Prasanna Venkatachari

Characterization of Wintertime Reactive Oxygen Species Concentrations in Flushing, New York

One of the main hypotheses for the species causing the observed health effects of ambient particulate matter is peroxides and other reactive oxygen species (ROS). However, there is currently very little data available on the concentrations of particle-bound ROS or their behavior in different physical locations and seasons. The concentrations of particle-bound ROS were determined for various size fractions of the aerosol, ranging from 10 nm to 18 μ m, in Flushing, New York during the period of January and early February 2004. Sampling was carried out at 3-hour intervals using a MOUDI™ cascade impactor. The collected particles were treated with the non-fluorescent probe dichlorofluorescin (DCFH) that fluoresces when oxidized by the presence of ROS. The measured fluorescent intensities were converted into equivalent hydrogen peroxide concentrations, which were used as indicators of ROS reactivity, by calibrations using H 2 O 2 standards. Diurnal profiles of the ROS concentrations were obtained. Correlations of the particulate ROS concentrations with the intensity of photochemical reaction, estimated secondary organic carbon (SOC) and gas phase OH and HO 2 radical concentrations were explored. The intensity of photochemical reactions and gas phase radical concentrations were found to be moderate factors affecting particulate ROS concentrations. The concentrations of ROS were found to be higher in the submicron size particles of the ambient aerosol.

An Intercomparison of Measurement Methods for Carbonaceous Aerosol in the Ambient Air in New York City

Measurement methods for fine carbonaceous aerosol were compared under field sampling conditions in Flushing, New York during the period of January and early February 2004. In-situ 5- to 60-minute average PM 2.5 organic carbon (OC), elemental carbon (EC), and black carbon (BC) concentrations were obtained by the following methods: Sunset Laboratory field OC/EC analyzer, Rupprecht and Patashnick (R&P) series 5400 ambient carbon particulate monitor, Aerodyne aerosol mass spectrometer (AMS) for total organic matter (OM), and a two-wavelength AE-20 Aethalometer. Twenty-four hour averaged PM 2.5 filter measurements for OC and EC were also made with a Speciation Trends Network (STN) sampler. The diurnal variations in OC/EC/BC concentrations peaked during the morning and afternoon rush hours indicating the dominant influence of vehicle emissions. BC/EC slopes are found to range between 0.86 and 1.23 with reasonably high correlations (r > 0.75). Low mixing heights and absence of significant transported carbonaceous aerosol are indicated by the measurements. Strong correlations are observed between BC and thermal EC as measured by the Sunset instrument and between Sunset BC and Aethalometer BC. Reasonable correlations are observed among collocated OC/EC measurements by the various instruments.

Development and Laboratory Testing of an Automated Monitor for the Measurement of Atmospheric Particle-Bound Reactive Oxygen Species (ROS)

Previous studies have found significant quantities of oxidative species associated with airborne particulate matter. Although oxidative stress is thought to be an important part of the mechanism by which particles produce adverse health effects, the lack of a suitable method to measure ROS on a routine basis has resulted in no work being undertaken to assess the effects of particle-bound ROS on health. In order to fill this need, an automated monitor for the continuous sampling of ambient aerosol and the measurement of concentrations of ROS on the sampled aerosol was developed. Potential methods to quantify ROS were compared in order to arrive at a suitable method to automate. The dichlorofluorescein (DCFH) fluorescence method was found to be the most non-specific, general indicator of particle-bound oxidants. Hence it was deemed the best suited method for the automated monitor. An integrated sampling-analysis system was designed and constructed based on collection of atmospheric particles in an aqueous slurry, and subsequent detection of the ROS concentration of the slurry using the DCFH fluorescence method. The results of the lab-scale investigation of the ROS sampling-analysis system suggested that the prototype continuous system was capable of detecting particle-bound ROS, and accounting for short-term variabilities in the same. The instrument was found to be capable of detecting nanomolar equivalent concentrations of ROS.

Real-Time Characterization of the Composition of Individual Particles Emitted From Ultrafine Particle Concentrators

Particle concentrators are commonly used for controlling exposure levels to ambient ultrafine, fine, and coarse aerosols over a broad range of concentrations. For ultrafine aerosols, these concentrators require water condensation technology to grow and enrich these smaller sized particles (D a < 100 nm). Because the chemistry of the particles is directly related to their toxicity, any changes induced by ultrafine concentrators on ambient particles need to be better characterized in order to fully understand the results obtained in health exposure studies. Using aerosol time-of-flight mass spectrometry (ATOFMS), the size-resolved chemistry was measured of concentrated ultrafine and accumulation mode (50–300 nm) particles from several particle concentrators with different designs. This is the first report detailing the size-resolved distributions of elemental carbon (EC) and organic carbon (OC) particles sampled from concentrators. Experimental measurements of the single particle mixing state of particles in concentrated versus non-concentrated ambient air show transformations of ultrafine EC particles occur as they become coated with organic carbon (OC) species during the concentration process. Based on relative ion intensities, concentrated ultrafine particles showed a 30% increase in the amount of OC on the EC particles for the same aerodynamic size. An increase in the number fraction of aromatic- and polycyclic aromatic hydrocarbon-containing particles was also observed in both the ultrafine and fine size modes. The most likely explanation for such changes is gas-to-particle partitioning of organic components (e.g., water-soluble organic compounds) from the high volume of air used in the concentrator into aqueous phase ultrafine and fine aqueous particles created during the particle enrichment process.