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The Plantower PMS5003 sensors (PMS) used in the PurpleAir monitor PA-II-SD configuration (PA-PMS) are equivalent to cell-reciprocal nephelometers using a 657 nm perpendicularly polarized light source that integrates light scattering from 18 to 166∘. Yearlong field data at the National Oceanic and Atmospheric Administration's (NOAA) Mauna Loa Observatory (MLO) and Boulder Table Mountain (BOS) sites show that the 1 h average of the PA-PMS first size channel, labeled “> 0.3 µm” (“CH1”), is highly correlated with submicrometer aerosol scattering coefficients at the 550 and 700 nm wavelengths measured by the TSI 3563 integrating nephelometer, from 0.4 to 500 Mm−1. This corresponds to an hourly average submicrometer aerosol mass concentration of approximately 0.2 to 200 µg m−3. A physical–optical model of the PMS is developed to estimate light intensity on the photodiode, accounting for angular truncation of the volume scattering function as a function of particle size. The model predicts that the PMS response to particles > 0.3 µm decreases relative to an ideal nephelometer by about 75 % for particle diameters ≥ 1.0 µm. This is a result of using a laser that is polarized, the angular truncation of the scattered light, and particle losses (e.g., due to aspiration) before reaching the laser. It is shown that CH1 is linearly proportional to the model-predicted intensity of the light scattered by particles in the PMS laser to its photodiode over 4 orders of magnitude. This is consistent with CH1 being a measure of the scattering coefficient and not the particle number concentration or particulate matter concentration. The model predictions are consistent with data from published laboratory studies which evaluated the PMS against a variety of aerosols. Predictions are then compared with yearlong fine aerosol size distribution and scattering coefficient field data at the BOS site. Field data at BOS confirm the model prediction that the ratio of CH1 to the scattering coefficient would be highest for aerosols with median scattering diameters < 0.3 µm. The PMS detects aerosols smaller than 0.3 µm diameter in proportion to their contribution to the scattering coefficient. The results of this study indicate that the PMS is not an optical particle counter and that its six size fractions are not a meaningful representation of particle size distribution. The relationship between the PMS 1 h average CH1 and bsp1, the scattering coefficient in Mm−1 due to particles below 1 µm aerodynamic diameter, at wavelength 550 nm, is found to be bsp1 = 0.015 ± 2.07 × 10−5 × CH1, for relative humidity below 40 %. The coefficient of determination r2 is 0.97. This suggests that the low-cost and widely used PA monitors can be used to measure and predict the submicron aerosol light scattering coefficient in the mid-visible nearly as well as integrating nephelometers. The effectiveness of the PA-PMS to serve as a PM2.5 mass concentration monitor is due to both the sensor behaving like an imperfect integrating nephelometer and the mass scattering efficiency of ambient PM2.5 aerosols being roughly constant.

Deriving aerosol optical depth (AOD) from space-borne observations is still challenging due to uncertainties associated with sensor calibration drift, cloud screening, aerosol type classification, and surface reflectance characterization. As an initial step to understanding the physical processes impacting these uncertainties in satellite AOD retrievals, this study outlines a theoretical approach to estimate biases in the satellite aerosol retrieval algorithm affected by surface albedo and prescribed aerosol optical properties using a simplified radiative transfer model with a traditional error propagation approach. We expand the critical surface reflectance concept to obtain the critical surface albedo (CSA), critical single scattering albedo (CSSA), and critical asymmetry parameter (CAP). The top-of-atmosphere (TOA) reflectance is not sensitive to significant variability in aerosol loading (AOD) at the critical value; thus, the AOD cannot be determined. Results show that 5% bias in surface albedo (A), single scattering albedo (SSA), or asymmetry parameter (g) lead to large retrieved AOD errors, especially high under conditions when A, SSA, or g are close to their critical values. The results can be useful for future research related to improvements of satellite aerosol retrieval algorithms and provide a preliminary framework to analytically quantify AOD uncertainties from satellite retrievals.

