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Aerosol composition was measured by using the high resolution time-of-flight aerosol mass spectrometer (HR ToF-AMS). The data were collected at five different sites (AMF1, Aldine, University of Houston (UH), Jones Forest (JF), San Jacinto Battleground (BG)) from July to August, 2022. Dataset includes time series of five species of aerosol composition: Organic, sulfate (SO4), nitrate (NO3), ammonium (NH4), chlorine (Chl)
Aqueous aerosols are useful model systems for understanding the physical chemistry that takes place in the Earth’s atmosphere, as well as the chemistry of other solar system objects. Ammonium sulfate aerosols are impacted by anthropogenic sources such as farming and shipping and are understood to be important seeds of cloud nucleation in the atmosphere, affecting climate. X-ray photoelectron spectroscopy and near edge x-ray absorption fine structure spectroscopy were used in tandem to probe the surface and bulk properties of aqueous (NH 4 ) 2 SO 4 , respectively. Aerosolized solutions of (NH 4 ) 2 SO 4 , some altered with NaOH to modify pH, were introduced via an aerodynamic lens to a velocity map imaging instrument for detection. The results show that as pH and sodium cation concentration increase, sulfate anion and ammonia become more prevalent at the surface, and the aerosol surface appears to become drier. However, most of the aerosol remains aqueous, with ion concentrations insensitive to the addition of NaOH. Density functional theory calculations were also performed to probe the coordination environment at the aerosol surfaces to understand the underlying phenomena. Finally, the changes seen on the surface of the aerosol underscore the importance of pH in regulating the structure and chemical properties of atmospherically relevant aerosols.
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These data report aerosol liquid water content (ALWC) and aerosol pH for the S2 (Mt. Airy) site during CoURAGE for April - June 2025. The ISORROPIA-II aerosol thermodynamic equilibrium model was used to compute ALWC and pH. The model was run in forward mode, with solids formation disabled (metastable mode), according to Pye et al. (Atmospheric Chemistry and Physics, 2020). Information about the model can be found at https://www.epfl.ch/labs/lapi/models-and-software/isorropia/, and in Fountoukis and Nenes (Atmospheric Chemistry and Physics, 2007). Inputs to the model were: (1) measured Temperature and relative humidity, both from the DoE ARM “metwxt” data products at S2, (2) aerosol chemical composition from the ARM ACSM, and (3) gas-phase ammonia concentrations. For ISORROPIA-II, ambient RH values above 0.995 were input to the model as 0.995; therefore, caution should be exercised interpreting ALWC when RH was above 0.995. Aerosol composition or NH3(g) concentrations below the LOD were input into the model as 0.5*LOD. Model runs were only conducted for data points at 30-min resolution with all three inputs (meteorology, ACSM, and NH3). If any of the three model inputs were missing, aerosol thermodynamic outputs are flagged as -999. Similarly, aerosol thermodynamic outputs are flagged as -999 if measured NH3(g) and aerosol ammonium (NH4+) were simultaneously below the respective LODs. The ALWC includes liquid water from inorganic aerosol components, calculated directly by ISORROPIA-II, as well as liquid water from organics, estimated from the ACSM organics assuming a kappa value of 0.12 according to Guo et al. (Atmospheric Chemistry and Physics, 2015).
Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NO(sub x) ratio of 0.02 was found to have a significant impact on the global budgets of HO(sub x) (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.
Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation
Topics presented include the adsorption and reaction of trichlorofluoromethane on various particles, equilibria of the marine multiphase ammonia system, a novel ozone sensor for direct eddy flux measurements, and characterization of the carbonate content of atmospheric aerosols. Also presented are variations in heavy metals concentrations in Antarctic snows, sources of continental dust over Antarctica during the last glacial cycle, an inventory of anthropogenic emissions and air pollution in the USSR, and atmospheric nuclei in the remote free-troposphere.
