The remote tropical free troposphere (FT) is one of the most relevant atmospheric environments on Earth. About 75% of the global tropospheric O3 and CH4 loss occurs at tropical latitudes. Tropospheric bromine and iodine catalytically destroy tropospheric O₃, oxidize atmospheric mercury, and modify oxidative capacity, and aerosols. Oxygenated VOCs (OVOC) modify HO_x (= OH + HO₂), NOx (= NO + NO₂), tropospheric O₃, aerosols, and are a sink for BrO_x (= Br + BrO). Until recently, atmospheric models were untested for lack of vertically resolved measurements of BrO and IO radicals in the tropical troposphere. BrO and IO are highly reactive trace gases. Even very low concentrations (parts per trillion; 1 pptv = 10⁻¹² volume mixing ratio) can significantly modify the lifetime of climate active gases, and determine (bromine) the rate limiting step of mercury oxidation in air (that is washed out, and subsequently bio-accumulates in fish). Analytical challenges arise when these radicals modify in sampling lines. Sensitive yet robust, portable, and inherently calibrated measurements directly in the open atmosphere have recently been demonstrated by means of limb-measurements of scattered solar photons by the University of Colorado Airborne Multi-AXis DOAS instrument (CU AMAX-DOAS) from research aircraft. The CU AMAX-DOAS instrument is optimized to (1) locate BrO, IO and glyoxal (a short lived OVOC) in the troposphere, (2) decouple stratospheric absorbers, (3) maximize sensitivity at instrument altitude, (4) facilitate altitude control and (5) enable observations over a wide range of solar zenith angles. Further, (6) the filling-in of Fraunhofer lines (Ring-effect) by Raman Scattering offers interesting opportunities for radiative closure studies to assess the effects of aerosols on Climate.

For the past 20 years, high resolution infrared spectroscopy has served as a valuable tool to measure gas-phase concentrations of ambient gas samples. We review recent advances in atmospheric sampling using direct absorption high resolution mid-infrared spectroscopy from the perspective of light sources, detectors, and optical designs. Developments in diode, quantum cascade and interband cascade laser technology have led to thermoelectrically-cooled single-mode laser sources capable of operation between 800 cm⁻¹and 3100 cm⁻¹, with 10 MHz resolution and 10 mW power. Advances in detector and preamplifier technology have yielded thermoelectriocally-cooled sensors capable of room-temperature operation with extremely high detectivities. Finally, novel spectrometer optical designs have led to robust multipass absorption cells capable of 400 m effective pathlength in a compact package. In combination with accurate spectroscopic databases, these developments have afforded dramatic improvements in measurement sensitivity, accuracy, precision, and selectivity. We will present several examples of the applications of high resolution mid-IR spectrometers in real-world field measurements at sampling towers and aboard mobile platforms such as vehicles and airplanes.

Dual frequency comb (DFC) spectroscopy is a new technique that combines broad spectral bandwidth, high spectral resolution, rapid data acquisition, and high sensitivity. In addition, unlike standard Fourier-transform spectroscopy, it has an almost ideal instrument lineshape function, does not require recalibration, and has no moving parts. These features make DFC spectroscopy well suited for accurate measurements of multiple species simultaneously. Because the frequency comb lasers can be well collimated, such a system can be used for long open-path measurements with path lengths ranging from hundreds of meters to several kilometersG. B. Rieker, F. R. Giorgetta, W. C. Swann, J. Kofler, A. M. Zolot, L. C. Sinclair, E. Baumann, C. Cromer, G. Petron, C. Sweeney, P. P. Tans, I. Coddington, and N. R. Newbury, Frequency-comb-based remote sensing of greenhouse gases over kilometer air paths, Optica, 1(5), 290-298 (2014). This length scale bridges the gap between point measurements and satellite-based measurements and is ideal for providing information about local sources and quantifying emissions. Here we show a fully portable DFC spectrometer operating over a wide spectral region in the near-infrared (about 1.5-2.1 μm or 6670-4750 cm⁻¹ sampled at 0.0067 cm⁻¹) and across several different open-air paths up to a path length of 11.8 km. The current spectrometer fits in about a 500 L volume and has low power consumption. It provides simultaneous measurements of CO₂, CH₄, and water isotopes with a time resolution of seconds to minutes. This system has several potential applications for atmospheric measurements including continuous monitoring city-scale emissions and localizing methane leaks from oil and gas wells.

