M. A. Tolbert

• University of Colorado Boulder

Among the atmospheric gases that have been proposed as possible biosignatures in exoplanetary atmospheres, organosulfur gases are currently considered one of the more robust indicators of extant life. These gases include dimethyl sulfide (DMS; CH 3 SCH 3 ), carbonyl sulfide (OCS), and carbon disulfide (CS 2 ), which are predominantly secondary meta...

Planetary organic hazes can play a significant role in influencing a planet’s radiative balance and climate, with their impact determined by the optical properties of the haze. The optical properties, in turn, are partly influenced by particle composition. Our previous work, Reed et al., demonstrated that trace amounts of hydrogen sulfide (H 2 S) i...

Although previous studies have shown that the near-surface environmental conditions on Mars may permit salt deliquescence and therefore brine production, there is significant uncertainty in the kinetics of the process. Indeed, experimental studies have shown that deliquescence is either very rapid or too slow to be relevant to Mars. To resolve this...

An accepted murine analogue for the environmental behavior of human SARS coronaviruses was aerosolized in microdroplets of its culture media and saliva to observe the decay of its airborne infectious potential under relative humidity (RH) conditions relevant to conditioned indoor air. Contained in a dark, 10 m3 chamber maintained at 22 °C, Murine H...

The composition, sizes and shapes of particles in the clouds of Venus have previously been studied with a variety of in situ and remote sensor measurements. A number of major questions remain unresolved, however, motivating the development of an exploratory mission that will drop a small probe, instrumented with a single-particle autofluorescence n...

The composition, sizes and shapes of particles in the clouds of Venus have previously been studied with a variety of in situ and remote sensor measurements. A number of major questions remain unresolved, however, motivating the development of an exploratory mission that will drop a small probe, instrumented with a single-particle autofluorescence n...

Plain Language Summary The Archean Eon (4.0–2.5 billion years ago) atmosphere was much different from the modern one, with very little oxygen and higher amounts of carbon dioxide (CO2) and methane (CH4). Light from the sun would have jump‐started chemical reactions leading to a mixture of organic molecules and particles (“organic haze”). Gases in s...

Chlorine is ubiquitous on Mars, some of it in the form of oxy-chlorine salts. Chlorine-containing salts have been found at several landing sites, including that of Phoenix and Curiosity, in the form of perchlorates and chlorides. Several intermediate states also exist, of which chlorate is the most stable. While perchlorates have received much atte...

Volcanic ash is often neglected in climate simulations because ash particles are assumed to have a short atmospheric lifetime, and to not participate in sulfur chemistry. After the Mt. Kelut eruption in 2014, stratospheric ash-rich aerosols were observed for months. Here we show that the persistence of super-micron ash is consistent with a density...

Alpha-dicarbonyl compounds are believed to form brown carbon in the atmosphere via reactions with ammonium sulfate (AS) in cloud droplets and aqueous aerosol particles. In this work, brown carbon formation in AS and other aerosol particles was quantified as a function of relative humidity (RH) during exposure to gas-phase glyoxal (GX) in chamber ex...

Recurring slope lineae (RSL) are seasonal flows on steep slopes on Mars. Their formation mechanism is unknown, but dry granular flows are a likely explanation. Any proposed trigger for these flows must be consistent with the observed temperature dependence of RSL: more active in warmer months or when sun‐facing. Here, we use atmospheric modeling an...

Oxalic acid and sulfate salts are major components of aerosol particles. Here we explore the potential for their respective precursor species, glyoxal and SO2, to form atmospheric brown carbon via aqueous-phase reactions in a series of bulk aqueous and flow chamber aerosol experiments. In bulk aqueous solutions, UV- and visible-light absorbing prod...

Abstract. Alpha-dicarbonyl compounds are believed to form brown carbon in the atmosphere via reactions with ammonium sulfate (AS) in cloud droplets and aqueous aerosol particles. In this work, brown carbon formation in AS and other aerosol particles was quantified as a function of relative humidity (RH) during exposure to gas-phase glyoxal (GX) in...

