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Artifacts in the Aerosol Size Distribution Measured by the Ultra-High-Sensitivity Aerosol Spectrometer (UHSAS)

The ultra-high-sensitivity aerosol spectrometer (UHSAS) (Droplet Measurement Technologies, Longmont, Colorado) is an optical particle size spectrometer that determines aerosol size distributions in the diameter range from 60 to 1000 nm in 100 logarithmically spaced diameter bins1 by measuring the amount of light scattered by individual aerosol particles from a 1054-nm laser. Recently, it was noticed that aerosol size distributions determined by the UHSAS from all U.S. Department of Energy Atmospheric Radiation Measurement (ARM) user facility sites exhibited modes at diameters greater than ~500 nm (Figure 1, blue arrows). These modes were not present in size distributions determined by another aerosol spectrometer that was co-located with the UHSAS, the Grimm 11D optical particle counter (OPC) (GRIMM Aerosol Technik Ainring GmbH & Co. KG, Germany), which sizes particles into 31 linearly spaced diameters bins from 253 to 35,150 nm using a 683-nm wavelength laser. Additionally, abrupt changes in aerosol particle number concentration with changing particle diameter are seen in UHSAS data at several diameters (Figure 1, red arrows). The purpose of this report is to explain the origin of the modes and the abrupt changes in aerosol size distributions observed by the UHSAS and why they are absent in the data from the Grimm OPC.

54 ENVIRONMENTAL SCIENCES↗

Arctic Black Carbon Aerosol Deposition Study North Slope of Alaska 2020- UHSAS Measurements

Particles are removed from the atmosphere through both wet and dry deposition. These processes are poorly understood, though they constitute important uncertainties in climate and air quality models. This project aims to use observational constraints on particle fluxes to improve model representations of dry deposition. Within this data set, we measured fluxes of size resolved particles with an ultrahigh sensitivity aerosol spectrometer (UHSAS) at the ARM facility’s North Slope Alaska site. Measurements were made at the meteorological tower between 9 Sept and 25 Oct 2021. This site is a coastal tundra location and received snow during the project.

Aerosol concentration↗

Ultra-High-Sensitivity Aerosol Spectrometer (UHSAS) Instrument Handbook

The Ultra-High-Sensitivity Aerosol Spectrometer (UHSAS) (Figure 1) is an optical-scattering, laser-based aerosol particle spectrometer system for sizing particles in the 60 to 1000 nanometer (nm) range [1–3]. The instrument counts particles in up to 100 user-specified sizing bins. The instrument’s laser illuminates particles, which scatter light. The system captures the peak light signals that are generated. These signals are used for particle sizing, since the amount of light scattered correlates strongly with particle size.

54 ENVIRONMENTAL SCIENCES↗

The impact of optical measurement techniques on measured aerosol particle size distributions

Ambient aerosol particle size distributions measured by the Ultra-High Sensitivity Aerosol Spectrometer (UHSAS) at various sites around the world exhibit modes at optical diameters near 600 nm and 850 nm. These modes are not present in concurrent measurements with the Grimm 11-D Optical Particle Counter (OPC). Here, in this study, we argue that these modes result from the optical measurement technique itself, and we explain why they appear in measurements by the UHSAS but not in those by the Grimm OPC. We construct computer models of the UHSAS and Grimm (“digital UHSAS” and “digital Grimm”) and use these to investigate the size distribution that would result from measurements of artificial aerosol particle size distributions that do not contain modes. The appearance of modes for the structureless incoming size distributions sampled by the digital UHSAS is explained by the nonlinear behavior of partial scattering cross sections of uniform spherical particles as a function of their diameter. The absence of modes in the digital Grimm is explained by the coarser size resolution of that instrument. Detailed analysis of the relationship between optical and geometric diameters for uniform spherical particles reveals two important results. First, these diameters generally have different numerical values for the same particle, and second, the relationship is nonlinear; thus, widths of size bins in terms of optical diameter differ from those in geometric diameter. These results explain the modes observed in the ambient size distributions and highlight concerns with attempts to create a merged size distribution by combining measurements from different instruments.

