Oxygen exchange between nitrogen oxides and H2O can occur during nitrifier pathways

Interpretation of the oxygen isotopic signature of soil-derived N₂O may be flawed when it is based on reaction stoichiometry and fractionation alone. In fact, oxygen (O) exchange between H₂O and intermediates of N₂O production pathways may largely determine this O isotopic signature. Although in our previous work we conclusively proved the occurrence of O exchange during N₂O production by denitrification of NO₃⁻, its occurrence in N₂O production pathways by nitrifiers remains unclear. The aim of this study was to examine the likeliness of O exchange during various stages of N₂O production in soil via nitrification, nitrifier denitrification and denitrification. We evaluated a set of scenarios on the presence of such exchange using data from a series of ¹⁸O and ¹⁵N tracing experiments. The measured actual O incorporation from H₂O into N₂O (AOI) was compared with the theoretical maximum O incorporation (MOI) from various scenarios that differed in their assumptions on the presence of O exchange. We found that scenarios where O exchange was assumed to occur exclusively during denitrification could not explain the observed AOI, as it exceeded the MOI for 9 out of 10 soils. This demonstrates that additional O exchange must have occurred in N₂O production through nitrifier pathways. It remains to be determined in which steps of these pathways O exchange can take place. We conclude that O exchange is likely to be mediated by ammonia oxidizers during NO₂⁻ reduction (nitrifier denitrification), and that it could possibly occur during NO₂⁻ oxidation to NO₃⁻ by nitrite oxidizers as well.     

Tracing sources of soil nitrate using the dual isotopic composition of nitrate in 2 M KCl-extracts

Soils comprise a critical interface between the atmosphere, lithosphere, hydrosphere and biosphere, and play a major role in the cycling of nitrogen (N), an element crucial to plant growth. Isotope techniques constitute a powerful tool to study the origin and fate of N compounds (e.g. NO₃⁻) within the environment including soils. The objective of our study was to test the usefulness of the isotope composition of soil NO₃⁻ extracted with 2 M KCl (soil NO₃) as a tool to investigate the origin and fate of NO₃⁻ in the environment. Specifically issues related to repeat extractions, crop type, length of fertilization, and soil depth were addressed. Soils from four contrasting agricultural management regimes were sampled. Within the relatively confined study area (4 ha), the isotopic compositions of soil NO₃ differed markedly due to management treatments (up to 6 and 17‰ for δ¹⁵N and δ¹⁸O, respectively), but were repeatable among replicate plots (±1‰). Differences in both δ¹⁵N and δ¹⁸O values were observed between legume and non-legume treatments, as well as fertilized versus non-fertilized treatments, which were larger than the variability observed between replicate plots. Differences in the isotopic composition of extractable soil nitrate were not limited to the surface layer, but also occurred within deeper soil layers. This study indicates that the analysis of the natural abundance stable isotope composition of soil NO₃ may provide a promising additional tool for tracing the origin and fate of NO₃⁻ in the soil zone.     

Identifying resource competition in maize-based soil conservation systems using 13C and 15N isotopic discrimination

Soil conservation measures such as establishing grass barriers or cover crops effectively control erosion but also provoke competition, which reduces yields of companion crops. We used ¹³C and ¹⁵N natural abundance profiles to identify the causes of competition of soil conservation measures on a field with 59% slope in Northwest Vietnam three years after establishment. Treatments were maize under farmer’s practice (T1, control), maize with Guinea grass barriers (T2), maize under minimum tillage (MT) with Pinto peanuts as cover crop (T3), and maize under MT and relay cropped with Adzuki beans (T4). A pretest using data from zero-N plots revealed that abundance of water and limited nitrogen availability induced low grain N concentrations, enriched leaf δ¹³C, and reduced maize grain yield. Similar low N leaf concentrations and elevated δ¹³C values were observed in maize growing close to frequently pruned grass barriers under positive water balance conditions, indicating that yield decline in these rows can be attributed mainly to N competition. Enriched δ¹⁵N values of maize from rows next to barriers indicated reliance on soil N rather than on ¹⁵N-depleted fertiliser N. Vigorous cover crop growth under MT resulted in maize yield decline due to N competition while relay-cropped legumes did not trigger inter-species competition having a similar maize yield, leaf N concentration, δ¹³C, and δ¹⁵N as the control.     

