Nitrite in soils: accumulation and role in the formation of gaseous N compounds

Nitrite is an intermediary compound formed during nitrification as well as denitrifiication. It occasionally accumulates in soils and drainage water. The nitrite can then undergo transformations to gaseous nitrogen compounds such as NO and NO₂. Soil pH controls the abiotic nitrite decomposition to a large extent. Under acidic conditions(pH <5.5), nitrous acid spontaneously decomposes preferentially to NO and NO₂. Nitrite also undergoes reactions with metallic cations (especially ferrous iron) and with organic matter. As a result of these reactions gaseous compounds such as NO, NO₂, N₂O and CH₃ONO can be formed. Through reaction of nitrite with phenolic compounds nitroand nitrosocompounds can be formed, building up organic N. With normal agricultural practices on slightly acidic soils, the nitrite instability usually does not lead to economically important N losses from soils. However, the compounds formed through its degradation or interaction with other soil constituents are linked to environmental problems such as tropospheric ozone formation, acid rain, the greenhouse effect and the destruction of the stratospheric ozone.     

填料塔中亚硝酸甲酯再生过程模拟

在气相偶联合成草酸酯工艺过程中,亚硝酸甲酯(MN)再生过程与偶联反应有效匹配是实现整个系统绿色无污染的关键,也是影响草酸酯合成工业放大过程的关键一步。对于MN再生过程的工艺优化和宏观动力学方面进行了较多研究和报道,而对MN再生过程的数学模拟研究较少。通对MN再生过程中发生的主要化学反应进行分析简化,并结合MN再生反应动力学参数,在填料塔中建立了MN再生反应数学模型,并计算了主要工艺参数对MN收率的影响。模拟结果表明,随温度升高、气体流速增大、N₂体积分数增大,MN的收率减小,液体流速增大和NO/O₂摩尔比增大,MN收率增大。通过实验验证了该模型的准确性,MN收率的模拟结果与实验数据的最大相对偏差为-4.39%,为MN再生反应过程的设计和操作提供了理论依据;最后,对于两种不同的NO和O₂混合方式进行了比较,通过模拟计算比较了这两种不同操作方式对MN收率的影响。     

Possible role of nitrite/nitrate redox cycles in N2O decomposition and light-off over Fe-ZSM-5

Surface nitrite/nitrate redox cycles were proposed to explain light-off behavior that was observed during the decomposition of N₂O over Fe-ZSM-5. Further study has demonstrated that while the nitrite/nitrate model can explain the original observations as an isothermal, mechanistic phenomenon, the light-off behavior is thermal, and not a mechanistic effect. Nonetheless, a pathway involving nitrite/nitrate redox cycles appears to be more consistent with experimental observation than the simple two-step pathway involving cation redox cycles. In particular, the nitrite/nitrate pathway can explain the effect of added NO upon the reaction kinetics and the reported isotopic product composition when unlabeled N₂O reacts over an oxygen-labeled catalyst. Further, a nitrite/nitrate pathway is consistent with the steady-state kinetics as well as published thermal desorption and infrared spectroscopic results.     

Nitrate and nitrite reduction of a sulphide-rich environment

A sulphide-rich anaerobic sludge acclimated with a molasses wastewater was used to carry out studies on nitrate and nitrite reductions in continuously stirred batch reactors. It was shown that a COD/N-NO_x ratio as high as 65·6 mg mg⁻¹ did not promote dissimilatory reduction of nitrogen oxides to ammonia. Denitrification was characterized by a probable accumulation of gaseous intermediates, nitric oxide (NO) and nitrous oxide (N₂O), by sulphide consumption with concomitant elemental sulphur production and by an increase of the redox potential. In addition, sulphate reducers were completely inhibited by nitrogenous oxides. Cultures performed without any carbon source proved that denitrifiers were able to use sulphides as electron donors. Furthermore, while a lag phase preceded nitrate denitrification, nitrite was consumed immediately. Chemical reduction of nitrite by ferrous iron (Fe²⁺) was considered to be responsible for this difference. Evidence of such a chemodenitrification has been presented by using a sterilized sludge which kept its ability to reduce nitrite while it lost its capacity to use nitrate. Moreover, this chemical activity was favoured by Fe²⁺ addition. Finally, it has been suggested that during the cultures performed with non-sterilized sludge, a biological reduction of the ferric ions (Fe³⁺) would be coupled to nitrite chemodenitrification and would allow a regeneration of Fe²⁺. © 1998 SCI     

