Grantee Research Project Results
2008 Progress Report: Polar Organic Compounds in Fine Particles from the New York, New Jersey, and Connecticut Regional Airshed
EPA Grant Number: R832165Title: Polar Organic Compounds in Fine Particles from the New York, New Jersey, and Connecticut Regional Airshed
Investigators: Mazurek, Monica
Institution: Rutgers
EPA Project Officer: Chung, Serena
Project Period: January 1, 2005 through December 31, 2007 (Extended to December 31, 2009)
Project Period Covered by this Report: January 1, 2008 through December 31,2008
Project Amount: $449,150
RFA: Source Apportionment of Particulate Matter (2004) RFA Text | Recipients Lists
Research Category: Air Quality and Air Toxics , Particulate Matter , Air
Objective:
Fine particles in urban atmospheres are composed of highly complex mixtures of organic compounds spanning large ranges of molecular weight and compound group classifications. However, nearly 50% of the organic carbon mass collected as fine particles cannot be analyzed using current molecular level mass spectrometric analytical methods (e.g., gas chromatography/mass spectrometry, GC/MS) due to low volatility in the gas chromatographic system. The original intent of the project was to develop and use Liquid Chromatography Mass Spectrometry (LCMS) to study polar organic compounds extracted from fine particles. However for multiple reasons, the LCMS instrument did not prove a stable, quantitative measurement device for polar atmospheric organic compounds. We developed two quantitative High Pressure Liquid Chromatography (HPLC) methods using UV-VIS detection and a monolithic silica column to separate and measure oxocarboxylic acids and carbonyl compounds as DNPH derivatives. However, HPLC UV-VIS analysis is not a comprehensive method for polar organic compounds in the PM extractable matter without a carbonyl functional group. To meet this analytical challenge for polar compounds with –OH and –COOH functional groups, we refined a GCMS derivatization procedure using BSTFA to produce trimethylsilyl ethers. The is alternative method for PM polar compounds provided stable, quantitative measurements for a suite of 31 polar organic marker, including smoke anhydrous sugars and phenols (e.g. levoglucosan), sterols (cholesterol, β-sitosterol, campesterol), n-alkanols, aromatic carboxylic acids, and aliphatic low-molecular weight oxocarboxylic acids and dicarboxylic acids. The main goals of this project were: 1) to identify and measure the ambient abundances of polar organic compounds found as PM2.5 in the NY, NJ and CT regional airshed using GCMS with BSTFA chemical analysis; 2) to measure and identify both known and potential secondary organic aerosol source markers found within the fine particle acidic organic fraction; and 3) to screen the Speciation of Organics for Apportionment of PM2.5 (SOAP) program 2002-2003 and SOAP 2005-2007 seasonal filter composites extractable organic mixtures for polar molecular markers from primary sources of urban fine particles.
Progress Summary:
We have focused this period on the completion of GCMS analysis and marker quantitation of polar organic compounds as BSTFA derivatives from the two SOAP NY sampling campaigns. In SOAP 2002-2003 study (May 2002-May 2003), fifteen seasonal composites were generated from a full annual cycle of 24-hour filter samples collect in the NY area fine; Elizabeth, NJ (urban, NJ Turnpike Toll Plaza 13), Chester, NJ (rural, upwind low density residential); Flushing Queens, NYC (urban, high density residential); and Westport, CT (downwind, low density residential). For SOAP 2005-2007 (October, 2005 to March, 2007), an upwind rural site (Pinnacle State Park, NY) and an urban highly-populated site (IS52, Bronx, NY ) were the two study locations. The sites operated from October, 2005 to March, 2007. Tisch 2 or 4-channel sample collectors were used. Filters were collected according to the Speciation Trends Network (STN) schedule either as one-in-three day (SOAP 2002-2003) or one-in-six day daily (SOAP 2005-2007) samples. The filter composites were extracted with acetone/methylene chloride (1:1). One half of the extract was derivatized with N,O-bis(Trimethylsilyl)triflouro-acetamide (BSTFA) and 1% trimethy-chlorosilane (TMS) to convert –OH and COOH groups to trimethylsilyl ethers and esters, respectively. Standard solutions for 31 polar marker compounds were prepared and analyzed as 5-point calibration series for both.
