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Tropical Tropopause Layer cirrus clouds and their radiative effects represent a major uncertainty in the evaluation of Earth’s energy budget. High altitude aircraft offer an opportunity to provide observations at cirrus cloud altitudes, most commonly using in-situ measurements of ice particle optical properties and composition. In particular, remote sensing of scattering properties and near-IR ice water absorption in the limb can provide unique insights into thin and sub-visible cirrus clouds. Here we present novel spectroscopic observations of path-averaged ice water absorptions onboard NASA’s Global Hawk aircraft, during the Airborne Tropical TRopopause Experiment, which took place in 2011, 2013, and 2014. The University of California Los Angeles and University of Heidelberg mini-DOAS instrument provided multi-angle limb-scanning observations of scattered solar radiation in the near-IR (900–1726 nm), allowing the identification of ice and liquid water, O2, CO2 and H2O. The VLIDORT-QS radiative transfer (RT) code was specifically developed for this study and used to simulate high altitude limb observations for varied cloud scenarios. We performed a comprehensive sensitivity study, developing a fundamental understanding of airborne near-IR limb observations of cirrus clouds. We identified two general distinct cases: a linear regime for optically thin clouds, where the ice absorption is proportional to ice water content (IWC), and a regime for optically thick cirrus clouds, where ice absorption is in saturation and independent of IWC. Results also demonstrate how molecular oxygen absorption can be used to infer information on optical properties of ice particles in the second regime only, with minimal information for thin cirrus clouds. We also explored the feasibility of retrieving IWC from mini-DOAS path-averaged ice water absorption (SIWP) measurements. This innovative interpolation-based approach requires a small number of RT calculations per observation to determine the sensitivity of SIWP to IWC. Spectral retrievals were applied for a particularly interesting case during Science Flight 2 over Guam in February 2014, during which the aircraft flew in circles in the same general area for an extended period. Retrieved IWC results are consistent with independent in situ measurements from other instruments on board. The measurements of ice particle scattering and absorption at different azimuths relative to the sun and at different altitudes represents a unique opportunity to test our approach and to infer properties of the ice particles, together with information on cirrus cloud radiative transfer.

External cycling routes regenerating NOx from its oxidative reservoir, NOz, might reshape the temporal–spatial distribution of NOx and consequently OH, the most important atmospheric oxidant. However, the kinetics and mechanisms of the external cycling are still in dispute. Here, we present two critical pieces of evidence from aircraft observations in various atmospheric chemical regimes to verify the external cycling, i.e., unexpectedly high HONO/NO2 and NO2/NOy (≡ NOx + NOz) ratios and atypical HONO and NO2 diurnal profiles, both of which cannot be captured by GEOS-Chem modeling. Additionally, two features of the external cycling were portrayed, i.e., HONO as an intermediate for NOx production in the external cycling and promotion of the atmospheric photochemistry by external cycling in the low-NOx troposphere. Chemical model omitting the external cycling yields OH underestimation by 41% in low-NOx atmospheres. Our data provide a global view of the external cycling and its perturbations on the atmospheric oxidative capacity, which challenges the traditional view involving the continuous oxidative decay of NOx that leads to an extremely low abundance of NOx and thus suppressed OH in the troposphere.

Near-surface mercury and ozone depletion events occur in the lowest part of the atmosphere during Arctic spring. Mercury depletion is the first step in a process that transforms long-lived elemental mercury to more reactive forms within the Arctic that are deposited to the cryosphere, ocean, and other surfaces, which can ultimately get integrated into the Arctic food web. Depletion of both mercury and ozone occur due to the presence of reactive halogen radicals that are released from snow, ice, and aerosols. In this work, we added a detailed description of the Arctic atmospheric mercury cycle to our recently published version of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem 4.3.3) that includes Arctic bromine and chlorine chemistry and activation/recycling on snow and aerosols. The major advantage of our modelling approach is the online calculation of bromine concentrations and emission/recycling that is required to simulate the hourly and daily variability of Arctic mercury depletion. We used this model to study coupling between reactive cycling of mercury, ozone, and bromine during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) spring season in 2020 and evaluated results compared to land-based, ship-based, and remote sensing observations. The model predicts that elemental mercury oxidation is driven largely by bromine chemistry and that particulate mercury is the major form of oxidized mercury. The model predicts that the majority (74%) of oxidized mercury deposited to land-based snow is re-emitted to the atmosphere as gaseous elemental mercury, while a minor fraction (4%) of oxidized mercury that is deposited to sea ice is re-emitted during spring. Our work demonstrates that hourly differences in bromine/ozone chemistry in the atmosphere must be considered to capture the springtime Arctic mercury cycle, including its integration into the cryosphere and ocean.

Wintertime episodes of high aerosol concentrations occur frequently in urban and agricultural basins and valleys worldwide. These episodes often arise following development of persistent cold-air pools (PCAPs) that limit mixing and modify chemistry. While field campaigns targeting either basin meteorology or wintertime pollution chemistry have been conducted, coupling between interconnected chemical and meteorological processes remains an insufficiently studied research area. Gaps in understanding the coupled chemical–meteorological interactions that drive high-pollution events make identification of the most effective air-basin specific emission control strategies challenging. To address this, a September 2019 workshop occurred with the goal of planning a future research campaign to investigate air quality in western U.S. basins. Approximately 120 people participated, representing 50 institutions and five countries. Workshop participants outlined the rationale and design for a comprehensive wintertime study that would couple atmospheric chemistry and boundary layer and complex-terrain meteorology within western U.S. basins. Participants concluded the study should focus on two regions with contrasting aerosol chemistry: three populated valleys within Utah (Salt Lake, Utah, and Cache Valleys) and the San Joaquin Valley in California. This paper describes the scientific rationale for a campaign that will acquire chemical and meteorological datasets using airborne platforms with extensive range, coupled to surface-based measurements focusing on sampling within the near-surface boundary layer, and transport and mixing processes within this layer, with high vertical resolution at a number of representative sites. No prior wintertime basin-focused campaign has provided the breadth of observations necessary to characterize the meteorological–chemical linkages outlined here, nor to validate complex processes within coupled atmosphere–chemistry models.

