Thermal Desorption Chemical Ionization Mass Research Articles

Implications for new particle formation in air of the use of monoethanolamine in carbon capture and storage.

Alkanolamines are currently being deployed in carbon capture and storage (CCS) technology worldwide, and atmospheric emissions have been found to coincide with locations exhibiting elevated concentrations of methanesulfonic acid (MSA). It is thus critical to understand the fate and potential atmospheric reactions of these chemicals. This study reports the characterization of sub-10 nm nanoparticles produced through the acid-base reaction between gas phase monoethanolamine (MEA) and MSA, a product of organosulfur compound oxidation in air, using a flow reactor under dry and humid (up to ∼60% RH) conditions. Number size distribution measurements show that MEA is even more efficient than methylamine in forming nanoparticles on reaction with MSA. This is attributed to the fact that the MEA structure contains both an -NH2 and an -OH group that facilitate hydrogen bonding within the clusters, in addition to the electrostatic interactions. Due to this already strong H-bond network, water has a relatively small influence on new particle formation (NPF) and growth in this system, in contrast to MSA reactions with alkylamines. Acid/base molar ratios of unity for 4-12 nm particles were measured using thermal desorption chemical ionization mass spectrometry. The data indicate that reaction of MEA with MSA may dominate NPF under some atmospheric conditions. Thus, the unique characteristics of alkanolamines in NPF must be taken into account for accurate predictions of impacts of CCS on visibility, health and climate.

Seasonal variations in composition and sources of atmospheric ultrafine particles in urban Beijing based on near-continuous measurements

Abstract. Understanding the composition and sources of atmospheric ultrafine particles (UFPs) is essential in evaluating their exposure risks. It requires long-term measurements with high time resolution, which are scarce to date. We performed near-continuous measurements of UFP composition during four seasons in urban Beijing using a thermal desorption chemical ionization mass spectrometer, accompanied by real-time size distribution measurements. We found that UFPs in urban Beijing are dominated by organic components, varying seasonally from 68 % to 81 %. CHO organics (i.e., molecules containing carbon, hydrogen, and oxygen) are the most abundant in summer, while sulfur-containing organics, some nitrogen-containing organics, nitrate, and chloride are the most abundant in winter. With the increase of particle diameter, the contribution of CHO organics decreases, while that of sulfur-containing and nitrogen-containing organics, nitrate, and chloride increases. Source apportionment analysis of the UFP organics indicates contributions from cooking and vehicle sources, photooxidation sources enriched in CHO organics, and aqueous/heterogeneous sources enriched in nitrogen- and sulfur-containing organics. The increased contributions of cooking, vehicle, and photooxidation components are usually accompanied by simultaneous increases in UFP number concentrations related to cooking emission, vehicle emission, and new particle formation, respectively, while the increased contribution of the aqueous/heterogeneous composition is usually accompanied by the growth of UFP mode diameters. The highest UFP number concentrations in winter are due to the strongest new particle formation, the strongest local primary particle number emissions, and the slowest condensational growth of UFPs to larger sizes. This study provides a comprehensive understanding of urban UFP composition and sources and offers valuable datasets for the evaluation of UFP exposure risks.

Insufficient Condensable Organic Vapors Lead to Slow Growth of New Particles in an Urban Environment.

