Sean Coburn

Active and widespread halogen chemistry in the tropical and subtropical free troposphere

Significance Our measurements show that tropospheric halogen chemistry has a larger capacity to destroy O3 and oxidize atmospheric mercury than previously recognized. Halogen chemistry is currently missing in most global and climate models, and is effective at removing O3 at altitudes where intercontinental O3 transport occurs. It further helps explain the low O3 levels in preindustrial times. Public health concerns arise from bioaccumulation of the neurotoxin mercury in fish. Our results emphasize that bromine chemistry in the free troposphere oxidizes mercury at a faster rate, and makes water-soluble mercury available for scavenging by thunderstorms. Naturally occurring bromine in air aloft illustrates global interconnectedness between energy choices affecting mercury emissions in developing nations and mercury deposition in, e.g., Nevada, or the southeastern United States. Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O3), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O3 and methane (CH4) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O3. The observed BrO concentrations increase strongly with altitude (∼3.4 pptv at 13.5 km), and are 2–4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5–6.4 pptv total inorganic bromine (Bry), or model overestimated Bry wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Bry source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O3 needs to be considered when estimating past and future ozone radiative effects.

Regional sensing with an open-path dual comb spectroscopy and a UAS (Conference Presentation)

The output of a laser frequency comb is composed of 100,000+ perfectly spaced, discrete wavelength elements or comb teeth, that act as a massively parallel set of single frequency (CW) lasers with highly stable, well-known frequencies. In dual-comb spectroscopy, two such frequency combs are interfered on a single detector yielding absorption information for each individual comb tooth. This approach combines the strengths of both cw laser spectroscopy and broadband spectroscopy providing high spectral resolution and broad optical bandwidths, all with a single-mode, high-brightness laser beam and a simple, single photodetector, detection scheme. Here we show that this novel spectroscopy source can be employed for regional (~kilometer squared) monitoring using an array of stationed retros or in conjunction with an unmanned aerial systems (UAS). Both fixed and UAS systems combine the high-precision, multi-species detection capabilities of open-path DCS with the spatial scanning capabilities to enable spatial mapping of atmospheric gas concentrations. The DCS systems measure the atmospheric absorption over long, 100m to 1 km, open air paths with 0.007cm-1 resolution over 1.57 to 1.66 um, covering absorption bands of CO2, CH4, H2O and isotopologues.

Dual-Comb spectroscopy for GHG quantification

Near-infrared frequency-comb spectroscopy is a powerful tool with which to measure concentrations of gasses relevant to combustion and atmospheric monitoring (CO2, CH4, H2O, HDO) over meter and kilometer scale paths.

Combustion Diagnostics and Chemical Sensing with Frequency Comb Lasers

Recent advancements in robust frequency comb laser design have enabled the first industrial implementations of dual-comb gas sensors. As an example, we demonstrate dual-comb spectroscopy in the exhaust of a 16 MW stationary gas turbine.

A portable dual frequency comb spectrometer for atmospheric applications

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 kilometers. This length scale bridges the gap between point measurements and satellite-based measurements and is ideal for providing information about local sources and quanitfying emissions.

Measurements of the Absorption Cross Section of 13CHO13CHO at Visible Wavelengths and Application to DOAS Retrievals

The trace gas glyoxal (CHOCHO) forms from the atmospheric oxidation of hydrocarbons and is a precursor to secondary organic aerosol. We have measured the absorption cross section of disubstituted (13)CHO(13)CHO ((13)C glyoxal) at moderately high (1 cm(-1)) optical resolution between 21 280 and 23 260 cm(-1) (430-470 nm). The isotopic shifts in the position of absorption features were found to be largest near 455 nm (Δν = 14 cm(-1); Δλ = 0.29 nm), whereas no significant shifts were observed near 440 nm (Δν < 0.5 cm(-1); Δλ < 0.01 nm). These shifts are used to investigate the selective detection of (12)C glyoxal (natural isotope abundance) and (13)C glyoxal by in situ cavity enhanced differential optical absorption spectroscopy (CE-DOAS) in a series of sensitivity tests using synthetic spectra, and laboratory measurements of mixtures containing (12)C and (13)C glyoxal, nitrogen dioxide, and other interfering absorbers. We find the changes in apparent spectral band shapes remain significant at the moderately high optical resolution typical of CE-DOAS (0.55 nm fwhm). CE-DOAS allows for the selective online detection of both isotopes with detection limits of ∼200 pptv (1 pptv = 10(-12) volume mixing ratio), and sensitivity toward total glyoxal of few pptv. The (13)C absorption cross section is available for download from the Supporting Information.