skip to main content

Title: Digital Microfluidics for the Detection of Selected Inorganic Ions in Aerosols
A prototype aerosol detection system is presented that is designed to accurately and quickly measure the concentration of selected inorganic ions in the atmosphere. The aerosol detection system combines digital microfluidics technology, aerosol impaction and chemical detection integrated on the same chip. Target compounds are the major inorganic aerosol constituents: sulfate, nitrate and ammonium. The digital microfluidic system consists of top and bottom plates that sandwich a fluid layer. Nozzles for an inertial impactor are built into the top plate according to known, scaling principles. The deposited air particles are densely concentrated in well-defined deposits on the bottom plate containing droplet actuation electrodes of the chip in fixed areas. The aerosol collection efficiency for particles larger than 100 nm in diameter was higher than 95%. After a collection phase, deposits are dissolved into a scanning droplet. Due to a sub-microliter droplet size, the obtained extract is highly concentrated. Droplets then pass through an air/oil interface on chip for colorimetric analysis by spectrophotometry using optical fibers placed between the two plates of the chip. To create a standard curve for each analyte, six different concentrations of liquid standards were chosen for each assay and dispensed from on-chip reservoirs. The droplet mixing more » was completed in a few seconds and the final droplet was transported to the detection position as soon as the mixing was finished. Limits of detection (LOD) in the final droplet were determined to be 11 ppm for sulfate and 0.26 ppm for ammonium. For nitrate, it was impossible to get stable measurements. The LOD of the on-chip measurements for sulfate was close to that obtained by an off-chip method using a Tecan spectrometer. LOD of the on-chip method for ammonium was about five times larger than what was obtained with the off-chip method. For the current impactor collection air flow (1 L/min) and 1 h collection time, the converted LODs in air were: 0.275 μg/m3 for sulfate, 6.5 ng/m3 for ammonium, sufficient for most ambient air monitoring applications. « less
Authors:
; ; ;
Award ID(s):
1408241
Publication Date:
NSF-PAR ID:
10156895
Journal Name:
Sensors
Volume:
20
Issue:
5
Page Range or eLocation-ID:
1281
ISSN:
1424-8220
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract
    Excessive phosphorus (P) applications to croplands can contribute to eutrophication of surface waters through surface runoff and subsurface (leaching) losses. We analyzed leaching losses of total dissolved P (TDP) from no-till corn, hybrid poplar (Populus nigra X P. maximowiczii), switchgrass (Panicum virgatum), miscanthus (Miscanthus giganteus), native grasses, and restored prairie, all planted in 2008 on former cropland in Michigan, USA. All crops except corn (13 kg P ha−1 year−1) were grown without P fertilization. Biomass was harvested at the end of each growing season except for poplar. Soil water at 1.2 m depth was sampled weekly to biweekly for TDP determination during March–November 2009–2016More>>
  2. Abstract. Airborne and ground-based measurements of aerosol concentrations, chemicalcomposition, and gas-phase precursors were obtained in three valleys innorthern Utah (USA). The measurements were part of the Utah Winter FineParticulate Study (UWFPS) that took place in January–February 2017. Totalaerosol mass concentrations of PM1 were measured from a Twin Otteraircraft, with an aerosol mass spectrometer (AMS). PM1 concentrationsranged from less than 2µgm−3 during clean periods to over100µgm−3 during the most polluted episodes, consistent withPM2.5 total mass concentrations measured concurrently at groundsites. Across the entire region, increases in total aerosol massmore »above∼2µgm−3 were associated with increases in theammonium nitrate mass fraction, clearly indicating that the highest aerosolmass loadings in the region were predominantly attributable to an increase inammonium nitrate. The chemical composition was regionally homogenous fortotal aerosol mass concentrations above 17.5µgm−3, with 74±5% (average±standard deviation) ammonium nitrate, 18±3%organic material, 6±3% ammonium sulfate, and 2±2%ammonium chloride. Vertical profiles of aerosol mass and volume in the regionshowed variable concentrations with height in the polluted boundary layer.Higher average mass concentrations were observed within the first few hundredmeters above ground level in all three valleys during pollution episodes. Gas-phase measurements of nitric acid (HNO3) and ammonia (NH3) duringthe pollution episodes revealed that in the Cache and Utah valleys, partitioningof inorganic semi-volatiles to the aerosol phase was usually limited by theamount of gas-phase nitric acid, with NH3 being in excess. The inorganicspecies were compared with the ISORROPIA thermodynamic model. Total inorganicaerosol mass concentrations were calculated for various decreases in totalnitrate and total ammonium. For pollution episodes, our simulations of a50% decrease in total nitrate lead to a 46±3% decrease in totalPM1 mass. A simulated 50% decrease in total ammonium leads to a36±17%µgm−3 decrease in total PM1 mass, over the entirearea of the study. Despite some differences among locations, ourresults showed a higher sensitivity to decreasing nitric acid concentrationsand the importance of ammonia at the lowest total nitrate conditions. In theSalt Lake Valley, both HNO3 and NH3 concentrations controlledaerosol formation.

