Nitric Acid Partitioning Research Articles

High atmospheric oxidation capacity drives wintertime nitrate pollution in the eastern Yangtze River Delta of China

Abstract. Nitrate aerosol plays an increasingly important role in wintertime haze pollution in China. Despite intensive research on wintertime nitrate chemistry in recent years, quantitative constraints on the formation mechanisms of nitrate aerosol in the Yangtze River Delta (YRD), one of the most developed and densely populated regions in eastern China, remain inadequate. In this study, we identify the major nitrate formation pathways and their key controlling factors during the winter haze pollution period in the eastern YRD using 2-year (2018–2019) field observations and detailed observation-constrained model simulations. We find that the high atmospheric oxidation capacity, coupled with high aerosol liquid water content (ALWC), made both the heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) and the gas-phase OH oxidation of nitrogen dioxide (NO2) important pathways for wintertime nitrate formation in this region, with contribution percentages of 69 % and 29 % in urban areas and 63 % and 35 % in suburban areas during the haze pollution episodes, respectively. We further find that the gas-to-particle partitioning of nitric acid (HNO3) was very efficient so that the rate-determining step in the overall formation process of nitrate aerosol was the oxidation of NOx to HNO3 through both heterogeneous and gas-phase processes. The atmospheric oxidation capacity (i.e., the availability of O3 and OH radicals) was the key factor controlling the production rate of HNO3 from both processes. During the COVID-19 lockdown (January–February 2020), the enhanced atmospheric oxidation capacity greatly promoted the oxidation of NOx to nitrate and hence weakened the response of nitrate aerosol to the emission reductions in urban areas. Our study sheds light on the detailed formation mechanisms of wintertime nitrate aerosol in the eastern YRD and highlights the demand for the synergetic regulation of atmospheric oxidation capacity and NOx emissions to mitigate wintertime nitrate and haze pollution in eastern China.

How alkaline compounds control atmospheric aerosol particle acidity

Abstract. The acidity of atmospheric particulate matter regulates its mass, composition, and toxicity and has important consequences for public health, ecosystems and climate. Despite these broad impacts, the global distribution and evolution of aerosol particle acidity are unknown. We used the comprehensive atmospheric multiphase chemistry–climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry) to investigate the main factors that control aerosol particle acidity and uncovered remarkable variability and unexpected trends during the past 50 years in different parts of the world. Aerosol particle acidity decreased strongly over Europe and North America during the past decades while at the same time it increased over Asia. Our simulations revealed that these particle acidity trends are strongly related to changes in the phase partitioning of nitric acid, production of sulfate in aqueous aerosols, and the aerosol hygroscopicity. It is remarkable that the aerosol hygroscopicity (κ) has increased in many regions following the particle pH. Overall, we find that alkaline compounds, notably ammonium and to a lesser extent crustal cations, regulate the particle pH on a global scale. Given the importance of aerosol particles for the atmospheric energy budget, cloud formation, pollutant deposition, and public health, alkaline species hold the key to control strategies for air quality and climate change.

Measurements of the partitioning of nitric acid and sulfuric acid in aqueous/organic phase-separated systems

Measurements of partitioning of nitric acid and sulfuric acid between aqueous and organic phases show organic-phase acid is significant, which has implications for aerosol chemistry factors. These acids can then participate in organic reactions.

Fine particle pH and gas–particle phase partitioning of inorganic species in Pasadena, California, during the 2010 CalNex campaign

