Green rust, a family of Fe(II), Fe(III) layered double hydroxides, is believed to be present in environments close to the Fe(II)/ Fe(III) transition zone. Attempts to identify members of this family in nature have proven difficult because the material is oxidized after only a few minutes exposure to air. In this paper, we present a sampling method for capturing green rust so it is not oxidized. We then we used the method to identify the compound in a groundwater sample taken below the water table from fractures in granite. X-ray diffraction patterns were weak, but clearly identical to those of synthetic GR(CO3), the green rustfamily memberwhere carbonate and water occupy the interlayer between the iron-hydroxide layers. The method was then tested on samples taken from an artesian well and a deep underground experimental station, both within the Fe(II)/ Fe(III) redox zone. In both cases, GR(CO3), could be identified. Currently, transport models for predicting the behavior of contaminants in groundwater do not include parameters for green rust This work demonstrates they should.