A calibrated source of N2O5

A calibrated source of N₂O₅ was developed for use in evaluating instruments designed to measure reactive odd-nitrogen species in the atmosphere. The desirable features of the source are the output of a very low mixing ratio of N₂O₅, the measurement of total reactive nitrogen NO_y in the source output, and the use of commercially-available detection and calibration equipment. N₂O₅ was derived from a solid crystalline sample at 192 K. Mixing ratios of N₂O₅ less than 2 ppmv (parts per million by volume) were produced in a small flow ( < 50 STPcc min⁻¹) of He carrier gas. This small flow was then diluted to obtain mixing ratios less than 50 ppbv (parts per billion by volume) in flows greater than 1 STPℓ min⁻¹. The N₂O₅ mixing ratio was determined with an accuracy of ± 15 % by using a thermal dissociator, calibrated NO/N₂ mixtures, and an NO chemiluminescence detector. The level of other reactive nitrogen species in the source output was determined with an Au catalytic converter and the NO detector.     

Estimation of night-time N2O5 concentrations from ambient NO2 and NO3 radical concentrations and the role of N2O5 in night-time chemistry

Dinitrogen pentoxide (N₂O₅), which is present in equilibrium with NO₃ radicals and NO₂, has been recognized for some time as an intermediate in the NO_x chemistry of night-time atmospheres. However, until the advent of long pathlength spectroscopic techniques for the measurement of atmospheric NO₃ radical concentrations, no reliable method for estimating N₂O₅ concentrations has been available. We have calculated maximum night-time N₂O₅ concentrations from the available experimentally determined concentrations of the NO₃ radical and NO₂ in the U.S. and Germany, and find that N₂O₅ concentrations as high as ~ 15 ppb can occur. We have also estimated removal rates for N₂O₅ and for NO₃ radicals during these nights. From data obtained under conditions devoid of point sources of NO_x, upper limit estimates of the homogeneous rate constant for the reaction of N₂O₅ with water vapor are obtained, leading to the conclusion that the homogeneous gas phase rate constant for this reaction is ⩽ 1 × 10⁻²¹ cm³ molecule⁻¹ s⁻¹ at 298 K, consistent with recent environmental chamber data.     

超声-过氧化氢-氧化铜组合技术催化氧化水中苯酚

研究了超声-H2O2-CuO组合技术对苯酚的降解效果。考察了苯酚初始浓度、溶液温度及鼓入空气对苯酚去除率的影响。实验结果表明，与未鼓入空气时相比，连续鼓气时苯酚的降解效果较好；初始浓度低，苯酚去除率高；溶液温度从20％上升到55％时，苯酚去除率随温度升高而增大，温度对该过程的影响主要表现为对催化剂的影响而不是对超声作用的影响。高效液相色谱分析表明，苯酚降解的中间产物主要为对苯二酚、邻苯二酚及其他有机小分子物质，最终产物为草酸、二氧化碳和水。     

超声-过氧化氢-氧化铜组合技术催化氧化水中苯酚

研究了超声-H2O2-CuO组合技术对苯酚的降解效果。考察了苯酚初始浓度、溶液温度及鼓入空气对苯酚去除率的影响。实验结果表明,与未鼓入空气时相比,连续鼓气时苯酚的降解效果较好;初始浓度低,苯酚去除率高;溶液温度从20℃上升到55℃时,苯酚去除率随温度升高而增大,温度对该过程的影响主要表现为对催化剂的影响而不是对超声作用的影响。高效液相色谱分析表明,苯酚降解的中间产物主要为对苯二酚、邻苯二酚及其他有机小分子物质,最终产物为草酸、二氧化碳和水。     

N2O profiles in the enhanced CANON process via long-term N2H4 addition: minimized N2O production and the influence of exogenous N2H4 on N2O sources

Environmental Science and Pollution Research - Production of the greenhouse gas nitrous oxide (N2O) from the completely autotrophic nitrogen removal over nitrite (CANON) process is of growing...     

