Nitrogenous air pollutants at a southern California mountain forest smog receptor site

Ambient levels of the nitrogenous pollutants NO, NO₂, nitric acid, nitrous acid, ammonia, particulate nitrate, particulate ammonium, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured at a southern California mountain forest location severely impacted by urban photochemical smog. Air quality at the mountain forest location was characterized by high levels of nitric acid (up to 18 ppb) and the phytotoxic peroxyacyl nitrates PAN (up to 22 ppb) and PPN (up to 5 ppb). Alkyl nitrates were below our detection limits of 0.05–0.5 ppb. The (PAN + PPN)/NO₂ ratios varied substantially (range 0.03–2.27) and were generally large, with typical 24-h averages of 0.19–0.50. Diurnal variations of the (PAN/PPN)/NO₂ ratio exhibited both nighttime and daytime maxima reflecting diurnal variations in PAN (and PPN) thermal stability and photochemical production rates, respectively. Organic nitrogen-containing oxidation products (PAN + PPN) were more abundant than inorganic nitrate (HNO₃ + NO₃⁻), with an average organic/inorganic concentration ratio of 2.5 (daytime ratio 1.0; nighttime ratio 3.7). The four oxidation products PAN, PPN, HNO₃ and NO₃⁻ together accounted for 0.26 of the total reactive nitrogen. The results are discussed with respect to diurnal and seasonal variations and in terms of NO₂ atmospheric oxidation pathways. Deposition fluxes and velocities to ponderosa pine have been measured for inorganic nitrate and for ammonium and have been compared with those obtained at other mountain forest locations.     

Kinetics of evaporation of ammonium chloride and ammonium nitrate aerosols

The evaporation rates of ammonium chloride and ammonium nitrate were measured by continuously and rapidly removing gaseous NH₃ and HNO₃ or HCl from aerosols in an annular denuder. The experiments gave the evaporation rates in terms of mass loss of chloride or nitrate which can be expressed conveniently as the rates of reduction of aerosol radius with time. Both dry aerosols (humidity 30–60% r.h.) and aqueous aerosols (humidity ca 97% r.h.) were studied. Dry aerosols evaporate at rates of −1.05 Å s⁻¹ for NH₄Cl and −0.45Å s⁻¹ for NH₄NO₃, while the evaporation rates of aqueous aerosols expressed as for equivalent dry particles are −4.52 Å s⁻¹ for NH₄Cl and −0.49 Å s⁻¹ for NH₄NO₃. The experimentally measured rates are independent of particle radius and remarkably low compared with those predicted from existing theories of aerosol evaporation, thus implying that there is an unknown kinetic constraint to the achievement of equilibrium at atmospheric temperature and pressures.     

Characterization of atrazine degradation and nitrate reduction by Pseudomonas sp. strain ADP

Concomitant atrazine degradation and nitrate reduction by a pure culture of Pseudomonas sp. strain ADP were studied. Under anoxic conditions, Ps ADP grew well and degraded atrazine efficiently in the presence of nitrate. Similar atrazine degradation rates were observed under both anoxic and aerobic conditions: 30.7±2.83 and 36.2±0.44 mg atrazine g⁻¹ cell h⁻¹, respectively. A high denitrification rate of 90.8±8.22 mg NO₃⁻-N g⁻¹ cell h⁻¹ was also observed using Ps ADP with citrate as the electron donor. The required citrate to nitrate ratio for complete denitrification was 5.11±0.15 g citrate g⁻¹ NO₃⁻-N.     

