Characterizing elemental, equivalent black, and refractory black carbon aerosol particles: a review of techniques, their limitations and uncertainties.

Elemental-, equivalent black- and refractory black-carbon are terms that have been defined in order to dissect the more general term, black carbon, into its component parts related to its specific chemical and optical properties and its impact on climate and health. Recent publications have attempted to clarify the meaning of these terms with respect to their environmental impact, particularly on climate. Here, we focus on the measurement aspects, reviewing the most commonly implemented techniques for the direct and indirect derivation of black carbon properties, their strengths, limitations, and uncertainties, and provide a non-exhaustive bibliography where the reader can find more detailed information. This review paper is designed as a guide for those wishing to learn about the current state of black carbon measurement instrumentation, how calibration is carried out, when one instrument may have the advantage over another, and where new techniques are needed to fill important knowledge gaps.

Response to comment on "Radiative absorption enhancements due to the mixing state of atmospheric black carbon".

Jacobson argues that our statement that "many climate models may overestimate warming by BC" has not been demonstrated. Jacobson challenges our results on the basis that we have misinterpreted some model results, omitted optical focusing under high relative humidity conditions and by involatile components, and because our measurements consist of only two locations over short atmospheric time periods. We address each of these arguments, acknowledging important issues and clarifying some misconceptions, and stand by our observations. We acknowledge that Jacobson identified one detail in our experimental technique that places an additional constraint on the interpretation of our observations and reduces somewhat the potential consequences of the stated implications.

Radiative absorption enhancements due to the mixing state of atmospheric black carbon.

Atmospheric black carbon (BC) warms Earth's climate, and its reduction has been targeted for near-term climate change mitigation. Models that include forcing by BC assume internal mixing with non-BC aerosol components that enhance BC absorption, often by a factor of ~2; such model estimates have yet to be clearly validated through atmospheric observations. Here, direct in situ measurements of BC absorption enhancements (E(abs)) and mixing state are reported for two California regions. The observed E(abs) is small-6% on average at 532 nm-and increases weakly with photochemical aging. The E(abs) is less than predicted from observationally constrained theoretical calculations, suggesting that many climate models may overestimate warming by BC. These ambient observations stand in contrast to laboratory measurements that show substantial E(abs) for BC are possible.

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.

Rock climbing rescues: causes, injuries, and trends in Boulder County, Colorado.

OBJECTIVE: To describe rates and patterns of rock climbing rescue incidents, morbidity and mortality in Boulder County, CO. METHODS: Rocky Mountain Rescue Group incident reports from 1998 to 2011 were reviewed to provide a 14-year statistical account of rock climbing incidents. RESULTS: Rock climbing rescues in Boulder accounted for 428 of a total of 2198 (19.5%) mountain and wilderness rescue victims. Most rock climbing victims were male (78%), and 46% of victims were between the ages of 20 and 29 years; most rock climbing incidents occurred on weekend days (median time of 3:30 pm) during the spring, summer, and autumn. Technical roped climbers accounted for 58% of climbing victims, whereas unroped climbers accounted for 34%. Belay incidents accounted for 12% of climbing victims, whereas rock fall incidents accounted for 4.5% of victims. Most victims were uninjured (43% stranded or lost), whereas lower extremity injuries were the most common injury (29.5% of injured victims). A total of 5.5% of climbing victims were fatally injured (23 victims: 5 from lead falls and 9 from unroped falls). CONCLUSIONS: The occurrence of rock climbing-related rescue victims comprised one fifth of all rescue victims in Boulder County. A large fraction of incidents and fatalities resulted from unroped climbing. Incidents of lost or uninjured stranded climbers and belay incidents account for more than half of victims, which can likely be prevented by gaining appropriate experience, seeking local information, and applying some simple safety measures for control of rope belays.

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.

Impact of fuel quality regulation and speed reductions on shipping emissions: implications for climate and air quality.

Atmospheric emissions of gas and particulate matter from a large ocean-going container vessel were sampled as it slowed and switched from high-sulfur to low-sulfur fuel as it transited into regulated coastal waters of California. Reduction in emission factors (EFs) of sulfur dioxide (SO2), particulate matter, particulate sulfate and cloud condensation nuclei were substantial (≥ 90%). EFs for particulate organic matter decreased by 70%. Black carbon (BC) EFs were reduced by 41%. When the measured emission reductions, brought about by compliance with the California fuel quality regulation and participation in the vessel speed reduction (VSR) program, are placed in a broader context, warming from reductions in the indirect effect of SO4 would dominate any radiative changes due to the emissions changes. Within regulated waters absolute emission reductions exceed 88% for almost all measured gas and particle phase species. The analysis presented provides direct estimations of the emissions reductions that can be realized by California fuel quality regulation and VSR program, in addition to providing new information relevant to potential health and climate impact of reduced fuel sulfur content, fuel quality and vessel speed reductions.