Gross and net nitrogen transformation rates and availability in late summer in tall shrub and birch hummock ecosystems of the Canadian low Arctic

Climate change is occurring most rapidly in the Arctic where warming has been twice as fast as the rest of the globe over the last few decades. Arctic soils contain a vast store of carbon and warmer arctic soils may mediate current atmospheric CO2 concentrations and global warming trends. Warmer soils could increase nutrient availability to plants, leading to increased primary production and sequestration of CO2. Presumably because of these effects of warming on shrub ecosystems, shrubs have been expanding across the arctic over the last 50 years, Arctic shrub expansion may track or cause changes in nutrient cycling and availability that favour growth of larger, denser shrubs. This study aimed at measuring gross and net nitrogen cycling rates, major soil nitrogen and carbon pool sizes, and elucidating controls on nutrient cycling and availability between a mesic birch (Betula nana) hummock tundra ecosystem and an ecosystem of dense, tall, birch (B. nana) shrubs. Nitrogen cycling and availability was enhanced at the tall shrub ecosystem compared to the birch hummock ecosystem. Net nitrogen immobilization by microbes was approximately threefold greater at the tall shrub ecosystem. This was in part because of larger microbial biomass nitrogen and carbon (interpreted as a larger microbial community) at the tall shrub ecosystem. Nitrogen inputs via litter were significantly larger at the tall shrub ecosystem and were hypothesized to be the major contributor to the higher dissolved organic and inorganic nitrogen pools in the soil at the tall shrub ecosystem. The results from this study suggest a positive feedback mechanism between litter nitrogen inputs and the enhancement of nitrogen cycling and availability as a driver of shrub expansion across the Arctic.

Sensitivity analysis of a catchment-scale nitrogen model

There are now considerable expectations that semi-distributed models are useful tools for supporting catchment water quality management. However, insufficient attention has been given to evaluating the uncertainties inherent to this type of model, especially those associated with the spatial disaggregation of the catchment. The Integrated Nitrogen in Catchments model (INCA) is subjected to an extensive regionalised sensitivity analysis in application to the River Kennet, part of the groundwater-dominated upper Thames catchment, UK The main results are: (1) model output was generally insensitive to land-phase parameters, very sensitive to groundwater parameters, including initial conditions, and significantly sensitive to in-river parameters; (2) INCA was able to produce good fits simultaneously to the available flow, nitrate and ammonium in-river data sets; (3) representing parameters as heterogeneous over the catchment (206 calibrated parameters) rather than homogeneous (24 calibrated parameters) produced a significant improvement in fit to nitrate but no significant improvement to flow and caused a deterioration in ammonium performance; (4) the analysis indicated that calibrating the flow-related parameters first, then calibrating the remaining parameters (as opposed to calibrating all parameters together) was not a sensible strategy in this case; (5) even the parameters to which the model output was most sensitive suffered from high uncertainty due to spatial inconsistencies in the estimated optimum values, parameter equifinality and the sampling error associated with the calibration method; (6) soil and groundwater nutrient and flow data are needed to reduce. uncertainty in initial conditions, residence times and nitrogen transformation parameters, and long-term historic data are needed so that key responses to changes in land-use management can be assimilated. The results indicate the general, difficulty of reconciling the questions which catchment nutrient models are expected to answer with typically limited data sets and limited knowledge about suitable model structures. The results demonstrate the importance of analysing semi-distributed model uncertainties prior to model application, and illustrate the value and limitations of using Monte Carlo-based methods for doing so. (c) 2005 Elsevier B.V. All rights reserved.

Nitrogen cycling driven by organic matter export in the South Pacific oxygen minimum zone

Oxygen minimum zones are expanding globally, and at present account for around 20-40% of oceanic nitrogen loss. Heterotrophic denitrification and anammox-anaerobic ammonium oxidation with nitrite-are responsible for most nitrogen loss in these low-oxygen waters. Anammox is particularly significant in the eastern tropical South Pacific, one of the largest oxygen minimum zones globally. However, the factors that regulate anammox-driven nitrogen loss have remained unclear. Here, we present a comprehensive nitrogen budget for the eastern tropical South Pacific oxygen minimum zone, using measurements of nutrient concentrations, experimentally determined rates of nitrogen transformation and a numerical model of export production. Anammox was the dominant mode of nitrogen loss at the time of sampling. Rates of anammox, and related nitrogen transformations, were greatest in the productive shelf waters, and tailed off with distance from the coast. Within the shelf region, anammox activity peaked in both upper and bottom waters. Overall, rates of nitrogen transformation, including anammox, were strongly correlated with the export of organic matter. We suggest that the sinking of organic matter, and thus the release of ammonium into the water column, together with benthic ammonium release, fuel nitrogen loss from oxygen minimum zones.