A proposed use of ion exchange resins to measure nitrogen mineralization and nitrification in intact soil cores

Abstract

A procedure is proposed for measuring nitrogen mineralization and nitrification in intact soil cores. The method relies on ion exchange resins to trap ammonium and nitrate entering and leaving cores of soil otherwise open at the top and bottom. Changes in soil concentrations plus an accounting of ions trapped by the lower resin after field incubations, indicate rates of nitrogen reactions. Using this technique, we estimated net ammonification rates from 0–36 mg N/kg/mo and nitrification rates from 0–16 mg N/kg/mo for the surface of a sandy, low nutrient soil under pine cultivation in north Florida; higher rates occurred after urea fertilization. The procedure has potential advantages over others, but must be more fully evaluated under a variety of conditions.     

Phosphate interference in the Devarda's alloy reduction method for nitrate

Abstract

Phosphate interfered markedly with a Devarda's alloy distillation method for the determination of nitrate. Only 9% of added nitrate was recovered by this method when 200 mg P was present. This interference can be overcome by the addition of calcium ions, to precipitate the phosphate, and an extended distillation time.     

Turnover of interlayer ammonium in loess-derived soil grown with winter wheat in the Shaanxi Province of China

Summary The turnover of interlayer NH _inf4 ^sup+ in a loess-derived agricultural soil from the Shaanxi Province in China was studied. The concentration of ¹⁵N-labeled interlayer NH _inf4 ^sup+ and total interlayer NH _inf4 ^sup+ (labeled + unlabeled) in a soil grown with winter wheat was significantly higher at the beginning of the season (March) than when the crop was mature (June). In a further experiment with winter wheat it was shown that under field conditions the concentration of interlayer NH _inf4 ^sup+ decreased significantly in the two upper soil layers (0–20 and 20–55 cm) during March and in the deeper soil layer (55–75 cm) during April. When the heading stage of wheat was reached, about 200 kg N ha^-1 of interlayer NH _inf4 ^sup+ had been released. During the following growth period (heading until flowering of wheat) the concentration of interlayer NH _inf4 ^sup+ increased significantly in the upper soil layers. Fertilizer application in the form of 70 kg N ha^-1 as urea led to a considerable increase in the nitrate concentration in the upper soil layer but had no influence on the level of interlayer NH _inf4 ^sup+ concentration. It is concluded that interlayer NH _inf4 ^sup+ takes part in the N cycle of the soil and that it contributes to the N nutrition of the crop. NH _inf4 ^sup+ originating from the mineralization of soil organic N may be rapidly incorporated into the interlayer of clay minerals and later released, when the N demand of the crop is high.     

Control of soil solution interferences in an automated nitrate method

Abstract

An AutoAnalyzer method for nitrate nitrogen based on hydrazine reduction followed by diazotization was re‐examined after certain soil solutions had given poor recoveries. Modifications to the reaction parameters, particularly in the reduction stage improved the recovery of nitrate as nitrite. Soluble organic compounds in the samples were more critical than inorganic salts, but the proposed method allowed tolerance of up to 30 mgl^‐1 total organic carbon. Concentrations of various inorganic ions in soil solutions and natural waters were usually below the limits shown to be critical for the improved method.     