Atmospheric organic hazes are common in planetary bodies in our solar system and likely exoplanet atmospheres as well. In addition, geochemical data support the existence of an organic haze in the early Earth's atmosphere. Much of what is known about organic haze formation derives from studies of Saturn's moon Titan. It is believed that on Titan io...

Although photochemically produced organic hazes are common in planetary atmospheres, there have been few experimental investigations of the gas-phase chemistry leading to organic haze formation. We report a laboratory study of the gas-phase compounds formed by far-ultraviolet irradiation of a CH 4 /N 2 mixture. Using high-resolution chemical ioniza...

Water vapor is likely being exchanged between the regolith and the atmosphere on Mars, according to evidence from multiple landing sites (including Gale Crater), satellite measurements and numerical modeling. The mechanism of this exchange is largely unknown but could involve the formation of water frost, the adsorption of thin films of water onto...

The organic haze in the atmosphere of Saturn's moon Titan affects the moon's atmospheric and surface properties. Ions are known to play an important role in haze formation chemistry; however, the role of ions in laboratory simulations of haze formation is poorly characterized. Here, we use a high-resolution time-of-flight mass spectrometer with an...

The Mars Science Laboratory (MSL) Rover Environmental Monitoring Station (REMS) has now made continuous in-situ meteorological measurements for several martian years at Gale crater, Mars. Of importance in the search for liquid formation are REMS' measurements of ground temperature and in-air measurements of temperature and relative humidity, which...

The water uptake and release by perchlorate salts have been well studied since the first in situ identification of such salts in the Martian soil by the Phoenix mission in 2008. However, there have been few studies on the effect of the insoluble regolith minerals on the interaction of perchlorate with water vapor. In this work, we investigate the i...

Aerosols have a profound impact on cloud microphysics through their ability to serve as ice nucleating particles (INPs). As a result, cloud radiative properties and precipitation processes can be modulated by such aerosol–cloud interactions. However, one of the largest uncertainties associated with atmospheric processes is the indirect effect of ae...

Volcanic ash produced during explosive eruptions may serve as ice nuclei in the atmosphere, contributing to the occurrence of volcanic lightning due to tribocharging from ice-ice or ice-ash collisions. Here, different ash samples were tested using deposition-mode and immersion-mode ice nucleation experiments. Results show that bulk composition and...

Atmospheric organic hazes are present on many planetary bodies, possibly including the ancient Earth and exoplanets, and can greatly influence surface and atmospheric properties. Here we examine the physical and optical properties of organic hazes produced with molecular nitrogen, methane, carbon dioxide, and increasing amounts of molecular oxygen,...

Previous studies of haze formation in the atmosphere of the Early Earth have focused on N$_{2}$/CO$_{2}$/CH$_{4}$ atmospheres. Here, we experimentally investigate the effect of O$_{2}$ on the formation and composition of aerosols to improve our understanding of haze formation on the Neoproterozoic Earth. We obtained in situ size, particle density,...

Previous studies of haze formation in the atmosphere of the Early Earth have focused on N$_{2}$/CO$_{2}$/CH$_{4}$ atmospheres. Here, we experimentally investigate the effect of O$_{2}$ on the formation and composition of aerosols to improve our understanding of haze formation on the Neoproterozoic Earth. We obtained in situ size, particle density,...

The Mars Science Laboratory (MSL) Rover Environmental Monitoring Station (REMS) has now made continuous in situ meteorological measurements for several Martian years at Gale crater, Mars. Of importance in the search for liquid formation are REMS' measurements of ground temperature and in-air measurements of temperature and relative humidity, which...

Aerosols have a profound impact on cloud microphysics through their ability to serve as ice nucleating particles (INPs). As a result, cloud radiative properties and precipitation processes are modulated by such aerosol-cloud interactions. However, one of the largest uncertainties associated with atmospheric processes is the indirect effect of aeros...