Glaciers in the tropical Andes have been rapidly losing mass since the 1970s. In addition to the documented increase in temperature, increases in light-absorbing particles deposited on glaciers could be contributing to the observed glacier loss. Here we report on measurements of light-absorbing particles sampled from glaciers during three surveys in the Cordillera Blanca Mountains in Peru. During three research expeditions in the dry seasons (May–August) of 2011, 2012 and 2013, 240 snow samples were collected from 15 mountain peaks over altitudes ranging from 4800 to nearly 6800 m. Several mountains were sampled each of the 3 years and some mountains were sampled multiple times during the same year. Collected snow samples were melted and filtered in the field then later analyzed using the Light Absorption Heating Method (LAHM), a new technique that measures the ability of particles on filters to absorb visible light. LAHM results have been calibrated using filters with known amounts of fullerene soot, a common industrial surrogate for black carbon (BC). As sample filters often contain dust in addition to BC, results are presented in terms of effective black carbon (eBC). During the 2013 survey, snow samples were collected and kept frozen for analysis with a Single Particle Soot Photometer (SP2). Calculated eBC mass from the LAHM analysis and the SP2 refractory black carbon (rBC) results were well correlated (r2 = 0.92). These results indicate that a substantial portion of the light-absorbing particles in the more polluted regions were likely BC. The 3 years of data show that glaciers in the Cordillera Blanca Mountains close to human population centers have substantially higher levels of eBC (as high as 70 ng g−1) than remote glaciers (as low as 2.0 ng g−1 eBC), indicating that population centers can influence local glaciers by sourcing BC.

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.

A question of importance for urban planning and attainment of air quality standards is how pollutant concentrations scale with city population. This study uses measurements of light absorption and light scattering coefficients as proxies for primary (i.e., black carbon aerosols) and total pollutant concentration to start addressing the relationship between per capita air pollutant concentration and city population. Analyses of aerosol light scattering and absorption measurements in suburban Mexico City, Mexico; Las Vegas, Nevada; Reno, Nevada; Beijing, China; and Delhi, India, suggest that common air pollutant concentrations scale approximately as the square root of the urban population, which is consistent with a simple 2D box model. This simple scaling relationship for per capita air pollution concentration might be useful both as a guide for comparing cities as well as for preparing for future projections of increased urbanization, especially for cities having more than 10 million inhabitants.

Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program's Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was routinely transported into the forested Sierra Nevada foothills area. Urban aerosols and trace gases experienced significant physical and chemical transformations as they mixed with the reactive biogenic hydrocarbons emitted from the forest. Two heavily-instrumented ground sites – one within the Sacramento urban area and another about 40 km to the northeast in the foothills area – were set up to characterize the evolution of meteorological variables, trace gases, aerosol precursors, aerosol size, composition, and climate-related properties in freshly polluted and "aged" urban air. On selected days, the DOE G-1 aircraft was deployed to make similar measurements upwind and across the evolving Sacramento plume in the morning and again in the afternoon. The NASA B-200 aircraft, carrying remote sensing instruments, was also deployed to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties within and around the plume. This overview provides: (a) the scientific background and motivation for the study, (b) the operational and logistical information pertinent to the execution of the study, (c) an overview of key observations and initial findings from the aircraft and ground-based sampling platforms, and (d) a roadmap of planned data analyses and focused modeling efforts that will facilitate the integration of new knowledge into improved representations of key aerosol processes and properties in climate models., United States. Dept. of Energy. Atmospheric System Research Program (Contract DE-AC06-76RLO 1830), United States. National Oceanic and Atmospheric Administration, United States. National Aeronautics and Space Administration. HQ Science Mission Directorate Radiation Sciences Program, United States. National Aeronautics and Space Administration. CALIPSO Program, United States. Dept. of Energy. Atmospheric Radiation Measurement Program (Interagency Agreement No. DE-AI02-05ER63985)

We present the first laboratory and ambient photoacoustic (PA) measurement of aerosol light absorption coefficients at ultraviolet (UV) 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. Exact T-matrix method calculations were used to model the absorption and scattering characteristics of fractal-like agglomerates of different compactness and varying number of monomers. With these calculations, we attempted to estimate the number of monomers and fractal dimension of laboratory generated kerosene soot. 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.