亚硝酸乙酯再生新工艺

用滴流床反应器代替原有的鼓泡塔式反应器,进行亚硝酸乙酯(简称亚酯)再生试验研究,采用惰性瓷环和分子筛为填充介质,考察了工艺条件,如原料气进气方式、反应温度和NO/O2体积比对O2转化率的影响。试验发现填充介质采用碗状瓷环为最佳,适宜的工艺条件:反应温度范围在40~60℃之间,NO/O2的摩尔比为6∶1,惰性气体N2的体积分数为50%。     

Nitrite Concentration in the Striated Muscles Is Reversely Related to Myoglobin and Mitochondrial Proteins Content in Rats

Skeletal muscles are an important reservoir of nitric oxide (NO^•) stored in the form of nitrite [NO₂⁻] and nitrate [NO₃⁻] (NO_x). Nitrite, which can be reduced to NO^• under hypoxic and acidotic conditions, is considered a physiologically relevant, direct source of bioactive NO^•. The aim of the present study was to determine the basal levels of NO_x in striated muscles (including rat heart and locomotory muscles) with varied contents of tissue nitrite reductases, such as myoglobin and mitochondrial electron transport chain proteins (ETC-proteins). Muscle NO_x was determined using a high-performance liquid chromatography-based method. Muscle proteins were evaluated using western-immunoblotting. We found that oxidative muscles with a higher content of ETC-proteins and myoglobin (such as the heart and slow-twitch locomotory muscles) have lower [NO₂⁻] compared to fast-twitch muscles with a lower content of those proteins. The muscle type had no observed effect on the [NO₃⁻]. Our results demonstrated that fast-twitch muscles possess greater potential to generate NO^• via nitrite reduction than slow-twitch muscles and the heart. This property might be of special importance for fast skeletal muscles during strenuous exercise and/or hypoxia since it might support muscle blood flow via additional NO^• provision (acidic/hypoxic vasodilation) and delay muscle fatigue.     

Evaluation of heterotrophic nitrite removal by a sulphide and acetate oxidizing mixed culture originated from an oil reservoir

BACKGROUND: Shortcut biological nitrogen removal (SBNR) has attracted much attention in recent years due to lower aeration and chemical oxygen demand (COD) requirements, shorter residence time and smaller biomass production. In this work an oil reservoir denitrifying culture, with the ability to function under autotrophic and heterotrophic conditions was used for heterotrophic denitritation. Using freely suspended cells, effects of nitrite concentration (10–50 mmol L^?1) and temperature (15–35 °C) on the kinetics of denitritation were investigated and a kinetic model was developed. Potential for enhancement of nitrite removal rate, and impacts of nitrite concentration and loading rate were investigated in a continuous biofilm reactor. RESULTS: Nitrite did not impose any inhibitory effect, even at the highest applied concentration of 50 mmol L^?1. Increase of temperature in the range 15–35 °C enhanced the reduction rate significantly. Fitting the experimental data into the model developed, values of biokinetic coefficients (µ_max?NO2, K_S?NO2, Y_X?NO2, Y_X?Ace?NO2 and Eµ‐_NO2) were determined. In the biofilm reactor increases in nitrite loading rate (through flow rate or feed nitrite concentration) led to a linear increase of nitrite removal rate, with the highest removal rate of 140.6 mmol L^?1 h^?1 achieved with a residence time of 0.19 h. CONCLUSION: The enrichment culture used in this study is not only a superior biocatalyst for simultaneous removal of sulphide, nitrate and BOD, it could also be used effectively in the denitritation step of an SBNR process. The kinetic model developed would certainly have beneficial applications in the design, operation and control of the SBNR process. Copyright © 2011 Society of Chemical Industry     

甲醇为碳源时C/N对反硝化过程中亚硝酸盐积累的影响

如何获得稳定的NO2--N作为厌氧氨氧化细菌的电子受体是城镇污水通过厌氧氨氧化途径脱氮的瓶颈问题。为此考虑利用反硝化途径获取稳定的NO2--N。以甲醇为碳源,采用小试装置的SBR反应器,通过控制进水C/N(COD与NO3--N质量浓度比)的策略,研究了反硝化过程中的NO2--N积累的状况。试验结果表明以甲醇为碳源且投加量不足时(C/N3.2),反硝化过程中和反硝化结束后会产生稳定的NO2--N积累;在C/N不足的前提下,NO2--N积累量随甲醇投加量的增加而增加;进水C/N为2.4～3.2时,可获得约25%的NO2--N积累率;进水C/N为0.8时,NO2--N积累率仅为5.6%;C/N1时,NO2--N与NO3--N的还原速率随着COD浓度的增加而增加;C/N≥1时,COD浓度不再影响NO2--N与NO3--N的还原速率。     

