Daniel D. Riemer

HO x budgets in a deciduous forest: Results from the PROPHET summer 1998 campaign

Results from a tightly constrained photochemical point model for OH and HO2 are compared to OH and HO2 data collected during the Program for Research on Oxidants: Photochemistry, Emissions, and Transport (PROPHET) summer 1998 intensive campaign held in northern Michigan. The PROPHET campaign was located in a deciduous forest marked by relatively low NOx levels and high isoprene emissions. Detailed HOx budgets are presented. The model is generally unable to match the measured OH, with the observations 2.7 times greater than the model on average. The model HO2, however, is in good agreement with the measured HO2. Even with an additional postulated OH source from the ozonolysis of unmeasured terpenes, the measured OH is 1.5 times greater than the model; the model HO2 with this added source is 15% to 30% higher than the measured HO2. Moreover, the HO2/OH ratios as modeled are 2.5 to 4 times higher than the measured ratios, indicating that the cycling between OH and HO2 is poorly described by the model. We discuss possible reasons for the discrepancies.

Nighttime observations of anomalously high levels of hydroxyl radicals above a deciduous forest canopy

Diurnal measurements of hydroxyl and hydroperoxy radicals (OH and HO2) made during the Program for Research on Oxidants: Photochemistry, Emissions, and Transport (PROPHET) summer intensive of 1998 indicate that these key components of gas phase atmospheric oxidation are sustained in significant amounts throughout the night in this northern forested region. Typical overnight levels of OH observed were 0.04 parts per trillion (pptv) (1.1 × 106 molecules/cm3), while HO2 concentrations ranged from 1 to 4 pptv. Results of diagnostic testing performed before, after, and during the deployment suggest little possibility of interferences in the measurements. Collocated measurements of the reactive biogenic hydrocarbon isoprene corroborate the observed levels of OH by exhibiting significant decays overnight above the forest canopy. The observed isoprene lifetimes ranged from 1.5 to 12 hours in the dark, and they correlate well to those expected from chemical oxidation by the measured OH abundances. Possible dark reactions that could generate such elevated levels of OH include the ozonolysis of extremely reactive biogenic terpenoids. However, in steady state models, which include this hypothetical production mechanism, HO2 radicals are generated in greater quantities than were measured. Nonetheless, if the measurements are representative of the nocturnal boundary layer in midlatitude temperate forests, this observed nocturnal phenomenon might considerably alter our understanding of the diurnal pattern of atmospheric oxidation in such pristine, low-NOx environments.

The Deep Convective Clouds and Chemistry (DC3) Field Campaign

AbstractThe Deep Convective Clouds and Chemistry (DC3) field experiment produced an exceptional dataset on thunderstorms, including their dynamical, physical, and electrical structures and their impact on the chemical composition of the troposphere. The field experiment gathered detailed information on the chemical composition of the inflow and outflow regions of midlatitude thunderstorms in northeast Colorado, west Texas to central Oklahoma, and northern Alabama. A unique aspect of the DC3 strategy was to locate and sample the convective outflow a day after active convection in order to measure the chemical transformations within the upper-tropospheric convective plume. These data are being analyzed to investigate transport and dynamics of the storms, scavenging of soluble trace gases and aerosols, production of nitrogen oxides by lightning, relationships between lightning flash rates and storm parameters, chemistry in the upper troposphere that is affected by the convection, and related source character...

Measurement of vertical distribution of isoprene in surface seawater, its chemical fate, and its emission from several phytoplankton monocultures

Abstract Concurrent measurements of isoprene (2-methyl-1,3-butadiene) in seawater together with atmospheric concentrations in the Gulf Stream off the Florida coast were made. Florida Straits surface water concentrations of isoprene varied between 9.8 and 50.8 pmol 1 −1 . Surface water isoprene concentrations showed a positive correlation with measured chlorophyll fluorescence, consistent with the biogenic origin of this non-methane hydrocarbon. Depth profiles showed a maximum in isoprene concentration similar to that of biological productivity as indicated by chlorophyll fluorescence. Daytime atmospheric mixing ratios of isoprene were never above 11 parts-per-trillion (pptv) and eight of eleven samples taken were below the ~ 5 pptv detection limit. Using an estimated value of the Henrys law constant ( K H ~ 3.1) a supersaturation of surface seawater of 2 to 3 orders of magnitude is estimated. Laboratory grown monocultures of several common phytoplankton species showed production of isoprene. Processes controlling the isoprene concentration in the photic zone of the ocean and the marine boundary layer are discussed. A calculation using a simple time dependent photochemical box model confirmed that isoprene is rapidly consumed by its reaction with the OH radical in the marine atmosphere.

