北京大气气溶胶部分无机组分及相关气体的浓度变化

利用SJAC-MOBIC在2000-05～2000-09的3个采样时段测量了北京大气中的气溶胶SO₄^2-、NO₃^-、NO₂^-、Cl^-及相关气体组分,得出了这些污染组分的逐时变化.结果表明气溶胶Cl^-、NO₂^-、NO₃^-及气体HCl、HNO₂和HNO₃有明显的变化规律,SO₂和气溶胶SO₄^2-的变化取决于SO₂的排放,SO₄^2-的峰值一般比SO₂的峰值晚2h左右.     

Products and mechanism of the reaction between NO3 and dimethylsulphide in air

The reaction between NO₃ and dimethylsulphide (DMS) in air has been studied in a 480 ℓ reaction chamber. Intermediates and end products were identified by FT-IR and ion chromatography.HNO₃, CH₂O, SO₂ and methanesulphonic acid were found to be the main products of the reaction, with methanesulphonic acid as the most abundant sulphur compound. Organic peroxynitrates and CH₃SNO₂ have been identified as intermediates from their characteristics spectral features. Based on the results obtained a mechanism for the reaction DMS+NO₃ is proposed, which has hydrogen abstraction as the first step. The formation of HNO₃ followed by removal of HNO₃ by deposition may represent an efficient night-time sink of NO_x in the marine troposphere.     

Ambient concentrations,scavenging ratios,and source regions of acid related compounds and trace metals during winter in northern michigan

Daily measurements the atmospheric cocnentrations of HNO₃, NO₃^-, NO₂, SO₂, SO₄²⁻, NH₄⁺, and several trace metals were made at the University of Michigan Biological Station over a 124-day period during the 1984–1985 winter. The composition of the daily precipitation was also determined. The relative contributions of scavenged NO₃⁻ and HNO₃ to the precipitation was estimated by assuming that the NO₃⁻ scavenging ratio was the same as that of trace metals with a similar particle size. Similarly, the SO₄²⁻ and SO₂ contributions were based on the scavenging ratios of NH₄⁺ and trace metals. On this basis, it was determined that the event median NO₃⁻ and HNO₃ scavenging ratios were 500 and 3500, respectively. HNO₃ scavenging accounted for 83% of the total scavenged NO₃⁻. Scavenging of SO₄²⁻ accounted for all the snow SO₄²⁻ in 67% of the events. In the remaining events, some SO₂ was scavenged, with a median scavenging ratio of 219. Overall, 67% of the snowfall acidity appeared to be due to HNO₃ scavenging. Backward air-mass trajectories that were calculated for each event were used to determine the general source regions of the acidic species. Snow associated with air masses from the south and west accounted for 81 and 75% of the deposited NO₃⁻ and SO₄²⁻, respectively.     

Fogwater chemistry at Riverside,California

Fog, aerosol, and gas samples were collected during the winter of 1986 at Riverside, California. The dominant components of the aerosol were NH₄⁺, NO₃⁻, and SO₄₂₋. Gaseous NH₃ was frequently present at levels equal to or exceeding the aerosol NH₄⁺. Maximum level were 3800, 3100, 690 and 4540 neq m⁻³ for NH₄⁺, NO₃²⁻ and NH_3(g), respectively. The fogwater collected at Riverside had very high concentrations, particularly of the major aerosol components. Maximum concentrations were 26,000 29,000 and 6200 μM for NH₄⁺, NO₃⁻ and SO₄²⁻, respectively. pH values in fogwater ranged from 2.3 to 5.7. Formate and acetate concentrations as high as 1500 and 580 μM, respectively, were measured. The maximum CH₂O concentration was 380 μM. Glyoxal and methylglyoxal were found in all the samples; their maximum concentrations were 280 and 120 μM, respectively. Comparison of fogwater and aerosol concentrations indicates that scavenging of precursor aerosol by fog droplets under the conditions at Riverside is less than 100% efficient.The chemistry at Riverside is controlled by the balance between HNO₃ production from NO_x emitted throughout the Los Angeles basin and NH₃ emitted from dairy cattle feedlots just west of Riverside. The balance is controlled by local mixing. Acid fogs result at Riverside when drainage flows from the surrounding mountains isolate the site from the NH₃ source. Continued formation of HNO_3(g) in this air mass eventually depletes the residual NH_3(g). A simple box model that includes deposition, fog scavenging, and dilution is used to assess the effect of curtailing the dairy cattle feedlot operations. The calculations suggest that the resulting reduction of NH₃ levels would decrease the total NO₃⁻ in the atmosphere, but nearly all remaining NO₃⁻ would exist as HNO₃. Fogwater in the basin would be uniformly acidic.     

