Total column CO_2 measurements at Darwin, Australia – site description and calibration against in situ aircraft profiles

An automated Fourier Transform Spectroscopic (FTS) solar observatory was established in Darwin, Australia in August 2005. The laboratory is part of the Total Carbon Column Observing Network, and measures atmospheric column abundances of CO_2 and O_2 and other gases. Measured CO_2 columns were calibrated against integrated aircraft profiles obtained during the TWP-ICE campaign in January–February 2006, and show good agreement with calibrations for a similar instrument in Park Falls, Wisconsin. A clear-sky low airmass relative precision of 0.1% is demonstrated in the CO2 and O2 retrieved column-averaged volume mixing ratios. The 1% negative bias in the FTS X_(CO_2) relative to the World Meteorological Organization (WMO) calibrated in situ scale is within the uncertainties of the NIR spectroscopy and analysis

Vertical Transport Rates in the Stratosphere in 1993 from Observations of CO2, N2O and CH4

Measurements of CO2, N2O and CH4 are analyzed to define hemispheric average vertical exchange rates in the lower stratosphere from November 1992 to October 1993. Effective vertical diffusion coefficients were small in summer, less than or equal to 1 m(exp 2)/sec at altitudes below 25 km; values were similar near the tropopause in winter, but increased markedly with altitude. The analysis suggests possibly longer residence times for exhaust from stratospheric aircraft, and more efficient transport from 20 km to the middle stratosphere, than predicted by many current models. Seasonally-resolved measurements of stratospheric CO2 and N2O provide significant new constraints on rates for global-scale vertical transport

Seasonal Controls on the Exchange of Carbon and Water in an Amazonian Rain Forest

The long-term resilience of Amazonian forests to climate changes and the fate of their large stores of organic carbon depend on the ecosystem response to climate and weather. This study presents 4 years of eddy covariance data for CO2 and water fluxes in an evergreen, old-growth tropical rain forest examining the forest's response to seasonal variations and to short-term weather anomalies. Photosynthetic efficiency declined late in the wet season, before appreciable leaf litter fall, and increased after new leaf production midway through the dry season. Rates of evapotranspiration were inelastic and did not depend on dry season precipitation. However, ecosystem respiration was inhibited by moisture limitations on heterotrophic respiration during the dry season. The annual carbon balance for this ecosystem was very close to neutral, with mean net loss of 890 ± 220 kg C ha−1 yr−1, and a range of −221 ± 453 (C uptake) to +2677 ± 488 (C loss) kg C ha−1 yr−1 over 4 years. The trend from large net carbon release in 2002 towards net carbon uptake in 2005 implies recovery from prior disturbance. The annual carbon balance was sensitive to weather anomalies, particularly the timing of the dry-to-wet season transition, reflecting modulation of light inputs and respiration processes. Canopy carbon uptake rates were largely controlled by phenology and light with virtually no indication of seasonal water limitation during the 5-month dry season, indicating ample supplies of plant-available-water and ecosystem adaptation for maximum light utilization.Earth and Planetary SciencesEngineering and Applied SciencesOrganismic and Evolutionary Biolog

Sources of Carbon Monoxide and Formaldehyde in North America Determined from High-Resolution Atmospheric Data

We analyze the North American budget for carbon monoxide using data for CO and formaldehyde concentrations from tall towers and aircraft in a model-data assimilation framework. The Stochastic Time-Inverted Lagrangian Transport model for CO (STILT-CO) determines local to regional-scale CO contributions associated with production from fossil fuel combustion, biomass burning, and oxidation of volatile organic compounds (VOCs) using an ensemble of Lagrangian particles driven by high resolution assimilated meteorology. In many cases, the model demonstrates high fidelity simulations of hourly surface data from tall towers and point measurements from aircraft, with somewhat less satisfactory performance in coastal regions and when CO from large biomass fires in Alaska and the Yukon Territory influence the continental US. Inversions of STILT-CO simulations for CO and formaldehyde show that current inventories of CO emissions from fossil fuel combustion are significantly too high, by almost a factor of three in summer and a factor two in early spring, consistent with recent analyses of data from the INTEX-A aircraft program. Formaldehyde data help to show that sources of CO from oxidation of CH4 and other VOCs represent the dominant sources of CO over North America in summer.Earth and Planetary Science

A new Differential Optical Absorption Spectroscopy instrument to study atmospheric chemistry from a high-altitude unmanned aircraft

