Aircraft and satellite observations indicate the presence of ppt (ppt ≡ pmol/mol) levels of BrO in the free troposphere with important implications for the tropospheric budgets of ozone, OH, and ...mercury. We can reproduce these observations with the GEOS‐Chem global tropospheric chemistry model by including a broader consideration of multiphase halogen (Br‐Cl) chemistry than has been done in the past. Important reactions for regenerating BrO from its nonradical reservoirs include HOBr + Br−/Cl− in both aerosols and clouds, and oxidation of Br− by ClNO3 and ozone. Most tropospheric BrO in the model is in the free troposphere, consistent with observations and originates mainly from the photolysis and oxidation of ocean‐emitted CHBr3. Stratospheric input is also important in the upper troposphere. Including production of gas phase inorganic bromine from debromination of acidified sea salt aerosol increases free tropospheric Bry by about 30%. We find HOBr to be the dominant gas‐phase reservoir of inorganic bromine. Halogen (Br‐Cl) radical chemistry as implemented here in GEOS‐Chem drives 14% and 11% decreases in the global burdens of tropospheric ozone and OH, respectively, a 16% increase in the atmospheric lifetime of methane, and an atmospheric lifetime of 6 months for elemental mercury. The dominant mechanism for the Br‐Cl driven tropospheric ozone decrease is oxidation of NOx by formation and hydrolysis of BrNO3 and ClNO3.
Key Points
Recent BrO observations are interpreted using a new GEOS‐Chem coupled Br‐Cl simulation
Multiphase oxidation of Br‐ by ozone is critical for maintaining the high observed levels of BrO
Br and Cl lower the global burden of O3 by 14% by increasing NOx loss and shortening the O3 lifetime
Here, tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically ...resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2–O2 collision complexes (O4) were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity-enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2–0.55 pptv IO and 32–36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and aircraft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6° N; 101.2 to 97.4° W). At 14.5 km, 5–10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12–20 degrees of freedom (DoF) and up to 500 m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 × 1013 molec cm–2 (RF12) and at least 0.5 × 1013 molec cm–2 (RF17, 0–10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 × 1012 molec cm–2 (RF12) and 2.5 × 1012 molec cm–2 (RF17) and glyoxal VCDs of 2.6 × 1014 molec cm–2 (RF12) and 2.7 × 1014 molec cm–2 (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 ± 5%, 0.1–0.2 pptv; glyoxal: 52 ± 5%, 3–20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.
The University of Colorado Airborne Multi-Axis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument uses solar stray light to detect and quantify multiple trace gases, including ...nitrogen dioxide (NO2), glyoxal (CHOCHO), formaldehyde (HCHO), water vapor (H2O), nitrous acid (HONO), iodine monoxide (IO), bromine monoxide (BrO), and oxygen dimers (O4) at multiple wavelengths (absorption bands at 360, 477, 577, 632 nm) simultaneously in the open atmosphere. The instrument is unique as it (1) features a motion compensation system that decouples the telescope field of view from aircraft movements in real time (<0.35° accuracy), and (2) includes measurements of solar stray light photons from nadir, zenith, and multiple elevation angles forward and below the plane by the same spectrometer/detector system. Sets of solar stray light spectra collected from nadir to zenith scans provide some vertical profile information within 2 km above and below the aircraft altitude, and the vertical column density (VCD) below the aircraft is measured in nadir view. Maximum information about vertical profiles is derived simultaneously for trace gas concentrations and aerosol extinction coefficients over similar spatial scales and with a vertical resolution of typically 250 m during aircraft ascent/descent. The instrument is described, and data from flights over California during the CalNex (California Research at the Nexus of Air Quality and Climate Change) and CARES (Carbonaceous Aerosols and Radiative Effects Study) air quality field campaigns is presented. Horizontal distributions of NO2 VCD (below the aircraft) maps are sampled with typically 1 km resolution, and show good agreement with two ground-based MAX-DOAS instruments (slope = 0.95 ± 0.09, R2 = 0.86). As a case study vertical profiles of NO2, CHOCHO, HCHO, and H2O concentrations and aerosol extinction coefficients, ε, at 477 nm calculated from O4 measurements from a low approach at Brackett airfield inside the South Coast Air Basin (SCAB) are presented. These profiles contain ~12 degrees of freedom (DOF) over a 3.5 km altitude range, an independent information approximately every 250 m. The boundary layer NO2 concentration, and the integral aerosol extinction over height (aerosol optical depth, AOD) agrees well with nearby ground-based in situ NO2 measurement, and AERONET station. The detection limits of NO2, CHOCHO, HCHO, H2O442, ϵ360, ϵ477 for 30 s integration time spectra recorded forward of the plane are 5 ppt, 3 ppt, 100 ppt, 42 ppm, 0.004 km−1, 0.002 km−1 in the free troposphere (FT), and 30 ppt, 16 ppt, 540 ppt, 252 ppm, 0.012 km−1, 0.006 km−1 inside the boundary layer (BL), respectively. Mobile column observations of trace gases and aerosols are complimentary to in situ observations, and help bridge the spatial scales that are probed by satellites and ground-based observations, and predicted by atmospheric models.
