2009 Progress Report: PM Characterization and Exposure Assessment (Project 2)EPA Grant Number: R832417C002
Subproject: this is subproject number 002 , established and managed by the Center Director under grant R832417
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: Johns Hopkins Particulate Matter Research Center
Center Director: Samet, Jonathan M.
Title: PM Characterization and Exposure Assessment (Project 2)
Investigators: Geyh, Alison , Breysse, Patrick N. , Chillrud, Steven , Datta, Saugatta , Han, Inkyu , Ondov, John M. , Ramos-Bonilla, Juan , Rule, Ana
Institution: The Johns Hopkins University
Current Institution: The Johns Hopkins University , Kansas State University , Lamont-Doherty Earth Observatory , University of Maryland
EPA Project Officer: Chung, Serena
Project Period: October 1, 2005 through September 30, 2010
Project Period Covered by this Report: August 1, 2008 through July 31,2009
RFA: Particulate Matter Research Centers (2004) RFA Text | Recipients Lists
Research Category: Health Effects , Air
The focus of Project 2 is the measurement of specific chemical components and physical characteristics of PM collected from different areas of the country in support of the Center focus, which is assessing characteristics of PM that determine toxicity. The goals of Project 2 are to collect bulk PM samples for use in biological assays and for detailed characterization including mass, inorganic ions, elemental carbon and organic compounds, specifically polycyclic aromatic hydrocarbons , and elemental metals and their oxides, as well as platinum group elements. We will also collect information on the distribution of particle size. The objectives of Project 2 include: 1) the development of methods for collecting bulk ambient PM, and a system for characterizing the chemical and physical properties of ambient PM; 2) the identification of specific regional differences in PM characteristics that may contribute to differential biological responses demonstrated by in vitro and in vivo bioassay systems.
The rationale for this project is based on the conclusion that “[t]he diversity of PM characteristics and the array of possible health effects define a potentially large and complex matrix for investigation; in fact different features of particles might be relevant to different health outcomes” (NRC 2004) As a result we proposed to assess the specific chemical components and physical characteristics of particulate matter (PM) from samples taken in different areas of the country. These locations have been selected based on a gradient of estimated risks to health. Specifically, we proposed to develop a new method for collecting bulk PM for use in biological assays; to develop a portable system for the characterization of chemical and physical properties of ambient PM; and to identify specific regional differences in PM characteristics that may contribute to differential biological responses in in vitro and in vivo bioassay systems. This report will describe activities carried out by Project 2 (PI.Patrick Breysse) and the PM Characterization, Sampling and Analysis Core (PI Alison Geyh) since funding, giving emphasis to progress during the past year. The overall goal of developing a PM monitoring and collection approach and then deploying it at the sites identified through the Project 1 analyses has been accomplished.
- II. PM Monitoring
PM Monitoring and locations: Monitoring locations identified by Project 1 are found in Table 1.
County/locations monitored during the YR4 project period include Hennepin MN, Harris TX, Pinellas FL, and Jefferson KY. .
Table 1 summarizes the status of the field monitoring effort to date.
Table 1. Monitoring Schedule Order County Start Date End Date 1 King, WA* (SEA) October 25, 2007 December 1, 2007 2 Sacramento CA* (SAC) January 12, 2008* March 13, 2008 3 Maricopa AZ* (PHX) June 1, 2008 July 20, 2008 4 Hennepin MN* (MSP) September 15, 2008 October 30, 2008 5 Harris TX* (HOU) January 11, 2008 February 20, 2009 6 Pinellas FL* (TSP) April 13, 2009 May 31, 2009 7 Jefferson KY** (LOU) August 3, 2009 September 14, 2009** 8 Allegheny PA TBD 9 Queens NY TBD * Completed ** To be completed TBD – to be decided
Hennepin County, MN: The negotiation for a monitoring site in Hennepin MN was described in detail in our previous progress report. The monitoring site selected was the Anoka County Airport, Blaine MN approximately 3 miles north of the border of Hennepin county. The justification for selecting this site is described in the previous progress report. Drs. Ramos-Bonilla, Han, and Breysse began site set up September 14, 2008. Site setup took 4 days. Dr. Han and Ms. Polyak were responsible for site management. The site was shutdown and packed for shipment to Houston TX by Dr. Ramos-Bonilla and Ms. Polyak.