The gas-phase reaction of naphthalene with N2O5 to form nitronaphthalenes

While the formation of nitroarenes from the reaction of NO₂, containing traces of HNO₃, in air with polycyclic aromatic hydrocarbons (PAH) adsorbed on combustion generated particles is now well recognized, little is known about the gas-phase reactions of PAH. In this study, the gas-phase reactions in air of N₂O₃ with part-per-million levels of naphthalene have been studied at room temperature and atmospheric pressure in a 5800V Teflon-coated environmental chamber. The kinetic data obtained showed that in these N₂O₅-NO₃-NO₂-air mixtures studied, naphthalene did not react with the NO₃ radical at an observable rate, but that it reacted with N₂O₅ with a rate constant of ~ (2–3) × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹. Significant yields of 1-nitronaphthalene and 2-nitronaphthalene ( ~ 18 and ~ 7.5%, respectively) were obtained from this reaction. The latter is a procarcinogen capable of being metabolized in animals to the carcinogen β-naphthylamine. These results and their atmospheric implications are discussed.     

A2O工艺中N2O的产生与逸散特征

目前污水处理过程中产生温室气体的问题已经引起普遍关注。本文通过实验室小试,研究了不同污水水质条件下A2O工艺中N2O的产生特征,以及氧化亚氮还原酶编码基因nosZ含量对N2O产生量的影响。结果表明,在A2O工艺中的各单元均有N2O产生,其中厌氧池产生量最大,约占总产生量的32％～85％;A2O工艺产生的N2O主要通过逸散进入大气,少量随二沉池出水进入到环境中。N2O的产生量与污泥中nosZ的含量成负相关,而碳源和DO对含有nosZ基因的反硝化细菌有明显的影响,低DO环境和充足的碳源能够极大的促进其含量的提高,从而显著减少N2O的产生量。     

Reactions of adsorbed pyrene and perylene with gaseous N2O5 under simulated atmospheric conditions

We report here results of studies concerning the reactions of two representative polycyclic aromatic hydrocarbons (PAH), pyrene and perylene, adsorbed on glass fiber filters, towards gaseous N₂O₅, NO₃ radicals, NO₂ and HNO₃ at part-per-million or lower concentrations and at ⩽ 5% relative humidity. These exposures were carried out in a passive mode in an ~ 6400-ℓ all-Teflon environmental chamber. As is the case for naphthalene vapor, neither adsorbed pyrene nor perylene reacted to any observable extent with the NO₃ radical. However, pyrene reacted rapidly with N₂O₃ to form 1-nitropyrene (1-NP) with a 60–70% yield after 50 min exposure to an initial N₂O₅ concentration of 1.5 ppm. Under these conditions, no reaction of perylene with N₂O₅ was observed. In control runs of the same duration, neither pyrene nor perylene reacted significantly ( < 0.5%) with 1.7 ppm of gaseous HNO₃ but, consistent with earlier studies, a ~ 3% yield of 3-nitroperylene (and < 0.5 % 1-NP) was formed when they were exposed to a mixture of 0.5 ppm NO₂ + 0.35 ppm HNO₃. These data show for the first time that gas phase N₂O₅ can be a strong nitrating agent for adsorbed pyrene to produce 1-nitropyrene, a powerful bacterial mutagen. Clearly, uncertainties occur in extrapolating our laboratory data to ambient atmospheres. However, when our results are combined with estimated N₂O₅ concentrations of up to ~ 15 ppb in polluted night-time atmospheres, they suggest that nitro-PAH, could be formed at significant rates in ambient air.     

羧基裂解酶基因对施氏假单胞菌N2代谢苯酚的影响

研究了羧基裂解酶基因对施氏假单胞菌N2降解苯酚的影响。结果表明,施氏假单胞菌N2以唯一碳源苯酚生长时,与野生菌相比,突变菌株的生长明显受到抑制,ubiD和ubiX等羧基裂解酶基因发挥重要作用,并且,就生长特性而言,ubiD基因起关键作用。降解反应期间,对开环产物进行研究发现,基因ubiD主导的是邻苯二酚间位开环,而基因ubiX主导的是邻苯二酚邻位开环。从质谱结果分析,野生菌和突变菌以苯酚为碳源生长时,均能通过羟化和羧化开环裂解途径将苯酚转化成相应的中间产物：顺,顺-己二烯二酸和2-HMS。其中,单突变株N2ubiX-降解苯酚过程中生成的中间产物与野生菌相比,种类相等,但各中间产物含量明显低于野生菌,而单突变株N2ubiD-和双突变菌株N2ubiX-ubiD-代谢苯酚的中间产物的含量及种类都明显低于野生菌。     