An airborne vapor analyzer for detecting sub- to low- parts-per-million (ppm) hydrazine in the presence of higher concentration levels of ammonia has been under development for the Orion program. The detector is based on ambient pressure ionization and ion mobility characterization. The detector encompasses: 1) a membrane inlet to exclude particulate and aerosols from the analyzer inlet; 2) a method to separate hydrazine from ammonia which would otherwise lead to loss of calibration and quantitative accuracy for the hydrazine determination; and 3) response and quantitative determinations for both hydrazine and ammonia. Laboratory studies were made to explore some of these features including mobility measurements mindful of power, size, and weight issues. The study recommended the use of a mobility spectrometer of traditional design with a reagent gas and equipped with an inlet transfer line of bonded phase fused silica tube. The inlet transfer line provided gas phase separation of neutrals of ammonia from hydrazine at 50 C simplifying significantly the ionization chemistry that underlies response in a mobility spectrometer. Performance of the analyzer was acceptable between ranges of 30 to 80 C for both the pre-fractionation column and the drift tube. An inlet comprised of a combined membrane with valve-less injector allowed high speed quantitative determination of ammonia and hydrazine without cross reactivity from common metabolites such as alcohols, esters, and aldehydes. Preliminary test results and some of the design features are discussed.
Papers are presented which originate from a conference on 'The Non-Urban Troposphere Composition', held in 1976. Attention is given to distributions of nitrous oxide in the atmosphere, and to tropospheric and stratospheric compositions which are perturbed by NO(x) emissions from high-altitude aircraft. Ozone is studied in terms of in situ measurements; various meteorological analyses of tropopause folding, ozone measurements in the Boston area, and ozone measurements in rural areas are presented. A one-dimensional model used to study tropospheric photochemistry numerically is presented as are vertical profiles of tropospheric and stratospheric molecular hydrogen. The oxidation of ammonia, methane, and hydrogen sulfide is assessed in nonurban tropospheres along with nonurban measurements of ethane and methane for various atmospheric conditions. With reference to the particle size distribution of chloride in the marine aerosol, organic and inorganic chlorine concentrations are evaluated, and measurements of sea-air CO2 flux by eddy correlation are investigated.
New particle formation (NPF) and subsequent growth to sizes at which the aerosol particles can act as cloud condensation nuclei (CCN) is critical for understanding and modeling aerosol-climate interactions (Gordon et al. 2017, Dunne et al. 2016). While sulfuric acid is generally understood to play a central role in NPF and growth, measured sulfuric acid concentrations are insufficient to explain measured formation and growth rates in many locations even when stabilization by ammonia is considered (Kulmala et al. 2014, Riipinen et al. 2012). Extensive laboratory investigations have revealed that amines (Almeida et al. 2013), other reduced nitrogen compounds (Glasoe et al. 2015), and/or oxidized organic compounds (Kirkby et al. 2016) can enhance new particle formation rates and thus may explain, at least in part, the gap between our understanding of new particle formation and the measurements. Our knowledge, however, of the relative importance of these various pathways remains incomplete due to the limited number of ambient measurements, particularly in diverse ecosystems. Agricultural land use areas are particularly understudied despite accounting for ~41% of global land cover (Ellis et al. 2010). Improving our understanding of NPF requires measurements of NPF and the precursors to NPF and growth in a variety of ecosystems and ideally across seasons.
Global aerosol direct radiative forcing (DRF) is an important metric for assessing potential climate impacts of future emissions changes. However, the radiative consequences of emissions perturbations are not readily quantified nor well understood at the level of detail necessary to assess realistic policy options. To address this challenge, here we show how adjoint model sensitivities can be used to provide highly spatially resolved estimates of the DRF from emissions of black carbon (BC), primary organic carbon (OC), sulfur dioxide (SO2), and ammonia (NH3), using the example of emissions from each sector and country following multiple Representative Concentration Pathway (RCPs). The radiative forcing efficiencies of many individual emissions are found to differ considerably from regional or sectoral averages for NH3, SO2 from the power sector, and BC from domestic, industrial, transportation and biomass burning sources. Consequently, the amount of emissions controls required to attain a specific DRF varies at intracontinental scales by up to a factor of 4. These results thus demonstrate both a need and means for incorporating spatially refined aerosol DRF into analysis of future emissions scenario and design of air quality and climate change mitigation policies.
