Search for: All records

Abstract. Bromine monoxide (BrO) is relevant to atmospheric oxidative capacity, affecting the lifetime of greenhouse gases (i.e., methane, dimethylsulfide) and mercury oxidation. However, measurements of BrO radical vertical profiles are rare, and BrO is highly variable. As a result, the few available aircraft observations in different regions of the atmosphere are not easily reconciled. Autonomous multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments placed at remote mountaintop observatories (MT-DOAS) present a cost-effective alternative to aircraft, with the potential to probe the climate-relevant yet understudied free troposphere more routinely. Here, we describe an innovative full-atmosphere BrO and formaldehyde (HCHO) profile retrieval algorithm using MT-DOAS measurements at Mauna Loa Observatory (MLO – 19.536° N, 155.577° W; 3401 m a.s.l.). The retrieval is based on time-dependent optimal estimation and simultaneously inverts 190+ individual BrO (and formaldehyde, HCHO) SCDs (slant column densities; SCD = dSCD + SCDRef) from solar stray light spectra measured in the zenith and off-axis geometries at high and low solar zenith angles (92° > SZA > 30°) to derive BrO concentration profiles from 1.9 to 35 km with 7.5 degrees of freedom (DoFs). Two case study days are characterized by the absence (26 April 2017, base case) and presence of a Rossby-wave-breaking double tropopause (29 April 2017, RW-DT case). Stratospheric-BrO vertical columns are nearly identical on both days (VCD = (1.5 ± 0.2) × 1013 molec. cm−2), and the stratospheric-BrO profile peaks at a lower altitude during the RW-DT (1.6–2.0 DoFs). Tropospheric-BrO VCDs increase from (0.70 ± 0.14) × 1013 molec. cm−2 (base case) to (1.00 ± 0.14) × 1013 molec. cm−2 (RW-DT) owing to a 3-fold increase in BrO in the upper troposphere (1.7–1.9 DoFs). BrO at MLO increases from (0.23 ± 0.03) pptv (base case) to (0.46 ± 0.03) pptv (RW-DT) and is characterized by an added time resolution (∼ 3.8 DoFs). Up to (0.9 ± 0.1) pptv BrO is observed above MLO in the lower free troposphere in the absence of the double tropopause. We validate the retrieval using aircraft BrO profiles and in situ HCHO measurements aboard the NSF/NCAR GV aircraft above MLO (11 January 2014) that establish BrO peaks around 2.4 pptv above 13 km in the upper troposphere–lower stratosphere (UTLS) during a similar RW-DT event (0.83 × 1013 molec. cm2 tropospheric-BrO VCD above 2 km). The tropospheric-BrO profile measured using MT-DOAS (RW-DT case) and using the aircraft agree well (after averaging-kernel smoothing). Furthermore, these tropospheric-BrO profiles over the central Pacific Ocean are found to closely resemble those over the eastern Pacific Ocean (2–14 km) and are in contrast to those over the western Pacific Ocean, where a C-shaped tropospheric-BrO profile shape has been observed. 

Abstract. Field-deployable real-time aerosol mass spectrometers (AMSs) typically use an aerodynamic lens as an inlet that collimates aerosols into a narrow beam over a wide range of particle sizes. Such lenses need constant upstream pressure to work consistently. Deployments in environments where the ambient pressure changes, e.g., on aircraft, typically use pressure-controlled inlets (PCIs). These have performed less well for supermicron aerosols, such as the larger particles in stratospheric air and some urban hazes. In this study, we developed and characterized a new PCI design (“CU PCI-D”) coupled with a recently developed PM2.5 aerodynamic lens, with the goal of sampling the full accumulation mode of ambient aerosols with minimal losses up to upper troposphere and lower stratosphere (UTLS) altitudes. A new computer-controlled lens alignment system and a new 2D particle beam imaging device that improves upon the Aerodyne aerosol beam width probe (BWP) have been developed and tested. These techniques allow for fast automated aerosol beam width and position measurements and ensure the aerodynamic lens is properly aligned and characterized for accurate quantification, in particular for small sizes that are hard to access with monodisperse measurements. The automated lens alignment tool also allows position-dependent thermal decomposition to be investigated on the vaporizer surface. The CU PCI-D was tested on the TI3GER campaign aboard the NCAR/NSF G-V aircraft. Based on comparisons with the co-sampling UHSAS particle sizer, the CU aircraft AMS with the modified PCI consistently measured ∼ 89 % of the accumulation-mode particle mass in the UTLS. 