催化剂Cu/HZSM-5的硅铝比对催化分解N2O的影响

为系统研究Cu/HZSM-5硅铝比对其各类性能的影响,采用等体积浸渍法与离子交换法,以硅铝比为27、50、117的HZSM-5为载体,制备负载型N_2O催化分解催化剂Cu/HZSM-5和Cu/ZSM-5,催化剂的活性组分为CuO。通过催化剂反应活性评价、X射线荧光光谱分析、X射线衍射分析结果,对2种方法制备催化剂活性的差异进行了分析。利用比表面积孔径分析仪(BET)、X射线衍射分析(XRD)、场发射扫描电镜(SEM)、X射线荧光光谱分析(XRF)、氢气程序升温还原分析(H_2-TPR)、氨气程序升温脱附分析(NH_3-TPD)等表征手段对催化剂物化性质等进行分析,得到载体HZSM-5的硅铝比差异对催化剂特征结构、比表面积、特征形貌、酸性位数量、可还原性能的影响规律。等体积浸渍法制备的催化剂活性评价结果表明,硅铝比为27的Cu_8/HZSM-5催化剂活性最好,完全催化分解N_2O的温度在400℃左右。水热稳定性实验结果以及寿命实验结果表明,硅铝比为27的Cu_8/HZSM-5具有良好的水热稳性,3种硅铝比的Cu_8/HZSM-5催化剂均具备良好的热稳定性。Cu/HZSM-5的活性评价以及各种表征结果显示,在一定范围内,硅铝比越低,催化剂活性越好。     

Catalytic reduction of N2O over Ag-Pd/Al2O3 bimetallic catalysts

A study of the catalytic conversion of N2O to N2 over a bimetallic Ag-Pd catalyst is described in this article. Several Ag-Pd catalytic systems were prepared supported on Al2O3 with different ratios and their catalytic activity for the direct decomposition of N2O and their reduction with CO was measured. Based on the experimental results, it was observed that Ag-Pd bimetallic catalyst (5-0.5%) was the most active for both nitrous oxide reduction and direct decomposition. This high activity seems to be connected with a synergistic effect between Ag and Pd.     

Influence of environmental factors on net N2 and N2O production in sediment of freshwater rivers

Denitrification is an important N removal process in aquatic systems but is also implicated as a potential source of global N₂O emissions. However, the key factors controlling this process as well as N₂O emissions remain unclear. In this study, we identified the main factors that regulate the production of net N₂ and N₂O in sediments collected from rivers with a large amount of sewage input in the Taihu Lake region. Net N₂ and N₂O production were strongly associated with the addition of NO₃ ^?-N and NH₄ ⁺-N. Specifically, NO₃ ^?-N controlled net N₂ production following Michaelis–Menten kinetics. The maximum rate of net N₂ production (V _max) was 116.3 μmol N₂-N m^?2 h^?1, and the apparent half-saturation concentration (k _m) was 0.65 mg N L^?1. N₂O to N₂ ratios increased from 0.18?±?0.03 to 0.68?±?0.16 with the addition of NO₃ ^?-N, suggesting that increasing NO₃ ^?-N concentrations favored the production of N₂O more than N₂. The addition of acetate enhanced net N₂ production and N₂O to N₂ ratios, but the ratios decreased by about 59.5 % when acetate concentrations increased from 50 to 100 mg C L^?1, suggesting that the increase of N₂O to N₂ ratios had more to do with the net N₂ production rate rather than acetate addition in this experiment. The addition of Cl^? did not affect the net N₂ production rates, but significantly enhanced N₂O to N₂ ratios (the ratios increased from 0.02?±?0.00 to 0.10?±?0.00), demonstrating that the high salinity effect might have a significant regional effect on N₂O production. Our results suggest that the presence of N-enriching sewage discharges appear to stimulate N removal but also increase N₂O to N₂ ratios.     