Effects of nitrification inhibitors on denitrification of nitrate in soil

Summary The influence of 28 nitrification inhibitors on denitrification of nitrate in soil was studied by determining the effects of different amounts of each inhibitor on the amounts of nitrate lost and the amounts of nitrite, N₂O and N₂ produced when soil samples were incubated anaerobically after treatment with nitrate or with nitrate and mannitol. The inhibitors used included nitrapyrin (N-Serve), etridiazole (Dwell), potassium azide, 2-amino-4-chloro-6-methylpyrimidine (AM), sulfathiazole (ST), 4-amino-1,2,4-triazole(ATC),2,4-diamino-6-trichloromethyl-s-triazine (CL-1580), potassium ethylxanthate, guanylthiourea (ASU), 4-nitrobenzotrichloride, 4-mesylbenzotrichloride, sodium thiocarbonate (STC), phenylmercuric acetate (PMA), and dicyandiamide (DCD).Only one of the nitrification inhibitors studied (potassium azide) retarded denitrification when applied at the rate of 10 g g^–1 soil, and only two (potassium azide and 2,4-diamino-6-trichloromethyl-s-triazine) inhibited denitrification when applied at the rate of 50 g g^–1 soil. The other inhibitors either had no appreciable effect on denitrification, or enhanced denitrification, when applied at the rate of 10 or 50 g g^–1 soil, enhancement being most marked with 3-mercapto-1,2,4-triazole. Seven of the inhibitors (potassium azide, sulfathiazole, potassium ethylxanthate, sodium isopropylxanthate, 4-nitrobenzotrichloride, sodium thiocarbonate, and phenylmercuric acetate) retarded denitrification when applied at the rate of 50 g g^–1 soil to soil that had been amended with mannitol to promote microbial activity.Reports that nitrapyrin (N-Serve) and etridiazole (Dwell) inhibit denitrification when applied at rates as low as 0.5 g g^–1 soil could not be confirmed. No inhibition of denitrification was observed when these compounds were applied at the rate of 10 g g^–1 soil, and enhancement of denitrification was observed when they were applied at the rate of 50 or 100 g g^–1 soil.     

Constraining the conditions conducive to dissimilatory nitrate reduction to ammonium in temperate arable soils

Here we offer the first assessment of conditions conducive to dissimilatory nitrate reduction to ammonium (DNRA) in temperate arable soils, through an examination of the potential for this process to occur in a range of soils of contrasting characteristics. NH₄¹⁵NO₃ (6.2 g N m⁻², 25 atom % excess ¹⁵N) was applied, and recovery of ¹⁵N in the pool taken as indicative of occurrence of DNRA. Up to 5% of applied ¹⁵N was recovered in the pool 2 d after addition of N, glucose (44.6 g C m⁻²) and l-cysteine (7.7 g m⁻², 0.9 g N m⁻², 2.3 g C m⁻²). concentrations were positively correlated with soil pH, ratio, bulk density, sand content and concentration, but negatively correlated with soil C and organic N content. Our results demonstrate the potential for DNRA to contribute to N cycling in temperate arable soils, but its detection and significance is likely to depend on the provision of a low molecular weight C source.     

高产农田土壤硝态氮淋失与地下水污染动态研究

对桓台县区域农田监测研究表明,水肥管理不同的2个监测区域郭家区、李家区高产农田土体内NO_3~--N淋失迁移动态有差异,地下水污染亦不同。春天始土体内NO_3~--N含量趋于持续降低,浅层地下水NO_3~--N含量则持续升高,雨季后地下水中NO_3~--N含量尤剧烈升高,并达年内最高值,表现出农田N肥对地下水的直接污染,这可能与李家区灌溉次数多、土壤质地较轻和地下水位较浅有关。     

Determination of N in lignin together with nitrite or nitrate

Summary Various methods were used to determine N in lignin, both directly and in buffered aqueous solutions (pH 7.0 and 5.5) containing lignin and NO ₂ ^\t or lignin and NO ₃ ^·t . The percentage recovery of N was highly variable, being dependent on the analytical method and on pH. There appeared to be a reaction between lignin and NO ₂ ^·t or NO ₃ ^·t during the analytical procedure. The Kjeldahl method achieved a higher recovery of organic N from pure lignin than the persulphate method, but it showed a higher coefficient of variation. In buffered samples containing lignin together with NO ₂ ^·t or NO ₃ ^·t , recoveries of NO ₂ ^·t and NO ₃ ^·t were considerably lower for the Montgomery and Dymock and the Devarda methods than for the procedure using an auto-analyzer. The former procedures appeared to fix NO _x ^·t . With the auto-analyzer and the Devarda methods, recovery was increased with increasing pH values. The Kjeldahl method gave very high standard deviations. It proved unreliable for the analysis of organic N in samples containing both lignin and NO _x ^·t . During the persulphate analysis, significant N losses were calculated, probably because of acid-induced nitrosation or nitration and subsequent volatilization of N during the persulphate analysis itself.     

