Bruce B. Hanshaw

On the Maintenance of Anomalous Fluid Pressures: I. Thick Sedimentary Sequences

Various physical and chemical processes may be envisioned which will cause anomalous pressures on an underground fluid. In order to consider the maintenance of anomalous pressure, it is necessary to consider the problem as one of nonsteady fluid flow. The time rate of pressure change and maintenance depends upon the hydrodynamics of flow through porous media and the particular boundary conditions. This paper presents a series of general solutions to hydrodynamic models which are germane to the problem of creating and maintaining excess-fluid pressures in a thick sedimentary sequence. The creation and maintenance of fluid pressures approaching lithostatic pressure through a process of continuous sedimentation was evaluated. Our results indicate that a sedimentation rate of 500 m/106 yr (reasonable for the Gulf Coast) will create fluid pressures approaching lithostatic in a sedimentary column that has a hydraulic conductivity of 10−8 cm sec−1, or lower. It is apparent that the creation of anomalous pressure and its maintenance depends, to a large degree, upon the hydraulic conductivity and, to a lesser extent, upon the specific storage of clay layers within the system.

Comparison of chemical hydrogeology of the carbonate peninsulas of Florida and Yucatan

Abstract Aquifers of the peninsulas of Florida and northern Yucatan are Tertiary marine carbonate formations showing many lithologic and faunal similarities. In addition, the tropical to subtropical climates of the two areas are similar, each having annual rainfall of about 1000 to 1500 mm. Despite similarities in these fundamental controls, contrasts in the hydrologic and geochemical systems are numerous and striking. For example, Florida has many rivers; Yucatan has none. Maximum thickness of fresh ground water in Florida is about 700 meters; in the Yucatan it is less than 70 meters. In Florida the gradient of the potentiometric surface averages about 1 meter per kilometer; in the Yucatan it is exceedingly low, averaging about 0.02 meter per kilometer. In Florida the chemical character of water changes systematically downgradient, owing to solution of minerals of the aquifer and corresponding increases in total dissolved solids, sulfate, calcium, and Mg-Ca ratio; in the Yucatan no downgradient change exists, and dominant processes controlling the chemical character of the water are solution of minerals and simple mixing of the fresh water and the body of salt water that underlies the peninsula at shallow depth. Hydrologic and chemical differences are caused in part by the lower altitude of the Yucatan plain. More important, however, these differences are due to the lack of an upper confining bed in Yucatan that is hydrologically equivalent to the Hawthorn Formation of Florida. The Hawthorn cover prevents recharge and confines the artesian water except where it is punctured by sinkholes, but sands and other unconsolidated sediments fill sinkholes and cavities and impede circulation. In the Yucatan the permeability of the entire section is so enormous that rainfall immediately infiltrates to the water table and then moves laterally to discharge areas along the coasts.

Ultrafiltration by a compacted clay membrane—I. Oxygen and hydrogen isotopic fractionation

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

Process and rate of dedolomitization: Mass transfer and 14C dating in a regional carbonate aquifer

Regional dedolomitization is the major process that controls the chemical character of water in the Mississippian Pahasapa Limestone (Madison equivalent) surrounding the Black Hills, South Dakota and Wyoming. The process of dedolomitization consists of dolomite dissolution and concurrent precipitation of calcite; it is driven by dissolution of gypsum. Deuterium and oxygen isotopic data from the ground water, coupled with regional potentiometric maps, show that recharge occurs on the western slope of the Black Hills and that the water flows northward and westward toward the Powder River Basin. A significant part flows around the southern end of the Black Hills to replenish the aquifer to the east of the Hills. Depth of flow was inferred from interpretation of the silica geothermometer based on the temperature-dependent solubilities of quartz and chalcedony in water. Chemical effects of warm water in the Pahasapa Limestone include changes in the solubility products of minerals, conversion of gypsum to anhydrite, solution and precipitation of minerals, and increases in the tendency for outgassing of carbon dioxide. Where sulfate reduction is not important, sulfur isotope data show that (1) in the Mississippian aquifer, most of the sulfate is from dissolution of gypsum and (2) some wells and springs have a hydrologic connection with overlying Permian and Pennsylvanian evaporites. Sulfate ion concentration, a progress variable, shows a strong correlation with pH as a result of the combined effects of the dedolomitization reactions. Mass-balance and mass-transfer calculations were used to adjust 14C values to determine a range of ground-water flow velocities between 2 and 20 m/yr. These velocities are characteristic of carbonate aquifers. The average rates of dolomite and gypsum dissolution are 1.7 × 10−4 and 3.4 × 10−4 mmol/kg of H2O/yr, respectively. The precipitation of calcite is occurring at the rate of 3.4 × 10−4 mmol/kg of H2O/yr. The close agreement among the model results demonstrates that dedolomitization is controlling water-rock interactions in this regional carbonate aquifer system.