The phenology of montane conifer forests is likely to shift in response to climate change and altered seasonal dynamics of light, temperature, and moisture. Solar-induced fluorescence (SIF) is expected to provide substantial improvement for mapping temporal changes in evergreen gross primary production (GPP) over greenness-based remote sensing indices. The utility of SIF to monitor seasonal changes in the phenology of conifer photosynthesis depends on the degree to which GPP and SIF respond in synchrony to key environmental drivers. However, to what extent SIF and GPP become decoupled by responding differently to the combined effects of light and other environmental conditions remains unknown. The goal of this study was to characterize the responses of GPP and SIFred to a suite of environmental drivers at the half-hour time scale and determine how these relationships change across seasons. We analyzed one year of tower-based SIFred and eddy covariance-derived GPP data from a conifer forest at Niwot Ridge, Colorado. We compared the light responses of GPP and SIFred across the year, finding that SIFred increased in response to light earlier in the year than did GPP. The light response of GPP had a positive temperature dependence in spring, and this dependency reversed in summer due to increased evaporative demand, while the light response of SIFred was less temperature dependent. Using artificial neural network ensemble analysis, we found that from spring to summer, SIFred did not exhibit a parallel response to the seasonally dynamic temperature and moisture controls on GPP. In summer SIFred was not correlated with canopy conductance, suggesting that SIF is less sensitive to stomatal control than GPP. Our results suggest that, in conifers, photosystems begin to activate in spring prior to when water becomes available for photosynthesis, presenting a challenge for the use of SIF as a phenological indicator in conifer forests.

Polar halogen chemistry has long been known to be active, especially in spring, and has an important influence on the lifetime of some volatile organics, ozone, and mercury. Reactive chlorine and bromine species, produced from snow and aerosols, can have significant impacts on the oxidative capacity of the polar boundary layer. However, halogen production mechanisms from snow remain highly uncertain, making it challenging to include descriptions of halogen snow emissions in models and to understand the impact on atmospheric chemistry. In this work, we investigate the role of Arctic chlorine and bromine emissions from snow on boundary layer oxidation processes using a one-dimensional atmospheric chemistry and transport model (PACT-1D). We explore the impact of halogen snow emissions and boundary layer dynamics on atmospheric chemistry by modelling primary emissions of Cl2 and Br2 from snow, and heterogeneous recycling reactions on snow and aerosols. We present a two-day case study from the 2009 Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) campaign at Utqiagvik, Alaska. The model reproduces both the diurnal cycle and high quantity of Cl2 measured, along with the observed concentrations of Br2, BrO, and HOBr. Due to a combination of chemical emissions, recycling, vertical mixing, and atmospheric chemistry, reactive chlorine is confined to the lowest 15 m of the atmosphere, whilst bromine impacts chemistry up to the boundary layer height. Following the inclusion of halogen emissions and recycling, HOx concentrations (HOx = OH+HO2) increase by as much as a factor of 30 at the surface at mid-day. Consequently, volatile organic compound (VOC) lifetimes are significantly reduced within a shallow layer near the surface, due to chlorine atoms from Cl2 snow emissions and increased HOx attributable to halogen chemistry.

Remote sensing of solar-induced chlorophyll fluorescence (SIF) provides a powerful proxy for gross primary productivity (GPP). It is particularly promising in boreal ecosystems where seasonal downregulation of photosynthesis occurs without significant changes in canopy structure or chlorophyll content. The use of SIF as a proxy for GPP is complicated by inherent non-linearities due to both physical (illumination effects) and ecophysiological (light use efficiencies) controls at fine spatial (tower/leaf) and temporal (half-hourly) scales. To study the SIF-GPP relationship, we investigated the diurnal and seasonal dynamics of continuous tower-based measurements of SIF, GPP, and common vegetation indices at the Southern Old Black Spruce Site (SOBS) in Saskatchewan, CA over the course of two years. We find that SIF outperforms other vegetation indices as a proxy for GPP at all temporal scales but shows a non-linear relationship with GPP at a half-hourly resolution. At small temporal scales, SIF and GPP are predominantly driven by light and non-linearity between SIF and GPP is due to the light saturation of GPP. Averaged over daily and monthly scales, the relationship between SIF and GPP is linear due to a reduction in the observed PAR range. Seasonal changes in the light responses of SIF and GPP are driven by changes in light use efficiency which co-vary with changes in temperature, while illumination and canopy structure partially linearize the SIF-GPP relationship. Additionally, we find that the SIF-GPP relationship has a seasonal dependency. Our results help clarify the utility of SIF for estimating carbon assimilation in boreal forests.

Elevated concentrations of atmospheric bromine are known to cause ozone depletion in the Arctic, which is most frequently observed during springtime. We implement a detailed description of bromine and chlorine chemistry within the WRF‐Chem 4.1.1 model, and two different descriptions of Arctic bromine activation: (1) heterogeneous chemistry on surface snow on sea ice, triggered by ozone deposition to snow (Toyota et al., 2011 https://doi.org/10.5194/acp-11-3949-2011), and (2) heterogeneous reactions on sea salt aerosols emitted through the sublimation of lofted blowing snow (Yang et al., 2008, https://doi.org/10.1029/2008gl034536). In both mechanisms, bromine activation is sustained by heterogeneous reactions on aerosols and surface snow. Simulations for spring 2012 covering the entire Arctic reproduce frequent and widespread ozone depletion events, and comparisons with observations of ozone show that these developments significantly improve model predictions during the Arctic spring. Simulations show that ozone depletion events can be initiated by both surface snow on sea ice, or by aerosols that originate from blowing snow. On a regional scale, in spring 2012, snow on sea ice dominates halogen activation and ozone depletion at the surface. During this period, blowing snow is a major source of Arctic sea salt aerosols but only triggers a few depletion events., Key Points Halogen activation and its role in Arctic surface ozone depletion events (ODEs) is modeled using WRF‐ChemTwo halogen activation mechanisms are implemented (1) surface snow and (2) blowing snowA spring 2012 case study indicates that both mechanisms can trigger near‐surface ODEs, but that surface snow dominates