Effect of Two Nitrogen Forms on the Growth and Iron Nutrition of Pea Cultivated in Presence of Bicarbonate

ABSTRACT

Two cultivars of pea: ‘PS210713’ (‘PS’), sensitive to iron deficiency, and ‘Marveille de Kelvedon’ (‘MK’), tolerant, were cultivated in controlled climatic conditions during one month, on a nutrient solution containing either nitrate (NO₃ ^?, 4 mM) or ammonium (NH₄ ⁺, 4 mM) and in the presence of bicarbonate (10 mM). The effects of these nitrogen forms on the growth and the mineral nutrition, and especially iron nutrition are analyzed.

The reduction of growth by bicarbonate was approximately 30% in case of NO₃ ^? nutrition in the two cultivars, whereas in ammoniacal treatment the reduction is only 6% and 18% respectively in ‘PS’ and ‘MK’ cultivars.

In presence of bicarbonate, the plant growth is not stimulated by NO₃ ^?relatively to its growth on ammoniacal medium, as often noticed when plants are cultivated on medium without bicarbonate: In presence of this compound, the biomass production of plant pea, was not influenced by the nitrogen forms. The nitric source led to a ferric chlorosis in the sensitive cultivar plants whereas any chlorosis was noted when ammoniacal source was applied. On the other hand, nitric nitrogen form decreased the nitrogen feeding of plants and increased the potassium one, while the effect of the ammoniacal nitrogen form on these nutrients was quite the inverse. In addition, the later increased the allocation of iron towards shoots. Besides, with this nitrogen source there was not accumulation of nitrate in the plant tissues. In nitric feeding case, the nitrate is mainly accumulated in the roots of the two cultivars. It is noticeable that the sensitive cultivar (‘PS’) accumulates three times more nitrate than the tolerant one (‘MK’).

On the level of the whole plant, the iron and phosphorus nutrition seems unaltered by the nitrogen form.     

Nitrogen isotopic composition of leached nitrate and soil organic matter as an indicator of denitrification in a sloping drained agricultural plot and adjacent uncultivated riparian buffer strips

In the small, agricultural, artificially drained Orgeval watershed δ¹⁵N values of leached nitrates and soil organic nitrogen were found to be significantly higher than the primary nitrogen (N) sources from which they are derived, namely, synthetic fertilizers, atmospheric deposition, and symbiotic or nonsymbiotic N₂ fixation (all with δ¹⁵N close to zero). In vertical soil profiles, the δ¹⁵N of organic N increased with depth, reaching higher values (up to 8‰) particularly at stations that were frequently waterlogged as judged from ochre iron traces, such as downhill field sites or in riparian buffer strips. Nitrification, volatilization, and denitrification are the main fractionating processes able to modify the isotopic composition of soil N. Using a newly designed algorithm for calculating the equilibrium isotopic composition of all soil N species, resulting from the average annual balance of their transformations, we show that the observed trends can be explained by the action of denitrification. We suggest that the isotopic composition of soil organic N can be used as a semiquantitative indicator of the intensity of denitrification integrated over century-long periods.     

An evaluation of some manual colorimetric methods for the determination of inorganic nitrogen in soil extracts

Abstract

A number of manual colorimetric methods for the determination of inorganic nitrogen in 1 M KCl soil extracts were investigated to find techniques that were inexpensive, rapid, versatile and suitable for laboratories with limited analytical equipment. Three colorimetric methods for No^? ₃‐N determination were evaluated and only the copperised/cadmium reduction technique suffered no significant interference from the Cl^? present in the extracting solution. A phenol‐hypo‐chlorite (Berthelot) procedure for NH⁺ ₄‐N determination and the Griess‐Ilosvay method for NO^? ₂‐N determination were both found suitable for N determination in 1M KC1 soil extracts. The reliability and accuracy obtainable with the manual colorimetric methods described was shown to be comparable with that obtained from colorimetric analyses performed using an AutoAnalyser.     

