Mineralogical studies of coatings on quartz grains and bulk sediments from an aquifer on Western Cape Cod, Massachusetts, USA were carried out using a variety of transmission electron microscopy (TEM) techniques. Previous studies demonstrated that coatings on quartz grains control the adsorption properties of these sediments. Samples for TEM characterization were made by a gentle mechanical grinding method and focused ion beam (FIB) milling. The former method can make abundant electron-transparent coating assemblages for comprehensive and quantitative X-ray analysis and the latter technique protects the coating texture from being destroyed. Characterization of the samples from both a pristine area and an area heavily impacted by wastewater discharge shows similar coating textures and chemical compositions. Major constituents of the coating include Al-substituted goethite and illite/chlorite clays. Goethite is aggregated into well-crystallized domains through oriented attachment resulting in increased porosity. Illite/chlorite clays with various chemical compositions were observed to be mixed with goethite aggregates and aligned sub-parallel to the associated quartz surface. The uniform spatial distribution of wastewater-derived phosphorus throughout the coating from the wastewater-contaminated site suggests that all of the coating constituents, including those adjacent to the quartz surface, are accessible to groundwater solutes. Both TEM characterization and chemical extraction results indicate there is a significantly greater amount of amorphous iron oxide in samples from wastewater discharge area compared to those from the pristine region, which might reflect the impact of redox cycling of iron under the wastewater-discharge area. Coating compositions are consistent with the moderate metal and oxy-metalloid adsorption capacities, low but significant cation exchange capacities, and control of iron(III) solubility by goethite observed in reactive transport experimental and modeling studies conducted at the site.