Ammonia measurements at Niwot Ridge,Colorado and point arena,California using the tungsten oxide denuder tube technique

The applicability of the tungsten oxide denuder tube technique for the measurement of ammonia in the rural troposphere was investigated. The technique is based on selective chemisorption of NH₃ from a gas stream, thermal desorption, conversion to NO, and analysis by NO–O₃ chemiluminescence. Nitric acid, which is also collected and desorbed as NO, was distinguished from NH₃ by differences in desorption temperature. Substituted amines were also collected, but desorbed at a slightly lower temperature than NH₃ in dry air. At high relative humidities, alkylamines may be hydrolyzed to NH₃ on the denuder surface and hence detected as NH₃. Overheating of the denuder tube during the temperature-programmed desorption was found to cause significant irreversible degradation of system performance.The technique was used to measure NH₃ mixing ratios at two rural locations in the United States. At a mountain site in Colorado during the winter of 1984, the average NH₃ mixing ratio was 0.20 ppbv (=0.08 ppbv). At an isolated coastal site in northern California during the spring of 1985, the average NH₃ mixing ratio was 0.36 ppbv (=0.17 ppbv). Correlations of the latter measurements with wind direction and NO _x level suggest that the NH₃ mixing ratio in Pacific marine air at 40°N is <-0.25 ppbv.     

A molybdenum oxide annular denuder system for gas phase ambient ammonia measurements

An automated molybdenum oxide annular denuder system (MOADS) has been developed for gas phase ambient ammonia measurements. This system combines high sensitivity (detection limit <50 pptv) with continuous sampling, moderate collection times (30 min) and automated operation. The present denuder design confers two important advantages over the tungsten oxide coated quartz denuder tubes used previously for nitric acid and ammonia measurements. First, the present denuders use oxidized metal substrates and are easier to fabricate and more durable than denuders made from metal oxide coated glass or quartz tubes. Second, molybdenum (VI) oxide surfaces are used which oxidize a reproducible fraction of the adsorbed NH₃ directly to NO upon desorption eliminating the need for a secondary catalytic converter. Laboratory tests of the collection/recovery characteristics of annular denuders made from both the (IV) and (VI) oxides of tungsten and molybdenum are described and preliminary results from field tests are presented.     

Gaseous and Particulate Oxidized and Reduced Nitrogen Species in the Atmospheric Boundary Layer in Scandinavia in Spring

Observations of the concentration of several nitrogen containing compounds at five rural Scandinavian sites during March–June 1993 are reported. Total nitrate (NO ₃ ^- + HNO₃) and total ammonium (NH ₄ ⁺ + NH₃) were measured by denuder and filter pack. In general the methods agree well. At all sites the particulate fraction dominated, with the largest fraction of NO ₃ ^- and the lowest of NH ₄ ⁺ at the sites which were closest to the emission sources. The fraction of NO ₃ ^- of total nitrate increased with increasing NO₂ concentrations, indicating that the nighttime conversion of NO₂ to NO ₃ ^- is an important route of formation for NO ₃ ^- . A positive correlation was found between HNO₃ and O₃ in June at all sites, while no correlation was found early in the spring. Model calculations were made with a lagrangian boundary layer photooxidant model for the whole period, and compared to the measured concentrations. The calculated ratio between mean observed and modelled daily maximum concentrations of ozone over the measurement period were within +/–10% at all sites. The models ability to describe the daily ozone maximum concentration was satisfactory with an average deviation of 19–22% from the observed concentrations. HNO₃ was underestimated by over 50% at all sites except the one closest to the emission sources. The correlation between modelled and observed concentrations was generally best for the sites with shortest transport distance from the sources of emission.     

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%.     

Gas-Particle Partitioning of Nitric Acid Modulated by Alkaline Aerosol

The role of alkaline mineral aerosol in controlling HNO₃ partitioning between gas and aerosol phases is explored using a comprehensive, process oriented three-dimensional model. Simulation results for March 1994, a period from the PEM West B experiment, are presented. It is found that in the dust impacted regions of the boundary layer and free troposphere, more than 50% of HNO₃ ispartitioned onto dust particles; while 1050% of HNO₃ in the boundarylayer and 10 30% of HNO₃ in the free troposphere is partitionedonto sea-salt particles. This higher capacity of mineral dust to uptake HNO₃ is due to the fact that carbonate in the dust particles is more volatile (thus easily replaced by nitrate) than chloride in the sea-salt particles. When this process of nitric acid partitioning onto alkaline particles is included in the analysis, model predicted HNO₃-to-NO_x ratios are much closer to observed valuesthat typically range between 1 and 9.     

