Joseph P. Pinto

Photochemistry of the atmosphere of Titan - Comparison between model and observations

The photochemistry of simple molecules containing carbon, hydrogen, nitrogen, and oxygen atoms in the atmosphere of Titan has been investigated using updated chemical schemes and our own estimates of a number of key rate coefficients. Proper exospheric boundary conditions, vertical transport, and condensation processes at the tropopause have been incorporated into the model. It is argued that he composition, climatology, and evolution of Titans atmosphere are controlled by five major processes: (a) photolysis and photosensitized dissociation of CH4; (b) conversion of H to H2 and escape of hydrogen; (c) synthesis of higher hydrocarbons; (d) coupling between nitrogen and hydrocarbons; (e) coupling between oxygen and hydrocarbons. Starting with N2, CH4, and H2O, and invoking interactions with ultraviolet sunlight, energetic electrons, and cosmic rays, the model satisfactorily accounts for the concentrations of minor species observed by the Voyager IRIS and UVS instruments. Photochemistry is responsible for converting the simpler atmospheric species into more complex organic compounds, which are subsequently condensed at the tropopause and deposited on the surface. Titan might have lost 5.6 x 10(4), 1.8 x 10(3), and 4.0 g cm-2, or the equivalent of 8, 0.25, and 5 x 10(-4) bars of CH4, N2, and CO, respectively, over geologic time. Implications of abiotic organic synthesis on Titan for the origin of life on Earth are briefly discussed.

Atmospheric bromine and ozone perturbations in the lower stratosphere

The role of bromine compounds in the photochemistry of the natural and perturbed stratosphere has been reexamined using an expanded reaction scheme and the results of recent laboratory studies of several key reactions. The most important finding is that through the reaction BrO + CIO → Br + Cl + O2, there is a synergistic effect between bromine and chlorine which results in an efficient catalytic destruction of ozone in the lower stratosphere. One-dimensional photochemical model results indicate that BrO is the major bromine species throughout the stratosphere, followed by BrONO2, HBr, HOBr and Br. We show from the foregoing that bromine is more efficient than chlorine as a catalyst for destroying ozone, and discuss the implications for stratospheric ozone of possible future growth in the industrial and agricultural use of bromine. Bromine concentrations of 20 pptv (2 × 10^−11), as suggested by recent observations, can decrease the present-day integrated ozone column density by 2.4%, and can enhance ozone depletion from steady-state chlorofluoromethane release at 1973 rates by a factor of 1.1–1.2.

PM source apportionment and health effects: 1. Intercomparison of source apportionment results

During the past three decades, receptor models have been used to identify and apportion ambient concentrations to sources. A number of groups are employing these methods to provide input into air quality management planning. A workshop has explored the use of resolved source contributions in health effects models. Multiple groups have analyzed particulate composition data sets from Washington, DC and Phoenix, AZ. Similar source profiles were extracted from these data sets by the investigators using different factor analysis methods. There was good agreement among the major resolved source types. Crustal (soil), sulfate, oil, and salt were the sources that were most unambiguously identified (generally highest correlation across the sites). Traffic and vegetative burning showed considerable variability among the results with variability in the ability of the methods to partition the motor vehicle contributions between gasoline and diesel vehicles. However, if the total motor vehicle contributions are estimated, good correspondence was obtained among the results. The source impacts were especially similar across various analyses for the larger mass contributors (e.g., in Washington, secondary sulfate SE=7% and 11% for traffic; in Phoenix, secondary sulfate SE=17% and 7% for traffic). Especially important for time-series health effects assessment, the source-specific impacts were found to be highly correlated across analysis methods/researchers for the major components (e.g., mean analysis to analysis correlation, r>0.9 for traffic and secondary sulfates in Phoenix and for traffic and secondary nitrates in Washington. The sulfate mean r value is >0.75 in Washington.). Overall, although these intercomparisons suggest areas where further research is needed (e.g., better division of traffic emissions between diesel and gasoline vehicles), they provide support the contention that PM2.5 mass source apportionment results are consistent across users and methods, and that todays source apportionment methods are robust enough for application to PM2.5 health effects assessments.