A series of laboratory experiments at the Fire Laboratory at Missoula (FLAME) investigated chemical, physical, and optical properties of fresh smoke samples from combustion of wildland fuels that are burned annually in the western and southeastern US The burns were conducted in the combustion chamber of the US Forest Service Fire Sciences Laboratory in Missoula, Montana. Here we discuss retrieval of optical properties for a variety of fuels burned in FLAME 2, using nephelometer-measured scattering coefficients, photoacoustically-measured aerosol absorption coefficients, and size distribution measurements. Uncertainties are estimated from various instrument characteristics and instrument calibration studies. Our estimates of single scattering albedo for different dry smoke samples varied from 0.428 to 0.990, indicative of observed wide variations in smoke aerosol chemical composition. In selected case studies, we retrieved the complex refractive index from measurements but show that these are highly sensitive to uncertainties in measured size distributions.

We report the direct observation of laboratory production of spherical, carbonaceous particles – "tar balls" – from smoldering combustion of two commonly occurring dry mid-latitude fuels. Real-time measurements of spectrally varying absorption Ångström coefficients (AAC) indicate that a class of light absorbing organic carbon (OC) with wavelength dependent imaginary part of its refractive index – optically defined as "brown carbon" – is an important component of tar balls. The spectrum of the imaginary parts of their complex refractive indices can be described with a Lorentzian-like model with an effective resonance wavelength in the ultraviolet (UV) spectral region. Sensitivity calculations for aerosols containing traditional OC (no absorption at visible and UV wavelengths) and brown carbon suggest that accounting for near-UV absorption by brown carbon leads to an increase in aerosol radiative forcing efficiency and increased light absorption. Since particles from smoldering combustion account for nearly three-fourths of the total carbonaceous aerosol mass emitted globally, inclusion of the optical properties of tar balls into radiative forcing models has significance for the Earth's radiation budget, optical remote sensing, and understanding of anomalous UV absorption in the troposphere.

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., Atmospheric Chemistry and Physics, 10 (12), ISSN:1680-7375, ISSN:1680-7367

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.

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.

As part of a major atmospheric chemistry and aerosol field program carried out in March 2006, a study was conducted in the area to the north and northeast of Mexico City to investigate the evolution of aerosols and their associated optical properties in the first few hours after their emission. The focus of the T1-T2 aerosol study was to investigate changes in the specific absorption αABS (absorption per unit mass, with unit of m2 g−1) of black carbon as it aged and became coated with compounds such as sulfate and organic carbon, evolving from an external to an internal mixture. Such evolution has been reported in previous studies. The T1 site was located just to the north of the Mexico City metropolitan area; the T2 site was situated approximately 35 km farther to the northeast. Nephelometers, particle soot absorption photometers, photoacoustic absorption spectrometers, and organic and elemental carbon analyzers were used to measure the optical properties of the aerosols and the carbon concentrations at each of the sites. Radar wind profilers and radiosonde systems helped to characterize the meteorology and to identify periods when transport from Mexico City over T1 and T2 occurred. Organic and elemental carbon concentrations at T1 showed diurnal cycles reflecting the nocturnal and early morning buildup from nearby sources, while concentrations at T2 appeared to be more affected by transport from Mexico City. Specific absorption during transport periods was lower than during other times, consistent with the likelihood of fresher emissions being found when the winds blew from Mexico City over T1 and T2. The specific absorption at T2 was larger than at T1, which is also consistent with the expectation of more aged particles with encapsulated black carbon being found at the more distant location. In situ measurements of single scattering albedo with an aircraft and a ground station showed general agreement with column-averaged values derived from rotating shadowband radiometer data, although some differences were found that may be related to boundary-layer evolution.

