Measurements Of HNO3 Research Articles

Roles of HNO x and Carboxylic Acids in the Thermal Stability of Nitroplasticizer.

In the thermal aging of nitroplasticizer (NP), the produced nitrous acid (HONO) can decompose into reactive nitro-oxide species and nitric acid (HNO3). These volatile species are prone to cause cascaded deterioration of NP and give rise to various acidic constituents. To gain insight on the early stage of NP degradation, an adequate method for measuring changes in the concentrations of HONO, HNO3, and related acidic species is imperative. The typical assessment of acidity in nonaqueous solutions (i.e., acid number) cannot differentiate acidic species and thus presents difficulty in the measurement of HONO and HNO3 at a micromolar concentration level. Using liquid-liquid extraction and ion chromatography (IC), we developed a fast and unambiguous analytical method to accurately determine the concentration of HONO, HNO3, acetic/formic acids, and oxalic acid in aged NP samples. Given by the overlay analysis results of liquid chromatography coupled with quadrupole time-of-flight mass spectrometry and IC, the prominent increase of produced HONO after the depletion of antioxidants is the primary cause of HNO3 formation in the late stage of NP degradation, which results in the acid-catalyzed hydrolysis of NP into 2,2-dinitropropanol and acetic/formic acids. Our study has demonstrated that the aging temperature plays a crucial role in accelerating the formation and decomposition of HONO, which consequently increases the acidity of aged NP samples and hence accelerates the hydrolyzation of NP. Therefore, to prevent NP from undergoing rapid degradation, we suggest that the concentration of HNO3 should be maintained below 1.35 mM and the temperature under 38 °C.

A High-Precision Mid-Infrared Spectrometer for Ambient HNO3 Measurements.

Precise and accurate measurements of ambient HNO3 are crucial for understanding various atmospheric processes, but its ultra-low trace amounts and the high polarity of HNO3 have strongly hindered routine, widespread, direct measurements of HNO3 and restricted field studies to mostly short-term, localized measurement campaigns. Here, we present a custom field-deployable direct absorption laser spectrometer and demonstrate its analytical capabilities for in situ atmospheric HNO3 measurements. Detailed laboratory characterizations with a particular focus on the instrument response under representative conditions for tropospheric measurements, i.e., the humidity, spectral interference, changing HNO3 amount fractions, and air-sampling-related artifacts, revealed the key aspects of our method: (i) a good linear response (R2 > 0.98) between 0 and 25 nmol·mol−1 in both dry and humid conditions with a limit of detection of 95 pmol·mol−1; (ii) a discrepancy of 20% between the spectroscopically derived amount fractions and indirect measurements using liquid trapping and ion chromatography; (iii) a systematic spectral bias due to water vapor. The spectrometer was deployed in a three-week field measurement campaign to continuously monitor the HNO3 amount fraction in ambient air. The measured values varied between 0.1 ppb and 0.8 ppb and correlated well with the daily total nitrates measured using a filter trapping method.

High-Resolution Measurements of SO2, HNO3 and HCl at the Urban Environment of Athens, Greece: Levels, Variability and Gas to Particle Partitioning

High-resolution measurements of sulfur dioxide (SO2), nitric acid (HNO3), and hydrochloric acid (HCl) were conducted in Athens, Greece, from 2014 to 2016 via a wet rotating annular denuder system paired with an ion chromatograph. Decreased mean annual levels of SO2 and HNO3 (equal to 3.3 ± 4.8 μg m−3 and 0.7 ± 0.6 μg m−3, respectively) were observed relative to the past, whereas for HCl (mean of 0.4 μg m−3 ) no such comparison was possible as the past measurements are very scarce. Regional and local emission sources regulated the SO2 levels and contributed to both the December and the July maxima of 6.6 μg m−3 and 5.5 μg m−3, respectively. Similarly, the significant enhancement at noon and during the winter nighttime was due to transported SO2 and residential heating, respectively. The oxidation of NO2 by OH radicals and the heterogeneous reactions of HNO3 on sea salt seemed to drive the HNO3 and HCl formation, respectively, whereas nighttime biomass burning affected only the former by almost 50%. During summer, the sulfate anions dominated over the SO2, in contrast to the chloride and nitrate ions that prevailed during the winter and were linked to the aerosol acidity that influences their lifetime as well as their impact on ecosystems.

