Ian C. Faloona

Dynamics and chemistry of marine stratocumulus - DYCOMS II

The second Dynamics and Chemistry of Marine Stratocumulus (DYCOMS-II) field study is described. The field program consisted of nine flights in marine stratocumulus west-southwest of San Diego, California. The objective of the program was to better understand the physics a n d dynamics of marine stratocumulus. Toward this end special flight strategies, including predominantly nocturnal flights, were employed to optimize estimates of entrainment velocities at cloud-top, large-scale divergence within the boundary layer, drizzle processes in the cloud, cloud microstructure, and aerosol–cloud interactions. Cloud conditions during DYCOMS-II were excellent with almost every flight having uniformly overcast clouds topping a well-mixed boundary layer. Although the emphasis of the manuscript is on the goals and methodologies of DYCOMS-II, some preliminary findings are also presented—the most significant being that the cloud layers appear to entrain less and drizzle more than previous theoretical work led investigat...

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.

Photochemistry of HO x in the upper troposphere at northern midlatitudes

The factors controlling the concentrations of HOx radicals (= OH + peroxy) in the upper troposphere (8–12 km) are examined using concurrent aircraft observations of OH, HO2, H2O2, CH3OOH, and CH2O made during the Subsonic Assessment Ozone and Nitrogen Oxide Experiment (SONEX) at northern midlatitudes in the fall. These observations, complemented by concurrent measurements of O3, H2O, NO, peroxyacetyl nitrate (PAN), HNO3, CH4, CO, acetone, hydrocarbons, actinic fluxes, and aerosols, allow a highly constrained mass balance analysis of HOx and of the larger chemical family HOy (= HOx + 2 H2O2 + 2 CH3OOH + HNO2 + HNO4). Observations of OH and HO2 are successfully simulated to within 40% by a diel steady state model constrained with observed H2O2 and CH3OOH. The model captures 85% of the observed HOx variance, which is driven mainly by the concentrations of NOx (= NO + NO2) and by the strength of the HOx primary sources. Exceptions to the good agreement between modeled and observed HOx are at sunrise and sunset, where the model is too low by factors of 2–5, and inside cirrus clouds, where the model is too high by factors of 1.2–2. Heterogeneous conversion of NO2 to HONO on aerosols (γNO2 = 10−3) during the night followed by photolysis of HONO could explain part of the discrepancy at sunrise. Heterogeneous loss of HO2 on ice crystals (γice_HO2 = 0.025) could explain the discrepancy in cirrus. Primary sources of HOx from O(1D)+H2O and acetone photolysis were of comparable magnitude during SONEX. The dominant sinks of HOy were OH+HO2 (NOx 50 pptv). Observed H2O2 concentrations are reproduced by model calculations to within 50% if one allows in the model for heterogeneous conversion of HO2 to H2O2 on aerosols (γHO2 = 0.2). Observed CH3OOH concentrations are underestimated by a factor of 2 on average. Observed CH2O concentrations were usually below the 50 pptv detection limit, consistent with model results; however, frequent occurrences of high values in the observations (up to 350 pptv) are not captured by the model. These high values are correlated with high CH3OH and with cirrus clouds. Heterogeneous oxidation of CH3OH to CH2O on aerosols or ice crystals might provide an explanation (γice_CH3OH ∼ 0.01 would be needed).

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.

Airborne in-situ OH and HO2 observations in the cloud-free troposphere and lower stratosphere during SUCCESS

The hydroxyl (OH) and hydroperoxyl (HO2) radicals were measured for the first time throughout the troposphere and in the lower stratosphere with a new instrument aboard the NASA DC-8 aircraft during the 1996 SUCCESS mission. Typically midday OH was 0.1-0.5 pptv and HO2 was 3-15 pptv. Comparisons with a steady-state model yield the following conclusions. First, even in the lower stratosphere OH was sensitive to the albedo of low clouds and distant high clouds. Second, although sometimes in agreement with models, observed OH and HO2 were more than 4 times larger at other times. Evidence suggests that for the California upper troposphere on 10 May this discrepancy was due to unmeasured HOx sources from Asia. Third, observed HO2/OH had the expected inverse dependence with NO, but was inexplicably higher than modeled HO2/OH by an average of 30%. Finally, small-scale, midday OH and HO2 features were strongly linked to NO variations.

