Method development for simultaneous analyses of multiple legacy and emerging organic chemicals in sediments

The objective of this work was to investigate the feasibility of using a single pretreatment procedure for the analyses of multiple groups of organics, which have a wide range of chemical structures and physicochemical properties, in sediment samples. Nine groups of 162 individual compounds (including 11 surrogates) were investigated, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PCDEs), polychlorinated naphthalenes (PCNs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), novel halogenated flame retardants (nXFRs), musk fragrances (MFs) and organophosphate flame retardants (OPFRs). The individual and grouped recoveries of spiked analytes from adsorption chromatographic columns using either only fully activated, neutral silica gel (SG) or the combinations of silica gel and alumina (Si/Al) sorbents were compared. The results showed a generally stronger adsorption and more effective fractionation on the Si/Al column than on the SG column. The dependence of fractionation on halogen substitution, molecular planarity, and polar functional groups was discussed. The effects of adding sulfuric acid with two different methods were investigated, and the recoveries of a number of MFs, OCPs, nXFRs and OPFRs were recovered less than 60%. Sodium hydroxide treatment of silica gel had minor effects on some OPFRs. Copper used to remove elemental sulfur did not affect the recoveries of all target analytes except chloroneb. The finalized method was validated by spiking the target analysts into the sediment samples and comparing the analytical results of this work on two standard reference materials for sediment (SRMs 1941b and 1944) with the certified or reference values.