快速检测土壤阳离子交换量的研究

针对土壤阳离子交换量检测行业标准推荐方法耗时长、操作繁琐,介绍了一种定氮仪配合漩涡振荡仪测定土壤阳离子交换量的快速蒸馏法,改进了离心处理环节和蒸馏步骤,讨论了关键流程和注意事项。该方法与行业标准乙酸铵法相比,试剂消耗明显减少,检测效率提高45%,检测精度和准确度符合标准要求,特别适于大批量及快速检出的土壤样品分析。     

Effect of convection on the exchange coefficient of oxygen and estimation of net production rate of oxygen in ponded water of a paddy field

Abstract

Dissolved oxygen (DO) in ponded water is essential to biological activities in paddy fields. DO concentrations results from the balance among photosynthesis, respiration, and exchange of oxygen between the atmosphere and water, all of which show daily changes. For the estimation of the net production rate of oxygen that is the overall response of photosynthesis and respiration, it is necessary to determine the exchange rate of oxygen between the atmosphere and water. The exchange of oxygen occurs in the form of reaeration and deaeration in the paddy fields. The exchange coefficients of reaeration and deaeration were determined in the laboratory considering field conditions. The coefficients of reaeration and deaeration were not identical. Both coefficients increased as the convective velocity in the water increased. It was considered that the convection in bulk water reduced the thickness of the water film at the air-water interface and increased the exchange coefficient. The reaeration and de aeration coefficients ranged from 2.1 to 2.4 and 5.7 to 6.3 d^?1, respectively. The rates of reaeration and de aeration were estimated using these exchange coefficients. The exchange rate was not constant in the paddy field throughout the day but varied with the convection, water temperature, and the degree of saturation in the ponded water. Taking these factors into consideration, the net production rate was estimated from the DO mass balance. The net production rate was positive from 5 : 30 to 15 : 30 and negative in the other part of the day. These results and analytical methods would contribute to the understanding of the physical, chemical, and biological processes in a paddy field.     

Responses of net ecosystem CO2 exchange to nitrogen fertilization in experimentally manipulated grassland ecosystems

Nitrogen (N) addition enhances primary productivity of terrestrial ecosystems. However, the effects of N fertilization and/or deposition on net ecosystem CO₂ exchange (NEE) are not fully understood. The effects of N on NEE were investigated in two experimental cheatgrass ecosystems in Ecologically Controlled Enclosed Lysimeter Laboratories (EcoCELLs), Reno, Nevada. In this experiment, no N fertilization was added to the two EcoCELLs in the first year and two different N fertilization regimes were applied in the second year. N fertilizer was applied once to one EcoCELL (pulse fertilization, PF), and the same total amount of N in biweekly increments to the other EcoCell (gradual fertilization, GF). NEE, photosynthetically active radiation (PAR) and canopy green leaf area index (LAI) were continuously measured in the two EcoCELLs during the pretreatment and N-fertilized years. Plant N content and biomass were measured at the end of the growing season in each year. Radiation-use efficiency (RUE_CO2) was calculated as the ratio of gross ecosystem photosynthesis (GEP) to the intercepted photosynthetically active radiation (IPAR). The responses of NEE to IPAR were used to estimate the maximum ecosystem photosynthetic capacity (F_max). N fertilization stimulated canopy LAI, plant N content, F_max, RUE_CO2, NEE and biomass in both methods of N supply applications. PF led to higher LAI, F_max and NEE than GF, but both had a similar RUE_CO2 during the early growing season. GF maintained higher LAI, F_max, RUE_CO2 and NEE than PF during the late growing season. At the ecosystem level, N fertilization stimulated daily NEE directly by increasing canopy LAI, plant N content, shoot/root ratio and the maximum ecosystem photosynthetic capacity, and increased the seasonally accumulated NEE indirectly by extending the growing season. PF differed significantly from GF in its effects on NEE and RUE_CO2, possibly due to differential rates and timing of N availability. Our study suggested that these changes in the canopy RUE_CO2 and growing season under N fertilization or N deposition regimes should be considered in modeling studies of ecosystem C sequestration.     

