Cloud water chemistry in Sequoia National Park

Interception of cloudwater by forests in the Sierra Nevada Mountains may contribute significantly to acidic deposition in the region. Cloudwater sampled in Sequoia National Park had pH values ranging from 4.4 to 5.7. The advance of cold fronts into the Park appears to lead to higher aerosol and gas phase concentrations than are seen under normal mountain-valley circulations, producing higher cloud-water concentrations than might otherwise be expected. Estimates of annual deposition rates of NO_3^−, SO_4^(2−), NH_4^+ and H^+ due to cloudwater impaction are comparable to those measured in precipitation

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

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

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

Carbon dioxide column abundances at the Wisconsin Tall Tower site

We have developed an automated observatory for measuring atmospheric column abundances of CO_2 and O_2 using near-infrared spectra of the Sun obtained with a high spectral resolution Fourier Transform Spectrometer (FTS). This is the first dedicated laboratory in a new network of ground-based observatories named the Total Carbon Column Observing Network. This network will be used for carbon cycle studies and validation of spaceborne column measurements of greenhouse gases. The observatory was assembled in Pasadena, California, and then permanently deployed to northern Wisconsin during May 2004. It is located in the heavily forested Chequamegon National Forest at the WLEF Tall Tower site, 12 km east of Park Falls, Wisconsin. Under clear sky conditions, ∼0.1% measurement precision is demonstrated for the retrieved column CO_2 abundances. During the Intercontinental Chemical Transport Experiment–North America and CO_2 Boundary Layer Regional Airborne Experiment campaigns in summer 2004, the DC-8 and King Air aircraft recorded eight in situ CO_2 profiles over the WLEF site. Comparison of the integrated aircraft profiles and CO_2 column abundances shows a small bias (∼2%) but an excellent correlation

Ethylene oxide monitor with part-per-trillion precision for in situ measurements

An Aerodyne tunable infrared laser direct absorption spectrometer with a multipass cell with a 413 m pathlength for the detection of ethylene oxide (EtO) is presented (TILDAS-FD-EtO). This monitor achieves precisions of &lt;75 ppt or &lt;0.075 ppb s−1 and &lt;20 ppt in 100 s (1σ). We demonstrate precisions averaging down to 4 ppt h−1 (1σ precision) when operated with frequent humidity-matched zeroes. A months-long record of 2022 ambient concentrations at a site in the eastern United States is presented. Average ambient EtO concentration is on the order of 18 ppt (22 ppt standard deviation, SD). Enhancement events of EtO lasting a few hours are observed, with peaks as high as 600 ppt. Back-trajectory simulations suggest an EtO source nearly 35 km away. This source along with another are confirmed as emitters through mobile near-source measurements, with downwind concentrations in the 0.5 to 700 ppb range depending on source identity and distance downwind.</p

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)

Atmospheric Acetaldehyde: Importance of Air-Sea Exchange and a Missing Source in the Remote Troposphere.

We report airborne measurements of acetaldehyde (CH3CHO) during the first and second deployments of the National Aeronautics and Space Administration (NASA) Atmospheric Tomography Mission (ATom). The budget of CH3CHO is examined using the Community Atmospheric Model with chemistry (CAM-chem), with a newly-developed online air-sea exchange module. The upper limit of the global ocean net emission of CH3CHO is estimated to be 34 Tg a-1 (42 Tg a-1 if considering bubble-mediated transfer), and the ocean impacts on tropospheric CH3CHO are mostly confined to the marine boundary layer. Our analysis suggests that there is an unaccounted CH3CHO source in the remote troposphere and that organic aerosols can only provide a fraction of this missing source. We propose that peroxyacetic acid (PAA) is an ideal indicator of the rapid CH3CHO production in the remote troposphere. The higher-than-expected CH3CHO measurements represent a missing sink of hydroxyl radicals (and halogen radical) in current chemistry-climate models