The modified anomalous diffraction approximation (MADA) is used to predict absorption and extinction in water and ice clouds, but it does not predict the scattering phase function or asymmetry parameter g. In conjunction with g parameterizations, it has been used in satellite remote sensing and to treat the radiative properties of ice clouds in global climate models. However, it has undergone only limited testing. This study 1) compares extinction efficiencies (Qext) predicted by MADA for a laboratory grown ice cloud against corresponding Qext measurements over the wavelength range 2–14 μm; 2) tests absorption efficiencies (Qabs) and Qext predicted by MADA against those predicted by T-matrix theory and the finite difference time domain (FDTD) method; and 3) compares MADA with three popular schemes used for predicting the radiative properties of cirrus clouds. In addition, the photon tunneling process may contribute up to 45% of the absorption in water clouds at some terrestrial wavelengths, but its role in ice clouds is uncertain since it depends on particle shape. For the first time, the efficiency of photon tunneling was parameterized in terms of ice particle shape. Finally, an alternate formulation of MADA that offers some physical insights is presented. MADA errors relative to the Qext measurements were 3.0% on average, while mean MADA errors relative to Qabs from T-matrix, over the wavelength range 2–18 μm (size parameter range 2–22), were 5.9%. The mean error for the single scattering albedo relative to T-matrix calculations was 2.5%. MADA absorption errors relative to FDTD over the wavelength range 3–100 μm were no greater than 15% for six ice particle shapes. Finally, the absorption coefficients predicted by MADA and two other popular parameterizations generally agreed within 5%.

An optical extinction cell (OEC) was used to measure aerosol particle extinction coefficient σEP at three wavelengths, 467, 530, and 660 nm. The details of the design and the results of its use in the Reno Aerosol Optics Study (RAOS) in June 2002 are presented. The OEC agreed well with the scattering coefficient σSP measured using an integrating nephelometer for nonabsorbing aerosols. Linear regression of 1 min-averaged σEP versus σSP yielded slopes 1.00 ± 0.02 and offsets < 4 Mm−1 in the range ∼50 to 900 Mm−1. The difference, (σEP − σSP) was taken as a standard measure of absorption coefficient, σAP. The noise calculated as the standard deviation of (σEP − σSP) from 1 min-averaged white aerosol data was about 10, 11, and 5 Mm− 1 for the blue, green and red wavelengths, respectively. The absorption coefficients calculated from σEP − σSP were compared with the absorption coefficients measured using a photoacoustic instrument. In general, the two methods agreed better than 10%. The data gives also a way for...

Emission measurements were obtained for a variety of military vehicles at Hill Air Force Base (Ogden, UT) in November 2000 as part of a Strategic Environmental Research and Development Program. Aircraft ground support equipment vehicles using gasoline, diesel, and JP8 fuels were tested using chassis dynamometers under predetermined load. The exhaust from the tested vehicle was passed to a dilution tunnel where it was diluted 30-40 times and collected using Micro-Orifice Uniform Deposit Impactor (MOUDI) fitted with aluminum substrates, an XAD-coated annular denuder, and a filter followed by a solid adsorbent. All MOUDI substrates were analyzed for mass and for organic and elemental (EC) carbon by the thermal/optical reflectance method and for polycyclic aromatic hydrocarbons (PAHs) by GC/MS. Black carbon was measured with a photoacoustic instrument. The denuder and filter/solid adsorbent samples were analyzed for semivolatile PAH. Overall, there is more mass and higher EC contribution when the vehicle is run under higher load in comparison with the low load. However, older vehicles generally show more mass and EC emissions than newer vehicles, and there is a shift toward smaller particle sizes for the low load, which is most pronounced for newer vehicles. The particle-associated semivolatile PAHs and nonvolatile four-through six-ring PAHs are present predominantly on the submicron particles collected on MOUDI stages 0.1-0.18, 0.18-0.32, and 0.32-0.56 microm. For the low-load runs, the distribution of PAHs seems to be shifted toward smaller size particles. The gas-particle phase distribution of semivolatile PAHs depends also on the engine loading. For idle, not only are the more volatile two- and three-ring PAHs, from naphthalene to dimethylphenanthrenes, retained on the denuder portion, but also less volatile four-ring PAHs, such as fluoranthene and pyrene, are retained by the denuder at the 80-90% range, which implies that they are present predominantly in the gas phase. In contrast, for engines under high loads, a much larger portion of three- and four-ring PAHs are partitioned to the particle phase.