Atmospheric new particle formation significantly affects global climate and air quality after newly formed particles grow above ∼50 nm. In polluted urban atmospheres with 1-3 orders of magnitude higher new particle formation rates than those in clean atmospheres, particle growth rates are comparable or even lower for reasons that were previously unclear. Here, we address the slow growth in urban Beijing with advanced measurements of the size-resolved molecular composition of nanoparticles using the thermal desorption chemical ionization mass spectrometer and the gas precursors using the nitrate CI-APi-ToF. A particle growth model combining condensational growth and particle-phase acid-base chemistry was developed to explore the growth mechanisms. The composition of 8-40 nm particles during new particle formation events in urban Beijing is dominated by organics (∼80%) and sulfate (∼13%), and the remainder is from base compounds, nitrate, and chloride. With the increase in particle sizes, the fraction of sulfate decreases, while that of the slow-desorbed organics, organic acids, and nitrate increases. The simulated size-resolved composition and growth rates are consistent with the measured results in most cases, and they both indicate that the condensational growth of organic vapors and H2SO4 is the major growth pathway and the particle-phase acid-base reactions play a minor role. In comparison to the high concentrations of gaseous sulfuric acid and amines that cause high formation rates, the concentration of condensable organic vapors is comparably lower under the high NOx levels, while those of the relatively high-volatility nitrogen-containing oxidation products are higher. The insufficient condensable organic vapors lead to slow growth, which further causes low survival of the newly formed particles in urban environments. Thus, the low growth rates, to some extent, counteract the impact of the high formation rates on air quality and global climate in urban environments.

Composition of Ultrafine Particles in Urban Beijing: Measurement Using a Thermal Desorption Chemical Ionization Mass Spectrometer.

Ultrafine particles (UFPs) dominate the particle number population in the urban atmosphere and revealing their chemical composition is important. The thermal desorption chemical ionization mass spectrometer (TDCIMS) can semicontinuously measure UFP composition at the molecular level. We modified a TDCIMS and deployed it in urban Beijing. Radioactive materials in the TDCIMS for aerosol charging and chemical ionization were replaced by soft X-ray ionizers so that it can be operated in countries with tight regulations on radioactive materials. Protonated N-methyl-2-pyrrolidone ions were used as the positive reagent ion, which selectively detects ammonia and low-molecular weight-aliphatic amines and amides vaporized from the particle phase. With superoxide as the negative reagent ion, a wide range of inorganic and organic compounds were observed, including nitrate, sulfate, aliphatic acids with carbon numbers up to 18, and highly oxygenated CHO, CHON, and CHOS compounds. The latter two can be attributed to parent ions or the decomposition products of organonitrates and organosulfates/organosulfonates, respectively. Components from both primary emissions and secondary formation of UFPs were identified. Compared to the UFPs measured at forest and marine sites, those in urban Beijing contain more nitrogen-containing and sulfur-containing compounds. These observations illustrate unique features of the UFPs in the urban environment and provide insights into their origins.

Chemical composition of ultrafine aerosol particles in central Amazonia during the wet season

Abstract. Central Amazonia serves as an ideal location to study atmospheric particle formation, since it often represents nearly natural, pre-industrial conditions but can also experience periods of anthropogenic influence due to the presence of emissions from large metropolitan areas like Manaus, Brazil. Ultrafine (sub-100 nm diameter) particles are often observed in this region, although new particle formation events seldom occur near the ground despite being readily observed in other forested regions with similar emissions of volatile organic compounds (VOCs). This study focuses on identifying the chemical composition of ultrafine particles as a means of determining the chemical species and mechanisms that may be responsible for new particle formation and growth in the region. These measurements were performed during the wet season as part of the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign at a site located 70 km southwest of Manaus. A thermal desorption chemical ionization mass spectrometer (TDCIMS) characterized the most abundant compounds detected in ultrafine particles. Two time periods representing distinct influences on aerosol composition, which we label as “anthropogenic” and “background” periods, were studied as part of a larger 10 d period of analysis. Higher particle number concentrations were measured during the anthropogenic period, and modeled back-trajectory frequencies indicate transport of emissions from the Manaus metropolitan area. During the background period there were much lower number concentrations, and back-trajectory frequencies showed that air masses arrived at the site predominantly from the forested regions to the north and northeast. TDCIMS-measured constituents also show distinct differences between the two observational periods. Although bisulfate was detected in particles throughout the 10 d period, the anthropogenic period had higher levels of particulate bisulfate overall. Ammonium and trimethyl ammonium were positively correlated with bisulfate. The background period had distinct diurnal patterns of particulate cyanate and acetate, while oxalate remained relatively constant during the 10 d period. 3-Methylfuran, a thermal decomposition product of a particulate-phase isoprene epoxydiol (IEPOX), was the dominant species measured in the positive-ion mode. Principal component analysis (PCA) was performed on the TDCIMS-measured ion abundance and aerosol mass spectrometer (AMS) mass concentration data. Two different hierarchical clusters representing unique influences arise: one comprising ultrafine particulate acetate, hydrogen oxalate, cyanate, trimethyl ammonium and 3-methylfuran and another made up of ultrafine particulate bisulfate, chloride, ammonium and potassium. A third cluster separated AMS-measured species from the two TDCIMS-derived clusters, indicating different sources or processes in ultrafine aerosol particle formation compared to larger submicron-sized particles.