Sources of HOx and production of ozone in the upper troposphere over the United States

The sources of HO x (OH+peroxy radicals) and the associated production of ozone at 8-12 km over the United States are examined by modeling observations of OH, HO 2 , NO, and other species during the SUCCESS aircraft campaign in April-May 1996. The HO x concentrations measured in SUCCESS are up to a factor of 3 higher than can be calculated from oxidation of water vapor and photolysis of acetone. The highest discrepancy was seen in the outflow of a convective storm. We show that convective injection of peroxides (CH 3 OOH and H 2 O 2 ) and formaldehyde (CH 2 O) from the boundary layer to the upper troposphere could resolve this discrepancy. More generally, the data collected over the central United States during SUCCESS suggest that local convection was a major source of HO x and NO x to the upper troposphere. The OH and HO 2 observations together with the observations of NO allow us to directly calculate the ozone production in the upper troposphere and its dependence on NO x . We find an average net ozone production of 2 ppbv day -1 between 8 and 12 km over the continental United States in the spring. Ozone production was NO x -limited under essentially all the conditions encountered in SUCCESS. The high levels of HO x present in the upper troposphere stimulate ozone production and increase the sensitivity of ozone to NO x emissions from aircraft and other sources.

Observations of Entrainment in Eastern Pacific Marine Stratocumulus Using Three Conserved Scalars

Abstract Fast measurements of three scalars, ozone, dimethyl sulfide (DMS), and total water, are used to investigate the entrainment process in the stratocumulus-topped boundary layer (STBL) observed over the eastern subtropical Pacific during the second Dynamics and Chemistry of Marine Stratocumulus Experiment (DYCOMS-II). Direct measurement of the flux profiles by eddy covariance is used to estimate the entrainment velocity, the average rate at which the boundary layer grows diabatically via incorporation of overlying free tropospheric air. The entrainment velocities observed over the course of the mission, which took place during July 2001, ranged from 0.12 to 0.72 cm s−1, and appear to outpace the estimated large-scale subsidence as the boundary layer advects over warmer sea surface temperatures. Observed entrainment velocities display only a weak correlation with the buoyancy Richardson number defined at the inversion, which suggests that processes other than inversion strength, such as wind shear, m...

Deep convection as a source of new particles in the midlatitude upper troposphere

downwind of the cirrus anvil, with maximum concentrations of 45,000 per standard cm 3 . Volatility and electron microscope measurements indicated that most of the particles were likely to be small sulfate particles. The enhancement extended over at least a 600-km region. Multivariate statistical analysis revealed that high CN concentrations were associated with surface tracers, as well as convective elements. Convection apparently brings gas-phase particle precursors from the surface to the storm outflow region, where particle nucleation is favored by the extremely low temperatures. Simple calculations showed that deep convective systems may contribute to a substantial portion of the background aerosol in the upper troposphere at midlatitudes. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0320 Atmospheric Composition and Structure: Cloud physics and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry;

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.

Observations of HO x and its relationship with NO x in the upper troposphere during SONEX

Simultaneous measurements of the oxides of hydrogen and nitrogen made during the NASA Subsonic Assessment, Ozone and Nitrogen Oxide Experiment (SONEX) afforded an opportunity to study the coupling between these two important families throughout the free troposphere and lowermost stratosphere. Moreover, the suite of measurements made during the campaign was unprecedented in its completeness, thus providing a uniquely detailed picture of the radical photochemistry that drives oxidation and ozone production in this part of the atmosphere. On average, observed hydrogen oxides (HOx = OH + HO2) agree well with both instantaneous and diel steady-state models; however, there is a persistent deviation of the observations that correlates with the abundance of nitrogen oxides (NOx = NO + NO2) in the sampled air mass. Specifically, the observed HOx tends to exceed the model predictions in the presence of high NOx concentrations, by as much as a factor of 5 (> 500 pptv NOx), and is sometimes as little as half that expected by steady state at lower NOx levels. While many possibilities for these discrepancies are discussed, it is argued that an instrumental artifact is not probable and that the discrepancy may bespeak a shortcoming of our understanding of HOx chemistry. The consistently elevated HOx in the presence of elevated NOx leads directly to greater ozone production than expected, thereby extending the NOx-limited regime of the upper troposphere. These results could thus have bearing on the predicted impacts of increasing NOx emissions into this region of the atmosphere from, for example, the growth of global air traffic.