Chemical imaging analysis of internally mixed sea salt/organic particles collected on board the Department of Energy (DOE) G-1 aircraft during the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) was performed using electron microscopy and X-ray spectro-microscopy techniques. Substantial chloride depletion in aged sea salt particles was observed, which could not be explained by the known atmospheric reactivity of sea salt with inorganic nitric and sulfuric acids. We present field evidence that chloride components in sea salt particles may effectively react with organic acids releasing HCl gas to the atmosphere, leaving behind particles depleted in chloride and enriched in the corresponding organic salts. While formation of the organic salts products is not thermodynamically favored for bulk aqueous chemistry, these reactions in aerosol are driven by high volatility and irreversible evaporation of the HCl product from drying particles. These field observations were corroborated in a set of laboratory experiments where NaCl particles mixed with organic acids were found to be depleted in chloride. Combined together, the results indicate substantial chemical reactivity of sea salt particles with secondary organics that has been largely overlooked in the atmospheric aerosol chemistry. Atmospheric aging, and especially hydration-dehydration cycles of mixed sea salt/organic particles may resultmore » in formation of organic salts that will modify acidity, hygroscopic and optical properties of aged particles.« less

https://agupubs.onlinelibrary.wiley.com/doi/epdf/10.1029/2012JD017743

Tropospheric chemistry of internally mixed sea salt and organic particles: Surprising reactivity of NaCl with weak organic acids

. The Amazon Basin plays key roles in the carbon and water cycles, climate change, atmospheric chemistry, and biodiversity. It has already been changed significantly by human activities, and more pervasive change is expected to occur in the coming decades. It is therefore essential to establish long-term measurement sites that provide a baseline record of present-day climatic, biogeochemical, and atmospheric conditions and that will be operated over coming decades to monitor change in the Amazon region, as human perturbations increase in the future. The Amazon Tall Tower Observatory (ATTO) has been set up in a pristine rain forest region in the central Amazon Basin, about 150 km northeast of the city of Manaus. Two 80 m towers have been operated at the site since 2012, and a 325 m tower is nearing completion in mid-2015. An ecological survey including a biodiversity assessment has been conducted in the forest region surrounding the site. Measurements of micrometeorological and atmospheric chemical variables were initiated in 2012, and their range has continued to broaden over the last few years. The meteorological and micrometeorological measurements include temperature and wind profiles, precipitation, water and energy fluxes, turbulence components, soil temperature profiles and soil heat fluxes, radiation fluxes, and visibility. A tree has been instrumented to measure stem profiles of temperature, light intensity, and water content in cryptogamic covers. The trace gas measurements comprise continuous monitoring of carbon dioxide, carbon monoxide, methane, and ozone at five to eight different heights, complemented by a variety of additional species measured during intensive campaigns (e.g., VOC, NO, NO2, and OH reactivity). Aerosol optical, microphysical, and chemical measurements are being made above the canopy as well as in the canopy space. They include aerosol light scattering and absorption, fluorescence, number and volume size distributions, chemical composition, cloud condensation nuclei (CCN) concentrations, and hygroscopicity. In this paper, we discuss the scientific context of the ATTO observatory and present an overview of results from ecological, meteorological, and chemical pilot studies at the ATTO site.

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The Amazon Tall Tower Observatory (ATTO): overview of pilot measurements on ecosystem ecology, meteorology, trace gases, and aerosols

This study presents, for the first time, field evidence of complete, irreversible processing of solid calcium carbonate (calcite)-containing particles and quantitative formation of liquid calcium nitrate particles apparently as a result of heterogeneous reaction of calcium carbonate-containing mineral dust particles with gaseous nitric acid. Formation of nitrates from individual calcite and sea salt particles was followed as a function of time in aerosol samples collected at Shoresh, Israel. Morphology and compositional changes of individual particles were observed using conventional scanning electron microscopy with energy dispersive analysis of X-rays (SEM/EDX) and computer controlled SEM/EDX. Environmental scanning electron microscopy (ESEM) was utilized to determine and demonstrate the hygroscopic behavior of calcium nitrate particles found in some of the samples. Calcium nitrate particles are exceptionally hygroscopic and deliquesce even at very low relative humidity (RH) of 9–11% which is lower than typical atmospheric environments. Transformation of non-hygroscopic dry mineral dust particles into hygroscopic wet aerosol may have substantial impacts on light scattering properties, the ability to modify clouds and heterogeneous chemistry.

Direct observation of completely processed calcium carbonate dust particles.

