Liu and Greaver (Ecology Letters, 2009, 12:1103–1117). There was also greater stimulation of soil C pools (15.70 kg C ha^?1 year^?1 per kg N ha^?1 year^?1) than previously reported under N deposition globally. The global N deposition results showed that croplands were the largest GHG sources (calculated as CO₂ equivalents), followed by wetlands. However, forests and grasslands were two important GHG sinks. Globally, N deposition increased the terrestrial soil C sink by 6.34 Pg CO₂/year. It also increased net soil GHG emissions by 10.20 Pg CO₂‐Geq (CO₂ equivalents)/year. Therefore, N deposition not only increased the size of the soil C pool but also increased global GHG emissions, as calculated by the global warming potential approach.     

Soil-Atmosphere Exchange of N<Subscript>2</Subscript>O and NO in Near-Natural Savanna and Agricultural Land in Burkina Faso (W. Africa)

In a combined field and laboratory study in the southwest of Burkina Faso, we quantified soil-atmosphere N₂O and NO exchange. N₂O emissions were measured during two field campaigns throughout the growing seasons 2005 and 2006 at five different experimental sites, that is, a natural savanna site and four agricultural sites planted with sorghum (n = 2), cotton and peanut. The agricultural fields were not irrigated and not fertilized. Although N₂O exchange mostly fluctuated between −2 and 8 μg N₂O–N m⁻² h⁻¹, peak N₂O emissions of 10–35 μg N₂O–N m⁻² h⁻¹ during the second half of June 2005, and up to 150 μg N₂O–N m⁻² h⁻¹ at the onset of the rainy season 2006, were observed at the native savanna site, whereas the effect of the first rain event on N₂O emissions at the crop sites was low or even not detectable. Additionally, a fertilizer experiment was conducted at a sorghum field that was divided into three plots receiving different amounts of N fertilizer (plot A: 140 kg N ha⁻¹; plot B: 52.5 kg N ha⁻¹; plot C: control). During the first 3 weeks after fertilization, only a minor increase in N₂O emissions at the two fertilized plots was detected. After 24 days, however, N₂O emission rates increased exponentially at plot A up to a mean of 80 μg N₂O–N m⁻² h⁻¹, whereas daily mean values at plot B reached only 19 μg N₂O–N m⁻² h⁻¹, whereas N₂O flux rates at plot C remained unchanged. The calculated annual N₂O emission of the nature reserve site amounted to 0.52 kg N₂O–N ha⁻¹ a⁻¹ in 2005 and to 0.67 kg N₂O–N ha⁻¹ a⁻¹ in 2006, whereas the calculated average annual N₂O release of the crop sites was only 0.19 kg N₂O–N ha⁻¹ a⁻¹ and 0.20 kg N₂O–N ha⁻¹ a⁻¹ in 2005 and 2006, respectively. In a laboratory study, potential N₂O and NO formation under different soil moisture regimes were determined. Single wetting of dry soil to medium soil water content with subsequent drying caused the highest increase in N₂O and NO emissions with maximum fluxes occurring 1 day after wetting. The stimulating effect lasted for 3–4 days. A weaker stimulation of N₂O and NO fluxes was detected during daily wetting of soil to medium water content, whereas no significant stimulating effect of single or daily wetting to high soil water content (>67% WHC_max) was observed. This study demonstrates that the impact of land-use change in West African savanna on N trace gas emissions is smaller—with the caveat that there could have been potentially higher N₂O and NO emissions during the initial conversion—than the effect of timing and distribution of rainfall and of the likely increase in nitrogen fertilization in the future.     

