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retardant and is still manufactured for export. ... and has been demonstrated to have anticholinesterase activity (1). Furthermore .... 1.0. 1.2. 1.4...
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13 Sampling and Analysis for Semivolatile Brominated Organics in Ambient Air

Downloaded by UNIV OF MICHIGAN ANN ARBOR on February 18, 2015 | http://pubs.acs.org Publication Date: March 13, 1979 | doi: 10.1021/bk-1979-0094.ch013

RUTH A. ZWEIDINGER, STEPHEN D. COOPER, MITCHELL D. ERICKSON, LARRY C. MICHAEL, and EDO D. PELLIZZARI Research Triangle Institute, Post Office Box 12194, Research Triangle Park, NC 27709

Introduction Increasingly strict guidelines regarding the flammability of textiles, particularly synthetic materials used in infant garments, have initiated the development and use of more effective flame retardant chemicals. Among the flame retardants which have been widely used is tris(2,3-dibromopropyl)phosphate (TRIS). Although currently banned for domestic use, TRIS has been widely used in the past as a textile flame retardant and is still manufactured for export. The compound is extremely toxic to fish and has been demonstrated to have anticholinesterase activity (1). Furthermore, recent tests have implicated it as a carcinogen (2) and mutagen (Chapter 1, this volume). Due to this imminent health hazard and its extensive historical usage, assessment of the introduction of TRIS and other brominated organics into the environment is of para­ mount importance. The volatility of TRIS is very low, on the order of 4.8 χ 10-3 Torr at 65°C. This low volatility and the thermal instability of alkyl phosphates in general, particularly halogenated alkyl phosphates, presents a number of unique problems in the development of sampling and analytical methodology. The method development for TRIS was initiated with the evaluation of several detection methods. Taking into account its low volatility and relative thermal instability, sampling and analysis protocols were fomulated for the determination of TRIS. These protocols were extended to decabromobiphenyl ether (Decabrom), 2,2-bis(dibromo-4-hydroxy phenol) propane (Tetrabrom) and l,2-bis(2,4,6-tribromophenoxy)-ethane (Firemaster 680®). Field samples were col­ lected to validate the aforementioned protocols and evaluate the atmospheric levels of brominated organic aerosols in the vicinity of organo-bromine synthesis facilities. Analytical Method Development for TRIS. The detection of brominated com­ pounds of very low volatility such as TRIS posed special analytical problems. Since TRIS has no recognizable chromophore, the detection systems which are commonly used with high performance liquid chromatography (hplc), such as refractive index or short wavelength (