The phase state of inorganic salt aerosols impacts their properties including the ability to undergo hygroscopic growth, catalyze heterogeneous reactions, and act as cloud condensation nuclei. Here, we report the first observation of contact efflorescence by mineral dust aerosol. The efflorescence of aqueous ammonium sulfate ((NH4)2SO4) and sodium...

The observed darkening of water tracks near Don Juan Pond (DJP) as well as the formation of wet patches elsewhere in the McMurdo Dry Valleys is attributed at least partially to deliquescence, a process by which salts absorb atmospheric water vapor and form brine, coupled with liquid-phase growth when the atmospheric relative humidity exceeds the wa...

Prior to the arrival of Cassini-Huygens, aerosol production in Titan's atmosphere was believed to begin in the stratosphere where chemical processes are predominantly initiated by FUV radiation. However, measurements taken by Cassini UVIS and CAPS indicate that haze formation initiates in the thermosphere where there is a greater flux of EUV photon...

Prior to the arrival of Cassini-Huygens, aerosol production in Titan's atmosphere was believed to begin in the stratosphere where chemical processes are predominantly initiated by FUV radiation. However, measurements taken by Cassini UVIS and CAPS indicate that haze formation initiates in the thermosphere where there is a greater flux of EUV photon...

Particle collisions are a common occurrence in the atmosphere, but no empirical observations exist to fully predict the potential effects of these collisions on air quality and climate projections. The current consensus of heterogeneous crystal nucleation pathways relevant to the atmosphere dictates that collisions with amorphous particles have no...

Perchlorate and chloride salts on Mars could readily absorb water vapor and deliquesce into aqueous solutions. The deliquescence relative humidity (RH) as well as the efflorescence (recrystallization) RH of several Mars-relevant salts are now well known; however, the conditions that could cause a brine to freeze are not well established. It is ofte...

Organic hazes formed from methane are present in many planetary and satellite atmospheres and influence surface and atmospheric processes. Here we examine the compositional and optical properties of laboratory generated hazes, or tholins, formed with varying amounts of methane using spark discharge excitation. By studying the optical and chemical p...

Mineral dust particles are known to be efficient ice nuclei in the atmosphere. Previous work has probed heterogeneous ice nucleation on various laboratory dust samples including Arizona Test Dust, kaolinite, montmorillonite, and illite as atmospheric dust surrogates. However, it has recently been suggested that NX illite may be a better representat...

Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry....

There is significant interest in the potential existence of even small amounts of liquid brine on current Mars. It has been proposed that aqueous solutions could form on Mars via the deliquescence of hygroscopic salts in contact with atmospheric water vapor, and these hygroscopic salts have recently been detected in recurring slope linae (RSL). Whi...

Air pollution is attributable to 7 million deaths per year, or one out of every eight deaths globally. In particular, high concentrations of particulate matter (PM), a major air pollutant, have significant impacts on health and regional climate in urban centers. Many of the most polluted places, largely in developing countries, go severely understu...

Significance Atmospheric particles contain inorganic material that can effloresce to form a crystalline solid. The phase state of atmospheric particles influences the particle’s effect on climate and air quality. Despite the importance of particle phase, there is no comprehensive understanding of particle crystallization, and many climate models as...

Ice nucleation of volcanic ash controls both ash aggregation and cloud glaciation, which affect atmospheric transport and global climate. Previously, it has been suggested that there is one characteristic ice nucleation efficiency for all volcanic ash, regardless of its composition, when accounting for surface area; however, this claim is derived f...

A novel optical trapping technique is described that combines an upward propagating Gaussian beam and a downward propagating Bessel beam. Using this optical arrangement and an on-demand droplet generator makes it possible to rapidly and reliably trap particles with a wide range of particle diameters (~1.5-25 μm), in addition to crystalline particle...

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an int...

Elemental analysis of unit-mass resolution (UMR) mass spectra is limited by the amount of information available to definitively elucidate the molecular formula of a molecule ionized by electron impact. The problem is compounded when a mixture of organic molecules (such as those found in organic aerosols) is analyzed without the benefit of prior sep...

