Results for the solar heating rates in ambient air due to absorption by black-carbon (BC) containing particles and ozone are presented as calculated from airborne observations made in the tropical ...tropopause layer (TTL) in January-February 2006. The method uses airborne in situ observations of BC particles, ozone and actinic flux. Total BC mass is obtained along the flight track by summing the masses of individually detected BC particles in the range 90 to 600-nm volume-equivalent diameter, which includes most of the BC mass. Ozone mixing ratios and upwelling and partial downwelling solar actinic fluxes were measured concurrently with BC mass. Two estimates used for the BC wavelength-dependent absorption cross section yielded similar heating rates. For mean altitudes of 16.5, 17.5, and 18.5 km (0.5 km) in the tropics, average BC heating rates were near 0.0002 K/d. Observed BC coatings on individual particles approximately double derived BC heating rates. Ozone heating rates exceeded BC heating rates by approximately a factor of 100 on average and at least a factor of 4, suggesting that BC heating rates in this region are negligible in comparison.
A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time high latitude ...troposphere based on aircraft and satellite measurements of bromine oxide (BrO) and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometer (CIMS) to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br−) was 0.9±0.1, 1.06+0.30/−0.35, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R2 = 0.76; slope = 0.95; intercept = −3.4 pmol mol−1) between modeled and observed soluble bromide, when BrO was above detection limit (>2 pmol mol−1) under unpolluted conditions (NO<10 pmol mol−1), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide and that a well characterized MC can be used to derive mixing ratios of some reactive bromine compounds. Tropospheric BrO vertical column densities (BrOVCD) derived from CIMS BrO observations compare well with BrOTROPVCD from OMI on 17 April 2008.
The measurement of OH reactivity, the inverse of the OH lifetime, provides a powerful tool to investigate atmospheric photochemistry. A new airborne OH reactivity instrument was designed and deployed ...for the first time on the NASA DC-8 aircraft during the second phase of Intercontinental Chemical Transport Experiment-B (INTEX-B) campaign, which was focused on the Asian pollution outflow over Pacific Ocean and was based in Hawaii and Alaska. The OH reactivity was measured by adding OH, generated by photolyzing water vapor with 185 nm UV light in a moveable wand, to the flow of ambient air in a flow tube and measuring the OH signal with laser induced fluorescence. As the wand was pulled back away from the OH detector, the OH signal decay was recorded; the slope of −Δln(signal)/Δ time was the OH reactivity. The overall absolute uncertainty at the 2σ confidence levels is about 1 s−1 at low altitudes (for decay about 6 s−1), and 0.7 s−1 at high altitudes (for decay about 2 s−1). From the median vertical profile obtained in the second phase of INTEX-B, the measured OH reactivity (4.0±1.0 s−1) is higher than the OH reactivity calculated from assuming that OH was in steady state (3.3±0.8 s−1), and even higher than the OH reactivity that was calculated from the total measurements of all OH reactants (1.6±0.4 s−1). Model calculations show that the missing OH reactivity is consistent with the over-predicted OH and under-predicted HCHO in the boundary layer and lower troposphere. The over-predicted OH and under-predicted HCHO suggest that the missing OH sinks are most likely related to some highly reactive VOCs that have HCHO as an oxidation product.
Tropospheric O3 concentrations are functions of the chain lengths of NOx (NOx ≡ NO + NO2) and HOx (HOx ≡ OH + HO2 + RO2) radical catalytic cycles. For a fixed HOx source at low NOx concentrations, ...kinetic models indicate the rate of O3 production increases linearly with increases in NOx concentrations (NOx limited). At higher NOx concentrations, kinetic models predict ozone production rates decrease with increasing NOx (NOx saturated). We present observations of NO, NO2, O3, OH, HO2, H2CO, actinic flux, and temperature obtained during the 1999 Southern Oxidant Study from June 15 to July 15, 1999, at Cornelia Fort Airpark, Nashville, Tennessee. The observations are used to evaluate the instantaneous ozone production rate (PO3) as a function of NO abundances and the primary HOx production rate (PHOx). These observations provide quantitative evidence for the response of PO3 to NOx. For high PHOx (0.5 < PHOx < 0.7 ppt/s), O3 production at this site increases linearly with NO to ∼500 ppt. PO3 levels out in the range 500–1000 ppt NO and decreases for NO above 1000 ppt. An analysis along chemical coordinates indicates that models of chemistry controlling peroxy radical abundances, and consequently PO3, have a large error in the rate or product yield of the RO2 + HO2 reaction for the classes of RO2 that predominate in Nashville. Photochemical models and our measurements can be forced into agreement if the product of the branching ratio and rate constant for organic peroxide formation, via RO2 + HO2 → ROOH + O2, is reduced by a factor of 3–12. Alternatively, these peroxides could be rapidly photolyzed under atmospheric conditions making them at best a temporary HOx reservoir. This result implies that O3 production in or near urban areas with similar hydrocarbon reactivity and HOx production rates may be NOx saturated more often than current models suggest.
