Measurement of Atmospheric Mercury: Current Limitations and Suggestions for Paths Forward.

Mercury (Hg) researchers have made progress in understanding atmospheric Hg, especially with respect to oxidized Hg (HgII) that can represent 2 to 20% of Hg in the atmosphere. Knowledge developed over the past ∼10 years has pointed to existing challenges with current methods for measuring atmospheric Hg concentrations and the chemical composition of HgII compounds. Because of these challenges, atmospheric Hg experts met to discuss limitations of current methods and paths to overcome them considering ongoing research. Major conclusions included that current methods to measure gaseous oxidized and particulate-bound Hg have limitations, and new methods need to be developed to make these measurements more accurate. Developing analytical methods for measurement of HgII chemistry is challenging. While the ultimate goal is the development of ultrasensitive methods for online detection of HgII directly from ambient air, in the meantime, new surfaces are needed on which HgII can be quantitatively collected and from which it can be reversibly desorbed to determine HgII chemistry. Discussion and identification of current limitations, described here, provide a basis for paths forward. Since the atmosphere is the means by which Hg is globally distributed, accurately calibrated measurements are critical to understanding the Hg biogeochemical cycle.

Ultrasonic study of water adsorbed in nanoporous glasses.

Thermodynamic properties of fluids confined in nanopores differ from those observed in the bulk. To investigate the effect of nanoconfinement on water compressibility, we perform water sorption experiments on two nanoporous glass samples while concomitantly measuring the speed of longitudinal and shear ultrasonic waves in these samples. These measurements yield the longitudinal and shear moduli of the water-laden nanoporous glass as a function of relative humidity that we utilize in the Gassmann theory to infer the bulk modulus of the confined water. This analysis shows that the bulk modulus (inverse of compressibility) of confined water is noticeably higher than that of the bulk water at the same temperature. Moreover, the modulus exhibits a linear dependence on the Laplace pressure. The results for water, which is a polar fluid, agree with previous experimental and numerical data reported for nonpolar fluids. This similarity suggests that irrespective of intermolecular forces, confined fluids are stiffer than bulk fluids. Accounting for fluid stiffening in nanopores may be important for accurate interpretation of wave propagation measurements in fluid-filled nanoporous media, including in petrophysics, catalysis, and other applications, such as in porous materials characterization.

Surface Tension of Organophosphorus Compounds: Sarin and its Surrogates.

While the production and stockpiling of organophosphorus chemical warfare agents (CWAs), such as sarin, was banned three decades ago, CWAs have remained a threat. New approaches for decontamination and destruction of CWAs require detailed knowledge of their various physicochemical properties. In particular, surface tension is needed to describe the formation and evolution of hazardous aerosols when CWA liquids are dispersed in the air. Due to the extreme toxicity of sarin, most experimental studies are carried out using its surrogates─organophosphorus compounds which, while having similar structures, are much less toxic, e.g., dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP). However, not only for sarin, but also for its surrogates, literature data on the surface tension are scarce. Here we present experimental measurements and computational predictions of the surface tension of DMMP and DIMP. Classical molecular dynamics simulations using the Transferable Potentials for Phase Equilibria (TraPPE) force field produced an excellent agreement with the experimental results in the temperature range from 3 to 60 °C, validating the predictive capability of TraPPE. Consequently, we applied the TraPPE force field to sarin. Our modeled values for the sarin surface tension cover the range of temperatures from 0 to 85 °C, and the four experimental data points from the literature measured between 20 and 35 °C agree perfectly with our predictions. The temperature-dependent surface tension values for sarin and its surrogates obtained in our study can be used in models predicting the formation and evolution of aerosols made of these chemicals. Furthermore, our results justify the use of the TraPPE force field to derive the thermodynamic properties of other organophosphorus compounds with structures similar to the ones studied here.

Vapor Condensation and Coating Evaporation Are Both Responsible for Soot Aggregate Restructuring.