An Experimental and Modeling Study of Nanoparticle Formation and Growth from Dimethylamine and Nitric Acid.

The size-resolved composition of nanoparticles formed and grown through acid-base reactive uptake has been studied in the laboratory by reacting gas-phase nitric acid (HNO3) and dimethylamine (DMA) in a flow tube under dry (<5% RH) and humid (∼55% RH) conditions. Size-resolved nanoparticle composition was measured by a thermal desorption chemical ionization mass spectrometer over the diameter range of 9-30 nm. The nanoparticle geometric mean diameter grew in the presence of water compared to dry conditions. Acid/base ratios of HNO3-DMA particles at all measured sizes did not strongly deviate from neutral (1:1) in either RH condition, which contrasts with prior laboratory studies of nanoparticles made from sulfuric acid (H2SO4) and base. Theoretical methods were used to investigate the underlying chemical processes that explain observed differences in the compositions of HNO3-DMA and H2SO4-DMA particles. Calculations of HNO3-DMA cluster stability indicated that a 1:1 acid/base ratio has >107 smaller evaporation rates than any other acid/base ratio in this system, and measured nanoparticle composition confirm this to be the most stable pathway for growth up to 30 nm particles. This study demonstrates that nanoparticle formation and growth via acid-base reactive uptake of HNO3 and DMA follow the thermodynamic theory, likely because of both components' volatility.

A soft X-ray unipolar charger for ultrafine particles

The performance of a unipolar particle charger using soft X-ray as the ion production source was optimized and characterized in this study. The charger design was based on the high efficiency particle charger reported by Chen and Pui (1999), in which the radioactive material (210Po) as the ion source and sheath flow for minimizing the particle loss were used. The use of 210Po source makes it challenging for field investigation due to the regulation of controlled substances. The inclusion of sheath flow in the high efficiency charger inevitably dilutes the output particle concentration, which is an undesired effect for the measurement of atmospheric ultrafine particles. The current soft X-ray charger was designed to ease the above concerns. The penetration efficiency, intrinsic and extrinsic charging efficiency, and extrinsic charge distributions of particles passing through the charger were measured under the optimal voltage operation. It was found that the loss of ultrafine particles in the charger was higher than that in the high efficiency charger (due to the lack of applying sheath flow). At the flow rate of 5.0 lpm, the measured extrinsic charging efficiency was comparable to that of the charger applied in the thermal desorption chemical ionization mass spectrometer (Smith et al., 2004). The measured extrinsic charge distribution of particles further showed that more than 50% of particles in the size range of 20–40 nm and 20–50 nm were singly charged at the flow rate of 1.5 lpm and 5.0 lpm, respectively.