DMPP reduced nitrification,but not annual N2O emissions from mineral fertilizer applied to oilseed rape on a sandy loam soil

Direct field emissions of nitrous oxide (N₂O) may determine whether biodiesel from oilseed rape (Brassica napus L.) fulfills the EU requirement of at least 50% reduction of greenhouse gas emissions as compared to fossil diesel. However, only few studies have documented fertilizer N emission factors (EF) and mitigation options for N₂O emissions from oilseed rape cropping systems. We conducted a field experiment with three N levels (0, 171, and 217 kg/ha), where the N fertilizer was applied as ammonium sulfate nitrate with or without the nitrification inhibitor 3,4‐dimethylpyrazole phosphate (DMPP). N₂O fluxes were measured using static chambers technique and soil samples were analyzed for water and mineral N content during a monitoring period of 368 days. The DMPP treatments showed a significantly increased level of ammonium () for up to 18 weeks after spring fertilization as compared to the treatments without DMPP. However, this difference did not result in a corresponding decrease in soil content, and no differences in cumulative N₂O emissions were found between any fertilized treatments with or without DMPP (mean, 1.26 kg N₂O‐N ha^?1 year^?1). More field experiments are needed to clarify whether DMPP‐coated mineral fertilizers could mitigate N₂O emissions under different weather conditions, for example, under conditions where fertilization events concurred with rainfall events increasing water‐filled pore space to the assumed 60% threshold for denitrification. Emission factors for mineral N fertilizer were 0.28%–0.36% with a mean of 0.32% across the fertilized treatments. These data concur with recent European studies suggesting that the EF for mineral N fertilizers in oilseed rape cropping systems may typically be lower than the default IPCC value of 1%. Further studies are needed to consolidate an EF for oilseed rape under temperate conditions, which will be determining for the sustainability of Northern European oilseed rape cultivation for biodiesel.     

Asymmetry in above‐ and belowground productivity responses to N addition in a semi‐arid temperate steppe

Nitrogen (N) enrichment often increases aboveground net primary productivity (ANPP) of the ecosystem, but it is unclear if belowground net primary productivity (BNPP) track responses of ANPP. Moreover, the frequency of N inputs may affect primary productivity but is rarely studied. To assess the response patterns of above‐ and belowground productivity to rates of N addition under different addition frequencies, we manipulated the rate (0–50 g N m^?2 year^?1) and frequency (twice vs. monthly additions per year) of NH₄NO₃ inputs for six consecutive years in a temperate grassland in northern China and measured ANPP and BNPP from 2012 to 2014. In the low range of N addition rates, BNPP showed the greatest negative response and ANPP showed the greatest positive responses with increases in N addition (<10 g N m^?2 year^?1). As N addition increased beyond 10 g N m^?2 year^?1, increases in ANPP dampened and decreases in BNPP ceased altogether. The response pattern of net primary productivity (combined above‐ and belowground; NPP) corresponded more closely to ANPP than to BNPP. The N effects on BNPP and BNPP/NPP (f_BNPP) were not dependent on N addition frequency in the range of N additions typically associated with N deposition. BNPP was more sensitive to N addition frequency than ANPP, especially at low rates of N addition. Our findings provide new insights into how plants regulate carbon allocation to different organs with increasing N rates and changing addition frequencies. These root response patterns, if incorporated into Earth system models, may improve the predictive power of C dynamics in dryland ecosystems in the face of global atmospheric N deposition.     

Fluxes of greenhouse gases from Andosols under coffee in monoculture or shaded by <Emphasis Type="Italic">Inga densiflora</Emphasis> in Costa Rica