54 ENVIRONMENTAL SCIENCES↗

Microscopic Origins of the Nonlinear Behavior of Particle-Filled Rubber Probed with Dynamic Strain XPCS

The underlying microscopic response of filler networks in reinforced rubber to dynamic strain is not well understood due to the experimental difficulty of directly measuring filler network behavior in samples undergoing dynamic strain. This difficulty can be overcome with in situ X-ray photon correlation spectroscopy (XPCS) measurements. The contrast between the silica filler and the rubber matrix for X-ray scattering allows us to isolate the filler network behavior from the overall response of the rubber. This in situ XPCS technique probes the microscopic breakdown and reforming of the filler network structure, which are responsible for the nonlinear dependence of modulus on strain, known in the rubber science community as the Payne effect. These microscopic changes in the filler network structure have consequences for the macroscopic material performance, especially for the fuel efficiency of tire tread compounds. In this work, we elucidate the behavior with in situ dynamic strain XPCS experiments on industrially relevant, vulcanized rubbers filled (13 vol %) with novel air-milled silica of ultrahigh-surface area (UHSA) (250 m 2 /g). The addition of a silane coupling agent to rubber containing this silica causes an unexpected and counterintuitive increase in the Payne effect and decrease in energy dissipation. For this rubber, we observe a nearly two-fold enhancement of the storage modulus and virtually equivalent loss tangent compared to a rubber containing a coupling agent and conventional silica. Interpretation of our in situ XPCS results simultaneously with interpretation of traditional dynamic mechanical analysis (DMA) strain sweep experiments reveals that the debonding or yielding of bridged bound rubber layers is key to understanding the behavior of rubber formulations containing the silane coupling agent and high-surface area silica. These results demonstrate that the combination of XPCS and DMA is a powerful method for unraveling the microscale filler response to strain which dictates the dynamic mechanical properties of reinforced soft matter composites. With this combination of techniques, we have elucidated the great promise of UHSA silica when used in concert with a silane coupling agent in filled rubber. Such composites simultaneously exhibit large moduli and low hysteresis under dynamic strain.

36 MATERIALS SCIENCE↗

Aircraft Measurements of BrO, IO, Glyoxal, NO2, H2O, O2-O2 and Aerosol Extinction Profiles in the Tropics: Comparison with Aircraft-/Ship-Based in Situ and Lidar Measurements

Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4/ were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAXDOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/ National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity-enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2-0.55 pptv IO and 32-36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and air-craft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6 deg N; 101.2 to 97.4 deg W). At 14.5 km, 5-10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12-20 degrees of freedom (DoF) and up to 500m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 x 10(exp 13) molec cm(exp -2) (RF12) and at least 0.5 x 10(exp 13) molec cm(exp -2) (RF17, 0- 10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 x 10(exp 12) molec cm(exp -2) (RF12) and 2.5 x 10(exp 12) molec cm(exp -2) (RF17) and glyoxal VCDs of 2.6 x 10(exp 14) molec cm(exp -2) (RF12) and 2.7 x 10(exp 14) molec cm(exp -2) (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 plus or minus 5 %, 0.1-0.2 pptv; glyoxal: 52 plus or minus 5 %, 3-20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.

Volkamer, R.↗

aosccnuhsaskappa.c1

Hygroscopicity parameter kappa derived from CCN and UHSAS data sources

54 ENVIRONMENTAL SCIENCES↗

mergedsmpsuhsas.c1

Merged aerosol particle size distribution from the SMPS and UHSAS datastreams

54 ENVIRONMENTAL SCIENCES↗

CACTI: Best Estimate Aerosol Size Distribution by airborne measurements

These data were collected during the Cloud, Aerosol, and Complex Terrain Interactions (CACTI; https://www.arm.gov/research/campaigns/amf2018cacti ) field campaign in the Sierras de Córdoba mountain range of north-central Argentina as part of ARM Aerial Facility (AAF) deployment. The ARM Aerial Facility Gulfstream-1 was operated from Las Higueras Airport (IATA: RCU, ICAO: SAOC), Río Cuarto, Córdoba, Argentina, for the Intensive Observation Period (IOP) from Nov. 1 through Dec. 15, 2018. The G-1 aircraft performed 22 research flights over the first ARM Mobile Facility (AMF1) location in the Sierras de Córdoba mountain range to measure atmospheric state and turbulence, cloud water content and droplet size distributions, aerosol precursor gases, aerosol chemical composition and size distributions. The current data set presents Best Estimate Aerosol Size Distribution: a merged aerosol size distribution composed of the data from 5 sensors; three aerosol spectrometers: Scanning Mobility Particle Sizer (SMPS), Ultra-High Sensitivity Aerosol Spectrometer (UHSAS), and Passive Cavity Aerosol Spectrometer (PCASP); and two cloud probes: Cloud Aerosol Spectrometer (CAS) and Fast Cloud Droplet Probe (FCDP). The SMPS data were interpolated to 1 second from “native” time resolution of about 64 second to match all other probes.