Evidence for Diverse Biogeochemical Drivers of Boreal Forest New Particle Formation

AbstractNew particle formation (NPF) is an important contributor to particle number in many locations, but the chemical drivers for this process are not well understood. Daytime NPF events occur regularly in the springtime Finnish boreal forest and strongly impact aerosol abundance. In April 2014 size‐resolved chemical measurements of ambient nanoparticles were made using the Time‐of‐Flight Thermal Desorption Chemical ionization Mass Spectrometer and we report results from two NPF events. While growth overall was dominated by terpene oxidation products, newly formed 20–70 nm particles showed enhancement in apparent alkanoic acids. The events occurred on days with rapid transport of marine air, which correlated with low background aerosol loading and higher gas phase methanesulfonic acid levels. These results are broadly consistent with previous studies on Nordic NPF but indicate that further attention should be given to the sources and role of non‐terpenoid organics and the possible contribution of transported marine compounds in this process.

Unexpectedly acidic nanoparticles formed in dimethylamine–ammonia–sulfuric-acid nucleation experiments at CLOUD

Abstract. New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.

Atmospheric amines and ammonia measured with a chemical ionization mass spectrometer (CIMS)

Abstract. We report measurements of ambient amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a southeastern US forest and a moderately polluted midwestern site during the summer. At the forest site, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected, and they both showed temperature dependencies. Aerosol-phase amines measured thermal-desorption chemical ionization mass spectrometer (TDCIMS) showed a higher mass fraction in the evening with cooler temperatures and lower in the afternoon with warmer temperatures, a trend opposite to the gas-phase amines. Concentrations of aerosol-phase primary amines measured with Fourier transform infrared spectroscopy (FTIR) from micron and submicron particles were 2 orders of magnitude higher than the gas-phase amines. These results indicate that gas to particle conversion is one of the major processes that control the ambient amine concentrations at this forest site. Temperature dependencies of C3-amines and ammonia also imply reversible processes of evaporation of these nitrogen-containing compounds from soil surfaces in daytime and deposition to soil surfaces at nighttime. During the transported biomass burning plume events, various amines (C1–C6) appeared at the pptv level, indicating that biomass burning is a substantial source of amines in the southeastern US. At the moderately polluted Kent site, there were higher concentrations of C1- to C6-amines (pptv to tens of pptv) and ammonia (up to 6 ppbv). C1- to C3-amines and ammonia were well correlated with the ambient temperature. C4- to C6-amines showed frequent spikes during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Higher amine concentrations measured at the polluted site than at the rural forested site highlight the importance of constraining anthropogenic emission sources of amines.

Composition of 15–85 nm particles in marine air

Abstract. The chemical composition of 15–85 nm diameter particles was measured at Mace Head, Ireland, during May 2011 using the TDCIMS (thermal desorption chemical ionization mass spectrometer). Measurable levels of chloride, sodium, and sulfate were present in essentially all collected samples of these particles at this coastal Atlantic site. Acetaldehyde and benzoic acid were also frequently detected. Concomitant particle hygroscopicity observations usually showed a sea-salt mode and a lower hygroscopicity mode with growth factors near to that of ammonium sulfate. There were many periods lasting from hours to about 2 days during which the 10–60 nm particle number increased dramatically in polar oceanic air. These periods were correlated with the presence of benzoic acid in the particles and an increase in the number of lower hygroscopicity mode particles. Very small (&lt; 10 nm) particles were also present, suggesting that new particle formation contributed to these nanoparticle enhancement events.

Identification of the biogenic compounds responsible for size‐dependent nanoparticle growth

The probability that freshly nucleated nanoparticles can survive to become cloud condensation nuclei is highly sensitive to particle growth rates. Much of the growth of newly formed ambient nanoparticles can be attributed to oxidized organic vapors originating from biogenic precursor gases. In this study we investigated the chemical composition of size‐selected biogenic nanoparticles in the size range from 10 to 40 nm. Particles were formed in a flow tube reactor by ozonolysis ofα‐pinene and analyzed with a Thermal Desorption Chemical Ionization Mass Spectrometer. While we found similar composition in 10 and 20 nm particles, the relative amounts of individual species varied significantly when compared to 40 nm particles. Smaller particles (10 and 20 nm) were characterized by enhancements in carboxylic acids and larger particles (40 nm) showed higher concentrations of carbonyl‐containing compounds and low molecular weight organic acids. This composition change from smaller to larger size particles reflects a vapor pressure increase of the condensing vapors by 1–2 orders of magnitude indicating that the Kelvin effect plays a decisive role in the growth of biogenic nanoparticles.

