Complexities in Modeling Organic Aerosol Light Absorption.

Aerosol particles dynamically evolve in the atmosphere by physicochemical interactions with sunlight, trace chemical species, and water. Current modeling approaches fix properties such as aerosol refractive index, introducing spatial and temporal errors in the radiative impacts. Further progress requires a process-level description of the refractive indices as the particles age and experience physicochemical transformations. We present two multivariate modeling approaches of light absorption by brown carbon (BrC). The initial approach was to extend the modeling framework of the refractive index at 589 nm (nD), but that result was insufficient. We developed a second multivariate model using aromatic rings and functional groups to predict the imaginary part of the complex refractive index. This second model agreed better with measured spectral absorption peaks, showing promise for a simplified treatment of BrC optics. In addition to absorption, organic functionalities also alter the water affinity of the molecules, leading to a hygroscopic uptake and increased light absorption, which we show through measurements and modeling.

Multiscale observations of CO2, 13CO2, and pollutants at Four Corners for emission verification and attribution.

There is a pressing need to verify air pollutant and greenhouse gas emissions from anthropogenic fossil energy sources to enforce current and future regulations. We demonstrate the feasibility of using simultaneous remote sensing observations of column abundances of CO2, CO, and NO2 to inform and verify emission inventories. We report, to our knowledge, the first ever simultaneous column enhancements in CO2 (3-10 ppm) and NO2 (1-3 Dobson Units), and evidence of δ(13)CO2 depletion in an urban region with two large coal-fired power plants with distinct scrubbing technologies that have resulted in ∆NOx/∆CO2 emission ratios that differ by a factor of two. Ground-based total atmospheric column trace gas abundances change synchronously and correlate well with simultaneous in situ point measurements during plume interceptions. Emission ratios of ∆NOx/∆CO2 and ∆SO2/∆CO2 derived from in situ atmospheric observations agree with those reported by in-stack monitors. Forward simulations using in-stack emissions agree with remote column CO2 and NO2 plume observations after fine scale adjustments. Both observed and simulated column ∆NO2/∆CO2 ratios indicate that a large fraction (70-75%) of the region is polluted. We demonstrate that the column emission ratios of ∆NO2/∆CO2 can resolve changes from day-to-day variation in sources with distinct emission factors (clean and dirty power plants, urban, and fires). We apportion these sources by using NO2, SO2, and CO as signatures. Our high-frequency remote sensing observations of CO2 and coemitted pollutants offer promise for the verification of power plant emission factors and abatement technologies from ground and space.

Regional Influence of Aerosol Emissions from Wildfires Driven by Combustion Efficiency: Insights from the BBOP Campaign.

Wildfires are important contributors to atmospheric aerosols and a large source of emissions that impact regional air quality and global climate. In this study, the regional and nearfield influences of wildfire emissions on ambient aerosol concentration and chemical properties in the Pacific Northwest region of the United States were studied using real-time measurements from a fixed ground site located in Central Oregon at the Mt. Bachelor Observatory (∼2700 m a.s.l.) as well as near their sources using an aircraft. The regional characteristics of biomass burning aerosols were found to depend strongly on the modified combustion efficiency (MCE), an index of the combustion processes of a fire. Organic aerosol emissions had negative correlations with MCE, whereas the oxidation state of organic aerosol increased with MCE and plume aging. The relationships between the aerosol properties and MCE were consistent between fresh emissions (∼1 h old) and emissions sampled after atmospheric transport (6-45 h), suggesting that biomass burning organic aerosol concentration and chemical properties were strongly influenced by combustion processes at the source and conserved to a significant extent during regional transport. These results suggest that MCE can be a useful metric for describing aerosol properties of wildfire emissions and their impacts on regional air quality and global climate.

Methane Isotope Instrument Validation and Source Identification at Four Corners, New Mexico, United States.

