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 rust familymemberwherecarbonate 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.