@article {95, title = {Mutagenic Azo Dyes, Rather Than Flame Retardants, Are the Predominant Brominated Compounds in House Dust.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 12 06}, pages = {12669-12677}, abstract = {

Characterization of toxicological profiles by use of traditional targeted strategies might underestimate the risk of environmental mixtures. Unbiased identification of prioritized compounds provides a promising strategy for meeting regulatory needs. In this study, untargeted screening of brominated compounds in house dust was conducted using a data-independent precursor isolation and characteristic fragment (DIPIC-Frag) approach, which used data-independent acquisition (DIA) and a chemometric strategy to detect peaks and align precursor ions. A total of 1008 brominated compound peaks were identified in 23 house dust samples. Precursor ions and formulas were identified for 738 (73\%) of the brominated compounds. A correlation matrix was used to cluster brominated compounds; three large groups were found for the 140 high-abundance brominated compounds, and only 24 (17\%) of these compounds were previously known flame retardants. The predominant class of unknown brominated compounds was predicted to consist of nitrogen-containing compounds. Following further validation by authentic standards, these compounds (56\%) were determined to be novel brominated azo dyes. The mutagenicity of one major component was investigated, and mutagenicity was observed at environmentally relevant concentrations. Results of this study demonstrated the existence of numerous unknown brominated compounds in house dust, with mutagenic azo dyes unexpectedly being identified as the predominant compounds.

}, keywords = {Azo Compounds, Dust, Flame Retardants, Halogenated Diphenyl Ethers, Hydrocarbons, Brominated, Mutagens}, issn = {1520-5851}, doi = {10.1021/acs.est.6b03954}, author = {Peng, Hui and Saunders, David M V and Sun, Jianxian and Jones, Paul D and Wong, Chris K C and Liu, Hongling and Giesy, John P} } @article {103, title = {Untargeted Screening and Distribution of Organo-Bromine Compounds in Sediments of Lake Michigan.}, journal = {Environ Sci Technol}, volume = {50}, year = {2016}, month = {2016 Jan 05}, pages = {321-30}, abstract = {

Previously unreported natural and synthetic organo-bromine compounds (NSOBCs) have been found to contribute more than 99\% of total organic bromine (TOB) in environmental matrices. We recently developed a novel untargeted method (data-independent precursor isolation and characteristic fragment, DIPIC-Frag) and identified \~{}2000 NSOBCs in two sediments from Lake Michigan. In this study, this method was used to investigate the distributions of these NSOBCs in 23 surficial samples and 24 segments of a sediment core from Lake Michigan. NSOBCs were detected in all 23 surficial samples and exhibited 10- to 100-fold variations in peak abundance among locations. The pattern of distributions of NSOBCs was correlated with depth of the water column (r(2) = 0.61, p \< 0.001). Hierarchical cluster analysis showed that sediments in close proximity exhibited similar profiles of NSOBCs. Distributions of NSOBCs in 24 segments of a sediment core dated from 1766 to 2008 were investigated, and samples from similar depths exhibited similar profiles of NSOBCs. NSOBCs were grouped into four clusters (soft-cluster analysis) with different temporal trends of abundances. 515 and 768 of the NSOBCs were grouped into cluster 1 and cluster 3 with increasing temporal trends, especially since 1950, indicating that abundances of these compounds might have been affected by human activities.

}, keywords = {Bromine Compounds, Environmental Monitoring, Geologic Sediments, Halogenated Diphenyl Ethers, Hydrocarbons, Brominated, Lakes, Michigan, Water Pollutants, Chemical}, issn = {1520-5851}, doi = {10.1021/acs.est.5b04709}, author = {Peng, Hui and Chen, Chunli and Cantin, Jenna and Saunders, David M V and Sun, Jianxian and Tang, Song and Codling, Garry and Hecker, Markus and Wiseman, Steve and Jones, Paul D and Li, An and Rockne, Karl J and Sturchio, Neil C and Giesy, John P} } @article {105, title = {Untargeted Identification of Organo-Bromine Compounds in Lake Sediments by Ultrahigh-Resolution Mass Spectrometry with the Data-Independent Precursor Isolation and Characteristic Fragment Method.}, journal = {Anal Chem}, volume = {87}, year = {2015}, month = {2015 Oct 20}, pages = {10237-46}, abstract = {

While previous studies have found that unknown natural and synthetic organo-bromine compounds (NSOBCs) contributed more than 99\% of the total organic bromine (Br) in the environment, there was no efficient method for untargeted screening to identify NSOBCs in environmental matrixes. A novel untargeted method for identifying NSOBCs, based on ultrahigh-resolution mass spectrometry (UHRMS) with the Q Exactive instrument was developed. This method included a data-independent precursor isolation and characteristic fragment (DIPIC-Frag) procedure to identify NSOBCs. A total of 180 successive 5-m/z-wide windows were used to isolate precursor ions. This resulted in a sufficient dynamic range and specificity to identify peaks of Br fragment ions for analysis. A total of 2520 peaks of NSOBC compounds containing Br were observed in sediments from Lake Michigan, United States. A new chemometric strategy which combined chromatographic profiles, isotopic peaks, precursor isolation window information, and intensities was used to identify precursor ions and chemical formulas for detecting NSOBCs. Precursor ions for 2163 of the 2520 NSOBCs peaks (86\%) were identified, and chemical formulas for 2071 NSOBCs peaks (82\%) were determined. After exclusion of isotopic peaks, 1593 unique NSOBCs were identified and chemical formulas derived for each. Most of the compounds identified had not been reported previously and had intensities which were 100- to 1000-fold greater than the congeners of polybrominated diphenyl ethers (PBDEs). In extracts of sediments, these compounds exhibited variations in intensities (\<10(3) to \~{}10(8)), m/z values (170.9438-997.5217), retention times on a C18 column (1.0-29.3 min), and the number of Br atoms (1-8). Generally, compounds with greater m/z values had longer retention times and greater numbers of Br atoms. Three compounds were used in a proof-of-concept experiment to demonstrate that structures of some of the screened NSOBCs could be further predicted by combining searching of database libraries and high-resolution MS(2) spectra.

}, keywords = {Databases, Chemical, Geologic Sediments, Hydrocarbons, Brominated, Lakes, Mass Spectrometry}, issn = {1520-6882}, doi = {10.1021/acs.analchem.5b01435}, author = {Peng, Hui and Chen, Chunli and Saunders, David M V and Sun, Jianxian and Tang, Song and Codling, Garry and Hecker, Markus and Wiseman, Steve and Jones, Paul D and Li, An and Rockne, Karl J and Giesy, John P} }