Updated tropospheric chemistry reanalysis and emission estimates, TCR-2, for 2005–2018

Abstract. This study presents the results from the Tropospheric Chemistry Reanalysis version 2 (TCR-2) for the period 2005–2018 at 1.1∘ horizontal resolution obtained from the assimilation of multiple updated satellite measurements of ozone, CO, NO2, HNO3, and SO2 from the OMI, SCIAMACHY, GOME-2, TES, MLS, and MOPITT satellite instruments. The reanalysis calculation was conducted using a global chemical transport model MIROC-CHASER and an ensemble Kalman filter technique that optimizes both chemical concentrations of various species and emissions of several precursors, which was efficient for the correction of the entire tropospheric profile of various species and its year-to-year variations. Comparisons against independent aircraft, satellite, and ozonesonde observations demonstrate the quality of the reanalysis fields for numerous key species on regional and global scales, as well as for seasonal, yearly, and decadal scales, from the surface to the lower stratosphere. The multi-constituent data assimilation brought the model vertical profiles and interhemispheric gradient of OH closer to observational estimates, which was important in improving the description of the oxidation capacity of the atmosphere and thus vertical profiles of various species. The evaluation results demonstrate the capability of the chemical reanalysis to improve understanding of the processes controlling variations in atmospheric composition, including long-term changes in near-surface air quality and emissions. The estimated emissions can be employed for the elucidation of detailed distributions of the anthropogenic and biomass burning emissions of co-emitted species (NOx, CO, SO2) in all major regions, as well as their seasonal and decadal variabilities. The data sets are available at https://doi.org/10.25966/9qgv-fe81 (Miyazaki et al., 2019a).

Anti-aging scheme

Atmospheric Mixing The air of the lower stratosphere in the Southern Hemisphere has been getting younger since 1994. Strahan et al. report measurements of atmospheric HNO3 and HCl showing that changes in the transport circulation between the troposphere and stratosphere in the Southern Hemisphere are decreasing the age of its stratospheric air, whereas the age of its Northern Hemisphere counterpart is not declining. Understanding and quantifying the processes behind this differential aging is important for modeling how the protective stratospheric ozone layer will evolve in the future. Geophys. Res. Lett. 47 , e2020GL088567 (2020).

Atmospheric dry and bulk nitrogen deposition to forest environment in the North China Plain

Atmospheric nitrogen (N) deposition fluxes has dramatically increased in past few decades and has aroused great concerns of its impacts on forest ecosystems. However, complete quantitative information on dry and wet deposition of various reactive nitrogen (Nr) species is very limited for forest environments. Therefore, two-year (2014–2015) measurements of gaseous NH3, NO2, and HNO3 and particulate NH4+ and NO3− (pNH4+ and pNO3-) in air and/or precipitation were conducted in Jigong Mountain National Nature Reserve in the North China Plain (NCP). Our results showed that ambient concentrations of all Nr species were highest in winter and lowest in summer except for NH3; conversely, bulk deposition fluxes of each Nr species generally peaked in summer and were lowest in winter. Annual mean bulk Nr deposition fluxes was 15.5 kg N ha−1 yr−1 (7.9 kg N ha−1 yr−1 for NH4+ and 7.6 kg N ha−1 yr−1 for NO3−), with higher monthly fluxes occurring in spring and summer. Average annual dry Nr deposition fluxes was 44.3 kg N ha−1 yr−1 (30.1 kg N ha−1 yr−1 for reduced N (NH3 plus pNH4+) and 14.2 kg N ha−1 yr−1 for oxidized N (the sum of HNO3, NO2 and pNO3-). Total Nr deposition fluxes (dry plus bulk) reached 59.8 kg N ha−1 yr−1 with more contributions from reduced N than from oxidized N (64% vs 36%). When consider the N critical load (10–20 kg N ha−1 yr−1) in forest ecosystem, potential negative effects may cause by N deposition in the NCP which should be paid more attention.

Spatial–temporal patterns of inorganic nitrogen air concentrations and deposition in eastern China

Abstract. Five-year (2011–2015) measurements of gaseous NH3, NO2, and HNO3 and particulate NH4+ and NO3− in air and/or precipitation were conducted at 27 sites in the Nationwide Nitrogen Deposition Monitoring Network (NNDMN) to better understand spatial and temporal (seasonal and annual) characteristics of reactive nitrogen (Nr) concentrations and deposition in eastern China. Our observations reveal annual average concentrations (16.4–32.6 µg N m−3), dry deposition fluxes (15.8–31.7 kg N ha−1 yr−1), and wet/bulk deposition fluxes (18.4–28.0 kg N ha−1 yr−1) based on land use, ranked as urban > rural > background sites. Annual concentrations and dry deposition fluxes of each Nr species in air were comparable at urban and background sites in northern and southern regions, but were significantly higher at northern rural sites. These results, together with good agreement between spatial distributions of NH3 and NO2 concentrations determined from ground measurements and satellite observations, demonstrate that atmospheric Nr pollution is heavier in the northern region than in the southern region. No significant inter-annual trends were found in the annual Nr dry and wet/bulk N deposition at almost all of the selected sites. A lack of significant changes in annual averages between the 2013–2015 and 2011–2012 periods for all land use types suggests that any effects of current emission controls are not yet apparent in Nr pollution and deposition in the region. Ambient concentrations of total Nr exhibited non-significant seasonal variation at all land use types, although significant seasonal variations were found for individual Nr species (e.g. NH3, NO2, and pNO3−) in most cases. In contrast, dry deposition of total Nr exhibited a consistent and significant seasonal variation at all land use types, with the highest fluxes in summer and the lowest in winter. Based on sensitivity tests by the GEOS-Chem model, we found that NH3 emissions from fertilizer use (including chemical and organic fertilizers) were the largest contributor (36 %) to total inorganic Nr deposition over eastern China. Our results not only improve the understanding of spatial–temporal variations of Nr concentrations and deposition in this pollution hotspot, but also provide useful information for policy-makers that mitigation of NH3 emissions should be a priority to tackle serious N deposition in eastern China.