Observations of aminium salts in atmospheric nanoparticles and possible climatic implications

We present laboratory studies and field observations that explore the role of aminium salt formation in atmospheric nanoparticle growth. These measurements were performed using the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) and Ultrafine Hygroscopicity Tandem Differential Mobility Analyzers. Laboratory measurements of alkylammonium-carboxylate salt nanoparticles show that these particles exhibit lower volatilities and only slightly lower hygroscopicities than ammonium sulfate nanoparticles. TDCIMS measurements of these aminium salts showed that the protonated amines underwent minimal decomposition during analysis, with detection sensitivities comparable to those of organic and inorganic deprotonated acids. TDCIMS observations made of a new particle formation event in an urban site in Tecamac, Mexico, clearly indicate the presence of protonated amines in 8-10 nm diameter particles accounting for about 47% of detected positive ions; 13 nm particles were hygroscopic with an average 90% RH growth factor of 1.42. Observations of a new particle formation event in a remote forested site in Hyytiälä, Finland, show the presence of aminium ions with deprotonated organic acids; 23% of the detected positive ions during this event are attributed to aminium salts while 10 nm particles had an average 90% RH growth factor of 1.27. Similar TDCIMS observations during events in Atlanta and in the vicinity of Boulder, Colorado, show that aminium salts accounted for 10-35% of detected positive ions. We conclude that aminium salts contribute significantly to nanoparticle growth and must be accounted for in models to accurately predict the impact of new particle formation on climate.

Direct analysis of sterols from dried plasma/blood spots by an atmospheric pressure thermal desorption chemical ionization mass spectrometry (APTDCI-MS) method for a rapid screening of Smith–Lemli–Opitz syndrome

Here is proposed a rapid and sensitive method involving atmospheric pressure thermal desorption chemical ionization mass spectrometry (APTDCI-MS) for specific laboratory screening of the Smith-Lemli-Opitz syndrome (SLOS), an inherited defect of cholesterol biosynthesis. Biochemical findings in the blood of SLOS patients are low cholesterol (Chol), high 7- and 8-dehydrocholesterol (DHCs) levels and high DHCs/Chol ratios. The APTDCI proposed method is able to ionize sterols for qualitative and quantitative analysis directly from dried plasma/blood spots. Critical APTDCI parameters--desolvation gas flow and temperature--were optimized analyzing Chol, 7-DHC and cholesteryl stearate standards spotted onto a glass slide acquiring the full scan spectra in positive ion mode. Chol levels in dried plasma spots of unaffected controls (n = 23) obtained by the proposed method were compared with those of the enzymatic method (y = 0.9166x + 0.3811; r = 0.8831) while Chol and DHCs of SLOS patients (n = 9) were compared with the gas chromatography flame ionization detection (GC-FID) method (y = 0.8214x + 0.7388; r = 0.8288). The APTDCI-MS method is also able to differentiate normal from SLOS samples directly analyzing whole blood and washed red cells spotted on paper. In conclusion, the intrinsic analytical high-throughput of APTDCI-MS method for sterol analysis could be useful to screen SLO syndrome.

