Deposits of the metalloids arsenic and antimony occur in quartz veins of mesothermal hydrothermal systems in the South Island as arsenopyrite (AsFeS) and stibnite (Sb2S3). Arsenopyrite and stibnite occur in natural exposures in gold-mining areas, and additional arsenopyrite and stibnite have been exposed to the atmosphere by mining activity. At present the drinking water limits for dissolved As and Sb are 10 ppb and 3 ppb respectively. Sampling and analysis techniques are critical to determination of metalloid concentrations at these low levels. Endeavour Inlet in the Marlborough Sounds is an historic mining area (late 19th Century) with elevated As and Sb in waters emanating from mineralised rocks. Waters running out of abandoned adits have concentrations of As and/or Sb up to ppm levels. Natural waters have high Sb and low As, and the As levels increase markedly where anthropogenic activity has exposed rock. Changes in Sb/As ratio could potentially be used to quantify the anthropogenic component of metalloid mobility on mine sites on the 100-year time scale.