北方农牧交错区土地利用（管理）方式对土壤氮素转化的影响

土壤氮素矿化是陆地生态系统氮素转化的重要组成部分。不同的土地利用（管理）方式会改变土壤氮素转化过程，影响土壤肥力的保持，进而可能造成土壤内氮素渗漏流失。为系统了解内蒙古农牧交错区土壤氮素转化的特点，本实验采用原位培养顶盖埋管法进行野外培养，每间隔一个月定期取样，于2004年7月-2006年10月在植物所恢复生态学实验站进行了两个试验，1：选择农牧交错区四种有代表性的土地类型（围封样地：FS，放牧样地：GS，弃耕地：AF，和农田：CF），比较土地利用方式之间氮素矿化的异同;2：在施肥样地通过不同施肥处理(F0: 1g N m-2, F1: 1g N m-2, F2: 2g N m-2, F3: 4g N m-2, F4: 8g N m-2, F5: 16g N m-2, F6: 32g N m-2, F7: 64g N m-2) 的土壤氮素转化动态，确定过度放牧的典型草原围封禁牧后，植被恢复过程中最适宜的施肥量。主要结论如下： 1. 与试验初期相比，整个非生长季围封样地、弃耕地和农田的铵态氮和无机氮含量逐渐降低，培养结束时铵态氮含量分别减少了67.04％，77.31％和70.54％，而放牧地的含量增加1.63％。围封样地、放牧地、弃耕地和农田的硝态氮含量分别增加了61.61%，376.43%，199.75%和133.16%。非生长季四种土地类型的土壤氮素转化速率主要受温度影响。围封样地、放牧地、弃耕地和农田非生长季矿化速率均值分别为-0.016，0.0429，-0.0051和-0.0030 μg g-1 d-1。硝化速率均值变幅为-0.43-0.17 μg g-1d-1。 2. 与没有冷冻而融化的土壤相比，冻融显著影响土壤无机氮含量的变化。只有在较低的土壤温度条件下冷冻以后，融化才会促进土壤氮素矿化。不同的冷冻时间长度下融化均会促进土壤硝化速率。土壤温度、土壤含水量变化是影响氮素转化速率的重要因子。 3. 四种土地类型的年日均矿化速率为放牧样地>农田>弃耕地>围封样地，分别为0.25，0.11，0.10，0.06μg g-1d-1，其年平均速率分别为11.65，5.50，5.00和2.46g m-2 y-1，而年日平均硝化速率分别为0.27，0.095，0.097和0.05μg g-1d-1。其中生长季日均矿化速率和日均硝化速率均为其年日均速率的两倍。因此，生长季形成的矿化氮是全年的93％，而形成的硝态氮占全年的86％。四种土地类型年均矿化氮的累积量平均为615.04 kg ha-1，而硝化作用的累积量变幅为230.44-1218.86 kg ha-1。四种土地类型的矿化速率和硝化速率的季节动态变化与气候因子的变化一致。 4. 不同施肥处理对典型草原土壤氮素转化均有显著影响。与对照相比，少量施肥（F1，F2）土壤铵态氮，硝态氮和无机氮含量分别减少20.57％，11.18％和17.18％。当施肥量大于F4（8g N m-2）时，随施肥量增加土壤铵态氮，硝态氮和无机氮含量增加18％-1191％。除F5（16g N m-2）外，与对照相比，随施肥量增加，土壤矿化速率增加了5-21倍。4 g N m-2 (F3)左右是典型草原生态系统比较合适的施肥量。 5. 氨气挥发速率的季节动态特征与气象因子的变化一致，其速率变幅为17.65 - 1228.39µg m-2 d-1，其中7月挥发量占全年的37％。与对照相比，少量施肥氨气挥发速率降低了1-2％，施肥量大于F3 (4g N m-2)，速率增加了1-4倍。实验期间总的流失量变幅为23.76-84.91mg m-2，而且通过氨气挥发流失量低于土壤全氮的3%。氨气挥发不是典型草原过量氮素流失的主要方式。 6. 氮素限制的典型草原，植被恢复过程中外源氮素添加阈值为：4 g N m-2 (F3)。与对照相比，短期施肥（3年）不会显著影响根系碳储量和土壤碳氮储量。施肥处理的土壤硝态氮和无机氮含量显著增加，说明施肥显著刺激硝化作用。典型草原60%植物根系主要分布在地下0-10cm，这里的碳储量占地下储量（0-50cm）的63%以上。随土壤深度增加，土壤全氮，全碳，无机氮储量降低。而铵态氮储量和可利用的无机氮含量随土壤深度增加，说明植物根系主要吸收利用上层可利用氮素，而且下层氮素矿化速率降低。