Fresh soot is made of fractal aggregates, which often appear collapsed in atmospheric samples. A body of work has concluded that the collapse is caused by liquid shells when they form by vapor condensation around soot aggregates. However, some recent studies argue that soot remains fractal even when engulfed by the shells, collapsing only when the shells evaporate. To reconcile this disagreement, we investigated soot restructuring under conditions ranging from capillary condensation to full encapsulation, also including condensate evaporation. In these experiments, airborne fractal aggregates were exposed to vapors of wetting liquids, and particle size was measured before and after coating loss, allowing us to isolate the contribution from condensation toward restructuring. We show the existence of three distinct regions along the path connecting the initial fractal and final collapsed aggregates, where minor restructuring occurs already at zero vapor supersaturation due to capillary condensation. Increasing supersaturation increases the amount of condensate, producing a more notable aggregate shrinkage. At even higher supersaturations, the aggregates become encapsulated, and subsequent condensate evaporation leaves behind fully compacted aggregates. Hence, for wetting liquids, minor restructuring begins already during capillary condensation and significant restructuring occurs as the coating volume increases. However, at this time, we cannot precisely quantify the contribution of condensate evaporation to the full aggregate compaction.

Heterogeneous Chemistry of Mercuric Chloride on Inorganic Salt Surfaces.

Gaseous oxidized mercury (GOM) is a major chemical form responsible for deposition of atmospheric mercury, but its interaction with environmental surfaces is not well understood. To address this knowledge gap, we investigated the uptake of gaseous HgCl2, used as a GOM surrogate, by several inorganic salts representative of marine and urban aerosols. The process was studied in a fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer, where gaseous HgCl2 was quantitatively detected as HgCl2·NO3-. Uptake curves showed a common behavior, where upon exposure of the salt surface to HgCl2, the gas-phase concentration of the latter dropped rapidly and then recovered gradually. None of the salts produced a full recovery of HgCl2, indicating the presence of an irreversible chemical reaction in addition to reversible adsorption, and all salts showed reactive behavior consistent with the presence of surface sites of a high and a low reactivity. On the basis of the decrease in the uptake coefficient with increasing concentration of gaseous HgCl2, we conclude that the interaction follows the Langmuir-Hinshelwood mechanism. The reactivity of a deactivated salt surface after uptake could be partially restored by cycling through an elevated relative humidity at atmospheric pressure. The overall surface reactivity decreased in the series Na2SO4 > NaCl > (NH4)2SO4 > NH4NO3. The uptake on NH4NO3 was nearly fully reversible, with low values of the initial (0.4 × 10-2) and steady-state (3.3 × 10-4) uptake coefficients, whereas Na2SO4 was significantly more reactive (3.1 × 10-2 and 1.7 × 10-3). Depending on the aerosol loading, the lifetimes of gaseous HgCl2 on dry urban and marine particles (as pure (NH4)2SO4 and NaCl, respectively) were estimated to range from half an hour to about a day.

Single Parameter for Predicting the Morphology of Atmospheric Black Carbon.

Black carbon (BC) from fuel combustion is an effective light absorber that contributes significantly to direct climate forcing. The forcing is altered when BC combines with other substances, which modify its mixing state and morphology, making the evaluation of its atmospheric lifetime and climate impact a challenge. To elucidate the associated mechanisms, we exposed BC aerosol to supersaturated vapors of different chemicals to form thin coatings and measured the coating mass required to induce the restructuring of BC aggregates. We found that studied chemicals fall into two distinct groups based on a single dimensionless parameter, χ, which depends on the diameter of BC monomer spheres and the coating material properties, including vapor supersaturation, molar volume, and surface tension. We show that when χ is small (low-volatility chemicals), the highly supersaturated vapor condenses uniformly over aggregates, including convex monomers and concave junctions in between monomers, but when χ is large (intermediate-volatility chemicals), junctions become preferred. The aggregates undergo prompt restructuring when condensation in the junctions dominates over condensation on monomer spheres. For a given monomer diameter, the coating distribution is mostly controlled by vapor supersaturation. The χ factor can be incorporated straightforwardly into atmospheric models to improve simulations of BC aging.

Thermal Stability of Particle-Phase Monoethanolamine Salts.

