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We apply a high-resolution chemical transport model (GEOS-Chem CTM) with updated treatment of volatile organic compounds (VOCs) and a comprehensive suite of airborne datasets over North America to (i) characterize the VOC budget and (ii) test the ability of current models to capture the distribution and reactivity of atmospheric VOCs over this region. Biogenic emissions dominate the North American VOC budget in the model, accounting for 70 % and 95 % of annually emitted VOC carbon and reactivity, respectively. Based on current inventories anthropogenic emissions have declined to the point where biogenic emissions are the dominant summertime source of VOC reactivity even in most major North American cities. Methane oxidation is a 2x larger source of nonmethane VOCs (via production of formaldehyde and methyl hydroperoxide) over North America in the model than are anthropogenic emissions. However, anthropogenic VOCs account for over half of the ambient VOC loading over the majority of the region owing to their longer aggregate lifetime. Fires can be a significant VOC source episodically but are small on average. In the planetary boundary layer (PBL), the model exhibits skill in capturing observed variability in total VOC abundance (R 2 = 0:36) and reactivity (R 2 = 0:54). The same is not true in the free troposphere (FT), where skill is low and there is a persistent low model bias (~ 60 %), with most (27 of 34) model VOCs underestimated by more than a factor of 2. A comparison of PBL: FT concentration ratios over the southeastern US points to a misrepresentation of PBL ventilation as a contributor to these model FT biases. We also find that a relatively small number of VOCs (acetone, methanol, ethane, acetaldehyde, formaldehyde, isoprene C oxidation products, methyl hydroperoxide) drive a large fraction of total ambient VOC reactivity and associated model biases; research to improve understanding of their budgets is thus warranted. A source tracer analysis suggests a current overestimate of biogenic sources for hydroxyacetone, methyl ethyl ketone and glyoxal, an underestimate of biogenic formic acid sources, and an underestimate of peroxyacetic acid production across biogenic and anthropogenic precursors. Future work to improve model representations of vertical transport and to address the VOC biases discussed are needed to advance predictions of ozone and SOA formation.

We describe the design and performance of a lightweight broadband cavity-enhanced spectrometer for measurement of NO2 on uncrewed aerial vehicles and light aircraft. The instrument uses an LED centered at 457 nm, high-finesse mirrors (reflectivity=0.999963 at 450 nm), and a grating spectrometer to determine optical extinction coefficients between 430–476 nm, which are fit with custom spectral fitting software and published absorption cross sections. The instrument weighs 3.05 kg and has power consumption less than 35 W at 25 °C. A ground calibration unit provides helium and zero air flows to periodically determine the reflectivity of the cavity mirrors using known Rayleigh scattering cross sections. The precision (1σ) for laboratory measurements is 43 ppt NO2 in 1 s and 7 ppt NO2 in 30 s. Measurement of air with known NO2 mixing ratios in the range of 0–70 ppb agreed with the known values within 0.3% (slope=0.997±0.007; r2=0.99983). We demonstrate instrument performance using vertical profiles of NO2 mixing ratio acquired onboard an uncrewed aerial vehicle between 0- 120 m above ground level in Boulder, Colorado. [ABSTRACT FROM AUTHOR]

Author(s): Peter M. Edwards [1, 2, 8]; Steven S. Brown (corresponding author) [1]; James M. Roberts [1]; Ravan Ahmadov [1, 2]; Robert M. Banta [1]; Joost A. deGouw [1, 2]; [...]

Biomass burning aerosol is a major source of PM2.5, and significantly affects Earth's radiative budget. The magnitude of its radiative effect is poorly quantified due to uncertainty in the optical properties of aerosol formed from biomass burning. Using a broadband cavity enhanced spectrometer with a recently increased spectral range (360-720 nm) coupled to a size-selecting aerosol inlet, we retrieve complex refractive indices of aerosol throughout the near-ultraviolet and visible spectral region. We demonstrate refractive index retrievals for two standard aerosol samples: polystyrene latex spheres and ammonium sulfate. We then retrieve refractive indices for biomass burning aerosol from 13 controlled fires during the 2016 Missoula Fire Science Laboratory Study. We demonstrate that the technique is highly sensitive to the accuracy of the aerosol size distribution method, and find that while we can constrain the optical properties of brown carbon aerosol for many fires, fresh smoke dominated by fractal-like black carbon aerosol presents unique challenges and is not well-represented by Mie theory. For the 13 fires, we show that the accuracy of Mie theory retrievals decreases as the fraction of black carbon mass increases. At 475 nm, the average refractive index is (1.635 ± 0.056) + (0.06 ± 0.12)i. [ABSTRACT FROM AUTHOR]

