A model investigation of the impact of increases in anthropogenic NO x emissions between 1967 and 1980 on tropospheric ozone

Recent observations suggest that the abundance of ozone between 2 and 8 km in the Northern Hemisphere mid-latitudes has increased by about 12% during the period from 1970 to 1981. Earlier estimates were somewhat more conservative suggesting increases at the rate of 7% per decade since the start of regular observations in 1967. Previous photochemical model studies have indicated that tropospheric ozone concentrations would increase with increases in emissions of CO, CH₄ and NO _x . This paper presents an analysis of tropospheric ozone which suggests that a significant portion of its increase may be attributed to the increase in global anthropogenic NO _x emissions during this period while the contribution of CH₄ to the increase is quite small. Two statistical models are presented for estimating annual global anthropogenic emissions of NO _x and are used to derive the trend in the emissions for the years 1966–1980. These show steady increase in the emissions during this interval except for brief periods of leveling off after 1973 and 1978. The impact of this increase in emissions on ozone is estimated by calculations with a onedimensional (latitudinal) model which includes coupled tropospheric photochemistry and diffusive meridional transport. Steady-state photochemical calculations with prescribed NO _x emissions appropriate for 1966 and 1980 indicate an ozone increase of 8–11% in the Northern Hemisphere, a result which is compatible with the rise in ozone suggested by the observations.     

Global NOx Production by Lightning

Lightning is thought to represent an important source of tropospheric reactive nitrogen species NO_x (NO + NO₂),but estimates of global production of NO_x by lightning varyconsiderably. We evaluate the production of NO_x by lightning using a global chemical/transport model, satellite lightning observations, and airborne NO_x measurements. Various model calculations are conducted toassess the global NO_x production rate of lightning by comparing the model calculations with airborne measurements. The results show that the simulated NO_x in the tropical middle and upper troposphere are very sensitiveto the amount and altitude of the lightning NO_x used in the model. A global lightning NO_x production of 7 Tg N yr^–1uniformly distributed in convective clouds or 3.5 Tg N yr^–1 distributedin the upper cloud regions produces good agreement between calculated and measured NO_x concentrations in the tropics.     

Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.     

中国地区闪电和对流层上部NOx的时空分布特征及其相关性分析

为了解闪电对对流层上部NO_x的贡献,本文利用美国全球水资源和气候中心（GHRC）提供的1995年4月~2005年12月的闪电卫星格点资料及高层大气研究卫星 (UARS) 上的卤素掩星试验装置 (HALOE) 1991年10 月~2005 年11月的观测资料,分析了中国地区闪电与对流层上部NO_x体积混合比的时空分布特征及两者的相关性.结果表明:中国地区闪电和对流层上部的NO_x在季节分布、年际分布和空间分布上保持很好的一致性,闪电是对流层上部NO_x的重要来源;NO极值高度在350 hPa左右,云闪直接产生的NO是极值产生的主要原因,NO₂的极值高度在250 hPa左右,因为闪电产生的NO在传输过程中会被氧化成NO₂并通过雷暴的垂直输送作用抬升到更高高度;强对流活动有利于NO_x的传输,而人类活动产生的NO_x一般较难输送到对流层上部,因此闪电多发区的NO_x极值较大,所在的高度也较高.     

On the Spatial Distribution and Seasonal Variation of Lower-Troposphere Ozone over Europe

Surface ozone data from 25 Europeanlow-altitude sites and mountain sites located between79°N and 28°N were studied. The analysiscovered the time period March 1989–February 1993.Average summer and winter O₃ concentrations inthe boundary layer over the continent gave rise togradients that were strongest in the north-west tosouth-east direction and west-east direction, respectively. WintertimeO₃ ranged from 19 to 27 ppbover the continent, compared to about 32 ppb at thewestern border, while for summer the continentalO₃ values ranged between 39 and 56 ppb and theoceanic mixing ratios were around 37 ppb. In the lowerfree troposphere average wintertime O₃ mixingratios were around 38 ppb, with only an 8 ppbdifference between 28°N and 79°N. For summerthe average O₃ levels decreased from about 55 ppbover Central Europe to 32 ppb at 79°N. Inaddition, O₃ and O_x(= O₃ + NO₂)in polluted and clean air were compared. Theamplitudes of the seasonal ozone variations increasedin the north-west to south-east direction, while thetime of the annual maximum was shifted from spring (atthe northerly sites) to late summer (at sites inAustria and Hungary), which reflected the contributionof photochemical ozone production in the lower partsof the troposphere.     