Nitrate formation on sea-salt and mineral particles—A single particle approach

Heterogeneous reactions of NO₂ and HNO₃ at sub-ppm levels with individual sea-salt and mineral particles were investigated. Particles deposited on filters and on electron microscope grids placed in a Teflon reaction chamber, were exposed to NO₂ or HNO₃ under controlled conditions. Experiments were carried out under dark conditions and were repeated under u.v. radiation (solar simulation). Nitrates formed on the particles were determined by bulk and individual particle analyses. Individual sea-salt and mineral particles were observed in a transmission electron microscope for the presence of nitrate on the particle surface.The formation of nitrates on sea-salt particles under dark conditions, was in the range of 0.1–3.3 mg NO₃⁻ g⁻¹ NaCl. Higher values were obtained for mineral particles: 0.2–8.2 mg NO₃⁻ g⁻¹ aerosol ([NO₂] =0.18 and 0.54 ppm; [HNO₃] = 0.04 ppm; exposure time 1–7 days; relative humidity = 70%). The formation of nitrates on sea-salt particles increased from 3.0 to 16.1 mg NO₃⁻ g⁻ NaCl when u.v. radiation was added. Mineral particles did not show a significant increase in nitrate formation under u.v. radiation.Microscopy showed that about 50% of the soil particles reacted with NO₂ and HNO₃ to form mixed nitrate particles. Almost all sea-salt particles (above 95%) reacted with both gases, although the reaction was not complete and took place only on the particle surface.Application of electron microscopy and a specific microspot technique provided direct evidence for the formation of nitrate on sea-salt and mineral particles exposed to NO₂ and HNO₃.     

菌株Desulfovibrio sp. CMX的DNRA性能和影响因素

微生物的硝酸盐异化还原为铵(DNRA)过程对自然界中铵根离子的存在和转化具有重要影响,然而关于SRB菌株DNRA过程影响和机制尚未探明.本文考察了实验室筛选的SRB菌株Desulfovibrio sp.CMX的DNRA能力、影响因素及其影响机制.结果表明,无外加氮源的情况下,分别以10 mmol·L-1NO_3~-和NO_2~-作为唯一电子受体,菌株Desulfovibrio sp.CMX最终NH_4~+生成率分别达到85.8%和97.3%,且无N2和N2O等副产物产生.实验探究了不同外加氮源、不同初始浓度的SO_4~(2-)、S~(2-)对菌株DNRA过程的影响.酵母浸粉作为外加氮源可促进菌株的生长和代谢从而促进菌株DNRA过程;SO_4~(2-)对于NO_3~-还原为NO_2~-阶段起促进作用,而对NO_2~-还原为NH_4~+阶段起抑制作用,综合两方面影响,最终表现出对菌株DNRA过程的抑制作用;S~(2-)对菌株生长及DNRA过程都表现出抑制作用,且S~(2-)浓度越高抑制作用越强,当S~(2-)浓度达到6 mmol·L-1后,S~(2-)对于NO_3~-还原为NO_2~-阶段的抑制作用强于NO_2~-还原为NH_4~+阶段的抑制作用,NO_3~-还原为NO_2~-速率低于NO_2~-还原为NH_4~+速率,此时体系中不再有NO_2~-的积累.     

1株异养硝化-好氧反硝化细菌DK1的分离鉴定及其脱氮特性

从某反应器活性污泥中分离筛选出1株假单胞菌属(Pseudomonas sp.)细菌,命名为DK1,并对该菌进行脱氮特性研究.在以葡萄糖为碳源,C/N量比为5时,分别以NaNO_3和NaNO_2为氮源,二者的好氧反硝化速率为4.09 mg·(L·h)-1和4.43mg·(L·h)~(-1).以二者同时为氮源脱氮率为100%;此外,菌株DK1具有异养硝化性能,NH_4~+-N平均去除速率为2.32mg·(L·h)-1.缺氧时以NO_2~--N为氮源菌株DK1可将一系列梯度浓度NO_2~--N(约100~300 mg·L-1)在36 h内降为0.当NO_3~--N和NO_2~--N同时存在时,菌株DK1会优先利用NO_3~--N进行反硝化.同时该菌株还具有同步硝化反硝化(SND)性能,可同时去除NH_4~+-N、NO_2~--N或NH_4~+-N、NO_3~--N,30 h内脱氮率分别达95.06%和94.69%.相同时间内在NH_4~+-N、NO_2~--N和NO_3~--N三者均存在时,脱氮效果最佳,达100%.菌株DK1的高效SND及反硝化性能表明其在处理含氮废水方面有一定的潜力和应用价值.     