Measurements of δ(13)CH4 and CH4 concentration were made at a field site in Four Corners, New Mexico (FC), where we observed large sustained CH4 enhancements (2-8 ppm peaks for hours) during nocturnal inversions. Potential sources of this large CH4 signal at FC include (1) fugitive emissions from coal mining and gas processing that are thermogenic and isotopically (13)C enriched relative to background atmosphere and (2) emissions from agriculture, ruminants, landfills, and coalbed biogenic methane that are(13)C depleted relative to background atmosphere. We analyze our measurements of methane concentration and δ(13)C during spring and summer of 2012 to identify fugitive methane sources. We find CH4 plumes that are both enriched and depleted in (13)C relative to CH4 in background air. Keeling plots show a continuum of δ(13)C source compositions between -40‰ and -60‰ that are consistent with thermogenic and biogenic sources. The Picarro Mobile Methane Investigator (PMMI), a mobile δ(13)CH4 instrument platform, was deployed in the spring of 2013 and used to verify the isotopic enrichment of coal bed methane in the region. We combine our results with meteorological data to spatially separate these sources in the Four Corners regions. Using CO and CO2 data, along with meteorological data, we propose that the high methane concentration events ([CH4] > 3.5 ppm) are from both thermogenic and biogenic methane released from coal beds.

Light absorption properties and radiative effects of primary organic aerosol emissions.

Organic aerosols (OAs) in the atmosphere affect Earth's energy budget by not only scattering but also absorbing solar radiation due to the presence of the so-called "brown carbon" (BrC) component. However, the absorptivities of OAs are not represented or are poorly represented in current climate and chemical transport models. In this study, we provide a method to constrain the BrC absorptivity at the emission inventory level using recent laboratory and field observations. We review available measurements of the light-absorbing primary OA (POA), and quantify the wavelength-dependent imaginary refractive indices (kOA, the fundamental optical parameter determining the particle's absorptivity) and their uncertainties for the bulk POA emitted from biomass/biofuel, lignite, propane, and oil combustion sources. In particular, we parametrize the kOA of biomass/biofuel combustion sources as a function of the black carbon (BC)-to-OA ratio, indicating that the absorptive properties of POA depend strongly on burning conditions. The derived fuel-type-based kOA profiles are incorporated into a global carbonaceous aerosol emission inventory, and the integrated kOA values of sectoral and total POA emissions are presented. Results of a simple radiative transfer model show that the POA absorptivity warms the atmosphere significantly and leads to ∼27% reduction in the amount of the net global average POA cooling compared to results from the nonabsorbing assumption.

Contribution of nitrated phenols to wood burning brown carbon light absorption in Detling, United Kingdom during winter time.

We show for the first time quantitative online measurements of five nitrated phenol (NP) compounds in ambient air (nitrophenol C6H5NO3, methylnitrophenol C7H7NO3, nitrocatechol C6H5NO4, methylnitrocatechol C7H7NO4, and dinitrophenol C6H4N2O5) measured with a micro-orifice volatilization impactor (MOVI) high-resolution chemical ionization mass spectrometer in Detling, United Kingdom during January-February, 2012. NPs absorb radiation in the near-ultraviolet (UV) range of the electromagnetic spectrum and thus are potential components of poorly characterized light-absorbing organic matter ("brown carbon") which can affect the climate and air quality. Total NP concentrations varied between less than 1 and 98 ng m(-3), with a mean value of 20 ng m(-3). We conclude that NPs measured in Detling have a significant contribution from biomass burning with an estimated emission factor of 0.2 ng (ppb CO)(-1). Particle light absorption measurements by a seven-wavelength aethalometer in the near-UV (370 nm) and literature values of molecular absorption cross sections are used to estimate the contribution of NP to wood burning brown carbon UV light absorption. We show that these five NPs are potentially important contributors to absorption at 370 nm measured by an aethalometer and account for 4 ± 2% of UV light absorption by brown carbon. They can thus affect atmospheric radiative transfer and photochemistry and with that climate and air quality.

Plant versus local soil inorganic ionic composition: The relationship to biomass smoke.

