On-Line Analysis of Organic Compounds in Diesel Exhaust Using Proton-Transfer-Reaction Mass Spectrometry

In this study, diesel exhaust (DE) was measured in real time using a proton-transfer-reaction mass spectrometer (PTR-MS) to determine the effect of an after-treatment catalyst on gas phase volatile organic compounds (VOCs). DE after-treatment catalysts are being designed to reduce the pollutants in exhaust, which contains both particulate matter and gas phase constituents. The PTR-MS can make in-situ real time measurements of hydrocarbons in the air, from concentrations in the parts per million by volume (ppmV) down to the low part per trillion by volume (pptV) range. Spectrum scans were performed at varied engine loads from mass range m/z (mass to charge ratio) = 20 to 200. This showed the relative abundance of gas phase VOCs produced as the engine ran between idle mode and 80% of its maximum load. The mass spectrum was complex and appeared to be composed of aromatic species ionized by PTR (M+1) through the anticipated proton transfer reactions as well as unexpected alkane fragments, evidenced by a strong 14n+1 ion pattern showing intense peaks at m/z = 43, 57, and 71. A number of protonated M+1 masses could be identified. These compounds displayed M+2 peaks consistent with known 13C isotopic abundance. As the engine load increased, the concentrations of over 90% of the species decreased. An attached smoke meter showed that soot concentrations increased over the same conditions. In addition, the decrease in the concentration of compounds with a larger molecular weight (m/z>100) was greater than the rate that the smaller compounds experienced. This appears to be due to the affinity of VOCs, larger masses in particular, to adhere to soot particles. Further PTR-MS measurements of VOCs on soot confirmed this by producing a mass spectrum comprised of masses predominantly over 100 amu. On-line analysis of diesel exhaust by PTR-MS is a practical tool for quantifying selected organic species in diesel exhaust and should prove useful for developing better diesel exhaust after-treatment system

In-canopy gas-phase chemistry during CABINEX 2009: Sensitivity of a 1-D canopy model to vertical mixing and isoprene chemistry

Vegetation emits large quantities of biogenic volatile organic compounds (BVOC). At remote sites, these compounds are the dominant precursors to ozone and secondary organic aerosol (SOA) production, yet current field studies show that atmospheric models have difficulty in capturing the observed HOx cycle and concentrations of BVOC oxidation products. In this manuscript, we simulate BVOC chemistry within a forest canopy using a one-dimensional canopy-chemistry model (Canopy Atmospheric CHemistry Emission model; CACHE) for a mixed deciduous forest in northern Michigan during the CABINEX 2009 campaign. We find that the base-case model, using fully-parameterized mixing and the simplified biogenic chemistry of the Regional Atmospheric Chemistry Model (RACM), underestimates daytime in-canopy vertical mixing by 50–70% and by an order of magnitude at night, leading to discrepancies in the diurnal evolution of HOx, BVOC, and BVOC oxidation products. Implementing observed micrometeorological data from above and within the canopy substantially improves the diurnal cycle of modeled BVOC, particularly at the end of the day, and also improves the observation-model agreement for some BVOC oxidation products and OH reactivity. We compare the RACM mechanism to a version that includes the Mainz isoprene mechanism (RACM-MIM) to test the model sensitivity to enhanced isoprene degradation. RACM-MIM simulates higher concentrations of both primary BVOC (isoprene and monoterpenes) and oxidation products (HCHO, MACR+MVK) compared with RACM simulations. Additionally, the revised mechanism alters the OH concentrations and increases HO2. These changes generally improve agreement with HOx observations yet overestimate BVOC oxidation products, indicating that this isoprene mechanism does not improve the representation of local chemistry at the site. Overall, the revised mechanism yields smaller changes in BVOC and BVOC oxidation product concentrations and gradients than improving the parameterization of vertical mixing with observations, suggesting that uncertainties in vertical mixing parameterizations are an important component in understanding observed BVOC chemistry

Measurements of C2-C7 hydrocarbons during the polar sunrise experiment 1994: Further evidence for halogen chemistry in the troposphere

Air samples for nonmethane hydrocarbon (NMHC) analysis were collected at two ground‐based sites: Alert, Northwest Territories (82.5°N, 62.3°W) and Narwhal ice camp, an ice floe 140 km northwest of Alert, from Julian days 90 to 117, 1994, and on a 2‐day aerial survey conducted on Julian days 89 and 90, 1994 over the Arctic archipelago. Several ozone depletion events and concurrent decreases in hydrocarbon concentrations relative to their background levels were observed at Alert and Narwhal ice camp. At Narwhal, a long period (≥7 days) of ozone depletion was observed during which a clear decay of alkane concentration occurred. A kinetic analysis led to a calculated Cl atom concentration of 4.5 × 103 cm−3 during this period. Several low‐ozone periods concurrent with NMHC concentration decreases were observed over a widespread region of the Arctic region (82°–85°N, and 51°–65°W). Hydrocarbon measurements during the aerial survey indicated that the low concentrations of these species occurred only in the boundary layer. In all ozone depletion periods, concentration changes of alkanes and toluene were consistent with Cl atom reactions. The changes in ethyne concentration from its background level were in excess of those expected from Cl atom kinetics alone and are attributed to additional Br atom reactions. A box modeling exercise suggested that the Cl and particularly Br atom concentrations required to explain the hydrocarbon behavior are also sufficient to destroy ozone

Chemically-resolved aerosol eddy covariance flux measurements in urban Mexico City during MILAGRO 2006

As part of the MILAGRO 2006 field campaign, the exchange of atmospheric aerosols with the urban landscape was measured from a tall tower erected in a heavily populated neighborhood of Mexico City. Urban submicron aerosol fluxes were measured using an eddy covariance method with a quadrupole aerosol mass spectrometer during a two week period in March, 2006. Nitrate and ammonium aerosol concentrations were elevated at this location near the city center compared to measurements at other urban sites. Significant downward fluxes of nitrate aerosol, averaging −0.2 μg m−2 s−1, were measured during daytime. The urban surface was not a significant source of sulfate aerosols. The measurements also showed that primary organic aerosol fluxes, approximated by hydrocarbon-like organic aerosols (HOA), displayed diurnal patterns similar to CO2 fluxes and anthropogenic urban activities. Overall, 47% of submicron organic aerosol emissions were HOA, 35% were oxygenated (OOA) and 18% were associated with biomass burning (BBOA). Organic aerosol fluxes were bi-directional, but on average HOA fluxes were 0.1 μg m−2 s−1, OOA fluxes were −0.03 μg m−2 s−1, and BBOA fluxes were −0.03 μg m−2 s−1. After accounting for size differences (PM1 vs PM2.5) and using an estimate of the black carbon component, comparison of the flux measurements with the 2006 gridded emissions inventory of Mexico City, showed that the daily-averaged total PM emission rates were essentially identical for the emission inventory and the flux measurements. However, the emission inventory included dust and metal particulate contributions, which were not included in the flux measurements. As a result, it appears that the inventory underestimates overall PM emissions for this location