A cavity-enhanced absorption spectrometer (CEAS) for quantification of atmospheric trace gases that absorb in the cyan region of the electromagnetic spectrum (470 to 540 nm), including NO2 and I2, is described. The instrument uses a light-emitting diode coupled to a 1 m optical cavity consisting of a pair of mirrors in stable resonator configuration. Transmitted light is monitored using a grating spectrometer and charge-coupled device array detector. The average mirror reflectivity was determined from the N2/He and Ar/He ratios of scattering coefficients and was ~99.98 % at its maximum, yielding an effective optical path length of 6.3 km. Cross-sections of N2, O2, air, Ar, CO2, and CH4 scattering and of O4 absorption were measured and agree with literature values within the measurement uncertainty. Trace gas mixing ratios were retrieved using the spectral fitting software DOASIS from 480 to 535 nm. Under laboratory conditions, the 60 s, 1σ measurement precisions were ±105 and ±38 pptv for NO2 and I2, respectively. The CEAS sampled ambient air in Ucluelet, BC, in July 2015. CEAS retrievals agreed with independent measurements of NO2 by blue diode laser cavity ring-down spectroscopy (r² = 0.975), but ambient I2 concentrations were below the detection limit. [ABSTRACT FROM AUTHOR]

The chemical composition of aerosol particles is a key aspect in determining their impact on the environment. For example, nitrogen (N)-containing particles impact atmospheric chemistry, air quality, and ecological N-deposition. Instruments that measure total reactive nitrogen (Nr = all nitrogen compounds except for N2 and N2O) focus on gas-phase nitrogen and very few studies directly discuss the instrument capacity to measure the mass of Nr-containing particles. Here, we investigate the mass quantification of particle-bound nitrogen using a custom Nr system that involves total conversion to nitric oxide (NO) across platinum and molybdenum catalysts followed by NO-O3 chemiluminescence detection. We evaluate the particle conversion of the Nr instrument by comparing to mass derived concentrations of size-selected and counted ammonium sulfate ((NH4)2SO4), ammonium nitrate (NH4NO3), ammonium chloride (NH4Cl), sodium nitrate (NaNO3), and ammonium oxalate ((NH4)2C2O4) particles determined using instruments that measure particle number and size. These measurements demonstrate Nr-particle conversion across the Nr catalysts that is independent of particle size with 98 ± 10 % efficiency for 100-600 nm particle diameters. We also show conversion of particle-phase organic carbon species to CO2 across the instrument's platinum catalyst followed by a non-dispersive infrared (NDIR) CO2 detector. We show the Nr system is an accurate particle mass measurement method and demonstrate its ability to calibrate particle mass measurement instrumentation using single component, laboratory generated, Nr-containing particles below 2.5 µm in size. In addition we show agreement with mass measurements of an independently calibrated on-line particle-into-liquid sampler directly coupled to the electrospray ionization source of a quadrupole mass spectrometer (PILS-ESI/MS) sampling in the negative ion mode. We obtain excellent correlations (R² = 0.99) of particle mass measured as Nr with PILS-ESI/MS measurements converted to the corresponding particle anion mass (e.g. nitrate, sulfate, and chloride). The Nr and PILS-ESI/MS are shown to agree to within ~ 6 % for particle mass loadings up to 120 µg m-3. Consideration of all the sources of error in the PILS-ESI/MS technique yields an overall uncertainty of ±20 % for these single component particle streams. These results demonstrate the Nr system is a reliable direct particle mass measurement technique that differs from other particle instrument calibration techniques that rely on knowledge of particle size, shape, density, and refractive index. [ABSTRACT FROM AUTHOR]

