To simultaneously quantify and profile
the complex mixture of short-,
median-, and long-chain CPs (SCCPs, MCCPs, and LCCPs) in Australian
sewage sludge, we applied and further validated a recently developed
novel instrumental technique, using quadrupole time-of-flight high
resolution mass spectrometry running in the negative atmospheric pressure
chemical ionization mode (APCI-qTOF-HRMS). Without using an analytical
column the cleaned extracts were directly injected into the qTOF-HRMS
followed by quantification of the CPs by a mathematical algorithm.
The recoveries of the four SCCP, MCCP and LCCP-spiked sewage sludge
samples ranged from 86 to 123%. This APCI-qTOF-HRMS method is a fast
and promising technique for routinely measuring SCCPs, MCCPs, and
LCCPs in sewage sludge. Australian sewage sludge was dominated by
MCCPs with concentrations ranging from 542 to 3645 ng/g dry weight
(dw). Lower SCCPs concentrations (<57–1421 ng/g dw) were
detected in the Australian sewage sludge, which were comparable with
the LCCPs concentrations (116–960 ng/g dw). This is the first
time that CPs were reported in Australian sewage sludge. The results
of this study gives a first impression on the distribution of the
SCCPs, MCCPs, and LCCPs in Australia wastewater treatment plants (WWTPs).
We studied the presence of hydroxylated metabolites of hexabromocyclododecane (HBCD) in three wildlife species (tern egg, seal, and flounder) and in Wistar rats exposed to 30 and 100 mg HBCD/kg bw/day for 28 days. A nondestructive extraction, fractionation, and cleanup method was developed to separate the hydroxylated HBCD metabolites from the biotic sample matrix. Four different groups of hydroxylated HBCD metabolites were identified in rat adipose, liver, lung, and muscle tissues by liquid and gas chromatography (LC and GC) combined with mass spectrometry (MS): monohydroxy metabolites of HBCD, pentabromocyclododecene (PBCDe), tetrabromocyclododecene (TBCDe), and dihydroxy-HBCD. Dihydroxy-PBCDe was identified by GC-MS but could not be confirmed by LCMS. Debromination of HBCD to PBCDe was another metabolic pathway observed. In tern eggs from the Western Scheldt the monohydroxy-HBCD was found and in the blubber of harbor seal (Wadden Sea) the monohydroxy metabolites of HBCD and PBCDe were found. No hydroxylated metabolites were detected in the tissue of flounder (Wadden Sea). To our knowledge, this is the first study to identify different hydroxylated metabolite groups of HBCD in rat and wildlife samples.
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