Differential dissolution of a Pleistocene reef in the ground-water mixing zone of coastal Yucatan, Mexico

A geochemical explanation is provided for the extensive dissolution observed along the carbonate coast of the Yucatan Peninsula, Mexico. Mixing of fresh ground water with subterranean Caribbean seawater generates a highly reactive geochemical zone that enhances aragonite and calcite dissolution and permits neomorphism of aragonite. Mixing-zone dissolution caused by ground-water discharge is a major geomorphic process in developing caves, coves, and crescent-shaped beaches along the Yucatan coast. Such dissolution has probably been a significant control on permeability and porosity distribution in carbonate rocks in the geologic record.

Major geochemical processes in the evolution of carbonate-Aquifer systems

Abstract As a result of recent advances by carbonate petrologists and geochemists, hydrologists are provided with new insights into the origin and explanation of many aquifer characteristics and hydrologic phenomena. Some major advances include the recognition that: (1) most carbonate sediments are of biological origin; (2) they have a strong bimodal size-distribution; and (3) they originate in warm shallow seas. Although near-surface ocean water is oversaturated with respect to calcite, aragonite, dolomite and magnesite, the magnesium-hydration barrier effectively prevents either the organic or inorganic formation of dolomite and magnesite. Therefore, calcareous plants and animals produce only calcite and aragonite in hard parts of their bodies. Most carbonate aquifers that are composed of sand-size material have a high initial porosity; the sand grains that formed these aquifers originated primarily as small shells, broken shell fragments of larger invertebrates, or as chemically precipitated oolites. Carbonate rocks that originated as fine-grained muds were initially composed primarily of aragonite needles precipitated by algae and have extremely low permeability that requires fracturing and dissolution to develop into aquifers. Upon first emergence, most sand beds and reefs are good aquifers; on the other hand, the clay-sized carbonate material initially has high porosity but low permeability, a poor aquifer property. Without early fracture development in response to influences of tectonic activity these calcilutites would not begin to develop into aquifers. As a result of selective dissolution, inversion of the metastable aragonite to calcite, and recrystallization, the porosity is collected into larger void spaces, which may not change the overall porosity, but greatly increases permeability. Another major process which redistributes porosity and permeability in carbonates is dolomitization, which occurs in a variety of environments. These environments include back-reefs, where reflux dolomites may form, highly alkaline, on-shore and continental lakes, and sabkha flats; these dolomites are typically associated with evaporite minerals. However, these processes cannot account for most of the regionally extensive dolomites in the geologic record. A major environment of regional dolomitization is in the mixing zone (zone of dispersion) where profound changes in mineralogy and redistribution of porosity and permeability occur from the time of early emergence and continuing through the time when the rocks are well-developed aquifers. The reactions and processes, in response to mixing waters of differing chemical composition, include dissolution and precipitation of carbonate minerals in addition to dolomitization. An important control on permeability distribution in a mature aquifer system is the solution of dolomite with concomitant precipitation of calcite in response to gypsum dissolution (dedolomitization). Predictive models developed by mass-transfer calculations demonstrate the controlling reactions in aquifer systems through the constraints of mass balance and chemical equilibrium. An understanding of the origin, chemistry, mineralogy and environments of deposition and accumulation of carbonate minerals together with a comprehension of diagenetic processes that convert the sediments to rocks and geochemical, tectonic and hydrologic phenomena that create voids are important to hydrologists. With this knowledge, hydrologists are better able to predict porosity and permeability distribution in order to manage efficiently a carbonate—aquifer system.