Carboxylic acid characterization in nanoparticles by thermal desorption chemical ionization mass spectrometry

Recent improvements in the operation of the thermal desorption chemical ionization mass spectrometer allow for the characterization of organic species in 8–40 nm diameter particles. Here we describe the application of this technique to monocarboxylic and dicarboxylic acids, focusing on the response of the instrument to picogram amounts of pure and multicomponent mixtures. Monocarboxylic acids underwent minimal decomposition during analysis, and were identified by the deprotonated parent ion with a sensitivity of 3–8 Hz of integrated ion signal per picogram of sample. Measurements of a binary mixture of monocarboxylic acids showed that desorption and subsequent ionization of these compounds occur independently and have mass-normalized responses identical to pure samples. Dicarboxylic acids appear as the deprotonated parent ion as well as an important decomposition product corresponding to the loss of formic acid from the deprotonated parent. Sensitivities towards these compounds were up to 100 times higher than for the monocarboxylic acids. Experiments using 10–30 nm diameter butanedioic acid particles showed a linear response to collected particulate mass with sufficient sensitivity to support the application of this technique to the characterization of carboxylic acids in ambient atmospheric nanoparticles.

Chemical composition of atmospheric nanoparticles formed from nucleation in Tecamac, Mexico: Evidence for an important role for organic species in nanoparticle growth

We report Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) measurements of the composition of ambient 10–33 nm diameter particles formed from nucleation on 16 March 2006 in Tecamac, Mexico during the Megacity Initiative: Local and Global Research Observations (MILAGRO) field study. On this day, nucleated particles contained far more organics than sulfates: average ion molar ratios with measurement uncertainties for nitrate, organics and sulfur species were 6 ± 2%, 84 ± 5%, and 10 ± 1%, respectively. The measured organic species include nitrogen‐containing organic compounds, organic acids, and hydroxy organic acids. Independent calculations show that sulfuric acid condensation could have accounted for only 10 ± 2% of the growth that was observed on this day, which is consistent with the TDCIMS measurements of composition. It follows that organic compounds play a dominant role the high growth rates that were observed.

Preface to topical collection on new particle formation in Atlanta

[1] The Aerosol Nucleation and Real Time Characterization Experiment (ANARChE) took place in Atlanta, Georgia, during late July and through August 2002. The study was aimed at providing new insights into several discrepancies that arose from our previous observations on atmospheric new particle formation. These include (1) rates of new particle formation near the Earth’s surface are often orders of magnitude higher than are predicted by the binary theory of nucleation for sulfuric acid and water; (2) new particle formation rates often vary in proportion to the first or second power of sulfuric acid concentration, rather than the much stronger dependence predicted by nucleation theories; and (3) the growth rates of freshly nucleated particles are typically two to ten times faster than can be explained by the condensation of sulfuric acid and its associated water and ammonia. Established methods were used to measure sulfuric acid vapor concentration and particle size distributions down to 3 nm. Ammonia concentrations were measured with high time resolution by chemical ionization mass spectrometry to explore ammonia’s role in particle production. Two new instruments were developed to enable measurements aimed at explaining the above observations. These include the thermal desorption chemical ionization mass spectrometer (TDCIMS) for measuring the composition of nanoparticles down to 7 nm and the nanometer tandem differential mobility analyzer (Nano TDMA) for measuring the volatility and hygroscopicity of 4–10 nm particles. Measurements by the latter instruments allowed the primary growth species to be identified, and therefore a direct comparison could be made between precursor concentration and growth rates. [2] ANARChE measurements were carried out at the Jefferson Street site located about 4 km northwest of downtown Atlanta [Solomon et al., 2003]. We chose this site because continuous measurements of size distributions from August 1998 through August 2000 showed that new particle formation often occurs there, especially in late summer; that the concentrations of new sub-10 nm particles produced can be extremely high; and that new particle formation is associated with elevated levels of SO2 [Woo et al., 2001; McMurry and Woo, 2002]. Thus this study gave us the opportunity to investigate new particle formation in a polluted environment where SO2 is likely a major precursor. Also, measurements of meteorological parameters and gas and particle concentrations that are carried out routinely at the Jefferson Street site as a part of the SEARCH and ARIES programs were made available to us. [3] Our results show that the collision-controlled theory for nucleation in a chemically reacting system [McMurry, 1983] (also referred to as ‘‘kinetic’’ or ‘‘barrierless’’ nucleation) provides an upper limit to the number of particles produced. However, the number of particles observed is typically less than the number predicted by this theory, by factors that range from about ten to one thousand. We found some evidence for an association between ammonia and the number of particles produced, but ammonia apparently did not account for much of the observed variability. In addition, three separate observations (direct measurements of composition, measurements of nanoparticle hygroscopicity and volatility, and comparison of measured and predicted growth rates) support the conclusion that sub-40 nm particles that were recently formed by nucleation consisted primarily of sulfates neutralized to some extent by ammonia. However, growth rates of particles larger than 40 nm were about a factor of five greater than could be explained by the condensation of sulfuric acid. We did not measure the composition of nucleated particles as they grew past 40 nm during this study, but such measurements are clearly needed.