We examine the relationship between soil and plant inorganic chemical composition as a precursor to biomass smoke aerosol particle (PM2.5) properties in desert landscapes of the Southwestern United States. Past work underscored the importance of plant species and in particular the dependence of smoke PM2.5 water uptake on the water-soluble inorganics important in select plant species (e.g., halophytes) versus absent in other species (e.g., conifers). This study extends this work by looking at a range of soil types and salinity in examining native and invasive species in the Desert Southwest US region. Eighteen plant samples and surrounding soils were taken from four ecosystems in New Mexico, USA. Results here support the conclusion that plant species are the primary controller over the inorganic plant composition that is relevant to biomass smoke and controls its hygroscopicity. The role of soil type is secondary to plant inorganic composition but is found to be important on the ecosystem level in determining what plant species are viable in a given ecosystem. This ultimately affects the smoke properties, including PM2.5 hygroscopicity (water uptake), produced in landscape fires. Knowledge of ecosystem features including plant species distribution and soil salinity may be combined as a first-order predictor of PM2.5 hygroscopicity of the primary smoke emissions. This can be particularly useful when combined with knowledge of burn characteristics such as flame temperature, which also plays a key role in determining PM2.5 water uptake response.

Extensive Soot Compaction by Cloud Processing from Laboratory and Field Observations.

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

NOx instrument intercomparison for laboratory biomass burning source studies and urban ambient measurements in Albuquerque, New Mexico.

Understanding nitrogen oxides (NOx = NO + NO2) measurement techniques is important as air-quality standards become more stringent, important sources change, and instrumentation develops. NOx observations are compared in two environments: source testing from the combustion of Southwestern biomass fuels, and urban, ambient NOx. The latter occurred in the urban core of Albuquerque, NM, at an EPA NCORE site during February-March 2017, a relatively clean photochemical environment with ozone (O3) <60 ppb for all but 6 hr. We compare two techniques used to measure NOx in biomass smoke during biomass burning source testing: light absorption at 405 nm and a traditional chemiluminescence monitor. Two additional oxides of nitrogen techniques were added in urban measurements: a cavity attenuated phase shift instrument for direct NO2, and the NOy chemiluminescence instrument (conversion of NOy to NO by molybdenum catalyst). We find agreement similar to laboratory standards for NOx, NO2, and NO comparing all four instruments (R2 > 0.97, slopes between 0.95 and 1.01, intercepts < 2 ppb for 1-hr averages) in the slowly varying ambient setting. Little evidence for significant interferences in NO2 measurements was observed in comparing techniques in late-winter urban Albuquerque. This was also confirmed by negligible NOz contributions as measured with an NOy instrument. For the rapidly varying (1-min) higher NOx concentrations in biomass smoke source testing, larger variability characterized chemiluminescence and absorption instruments. Differences between the two instruments were both positive and negative and occurred for total NOx, NO, and NO2. Nonetheless, integrating the NOx signals over an entire burn experiment and comparing 95 combustion experiments, showed little evidence for large systematic influences of possible interfering species biasing the methods. For concentrations of <2 ppm, a comparison of burn integrated NOx, NO2, and NO yielded slopes of 0.94 to 0.96, R2 of 0.83 to 0.93, and intercepts of 8 to 25 ppb. We attribute the latter, at least in part, to significant noise particularly at low NOx concentrations, resulting from short averaging times during highly dynamic lab burns. Discrepancies between instruments as indicated by the intercepts urge caution with oxides of nitrogen measurements at concentrations <50 ppb for rapidly changing conditions. Implications: Multiple NOx measurement methods were employed to measure NOx concentrations at an EPA NCORE site in Albuquerque, NM, and in smoke produced by the combustion of Southwestern biomass fuels. Agreement shown during intercomparison of these NOx techniques indicated little evidence of significant interfering species biasing the methods in these two environments. Instrument agreement is important to understand for accurately characterizing ambient NOx conditions in a range of environments.

Enhanced light absorption by mixed source black and brown carbon particles in UK winter.