Measurement of gaseous HNO3 over the Atlantic Ocean

A latitudinal profile (30° W, from 30° N to 30° S) of mixing ratios of nitric acid and particulate nitrate was determined on the Atlantic Ocean during the Polarstern cruise ANT VII/1 from Bremerhaven, Germany, to Rio Grande, Brazil. The detection of HNO₃ was performed simultaneously by laser-photolysis fragment-fluorescence (LPFF) and by nylon filter packs. The detection limit was about 30 pptv for a signal accumulation time of 1 h for LPFF and about 5 pptv for the filters at a collection time of 4 h. In general, the mixing ratios of HNO₃ in the Northern Hemisphere were found to be significantly higher than those in the Southern Hemisphere. The Atlantic background concentrations frequently varied between 80 pptv and the detection limit. Larger deviations from this trend were found for the more northern latitudes and for episodes like crossings of exhaust plumes from ships or from continental pollutions sources.     

Seasonal variation of gaseous HNO3 and NH3 at a Tropical Savannah site

Gaseous nitric acid and ammonia were sampled with annular denuders at a forest savannah site from April to December 1987. The analysis of the extract was made spectrophotometrically and by a selective electrode for NO₃ ^– and NH₄ ⁺, respectively. Higher concentrations were observed during the vegetation burning period at the end of the dry season. In the studied savannah area, large soil emissions of NO occur during the rainy season, although very low concentrations of HNO₃ (0.035 ppb) and also of particulate NO₃ ^– (0.43 g m^-3) were observed; it is likely that NO_x are lost by fast vertical transport to the upper troposphere. During the nonburning period, the average concentration of NH₃ was 2.7 ppb, which is much lower than values given in the literature for the tropical America atmosphere. The concentrations of HNO₃ and NH₃ were always below the values needed to produce ammonium nitrate aerosols.     

In Situ Trace Gas and Particle Measurements in the Summer Lower Stratosphere during STREAM II: Implications for O3 Production

In situ aircraft measurements of O₃, CO,HNO₃, and aerosol particles are presented,performed over the North Sea region in the summerlower stratosphere during the STREAM II campaign(Stratosphere Troposphere Experiments by AircraftMeasurements) in July 1994. Occasionally, high COconcentrations of 200-300 pbbv were measured in thelowermost stratosphere, together with relatively highHNO₃ concentrations up to 1.6 ppbv. The particlenumber concentration (at standard pressure andtemperature) between 0.018-1 m decreased acrossthe tropopause, from >1000 cm^-3 in the uppertroposphere to <500 cm^-3 in the lowermoststratosphere. Since the CO sources are found in thetroposphere, the elevated CO mixing ratios areattributed to mixing of polluted tropospheric air intothe lowermost extratropical stratosphere. Further wehave used a chemical model to illustrate that nitrogenoxide reservoir species (mainly HNO₃) determinethe availability of NO_x (=NO + NO₂) andtherefore largely control the total net O₃production in the lower kilometers of thestratosphere. Model simulations, applying additionalNO_x perturbations from aircraft, show that theO₃ production efficiency of NO_x is smallerthan previously assumed, under conditions withrelatively high HNO₃ mixing ratios, as observedduring STREAM II. The model simulations furthersuggest a relatively high O₃ productionefficiency from CO oxidation, as a result of therelatively high ambient HNO₃ and NO_xconcentrations, implying that upward transport of COrich air enhances O₃ production in the lowermoststratosphere. Analysis of the measurements and themodel calculations suggest that the lowermoststratosphere is a transition region in which thechemistry deviates from both the upper troposphere andlower stratosphere.     

Evaluation of a catalytic reduction technique for the measurement of total reactive odd-nitrogen NO y in the atmosphere

A catalytic reduction technique for the measurement of total reactive odd-nitrogen NO _y in the atmosphere was evaluated in laboratory and field tests. NO _y component species include NO, NO₂, NO₃, HNO₃, N₂O₅, CH₃COO₂NO₂(PAN), and particulate nitrate. The technique utilizes the reduction of the higher oxides to NO in reaction with CO on a metal catalyst and the subsequent detection of NO by chemiluminescence produced in reaction with O₃. The efficiency and linearity of the conversion of the principal NO _y species were examined for mixing ratios in the range of 0.1 to 100 parts per billion by volume (ppbv). Results of tests with Au, Ni, and stainless steel as the catalyst in the temperature range of 25–500°C showed Au to be the preferred catalyst. NH₃, HCN, N₂O, CH₄, and various chlorine and sulfur compounds were checked as possible sources of NO _y interference with the Au catalyst. The effects of pressure, O₃, and H₂O on NO _y conversion were also examined. The results of the checks and tests in the laboratory showed the technique to be suitable for initial NO _y measurements in the atmosphere. The technique was subsequently tested in ambient air at a remote ground-based field site located near Niwot Ridge, Colorado. The results of conversion and inlet tests made in the field and a summary of the NO _y data are included in the discussion.     