On the Budget of OH Radicals and Ozone in an Urban Plume from the Decay of C5–C8 Hydrocarbons and NOx

Simultaneous measurements of ozone and ozoneprecursors were made during a field campaign atSchauinsland in the Black Forest and in the valleynorth of Schauinsland that channels the flow ofpolluted air from the city of Freiburg to the site.From the decay of hydrocarbons and NO_x between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HO_x it is concluded that therelatively high OH concentrations (5–8 ×10⁶cm^-3) in the presence of high NO₂concentrations cannot be explained by the knownprimary sources. The budget can be closed if efficientrecycling of OH via HO₂ is assumed to occur andthat, based on the measured hydrocarbons, 2 HO₂molecules are formed for each OH radical that reactswith a hydrocarbon molecule. This assumption is inaccordance with the budget of O_x obtained from ourmeasurements and with results from earliermeasurements of alkylnitrates and peroxy radicals atSchauinsland. A possible conclusion is that the decayof precursors and production of photooxidants in urbanplumes proceeds at a faster rate than is currentlyassumed. The potential role of biogenichydrocarbons for the radical budget is alsodiscussed.     

Catalysed self-cleaning of air on the earth's surface

Generally, it is assumed that UV-light, high temperature or reactive molecules like O₃ and OH are needed to activate gas reactions in air. In consequence, the catalytic activity on natural materials such as sand and soil on the earth's surface is assumed to be insignificant. We have measured O₂-dissociation rates on natural quartz sand at 40˚C and compared these with O₂-dissociation rates near 500˚C on materials with well-known catalytic activity. In terms of probabilities for dissociation of impinging O₂-molecules the measured rates are in the 10⁻¹²–10⁻⁴ range. We have also measured dissociation rates of H₂ and N₂, water-formation from H₂ and O₂ mixtures, exchange of N between N₂, NO _x and a breakdown of HNO₃, NO₂ and CH₄ on natural quartz sand at 40˚C. The measured rates together with an effective global land area have been used to estimate the impact of thermodynamically driven reactions on the earth's surface on the global atmospheric budgets of H₂, NO₂ and CH₄. The experimental data on natural quartz sand together with data from equilibrium calculations of air suggest that an expected increase in anthropogenic supply of air pollutants, such as NO _x or other “reactive” nitrogen compounds, hydrogen and methane, will be counter-acted by catalysis on the earth's surface. On the other hand, at Polar Regions and boreal forests where the “reactive” nitrogen concentration is below equilibrium, the same catalytic effect activates formation of bio-available nitrogen compounds from N₂, O₂ and H₂O.     

青藏高原闪电与NO_2的分析及中国内陆地区LNO_x产量的估算

为了进一步认识闪电活动与对流层氮氧化物的关系及更准确地估算中国地区闪电产生的氮氧化物(LNOx)总量,选取人口稀疏,工业生产水平较低的青藏高原地区作为研究区域,基于LIS(Lightning Imaging Sensor)和GOME-2(The Global Ozone Monitoring Experiment-2)卫星探测仪资料,分析了青藏高原中部区域2009年1月至2012年2月闪电与对流层NO2垂直浓度(VCD)月均值资料的时空分布特性和相关性。在此基础上,结合Beirle et al.(2004)的LNOx估算方法,估算了中国内陆地区的LNOx产量。结果表明:青藏高原地区对流层NO2与闪电与在年际趋势、空间分布及季节变化上保持很好的一致性,闪电密度与NO2VCD的线性拟合相关系数为0.84,这表明青藏高原地区NOx受人为源影响小,是研究LNOx的理想区域。基于拟合结果,估算得到中国内陆地区LNOx的年均产量为0.15(0.03~0.38)Tg(N)a-1。这一结论进一步缩小了以往研究中中国地区LNOx产量估算的不确定范围,有助于更清楚地认识闪电在中国气候变化中的重要作用。     

A one-dimensional photochemical model of the troposphere with planetary boundary-layer parameterization

