Abstract

Airborne flux measurements of isoprene were performed over the Californian oak belts surrounding the Central Valley. The authors demonstrate for the first time 1) the feasibility of airborne eddy covariance measurements of reactive biogenic volatile organic compounds; 2) the effect of chemistry on the vertical transport of reactive species, such as isoprene; and 3) the applicability of wavelet analysis to estimate regional fluxes of biogenic volatile organic compounds. These flux measurements demonstrate that instrumentation operating at slower response times (e.g., 1–5 s) can still be used to determine eddy covariance fluxes in the mixed layer above land, where typical length scales of 0.5–3 km were observed. Flux divergence of isoprene measured in the planetary boundary layer (PBL) is indicative of OH densities in the range of 4–7 × 10⁶ molecules per cubic centimeter and allows extrapolation of airborne fluxes to the surface with Damköhler numbers (ratio between the mixing time scale and the chemical time scale) in the range of 0.3–0.9. Most of the isoprene is oxidized in the PBL with entrainment fluxes of about 10% compared to the corresponding surface fluxes. Entrainment velocities of 1–10 cm s⁻¹ were measured. The authors present implications for parameterizing PBL schemes of reactive species in regional and global models.

Nonmethane hydrocarbons are ubiquitous trace atmospheric constituents yet they control the oxidation capacity of the atmosphere. Both anthropogenic and biogenic processes contribute to the release of hydrocarbons to the atmosphere. In this manuscript, the state of the science concerning biosynthesis, transport, and chemical transformation of hydrocarbons emitted by the terrestrial biosphere is reviewed. In particular, the focus is on isoprene, monoterpenes, and oxygenated hydrocarbons. The generated science during the last 10 years is reviewed to explain and quantify hydrocarbon emissions from vegetation and to discern impacts of biogenic hydrocarbons on local and regional atmospheric chemistry. Furthermore, the physiological and environmental processes controlling biosynthesis and production of hydrocarbon compounds are reported on. Many advances have been made on measurement and modeling approaches developed to quantify hydrocarbon emissions from leaves and forest ecosystems. A synthesis of the atmospheric chemistry of biogenic hydrocarbons and their role in the formation of oxidants and aerosols is presented. The integration of biogenic hydrocarbon kinetics and atmospheric physics into mathematical modeling systems is examined to assess the contribution of biogenic hydrocarbons to the formation of oxidants and aerosols, thereby allowing us to study their impacts on the earth's climate system and to develop strategies to reduce oxidant precursors in affected regions.

Abstract

Measurements of aerosol size distribution, chemical composition, and cloud condensation nuclei (CCN) concentration were performed during the Chemical Emission, Loss, Transformation, and Interactions with Canopies (CELTIC) field program at Duke Forest in North Carolina. A kinetic model of the cloud activation of ambient aerosol in the chamber of the CCN instrument was used to perform an aerosol–CCN closure study. This study advances prior investigations by employing a novel fitting algorithm that was used to integrate scanning mobility particle sizer (SMPS) measurements of aerosol number size distribution and aerosol mass spectrometer (AMS) measurements of the mass size distribution for sulfate, nitrate, ammonium, and organics into a single, coherent description of the ambient aerosol in the size range critical to aerosol activation (around 100-nm diameter). Three lognormal aerosol size modes, each with a unique internally mixed composition, were used as input into the kinetic model. For the two smaller size modes, which control CCN number concentration, organic aerosol mass fractions for the defined cases were between 58% and 77%. This study is also unique in that the water vapor accommodation coefficient was estimated based on comparing the initial timing for CCN activation in the instrument chamber with the activation predicted by the kinetic model. The kinetic model overestimated measured CCN concentrations, especially under polluted conditions. Prior studies have attributed a positive model bias to an incomplete understanding of the aerosol composition, especially the role of organics in the activation process. This study shows that including measured organic mass fractions with an assumed organic aerosol speciation profile (pinic acid, fulvic acid, and levoglucosan) and an assumed organic aerosol solubility of 0.02 kg kg⁻¹ still resulted in a significant model positive bias for polluted case study periods. The slope and y intercept for the CCN predicted versus CCN observed regression was found to be 1.9 and −180 cm⁻³, respectively. The overprediction generally does not exceed uncertainty limits but is indicative that a bias exists in the measurements or application of model. From this study, uncertainties in the particle number and mass size distributions as the cause for the model bias can be ruled out. The authors are also confident that the model is including the effects of growth kinetics on predicted activated number. However, one cannot rule out uncertainties associated with poorly characterized CCN measurement biases, uncertainties in assumed organic solubility, and uncertainties in aerosol mixing state. Sensitivity simulations suggest that assuming either an insoluble organic fraction or external aerosol mixing were both sufficient to reconcile the model bias.

