Elemental Characterization of Ambient Particulate Matter for a Globally Distributed Monitoring Network: Methodology and Implications.

Global ground-level measurements of elements in ambient particulate matter (PM) can provide valuable information to understand the distribution of dust and trace elements, assess health impacts, and investigate emission sources. We use X-ray fluorescence spectroscopy to characterize the elemental composition of PM samples collected from 27 globally distributed sites in the Surface PARTiculate mAtter Network (SPARTAN) over 2019-2023. Consistent protocols are applied to collect all samples and analyze them at one central laboratory, which facilitates comparison across different sites. Multiple quality assurance measures are performed, including applying reference materials that resemble typical PM samples, acceptance testing, and routine quality control. Method detection limits and uncertainties are estimated. Concentrations of dust and trace element oxides (TEO) are determined from the elemental dataset. In addition to sites in arid regions, a moderately high mean dust concentration (6 µg/m3) in PM2.5 is also found in Dhaka (Bangladesh) along with a high average TEO level (6 µg/m3). High carcinogenic risk (>1 cancer case per 100000 adults) from airborne arsenic is observed in Dhaka (Bangladesh), Kanpur (India), and Hanoi (Vietnam). Industries of informal lead-acid battery and e-waste recycling as well as coal-fired brick kilns likely contribute to the elevated trace element concentrations found in Dhaka.

Improvement of Surface PM2.5 Diurnal Variation Simulations in East Africa for the MAIA Satellite Mission.

The Multi-Angle Imager for Aerosols (MAIA), supported by NASA and the Italian Space Agency, is planned for launch into space in 2025. As part of its mission goal, outputs from a chemical transport model, the Unified Inputs for Weather Research and Forecasting Model coupled with Chemistry (UI-WRF-Chem), will be used together with satellite data and surface observations for estimating surface PM2.5. Here, we develop a method to improve UI-WRF-Chem with surface observations at the U.S. embassy in Ethiopia, one of MAIA's primary target areas in east Africa. The method inversely models the diurnal profile and amount of anthropogenic aerosol and trace gas emissions. Low-cost PurpleAir sensor data are used for validation after applying calibration functions obtained from the collocated data at the embassy. With the emission updates in UI-WRF-Chem, independent validation for February 2022 at several different PurpleAir sites shows an increase in the linear correlation coefficients from 0.1-0.7 to 0.6-0.9 between observations and simulations of the diurnal variation of surface PM2.5. Furthermore, even by using the emissions optimized for February 2021, the UI-WRF-Chem forecast for March 2022 is also improved. Annual update of monthly emissions via inverse modeling has the potential and is needed to improve MAIA's estimate of surface PM2.5.

SPEX airborne spectropolarimeter calibration and performance.

To improve our understanding of the complex role of aerosols in the climate system and on air quality, measurements are needed of optical and microphysical aerosol. From many studies, it has become evident that a satellite-based multiangle, multiwavelength polarimeter will be essential to provide such measurements. Here, high accuracy (∼0.003) on the degree of linear polarization (DoLP) measurements is important to retrieve aerosol properties with an accuracy needed to advance our understanding of the aerosol effect on climate. SPEX airborne, a multiangle hyperspectral polarimeter, has been developed for observing and characterizing aerosols from NASA's high-altitude research aircraft ER-2. It delivers measurements of radiance and DoLP at visual wavelengths with a spectral resolution of 3 and 7-30 nm, respectively, for radiance and polarization, at nine fixed equidistant viewing angles from -56° to +56° oriented along the ground track, and a swath of 7° oriented across-track. SPEX airborne uses spectral polarization modulation to determine the state of linear polarization of scattered sunlight. This technique has been developed in the Netherlands and has been demonstrated with ground-based instruments. SPEX airborne serves as a demonstrator for a family of space-based SPEX instruments that have the ability to measure and characterize atmospheric aerosol by multiangle hyperspectral polarimetric imaging remotely from a satellite platform. SPEX airborne was calibrated radiometrically and polarimetrically using Jet Propulsion Laboratory (JPL) facilities including the Polarization Stage Generator-2 (PSG-2), which is designed for polarimetric calibration and validation of the Airborne Multiangle SpectroPolarimetric Imager (AirMSPI). Using the PSG-2, the accuracy of the SPEX airborne DoLP measurements in the laboratory setup is found to be 0.002-0.004. Radiometric calibration is realized with an estimated accuracy of 4%. In 2017, SPEX airborne took part in the "Aerosol Characterization from Polarimeters and Lidar" campaign on the ER-2 that included four polarimeters and two lidars. Polarization measurements of SPEX airborne and the coflying Research Scanning Polarimeter (RSP), recorded during the campaign, were compared and display root-mean-square (RMS) differences ranging from 0.004 (at 555 nm) up to 0.02 (at 410 nm). For radiance measurements, excellent agreement between SPEX airborne and RSP is obtained with an RMS difference of ∼4%. The lab- and flight-performance values for polarization are similar to those recently published for AirMSPI, where also an intercomparison with RSP was made using data from field campaigns in 2013. The intercomparison of radiometric and polarimetric data both display negligible bias. The in-flight comparison results provide verification of SPEX airborne's capability to deliver high-quality data.