The use of monoethanolamine (MEA, 2-hydroxyethanamine) for scrubbing of carbon dioxide from combustion flue gases may become the dominant technology for carbon capture in the near future. The widespread implementation of this technology will result in elevated emissions of MEA to the environment that may increase the loading and modify the properties of atmospheric aerosols. We have utilized experimental measurements together with aerosol microphysics calculations to derive thermodynamic properties of several MEA salts, potentially the dominant forms of MEA in atmospheric particles. The stability of the salts was found to depend strongly on the chemical nature of the acid counterpart. The saturation vapor pressures and vaporization enthalpies obtained in this study can be used to evaluate the role of MEA in the aerosol and haze formation, helping to assess impacts of the MEA-based carbon capture technology on air quality and climate change.

High sensitivity of diesel soot morphological and optical properties to combustion temperature in a shock tube.

Carbonaceous particles produced from combustion of fossil fuels have strong impacts on air quality and climate, yet quantitative relationships between particle characteristics and combustion conditions remain inadequately understood. We have used a shock tube to study the formation and properties of diesel combustion soot, including particle size distributions, effective density, elemental carbon (EC) mass fraction, mass-mobility scaling exponent, hygroscopicity, and light absorption and scattering. These properties are found to be strongly dependent on the combustion temperature and fuel equivalence ratio. Whereas combustion at higher temperatures (∼2000 K) yields fractal particles of a larger size and high EC content (90 wt %), at lower temperatures (∼1400 K) smaller particles of a higher organic content (up to 65 wt %) are produced. Single scattering albedo of soot particles depends largely on their organic content, increasing drastically from 0.3 to 0.8 when the particle EC mass fraction decreases from 0.9 to 0.3. The mass absorption cross-section of diesel soot increases with combustion temperature, being the highest for particles with a higher EC content. Our results reveal that combustion conditions, especially the temperature, may have significant impacts on the direct and indirect climate forcing of atmospheric soot aerosols.

Role of OH-initiated oxidation of isoprene in aging of combustion soot.

We have investigated the contribution of OH-initiated oxidation of isoprene to the atmospheric aging of combustion soot. The experiments were conducted in a fluoropolymer chamber on size-classified soot aerosols in the presence of isoprene, photolytically generated OH, and nitrogen oxides. The evolution in the mixing state of soot was monitored from simultaneous measurements of the particle size and mass, which were used to calculate the particle effective density, dynamic shape factor, mass fractal dimension, and coating thickness. When soot particles age, the increase in mass is accompanied by a decrease in particle mobility diameter and an increase in effective density. Coating material not only fills in void spaces, but also causes partial restructuring of fractal soot aggregates. For thinly coated aggregates, the single scattering albedo increases weakly because of the decreased light absorption and practically unchanged scattering. Upon humidification, coated particles absorb water, leading to an additional compaction. Aging transforms initially hydrophobic soot particles into efficient cloud condensation nuclei at a rate that increases in the presence of nitrogen oxides. Our results suggest that ubiquitous biogenic isoprene plays an important role in aging of anthropogenic soot, shortening its atmospheric lifetime and considerably altering its impacts on air quality and climate.

Soot aging from OH-initiated oxidation of toluene.

We have conducted laboratory experiments to investigate the impacts of secondary organic aerosol formation on soot properties from OH-initiated oxidation of toluene. Monodisperse soot particles are exposed to the oxidation products of the OH-toluene reaction in an environmental chamber, and variations in particle size, mass, organic mass faction, morphology, effective density, hygroscopicity, and optical properties are simultaneously determined by an integrated aerosol analytical system. The thickness of the organic coating, correlated to reaction time and initial reactant concentrations, is shown to largely govern the particle properties. With the development of organic coating, the soot core is changed from a highly fractal to compact form, evident from the measured effective density and dynamic shape factor. The organic coating increases the particle hygroscopicity, and further exposure of coated soot to elevated relative humidity results in a more spherical particle. The single scattering albedo and scattering and absorption cross sections are also enhanced with the organic coating. Our results suggest that the oxidation products of anthropogenic pollutants alter the composition and properties of soot particles and lead to increased particle density, hygroscopicity, and optical properties, considerably enhancing their impacts on air quality, climate forcing, and human health.

