The adsorption of nitric acid (HNO3) from a flowing gas stream is studied for a variety of wall materials to determine their suitability for use in atmospheric sampling instruments. Parts per billion ...level mixtures of HNO3 in synthetic air flow through tubes of different materials such that >80% of the molecules interact with the walls. A chemical ionization mass spectrometer with a fast time response and high sensitivity detects HNO3 that is not adsorbed on the tube walls. Less than 5% of available HNO3 is adsorbed on Teflon fluoropolymer tubing after 1 min of HNO3 exposure, whereas >70% is lost on walls made of stainless steel, glass, fused silica, aluminum, nylon, silica-steel, and silane-coated glass. Glass tubes exposed to HNO3 on the order of hours passivate with HNO3 adsorption dropping to zero. The adsorption of HNO3 on PFA Teflon tubing (PFA) is nearly temperature-independent from 10 to 80 °C, but below −10 °C nearly all HNO3 that interacts with PFA is reversibly adsorbed. In ambient and synthetic air, humidity increases HNO3 adsorption. The results suggest that Teflon at temperatures above 10 °C is an optimal choice for inlet surfaces used for in situ measurements of HNO3 in the ambient atmosphere.
The Convective Transport of Active Species in the Tropics (CONTRAST) experiment was conducted from Guam (13.5°N, 144.8°E) during January–February 2014. Using the NSF/NCAR Gulfstream V research ...aircraft, the experiment investigated the photochemical environment over the tropical western Pacific (TWP) warm pool, a region of massive deep convection and the major pathway for air to enter the stratosphere during Northern Hemisphere (NH) winter. The new observations provide a wealth of information for quantifying the influence of convection on the vertical distributions of active species. The airborne in situ measurements up to 15-km altitude fill a significant gap by characterizing the abundance and altitude variation of a wide suite of trace gases. These measurements, together with observations of dynamical and microphysical parameters, provide significant new data for constraining and evaluating global chemistry–climate models. Measurements include precursor and product gas species of reactive halogen compounds that impact ozone in the upper troposphere/lower stratosphere. High-accuracy, in situ measurements of ozone obtained during CONTRAST quantify ozone concentration profiles in the upper troposphere, where previous observations from balloonborne ozonesondes were often near or below the limit of detection. CONTRAST was one of the three coordinated experiments to observe the TWP during January–February 2014. Together, CONTRAST, Airborne Tropical Tropopause Experiment (ATTREX), and Coordinated Airborne Studies in the Tropics (CAST), using complementary capabilities of the three aircraft platforms as well as ground-based instrumentation, provide a comprehensive quantification of the regional distribution and vertical structure of natural and pollutant trace gases in the TWP during NH winter, from the oceanic boundary to the lower stratosphere.
A measurement intensive was carried out in Barrow, Alaska, in spring 2009 as part of the Ocean‐Atmosphere‐Sea‐Ice–Snowpack (OASIS) program. The central focus of this campaign was the role of halogen ...chemistry in the Arctic. A chemical ionization mass spectrometer (CIMS) performed in situ bromine oxide (BrO) measurements. In addition, a long path‐differential optical absorption spectrometer (LP‐DOAS) measured the average concentration of BrO along light paths of either 7.2 or 2.1 km. A comparison of the 1 min observations from both instruments is presented in this work. The two measurements were highly correlated and agreed within their uncertainties (R2 = 0.74, slope = 1.10, and intercept = −0.15 pptv). Better correlation was found (R2 = 0.85, slope = 1.04, and intercept = −0.11 pptv) for BrO observations at moderate wind speeds (>3 m s−1 and <8 m s−1) and low nitric oxide (NO) mixing ratios (<100 pptv). The improved agreement is likely due to the elimination of periods when the spatial distribution of BrO is inhomogeneous. The detection limit obtained for the CIMS was 2.6 pptv (3σ) for a 4 s integration period, and the estimated uncertainty was ∼30%. The detection limits for the LP‐DOAS ranged from 0.7 to 5 pptv (3σ) depending on the level of ambient light and the chosen light path, and the estimated systematic error was 10%. The agreement between the CIMS and LP‐DOAS is excellent and demonstrates the capability of both instruments to selectively and accurately measure BrO with high sensitivity.
Peroxyacetyl nitrate (PAN) and its chemical analogues are increasingly being quantified in the ambient atmosphere by thermal dissociation (TD) followed by detection of either the peroxyacyl radical ...or the NO2 product. Here we present details of the technique developed at University of California, Berkeley which detects the sum of all peroxynitrates (ΣPNs) via laser-induced fluorescence (LIF) of the NO2 product. We review the various deployments and compare the Berkeley ΣPNs measurements with the sums of PAN and its homologue species detected individually by other instruments. The observed TD-LIF ΣPNs usually agree to within 10% with the summed individual species, thus arguing against the presence of significant concentrations of unmeasured PAN-type compounds in the atmosphere, as suggested by some photochemical mechanisms. Examples of poorer agreement are attributed to a sampling inlet design that is shown to be inappropriate for high NOx conditions. Interferences to the TD-LIF measurements are described along with strategies to minimize their effects.