    « less
  3. This study characterizes the impact of the Chesapeake Bay and associated meteorological phenomena on aerosol chemistry during the second Ozone Water-Land Environmental Transition Study (OWLETS-2) field campaign during summer 2018. Measurements of inorganic PM2.5 composition, gas-phase ammonia (NH3), and an array of meteorological parameters were undertaken at Hart-Miller Island (HMI), a land-water transition site just east of downtown Baltimore on the Chesapeake Bay. The observations at HMI were characterized by abnormally high NH3 concentrations (maximum of 19.3 μg m-3, average of 3.83 μg m-3), which were more than a factor of three higher than NH3 levels measured at the closest Atmospheric Ammonia Network (AMoN)more »site (approximately 45 km away). While sulfate concentrations at HMI agreed quite well with those measured at a regulatory monitoring station 45 km away, aerosol ammonium and nitrate concentrations were significantly higher, due to the ammonia-rich conditions that resulted from the elevated NH3. The high NH3 concentrations were largely due to regional agricultural emissions, including dairy farms in southeastern Pennsylvania and poultry operations in the Delmarva Peninsula (Delaware-Maryland-Virginia). Reduced NH3 deposition during transport over the Chesapeake Bay likely contributed to enhanced concentrations at HMI compared to the more inland AMoN site. Several peak NH3 events were recorded, including the maximum NH3 observed during OWLETS-2, that appear to originate from a cluster of industrial sources near downtown Baltimore. Such events were all associated with nighttime emissions and advection to HMI under low 15 wind speeds (< 1 m s-1) and stable atmospheric conditions. Our results demonstrate the importance of industrial sources, including several that are not represented in the emissions inventory, on urban air quality. Together with our companion paper, which examines aerosol liquid water and pH during OWLETS-2, we highlight unique processes affecting urban air quality of coastal cities that are distinct from continental locations.« less
  4. Abstract. This study characterizes the impact of the Chesapeake Bay and associated meteorological phenomena on aerosol chemistry during the second Ozone Water-Land Environmental Transition Study (OWLETS-2) field campaign, which took place from 4 June to 5 July 2018. Measurements of inorganic PM2.5 composition, gas-phase ammonia (NH3), and an array of meteorological parameters were undertaken at Hart-Miller Island (HMI), a land–water transition site just east of downtown Baltimore on the Chesapeake Bay. The observations at HMI were characterized by abnormally high NH3 concentrations (maximum of 19.3 µg m−3, average of 3.83 µg m−3), which were more than a factor of 3 higher than NH3 levels measured at themore »closest atmospheric Ammonia Monitoring Network (AMoN) site (approximately 45 km away). While sulfate concentrations at HMI agreed quite well with those measured at a regulatory monitoring station 45 km away, aerosol ammonium and nitrate concentrations were significantly higher, due to the ammonia-rich conditions that resulted from the elevated NH3. The high NH3 concentrations were largely due to regional agricultural emissions, including dairy farms in southeastern Pennsylvania and poultry operations in the Delmarva Peninsula (Delaware–Maryland–Virginia). Reduced NH3 deposition during transport over the Chesapeake Bay likely contributed to enhanced concentrations at HMI compared to the more inland AMoN site. Several peak NH3 events were recorded, including the maximum NH3 observed during OWLETS-2, that appear to originate from a cluster of industrial sources near downtown Baltimore. Such events were all associated with nighttime emissions and advection to HMI under low wind speeds (< 1 m s−1) and stable atmospheric conditions. Our results demonstrate the importance of industrial sources, including several that are not represented in the emissions inventory, on urban air quality. Together with our companion paper, which examines aerosol liquid water and pH during OWLETS-2, we highlight unique processes affecting urban air quality of coastal cities that are distinct from continental locations.« less
  5. Due to their small size, measurements of the complex composition of atmospheric aerosol particles and their surfaces are analytically challenging. This is particularly true for microspectroscopic methods, where it can be difficult to optically identify individual particles smaller than the diffraction limit of visible light (∼350 nm) and measure their vibrational modes. Recently, surface enhanced Raman spectroscopy (SERS) has been applied to the study of aerosol particles, allowing for detection and characterization of previously undistinguishable vibrational modes. However, atmospheric particles analyzed via SERS have primarily been >1 μm to date, much larger than the diameter of the most abundant atmosphericmore »aerosols (∼100 nm). To push SERS towards more relevant particle sizes, a simplified approach involving Ag foil substrates was developed. Both ambient particles and several laboratory-generated model aerosol systems (polystyrene latex spheres (PSLs), ammonium sulfate, and sodium nitrate) were investigated to determine SERS enhancements. SERS spectra of monodisperse, model aerosols between 400–800 nm were compared with non-SERS enhanced spectra, yielding average enhancement factors of 10 2 for both inorganic and organic vibrational modes. Additionally, SERS-enabled detection of 150 nm size-selected ambient particles represent the smallest individual aerosol particles analyzed by Raman microspectroscopy to date, and the first time atmospheric particles have been measured at sizes approaching the atmospheric number size distribution mode. SERS-enabled detection and identification of vibrational modes in smaller, more atmospherically-relevant particles has the potential to improve understanding of aerosol composition and surface properties, as well as their impact on heterogeneous and multiphase reactions involving aerosol surfaces.« less