Due to their stability in low temperature conditions, aqueous salt solutions are the favored explanation for potential fluid features observed on present-day Mars. A salt analog was developed to closely match the individual cation and anion concentrations at the Phoenix landing site as reported by the Wet Chemistry Laboratory instrument. ’Instant M...

Ice nucleation on volcanic ash controls both ash aggregation and cloud glaciation, which affect atmospheric transport and global climate. Previously, it has been suggested that there is one characteristic ice nucleation efficiency for all volcanic ash, regardless of its composition, when accounting for surface area; however, this claim is derived f...

The deliquescence and heterogeneous ice nucleation behavior of simulated sea-spray aerosol was probed from 215 to 235 K using Raman microscopy coupled to an environmental cell. Water uptake prior to deliquescence was also probed on sea-salt particles along deliquescence/ice nucleation experimental trajectories. Synthetic sea-salt particles were gen...

Knowledge about Rayleigh scattering cross sections is relevant to predictions about radiative transfer in the atmosphere, and needed to calibrate the reflectivity of mirrors that are used in high-finesse optical cavities to measure atmospheric trace gases and aerosols. In this work we have measured the absolute Rayleigh scattering cross-section of...

Accurate refractive index values are required to determine the effects of aerosol particles on direct radiative forcing. Theoretical retrievals using extinction data alone or extinction plus absorption data have been simulated to determine the sensitivity of each retrieval. A range of aerosol types with a range of different refractive indices were...

Mineral dust aerosol is one of the largest contributors to global ice nuclei, but physical and chemical processing of dust during atmospheric transport can alter its ice nucleation activity. In particular, several recent studies have noted that sulfuric and nitric acids inhibit heterogeneous ice nucleation in the regime below liquid water saturatio...

Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice nucleating particles (INPs). However,...

Light extinction by atmospheric particles is strongly dependent on their chemical composition and water content. Since light extinction directly impacts climate, optical measurements of atmospherically relevant aerosols at varying relative humidities (RH) are needed. Recent studies have highlighted the possibility that some atmospheric aerosols are...

During the Cassini mission to the saturnian system, benzene (C6H6) was observed throughout Titan’s atmosphere. Although present in trace amounts, benzene has been proposed to be an important precursor for polycyclic aromatic hydrocarbon formation, which could eventually lead to haze production. In this work, we simulate the effect of benzene in Tit...

Perchlorate salts, known to exist on Mars, can readily absorb water vapor and deliquesce into aqueous solutions even at low temperatures. The multiple soluble ionic species, such as chloride salts, present in the Martian subsurface may affect this deliquescence. Here we study the deliquescence (solid to aqueous transition) and efflorescence (aqueou...

Perchlorate salts, recently discovered on Mars, are known to readily absorb water vapor from the atmosphere and deliquesce into the aqueous phase at room temperature. Here we study the deliquescence (crystalline solid to liquid transition) and efflorescence (liquid to crystalline solid transition) of perchlorate salts at low temperatures relevant t...

Organic haze plays a key role in many planetary processes ranging from influencing the radiation budget of an atmosphere to serving as a source of prebiotic molecules on the surface. Numerous experiments have investigated the aerosols produced by exposing mixtures of N2/CH4 to a variety of energy sources. However, many N2/CH4 atmospheres in both ou...

Glyoxal, methylglyoxal, glycolaldehyde, and hydroxyacetone form N-containing and oligomeric compounds during simulated cloud processing with small amines. Using a novel hygroscopicity tandem differential mobility analysis (HTDMA) system that allows varied humidification times, the hygroscopic growth (HG) of each of the resulting products of simulat...

In this study, we have explored the phase behavior and the ice nucleation properties of secondary organic aerosol made from aqueous processing (aqSOA). AqSOA was made from the dark reactions of methylglyoxal with methylamine in simulated evaporated cloud droplets. The resulting particles were probed from 215-250 K using Raman spectroscopy coupled t...