The objective of this study was to evaluate the effect of N fertilization and the presence of N₂ fixing leguminous trees on soil fluxes of greenhouse gases. For a one year period, we measured soil fluxes of nitrous oxide (N₂O), carbon dioxide (CO₂) and methane (CH₄), related soil parameters (temperature, water-filled pore space, mineral nitrogen content, N mineralization potential) and litterfall in two highly fertilized (250 kg N ha⁻¹ year⁻¹) coffee cultivation: a monoculture (CM) and a culture shaded by the N₂ fixing legume species Inga densiflora (CIn). Nitrogen fertilizer addition significantly influenced N₂O emissions with 84% of the annual N₂O emitted during the post fertilization periods, and temporarily increased soil respiration and decreased CH₄ uptakes. The higher annual N₂O emissions from the shaded plantation (5.8 ± 0.3 kg N ha⁻¹ year⁻¹) when compared to that from the monoculture (4.3 ± 0.1 kg N ha⁻¹ year⁻¹) was related to the higher N input through litterfall (246 ± 16 kg N ha⁻¹ year⁻¹) and higher potential soil N mineralization rate (3.7 ± 0.2 mg N kg⁻¹ d.w. d⁻¹) in the shaded cultivation when compared to the monoculture (153 ± 6.8 kg N ha⁻¹ year⁻¹ and 2.2 ± 0.2 mg N kg⁻¹ d.w. d⁻¹). This confirms that the presence of N₂ fixing shade trees can increase N₂O emissions. Annual CO₂ and CH₄ fluxes of both systems were similar (8.4 ± 2.6 and 7.5 ± 2.3 t C-CO₂ ha⁻¹ year⁻¹, −1.1 ± 1.5 and 3.3 ± 1.1 kg C-CH₄ ha⁻¹ year⁻¹, respectively in the CIn and CM plantations) but, unexpectedly increased during the dry season.     

Conformational preferences of modified nucleoside N(2)-methylguanosine (m(2)G) and its derivative N(2), N(2)-dimethylguanosine (m(2)(2)G) occur at 26th position (hinge region) in tRNA

Conformational preferences of the modified nucleosides N²-methylguanosine (m²G) and N², N²-dimethylguanosine (m₂²G) have been studied theoretically by using quantum chemical perturbative configuration interaction with localized orbitals (PCILO) method. Automated complete geometry optimization using semiempirical quantum chemical RM1, along with ab initio molecular orbital Hartree–Fock (HF-SCF), and density functional theory (DFT) calculations has also been made to compare the salient features. Single-point energy calculation studies have been made on various models of m²G26:C/A/U44 and m₂²G26:C/A/U44. The glycosyl torsion angle prefers “syn” (χ = 286°) conformation for m²G and m₂²G molecules. These conformations are stabilized by N(3)–HC2′ and N(3)–HC3′ by replacing weak interaction between O5′–HC(8). The N²-methyl substituent of (m²G26) prefers “proximal” or s-trans conformation. It may also prefer “distal” or s-cis conformation that allows base pairing with A/U44 instead of C at the hinge region. Thus, N²-methyl group of m²G may have energetically two stable s-trans m²G:C/A/U or s-cis m²G:A/U rotamers. This could be because of free rotations around C–N bond. Similarly, N², N²-dimethyl substituent of (m₂²G) prefers “distal” conformation that may allow base pairing with A/U instead of C at 44th position. Such orientations of m²G and m₂²G could play an important role in base-stacking interactions at the hinge region of tRNA during protein biosynthesis process.     

Nitrous oxide emissions from silage maize fields under different mineral nitrogen fertilizer and slurry applications

Intensive dairy farming systems are a large source of emission of the greenhouse gas nitrous oxide (N₂O), because of high nitrogen (N) application rates to grasslands and silage maize fields. The objective of this study was to compare measured N₂O emissions from two different soils to default N₂O emission factors, and to look at alternative emission factors based on (i) the N uptake in the crop and (ii) the N surplus of the system, i.e., N applied minus N uptake by the crop. Twelve N fertilization regimes were implemented on a sandy soil (typic endoaquoll) and a clay soil (typic endoaquept) in the Netherlands, and N₂O emissions were measured throughout the growing season. Highest cumulative fluxes of 1.92 and 6.81 kg N₂O-N ha^–1 for the sandy soil and clay soil were measured at the highest slurry application rate of 250 kg N ha^–1. Background emissions from unfertilized soils were 0.14 and 1.52 kg N₂O-N ha^–1 for the sandy soil and the clay soil, respectively. Emission factors for the sandy soil averaged 0.08, 0.51 and 0.26% of the N applied via fertilizer, slurry, and combinations of both. For the clay soil, these numbers were 1.18, 1.21 and 1.69%, respectively. Surplus N was linearly related to N₂O emission for both the sandy soil (R²=0.60) and the clay soil (R²=0.40), indicating a possible alternative emission factor. We concluded that, in our study, N₂O emission was not linearly related to N application rates, and varied with type and application rate of fertilizer. Finally, the relatively high emission from the clay soil indicates that background emissions might have to be taken into account in N₂O budgets.     