The SOAP 2002-2003 and 2005-2007 continuous field campaigns provide a unique opportunity to compare seasonal trends and spatial concentrations for 31 polar organic marker compounds at two rural upwind sites (Chester, NJ, Pinnacle State Park, Addison, NY) and four urban/downwind sites (Elizabeth, NJ, Flushing-Queens NYC, NY, Bronx, NY, and Westport, CT). Viewed in total, the two SOAP studies provide a five-year sampling period to examine changes in primary and secondary sources of polar fine PM in the NYC area and upwind and downwind sites. Simple descriptive statistics and ANOVA analysis were applied to the two SOAP studies. We are continuing with data analysis and interpretation of the 31 markers with EC, OC and fine PM mass.
Statistical analysis of the SOAP 2002-2007 molecular markers demonstrated seasonal variations of wood smoke at two sites (Westport, CT and Bronx, NY), meat charbroiling at only one site (Bronx, NY), and levulinic acid at three sites (Westport, CT, Bronx, NY and Pinnacle State Park, NY). When the samples were grouped as urban and rural areas for the 2002-2007 combined study period, the ANOVA results showed there was no spatial or seasonal trend in levoglucosan, total n-alkanols or levulinic acid. A significant finding was the wood smoke marker, levoglucosan, was higher for the NYC metropolitan and suburban sites than for the rural sites and was found year-round. Apparently, there are significant sources of wood smoke in NYC that persist throughout year. Emissions from wood-fired pizza ovens, outdoor vendor carts, and other commercial food preparation using wood-fired cooking sources are possible sources of the wood smoke in the NYC metropolitan area. The levoglucosan, total n-alkanols, cholesterol, cis-pinonic acid and levulinic acid normalized to elemental carbon did show statistical differences between urban and rural sites, indicating the sites were influenced by local emission sources and meteorological conditions.
Future Activities:
The project continues as a no-cost extension pending resolution of the current legal negotiation between Rutgers University and the manufacturer of the LCMS instrument. We will continue data analysis and manuscript preparation for the SOAP 2002-2007 field campaigns of fine PM samples and polar markers.
Journal Articles on this Report : 3 Displayed | Download in RIS Format
| Other project views: | All 15 publications | 4 publications in selected types | All 4 journal articles |
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Hawley HA, Mazurek MA. Oxocarboxylic acids as DNPH derivatives with a monolithic silica column and UV-VIS detection. American Laboratory Online 2008;1(3 Part 2):23-27. |
R832165 (2007) R832165 (2008) R832165 (Final) |
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Li M, McDow SR, Tollerud DJ, Mazurek MA. Seasonal abundance of organic molecular markers in urban particulate matter from Philadelphia, PA. Atmospheric Environment 2006;40(13):2260-2273. |
R832165 (2008) R832165 (Final) |
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McDow SR, Mazurek MA, Li M, Alter L, Graham J, Felton HD, McKenna T, Pietarinen C, Leston A, Bailey S, Argao SWT. Speciation and atmospheric abundance of organic compounds in PM2.5 from the New York City area. I. Sampling network, sampler evaluation, molecular level blank evaluation. Aerosol Science and Technology 2008;42(1):50-63. |
R832165 (2008) R832165 (Final) |
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Supplemental Keywords:
ambient air, atmosphere, sources, particulates, PAHs, organics, analytical, measurement methods, LCMS, northeast, Atlantic coast, mid-Atlantic, New York, NY, New Jersey, NJ, Connecticut, CT, EPA Region 2,, RFA, Scientific Discipline, Air, Ecosystem Protection/Environmental Exposure & Risk, POLLUTANTS/TOXICS, Air Quality, particulate matter, air toxics, Environmental Chemistry, Air Pollution Effects, Chemicals, Monitoring/Modeling, Environmental Monitoring, Atmospheric Sciences, Engineering, Chemistry, & Physics, Environmental Engineering, particle size, atmospheric particulate matter, health effects, air quality modeling, mass spectrometry, aerosol particles, motor vehicle emissions, human health effects, PM 2.5, wood combustion, atmospheric particles, air quality models, airborne particulate matter, particulate emissions, air modeling, air sampling, gas chromatography, thermal desorption, air quality model, emissions, benzene, particulate matter mass, human exposure, particle phase molecular markers, particle dispersion, aerosol analyzersProgress and Final Reports:
Original AbstractThe perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.