A pilot study of gaseous pollutants' measurement (NO<sub>2</sub>, SO<sub>2</sub>, NH<sub>3</sub>, HNO<sub>3</sub> and O<sub>3</sub>) in Abidjan, Côte d'Ivoire: contribution to an overview of gaseous pollution in African cities

Abstract. This work is part of the DACCIWA FP7 project (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) in the framework of the Work Package 2 Air Pollution and Health. This study aims to characterize urban air pollution levels through the measurement of NO2, SO2, NH3, HNO3 and O3 in Abidjan, the economic capital of Côte d'Ivoire. Measurements of inorganic gaseous pollutants, i.e. NO2, SO2, NH3, HNO3 and O3 were performed in Abidjan during an intensive campaign within the dry season (15 December 2015 to 16 February 2016), using INDAAF (International Network to study Deposition and Atmospheric chemistry in AFrica) passive samplers exposed in duplicate for 2-week periods. Twenty-one sites were selected in the district of Abidjan to be representative of various anthropogenic and natural sources of air pollution in the city. Results from this intensive campaign show that gas concentrations are strongly linked to surrounding pollution sources and show a high spatial variability. Also, NH3, NO2 and O3 gases were present at relatively higher concentrations at all the sites. NH3 average concentrations varied between 9.1 ± 1.7 ppb at a suburban site and 102.1 ± 9.1 ppb at a domestic fires site. NO2 mean concentration varied from 2.7 ± 0.1 ppb at a suburban site to 25.0 ± 1.7 ppb at an industrial site. Moreover, we measured the highest O3 concentration at the two coastal sites of Gonzagueville and Félix-Houphouët-Boigny International Airport located in the southeast of the city, with average concentrations of 19.1 ± 1.7 and 18.8 ± 3.0 ppb, respectively. The SO2 average concentration never exceeded 7.2 ± 1.2 ppb over all the sites, with 71.5 % of the sampling sites showing concentrations ranging between 0.4 and 1.9 ppb. The HNO3 average concentration ranged between 0.2 and 1.4 ppb. All these results were combined with meteorological parameters to provide the first mapping of gaseous pollutants on the scale of the district of Abidjan using geostatistical analysis (ArcGIS software). Spatial distribution results emphasize the importance of the domestic fires source and the significant impact of the traffic emissions on the scale of the city. In addition, in this work we propose a first overview of gaseous SO2 and NO2 concentrations on the scale of several African cities by comparing literature to our values. The daily SO2 standard of World Health Organization (WHO) is exceeded in most of the cities reported in the overview, with concentrations ranging from 0.2 to 3662 µg m−3. Annual NO2 concentrations ranged from 2 to 175 µg m−3, which are lower than the WHO threshold. As a conclusion, this study constitutes an original database to characterize urban air pollution and a first attempt towards presenting a spatial distribution of the pollution levels at the scale of the metropolis of Abidjan. This work should draw the attention of the African public authorities to the necessity of building an air quality monitoring network in order to (1) to define national standards and to better control the pollutants emissions and (2) to investigate the impact on the health of the growing population in developing African countries.

Accuracy and precision of polar lower stratospheric temperatures from reanalyses evaluated from A-Train CALIOP and MLS, COSMIC GPS RO, and the equilibrium thermodynamics of supercooled ternary solutions and ice clouds