Estimating PM2.5 speciation concentrations using prototype 4.4 km-resolution MISR aerosol properties over Southern California.

Research efforts to better characterize the differential toxicity of PM2.5 (particles with aerodynamic diameters less than or equal to 2.5 µm) speciation are often hindered by the sparse or non-existent coverage of ground monitors. The Multi-angle Imaging SpectroRadiometer (MISR) aboard NASA's Terra satellite is one of few satellite aerosol sensors providing information of aerosol shape, size and extinction globally for a long and continuous period that can be used to estimate PM2.5 speciation concentrations since year 2000. Currently, MISR only provides a 17.6 km product for its entire mission with global coverage every 9 days, a bit too coarse for air pollution health effects research and to capture local spatial variability of PM2.5 speciation. In this study, generalized additive models (GAMs) were developed using MISR prototype 4.4 km-resolution aerosol data with meteorological variables and geographical indicators, to predict ground-level concentrations of PM2.5 sulfate, nitrate, organic carbon (OC) and elemental carbon (EC) in Southern California between 2001 and 2015 at the daily level. The GAMs are able to explain 66%, 62%, 55% and 58% of the daily variability in PM2.5 sulfate, nitrate, OC and EC concentrations during the whole study period, respectively. Predicted concentrations capture large regional patterns as well as fine gradients of the four PM2.5 species in urban areas of Los Angeles and other counties, as well as in the Central Valley. This study is the first attempt to use MISR prototype 4.4 km-resolution AOD (aerosol optical depth) components data to predict PM2.5 sulfate, nitrate, OC and EC concentrations at the sub-regional scale. In spite of its low temporal sampling frequency, our analysis suggests that the MISR 4.4 km fractional AODs provide a promising way to capture the spatial hotspots and long-term temporal trends of PM2.5 speciation, understand the effectiveness of air quality controls, and allow our estimated PM2.5 speciation data to be linked with common spatial units such as census tract or zip code in epidemiological studies. This modeling strategy needs to be validated in other regions when more MISR 4.4 km data becoming available in the future.

Calibration and validation of Airborne Multiangle SpectroPolarimetric Imager (AirMSPI) polarization measurements.

The Airborne Multiangle SpectroPolarimetric Imager (AirMSPI), a precursor to the future Multi-Angle Imager for Aerosols satellite instrument, is a remote-sensing instrument for the characterization of atmospheric aerosols and clouds. To help discriminate between different aerosol particle types, which is crucial to improve our understanding of their impact on climate and air quality, AirMSPI acquires imagery over multiple view angles in the ultraviolet, visible, and near-infrared, and it employs dual photoelastic modulators (PEMs) to target an uncertainty requirement of ±0.005 in the degree of linear polarization (DoLP) at selected wavelengths. Laboratory polarimetric calibrations using a second-generation Polarization State Generator-2 (PSG-2) and validation measurements at 0

Intra-annual variations of regional aerosol optical depth, vertical distribution, and particle types from multiple satellite and ground-based observational datasets.

The climatic and health effects of aerosols are strongly dependent on the intra-annual variations in their loading and properties. While the seasonal variations of regional aerosol optical depth (AOD) have been extensively studied, understanding the temporal variations in aerosol vertical distribution and particle types is also important for an accurate estimate of aerosol climatic effects. In this paper, we combine the observations from four satellite-borne sensors and several ground-based networks to investigate the seasonal variations of aerosol column loading, vertical distribution, and particle types over three populous regions: the Eastern United States (EUS), Western Europe (WEU), and Eastern and Central China (ECC). In all three regions, column AOD, as well as AOD at heights above 800 m, peaks in summer/spring, probably due to accelerated formation of secondary aerosols and hygroscopic growth. In contrast, AOD below 800m peaks in winter over WEU and ECC regions because more aerosols are confined to lower heights due to the weaker vertical mixing. In the EUS region, AOD below 800m shows two maximums, one in summer and the other in winter. The temporal trends in low-level AOD are consistent with those in surface fine particle (PM2.5) concentrations. AOD due to fine particles (< 0.7 µm diameter) is much larger in spring/summer than in winter over all three regions. However, the coarse mode AOD (> 1.4 µm diameter), generally shows small variability, except that a peak occurs in spring in the ECC region due to the prevalence of airborne dust during this season. When aerosols are classified according to sources, the dominant type is associated with anthropogenic air pollution, which has a similar seasonal pattern as total AOD. Dust and sea-spray aerosols in the WEU region peak in summer and winter, respectively, but do not show an obvious seasonal pattern in the EUS region. Smoke aerosols, as well as absorbing aerosols, present an obvious unimodal distribution with a maximum occurring in summer over the EUS and WEU regions, whereas they follow a bimodal distribution with peaks in August and March (due to crop residue burning) over the ECC region.