Abstract. Aircraft-based measurements enable large-scale characterization of gas-phase atmospheric composition, but these measurements are complicated by the challenges of sampling from high-speed flow. Under such sampling conditions, the sample flow will likely experience turbulence, accelerating and mixing of potential contamination of the gas-phase from the condensed-phase components on walls, and reduced vapor transmission due to losses to the inner walls of the sampling line. While a significant amount of research has gone into understanding aerosol sampling efficiency for aircraft inlets, a similar research investment has not been made for gas sampling. Here, we analyze the performance of a forward-facing laminar flow gas inlet to establish its performance as a function of operating conditions, including ambient pressure, freestream velocities, and sampling conditions. Using computational fluid dynamics (CFD) modeling we simulate flow inside and outside the inlet to determine the extent of freestream turbulent interaction with the sample flow and its implication for gas sample transport. The CFD results of flow features in the inlet are compared against measurements of air speed and turbulent intensity from full-sized high-speed wind tunnel experiments. These comparisons suggest that the Reynolds-averaged Navier–Stokes (RANS) CFD simulations using the shear stress transport (SST) modeling approach provide the most reasonable prediction of the turbulence characteristics of the inlet. 

Anthropogenic ammonia (NH₃) emissions have significantly increased in recent decades due to enhanced agricultural activities, contributing to global air pollution. While the effects of NH₃on surface air quality are well documented, its influence on particle dynamics in the upper troposphere-lower stratosphere (UTLS) and related aerosol impacts remain unquantified. NH₃reaches the UTLS through convective transport and can enhance new particle formation (NPF). This modeling study evaluates the global impact of anthropogenic NH₃on UTLS particle formation and quantifies its effects on aerosol loading and cloud condensation nuclei (CCN) abundance. We use the EMAC Earth system model, incorporating multicomponent NPF parameterizations from the CERN CLOUD experiment. Our simulations reveal that convective transport increases NH₃-driven NPF in the UTLS by one to three orders of magnitude compared to a baseline scenario without anthropogenic NH₃, causing a doubling of aerosol numbers over high-emission regions. These aerosol changes induce a 2.5-fold increase in upper tropospheric CCN concentrations. Anthropogenic NH₃emissions increase the relative contribution of water-soluble inorganic ions to the UTLS aerosol optical depth (AOD) by 20% and increase total column AOD by up to 80%. In simulations without anthropogenic NH₃, UTLS aerosol composition is dominated by sulfate and organic species, with a marked reduction in ammonium nitrate and aerosol water content. This results in a decline of aerosol mass concentration by up to 50%. These findings underscore the profound global influence of anthropogenic NH₃emissions on UTLS particle formation, AOD, and CCN production, with important implications for cloud formation and climate. 

Abstract. The air–sea exchange of ozone (O3) is controlled by chemistry involving halogens, dissolved organic carbon, and sulfur in the sea surface microlayer. Calculations also indicate faster ozone photolysis at aqueous surfaces, but the role of clouds as an ozone sink is currently not well established. Fast-response ozone sensors offer opportunities to measure eddy covariance (EC) ozone fluxes in the marine boundary layer. However, intercomparisons of fast airborne O3 sensors and EC O3 fluxes measured on aircraft have not been conducted before. In April 2022, the Technological Innovation Into Iodine and GV Environmental Research (TI3GER) field campaign deployed three fast ozone sensors (gas chemiluminescence and a combination of UV absorption with coumarin chemiluminescence detection, CID) together with a fast water vapor sensor and anemometer to study iodine chemistry in the troposphere and stratosphere over Colorado and over the Pacific Ocean near Hawaii and Alaska. Here, we present an instrument comparison between the NCAR Fast O3 instrument (FO3, gas-phase CID) and two KIT Fast AIRborne Ozone instruments (FAIRO, UV absorption and coumarin CID). The sensors have comparable precision < 0.4 % Hz−0.5 (0.15 ppbv Hz−0.5), and ozone volume mixing ratios (VMRs) generally agreed within 2 % over a wide range of environmental conditions: 10 < O3 < 1000 ppbv, below detection < NOx < 7 ppbv, and 2 ppmv < H2O < 4 % VMR. Both instrument designs are demonstrated to be suitable for EC flux measurements and were able to detect O3 fluxes with exchange velocities (defined as positive for upward) as slow as −0.010 ± 0.004 cm s−1, which is in the lower range of previously reported measurements. Additionally, we present two case studies. In one, the direction of ozone and water vapor fluxes was reversed (vO3 = +0.134 ± 0.005 cm s−1), suggesting that overhead evaporating clouds could be a strong ozone sink. Further work is needed to better understand the role of clouds as a possibly widespread sink of ozone in the remote marine boundary layer. In the second case study, vO3 values are negative (varying by a factor of 6–10 from −0.036 ± 0.006 to −0.003 ± 0.004 cm s−1), while the water vapor fluxes are consistently positive due to evaporation from the ocean surface and spatially homogeneous. This case study demonstrates that the processes governing ozone and water vapor fluxes can become decoupled and illustrates the need to elucidate possible drivers (physical, chemical, or biological) of the variability in ozone exchange velocities on fine spatial scales (∼ 20 km) over remote oceans. 