Bioturbation determines the response of benthic ammonia-oxidizing microorganisms to ocean acidification

Ocean acidification (OA), caused by the dissolution of increasing concentrations of atmospheric carbon dioxide (CO2) in seawater, is projected to cause significant changes to marine ecology and biogeochemistry. Potential impacts on the microbially driven cycling of nitrogen are of particular concern. Specifically, under seawater pH levels approximating future OA scenarios, rates of ammonia oxidation (the rate-limiting first step of the nitrification pathway) have been shown to dramatically decrease in seawater, but not in underlying sediments. However, no prior study has considered the interactive effects of microbial ammonia oxidation and macrofaunal bioturbation activity, which can enhance nitrogen transformation rates. Using experimental mesocosms, we investigated the responses to OA of ammonia oxidizing microorganisms inhabiting surface sediments and sediments within burrow walls of the mud shrimp Upogebia deltaura. Seawater was acidified to one of four target pH values (pHT 7.90, 7.70, 7.35 and 6.80) in comparison with a control (pHT 8.10). At pHT 8.10, ammonia oxidation rates in burrow wall sediments were, on average, fivefold greater than in surface sediments. However, at all acidified pH values (pH < = 7.90), ammonia oxidation rates in burrow sediments were significantly inhibited (by 79-97%; p < 0.01), whereas rates in surface sediments were unaffected. Both bacterial and archaeal abundances increased significantly as pHT declined; by contrast, relative abundances of bacterial and archaeal ammonia oxidation (amoA) genes did not vary. This research suggests that OA could cause substantial reductions in total benthic ammonia oxidation rates in coastal bioturbated sediments, leading to corresponding changes in coupled nitrogen cycling between the benthic and pelagic realms.

A novel oxidative transformation of alcohols to nitriles: an efficient utility of azides as a nitrogen source

An efficient methodology to oxidize benzylic and cinnamyl alcohols to their corresponding nitriles in excellent yields has been developed. This methodology employs DDQ as an oxidant and TMSN3 as a source of nitrogen in the presence of a catalytic amount of Cu(ClO4)(2)center dot 6H(2)O.

Copper-Catalyzed Direct Transformation of Secondary Allylic and Benzylic Alcohols into Azides and Amides: An Efficient Utility of Azide as a Nitrogen Source

A mild and convenient method for the synthesis of amides has been explored by using secondary alcohols, Cu(ClO4)(2)6H(2)O as a catalyst, and trimethylsilyl azide (TMSN3) as a nitrogen source in the presence of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) at ambient temperature. This method has been successfully adapted to the preparation of azides directly from their corresponding alcohols and offers excellent chemoselectivity in the formation of -halo azides and the azidation of allylic alcohols in the presence of a benzyl alcohol moiety. In addition, this strategy provides an opportunity to synthesize azides that can serve as precursors to -amino acids.