AMPK–mTOR Signaling and Cellular Adaptations in Hypoxia

Cellular energy is primarily provided by the oxidative degradation of nutrients coupled with mitochondrial respiration, in which oxygen participates in the mitochondrial electron transport chain to enable electron flow through the chain complex (I–IV), leading to ATP production. Therefore, oxygen supply is an indispensable chapter in intracellular bioenergetics. In mammals, oxygen is delivered by the bloodstream. Accordingly, the decrease in cellular oxygen level (hypoxia) is accompanied by nutrient starvation, thereby integrating hypoxic signaling and nutrient signaling at the cellular level. Importantly, hypoxia profoundly affects cellular metabolism and many relevant physiological reactions induce cellular adaptations of hypoxia-inducible gene expression, metabolism, reactive oxygen species, and autophagy. Here, we introduce the current knowledge of hypoxia signaling with two-well known cellular energy and nutrient sensing pathways, AMP-activated protein kinase (AMPK) and mechanistic target of rapamycin complex 1 (mTORC1). Additionally, the molecular crosstalk between hypoxic signaling and AMPK/mTOR pathways in various hypoxic cellular adaptions is discussed.     

Kinetics and mechanism of the reaction between ammonium and nitrite ions: experimental and theoretical studies

The kinetics of the reaction between ammonium ion (NH₄⁺) and nitrite ion (NO₂⁻) in aqueous solutions was studied as a function of pH, temperature, and activities of the reactants. This reaction belongs to a class of fused chemical reactions that can be used to remediate paraffin and asphaltene deposition problems in oil pipelines. The reaction rate was found to be first-order with respect to the total concentration of ammonium species and second-order with respect to the total concentration of nitrite species. The reaction is strongly dependent on the pH of the solution, increasing the rate by a factor of 4000 as pH decreased from 7 to 3. The activity of hydrogen ion catalyzes the reaction by changing the concentrations of the two true reactants (ammonia (NH₃) and nitrogen trioxide (N₂O₃)), not by changing the reaction pathway. Reaction mechanisms were developed. A mechanism involving the S_N2 reaction in which the nucleophile NH₃ reacts with the electrophile N₂O₃ in the rate-limiting step was found to fit all experimental observations. This reaction mechanism releases the nitrite ion (NO₂⁻) to produce an intermediate (nitrosamine (H₂NNO)) which dissociates very rapidly to form the final products (nitrogen (N₂) and water (H₂O)).     

Denitrification in aqueous FeEDTA solutions

The biological reduction of nitric oxide (NO) in aqueous solutions of FeEDTA is an important key reaction within the BioDeNOx process, a combined physico‐chemical and biological technique for the removal of NO_x from industrial flue gasses. To explore the reduction of nitrogen oxide analogues, this study investigated the full denitrification pathway in aqueous FeEDTA solutions, ie the reduction of NO₃^?, NO₂^?, NO via N₂O to N₂ in this unusual medium. This was done in batch experiments at 30 °C with 25 mmol dm^?3 FeEDTA solutions (pH 7.2 ± 0.2). Also Ca²⁺ (2 and 10 mmol dm^?3) and Mg²⁺ (2 mmol dm^?3) were added in excess to prevent free, uncomplexed EDTA. Nitrate reduction in aqueous solutions of Fe(III)EDTA is accompanied by the biological reduction of Fe(III) to Fe(II), for which ethanol, methanol and also acetate are suitable electron donors. Fe(II)EDTA can serve as electron donor for the biological reduction of nitrate to nitrite, with the concomitant oxidation of Fe(II)EDTA to Fe(III)EDTA. Moreover, Fe(II)EDTA can also serve as electron donor for the chemical reduction of nitrite to NO, with the concomitant formation of the nitrosyl‐complex Fe(II)EDTA–NO. The reduction of NO in Fe(II)EDTA was found to be catalysed biologically and occurred about three times faster at 55 °C than NO reduction at 30 °C. This study showed that the nitrogen and iron cycles are strongly coupled and that FeEDTA has an electron‐mediating role during the subsequent reduction of nitrate, nitrite, nitric oxide and nitrous oxide to dinitrogen gas. Copyright © 2004 Society of Chemical Industry     

亚硝酸钙溶液中硝酸根含量的测定

氯化铵法测定亚硝酸钙溶液中硝酸根含量时 ,影响测定结果准确性的因素主要为 :加热微沸时间和诱导反应。消除影响因素后加标回收率达 96 6 0 %以上 ,与成品甲醇法相比具有操作简便、快速的优点 ,可以满足中控分析要求     