FTIR spectroscopic measurements of surface bond products of nitrogen oxides on aerosol surfaces—implications for heterogeneous HNO2 production

FTIR spectroscopy measurements have been made to investigate the products of heterogeneous reactions of nitrogen oxides like NO₂, N₂O₅ and HNO₂ in the presence of water vapour on artificial and natural aerosol surfaces. Surface species on NaCl particles differ significantly from those on urban aerosols or fly ash. Evidence for a nighttime production of NO₂⁻ on sea-salt surfaces from reactions of N₂O₅ and water vapour is given.     

Nitrous and nitric acid measurements at sites in South-East England

Measurements of HONO and HNO₃ have been made using annular denuder samplers at sites in south-east England. Whilst concentrations of HNO₃ exhibited a diurnal variation, with a maximum in mid-afternoon nitrous acid shows the opposite diurnal cycle with maximum levels at night due to daytime photolysis. Concentrations of HONO increase with those of NO₂, and elevated nighttime HONO level appear to be followed by high levels of HNO₃ the following day. Average concentrations of HONO (0.45± 0.26 ppb in 24 h samples are comparable to those of HNO₃ (0.56±0.36 ppb in 24 h samples), each representing about 5–10% of the concentration of NO₂. Although NO₂ oxidation provides the source of HNO₃ concentrations of the two compounds are not related, presumably since the formation of NH₄NO₃ aerosol limits HNO₃ concentrations at out site.     

Physicochemical damage parameters for the action of SO2 and NO2 on single pieces of marble

The theoretical analysis for measurement of building-damage parameters by RF-GC technique is applied to the action of SO₂ and NO₂ on marble. The experiments with SO₂ were performed with five different geometric forms of single pieces of marble at 373.2 K and were repeated after washing these pieces 8 times with three-distilled water. All six physicochemical parameters determined show negligible variations for the same solid form at the same temperature, but they are different for the various geometrical forms. The mass transfer coefficients K_g and K_s and their ratio K seem to be the most invariant parameters with respect to the form. After washing with water, some of the parameters change considerably.The action of NO₂ was studied on a sphere only, but at five different temperatures. The physicochemical parameters for the action of this gas are three orders of magnitude smaller than those of SO₂ (except K), leading to 3700 times bigger resistance of marble to mass transfer of NO₂ than of SO₂. From the variation of the parameters with temperature, it is concluded that both mass transfer coefficients, K_g and K_s, pertain to activated processes with activation energies 39 and 27 kJ mol⁻¹, respectively. The reaction of the adsorbed gas with the solid is less activated, whereas the adsorption equilibrium constant K does not change with temperature.     

A diffusion tube survey of NO2 levels in urban areas of the U.K.

A nationwide survey of ambient NO₂ concentrations has been carried out by Warren Spring Laboratory and AEA Technology, Harwell, in urban areas of the U.K. The survey utilised passive diffusion tube samplers, deployed at 363 existing smoke/SO₂ monitoring stations, and ran from July to December 1986.Although undertaken primarily to provide an independent check on the siting of monitoring stations to determine compliance with the European Community NO₂ Directive, the survey provides for the first time a nationwide picture of urban levels of this pollutant. London was found to experience the highest average NO₂ concentrations in the U.K., with these being highest close to busy roads. Concentrations were found to be only moderately higher in winter than in summer.Correlations between measurements of SO₂, smoke and NO₂ were examined. The closest correlation is observed between NO₂ and smoke, indicating traffic to be a dominant source of these pollutants. NO₂ data are also shown to correlate well with disaggregated NO_x emission data for the U.K.     

