Liquid Cathode Glow Discharge as an Excitation Source for the Analysis of Complex Water Samples with Atomic Emission Spectrometry.

A liquid cathode glow discharge (LCGD) was developed as a low-power and miniaturized excitation source of atomic emission spectrometry (AES) for the determination of K, Na, Ca, and Mg in water samples from rivers and lakes. The discharge stability and parameter influencing the analytical performance of LCGD-AES were systematically examined. Moreover, the measurement results of water samples using LCGD-AES were verified by ion chromatography (IC). The results showed that the optimized operating parameters are a 660 V discharge voltage, pH = 1.0 HNO as the supporting electrolyte, and a 4.0 mL min solution flow rate. High concentrations of some metals may interfere with the detection of Ca and Mg. Low-molecular-weight organic substances do not have a remarkable enhancement on signal intensity. With the addition of 0.5% cetyltrimethylammonium chloride (CTAC), the emission intensity of elements can enhance significantly. However, it is not used to further evaluate the analytical performance due to instability of plasma after adding CTAC. The maximum power of LCGD is 52 W. The limits of detection and precision (RSD, in 1 mg L) of K, Na, Ca, and Mg are 0.20, 0.02, 0.01, and 0.01 mg L and 0.9, 1.5, 0.6, and 1.2%, respectively. The measurement results of K, Na, Ca, and Mg in water samples by LCGD-AES are basically in agreement with the reference values measured by IC. The recovery of samples ranged from 84 to 113% except for Na, suggesting that the measurement results have high accuracy and reliability. All the results indicated that the LCGD-AES can provide an alternative analytical method for in situ, real-time, on-line determination of K, Na, Ca, and Mg in water samples from rivers and lakes.