Abstract. pH is a fundamental aerosol property that affects ambient particle concentration and composition, linking pH to all aerosol environmental impacts. Here, PM1 and PM2. 5 pH are calculated based on data from measurements during the California Research at the Nexus of Air Quality and Climate Change (CalNex) study from 15 May to 15 June 2010 in Pasadena, CA. Particle pH and water were predicted with the ISORROPIA-II thermodynamic model and validated by comparing predicted to measured gas–particle partitioning of inorganic nitrate, ammonium, and chloride. The study mean ± standard deviation PM1 pH was 1.9 ± 0.5 for the SO42−–NO3−–NH4+–HNO3–NH3 system. For PM2. 5, internal mixing of sea salt components (SO42−–NO3−–NH4+–Na+–Cl−–K+–HNO3–NH3–HCl system) raised the bulk pH to 2.7 ± 0.3 and improved predicted nitric acid partitioning with PM2. 5 components. The results show little effect of sea salt on PM1 pH, but significant effects on PM2. 5 pH. A mean PM1 pH of 1.9 at Pasadena was approximately one unit higher than what we have reported in the southeastern US, despite similar temperature, relative humidity, and sulfate ranges, and is due to higher total nitrate concentrations (nitric acid plus nitrate) relative to sulfate, a situation where particle water is affected by semi-volatile nitrate concentrations. Under these conditions nitric acid partitioning can further promote nitrate formation by increasing aerosol water, which raises pH by dilution, further increasing nitric acid partitioning and resulting in a significant increase in fine particle nitrate and pH. This study provides insights into the complex interactions between particle pH and nitrate in a summertime coastal environment and a contrast to recently reported pH in the eastern US in summer and winter and the eastern Mediterranean. All studies have consistently found highly acidic PM1 with pH generally below 3.

Size-resolved simulations of the aerosol inorganic composition with the new hybrid dissolution solver HyDiS-1.0: description, evaluation and first global modelling results

Abstract. The dissolution of semi-volatile inorganic gases such as ammonia and nitric acid into the aerosol aqueous phase has an important influence on the composition, hygroscopic properties, and size distribution of atmospheric aerosol particles. The representation of dissolution in global models is challenging due to inherent issues of numerical stability and computational expense. For this reason, simplified approaches are often taken, with many models treating dissolution as an equilibrium process. In this paper we describe the new dissolution solver HyDiS-1.0, which was developed for the global size-resolved simulation of aerosol inorganic composition. The solver applies a hybrid approach, which allows for some particle size classes to establish instantaneous gas-particle equilibrium, whereas others are treated time dependently (or dynamically). Numerical accuracy at a competitive computational expense is achieved by using several tailored numerical formalisms and decision criteria, such as for the time- and size-dependent choice between the equilibrium and dynamic approaches. The new hybrid solver is shown to have numerical stability across a wide range of numerical stiffness conditions encountered within the atmosphere. For ammonia and nitric acid, HyDiS-1.0 is found to be in excellent agreement with a fully dynamic benchmark solver. In the presence of sea salt aerosol, a somewhat larger bias is found under highly polluted conditions if hydrochloric acid is represented as a third semi-volatile species. We present first results of the solver's implementation into a global aerosol microphysics and chemistry transport model. We find that (1) the new solver predicts surface concentrations of nitrate and ammonium in reasonable agreement with observations over Europe, the USA, and East Asia, (2) models that assume gas-particle equilibrium will not capture the partitioning of nitric acid and ammonia into Aitken-mode-sized particles, and thus may be missing an important pathway through which secondary particles may grow to radiation- and cloud-interacting size, and (3) the new hybrid solver's computational expense is modest, at around 10 % of total computation time in these simulations.

Impacts of the Denver Cyclone on regional air quality and aerosol formation in the Colorado Front Range during FRAPPÉ 2014

