The 1999 Regional Haze Rule provides a context for this review of visibility, the science that describes it, and the use of that science in regulatory guidance The scientific basis for the 1999 regulation is adequate The deciview metric that tracks progress is an imperfect but objective measure of what people see near the prevailing visual range The definition of natural visibility conditions is adequate for current planning, but it will need to be refined as visibility improves Emissions from other countries will set achievable levels above those produced by natural sources Some natural events, notably dust storms and wildfires, are episodic and cannot be represented by annual average background values or emission estimates Sulfur dioxide (SO2) emission reductions correspond with lower sulfate (SO4 2−) concentrations and visibility im-provements in the regions where these have occurred Non-road emissions have been growing more rapidly than emissions from other sources, which have remained

Visibility: Science and Regulation

Understanding how comets work, i,e., what drives their activity, is crucial to using comets to study the early solar system. EPOXI flew past comet 103P/Hartley 2, one with an unusually small but very active nucleus. taking both images and spectra. Unlike large, relatively inactive nuclei, this nncleus is outgassing primarily due to CO2, which drags chnnks of ice out of the nnclens. It also shows significant differences in the relative abundance of volatiles from various parts of the nucleus.

/pdf/epoxi-at-comet-hartley-2-5006w6l0jb.pdf

EPOXI at Comet Hartley 2

The morphology of amorphous solid water grown by vapor deposition was found to depend strongly on the angular distribution of the water molecules incident from the gas phase. Systematic variation of the incident angle during deposition using a collimated beam of water led to the growth of nonporous to highly porous amorphous solid water. The physical and chemical properties of amorphous solid water are of interest because of its presence in astrophysical environments. The ability to control its properties in the laboratory may shed light on some of the outstanding conflicts related to this important material.

https://science.sciencemag.org/content/sci/283/5407/1505.full.pdf

Controlling the morphology of amorphous solid water

. The volatilities of different chemical species in ambient aerosols are important but remain poorly characterized. The coupling of a recently developed rapid temperature-stepping thermodenuder (TD, operated in the range 54–230°C) with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during field studies in two polluted megacities has enabled the first direct characterization of chemically-resolved urban particle volatility. Measurements in Riverside, CA and Mexico City are generally consistent and show ambient nitrate as having the highest volatility of any AMS standard aerosol species while sulfate showed the lowest volatility. Total organic aerosol (OA) showed volatility intermediate between nitrate and sulfate, with an evaporation rate of 0.6%·K−1 near ambient temperature, although OA dominates the residual species at the highest temperatures. Different types of OA were characterized with marker ions, diurnal cycles, and positive matrix factorization (PMF) and show significant differences in volatility. Reduced hydrocarbon-like OA (HOA, a surrogate for primary OA, POA), oxygenated OA (OOA, a surrogate for secondary OA, SOA), and biomass-burning OA (BBOA) separated with PMF were all determined to be semi-volatile. The most aged OOA-1 and its dominant ion, CO2+, consistently exhibited the lowest volatility, with HOA, BBOA, and associated ions for each among the highest. The similar or higher volatility of HOA/POA compared to OOA/SOA contradicts the current representations of OA volatility in most atmospheric models and has important implications for aerosol growth and lifetime. A new technique using the AMS background signal was demonstrated to quantify the fraction of species up to four orders-of-magnitude less volatile than those detectable in the MS mode, which for OA represent ~5% of the non-refractory (NR) OA signal. Our results strongly imply that all OA types should be considered semivolatile in models. The study in Riverside identified organosulfur species (e.g. CH3HSO3+ ion, likely from methanesulfonic acid), while both studies identified ions indicative of amines (e.g. C5H12N+) with very different volatility behaviors than inorganic-dominated ions. The oxygen-to-carbon ratio of OA in each ambient study was shown to increase both with TD temperature and from morning to afternoon, while the hydrogen-to-carbon ratio showed the opposite trend.

