We present the laboratory and ambient photoacoustic (PA) measurement of aerosol light absorption coefficients at ultraviolet wavelength (i.e., 355 nm) and compare with measurements at 405, 532, 870, ...and 1047 nm. Simultaneous measurements of aerosol light scattering coefficients were achieved by the integrating reciprocal nephelometer within the PA's acoustic resonator. Absorption and scattering measurements were carried out for various laboratory-generated aerosols, including salt, incense, and kerosene soot to evaluate the instrument calibration and gain insight on the spectral dependence of aerosol light absorption and scattering. Ambient measurements were obtained in Reno, Nevada, between 18 December 2009 and 18 January 2010. The measurement period included days with and without strong ground level temperature inversions, corresponding to highly polluted (freshly emitted aerosols) and relatively clean (aged aerosols) conditions. Particulate matter (PM) concentrations were measured and analyzed with other tracers of traffic emissions. The temperature inversion episodes caused very high concentration of PM2.5 and PM10 (particulate matter with aerodynamic diameters less than 2.5 μm and 10 μm, respectively) and gaseous pollutants: carbon monoxide (CO), nitric oxide (NO), and nitrogen dioxide (NO2). The diurnal change of absorption and scattering coefficients during the polluted (inversion) days increased approximately by a factor of two for all wavelengths compared to the clean days. The spectral variation in aerosol absorption coefficients indicated a significant amount of absorbing aerosol from traffic emissions and residential wood burning. The analysis of single scattering albedo (SSA), Ångström exponent of absorption (AEA), and Ångström exponent of scattering (AES) for clean and polluted days provides evidences that the aerosol aging and coating process is suppressed by strong temperature inversion under cloudy conditions. In general, measured UV absorption coefficients were found to be much larger for biomass burning aerosol than for typical ambient aerosols.
Values for Mie‐equivalent aerosol asymmetry parameter (g) were derived using a variety of methods from the large suite of measurements (in situ and remote from surface and aircraft) made in Oklahoma ...during the 2003 aerosol Intensive Operations Period (IOP). Median values derived for dry asymmetry parameter at 550 nm ranged between 0.55 and 0.63 over all instruments and for all derivation methods, with the exception of one instrument which did not measure over the full size range of optically important aerosol. Median values for the “wet” asymmetry parameter (i.e., asymmetry parameter at humidity conditions closer to ambient) were between 0.59 and 0.72. Values for g derived for surface and airborne in situ measurements were highly correlated, but in situ and remote sensing measurements both at the surface and aloft did not agree as well because of vertical inhomogeneity of the aerosol. Radiative forcing calculations suggest that a 10% decrease in g would result in a 19% reduction in top of atmosphere radiative forcing for the conditions observed during the IOP. Comparison of the different methods for deriving g suggests that in computing the asymmetry parameter, aerosol size is the most important parameter to measure; composition is less important except for how it influences the hygroscopic growth (i.e., size) of particles.
Inter-comparison studies of well-characterized fractal soot particles were conducted using the following four instruments: Aerosol Mass Spectrometer-Scanning Mobility Particle Sizer (AMS-SMPS), ...Single Particle Soot Photometer (SP2), Multi-Angle Absorption Photometer (MAAP), and Photoacoustic Spectrometer (PAS). These instruments provided measurements of the refractory mass (AMS-SMPS), incandescent mass (SP2) and optically absorbing mass (MAAP and PAS). The particles studied were in the mobility diameter range from 150 nm to 460 nm and were generated by controlled flames with fuel equivalence ratios ranging between 2.3 and 3.5. The effect of organic coatings (oleic acid and anthracene) on the instrument measurements was determined. For uncoated soot particles, the mass measurements by the AMS-SMPS, SP2, and PAS instruments were in agreement to within 15%, while the MAAP measurement of optically-absorbing mass was higher by ∼ 50%. Thin organic coatings (∼ 10 nm) did not affect the instrument readings. A thicker (∼ 50 nm) oleic acid coating likewise did not affect the instrument readings. The thicker (∼60 nm) anthracene coating did not affect the readings provided by the AMS-SMPS or SP2 instruments but increased the reading of the MAAP instrument by ∼ 20% and the reading of the PAS by ∼ 65%. The response of each instrument to the different particle types is discussed in terms of particle morphology and coating material.
