Investigation and amelioration of long-term instrumental drifts in water vapor and nitrous oxide measurements from the Aura Microwave Limb Sounder (MLS) and their implications for studies of variability and trends

The Microwave Limb Sounder (MLS), launched on NASA's Aura spacecraft in 2004, measures vertical profiles of the abundances of key atmospheric species from the upper troposphere to the mesosphere with daily near-global coverage. We review the first 15 years of the record of H2O and N2O measurements from the MLS 190 GHz subsystem (along with other 190 GHz information), with a focus on their long-term stability, largely based on comparisons with measurements from other sensors. These comparisons generally show signs of an increasing drift in the MLS “version 4” (v4) H2O record starting around 2010. Specifically, comparisons with v4.1 measurements from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) indicate a ∼ 2 %–3 % per decade drift over much of the stratosphere, increasing to as much as ∼ 7 % per decade around 46 hPa. Larger drifts, of around 7 %–11 % per decade, are seen in comparisons to balloon-borne frost point hygrometer measurements in the lower stratosphere. Microphysical calculations considering the formation of polar stratospheric clouds in the Antarctic winter stratosphere corroborate a drift in MLS v4 water vapor measurements in that region and season. In contrast, comparisons with the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on NASA's Thermosphere Ionosphere Mesosphere Energetics and Dynamics (TIMED) mission, and with ground-based Water Vapor Millimeter-wave Spectrometer (WVMS) instruments, do not show statistically significant drifts. However, the uncertainty in these comparisons is large enough to encompass most of the drifts identified in other comparisons. In parallel, the MLS v4 N2O product is shown to be generally decreasing over the same period (when an increase in stratospheric N2O is expected, reflecting a secular growth in emissions), with a more pronounced drift in the lower stratosphere than that found for H2O. Comparisons to ACE-FTS and to MLS N2O observations in a different spectral region, with the latter available from 2004 to 2013, indicate an altitude-dependent drift, growing from 5 % per decade or less in the mid-stratosphere to as much as 15 % per decade in the lower stratosphere. Detailed investigations of the behavior of the MLS 190 GHz subsystem reveal a drift in its “sideband fraction” (the relative sensitivity of the 190 GHz receiver to the two different parts of the microwave spectrum that it observes). Our studies indicate that sideband fraction drift accounts for much of the observed changes in the MLS H2O product and some portion of the changes seen in N2O. The 190 GHz sideband fraction drift has been corrected in the new “version 5” (v5) MLS algorithms, which have now been used to reprocess the entire MLS record. As a result of this correction, the MLS v5 H2O record shows no statistically significant drifts compared to ACE-FTS. However, statistically significant drifts remain between MLS v5 and frost point measurements, although they are reduced. Drifts in v5 N2O are about half the size of those in v4 but remain statistically significant. Scientists are advised to use MLS v5 data in all future studies. Quantification of interregional and seasonal to annual changes in MLS H2O and N2O will not be affected by the drift. However, caution is advised in studies using the MLS record to examine long-term (multiyear) variability and trends in either of these species, especially N2O; such studies should only be undertaken in consultation with the MLS team. Importantly, this drift does not affect any of the MLS observations made in other spectral regions such as O3, HCl, CO, ClO, or temperature.

Deep ice as a geochemical reactor: insights from iron speciation and mineralogy of dust in the Talos Dome ice core (East Antarctica)

Thanks to its insolubility, mineral dust is considered a stable proxy in polar ice cores. With this study we show that the Talos Dome ice core (TALDICE, Ross Sea sector of East Antarctica) displays evident and progressive signs of post-depositional processes affecting the mineral dust record below 1000 m deep. We apply a suite of established and cutting-edge techniques to investigate the properties of dust in TALDICE, ranging from concentration and grain size to elemental composition and Fe mineralogy. Results show that through acidic/oxidative weathering, the conditions of deep ice at Talos Dome promote the dissolution of specific minerals and the englacial formation of others, affecting primitive dust features. The expulsion of acidic atmospheric species from ice grains and their concentration in localized environments is likely the main process responsible for englacial reactions. Deep ice can be seen as a “geochemical reactor” capable of fostering complex reactions which involve both soluble and insoluble impurities. Fe-bearing minerals can efficiently help in exploring such transformations.