Abstract. We investigate the accuracy and precision of polar lower stratospheric temperatures (100–10 hPa during 2008–2013) reported in several contemporary reanalysis datasets comprising two versions of the Modern-Era Retrospective analysis for Research and Applications (MERRA and MERRA-2), the Japanese 55-year Reanalysis (JRA-55), the European Centre for Medium-Range Weather Forecasts (ECMWF) interim reanalysis (ERA-I), and the National Oceanic and Atmospheric Administration (NOAA) National Centers for Environmental Prediction (NCEP) Climate Forecast System Reanalysis (NCEP-CFSR). We also include the Goddard Earth Observing System model version 5.9.1 near-real-time analysis (GEOS-5.9.1). Comparisons of these datasets are made with respect to retrieved temperatures from the Aura Microwave Limb Sounder (MLS), Constellation Observing System for Meteorology, Ionosphere and Climate (COSMIC) Global Positioning System (GPS) radio occultation (RO) temperatures, and independent absolute temperature references defined by the equilibrium thermodynamics of supercooled ternary solutions (STSs) and ice clouds. Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) observations of polar stratospheric clouds are used to determine the cloud particle types within the Aura MLS geometric field of view. The thermodynamic calculations for STS and the ice frost point use the colocated MLS gas-phase measurements of HNO3 and H2O. The estimated bias and precision for the STS temperature reference, over the 68 to 21 hPa pressure range, are 0.6–1.5 and 0.3–0.6 K, respectively; for the ice temperature reference, they are 0.4 and 0.3 K, respectively. These uncertainties are smaller than those estimated for the retrieved MLS temperatures and also comparable to GPS RO uncertainties (bias < 0.2 K, precision > 0.7 K) in the same pressure range. We examine a case study of the time-varying temperature structure associated with layered ice clouds formed by orographic gravity waves forced by flow over the Palmer Peninsula and compare how the wave amplitudes are reproduced by each reanalysis dataset. We find that the spatial and temporal distribution of temperatures below the ice frost point, and hence the potential to form ice polar stratospheric clouds (PSCs) in model studies driven by the reanalyses, varies significantly because of the underlying differences in the representation of mountain wave activity. High-accuracy COSMIC temperatures are used as a common reference to intercompare the reanalysis temperatures. Over the 68–21 hPa pressure range, the biases of the reanalyses with respect to COSMIC temperatures for both polar regions fall within the narrow range of −0.6 K to +0.5 K. GEOS-5.9.1, MERRA, MERRA-2, and JRA-55 have predominantly cold biases, whereas ERA-I has a predominantly warm bias. NCEP-CFSR has a warm bias in the Arctic but becomes substantially colder in the Antarctic. Reanalysis temperatures are also compared with the PSC reference temperatures. Over the 68–21 hPa pressure range, the reanalysis temperature biases are in the range −1.6 to −0.3 K with standard deviations ∼ 0.6 K for the CALIOP STS reference, and in the range −0.9 to +0.1 K with standard deviations ∼ 0.7 K for the CALIOP ice reference. Comparisons of MLS temperatures with the PSC reference temperatures reveal vertical oscillations in the MLS temperatures and a significant low bias in MLS temperatures of up to 3 K.

Multi-decadal records of stratospheric composition and their relationship to stratospheric circulation change

Abstract. Constituent evolution for 1990–2015 simulated using the Global Modeling Initiative chemistry and transport model driven by meteorological fields from the Modern-Era Retrospective analysis for Research and Applications version 2 (MERRA-2) is compared with three sources of observations: ground-based column measurements of HNO3 and HCl from two stations in the Network for the Detection of Atmospheric Composition Change (NDACC, ∼ 1990–ongoing), profiles of CH4 from the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS, 1992–2005), and profiles of N2O from the Microwave Limb Sounder on the Earth Observing System satellite Aura (2005–ongoing). The differences between observed and simulated values are shown to be time dependent, with better agreement after ∼ 2000 compared with the prior decade. Furthermore, the differences between observed and simulated HNO3 and HCl columns are shown to be correlated with each other, suggesting that issues with the simulated transport and mixing cause the differences during the 1990s and that these issues are less important during the later years. Because the simulated fields are related to mean age in the lower stratosphere, we use these comparisons to evaluate the time dependence of mean age. The ongoing NDACC column observations provide critical information necessary to substantiate trends in mean age obtained using fields from MERRA-2 or any other reanalysis products.

Application of an online ion-chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur

Abstract. The dry component of total nitrogen and sulfur atmospheric deposition remains uncertain. The lack of measurements of sufficient chemical speciation and temporal extent make it difficult to develop accurate mass budgets and sufficient process level detail is not available to improve current air–surface exchange models. Over the past decade, significant advances have been made in the development of continuous air sampling measurement techniques, resulting with instruments of sufficient sensitivity and temporal resolution to directly quantify air–surface exchange of nitrogen and sulfur compounds. However, their applicability is generally restricted to only one or a few of the compounds within the deposition budget. Here, the performance of the Monitor for AeRosols and GAses in ambient air (MARGA 2S), a commercially available online ion-chromatography-based analyzer is characterized for the first time as applied for air–surface exchange measurements of HNO3, NH3, NH4+, NO3−, SO2 and SO42−. Analytical accuracy and precision are assessed under field conditions. Chemical concentrations gradient precision are determined at the same sampling site. Flux uncertainty measured by the aerodynamic gradient method is determined for a representative 3-week period in fall 2012 over a grass field. Analytical precision and chemical concentration gradient precision were found to compare favorably in comparison to previous studies. During the 3-week period, percentages of hourly chemical concentration gradients greater than the corresponding chemical concentration gradient detection limit were 86, 42, 82, 73, 74 and 69 % for NH3, NH4+, HNO3, NO3−, SO2 and SO42−, respectively. As expected, percentages were lowest for aerosol species, owing to their relatively low deposition velocities and correspondingly smaller gradients relative to gas phase species. Relative hourly median flux uncertainties were 31, 121, 42, 43, 67 and 56 % for NH3, NH4+, HNO3, NO3−, SO2 and SO42−, respectively. Flux uncertainty is dominated by uncertainty in the chemical concentrations gradients during the day but uncertainty in the chemical concentration gradients and transfer velocity are of the same order at night. Results show the instrument is sufficiently precise for flux gradient applications.

Measurements of NO2, SO2, NH3, HNO3 and O3 in West African urban environments

In this paper, we present the measurements of atmospheric gas concentrations of NO2, SO2, NH3, HNO3, and O3 performed at two traffic sites in the context of the POLCA (Pollution of African Capitals) program. These gases were measured using a passive sampling technique from Jan. 2008 to Dec. 2009 at Dakar and from Jun. 2008 to Dec. 2009 at Bamako. In addition, during these periods there were two intensive measurement campaigns (from 19 Jan. to 2 Feb. 2009 at Bamako and from 30 Nov. to 13 Dec. 2009 at Dakar) where real-time active analysers were used to measure NO2 and SO2. Results show that Dakar has a pollution level for NO2 and SO2 higher than that of Bamako, whereas it is lower for NH3 concentrations. Monthly values of NO2 range between 21.1 and 43.5 ppb in Dakar with an annual mean concentration of 31.7 ppb (59.6 μg/m3). NO2 values in Bamako are 9.4–22.6 ppb with a mean of 16.2 ppb. At Dakar, the mean annual NO2 limit value (21.3 ppb or 40 μg/m3) recommended by the World Health Organization (WHO) is widely exceeded. The mean annual concentration of SO2 is 15.9 ppb in Dakar and 3.6 ppb in Bamako. These differences may be explained by different sources of traffic between Bamako (with mainly gasoline vehicles) and Dakar (with mainly diesel vehicles). The annual mean NH3 concentration is about two times higher in Bamako (46.7 ppb) than in Dakar (21.1 ppb). In addition to other possible sources, we assume that the ammonia from domestic fires and uncontrolled garbage incineration may have more influence at Bamako than at Dakar. The mean annual concentrations of HNO3 and O3 are 1.3 ppb and 7.7 ppb in Dakar and 0.6 ppb and 5.1 ppb in Bamako, respectively. Seasonal variation in measured gas concentrations are low in Bamako and more pronounced in Dakar, except for HNO3 and NH3. At Dakar, NO2 and SO2 daily mean concentrations are higher during the weekdays than on weekends, when urban activities are reduced, whereas at Bamako, no significant difference was observed between weekdays and weekends. At Dakar, the daily average concentrations of SO2 in the dry season (11.6–39.6 ppb) widely exceed the WHO air quality guideline (7.6 ppb or 20 μg/m3 as 24-h average). Finally, the spatial distribution of gases at different sites in these two capitals have been investigated and showed higher pollution levels at the traffic sites, especially for NO2, NH3 and SO2, and lower levels in the suburban area, with the exception of ozone.

Characteristics of ammonia, acid gases, and PM2.5 for three typical land-use types in the North China Plain.

Air pollution is one of the most serious environmental problems in China due to its rapid economic development alongside a very large consumption of fossil fuel, particularly in the North China Plain (NCP). During the period 2011–2014, we integrated active and passive sampling methods to perform continuous measurements of NH3, HNO3, NO2, and PM2.5 at two urban, one suburban, and two rural sites in the NCP. The annual average concentrations of NH3, NO2, and HNO3 across the five sites were in the ranges 8.5–23.0, 22.2–50.5, and 5.5–9.7 μg m−3, respectively, showing no significant spatial differences for NH3 and HNO3 but significantly higher NO2 concentration at the urban sites. At each site, annual average concentrations of NH3 and NO2 showed increasing and decreasing trends, respectively, while there was no obvious trend in annual HNO3 concentrations. Daily PM2.5 concentrations ranged from 11.8 to 621.0 μg m−3 at the urban site, from 19.8 to 692.9 μg m−3 at the suburban site, and from 23.9 to 754.5 μg m−3 at the two rural sites, with more than 70 % of sampling days exceeding 75 μg m−3. Concentrations of water-soluble ions in PM2.5 ranked differently between the non-rural and rural sites. The three dominant ions were NH4+, NO3−, and SO42− and mainly existed as (NH4)2SO4, NH4HSO4, and NH4NO3, and their concentrations averaged 48.6 ± 44.9, 41.2 ± 40.8, and 49.6 ± 35.9 μg m−3 at the urban, suburban, and rural sites, respectively. Ion balance calculations indicated that PM2.5 was neutral at the non-rural sites but acidic at the rural sites. Seasonal variations of the gases and aerosols exhibited different patterns, depending on source emission strength and meteorological conditions. Our results suggest that a feasible pathway to control PM2.5 pollution in the NCP should target ammonia and acid gases together.Electronic supplementary materialThe online version of this article (doi:10.1007/s11356-015-5648-3) contains supplementary material, which is available to authorized users.