Ecological stoichiometry controls the transformation and retention of plant-derived organic matter to humus in response to nitrogen fertilisation

Carbon (C) sequestration in soils is a means for increasing soil organic carbon (SOC) stocks and is a potential tool for climate change mitigation. One recommended management practice to increase SOC stocks is nitrogen (N) fertilisation, however examples of positive, negative or null SOC effects in response to N addition exist. We evaluated the relative importance of plant molecular structure, soil physical properties and soil ecological stoichiometry in explaining the retention of SOC with and without N addition. We tracked the transformation of 13C pulse-labelled buffel grass (Cenchrus ciliaris L.), wheat (Triticum aestivum L.) and lucerne (Medicago sativa L.) material to the <53 μm silt + clay soil organic C fraction, hereafter named “humus”, over 365-days of incubation in four contrasting agricultural soils, with and without urea-N addition. We hypothesised that: a) humus retention would be soil and litter dependent; b) humus retention would be litter independent once litter C:N ratios were standardised with urea-N addition; and c) humus retention would be improved by urea-N addition. Two and three-way factorial analysis of variance indicated that 13C humus was consistently soil and litter dependent, even when litter C:N ratios were standardised, and that the effect of urea-N addition on 13C humus was also soil and litter dependent. A boosted regression analysis of the effect of 44 plant and soil explanatory variables demonstrated that soil biological and chemical properties had the greatest relative influence on 13C humus. Regression tree analyses demonstrated that the greatest gains in 13C humus occurred in soils of relatively low total organic C, dissolved organic C and microbial biomass C (MBC), or with a combination of relatively high MBC and low C:N ratio. The greatest losses in 13C humus occurred in soils with a combination of relatively high MBC and low total N or increasing C:N ratio. We conclude that soil variables involved in soil ecological stoichiometry exert a greater relative influence on incorporating organic matter as humus compared to plant molecular structure and soil physical properties. Furthermore, we conclude that the effect of N fertilisation on humus retention is dependent upon soil ecological stoichiometry.

Conversion of n-type CuTCNQ into p-type nitrogen-doped CuO and the implication for room temperature gas sensing

Sensors to detect toxic and harmful gases are usually based on metal oxides that are operated at elevated temperature. However, enabling gas detection at room temperature (RT) is a significant ongoing challenge. Here, we address this issue by demonstrating that microrods of semiconducting CuTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) with nanostructured features can be employed as conductometric gas sensors operating at 50°C for detection of oxidizing and reducing gases such as NO2 and NH3. The sensor is evaluated at RT and up to 200°C. It was found that CuTCNQ is transformed into a N-doped CuO material with p-type conductivity when annealed at the maximum temperature. This is the first time that such a transformation, from a semiconducting charge transfer material into a N-doped metal oxide is detected. It is shown here that both the surface chemistry and the type of majority charge carrier within the sensing layer is critically important for the type of response towards oxidizing and reducing gases. A detailed physical description of NO2 and NH3 sensing mechanism at CuTCNQ and N-doped CuO is provided to explain the difference in the response. For the N-doped CuO sensor, a detection limit of 1 ppm for NO2 and 10 ppm for NH3 are achieved.

Microbial transformation of a fungicide-derived amine, dimethyl-p-phenylene diamine by Alcaligenes DM4

Abstract Microbial transformation of N, N-dimethyl-p-phenylene diamine (DMPDA), a microbial product formed from the fungicide fenaminosulf (p-dimethylaminobenzenediazo sodium sulfonate) was studied by enriching microbes in soils treated with the amine. Microorganisms isolated from DMPDA-treated soil belonged to the genera of Micrococcus, Alcaligenes, and Corynebacterium. Of the various isolates, Alcaligenes DM4 showed maximal growth on DMPDA utilizing it as sources of carbon and nitrogen. When grown in mineral salts basal medium containing 0.05% DMPDA to serve as carbon and nitrogen sources, Alcaligenes DM4 grew exponentially up to 18 h. Even though the characterization of the complete pathway of microbial degradation of DMPDA could not be carried out due to the auto-oxidation of the compound, the initial transformation product of DMPDA by Alcaligenes DM4 has been identified as a dimer. The dimer is generated into the culture medium presumably by the extra-cellular oxidase of Alcaligenes DM4. It is suggested that the risk-benefit evaluation on the use of fenaminosulf is to be made taking into consideration the microbial transformations of the fungicide.

Synthesis, Structure, and Properties of Boron- and Nitrogen-Doped Graphene

Boron- and nitrogen-doped graphenes are are prepared by the arc discharge between carbon electrodes or by the transformation of nanodiamond under appropriate atmospheres. Using a combination of experiment and theories based on first principles, systematic changes in the carrier-concentration and electronic structure of the doped graphenes are demonstrated. Stiffening of the G-band mode and intensification of the defect-related D-band in the Raman spectra are also observed.