Submicron aerosol was analyzed during the MILAGRO field campaign in March 2006 at the T0 urban supersite in Mexico City with a High-Resolution Aerosol Mass Spectrometer (AMS) and complementary ...instrumentation. Positive Matrix Factorization (PMF) of high resolution AMS spectra identified a biomass burning organic aerosol (BBOA) component, which includes several large plumes that appear to be from forest fires within the region. Here, we show that the AMS BBOA concentration at T0 correlates with fire counts in the vicinity of Mexico City and that most of the BBOA variability is captured when the FLEXPART model is used for the dispersion of fire emissions as estimated from satellite fire counts. The resulting FLEXPART fire impact factor (FIF) correlates well with the observed BBOA, acetonitrile (CH3CN), levoglucosan, and potassium, indicating that wildfires in the region surrounding Mexico City are the dominant source of BBOA at T0 during MILAGRO. The impact of distant BB sources such as the Yucatan is small during this period. All fire tracers are correlated, with BBOA and levoglucosan showing little background, acetonitrile having a well-known tropospheric background of ~100–150 pptv, and PM2.5 potassium having a background of ~160 ng m−3 (two-thirds of its average concentration), which does not appear to be related to BB sources. We define two high fire periods based on satellite fire counts and FLEXPART-predicted FIFs. We then compare these periods with a low fire period when the impact of regional fires is about a factor of 5 smaller. Fire tracers are very elevated in the high fire periods whereas tracers of urban pollution do not change between these periods. Dust is also elevated during the high BB period but this appears to be coincidental due to the drier conditions and not driven by direct dust emission from the fires. The AMS oxygenated organic aerosol (OA) factor (OOA, mostly secondary OA or SOA) does not show an increase during the fire periods or a correlation with fire counts, FLEXPART-predicted FIFs or fire tracers, indicating that it is dominated by urban and/or regional sources and not by the fires near the MCMA. A new 14C aerosol dataset is presented. Both this new and a previously published dataset of 14C analysis suggest a similar BBOA contribution as the AMS and chemical mass balance (CMB), resulting in 13% higher non-fossil carbon during the high vs. low regional fire periods. The new dataset has ~15% more fossil carbon on average than the previously published one, and possible reasons for this discrepancy are discussed. During the low regional fire period, 38% of organic carbon (OC) and 28% total carbon (TC) are from non-fossil sources, suggesting the importance of urban and regional non-fossil carbon sources other than the fires, such as food cooking and regional biogenic SOA. The ambient BBOA/ΔCH3CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day. Also, there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts. Both facts may explain some apparent disagreements between BB impacts estimated from afternoon aircraft flights vs. those from 24-h ground measurements. We show that by properly accounting for the non-BB sources of K, all of the BB PM estimates from MILAGRO can be reconciled. Overall, the fires from the region near the MCMA are estimated to contribute 15–23% of the OA and 7–9% of the fine PM at T0 during MILAGRO, and 2–3% of the fine PM as an annual average. The 2006 MCMA emissions inventory contains a substantially lower impact of the forest fire emissions, although a fraction of these emissions occur just outside of the MCMA inventory area.