Pd/N共掺杂TiO_2的制备及其光催化降解苯酚的研究

将纳米管钛酸浸入含尿素和金属(Pd)硝酸盐的乙醇溶液中,乙醇超声挥发后所得样品先在空气气氛、600℃下煅烧,再在H2气氛、400℃下热还原制备得到Pd/N共掺杂TiO2光催化剂(Pd/N-TiO2)。利用光电子能谱(XPS)仪研究了催化剂表面N、Pd元素的化学态。结果表明,N元素以Ti—O—N形式存在,Pd元素以单质金属状态存在。考察了Pd/N-TiO2的紫外光光催化降解苯酚的活性,与单纯TiO2光催化剂和N掺杂TiO2光催化剂相比,Pd/N-TiO2活性明显提高。研究了催化剂用量、苯酚初始浓度和pH、O2流量以及外加双氧水等条件对紫外光光催化降解苯酚的活性的影响,得到光催化降解苯酚的最佳工艺条件:苯酚初始质量浓度为120mg/L,催化剂用量为0.10g/L,苯酚溶液初始pH为8,O2流量为80mL/min,加入适量双氧水。     

CWAO of phenol using CeO2/gamma-Al2O3 with promoter--effectiveness of promoter addition and catalyst regeneration

The effect of promoter addition on activity of CeO(2)/gamma-Al(2)O(3) was assessed via the CWAO of phenol. Adding Cu as the promoter rendered the most effective performance, followed by Mn, although the performance of Mn-promoted catalyst was inferior to CeO(2)/gamma-Al(2)O(3). Mineralization of phenol was effectively implemented at 160 degrees C using Cu-promoted catalyst (Ce15Cu5). Furthermore, at 180 degrees C this catalyst produced about 100% conversion of phenol (1h) and 95% removal of chemical oxygen demand (4h), higher than that of CeO(2)/gamma-Al(2)O(3). In contrast, Mn-promoted catalyst (Ce15Mn5) required a temperature above 220 degrees C for acceptable performance. Activity of re-used catalyst declined noticeably, due to deposits of carbonaceous compounds and leaching of metal ions. Regeneration with acetone rinsing after the first run was effective in recovering activity of Ce15Cu5, although after a second run further regeneration with acetone rinsing had only a moderate effect, due to residual carbonaceous deposits and the additive effect of leached metal species in each run. As an alternative to acetone, HCl or HNO(3) solution (0.01 M) was less effective at regenerating activity. In promoted catalysts, leached metal ions accounted for the majority of mineralization of phenol, while the solid catalyst played a dual role of initiator and terminator of free radicals. Despite a superior catalytic performance, leaching of Cu(2+) from the promoted catalyst caused a severe decline in activity and poses the problem of secondary pollution of treated wastewater. Therefore, addition of Cu, as well as other metal species, is unfavorable in promoting the CeO(2)/gamma-Al(2)O(3) catalyst.     

The oxidation of SO2 on carbon particles in the presence of O3, NO2 and N2O

The oxidation of SO₂ on carbon particles at 65 % relative humidity (RH) by O₃, NO₂ and N₂O was investigated gravimetrically and compared with oxidation by air. Approximately 1 mg samples of carbon black were exposed to continuously flowing mixtures of SO₂, SO₂ + O₃, SO₂ + NO₂, and SO₂ + N₂O in air (or in N₂). Both O₃ and NO₂ in the 0.07–10ppmv range with 20–40ppmv SO₂ were found to produce sorption and desorption coverages significantly higher than those for corresponding SO₂ in air exposures. N₂O was determined to be much less effective as an oxidant than O₃ or NO₂. Identical concentrations of O₃ or NO₂ were found to produce equivalent conversions of SO₂ to sulfate on carbon for equal exposure times. Wet chemical analysis of the residue following desorption indicated that sulfate generally accounted for well over half of the retained weight.Exposure at low concentrations (0.10 ppmv SO₂ + 0.02 ppmv O₃ or NO₂), however, appeared to produce little, if any, enhancement in SO₂ transformation when compared with equivalent SO₂ in air. Weight retentions for these runs were very small, however, and measurement errors of up to 25% would be anticipated.     

煤吸附CO2、O2和N2的能力与竞争性差异

应用Materials Studio软件,采用巨正则系综蒙特卡洛方法,依据电厂烟气注入采空区防火与封存实际,对煤吸附CO2、O2和N2的能力与竞争性差异进行分析。由计算结果可知,相比于吸附O2、N2,煤吸附单组分CO2除了范德华能起主要作用,还有很强的静电作用能。由相互作用能和等量吸附热计算结果可知,煤容易吸附CO2,而不容易吸附O2和N2。298.15 K时,CO2对N2和O2吸附选择性及O2对N2的吸附选择性分别为42.396、32.357和1.310,揭示了竞争能力大小为CO2 > O2 > N2。分压分别为CO2 16.5 kPa+N2 79 kPa+O2 4.5 kPa内系统竞争吸附时,受吸附能力、竞争性和分压影响,CO2被大量吸附,而O2吸附抑制。     