Particle morphology is an important parameter affecting aerosol optical properties that are relevant to climate and air quality, yet it is poorly constrained due to sparse in situ measurements. Biomass burning is a large source of aerosol that generates particles with different morphologies. Quantifying the optical contributions of non-spherical aerosol populations is critical for accurate radiative transfer models, and for correctly interpreting remote sensing data. We deployed a laser imaging nephelometer at the Missoula Fire Sciences Laboratory to sample biomass burning aerosol from controlled fires during the FIREX intensive laboratory study. The laser imaging nephelometer measures the unpolarized scattering phase function of an aerosol ensemble using diode lasers at 375 nm and 405 nm. Scattered light from the bulk aerosol in the instrument is imaged onto a CCD using a wide-angle field-of-view lens, which allows for measurements at 4-175° scattering angle with ~ 0.5° angular resolution. Along with a suite of other instruments, the laser imaging nephelometer sampled fresh smoke emissions both directly and after removal of volatile components with a thermodenuder at 250 °C. The total integrated aerosol scattering signal agreed with both a cavity ring-down photoacoustic spectrometer system and a traditional integrating nephelometer within instrumental uncertainties. We compare the measured scattering phase functions at 405 nm to theoretical models for spherical (Mie) and fractal (Rayleigh-Debye-Gans) particle morphologies based on the size distribution reported by an optical particle counter. Results from representative fires demonstrate that particle morphology can vary dramatically for different fuel types. In some cases, the measured phase function cannot be described using Mie theory. This study demonstrates the capabilities of the laser imaging nephelometer instrument to provide real-time, in situ information about dominant particle morphology, which is vital for understanding remote sensing data and accurately describing the aerosol population in radiative transfer calculations. [ABSTRACT FROM AUTHOR]

Glyoxal (CHOCHO) is produced in the atmosphere by oxidation of volatile organic compounds (VOCs). It is measurable from space by solar backscatter along with formaldehyde (HCHO), another oxidation product of VOCs. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the SENEX campaign over the Southeast US in summer 2013 to better understand the time-dependent yields from isoprene oxidation, their dependences on nitrogen oxides (NOx ≡ NO + NO2), the behaviour of the CHOCHO-HCHO relationship, the quality of OMI satellite observations, and the implications for using satellite CHOCHO observations as constraints on isoprene emission. We simulate the SENEX and OMI observations with the GEOS-Chem chemical transport model featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NOx conditions following the isomerization of the isoprene peroxy radical (ISOPO2). The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NOx conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free tropospheric background and show Southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the Southeast US are tightly correlated and provide redundant proxies of isoprene emission. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NOx conditions apparent in the SENEX data. [ABSTRACT FROM AUTHOR]

We report near-ultraviolet and visible absorption crosssections of hydrogen peroxide (H2O2) using incoherentbroad-band cavity-enhanced absorption spectroscopy (IBBCEAS), a recentlydeveloped, high-sensitivity technique. The measurements reported herespan the range of 353–410 nm and extend published electronicabsorption cross sections by 60 nm to absorption cross sections below1 × 10–23cm2molecule–1. We have calculated photolysis rate constants for H2O2in the lower troposphere at a range of solar zenith anglesby combining the new measurements with previously reported data atwavelengths shorter than 350 nm. We predict that photolysis at wavelengthslonger than those included in the current JPL recommendation may accountfor up to 28% of the total hydroxyl radical (OH) production from H2O2photolysis under some conditions. Loss of H2O2via photolysis may be of the same order of magnitudeas reaction with OH and dry deposition in the lower atmosphere; theseprocesses have very different impacts on HOxloss and regeneration. [ABSTRACT FROM AUTHOR]

A global network of ground-based Fourier transform spectrometers has been founded to remotely measure column abundances of CO(2), CO, CH(4), N(2)O and other molecules that absorb in the near-infrared. These measurements are directly comparable with the near-infrared total column measurements from space-based instruments. With stringent requirements on the instrumentation, acquisition procedures, data processing and calibration, the Total Carbon Column Observing Network (TCCON) achieves an accuracy and precision in total column measurements that is unprecedented for remote-sensing observations (better than 0.25% for CO(2)). This has enabled carbon-cycle science investigations using the TCCON dataset, and allows the TCCON to provide a link between satellite measurements and the extensive ground-based in situ network., (© 2011 The Royal Society)