My postdoctorate from August 1988 to December 1991 at the University of Mississippi and NCPA favorably influenced my career. Thinking back on the cast of characters and the dramatic science being pursued there brings a smile. My main mentors were Dr. James Sabatier, Dr. Richard Raspet, and Dr. Henry Bass. I was involved with theory and experiments for acoustic to seismic coupling; land mine detection; nondestructive measurements of soil properties; and fundamental analysis of Celcor extruded ceramic catalysts as materials for thermoacoustic stacks. We often worked in real-world settings—cotton and soybean fields, and at “Audi Acres” where we used massive low frequency speaker elevated with construction scaffolding and a winch as sound sources. I worked hours with Mike the machinist constructing acoustical resonators and thermoacoustic heat engines. The vibrant social and political scene was something to behold—including early morning jogging in the Faulkner woods, regular basketball games at lunch; visiti...

Glaciers in the tropical Andes have been rapidly losing mass since the 1970s. In addition to the documented increase in air temperature, increases in light absorbing particulates deposited on glaciers could be contributing to the observed glacier loss. Here we report on measurements of light absorbing particulates sampled from glaciers during three surveys in the Cordillera Blanca in Peru. During three research expeditions in the dry seasons (May–August) of 2011, 2012 and 2013, two hundred and forty snow samples were collected from fifteen mountain peaks over altitudes ranging from 4800 to nearly 6800 m. Several mountains were sampled each of the three expeditions and some mountains were sampled multiple times during the same expedition. Collected snow samples were melted and filtered in the field then later analyzed using the Light Absorption Heating Method (LAHM), a new technique that measures the ability of particulates on filters to absorb visible light. LAHM results have been calibrated using filters with known amounts of fullerene soot, a common industrial surrogate for black carbon (BC). As sample filters often contain dust in addition to BC, results are presented in terms of effective Black Carbon (eBC). During the 2013 survey, snow samples were collected and kept frozen for analysis with a Single Particle Soot Photometer (SP2). Calculated eBC mass from the filter analysis and the SP2 refractory Black Carbon (rBC) results were well correlated (r2 = 0.92). These results indicate that a substantial portion of the light absorbing particulates in the more polluted areas were likely BC. The three years of data show that glaciers in the Cordillera Blanca Mountains close to human population centers have substantially higher levels of eBC (as high as 70 ng g−1) than remote glaciers (as low as 2.0 ng g−1 eBC), indicating that population centers can influence local glaciers by sourcing BC.

The measurement of diesel vehicle exhaust particulate mass is currently accomplished using filter collection methods according to the Code of Federal Regulations (CFR). Such filter methods limit time resolution to a minimum of several minutes, making it impossible to study emissions during transient operating conditions. Extensive testing of five different measurement methods has demonstrated that fast response measurements of diesel exhaust particulate mass concentrations, consistent with CFR filter measurements, are feasible using existing technology. The measurement principles of choice are the real time weighing of exhaust samples as implemented in the tapered element oscillating microbalance (TEOM) and the measurement of light scattering from exhaust particles as implemented in the DustTrak nephelometer. Each of these two instruments has distinctive strengths. The TEOM excels in the area of constant calibration, independent of vehicle. For the DustTrak, this calibration varies by vehicle. On the other hand, the DustTrak has an excellent signal-to-noise ratio, freedom from interference due to other exhaust sample properties, good time resolution, and simplicity. The strengths of the two measurement methods are complimentary, so an obvious suggestion is to integrate them. The nephelometer would obtain a fast response signal, with near real time calibration provided by the microbalance.

