New Methods for Measuring Spatial, Temporal and Chemical Distributions of Volatile Organic Compounds

Volatile organic compounds (VOCs) are those chemical species having sufficiently high vapor pressures to exist largely or entirely in the gaseous phase, whereas reactive organic carbon (ROC) encompasses all organics except methane. ROC can be emitted biogenically and anthropogenically, usually in a pure hydrocarbon form that is susceptible to reaction with common atmospheric oxidants such as hydroxyl and ozone in the initial steps to the formation of particulate matter, the criteria pollutant most strongly implicated in human mortality. The diversity of both the emitted VOCs and their possible atmospheric reactions yields countless different compounds existing in the atmosphere with a correspondingly wide range of volatility, solubility, reactivity, etc.. Moreover, the temporal and spatial variability of a given analyte is often large. Real-time chemical characterization of gaseous and particulate organic compounds can be achieved by instrumentation utilizing chromatographic and/or mass spectrometric techniques, but these methods are expensive, often logistically challenging, and require high levels of skills for both operation and data analysis. Conversely, filter-based measurements for organic particulates are inexpensive and straightforward, but do not give real-time data and analytes may be lost or transformed before analysis. There is a niche for robust, low-maintenance, moderate-cost instrumentation that offers chemical information on atmospheric carbon. Presented here are two projects that develop and validate instrumentation for measuring ROC. The first combines flame ionization detection (FID) with a CO2 detector to estimate the O/C ratios of sampled gases and particulates. O/C ratios are a particularly valuable piece of chemical information as higher ratios give lower volatility and higher solubility, meaning increased propensity to partition into the condensed phase. The second project utilizes portable VOC samplers with sorbent tubes that trap and protect analytes for detailed analysis. The samplers' portability and programmable microcontrollers offers the investigator great flexibility, both spatially and temporally. A third project analyzed the chemical composition of commercially available fragrance mixtures and modeled their emissions' impact on oxidant reactivity. It was observed that terpenes, despite their low mole fractions in the mixtures, represent the vast majority of emitted reactivity and are quantitatively evolved from the mixtures in a matter of hours.