AbstractEnvironmental tracer methods have been used to quantify groundwater discharge to rivers for the past few decades. A number of different tracers have been used in these studies, including individual ion concentrations, electrical conductivity, stable isotopes 2H and 18O, and the dissolved gases helium, chlorofluorocarbons and radon. This paper discusses the assumptions of the method, as well as its resolution and accuracy. The method will be most accurate when the tracer concentration in groundwater is very distinct from that in the river. On the basis of typical parameters, groundwater inflow rates as low as 5 mm/day can usually be estimated with electrical conductivity and ion tracers. A lower limit of resolution of approximately 2 mm/day is usually possible with radon, principally because the ratio of the river concentration to the groundwater concentration will be higher. However, hyporheic exchange can also contribute radon to the river. Where this process is significant, it is more difficult to estimate groundwater inflow from radon activities in the river, thus reducing the accuracy of the method. For CFCs, the lower limit of resolution is approximately 30 mm/day. Helium has not been widely used but can potentially be very accurate if the groundwater is old.The method assumes steady‐state conditions and so can only be applied when river flows are stable. Sampling resolution is also particularly important for dissolved gases, and uncertainty in where groundwater inflow occurs between sampling points can cause large uncertainty in inflow rates if the distance between sample locations is large. Poor mixing of solutes within the river can limit the method if the river is wide and shallow. When correctly applied, however, the environmental tracer method is able to provide robust estimates of groundwater discharge at a scale and accuracy that is not possible with most other methods. Copyright © 2012 John Wiley & Sons, Ltd.