OH and HO2 mixing ratios and total OH reactivity were measured together with photolysis frequencies, NOx, O3, many VOCs, and other trace gases during the midsummer 1999 SOS campaign in Nashville, ...Tennessee. These measurements provided an excellent opportunity to study OH and HO2 (collectively called HOx), and their sources and sinks in a polluted metropolitan environment. HOx generally showed the expected diurnal evolution, with maxima around noon of up to about 0.8 pptv of OH and 80 pptv of HO2 during sunny days. Overall, daytime observed OH and HO2 were a factor of 1.33 and 1.56 times modeled values, within the combined 2σ instrument and model uncertainties. The chain length of HOx, which is determined from the ratio of the measured total OH reactivity that cycles OH to the total HOx loss, was on average 3–8 during daytime and up to 3 during nighttime, in general agreement with expectations. However, differences occurred between observed HOx behavior and expectations from theory and models. First, HO2 was greater than expected during daytime when NO mixing ratios were high; ozone production did not decrease as expected when NO was greater than 2 ppbv. Ozone production determined by the imbalance of the NOx photostationary state, which was almost twice that from HO2, also shows this dependence on NO. Second, the calculated OH production rate, which should equal the measured OH loss rate because OH is in steady state, is instead less than the measured OH loss rate by (1–2) × 107 molecules cm‐3 s‐1, with low statistical significance during the day and high statistical significance at night. Third, surprisingly high OH and HO2 mixing ratios were often observed during nighttime. The nighttime OH mixing ratio and the HO2/OH ratio cannot be explained by known reaction mechanisms, even those involving O3 and alkenes. Because instrument tests have failed to reveal any instrument artifacts, more exotic chemicals or chemistry, such as OH adducts or other radicals that fall apart into OH inside the instrument, are suspected.
Detailed comparisons of airborne CH2O measurements acquired by tunable diode laser absorption spectroscopy with steady state box model calculations were carried out using data from the 2006 INTEX-B ...and MILARGO campaign in order to improve our understanding of hydrocarbon oxidation processing. This study includes comparisons over Mexico (including Mexico City), the Gulf of Mexico, parts of the continental United States near the Gulf coast, as well as the more remote Pacific Ocean, and focuses on comparisons in the boundary layer. Select previous comparisons in other campaigns have highlighted some locations in the boundary layer where steady state box models have tended to underpredict CH2O, suggesting that standard steady state modeling assumptions might be unsuitable under these conditions, and pointing to a possible role for unmeasured hydrocarbons and/or additional primary emission sources of CH2O. Employing an improved instrument, more detailed measurement-model comparisons with better temporal overlap, up-to-date measurement and model precision estimates, up-to-date rate constants, and additional modeling tools based on both Lagrangian and Master Chemical Mechanism (MCM) runs, we have explained much of the disagreement between observed and predicted CH2O as resulting from non-steady-state atmospheric conditions in the vicinity of large pollution sources, and have quantified the disagreement as a function of plume lifetime (processing time). We show that in the near field (within ~4 to 6 h of the source), steady-state models can either over-or-underestimate observations, depending on the predominant non-steady-state influence. In addition, we show that even far field processes (10–40 h) can be influenced by non-steady-state conditions which can be responsible for CH2O model underestimations by ~20%. At the longer processing times in the 10 to 40 h range during Mexico City outflow events, MCM model calculations, using assumptions about initial amounts of high-order NMHCs, further indicate the potential importance of CH2O produced from unmeasured and multi-generation hydrocarbon oxidation compounds, particularly methylglyoxal, 3-hydroxypropanal, and butan-3-one-al.
A three‐dimensional regional chemical transport model, STEM 2K1, coupled with a detailed radiation model is used to study the influences of aerosols and clouds on photolysis rates and photochemical ...processes over East Asia‐Western Pacific during the TRACE‐P period. Measured J‐values are compared with those calculated using three‐dimensional modeled fields of clouds and aerosols. The model is shown to accurately represent observed J‐values over a broad range of conditions. Model studies with and without aerosols and clouds are performed and compared with clear‐sky conditions to isolate the various influences. Clouds are shown to have a large impact on photolysis rates during the observation periods of TRACE‐P, with JNO2 decreased by 20% below clouds and enhanced by ∼30% from 1 km to 8 km. Clouds also exert a dominant influence on short‐lived radicals, like OH and HO2. For March, clouds reduce OH by 23% at altitudes below 1 km and increase OH by ∼25% above 1 km. Asian aerosols contain large amounts of carbonaceous material, inorganic components such as sulfates, and mineral oxides. These aerosols significantly influence J‐values and photochemical processes. When averaged over all TRACE‐P DC‐8 and P‐3 flights, the aerosol influence via affecting J‐values reduces OH by ∼40% below 1 km, and by ∼24% above 1 km. Aerosols have a stronger impact on longer‐lived chemical species than clouds do because aerosols tend to be coemitted with precursors and have a longer contact time with the polluted air masses. The accumulated aerosol impact generally is to reduce O3 concentrations by about 6 ppbv in the biomass burning plumes emitted from Southeast Asia. In megacity plumes, aerosols can increase NOx concentration by 40% via reducing its photolytic loss and reduce NOz concentration by a similar amount. A detailed case study of the DC‐8 and P‐3 flights on 27 March is used to make comparisons for cloud and aerosol influences. During these flights, the cloud impact on J‐values is stronger than the aerosol impact, but aerosols are shown to exert a much stronger accumulated influence on O3 production.
