A regional scale modeling analysis of aerosol and trace gas distributions over the eastern Pacific during the INTEX-B field campaign

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%)

Rain in Shallow Cumulus Over the Ocean: The RICO Campaign

Shallow, maritime cumuli are ubiquitous over much of the tropical oceans, and characterizing their properties is important to understanding weather and climate. The Rain in Cumulus over the Ocean (RICO) field campaign, which took place during November 2004–January 2005 in the trades over the western Atlantic, emphasized measurements of processes related to the formation of rain in shallow cumuli, and how rain subsequently modifies the structure and ensemble statistics of trade wind clouds. Eight weeks of nearly continuous S-band polarimetric radar sampling, 57 flights from three heavily instrumented research aircraft, and a suite of ground- and ship-based instrumentation provided data on trade wind clouds with unprecedented resolution. Observational strategies employed during RICO capitalized on the advances in remote sensing and other instrumentation to provide insight into processes that span a range of scales and that lie at the heart of questions relating to the cause and effects of rain from shallow maritime cumuli

The Deep Convective Clouds and Chemistry (DC3) Field Campaign

The 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 characterization of the three sampling regions. DC3 also documented biomass-burning plumes and the interactions of these plumes with deep convection

Atmospheric sampling of Supertyphoon Mireille with NASA DC-8 aircraft on September 27, 1991, during PEM-West A

The DC‐8 mission of September 27, 1991, was designed to sample air flowing into Typhoon Mireille in the boundary layer, air in the upper tropospheric eye region, and air emerging from the typhoon and ahead of the system, also in the upper troposphere. The objective was to find how a typhoon redistributes trace constituents in the West Pacific region and whether any such redistribution is important on the global scale. The boundary layer air (300 m), in a region to the SE of the eye, contained low mixing ratios of the tracer species O3, CO, C2H6, C2H2, C3H8, C6H6 and CS2 but high values of dimethylsulfide (DMS). The eye region relative to the boundary layer, showed somewhat elevated levels of CO, substantially increased levels of O3, CS2 and all nonmethane hydrocarbons (NMHCs), and somewhat reduced levels of DMS. Ahead of the eye, CO and the NMHCs remained unchanged, O3 and CS2 showed a modest decrease, and DMS showed a substantial decrease. There was no evidence from lidar cross sections of ozone for the downward entrainment of stratospheric air into the eye region; these sections show that low ozone values were measured in the troposphere. The DMS data suggest substantial entrainment of boundary layer air into the system, particularly into the eye wall region. Estimates of the DMS sulphur flux between the boundary layer and the free troposphere, based on computations of velocity potential and divergent winds, gave values of about 69 μg S m−2 d−1 averaged over a 17.5° grid square encompassing the typhoon. A few hours after sampling with the DC‐8, Mireille passed over Oki Island, just to the north of Japan, producing surface values of ozone of 5.5 ppbv. These O3 levels are consistent with the low tropospheric values found by lidar and are more typical of equatorial regions. We suggest that the central eye region may act like a Taylor column which has moved poleward from low latitudes. The high‐altitude photochemical environment within Typhoon Mireille was found to be quite active as evidenced by significant levels of measured gas phase H2O2 and CH3OOH and model‐computed levels of OH

Ozone production efficiencies of acetone and peroxides in the upper troposphere

HOx concentrations in the upper tropical troposphere can be enhanced by the presence of acetone and the convective injection of peroxides. These enhancements in HOx might be expected to increase ozone production by increasing the rate of the HO2+NO reaction. We show however that the convective enhancements of hydrogen peroxide (H2O2) and methyl hydroperoxide (CH3OOH) above steady state during the PEM West B campaign were largely restricted to air parcels of marine boundary layer origin in which the mean NO concentration was 8 pptv. The ozone production efficiencies of the two peroxides at such low NO concentrations are very small. Their impact on the ozone budget of the upper tropical troposphere during PEM West B was therefore probably modest. Unlike the peroxides, acetone in the upper tropical troposphere during PEM West B exhibited a positive correlation with NO. It also has a much larger ozone production efficiency than either H2O2 or CH3OOH. It therefore has a much greater potential for significantly increasing ozone production rates in the upper tropical troposphere

Method for the Collection and HPLC Analysis of Hydrogen Peroxide and C\u3csub\u3el\u3c/sub\u3e and C\u3csub\u3e2\u3c/sub\u3e Hydroperoxides in the Atmosphere

