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Porewater extractions and acid leachates of rock core from a 250 m thick sequence of low-permeability Ordovician-age shales and limestones, on the eastern flank of the Michigan Basin, were analysed for strontium isotope ratios in an attempt to infer porewater ages from observed 87Sr/86Sr enrichments. The porewaters originated as Ordovician seawater, which subsequently mixed with evaporated Silurian seawater infiltrating from above, and, to some extent, with a deep brine—with an enriched 87Sr/86Sr signature—from the underlying crystalline shield or deep basin. The porewater 87Sr/86Sr ratios are more radiogenic than contemporaneous seawater but show no obvious correlation to those leached from the solid rock phases. Accepting that the initial 87Sr/86Sr signatures in porewaters were dominated by Late Silurian brine, potentially with an additional deep brine component, the excess of radiogenic 87Sr appears to represent ingrowth from 87Rb decay over a time span of some 420 million years, approaching the depositional age of the rocks. Similarly, Rb/Sr errochron ages of acid leachates of solid phases, and the calculated initial 87Sr/86Sr isotopic ratios, are consistent with a proposition that the calcites inherited their Sr from Ordovician seawater and were dolomitized shortly afterwards by infiltrating Mg-enriched evaporative brine, indicating long-term conservative behaviour for the enclosing carbonate rocks. The errochron for leachates from (alumino)silicates yields a high initial 87Sr/86Sr, but with an errochron age of about 340 ± 48 Ma, likely owing to variable admixtures of diagenetic illite in the shales. Overall, the data provide evidence for a stable hydrologic regime since Paleozoic time.

Through-diffusion experiments with tritiated water (HTO) and 36Cl− as a function of pore water concentration (0.01–5 M) were performed on two Ordovician-age argillaceous rock samples from the Blue Mountain Fm and Queenston Fm shales of the Paleozoic intracratonic Michigan Basin in Canada. This study reveals that the effect of ionic strength on the anion-transport porosity is similar, and only the minimal anion excluded porosity is higher in the Blue Mountain Fm shale. The differences in rock sample mineralogy cannot explain this effect. It is hypothesized that the structure of the Blue Mountain Fm shale samples has led to pore space openings sufficiently small that they behave as interlayers. Such pores are defined as interlayer equivalent (ILE) pores. These ILE pores, as in the case of interlayer pores, can act to permanently limit the anion-accessible porosity. Pore-size distribution measurements provide further evidence of increased potential for ILE pores within the Blue Mountain Fm samples. A Donnan model, which includes consideration of both ILE and uncharged pores, is shown to describe the effect of molar concentration on the anion-accessible porosity in the argillaceous rocks investigated.

Interest in the origin and migrational history of methane in low permeability shales reaches beyond that of resource potential to include the evaluation of such formations as geological barriers for the purposes of isolating surface environments from the impacts of deep exploitation and the deep disposal of waste. Here, we present detailed isotope and geochemical profiles of porewaters and methane from an Ordovician shale and carbonate aquiclude on the eastern flank of the Michigan Basin, where a deep geological repository for low and intermediate level nuclear waste is proposed. The solute concentrations and stable isotopes of water (δ 18 O and δD) indicate that this aquiclude hosts saline brine (39% TDS), originating as evaporated seawater. Methane concentrations are 13 C and δD signatures that are consistent with archaeal methanogenesis and are accompanied by a well defined positive excursion in δ 13 C of CO 2 . Below the aquiclude, porewaters contain lower concentrations of methane with a thermocatalytic signature, consistent with regional methane elsewhere in the Michigan Basin. No evidence for archaea was identified by microcosm experiments or through PCR rRNA analysis, suggesting that the microbial methane present in these sediments is not the result of recent microbial activity. Based on these results and considering that archaeal activity has not been observed in such hypersaline brines with low water activities (