The spatial distribution of aerosols and their chemical composition dictates whether aerosols have a cooling or a warming effect on the climate system. Hence, properly modeling the three-dimensional distribution of aerosols is a crucial step for coherent climate simulations. Since surface measurement networks only give 2-D data, and most satellites supply integrated column information, it is thus important to integrate aircraft measurements in climate model evaluations. In this study, the vertical distribution of secondary inorganic aerosol (i.e., sulfate, ammonium, and nitrate) is evaluated against a collection of 14 AMS flight campaigns and surface measurements from 2000 to 2010 in the USA and Europe. GISS ModelE2 is used with multiple aerosol microphysics (MATRIX, OMA) and thermodynamic (ISORROPIA II, EQSAM) configurations. Our results show that the MATRIX microphysical scheme improves the model performance for sulfate, but that there is a systematic underestimation of ammonium and nitrate over the USA and Europe in all model configurations. In terms of gaseous precursors, nitric acid concentrations are largely underestimated at the surface while overestimated in the higher levels of the model. Heterogeneous reactions on dust surfaces are an important sink for nitric acid, even high in the troposphere. At high altitudes, nitrate formation is calculated to be ammonia limited. The underestimation of ammonium and nitrate in polluted regions is most likely caused by a too simplified treatment of the NH3/NH4(+) partitioning which affects the HNO3/NO3(-) partitioning.
The cryovolcanic regions of Titan offer transient opportunities for prebiotic molecules to exist in water–ammonia solutions on the surface of the Saturnian moon. The upcoming NASA’s Dragonfly mission will search for high nitrogen concentrations and amino acids on Titan’s equatorial terrains. Cryovolcanic features, however, are most common on the polar regions. To mitigate the distance, bubble bursting may encapsulate the prebiotic molecules into aerosols, which Titan’s Hadley circulation would subsequently transport to the equator. Here we investigate whether alanine and glycine survive this meridional journey. Despite the unconstrained meridional wind velocities, our results suggest that the amino acids can survive the transport through the mesosphere. Dragonfly may find cryo-volcanogenic amino acids on Titan’s equator. Further, the interaction between the two amino acids increased 10-fold the photodegradation rate of glycine. We justify it based on changes in the environment polarity.
This study investigated the hourly inorganic aerosol chemistry and its impact on atmospheric visibility over an urban area in Central Taiwan, by relying on measurements of aerosol light extinction, inorganic gases, and PM 2.5 water-soluble ions (WSIs), and simulations from a thermodynamic equilibrium model. On average, the sulfate (SO 4 2− ), nitrate (NO 3 − ), and ammonium (NH 4 + ) components (SNA) contributed ∼90% of WSI concentrations, which in turn made up about 50% of the PM 2.5 mass. During the entire observation period, PM 2.5 and SNA concentrations, aerosol pH, aerosol liquid water content (ALWC), and sulfur and nitrogen conversion ratios all increased with decreasing visibility. In particular, the NO 3 − contribution to PM 2.5 increased, whereas the SO 4 2− contribution decreased, with decreasing visibility. The diurnal variations of the above parameters indicate that the interaction and likely mutual promotion between NO 3 − and ALWC enhanced the hygroscopicity and aqueous-phase reactions conducive for NO 3 − formation, thus led to severely impaired visibility. The high relative humidity (RH) at the study area (average 70.7%) was a necessary but not sole factor leading to enhanced NO 3 − formation, which was more directly associated with elevated ALWC and aerosol pH. Simulations from the thermodynamic model depict that the inorganic aerosol system in the study area was characterized by fully neutralized SO 4 2− (i.e. a saturated factor in visibility reduction) and excess NH 4 + amidst a NH 3 -rich environment. As a result, PM 2.5 composition was most sensitive to gas-phase HNO 3 , and hence NOx, and relatively insensitive to NH 3 . Consequently, a reduction of NOx would result in instantaneous cuts of NO 3 − , PM 2.5 , and ALWC, and hence improved visibility. On the other hand, a substantial amount of NH 3 reduction (>70%) would be required to lower the aerosol pH, driving more than 50% of the particulate phase NO 3 − to the gas phase, thereby making NH 3 a limiting factor in shifting PM 2.5 composition.