Harris County TX: The negotiation for a monitoring site in Harris county TX was described in detail in our previous progress report. We were offered space at the Deer Park monitoring station which is the STN site just outside of Houston and anticipated the beginning of the field effort for February 2009. Dr. Rule and Ms. Mihalic traveled to Houston Nov 17-18 2008 to meet with the Deer Park site managers Earle Wright and Mark Wooten to determine if the space and power being offered would be adequate for housing our instruments. The site is located in a residential area next to a baseball field and contained 3 trailers and one storage shed. We were offered any available space in any of the trailers. Drs. Geyh and Rule, and Ms. Polyak began site setup January 12, 2009. Monitoring commenced January 15 and ended February 20, 2009. Site management was carried out by Ms. Mihalic, and Dr. Rule. Dr. Geyh assisted Dr. Rule in dismantleing the site for shipment to FL.
Pinellas County FL: On February 14, 2009 Dr. Rule traveled from Houston TX to Tampa FL to meet with Mr. Thomas Stringfellow of the Pinella County Department of the Environment Air Quality Division who we had been in discussion with regarding monitoring in Pinellas county.. Mr. Stringfellow spent the day with Dr. Rule, showing her monitoring stations where JHPMRC monitoring could potentially be established. The final decision was the Sandy Lane Elementary School site in Clearwater FL, which had adequate power but needed a shelter and fencing. Mr. Stringfellow offered to provide a trailer and we contracted to have extra fencing installed to create a temporary boundary around the trailer. We also contracted with an electrician to connect the trailer to the existing power supply. Mr. Stringfellow generously offered to oversee the installation of the fence and the connection of the power before we arrived. Site set up commenced April 13th with monitoring starting 4 days later. Monitoring ended May 28, 2009. Site set up and management was the responsibility to Drs. Ramos-Bonilla, and Han and Ms. Mihalic. Dr. Geyh worked with Ms. Mihalic to dismantled the site for shipment to the next location which was Louisville KY and to organize the disconnection of the power and the removal of the fence.
Jefferson County KY: On June 1, 2009 Dr. Geyh and Dr. Rule traveled to Louisville KY to meet with Mr. Larry Garrison, who we had been in discussion with starting in February about potential monitoring sites in Jefferson county. It had been Mr. Garrison’s preference that we set in the newly constructed Cannons Lane monitoring station located at the Bowman Airfield. However, the new station was a brick wall construction that would have prevented us from drilling new holes in the walls that would have been needed for the inlets to our various instruments. The site finally agreed upon was an older trailer located behind the Bates Elementary school. At the time of the visit, we learned a Hold Harmless Agreement, or equivalent, between JHU and the Louisville Metro Air Pollution Control District was required before we could start monitoring. A copy of the Hold Harmless agreement between JHU and Sacramento County Air Quality Management District was provided as an example. A final abbreviated version in the form of an MOU was signed July 23, 2009. Site set up was carried out by Drs. Geyh and Han, and Ms. Mihalic. Site set up began July 29 and lasted 4 days. Site management was the responsibility of Ms. Mihalic and Polyak. The site will be shutdown September 14, 2009.
Establishing a site: At each location, the equipment listed in Table 2 is deployed.
Table 2. Summary of PM Sampling Continuous PM Monitoring Instruments Integrated PM Sampling Instruments Type Analyte (units) Sampling Frequency Type Analyte Collection Frequency No. samples per sampling period TSI Aerosol Particle Sizer <0.5 - 20 um (particle counts/cm3) every 15 min Hopkins Sequential Cyclone System coarse PM integrated over entire site monitoring period 1 fine PM integrated over entire site monitoring period 1 TSI Scanning Mobility Particle Analyzer 17.9 - 881.7 nm (particle counts/cm3) every 15 min Harvard Impactor (Telfon filters) PM10 7 days 2 PM2.5 7 days 2 Echochem PAS2000 un-differentiated particle-bound PAHs (ng/m3) every 5 min PMASS (quartz fiber filters) PM2.5 7 days 4 Magee Scientific Aethalometer black carbon (ng/m3) every 5 min Thermo Environmental SPA 5020 particulate sulfate (ug/m3) every 15 min
Yields for bulk PM collected from deployment of the HSCS are reported in Table 3.