Workgroup Report: Workshop on Source Apportionment of Particulate Matter Health Effects—Intercomparison of Results and Implications

Although the association between exposure to ambient fine particulate matter with aerodynamic diameter < 2.5 μm (PM2.5) and human mortality is well established, the most responsible particle types/sources are not yet certain. In May 2003, the U.S. Environmental Protection Agency’s Particulate Matter Centers Program sponsored the Workshop on the Source Apportionment of PM Health Effects. The goal was to evaluate the consistency of the various source apportionment methods in assessing source contributions to daily PM2.5 mass–mortality associations. Seven research institutions, using varying methods, participated in the estimation of source apportionments of PM2.5 mass samples collected in Washington, DC, and Phoenix, Arizona, USA. Apportionments were evaluated for their respective associations with mortality using Poisson regressions, allowing a comparative assessment of the extent to which variations in the apportionments contributed to variability in the source-specific mortality results. The various research groups generally identified the same major source types, each with similar elemental makeups. Intergroup correlation analyses indicated that soil-, sulfate-, residual oil-, and salt-associated mass were most unambiguously identified by various methods, whereas vegetative burning and traffic were less consistent. Aggregate source-specific mortality relative risk (RR) estimate confidence intervals overlapped each other, but the sulfate-related PM2.5 component was most consistently significant across analyses in these cities. Analyses indicated that source types were a significant predictor of RR, whereas apportionment group differences were not. Variations in the source apportionments added only some 15% to the mortality regression uncertainties. These results provide supportive evidence that existing PM2.5 source apportionment methods can be used to derive reliable insights into the source components that contribute to PM2.5 health effects.

Sulfur, ultraviolet radiation, and the early evolution of life

The present biosphere is shielded from harmful solar near ultraviolet (UV) radiation by atmospheric ozone. We suggest here that elemental sulfur vapor could have played a similar role in an anoxic, ozone-free, primitive atmosphere. Sulfur vapor would have been produced photochemically from volcanogenic SO2 and H2S. It is composed of ring molecules, primarily S8, that absorb strongly throughout the near UV, yet are expected to be relatively stable against photolysis and chemical attack. It is also insoluble in water and would thus have been immune to rainout or surface deposition over the oceans. The concentration of S8 in the primitive atmosphere would have been limited by its saturation vapor pressure, which is a strong function of temperature. Hence, it would have depended on the magnitude of the atmospheric greenhouse effect. Surface temperatures of 45 °C or higher, corresponding to carbon dioxide partial pressures exceeding 2 bars, are required to sustain an effective UV screen. Two additional requirements are that the ocean was saturated with sulfite and bisulfite, and that linear S8 chains must tend to reform rings faster than they are destroyed by photolysis. A warm, sulfur-rich, primitive atmosphere is consistent with inferences drawn from molecular phylogeny, which suggest that some of the earliest organisms were thermophilic bacteria that metabolized elemental sulfur.

Spatial Variability of PM2.5 in Urban Areas in the United States

Abstract Data from the U.S. Environmental Protection Agencys Aerometric Information Retrieval System (now known as the Air Quality System) database for 1999 and 2000 have been used to characterize the spatial variability of concentrations of particulate matter with aerodynamic diameter ≤2.5 μg (PM2.5) in 27 urban areas across the United States. Different measures were used to quantify the degree of uniformity of PM2.5 concentrations in the urban areas characterized. It was observed that PM2.5 concentrations varied to differing degrees in the urban areas examined. Analyses of several urban areas in the Southeast indicated high correlations between site pairs and spatial uniformity in concentration fields. Considerable spatial variation was found in other regions, especially in the West. Even within urban areas in which all site pairs were highly correlated, a variable degree of heterogeneity in PM2.5 concentrations was found. Thus, even though concentrations at pairs of sites were highly correlated, their concentrations were not necessarily the same. These findings indicate that the potential for exposure misclassification errors in time-series epidemiologic studies exists.