Modeling heterogeneous ClNO2 formation,chloride availability,and chlorine cycling in Southeast Texas

Nitryl Chloride (ClNO₂) mixing ratios above 1 ppbv have been measured off the coast of Southeast Texas. ClNO₂ formation, the result of heterogeneous N₂O₅ uptake on chloride-containing aerosols, has a significant impact on oxidant formation for the Houston area. This work reports on the modeling of ClNO₂ formation and describes the sensitivity of ClNO₂ formation to key parameters. Model sensitivity analyses found that: (1) Chloride availability limits the formation of nitryl chloride at ground level but not aloft; (2) When excess particulate chloride was assumed to be present at ground level through sea salt, ClNO₂ concentrations increased in some locations by a factor of 13, as compared to cases where sea salt chloride was assumed to be limited; (3) Inland formation of ClNO₂ seems feasible based on chloride availability and could have a large impact on total ClNO₂ formed in the region; and (4) ClNO₂ formation is quite sensitive to the assumed yield of ClNO₂ from N₂O₅ uptake. These results demonstrate that there is a need for further field studies to better understand the geographic extent of ClNO₂ formation and the atmospheric conditions which control partitioning of chloride into the particle phase. In addition, this work examined the role of ClNO₂ in the cycling of chlorine between chloride and reactive chlorine radicals. The modeling indicated that the majority of reactive chlorine in Texas along the Gulf coast is cycled through ClNO₂, demonstrating the importance of including ClNO₂ into photochemical models for this region.     

Continuous Infrared Analysis of N2O in Combustion Products

Nitrous oxide (N₂O) levels in the atmosphere are increasing, potentially contributing to the greenhouse effect and depletion of stratospheric ozone. From a limited data base, combustion sources have been identified as a major anthropogenic source of N₂O. However, the existing data base (obtained by traditional grab sampling techniques followed by gas chromatographic analysis) is in question due to the discovery of a sampling artifact. A continuous on-line N₂O analyzer would enable and facilitate the accurate characterization of combustion sources over a range of operating conditions, and also aid in the development of an appropriate sampling technique. This paper addresses the development of a continuous measurement technique, and the evaluation and initial use of a field prototype continuous N₂O analyzer developed at the UCI Combustion Laboratory in cooperation with a major instrument manufacturer. The analyzer is capable of measuring N₂O levels down to a few ppm. The analyzer has been evaluated and used to study the N₂O emissions from a pulverized coal-fired boiler. The N₂O levels found with the analyzer are substantially lower than levels previously attributed to such sources. Initial N₂O measurements made with the analyzer suggest that N₂O levels are not a substantial fraction of the NO_X levels, as previously suggested.     

NiO-MgO复合金属氧化物催化分解N2O

采用溶胶凝胶法制备了一系列不同Ni/Mg比的NiO-MgO复合氧化物催化剂,并考察了其N2O催化分解性能。结果表明,NiO-MgO催化剂的N2O催化分解活性明显优于单一NiO和MgO,当MgO含量为5%时,NiO-MgO复合金属氧化物上N2O分解活性最佳。XRD、H2-TPR和XPS结果表明,Ni2+是催化分解N2O的主要活性位点。Mg不作为活性组分,但可通过Ni、Mg之间强烈的相互作用提高催化剂氧化还原能力,进而促进N2O的催化分解。此外,Mg的加入促进了催化剂中NiO的形成。     

Replacement of H2O2 by O2 in Fenton and photo-Fenton reactions

The consumption of oxygen during the degradation of aniline by Fenton and photo-Fenton reactions is studied. The effect that parameters like aniline, Fe(II) and H2O2 initial concentration, pH, temperature and O2 flow rate have on the ratio O2 consumed/H2O2 consumed is examined. The determination of those combinations of experimental conditions for which an effective partial replacement of H2O2 by O2 as electron acceptor takes place is investigated. The results show that this replacement takes place in a variable extent, but the presence of H2O2 is necessary along the reaction, and the maximum consumption of O2 only takes place when the ratio amount of aniline mineralized vs. initial aniline concentration is minimal.