Effect of heat wave on N2 fixation and N remobilisation of lentil (Lens culinaris MEDIK) grown under free air CO2 enrichment in a mediterranean‐type environment

• The stimulatory effect of elevated [CO₂] (e[CO₂]) on crop production in future climates is likely to be cancelled out by predicted increases in average temperatures. This effect may become stronger through more frequent and severe heat waves, which are predicted to increase in most climate change scenarios. Whilst the growth and yield response of some legumes grown under the interactive effect of e[CO₂] and heat waves has been studied, little is known about how N₂ fixation and overall N metabolism is affected by this combination.
• To address these knowledge gaps, two lentil genotypes were grown under ambient [CO₂] (a[CO₂], ~400 µmol·mol^?1) and e[CO₂] (~550 µmol·mol^?1) in the Australian Grains Free Air CO₂ Enrichment facility and exposed to a simulated heat wave (3‐day periods of high temperatures ~40 °C) at flat pod stage. Nodulation and concentrations of water‐soluble carbohydrates (WSC), total free amino acids, N and N₂ fixation were assessed following the imposition of the heat wave until crop maturity.
• Elevated [CO₂] stimulated N₂ fixation so that total N₂ fixation in e[CO₂]‐grown plants was always higher than in a[CO₂], non‐stressed control plants. Heat wave triggered a significant decrease in active nodules and WSC concentrations, but e[CO₂] had the opposite effect. Leaf N remobilization and grain N improved under interaction of e[CO₂] and heat wave.
• These results suggested that larger WSC pools and nodulation under e[CO₂] can support post‐heat wave recovery of N₂ fixation. Elevated [CO₂]‐induced accelerated leaf N remobilisation might contribute to restore grain N concentration following a heat wave.

     

Silicon Nitride-BP-Based Surface Plasmon Resonance Highly Sensitive Biosensor for Virus SARS-CoV-2 Detection

In this study, we propose a surface plasmon resonance (SPR)-based biosensor using silicon nitride (Si₃N₄), black phosphorous (BP), and thiol-tethered DNA as a ligand for fast detection of the SARS-CoV-2 virus. In the proposed biosensor, we have deposited silver (Ag), Si₃N₄, and BP on the base of the BK-7 prism and investigated the performance parameters on the probe in different combinations of the mentioned materials. Herein, three (Ag, Si₃N₄, and BP) different configurations are introduced and compared for the detection of SARS-CoV-2. Furthermore, with the help of the transfer matrix method (TMM), all the three configurations have been analyzed. Notably, the combination of Ag, Si₃N₄, and BP shows better sensitivity (154°/RIU) when compared with other configurations for the detection of SARS-CoV-2. This work may facilitate a new sensing device to detect SARS-CoV-2, based on the hybrid materials.

     

