Polyhalogenated carbazoles in sediments of Lake Michigan: a new discovery.

Previously unknown halogenated compounds were detected during the analysis of halogenated flame retardants in two sediment cores collected from Lake Michigan. Gas chromatography coupled with high- or low-resolution mass spectrometry (MS) was used to determine the chemical structures for a total of 15 novel polyhalogenated carbazoles (PHCs) with the general molecular formula C12H9-x-y-zNClxBryIz. On the basis of the mass spectra generated by electron impact (EI) and electron capture negative ionization (ECNI) MS, eight PHCs were tentatively identified as polybrominated carbazoles, while the others were mixed halogenated carbazoles containing, in addition to bromine, either chlorine or iodine or both. Patterns of halogen substitution of PHCs included Br2 to Br5, ClBr2, ClBr3, ClBr4, ClBr3I, Br4I, and Br3I2. 3,6-Dibromocarbazole and 1,3,6,8-tetrabromocarbazole were also found among the PHCs. Profiles of the concentration versus depth of sediment at the two sites showed various patterns among polybrominated carbazoles. The abundance of mixed halogenated carbazoles peaked at depths of 12-16 cm, remained at relatively constant levels in deeper sediment, but declined markedly in more recently deposited sediments. This is the first study discovering the seven mixed halogenated carbazoles in the environment. Detailed methods for their detection and identification are provided.

[1]  Paul D. Jones,et al.  Contribution of synthetic and naturally occurring organobromine compounds to bromine mass in marine organisms. , 2010, Environmental science & technology.

[2]  R. Weber,et al.  THE FINGERPRINT OF CHLORINATED AROMATIC COMPOUNDS IN CONTAMINATED SITES FROM CHLORALKALI PROCESSES AND A HISTORIC CHLORINE PRODUCTION USING GC-HR-TOF-MS SCREENING , 2009 .

[3]  P. Krogh,et al.  Effects of eight polycyclic aromatic compounds on the survival and reproduction of Enchytraeus crypticus (Oligochaeta, Clitellata) , 2002, Environmental toxicology and chemistry.

[4]  C. Rostad,et al.  Mount St. Helens, Washington, 1980 volcanic eruption: Characterization of organic compounds in ash samples , 1980 .

[5]  G. Gribble.  Natural Organohalogens:: Many More Than You Think! , 1994 .

[6]  A. Negrusz,et al.  Dependence of Mass Spectrometric Fragmentation on the Bromine Substitution Pattern of Polybrominated Diphenyl Ethers , 2014, Journal of The American Society for Mass Spectrometry.

[7]  G. Gribble,et al.  The diversity of naturally produced organohalogens. , 2003, Chemosphere.

[8]  D. Lenoir,et al.  Degradative fate of 3-chlorocarbazole and 3,6-dichlorocarbazole in soil , 2011, Environmental science and pollution research international.

[9]  A. Reischl,et al.  Chlorcarbazole in Böden , 2005 .

[10]  P. Howard,et al.  Identifying new persistent and bioaccumulative organics among chemicals in commerce. , 2010, Environmental science & technology.

[11]  Paul D. Jones,et al.  Polybrominated diphenyl ethers and their hydroxylated/methoxylated analogs: environmental sources, metabolic relationships, and relative toxicities. , 2011, Marine pollution bulletin.

[12]  Christopher M Reddy,et al.  Two Abundant Bioaccumulated Halogenated Compounds Are Natural Products , 2005, Science.

[13]  Gordon W. Gribble,et al.  Naturally Occurring Organohalogen Compounds - A Comprehensive Update , 2010 .

[14]  A. M. Jha,et al.  Mutagenic profiles of carbazole in the male germ cells of Swiss albino mice. , 2002, Mutation research.

[15]  R. Hites.  Electron impact and electron capture negative ionization mass spectra of polybrominated diphenyl ethers and methoxylated polybrominated diphenyl ethers. , 2008, Environmental science & technology.

[16]  A. Lagalante,et al.  Levels of polybrominated diphenyl ethers (PBDEs) in dust from personal automobiles in conjunction with studies on the photochemical degradation of decabromodiphenyl ether (BDE-209). , 2011, Environment international.

[17]  C. Reddy,et al.  Halogenated organic compounds in archived whale oil: a pre-industrial record. , 2007, Environmental pollution.

[18]  D. Lenoir,et al.  Enzymatic synthesis of bromo- and chlorocarbazoles and elucidation of their structures by molecular modeling , 2013, Environmental Science and Pollution Research.

[19]  H. Hübschmann.  Chapter 3. Evaluation of GC/MS Analyses , 2008 .

[20]  Paul D. Jones,et al.  Interconversion of hydroxylated and methoxylated polybrominated diphenyl ethers in Japanese medaka. , 2010, Environmental science & technology.

[21]  H. Hübschmann.  Evaluation of GC/MS Analyses , 2015 .

[22]  J. Paasiv́irta,et al.  Complex Dibenzofurans. XII. The Use of Oxygen-18 Labelling in the Interpretation of Mass Spectra of Some Biphenyl and Dibenzofuran Derivatives. , 1968 .

[23]  G. Gribble.  Natural Organohalogens: A New Frontier for Medicinal Agents?. , 2004 .

[24]  G. Gribble.  The abundant natural sources and uses of chlorinated chemicals. , 1994, American journal of public health.

[25]  A. Hagiwara,et al.  Carcinogenic effect of carbazole in the liver of (C57BL/6N x C3H/HeN)F1 mice. , 1982, Journal of the National Cancer Institute.

[26]  E. Durhan,et al.  Tetrachloro-9H-Carbazole, a Previously Unrecognized Contaminant in Sediments of the Buffalo River , 1984 .

[27]  R. Letcher,et al.  Novel methoxylated polybrominated diphenoxybenzene congeners and possible sources in herring gull eggs from the Laurentian Great Lakes of North America. , 2011, Environmental science & technology.

[28]  Karl J. Jobst,et al.  Identification of potential novel bioaccumulative and persistent chemicals in sediments from Ontario (Canada) using scripting approaches with GC×GC-TOF MS analysis. , 2014, Environmental science & technology.

[29]  Jan Schwarzbauer,et al.  Non-target Screening of Organic Contaminants in Sediments from the Industrial Coastal Area of Kavala City (NE Greece) , 2011 .

[30]  R. Hites,et al.  Identification of brominated carbazoles in sediment cores from Lake Michigan. , 2005, Environmental science & technology.

[31]  Alexander Kronimus,et al.  Anthropogenic organic contaminants in sediments of the Lippe river, Germany. , 2004, Water research.