Simultaneous detection of trace metal ions in water by solid phase extraction spectroscopy combined with multivariate calibration

• The simultaneous determination of metal ions based on SPES and UV-Visible couple with multivariate calibration spectroscopy was proposed.
• The spectra of the analytes on the membranes were measured directly without eluting.
• The method was used to quantify trace cobalt (II) and zinc (II) in three real samples.
• The proposed method is simple, sensitive and selective.
• The applicability of the method can be extended to other analytes.

Solid Phase Extraction Spectroscopy (SPES) developed in this paper is a technique to measure spectrum directly on the solid phase material where the analytes are concentrated in SPE process. Membrane enrichment and UV–Visible spectroscopy were utilized to fulfill SPES, and multivariate calibration method of partial least squares (PLS) was used to simultaneously detect the concentrations of trace cobalt (II) and zinc (II) in water samples. The proposed method is simple, sensitive and selective. The complexes of analyte ions were collected on the cellulose acetate membranes via membrane filtration after the complexation reaction with 1-2-pyridylazo 2-naphthol (PAN). The spectra of the membranes which contained the complexes of metal ions and PAN were measured directly without eluting. The analytical conditions including pH, reaction time, sample volume, the amount of PAN, and flow rates were optimized. Nonionic surfactant Brij-30 was absorbed on the membranes prior to SPES to modify the membranes for improving the enrichment and spectrum measurement. The interference from other ions to the determination was investigated. Under the optimal condition, the absorbance was linearly related to the concentration at the range of 0.1–3.0 μg/L and 0.1–2.0 μg/L, with the correlation coefficients (R2) of 0.9977 and 0.9951 for Co (II) and Zn (II), respectively. The limits of detection were 0.066 μg/L for cobalt (II) and 0.104 μg/L for zinc (II). PLS regression with leave-one-out cross-validation was utilized to build models to detect cobalt (II) and zinc (II) in drinking water samples simultaneously. The correlation coefficient between ion concentration and spectrum of calibration set and independent prediction set were 1.0000 and 0.9974 for cobalt (II) and 1.0000 and 0.9956 for zinc (II). For cobalt (II) and zinc (II), the errors of the prediction set were in the range 0.0406–0.1353 μg/L and 0.0025–0.1884 μg/L.

SPES that is introduced in this work is a simple, sensitive and low cost technique for UV–Vis spectrometric simultaneous determination of metal ions in water samples. With the support of multivariate calibration, simultaneous detection of trace cobalt (II) and zinc (II) becomes feasible. And its applicability of the method can be extended to other analytes.Figure optionsDownload as PowerPoint slide