Heterogeneous reactions of epoxides in acidic media.

Epoxides have recently been identified as important intermediates in the gas phase oxidation of hydrocarbons, and their hydrolysis products have been observed in ambient aerosols. To evaluate the role of epoxides in the formation of secondary organic aerosols (SOA), the kinetics and mechanism of heterogeneous reactions of two model epoxides, isoprene oxide and α-pinene oxide, with sulfuric acid, ammonium bisulfate, and ammonium sulfate have been investigated using complementary experimental techniques. Kinetic experiments using a fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS) show a fast irreversible loss of the epoxides with the uptake coefficients (γ) of (1.7 ± 0.1) × 10(-2) and (4.6 ± 0.3) × 10(-2) for isoprene oxide and α-pinene oxide, respectively, for 90 wt % H(2)SO(4) and at room temperature. Experiments using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) reveal that diols are the major products in ammonium bisulfate and dilute H(2)SO(4) (<25 wt %) solutions for both epoxides. In concentrated H(2)SO(4) (>65 wt %), acetals are formed from isoprene oxide, whereas organosulfates are produced from α-pinene oxide. The reaction of the epoxides with ammonium sulfate is slow and no products are observed. The epoxide reactions using bulk samples and Nuclear Magnetic Resonance (NMR) spectroscopy reveal the presence of diols as the major products for isoprene oxide, accompanied by aldehyde formation. For α-pinene oxide, organosulfate formation is observed with a yield increasing with the acidity. Large yields of organosulfates in all NMR experiments with α-pinene oxide are attributed to the kinetic isotope effect (KIE) from the use of deuterated sulfuric acid and water. Our results suggest that acid-catalyzed hydrolysis of epoxides results in the formation of a wide range of products, and some of the products have low volatility and contribute to SOA growth under ambient conditions prevailing in the urban atmosphere.

Laboratory investigation on the role of organics in atmospheric nanoparticle growth.

The uptake of organic vapors by 4-20 nm H(2)SO(4) particles has been investigated to assess the role of organics in atmospheric nanoparticle growth. Sulfuric acid nanoparticles are generated from homogeneous binary nucleation of H(2)SO(4) and H(2)O vapors in a laminar flow chamber. The growth factor of H(2)SO(4) nanoparticles exposed to methyglyoxal, ethanol, 1-butanol, 1-heptanol, and 1-decanol is measured using a nanotandem differential mobility analyzer (nano-TDMA). The measured growth factor is close to unity when nanoparticles are exposed to methylglyoxal, ethanol, 1-butanol, 1-heptanol, and 1-decanol, indicating no apparent growth within the experimental uncertainty. In addition, spectroscopic evolution of functional groups in H(2)SO(4) particles of ∼40 nm diameter size, deposited on ZnSe crystal and subsequently exposed to glyoxal and 2,4-hexadienal, is studied using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FT-IR). The ATR-FT-IR measurements present the first spectroscopic signatures of high molecular weight aldol and oligomer products and show that polymerization and oligomerization reactions are partially reversible. The implications of the present results to nanoparticle growth in the atmosphere are discussed.

Heterogeneous reactions of alkylamines with ammonium sulfate and ammonium bisulfate.

The heterogeneous reactions between alkylamines and ammonium salts (ammonium sulfate and ammonium bisulfate) have been studied using a low-pressure fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS) at 293 ± 2 K. The uptake of three alkylamines, i.e., monomethylamine, dimethylamine, and trimethylamine, on ammonium sulfate shows a displacement reaction of ammonium by aminium, evidenced by the release of ammonia monitored using protonated acetone dimer as the reagent ion. For the three alkylamines, the initial uptake coefficients (γ(0)) range from 2.6 × 10(-2) to 3.4 × 10(-2) and the steady-state uptake coefficients (γ(ss)) range from 6.0 × 10(-3) to 2.3 × 10(-4) and decrease as the number of methyl groups on the alkylamine increases. A different reaction mechanism is observed for the uptake of the three alkylamines on ammonium bisulfate, which is featured by an acid-base reaction (neutralization) with irreversible alkylamine loss and no ammonia generation and occurs at a rate limited by diffusion of gaseous alkylamines to the ammonium bisulfate surface. Our results reveal that the reactions between alkylamines and ammonium salts contribute to particle growth and alter the composition of ammonium sulfate and bisulfate aerosols in the atmosphere.