An HPLC (high-performance liquid chromatography) method was developed to quantify hydrogen peroxide, methyl hydroperoxide. Hydroxymethyl hydroperoxide, ethyl hydroperoxide, and peroxyaectic acid in the atmosphere. Gas-phase hydroperoxides are collected in aqueous solution using a continuous-flow glass scrubbing coil and then analyzed by an HPLC postcolumn derivatization system. The detection system is based on fluorescence, produced by the product of the reaction of hydroperoxides with peroxidase and p-hydroxyphenylacetic acid. Reproducibilities are better than 3% for all hydroperoxides in aqueous concentrations of 1 × 10−7–6 × 10−7 M. Detection limits in aqueous concentration are 1.2 × 10−9 M for hydrogen peroxide, 1.5 × 10−9 M for hydroxymethyl hydroperoxide, 2.9 × 10−9 M for methyl hydroperoxide, 16 × 10−9 M for peroxyaectic acid, and 19 × 10−9 M for ethyl hydroperoxide. Corresponding gas-phase detection limits are 5 PPtv for hydrogen peroxide, 7 pptv for hydroxymethyl hydroperoxide, 13 pptv for methyl hydroperoxide, 72 pptv for peroxyacetic acid, and 84 pptv for ethyl hydroperoxide for an air sample flow rate of two standard liters per minute and collection solution flow rate of 4 × 10−4 L min−1. The gas-phase detection limits for the latter three hydroperoxides vary depending on temperature, pressure, air sample flow rate, and collection solution flow rate. This system was used for several airborne and ground measurements and showed reliable performance

An Ion-Neutral Model to Investigate Chemical Ionization Mass Spectrometry Analysis of Atmospheric Molecules – Application to a Mixed Reagent Ion System for Hydroperoxides and Organic Acids

An ion-neutral chemical kinetic model is described and used to simulate the negative ion chemistry occurring within a mixed-reagent ion chemical ionization mass spectrometer (CIMS). The model objective was the establishment of a theoretical basis to understand ambient pressure (variable sample flow and reagent ion carrier gas flow rates), water vapor, ozone and oxides of nitrogen effects on ion cluster sensitivities for hydrogen peroxide (H2O2), methyl peroxide (CH3OOH), formic acid (HFo) and acetic acid (HAc). The model development started with established atmospheric ion chemistry mechanisms, thermodynamic data and reaction rate coefficients. The chemical mechanism was augmented with additional reactions and their reaction rate coefficients specific to the analytes. Some existing reaction rate coefficients were modified to enable the model to match laboratory and field campaign determinations of ion cluster sensitivities as functions of CIMS sample flow rate and ambient humidity. Relative trends in predicted and observed sensitivities are compared as instrument specific factors preclude a direct calculation of instrument sensitivity as a function of sample pressure and humidity. Predicted sensitivity trends and experimental sensitivity trends suggested the model captured the reagent ion and cluster chemistry and reproduced trends in ion cluster sensitivity with sample flow and humidity observed with a CIMS instrument developed for atmospheric peroxide measurements (PCIMSs). The model was further used to investigate the potential for isobaric compounds as interferences in the measurement of the above species. For ambient O3 mixing ratios more than 50 times those of H2O2, O3−(H2O) was predicted to be a significant isobaric interference to the measurement of H2O2 using O2−(H2O2) at m∕z 66. O3 and NO give rise to species and cluster ions, CO3−(H2O) and NO3−(H2O), respectively, which interfere in the measurement of CH3OOH using O2−(CH3OOH) at m∕z 80. The CO3−(H2O) interference assumed one of its O atoms was 18O and present in the cluster in proportion to its natural abundance. The model results indicated monitoring water vapor mixing ratio, m∕z 78 for CO3−(H2O) and m∕z 98 for isotopic CO3−(H2O)2 can be used to determine when CO3−(H2O) interference is significant. Similarly, monitoring water vapor mixing ratio, m∕z 62 for NO3− and m∕z 98 for NO3−(H2O)2 can be used to determine when NO3−(H2O) interference is significant

Hydrogen peroxide, organic hydroperoxide, and formaldehyde as primary pollutants from biomass burning

Hydrogen peroxide, organic hydroperoxide species, and formaldehyde were found to be enhanced within biomass burning plumes during the Transport and Atmospheric Chemistry near the Equator - Atlantic (TRACE A) experiment. This enhancement could have resulted from direct emission by the fires or by secondary photochemical production. In this study, direct production of hydroperoxide and formaldehyde from biomass burning is proposed and examined through comparisons of hydroperoxide and formaldehyde measurements, obtained from three fire flights in TRACE A, with model estimates, with other measurement data, and with results from fire experiments at the University of Rhode Island (URI). For highest concentrations of hydroperoxide and formaldehyde, model predictions fall short of those observed, and an additional source is required. H2O2 and CH3OOH were noted to increase with CO and were significantly correlated with other measured species known to be produced from biomass burning. The enhancements of H2O2 and CH3OOH relative to CO were different between flights in which the relative enhancements of CO to CO2 were also different. The enhancement ratio of H2O2 and CH3OOH relative to CO was 1–5×10−2 and 2–4×10−3, respectively. CH2O was correlated with CO. The enhancement ratios of CH2O were determined in relation to both CO and CO2 for three flights and were 7–19×10−3 and 3–5×10−4, respectively. The correlations of CH2O with other measured combustion species were more significant than those of H2O2 and CH3OOH. To determine whether hydroperoxide and formaldehyde can be directly produced from biomass burning, simple biomass fire experiments were performed at URI. These species were observed to be clearly elevated in test biomass fires. These experiments present unequivocal evidence for the direct production of hydrogen peroxide and formaldehyde from biomass burning. The results from both TRACE A and our fire experiments also fit possible mechanisms of direct formation of hydroperoxide and formaldehyde in combustion processes. The atmospheric implication of the direct production of these species from biomass burning is their contribution to odd-hydrogen radical production, thereby affecting the oxidizing capacity of the atmosphere before O3 would be photochemically developed. In TRACE A, odd-hydrogen radical production from the direct source of these species is estimated to be near 30% of the total radical production.Engineering and Applied Science

