Photoacoustic studies of energy transfer from ozone photoproducts to bath gases following Chappuis band photoexcitation.

Photoacoustic spectroscopy (PAS) is a sensitive technique for the detection of trace gases and aerosols and measurements of their absorption coefficients. The accuracy of such measurements is often governed by the fidelity of the PAS instrument calibration. Gas samples laden with O3 of a known or independently measured absorption coefficient are a convenient and commonplace route to calibration of PAS instruments operating at visible wavelengths (λ), yet the accuracy of such calibrations remains unclear. Importantly, the photoacoustic detection of O3 in the Chappuis band (λ ∼ 400-700 nm) depends strongly on the timescales for energy transfer from the nascent photoproducts O(3P) and O2(X, v > 0) to translational motion of bath gas species. Significant uncertainties remain concerning the dependence of these timescales on both the sample pressure and the bath gas composition. Here, we demonstrate accurate characterisation of microphone response function dependencies on pressure using a speaker transducer to excite resonant acoustic modes of our photoacoustic cells. These corrections enable measurements of photoacoustic response amplitudes (also referred to as PAS sensitivities) and phase shifts with variation in static pressure and bath gas composition, at discrete visible wavelengths spanning the Chappuis band. We develop and fit a photochemical relaxation model to these measurements to retrieve the associated variations in the aforementioned relaxation timescales for O(3P) and O2(X, v > 0). These timescales enable a full assessment of the accuracy of PAS calibrations using O3-laden gas samples, dependent on the sample pressure, bath gas composition and PAS laser modulation frequency.

Brown carbon and internal mixing in biomass burning particles.

Biomass burning (BB) contributes large amounts of black carbon (BC) and particulate organic matter (POM) to the atmosphere and contributes significantly to the earth's radiation balance. BB particles can be a complicated optical system, with scattering and absorption contributions from BC, internal mixtures of BC and POM, and wavelength-dependent absorption of POM. Large amounts of POM can also be externally mixed. We report on the unique ability of multi-wavelength photo-acoustic measurements of dry and thermal-denuded absorption to deconstruct this complicated wavelength-dependent system of absorption and mixing. Optical measurements of BB particles from the Four Mile Canyon fire near Boulder, Colorado, showed that internal mixtures of BC and POM enhanced absorption by up to 70%. The data supports the assumption that the POM was very weakly absorbing at 532 nm. Enhanced absorption at 404 nm was in excess of 200% above BC absorption and varied as POM mass changed, indicative of absorbing POM. Absorption by internal mixing of BC and POM contributed 19( ± 8)% to total 404-nm absorption, while BC alone contributed 54( ± 16)%. Approximately 83% of POM mass was externally mixed, the absorption of which contributed 27( ± 15)% to total particle absorption (at 404 nm). The imaginary refractive index and mass absorption efficiency (MAE) of POM at 404 nm changed throughout the sampling period and were found to be 0.007 ± 0.005 and 0.82 ± 0.43 m(2) g(-1), respectively. Our analysis shows that the MAE of POM can be biased high by up to 50% if absorption from internal mixing of POM and BC is not included.

CCN spectra, hygroscopicity, and droplet activation kinetics of secondary organic aerosol resulting from the 2010 Deepwater Horizon oil spill.

Secondary organic aerosol (SOA) resulting from the oxidation of organic species emitted by the Deepwater Horizon oil spill were sampled during two survey flights conducted by a National Oceanic and Atmospheric Administration WP-3D aircraft in June 2010. A new technique for fast measurements of cloud condensation nuclei (CCN) supersaturation spectra called Scanning Flow CCN Analysis was deployed for the first time on an airborne platform. Retrieved CCN spectra show that most particles act as CCN above (0.3 ± 0.05)% supersaturation, which increased to (0.4 ± 0.1)% supersaturation for the most organic-rich aerosol sampled. The aerosol hygroscopicity parameter, κ, was inferred from both measurements of CCN activity and from humidified-particle light extinction, and varied from 0.05 to 0.10 within the emissions plumes. However, κ values were lower than expected from chemical composition measurements, indicating a degree of external mixing or size-dependent chemistry, which was reconciled assuming bimodal, size-dependent composition. The CCN droplet effective water uptake coefficient, γ(cond), was inferred from the data using a comprehensive instrument model, and no significant delay in droplet activation kinetics from the presence of organics was observed, despite a large fraction of hydrocarbon-like SOA present in the aerosol.