水环境中不同形态氮对甲芬那酸光降解影响机制的研究

研究了紫外光照射下水环境中不同形态的无机氮(NO-3、NO-2和NH+4)对甲芬那酸(MEF)光解的影响.NO-3与NO-2均促进MEF的光解,NH+4对MEF的光解基本无影响;在NO-3、NO-2存在下添加适量异丙醇,显著抑制MEF的降解,实验表明NO-3、NO-2在光照下产生了·OH并参与对MEF的氧化降解.同时模拟研究了水体处于不同p E值下,水中存在的不同形态的无机氮对MEF光解的复合影响,其对MEF光解促进作用不是简单的叠加关系,增大p E值,MEF的光解速率先增大后减小.当NO-2和NH+4共存时,对MEF的光解主要表现为NO-2的影响;当NO-2和NO-3共存时,两者对MEF的光解存在拮抗作用.     

微氧条件下以甲烷为碳源的反硝化实验研究

为探清微氧条件下以甲烷为碳源的反硝化是甲烷好氧氧化偶联反硝化(AME-D),还是甲烷厌氧氧化偶联反硝化(ANME-D),本研究以污水处理厂厌氧污泥为接种物,在微氧条件下以甲烷为碳源进行硝酸盐和亚硝酸盐反硝化的富集培养,考察硝酸盐和亚硝酸盐的反硝化速率,并对富集培养物的微生物群落和甲烷单加氧酶功能基因进行分析.结果表明:微氧条件下硝氮/亚硝氮的还原主要以AME-D过程为主,稳定阶段硝氮和亚硝氮的平均去除速率分别为3.69 mg·L~(-1)·d~(-1)(以N计)和18.04 mg·L~(-1)·d~(-1)(以N计),富集培养物中的优势微生物为甲基球菌科(Methylococcaceae)中的甲基单胞菌属(Methylomonas),相对含量为21.86%.     

Fluxes of nitric and nitrous oxides from agricultural soils in a cool temperate climate

Fluxes of NO and N₂O from sandy loam soils cropped with winter wheat and a clay loam soil under ryegrass, with and without the addition of NH₄NO₃ fertilizer, were measured using static and dynamic chamber methods. Nitric oxide fluxes ranged from −0.3 (deposition) to 6.9 (emission) ng NO-N m⁻² s⁻¹. The corresponding N₂O flux ranged from 0 to 91 (emission) ng N₂O-N m⁻² s⁻¹. The NO flux was temperature dependent. Activation energies ranged from 40 to 81 kJ mol⁻¹. Nitric oxide and N₂O fluxes increased linearly with soil available nitrogen (NH₄ + NO₃). Emissions of NO and N₂O were not detectable from unfertilized ryegrass plots. Instead, nitric oxide was absorbed by the soil and vegetation at a maximum rate of 0.31 ng NO-N m⁻² s⁻¹. The aeration state of the soil controlled the relative rates of NO and N₂O emission. Nitric oxide was the major gas emitted from well aerated soils, conditions that favour nitrification. The NO/N₂O emission ratio was >100 for the coarse-textured sandy loam soil and the clay loam soil only during low rainfall periods. Nitrous oxide was the major gas emitted from less aerated soils, conditions that allowed denitrification to occur. The NO/N₂O emission ratio was <0.001 for the clay loam soil when rainfall was high and soils were wet. Extrapolation to the U.K. situation showed that agricultural land may account for 2–6% of the total annual NO_x emission and for 16–64% of the total annual N₂O emission in the U.K.     

去除地下水中硝酸盐的渗透性反应墙研究

通过土柱试验模拟地下水环境,研究以发酵树皮和沙子混合物为反应介质的渗透性反应墙(生物墙)对地下水中硝酸盐的去除情况,探讨其作用机制与影响因素,为硝酸盐污染地下水的修复提供经济有效的方法.结果表明,从模拟生物墙运行的第3 d起,墙内为强还原环境(Eh在-100 mV之下),有利于硝酸盐的还原降解.在15 d的运行时间内,模拟生物墙对水中硝态氮(NO3--N)的去除率为80%～90%左右(NO3--N由进水的20 mg·L-1可降至出水的1.6 mg·L-1);出水中亚硝态氮(NO2--N)的浓度较低,一直小于2.5 mg·L-1;出水中铵态氮(NH4+-N)的浓度在前2 d较低,从第3 d起升至12 mg·L-1.模拟生物墙对NO3--N的去除机制主要为吸附和微生物降解.提高模拟生物墙内水流速度后,NO3--N的去除率有所下降,出水中NH4+-N的浓度明显降低.在模拟生物墙下游串联一个模拟沸石墙,可去除水中98%的NH4+-N.     

