Calibration and assessment of electrochemical air quality sensors by co-location with regulatory-grade instruments

The use of low-cost air quality sensors for air pollution research has outpaced our understanding of their capabilities and limitations under real-world conditions, and there is thus a critical need for understanding and optimizing the performance of such sensors in the field. Here we describe the deployment, calibration, and evaluation of electrochemical sensors on the island of Hawai'i, which is an ideal test bed for characterizing such sensors due to its large and variable sulfur dioxide (SO 2 ) levels and lack of other co-pollutants. Nine custom-built SO 2 sensors were co-located with two Hawaii Department of Health Air Quality stations over the course of 5 months, enabling comparison of sensor output with regulatory-grade instruments under a range of realistic environmental conditions. Calibration using a nonparametric algorithm (k nearest neighbors) was found to have excellent performance (RMSE 0.997) across a wide dynamic range in SO 2 ( 2ppm). However, since nonparametric algorithms generally cannot extrapolate to conditions beyond those outside the training set, we introduce a new hybrid linear-nonparametric algorithm, enabling accurate measurements even when pollutant levels are higher than encountered during calibration. We find no significant change in instrument sensitivity toward SO 2 after 18 weeks and demonstrate that calibration accuracy remains high when a sensor is calibrated at one location and then moved to another. The performance of electrochemical SO 2 sensors is also strong at lower SO 2 mixing ratios ( < 25ppb), for which they exhibit an error of less than 2.5ppb. While some specific results of this study (calibration accuracy, performance of the various algorithms, etc.) may differ for measurements of other pollutant species in other areas (e.g., polluted urban regions), the calibration and validation approaches described here should be widely applicable to a range of pollutants, sensors, and environments.United States. Environmental Protection Agency (Grant RD-83618301

Online measurements of the emissions of intermediate-volatility and semi-volatile organic compounds from aircraft

A detailed understanding of the climate and air quality impacts of aviation requires measurements of the emissions of intermediate-volatility and semi-volatile organic compounds (I/SVOCs) from aircraft. Currently both the amount and chemical composition of aircraft I/SVOC emissions remain poorly characterized. Here we characterize I/SVOC emissions from aircraft, using a novel instrument for the online, quantitative measurement of the mass loading and composition of low-volatility organic vapors. Emissions from the NASA DC8 aircraft were sampled on the ground 143 m downwind of the engines and characterized as a function of engine power from idle (4% maximum rated thrust) through 85% power. Results show that I/SVOC emissions are highest during engine idle operating conditions, with decreasing but non-zero I/SVOC emissions at higher engine powers. Comparison of I/SVOC emissions with total hydrocarbon (THC) measurements, VOC measurements, and an established emissions profile indicates that I/SVOCs comprise 10–20% of the total organic gas-phase emissions at idle, and an increasing fraction of the total gas-phase organic emissions at higher powers. Positive matrix factorization of online mass spectra is used to identify three distinct types of I/SVOC emissions: aliphatic, aromatic and oxygenated. The volatility and chemical composition of the emissions suggest that unburned fuel is the dominant source of I/SVOCs at idle, while pyrolysis products make up an increasing fraction of the I/SVOCs at higher powers. Oxygenated I/SVOC emissions were detected at lower engine powers (≤30%) and may be linked to cracked, partially oxidized or unburned fuel components.United States. Dept. of Energy. Office of Science (Small Business Innovation Research Program Grant DE-SC0001666)United States. Environmental Protection Agency (National Center for Environmental Research Grant RD834560

Measurement and characterization of low volatility organic compounds in the atmosphere