The first direct in situ measurements of HO2NO2 in the upper troposphere were performed from the NASA DC‐8 during the Intercontinental Chemical Transport Experiment–North America 2004 with a chemical ...ionization mass spectrometer (CIMS). These measurements provide an independent diagnostic of HOx chemistry in the free troposphere and complement direct observations of HOx, because of the dual dependency of HO2NO2 on HOx and NOx. On average, the highest HO2NO2 mixing ratio of 76 pptv (median = 77 pptv, σ = 39 pptv) was observed at altitudes of 8–9 km. Simple steady state calculations of HO2NO2, constrained by measurements of HOx, NOx, and J values, are in good agreement (slope = 0.90, R2 = 0.60, and z = 5.5–7.5 km) with measurements in the midtroposphere where thermal decomposition is the major loss process. Above 8 km the calculated steady state HO2NO2 is in poor agreement with observed values (R2 = 0.20) and is typically larger by a factor of 2.4. Conversely, steady state calculations using model‐derived HOx show reasonable agreement with the observed HO2NO2 in both the midtroposphere (slope = 0.96, intercept = 7.0, and R2 = 0.63) and upper troposphere (slope = 0.80, intercept = 32.2, and R2 = 0.58). These results indicate that observed HO2 and HO2NO2 are in poor agreement in the upper troposphere but that HO2NO2 levels are consistent with current photochemical theory.
The Sulfur Transport and dEposition Model (STEM) is applied to the analysis of observations obtained during the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), conducted over the ...eastern Pacific Ocean during spring 2006. Predicted trace gas and aerosol distributions over the Pacific are presented and discussed in terms of transport and source region contributions. Trace species distributions show a strong west (high) to east (low) gradient, with the bulk of the pollutant transport over the central Pacific occurring between ~20° N and 50° N in the 2–6 km altitude range. These distributions are evaluated in the eastern Pacific by comparison with the NASA DC-8 and NSF/NCAR C-130 airborne measurements along with observations from the Mt. Bachelor (MBO) surface site. Thirty different meteorological, trace gas and aerosol parameters are compared. In general the meteorological fields are better predicted than gas phase species, which in turn are better predicted than aerosol quantities. PAN is found to be significantly overpredicted over the eastern Pacific, which is attributed to uncertainties in the chemical reaction mechanisms used in current atmospheric chemistry models in general and to the specifically high PAN production in the SAPRC-99 mechanism used in the regional model. A systematic underprediction of the elevated sulfate layer in the eastern Pacific observed by the C-130 is another issue that is identified and discussed. Results from source region tagged CO simulations are used to estimate how the different source regions around the Pacific contribute to the trace gas species distributions. During this period the largest contributions were from China and from fires in South/Southeast and North Asia. For the C-130 flights, which operated off the coast of the Northwest US, the regional CO contributions range as follows: China (35%), South/Southeast Asia fires (35%), North America anthropogenic (20%), and North Asia fires (10%). The transport of pollution into the western US is studied at MBO and a variety of events with elevated Asian dust, and periods with contributions from China and fires from both Asia and North America are discussed. The role of heterogeneous chemistry on the composition over the eastern Pacific is also studied. The impacts of heterogeneous reactions at specific times can be significant, increasing sulfate and nitrate aerosol production and reducing gas phase nitric acid levels appreciably (~50%).
This study examines the agreement between photolysis frequency measurements by the NCAR scanning actinic flux spectroradiometer (SAFS) and calculations from a cloud‐free model (CFM) and investigates ...the impact of these differences on ozone photochemistry. Overall, the mean jNO2measurement to model ratio for all flights of TRACE‐P was 0.943 ± 0.271. The sky conditions during the Transport and Chemical Evolution over the Pacific (TRACE‐P) experiment were determined to be “cloud‐free” 40% of the time; hence a CFM is frequently not representative of the local atmospheric conditions. Our analysis indicates that clouds have a larger impact on photolysis frequencies (from −90 to +200%) than do aerosols (maximum of ±20%). The CFM and SAFS jNO2 and jO(1D) values differed by 9% and 0–7%, respectively, during a vertical profile through a cloud‐free and low AOD atmosphere. This suggests that measurement/model agreement to less than 10% may be difficult without better aerosol optical parameter inputs even under low‐AOD conditions. For the TRACE‐P chemical environment, OH, NO, and HO2 were more sensitive than other compounds (e.g., CH3C(O)O2, CH3OOH) to changes (or errors) in photolysis frequency inputs to a photochemical box model. Compounds including NO2, PAN, and HCHO exhibited different relationships to j‐value changes below and above the boundary layer. Ozone production and loss rates increased linearly with changes (or errors) in the photolysis frequency with the resulting net O3 tendency increasing with a linear slope near unity. During the TRACE‐P mission the net photochemical effect of clouds and aerosols was a large decrease in photochemical O3 production in the boundary layer.