Aerosol chemical composition in cloud events by high resolution time-of-flight aerosol mass spectrometry.

This study presents results of direct observations of aerosol chemical composition in clouds. A high-resolution time-of-flight aerosol mass spectrometer was used to make measurements of cloud interstitial particles (INT) and mixed cloud interstitial and droplet residual particles (TOT). The differences between these two are the cloud droplet residuals (RES). Positive matrix factorization analysis of high-resolution mass spectral data sets and theoretical calculations were performed to yield distributions of chemical composition of the INT and RES particles. We observed that less oxidized hydrocarbon-like organic aerosols (HOA) were mainly distributed into the INT particles, whereas more oxidized low-volatile oxygenated OA (LVOOA) mainly in the RES particles. Nitrates existed as organic nitrate and in chemical form of NH(4)NO(3). Organic nitrates accounted for 45% of total nitrates in the INT particles, in clear contrast to 26% in the RES particles. Meanwhile, sulfates coexist in forms of acidic NH(4)HSO(4) and neutralized (NH(4))(2)SO(4). Acidic sulfate made up 64.8% of total sulfates in the INT particles, much higher than 10.7% in the RES particles. The results indicate a possible joint effect of activation ability of aerosol particles, cloud processing, and particle size effects on cloud formation.

Automated single-ion peak fitting as an efficient approach for analyzing complex chromatographic data.

Chromatography provides important detail on the composition of environmental samples and their chemical processing. However, the complexity of these samples and their tendency to contain many structurally and chemically similar compounds frequently results in convoluted or poorly resolved data. Data reduction from raw chromatograms of complex environmental data into integrated peak areas consequently often requires substantial operator interaction. This difficulty has led to a bottleneck in analysis that increases analysis time, decreases data quality, and will worsen as advances in field-based instrumentation multiply the quantity and informational density of data produced. In this work, we develop and validate an automated approach to fitting chromatographic data within a target retention time window with a combination of multiple idealized peaks (Gaussian peaks either with or without an exponential decay component). We compare this single-ion peak fitting approach to drawn baseline integration methods of more than 70,000 peaks collected by field-based chromatographs spanning across a wide range of volatilities and functionalities. Accuracy of peak fitting under real-world conditions is found to be within 10%. The quantitative parameters describing the fit (e.g. coefficients, fit residuals, etc.) are found to provide valuable information to increase the efficiency of quality control and provide constraints to accurately integrate peaks that are significantly convoluted with neighboring peaks. Implementation of the peak fitting method is shown to yield accurate integration of peaks otherwise too poorly resolved to separate into individual compounds and improved quantitative metrics to determine the fidelity of the data reduction process, while substantially decreasing the time spent by operators on data reduction.

O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry.

A recently developed method to rapidly quantify the elemental composition of bulk organic aerosols (OA) using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) is improved and applied to ambient measurements. Atomic oxygen-to-carbon (O/C) ratios characterize the oxidation state of OA, and O/C from ambient urban OA ranges from 0.2 to 0.8 with a diurnal cycle that decreases with primary emissions and increases because of photochemical processing and secondary OA (SOA) production. Regional O/C approaches approximately 0.9. The hydrogen-to-carbon (H/C, 1.4--1.9) urban diurnal profile increases with primary OA (POA) as does the nitrogen-to-carbon (N/C, approximately 0.02). Ambient organic-mass-to-organic-carbon ratios (OM/OC) are directly quantified and correlate well with O/C (R2 = 0.997) for ambient OA because of low N/C. Ambient O/C and OM/OC have values consistent with those recently reported from other techniques. Positive matrix factorization applied to ambient OA identifies factors with distinct O/C and OM/OC trends. The highest O/C and OM/OC (1.0 and 2.5, respectively) are observed for aged ambient oxygenated OA, significantly exceeding values for traditional chamber SOA,while laboratory-produced primary biomass burning OA (BBOA) is similar to ambient BBOA, O/C of 0.3--0.4. Hydrocarbon-like OA (HOA), a surrogate for urban combustion POA, has the lowest O/C (0.06--0.10), similar to vehicle exhaust. An approximation for predicting O/C from unit mass resolution data is also presented.