We report new microchip non-aqueous capillary electrophoresis (μNACE) methods for the electrophoretic separation and analysis of organic compounds of relevance to astrobiology. We previously reported [1] a protocol for μNACE of primary aliphatic amines in ethanol, and demonstrated separations of short- and long-chain amines down to-20°C. We have op...

Light extinction by particles in Earth's atmosphere is strongly dependent on particle size, chemical composition, hygroscopic growth properties and particle mixing state. Here, the influence of an organic coating on particle optical growth was studied. The particle optical growth factor, fRHext, was measured using cavity ring-down aerosol extinctio...

Amorphous (semi-)solid organic aerosol particles have the potential to serve as surfaces for heterogeneous ice nucleation in cirrus clouds. Raman spectroscopy and optical microscopy have been used in conjunction with a cold stage to examine water uptake and ice nucleation on individual amorphous (semi-)solid particles at atmospherically relevant te...

The organic haze produced from complex CH4/N2 chemistry in the atmosphere of Titan plays an important role in processes that occur in the atmosphere and on its surface. The haze particles act as condensation nuclei and are therefore involved in Titan's methane hydrological cycle. They also may behave like sediment on Titan's surface and participate...

The organic haze produced from complex CH4/N2 chemistry in the atmosphere of Titan plays an important role in processes that occur in the atmosphere and on its surface. The haze particles act as condensation nuclei and are therefore involved in Titan's methane hydrological cycle. They also may behave like sediment on Titan's surface and participate...

The depositional and immersion mode ice nucleation efficiency of volcanic ash has been explored using a Raman microscope coupled to an environmental cell. Three separate ash samples from geographically distinct regions were specifically chosen to contain varying amounts of metal oxides and crystalline material, which could be integral factors in de...

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on bot...

To understand the phase of Ca(ClO_4)_2 on the martian surface, we report the humidity where deliquescence and efflorescence occur over a range of temperatures.

Benzene has been detected in Titan's atmosphere by Cassini instruments, with concentrations ranging from sub-ppb in the stratosphere to ppm in the ionosphere. Sustained levels of benzene in the haze formation region could signify that it is an important reactant in the formation of Titan's organic aerosol. To date, there have not been laboratory in...

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on bot...

Glassy or amorphous (semi-)solid organic aerosol particles have the potential to serve as surfaces for heterogeneous ice nucleation in cirrus clouds. Raman spectroscopy and optical microscopy have been used in conjunction with a cold stage to examine water uptake and ice nucleation on individual aqueous organic glass particles at atmospherically re...

Analyses of data obtained by multiple instruments carried by Cassini and Huygens have increased our knowledge of the composition of Titan’s atmosphere. While a wealth of new information about the aerosols in Titan’s atmosphere was obtained, their composition is still not well constrained. Laboratory experiments will therefore play a key role in fur...

Measurements from the Cassini Plasma Spectrometer (CAPS) have revealed the presence of molecules in Titan's ionosphere with masses in excess of hundreds of amu. Negative ions with mass/charge (m/z) up to 10,000 amu/q [1] and positive ions with m/z up to 400 amu/q [2] have been detected. CAPS has also observed O+ flowing into Titan's upper atmospher...

To understand the formation of briny aqueous solutions on Mars, salt analogs were developed to closely match the cation and anion concentrations as reported by Wet Chemistry Laboratory.

A comparison of the composition aerosols produced from N2/CH4/CO gas mixtures using two different energy sources (spark, FUV) and the effect of variation of CO mixing ratio on aerosol production and composition will be presented.

Using cavity ring-down aerosol extinction spectroscopy, we determine the real and imaginary refractive index at 532 nm of particles formed by benzene photolysis and Titan analog particles formed with ppm-levels of benzene.