Drill cores collected from an 860-m-thick Paleozoic (Cambrian to Devonian) sedimentary sequence of the Michigan Basin in southwest Ontario, Canada, were used to develop vertical profiles of natural tracers in porewater from the sedimentary sequence and build a conceptual model regarding processes and timing of solute migration. In this paper, the conceptual model is quantitatively assessed with numerical simulations of diffusion-dominated solute transport (Cl− and 18O). The conceptual model suggests that the tracer profiles result from mixing between a deep shield brine with isotopic characteristics consistent with water–rock interaction over a long period of geologic time, Ordovician seawater at intermediate depth, and an overlying hypersaline brine formed by evaporation of seawater in a restricted basin during the Silurian. Between the peak of basin consolidation at 300 Ma BP and the Pleistocene (2.6 Ma BP), salinity and isotopic concentration gradients are thought to have driven mixing, dominantly by diffusion. Water isotope data indicate that in the Pleistocene, melt water infiltrated to a maximum depth of 330 m in the Silurian Salina Formation, likely in response to transient glacial loading and elevated sub-glacial hydraulic pressures. Also in the Pleistocene, over-pressured conditions in deep regions of the basin drove high-salinity brine eastward in the basal Cambrian aquifer, interrupting pre-existing tracer-diffusion profiles. A base case set of boundary and initial conditions provides a good fit between simulated and measured tracer profiles, but requires effective diffusion coefficients (De) in the Ordovician limestones that are lower than the average values obtained in laboratory measurements by as much as a factor of 10. The base-case values are still within the overall range of measured values. At the formation scale, relatively low in-situ De values are attributed to the intermittent occurrence of gas and liquid hydrocarbons in the Ordovician carbonate units and the effect of lithostatic confining pressure; neither of which are accounted for in the laboratory measurements but both would have the effect of decreasing De for aqueous solutes. The numerical model is most sensitive to the formation-specific De values and geologically reasonable variations in initial and boundary conditions have a relatively small influence on the results. Additional simulations indicate that hydraulic disturbance and ingress of meltwater during the Pleistocene can explain second-order features observed in the measured tracer profiles. This work provides supporting evidence for previous research indicating that the porewater residence time in the Ordovician sequence approaches the age of the rocks.

Consideration of the geosphere for isolation of nuclear waste has generated substantial interest in the origin, age, and movement of fl uids and gases in low-permeability rock formations. Here, we present profi les of isotopes, solutes, and helium in porewaters recovered from 860 m of Cambrian to Devonian strata on the eastern fl ank of the Michigan Basin. Of particular interest is a 240-m-thick, halite-mineralized, Ordovician shale and carbonate aquiclude, which hosts Br–-enriched, post-dolomitic brine (5.8 molal Cl) originating as evaporated Silurian seawater. Authigenic helium that has been accumulating in the aquiclude for more than 260 m.y. is found to be isolated from underlying allochthonous, 3He-enriched helium that originated from the rifted base of the Michigan Basin and the Canadian Shield. The Paleozoic age and immobility of the pore fl uids in this Ordovician aquiclude considerably strengthen the safety case for deep geological repositories, but also provide new insights into the origin of deep crustal brines and opportunities for research on other components of a preserved Paleozoic porewater system.

The evolution of the landscape and the behavior of the groundwater system are key concerns for the long-term management of radioactive waste in deep geological repositories. At time scales relevant for repository safety assessments (i.e., 1 Ma), future ice ages are an important external perturbation to repository integrity in mid-latitudes and northern latitudes. Ice ages result in the alteration of the landscape by glacial erosion and sedimentation; lead to the formation of periglacial permafrost; and impose significant transient hydraulic, mechanical, thermal, and chemical changes that can influence groundwater flow and radionuclide mobility. Four case studies are presented: (1) discussing the processes involved in the formation of deeply incised troughs and overdeepened valleys in the Swiss Plateau; (2) outlining the occurrence and dimensions of tunnel valleys in the North German Plain and their impact on repository host rocks; (3) illustrating the integration of techniques and geoscientific evidence, as applied in assessing the stability and resilience of a deep-seated groundwater system in the Great Lakes Basin of North America; and (4) detailing results of a numerical modeling study of the impact of periglacial and glacial climate conditions on groundwater flow in the Fennoscandian Shield.