Traditional methods of carbon monitoring in mountainous regions are challenged by complex terrain. Recently, solar‐induced fluorescence (SIF) has been found to be an indicator of gross primary production (GPP), and the increased availability of remotely sensed SIF provides an opportunity to estimate GPP across the Western United States. Although the empirical linkage between SIF and GPP is strong, the current mechanistic understanding of this linkage is incomplete and depends upon changes in leaf biochemical processes in which absorbed sunlight leads to photochemistry, heat (via nonphotochemical quenching [NPQ]), fluorescence, or tissue damage. An improved mechanistic understanding is necessary to leverage SIF observations to improve representation of ecosystem processes within land surface models. Here we included an improved fluorescence model within the Community Land Model, Version 4.5 (CLM 4.5), to simulate seasonal changes in SIF at a subalpine forest in Colorado. We found that when the model accounted for sustained NPQ, this provided a larger seasonal change in fluorescence yield leading to simulated SIF that more closely resembled the observed seasonal pattern (Global Ozone Monitoring Experiment‐2 [GOME‐2] satellite platform and a tower‐mounted spectrometer system). We found that an acclimation model based on mean air temperature was a useful predictor for sustained NPQ. Although light intensity was not an important factor for this analysis, it should be considered before applying the sustained NPQ and SIF to other cold climate evergreen biomes. More leaf‐level fluorescence measurements are necessary to better understand the seasonal relationship between sustained and reversible components of NPQ and to what extent that influences SIF.

Northern hemisphere evergreen forests assimilate a significant fraction of global atmospheric CO 2 but monitoring large-scale changes in gross primary production (GPP) in these systems is challenging. Recent advances in remote sensing allow the detection of solar-induced chlorophyll fluorescence (SIF) emission from vegetation, which has been empirically linked to GPP at large spatial scales. This is particularly important in evergreen forests, where traditional remote-sensing techniques and terrestrial biosphere models fail to reproduce the seasonality of GPP. Here, we examined the mechanistic relationship between SIF retrieved from a canopy spectrometer system and GPP at a winter-dormant conifer forest, which has little seasonal variation in canopy structure, needle chlorophyll content, and absorbed light. Both SIF and GPP track each other in a consistent, dynamic fashion in response to environmental conditions. SIF and GPP are well correlated ( R 2 = 0.62–0.92) with an invariant slope over hourly to weekly timescales. Large seasonal variations in SIF yield capture changes in photoprotective pigments and photosystem II operating efficiency associated with winter acclimation, highlighting its unique ability to precisely track the seasonality of photosynthesis. Our results underscore the potential of new satellite-based SIF products (TROPOMI, OCO-2) as proxies for the timing and magnitude of GPP in evergreen forests at an unprecedented spatiotemporal resolution.

Polar halogen chemistry has long been known to be active, especially in spring, and is known to have an important influence on the lifetime of some volatile organics, ozone and mercury. Our understanding of polar halogen chemistry is changing, including the recognition that there is active chlorine, bromine and iodine chemistry occurring within the polar boundary. Recently, very high concentrations of molecular chlorine (Cl2) were recorded at Utqiaġvik, Alaska during the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) campaign in spring 2009, with a correlation between daytime Cl2 mixing ratios, ozone concentrations and sunlight. However, the chlorine radical concentrations inferred from these Cl2 measurements, with the observed VOC abundances and lifetimes, cannot yet be fully explained via chemical box modelling alone. To explain these discrepancies, modelling that includes surface snow Cl2 formation processes, subsequent atmospheric chemistry and vertical mixing is needed and is an essential tool in quantifying impacts on VOC lifetimes and the role of vertical mixing in controlling boundary layer chemistry.In this work, we use a one-dimensional atmospheric chemistry and transport model (Platform for Atmospheric Chemistry and Transport in 1-Dimension, PACT-1D) to investigate surface Cl2 production from snow, snowpack recycling, vertical transport and reactivity with VOCs at Utqiaġvik, Alaska during the OASIS campaign. We implement a new surface parameterization of chlorine emissions from the snowpack based on the solar irradiance and surface ozone levels and consider the role of vertical mixing processes. By considering both production and transport mechanisms, we are able to obtain good agreement between the model predicted Cl2 mixing ratios and observations at 1.5 meters. The model predicts that nearly all reactive chlorine resides within the lowest 15 m of the boundary layer, resulting in increased chemical reactivities and oxidation rates in the lowest part of the atmosphere. VOC abundances near the surface that are co-located with elevated chlorine can be explained by downward mixing of VOCs from aloft, which replenishes VOCs from free tropospheric reservoirs. The proposed surface emission parameterization of chlorine in this work could be used to develop current 3D numerical models in order to explore chlorine emissions and reactivity over the entire Arctic as well as the effects of future Arctic climate scenarios on atmospheric halogen chemistry.

Solar-Induced chlorophyll Fluorescence (SIF) provides a powerful proxy for determining forest gross primary production (GPP), particularly in evergreen ecosystems where traditional measures of gree...

International audience; Nitrous acid (HONO) is an important radical precursor that can impact secondary pollutant levels, especially in urban environments. Due to uncertainties in its heterogeneous formation mechanisms, models often under predict HONO concentrations. A number of heterogeneous sources at the ground have been proposed but there is no consensus about which play a significant role in the urban boundary layer. We present a new one-dimensional chemistry and transport model which performs surface chemistry based on molecular collisions and chemical conversion, allowing us to add detailed HONO formation chemistry at the ground. We conducted model runs for the 2010 CalNex campaign, finding good agreement with observations for key species such as O3, NOx, and HOx. With the ground sources implemented, the model captures the diurnal and vertical profile of the HONO observations. Primary HOx production from HONO photolysis is 2–3 times more important than O3 or HCHO photolysis at mid-day, below 10 m. The HONO concentration, and its contribution to HOx, decreases quickly with altitude. Heterogeneous chemistry at the ground provided a HONO source of 2.5 × 1011 molecules cm−2 s−1 during the day and 5 × 1010 molecules cm−2 s−1 at night. The night time source was dominated by NO2 hydrolysis. During the day, photolysis of surface HNO3/nitrate contributed 45%–60% and photo-enhanced conversion of NO2 contributed 20%–45%. Sensitivity studies addressing the uncertainties in both photolytic mechanisms show that, while the relative contribution of either source can vary, HNO3/nitrate is required to produce a surface HONO source that is strong enough to explain observations.