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.     

A modified profile method for determining the vertical fluxes of NO,NO2, ozone,and HNO3 in the atmospheric surface layer

A modified profile method for determining the vertical deposition (or/and exhalation) fluxes of NO, NO₂, ozone, and HNO₃ in the atmospheric surface layer is presented. This method is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these trace gases. The analysis (aerodynamic profile method) includes a detailed determination of the micrometeorological quantities (such as the friction velocity, the fluxes of sensible and latent heat, the roughness length and the zero plane displacement), and of the height-invariant fluxes of the composed chemically conservative trace gases with group concentrations c ₁=[NO]+[NO₂]+[HNO₃], c ₂=[NO₂]+[O₃]+3/2·[HNO₃], and c ₃=[NO]–[O₃]–1/2·[HNO₃]. The fluxes of the individual species are finally determined by the numerical solution of a system of coupled nonlinear ordinary differential equations for the concentrations of ozone and HNO₃ (decoding method). The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The model requires only the vertical profile data of wind velocity, temperature and humidity and concentrations of NO, NO₂, ozone, and HNO₃.The method has been applied to vertical profile data obtained at Jülich (September 1984) and collected in the BIATEX joint field experiment LOVENOX (Halvergate, U.K., September 1989).     

Measurements of Trace Substances in the Arctic Troposphere as Potential Precursors and Constituents of Arctic Haze

During two measuring campaigns in early spring 1994 and 1995 (March/April) and one campaign in summer 1994, measurements of ozone, PAN, sulfur dioxide, nitric acid, and particulate nitrate, sulfate, and ammonium (only 1995) were recorded in the Arctic. Observations were made by aircraft at various sites in the eastern and western Arctic. Ozone concentrations showed a steady increase with altitude both in spring and summer. During five flights in springtime, low ozone events (LOEs) could be observed near the surface and up to altitudes of 2000 m. SO₂ background concentrations, ranging from detection limit (0.5 nmol/m³) to 5 nmol/m³, were observed during both spring and summer. Distinct maxima up to 55 nmol/m³ in lower altitudes were only obtained in springtime. Concentrations of the organic nitrate PAN were within a similar range as those of the inorganic nitrate HNO₃ during spring campaigns. In contrast, concentrations of particulate nitrate were one half an order of magnitude lower. HNO₃ concentrations increased significantly with altitude. Evidently, HNO₃ was intruded from the stratosphere into the troposphere. Sulfate concentrations ranged between 5 and 30 nmol/m³; ammonium concentrations were obtained within a range from 10 to 50 nmol/m³.     

Measurements of PM<Subscript>10</Subscript> ions and trace gases with the online system MARGA at the research station Melpitz in Germany – A five-year study

An hourly quantification of inorganic water-soluble PM₁₀ ions and corresponding trace gases was performed using the Monitor for AeRosols and Gases in ambient Air (MARGA) at the TROPOS research site in Melpitz, Germany. The data availability amounts to over 80% for the five-year measurement period from 2010 to 2014. Comparisons were performed for the evaluation of the MARGA, resulting in coefficients of determinations (slopes) of 0.91 (0.90) for the measurements against the SO₂ gas monitor, 0.84 (0.88), 0.79 (1.39), 0.85 (1.20) for the ACSM NO₃ ^?, SO₄ ^2? and NH₄ ⁺ measurements, respectively, and 0.85 (0.65), 0.88 (0.68), 0.91 (0.83), 0.86 (0.82) for the filter measurements of Cl^?, NO₃ ^?, SO₄ ^2? and NH₄ ⁺, respectively. A HONO comparison with a batch denuder shows large scatter (R² = 0.41). The MARGA HNO₃ is underestimated compared to a batch and coated denuder with shorter inlets (slopes of 0.16 and 0.08, respectively). Less NH₃ was observed in coated denuders for high ambient concentrations. Long-time measurements show clear daily and seasonal variabilities. Potential Source Contribution Function (PSCF) analysis indicates the emission area of particulate ions Cl^?, NO₃ ^?, SO₄ ^2?, NH₄ ⁺, K⁺ and gaseous SO₂ to lie in eastern European countries, predominantly in wintertime. Coarse mode sea salt particles are transported from the North Sea to Melpitz. The particles at Melpitz are nearly neutralised with a mean molar ratio of 0.90 for the five-year study. A slight increase of the neutralization ratio over the last three years indicates a stronger decrease of the anthropogenically emitted NO₃ ^? and SO₄ ^2? compared to NH₄ ⁺.     