The results from a one-dimensional photochemical model of the troposphere representative of summertime conditions at Northern Hemisphere mid-latitudes are presented. A parameterization of mixing processes within the planetary boundary layer (PBL) has been incorporated into the model for both the daytime convective PBL and the formation of the nocturnal PBL. One result of the parameterized PBL is that the concentrations of some trace species in the free troposphere are 20–30% higher than when mixing processes are described by a vertical eddy diffusion coefficient which is held constant with respect to height and time.The calculations indicate that the lifetime of the oxides of nitrogen (NO _x =NO+NO₂) against photochemical conversion to nitric acid (HNO₃) during summertime conditions is on the order of 6 h. This lifetime is short enough to deplete most of the NO _x in the PBL, resulting in the finding that other reactive nitrogen species (HNO₃ and peroxyacetyl nitrate) are more abundant than NO _x throughout the free troposphere, even though NO _x is the most abundant reactive nitrogen species at the surface. The effects of the inclusion of anthropogenic nonmethane hydrocarbon (NMHC) chemistry are also discussed. The inclusion of NMHC chemistry has a pronounced effect on the photochemistry of tropospheric oxone and increases thein situ column production by more than 30%.     

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 10³ cm^-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO₂) and methyl nitrate (CH₃ONO₂) were shown to be minor components of the total NO _y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO₂ to HOCl or Cl₂ were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.     

A three-dimensional model of the global ammonia cycle

Using a three-dimensional (3-D) transport model of the troposphere, we calculated the global distributions of ammonia (NH₃) and ammonium (NH ₄ ⁺ ), taking into account removal of NH₃ on acidic aerosols, in liquid water clouds and by reaction with OH. Our estimated global 10°×10° NH₃ emission inventory of 45 Tg N-NH₃ yr^– provides a reasonable agreement between calculated wet NH ₄ ⁺ deposition and measurements and of measured and modeled NH ₄ ⁺ in aerosols, although in Africa and Asia especially discrepancies exist.NH₃ emissions from natural continental ecosystems were calculated applying a canopy compensation point and oceanic NH₃ emissions were related to those of DMS (dimethylsulfide). In many regions of the earth, the pH found in rain and cloud water can be attributed to acidity derived from NO, SO₂ and DMS emissions and alkalinity from NH₃. In the remote lower troposphere, sulfate aerosols are calculated to be almost neutralized to ammonium sulfate (NH₄)₂SO₄, whereas in the middle and upper troposphere, according to our calculations, the aerosol should be more acidic, as a result of the oxidation of DMS and SO₂ throughout the troposphere and removal of NH₃ on acidic aerosols at lower heights. Although the removal of NH₃ by reaction with the OH radical is relatively slow, the intermediate NH₂ radical can provide a substantial annual N₂O source of 0.9 _–0.4 ^+0.9 Tg, thus contributing byca. 5% to estimated global N₂O production. The oxidation by OH of NH₃ from anthropogenic sources accounts for 10% of the estimated total anthropogenic sources of N₂O. This source was not accounted for in previous studies, and is mainly located in the tropics, which have high NH₃ and OH concentrations. Biomass burning plumes, containing high NO _x and NH₃ concentrations provide favourable conditions for gas phase N₂O production. This source is probably underestimated in this model study, due to the coarse resolution of the 3-D model, and the rather low biomass burning NH₃ and NO _x emissions adopted. The estimate depends heavily on poorly known concentrations of NH₃ (and NO _x ) in the tropics, and uncertainties in the rate constants of the reactions NH₂ + NO₂ N₂O + H₂O (R4), and NH₂ + O₃ NH₂O + O₂ (R7).     

Development of a Ground-Based LIF Instrument for Measuring HOx Radicals: Instrumentation and Calibrations

An instrument for measuringtropospheric OH/HO₂ radicals by laser-inducedfluorescence developed in our laboratory is presentedin detail. It is based on FAGE (fluorescence assay bygas expansion) technique and OH is both excited anddetected at 308 nm corresponding to its A-X(0,0) band.The alignment of the laser beam, the design of thesample gas inlet, and the devices for the fluorescencedetection are optimized so as to reduce the backgroundsignal while keeping the OH sensitivity as high aspossible. A thermalized position of the expanding gasbeam is probed in our system and we did not observe asevere decrease of the HO_x sensitivities under humidconditions. An optical fiber is used for deliveringthe laser light to the fluorescence detection cellmounted outside at a high position. Thus the laserbeam alignment is by far simplified and is made highlyreproducible, once settled properly. For thecalibration, two methods are employed: a system withlaser absorption measurements of OH and a system ofsimultaneous photolysis of H₂O and O₂. Thecalibration factors are compared well within thecombined uncertainty. Using the latter system, theconversion efficiency of HO₂ to OH by NO additionis measured to be around 90%. The detection limitsfor OH and HO₂ (S/N = 2) are estimated to be3.3 × 10⁶ and 3.6 × 10⁶cm^–3 at noon,respectively, with an integration time of 1 min. Theresults of test observations at our institute are alsopresented.     