With a multi-instrument approach, we determined the particle size spectrum between 20 nm and 1.6 mm diameter in the outflow portions of a convective tropical cloud. The measured particle size spectrum covered ≈ 12 orders of magnitude particle concentration over ≈ orders of magnitude particle size. Within this size interval, the particle spectrum revealed three modes: A cirrus haze nucleus mode, a cirrus haze particle mode, and a cirrus ice particle mode. In the optically active size range D > 0.4 μm, the particle population inside the cirrus cloud was enhanced above “background” concentrations by almost 4 orders of magnitude The prevalence of submicron particles led to the definition of cirrus haze nuclei which can grow along Kohler curves to radiatively important sizes. While cirrus ice particles carried most of the condensate mass, the cirrus haze particles dominated the surface area. Consequently, the presence of cirrus haze particles tripled extinction across the whole (visible and infrared) spectrum, and enhanced the IR single-scatter albedo of the cloud.

A combination of the finite-difference time domain technique and a ray-by-ray integration method has been applied to compute the extinction efficiency and single-scattering albedo for various size distributions associated with nonspherical ice crystals in laboratory and natural cirrus clouds. The two methods are applicable to small and large size parameters, respectively. The results obtained by the two methods converge when effective size parameters are larger than about 6. For laboratory ice crystals the overall features of the computed extinction efficiency are in general agreement with those determined from measurements. In particular, significant extinction windows at 2.85 and 10.5 μm, associated with the Christiansen effect, are observed in both theoretical and experimental results. These extinction minima appear because the real part of the refractive index approaches unity, so that absorption dominates light attenuation. The single-scattering albedos at the two Christiansen spectral regions are found to be smaller than 0.5 for the laboratory ice crystals. The contours of extinction efficiency and single-scattering albedo versus wavelength and particle size show that the magnitude of the Christiansen effect is dependent on particle size. For large ice crystals, the extinction windows are not significant because the extinction efficiency converges to its asymptotic value of 2, regardless of size parameters. For a number of size distributions observed during FIRE II IFO, the Christiansen effect is small. However, for cold cirrus, the extinction efficiencies in the Christiansen bands are approximately one half of the values at nearby wavelengths due to a significant number of small ice crystals that are present in cold cirrus clouds. It is concluded that the Christiansen effect must be accounted for in the determination of the extinction efficiency and the single-scattering albedo for small ice particles in order to obtain a reliable optical depth and emissivity for cirrus clouds at infrared wavelengths. Finally, we show that using spherical particles with Mie theory is inadequate to explain the extinction measurements.

Light extinction by aerosols is due to scattering and absorption. The anthropogenic contribution is generally dominated by light scattering by sulfate particles and light absorption by elemental carbon. While real-time, in situ instrumentation for the measurement of ambient light scattering exists and is widely used (i.e., nephelometers), no such instrumentation is currently in use for the sensitive measurement of ambient light absorption by aerosols. Instrumentation for this purpose has been developed in the past, mostly for the measurement of gaseous light absorption, but it has also been applied to the measurement of aerosol light absorption. This instrumentation is based on measuring the absorbed energy, as opposed to measuring light extinction, which is complicated by the scattering component and is also less sensitive. For aerosols, the absorbed energy heats the gas, leading to its thermal expansion. The two most sensitive techniques to detect this expansion are photoacoustic detection, in which the light source is modulated and the periodic expansion of the gas results in a sound wave at the modulation frequency, which may be detected with a microphone; and optical homodyne interferometry, in which the changed gas density is detected with a Mach-Zehnder type interferometer via the directly related change in refractive index. This article reviews the current state of both photoacoustic and interferometric detection methods. In addition, new ideas are discussed that are currently implemented by our group and should lead to substantial improvements. Size and reliability are being improved by utilizing modern, compact solid state lasers. New designs both for the photoacoustic cell and the interferometer promise to be less susceptible to acoustic background noise. In the case of the photoacoustic cell, the new design also virtually eliminates the previously dominant noise source, coherent window noise. Furthermore, an acoustic amplifier, based on the thermoacoustic effect, is being integrated into the photoacoustic cell to further improve its sensitivity.