Abstract. We present airborne measurements made during the 2014 Front Range Air Pollution and Photochemistry Experiment (FRAPPÉ) project to investigate the impacts of the Denver Cyclone on regional air quality in the greater Denver area. Data on trace gases, non-refractory submicron aerosol chemical constituents, and aerosol optical extinction (βext) at λ = 632 nm were evaluated in the presence and absence of the surface mesoscale circulation in three distinct study regions of the Front Range: In-Flow, Northern Front Range, and the Denver metropolitan area. Pronounced increases in mass concentrations of organics, nitrate, and sulfate in the Northern Front Range and the Denver metropolitan area were observed during the cyclone episodes (27–28 July) compared to the non-cyclonic days (26 July, 2–3 August). Organic aerosols dominated the mass concentrations on all evaluated days, with a 45 % increase in organics on cyclone days across all three regions, while the increase during the cyclone episode was up to ∼ 80 % over the Denver metropolitan area. In the most aged air masses (NOx / NOy < 0.5), background organic aerosols over the Denver metropolitan area increased by a factor of ∼ 2.5 due to transport from Northern Front Range. Furthermore, enhanced partitioning of nitric acid to the aerosol phase was observed during the cyclone episodes, mainly due to increased abundance of gas phase ammonia. During the non-cyclone events, βext displayed strong correlations (r = 0.71) with organic and nitrate in the Northern Front Range and only with organics (r = 0.70) in the Denver metropolitan area, while correlation of βext during the cyclone was strongest (r = 0.86) with nitrate over Denver. Mass extinction efficiency (MEE) values in the Denver metropolitan area were similar on cyclone and non-cyclone days despite the dominant influence of different aerosol species on βext. Our analysis showed that the meteorological patterns associated with the Denver Cyclone increased aerosol mass loadings in the Denver metropolitan area mainly by transporting aerosols and/or aerosol precursors from the northern regions, leading to impaired visibility and air quality deterioration.

Fine particle pH and the partitioning of nitric acid during winter in the northeastern United States

Particle pH is a critical but poorly constrained quantity that affects many aerosol processes and properties, including aerosol composition, concentrations, and toxicity. We assess PM1 pH as a function of geographical location and altitude, focusing on the northeastern US, based on aircraft measurements from the Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) campaign (01 Feb to 15 Mar 2015). Particle pH and water were predicted with the ISORROPIA-II thermodynamic model and validated by comparing predicted to observed partitioning of inorganic nitrate between the gas and particle phases. Good agreement was found for relative humidity (RH) above 40%; at lower RH observed particle nitrate was higher than predicted, possibly due to organic-inorganic phase separations or nitrate measurement uncertainties associated with low concentrations (nitrate < 1 µgm-3). Including refractory ions in the pH calculations did not improve model predictions, suggesting they were externally mixed with PM1 sulfate, nitrate, and ammonium. Sample line volatilization artifacts were found to be minimal. Overall, particle pH for altitudes up to 5000 m ranged between -0.51 and 1.9 (10th and 90th percentiles) with a study mean of 0.77 ± 0.96, similar to those reported for the southeastern US and eastern Mediterranean. This expansive aircraft data set is used to investigate causes in variability in pH and pH-dependent aerosol components, such as PM1 nitrate, over a wide range of temperatures (-21 to 19 °C), RH (20 to 95%), inorganic gas and particle concentrations and also provides further evidence that particles with low pH are ubiquitous.

Formation of semivolatile inorganic aerosols in the Mexico City Metropolitan Area during the MILAGRO campaign