Multi AXis Differential Optical Absorption Spectroscopy (MAX‐DOAS) observations of the oxygen dimer O
4
which can serve as a new method for the determination of atmospheric aerosol properties are ...presented. Like established methods, e.g., Sun radiometer and LIDAR measurements, MAX‐DOAS O
4
observations determine optical properties of aerosol under atmospheric conditions (not dried). However, the novel technique has two major advantages: It utilizes differential O
4
absorption structures and thus does not require absolute radiometric calibration. In addition, O
4
observations using this method provide a new kind of information: since the atmospheric O
4
profile depends strongly on altitude, they can yield information on the atmospheric light path distribution and in particular on the atmospheric aerosol profile. From O
4
observations during clear days and from atmospheric radiative transfer modeling, we conclude that our new method is especially sensitive to the aerosol extinction close to the ground. In addition, O
4
observations using this method yield information on the penetration depth of the incident direct solar radiation. O
4
observations at different azimuth angles can also provide information on the aerosol scattering phase function. We found that MAX‐DOAS O
4
observations are a very sensitive method: even aerosol extinction below 0.001 could be detected. In addition to the O
4
absorptions we also investigated the magnitude of the Ring effect and the (relative) intensity. Both quantities yield valuable further information on atmospheric aerosols. From the simultaneous analysis of the observed O
4
absorption and the measured intensity, in particular, information on the absorbing properties of the aerosols might be derived. The aerosol information derived from MAX‐DOAS observations can be used for the quantitative analysis of various trace gases also analyzed from the measured spectra.
We designed and assembled the University of Colorado Ground Multi AXis Differential Optical Absorption Spectroscopy (CU GMAX-DOAS) instrument to retrieve bromine oxide (BrO), iodine oxide (IO), ...formaldehyde (HCHO), glyoxal (CHOCHO), nitrogen dioxide (NO2) and the oxygen dimer (O4) in the coastal atmosphere of the Gulf of Mexico. The detection sensitivity of DOAS measurements is proportional to the root mean square (RMS) of the residual spectrum that remains after all absorbers have been subtracted. Here we describe the CU GMAX-DOAS instrument and demonstrate that the hardware is capable of attaining RMS of ∼6 × 10−6 from solar stray light noise tests using high photon count spectra (compatible within a factor of two with photon shot noise). Laboratory tests revealed two critical instrument properties that, in practice, can limit the RMS: (1) detector non-linearity noise, RMSNLin, and (2) temperature fluctuations that cause variations in optical resolution (full width at half the maximum, FWHM, of atomic emission lines) and give rise to optical resolution noise, RMSFWHM. The non-linearity of our detector is low (∼10−2) yet – unless actively controlled – is sufficiently large to create RMSNLin of up to 2 × 10−4. The optical resolution is sensitive to temperature changes (0.03 detector pixels °C−1 at 334 nm), and temperature variations of 0.1°C can cause RMSFWHM of ~1 × 10−4. Both factors were actively addressed in the design of the CU GMAX-DOAS instrument. With an integration time of 60 s the instrument can reach RMS noise of 3 × 10−5, and typical RMS in field measurements ranged from 6 × 10−5 to 1.4 × 10−4. The CU GMAX-DOAS was set up at a coastal site near Pensacola, Florida, where we detected BrO, IO and CHOCHO in the marine boundary layer (MBL), with daytime average tropospheric vertical column densities (average of data above the detection limit), VCDs, of ∼2 × 1013 molec cm−2, 8 × 1012 molec cm−2 and 4 × 1014 molec cm−2, respectively. HCHO and NO2 were also detected with typical MBL VCDs of 1 × 1016 and 3 × 1015 molec cm−2. These are the first measurements of BrO, IO and CHOCHO over the Gulf of Mexico. The atmospheric implications of these observations for elevated mercury wet deposition rates in this area are briefly discussed. The CU GMAX-DOAS has great potential to investigate RMS-limited problems, like the abundance and variability of trace gases in the MBL and possibly the free troposphere (FT).
Due to the rising scarcity of clean water in arid climates, there is an increased relevance in accessing clean and renewable water resources. One such perspective method, sorption-based atmospheric ...water harvesting, collects atmospheric water as an alternative to ground and surface water. Metal-organic frameworks (MOFs) are proposed as excellent porous materials for the capture and storage of small molecules, including water, owing to their large pore volume, high surface area, and chemical and structural tunability. Here a zwitterionic MOF (Ni-ZW-MOF), Ni(dcpb)(H
2
O)
4
·14H
2
O
n
, was synthesized and studied for its water sorption performance, displaying selective water adsorption and desorption capabilities. Respective sorption properties were tested in controlled low and high humidity environments over multiple cycles, demonstrating its regenerative ability and high working capacity (126.4 mL kg
−1
per cycle).