The removal of nitric acid to atmospheric particles during a wintertime field study

A field was conducted in Warren, MI, during the 1987/88 winter period to examined the reaction of HNO₃ with particulate salt from road deicing. Samples of gases and particles were collected on a daily basis over a 4-month period. If HNO₃ reacts with particulate salt, particles of sodium nitrate will be formed and gaseous hydrochloric acid will be released. Thus, during the periods of high salt concentrations, one would expect increases in HCl and particulate NO₃⁻ and a decrease in HNO₃. The effect was observed, although the total amount of NaNO₃ formed was not large. The increase in particulate NO₃⁻ did not appear in the large particle mode. Although more than 40% of the salt was present as very large particles (> 8 μm), most of the surface area was associated with small particles. Since the reaction occurred at the particle surface, the NO₃⁻ appeared in the small particle mode. Large-particle nitrate has been observed in association with sea salt and crustal particles and has also been attributed to reactions with HNO₃. These cases will be reconsidered based on the road salt results.     

城市污水处理厂缺氧池短程反硝化现象及影响因素研究

调研了北方某城市污水处理厂缺氧池亚硝态氮积累的现象.该污水处理厂采用传统厌氧/缺氧/好氧（A/A/O）工艺,在缺氧池中存在稳定的短程反硝化过程,且缺氧池中亚硝态氮积累率最高可达88.4%.16S rRNA高通量测序分析表明Saccharibacteria_genera_incertae_sedis和Thauera可能是导致该厂缺氧池亚硝态氮积累的主要菌种,而短程反硝化现象出现的主要原因可能为外加碳源乙酸钠和系统较高的pH值.取活性污泥在COD/NO₃^--N为2~5条件下进行反硝化批次试验,结果表明硝态氮的还原速率均高于亚硝态氮的还原速率,且最大硝态氮到亚硝态氮的转换率均在50%左右.但碳源充足时,积累的NO₂^-会在NO₃^-被还原完后继续发生还原反应,从而导致最终亚硝态氮积累效果变差.本研究,以乙酸钠为碳源,COD/NO₃^--N为3可使反硝化过程获得最高亚硝态氮积累.因此,控制合适COD/NO₃^--N或缺氧反应时间是短程反硝化工艺运行的关键控制参数.本研究可为实际污水处理厂构建短程反硝化并进一步耦合厌氧氨氧化技术提供参考.     

黄土高塬沟壑区典型城郊流域地表水硝酸盐来源示踪

随着工农业的快速发展,地表水硝酸盐污染已成为黄土高原地区严重的环境问题之一.以黄土高塬沟壑区典型城郊流域砚瓦川为研究区,采用水化学分析方法和氮氧双稳定同位素技术,并结合SIAR模型,定量识别旱季和雨季研究区地表水硝酸盐不同污染源的贡献率,阐明不同污染源季节性差异的主要原因.结果表明,流域地表水无机氮主要以NO₃^--N和NO₂^--N形态存在,NO₃^--N和NO₂^--N雨季浓度平均值均高于旱季,而NH₄⁺-N则呈现相反特征;流域内地表水硝酸盐的转化过程主要以硝化作用为主,雨季其主要来源是粪肥污水,而旱季主要为粪肥污水和土壤氮淋溶,铵肥次之;不同污染源对流域地表水硝酸盐的贡献比例具有显著的季节性差异,旱季与雨季城镇污水排放的贡献比例均为最高,分别为31.40%和65.66%,且雨季污水排放对NO₃^-的影响远高于旱季,夏季居民用水增加导致大量污水排放至流域内是引起这一现象的主要原因.     

