Selective non-chromatographic determination of tributyltin in sediments using EDTA and diphenylcarbazone as masking agent

Abstract

ABSTRACTTwo analytical procedures based on the generation of volatile tributyltin derivatives, their separation by headspace solid-phase microextraction (HS SPME) and subsequent determination using plasma optical emission spectrometry (OES) have been developed for the selective determination of trace tributyltin (TBT) in the presence of other butyltins and inorganic tin in sediments without the use of chromatography. A microwave-assisted leaching of tin compounds from the sediment using 25%v/v acetic acid is applied for sample pretreatment. The first method takes advantage of TBT chloride releasing from the lecheate after adding 3 M hydrochloric acid, and subsequent separation of the analyte by HS SPME using Carboxen-poly(dimethylsiloxane) (CAR/PDMS). The second method involves the use of masking agents, namely ethylenediaminetetraacetic acid (EDTA) and diphenylcarbazone (DFC), which form stable chelates with monobutyltin (MBT) and dibutyltin (DBT), respectively, followed by the ethylation of tributyltin at pH 5 using sodium tetraethylborate (NaBEt4) solution. The final concentration of NaBEt4 is 0.05%w/v. The parameters affecting the TBT derivatisation and separation by HS SPME have been optimised including the selection of SPME fibre coating (PDMS, CAR/PDMS), the amount of masking agents and NaBEt4 added, sorption time (2–40 min) and sorption temperature (25–60°C). Higher sensitivity and robustness are attained with the method involving ethylation derivatisation, leading to the limit of detection (LOD) of 3 ng L−1. The selective release of TBT is observed from aqueous solutions, where the concentrations of MBT and DBT were in 2–50-fold excess to TBT. The SPME-TD-MIP-OES methods have been validated against several certified reference materials (CRMs), including SOPH-1 marine sediment, PACS-2 marine sediment and BCR 646 freshwater sediment.