During the NOAA Southern Oxidant Study 1999 (SOS1999), Texas Air Quality Study 2000 (TexAQS2000), International Consortium for Atmospheric Research on Transport and Transformation (ICARTT2004), and ...Texas Air Quality Study 2006 (TexAQS2006) campaigns, airborne measurements of isoprene and monoterpenes were made in the eastern United States and in Texas, and the results are used to evaluate the biogenic emission inventories BEIS3.12, BEIS3.13, MEGAN2, and WM2001. Two methods are used for the evaluation. First, the emissions are directly estimated from the ambient isoprene and monoterpene measurements assuming a well‐mixed boundary layer and are compared with the emissions from the inventories extracted along the flight tracks. Second, BEIS3.12 is incorporated into the detailed transport model FLEXPART, which allows the isoprene and monoterpene mixing ratios to be calculated and compared to the measurements. The overall agreement for all inventories is within a factor of 2 and the two methods give consistent results. MEGAN2 is in most cases higher, and BEIS3.12 and BEIS3.13 lower than the emissions determined from the measurements. Regions with clear discrepancies are identified. For example, an isoprene hot spot to the northwest of Houston, Texas, was expected from BEIS3 but not observed in the measurements. Interannual differences in emissions of about a factor of 2 were observed in Texas between 2000 and 2006.
One of the objectives of the Deep Convective Clouds and Chemistry (DC3) field experiment was to determine the scavenging of soluble trace gases by thunderstorms. We present an analysis of scavenging ...of hydrogen peroxide (H2O2) and methyl hydrogen peroxide (CH3OOH) from six DC3 cases that occurred in Oklahoma and northeast Colorado. Estimates of H2O2 scavenging efficiencies are comparable to previous studies ranging from 79 to 97% with relative uncertainties of 5–25%. CH3OOH scavenging efficiencies ranged from 12 to 84% with relative uncertainties of 18–558%. The wide range of CH3OOH scavenging efficiencies is surprising, as previous studies suggested that CH3OOH scavenging efficiencies would be <10%. Cloud chemistry model simulations of one DC3 storm produced CH3OOH scavenging efficiencies of 26–61% depending on the ice retention factor of CH3OOH during cloud drop freezing, suggesting ice physics impacts CH3OOH scavenging. The highest CH3OOH scavenging efficiencies occurred in two severe thunderstorms, but there is no obvious correlation between the CH3OOH scavenging efficiency and the storm thermodynamic environment. We found a moderate correlation between the estimated entrainment rates and CH3OOH scavenging efficiencies. Changes in gas‐phase chemistry due to lightning production of nitric oxide and aqueous‐phase chemistry have little effect on CH3OOH scavenging efficiencies. To determine why CH3OOH can be substantially removed from storms, future studies should examine effects of entrainment rate, retention of CH3OOH in frozen cloud particles during drop freezing, and lightning‐NOx production.
Key Points
Peroxide scavenging efficiencies derived from measurements
Hydrogen peroxide is readily removed by storms
Methyl hydrogen peroxide scavenging correlated with cloud physics and entrainment rate
HONO was measured by a LOPAP instrument (LOng Path Absorption Photometer) for one month during the OASIS spring 2009 campaign in Barrow, Alaska. HONO concentrations between ≤ 0.4 pptv (DL) and ∼500 ...pptv were measured. The very high concentrations observed on several days were caused by local direct emissions and were highly correlated with the NOx and CO data. When only “clean days” were considered, average HONO concentrations varied between ≤ 0.4 ‐ 10 pptv. Average HONO/NOx and HONO/NOy ratios of ∼6% and ∼1% were observed, respectively, in good agreement with other remote LOPAP measurement data, but lower than measured in most other polar regions by other methods. The strong correlation between sharp peaks of OH and HONO during daytime, which was not observed for any other measured radical precursor, suggested that HONO photolysis was a major source of OH radicals in Barrow. This was supported by calculated net OH radical production by HONO and O3 photolysis for which the contribution of O3 (2%) could be neglected compared to that of HONO (98%). A net extra HONO/OH source necessary to explain elevated HONO levels during daytime of up to 90 pptv/h was determined, which was highly correlated with the actinic flux. Accordingly, a photochemical HONO source is proposed here, in good agreement with recent studies. From the higher correlation of the net HONO source with and NO2 compared to and NO3−, photosensitized conversion of NO2 on humic acid containing snow surfaces may be a more likely source of HONO in the polar atmosphere of Barrow than nitrate photolysis.
Key Points
Polar HONO concentrations much lower compared to previous studies
HONO is still a major source of OH radicals in the polar atmosphere
Photochemical HONO formation by a long wavelength range process including NO2
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