稻田气溶胶NH3和气体NOx排放在线测定研究

气溶胶NH3和气体NOx是大气颗粒物和降水的主要成分,是形成气溶胶的关键物种.田间集约化氮肥施用是气溶胶NH3和气体NOx的一个重要来源,目前该领域的研究鲜有报道.2010年5月～2010年10月,在线监测了稻田施用尿素后气溶胶NH3和气体NOx的排放情况.监测系统的时间分辨率设置为1 h.在4次稻田施肥试验中,施肥后对气溶胶NH3排放和相应的气象因子连续采样20 d.在第4次施肥试验中,施肥后连续采样47 d,进而研究气体NOx的排放规律及其与气象因子的关系.结果表明,气溶胶NH3的排放因子分别为2.6%、5.5%、4.0%和1.6%,相应的排放通量分别为3.97、2.08、1.52和1.22 kg·hm-2.温度(空气温度和土壤温度)是影响稻田施肥气溶胶NH3排放的主要因子,而空气湿度和土壤水分对其排放的影响却不明确.通过分析监测数据可知,稻田施肥后NO2-N排放量与NO-N排放量的比值为9/4,气体NOx的排放因子和排放通量分别为0.14%和0.30 kg·hm-2.气象因子与气体NOx排放通量的关系也进行了初步探讨.     

Urban NO2 concentrations in the U.K. in 1987

A mational air quality monitoring network has been established in the U.K. by Warren Spring Laboratory, on behalf of the U.K. Department of the Environment, to determine compliance with the European Community Directive for nitrogen dioxide. Data from the six network sites for 1987 are presented and analysed.No site in the U.K. breached the NO₂ Directive Limit Value during this year, though the closest approaches were at the two London stations. Annual average NO₂ concentrations, which varied from 23 to 39 ppb, were consistent with the top five percentile of long-term measurements from a national survey of over 360 U.K. urban areas carried out in 1986.The temporal variability of NO₂ concentrations was substantially lower over all time scales than that for NO: winter/summer ratios for all sites averaged 2.9 for NO and 1.3 for NO₂. Most sites showed strong diurnal variations for NO which were primarily influenced by traffic emissions during rush hours, although these variations were less marked for NO₂.A markedly non-proportional relationship between annual and daily average NO₂ and NO_x levels was observed, and this has important implications for its efficacy of possible NO_x emission control strategies. An analysis of measured NO₂/NO_x ratios over weekends and weekday periods demonstrates, for instance, that a 20% emission cutback may result, typically, in a corresponding NO₂ reduction of 12% at urban locations in the U.K. NO_x reductions, however, exert a more proportional effect on NO₂ concentrations at kerbside and rural locations.     

Uptake of NO,NO2 and O3 by sunflower (Helianthus annuus L.) and tobacco plants (Nicotiana tabacum L.): dependence on stomatal conductivity

The uptake of NO, NO₂ and O₃ by sunflowers (Helianthus annuus L. var. giganteus) and tobacco plants (Nicotiana tabacum L. var. Bel W3), using concentrations representative for moderately polluted air, has been determined by gas exchange experiments. Conductivities for these trace gases were measured at different light fluxes ranging from 820 μEm⁻²s⁻¹ to darkness. The conductivities to water vapor and the trace gases are highly correlated. It is concluded that the uptake of NO, NO₂ and O₃ by sunflowers and tobacco plants is linearly dependent on stomatal opening. While the uptake of NO is limited by the mesophyll resistance, the uptake of NO₂ is only by diffusion through the stomata. Loss processes by deposition to the leaf surfaces are more pronounced for O₃ than for NO and NO₂.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.     