Timely and accurate monitoring of crops is essential for food security. Here, we examine how well solar-induced chlorophyll fluorescence (SIF) can inform crop productivity across the United States. Based on tower-level observations and process-based modeling, we find highly linear gross primary production (GPP):SIF relationships for C4 crops, while C3 crops show some saturation of GPP at high light when SIF continues to increase. C4 crops yield higher GPP:SIF ratios (30�50) primarily because SIF is most sensitive to the light reactions (does not account for photorespiration). Scaling to the satellite, we compare SIF from the TROPOspheric Monitoring Instrument (TROPOMI) against tower-derived GPP and county-level crop statistics. Temporally, TROPOMI SIF strongly agrees with GPP observations upscaled across a corn and soybean dominated cropland (R2 = 0.89). Spatially, county-level TROPOMI SIF correlates with crop productivity (R2 = 0.72; 0.86 when accounting for planted area and C3/C4 contributions), highlighting the potential of SIF for reliable crop monitoring. ©2020. American Geophysical Union. All Rights Reserved.

Recent successes in passive remote sensing of far-red solar induced chlorophyll fluorescence (SIF) have spurred development and integration of canopy-level fluorescence models in global terrestrial biosphere models (TBMs) for climate and carbon cycle research. The interaction of fluorescence with photochemistry at the leaf- and canopy- scale provides opportunities to diagnose and constrain model simulations of photosynthesis and related processes, through direct comparison to and assimilation of tower, airborne, and satellite data. TBMs describe key processes relating to absorption of sunlight, leaf-level fluorescence emission, scattering and reabsorption throughout the canopy. Here, we analyze simulations from an ensemble of process-based TBM-SIF models (SiB3, SiB4, CLM4.5, CLM5.0, BETHY, ORCHIDEE, BEPS) at a subalpine evergreen needleleaf forest near Niwot Ridge, Colorado. These models are forced with tower observed meteorological data, and analyzed against continuous far-red SIF and gross primary productivity (GPP) partitioned eddy covariance data at diurnal and synoptic scales during the growing season (July–August 2017). Our primary objective is to summarize the site-level state of the art in TBM-SIF modeling over a relatively short time period (summer) when light, structure, and pigments are similar, setting the stage for regional- to global-scale analyses. We find that these models are generally well constrained in simulating photosynthetic yield, but show strongly divergent patterns in the simulation of absorbed photosynthetic active radiation (PAR), absolute GPP and fluorescence, quantum yields, and light response at leaf and canopy scale. This study highlights the need for mechanistic modeling of non-photochemical quenching in stressed and unstressed environments, and improved representation of light absorption (APAR), distribution of sunlit and shaded light, and radiative transfer from leaf to canopy scale.

To study regional-scale carbon dioxide (CO2) transport, temporal variability, and budget over the Southern California Air Basin (SoCAB) during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign period, a model that couples the Weather Research and Forecasting (WRF) Model with the Vegetation Photosynthesis and Respiration Model (VPRM) has been used. Our numerical simulations use anthropogenic CO2 emissions of the Hestia Project 2010 fossil-fuel CO2 emissions data products along with optimized VPRM parameters at “FLUXNET” sites, for biospheric CO2 fluxes over SoCAB. The simulated meteorological conditions have been validated with ground and aircraft observations, as well as with background CO2 concentrations from the coastal Palos Verdes site. The model captures the temporal pattern of CO2 concentrations at the ground site at the California Institute of Technology in Pasadena, but it overestimates the magnitude in early daytime. Analysis of CO2 by wind directions reveals the overestimate is due to advection from the south and southwest, where downtown Los Angeles is located. The model also captures the vertical profile of CO2 concentrations along with the flight tracks. The optimized VPRM parameters have significantly improved simulated net ecosystem exchange at each vegetation-class site and thus the regional CO2 budget. The total biospheric contribution ranges approximately from −24% to −20% (daytime) of the total anthropogenic CO2 emissions during the study period.

Formaldehyde (HCHO) is either directly emitted from sources or produced during the oxidation of volatile organic compounds (VOCs) in the troposphere. It is possible to infer atmospheric HCHO concentrations using space-based observations, which may be useful for studying emissions and tropospheric chemistry at urban to global scales depending on the quality of the retrievals. In the near future, an unprecedented volume of satellite-based HCHO measurement data will be available from both geostationary and polar-orbiting platforms. Therefore, it is essential to develop retrieval methods appropriate for the next-generation satellites that measure at higher spatial and temporal resolution than the current ones. In this study, we examine the importance of fine spatial and temporal resolution a priori profile information on the retrieval by conducting approximately 45 000 radiative transfer (RT) model calculations in the Los Angeles Basin (LA Basin) megacity. Our analyses suggest that an air mass factor (AMF, a factor converting observed slant columns to vertical columns) based on fine spatial and temporal resolution a priori profiles can better capture the spatial distributions of the enhanced HCHO plumes in an urban area than the nearly constant AMFs used for current operational products by increasing the columns by ∼ 50 % in the domain average and up to 100 % at a finer scale. For this urban area, the AMF values are inversely proportional to the magnitude of the HCHO mixing ratios in the boundary layer. Using our optimized model HCHO results in the Los Angeles Basin that mimic the HCHO retrievals from future geostationary satellites, we illustrate the effectiveness of HCHO data from geostationary measurements for understanding and predicting tropospheric ozone and its precursors.