Observations of atmospheric trace gases in the tropical upper troposphere (UT), tropical tropopause layer (TTL), and lower stratosphere (LS) require dedicated measurement platforms and instrumentation. Here we present a new limb-scanning Differential Optical Absorption Spectroscopy (DOAS) instrument developed for NASA's Global Hawk (GH) unmanned aerial system and deployed during the Airborne Tropical TRopopause EXperiment (ATTREX). The mini-DOAS system is designed for automatic operation under unpressurized and unheated conditions at 14–18 km altitude, collecting scattered sunlight in three wavelength windows: UV (301–387 nm), visible (410–525 nm), and near infrared (900–1700 nm). A telescope scanning unit allows selection of a viewing angle around the limb, as well as real-time correction of the aircraft pitch. Due to the high altitude, solar reference spectra are measured using diffusors and direct sunlight. The DOAS approach allows retrieval of slant column densities (SCDs) of O₃, O₄, NO₂, and BrO with relative errors similar to other aircraft DOAS systems. Radiative transfer considerations show that the retrieval of trace gas mixing ratios from the observed SCD based on O₄ observations, the most common approach for DOAS measurements, is inadequate for high-altitude observations. This is due to the frequent presence of low-altitude clouds, which shift the sensitivity of the O₄ SCD into the lower atmosphere and make it highly dependent on cloud coverage. A newly developed technique that constrains the radiative transfer by comparing in situ and DOAS O₃ observations overcomes this issue. Extensive sensitivity calculations show that the novel O₃-scaling technique allows the retrieval of BrO and NO₂ mixing ratios at high accuracies of 0.5 and 15 ppt, respectively. The BrO and NO₂ mixing ratios and vertical profiles observed during ATTREX thus provide new insights into ozone and halogen chemistry in the UT, TTL, and LS

Probing the subtropical lowermost stratosphere and the tropical upper troposphere and tropopause layer for inorganic bromine

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)

Carboxylic acids in clouds at a high-elevation forested site in central Virginia

During September 1990 we sampled coarse (>18-μm diameter) and fine (18- to 5.5-μm diameter) droplets and liquid-water content (LWC) in cloud from a tower on a forested ridge top in Shenandoah National Park, Virginia. Cloud-water pH and aqueous- and vapor-phase concentrations of carboxylic acids (HCOOH and CH3COOH) and formaldehyde (HCHO) were measured in parallel over 1- to 1.5-hour intervals. Both size fractions of cloud droplets contained similar concentrations of carboxylic species and H+ during most sampling; most cloud water was in coarse droplets. The pH of coarse (3.27–4.76) and fine (3.22–4.70) droplets coupled with total LWC of 0.04–0.56 g m−3 STP (standard m3 at 0°C and 1 atm) resulted in the partitioning of carboxylic acids primarily in the vapor phase. The observed phase partitioning for CH3COOH was within the uncertainty range of thermodynamic data. However, HCOOH exhibited significant phase disequilibria, which could not be explained by artifacts from variable LWC or from mixing droplets of different acidities. We hypothesize that the large volume of liquid water deposited on the forest canopy interacted with the near-surface cloud leading to apparent disequilibria based on time-integrated samples. HCOOH was selectively depleted relative to CH3COOH in cloud, particularly at higher pH, suggesting rapid removal of HCOOH by cloud-water deposition. We saw no evidence for significant production of HCOOH from the aqueous-phase oxidation of HCHO.Engineering and Applied Science

Carboxylic acids in the rural continental atmosphere over the eastern United States during the Shenandoah Cloud and Photochemistry Experiment

The Shenandoah Cloud and Photochemistry Experiment (SCAPE) was conducted during September 1990 in the rural continental atmosphere at a mountain top site (1014 m) in Shenandoah National Park, Virginia. We report here the extensive set of trace gas measurements performed during clear sky periods of SCAPE, with particular focus on the carboxylic acids, formic, acetic, and pyruvic. Median mixing ratios were 5.4 and 2.1 parts per billion by volume (ppbv) for formic and acetic acid, respectively, and they did not exhibit the diurnal variation characteristic of low-elevation sites. Mixing ratios of formic acid often approached or exceeded 10 ppbv, which are the largest values yet reported for the nonurban troposphere. Over the rural eastern United States, formic and acetic acid appear to have significant nonphotochemical sources. Secondary production from suspected pathways appears to be relatively unimportant. The observed lack of correlation between formic and acetic acid with peroxide species argues against a significant source from permutation reactions of peroxy radicals. In addition, model calculations using the SCAPE data indicate minimal production of carboxylics from olefin/O3 oxidation reactions. The tight correlation (r2 = 0.88) between mixing ratios of formic and acetic acid is strongly suggestive of a commonality in their sources. The seasonal cycle of carboxylic acids in the atmosphere and precipitation over the eastern United States is evidence that combustion emissions are not a principal source of these species. It appears that direct biogenic emissions from vegetation and soils cannot be ruled out as important sources. In particular, the correlation between the seasonal variation of formic and acetic acid and the ambient temperature is consistent with a soil microbial source. Similar conclusions were reached for pyruvic acid, with its mixing ratio ranging 4–266 parts per trillion by volume (pptv) (median = 63) and most likely supported by biogenic emissions and possibly photochemical sources.Engineering and Applied Science