Person:

Santoni, Gregory

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.

We apply a continental-scale inverse modeling system for North America based on the GEOS-Chem model to optimize California methane emissions at 1/2° × 2/3° horizontal resolution using atmospheric observations from the CalNex aircraft campaign (May–June 2010) and from satellites. Inversion of the CalNex data yields a best estimate for total California methane emissions of 2.86 ± 0.21 Tg a−1, compared with 1.92 Tg a−1 in the EDGAR v4.2 emission inventory used as a priori and 1.51 Tg a−1 in the California Air Resources Board (CARB) inventory used for state regulations of greenhouse gas emissions. These results are consistent with a previous Lagrangian inversion of the CalNex data. Our inversion provides 12 independent pieces of information to constrain the geographical distribution of emissions within California. Attribution to individual source types indicates dominant contributions to emissions from landfills/wastewater (1.1 Tg a−1), livestock (0.87 Tg a−1), and gas/oil (0.64 Tg a−1). EDGAR v4.2 underestimates emissions from livestock, while CARB underestimates emissions from landfills/wastewater and gas/oil. Current satellite observations from GOSAT can constrain methane emissions in the Los Angeles Basin but are too sparse to constrain emissions quantitatively elsewhere in California (they can still be qualitatively useful to diagnose inventory biases). Los Angeles Basin emissions derived from CalNex and GOSAT inversions are 0.42 ± 0.08 and 0.31 ± 0.08 Tg a−1 that the future TROPOMI satellite instrument (2015 launch) will be able to constrain California methane emissions at a detail comparable to the CalNex aircraft campaign. Geostationary satellite observations offer even greater potential for constraining methane emissions in the future.

The atmospheric concentration of methane ((CH_4)) - the most significant non-(CO_2) anthropogenic long-lived greenhouse gas - stabilized between 1999 and 2006 and then began to rise again. Explanations for this behavior differ but studies agree that more measurements and better modeling are needed to reliably explain the model-data discrepancies and predict future change. This dissertation focuses on measurements of (CH_4) and inverse modeling of atmospheric (CH_4) fluxes using field measurements at a variety of spatial scales. We first present a new fast-response instrument to measure the isotopic composition of (CH_4) in ambient air. The instrument was used to characterize mass fluxes and isofluxes (a isotopically-weighted mass flux) from a well-studied research fen in New Hampshire. Eddy-covariance and automatic chamber techniques produced consistent estimates of both the (CH_4) fluxes and their isotopic composition at sub-hourly resolution. We then characterize fluxes of (CH_4) from aircraft engines using measurements made with the same instrument during the Alternative Aviation Fuel Experiment (AAFEX), a study that aimed to determine the atmospheric impacts of alternative fuel use in the growing aviation industry. Emissions of (CO_2), (CH_4), and (N_2O) from different synthetic fuels were statistically indistinguishable from those of the widely used JP-8 jet fuel. We then present airborne observations of the long-lived greenhouse gas suite – (CO_2), (CH_4), (N_2O), and CO – during two aircraft campaigns, HIPPO and CalNex, made using a similar instrument built specifically for the NCAR HIAPER GV aircraft. These measurements are compared to data from other onboard sensors and show excellent agreement. We discuss the details of the end-to-end calibration procedures and the data quality-assurance and quality-control (QA/QC). Lastly, we quantify a top-down estimate of California’s (CH_4) emission inventory using the CalNex (CH_4) observations. Observed (CH_4) enhancements above background concentrations are simulated using a lagrangian transport model driven by validated meteorology. A priori source-specific emission inventories are optimized in a Bayesian inversion framework to show that California’s (CH_4) budget is 1.6 ± 0.34 times larger than the current estimate of California’s Air Resources Board (CARB), the body charged with enforcing the California Global Solutions Act and tracking emission changes over time. Findings highlight large underestimates of emissions from cattle and natural gas infrastructure.

Amazon forests are potentially globally significant sources or sinks for atmospheric carbon dioxide. In this study, we characterize the spatial trends in carbon storage and fluxes in both live and dead biomass (necromass) in two Amazonian forests, the Biological Dynamic of Forest Fragments Project (BDFFP), near Manaus, Amazonas, and the Tapajós National Forest (TNF) near Santarém, Pará. We assessed coarse woody debris (CWD) stocks, tree growth, mortality, and recruitment in ground-based plots distributed across the terra firme forest at both sites. Carbon dynamics were similar within each site, but differed significantly between the sites. The BDFFP and the TNF held comparable live biomass (167 ± 7.6 MgC·ha−1 versus 149 ± 6.0 MgC·ha−1, respectively), but stocks of CWD were 2.5 times larger at TNF (16.2 ± 1.5 MgC·ha−1 at BDFFP, versus 40.1 ± 3.9 MgC·ha−1 at TNF). A model of current forest dynamics suggests that the BDFFP was close to carbon balance, and its size class structure approximated a steady state. The TNF, by contrast, showed rapid carbon accrual to live biomass (3.24 ± 0.22 MgC·ha−1·a−1 in TNF, 2.59 ± 0.16 MgC·ha−1·a−1 in BDFFP), which was more than offset by losses from large stocks of CWD, as well as ongoing shifts of biomass among size classes. This pattern in the TNF suggests recovery from a significant disturbance. The net loss of carbon from the TNF will likely last 10–15 years after the initial disturbance (controlled by the rate of decay of coarse woody debris), followed by uptake of carbon as the forest size class structure and composition continue to shift. The frequency and longevity of forests showing such disequilibruim dynamics within the larger matrix of the Amazon remains an essential question to understanding Amazonian carbon balance.

We present an evaluation of aircraft observations of the carbon and greenhouse gases CO2, CH4, N2O, and CO using a direct-absorption pulsed quantum cascade laser spectrometer (QCLS) operated during the HIPPO and CalNex airborne experiments. The QCLS made continuous 1 Hz measurements with 1σ Allan precisions of 20, 0.5, 0.09, and 0.15 ppb for CO2, CH4, N2O, and CO, respectively, over > 500 flight hours on 79 research flights. The QCLS measurements are compared to two vacuum ultraviolet (VUV) CO instruments (CalNex and HIPPO), a cavity ring-down spectrometer (CRDS) measuring CO2 and CH4 (CalNex), two broadband non-dispersive infrared (NDIR) spectrometers measuring CO2 (HIPPO), two onboard gas chromatographs measuring a variety of chemical species including CH4, N2O, and CO (HIPPO), and various flask-based measurements of all four species. QCLS measurements are tied to NOAA and WMO standards using an in-flight calibration system, and mean differences when compared to NOAA CCG flask data over the 59 HIPPO research flights were 100, 1, 1, and 2 ppb for CO2, CH4, N2O, and CO, respectively. The details of the end-to-end calibration procedures and the data quality assurance and quality control (QA/QC) are presented. Specifically, we discuss our practices for the traceability of standards given uncertainties in calibration cylinders, isotopic and surface effects for the long-lived greenhouse gas tracers, interpolation techniques for in-flight calibrations, and the effects of instrument linearity on retrieved mole fractions.