Atmospheric pressure-ion drift chemical ionization mass spectrometry for detection of trace gas species.

This paper describes atmospheric pressure-ion drift chemical ionization mass spectrometry (AP-ID-CIMS) for monitoring of ambient trace species. Operation of the drift tube at atmospheric pressure allows a significantly longer ion-molecule reaction time and eliminates dilution of the ambient samples, while a well-defined electric field inside the drift tube provides the benefits to confine the flight path and velocity of reagent/product ions, to break down ion clusters, and to control the ion-molecule reaction time. The AP-ID-CIMS exhibits advantages over the conventional low pressure ID-CIMS and flow tube AP-CIMS, improving the detection sensitivity by 3 orders of magnitude and a factor of 3, respectively. We demonstrate that the AP-ID-CIMS allows quantification of sulfuric acid concentrations and is capable of detecting gaseous sulfuric acid with a detection limit of less than 10(5) molecules cm(-3), on the basis of 3sigma of the baseline noise and an integration time of 12 s. A field evaluation of the AP-ID-CIMS is presented for ambient H(2)SO(4) measurements.

Heterogeneous reaction of NO(2) on fresh and coated soot surfaces.

The heterogeneous reaction of nitrogen dioxide (NO(2)) on fresh and coated soot surfaces has been investigated to assess its role in night-time formation of nitrous acid (HONO) in the atmosphere. Soot surfaces were prepared by incomplete combustion of propane and kerosene fuels under lean and rich flame conditions and then processed by heating to evaporate semivolatile species or by coating with pyrene, sulfuric acid, or glutaric acid. Uptake kinetics and HONO yield measurements were performed in a low-pressure fast-flow reactor coupled to a chemical ionization mass spectrometer (CIMS), using atmospheric-level NO(2) concentrations. The uptake coefficient and the HONO yield upon interaction of NO(2) with nascent soot depend on the type of fuel and combustion regime and are the highest for samples prepared using fuel rich flame. Heating the nascent soot samples before exposure to NO(2) removes the organic material from the soot backbone, leading to a significant increase in NO(2) uptake coefficient and HONO yield. Continuous exposure to NO(2) reduces the reactivity of soot because of irreversible deactivation of the surface sites. Our results support the oxidation-reduction mechanism involving adsorptive and reactive centers on soot surface where NO(2) is converted to HONO and other products. Coating of the soot surface by different materials to simulate atmospheric aging has a strong impact on its reactivity toward NO(2) and the resulting HONO production. Coating of pyrene has little effect on either reaction rate or HONO yield. Sulfuric acid coating does not alter the uptake coefficient, but significantly reduces the amount of HONO formed. Coating of glutaric acid significantly increases NO(2) uptake coefficient and HONO yield. The results of our study indicate that the reactivity and HONO generating capacity of internally mixed soot aerosol will depend on the chemical composition of the coating material and hence will vary considerably in different polluted environments.

Heterogeneous chemistry of alkylamines with sulfuric acid: implications for atmospheric formation of alkylaminium sulfates.

The heterogeneous interaction of alkylamines with sulfuric acid has been investigated to assess the role of amines in aerosol growth through the formation of alkylaminium sulfates. The kinetic experiments were conducted in a low-pressure fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS). The measurements of heterogeneous uptake of methylamine, dimethylamine, and trimethylamine were performed in the acidity range of 59-82 wt % H(2)SO(4) and between 243 and 283 K. Irreversible reactive uptakes were observed for all three alkylamines, with comparable uptake coefficients (gamma) in the range of 2.0 x 10(-2) to 4.4 x 10(-2). The measured gamma value was slightly higher in more concentrated sulfuric acid and at lower temperatures. The results imply that the heterogeneous reactions of alkylamines contribute effectively to the growth of atmospheric acidic particles and, hence, secondary organic aerosol formation.