During the Benzene and other Toxics Exposure (BEE-TEX) study, a remote sensing network based on long path Differential Optical Absorption Spectroscopy (DOAS) was set up in the Manchester neighborhood beside the Ship Channel of Houston, Texas in order to perform Computer Aided Tomography (CAT) scans of hazardous air pollutants. On 18–19 February 2015, the CAT scan network detected large nocturnal plumes of toluene and xylenes most likely associated with railcar loading and unloading operations at Ship Channel petrochemical facilities. The presence of such plumes during railcar operations was confirmed by a mobile laboratory equipped with a Proton Transfer Reaction—Mass Spectrometer (PTR-MS), which measured transient peaks of toluene and C 2 -benzenes of 50 ppb and 57 ppb respectively around 4 a.m. LST on 19 February 2015. Plume reconstruction and source attribution were performed using the 4D variational data assimilation technique and a 3D micro-scale forward and adjoint air quality model based on both tomographic and PTR-MS data. Inverse model estimates of fugitive emissions associated with railcar transfer emissions ranged from 2.0 to 8.2 kg/hr for toluene and from 2.2 to 3.5 kg/hr for xylenes in the early morning of 19 February 2015.

We report measurements of CH4 (measured in situ by the Harvard University Picarro Cavity Ringdown Spectrometer (HUPCRS) and NOAA Unmanned Aircraft System Chromatograph for Atmospheric Trace Species (UCATS) instruments), O3 (measured in situ by the NOAA dual-beam ultraviolet (UV) photometer), NO2, BrO (remotely detected by spectroscopic UV–visible (UV–vis) limb observations; see the companion paper of Stutz et al., 2016), and of some key brominated source gases in whole-air samples of the Global Hawk Whole Air Sampler (GWAS) instrument within the subtropical lowermost stratosphere (LS) and the tropical upper troposphere (UT) and tropopause layer (TTL). The measurements were performed within the framework of the NASA-ATTREX (National Aeronautics and Space Administration – Airborne Tropical Tropopause Experiment) project from aboard the Global Hawk (GH) during six deployments over the eastern Pacific in early 2013. These measurements are compared with TOMCAT/SLIMCAT (Toulouse Off-line Model of Chemistry And Transport/Single Layer Isentropic Model of Chemistry And Transport) 3-D model simulations, aiming at improvements of our understanding of the bromine budget and photochemistry in the LS, UT, and TTL.Changes in local O3 (and NO2 and BrO) due to transport processes are separated from photochemical processes in intercomparisons of measured and modeled CH4 and O3. After excellent agreement is achieved among measured and simulated CH4 and O3, measured and modeled [NO2] are found to closely agree with ≤ 15 ppt in the TTL (which is the detection limit) and within a typical range of 70 to 170 ppt in the subtropical LS during the daytime. Measured [BrO] ranges between 3 and 9 ppt in the subtropical LS. In the TTL, [BrO] reaches 0.5 ± 0.5 ppt at the bottom (150 hPa∕355 K∕14 km) and up to about 5 ppt at the top (70 hPa∕425 K∕18.5 km; see Fueglistaler et al., 2009 for the definition of the TTL used), in overall good agreement with the model simulations. Depending on the photochemical regime, the TOMCAT∕SLIMCAT simulations tend to slightly underpredict measured BrO for large BrO concentrations, i.e., in the upper TTL and LS. The measured BrO and modeled BrO ∕ Bryinorg ratio is further used to calculate inorganic bromine, Bryinorg. For the TTL (i.e., when [CH4] ≥ 1790 ppb), [Bryinorg] is found to increase from a mean of 2.63 ± 1.04 ppt for potential temperatures (θ) in the range of 350–360 K to 5.11 ± 1.57 ppt for θ = 390 − 400 K, whereas in the subtropical LS (i.e., when [CH4] ≤ 1790 ppb), it reaches 7.66 ± 2.95 ppt for θ in the range of 390–400 K. Finally, for the eastern Pacific (170–90° W), the TOMCAT/SLIMCAT simulations indicate a net loss of ozone of −0.3 ppbv day−1 at the base of the TTL (θ = 355 K) and a net production of +1.8 ppbv day−1 in the upper part (θ = 383 K).

The February–March 2014 deployment of the National Aeronautics and Space Administration (NASA) Airborne Tropical Tropopause Experiment (ATTREX) provided unique in situ measurements in the western Pacific tropical tropopause layer (TTL). Six flights were conducted from Guam with the long-range, high-altitude, unmanned Global Hawk aircraft. The ATTREX Global Hawk payload provided measurements of water vapor, meteorological conditions, cloud properties, tracer and chemical radical concentrations, and radiative fluxes. The campaign was partially coincident with the Convective Transport of Active Species in the Tropics (CONTRAST) and the Coordinated Airborne Studies in the Tropics (CAST) airborne campaigns based in Guam using lower-altitude aircraft (see companion articles in this issue). The ATTREX dataset is being used for investigations of TTL cloud, transport, dynamical, and chemical processes, as well as for evaluation and improvement of global-model representations of TTL processes. The ATTREX data are publicly available online (at https://espoarchive.nasa.gov/).

Aromatic hydrocarbons are well known air toxics which are regulated by the US EPA and other air quality agencies. Accurate, long-term monitoring of these compounds at low part-per-billion levels, as well as identifying emission point sources is therefore crucial to protect human health in neighborhoods near large emission sources. Here we present a new long-path differential optical absorption spectroscopy (LP-DOAS) instrument specifically designed to monitor aromatic hydrocarbons. The system is based on a novel dual - light emitting diode (LED) light source, which eliminates the requirement to suppress spectrometer stray light. This light source, together with a high stability fiber-based sending/receiving telescope, allows the measurement of aromatic hydrocarbons on once-folded absorptions paths of 200–1200 m length. The new instrument shows very good agreement with simultaneous in-situ measurements if inhomogeneities of the trace gas spatial distributions are considered. The new instrument performed well during a three-month field test as an automated fence-line monitor at a refinery, successfully distinguishing upwind background levels of ∼1 ppb from emissions reflected in elevated mixing ratios of 3–4 ppb. A two-dimensional measurement network based on two identical LP-DOAS instruments operating on seven crossed light paths was operated successfully in Houston, TX. Qualitative and quantitative analysis of two events with toluene and xylene plumes demonstrate how this setup can be used to derive the spatial distribution of aromatic hydrocarbons, and identify point sources.