The most common hypothesis discussed for life on Venus is a habitat in the dense, persistent clouds, which are primarily sulfuric acid with a secondary water component. Although Earth lacks a complete Venus analog environment, several partial analogs exist which can inform our understanding of the requirements for cloud habitability as well as serving as potential testbeds for future Venus instruments or missions. Earth’s tropospheric clouds have larger particles, more water, and shorter lifetimes than Venus’s; however, they have a partial overlap in pressure and temperature, and are our only example of an airborne habitat.They can inform how particle residence time and microbial generation time constrain habitable atmospheric regions. On the biological side, this includes available nutrients and energy, environmental stressors such as radiation, osmotic potential and acidity, and time spent in protective but inactive forms (endospores, cysts, akinetes); on the physical side, gravity, air density and viscosity, thermal lofting, gravity waves, scavenging due to precipitation, and other airflow dynamics, as well as effective particle radius and electrical charge. They can also enable sampling strategy tests for airborne life detection, ranging from10 2 to10 8 viable cells/mL (10 -3 to 10 -9 cells/particle). Conversely, Earth's stratospheric sulfate layer lacks an active microbial presence, and is at a colder and less dense altitude but has partially analogous values in terms of H2SO4 and water concentration, particle size, and number density. These aerosols are accessible to aircraft and high-altitude balloons. Even more accessible potential analogs include sea spray, which overlaps with the smaller (haze) particle sizes and densities at Venus and contains trace organic constituents; marine fog, which at higher densities can match Venus’s larger (Mode 2) particle properties and contains a range of trace compounds including ammonia, phosphates, sulfates, and nitrates; and spray from acidic hydrothermal systems, which can cover a wide variety of sizes, densities, and chemical compositions. These analogs could improve the development of Venus cloud sampling instruments or sondes, including field tests of material compatibility, particle capture efficiency, and analysis sensitivity.
A warm and wet climate scenario for early Mars has been explained by invoking a 5-bar CO2 atmosphere; however, Kasting has shown that CO2 will condense in the Martian atmosphere at these pressures. The formation of CO2 clouds will reduce the convection lapse rate and reduce the magnitude of the greenhouse effect. It is possible that additional greenhouse gases such as methane and ammonia were present in the early Mars atmosphere. We are using a one dimensional photochemical model to estimate the magnitude of the ammonia source required to maintain a given ammonia concentration in a dense CO2 atmosphere. Because CO2 is 2.5 times more efficient at Rayleigh scattering than Earth's N2 atmosphere, we anticipate increased scattering opacities and decreased photolytic destruction rates of ammonia on early Mars. The reduced gravity on Mars means that a 1 bar atmosphere will be approximately 3 times as thick as on Earth. It is possible that ammonia could have been shielded from photolysis by hydrocarbon aerosols which form as a product of methane photolysis.
Atmospheric aerosols influence climate through their interactions with radiation and clouds, yet large uncertainties remain in their simulation by global models. This study evaluates the United Kingdom Earth System Model version 1.1 (UKESM1.1) using global-scale aircraft observations from the Atmospheric Tomography (ATom) mission, focusing on aerosol lifecycle processes in the remote marine atmosphere. We assess model performance in simulating aerosol precursor vapours, number size distributions, chemical composition, and environmental conditions. Several process improvements are tested, including sulfuric acid-ammonia nucleation, ammonium nitrate scheme, methanesulfonic acid condensation, and low-temperature isoprene-derived secondary organic aerosol formation. Model biases differ significantly between the upper troposphere (UT) and the marine boundary layer (MBL). In the UT, UKESM1.1 overestimates nucleation and Aitken mode particles while underestimating accumulation mode, indicating insufficient growth. In the MBL, the model overestimates primary aerosols (e.g. seasalt) and precursor gases but underestimates nucleation and Aitken mode particles, even after incorporating updated nucleation and ammonium nitrate scheme. The persistence of low aerosol number concentrations, despite overestimated precursors, suggests missing formation pathways likely involving other species such as iodine, amines, and organic vapours. These limitations result in an unbalanced cloud condensation nuclei budget that over-relies on primary emissions. Sensitivity tests reveal that model outputs are strongly influenced by dimethyl sulfide emissions and vapour condensation schemes. Our results highlight the need for future model development to prioritise mechanistic representation of currently missing aerosol sources, rather than relying on empirical tuning, to improve aerosol-climate interaction estimates.
A method of producing submicron nonagglomerated particles in a single stage reactor includes introducing a reactant or mixture of reactants at one end while varying the temperature along the reactor to initiate reactions at a low rate. As homogeneously small numbers of seed particles generated in the initial section of the reactor progress through the reactor, the reaction is gradually accelerated through programmed increases in temperature along the length of the reactor to promote particle growth by chemical vapor deposition while minimizing agglomerate formation by maintaining a sufficiently low number concentration of particles in the reactor such that coagulation is inhibited within the residence time of particles in the reactor. The maximum temperature and minimum residence time is defined by a combination of temperature and residence time that is necessary to bring the reaction to completion. In one embodiment, electronic grade silane and high purity nitrogen are introduced into the reactor and temperatures of approximately 770.degree. K. to 1550.degree. K. are employed. In another embodiment silane and ammonia are employed at temperatures from 750.degree. K. to 1800.degree. K.