Using permutational and multivariate statistics to understand inorganic well water chemistry and the occurrence of methane in groundwater, southeastern New Brunswick, Canada.

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.

Aerobic biodegradation of chlorinated ethenes in a fractured bedrock aquifer: quantitative assessment by compound-specific isotope analysis (CSIA) and reactive transport modeling.

A model-based analysis of concentration and isotope data was carried out to assess natural attenuation of chlorinated ethenes in an aerobic fractured bedrock aquifer. Tetrachloroethene (PCE) concentrations decreased downgradient of the source, but constant delta13C signatures indicated the absence of PCE degradation. In contrast, geochemical and isotopic data demonstrated degradation of trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) under the prevailing oxic conditions. Numerical modeling was employed to simulate isotopic enrichment of chlorinated ethenes and to evaluate alternative degradation pathway scenarios. Existing field information on groundwater flow, solute transport, geochemistry, and delta13C signatures of the chlorinated ethenes was integrated via reactive transport simulations. The results provided strong evidence for the occurrence of aerobic TCE and DCE degradation. The chlorinated ethene concentrations together with stable carbon isotope data allowed us to reliably constrain the assessment of the extent of biodegradation at the site and plume simulations quantitatively linked aerobic biodegradation with isotope signatures in the field. Our investigation provides the first quantitative assessment of aerobic biodegradation of chlorinated ethenes in a fractured rock aquifer based on compound specific stable isotope measurements and reactive transport modeling.

Water striders (family Gerridae): mercury sentinels in small freshwater ecosystems.

To circumvent some of the previous limitations associated with contaminant-monitoring programs, we tested the suitability of the water strider (Hemiptera: Gerridae) as a mercury sentinel by comparing total mercury concentrations in water striders and brook trout (Salvelinus fontinalis) from a variety of stream sites in New Brunswick, Canada. There was a strong association between the two variables across sites (r(2)=0.81, P<0.001) in systems where both atmospheric deposition and a point source (an abandoned gold mine) were likely contributing to ambient mercury levels. In a small stream draining the gold mine tailings pile, water striders had mercury concentrations an order of magnitude higher than those from reference locations. Temporal variation at three southern New Brunswick stream sites was non-significant. These results suggest that water strider mercury levels accurately quantify food chain entry of the element. The use of sentinel species holds great potential for expanding contaminant-monitoring programs.