54 ENVIRONMENTAL SCIENCES↗

Experimental Report: Multi-Instrument Comparison of AAF Size Distribution Instruments

Aerosols are particles suspended in the atmosphere, ranging in size from nanometers to micrometers. Their size distribution affects key atmospheric processes, including nucleation, coagulation, scavenging, activation, and radiative properties (Seinfeld and Pandis 2016). Aerosol size distribution is a critical parameter in atmospheric science, influencing processes such as cloud formation and radiative forcing. Accurate representation of aerosol size distributions is essential for understanding their impact on climate, air quality, and human health. However, aerosol size and composition vary significantly across time and space due to meteorological conditions and natural or anthropogenic sources. (Wu and Boor 2021). Various instruments are used to measure aerosol size distributions, each with distinct principles, advantages, and limitations. This report begins with an in-depth overview of aerosol size-distribution comparison studies, focusing on the passive cavity aerosol spectrometer probe (PCASP), portable optical particle spectrometer (POPS), ultra-high-sensitivity aerosol spectrometer (UHSAS), aerodynamic particle sizer (APS), and scanning mobility particle sizer (SMPS). All of these instruments are used by the U.S. Department of Energy Atmospheric Radiation Measurement (ARM) Aerial Facility (AAF), which commissioned this comparison and report. The report evaluates the strengths and weaknesses of these instruments, highlights their applications, and discusses efforts to merge data from multiple instruments for comprehensive analysis.

54 ENVIRONMENTAL SCIENCES↗

Arctic Black Carbon Aerosol Deposition Study North Slope of Alaska 2020- ACSM Measurements

Particles are removed from the atmosphere through both wet and dry deposition. These processes are poorly understood, though they constitute important uncertainties in climate and air quality models. This project aims to use observational constraints on particle fluxes to improve model representations of dry deposition. In support of black carbon (SP2) and particles (UHSAS) flux measurements at the meteorological tower, we measured non-refractory chemically-speciated aerosol composition with an Aerosol Chemical Speciation Monitor at the the NSA Central Facility (C1). ACSM measurements were made between 9 Sept and 26 Oct 2021. This site is a coastal tundra location, and received snow during the project.

Chl_ACSM↗

Arctic Black Carbon Aerosol Deposition Study North Slope of Alaska 2020- ACSM Measurements

Particles are removed from the atmosphere through both wet and dry deposition. These processes are poorly understood, though they constitute important uncertainties in climate and air quality models. This project aims to use observational constraints on particle fluxes to improve model representations of dry deposition. In support of black carbon (SP2) and particles (UHSAS) flux measurements at the meteorological tower, we measured non-refractory chemically-speciated aerosol composition with an Aerosol Chemical Speciation Monitor at the the NSA Central Facility (C1). ACSM measurements were made between 9 Sept and 26 Oct 2021. This site is a coastal tundra location, and received snow during the project.

Aerosol Chemical Speciation Monitor↗

Intercomparison of Aerosol Volume Size Distributions Derived from AERONET Ground-Based Remote Sensing and LARGE in Situ Aircraft Profiles During the 2011–2014 DRAGON and DISCOVER-AQ Experiments

Aerosol volume size distribution (VSD) retrievals from the Aerosol Robotic Network (AERONET) aerosol monitoring network were obtained during multiple DRAGON (Distributed Regional Aerosol Gridded Observational Network) campaigns conducted in Maryland, California, Texas and Colorado from 2011 to 2014. These VSD retrievals from the field campaigns were used to make comparisons with near-simultaneous in situ samples from aircraft profiles carried out by the NASA Langley Aerosol Group Experiment (LARGE) team as part of four campaigns comprising the DISCOVER-AQ (Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality) experiments. For coincident (1 h) measurements there were a total of 91 profile-averaged fine-mode size distributions acquired with the LARGE ultra-high sensitivity aerosol spectrometer (UHSAS) instrument matched to 153 AERONET size distributions retrieved from almucantars at 22 different ground sites. These volume size distributions were characterized by two fine-mode parameters, the radius of peak concentration (rpeak_conc) and the VSD fine-mode width (widthpeak_conc). The AERONET retrievals of these VSD fine-mode parameters, derived from ground-based almucantar sun photometer data, represent ambient humidity values while the LARGE aircraft spiral profile retrievals provide dried aerosol (relative humidity; RH< 20 %) values. For the combined multiple campaign dataset, the average difference in rpeak_conc was 0:0330:035 μm (ambient AERONET values were 15.8% larger than dried LARGE values), and the average difference in widthpeak_conc was 0:0420:039 μm (AERONET values were 25.7% larger). For a subset of aircraft data, the LARGE data were adjusted to account for ambient humidification. For these cases, the AERONET–LARGE average differences were smaller, with rpeak_conc differing by 0:0110:019 μm (AERONET values were 5.2% larger) and widthpeak_conc average differences equal to 0:0300:037 μm (AERONET values were 15.8% larger).

Schafer, Joel S.↗