Air quality implications of the Deepwater Horizon oil spill.

During the Deepwater Horizon (DWH) oil spill, a wide range of gas and aerosol species were measured from an aircraft around, downwind, and away from the DWH site. Additional hydrocarbon measurements were made from ships in the vicinity. Aerosol particles of respirable sizes were on occasions a significant air quality issue for populated areas along the Gulf Coast. Yields of organic aerosol particles and emission factors for other atmospheric pollutants were derived for the sources from the spill, recovery, and cleanup efforts. Evaporation and subsequent secondary chemistry produced organic particulate matter with a mass yield of 8 ± 4% of the oil mixture reaching the water surface. Approximately 4% by mass of oil burned on the surface was emitted as soot particles. These yields can be used to estimate the effects on air quality for similar events as well as for this spill at other times without these data. Whereas emission of soot from burning surface oil was large during the episodic burns, the mass flux of secondary organic aerosol to the atmosphere was substantially larger overall. We use a regional air quality model to show that some observed enhancements in organic aerosol concentration along the Gulf Coast were likely due to the DWH spill. In the presence of evaporating hydrocarbons from the oil, NO(x) emissions from the recovery and cleanup operations produced ozone.

A broadband absorption spectrometer using light emitting diodes for ultrasensitive, in situ trace gas detection.

A broadband absorption spectrometer has been developed for highly sensitive and target-selective in situ trace gas measurements. The instrument employs two distinct modes of operation: (i) broadband cavity enhanced absorption spectroscopy (BBCEAS) is used to quantify the concentration of gases in sample mixtures from their characteristic absorption features, and (ii) periodic measurements of the cavity mirrors' reflectivity are made using step-scan phase shift cavity ringdown spectroscopy (PSCRDS). The latter PSCRDS method provides a stand-alone alternative to the more usual method of determining mirror reflectivities by measuring BBCEAS absorption spectra for calibration samples of known composition. Moreover, the instrument's two modes of operation use light from the same light emitting diode transmitted through the cavity in the same optical alignment, hence minimizing the potential for systematic errors between mirror reflectivity determinations and concentration measurements. The ability of the instrument to quantify absorber concentrations is tested in instrument intercomparison exercises for NO(2) (versus a laser broadband cavity ringdown spectrometer) and for H(2)O (versus a commercial hygrometer). A method is also proposed for calculating effective absorption cross sections for fitting the differential structure in BBCEAS spectra due to strong, narrow absorption lines that are under-resolved and hence exhibit non-Beer-Lambert law behavior at the resolution of the BBCEAS measurements. This approach is tested on BBCEAS spectra of water vapor's 4v+delta absorption bands around 650 nm. The most immediate analytical application of the present instrument is in quantifying the concentration of reactive trace gases in the ambient atmosphere. The instrument's detection limits for NO(3) as a function of integration time are considered in detail using an Allan variance analysis. Experiments under laboratory conditions produce a 1sigma detection limit of 0.25 pptv for a 10 s acquisition time, which improves with further signal averaging to 0.09 pptv in 400 s. Finally, an example of the instrument's performance under field work conditions is presented, in this case of measurements of the sum of NO(3)+N(2)O(5) concentrations in the marine boundary layer acquired during the Reactive Halogens in the Marine Boundary Layer field campaign.

A compact broadband cavity enhanced absorption spectrometer for detection of atmospheric NO(2) using light emitting diodes.

A compact and low power detector has been developed for the in situ measurement of atmospheric NO(2) using broadband cavity enhanced absorption spectroscopy. Absorption by the O(2)-O(2) collisional pair was used to determine the cavity mirror reflectivity, thus enabling the retrieval of absolute absorber concentrations by differential spectral fitting techniques. Quantitative amounts of ambient NO(2) (between 3 and 32 parts per billion) were retrieved from spectra recorded in the presence of ambient aerosol with statistical uncertainties approaching 100 ppt for a 60 s averaging period. The instrument's response was compared to that of a commercial chemiluminescence detector and was found to agree to within 6%.