Optimization of a solid-phase extraction step by experimental design for application to SPE-GC-ECD analysis of four bromobenzoquinones and 2,4,6-tribromophenol in chlorinated seawater

Bromobenzoquinones and 2,4,6-tribromophenol belong to disinfection or chlorination by-products than can be formed in bromide-rich waters during chlorination or chloramination. Due to their high toxicities, sensitive and cost-effective analytical methods are necessary to detect and quantify them in various environmental matrices. A determination method of 2,5-dibromo-1,4-benzoquinone, 2,6-dibromo-3,5-dimethyl-1,4-benzoquinone, 2,6-dibromo-3-chloro-5-methyl-1,4-benzoquinone, 2,3,5,6-tetrabromo-1,4-benzoquinone and, 2,4,6-tribromophenol was developed using solid-phase extraction and electron capture detector-gas chromatography separation and detection (SPE-GC-ECD). Preservation of the four bromobenzoquinones with ascorbic acid allow to stabilize them into their bromohydroquinone analogues and to quench residual chlorine. Efficiency of different sorbents was tested and extraction and elution parameters were optimized by use of an experimental design. The recovery rates of each of the five compounds studied were between 59 and 101.4 %. The limits of detection (LODs) of the SPE-GC-ECD method were between 7 and 22 ng L^-1. Applying this analytical procedure to real industrial chlorinated discharges in seawater, we report for the first time the presence of 2,6-dibromo-3- chloro-5-methyl-1,4-benzoquinone (up to 47 ng L^-1), 2,6-dibromo-3,5-dimethyl-1,4-benzoquinone (35 ng L^-1) and 2,4,6-tribromophenol (up to 42 ng L^-1) in such effluents.