Abstract. Aircraft-based measurements enable large-scale characterization of gas-phase atmospheric composition, but these measurements are complicated by the challenges of sampling from high-speed flow. Under such sampling conditions, the sample flow will likely experience turbulence, accelerating | mixing of potential contamination of the gas-phase from the condensed-phase components on walls and reduced vapor transmission due to losses to the inner walls of the sampling line. While a significant amount of research has gone into understanding aerosol sampling efficiency for aircraft inlets, a similar research investment has not been made for gas sampling. Here, we analyze the performance of a forward-facing laminar flow gas inlet to establish its performance as a function of operating conditions, including ambient pressure, freestream velocities, and sampling conditions. Using computational fluid dynamics (CFD) modeling we simulate flow inside and outside the inlet to determine the extent of freestream turbulent interaction with the sample flow and its implication for gas sample transport. The CFD results of flow features in the inlet are compared against measurements of air speed and turbulent intensity from full-sized high-speed wind-tunnel experiments. These comparisons suggest that the Reynolds Averaged Navier-Stokes (RANS) CFD simulations using the Shear Stress Transport (SST) modeling approach provide the most reasonable prediction of the turbulence characteristics of the inlet. 

Abstract Isoprene (C₅H₈) is the non-methane hydrocarbon with the highest emissions to the atmosphere. It is mainly produced by vegetation, especially broad-leaved trees, and efficiently transported to the upper troposphere in deep convective clouds, where it is mixed with lightning NO_x. Isoprene oxidation products drive rapid formation and growth of new particles in the tropical upper troposphere. However, isoprene oxidation pathways at low temperatures are not well understood. Here, in experiments at the CERN CLOUD chamber at 223 K and 243 K, we find that isoprene oxygenated organic molecules (IP-OOM) all involve two successive$${{{\rm{OH}}}}^{\bullet}$$ ${\mathrm{OH}}^{\bullet }$oxidations. However, depending on the ambient concentrations of the termination radicals ($${{{{\rm{HO}}}}_{2}}^{\bullet},\,{{{\rm{NO}}}}^{\bullet}$$ ${{\mathrm{HO}}_2}^{\bullet },{\mathrm{NO}}^{\bullet }$, and$${{{\rm{NO}}}}_{2}^{\bullet}$$ ${\mathrm{NO}}_2^{\bullet }$), vastly-different IP-OOM emerge, comprising compounds with zero, one or two nitrogen atoms. Our findings indicate high IP-OOM production rates for the tropical upper troposphere, mainly resulting in nitrate IP-OOM but with an increasing non-nitrate fraction around midday, in close agreement with aircraft observations. 

Abstract. Mercury (Hg) is a global atmospheric pollutant. In its oxidized form (HgII), it can readily deposit to ecosystems, where it may bioaccumulate and cause severe health effects. High HgII concentrations are reported in the free troposphere, but spatiotemporal data coverage is limited. Underestimation of HgII by commercially available measurement systems hinders quantification of Hg cycling and fate. During spring–summer 2021 and 2022, we measured elemental (Hg0) and oxidized Hg using a calibrated dual-channel system alongside trace gases, aerosol properties, and meteorology at the high-elevation Storm Peak Laboratory (SPL) above Steamboat Springs, Colorado. Oxidized Hg concentrations displayed diel and episodic behavior similar to previous work at SPL but were approximately 3 times higher in magnitude due to improved measurement accuracy. We identified 18 multi-day events of elevated HgII (mean enhancement of 36 pg m−3) that occurred in dry air (mean ± SD of relative humidity = 32 ± 16 %). Lagrangian particle dispersion model (HYSPLIT–STILT, Hybrid Single-Particle Lagrangian Integrated Trajectory–Stochastic Time-Inverted Lagrangian Transport) 10 d back trajectories showed that the majority of transport prior to events occurred in the low to middle free troposphere. Oxidized Hg was anticorrelated with Hg0 during events, with an average (± SD) slope of −0.39 ± 0.14. We posit that event HgII resulted from upwind oxidation followed by deposition or cloud uptake during transport. Meanwhile, sulfur dioxide measurements verified that three upwind coal-fired power plants did not influence ambient Hg at SPL. Principal component analysis showed HgII consistently inversely related to Hg0 and generally not associated with combustion tracers, confirming oxidation in the clean, dry free troposphere as its primary origin.