Hygroscopicity and volatility of 4–10 nm particles during summertime atmospheric nucleation events in urban Atlanta

Continuous measurements of hygroscopicity and volatility of atmospheric aerosol particles of 4–10 nm diameter were conducted with a nanometer tandem differential mobility analyzer (Nano TDMA) during the Aerosol Nucleation and Real‐time Characterization Experiment (ANARChE), which took place in Atlanta in July and August 2002. In the Nano TDMA measurements, particles were exposed to either a high humidity (∼90% RH) or an elevated temperature (∼100°C) downstream of the first differential mobility analyzer (DMA) and were then resized by the second DMA to determine the change in size due to water uptake or evaporation. There were several days when nucleation occurred and high concentrations of sub‐20 nm particles were observed, and during those events, particles of 4–10 nm diameter were very hygroscopic and nonvolatile. These observations, together with parallel Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) measurements of sub‐20 nm particle composition, suggest that the particles were mostly composed of ammoniated sulfates. This finding strongly supports the hypothesis that the nucleation and subsequent growth of nanoparticles were driven by reactions involving sulfuric acid and ammonia during this study.

Chemical composition of atmospheric nanoparticles during nucleation events in Atlanta

We report the first direct, in situ measurements of the chemical composition of size‐segregated atmospheric nanoparticles in the 6–15 nm diameter range. These measurements were made of ambient aerosol directly following nucleation events in Atlanta, Georgia, during the 2002 Aerosol Nucleation and Real‐time Characterization Experiment (ANARChE). The recently developed Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) was used to make these measurements and featured a new inlet that delivers mass of charged and size‐segregated nanoparticles at sufficiently high rates to enable analysis at a typical time resolution of 10 min. Measurements in both the positive and negative ion spectra revealed that particles formed recently from nucleation events have enhanced concentrations of ammonium and sulfate and that to within the uncertainty of our measurements, ammonium sulfate could account for all of the sampled nanoparticle mass. No other compounds were detected in the particles during these events. Concurrent measurements of particle hygroscopicity and volatility, made using a Nanometer Tandem Differential Mobility Analyzer, support the conclusion that ammonium and sulfate are primary components of these newly formed particles.

Atmospheric Measurements of Sub-20 nm Diameter Particle Chemical Composition by Thermal Desorption Chemical Ionization Mass Spectrometry

We report the first online measurements of the chemical composition of atmospheric aerosol in the 6–20 nm diameter range. These measurements were performed using the recently developed Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS), and were made possible by recent sensitivity enhancements resulting from (a) the development of a unipolar charger optimized for high aerosol flow rates, and (b) an improved flow system in the TDCIMS sample inlet. Measurements of atmospheric aerosol in Boulder, CO revealed large concentration variations in most detected compounds. The most dominant observed compounds in the negative ion TDCIMS spectra were nitrate and sulfate, while in the positive ion spectra ammonium dominated all other observed compounds. Comparison with laboratory data suggests that particles are composed primarily of ammonium sulfate during times of relatively low ambient aerosol concentration.