Technical Note: SWIFT – a fast semi-empirical model for polar stratospheric ozone loss

Abstract. An extremely fast model to estimate the degree of stratospheric ozone depletion during polar winters is described. It is based on a set of coupled differential equations that simulate the seasonal evolution of vortex-averaged hydrogen chloride (HCl), nitric acid (HNO3), chlorine nitrate (ClONO2), active forms of chlorine (ClOx = Cl + ClO + 2 ClOOCl) and ozone (O3) on isentropic levels within the polar vortices. Terms in these equations account for the chemical and physical processes driving the time rate of change of these species. Eight empirical fit coefficients associated with these terms are derived by iteratively fitting the equations to vortex-averaged satellite-based measurements of HCl, HNO3 and ClONO2 and observationally derived ozone loss rates. The system of differential equations is not stiff and can be solved with a time step of one day, allowing many years to be processed per second on a standard PC. The inputs required are the daily fractions of the vortex area covered by polar stratospheric clouds and the fractions of the vortex area exposed to sunlight. The resultant model, SWIFT (Semi-empirical Weighted Iterative Fit Technique), provides a fast yet accurate method to simulate ozone loss rates in polar regions. SWIFT's capabilities are demonstrated by comparing measured and modeled total ozone loss outside of the training period.

An assessment of the performance of the Monitor for AeRosols and GAses in ambient air (MARGA): a semi-continuous method for soluble compounds

Abstract. Ambient air monitoring as part of the US Environmental Protection Agency's (US EPA's) Clean Air Status and Trends Network (CASTNet) currently uses filter packs to measure weekly integrated concentrations. The US EPA is interested in supplementing CASTNet with semi-continuous monitoring systems at select sites to characterize atmospheric chemistry and deposition of nitrogen and sulfur compounds at higher time resolution than the filter pack. The Monitor for AeRosols and GAses in ambient air (MARGA) measures water-soluble gases and aerosols at an hourly temporal resolution. The performance of the MARGA was assessed under the US EPA Environmental Technology Verification (ETV) program. The assessment was conducted in Research Triangle Park, North Carolina, from 8 September to 8 October 2010 and focused on gaseous SO2, HNO3, and NH3 and aerosol SO42-, NO3-, and NH4+. Precision of the MARGA was evaluated by calculating the median absolute relative percent difference (MARPD) between paired hourly results from duplicate MARGA units (MUs), with a performance goal of ≤ 25%. The accuracy of the MARGA was evaluated by calculating the MARPD for each MU relative to the average of the duplicate denuder/filter pack concentrations, with a performance goal of ≤ 40%. Accuracy was also evaluated by using linear regression, where MU concentrations were plotted against the average of the duplicate denuder/filter pack concentrations. From this, a linear least squares line of best fit was applied. The goal was for the slope of the line of best fit to be between 0.8 and 1.2. The MARGA performed well in comparison to the denuder/filter pack for SO2, SO42−, and NH4+, with all three compounds passing the accuracy and precision goals by a significant margin. The performance of the MARGA in measuring NO3- could not be evaluated due to the different sampling efficiency of coarse NO3- by the MUs and the filter pack. Estimates of "fine" NO3- were calculated for the MUs and the filter pack. Using this and results from a previous study, it is concluded that if the MUs and the filter pack were sampling the same particle size, the MUs would have good agreement in terms of precision and accuracy. The MARGA performed moderately well in measuring HNO3 and NH3, though neither met the linear regression slope goals. However, recommendations for improving the measurement of HNO3 and NH3 are discussed. It is concluded that SO42-, SO2, NO3-, HNO3, NH4+, and NH3 concentrations can be measured with acceptable accuracy and precision when the MARGA is operated in conjunction with the recommendations outlined in the manuscript.

Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways

The first simultaneous measurements of formic and nitric acid mixing ratios around the United Kingdom were measured on the FAAM BAe-146 research aircraft with a chemical ionization mass spectrometer using I− reagent ions at 0.8 Hz. Analysis of the whole dataset shows that formic acid and nitric acid are positively correlated as illustrated by other studies (e.g. Veres et al., 2011). However, initial evidence indicates a prominent direct source of formic acid and also a significant source when O3 levels are high, suggesting the importance of the ozonolysis of 1-alkenes. A trajectory model was able to reproduce the formic acid concentrations by both the inclusion of a primary vehicle source and production via ozonolysis of propene equivalent 1-alkene levels. Inspection of data archives implies these levels of 1-alkene are possible after 11 am, but formic acid and nitric acid plumes early in the flight are too high for the model to replicate. These data show the relationship between nitric acid and formic acid cannot solely be attributed to related photochemical production. The simultaneous measurement of HCOOH and HNO3 has been implemented to estimate OH levels along the flight track assuming a relationship between formic and nitric acid in photochemical plumes and a constant source of 1-alkene.

New Analysis of the ν3 and ν4 Bands of HNO3 in the 7.6 μm Region

A new line position analysis of the ν3 and ν4 bands of nitric acid (HNO3) at 1326.186 and 1303.072 cm(-1) together with its associated interacting bands is presented. The 3(1) and 4(1) energy levels were obtained from an extended analysis of high-resolution Fourier transform spectra recorded at Giessen in the 7.6 μm region. The energy levels of 3(1) and 4(1) upper states of nitric acid are strongly interacting with those of the 9(3), 6(2), 5(1)9(1), and 7(1)8(1) dark states centered at 1288.899, 1289.46, 1341.05, and 1343.78 cm(-1), respectively. Informations on these perturbing dark states were achieved through previous partial investigations of hot bands in high-resolution Fourier transform spectra recorded at 22 μm in Giessen (for 3ν9-2ν9 and 3ν9-ν5), at 12 μm in Denver (for 3ν9-ν9), and at 11 μm in Orsay (for ν5+ν9-ν9). The energy levels calculation accounts for the various Fermi, anharmonic, A-type, B-type, and C-type Coriolis resonances, which couple together the {6(2),9(3),4(1),3(1),5(1)9(1),7(1)8(1)} interacting energy levels. For nitric acid, the ν9 mode (OH torsion relative to the -NO2 moiety) is a large amplitude motion. The theoretical model used in this work accounts also for large amplitude effects in the 9(3) dark state, which lead to a splitting of the 9(3) energy levels of about 0.060 cm(-1). In this way, the existence of torsional splittings for several ν4 perturbed lines was explained by the occurrence of local A-type and B-type Coriolis resonances coupling the 4(1) energy levels with those of 9(3). Because four dark bands had to be accounted for in the model, the results of the energy level calculations are reasonable, although not perfect. However, a very significant improvement was achieved in terms of understanding the 7.6 μm absorbing bands of nitric acid as compared to the analysis of the ν3 and ν4 bands performed several years ago [Perrin, A.; Lado-Bordowski, O.; Valentin, A. Mol. Phys. 1989, 67, 249-267]. Finally, the present analysis also features, for the first time, the ν3+ν9-ν9 hot band located at 1331.09 cm(-1). This study will help to improve HNO3 measurements by satellites. This will be indeed the case for the "Infrared Atmospheric Sounding Interferometer" (IASI) experiment.

Aircraft based four-channel thermal dissociation laser induced fluorescence instrument for simultaneous measurements of NO<sub>2</sub>, total peroxy nitrate, total alkyl nitrate, and HNO<sub>3</sub>

Abstract. A four-channel thermal dissociation laser induced fluorescence (TD-LIF) instrument has been developed for simultaneous measurements of nitrogen dioxide (NO2), total peroxy nitrate (∑PNs), total alkyl nitrate (∑ANs) and nitric acid (HNO3). NO2 is measured directly by LIF at 532 nm, whereas organic nitrates and nitric acid are thermally dissociated at distinct temperatures in the inlet to form NO2, which is then measured by LIF. The concentrations of each dissociated species are derived by the differences in measured NO2 relative to the reference colder inlet channel. The TD-LIF was adapted to fly on board the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe 146-301 atmospheric research aircraft in summer 2010, and to date has successfully flown in five field campaigns. This paper reports novel improvements in the TD-LIF instrumentations, including (1) the use of a single wavelength laser, which makes the system compact and relatively cheap; (2) the use of a single beam laser that allows easy alignment and optical stability against the vibrational aircraft environment; and (3) the optical assembly of four detection cells that allow simultaneous and fast (time resolution up to 0.1 s) measurements of NO2, ∑PNs, ∑ANs and HNO3. Laboratory-generated mixtures of PNs, ANs and HNO3 in zero air are converted into NO2 and used to fix the dissociation temperatures of each heated inlet to test the selectivity of the instrument and potential interferences due to recombination reactions of the dissociated products. The effectiveness of the TD-LIF was demonstrated during the RONOCO aircraft campaign (summer 2010). A chemiluminescence system that was measuring NO2 and a broadband cavity enhanced absorption spectrometer (BBCEAS) that was measuring one of the PNs (N2O5) were installed on the same aircraft during the campaign. The in-flight intercomparison of the new TD-LIF with the chemiluminescence system for NO2 measurements and the intercomparison between ∑PNs measured by the TD-LIF and N2O5 by the BBCEAS are used to assess the performance of the TD-LIF.