European scale application of atmospheric reactive nitrogen measurements in a low-cost approach to infer dry deposition fluxes

A European scale network was established in 2006 as part of the NitroEurope Integrated Project to infer reactive nitrogen (Nr) dry deposition fluxes, based on low-cost sampling of gaseous and aerosol species and inferential modelling. The network provides monthly measurements of NH₃, NH₄⁺, HNO₃ and NO₃⁻, as well as SO₂, SO₄²⁻, HCl, Cl⁻ and base cations at 58 sites. Measurements are made with an established low-cost denuder methodology (DELTA) as a basis to: (1) examine temporal trends and spatial patterns across Europe, (2) improve and calibrate inferential modelling techniques to estimate exchange of Nr species, (3) provide best estimates of atmospheric dry N deposition, and (4) permit an analysis of net GHG exchange in relation to atmospheric and agricultural N inputs at the European scale. Responsibility for measurements is shared among seven European laboratories. An inter-comparison of the DELTA implementation by 6 laboratories at 4 test sites (Montelibretti, Italy; Braunschweig, Germany; Paterna, Spain and Auchencorth, UK) from July to October 2006 provided training for the laboratories and showed that good agreement was achieved in different climatic conditions (87% of laboratory site-means within 20% of the inter-laboratory median). Results obtained from the first year of measurements show substantial spatial variability in atmospheric Nr concentrations, illustrating the major local (NH₃) and regional (HNO₃, NO₃⁻, and NH₄⁺) differences in Nr concentrations. These results provide the basis to develop future estimates of site-based Nr dry deposition fluxes across Europe, and highlight the role of NH₃, largely of agricultural origin, which was the largest single constituent and will dominate dry Nr fluxes at most sites.     

N-TiO2/PSF中空纤维复合膜光催化烟气脱硝研究

采用溶胶-凝胶法以聚砜(PSF)中空纤维膜为载体制备了N-Ti O2/PSF中空纤维复合膜催化剂,考察其光催化烟气脱硝性能.紫外光催化的NO去除效率可达63%,去除负荷可达213.6 g·m-3·h-1.采用紫外-可见光谱(UV-Vis)、X-射线光电子能谱(XPS)和傅里叶变换红外光谱(FTIR)表征了N-Ti O2/PSF中空纤维复合膜催化剂.UV-Vis光谱分析表明,掺杂N改性的Ti O2复合膜光催化层在紫外和可见光波段的吸收性能都有极大的改善.XPS证明了O—Ti—N键能的存在.N-Ti O2/PSF中空纤维膜光催化处理NO的作用机制为NO气体通过中空纤维膜传质到NTi O2催化膜,光催化产生羟基自由基和超氧负离子,NO气体被羟基自由基和超氧负离子氧化成易处理的NO2和HNO3.     

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.     

The spatial distribution and particle size of some inorganic nitrogen,sulphur and chlorine species over the North Sea

The use of filter packs and a cascade impactor during a series of research cruises in the southern area of the North Sea has yielded detailed spatial distribution patterns of aerosol concentrations, Cl⁻, NO₃⁻, SO₄²⁻¹ and NH₄⁺ and gaseous concentrations, HCl, HNO₃ and NH₃. The overall distribution of the atmospheric concentrations closely parallels published modelled results for metallic species. The chemical transformations of these aerosols and gases are investigated together with their interactions with the seasalt aerosol. Aerosol chloride loss is greatest in the more polluted areas, whilst concentrations products of NH₃ with HNO₃ and HCl appear insufficient to sustain the existence of NH₄NO₃ and NH₄Cl. Nitrate is associated predominantly with larger particles and appears to be present substantially as a surface coating on marine aerosol. The total dry deposition input for nitrogen species is calculated for the southern sector with extrapolation to the whole of the North Sea, using particle size weighted deposition velocities of 0.63 and 0.21 cm s⁻¹ for NO₃⁻¹ and NH₄⁺, respectively, and literature-derived values for the gaseous constituents. Finally the use of air-mass back trajectories illustrates the role of source regions in influencing the chemical composition of the North Sea atmosphere.     

