[1] A new retrieval algorithm for the determination of aerosol properties using MultiAXis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements based on nonlinear optimal estimation is presented. Using simulated MAX-DOAS measurements of the optical depth of the collision complex of oxygen (O 4 ) as well as the variation of the intensity of diffuse skylight measured at different viewing directions and wavelengths, the capability of this measurement technique to derive the aerosol extinction profile as well as information on the phase function and single scattering albedo is demonstrated. The information content, vertical resolution and retrieval errors under various atmospheric conditions are discussed. Furthermore, it is demonstrated that the assumption of a smooth variation of the aerosol properties between successive measurements can be used to improve the quality of the retrieval by applying a Kalman smoother. The results of these model studies suggest that the achievable precision of MAX-DOAS measurements of the aerosol total optical depth is better than 0.01 and thus comparable with established methods of aerosol detection by Sun photometers (e.g., within the AERONET network) over a wide range of atmospheric conditions. Moreover, MAX-DOAS measurements contain information on the vertical profile of the aerosol extinction, and can be performed with relatively simple, robust and self-calibrating instruments.

[1] 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.

Abstract. We present a simulation of the global present-day composition of the troposphere which includes the chemistry of halogens (Cl, Br, I). Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016) we do not include sea-salt debromination. Observations of halogen radicals (BrO, IO) are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens.Inclusion of Cl, Br, and I results in a general improvement in simulation of ozone (O 3 ) concentrations, except in polar regions where the model now underestimates O 3 concentrations. Halogen chemistry reduces the global tropospheric O 3 burden by 18.6 %, with the O 3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28 × 10 6 molecules cm −3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH 4 lifetime (10.8 %) due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH 4 by Cl is small (∼ 2 %) but Cl oxidation of other VOCs (ethane, acetone, and propane) can be significant (∼ 15-27 %). Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

Abstract. 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.

Abstract. We present a global simulation of tropospheric iodine chemistry within the GEOS-Chem chemical transport model. This includes organic and inorganic iodine sources, standard gas-phase iodine chemistry, and simplified higher iodine oxide (I 2 O X , X = 2, 3, 4) chemistry, photolysis, deposition, and parametrized heterogeneous reactions. In comparisons with recent iodine oxide (IO) observations, the simulation shows an average bias of ∼ +90 % with available surface observations in the marine boundary layer (outside of polar regions), and of ∼ +73 % within the free troposphere (350 hPa < p < 900 hPa) over the eastern Pacific. Iodine emissions (3.8 Tg yr −1 ) are overwhelmingly dominated by the inorganic ocean source, with 76 % of this emission from hypoiodous acid (HOI). HOI is also found to be the dominant iodine species in terms of global tropospheric I Y burden (contributing up to 70 %). The iodine chemistry leads to a significant global tropospheric O 3 burden decrease (9.0 %) compared to standard GEOS-Chem (v9-2). The iodine-driven O X loss rate 1 (748 Tg O X yr −1 ) is due to photolysis of HOI (78 %), photolysis of OIO (21 %), and re- action between IO and BrO (1 %). Increases in global mean OH concentrations (1.8 %) by increased conversion of hydroperoxy radicals exceeds the decrease in OH primary production from the reduced O 3 concentration. We perform sensitivity studies on a range of parameters and conclude that the simulation is sensitive to choices in parametrization of heterogeneous uptake, ocean surface iodide, and I 2 O X (X = 2, 3, 4) photolysis. The new iodine chemistry combines with previously implemented bromine chemistry to yield a total bromine-and iodine-driven tropospheric O 3 burden decrease of 14.4 % compared to a simulation without iodine and bromine chemistry in the model, and a small increase in OH (1.8 %). This is a significant impact and so halogen chemistry needs to be considered in both climate and air quality models.