Isotopic characterization of aerosol organic carbon components over the eastern United States

Author Posting. © American Geophysical Union, 2012. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 117 (2012): D13303, doi:10.1029/2011JD017153.Carbon isotopic signatures (δ13C, Δ14C) of aerosol particulate matter total organic carbon (TOC) and operationally defined organic carbon (OC) components were measured in samples from two background sites in the eastern U.S. TOC and water-soluble OC (WSOC) δ13C values (−27 to −24‰) indicated predominantly terrestrial C3 plant and fossil derived sources. Total solvent extracts (TSE) and their aliphatic, aromatic, and polar OC components were depleted in δ13C (−30 to −26‰) relative to TOC and WSOC. Δ14C signatures of aerosol TOC and TSE (−476 to +25‰) suggest variable fossil contributions (~5–50%) to these components. Aliphatic OC while comprising a small portion of the TOC (<1%), was dominated by fossil-derived carbon (86 ± 3%), indicating its potential utility as a tracer for fossil aerosol OC inputs. In contrast, aromatic OC contributions (<1.5%) contained approximately equal portions contemporary (52 ± 8%) and fossil (48 ± 8%) OC. The quantitatively significant polar OC fraction (6–25% of TOC) had fossil contributions (30 ± 12%) similar to TOC (26 ± 7%) and TSE (28 ± 9%). Thus, much of both of the fossil and contemporary OC is deduced to be oxidized, polar material. Aerosol WSOC consistently showed low fossil content (<8%) relative to the TOC (5–50%) indicating that the majority of fossil OC in aerosol particulates is insoluble. Therefore, on the basis of solubility and polarity, aerosols are predicted to partition differently once deposited to watersheds, and these chemically distinct components are predicted to contribute in quantitatively and qualitatively different ways to watershed carbon biogeochemistry and cycling.ASW was partially supported by a Graduate Fellowship from the Hudson River Foundation during the course of this study. Additional funding for this work came from a NOSAMS student internship award, a fellowship award from Sun Trust Bank administered through the VIMS Foundation, a student research grant from VIMS, and the following NSF awards: DEB Ecosystems grant DEB-0234533, Chemical Oceanography grant OCE-0327423, and Integrated Carbon Cycle Research Program grant EAR-0403949 to JEB; and Chemical Oceanography grant OCE-0727575 to RMD and JEB.2013-01-0

Transportable high sensitivity small sample radiometric calorimeter

A new small-sample, high-sensitivity transportable radiometric calorimeter, which can be operated in different modes, contains an electrical calibration method, and can be used to develop secondary standards, will be described in this presentation. The data taken from preliminary tests will be presented to indicate the precision and accuracy of the instrument. The calorimeter and temperature-controlled bath, at present, require only a 30-in. by 20-in. tabletop area. The calorimeter is operated from a laptop computer system using unique measurement module capable of monitoring all necessary calorimeter signals. The calorimeter can be operated in the normal calorimeter equilibration mode, as a comparison instrument, using twin chambers and an external electrical calibration method. The sample chamber is 0.75 in (1.9 cm) in diameter by 2.5 in. (6.35 cm) long. This size will accommodate most {sup 238}Pu heat standards manufactured in the past. The power range runs from 0.001 W to <20 W. The high end is only limited by sample size

Study of the PM Gas-Phase Filter Artifact Using a Setup for Mixing Diesel-Like Soot and Hydrocarbons

The filter artifact is a significant source of error in gravimetric measurements of particulate matter (PM) exhaust. However, only a few studies on the subject exist. Results from these studies show a large discrepancy mainly because the experiments were performed using real diesel vehicle exhaust with varying exhaust composition. In this study, a setup for mixing diesel-like soot and hydrocarbon vapor was constructed for generating a stable exhaust aerosol with adjustable composition. The particle size distribution of the diesel-fueled soot generator (GMD [geometric mean diameter] adjustable between 27 and 164 nm) was found to represent “real” exhaust particulate emission. This setup was applied for studying the filter artifact on Teflon-coated glass fiber filters using pentadecane as the hydrocarbon vapor. Experiments were performed using particle and hydrocarbon concentrations of 130–700 μg/m3 and 10–12 ppm, respectively. It was found that the particle concentration of the aerosol affects the filter artifact. At lower particle concentrations, more hydrocarbon adsorption was detected. In the absence of particles, the adsorption was highest. Furthermore, filter soot load, corresponding to 0.13%–0.66% of the clean filter mass, was found to affect adsorption. Sooty filters adsorbed less vapor than clean filters. However, increasing the soot load resulted in more adsorption. Moreover, it was found that the backup filter serves as a reasonable estimate of the filter artifact only for low particle concentrations and filter soot loads. These results indicate that the filter soot load is an important parameter influencing the filter artifact, and therefore, it should be considered when performing gravimetric sampling. The setup was proven to be a unique tool for quantitative studies of the filter artifact