Nighttime chemistry in the troposphere is closely tied to the dinitrogen pentoxide (N2O5) budget, but high uncertainties remain regarding the model representation of the heterogeneous hydrolysis of N2O5 on aerosol particles. In this study we used the community model WRF-Chem to simulate a 3-day period during the California Nexus (CalNex) Campaign in 2010. We extended WRF-Chem to include the heterogeneous hydrolysis of N2O5 and contrasted the impact of different published parameterizations of N2O5 heterogeneous hydrolysis on the spatial distribution of uptake coefficients and the resulting N2O5 concentrations. For all the cases, modeled N2O5 uptake coefficients showed strong spatial variability, with higher values in the nocturnal boundary layer compared to the residual layer, especially in environments with high relative humidities, such as over the ocean and along the coast. The best agreement of modeled and observed uptake coefficients was obtained using the parameterization by Davis et al. (2008) combined with the treatment of organic coating by Riemer et al. (2009). For this case the temporal evolution of lower boundary layer N2O5 mixing ratios was reproduced well, and the predictions of surface mixing ratios of ozone and NOx were improved. However, the model still overpredicted the uptake coefficients in the residual layer and consequently underpredicted N2O5 concentrations in the residual layer. This study also highlights that environments with low relative humidities pose a challenge for aerosol thermodynamic models in calculating aerosol water uptake, and this impacts N2O5 heterogeneous hydrolysis parameterizations.

Atmospheric absorption in the O2 A-band (12 950–13 200 cm−1) offers a unique opportunity to retrieve aerosol extinction profiles from space-borne measurements due to the large dynamic range of optical thickness in that spectral region. Absorptions in strong O2 lines are saturated; therefore, any radiance measured in these lines originates from scattering in the upper part of the atmosphere. Outside of O2 lines, or in weak lines, the atmospheric column absorption is small, and light penetrates to lower atmospheric layers, allowing for the quantification of aerosols and other scatterers near the surface.While the principle of aerosol profile retrieval using O2 A-band absorption from space is well-known, a thorough quantification of the information content, i.e., the amount of vertical profile information that can be obtained, and the dependence of the information content on the spectral resolution of the measurements, has not been thoroughly conducted. Here, we use the linearized vector radiative transfer model VLIDORT to perform spectrally resolved simulations of atmospheric radiation in the O2 A-band for four different aerosol extinction profile scenarios: urban (urban–rural areas), highly polluted (megacity areas with large aerosol extinction), elevated layer (identifying elevated plumes, for example for biomass burning) and low extinction (representative of small aerosol extinction, such as vegetated, marine and arctic areas). The high-resolution radiances emerging from the top of the atmosphere measurements are degraded to different spectral resolutions, simulating spectrometers with different resolving powers. We use optimal estimation theory to quantify the information content in the aerosol profile retrieval with respect to different aerosol parameters and instrument spectral resolutions. The simulations show that better spectral resolution generally leads to an increase in the total amount of information that can be retrieved, with the number of degrees of freedom (DoF) varying between 0.34–2.01 at low resolution (5 cm−1) to 3.43–5.38 at high resolution (0.05 cm−1) among all the different cases. A particularly strong improvement was found in the retrieval of tropospheric aerosol extinction profiles in the lowest 5 km of the atmosphere. At high spectral resolutions (0.05 cm−1), 1.18–1.48 and 1.31–1.96 DoF can be obtained in the lower (0–2 km) and middle (2–5 km) troposphere, respectively, for the different cases. Consequently, a separation of lower and mid tropospheric aerosols is possible, implying the feasibility of identification of elevated biomass burning aerosol plumes (elevated layer scenario). We find that a higher single scattering albedo (SSA) allows for the retrieval of more aerosol information. However, the dependence on SSA is weaker at higher spectral resolutions. The vegetation (surface albedo 0.3), marine (surface albedo 0.05) and arctic (surface albedo 0.9) cases show that the dependence of DoF on the surface albedo decreases with higher resolution. At low resolution (5 cm−1), the DoF are 1.19 for the marine case, 0.73 for the vegetation case and 0.34 for the arctic case, but increase considerably at 0.05 cm−1 resolution to 3.84 (marine) and 3.43 (both vegetation and arctic), showing an improvement of a factor of 10 for the arctic case. Vegetation and arctic case also show the same DoF at higher resolution, showing that an increase of albedo beyond a certain value, i.e., 0.3 in our case, does not lead to a larger information content. The simulations also reveal a moderate dependence of information content on the integration time of the measurements, i.e., the noise of the spectra. However, our results indicate that a larger increase in DoF is obtained by an increase in spectral resolution despite lower signal-to-noise ratios.

International audience; Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex-LA 2010 campaign using the laser-induced fluorescence-fluorescence assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero-dimensional model using the Regional Atmospheric Chemical Mechanism-2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.

High wintertime ozone levels have been observed in the Uintah Basin, Utah, a sparsely populated rural region with intensive oil and gas operations. The reactive nitrogen budget plays an important role in tropospheric ozone formation. Measurements were taken during three field campaigns in the winters of 2012, 2013 and 2014, which experienced varying climatic conditions. Average concentrations of ozone and total reactive nitrogen were observed to be 2.5 times higher in 2013 than 2012, with 2014 an intermediate year in most respects. However, photochemically active NOx (NO + NO2) remained remarkably similar all three years. Nitric acid comprised roughly half of NOz ( ≡ NOy − NOx) in 2013, with nighttime nitric acid formation through heterogeneous uptake of N2O5 contributing approximately 6 times more than daytime formation. In 2012, N2O5 and ClNO2 were larger components of NOz relative to HNO3. The nighttime N2O5 lifetime between the high-ozone year 2013 and the low-ozone year 2012 is lower by a factor of 2.6, and much of this is due to higher aerosol surface area in the high-ozone year of 2013. A box-model simulation supports the importance of nighttime chemistry on the reactive nitrogen budget, showing a large sensitivity of NOx and ozone concentrations to nighttime processes.