Thesis: Ph. D. in Environmental Chemistry, Massachusetts Institute of Technology, Department of Civil and Environmental Engineering, 2018.Cataloged from PDF version of thesis.Includes bibliographical references.Organic aerosol is a central topic in environmental science due to its role in climate forcing and negative health effects. The transformation of organic species from primary gas phase emissions to secondary organic aerosol (SOA) is highly complex and poorly understood, proving difficult for even stateof- the-art computational models to predict. This thesis describes the in-depth characterization and redesign of a previously developed technique for the quantification of intermediate volatility organic compounds (IVOCs), which are compounds with saturation vapor pressures of 10³-10⁷ [mu]g/m³. This analytical technique, the thermal-desorption electron ionization mass spectrometer (TD-EIMS) provides a volatility separated, bulk measurement of IVOCs and will be used to investigate the primary emissions as well as production and evolution of IVOCs in a series of experiments described in this thesis. Primary emissions of IVOCs have been previously measured in vehicle exhaust and have been theorized as a significant precursor to secondary organic aerosol (SOA) in urban atmospheres. IVOCs are predominately emitted during cold start periods, but maintain a similar chemical composition across all engine states. As emissions controls have tightened, emissions of non-methane hydrocarbons and primary particulate matter have decreased, however emissions of IVOCs have only decreased significantly (as much as 80%) between the newest ULEV and SULEV emissions control tiers. Laboratory studies examining the atmospheric oxidation of common biogenic and anthropogenic SOA precursors in environmental "smog" chambers show different production and evolution profiles of IVOCs. The comparison of IVOCs measured by the TD-EIMS with other analytical techniques sampling in parallel show the TD-EIMS may detect a previously characterized fraction of carbon. Production of secondary low volatility organic compounds can also occur in low oxygen systems, such as in planetary atmospheres or in the process of soot formation. Ultraviolet light or heat can form radical hydrocarbon species, which, in low oxygen environments, will react with other hydrocarbon or radical species, undergoing oxidation by molecular growth. Particles made from ethane and ethylene are composed of very saturated compounds. The particles produced from the photolysis of acetylene are fundamentally different showing significantly larger molecule sizes and substantially higher degrees of unsaturation. The results from this thesis demonstrate measurements of the production and evolution of primary and secondary low volatility organic gases by new analytical techniques and provide a new insight to the complex chemical processes in the atmosphere leading to the production of secondary organic aerosol.by Jonathan Pfeil Franklin.Ph. D. in Environmental Chemistr

Calibration and assessment of electrochemical air quality sensors by co-location with reference-grade instruments

The use of low-cost air quality sensors for air pollution research has outpaced our understanding of their capabilities and limitations under real-world conditions, and there is thus a critical need for understanding and optimizing the performance of such sensors in the field. Here we describe the deployment, calibration, and evaluation of electrochemical sensors on the island of Hawai`i, which is an ideal test bed for characterizing such sensors due to its large and variable sulfur dioxide (SO₂) levels and lack of other co-pollutants. Nine custom-built SO₂ sensors were co-located with two Hawaii Department of Health Air Quality stations over the course of 5 months, enabling comparison of sensor output with regulatory-grade instruments under a range of realistic environmental conditions. Calibration using a nonparametric algorithm (k nearest neighbors) was found to have excellent performance (RMSE  0.997) across a wide dynamic range in SO₂ ( 2 ppm). However, since nonparametric algorithms generally cannot extrapolate to conditions beyond those outside the training set, we introduce a new hybrid linear–nonparametric algorithm, enabling accurate measurements even when pollutant levels are higher than encountered during calibration. We find no significant change in instrument sensitivity toward SO₂ after 18 weeks and demonstrate that calibration accuracy remains high when a sensor is calibrated at one location and then moved to another. The performance of electrochemical SO₂ sensors is also strong at lower SO₂ mixing ratios (< 25 ppb), for which they exhibit an error of less than 2.5 ppb. While some specific results of this study (calibration accuracy, performance of the various algorithms, etc.) may differ for measurements of other pollutant species in other areas (e.g., polluted urban regions), the calibration and validation approaches described here should be widely applicable to a range of pollutants, sensors, and environments

Changes to the Chemical Composition of Soot from Heterogeneous Oxidation Reactions

The atmospheric aging of soot particles, in which various atmospheric processes alter the particles’ chemical and physical properties, is poorly understood and consequently is not well-represented in models. In this work, soot aging via heterogeneous oxidation by OH and ozone is investigated using an aerosol flow reactor coupled to a new high-resolution aerosol mass spectrometric technique that utilizes infrared vaporization and single-photon vacuum ultraviolet ionization. This analytical technique simultaneously measures the elemental and organic carbon components of soot, allowing for the composition of both fractions to be monitored. At oxidant exposures relevant to the particles’ atmospheric lifetimes (the equivalent of several days of oxidation), the elemental carbon portion of the soot, which makes up the majority of the particle mass, undergoes no discernible changes in mass or composition. In contrast, the organic carbon (which in the case of methane flame soot is dominated by aliphatic species) is highly reactive, undergoing first the addition of oxygen-containing functional groups and ultimately the loss of organic carbon mass from fragmentation reactions that form volatile products. These changes occur on time scales comparable to those of other nonoxidative aging processes such as condensation, suggesting that further research into the combined effects of heterogeneous and condensational aging is needed to improve our ability to accurately predict the climate and health impacts of soot particles.United States. Environmental Protection Agency (STAR RD-83503301)National Science Foundation (U.S.) (CHE-1012809)National Oceanic and Atmospheric Administration (Climate and Global Change Fellowship