Person:

Wofsy, Steven

Nitrous acid (HONO) is important as a significant source of hydroxyl radical (OH) in the troposphere and as a potent indoor air pollutant. It is thought to be generated in both environments via heterogeneous reactions involving nitrogen dioxide ((NO_2)). In order to enable fast-response HONO detection suitable for eddy-covariance flux measurements and to provide a direct method that avoids interferences associated with derivatization, we have developed a 2-channel tunable infrared laser differential absorption spectrometer (TILDAS) capable of simultaneous high-frequency measurements of HONO and NO2. Beams from two mid-infrared continuous-wave mode quantum cascade lasers (cw-QCLs) traverse separate 210 m paths through a multi-pass astigmatic sampling cell at reduced pressure for the direct detection of HONO ((1660 cm^{−1})) and ((NO_2)) ((1604 cm^{−1})). The resulting one-second detection limits (S/N=3) are 300 and 30 ppt (pmol/mol) for HONO and ((NO_2)), respectively. Our HONO quantification is based on revised line-strengths and peak positions for cis-HONO in the 6-micron spectral region that were derived from laboratory measurements. An essential component of ambient HONO measurements is the inlet system and we demonstrate that heated surfaces and reduced pressure minimize sampling artifacts.

The Total Carbon Column Observing Network (TCCON) produces precise measurements of the column average dry-air mole fractions of (CO_2), (CO), (CH_4), (N_2O) and (H_2O) at a variety of sites worldwide. These observations rely on spectroscopic parameters that are not known with sufficient accuracy to compute total columns that can be used in combination with in situ measurements. The TCCON must therefore be calibrated to World Meteorological Organization (WMO) in situ trace gas measurement scales. We present a calibration of TCCON data using WMO-scale instrumentation aboard aircraft that measured profiles over four TCCON stations during 2008 and 2009. These calibrations are compared with similar observations made in 2004 and 2006. The results indicate that a single, global calibration factor for each gas accurately captures the TCCON total column data within error.

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 (CO_2) and (O_2) 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.

We assess the significance of high-frequency variability of environmental parameters (sunlight, precipitation, temperature) for the structure and function of terrestrial ecosystems under current and future climate. We examine the influence of hourly, daily, and monthly variance using the Ecosystem Demography model version 2 in conjunction with the long-term record of carbon fluxes measured at Harvard Forest. We find that fluctuations of sunlight and precipitation are strongly and nonlinearly coupled to ecosystem function, with effects that accumulate through annual and decadal timescales. Increasing variability in sunlight and precipitation leads to lower rates of carbon sequestration and favors broad-leaved deciduous trees over conifers. Temperature variability has only minor impacts by comparison. We also find that projected changes in sunlight and precipitation variability have important implications for carbon storage and ecosystem structure and composition. Based on Intergovernmental Panel on Climate Change model estimates for changes in high-frequency meteorological variability over the next 100 years, we expect that terrestrial ecosystems will be affected by changes in variability almost as much as by changes in mean climate. We conclude that terrestrial ecosystems are highly sensitive to high-frequency meteorological variability, and that accurate knowledge of the statistics of this variability is essential for realistic predictions of ecosystem structure and functioning.

This paper describes the coupling between a mesoscale numerical weather prediction model, the Weather Research and Forecasting (WRF) model, and a Lagrangian Particle Dispersion Model, the Stochastic Time-Inverted Lagrangian Transport (STILT) model. The primary motivation for developing this coupled model has been to reduce transport errors in continental-scale top–down estimates of terrestrial greenhouse gas fluxes. Examples of the model’s application are shown here for backward trajectory computations originating at CO2 measurement sites in North America. Owing to its unique features, including meteorological realism and large support base, good mass conservation properties, and a realistic treatment of convection within STILT, the WRF–STILT model offers an attractive tool for a wide range of applications, including inverse flux estimates, flight planning, satellite validation, emergency response and source attribution, air quality, and planetary exploration.

Rates for large-scale vertical transport of air in the Tropical Tropopause Layer (TTL) were determined using high-resolution, in situ observations of CO2 concentrations in the tropical upper troposphere and lower stratosphere during the NASA Tropical Composition, Cloud and Climate Coupling (TC4) campaign in August 2007. Upward movement of trace gases in the deep tropics was notably slower in TC4 than during the Costa Rica AURA Validation Experiment (CR-AVE), in January 2006. Transport rates in the TTL were combined with in situ measurements of chlorinated and brominated organic compounds from whole air samples to determine chemical loss rates for reactive chemical species, providing empirical vertical profiles for 24-h mean concentrations of hydroxyl radicals (OH) and chlorine atoms in the TTL. The analysis shows that important short-lived species such as CHCl3, CH2Cl2, and CH2Br2 have longer chemical lifetimes than the time for transit of the TTL, implying that these species, which are not included in most models, could readily reach the stratosphere and make significant contributions of chlorine and/or bromine to stratospheric loading.