共振光散射光谱法测定亚硝酸根的研究

基于在盐酸介质中,亚硝酸根与氨基苯磺酸发生重氮化反应,氨基苯磺酸共振光散射强度随亚硝酸根的加入量增加而明显降低的现象,建立了新的共振光散射法测定亚硝酸根的方法。该方法对亚硝酸根检测的线性范围为0.01～0.70？g/mL,检出限为7.2ng/mL（3σ）。该方法应用于自来水中亚硝酸根离子的测定,回收率为93.1%～105.7%。     

TiO2光催化降解亚硝酸钠的研究

采用溶胶-凝胶法制备了TiO2光催化剂,以紫外光照射下的光催化降解亚硝酸钠为模型反应,以盐酸萘乙二胺显色法测定样品的吸光度,进而得出亚硝酸钠的转化率,并采用BET、XRD和IR对催化剂进行了表征。结果表明,500℃焙烧的TiO2催化剂比表面积为42.5 m2/g,平均孔径为5.8 nm,热稳定性好。400℃焙烧2 h的TiO2尚存在一定量的无定形相TiO2,500℃焙烧的TiO2完全转变为锐钛矿型TiO2,700℃时完全转化为金红石相。本实验最佳的反应条件为:TiO2(500℃,2 h)催化剂0.2 g,100 mL 0.125μg/mL亚硝酸钠溶液中,紫外光降解150 min,亚硝酸钠的降解率为100%;添加适量浓度的H2O2溶液,可促进亚硝酸钠溶液的转化。     

Developing Carrier Complexes for "Caged NO": RuCl(3)(NO)(H(2)O)(2) Complexes of Dipyridylamine, (dpaH), N,N,N'N'-Tetrakis (2-Pyridyl) Adipamide, (tpada), and (2-Pyridylmethyl) Iminodiacetate, (pida)

Delivery agents which can carry the {Ru(NO)}(6) chromophore ("caged NO") are desired for vasodilation and for photodynamic therapy of tumors. Toward these goals, complexes derived from [RuCl(3)(NO)(H(2)O)(2)]= (1) have been prepared using dipyridylamine (dpaH) as mono and bis adducts, [Ru(NO)Cl(3)(dpaH)] = (2) and [Ru(NO)Cl(dpaH)(2)]Cl(2) = (3). The dpaH ligands coordinate cis to the Ru(NO) axis.The mono derivative is a model for a potential DNA groove-spanning binuclear complex {[RuNO)Cl(3)](2)(tpada)} = (4) which has two DNA-coordinating Ru(II) centers, photo-labile {Ru(NO)}(6) sites, and a groove-spanning tether moiety.The binuclear assembly is prepared from the tethered dipyridylamine ligand N,N,N',N'-tetrakis(2-pyridylmethyl)adipamide (tpada) which has recently been shown to provide a binuclear carrier complex suited to transporting Ru(II) and Pd(II) agents. A related complex, [Ru(NO)Cl(pida)] = (5) with the {Ru(NO)}(6) moiety bound to (2-pyridylmethyl) iminodiacetate (pida(2-)) is also characterized as a potential "caged NO" carrier. Structural information concerning the placement of the pyridyl donor groups relative to the {Ru(NO)}(6) unit has been obtained from (1)H and (13)C NMR and infrared methods, noting that a pyridyl donor trans to NO+ causes "trans strengthening" of this ligand for [Ru(NO)Cl(pida)], whereas placement of pyridyl groups cis to NO+ causes a weakening of the N-O bond and a lower NO stretching frequency in the dpa-based complexes.     

Measurement and modeling of nitrous and nitric oxide emissions from a tea field in subtropical central China

Tea fields represent an important source of nitrous oxide (N₂O) and nitric oxide (NO) emissions due to high nitrogen (N) fertilizer applications and very low soil pH. To investigate the temporal characteristics of N₂O and NO emissions, daily emissions were measured over 2½ years period using static closed-chamber/gas chromatograph and chemiluminescent measurement system in a tea field of subtropical central China. Our results revealed that N₂O and NO fluxes showed similar temporal trends, which were generally driven by temporal variations in soil temperature and soil moisture content and were also affected by fertilization events. The measured average annual N₂O and NO emissions were 10.9 and 3.3 kg N ha^?1 year^?1, respectively, highlighting the high N₂O and NO emissions from tea fields. To improve our understanding of N-cycling processes in tea ecosystems, we developed a new nitrogenous gas emission module for the water and nitrogen management model (WNMM, V2) that simulated daily N₂O and NO fluxes, in which the NO was simulated as being emitted from both nitrification and nitrite chemical decomposition. The results demonstrated that the WNMM captured the general temporal dynamics of N₂O (NSE = 0.40; R² = 0.52, RMSE = 0.03 kg N ha^?1 day^?1, P < 0.001) and NO (NSE = 0.41; R² = 0.44, RMSE = 0.01 kg N ha^?1 day^?1, P < 0.001) emissions. According to the simulation, denitrification was identified as the dominant process contributing 76.5% of the total N₂O emissions, while nitrification and nitrite chemical decomposition accounted for 52.3 and 47.7% of the total NO emissions, respectively.     