Abstract. One of the most challenging tasks for chemical transport models (CTMs) is the prediction of the formation and partitioning of the major semi-volatile inorganic aerosol components (nitrate, chloride, ammonium) between the gas and particulate phases. In this work the PMCAMx-2008 CTM, which includes the recently developed aerosol thermodynamic model ISORROPIA-II, is applied in the Mexico City Metropolitan Area in order to simulate the formation of the major inorganic aerosol components. The main sources of SO2 (such as the Miguel Hidalgo Refinery and the Francisco Perez Rios Power Plant) in the Mexico City Metropolitan Area (MCMA) are located in Tula, resulting in high predicted PM1 (particulate matter with diameter less than 1 μm) sulfate concentrations (over 25 μg m-3) in that area. The average predicted PM1 nitrate concentrations are up to 3 μg m−3 (with maxima up to 11 μg m−3) in and around the urban center, mostly produced from local photochemistry. The presence of calcium coming from the Tolteca area (7 μg m−3) as well as the rest of the mineral cations (1 μg m−3 potassium, 1 μg m−3 magnesium, 2 μg m−3 sodium, and 3 μg m−3 calcium) from the Texcoco Lake resulted in the formation of a significant amount of aerosol nitrate in the coarse mode with concentrations up to 3 μg m−3 over these areas. PM1−10 (particulate matter with diameter between 1 and 10 μm) chloride is also high and its concentration exceeds 2 μg m−3 in Texcoco Lake. PM1 ammonium concentrations peak at the center of Mexico City (2 μg m−3) and the Tula vicinity (2.5 μg m−3). The performance of the model for the major inorganic PM components (sulfate, ammonium, nitrate, chloride, sodium, calcium, and magnesium) is encouraging. At the T0 measurement site, located in the Mexico City urban center, the average measured values of PM1 sulfate, nitrate, ammonium, and chloride are 3.5 μg m−3, 3.5 μg m−3, 2.1 μg m−3, and 0.36 μg m−3, respectively. The corresponding predicted values are 3.7 μg m−3, 2.7 μg m−3, 1.7 μg m−3, and 0.25 μg m−3. High sulfate concentrations are associated with the transport of sulfate from the Tula vicinity, while in periods where southerly winds are dominant; the concentrations of sulfate are low. The underprediction of nitrate can be attributed to the underestimation of OH levels by the model during the early morning. Ammonium is sensitive to the predicted sulfate concentrations and the nitrate levels. The performance of the model is also evaluated against measurements taken from a suburban background site (T1) located north of Mexico City. The average predicted PM2.5 (particulate matter with diameter less than 2.5 μm) sulfate, nitrate, ammonium, chloride, sodium, calcium, and magnesium are 3.3, 3.2, 1.4, 0.5, 0.3, 1.2, and 0.15 μg m−3, respectively. The corresponding measured concentrations are 3.7, 2.9, 1.5, 0.3, 0.4, 0.6, and 0.15 μg m−3. The overprediction of calcium indicates a possible overestimation of its emissions and affects the partitioning of nitric acid to the aerosol phase resulting occasionally in an overprediction of nitrate. Additional improvements are possible by improving the performance of the model regarding the oxidant levels, and revising the emissions and the chemical composition of the fugitive dust. The hybrid approach in which the mass transfer to the fine aerosol is simulated using the bulk equilibrium assumption and to the remaining aerosol sections using a dynamic approach, is needed in order to accurately simulate the size distribution of the inorganic aerosols. The bulk equilibrium approach fails to reproduce the observed coarse nitrate and overpredicts the fine nitrate. Sensitivity tests indicate that sulfate concentration in Tula decreases by up to 0.5 μg m−3 after a 50% reduction of SO2 emissions while it can increase by up to 0.3 μg m−3 when NOx emissions are reduced by 50%. Nitrate concentration decreases by up to 1 μg m−3 after the 50% reduction of NOx or NH3 emissions. Ammonium concentration decreases by up to 1 μg m−3, 0.3 μg m−3, and 0.1 μg m−3 after the 50% reduction of NH3, NOx, and SO2 emissions, respectively.

Equilibrium Study for the System Tri-n-butyl Phosphate, Normal Paraffin Hydrocarbon, and Nitric Acid

Tri-n-butyl phosphate (TBP) in diluent is generally used as a solvent for the extraction of fissile materials in the reprocessing of spent fuels by the PUREX process. The mutual solubility of TBP and water leads to the transfer of some finite amount of TBP into the aqueous phase. The distribution study of TBP between normal paraffin hydrocarbon (NPH) and nitric acid has been studied. Equilibrium curves have been generated for TBP in different concentrations of nitric acid and NPH. The distribution coefficient (Kd) is also calculated by measuring the concentration of associated TBP in the aqueous and organic phase. The effect of an inert diluent on the solubility of TBP in nitric acid is also studied. It has been found that the distribution coefficient value varies with the concentration of TBP, nitric acid, and NPH. Nitric acid partitioning between TBP and water has also been studied. The concentration of nitric acid in both phases was determined by the titration method. It has also been proven that the c...