污水氮浓度和NH4+/NO3-比对粉绿狐尾藻去氮能力和植物体氮组分的影响

采用溶液培养法,设置3个氮浓度20、100、200 mg·L-1和3个NH_4~+/NO_3~-比1∶0、0.5∶0.5、0∶1,研究污水氮浓度和NH_4~+/NO_3~-比对粉绿狐尾藻去氮能力和植物体氮组分的影响.结果表明,粉绿狐尾藻的生物量在第1周增长最快,其中氮浓度20 mg·L-1、100 mg·L-1时,生物量以NH_4~+/NO_3~-=1∶0处理最大;氮浓度200 mg·L-1时,以NH_4~+/NO_3~-=0.5∶0.5处理最大.粉绿狐尾藻在第1周对总氮、铵态氮和硝态氮去除速率最高,且随氮浓度升高而增加;氮浓度20 mg·L-1时,铵态氮和硝态氮的去除率无显著差异,氮浓度100 mg·L-1、200 mg·L-1时硝态氮的去除率高于铵态氮.粉绿狐尾藻氮积累量及对水体和底泥氮去除的贡献率均随氮浓度升高而增加,其氮含量和积累量均以第1周增长最快,氮浓度20 mg·L-1时氮积累贡献率以NH_4~+/NO_3~-=0∶1最大,氮浓度100 mg·L-1、200 mg·L-1时以NH_4~+/NO_3~-=0.5∶0.5最大.粉绿狐尾藻体内蛋白质、氨基态氮和硝态氮的含量均随氮浓度的升高而增加,且蛋白质氨基态氮硝态氮;NH_4~+/NO_3~-为1∶0和0.5∶0.5时蛋白质含量较高,NH_4~+/NO_3~-=1∶0时氨基态氮含量最高,NH_4~+/NO_3~-=0∶1时硝态氮含量最高.由此说明,在试验范围内,粉绿狐尾藻的去氮能力随污水氮浓度升高而提高,可以用于高氮浓度污水修复;粉绿狐尾藻喜铵态氮,但在100 mg·L-1以上的高氮浓度下以硝铵等比时生长和去除氮能力最强;粉绿狐尾藻体内氮组分受硝铵比调节,蛋白氮比例最高,铵态氮和硝态氮则分别随污水NH+4和NO-3比升高而提高.     

己唑醇在水溶液中的光化学降解研究

研究了高压汞灯光源下己唑醇在不同pH缓冲液中的光化学降解特性及NO3-和NO2-对光解的影响.结果表明,己唑醇在水溶液中的光解符合一级动力学规律.不同pH值缓冲溶液中的光解速率排序为:pH=7>pH=9>pH=5.在己唑醇水溶液中添加不同浓度的NO3-及NO2-,均会不同程度地影响己唑醇的光解速率.在0～20mg·L-1的浓度范围内,NO3-对己唑醇的光解均表现为促进作用,且随着添加浓度的增大促进作用增强;NO2-在0.4和2mg·L-1浓度下,对己唑醇的光解有一定的促进作用,而在10～20mg·L-1浓度时,表现为抑制作用.     

海水异养硝化-好氧反硝化芽孢杆菌SLWX2的筛选及脱氮特性

从分离自刺参养殖环境的7株候选菌株中筛选出1株具有较强异养硝化和好氧反硝化能力的菌株SLWX_2,通过形态学特征、生理生化特性和16S rRNA基因测序分析鉴定其为花津滩芽孢杆菌(Bacillus hwajinpoensis).该菌株脱氮特性研究结果表明,SLWX_224 h对氨氮、亚硝酸氮和硝酸氮的去除率分别达到100%、99.5%和85.6%;当3种无机氮源同时存在时,菌株优先利用氨氮,再利用NO_2~--N和NO_3~--N,72 h 3种无机氮的质量浓度均降至0.013 mg·L~(-1)以下,表明该菌株能同时进行异养硝化和好氧反硝化完成脱氮;在氨氮负荷500 mg·L~(-1)、亚硝酸氮负荷100 mg·L·~(-1)和硝酸氮负荷200 mg·L~(-1)范围内,该菌的脱氮能力不受明显抑制,对3种形态的氮均有良好去除效果,96 h最多可去除180 mg NH_4~+-N、30 mg NO_2~--N和120 mg NO_3~--N,并且在硝化过程中没有亚硝酸氮积累.该菌株在海水养殖和高盐高氮工业废水的脱氮处理方面具有更大潜力.     