Effects of cloudiness change on net ecosystem exchange, light use efficiency, and water use efficiency in typical ecosystems of China

As a weather element, clouds can affect CO₂ exchange between terrestrial ecosystems and the atmosphere by altering environmental conditions, such as solar radiation received on the ground surface, temperature, and moisture. Based on the flux data measured at five typical ecosystems of China during mid-growing season (June-August) from 2003 to 2006, we analyzed the responses of net ecosystem exchange of carbon dioxide (NEE), light use efficiency (LUE, defined as Gross ecosystem photosynthesis (GEP)/Photosynthetically active radiation (PAR)), and water use efficiency (WUE, defined as GEP/Evapotranspiration (ET)) to the changes in cloudiness. The five ecological sites included Changbaishan temperate mixed forest (CBS), Dinghushan subtropical evergreen broad-leaved forest (DHS), Xishuangbanna tropical rainforest (XSBN), Inner Mongolia semi-arid Leymus chinensis steppe (NMG), and Haibei alpine frigid Potentilla fruticosa shrub (HB). Our analyses show that cloudy sky conditions with cloud index (k_t) values between 0.4 and 0.6 increased NEE, LUE, and WUE of the ecosystems at CBS, DHS, NMG and HB from June to August. The LUE of tropical rainforest at XSBN was higher under cloudy than under clear sky conditions, but NEE and WUE did not decrease significantly under clear sky conditions from June to August. The increase in GEP with increasing diffuse radiation received by ecosystems under cloudy skies was the main reason that caused the increases in LUE and net carbon uptake in forest ecosystem at CBS, DHS, and alpine shrub ecosystem at HB, compared with clear skies. Moreover, for the ecosystem at CBS, DHS, and HB, when sky condition became from clear to cloudy, GEP increased and ET decreased with decreasing VPD, leading to the increase in WUE and NEE under cloudy sky conditions. The decrease in R_e with decreasing temperature and increase in GEP with decreasing VPD under cloudy skies led to the increase in LUE, WUE, and net carbon uptake of semi-arid steppe at NMG, compared to clear skies. These different responses among the five ecosystems are attributable to the differences in canopy characteristics and water conditions. From June to August, the peaks of the k_t frequency distribution in temperate ecosystems (e.g., CBS, NMG, and HB) were larger than 0.5, but they were smaller than 0.4 in subtropical/tropical forest ecosystems (e.g., DHS and XSBN). These results suggest that the pattern of cloudiness during the years from 2003 to 2006 in the five ecosystems was not the best condition for their net carbon uptake. This study highlights the importance of cloudiness factor in the prediction of net carbon absorption in the Asia monsoon region under climate change.     

Three approaches to the simulation of the self-diffusion and non-instantaneous isotopic exchange of phosphate in soil

Three models of the self-diffusion of phosphate in moist soil are presented, and their predictions compared to experimental data. The latter appeared to show that isotopic exchange was limited by access to exchange sites. The apparent rate of access was first described by a series of first-order reactions, then as the diffusion of isotope into, and within, uniformly distributed, porous spherical aggregates, where the majority of exchange sites were situated, and finally as an Nth order ( N 1) reversible reaction. All models were solved using Crank-Nicolson finite difference methods.
The first two gave similar predictions; they were not capable of giving an adequate fit to experimental results. The third, although purely an empirical model, not based on a possible mechanism, was able to simulate data well.
The mechanistic implications of each model, and of its relative success in simulating phosphate diffusion are discussed.     

离子交换树脂在土壤养分测试中的研究进展

概述了在农业领域中应用离子交换树脂获取土壤养分含量的研究进展,探讨了树脂的预处理方法、使用形式以及提取土壤养分的基本操作和影响因素,同时提出该技术在提取土壤养分中的应用前景及需要解决的问题。