V. Young

Atmospheric chemistry and distribution of formaldehyde and several multioxygenated carbonyl compounds during the 1995 Nashville/Middle Tennessee Ozone Study

Airborne measurements of formaldehyde (FA), glycolaldehyde (GA), glyoxal (GL), methylglyoxal (MG), and pyruvic acid (PD) were made on board instrumented aircraft platforms, the Department of Energy G1 and National Oceanic and Atmospheric Administration P3 (FA only), during the 1995 Nashville/Middle Tennessee Ozone Study. FA data determined on these two aircraft during three intercomparison flights agreed to within ∼10%. The mean and median (in parentheses) concentrations observed within the boundary layer ( 0.8) observed between FA and two other isoprene products, GA and MG. Further, the magnitudes of the nonzero FA intercept exhibited in these correlation plots are found to qualitatively agree with the fraction of precursors that did not concomitantly produce GA and MG. Inspection of specific flights showed direct evidence of the dominance of isoprene as a precursor for FA, appreciable contribution of FA to CO, and negligible decay of FA overnight. Because of the dominant role isoprene plays as a precursor of FA, FA could be used as a proxy of isoprene for assessing the applicability of various versions of biogenic emission inventory.

Regional ozone from biogenic hydrocarbons deduced from airborne measurements of PAN, PPN, and MPAN

NOx-catalyzed production of ozone over large regions of North America and Europe is a serious air quality problem that often involves biogenic hydrocarbons, mainly isoprene. Peroxy-methacrylic nitric anhydride (MPAN, CH2C(CH3)C(O)OONO2) is formed uniquely from isoprene-NOx photochemistry hence is an indicator of recent ozone production from isoprene. Presented here are the first airborne measurements of MPAN along with PAN (peroxyacetic nitric anhydride, CH3C(O)OONO2), PPN (peroxypropionic nitric anhydride, CH3CH2C(O)OONO2) and ozone measurements. Relationships between these species are used to estimate the contributions of anthropogenic and biogenic hydrocarbons (BHC) to regional tropospheric ozone production, providing direct evidence of ozone production from BHC-NOx photochemistry.

Measurements of PAN, PPN, and MPAN made during the 1994 and 1995 Nashville Intensives of the Southern Oxidant Study: Implications for regional ozone production from biogenic hydrocarbons

Isoprene and a variety of other reactive hydrocarbons are released in large quantities by vegetation in forested regions and are thought to participate in the NOx-catalyzed production of ozone, a serious air quality problem in North America and Europe [National Research Council, 1991]. The determination of the fraction of O3 formed from anthropogenic NOx and biogenic hydrocarbons (BHC) is a crucial step in the formulation of effective control strategies. Peroxymethacrylic nitric anhydride (MPAN, CH2C(CH3)C(O)OONO2) is formed almost entirely from the atmospheric oxidation of isoprene in the presence of NOx and is an excellent indicator of recent ozone production from isoprene and therefore biogenic hydrocarbons. Measurements are presented here of MPAN, peroxyacetic nitric anhydride (PAN, CH3C(O)OONO2), peroxypropionic nitric anhydride (PPN, CH3CH2C(O)OONO2) and ozone from separate data sets acquired during the 1994 and 1995 Nashville intensive studies of the Southern Oxidant Study. It was found that PAN, a general product of HC-NOx photochemistry, could be well represented as a simple linear combination of contributions from BHC and anthropogenic hydrocarbon (AHC) chemistries as indicated by MPAN and PPN, respectively. The PAN:MPAN ratios found to be characteristic of BHC-dominated chemistry ranged from 6 to 10. The PAN:PPN ratios found to be characteristic of AHC-dominated chemistry ranged from 5.8 to 7.4. These BHC and AHC attributions were used to estimate the contributions of anthropogenic and biogenic hydrocarbons to regional tropospheric ozone production, and substantial BHC-O3 (50–60 ppbv) was estimated in cases where high NOx from power plants was present in areas of high BHC emission. This estimation method provides direct evidence of significant photochemical ozone production from the oxidation of biogenic hydrocarbons in the presence of NOx.