Formation of nanoparticles of blue haze enhanced by anthropogenic pollution.

The molecular processes leading to formation of nanoparticles of blue haze over forested areas are highly complex and not fully understood. We show that the interaction between biogenic organic acids and sulfuric acid enhances nucleation and initial growth of those nanoparticles. With one cis-pinonic acid and three to five sulfuric acid molecules in the critical nucleus, the hydrophobic organic acid part enhances the stability and growth on the hydrophilic sulfuric acid counterpart. Dimers or heterodimers of biogenic organic acids alone are unfavorable for new particle formation and growth because of their hydrophobicity. Condensation of low-volatility organic acids is hindered on nano-sized particles, whereas ammonia contributes negligibly to particle growth in the size range of 3-30 nm. The results suggest that initial growth from the critical nucleus to the detectable size of 2-3 nm most likely occurs by condensation of sulfuric acid and water, implying that anthropogenic sulfur emissions (mainly from power plants) strongly influence formation of terrestrial biogenic particles and exert larger direct and indirect climate forcing than previously recognized.

Effects of dicarboxylic acid coating on the optical properties of soot.

Soot is a major component of atmospheric aerosols responsible for absorption of visible solar radiation. Internal mixing of soot with transparent materials can enhance its ability to absorb and scatter light, resulting in a larger role of soot in climate forcing. We have investigated the absorption and scattering of visible light (532 nm) by soot aerosol internally mixed with succinic and glutaric acids using a combination of a cavity ring-down spectrometer and an integrating nephelometer. The measurements were performed for flame-generated soot aerosol with well-characterized morphology and mixing state in the particle size range from 155 to 320 nm. Thin coatings of dicarboxylic acids on soot aggregates (with a mass fraction of 0.1-0.4) enhance significantly light scattering (up to 3.8 fold) and slightly light absorption (less than 1.2 fold). Cycling the coated soot aerosol through high relative humidity (humidified to 90% RH and then dried to 5% RH) promotes further increase in light absorption and scattering for soot internally mixed with glutaric acid, but not for soot mixed with succinic acid. The larger effect of glutaric acid on light absorption and scattering is caused by the irreversible restructuring of soot aggregates induced by the coating material. Our results indicate that the enhancement in the optical properties of soot by transparent coatings is strongly related to the ability of the coating materials to change the morphology of soot aggregates.

Effects of coating of dicarboxylic acids on the mass-mobility relationship of soot particles.

Atandem differential mobility analyzer (TDMA) and a differential mobility analyzer-aerosol particle mass analyzer (DMA-APM) have been employed to study morphology and hygroscopicity of soot aerosol internally mixed with dicarboxylic acids. The effective densities, fractal dimensions, and dynamic shape factors of soot particles before and after coating with succinic and glutaric acids are determined. Coating of soot with succinic acid results in a significant increase in the particle mobility diameter, mass, and effective density, but these properties recover to their initial values once succinic acid is removed by heating, suggesting that no restructuring of the soot core occurs. This conclusion is also supported from the observation of similar fractal dimensions and dynamic shape factors for fresh and coated/heated soot aggregates. Also, no change is observed when succinic acid-coated aggregates are cycled through elevated relative humidity (5% to 90% to 5% RH) below the succinic acid deliquescence point. When soot is coated with glutaric acid, the particle mass increases, but the mobility diameter shrinks by 10-40%. Cycling the soot aerosol coated with glutaric acid through elevated relative humidity leads to an additional mass increase, indicating that condensed water remains within the coating even at low RH. The fractal dimension of soot particles increases after coating and remains high when glutaric acid is removed by heating. The dynamic shape factor of glutaric acid-coated and heated soot is significantly lower than that of fresh soot, suggesting a significant restructuring of the soot agglomerates by glutaric acid. The results imply that internal mixing of soot aerosol during atmospheric aging leads to changes in hygroscopicity, morphology, and effective density, which likely modify their effects on direct and indirect climate forcing and deposition in the human respiratory system.