Modified HNO3 seasonality in volcanic layers of a polar ice core: Snow-pack effect or photochemical perturbation?

Using the chemical composition of snow and ice of a central Greenland ice core, we have investigated changes in atmospheric HNO₃ chemistry following the large volcanic eruptions of Laki (1783), Tambora (1815) and Katmai (1912). The concentration of several cations and anions, including SO ₄ ^2– and NO ₃ ^– , were measured using ion chromatography. We found that following those eruptions, the ratio of the concentration of NO ₃ ^– deposited during winter to that deposited during summer was significantly higher than during nonvolcanic periods. Although we cannot rule out that this pattern originates from snow pack effects, we propose that increased concentrations of volcanic H₂SO₄ particles in the stratosphere may have favored condensation and removal of HNO₃ from the stratosphere during Arctic winter. In addition, this pattern might have been enhanced by slower formation of HNO₃ during summer, caused by direct consumption of OH through oxidation of volcanic SO₂.     

全球闪电活动与对流层上部NO及O3的相关性分析

为了解闪电对对流层上部微量气体的贡献,利用全球水资源和气候中心(GHRC)提供的1995年4月—2006年6月的闪电卫星格点资料,以及高层大气研究卫星(UARS)上的卤素掩星试验(HALOE)1991年10月—2005年11月的观测资料,分析了全球闪电与对流层上部NO和O3体积分数的时空分布特征及其相关性。结果表明:全球闪电12、1、2月集中在南半球,6—8月集中在北半球,全球闪电的季节分布与NO、O3类似;NO体积分数在350 h Pa附近达到最大,该高度的南半球NO体积分数变化范围为7×10-12~11×10-12、北半球为3×10-12~17×10-12;450~300 h Pa,北半球夏季O3体积分数呈明显增加趋势,且同一高度上夏季的值比年平均值大25%左右,南半球夏季O3体积分数高于冬季,但差异并不大。结论进一步证明了闪电与对流层上部NO及O3的密切关系,也为研究全球气候变化提供有力证据。     

The Impact of Precipitation Scavenging on the Transport of Trace Gases: A 3-Dimensional Model Sensitivity Study

With the global Chemistry-Transport model MATCHsensitivity simulations were performed to determinethe degree to which especially upward transport ofgases from the earth's surface is limited byconvective and large-scale precipitation scavenging.When only dissolution of species in the liquid phaseis taken into account, mixing ratio reductions in themiddle and upper troposphere by 10% arecalculated for gases with a Henry's Law constant H of10³ mol/l/atm. The removal increases to 50% forH = 10⁴ mol/l/atm, and to 90% for H =10⁵ mol/l/atm. We also consider scavenging by theice phase, which is generally much less efficient thanby the aqueous phase. In fact, rejection of gases fromfreezing water droplets may be a source of trace gasat higher altitudes.H₂O₂ and the strong acids (H₂SO₄,HNO₃, HCl, HBr, HI) have such large solubilitiesthat they become largely removed by precipitation.When significant concentrations of these gases andsulfate aerosol exist above the liquid water domain ofthe atmosphere, they have likely been produced thereor at higher altitudes, although some could have comefrom trace gas rejection from ice particles or fromevaporating hydrometeors. Several other gases areaffected by precipitation, but not strongly enough toprevent fractional transfer to the middle and uppertroposphere: e.g., HNO₄, HNO₂ at pH 5,CH₂O, the organic acids at pH 6,CH₃SOCH₃, HOCl, HOBr, and HOI. NH₃ islargely removed by liquid phase scavenging at pH 7 and SO₂ atpH 7. At pH less thanabout 6, upward transport of SO₂ should largelydepend on the efficiency of oxidation processes in thewater droplets by O₃ and H₂O₂.Most gases have solubilities which are too low forsignificant precipitation scavenging and aqueous phaseoxidation to occur. This holds, e.g., for O₃, CO,the hydrocarbons, NO, NO₂, HCN, CH₃CN,CH₃SCH₃, CH₃O₂H, CH₃CHOandhigher aldehydes, CH₃OH and higher alcohols,peroxyacetylnitrate (PAN), CH₃COCH₃ andother ketones (note that some of these are not listedin Table I because their solubilities are below 10mol/l/atm). Especially for the short-lived gases,transfer from the boundary layer to the middle andupper troposphere is actually promoted by the enhancedupward transport that occurs in clouds.     