Solar-Induced Chlorophyll Fluorescence (SIF) is an emission of light in the 650–850 nm spectral range from the excited state of the chlorophyll-a pigment after absorption of photosynthetically active radiation (PAR). As this is directly linked to the electron transport chain in oxygenic photosynthesis, SIF is a powerful proxy for photosynthetic activity. SIF observations are relatively new and, while global scale measurements from satellites using high-resolution spectroscopy of Fraunhofer bands are becoming more available, observations at the intermediate canopy scale using these techniques are sparse. We present a novel ground-based spectrometer system - PhotoSpec - for measuring SIF in the red (670–732 nm) and far-red (729–784 nm) wavelength range as well as canopy reflectance (400–900 nm) to calculate vegetation indices, such as the normalized difference vegetation index (NDVI), the enhanced vegetation index (EVI), and the photochemical reflectance index (PRI). PhotoSpec includes a 2D scanning telescope unit which can be pointed to any location in a canopy with a narrow field of view (FOV = 0.7°). PhotoSpec has a high signal-to-noise ratio and spectral resolution, which allows high precision solar Fraunhofer line retrievals over the entire fluorescence wavelength range under all atmospheric conditions using a new two-step linearized least-squares retrieval procedure. Initial PhotoSpec observations include the diurnal SIF cycle of single broad leaves, grass, and dark-light transitions. Results from the first tower-based measurements in Costa Rica show that the instrument can continuously monitor SIF of several tropical species throughout the day. The PhotoSpec instrument can be used to explore the relationship between SIF, photosynthetic efficiencies, Gross Primary Productivity (GPP), and the impact of canopy radiative transfer, viewing geometry, and stress conditions at the canopy scale.

The Southeast Atmosphere Studies (SAS), which included the Southern Oxidant and Aerosol Study (SOAS); the Southeast Nexus (SENEX) study; and the Nitrogen, Oxidants, Mercury and Aerosols: Distributions, Sources and Sinks (NOMADSS) study, was deployed in the field from 1 June to 15 July 2013 in the central and eastern United States, and it overlapped with and was complemented by the Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. SAS investigated atmospheric chemistry and the associated air quality and climate-relevant particle properties. Coordinated measurements from six ground sites, four aircraft, tall towers, balloon-borne sondes, existing surface networks, and satellites provide in situ and remotely sensed data on trace-gas composition, aerosol physicochemical properties, and local and synoptic meteorology. Selected SAS findings indicate 1) dramatically reduced NOx concentrations have altered ozone production regimes; 2) indicators of “biogenic” secondary organic aerosol (SOA), once considered part of the natural background, were positively correlated with one or more indicators of anthropogenic pollution; and 3) liquid water dramatically impacted particle scattering while biogenic SOA did not. SAS findings suggest that atmosphere–biosphere interactions modulate ambient pollutant concentrations through complex mechanisms and feedbacks not yet adequately captured in atmospheric models. The SAS dataset, now publicly available, is a powerful constraint to develop predictive capability that enhances model representation of the response and subsequent impacts of changes in atmospheric composition to changes in emissions, chemistry, and meteorology.

Here we report the measurement results of nitrous acid (HONO) and a suite of relevant parameters on the NCAR C-130 research aircraft in the Southeast U.S. during NOMADSS 2013 summer field study. Daytime HONO concentrations ranged from low parts per trillion by volume (pptv) in the free troposphere (FT) to mostly within 5–15 pptv in the background terrestrial air masses, and to up to 40 pptv in the industrial and urban plumes in the planetary boundary layer (PBL). There was no discernable vertical HONO distribution trend in the PBL above the lowest flight altitude of 300 m, indicating that the ground surface HONO source was not a significant contributor to the HONO budget in the measurement altitude between 300 m and 4.7 km. While there was a strong correlation between the concentrations of HONO and oxides of nitrogen (NOx = NO + NO2) (R2 = 0.52), the sum of all known NOx-related HONO formation mechanisms was found to account for less 20 % of the daytime HONO source in the background terrestrial air masses, due to the low level of NOx and surface area density of aerosol particles. Photolysis of particulate nitrate (pNO3) appeared to be the major daytime HONO source in the background terrestrial air masses, based on the measured pNO3 concentration and the median value of 2.0 × 10−4 s−1 for pNO3 photolysis rate constant determined in the laboratory using ambient aerosol samples collected during the field study. Within the power plant and industrial plumes encountered, daytime HONO was predominantly produced by secondary formation processes involving both NOx and pNO3 as precursors. While HONO was not a significant OH precursor compared to O3 under low NOx conditions in the air column, it was an important intermediate product of a photochemical renoxification process recycling nitric acid and nitrate back to NOx. Finally, the HONO / NOx ratio stayed relatively constant for several hours after sunset in the nocturnal residual layer, suggesting no significant night-time volume HONO source existed in the nocturnal residual layer and the nocturnal FT under background conditions.