An ENDOR Study of Nitrosyl Myoglobin Single Crystals

¹⁴N, ¹⁵N and ¹H ENDOR spectra were taken from single crystals of ¹⁵NO ligated myoglobin at about 5 K in order to probe the spatial arrangement of the protons and nitrogens from the environment interacting with the Fe-N-O complex and to analyze its bonding configuration. The ¹⁴N hyperfine (20.4 MHz, 15.2 MHz and 16.8 MHz) and quadrupolar tensors (+1.67 MHz, −0.86 MHz, −0.98 MHz) of NE2 of the proximal histidine expand the previously reported picture from ESR analysis showing a distorted NO bond configuration. ¹⁵N data of the N(NO) ligand indicate, however, an orientation of the NO ligand differing from previous ESR reports. The single crystal spectra are applied to an interpretation of the more complex powder-type spectra. Nine different ¹H interaction tensors have been analyzed and assigned on the basis of theoretical simulation of the single crystal gamut of line positions. For the distal NE2 bound histidine proton, a small position distribution, combined with a strong anisotropy of interaction, is shown to broaden the ENDOR patterns beyond detection. The consequences of this finding with respect to the tetrameric molecule hemoglobin are discussed.     

Nitric Oxide Synthesis Is Increased in Cybrid Cells with m.3243A>G Mutation

Nitric oxide (NO) is a free radical and a signaling molecule in several pathways, produced by nitric oxide synthase (NOS) from the conversion of l-arginine to citrulline. Supplementation of l-arginine has been used to treat MELAS (mitochondrial encephalopathy with lactic acidosis and stroke like syndrome), a mitochondrial disease caused by the m.3243A>G mutation. Low levels of serum arginine and endothelium dysfunction have been reported in MELAS and this treatment may increase NO in endothelial cells and promote vasodilation, decreasing cerebral ischemia and strokes. Although clinical benefits have been reported, little is known about NO synthesis in MELAS. In this study we found that osteosarcoma derived cybrid cells with high levels of m.3243A>G had increased nitrite, an NO metabolite, and increased intracellular NO, demonstrated by an NO fluorescent probe (DAF-FM). Muscle vessels from patients with the same mutation had increased staining in NADPH diaphorase, suggestive of increased NOS. These results indicate increased production of NO in cells harboring the m.3243A>G, however no nitrated protein was detected by Western blotting. Further studies are necessary to clarify the exact mechanisms of l-arginine effect to determine the appropriate clinical use of this drug therapy.     

Catalytic oxidation of nitric oxide over modified carbide slag: Experimental and theoretical studies

In this work, experimental and theoretical methods were used to investigate the catalytic effect of K₂O on NO oxidation. Experimental results indicated that K₂O was the main active component. It enhanced the removal of NO and decreased the reaction temperature. Theoretical results indicated that the K₂O (001)-O surface was more suitable for the adsorption of NO and O₂. Also, NO and O₂ on the Ca(OH)₂ surface may migrate to the K₂O surface for reaction. NO₂ was formed via the interaction of (NO)₂ and O atoms. The formation of ON NO was the key step for NO oxidation, which was more conducive to the subsequent oxidation of NO.     

商用蜂窝式SCR催化剂脱除NO_x试验研究

为了评价燃煤电厂广泛采用的选择性催化还原工艺对不同形态NO_x的脱除效果,以某商用蜂窝式SCR催化剂为例,在SCR脱硝试验装置上研究了氧量、温度、空速、氨氮摩尔比等反应条件对NO、N_2O和NO_2脱除过程的影响。结果表明,氧量可以促进NO氧化以及NO与氨的催化还原反应;高温可以促进NO的脱除和氨气氧化为N_2O;空速升高会导致NO脱除率先升高后降低;氨氮摩尔比提高在促进NO脱除的同时会增加氨逃逸;与NO_2可以完全脱除相反,N_2O与氨气不发生反应。因此,为真正实现NO_x的超净排放,应适当控制锅炉运行参数避免N_2O的生成。