Linearization of Markov chain formalism for vector radiative transfer in a plane-parallel atmosphere/surface system.

The Markov chain formalism for polarized radiative transfer through a vertically inhomogeneous atmosphere is linearized comprehensively with respect to the aerosol and polarizing surface properties. For verification, numerical results are compared to those obtained by the finite difference method. We demonstrate the use of the linearized code as part of a retrieval of aerosol and surface properties for an atmosphere overlying a black and Fresnel-reflecting ocean surface.

Markov chain formalism for vector radiative transfer in a plane-parallel atmosphere overlying a polarizing surface.

We report on a way of building bidirectional surface reflectivity into the Markov chain formalism for polarized radiative transfer through a vertically inhomogeneous atmosphere. Numerical results are compared to those obtained by the Monte Carlo method, showing the accuracy of the Markov chain method when 90 streams are used to compute the radiation from a Rayleigh-plus-aerosol atmosphere that overlies a surface with a bidirectional reflection function consisting of both depolarizing and polarizing parts.

Analysis of static and time-varying polarization errors in the multiangle spectropolarimetric imager.

Multiangle Spectropolarimetric Imager (MSPI) sensitivity to static and time-varying polarization errors is examined. For a system without noise, static polarization errors are accurately represented by the calibration coefficients, and therefore do not impede correct mapping of measured to input Stokes vectors. But noise is invariably introduced during the detection process, and static polarization errors reduce the system's signal-to-noise ratio (SNR) by increasing noise sensitivity. Noise sensitivity is minimized by minimizing the condition number of the system data reduction matrix [Appl. Opt.41, 619 (2002)]. The sensitivity of condition numbers to static polarization errors is presented. The condition number of the nominal MSPI data reduction matrix is approximately 1.1 or less for all fields. The increase in the condition number above 1 results primarily from a quarter wave plate and mirror coating retardance magnitude errors. Sensitivity of the degree of linear polarization (DoLP) error with respect to time-varying diattenuation and retardance error was used to set a time-varying diattenuation magnitude tolerance of 0.005 and a time-varying retardance magnitude tolerance of ±0.2°. A Monte Carlo simulation of the calibration and measurements using anticipated static and time-varying errors indicates that MSPI has a probability of 0.9 of meeting its 0.005 DoLP uncertainty requirement.

First results from a dual photoelastic-modulator-based polarimetric camera.

We report on the construction and calibration of a dual photoelastic-modulator (PEM)-based polarimetric camera operating at 660?nm. This camera is our first prototype for a multispectral system being developed for airborne and spaceborne remote sensing of atmospheric aerosols. The camera includes a dual-PEM assembly integrated into a three-element, low-polarization reflective telescope and provides both intensity and polarization imaging. A miniaturized focal-plane assembly consisting of spectral filters and patterned wire-grid polarizers provides wavelength and polarimetric selection. A custom push-broom detector array with specialized signal acquisition, readout, and processing electronics captures the radiometric and polarimetric information. Focal-plane polarizers at orientations of 0 degrees and -45 degrees yield the normalized Stokes parameters q=Q/I and u=U/I respectively, which are then coregistered to obtain degree of linear polarization (DOLP) and angle of linear polarization. Laboratory test data, calibration results, and outdoor imagery acquired with the camera are presented. The results show that, over a wide range of DOLP, our challenging objective of uncertainty within +/-0.005 has been achieved.

Dual-photoelastic-modulator-based polarimetric imaging concept for aerosol remote sensing.

A dual-photoelastic-modulator- (PEM-) based spectropolarimetric camera concept is presented as an approach for global aerosol monitoring from space. The most challenging performance objective is to measure degree of linear polarization (DOLP) with an uncertainty of less than 0.5% in multiple spectral bands, at moderately high spatial resolution, over a wide field of view, and for the duration of a multiyear mission. To achieve this, the tandem PEMs are operated as an electro-optic circular retardance modulator within a high-performance reflective imaging system. Operating the PEMs at slightly different resonant frequencies generates a beat signal that modulates the polarized component of the incident light at a much lower heterodyne frequency. The Stokes parameter ratio q = Q/I is obtained from measurements acquired from each pixel during a single frame, providing insensitivity to pixel responsivity drift and minimizing polarization artifacts that conventionally arise when this quantity is derived from differences in the signals from separate detectors. Similarly, u = U/I is obtained from a different pixel; q and u are then combined to form the DOLP. A detailed accuracy and tolerance analysis for this polarimeter is presented.