Chlorinated solvents are among the most widespread pollutants of groundwater. As DNAPLs (dense nonaqueous phase liquids), they can move rapidly and in complex patterns through fractures to reach and contaminate large volumes of aquifer, and then dissolve to cause significant pollution of groundwater. However, clean-up of DNAPLs in fractured rocks is virtually impossible and certainly expensive. Risk assessment should be used to decide whether the pollution is serious enough to justify major expenditure on clean-up or containment. A key aspect of risk assessment for DNAPLs in fractured aquifers is to understand how deep they are likely to have penetrated through the fracture network. This paper addresses two aspects of such predictions: measuring fracture apertures in situ and the connectivity of fracture networks with respect to DNAPLs. Fracture aperture is an in-situ field technique that has been developed and implemented to measure aperture variability and NAPL entry pressure in an undisturbed, water-saturated rock fracture. The field experiment also provided the opportunity to measure the wetting phase relative permeability at residual non-wetting phase saturation. The RADIO (Radial Aperture Determination by the Injection of Oil) method employs a constant rate injection of a non-toxic NAPL into a fracture isolated by a double packer array. The method was applied at the field site in Scotland, and measured apertures out to ~5m from the borehole. It showed that hydraulic aperture (from packer tests) was a poor estimator of the controlling aperture for DNAPL movement. This is the first time such large-scale aperture measurements have been made, and the technique is the first which can provide useful aperture estimates for risk analysis of DNAPL movement. Network connectivity is a fundamental property of the fracture system. DNAPL connectivity extends the concept to take account of the fluid properties.