Table 3. Bulk PM mass results to date Site (County) Coarse PM (mg) Fine (mg) King 89 705 Sacramento 111 397 Maricopa 1181 1510 Hennepin 291 822 Harris 658 1266 Pinellas 449 837 Louisville in process in process
- Data Management
Details of Project 2 data management have been described previously.
- PM Characterization
Table 3 presents the analysis plan for the integrated PM samples collected at each location. Sample analysis has begun.
Table 3. Sample Analysis Plan
Type Mass Inorganic Ions Soluble Metals Insoluble Metals Elemental carbon Pt-Group Elements PAHs Oxidation States HI - PM10 P# P# P# P# P HI - PM2.5 P# P# P# P# P PMASS - PM2.5 P P PM Bulk Coarse P P P P P P P P PM Bulk Fine P P P P P P P P
The following analyses have been completed:
- Anion analysis for bulk (coarse and fine) SAC, PHX, TSP, MSP
- Total metals analysis for bulk (coarse and fine) SAC, JHU, PHX, TSP, HOU, MSP
- Soluble metals analysis for bulk (coarse and fine) SAC, PHX, TSP, MSP
- Insoluble metals analysis for bulk (coarse and fine) SAC, PHX, TSP, MSP
- Total metals analysis for filter (PM10 and PM2.5) JHU, SAC, PHX, HOU, MSP, TSP
- EC/OC analysis for filter (PM10 and PM2.5) JHU, SAC, PHX, HOU, MSP, TSP(?)
- Pt group metals analysis for bulk (coarse and fine see below) SAC, PHX, TSP, MSP, HOU, JHU
- Pt group metals analysis for filter (PM10 and PM2.5 see below) SAC, PHX, TSP, MSP, HOU, JHU
- Oxidation state data from synchrotron for Mn for bulk (fine) SAC, PHX, TSP, MSP, HOU, JHU
- EC/OC analysis for bulk (coarse and fine) JHU, SAC, PHX, TSP, MSP, HOU (results have not yet been received)
Pt - Group Element and PAH Analysis (Work conducted at LDEO-CU: Steven Chillrud, James Ross and Beizhan Yan)
The aims of the LDEO subcontract are to carryout measurements of platinum group elements and trace organics on samples collected by Project 2 of the Johns Hopkins PM Center. In addition, we collaborate on the experiments on PM samples at the National Light Source at Brookhaven National Labs.
Platinum Group Elements - In the past year we have developed and verified a procedure to extract PGEs from airborne particulate matter (PM2.5 and PM10) on Teflo® filters (teflon mesh on PMP ring). Using this technique for filters, we have found that we can recover PGEs from samples as small as 0.6 mg total, containing as little as 11 pg Rh and 45 pg Pt. The conclusion here is that we can accomplish our goal of determining PGE (at least Pt and Rh) in all samples of all types in the study.
Using this procedure we have completed extraction and analysis of PGEs for all PHX filter samples and for 1 pair of filters (PM2.5 and PM10) from each of the other cities (HOU< MSP< and SAC). The rest of the SAC samples are currently being processed, with the other cities due to be finished in a month.
Organic Analyses - In the past one year, two-dimensional gas chromatography was successfully established to separate saturated hydrocarbons, aromatic hydrocarbons, and other organic pollutants. By comparison, we found the currently used evaporation system (Turbovap IV) caused substantial loss of low molecular weight PAHs during concentration, which make the recovery rate relative low. For overcoming this loss, a Turbovap II system was purchased and installed. Recent experiments showed the recovery rate for low molecular weight hydrocarbons is much higher and similar to the published values (45-70%). Recoveries for high molecular weight hydrocarbons typically average ~90%. For determining PAHs in samples with limited mass of PM2.5, a cyrofocusing injection system was installed to GC/MS/MS so that large volume of extracted sample (~25-50 µl) can be analyzed, as compared to the traditional 2 µl of injection volume.
