Determination of total organic halogen (TOX) in humic acids after microwave-induced combustion

Chemically chlorinated organic matter as well as natural background humic acids contain significant amounts of organically bound halogens that must be determined for assessment of environmental pollution. In this work the use of ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) is proposed for the determination of total organic Cl, Br and I concentration in humic acids extracted from various forest soil horizons after a single digestion by microwave-induced combustion (MIC). Samples were pressed as pellets and combusted using 20bar of oxygen and ammonium nitrate solution as igniter. Analytes were absorbed in diluted alkaline solution (50mM (NH ₄) ₂CO ₃) and a reflux step was applied after combustion to improve analyte recoveries (5min, microwave power of 1400W). The accuracy was evaluated using certified reference materials (CRM) and spiked samples. Using MIC the agreement with CRM values and spike recoveries was higher than 97% for all analytes. As an advantage over conventional procedures, using MIC it was possible to digest up to eight samples in only 25min, obtaining a single solution suitable for all halogens determination in humic acids samples by different techniques (IC and ICP-MS). The limit of detection (3σ) for Cl, Br and I obtained by IC was 1.2, 2.5 and 4.3μgg ^-1 and by ICP-MS it was 1.4, 0.03 and 0.002μgg ^-1, respectively.