Isotopic exchange between carbon dioxide and ozone via O(1D) in the stratosphere

We propose a novel mechanism for isotopic exchange between CO2 and O3 via O(1D) + CO2 --> CO3* followed by CO3* --> CO2 + O(3P). A one-dimensional model calculation shows that this mechanism can account for the enrichment in 18O in the stratospheric CO2 observed by Gamo et al. [1989], using the heavy O3 profile observed by Mauersberger [1981]. The implications of this mechanism for other stratospheric species and as a source of isotopically heavy CO2 in the troposphere are briefly discussed.

Climatic Effects Due to Halogenated Compounds in the Earth’s Atmosphere

Using a one-dimensional radiative-convective model, we perform a sensitivity study of the effect of ozone depletion in the stratosphere on the surface temperature. There could be a cooling of the surface temperature by ~0.2 K due to chlorofluoromethane-induced ozone depletion at steady state (assuming 1973 release rates). This cooling reduces significantly the greenhouse effect due to the presence of chlorofluoromethanes. Carbon tetrafluoride has a strong ν_3 band at 7.8 μm, and the atmospheric greenhouse effect is shown to be 0.07 and 0.12 K (ppbv)^(−1) with and without taking into account overlap with CH_4 and N_2O bands. At concentration higher than 1 ppbv, absorption by the ν_3 band starts to saturate and the greenhouse effect becomes less efficient.

Czech air quality monitoring and receptor modeling study

An ongoing air quality monitoring program in the Czech Republic has provided nearly continuous data for the concentrations of aerosol and gas-phase pollutants since its inception in February 1992. In addition to PM-2.5 concentrations, the concentrations of sulfate, organic carbon, elemental carbon, trace elements (Al-Pb), and polynuclear aromatic hydrocarbons (PAHs) were also measured. Fine particulate matter (PM-2.5) was composed mainly of organic carbon and sulfate with smaller amounts of trace metals. Coarse particle mass concentrations were typically between 10 and 30% of PM-2.5 concentrations. The chemical composition of emissions from power plants, residential space heating, local factories, and motor vehicles was also characterized. The ambient monitoring and source characterization data were then used in receptor modeling calculations, the results of which indicate that residential space heating and power plant emissions accounted for most of fine particle mass concentrations observed during winter air pollution episodes. Motor vehicles, incinerators, and windblown dust contributed to the balance of the fine particle mass. Peak 24-h average TSP and SO 2 concentrations (1100 and 800 μg/m 3 , respectively) obtained at the main monitoring site at Teplice in northern Bohemia during a severe air pollution episode in 1993 were within a factor of 2 of smoke and SO 2 concentrations (1800 and 1600 μg/m 3 ) measured in London during the smog episode of December 5-9, 1952. That pollution episode was thought to have contributed to a substantial increase in mortality.

Source compositions of trace gases released during African savanna fires

Measurements of biomass burn-produced trace gases were made using low-altitude helicopter penetrations of smoke plumes above burning African savanna during the Southern African Fire-Atmosphere Research Initiative (SAFARI-92). Smoke from two large prescribed fires conducted in the Kruger National Park, South Africa, on September 18 and 24, 1992, was sampled at altitudes ranging from 20 to 100 m above ground level during flaming and smoldering phases of combustion. Carbon dioxide (CO2) normalized emission ratios (dX/dCO2 (vol/vol), where X denotes a trace gas) for carbon monoxide (CO), hydrogen (H2), methane (CH4), total nonmethane hydrocarbons (TNMHC), and nitrous oxide (N2O) were determined. The emission ratios were used in conjunction with fuel consumption estimates to calculate emission factors (grams of product per gram of fuel) for these gases. Emission factors for CO2, CO, CH4, and N2O of 1.61, 0.055, 0.003, and 1.6 × 10−4 g/g fuel, respectively, were determined. The fires advanced rapidly through the savanna (primarily grass) fuels with minimal amounts of smoldering combustion. The relatively low emission ratios determined for these fires indicated excellent combustion efficiency. About 93% of the carbon released into the atmosphere as a result of these fires was in the form of CO2.