A nanoporous zwitterionic metal-organic framework is accessed for its atmospheric water harvesting properties due to its strong Lewis acidity and water stability. Findings show high cycling output and unique hydrochromic behavior.
The ash cloud of the Eyjafjallajökull (also referred to as: Eyjafjalla (e.g. Schumann et al., 2011), Eyjafjöll or Eyjafjoll (e.g. Ansmann et al., 2010)) volcano on Iceland caused closure of large ...parts of European airspace in April and May 2010. For the validation and improvement of the European volcanic ash forecast models several research flights were performed. Also the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) flying laboratory, which routinely measures at cruise altitude (approximate11 km) performed three dedicated measurements flights through sections of the ash plume. Although the focus of these flights was on the detection and quantification of the volcanic ash, we report here on sulphur dioxide (SO2 ) and bromine monoxide (BrO) measurements with the CARIBIC DOAS (Differential Optical Absorption Spectroscopy) instrument during the second of these special flights on 16 May 2010. As the BrO and the SO2 observations coincide, we assume the BrO to have been formed inside the volcanic plume. Average SO2 and BrO mixing ratios of approximate40 ppb and approximate5 ppt respectively are retrieved inside the plume. The BrO to SO2 ratio retrieved from the CARIBIC observation is approximate1.3×10-4 . Both SO2 and BrO observations agree well with simultaneous satellite (GOME-2) observations. SO2 column densities retrieved from satellite observations are often used as an indicator for volcanic ash. As the CARIBIC O4 column densities changed rapidly during the plume observation, we conclude that the aerosol and the SO2 plume are collocated. For SO2 some additional information on the local distribution can be derived from a comparison of forward and back scan GOME-2 data. More details on the local plume size and position are retrieved by combining CARIBIC and GOME-2 data.
The results of a comparison exercise of radiative transfer models (RTM) of various international research groups for Multiple AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) viewing ...geometry are presented. Besides the assessment of the agreement between the different models, a second focus of the comparison was the systematic investigation of the sensitivity of the MAX-DOAS technique under various viewing geometries and aerosol conditions. In contrast to previous comparison exercises, box-air-mass-factors (box-AMFs) for different atmospheric height layers were modelled, which describe the sensitivity of the measurements as a function of altitude. In addition, radiances were calculated allowing the identification of potential errors, which might be overlooked if only AMFs are compared. Accurate modelling of radiances is also a prerequisite for the correct interpretation of satellite observations, for which the received radiance can strongly vary across the large ground pixels, and might be also important for the retrieval of aerosol properties as a future application of MAX-DOAS. The comparison exercises included different wavelengths and atmospheric scenarios (with and without aerosols). The strong and systematic influence of aerosol scattering indicates that from MAX-DOAS observations also information on atmospheric aerosols can be retrieved. During the various iterations of the exercises, the results from all models showed a substantial convergence, and the final data sets agreed for most cases within about 5%. Larger deviations were found for cases with low atmospheric optical depth, for which the photon path lengths along the line of sight of the instrument can become very large. The differences occurred between models including full spherical geometry and those using only plane parallel approximation indicating that the correct treatment of the Earth's sphericity becomes indispensable. The modelled box-AMFs constitute an universal data base for the calculation of arbitrary (total) AMFs by simple convolution with a given trace gas concentration profile. Together with the modelled radiances and the specified settings for the various exercises, they can serve as test cases for future RTM developments.
An airfreight container with automated instruments for measurement of atmospheric gases and trace compounds was operated on a monthly basis onboard a Boeing 767-300 ER of LTU International Airways ...during long-distance flights from 1997 to 2002 (CARIBIC, Civil Aircraft for Regular Investigation of the Atmosphere Based on an Instrument Container, http://www.caribic-atmospheric.com). Subsequently a more advanced system has been developed, using a larger capacity container with additional equipment and an improved inlet system. CARIBIC phase #2 was implemented on a new long-range aircraft type Airbus A340-600 of the Lufthansa German Airlines (Star Alliance) in December 2004, creating a powerful flying observatory. The instrument package comprises detectors for the measurement of O3, total and gaseous H2O, NO and NOy, CO, CO2, O2, Hg, and number concentrations of sub-micrometer particles (>4 nm, >12 nm, and >18 nm diameter). Furthermore, an optical particle counter (OPC) and a proton transfer mass spectrometer (PTR-MS) are incorporated. Aerosol samples are collected for analysis of elemental composition and particle morphology after flight. Air samples are taken in glass containers for laboratory analyses of hydrocarbons, halocarbons and greenhouse gases (including isotopic composition of CO2) in several laboratories. Absorption tubes collect oxygenated volatile organic compounds. Three differential optical absorption spectrometers (DOAS) with their telescopes mounted in the inlet system measure atmospheric trace gases such as BrO, HONO, and NO2. A video camera mounted in the inlet provides information about clouds along the flight track. The flying observatory, its equipment and examples of measurement results are reported.
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.
Celotno besedilo
Dostopno za:
BFBNIB, DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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