A novel multi-wavelength photoacoustic-nephelometer spectrometer (SC-PNS) has been developed for the optical characterization of atmospheric aerosol particles. This instrument integrates a white ...light supercontinuum laser with photoacoustic and nephelometric spectroscopy to measure aerosol absorption and scattering coefficients at five wavelength bands (centered at 417, 475, 542, 607, and 675 nm). These wavelength bands are selected from the continuous spectrum of the laser (ranging from 400-2200 nm) using a set of optical interference filters. Absorption and scattering measurements on laboratory-generated aerosol samples were performed sequentially at each wavelength band. To test the instrument we measured the wavelength dependence of absorption and scattering coefficients of kerosene soot and common salt aerosols. Results were favorably compared to those obtained with a commercial 3-wavelength photoacoustic and nephelometer instrument demonstrating the utility of the SC light source for studies of aerosol optical properties at selected wavelengths. Here, we discuss instrument design, development, calibration, performance and experimental results.
Light absorption by aerosols contributes to solar radiative forcing through absorption of solar radiation and heating of the absorbing aerosol layer. Besides the direct radiative effect, the heating ...can evaporate clouds and change the atmospheric dynamics. Aerosol light absorption in the atmosphere is dominated by black carbon (BC) with additional, significant contributions from the still poorly understood brown carbon and from mineral dust. Sources of these absorbing aerosols include biomass burning and other combustion processes and dust entrainment.
For particles much smaller than the wavelength of incident light, absorption is proportional to the particle volume and mass. Absorption can be calculated with Mie theory for spherical particles and with more complicated numerical methods for other particle shapes.
The quantitative measurement of aerosol light absorption is still a challenge. Simple, commonly used filter measurements are prone to measurement artifacts due to particle concentration and modification of particle and filter morphology upon particle deposition, optical interaction of deposited particles and filter medium, and poor angular integration of light scattered by deposited particles. In situ methods measure particle absorption with the particles in their natural suspended state and therefore are not prone to effects related to particle deposition and concentration on filters. Photoacoustic and refractive index-based measurements rely on the heating of particles during light absorption, which, for power-modulated light sources, causes an acoustic signal and modulation of the refractive index in the air surrounding the particles that can be quantified with a microphone and an interferometer, respectively. These methods may suffer from some interference due to light-induced particle evaporation. Laser-induced incandescence also monitors particle heating upon absorption, but heats absorbing particles to much higher temperatures to quantify BC mass from the thermal radiation emitted by the heated particles. Extinction-minus-scattering techniques have limited sensitivity for measuring aerosol light absorption unless the very long absorption paths of cavity ring-down techniques are used. Systematic errors can be dominated by truncation errors in the scattering measurement for large particles or by subtraction errors for high single scattering albedo particles. Remote sensing techniques are essential for global monitoring of aerosol light absorption. While local column-integrated measurements of aerosol light absorption with sun and sky radiometers are routinely done, global satellite measurements are so far largely limited to determining a semi-quantitative UV absorption index.
A filter-based single-wavelength photometer (Particle Soot Absorption Photometer, PSAP) for measuring light absorption by aerosols was modified to measure at three wavelengths, 467 nm, 530 nm, and ...660 nm. The modified and an unmodified photometer were calibrated during the Reno Aerosol Optics Study (RAOS) 2002 against two absorption standards: a photoacoustic instrument and the difference between the extinction and scattering coefficient. This filter-based absorption method has to be corrected for scattering aerosol and transmission changes. A simple function for this was derived from the calibration experiment as a function of transmission and single-scattering albedo. For an unmodified PSAP at typical atmospheric absorption coefficients the algorithm yields about 5-7% lower absorption coefficients than does the usually used method. The three-wavelength PSAP was used for atmospheric measurements both during RAOS and during the New England Air Quality Study (NEAQS).
The complexity of protein ubiquitination signals derives largely from the variety of polyubiquitin linkage types that can modify a target protein, each imparting distinct functional consequences. ...Free ubiquitin chains of uniform linkages and length are important tools in understanding how ubiquitin-binding proteins specifically recognize these different polyubiquitin modifications. While some free ubiquitin chain species are commercially available, mutational analyses and labeling schemes are limited to select, marketed stocks. Furthermore, the multimilligram quantities of material required for detailed biophysical and/or structural studies often makes these reagents cost prohibitive. To address these limitations, we have optimized known methods for the synthesis and purification of linear, K11-, K48-, and K63-linked ubiquitin dimers, trimers, and tetramers on a preparative scale. The high purity and relatively high yield of these proteins readily enables material-intensive experiments and provides flexibility for engineering specialized ubiquitin chain reagents, such as fluorescently labeled chains of discrete lengths.