Ground-based aerosol measurements made in June 2010 within Sacramento urban area (site T0) and at a 40-km downwind location (site T1) in the forested Sierra Nevada foothills area are used to investigate the evolution of multispectral optical properties as the urban aerosols aged and interacted with biogenic emissions. Along with black carbon and non-refractory aerosol mass and composition observations, spectral absorptio (βabs), scattering (βsca), and extinction (βext) coefficients for wavelengths ranging from 355 to 1064 nm were measured at both sites using photoacoustic (PA) instruments with integrating nephelometers and using cavity ring-down (CRD) instruments. The daytime average Ångström exponent of absorption (AEA) was ~1.6 for the wavelength pair 405 and 870 nm at T0, while it was ~1.8 for the wavelength pair 355 and 870 nm at T1, indicating a modest wavelength-dependent enhancement of absorption at both sites throughout the study. The measured and Mie theory calculations of multispectral βsca showed good correlation (R2=0.85–0.94). The average contribution of supermicron aerosol (mainly composed of sea salt particles advected in from the Pacific Ocean) to the total scattering coefficient ranged from less than 20% at 405 nm to greater than 80% at 1064 nm. From 22 to 28 June, secondary organic aerosol mass increased significantly at both sites due to increased biogenic emissions coupled with intense photochemical activity and air mass recirculation in the area. During this period, the short wavelength scattering coefficients at both sites gradually increased due to increase in the size of submicron aerosols. At the same time, BC mass-normalized absorption cross-section (MAC) values for ultraviolet wavelengths at T1 increased by ~60% compared to the relatively less aged urban emissions at the T0 site. In contrast, the average MAC values for 870 nm wavelength were identical at both sites. These results suggest formation of moderately brown secondary organic aerosols formed in biogenically-influenced urban air.

Extinction measurements with a laser diode (0.685 μm) and a Fourier transform infrared spectrometer (2–18 μm) were performed on laboratory ice clouds (5 μm ≤ D ≤ 70 μm) grown at a variety of temperatures, and thus at a variety of crystal habits and average projected crystal area. Ice clouds were grown by nucleation of a supercooled water droplet cloud with a rod cooled with liquid nitrogen. The ice crystals observed were mainly plates and dendrites at the coldest temperatures (≈−15 °C) and were mainly columns and needles at warmer temperatures (≈−5 °C). The crystals were imaged with both a novel microscope equipped with a video camera and a heated glass slide and a continuously running Formvar replicator. The IR spectral optical-depth measurements reveal a narrow (0.5-μm-width) extinction minimum at 2.84 μm and a wider (3-μm-width) minimum at 10.5 μm. These partial windows are associated with wavelengths where the real part of the index of refraction for bulk ice has a relative minimum so that extinction is primarily due to absorption rather than scattering (i.e., the Christiansen effect). Bulk ice has absorption maxima near the window wavelengths. IR extinction efficiency has a noticeable wavelength dependence on the average projected crystal area and therefore on the temperature-dependent crystal properties. The average-size parameters in the visible for different temperatures ranged from 64 to 128, and in the IR they ranged from 2.5 to 44. The extinction efficiency and the single-scatter albedo for ice spheres as computed from Mie scattering also show evidence of the Christiansen effect.