Analysis of Individual Environmental Particles Using Modern Methods of Electron Microscopy and X-Ray Microanalysis

A large field experiment of the Saharan Mineral Dust Experiment (SAMUM) was performed in Praia, Cape Verde, in January and February 2008. The aerosol at Praia is a superposition of mineral dust, sea-salt, sulphates and soot. Particles smaller than 500 nm are mainly mineral dust, mineral dust–sulphate mixtures, sulphates and soot–sulphate mixtures. Particles larger then 2.5 μm consist of mineral dust, sea-salt and few mineral dust–sulphate mixtures. A transition range exists in between. The major internal mixtures are mineral dust–sulphate and soot–sulphate. Mineral dust–sea-salt mixtures occur occasionally, mineral dust–soot mixtures were not observed. The aspect ratio was 1.3–1.4 for dry particles smaller than 500 nm and 1.6–1.7 for larger ones. Parameterizations are given for dry and humid state. Although the real part of the refractive index showed low variation (1.55–1.58 at 532 nm), a multi-modal imaginary part was detected as function of particle size, reflecting the complex composition. Soot mainly influences the absorption for wavelengths longer than the haematite absorption edge, whereas for shorter wavelengths dust is dominating. The refractive index of the aerosol depends on the source region of the mineral dust and on the presence/absence of a marine component. DOI: 10.1111/j.1600-0889.2011.00550.x

Electron microscopy of particles collected at Praia, Cape Verde, during the Saharan Mineral Dust Experiment: particle chemistry, shape, mixing state and complex refractive index

A versatile Monte Carlo program for quantitative particle analysis in electron probe X-ray microanalysis is presented. The program includes routines for simulating electron-solid interactions in microparticles lying on a flat surface and calculating the generated X-ray signal. Simulation of the whole X-ray spectrum as well as φ(z) curves is possible. The most important facility of the program is the reverse Monte Carlo quantification of the chemical composition of microparticles, including low-Z elements, such as C, N, O, and F. This quantification method is based on the combination of a single scattering Monte Carlo simulation and a robust successive approximation. An iteration procedure is employed; in each iteration step, the Monte Carlo simulation program calculates characteristic X-ray intensities, and a new set of concentration values for chemical elements in the particle is determined. When the simulated X-ray intensities converge to the measured ones, the input values of elemental concentrations u...

A Monte Carlo program for quantitative electron-induced X-ray analysis of individual particles.

A recently developed electron probe X-ray microanalysis (EPMA), called low-Z EPMA, employing an ultrathin window energy-dispersive X-ray detector, was applied to characterize aerosol particles collected at two sampling sites, namely, Kosan and 1100 Hill of Cheju Island, Korea, on a summer day in 1999. Since low-Z EPMA can provide quantitative information on the chemical composition of aerosol particles, the collected aerosol particles were classified and analyzed based on their chemical species. Many different particle types were identified, such as marine-originated, carbonaceous, soil-derived, and anthropogenic particles. Marine-originated particles, such as NaNO3- and Na2SO4-containing particles, are very frequently encountered in the two samples. In this study, it was directly proven that the observed nitrate particles were from sea salts. In addition, two types of nitrate particles from sea salts were observed, with and without Mg. The sodium nitrate particles without Mg were believed to be collected...

Single-particle analysis of aerosols at Cheju Island, Korea, using low-Z electron probe X-ray microanalysis: a direct proof of nitrate formation from sea salts.

In our previous studies, it has been demonstrated that both the excitation interactions between electrons and the atoms of the matrix and the matrix and geometric effects of electron-induced X-ray signals can be described by Monte Carlo simulation for low-Z elements, such as carbon, nitrogen, and oxygen, in individual atmospheric microparticles. In addition, by the application of a quantification method, which employs Monte Carlo simulation combined with successive approximations, at least semiquantitative specification of the chemical compositions could be done. This has enlarged the scope of electron probe X-ray microanalysis (EPMA) for the single particle analysis of atmospheric environmental aerosol particles. In this work, we demonstrate that the heterogeneity of individual particles, even of micrometer size, can be characterized by the application of EPMA. X-ray photons obtained with different primary electron beam energies carry information on the chemical compositions for different regions in the particles. Artificially generated heterogeneous CaCO 3 -CaSO 4 individual particles were measured at different accelerating voltages, and it was found that the Monte Carlo calculation is a powerful technique to extract the information on the heterogeneity of the particles that is contained in the measured X-ray data. Our approach can even estimate the thickness of the surface CaSO 4 species by the application of the Monte Carlo calculation. A preliminary result for carbon-coated glass particles is also presented. The complexity involved in the analysis of real world particles is briefly mentioned with a result for heterogeneous SiO 2 particle.

and Anna Worobiec

Papers

A Monte Carlo program for quantitative electron-induced X-ray analysis of individual particles.

Single-particle analysis of aerosols at Cheju Island, Korea, using low-Z electron probe X-ray microanalysis: a direct proof of nitrate formation from sea salts.

Heterogeneity assessment in individual CaCO3-CaSO4 particles using ultrathin window electron probe X-ray microanalysis.