Inhibition of photosynthesis and leaf conductance interactions induced by SO2, NO2 and SO2 + NO2

Effects of 2-h exposures to 0–1 μmol mol⁻¹ SO₂, NO₂ and (1:1) SO₂ + NO₂ on CO₂ uptake by standardized snap bean leaves were studied. Interactions resulting from pollutant-induced changes in leaf conductance were evaluated. Minimum exposure concentrations required to depress CO₂ exchange rates (CER) under the test conditions were:0.17 μmol mol⁻¹ SO₂, 0.38 μmol mol⁻¹ NO₂, and 0.08 μmol mol⁻¹ of each pollutant in the 1:1 mixture. Treatments with 1 μmol mol⁻¹ NO₂ reduced CER 10% without affecting leaf conductance. One μmol mol⁻¹ SO₂ depressed CER by 50%. Leaf conductances increased in SO₂-treated leaves showing 30% inhibition of CER. Greater inhibition led to subsequent stomatal closure. Inhibition caused by the individual pollutants (applied singly) was linear over the range of concentrations investigated. The dual-pollutant mixture produced a synergistic response that was most pronounced at the lower pollutant concentrations. The potentiated effect was correlated with marked stomatal closure.Experimental plants for this study were grown under low moisture stress conditions to enhance stomatal opening in the plant stock material and reduce (damp) the potential for further SO₂-induced stimulation of stomatal opening. The experiments were designed to obtain limiting data for the test conditions.     

大气NOx测量准确性问题分析

采用美国热电公司的NO-N02-NOx分析仪(Model 42i TL)和NOy分析仪(Model 42i NOy),在2011年1月-10月期间,对北京城市大气中的NO、NOx和NOy进行了连续在线测量.两台仪器对NO的测量结果具有较高的一致性(r＞0.998,p＜0.01),说明两台仪器测量精度基本一致.将NOy分析仪(Model 42i NOy)采样口处安装和不安装颗粒物过滤膜两种条件下测量的NOy结果与NO-NO2-NOx分析仪所测的NOx结果分别进行了相关性分析([NOy] =0.989x[NOx],R2 =0.993;[NOy] =1.134 ×[NOx],R2=0.959),得出以下两个结论:①以颗粒态硝酸盐为代表的颗粒物是造成NOx与NOy偏差的主要原因,其所占比例在10％左右;②目前Model 42i-TL所测NOx的浓度水平较真实值偏高,其测量值更接近气态NOy的浓度水平.为估算NO2测值被高估的程度(以2011年8月6日-15日观测数据为例),用扣除部分气态NOz物种(HONO、HNO3、PAN、PPN)的修正方法,推论出在夏季N02被高估约7％(R2=0.968).     

Transported acid aerosols measured in southern Ontario

During the period 29 June 1986–9 August 1986, a field health study assessing the acute health effects of air pollutants on children was conducted at a summer girls' camp on the northern shore of Lake Erie in SW Ontario. Continuous air pollution measurements of SO₂, O₃, NO_x, particulate sulfates, light scattering, and meteorological measurements including temperature, dew point, and wind speed and direction were made. Twelve-hour integrated samples of size fractioned particles were also obtained using dichotomous samplers and Harvard impactors equipped with an ammonia denuder for subsequent hydrogen ion determination. Particulate samples were analyzed for trace elements by X-ray fluorescence and Neutron Activation, and for organic and elemental carbon by a thermal/optical technique. The measured aerosol was periodically very acidic with observed 12-h averaged H⁺ concentrations in the range < 10–560 nmoles m⁻³. The aerosol H⁺ appeared to represent the net strong acidity after H₂SO₄ reaction with NH₃(g). Average daytime concentrations were higher than night-time for aerosol H⁺, sulfate, fine mass and ozone. Prolonged episodes of atmospheric acidity, sulfate, and ozone were associated with air masses arriving at the measurement site from the west and from the southwest over Lake Erie. Sulfate concentrations measured at the lakeshore camp were more than twice those measured at inland sites during extreme pollution episodes. The concentration gradient observed with onshore flow was potentially due to enhanced deposition near the lakeshore caused by discontinuities in the meteorological fields in this region.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.