CHAPTER 1. INTRODUCTION TO KARST. 1.1 Definitions. 1.2 The Relationship Between Karst And General Geomorphology And Hydrogeology. 1.3 The Global Distribution Of Karst. 1.4 The Growth Of Ideas. 1.5 Aims Of The Book. 1.6 Karst Terminology. CHAPTER 2. THE KARST ROCKS. 2.1 Carbonate Rocks And Minerals. 2.2 Limestone Compositions And Depositional Facies. 2.3 Limestone Diagenesis And The Formation Of Dolomite. 2.4 The Evaporite Rocks. 2.5. Quartzites And Siliceous Sandstones. 2.6 Effects Of Lithologic Properties Upon Karst Development. 2.7 Interbedded Clastic Rocks. 2.8 Bedding Planes, Joints, Faults And Fracture Traces. 2.9 Fold Topography. 2.10 Paleokarst Unconformities. CHAPTER 3. DISSOLUTION: CHEMICAL AND KINETIC BEHAVIOUR OF THE KARST ROCKS. 3.1 Introduction. 3.2 Aqueous Solutions And Chemical Equilibria. 3.3 The Dissolution Of Anhydrite, Gypsum And Salt. 3.4 The Dissolution Of Silica. 3.5 Bicarbonate Equilibria And The Dissolution Of Carbonate Rocks In Normal Meteoric Waters. 3.6 The S-O-H System And The Dissolution Of Carbonate Rocks. 3.7 Chemical Complications In Carbonate Dissolution. 3.8 Biokarst Processes. 3.9 Measurements In The Field And Lab Computer Programs. 3.10 Dissolution And Precipitation Kinetics Of Karst Rocks. CHAPTER 4. DISTRIBUTION AND RATE OF KARST DENUDATION. 4.1 Global Variations In The Solutional Denudation Of Carbonate Terrains. 4.2 Measurement And Calculation Of Solutional Denudation Rates. 4.3 Solution Rates In Gypsum, Salt And Other Non-Carbonate Rocks. 4.4 Interpretation Of Measurements. CHAPTER 5. KARST HYDROLOGY. 5.1 Basic Hydrological Concepts, Terms And Definitions. 5.2 Controls On The Development Of Karst Hydrologic Systems. 5.3 Energy Supply And Flow Network Development. 5.4 Development Of The Water Table And Phreatic Zones. 5.5 Development Of The Vadose Zone. 5.6 Classification And Characteristics Of Karst Aquifers. 5.7 Applicability Of Darcy's Law To Karst. 5.8 The Fresh Water/Salt Water Interface. CHAPTER 6. ANALYSIS OF KARST DRAINAGE SYSTEMS. 6.1 The 'Grey Box' Nature Of Karst. 6.2 Surface Exploration And Survey Techniques. 6.3 Investigating Recharge And Percolation In The Vadose Zone. 6.4 Borehole Analysis. 6.5 Spring Hydrograph Analysis. 6.6 Polje Hydrograph Analysis. 6.7 Spring Chemograph Interpretation. 6.8 Storage Volumes And Flow Routing Under Different States Of The Hydrograph. 6.9 Interpreting The Organisation Of A Karst Aquifer. 6.10 Water Tracing Techniques. 6.11 Computer Modelling Of Karst Aquifers. CHAPTER 7. SPELEOGENESIS: THE DEVELOPMENT OF CAVE SYSTEMS. 7.1 Classifying Cave Systems. 7.2 Building The Plan Patterns Of Unconfined Caves. 7.3 Unconfined Cave Development In Length And Depth. 7.4 System Modifications Occurring Within A Single Phase. 7.5 Multi-Phase Cave Systems. 7.6 Meteoric Water Caves Developed Where There Is Confined Circulation Or Basal Injection Of Water. 7.7 Hypogene Caves: (A) Hydrothermal Caves Associated Chiefly With Co2. 7.8 Hypogene Caves: (B) Caves Formed By Waters Containing H2s. 7.9 Sea Coast Eogenetic Caves. 7.10 Passage Cross-Sections And Smaller Features Of Erosional Morphology. 7.11 Condensation, Condensation Corrosion, And Weathering In Caves. 7.12 Breakdown In Caves. CHAPTER 8. CAVE INTERIOR DEPOSITS. 8.1 Introduction. 8.2 Clastic Sediments. 8.3 Calcite, Aragonite And Other Carbonate Precipitates. 8.4 Other Cave Minerals. 8.5 Ice In Caves. 8.6 Dating Of Calcite Speleothems And Other Cave Deposits. 8.7 Paleo-Environmental Analysis Of Calcite Speleothems. 8.8 Mass Flux Through A Cave System: The Example Of Friar's Hole, W.Va. CHAPTER 9. KARST LANDFORM DEVELOPMENT IN HUMID REGIONS. 9.1 Coupled Hydrological And Geochemical Systems. 9.2 Small Scale Solution Sculpture - Microkarren And Karren. 9.3 Dolines - The 'Diagnostic' Karst Landform? 9.4 The Origin And Development Of Solution Dolines. 9.5 The Origin Of Collapse And Subsidence Depressions. 9.6 Polygonal Karst. 9.7 Morphometric Analysis Of Solution Dolines. 9.8 Landforms Associated With Allogenic Inputs. 9.9 Karst Poljes. 9.10 Corrosional Plains And Shifts In Baselevel. 9.11 Residual Hills On Karst Plains. 9.12 Depositional And Constructional Karst Features. 9.13 Special Features Of Evaporite Terrains. 9.14 Karstic Features Of Quartzose And Other Rocks. 9.15 Sequences Of Carbonate Karst Evolution In Humid Terrains. CHAPTER 10.THE INFLUENCE OF CLIMATE, CLIMATIC CHANGE AND OTHER ENVIRONMENTAL FACTORS ON KARST DEVELOPMENT. 10.1 The Precepts Of Climatic Geomorphology. 10.2 The Hot Arid Extreme. 10.3 The Cold Extreme: 1 Karst Development In Glaciated Terrains. 10.4 The Cold Extreme: 2 Karst Development In Permafrozen Terrains. 10.5 Sea Level Changes, Tectonic Movement And Implications For Coastal Karst Development. 10.6 Polycyclic, Polygenetic And Exhumed Karsts. CHAPTER 11. KARST WATER RESOURCES MANAGEMENT. 11.1 Water Resources And Sustainable Yields. 11.2 Determination Of Available Water Resources. 11.3 Karst Hydrogeological Mapping. 11.4 Human Impacts On Karst Water. 11.5 Groundwater Vulnerability, Protection, And Risk Mapping. 11.6 Dam Building, Leakages, Failures And Impacts. CHAPTER 12. HUMAN IMPACTS AND ENVIRONMENTAL REHABILITATION. 12.1 The Inherent Vulnerability Of Karst Systems. 12.2 Deforestation, Agricultural Impacts And Rocky Desertification. 12.3 Sinkholes Induced By De-Watering, Surcharging, Solution Mining And Other Practices On Karst. 12.4 Problems Of Construction On And In The Karst Rocks - Expect The Unexpected! 12.5 Industrial Exploitation Of Karst Rocks And Minerals. 12.6 Restoration Of Karstlands And Rehabilitation Of Limestone Quarries. 12.7 Sustainable Management Of Karst. 12.8 Scientific, Cultural And Recreational Values Of Karstlands.