The heterogeneous ice nucleation efficiency of a series of thin C3-C6 monocarboxylic acid films between 180 and 200 K has been investigated using a Knudsen cell flow reactor. At each temperature, the critical ice saturation ratio for depositional nucleation as well as the effective contact angle was found to be strongly dependent on the chemical na...

Secondary organic aerosol makes up a significant fraction of the total aerosol mass, and a growing body of evidence indicates that reactions in the atmospheric aqueous phase are important contributors to aerosol formation and can help explain observations that cannot be accounted for using traditional gas-phase chemistry. In particular, aqueous pha...

Laboratory studies are described that suggest reactive uptake of glyoxal on particulate containing HNO(3) could contribute to the formation of secondary organic aerosol (SOA) in the upper troposphere (UT). Using a Knudsen cell flow reactor, glyoxal is observed to react on supercooled H(2)O/HNO(3) surfaces to form condensed-phase glyoxylic acid. Thi...

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λ<120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120-200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not i...

The discovery of very heavy ions (Coates et al., 2007) in Titan’s thermosphere has dramatically altered our understanding of the processes involved in the formation of the complex organic aerosols that comprise Titan’s characteristic haze. Before Cassini’s arrival, it was believed that aerosol production began in the stratosphere where the chemical...

In this study chemical compositions of background aerosol and ice nuclei were examined through laboratory investigations using Raman spectroscopy and field measurements by single-particle mass spectrometry. Aerosol sampling took place at Storm Peak Laboratory in Steamboat Springs, Colorado (elevation of 3210 m). A cascade impactor was used to colle...

Raman microscopy is used to study the deliquescence (solid to aqueous transition) and efflorescence (aqueous to solid transition) of three ClO_4^-/Cl^- mixed salt systems. We find that aqueous phases form at low RH values and may occur on current Mars.

Sea-salt aerosol (SSA) particles are ubiquitous in the marine boundary layer and over coastal areas. Therefore SSA have ability to directly and indirectly affect the Earth's radiation balance. The influence SSA have on climate is related to their water uptake and ice nucleation characteristics. In this study, optical microscopy coupled with Raman s...

Perchlorate salts, recently discovered on Mars, are known to readily absorb water vapor from the atmosphere and deliquesce into the aqueous phase at room temperature. Here we study the deliquescence (crystalline solid to liquid transition) and efflorescence (liquid to crystalline solid transition) of perchlorate salts at low temperatures relevant t...

Light extinction by particles is strongly dependent on chemical composition, particle size, and water uptake. Relative humidity affects extinction by causing changes in refractive index and particle size due to hygroscopic growth. The ability of particles to take up water depends on its composition and structure. Organic compounds and inorganic sal...

Organic material is ubiquitous in tropospheric aerosol and has significant natural and anthropogenic sources. Until recently it was believed that organic species present in or on aerosol particles acted only to inhibit ice nucleation. However, recent studies have shown that the relationship between ice formation and organic material is not straight...

Sea-salt aerosol particles (SSA) are ubiquitous in the marine boundary layer and over coastal areas. Therefore SSA have ability to directly and indirectly affect the Earth's radiation balance. The influence SSA have on climate is related to their water uptake and ice nucleation characteristics. In this study, optical microscopy coupled with Raman s...

We have explored the direct and indirect radiative effects on climate of organic particles likely to have been present on early Earth by measuring their hygroscopicity and cloud nucleating ability. The early Earth analog aerosol particles were generated via ultraviolet photolysis of an early Earth analog gas mixture, which was designed to mimic pos...

It has been reported by several groups that methane in the Martian atmosphere is both spatially and temporally variable. Gough et al. (2010) suggested that temperature dependent, reversible physical adsorption of methane onto Martian soils could explain this variability. However, it is also useful to consider if there might be chemical destruction...

Reactions of methylglyoxal with amino acids, methylamine, and ammonium sulfate can take place in aqueous aerosol and evaporating cloud droplets. These processes are simulated by drying droplets and bulk solutions of these compounds (at low millimolar and 1 M concentrations, respectively) and analyzing the residuals by scanning mobility particle siz...