Coarse, fine, and composite filter samples collected from HOU, PHX, SAC, MSP, TSP, and JHU were extracted using CH2Cl2, and purified and determined by Varian GC/MS/MS. In most cities, PAH concentrations in composite filters are about 4-5 folders higher than those in coarse and fine particles. Among different cites, TSP had the lowest PAH levels, while SAC had the highest PAH levels in air. Analyses of alkylated and hyroxylated PAHs from these cities are ongoing.
Oxidation States and Coordination Chemistry - Work conducted at the Brookhaven National Laboratory (BNL): Saugata Datta (KSU) and Steve Chillrud (LDEO), Ana Rule and Jana Mihalic During this last year samples collected during years 2 and 3 were assessed for Mn, Fe and Cr oxidation states by EXAFS and XANES, at the Synchrotron National Light Source ,Brookhaven National Laboratory. September 30, 2008 a proposal entitled “Synchrotron analysis of health relevant physico-chemical characteristics of ambient particulate matter collected from urban locations selected based on differential health risk of susceptible populations” was submitted to the NSLS Beamline Pass System for allocation of beamtime for 6 cycles starting Jan 2009 and ending in Dec 2010; our proposal was successfully ranked ( 2.6) on a scale of 1- 5. The three beamtime were allocated: i) Nov -2008 through Dec 2008 (5 days); ii) Mar 2009 (6 days) and iii) July 29-Aug 3rd (5 days). The focus of this year’s work was to optimize differences in composition between PM collected at our designated locations with initial focus on Mn. Several Mn standards (12) were run prior to sample run. Samples from six locations were covered in this time: SAC, PHX, MSP, HOU, TSP, and JHU. The fine fractions were primarily analysed under XANES to understand the various oxidation states present of the elements of interest. Quantification of oxidation states was accomplished using Athena software and Principles of Linear Combination Fitting. A poster of this work was presented Oct-08 at the AAAR meeting in Orlando FL.
Delivery of bulk PM to Project 3. Project 3 has requested and received bulk fine PM from SAC, PHX, as well as bulk PM collected at JHU. Use of the SEA PM in the in vivo studies has been designated lower priority as it has no regional partner city for comparison. Currently Project 2 can provide Project 3 with PM from PHX, MSP, HOU, TSP and by the middle of September LOU.
QA/QC: The investigators, along with the Center PI and the Quality Assurance Manager of the Center have collaborated to develop the Project Quality Assurance Project Plan for Project 2. The QAPP is being implemented at this time, and the investigators have systems in place to review, identify and correct any QA/QC issues. These include weekly review meetings, hierarchy of authority for problem resolution, planned calibration and performance assessments, and protocol for notifying all staff of changes.
Journal Articles:No journal articles submitted with this report: View all 13 publications for this subproject
Supplemental Keywords:Bulk particle collection, particle characterization, metals speciation, polycyclic aromatic hydrocarbons, anions,, RFA, Health, Scientific Discipline, PHYSICAL ASPECTS, Air, particulate matter, Health Risk Assessment, Epidemiology, Risk Assessments, Physical Processes, atmospheric particulate matter, atmospheric particles, long term exposure, acute cardiovascular effects, airway disease, exposure, human exposure, ambient particle health effects, atmospheric aerosol particles, ultrafine particulate matter, aersol particles, particulate matter components, cardiovascular disease
Progress and Final Reports:Original Abstract
Main Center Abstract and Reports:R832417 Johns Hopkins Particulate Matter Research Center
Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R832417C001 Estimation of the Risks to Human Health of PM and PM Components
R832417C002 PM Characterization and Exposure Assessment (Project 2)
R832417C003 Biological Assessment of the Toxicity of PM and PM Components