Observed levels and trends of gaseous SO2 and HNO3 at Mt. Waliguan, China: Results from 1997 to 2009

Long-term measurements of SO2 and HNO3, particularly those from the background sites, are rarely reported. We present for the first time the long-term measurements of SO2 and HNO3 at Waliguan (WLG), the only global baseline station in the back-land of the Eurasian Continent. The concentrations of SO2 and HNO3 were observed at WLG from 1997 to 2009. The observed annual mean concentrations of SO2 and HNO3 at WLG were 1.28 ± 0.41 and 0.22 ±0.19 μg/m3, respectively. The HNO3 concentrations were much higher in warmer seasons than in colder seasons, while the SO2 concentrations showed a nearly reversed seasonal pattern. In most months, the concentration of HNO3 was significantly correlated with that of SO2, suggesting that some common factors influence the variations of both gases and the precursors of HNO3 may partially be from the SO2-emitting sources. The SO2 concentration had a very significant (P < 0.0001) decreasing trend (−0.2 μg/(m3·yr)) in 1997–2002, but a significant (P < 0.05) increasing trend (+0.06 μg/(m3·yr)) in 2003–2009. The HNO3 concentration showed no statistically significant trend during 1997–2009. While the decrease of SO2 in 1997–2002 agrees with the trend of global SO2 emissions, the increase in 2003–2009 is not consistent with the decreasing trends in many other regions over the world. Trajectory analysis suggests that the airmasses from the northern Qinghai-Tibetan Plateau and the Takla Makan Desert regions contributed significantly to the increasing trends of SO2 and HNO3 at WLG in 2003–2009, with a rate of +0.13 μg/(m3·yr) and +0.007 μg/(m3·yr), respectively.

Characteristics of gas–phase nitric acid and ammonium–nitrate– sulfate aerosol, and their gas–phase precursors in a suburban area in Cairo, Egypt

Simultaneous measurements of gaseous SO2, NO2, HNO3, NH3 and particulate SO42–, NO3– and NH4+ were carried out in a suburban area in Cairo during summer 2009 and winter 2009–2010. PTFE membrane filters were used to collect particulate SO42–, NH4+ and NO3–, followed by the impregnated filter to collect HNO3. Colorimetric methods were used for determination of NO2, SO2, NH3, SO42–, NH4+ NO3–, and HNO3 levels. The mean concentrations of NO2, SO2 and NH3 were 75.0, 40.1 and 29.1 µg/m3 in winter and 54.1, 25.1 and 44.9 µg/m3 in summer, respectively. The daytime/nighttime concentration ratios were 1.3 and 1.2 for NO2, 1.3 and 1.2 for SO2 and 0.6, and 0.8 for NH3 during the winter and summer, respectively. The mean values of NH4+, SO42–, NO3–, HNO3 and total NO3– were 4.4, 19.0, 3.4, 1.1 and 4.5 µg/m3 in winter and 7.5, 28.0, 4.2, 3.1 and 7.3 µg/m3 in summer, respectively. The levels of NH4+, SO42–, NO3– and HNO3 were relatively higher in daytime than in nighttime. Sulfur conversion (Fs) and nitrogen conversion ratios (Fn) in summer were about 1.78 and 2.15 times higher than in winter, respectively. Fs and Fn were higher in daytime than in nighttime. Significant positive correlation was found between Fs and relative humidity. The positive correlation between Fn and relative humidity was insignificant. The correlation between the concentration of NH4+ and NO3– indicates that NO3– may be found in fine mode (NH4NO3) in winter and it may be present predominantly as a coarse mode, such as Ca(NO3)2, Mg(NO3)2 and NaNO3 in summer. The concentration of SO42– was significantly correlated with NH4+ concentration, suggesting neutralization by NH3 and indicating that the forms of (NH4)2SO4 and/or NH4HSO4 exist in the aerosol. The NH4+/SO42– molar ratio indicates that SO42– in aerosol may be present as (NH4)2SO4, (NH4)2SO4.CaSO4.2H2O and CaSO4.