Chemical mass-wasting of the northern Yucatan Peninsula by groundwater dissolution

The northern part of the Yucatan Peninsula is a relatively flat, low-lying carbonate terrane with no geomorphic expressions of stream channels. It is estimated that mean annual recharge to the groundwater system is 150 mm. For the 65,500 km 2 study area, mean annual discharge (equivalent to recharge) is 9.8 × 10 9 m 3 , or 8.6 × 10 6 m 3 for each 1 km of the 1,100-km-long coastline. In the interior of the peninsula, the recharging water annually dissolves about 37.5 t (metric tons) of calcite per 1 km 2 . When the groundwater has become saturated with calcite, little additional water-rock interaction occurs until the active mixing (dispersion) zone is reached near the coastline. Theoretical calculations and laboratory experiments have shown that when two waters, each calcite saturated and with different salinities, are mixed, the resulting solution generally becomes undersaturated with calcite and, therefore, is capable of dissolving additional calcite. On the basis of our study of the Xel Ha lagoon on the east coast of Yucatan, we calculate that as much as 1.2 mmol/L additional calcite can be dissolved in the brackish groundwater zone of dispersion. This indicates that if the total solution potential of the amount of water discharging at Xel Ha has focused within the lagoon area, the lagoon could be chemically incised in less than 3,000 yr. We postulate that chemical mass wasting by dissolution in the zone of groundwater mixing is an important geomorphic process in coastal areas of limestone terranes.

Ultrafiltration by a compacted clay membrane-II. Sodium ion exclusion at various ionic strengths

Abstract Several recent laboratory studies and field investigations have indicated that shales and compacted clay minerals behave as semipermeable membranes. One of the properties of semipermeable membranes is to retard or prevent the passage of charged ionic species through the membrane pores while allowing relatively free movement of uncharged species. This phenomenon is termed salt filtering, reverse osmosis, or ultrafiltration. This paper shows how one can proceed from the ion exchange capacity of clay minerals and, by means of Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane. Reasonable agreement between theory and laboratory results were found. The concentration of the ultrafiltrate was always greater than predicted because of uncertainty in values of some parameters in the equations. Ultrafiltration phenomena may be responsible for the formation of some subsurface brines and mineral deposits. The effect should also be taken into consideration in any proposal for subsurface waste emplacement in an environment containing large quantities of clay minerals.

On the Maintenance of Anomalous Fluid Pressures: II. Source Layer at Depth

Physico-chemical mechanisms have been suggested to account for anomalous fluid pressures in the geologic environment which require a fluid source at depth. The persistence of anomalous pressure is a problem that involves nonsteady fluid flow. The hydrodynamics and particular boundary conditions control the time rate of pressure change and its maintenance. A series of mathematical solutions germane to the maintenance of anomalous pressure caused by the injection of fluids into the system from a source layer are presented. The phase change, gypsum to anhydrite plus water, is used as an example of a fluid source at depth. The thermodynamics of the gypsum-dehydration reaction indicates that conversion will probably occur at shallow depths and produce fluid at a constant rate. The dehydration of montmorillonite will also produce fluids at a constant rate under geologic conditions where the reaction can occur. If horizons of material of low permeability are missing or scarce, it is doubtful that anomalous pore pressures can be maintained for more than a geologic instant. The creation and continuation of anomalous pressure depend largely upon the hydraulic conductivity and, to a lesser extent, upon the specific storage of clay layers within the system.

The origin and isotopic composition of dissolved sulfide in groundwater from carbonate aquifers in Florida and Texas

The δ34S values of dissolved sulfide and the sulfur isotope fractionations between dissolved sulfide and sulfate species in Floridan ground water generally correlate with dissolved sulfate concentrations which are related to flow patterns and residence time within the aquifer. The dissolved sulfide derives from the slow in situ biogenic reduction of sulfate dissolved from sedimentary gypsum in the aquifer. In areas where the water is oldest, the dissolved sulfide has apparently attained isotopic equilibrium with the dissolved sulfate (Δ34S = 65 per mil) at the temperature (28°C) of the system. This approach to equilibrium reflects an extremely slow reduction rate of the dissolved sulfate by bacteria; this slow rate probably results from very low concentrations of organic matter in the aquifer. In the reducing part of the Edwards aquifer, Texas, there is a general down-gradient increase in both dissolved sulfide and sulfate concentrations, but neither the δ34S values of sulfide nor the sulfide-sulfate isotope fractionation correlates with the ground-water flow pattern. The dissolved sulfide species appear to be derived primarily from biogenic reduction of sulfate ions whose source is gypsum dissolution although upgradient diffusion of H2S gas from deeper oil field brines may be important in places. The sulfur isotope fractionation for sulfide-sulfate (about 38 per mil) is similar to that observed for modern oceanic sediments and probably reflects moderate sulfate reduction in the reducing part of the aquifer owing to the higher temperature and significant amount of organic matter present; contributions of isotopically heavy H2S from oil field brines are also possible.