Drainage increases CO2 and N2O emissions from tropical peat soils

Tropical peatlands are vital ecosystems that play an important role in global carbon storage and cycles. Current estimates of greenhouse gases from these peatlands are uncertain as emissions vary with environmental conditions. This study provides the first comprehensive analysis of managed and natural tropical peatland GHG fluxes: heterotrophic (i.e. soil respiration without roots), total CO₂ respiration rates, CH₄ and N₂O fluxes. The study documents studies that measure GHG fluxes from the soil (n = 372) from various land uses, groundwater levels and environmental conditions. We found that total soil respiration was larger in managed peat ecosystems (median = 52.3 Mg CO₂ ha^?1 year^?1) than in natural forest (median = 35.9 Mg CO₂ ha^?1 year^?1). Groundwater level had a stronger effect on soil CO₂ emission than land use. Every 100 mm drop of groundwater level caused an increase of 5.1 and 3.7 Mg CO₂ ha^?1 year^?1 for plantation and cropping land use, respectively. Where groundwater is deep (≥0.5 m), heterotrophic respiration constituted 84% of the total emissions. N₂O emissions were significantly larger at deeper groundwater levels, where every drop in 100 mm of groundwater level resulted in an exponential emission increase (exp(0.7) kg N ha^?1 year^?1). Deeper groundwater levels induced high N₂O emissions, which constitute about 15% of total GHG emissions. CH₄ emissions were large where groundwater is shallow; however, they were substantially smaller than other GHG emissions. When compared to temperate and boreal peatland soils, tropical peatlands had, on average, double the CO₂ emissions. Surprisingly, the CO₂ emission rates in tropical peatlands were in the same magnitude as tropical mineral soils. This comprehensive analysis provides a great understanding of the GHG dynamics within tropical peat soils that can be used as a guide for policymakers to create suitable programmes to manage the sustainability of peatlands effectively.     

In silico identification of MicroRNAs targeting the key nucleator of stress granules,G3BP: Promising therapeutics for SARS-CoV-2 infection

Stress granules (SGs) are non-membrane ribonucleoprotein condensates formed in response to environmental stress conditions via liquid–liquid phase separation (LLPS). SGs are involved in the pathogenesis of aging and aging-associated diseases, cancers, viral infection, and several other diseases. GTPase-activating protein (SH3 domain)-binding protein 1 and 2 (G3BP1/2) is a key component and commonly used marker of SGs. Recent studies have shown that SARS-CoV-2 nucleocapsid protein via sequestration of G3BPs inhibits SGs formation in the host cells. In this study, we have identified putative miRNAs targeting G3BP in search of modulators of the G3BP expression. These miRNAs could be considered as new therapeutic targets against COVID-19 infection via the regulation of SG assembly and dynamics.     

A [4+2] mixed ligand approach to ruthenium DNA metallointercalators [Ru(tpa)(N–N)](PF6)2 using a tris(2-pyridylmethyl)amine (tpa) capping ligand

A series of five tris(2-pyridylmethyl)amine (tpa) ruthenium complexes [Ru(tpa)(N–N)](PF₆)₂ with N–N = bpy (2,2′-bipyridine), phen (1,10-phenanthroline), dpq (dipyrido[3,2-d:2′,3′-f]quinoxaline), dppz (dipyrido[3,2-a;2′,3′-c]phenazine), and dppn (4,5,9,16-tetraazadibenzo[a,c]naphthacene) was prepared and characterized by NMR, UV–Visible (UV/Vis), and fluorescence spectroscopy as well as cyclic voltammetry. Structures optimized with density functional theory methods (DFT, BP86, TZVP) without constraints show C₁ symmetry while in solution, the ¹H and ¹³C NMR spectra are in accordance with an average C_s symmetry. This is thought to be due to a low energy barrier for flipping of the equatorial pyridine ring from one side of the N–N plane to the other. The electronic structure of the compounds was studied with DFT and a change in the highest occupied molecular orbital (HOMO) character from Ru t_2g for the bpy, phen, and dpq to N–N ligand-based for the dppz and dppn complexes was found. TDDFT calculations showed dominant N–N-based intra-ligand charge transfer (ILCT) transitions in the latter two complexes mixed with metal-to-ligand charge transfer (MLCT) bands found for all five compounds. DNA binding of the complexes was studied with UV/Vis titrations, the fluorescent ethidium bromide displacement assay, and CD spectroscopy. The affinity increases with the aromatic surface area of of the bidentate N–N ligand in the order bpy  phen < dpq < dppz  dppn. Viscosity measurements support an intercalative binding mode for the latter three compounds, while the others did not show a pronounced effect of the hydrodynamic properties of calf thymus (CT) DNA.     

