On-line determination of silver in natural waters by inductively-coupled plasma mass spectrometry: Influence of organic matter

We investigated interference effects on the analysis of silver in estuarine and oceanic waters using on-line high resolution inductively coupled plasma mass spectrometry (ICP-MS). A mini-column packed with a strong anion exchange resin (Dowex 1-X8) was used in a flow-injection system to separate and concentrate silver from the saline samples prior to on-line determination by ICP-MS. A series of analyses showed the concentrations of silver measured in San Francisco Bay estuary and the North Pacific that had been acidified (pH < 2) and stored for periods of 1–2 years were 10–70% lower than those measured in aliquots of those samples after ultraviolet (UV) irradiation. Additional silver released after UV irradiation of the estuarine waters, but not the ocean waters, was positively correlated (r = 0.77, simple linear correlation) with chlorophyll-a concentrations, but not with dissolved organic carbon (DOC) concentrations. Spatial distributions of chlorophyll-a and UV-released silver also exhibited similar patterns along a salinity gradient in the San Francisco Bay estuary, suggesting an in situ biogenic source of the interferent for the silver measurements.