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Footnotes:

G. B. Rieker, F. R. Giorgetta, W. C. Swann, J. Kofler, A. M. Zolot, L. C. Sinclair, E. Baumann, C. Cromer, G. Petron, C. Sweeney, P. P. Tans, I. Coddington, and N. R. Newbury, Frequency-comb-based remote sensing of greenhouse gases over kilometer air paths, Optica, 1(5), 290-298 (2014)..

Considerable uncertainty exists regarding the contribution of oil and gas operations to anthropogenic emissions of atmospheric methane. Additionally, new proposed EPA regulations on volatile organic compound (VOC) emissions from oil and gas production facilities have been expanded to include methane, making this a topic of growing importance to the oil and gas industry as well as regulators. In order to gain a better understanding of emissions, reliable techniques that enable long-term monitoring of entire production facilities are needed. Recent advances in the development of compact and robust fiber frequency combs are enabling the use of this powerful spectroscopic tool outside of the laboratory. Here we characterize and demonstrate a dual comb spectrometer (DCS) system with the potential to locate and size methane leaks from oil and gas production sites over extended periods of time. The DCS operates over kilometer scale open paths, and the path integrated methane measurements will ultimately be coupled with an atmospheric inversion utilizing local meteorology and a high resolution fluid dynamics simulation to determine leak location and also derive a leak rate. High instrument precision is needed in order to accurately perform the measurement inversion on the highly varying methane background, thus the DCS system has been fully optimized for the detection of atmospheric methane in the methane absorption region around 180-184 THz.

The chemical kinetics of the OH+CO reaction plays important roles in combustion and atmospheric processes. OH+CO has two product channels, H+CO₂ and the stabilized HOCO intermediate, with a branching ratio that is highly pressure dependent. Therefore, establishing an accurate kinetic model for this chemical system requires knowledge of the reaction rates and product yields, and the lifetimes of all molecules along a particular reaction pathway. We report the application of time-resolved frequency comb spectroscopy (TRFCS) in the mid-infrared (3.7 μm) spectral region to address the complex reaction kinetics of OD+CO at room temperature. We use the deuterated forms to avoid atmospheric water interference. This technique allows us to detect the lowest energy conformer trans-DOCO intermediate with high time-resolution and sensitivity while also permitting the direct determination of rotational state distributions of all relevant molecules. We simultaneously observe the time-dependent concentrations of trans-DOCO, OD, and D₂O which are used in conjunction with kinetics modeling to obtain the pressure- and collision partner-dependent branching ratio of OD+CO.

The application of quantum cascade lasers (QCLs) in atmospheric science for trace detection of gases has been demonstrated using sensors in point or remote sensing configurations. Many of these systems utilize single narrowly-tunable ( ∼ 10 cm⁻¹) distributed feedback (DFB-) QCLs that limit simultaneous detection to a restricted number of small chemical species like H₂O or N₂O. The narrow wavelength range of DFB-QCLs precludes accurate quantification of large chemical species with broad rotationally-unresolved vibrational spectra, such as volatile organic compounds, that play an important role in the chemistry of the atmosphere. External-cavity (EC-) QCL systems are available that offer tuning ranges greater than 100 cm⁻¹, making them excellent IR sources for measuring multiple small and large chemical species in the atmosphere. While the broad wavelength coverage afforded by an EC system enables measurements of large chemical species, most commercial systems can only be swept over their entire wavelength range at less than 10 Hz. This prohibits broadband simultaneous measurements of multiple chemicals in plumes from natural or industrial sources where turbulence and/or chemical reactivity are resulting in rapid changes in chemical composition on sub-1s timescales. At Pacific Northwest National Laboratory we have developed rapidly-swept EC-QCL technology that acquires broadband absorption spectra ( ∼ 100 cm⁻¹) on ms timescales. The spectral resolution of this system has enabled simultaneous measurement of narrow rotationally-resolved atmospherically-broadened lines from small chemical species, while offering the broad tuning range needed to measure broadband spectral features from multiple large chemical species. In this talk the application of this technology for open-path atmospheric measurements will be discussed based on results from laboratory measurements with simulated plumes of chemicals. The performance offered by the system for simultaneous detection of multiple chemical species will be presented.