Karst Hydrogeology and Geomorphology

Dolomite: occurrence, evolution and economically important associations

/pdf/modification-and-preservation-of-environmental-signals-in-3icv6ero3u.pdf

Modification and preservation of environmental signals in speleothems

Structurally controlled hydrothermal dolomite (HTD) reservoir facies and associated productive leached limestones are major hydrocarbon producers in North America and are receiving increased exploration attention globally. They include multiple trends in the Ordovician (locally, Silurian and Devonian) of the Michigan, Appalachian, and other basins of eastern Canada and the United States, and in the Devonian and Mississippian of the Western Canada sedimentary basin. They also occur in Jurassic hosts along rifted Atlantic margins, in the Jurassic–Cretaceous of the Arabian Gulf region and elsewhere. Hydrothermal dolomitization is defined as dolomitization occurring under burial conditions, commonly at shallow depths, by fluids (typically very saline) with temperature and pressure (T and P) higher than the ambient T and P of the host formation. The latter commonly is limestone. Proof of a hydrothermal origin for HTD reservoir facies requires integration of burial-thermal history plots, fluid-inclusion temperature data, and constraints on timing of emplacement. Hydrothermal dolomite reservoir facies are part of a spectrum of hydrothermal mineral deposits that include sedimentary-exhalative lead-zinc ore bodies and HTD-hosted Mississippi Valley–type sulfide deposits. All three hydrothermal deposits show a strong structural control by extensional and/or strike-slip (wrench) faults, with fluid flow typically focused at transtensional and dilational structural sites and in the hanging wall. Transtensional sags above negative flower structures on wrench faults are favored drilling sites for HTD reservoir facies. Saddle dolomite in both replacive and void-filling modes is characteristic of HTD facies. For many reservoirs, matrix-replacive dolomite and saddle dolomite appear to have formed near-contemporaneously and from the same fluid and temperature conditions. The original host facies exerts a major influence on the lateral extent of dolomitization, resultant textures, pore type, and pore volume. Breccias, zebra fabrics, shear microfractures, and other rock characteristics record short-term shear stress and pore-fluid-pressure transients, particularly proximal to active faults. High-temperature hydrothermal pulses may alter kerogen in host limestones, a process designated “forced maturation.” Basement highs, underlying sandstone (and/or carbonate?) aquifers (probably overpressured), and overlying and internal shale seals and aquitards also may constrain or influence HTD emplacement. Although many questions and uncertainties remain, particularly in terms of Mg and brine source and mass balance, recognition and active exploration of the HTD play continues to expand. Increasing use of three-dimensional seismic imagery and seismic anomaly mapping, combined with horizontal drilling oblique to linear trends defined by structural sags, helps to reduce risk.