Investigation and amelioration of long-term instrumental drifts in water vapor and nitrous oxide measurements from the Aura Microwave Limb Sounder (MLS) and their implications for studies of variability and trends

The Microwave Limb Sounder (MLS), launched on NASA's Aura spacecraft in 2004, measures vertical profiles of the abundances of key atmospheric species from the upper troposphere to the mesosphere with daily near-global coverage. We review the first 15 years of the record of H2O and N2O measurements from the MLS 190-GHz subsystem (along with other 190-GHz information), with a focus on their long-term stability, largely based on comparisons with measurements from other sensors. These comparisons generally show signs of an increasing drift in the MLS version 4 (v4) H2O record starting around 2010. Specifically, comparisons with v4.1 measurements from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) indicate a ~2–3 %/decade drift over much of the stratosphere, increasing to as much as ~7 %/decade around 46 hPa. Larger drifts, of around 7–11 %/decade, are seen in comparisons to balloon-borne frost point hygrometer measurements in the lower stratosphere. In contrast, the MLS v4 N2O product is shown to be generally decreasing over the same period (when an increase in stratospheric N2O is expected, reflecting a secular growth in emissions), with a more pronounced drift in the lower stratosphere than that found for H2O. Detailed investigations of the behavior of the MLS 190-GHz subsystem reveal a drift in its sideband fraction (the relative sensitivity of the 190-GHz receiver to the two different parts of the microwave spectrum it observes). Our studies indicate that sideband fraction drift accounts for much of the observed changes in the MLS H2O product and some portion of the changes seen in N2O. The 190-GHz sideband fraction drift has been corrected in the new version 5 MLS algorithms, which have now been used to reprocess the entire MLS record. As a result of this correction, the MLS v5 H2O record shows no statistically significant drifts compared to ACE-FTS. However, statistically significant drifts remain between MLS v5 and frost point measurements, though they are reduced. Drifts in v5 N2O are about half the size of those in v4 but remain statistically significant. Scientists are advised to use MLS v5 data in all future studies. Quantification of inter-regional and seasonal-to-annual changes in MLS H2O and N2O will not be affected by the drift. However, caution is advised in studies using the MLS record to examine long-term (multi-year) variability and trends in either of these species, especially N2O; such studies should only be undertaken in consultation with the MLS team. Importantly, this drift does not affect any of the MLS observations made in other spectral regions such as O3, HCl, CO, ClO, or temperature.

Deep ice as a geochemical reactor: insights from iron speciation and mineralogy of dust in the Talos Dome ice core (East Antarctica)

Thanks to its insolubility, mineral dust is considered a stable proxy in polar ice cores. With this study we show that below an ice-depth of 1000 m, the Talos Dome ice core (Ross Sea sector of East Antarctica) presents evident and progressive signs of post-depositional processes affecting the mineral dust records. We applied a suite of established and cutting edge techniques to investigate the properties of dust present in the Talos Dome ice core, ranging from concentration and grain-size to elemental-composition and Fe-mineralogy. Results show that through acidic/oxidative weathering, the conditions of deep ice at Talos Dome promote the dissolution of specific minerals and the englacial formation of others, deeply affecting dust primitive features. The expulsion of acidic atmospheric species from ice-grains and their concentration in localized environments is likely the main process responsible for englacial reactions and is related with ice re-crystallization. Deep ice can be seen as a "geochemical reactor" capable of fostering complex reactions which involve both soluble and insoluble impurities. Fe-bearing minerals can efficiently be used to explore such transformations.

Application of Cross-Track Infrared Sounder (CrIS) Instrument for Remote Detection of Agricultural NH3 Emissions over Netherlands

<p>Satellite observations have great potential for monitoring emissions and concentrations of atmospheric species. This is especially true for atmospheric ammonia (NH<sub>3</sub>), which varies greatly in space and time and is difficult to measure in-situ due to its sticky nature.  NH<sub>3</sub> measurements are important as NH<sub>3</sub> is a significant contributor to the production of secondary inorganic aerosols (PM2.5) and can add excessive reactive nitrogen to the environment. In this study we demonstrate how satellite remote sensing observations can be used to monitor changes in NH<sub>3</sub> concentrations by evaluating timeseries of Cross-Track Infrared Sounder (CrIS) satellite data with in-situ NH<sub>3</sub> concentrations and meteorological parameters (i.e. soil temperature and soil moisture). We provide an example demonstrating the capability to monitor the annual springtime increase in atmospheric NH<sub>3</sub> concentrations in Netherlands, which is mainly associated with farming practices (e.g. manure spreading on fields in the springtime). We then combine these satellite observations of NH<sub>3</sub> with meteorological conditions, with the goal of developing a model to predict the timing of ammonia emissions based on past agricultural practices in the area (e.g. artificial fertilizer and manure spreading).    </p>

Developing high-resolution simulations of tropospheric NO2 over Flanders using WRF-Chem