Internal consistency tests for evaluation of measurements of anthropogenic hydrocarbons in the troposphere

Measurements of tropospheric nonmethane hydrocarbons (NMHCs) made in continental North America should exhibit a common pattern determined by photochemical removal and dilution acting upon the typical North American urban emissions. We analyze 11 data sets collected in the United States in the context of this hypothesis, in most cases by analyzing the geometric mean and standard deviations of ratios of selected NMHCs. In the analysis we attribute deviations from the common pattern to plausible systematic and random experimental errors. In some cases the errors have been independently verified and the specific causes identified. Thus this common pattern provides a check for internal consistency in NMHC data sets. Specific tests are presented which should provide useful diagnostics for all data sets of anthropogenic NMHC measurements collected in the United States. Similar tests, based upon the perhaps different emission patterns of other regions, presumably could be developed. The specific tests include (1) a lower limit for ethane concentrations, (2) specific NMHCs that should be detected if any are, (3) the relatively constant mean ratios of the longer-lived NMHCs with similar atmospheric lifetimes, (4) the constant relative patterns of families of NMHCs, and (5) limits on the ambient variability of the NMHC ratios. Many experimental problems are identified in the literature and the Southern Oxidant Study data sets. The most important conclusion of this paper is that a rigorous field intercomparison of simultaneous measurements of ambient NMHCs by different techniques and researchers is of crucial importance to the field of atmospheric chemistry. The tests presented here are suggestive of errors but are not definitive; only a field intercomparison can resolve the uncertainties.

Isoprene and its oxidation products, methacrolein and methylvinyl ketone, at an urban forested site during the 1999 Southern Oxidants Study

Isoprene (ISOP) and its oxidation products, methacrolein (MACR) and methyl vinyl ketone (MVK), were measured at an urban forested site in Nashville, Tennessee, as part of the 1999 Southern Oxidants Study (SOS). Hourly observations were performed at Cornelia Fort Airpark for a 4 week period between June 13 and July 14. At the midday photochemical peak (1200 local standard time, LST), average mixing ratios of isoprene, MACR, and MVK were 410 parts per trillion by volume (pptv), 240 pptv, and 430 pptv, respectively. Median isoprene, MACR, and MVK mixing ratios were 400 pptv, 200 pptv, and 360 pptv, respectively, at 1200 LST. An emissions inventory calculation for Davidson County, encompassing Nashville, suggests that MACR and MVK were produced predominately from isoprene oxidation rather than direct combustion emissions. The observations are compared with results from two chemical models: a simple sequential reaction scheme and a one-dimensional (1-D) numerical box model. The daytime ratios of MVK/ISOP and MACR/ISOP varied in a systematic manner and can be reproduced by the analytical solution of the sequential reaction scheme. Air masses with more photochemically aged isoprene were observed during SOS 1999 at Cornelia Fort (0.3-1.6 hours) compared to the SOS 1990 canopy study at Kinterbish (0.1-0.6 hours). This is consistent with the proximity of the tower inlets to the forest canopies during both campaigns. Isoprene had a chemical lifetime of 20 min at the average observed midday HO mixing ratio of 8 x 10 6 molecules/cm 3 . As a result, significant conversion of isoprene to its oxidation products was observed on the timescale of transport from the dense forest canopies surrounding Nashville. The systematic diurnal behavior in the MVK/MACR ratio can also be simulated with a 1-D photochemical box model. General agreement between the observations of MACR and MVK during SOS 1999 with the two chemical models suggests we have a comprehensive understanding of the first few stages of isoprene oxidation in this urban forested environment.

Direct measurements of urban OH reactivity during Nashville SOS in summer 1999

Emissions of volatile chemicals control the hydroxyl radical (OH), the atmospheres main cleansing agent, and thus the production of secondary pollutants. Accounting for all of these chemicals can be difficult, especially in environments with mixed urban and forest emissions. The first direct measurements of the atmospheric OH reactivity, the inverse of the OH lifetime, were made as part of the Southern Oxidant Study (SOS) at Cornelia Fort Airpark in Nashville, TN in summer 1999. Measured OH reactivity was typically 11 s(-1). Measured OH reactivity was 1.4 times larger than OH reactivity calculated from the sum of the products of measured chemical concentrations and their OH reaction rate coefficients. This difference is statistically significant at the 1sigma uncertainty level of both the measurements and the calculations but not the 2sigma uncertainty level. Measured OH reactivity was 1.3 times larger than the OH reactivity from a model that uses measured ambient concentrations of volatile organic compounds (VOCs), NO, NO2, SO2, and CO. However, it was within approximately 10% of the OH reactivity from a model that includes hydrocarbon measurements made in a Nashville tunnel and scaled to the ambient CO at Cornelia Fort Airpark. These comparisons indicate that 30% of the OH reactivity in Nashville may come from short-lived highly reactive VOCs that are not usually measured in field intensive studies or by US EPAs Photochemical Assessment Monitoring Stations.