Abstract

The chemical species emitted by forests create complex atmospheric oxidation chemistry and influence global atmospheric oxidation capacity and climate. The Southern Oxidant and Aerosol Study (SOAS) provided an opportunity to test the oxidation chemistry in a forest where isoprene is the dominant biogenic volatile organic compound. Hydroxyl (OH) and hydroperoxyl (HO₂) radicals were two of the hundreds of atmospheric chemical species measured, as was OH reactivity (the inverse of the OH lifetime). OH was measured by laser-induced fluorescence (LIF) and by taking the difference in signals without and with an OH scavenger that was added just outside the instrument’s pinhole inlet. To test whether the chemistry at SOAS can be simulated by current model mechanisms, OH and HO₂ were evaluated with a box model using two chemical mechanisms: Master Chemical Mechanism, version 3.2 (MCMv3.2), augmented with explicit isoprene chemistry and MCMv3.3.1. Measured and modeled OH peak at about 10⁶ cm⁻³ and agree well within combined uncertainties. Measured and modeled HO₂ peak at about 27 pptv and also agree well within combined uncertainties. Median OH reactivity cycled between about 11 s⁻¹ at dawn and about 26 s⁻¹ during midafternoon. A good test of the oxidation chemistry is the balance between OH production and loss rates using measurements; this balance was observed to within uncertainties. These SOAS results provide strong evidence that the current isoprene mechanisms are consistent with measured OH and HO₂ and, thus, capture significant aspects of the atmospheric oxidation chemistry in this isoprene-rich forest.

Abstract

The Observations and Modeling of the Green Ocean Amazon 2014–2015 (GoAmazon2014/5) experiment took place around the urban region of Manaus in central Amazonia across 2 years. The urban pollution plume was used to study the susceptibility of gases, aerosols, clouds, and rainfall to human activities in a tropical environment. Many aspects of air quality, weather, terrestrial ecosystems, and climate work differently in the tropics than in the more thoroughly studied temperate regions of Earth. GoAmazon2014/5, a cooperative project of Brazil, Germany, and the United States, employed an unparalleled suite of measurements at nine ground sites and on board two aircraft to investigate the flow of background air into Manaus, the emissions into the air over the city, and the advection of the pollution downwind of the city. Herein, to visualize this train of processes and its effects, observations aboard a low-flying aircraft are presented. Comparative measurements within and adjacent to the plume followed the emissions of biogenic volatile organic carbon compounds (BVOCs) from the tropical forest, their transformations by the atmospheric oxidant cycle, alterations of this cycle by the influence of the pollutants, transformations of the chemical products into aerosol particles, the relationship of these particles to cloud condensation nuclei (CCN) activity, and the differences in cloud properties and rainfall for background compared to polluted conditions. The observations of the GoAmazon2014/5 experiment illustrate how the hydrologic cycle, radiation balance, and carbon recycling may be affected by present-day as well as future economic development and pollution over the Amazonian tropical forest.

This paper provides a synthesis of results that have emerged from recent modeling studies of the potential sensitivity of U.S. regional ozone (O₃) concentrations to global climate change (ca. 2050). This research has been carried out under the auspices of an ongoing U.S. Environmental Protection Agency (EPA) assessment effort to increase scientific understanding of the multiple complex interactions among climate, emissions, atmospheric chemistry, and air quality. The ultimate goal is to enhance the ability of air quality managers to consider global change in their decisions through improved characterization of the potential effects of global change on air quality, including O₃ The results discussed here are interim, representing the first phase of the EPA assessment. The aim in this first phase was to consider the effects of climate change alone on air quality, without accompanying changes in anthropogenic emissions of precursor pollutants. Across all of the modeling experiments carried out by the different groups, simulated global climate change causes increases of a few to several parts per billion (ppb) in summertime mean maximum daily 8-h average O₃ concentrations over substantial regions of the country. The different modeling experiments in general do not, however, simulate the same regional patterns of change. These differences seem to result largely from variations in the simulated patterns of changes in key meteorological drivers, such as temperature and surface insolation. How isoprene nitrate chemistry is represented in the different modeling systems is an additional critical factor in the simulated O₃ response to climate change.

The Canopy Horizontal Array Turbulence Study (CHATS) took place in spring 2007 and is the third in the series of Horizontal Array Turbulence Study (HATS) experiments. The HATS experiments have been instrumental in testing and developing subfilterscale (SFS) models for large-eddy simulation (LES) of planetary boundary layer (PBL) turbulence. The CHATS campaign took place in a deciduous walnut orchard near Dixon, California, and was designed to examine the impacts of vegetation on SFS turbulence. Measurements were collected both prior to and following leafout to capture the impact of leaves on the turbulence, stratification, and scalar source/sink distribution. CHATS utilized crosswind arrays of fast-response instrumentation to investigate the impact of the canopy-imposed distribution of momentum extraction and scalar sources on SFS transport of momentum, energy, and three scalars. To directly test and link with PBL parameterizations of canopy-modified turbulent exchange, CHATS also included a 30-m profile tower instrumented with turbulence instrumentation, fast and slow chemical sensors, aerosol samplers, and radiation instrumentation. A highresolution scanning backscatter lidar characterized the turbulence structure above and within the canopy; a scanning Doppler lidar, mini sodar/radio acoustic sounding system (RASS), and a new helicopter-observing platform provided details of the PBL-scale flow. Ultimately, the CHATS dataset will lead to improved parameterizations of energy and scalar transport to and from vegetation, which are a critical component of global and regional land, atmosphere, and chemical models. This manuscript presents an overview of the experiment, documents the regime sampled, and highlights some preliminary key findings.

Abstract

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.