<p>Atmospheric chemistry is critical in determining air quality and thus impacts climate change. Anthropogenic species are released into the atmosphere, and undergo complex photochemical transformations leading to the production of secondary pollutants, among which ozone and particulate matter. This can induce adverse effects on human health, visibility, ecosystems and local meteorology.  The combination of state-of-the-art atmospheric models with accurate atmospheric measurements of atmospheric species abundances is needed to evaluate whether atmospheric models can successfully simulate the chemical and physical processes occurring, and hopefully monitor the emissions of anthropogenic compounds and help in the implementation and verification of abatement policies.</p><p>In this work, ground-based, airborne and spaceborne measuring techniques are used to evaluate the performance of the full chemistry on-line WRF-Chem model over Antwerp in Flanders, Belgium, one of the areas with the highest NO2 pollution in the world. The model is configured to allow two nested domains with spatial resolution changing from 5 to 1km, so as to pinpoint the most pollutant sources in the region, and applied to simulate the urban air quality over the Antwerp agglomeration.</p><p>We will briefly discuss the choices and adaptations made regarding the physical parameterizations, emission inventories and chemical mechanism. The model performance is evaluated through comparison with various observation types. The physics parameterizations in WRF model  are evaluated through comparison against ground-based data from two meteorological stations in the Antwerp region. The WRF-Chem NO2 distributions are evaluated against (1) hourly measured concentration values from monitoring stations in Flanders, (2) vertical columns measured by an airborne hyperspectral imager APEX, providing a 2-dimensional spatial mapping, on 27 and 29 June 2019, and (3) spaceborne NO2 columns over Belgium obtained from the high-resolution TROPOMI instrument aboard S5p. The consistency of the model biases across the three datasets will be discussed, and recommendations will be made for improving model performance in this region.</p>

A novel rocket-borne ion mass spectrometer with large mass range: instrument description and first-flight results

We present a novel rocket-borne ion mass spectrometer named ROMARA (ROcket-borne MAss spectrometer for Research in the Atmosphere) for measuring atmospheric positive and negative ions (atomic, molecular and cluster ions) and positively and negatively charged meteor smoke particles. Our ROMARA instrument has, compared to previous rocket-borne ion mass spectrometers, a markedly larger mass range of up to m/z 2000 and a larger sensitivity, particularly for meteor smoke particle detection. The major objectives of this first ROMARA flight included the following: a functional test of the ROMARA instrument, measurements between 55 and 121 km in the mass range of atmospheric positive and negative ions, a first attempt to conduct mass spectrometric measurements in the mass range of meteor smoke particles with mass-to-charge ratios up to m/z 2000, and measurements inside a polar mesospheric winter echo layer as detected by ground-based radar. Our ROMARA measurements took place on the Arctic island of Andøya, Norway, at around noon in April 2018 and represented an integral part of the polar mesospheric winter radar echo (PMWE) rocket campaign. During the rocket flight, ROMARA was operated in a measurement mode, offering maximum sensitivity and the ability to qualitatively detect total ion signatures even beyond its mass-resolving mass range. On this first ROMARA flight we were able to meet all of our objectives. We detected atmospheric species including positive atomic, molecular and cluster ions along with negative molecular ions up to about m/z 100. Above m/z 2000, ROMARA measured strong negative-ion signatures, which are likely due to negatively charged meteor smoke particles.

The application and improvement of TiO2 (titanate) based nanomaterials for the photoelectrochemical conversion of CO2 and N2 into useful products

In this review, we describe the photoelectrochemical (PEC) transformation of atmospheric species such as carbon dioxide (CO2) and nitrogen (N2) into useful industrial products on TiO2 and TiO2 composite photoelectrodes.

Computational mechanistic study of the unimolecular dissociation of ethyl hydroperoxide and its bimolecular reactions with atmospheric species

A detailed computational study of the atmospheric reaction of the simplest Criegee intermediate CH2OO with methane has been performed using the density functional theory (DFT) method and high-level calculations. Solvation models were utilized to address the effect of water molecules on prominent reaction steps and their associated energies. The structures of all proposed mechanisms were optimized using B3LYP functional with several basis sets: 6-31G(d), 6-31G (2df,p), 6-311++G(3df,3pd) and at M06-2X/6-31G(d) and APFD/6-31G(d) levels of theory. Furthermore, all structures were optimized at the B3LYP/6-311++G(3df,3pd) level of theory. The intrinsic reaction coordinate (IRC) analysis was performed for characterizing the transition states on the potential energy surfaces. Fifteen different mechanistic pathways were studied for the reaction of Criegee intermediate with methane. Both thermodynamic functions (ΔH and ΔG), and activation parameters (activation energies Ea, enthalpies of activation ΔHǂ, and Gibbs energies of activation ΔGǂ) were calculated for all pathways investigated. The individual mechanisms for pathways A1, A2, B1, and B2, comprise two key steps: (i) the formation of ethyl hydroperoxide (EHP) accompanying with the hydrogen transfer from the alkanes to the terminal oxygen atom of CIs, and (ii) a following unimolecular dissociation of EHP. Pathways from C1 → H1 involve the bimolecular reaction of EHP with different atmospheric species. The photochemical reaction of methane with EHP (pathway E1) was found to be the most plausible reaction mechanism, exhibiting an overall activation energy of 7 kJ mol−1, which was estimated in vacuum at the B3LYP/6-311++G(3df,3pd) level of theory. All of the reactions were found to be strongly exothermic, expect the case of the sulfur dioxide-involved pathway that is predicted to be endothermic. The solvent effect plays an important role in the reaction of EHP with ammonia (pathway F1). Compared with the gas phase reaction, the overall activation energy for the solution phase reaction is decreased by 162 and 140 kJ mol−1 according to calculations done with the SMD and PCM solvation models, respectively.