Accurate-mass identification of chlorinated and brominated products of 4-nonylphenol, nonylphenol dimers, and other endocrine disrupters

✍ Scribed by E. Michael Thurman

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 294 KB
• Volume: 41
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/jms.1097

✦ Synopsis

Abstract

LC/ToF‐MS was used to identify new chlorination and bromination products of 4‐nonylphenol (4‐NP), such as 4‐NPBr~2~, 4‐NPBrCl, 4‐NP dimer (2 isomers), 4‐NPCl dimer (2 isomers), 4‐NPBr dimer, and a series of methoxy bromo and chloro 4‐NPs from a laboratory study of nonylphenol chlorination. The identification procedure used the exact mass, exact mass of the isotope cluster, and their relative intensities, at an average mass accuracy of ∼1 ppm. The products were produced by a simulated study of industrial cleaning procedures where 4‐NP, nonylphenol ethoxylate (NPEO‐1 and 2), and nonylphenol carboxylate (NPEC‐1) were in contact with sodium hypochlorite solutions (with and without bromide) of various strengths (possible environmental scenarios) at neutral pH. The formation of the products was measured as a function of chlorine concentration, and it was found that 4‐NP was the most reactive, producing 4‐NPCl, 4‐NPCl~2~, 4‐NP (dimers), and the 4‐NPCl (dimers). In the presence of bromide ions, a mixture results with products of 4‐NPBr~2~, 4‐NPCl, 4‐NPCl~2~, 4‐NPBrCl, 4‐NPBr, and a 4‐NPBr dimer. Less reactive to halogenation was NPEO, which formed only the monochloro and monobromo products, and the least reactive was NPEC. A simple stereochemical model is used to explain halogenation reactivity for the family of 4‐NPs and NPEOs at neutral pH. The presence of halogenated 4‐NP dimers (bromo and chloro diphenyl ethers) is discussed as a possible source of new endocrine disrupters. Copyright © 2006 John Wiley & Sons, Ltd.