Evaluation of Modeled Spatially and Temporarily Highly Resolved Emission Inventories of Photosmog Precursors for the City of Augsburg: The Experiment EVA and Its Major Results

Emission inventories of NO_x, CO, and individual volatile organic compounds (VOC), highly resolved in space and time, belong to the most important input parameters for chemistry and transport models (CTM) used for ozone prediction. Because of the decisive influence of the input quality on the outcome of CTM simulations, the quality of emission inventories has to be assessed. This paper presents an experimental evaluation of the highly resolved emission inventories for the city of Augsburg. The emissions of the city, determined in March and October 1998 using mass balance and tracer techniques, and derived from the measured receptor concentration ratios, were compared with emissions modeled from an emission inventory. The modeled CO emissions were in agreement with the measured ones within the combined experimental and model uncertainties. More detailed CO emission model simulations suggest that the tendency of calculated CO emissions being smaller than the measured ones may be due to higher traffic activity in Augsburg. Modeled NO_x emissions were in agreement with the measured ones within the combined experimental and model uncertainties. Large deviations between modeled and measured values have been found for some individual NMHC compounds. The measured NMHC emission fingerprints were dominated by mobile sources. Substantial model predicted NMHC emissions from the solvent use could not be detected by measurements suggesting that they may not be correctly represented by the emission model.     

Subsonic aircraft and ozone trends

Growth in subsonic air traffic over the past 20 years has been dramatic, with an annual increase of }6.1% over the decade between 1978 and 1988. Furthermore, aircraft activities in the year 2000 are predicted to be double those of 1990, with a shift towards more high-flying, longhaul subsonics. Aircraft exhaust gases increase the amount of nitrogen oxides (NO _x ) in the upper troposphere/lower stratosphere through injection at cruise altitudes. Given that NO _x is instrumental in tropospheric ozone production and stratospheric ozone destruction, it is important to determine the influence of subsonic aircraft NO _x emissions on levels of atmospheric ozone. This paper describes calculations designed to investigate the impact that subsonic aircraft may already have had on the atmosphere during the 1980s, run in a 2-D chemical-radiative-transport model. The results indicate a significant increase in upper tropospheric ozone over the decade arising from aircraft emissions. However, when comparing model results with observational data, certain discrepancies appear. Lower stratospheric ozone loss over the 1980s does not appear to be greatly altered by the inclusion of aircraft emissions in the model. However, given the trend in greater numbers of long-haul subsonic aircraft, this factor must be considered in any further calculations.     

中美大气化学联合考察实验结果的初步分析与比较

根据临安区域本底站观测资料分析结果得出,中国中纬度地区秋、冬季O₃及其前体物NO_x等浓度偏高,可以对农作物和地表生态系统产生影响.观测结果表明:近地层大气O₃浓度主要决定于地面总辐射量控制下的光化学反应过程;O₃的生成受到前体物NO_x的控制,但O₃与NO_x存在着明显的非线性关系.从PEM-WESTA和B的实验及1995年的观测资料表明,O₃的生成效率随着NO_x浓度的增大而减小.尽管O₃的生成速率秋季比冬季的大,但由于秋季较高的NO_x抑制了过氧基的生成,因此冬季O₃的累积量几乎可以和秋季相比拟.在临安观测的NMHC和NO_x的比值比国外同纬度地区测值要大.这说明在临安本底站O₃的光化学生成中,NMHC不是控制物种.从而提示我们,在这些季节临安O₃光化学产物能够被NO_x浓度所控制.中美大气化学联合考察(PEM-WEST-B)实验期间,台湾省的卡盯站SO₂的平均浓度为0.29ppb,O₃的平均浓度为42.2ppb,可以认为此值为低纬度海岛的本底值.1994年PEM-WEST-B实验期间临安站的观测资料和台湾省的卡盯站资料相比,临安站SO₂的浓度约为卡盯站SO₂浓度的50倍左右,从而可以看出人类活动对大气本底的显着影响.     