/pdf/chemically-resolved-aerosol-volatility-measurements-from-two-2px6rn90br.pdf

Chemically-resolved aerosol volatility measurements from two megacity field studies

The adsorption of N2 was used to investigate the porosity/morphology of thin films of amorphous solid water. Molecular beams were used to vapor deposit amorphous solid water films on a Pt(111) crystal at a variety of incident growth angles. The amount of N2 adsorbed by the amorphous solid water depends very sensitively on the growth angle and thermal history of the film. For normal and nearly normal incidence growth, the water films are relatively dense and smooth and adsorb only a small amount of N2. For larger growth angles, the films are porous and adsorb large quantities of N2 with apparent surface areas as high as ∼2700 m2/g. The physical and chemical properties of amorphous solid water are of interest because of its presence in astrophysical environments. The observations have important implications for laboratory studies which use vapor deposited amorphous solid water films as analogs for astrophysical icy bodies such as comets.

Control of amorphous solid water morphology using molecular beams. I. Experimental results

Development of a mechanism explaining the internal source of energy of comet outbursts. A mechanism is proposed which automatically provides a source of particulate matter which creates a huge surface area which contains a substantial percentage of amorphous ice, so that the phase transition of the amorphous ice to a cubic structure provides a release of energy which may be responsible for the outbursts observed in many comets. In addition, the volume into which the transition can propagate is estimated for a spherical comet with a radius of 5 km.

Energy source for comet outbursts

In recent years, scientific discussion has included the influence of thermodynamic conditions (e.g., temperature, relative humidity, and filter face velocity) on PM retention efficiency of filter-based samplers and monitors. Method-associated thermodynamic conditions can, in some instances, dramatically influence the presence of particle-bound water and other light-molecular-weight chemical components such as particulate nitrates and certain organic compounds. The measurement of fine particle mass presents a new challenge for all PM measurement methods, since a relatively greater fraction of the mass is semi-volatile. The tapered element oscillating microbalance (TEOM) continuous PM monitor is a U.S. Environmental Protection Agency (EPA) PM10 equivalent method (EQPM-1090079). Several hundred of these monitors are deployed throughout the United States. The TEOM monitor has the unique characteristic of providing direct PM mass measurement without the calibration uncertainty inherent in mass surrogate methods. In addition, it provides high-precision, near-real-time continuous data automatically. Much attention has been given to semi-volatile species retention of the TEOM method.

https://www.tandfonline.com/doi/pdf/10.1080/10473289.2000.10464180

Development of a sample equilibration system for the TEOM continuous PM monitor.

The oscillating element in a microbalance is provided with a filter on its oscillating end for the entrapment of matter whose mass is to be determined by passing the medium containing such matter therethrough. The oscillating element itself is hollow and the medium passes first through the filter and then through the oscillating element.

Microbalance and method for measuring the mass of matter suspended within a fluid medium

Particulate matter (PM) in ambient air is composed of many chemical species of varying vapor pressures. A direct mass measurement of PM mass on filters is the basis of regulatory PM reference methods. The loss of semi-volatile PM mass collected on filters and filter sampling artifacts can produce nonquantifiable biases in reference method measurements depending on the thermodynamic history of the filter; therefore, a reference method cannot be considered a scientific reference standard. A new technique is introduced which has the potential to overcome the difficulties inherent in PM mass measurement and holds the promise of the measurement of PM mass as it exists in ambient air at ambient temperature. While comprehensive laboratory and field studies of the instrument and its components are needed to fully characterize the system, preliminary data have been obtained to provide a basic proof of concept for the technique.

Development of a Reference Standard for Particulate Matter Mass in Ambient Air

Particulate concentration of diesel exhaust is measured by collecting the diesel particulate on a filter (18) while measuring the amount of exhaust passing through the filter (18). The filtered particulate is then heated in an oxygen rich environment (32) to oxidize carbon within the particulate to carbon dioxide. The amount of resulting carbon dioxide is measured in meter (38) to derive a corresponding measurement of the amount of filtered particulate. Particulate concentration is calculated by comparing the amount of exhaust passed through the filter. Filtered particulate can be heated incrementally to obtain a measurement of volatile components within the particulate prior to the oxidation of the non-volatile carbon component. The filter (18) employed to collect the particulate is of a high temperature resistant type making it reusable and can be either integral with or inserted into the oxidation chamber of the instrument. Oxidation of the particulate inherently concurrently cleans the filter for reuse.

Harvey Patashnick

Papers

Energy source for comet outbursts

Development of a sample equilibration system for the TEOM continuous PM monitor.

Microbalance and method for measuring the mass of matter suspended within a fluid medium

Development of a Reference Standard for Particulate Matter Mass in Ambient Air

Diesel particulate monitor