Black carbon (BC) and light-absorbing organic carbon (brown carbon, BrC) play key roles in warming the atmosphere, but the magnitude of their effects remains highly uncertain. Theoretical modelling and laboratory experiments demonstrate that coatings on BC can enhance BC's light absorption, therefore many climate models simply assume enhanced BC absorption by a factor of ∼1.5. However, recent field observations show negligible absorption enhancement, implying models may overestimate BC's warming. Here we report direct evidence of substantial field-measured BC absorption enhancement, with the magnitude strongly depending on BC coating amount. Increases in BC coating result from a combination of changing sources and photochemical aging processes. When the influence of BrC is accounted for, observationally constrained model calculations of the BC absorption enhancement can be reconciled with the observations. We conclude that the influence of coatings on BC absorption should be treated as a source and regionally specific parameter in climate models.

Soot superaggregates from flaming wildfires and their direct radiative forcing.

Wildfires contribute significantly to global soot emissions, yet their aerosol formation mechanisms and resulting particle properties are poorly understood and parameterized in climate models. The conventional view holds that soot is formed via the cluster-dilute aggregation mechanism in wildfires and emitted as aggregates with fractal dimension Df ≈ 1.8 mobility diameter Dm ≤ 1 µm, and aerodynamic diameter Da ≤ 300 nm. Here we report the ubiquitous presence of soot superaggregates (SAs) in the outflow from a major wildfire in India. SAs are porous, low-density aggregates of cluster-dilute aggregates with characteristic Df ≈ 2.6, Dm > 1 µm, and Da ≤ 300 nm that form via the cluster-dense aggregation mechanism. We present additional observations of soot SAs in wildfire smoke-laden air masses over Northern California, New Mexico, and Mexico City. At 550 nm wavelength, [corrected] we estimate that SAs contribute, per unit optical depth, up to 35% less atmospheric warming than freshly-emitted (D(f) ≈ 1.8) [corrected] aggregates, and ≈90% more warming than the volume-equivalent spherical soot particles simulated in climate models.

Morphology and mixing state of individual freshly emitted wildfire carbonaceous particles.

Biomass burning is one of the largest sources of carbonaceous aerosols in the atmosphere, significantly affecting earth's radiation budget and climate. Tar balls, abundant in biomass burning smoke, absorb sunlight and have highly variable optical properties, typically not accounted for in climate models. Here we analyse single biomass burning particles from the Las Conchas fire (New Mexico, 2011) using electron microscopy. We show that the relative abundance of tar balls (80%) is 10 times greater than soot particles (8%). We also report two distinct types of tar balls; one less oxidized than the other. Furthermore, the mixing of soot particles with other material affects their optical, chemical and physical properties. We quantify the morphology of soot particles and classify them into four categories: ~50% are embedded (heavily coated), ~34% are partly coated, ~12% have inclusions and~4% are bare. Inclusion of these observations should improve climate model performances.

The atmospheric signature of carbon capture and storage.

Compared with other industrial processes, carbon capture and storage (CCS) will have an unusual impact on atmospheric composition by reducing the CO(2) released from fossil-fuel combustion plants, but not reducing the associated O(2) loss. CO(2) that leaks into the air from below-ground CCS sites will also be unusual in lacking the O(2) deficit normally associated with typical land CO(2) sources, such as from combustion or ecosystem exchanges. CCS may also produce distinct isotopic changes in atmospheric CO(2). Using simple models and calculations, we estimate the impact of CCS or leakage on regional atmospheric composition. We also estimate the possible impact on global atmospheric composition, assuming that the technology is widely adopted. Because of its unique signature, CCS may be especially amenable to monitoring, both regionally and globally, using atmospheric observing systems. Measurements of the O(2)/N(2) ratio and the CO(2) concentration in the proximity of a CCS site may allow detection of point leaks of the order of 1000 ton CO(2) yr(-1) from a CCS reservoir up to 1 km from the source. Measurements of O(2)/N(2) and CO(2) in background air from a global network may allow quantification of global and hemispheric capture rates from CCS to the order of ±0.4 Pg C yr(-1).