Science Inventory

IDENTIFICATION AND QUANTIFICATION OF AEROSOL POLAR OXYGENATED COMPOUNDS BEARING CARBOXYLIC AND/OR HYDROXYL GROUPS. 1. METHOD DEVELOPMENT

Citation:

Jaoui, M., T E. Kleindienst, M Lewandowski, AND E O. Edney. IDENTIFICATION AND QUANTIFICATION OF AEROSOL POLAR OXYGENATED COMPOUNDS BEARING CARBOXYLIC AND/OR HYDROXYL GROUPS. 1. METHOD DEVELOPMENT. Analytical Chemistry 76(16):4765-4778, (2004).

Impact/Purpose:

1. Using laboratory and field study data generated during FY99-FY04, develop a science version of a PM chemistry model for predicting ambient concentrations of water, inorganics, and organics in PM2.5 samples. The model will include the Aerosol Inorganic Model for predicting concentrations of inorganic compounds and a computational chemistry-based method for predicting concentrations of organic compounds.

2. Identify and evaluate methods for analyzing the polar fraction of PM2.5 samples.

3. Carry out short term field studies in Research Triangle Park, North Carolina in the summer and the winter to determine the composition of the organic fraction of ambient PM2.5 samples, with special emphasis placed on identifying and determining ambient concentrations of polar compounds.

4. Conduct laboratory studies to establish the chemical composition of secondary organic aerosol (SOA) and to determine source signatures for aromatic and biogenic SOA.

5. Conduct laboratory and theoretical investigations of thermodynamic properties of polar organic compounds.

6. Evaluate the science version of the PM chemistry model using laboratory and field data generated under this task as well as other available data in the literature.

7. Conduct PM chemistry-related special studies for OAQPS

Description:

In this study, a new analytical technique was developed for the identification and quantification of multi-functional compounds containing simultaneously at least one hydroxyl or one carboxylic group, or both. This technique is based on derivatizing first the carboxylic group(s) of the multi-functional compound using an alcohol (e.g., methanol, 1-butanol) in the presence of a relatively strong Lewis acid (BF3) as a catalyst. This esterification reaction quickly and quantitatively converts carboxylic acids to their ester forms. The second step is based on silylation of the ester compounds using bis(trimethylsilyl) trifluoroacetamide (BSTFA) as the derivatizing agent. For compounds bearing ketone groups in addition to carboxylic and hydroxyl groups, a third step was used based on PFBHA derivatization of the carbonyls. Different parameters including temperature, reaction time, and effect due to artifacts were optimized. A GC/MS in EI and in methane-CI mode was used for the analysis of these compounds.

The new approach was tested on a number of multifunctional compounds. The interpretation of their EI (70 eV) and CI mass spectra shows that critical information is gained leading to unambiguous identification of unknown compounds. For example, when derivatized only with BF3-methanol, their mass spectra comprise primary ions at m/z M + 1, M + 29, and M+. - 31 for compounds bearing only carboxylic groups and M+. + 1, M+. + 29, M - 31, and M - 17 for those bearing hydroxyl and carboxylic groups. However, when a second derivatization (BSTFA) was used, compounds bearing hydroxyl and carboxylic groups simultaneously show, in addition to the ions observed before, ions at m/z M+. + 73, M+. - 15, M+. - 59, M+. - 75, M+. - 89, and 73. To the best of our knowledge, this technique describes systematically for the first time a method for identifying multi-functional oxygenated compounds containing simultaneously one or more hydroxyl and carboxylic acid groups.

The U.S. Environmental Protection Agency through its Office of Research and Development funded and collaborated in the research described here under Contract 68-D-00-206 to ManTech Environmental Technology, Inc. It has been subjected to Agency review and approved for publication. Mention of trade names or commercial products does not constitute an endorsement or recommendation for use.

Record Details:

Record Type: DOCUMENT (JOURNAL/PEER REVIEWED JOURNAL)
Product Published Date: 08/15/2004
Record Last Revised: 07/25/2008
OMB Category: Other
Record ID: 85632

Organization:

U.S. ENVIRONMENTAL PROTECTION AGENCY

OFFICE OF RESEARCH AND DEVELOPMENT

NATIONAL EXPOSURE RESEARCH LABORATORY

HUMAN EXPOSURE AND ATMOSPHERIC SCIENCES DIVISION

PROCESS MODELING RESEARCH BRANCH