Biogenic volatile organic compounds (BVOCs) are emitted into Earth’s atmosphere by plants and are among the most abundant reactive organic species in the troposphere. These compounds play an important role in atmospheric chemistry, including the formation of secondary organic aerosols and production of surface-level ozone, a pollutant which can have negative health effects. BVOCs are generally measured and monitored using mass spectrometry and gas chromatography, but infrared spectroscopy is an excellent complementary tool for measuring these species. The development of quantum cascade lasers (QCLs) has provided robust, coherent light sources which give access to fundamental infrared transitions of BVOCs that lie in the "infrared window" from 8-14 um. At Connecticut College, we are developing a QCL-based spectrometer for measuring BVOCs with high resolution and high sensitivity. We will present details on the construction of our spectrometer and preliminary data for measurements of isoprene (C₅H₈), the most abundant BVOC in the troposphere.

Obtaining vertical profiles of tropospheric water vapor provides critically important information towards understanding short and long term global climate change. Ground-based Raman lidar technique is a powerful tool to precisely evaluating Water vapor Mixing Ratio (WVMR) in the troposphere. In this presentation, an overview of the design and basic components of a Raman water vapor lidar setup employing the third harmonic output (at 355 nm) of a high-powered laser with a telescope and three detection channels will be presented. Also, detailed discussion of the best method to calibrate and evaluate the performance of a typical water vapor Raman lidar will be shown and compared with most common calibration methods. By manipulating the inelastic backscattering lidar signals from the Raman nitrogen channel (386.7 nm) and Raman water vapor channel (407.5 nm), vertical profiles of water vapor mixing ratio (WVMR) will be deduced, calibrated, and compared against WVMR profiles obtained from coincident and collocated radiosonde profiles. This presented methodology will be shown to effectively yield high temporal and spatial resolution measurements of WVMR, with efficient dual detector capability both in the near-and-far fields.

Sulfur compounds have been observed in a number of planetary atmospheres throughout our solar system. Our current understanding of sulfur chemistry explains much of what we observe in Earth’s atmosphere. However, several discrepancies between modeling and observations of the Venusian atmosphere show there are still problems in our fundamental understanding of sulfur chemistry. This is of particular concern due to the important role sulfur compounds play in the formation of aerosols, which have a direct impact on planetary climates, including Earth’s. We investigate the role of water complexes in the hydration of sulfur oxides and dehydration of sulfur acids and will present spectroscopic studies to document such effects. I will present recent work investigating mixtures of SO₂ and water that generate large quantities of aerosol when irradiated with solar UV light, even in the absence of traditional OH chemistry. I will discuss a proposed mechanism for the formation of sulfurous acid (H₂SO₃) and present recent experimental work that supports this proposed mechanism. Additionally, the implications that photon-induced hydration of SO₂ has for aerosol formation in the atmosphere of earth as well as other planetary atmospheres will be discussed.

Methylglyoxal is a known oxidation product of volatile organic compounds (VOCs) in Earth’s atmosphere. While the gas phase chemistry of methylglyoxal is fairly well understood, its modeled concentration and role in the formation of secondary organic aerosol (SOA) continues to be controversial. The gas phase hydration of methylglyoxal to form a gemdiol has not been widely considered for water-restricted environments such as the atmosphere. However, this process may have important consequences for the atmospheric processing of VOCs. We will report on spectroscopic work done in the Vaida laboratory studying the hydration of methylglyoxal and discuss the implications for understanding the atmospheric processing and fate of methylglyoxal and similar molecules.