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.     

Modeling nitrous oxide emission from rivers: a global assessment

Estimates of global riverine nitrous oxide (N₂O) emissions contain great uncertainty. We conducted a meta‐analysis incorporating 169 observations from published literature to estimate global riverine N₂O emission rates and emission factors. Riverine N₂O flux was significantly correlated with NH₄, NO₃ and DIN (NH₄ + NO₃) concentrations, loads and yields. The emission factors EF(a) (i.e., the ratio of N₂O emission rate and DIN load) and EF(b) (i.e., the ratio of N₂O and DIN concentrations) values were comparable and showed negative correlations with nitrogen concentration, load and yield and water discharge, but positive correlations with the dissolved organic carbon : DIN ratio. After individually evaluating 82 potential regression models based on EF(a) or EF(b) for global, temperate zone and subtropical zone datasets, a power function of DIN yield multiplied by watershed area was determined to provide the best fit between modeled and observed riverine N₂O emission rates (EF(a): R² = 0.92 for both global and climatic zone models, n = 70; EF(b): R² = 0.91 for global model and R² = 0.90 for climatic zone models, n = 70). Using recent estimates of DIN loads for 6400 rivers, models estimated global riverine N₂O emission rates of 29.6–35.3 (mean = 32.2) Gg N₂O–N yr⁻¹ and emission factors of 0.16–0.19% (mean = 0.17%). Global riverine N₂O emission rates are forecasted to increase by 35%, 25%, 18% and 3% in 2050 compared to the 2000s under the Millennium Ecosystem Assessment's Global Orchestration, Order from Strength, Technogarden, and Adapting Mosaic scenarios, respectively. Previous studies may overestimate global riverine N₂O emission rates (300–2100 Gg N₂O–N yr⁻¹) because they ignore declining emission factor values with increasing nitrogen levels and channel size, as well as neglect differences in emission factors corresponding to different nitrogen forms. Riverine N₂O emission estimates will be further enhanced through refining emission factor estimates, extending measurements longitudinally along entire river networks and improving estimates of global riverine nitrogen loads.     

Nitrogen yield advantage from grass–legume mixtures is robust over a wide range of legume proportions and environmental conditions

Current challenges to global food security require sustainable intensification of agriculture through initiatives that include more efficient use of nitrogen (N), increased protein self‐sufficiency through homegrown crops, and reduced N losses to the environment. Such challenges were addressed in a continental‐scale field experiment conducted over 3 years, in which the amount of total nitrogen yield (N_tot) and the gain of N yield in mixtures as compared to grass monocultures (N_gainmix) was quantified from four‐species grass–legume stands with greatly varying legume proportions. Stands consisted of monocultures and mixtures of two N₂‐fixing legumes and two nonfixing grasses. The amount of N_tot of mixtures was significantly greater (P ≤ 0.05) than that of grass monocultures at the majority of evaluated sites in all 3 years. N_tot and thus N_gainmix increased with increasing legume proportion up to one‐third of legumes. With higher legume percentages, N_tot and N_gainmix did not continue to increase. Thus, across sites and years, mixtures with one‐third proportion of legumes attained ~95% of the maximum N_tot acquired by any stand and had 57% higher N_tot than grass monocultures. Realized legume proportion in stands and the relative N gain in mixture (N_gainmix/N_tot in mixture) were most severely impaired by minimum site temperature (R = 0.70, P = 0.003 for legume proportion; R = 0.64, P = 0.010 for N_gainmix/N_tot in mixture). Nevertheless, the relative N gain in mixture was not correlated to site productivity (P = 0.500), suggesting that, within climatic restrictions, balanced grass–legume mixtures can benefit from comparable relative gains in N yield across largely differing productivity levels. We conclude that the use of grass–legume mixtures can substantially contribute to resource‐efficient agricultural grassland systems over a wide range of productivity levels, implying important savings in N fertilizers and thus greenhouse gas emissions and a considerable potential for climate change mitigation.