[1] Refractory black carbon (rBC) aerosol loadings and mass size distributions have been quantified during the HIPPO campaign above the remote Pacific from 80N to 67S. Over 100 vertical profiles of rBC loadings, extending from ∼0.3 to ∼14 km were obtained with a Single-Particle Soot Photometer (SP2) during a two-week period in January 2009. The dataset provides a striking, and previously unobtainable, pole-to-pole snapshot of rBC mass loadings. rBC vertical concentration profiles reveal significant dependences on latitude, while associated rBC mass size distributions were highly uniform. The vertical profiles averaged in five latitude zones were compared to an ensemble of AEROCOM model fields. The model ensemble spread in each zone was over an order of magnitude, while the model average over-predicted rBC concentrations overall by a factor five. The comparisons suggest that rBC removal in global models may need to be evaluated separately in different latitude regions and perhaps enhanced.

The quantification of carbon fluxes between the terrestrial biosphere and the atmosphere is of scientific importance and also relevant to climate-policy making. Eddy covariance flux towers provide continuous measurements of ecosystem-level exchange of carbon dioxide spanning diurnal, synoptic, seasonal, and interannual time scales. However, these measurements only represent the fluxes at the scale of the tower footprint. Here we used remotely sensed data from the Moderate Resolution Imaging Spectroradiometer (MODIS) to upscale gross primary productivity (GPP) data from eddy covariance flux towers to the continental scale. We first combined GPP and MODIS data for 42 AmeriFlux towers encompassing a wide range of ecosystem and climate types to develop a predictive GPP model using a regression tree approach. The predictive model was trained using observed GPP over the period 2000–2004, and was validated using observed GPP over the period 2005–2006 and leave-one-out cross-validation. Our model predicted GPP fairly well at the site level. We then used the model to estimate GPP for each 1 km × 1 km cell across the U.S. for each 8-day interval over the period from February 2000 to December 2006 using MODIS data. Our GPP estimates provide a spatially and temporally continuous measure of gross primary production for the U.S. that is a highly constrained by eddy covariance flux data. Our study demonstrated that our empirical approach is effective for upscaling eddy flux GPP data to the continental scale and producing continuous GPP estimates across multiple biomes. With these estimates, we then examined the patterns, magnitude, and interannual variability of GPP. We estimated a gross carbon uptake between 6.91 and 7.33 Pg C yr− 1 for the conterminous U.S. Drought, fires, and hurricanes reduced annual GPP at regional scales and could have a significant impact on the U.S. net ecosystem carbon exchange. The sources of the interannual variability of U.S. GPP were dominated by these extreme climate events and disturbances.

The HIAPER Pole-to-Pole Observations (HIPPO) programme has completed three of five planned aircraft transects spanning the Pacific from 85° N to 67° S, with vertical profiles every approximately 2.2° of latitude. Measurements include greenhouse gases, long-lived tracers, reactive species, O2/N2 ratio, black carbon (BC), aerosols and CO2 isotopes. Our goals are to address the problem of determining surface emissions, transport strength and patterns, and removal rates of atmospheric trace gases and aerosols at global scales and to provide strong tests of satellite data and global models. HIPPO data show dense pollution and BC at high altitudes over the Arctic, imprints of large N2O sources from tropical lands and convective storms, sources of pollution and biogenic CH4 in the Arctic, and summertime uptake of CO2 and sources for O2 at high southern latitudes. Global chemical signatures of atmospheric transport are imaged, showing remarkably sharp horizontal gradients at air mass boundaries, weak vertical gradients and inverted profiles (maxima aloft) in both hemispheres. These features challenge satellite algorithms, global models and inversion analyses to derive surface fluxes. HIPPO data can play a crucial role in identifying and resolving questions of global sources, sinks and transport of atmospheric gases and aerosols.

Model calculations are conducted to investigate the production of carboxylic acids from photochemical decomposition of isoprene, one of the main natural hydrocarbons emitted from vegetation. Both gas-phase and aqueous-phase chemical reaction pathways are examined. A simple dynamical model is proposed to simulate the boundary layer of the Amazon rain forest, and model predictions are compared to measurements made in that region in July 1985. It is found that formic acid, methacrylic acid, and pyruvic acid can be produced in significant quantities by gas-phase decomposition of isoprene. In the Amazon basin, this source may yield concentrations of these acids in the order of 1 ppb, 0.1 ppb, and 0.02 ppb, respectively. Production of formic acid in cloud by aqueous-phase oxidation of CH2O does not greatly increase the formic acid concentration predicted from the gas-phase mechanism; cloud droplets with pH > 4 are actually expected to constitute net sinks for formic acid. No significant production of acetic acid is expected from the photochemical decomposition of isoprene. Comparisons of model predictions with field data indicates that isoprene could be a major source of formic acid and pyruvic acid observed in the gas phase and in rainwater; however, acetic acid must originate from another source.