A study of formaldehyde chemistry above a forest canopy

Gas-phase formaldehyde (HCHO) was measured at a mixed deciduous/coniferous forest site as a part of the PROPHET 1998 summer field intensive. For the measurement period of July 11 through August 20, 1998, formaldehyde mixing ratios ranged from 0.5 to 12 ppb at a height ∼10 m above the forest canopy, with the highest concentrations observed in southeasterly air masses. Concentrations varied on average from a mid-afternoon maximum influenced by photochemical production of 4.0 ppb, to a late night minimum of 2.2 ppb, probably resulting from dry depositional loss. An analysis of local HCHO sources revealed that isoprene was the most important of the measured formaldehyde precursors, contributing, on average, 82% of the calculated midday HCHO production rate. We calculate that the nighttime HCHO dry deposition velocity is 2.6 times that of ozone, or approximately 0.65 cm/s. In the daytime, photolysis, dry deposition, and reaction with hydroxyl radical (OH) are roughly equally important as loss processes. Explicit calculations of HCHO chemical behavior highlighted the probable importance of transport and surface deposition to understanding the diel behavior of formaldehyde.

Investigation of the nighttime decay of isoprene

A rapid nighttime decay of isoprene (2-methyl-1,3-butadiene) has been observed at several forest sites. Data from the Program for Research on Oxidants: PHotochemistry, Emissions, and Transport (PROPHET) have been carefully examined with respect to this phenomenon. Essentially every evening (at PROPHET), isoprene concentrations fall from several ppb to levels below 100 ppt, with an average lifetime of 2.7 hours. Since this decay rate exceeds that expected from established nighttime chemistry, other possible mechanisms are suggested and discussed. Reaction with ozone will not occur at a rate consistent with the observed decay. Calculations of nitrate radical concentrations reveal that this oxidant only becomes an important sink for isoprene after the majority of the isoprene decay has taken place. The isoprene flux data were not consistent with dry deposition playing a significant role in nighttime forest loss. On the basis of ambient measurements of OH radical concentrations at the PROPHET site, calculated isoprene decay rates were compared with observations. For some nights the observed decay can be fit strictly by OH consumption; however, the reported OH data overpredict the isoprene loss rate on most nights. We estimate that vertical mixing with isoprene-depleted air probably contributes to the fast isoprene decay observed; however, the measurements needed to support this suggestion have yet to be made.

Effects of wildland fire smoke on a tree-roosting bat: integrating a plume model, field measurements, and mammalian dose–response relationships

Faunal injury and mortality in wildland fires is a concern for wildlife and fire management although little work has been done on the mechanisms by which exposures cause their effects. In this paper, we use an integral plume model, field measurements, and models of carbon monoxide and heat effects to explore risk to tree-roosting bats during prescribed fires in mixed-oak forests of southeastern Ohio and eastern Kentucky. Tree-roosting bats are of interest primarily because of the need to mitigate risks for the endangered Indiana bat (Myotis sodalis), our focal species. Blood carboxyhemoglobin concentrations predicted from carbon monoxide data supplemented by model output only approached critical levels just above flames in the most intense fires. By contrast, an ear-heating model driven by plume model output suggested that in- jury to the bats thermally thin ears would occur up to heights similar to those of foliage necrosis, an effect for which pre- dictive relationships exist. Risks of heat injury increase with fireline intensity and decrease with both roost height and ambient wind. Although more information is needed on bat arousal from torpor and behavior during fires, strategies for re- ducing the risk of heat injury emerge from consideration of the underlying causal processes.

Mothers on the tenure track: what engineering and technology faculty still confront

Despite the many changes in policy and practice that colleges and universities in the United States have instituted to help women faculty achieve work life balance, challenges persist. This article discusses the difficulties still faced by female engineering and engineering technology faculty who are trying to balance the demands of a successful academic career and motherhood. The data, both qualitative and quantitative, are derived from a survey of tenure track female faculty who are members of the Women in Engineering Division of the American Society for Engineering Education (ASEE). Data indicate that, despite the widespread adoption of policies intended to create a more helpful and collegial environment, almost 40% of the respondents rated the quality of the institutional support they receive as fair, poor, or very poor. This research identifies policies that appear to have succeeded, and others that appear to have made little difference, suggesting structural and cultural changes that would address the continuing problems that motherhood creates for female engineering and technology faculty. Such changes could prove helpful to female faculty generally, regardless of their disciplines.