The exposure of millions of people to unsafe levels of arsenite (As III ) and arsenate (As V ) in drinking waters calls for the development of low-cost methods for on-site monitoring these two arsenic species in waters. Herein, for the first time, tetradecyl (trihexyl) phosphonium chloride ionic liquid was found to selectively bind with As III via extended Xray absorption fine structure (EXAFS) analysis. Based on the finding, an As III -specific probe was developed by modifying gold nanoparticles with the ionic liquid. Futhermore, Hofmeister effect was primarily observed to significantly affect the sensitivity of gold nanoparticle probe. With the colorimetric probe, we developed a protocol for naked eye speciation test of As III and As V at levels below the World Health Organization (WHO) guideline of 10 μg L −1 . This method featured with high tolerance to common coexisting ions such as 10 mM PO 4 3− , and was validated by assaying certified reference and environmental water samples. KEYWORDS: arsenic, ionic liquid, interaction, gold nanoparticle, Hofmeister effect, visual test
■ INTRODUCTIONArsenic shows various adverse health effects including carcinogenic disease relative to skin, lung, and kidney. 1−3 More than 140 million people worldwide are exposed to superfluous arsenic, mainly by drinking ground waters polluted by inorganic arsenic that are more toxic than the organic ones. 4,5 Although As III and As V are coexisting and undergo mutual transformation in groundwater, As III is usually the main form and more toxic than As V . 6 Consequently, monitoring of inorganic arsenic species in waters is of prior interest in arsenic detection. Numerous instrumental methods have been developed to quantify trace arsenic, 7−10 but the requirement of bulk equipment and strict laboratory conditions restricts their application in field analysis. On the contrary, the colorimetric or visual methods are quite suitable for field determination. Because of their poor sensitivity, however, traditional visual probes are incapable of detecting As III and As V at 10 μg L −1 level, which is the arsenic guideline value in drinking water required by the World Health Organization (WHO) and U.S. Environmental Protection Agency (EPA). Additionally, the fairly poor tolerance to interferences of these probes restricts their application in real sample analysis. 11−13 Several arsenic testing field kits are able to semiquantify 10 or 50 μg L −1 As, but most of them fail to meet the requirements of an ideal test kit for As. 14−16 Gold nanoparticles (AuNPs) are widely used as optical probes in colorimetric detection in recent years, 17−19 because of their higher extinction coefficient in the visible region and thus higher sensitivity in comparison to the organic probes. Since the pioneering work of the Mirkin group, 20 AuNPs have served as optical probes for sensing cations, anions, small organic compounds, and biological molecules, 21−23 with Hg 2+ as one of the most attractive target analytes. 24−31 Surprisingly, studies on the u...