We analyze an expanded data set of oxygenated volatile organic compounds (OVOCs) in air measured by several instruments at a surface site in Pasadena near Los Angeles during the National Oceanic and Atmospheric Administration California Nexus study in 2010. The contributions of emissions, chemical formation, and removal are quantified for each OVOC using CO as a tracer of emissions and the OH exposure of the sampled air masses calculated from hydrocarbon ratios. The method for separating emissions from chemical formation is evaluated using output for Pasadena from the Weather Research and Forecasting-Chemistry model. The model is analyzed by the same method as the measurement data, and the emission ratios versus CO calculated from the model output agree for ketones with the inventory used in the model but overestimate aldehydes by ~70%. In contrast with the measurements, nighttime formation of OVOCs is significant in the model and is attributed to overestimated precursor emissions and overestimated rate coefficients for the reactions of the precursors with ozone and NO3. Most measured aldehydes correlated strongly with CO at night, suggesting a contribution from motor vehicle emissions. However, the emission ratios of most aldehydes versus CO are higher than those reported in motor vehicle emissions and the aldehyde sources remain unclear. Formation of several OVOCs is investigated in terms of the removal of specific precursors. Direct emissions of alcohols and aldehydes contribute significantly to OH reactivity throughout the day, and these emissions should be accurately represented in models describing ozone formation. ©2018. American Geophysical Union. All Rights Reserved.

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

The chemical mechanisms used in regulatory air quality models typically allow for only homogeneous formation of nitrous acid (HONO), an important radical precursor. This study adds heterogeneous formation on surfaces as a HONO source to the Comprehensive Air quality Model with extensions (CAMx). Modeling was performed for the Houston, Texas, region on April 21, 2009. Comparisons to measurements made at Moody Tower during the Study of Houston Atmospheric Radical Precursors (SHARP) show that adding heterogeneous formation increases HONO concentrations, particularly in the early morning and at night. Heterogeneous HONO formation reduces normalized mean error for morning, daytime, and nighttime HONO concentrations from 77% to 67%, 66%–28%, and 99%–67%. Maximum daily 8-hr O3 concentrations were up to 3.5 ppb greater as a result of heterogeneous HONO formation. Direct HONO emissions equal to 0.8% of NOx emissions were also added to the model, but they were considered separately from heterogeneous HONO formation. Increases over the base case of HONO and O3 were seen, though the magnitudes are not as great as with heterogeneous HONO formation. Maximum daily 8-hr O3 concentrations were up to 0.4 ppb greater than with homogeneous HONO formation alone. Significant early morning and nighttime HONO under predictions were seen compared to SHARP measurements in the direct emissions scenario. Direct HONO emissions led to local increases of HONO and O3 in areas with high NOx emissions, but heterogeneous HONO formation led to regional increases of both. Process analysis was used to determine the effect on O3 chemistry in downtown Houston. Daily total hydroxyl radical (OH) production from HONO photolysis was 3.94 ppb/day with heterogeneous HONO formation, 2.40 ppb/day with direct emissions, and 1.40 ppb/day in the base case. A 10% increase of hydrocarbon and carbon monoxide oxidation by OH was seen with heterogeneous HONO formation, while the increase in the direct emissions scenario was 3%. Nitric oxide (NO) to NO2 conversion increased by 8% with heterogeneous formation, while the increase was only 3% with direct HONO emissions. Radical sources, radical propagation, and oxidant production were enhanced at each step in the chemical cycle – particularly just after sunrise – by the addition of heterogeneous HONO formation and direct HONO emissions, but the effects were greater with heterogeneous formation.

The photolysis of nitrous acid (HONO) is a potentially significant daytime source of the hydroxyl radical, OH, one of the main chemical species that controls the oxidizing capacity of the atmosphere and plays an important role in ozone and PM2.5 formation. Research based on both field measurements and modeling has shown that HONO significantly affects the HOx budget in urban environments. Measurements during the Study of Houston Atmospheric Radical Precursors (SHARP) showed that radical production in the early morning in Houston was dominated by HONO photolysis. Field and laboratory studies suggest that nighttime heterogeneous conversion of NO2 on ground or aerosol surfaces, as well as daytime photolysis of HNO3 and NO2 adsorbed onto ground surfaces, can be important sources of HONO. Air quality models that only simulate homogeneous formation of HONO have been shown to substantially under-estimate observed HONO concentrations. Direct emissions of HONO also cannot explain the high HONO:NO2 ratios often measured in the boundary layer. These findings indicate that heterogeneous HONO formation plays an important role in the atmosphere. Previous approaches to include heterogeneous HONO formation in photochemical models have used surface to volume ratios to parameterize the chemistry on ground and aerosol surfaces. This paper describes the adaptation of a photochemical model to explicitly include a surface model that allows the treatment of the surface as a reservoir of deposited species that can be sorbed or penetrate into soils and vegetation, and undergo chemical degradation and transformation, and volatilization back into the air (re-emissions). The reactions in the surface model include HONO formation from thermal and photolytic reactions of deposited NO2 and HNO3. The parameterizations for surface heterogeneous production of HONO are evaluated and refined using existing modeling databases for the Houston area during the SHARP study period. A companion paper describes the impacts of the new HONO formation pathways on radical sources and ozone chemistry in the Houston area.

Formaldehyde (HCHO) is either directly emitted from sources or produced during the oxidation of volatile organic compounds in the troposphere. It is possible to infer atmospheric HCHO concentrations using space-based observations, which may be useful for studying emissions and tropospheric chemistry at urban to global scales depending on the quality of the retrievals. In the near future, an unprecedented volume of satellite-based HCHO measurement data will be available from both geostationary and polar-orbiting platforms. Therefore, it is essential to develop retrieval methods appropriate for the next-generation satellites that measure at higher spatial and temporal resolution than the current ones. In this study, we examine the importance of fine spatial and temporal resolution a priori profile information on the retrieval by conducting approximately 45 000 radiative transfer model calculations in the Los Angeles Basin megacity. Our analyses suggest that an air mass factor (AMF, ratio of slant columns to vertical columns) based on fine spatial and temporal resolution a priori profiles can better capture the spatial distributions of the enhanced HCHO plumes in an urban area than the nearly constant AMFs used for current operational products. For this urban area, the AMF values are inversely proportional to the magnitude of the HCHO mixing ratios in the boundary layer. Using our optimized model HCHO results in the Los Angeles Basin that mimic the HCHO retrievals from future geostationary satellites, we illustrate the effectiveness of HCHO data from geostationary measurements for understanding and predicting tropospheric ozone and its precursors.