April 2013 Meeting Announcement, Delaware Valley Mass Spectrometry Discussion Group
PLEASE NOTE: We will meet in Mendel 154.
- Topic: "Analysis of Flame Retardants in Automobile Dust. Analytical Methods and Exposure Implications "
- Speaker: Anthony Lagalante, Villanova University
- Date: Monday, April 8, 2013. 6:30 PM
- Time: Social Hour: 6:30 PM.
Talk: 7:30 PM.
Please RSVP to Sergio Nanita firstname.lastname@example.org by Thursday April 4.
- Place: Department of Chemistry, Villanova University (Room 154, Mendel Hall)
In 2003, researchers in Sweden reported alarmingly high levels of brominated flame retardants present in humans; of particular concern today are the levels in pregnant and nursing mothers’ breast milk, infants, and children. Since then, a comprehensive, worldwide research effort has been undertaken to investigate the origin, exposure pathways, fate, and toxicity of this class of chemicals. As a result, voluntary reductions on the part of manufacturers, varying degrees of legislative bans worldwide, and consumer advocacy against this class of chemicals have ensued. Research in my group has developed new analytical methods to selectively measure these flame retardants using GC-MS and LC-MS/MS as well as uncovering a significant, unrealized exposure pathway through automobile interiors to account for a portion of the missing body-burden of these chemicals in humans. Taken in total, the worldwide body of scientific data has led to U.S. state legislative bans, culminating recently in heated Senate federal discussions that seek to reform the use and manufacture of these chemicals in the U.S. marketplace.
Methods for analysis of polybrominated diphenyl ether (PBDE) congeners of primary interest to the US EPA will be discussed. Liquid chromatography negative-ion atmospheric pressure photoionization (NI-APPI) with a toluene dopant produced precursor ions corresponding to [M–Br+O]– for the eight congeners studied. The liquid-phase separation of the LC/NI-APPI/MS/MS method is not prone to the thermal degradation issues that plague splitless GC based analyses of highly brominated PBDEs such as BDE-209.Each congener was quantified by tandem mass spectrometry through a unique, multiple reaction monitoring (MRM) transition. The LC/NI-APPI/MS/MS method was validated for the analysis of the eight PBDE congeners in NIST SRM 2585 (Organics in House Dust). Pressurized liquid extraction (PLE) with subsequent LC/NI-APPI/MS/MS analysis afforded quantitative recovery for all eight PBDE congeners. The LC/NI-APPI/MS/MS method was used to quantify PBDEs in the dust sampled from 60 automobiles that were available for resale at U.S.. dealerships. The dominant congener in automobile dust was BDE-209 comprising 95% of the total PBDE levels with a median level of 48.1 µg g-1. Statistical analysis of the vehicle attributes indicates that the BDE-209 levels are different (p < 0.05) with respect to groupings by vehicle model year, vehicle manufacturer, and the country of manufacture. Vehicle dust samples contained the characteristic profile of the PBDE congeners that comprise the PentaBDE formulation. As a follow-up to the dealership vehicle study, the levels of 21 PBDE congeners were determined in the dust sampled from 66 personal automobiles using a GC/MS method. The dominant congener in automobile dust was BDE-209 with a median level of 8.12 µg g-1. Personal vehicle dust samples contained the characteristic profile of the PBDE congeners that comprise the PentaBDE and DecaBDE commercial formulations. Levels of PBDEs in personal automobiles are generally reduced in comparison to our previously reported levels in resale vehicles on dealership lots presumably due to a dilution effect introduced by dust or debris that does not originate from the vehicle. Laboratory photochemical studies were conducted on both automobile dust collected from personal vehicles as well as BDE-209 adsorbed to sodium sulfate. No significant degradation occurred in the personal vehicle dust after 56 days of constant UVA irradiation while significant degradation did occur with BDE-209 adsorbed to sodium sulfate. PBDEs from the degradation of BDE-209 were identified and potential degradation pathways elucidated. Human exposure potential to PBDEs from automobile dust ingestion remains a serious concern in the U.S. population. While DecaBDE use is banned in Maine and Washington and is targeted for restriction in the near future by six U.S. states, vehicles and airplanes are exempt from the ban. It is anticipated that the human exposure potential to PBDEs from automobile dust ingestion will continue for an indefinite future period in the U.S. population.
- Bio: Anthony Lagalante received a B.S. in chemistry from Virginia Tech in 1990 and a Ph.D. in analytical chemistry from the University of Colorado, Boulder in 1995. He was a postdoc and later hired as a staff research chemist at the National Institute of Standards and Technology in Boulder, CO where he led a theoretical and experimental program on the solubility of solutes in supercritical fluids and alternative refrigerant solvents. In 2004, he joined the faculty in the chemistry department at Villanova University and was promoted with tenure to Associate Professor in 2006. He leads a diverse research program split between environmental chemistry and cultural heritage science. The analytical projects in his laboratory range from exposure of harmful chemicals in consumer products, methods to save and protect hemlock trees in the eastern United States, and technical studies to understand and preserve modern art and ancient artifacts. As a result, Prof. Lagalante and his students work in collaboration with environmental groups, foresters, entomologists, art conservators, and museum scientists worldwide. His research is funded through state and federal forestry agencies as well as through the National Science Foundation (NSF). Additionally, Prof. Lagalante instructs college and university professors in advanced methods in cultural heritage science through the NSF sponsored Chemistry Collaborations, Workshops and Communities of Scholars (cCWCS) program. Stemming from his teachings and research in the area of conservation science, in 2010, he was appointed to an adjunct Associate Professor of Art Conservation at the University of Delaware.
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