Determination of cadmium at ultratrace levels in environmental water samples by means of total reflection X-ray spectrometry after dispersive liquid-liquid microextraction

Until now, the determination of Cd at trace levels in aqueous samples by TXRF has been restricted. When Mo-target X-ray tubes are used, low sensitivity and interferences with Cd L-lines used for quantification prevent trace analysis. Alternatively, when W-target X-ray tubes are used Cd excitation is limited. For this reason, a sample pretreatment is usually necessary to extract, isolate and concentrate Cd prior to TXRF analysis. In the present contribution, the feasibility of a dispersive liquid-liquid microextraction approach (DLLME) combined with TXRF for ultratrace Cd determination in different types of environmental waters is shown. Parameters affecting the extraction procedure and TXRF measurement conditions have been carefully evaluated to ensure the highest sensitivity for Cd determination. Using the best analytical conditions, it was found that the minimum cadmium content that could be detected in an aqueous solution was 0.04 mu g L-1. This value is more than two orders of magnitude lower compared with the direct TXRF analysis of Cd in aqueous samples. The precision of the methodology was evaluated in terms of relative standard deviation (RSD) of six replicate analyses of a standard solution containing 3 mu g L-1. The precision of the method was determined to be approximately 5% RSD. In order to test the suitability of the method when dealing with complex matrices as well as the influence of interfering ions, the determination of Cd in spiked water samples (sea water, estuarine water and river water) at the levels of 1 mu g L-1 and 5 mu g L-1 was undertaken and Cd added to the samples was quantitatively determined. Our results give insight into the possibilities of the combination of DLLME and TXRF for ultratrace Cd determination in different types of environmental waters.