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► Methods for preparing multimilligram quantities of discrete ubiquitin chains ► Purifications and enzyme-driven chain syntheses use readily accessible protocols ► The high-quality ubiquitin chains can be used for biophysical/structural studies ► Methodology enables the incorporation of site-specific mutations and/or labels
Carbonaceous aerosols emitted from biomass burning influence radiative forcing and climate change. Of particular interest are emissions from high-latitude peat burning because amplified climate ...change makes the large carbon mass stored in these peatlands more susceptible to wildfires and their emission can affect cryosphere albedo and air quality after undergoing transport. We combusted Siberian peat in a laboratory biomass-burning facility and characterized the optical properties of freshly emitted combustion aerosols and those photochemically aged in an oxidation flow reactor (OFR) with a three-wavelength photoacoustic instrument. Total particle count increased with aging by a factor of 6 to 11 while the total particle volume either changed little (<8%) for 19 and 44 days of equivalent aging and increased by 88% for 61 days of equivalent aging. The aerosol single-scattering albedo (SSA) of both fresh and aged aerosol increased with the increasing wavelength. The largest changes in SSA due to OFR aging were observed at the shortest of the three wavelengths (i.e., at 405 nm) where SSA increased by less than ~2.4% for 19 and 44 days of aging. These changes were due to a decrease in the absorption coefficients by ~45%, with the effect on SSA somewhat reduced by a concurrent decrease in the scattering coefficients by 20 to 25%. For 61 days of aging, we observed very little change in SSA, namely an increase of 0.31% that was caused a ~56% increase in the absorption coefficients that was more than balanced by a somewhat larger (~71%) increase in the scattering coefficients. These large increases in the absorption and scattering coefficients for aging at 7 V are at least qualitatively consistent with the large increase in the particle volume (~88%). Overall, aging shifted the absorption toward longer wavelengths and decreased the absorption Ångström exponents, which ranged from ~5 to 9. Complex refractive index retrieval yielded real and imaginary parts that increased and decreased, respectively, with the increasing wavelength. The 405 nm real parts first increased and then decreased and imaginary parts decreased during aging, with little change at other wavelengths.
Smoke particle emissions from the combustion of biomass fuels typical for the western and southeastern United States were studied and compared under high humidity and ambient conditions in the ...laboratory. The fuels used were Montana ponderosa pine (Pinus ponderosa), southern California chamise (Adenostoma fasciculatum), and Florida saw palmetto (Serenoa repens). Information on the non-refractory chemical composition of biomass burning aerosol from each fuel was obtained with an aerosol mass spectrometer and through estimation of the black carbon concentration from light absorption measurements at 870 nm. Changes in the optical and physical particle properties under high humidity conditions were observed for hygroscopic smoke particles containing substantial inorganic mass fractions that were emitted from combustion of chamise and palmetto fuels. Light scattering cross sections increased under high humidity for these particles, consistent with the hygroscopic growth measured for 100 nm particles in HTDMA measurements. Photoacoustic measurements of aerosol light absorption coefficients revealed a 20% reduction with increasing relative humidity, contrary to the expectation of light absorption enhancement by the liquid coating taken up by hygroscopic particles. This reduction is hypothesized to arise from two mechanisms: (1) shielding of inner monomers after particle consolidation or collapse with water uptake; (2) the lower case contribution of mass transfer through evaporation and condensation at high relative humidity (RH) to the usual heat transfer pathway for energy release by laser-heated particles in the photoacoustic measurement of aerosol light absorption. The mass transfer contribution is used to evaluate the fraction of aerosol surface covered with liquid water solution as a function of RH.
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