K. A. Schilling

Size distribution dynamics reveal particle-phase chemistry in organic aerosol formation

Organic aerosols are ubiquitous in the atmosphere and play a central role in climate, air quality, and public health. The aerosol size distribution is key in determining its optical properties and cloud condensation nucleus activity. The dominant portion of organic aerosol is formed through gas-phase oxidation of volatile organic compounds, so-called secondary organic aerosols (SOAs). Typical experimental measurements of SOA formation include total SOA mass and atomic oxygen-to-carbon ratio. These measurements, alone, are generally insufficient to reveal the extent to which condensed-phase reactions occur in conjunction with the multigeneration gas-phase photooxidation. Combining laboratory chamber experiments and kinetic gas-particle modeling for the dodecane SOA system, here we show that the presence of particle-phase chemistry is reflected in the evolution of the SOA size distribution as well as its mass concentration. Particle-phase reactions are predicted to occur mainly at the particle surface, and the reaction products contribute more than half of the SOA mass. Chamber photooxidation with a midexperiment aldehyde injection confirms that heterogeneous reaction of aldehydes with organic hydroperoxides forming peroxyhemiacetals can lead to a large increase in SOA mass. Although experiments need to be conducted with other SOA precursor hydrocarbons, current results demonstrate coupling between particle-phase chemistry and size distribution dynamics in the formation of SOAs, thereby opening up an avenue for analysis of the SOA formation process.

Isoprene NO3 Oxidation Products from the RO2 + HO2 Pathway

We describe the products of the reaction of the hydroperoxy radical (HO(2)) with the alkylperoxy radical formed following addition of the nitrate radical (NO(3)) and O(2) to isoprene. NO(3) adds preferentially to the C(1) position of isoprene (>6 times more favorably than addition to C(4)), followed by the addition of O(2) to produce a suite of nitrooxy alkylperoxy radicals (RO(2)). At an RO(2) lifetime of ∼30 s, δ-nitrooxy and β-nitrooxy alkylperoxy radicals are present in similar amounts. Gas-phase product yields from the RO(2) + HO(2) pathway are identified as 0.75-0.78 isoprene nitrooxy hydroperoxide (INP), 0.22 methyl vinyl ketone (MVK) + formaldehyde (CH(2)O) + hydroxyl radical (OH) + nitrogen dioxide (NO(2)), and 0-0.03 methacrolein (MACR) + CH(2)O + OH + NO(2). We further examined the photochemistry of INP and identified propanone nitrate (PROPNN) and isoprene nitrooxy hydroxyepoxide (INHE) as the main products. INHE undergoes similar heterogeneous chemistry as isoprene dihydroxy epoxide (IEPOX), likely contributing to atmospheric secondary organic aerosol formation.

The effects of α-pinene versus toluene-derived secondary organic aerosol exposure on the expression of markers associated with vascular disease

Abstract To investigate the toxicological effects of biogenic- versus anthropogenic-source secondary organic aerosol (SOA) on the cardiovascular system, the Secondary Particulate Health Effects Research program irradiation chamber was used to expose atherosclerotic apolipoprotein E null (Apo E−/−) mice to SOA from the oxidation of either α-pinene or toluene for 7 days. SOA atmospheres were produced to yield 250–300 μg/m3 of particulate matter and ratios of 10:1:1 α-pinene:nitrogen oxide (NOx):ammonia (NH3); 10:1:1:1 α-pinene:NOx:NH3:sulfur dioxide (SO2) or 10:1:1 toluene:NOx:NH3; and 10:1:1:1 toluene:NOx:NH3:SO2. Resulting effects on the cardiovascular system were assessed by measurement of vascular lipid peroxidation (thiobarbituric acid reactive substance (TBARS)), as well as quantification of heme-oxygenase (HO)-1, endothelin (ET)-1, and matrix metalloproteinase (MMP)-9 mRNA expression for comparison to previous program exposure results. Consistent with similar previous studies, vascular TBARS were not increased significantly with any acute SOA exposure. However, vascular HO-1, MMP-9, and ET-1 observed in Apo E−/− mice exposed to α-pinene + NOx + NH3 + SO2 increased statistically, while α-pinene + NOx + NH3 exposure to either toluene + NOx + NH3 or toluene +NOx + NH3 + SO2 resulted in a decreased expression of these vascular factors. Such findings suggest that the specific chemistry created by the presence or absence of acidic components may be important in SOA-mediated toxicity in the cardiovascular system and/or progression of cardiovascular disease.

A chemically relevant artificial fingerprint material for the cross-comparison of mass spectrometry techniques

Abstract The development of a chemically relevant artificial fingerprint material as well as a preliminary method for artificial fingerprint deposition for mass spectrometric analysis and chemical imaging is presented. The material is an emulsified combination of artificial eccrine and sebaceous components designed to mimic the chemical profile of a latent fingerprint. In order to deposit this material in a manner that resembles a latent fingerprint, an artificial fingerprint stamp, created using 3-D printing, was used. Development of this material was spurred by the inability to cross-compare mass spectrometric techniques using real fingerprint deposits because of their inherent heterogeneity. To determine how well this material mimicked the chemical composition of actual fingerprint deposits, ambient ionization mass spectrometry and secondary ion mass spectrometry techniques were used to compare the signatures of the artificial and real fingerprint deposits. Chemical imaging comparisons of the artificial fingerprints across different imaging platforms are also presented as well as a comparison using fingerprint development agents. The use of a material such as this may provide a way to compare the capabilities of different techniques in analyzing a sample as complex as a fingerprint as well as providing a method to create fingerprints with controlled amounts of exogenous material for research and technique validation purposes.

Easily fabricated ion source for characterizing mixtures of organic compounds by direct analysis in real time mass spectrometry

The increasing use of atmospheric pressure mass spectrometry has led to the development of many ambient ionization sources, for which sampling versatility and low cost are desired features. One such recent ambient ionization method is direct analysis in real time mass spectrometry (DART-MS), which has proven to be well suited to the analysis of native samples of both simple and complex natures. We describe a home-built DART source (EZ-DART) with versatile sampling capabilities, low power requirements, and low assembly cost which can be easily interfaced to mass spectrometers equipped with an atmospheric pressure inlet. The operating temperature range (22–250 °C) enables the acquisition of both temperature programmed desorption-based DART mass spectra and the collection of multistep collision-induced dissociation (CID) mass spectra. We present here the validation of the EZ-DART source and a demonstration of its performance in a number of relevant applications. Additionally, we introduce the new DART application of reagent assisted desorption ionization (RADI) for the targeting of specific chemical functionality in complex organic mixtures through a host–guest chemical system.