闪电产生氮氧化物对青藏高原臭氧低谷形成的影响

为了进一步了解青藏高原闪电的产生氮氧化物（LNO_x）经由光化学反应对O₃浓度变化及夏季O₃低谷形成的可能影响,本文利用2005~2013年由OMI卫星得到的对流层NO₂垂直浓度柱（NO₂ VCD）、O₃总浓度柱（TOC）和O₃廓线以及星载光学瞬变探测器OTD和闪电成像仪LIS获取的总闪电数资料,对青藏高原和同纬度长江中下游地区的TOC和NO₂ VCD月均值时空分布特征、闪电与NO₂ VCD的相关性和O₃的垂直分布特征及其与LNO_x的关系进行了对比分析。结果表明,青藏高原的O₃低谷主要出现在夏季和秋季,其TOC值比同纬度长江中下游地区低约10~15 DU（Dobson unit）。青藏高原NO₂VCD总体较小,表现为夏高冬低的分布特征。青藏高原夏季O₃浓度受南亚高压的影响总体呈减小趋势,但因强雷暴天气导致对流层中上部LNO_x浓度升高,并随强上升气流向对流层顶输送,同时通过光化学反应使O₃浓度增加,缩小了青藏高原和同纬度地区的O₃浓度差,减缓了O₃总浓度的下降,抑制了夏季O₃低谷的进一步深化。     

The role of clouds in tropospheric photochemistry

We show that photochemical processes in the lower half of the troposphere are strongly affected by the presence of liquid water clouds. Especially CH₂O, an important intermediate of CH₄ (and of other hydrocarbon) oxidation, is subject to enhanced breakdown in the aqueous phase. This reduces the formation of HO _x -radicals via photodissociation of CH₂O in the gas phase. In the droplets, the hydrated form of CH₂O, its oxidation product HCO₂ ^–, and H₂O₂ recycle O₂ ^– radicals which, in turn, react with ozone. We show that the latter reaction is a significant sink for O₃. Further O₃ concentrations are reduced as a result of decreased formation of O₃ during periods with clouds. Additionally, NO _x , which acts as a catalyst in the photochemical formation of O₃, is depleted by clouds during the night via scavenging of N₂O₅. This significantly reduces NO _x -concentrations during subsequent daylight hours, so that less NO _x is available for O₃ production. Clouds thus directly reduce the concentrations of O₃, CH₂O, NO _x , and HO _x . Indirectly, this also affects the budgets of other trace gases, such as H₂O₂, CO, and H₂.     

Measurements of trace gases emitted by Australian savanna fires during the 1990 dry season

During 18–23 July 1990, 31 smoke samples were collected from an aircraft flying at low altitudes through the plumes of tropical savanna fires in the Northern Territory, Australia. The excess (above background) mixing ratios of 17 different trace gases including CO₂, CO, CH₄, several non-methane hydrocarbons (NMHC), CH₃CHO, NO _x (– NO + NO₂), NH₃, N₂O, HCN and total unspeciated NMHC and sulphur were measured. Emissionratios relative to excess CO₂ and CO, and emissionfactors relative to the fuel carbon, nitrogen or sulphur content are determined for each measured species. The emission ratios and factors determined here for carbon-based gases, NO _x , and N₂O are in good agreement with those reported from other biomass burning studies. The ammonia data represent the first such measurements from savanna fires, and indicate that NH₃ emissions are more than half the strength of NO _x emissions. The emissions of NO _x , NH₃, N₂O and HCN together represent only 27% of the volatilised fuel N, and are primarily NO _x (16%) and NH₃ (9%). Similarly, only 56% of the volatilised fuel S is accounted for by our measurements of total unspeciated sulphur.     

Nonlinear chemical couplings in the tropospheric NO x -HO x gas phase chemistry

A bifurcation phenomenon with relevance to atmospheric chemistry is discussed. The gasphase reactions in the troposphere exhibit two types of temporal evolution which are controlled by the strength of the source,Q, of nitric oxide, NO, via the nonlinear chemical coupling between the hydrogen oxides and nitrogen oxides chemistry. IfQ remains below a threshold value, all short-lived species, including NO, approach steady-state concentrations, while above the threshold bifurcation to another state with increasing (nonstationary) NO concentrations accompanied by a depletion of the OH and HO₂ abundances takes place.     

The influence of light intensity,SO2, NOx and C3H6 on sulfate aerosol formation

The photochemical oxidation of SO₂ in the presence of NO and C₃H₆ was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO₂ concentration were constant, SO₄ ^2- concentration, derived from the total volume of aerosol produced, peaked when [C₃H₆]/[NO] was approximately 6.0. Another increase im SO₄ ^2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO₂ oxidation mechanisms. At low [C₃H₆]/[NO] ratios, the processes proceed via the HO–SO₂ reaction, while at high ratios the O₃–C₃H₆ adduct is assumed to oxidize SO₂ to produce SO₄ ^2- aerosols.