Chemical characteristics of air from differing source regions during the Pacific Exploratory Mission‐Tropics A (PEM‐Tropics A)

Ten‐day backward trajectories are used to determine the origins of air parcels arriving at airborne DC‐8 chemical measurement sites during NASA\u27s Pacific Exploratory Mission‐Tropics A (PEM‐T) that was conducted during August‐October 1996. Those sites at which the air had a common geographical origin and transport history are grouped together, and statistical measures of chemical characteristics are computed. Temporal changes in potential temperature are used to determine whether trajectories experience a significant convective influence during the 10‐day period. Those trajectories that do not experience a significant convective influence are divided into four geographical categories depending on their origins and paths. Air parcels originating over Africa and South America are characterized by enhanced mixing ratios of O3, CO, HNO3, and PAN. The backward trajectories travel at high altitudes (∼10–11 km), covering long distances due to strong upper‐tropospheric westerly winds. The observed enhancement of combustion‐related species is attributed to biomass burning from distant sources to the west, extending even to South America. The relatively large value of Be‐7 probably is due either to less efficient removal of aerosols from upper tropospheric air or to small stratospheric contributions. Aged marine parcels are found to have relatively small concentrations of burning‐related species. Although these trajectories arrive at a wide range of aircraft altitudes, they do not pass over a land mass during the preceding 10‐day period. Air passing over Australia but no other land mass exhibits a combustion signature; however, photochemical product species such as O3 and PAN are less enhanced than in the long‐range transport category. These trajectories travel shorter distances and are at lower altitudes (∼5–8 km) than those reaching Africa and/or South America. The combustion influence on these parcels is attributed to biomass burning emissions injected over Australia. That burning is less widespread than in Africa and South America. Finally, trajectories originating over Southeast Asia appear to receive a weak combustion influence. However, compared to Africa and South America, Southeast Asia has a relatively small incidence of biomass burning. There is little combustion input from Australia due to the high transport altitudes compared to the lower heights of the convection. The Southeast Asian parcels exhibit the greatest NOx to ∑NOi ratio of any category, perhaps due to lightning. Parcels experiencing a significant convective influence also are examined. Most of these parcels pass through widespread, persistent convection along either the South Pacific Convergence Zone or Intertropical Convergence Zone approximately 5 days prior to arriving at the aircraft locations. Thus the category mostly represents marine convection. Mixing ratios of peroxides and acids in the convective category are found to be smaller than in parcels not experiencing convection. Small mixing ratios of Be‐7 and Pb‐210 suggest particle removal by precipitation

Biomass burning influences on the composition of the remote South Pacific troposphere: analysis based on observations from PEM-Tropics-A

Airborne, in situ measurements from PEM-Tropics-A (September/October 1996) are analyzed to show the presence of distinct pollution plumes in the middle-tropical troposphere of the remote South Pacific (10–30°S). These elevated plumes cause a relative maximum at about 5–7 km altitude in the vertical distribution of primary and secondary species characteristic of fuel combustion and biomass burning (CO, C2H2, C2H6, CH3Cl, PAN, O3). Similar plumes were also observed at mid-latitudes in the middle troposphere during three flights east of New Zealand (40–45°S). In all, pollution plumes with CO larger than 100 ppb were observed 24 times on seven separate flight days south of the equator. The observed plumes were frequently embedded in very dry air. Ten-day back trajectory analysis supports the view that these originated from the biomass burning regions of South Africa (and South America) and were transported to the South Pacific along long-distance subsiding trajectories. The chemical composition of the southern Pacific troposphere analyzed from the PEM-Tropics-A data is compared with data from the tropical regions of the northern Pacific (PEM-West-A) and southern Atlantic (TRACE-A) during the same Sept/Oct time period. Sizable perturbations in the abundance of ozone and its key precursors, resulting from the transport of pollution originating from biomass burning sources, are observed in much of the Southern Hemispheric troposphere