Measurement of PAN in the Polluted Boundary Layer and Free Troposphere Using a Luminol-NO2 Detector Combined with a Thermal Converter

Peroxyacetyl nitrate (PAN,CH³C(O)O₂NO₂) has been measured inthe polluted boundary layer and free troposphere by thermal conversion tonitrogen dioxide (NO₂) followed by detection of thedecomposition product with a Scintrex LMA-3 NO₂-luminolinstrument. Following laboratory tests of the efficiency of PAN conversionand investigations of possible interferences, the technique was evaluated atthe West Beckham TOR (Tropospheric Ozone Research) Station near the northNorfolk coast in Eastern England between September 1989 and August 1990. PANmeasured by the new technique was reasonably well correlated with PANrecorded using electron capture gas chromatography (EC/GC). PAN was alsowell correlated with ozone (O³) in the summer months. Springand autumn episodes of simultaneously high concentrations of PAN andO³ were examined in conjunction with air parcelback-trajectories and synoptic- and local-scale meteorology in a study ofthe sources of photooxidants on the east coast of England. Spring-timemeasurements of PAN made in the free troposphere in a light aircraft ataltitudes up to 3.1 km showed the presence of 0.54 and 0.26 ppbv PAN inpolar maritime and mid-latitude oceanic air masses, respectively. Thetechnique is particularly suited to airborne applications because potentialinterferences are minimised and the frequency of measurements is higher thangenerally achieved with EC/GC methods.     

Processing of oxidised nitrogen compounds by passage through winter-time orographic cloud

Four case studies are described, from a three-site field experiment in October/November 1991 using the Great Dun Fell flow-through reactor hill cap cloud in rural Northern England. Measurements of total odd-nitrogen nitrogen oxides (NO _y ) made on either side of the hill, before and after the air flowed through the cloud, showed that 10 to 50% of the NO _y , called NO _z , was neither NO nor NO₂. This NO _z failed to exhibit a diurnal variation and was often higher after passage through cloud than before. No evidence of conversion of NO _z to NO₃ ^- in cloud was found. A simple box model of gas-phase chemistry in air before it reached the cloud, including scavenging of NO₃ and N₂O₅ by aerosol of surface area proportional to the NO₂ mixing ratio, shows that NO₃ and N₂O₅ may build up in the boundary layer by night only if stable stratification insulates the air from emissions of NO. This may explain the lack of evidence for N₂O₅ forming NO₃ ^- in cloud under well-mixed conditions in 1991, in contrast with observations under stably stratified conditions during previous experiments when evidence of N₂O₅ was found. Inside the cloud, some variations in the calculated total atmospheric loading of HNO₂ and the cloud liquid water content were related to each other. Also, indications of conversion of NO _x to NO _z were found. To explain these observations, scavenging of NO _x and HNO₂ by cloud droplets and/or aqueous-phase oxidation of NO₂ ^- by nitrate radicals are considered. When cloud acidity was being produced by aqueous-phase oxidation of NO _x or SO₂, NO₃ ^- which had entered the cloud as aerosol particles was liberated as HNO₃ vapour. When no aqueous-phase production of acidity was occurring, the reverse, conversion of scavenged HNO₃ to particulate NO₃ ^-, was observed.     

An optimized chemiluminescence detector for tropospheric NO measurements

A detector for the chemiluminescent measurement of NO in background air is described. A large reduction of interferences is achieved by using a stabilized ozone generator which allows operation of the instrument at lower O₃ concentrations. Purification and humidification of the O₃ stream further reduces interferences and shortens the instrumental clean-up time, which is important for aircraft missions. From a series of laboratory tests and from measurements performed aboard an aircraft it is demonstrated that the remaining interferences are acceptable for measurements in the undisturbed troposphere. In particular, no remnant NO signal is observed in clean air at night. During flight, a detection limit (2) of 20 ppt is achieved for a 1 min integration time.     

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.