Airborne measurements of the nitric acid partitioning in persistent contrails

Abstract. This study reports the first systematic measurements of nitric acid (HNO3) uptake in contrail ice particles at typical aircraft cruise altitudes. During the CIRRUS-III campaign cirrus clouds and almost 40 persistent contrails were probed with in situ instruments over Germany and Northern Europe in November 2006. Besides reactive nitrogen, water vapor, cloud ice water content, ice particle size distributions, and condensation nuclei were measured during 6 flights. Contrails with ages up to 12 h were detected at altitudes 10–11.5 km and temperatures 211–220 K. These contrails had a larger ice phase fraction of total nitric acid (HNO3ice/HNO3tot = 6%) than the ambient cirrus layers (3%). On average, the contrails contained twice as much HNO3ice as the cirrus clouds, 14 pmol/mol and 6 pmol/mol, respectively. Young contrails with ages below 1 h had a mean HNO3ice of 21 pmol/mol. The contrails had higher nitric acid to water molar ratios in ice and slightly higher ice water contents than the cirrus clouds under similar meteorological conditions. The differences in ice phase fractions and molar ratios between developing contrails and cirrus are likely caused by high plume concentrations of HNO3 prior to contrail formation. The location of the measurements in the upper region of frontal cirrus layers might account for slight differences in the ice water content between contrails and adjacent cirrus clouds. The observed dependence of molar ratios as a function of the mean ice particle diameter suggests that ice-bound HNO3 concentrations are controlled by uptake of exhaust HNO3 in the freezing plume aerosols in young contrails and subsequent trapping of ambient HNO3 in growing ice particles in older (age &gt; 1 h) contrails.

Secondary acidification: Changes in gas‐aerosol partitioning of semivolatile nitric acid and enhancement of its deposition due to increased emission and concentration of SOx

Secondary acidification, or the indirect enhancement of semivolatile air pollutant deposition associated with increased SO42− concentrations, is shown to occur in general air pollution using data collected from six stations of the Acid Deposition Monitoring Network in East Asia (EANET) in Japan. This effect was first detected as a result of volcanic SO2 plumes in our previous studies. Results indicate that as SO42− concentration increases, gas‐aerosol partitioning of nitric acid shifts to the gas phase, increasing the HNO3 gas concentration. Since the dry and wet deposition rates of HNO3 gas are very high, deposition can be enhanced even when the emission of NOx remains unchanged. In western Japan, the indirect effect for wet deposition is most apparent from spring to autumn, when the Asian continental outflow carries sulfate‐rich contaminated air masses. However, it is not pronounced in air masses containing abundant sea‐salt particles and related cation components in aerosols. In areas such as forests or farmlands with low surface resistance, dry deposition of nitric acid is more pronounced than wet deposition as the dry deposition velocity of HNO3 gas is high. Increased dry deposition of t‐NO3 due to the indirect effect and consequent vegetation damage is thus of considerable concern in such regions. The deposition of other semivolatile components, such as hydrochloric acid and ammonia, can be altered and can also induce secondary acidification.

Nitric acid partitioning in cirrus clouds: the role of aerosol particles and relative humidity

Nitric acid partitioning in cirrus clouds: the role of aerosol particles and relative humidity

Nitric acid partitioning in cirrus clouds: the role of aerosol particles and relative humidity

Owing to the potential of cirrus clouds to vertically redistribute HNO3 in the upper troposphere, the uptake of HNO3 in ice particles is at the focus of recent research. Here, we investigate whether HNO3 residing in freezing aerosol particles could be a relevant source of HNO3 in ice clouds. To this end, model studies on the sensitivity of the uptake of HNO3 in aerosol particles to temperature, relative humidity with respect to ice (RHice), particle composition and amount of available HNO3 were performed. Combining the model results with the history of RHice during cirrus formation and comparison with field measurements indicates that at temperatures > 200 K a considerable part of the HNO3 in ice may originate from freezing particles containing HNO3.