[1] During the Fire Laboratory at Missoula Experiments (FLAME), we studied the physical, chemical, and optical properties of biomass burning smoke from the laboratory combustion of various wildland fuels. A good understanding of these properties is important in determining the radiative effects of biomass burning aerosols, with impacts on both local and regional visibility and global climate. We measured aerosol size distributions with two instruments: a differential mobility particle sizer (DMPS) and an optical particle counter (OPC). Volume size distributions from different burns varied from monomodal to multimodal, with geometric mean diameters ranging from 0.20–0.57 μm and geometric standard deviations ranging from 1.68–2.97. By reconciling the differences between the two sizing instruments, we estimated aerosol effective refractive indices with values ranging from 1.41 to 1.61. We reconstructed aerosol chemical composition for each burn using data from filters collected and analyzed with the Interagency Monitoring of Protected Visual Environments (IMPROVE) samplers and protocols. Aerosols were generally comprised of carbon with organic species accounting for the largest mass fraction in most cases. We used composition data to calculate aerosol density, which ranged from 1.22–1.92 g cm−3, and real and imaginary refractive indices, which had ranges of 1.55–1.80 and 0.01–0.50 respectively. Aerosol physical, chemical, and optical characterizations were combined to calculate dry mass scattering (MSE) and absorption (MAE) efficiencies at 532 nm. These parameters had values between 1.6–5.7 m2 g−1 and 0.04–0.94 m2 g−1.

A comparison between observed aerosol optical properties from the MILAGRO field campaign, which took place in the Mexico City Metropolitan Area (MCMA) during March 2006, and values simulated by the Weather Research and Forecasting (WRF-Chem) model, reveals large differences. To help identify the source of the discrepancies, data from the MILAGRO campaign are used to evaluate the "aerosol chemical to aerosol optical properties" module implemented in the full chemistry version of the WRF-Chem model. The evaluation uses measurements of aerosol size distributions and chemical properties obtained at the MILAGRO T1 site. These observations are fed to the module, which makes predictions of various aerosol optical properties, including the scattering coefficient, Bscat; the absorption coefficient, Babs; and the single-scattering albedo, ϖ0; all as a function of time. Values simulated by the module are compared with independent measurements obtained from a photoacoustic spectrometer (PAS) at a wavelength of 870 nm. Because of line losses and other factors, only "fine mode" aerosols with aerodynamic diameters less than 2.5 μm are considered here. Over a 10-day period, the simulations of hour-by-hour variations of Bscat are not satisfactory, but simulations of Babs and ϖ0 are considerably better. When averaged over the 10-day period, the computed and observed optical properties agree within the uncertainty limits of the measurements and simulations. Specifically, the observed and calculated values are, respectively: (1) Bscat, 34.1±5.1 Mm−1 versus 30.4±3.4 Mm−1; (2) Babs, 9.7±1.0 Mm−1 versus 11.7±1.2 Mm−1; and (3) ϖ0, 0.78±0.05 and 0.74±0.03. The discrepancies in values of ϖ0 simulated by the full WRF-Chem model thus cannot be attributed to the "aerosol chemistry to optics" module. The discrepancy is more likely due, in part, to poor characterization of emissions near the T1 site, particularly black carbon emissions.

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 OA (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 index correlates well with the observed BBOA, 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 ppt, 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 predicted fire impacts. 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 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 fire impacts 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 15% higher modern 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, 37% of organic carbon (OC) and 30% total carbon (TC) are from modern sources, suggesting the importance of urban and regional modern carbon sources other than the fires, such as food cooking and regional biogenic SOA. 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. The ambient BBOA/ΔCH3CN ratio is much higher in the afternoon when the wildfires are most intense than during the rest of the day, which may explain some disagreements between BB impacts from afternoon aircraft flights and those from 24-h ground measurements. Finally, we show that there are large differences in the contributions of the different OA components to the surface concentrations vs. the integrated column amounts.

A novel two-beam interferometer for the measurement of a refractive index or its induced changes is described. This interferometer consists of only two optical elements and is largely insensitive to their movement. A laboratory prototype has been built. It uses a polarized version of the folded Jamin interferometer to allow for convenient phase adjustment.