Observations of nonmethane hydrocarbons and oxygenated volatile organic compounds at a rural site in the southeastern United States

Measurements of an extensive range of nonmethane hydrocarbons (NMHCs) including alkanes, alkenes, and aromatics, and oxygenated volatile organic compounds (OVOCs) including alcohols, ketones, and aldehydes were conducted for several weeks during the summer of 1995 as part of the Southern Oxidants Study (SOS) at a rural experimental site (Youth, Inc.) 32 km southeast of Nashville, Tennessee, in the southeastern United States. These measurements were conducted to (1) determine the absolute magnitude and variability of oxygenated compounds found in a contemporary rural region; (2) assess the importance of the measured ambient levels of OVOCs on a photochemical reactivity basis relative to the more commonly determined NMHCs; and (3) to evaluate our ability to accurately measure oxygenates by the current techniques employed under a field study scenario. Several other physical (temperature, insolation, etc.), meteorological (wind velocity, wind direction, atmospheric structure, and boundary layer height), and chemical (criterion pollutants, NOx, SO2, CO, O3, etc.) parameters were measured concurrently with the NMHC and OVOC measurements. During the study period, OVOCs were consistently the dominant compounds present, and methanol and acetone had the highest mixing ratios. Although OVOCs made up the majority of the volatile organic compound component on a mass basis, a substantial sink for OH was isoprene and its immediate oxidation products, methacrolein and methyl vinyl ketone. In combination with CO and formaldehyde, these compounds comprised about 85% of the observed OH reactivity at the site. Acetaldehyde and methanol were responsible for an additional 10%, with the NMHCs and remaining OVOCs making up the final 5% of the measured OH reactivity at the site. These observed patterns reinforce recent studies which find OVOCs to be an important component of the rural troposphere.

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.

Direct evidence for chlorine-enhanced urban ozone formation in Houston, Texas

Urban air pollution is characterized by high ozone levels, formed when volatile organic compounds (VOCs) are oxidized in the presence of nitrogen oxides (NOx). VOC and NOx emissions controls have traditionally been implemented to reduce urban ozone formation, however, a separate chemical species implicated in ozone formation in Houston, TX and possibly other urban areas is the chlorine radical (Cl ). Cl enhances tropospheric VOC oxidation, but is not included in models used to develop air quality attainment plans. We present results of a three-fold approach to elucidate the importance of Cl in urban ozone formation: (1) the first direct evidence of chlorine chemistry in the urban troposphere, (2) enhanced ozone formation (>75 parts per 10 9 (ppb/h) observed when small amounts of chlorine (Cl2) are injected into captive ambient air, and (3) enhanced ozone formation (B16 ppb) predicted by regional photochemical models employing Cl chemistry. These results suggest that reducing chlorine emissions should be considered in urban ozone management strategies. r 2003 Elsevier Science Ltd. All rights reserved.

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.

Nighttime isoprene chemistry at an urban-impacted forest site

Isoprene and its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were measured over a 4 week period in July of 1995 at a rural/forest site near Nashville, Tennessee, as part of the 1995 Southern Oxidants Study (SOS) field intensive. High nighttime isoprene mixing ratios, measured during a 3 day period of stagnant high pressure, are reported. These high nighttime isoprene events are interpreted as a result of continuing emission of isoprene into a developing shallow nocturnal boundary layer in the early evening, followed by advective transport under the inversion to the measurement site. During some evenings, there is very rapid decay of isoprene just after sunset. These events occurred when the product [O 3 ].[NO 2 ] was relatively large, consistent with loss via reaction with NO 3 . A chemical box model showed that isoprene decays were consistent with the NO 3 mechanism but only for relatively high NO x conditions. This study indicates that nighttime processing of isoprene can be important for forested regions susceptible to high-NO x transport events. We also find that this nighttime NO 3 chemistry can lead to conditions where, at least at the surface, a significant fraction of the NO y is in the form of organic nitrates that are products of the NO 3 -isoprene reaction and that the NO 3 -isoprene reaction can be the dominant NO 3 sink.

Observations of isoprene chemistry and its role in ozone production at a semirural site during the 1995 Southern Oxidants Study

Isoprene and its oxidation products, methyl vinyl ketone (MVK) and methacrolein (MACR), were measured in a semirural environment that was occasionally heavily impacted by urban emissions. At this site, isoprene was the most important hydrocarbon in terms of kOH·[hydrocarbon], but the aldehydes HCHO and CH3CHO also appear to be very important. The local isoprene photochemistry appears to be occasionally enhanced in NOx-rich urban plumes that are adverted to the site over intermediate forested land. When O3 was being rapidly produced in urban plumes adverted to this forested site, isoprene was found to contribute ≈28% of the total ozone production. We observe that many of the peaks in isoprene oxidation products at this surface site arise from downward mixing of more photochemically processed air aloft, as the nocturnal inversion breaks up in the morning. We estimate that, in the daytime, typically 1–2% of the NOy at this NOx-rich site is composed of isoprene nitrates.