Novel Aerosol/Gas Inlet for Aircraft-Based Measurements

A novel inlet has been designed for selective sampling of gas and aerosol phases of volatile species from high-speed aircraft. A multistage flow system brings the flow nearly isokinetically towards the sampling port. Two small airfoil-shaped are placed close to the sample port to provide the flow conditions required for aerosol and gas sampling. Aerosols are sampled when these blades are positioned to operate the inlet as a counterflow virtual impactor (CVI). The design enables sampling of particles as small as 0.1 w m from a high-speed aircraft under stratospheric conditions, a substantial improvement over that possible with previous CVI designs. For gas sampling, one of the blades is moved by a stepper motor to occlude the inlet opening and gas is sampled perpendicular to the bulk flow. Boundary layer suction is used to prevent the sampled gas from coming in contact with the impactor walls. This is one of the first designs of an inlet that enables gas sampling free of wall contact. The inlet was flown on the NASA ER-2 aircraft during the SOLVE 2000 campaign to study aerosol/gas partitioning of nitric acid in the lower stratosphere. Data from the flight tests show that the inlet flow characteristics are broadly in agreement with computational fluid dynamics (CFD) simulations.

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 10∼50% 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-NOx ratios are much closer to observed valuesthat typically range between 1 and 9.

HNO3 partitioning in cirrus clouds

During the 1997 POLSTAR‐1 winter campaign in northern Sweden a flight was performed across a cold trough of air (≃ 196 K) in the tropopause region. Measurements of total water vapour, nitric acid, particles and reactive nitrogen (NOy) were taken. The particle measurements indicate that about 3% of the particles in the moist tropospheric air were ice particles. Forward and backward facing NOy inlets were used simultaneously to determine condensed phase HNO3. The combined NOy and particle measurements reveal that less than 1% of a monolayer of NOy could have resided on the ice particles. This casts doubt on the hypothesis that sedimenting cirrus particles generally lead to a strong downward flux of NOy. In addition to the NOy measurements, independent HNO3 measurements were used to determine total HNO3. Although quantitative uncertainties do not allow to completely rule out that the NOy uptake on ice was limited by total HNO3, the combined NOy and HNO3 data suggest that there was low uptake of NOy on ice despite abundant HNO3 in the gas phase. Model studies indicate, that the most likely explanation of the measured nitric acid partitioning is given by HNO3 in ternary solution droplets coexisting with almost HNO3 free ice in the same air mass.

The distribution of nitric acid between water and tributyl phosphate ‐ hexane solvents

AbstractThe distribution of nitric acid between water and solutions of tributyl phosphate in n‐hexane has been measured over a greater range of acid and tributylphosphate concentrations than have been reported previously.The partitioning of nitric acid between water and tributylphosphate‐hexane solvents has been satisfactorily explained on the basis of the commonly accepted equilibrium complexing reaction, with this modification: The over‐all aqueous‐to‐organic reaction is subdivided into the distribution of uncomplexed nitric acid and an organic phase complexing reaction. This alteration is found necessary to account for the behavior of the partitioning data of dilute acid over the entire tributylphosphate‐hexane range. The residual discrepancy between the theory and the data can be qualitatively attributed either to modest nonideality of the organic phase or to the effect of the varying water content of the solvent on the distribution coefficient of uncomplexed nitric acid.The sparse data on water extraction by tributylphosphate‐hexane solvents are not amenable to the same type of analysis, even though a type of complexing similar to that found for nitric acid has been previously proposed. The interaction between water and tributylphosphate appears to be stronger than that normally attributed to nonideality but weaker than a true chemical complex.