Laboratory exposure systems to simulate atmospheric degradation of building stone under dry and wet deposition conditions

The design philosophy, construction and use of two exposure test systems are described, in which the objective is to simulate the degradation of stone samples under, respectively, the ‘dry’ and ‘wet’ deposition of atmospheric pollutants. Some element of realistic acceleration is possible in certain experiments. Particular emphasis is placed upon using known presentation rates of the pollutants, both in respect of typical depositions of pollutants and their oxidation products appropriate for an industrial atmosphere. In the dry deposition rig, SO₂, NO₂, NO, HCl and the oxidant O₃ are presented individually or together at realistic deposition rates. In the wet deposition apparatus, SO²⁻₄, NO⁻₃ and Cl⁻ at a pH of 3.5, simulating ‘acid rain’ but in a more concentrated form, are deposited. The dry deposition chamber can be operated at constant relative humidity (typically 84%) with pre-dried or precisely wetted stones to simulate episodic rain wetting, or using other methods of wet/dry cycling, which are also a feature of the wet deposition chamber. Heating and cooling of the samples is also possible, as is the use of shaped or coupled stones of different kinds such as are found in a building facade. The results are illustrated in terms of data on the weight change, the anion content of stone and run-off, the pH change of run-off and the total calcium reacted, using Portland stone, as a prelude to later papers in which behaviour of a whole matrix of stone types and environments is presented and discussed. Such an approach permits the eventual production of ‘pollutant-material response’ relationships and damage functions for comparison with and prediction of external exposure results.     

FNA的抑制作用及反硝化过程的交叉影响

亚硝酸盐和硝酸盐通常被认为对反硝化细菌的代谢有抑制作用.通过大量批式试验,对不同浓度亚硝酸盐在不同pH条件下对硝酸盐还原的抑制作用及2种电子受体之间的交叉影响做了研究.结果表明,硝酸盐还原与游离亚硝酸(FNA)有显著的相关关系,FNA而非亚硝酸盐是硝酸盐还原的真正抑制剂.FNA浓度为0.01～0.025mg·L-1时硝酸盐还原能力受抑制程度为60%,当FNA浓度0.2mg·L-1时,硝酸盐还原反应被完全抑制.此外,污泥亚硝酸盐还原能力也受FNA抑制,当FNA浓度由0.01mg·L-1增至0.2mg·L-1,亚硝酸盐还原能力下降80%.研究还发现,亚硝酸盐还原受硝酸盐抑制影响很小,不同浓度抑制剂下还原能力恢复达90%以上.相反,硝酸盐还原能力仅恢复3.04%～72.54%,且恢复程度主要取决于抑制剂投加量,而受抑制时间和抑制剂投加方式影响较小.     

产色链霉菌(Streptomyces chromogenes)和立枯丝核菌(Rhizoctonia solani)转化NO3-的研究

筛选出２株真菌,产色链霉菌（Ｓｔｒｅｐｔｏｍｙｃｅｓ ｃｈｒｏｍｏｇｅｎｅｓ）和立枯丝核菌（Ｒｈｉｚｏｃｔｏｎｉａ ｓｏｌａｎｉ）具有转化ＮＯ３＾－的活性。它们的生比枯草芽孢杆菌（Ｂａｃｉｌｌｕｓ ｓｕｂｔｉｌｉｓ）还强。产色链霉菌和立枯丝核菌将ＮＨ４＾＋转化为ＮＯ３＾＿的机理也不同于真菌尖孢镰刀菌（Ｆｕｓａｒｉｕｍｏｘｙｓｐｏｒｉｕｍ）必需有ＮＯ３＾－或ＮＯ２＾－的诱导才具有活性,它们可直接将硫     

蠡河底泥中反硝化复合菌群富集及菌群结构研究

从无锡市滨湖区蠡河底泥中富集培养反硝化复合菌群,研究其在不同富集培养阶段TN、NO-3-N、NO-2-N、NH+4-N和COD动态变化,分析反硝化过程中气体释放总量、释放速率和成分,通过构建全长16S r DNA克隆文库研究其菌落结构.结果表明,反硝化复合菌群富集在阶段4时脱氮效果最佳,仅在9 h内,330 mg·L-1的TN负荷下,TN去除率达90.9%,NO-3-N去除率达100%,中间产物NO-2-N和NH+4-N积累量最少,分别为3.39 mg·L-1和16.64 mg·L-1,COD去除率达85%;释放气体260m L,气体主要成分为N2,同时还有少量的CH4和CO2等.富集培养反硝化复合菌群细菌属于Pseudomonadaceae科和Rhodocyclaceae科,为Proteobacteria门,OUT丰度分别为57.8%和31.6%,Pseudomonadaceae科是优势类群.