Concerns over possible impacts from the rapid expansion of unconventional oil and natural gas (ONG) resource development prompted a regional domestic well sampling program focusing on the Carboniferous Maritimes Basin bedrock in southeastern New Brunswick, Canada. This work applies recent developments in robust multivariate statistical methods to overcome issues with highly non-Gaussian data and support the development of a conceptual model for the regional groundwater chemistry and the occurrence of methane. Principal component analysis reveals that the redox-sensitive species, DO, NO3, Fe, Mn, methane, As and U are the most important parameters that differentiate the samples. Permutation-based MANOVA and ANOVA testing revealed that geology was more important than geographic location and topography in influencing groundwater composition. The statistical inferences are supported by chemistry trends observed in relation to road de-icing salt and other saline sources. However, source differentiation between Carboniferous brines, entrapped post-glacial marine water and modern seawater cannot be made. Furthermore, Cl:Br ratios lower than those of seawater or regional brines suggest an origin related to the diagenesis of organic-rich sediment and that the groundwater may be influenced by local low permeability units. Combined spatial, statistical and chemical analysis shows that, while trace or low levels of methane, <1 mg/L, are found ubiquitously throughout the Maritimes Basin, elevated concentrations, >1 mg/L, are associated with the Horton Group, consistent with it being the host and inferred source of ONG resources in the province. The highest methane concentrations (14-29 mg/L) were detected in the region with a complex history of cycles of uplift and erosion which, in some locations, resulted in the juxtaposition at the surface of the Horton Group with several other groups of the Maritimes Basin. It is thought that proximity to the Horton Group can lead to naturally high methane concentrations in non-ONG-bearing units.