Structurally controlled hydrothermal dolomite reservoir facies: An overview

Radiogenic Isotope Geology

Cave Minerals of the World

Sulfur-isotope data and pH-dependence of the mineral endellite support the hypothesis that Carlsbad Cavern and other caves in the Guadalupe Mountains were dissolved primarily by sulfuric acid rather than by carbonic acid. Floor gypsum deposits up to 10 m thick and native sulfur in the caves are significantly enriched in {32}S; (isotope){34}S values as low as -25.8 per mil (CDT) indicate that the cave sulfur and gypsum are the end products of microbial reactions associated with hydrocarbons. A model for a genetic connection between hydrocarbons in the basin and caves in the Guadalupe Mountains is proposed. As the Guadalupe Mountains were uplifted during the late Pliocene-Pleistocene, oil and gas moved updip in the basin. The gas reacted with sulfate anions derived from dissolution of the Castile anhydrite to form H[2]S, CO[2], and "castile" limestone. The hydrogen sulfide rose into the Capitan reef along joints, forereef carbonate beds, or Bell Canyon siliciclastic beds and there reacted with oxygenated groundwater to form sulfuric acid and Carlsbad Cavern. A sulfuric-acid mode of dissolution may be responsible for large-scale porosity of some Delaware basin reservoirs and for oil-field karst reservoirs in other petroleum basins of the world.

Sulfuric acid speleogenesis of Carlsbad Cavern and its relationship to hydrocarbons, Delaware Basin, New Mexico and Texas

The age and evolution of the Grand Canyon have been subjects of great interest and debate since its discovery. We found that cave mammillaries (water table indicator speleothems) from nine sites in the Grand Canyon showed uranium-lead dating evidence for an old western Grand Canyon on the assumption that groundwater table decline rates are equivalent to incision rates. Samples in the western Grand Canyon yielded apparent water table decline rates of 55 to 123 meters per million years over the past 17 million years, in contrast to eastern Grand Canyon samples that yielded much faster rates (166 to 411 meters per million years). Chronology and inferred incision data indicate that the Grand Canyon evolved via headward erosion from west to east, together with late-stage ( approximately 3.7 million years ago) accelerated incision in the eastern block.

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Age and Evolution of the Grand Canyon Revealed by U-Pb Dating of Water Table-Type Speleothems

The uplift and denudation of the Colorado Plateau is important in reconstructing the geomorphic and tectonic evolution of western North America A Late Cretaceous (64 ± 2 Ma) U-Pb age for the Long Point limestone on the Coconino Plateau, which overlies a regional erosional surface developed on Permo-Triassic formations, supports unroofing of the Coconino Plateau part of Grand Canyon by that time U-Pb analyses of three separate outcrops of this limestone gave ages of 640 ± 07, 605 ± 46, and 663 ± 39 Ma, which dates are older than a fossil-based, early Eocene age Samples of the Long Point limestone were dated using the isotope dilution isochron method on well-preserved carbonates having high-uranium and low-lead concentrations Our U-Pb ages on the Long Point limestone place important constraints on the (1) time of tectonic uplift of the southwestern Colorado Plateau and Kaibab arch, (2) time of denudation of the Coconino Plateau, and (3) Late Cretaceous models of paleocanyon incision west of, or across, the Kaibab arch We propose that the age of the Long Point limestone, interbedded within the Music Mountain Formation in the Long Point area, represents a period of regional aggradation and a time of drainage blockage northward and eastward across the Kaibab arch, with possible diversion of northward drainage on the Coconino Plateau westward around the arch via a Laramide paleo-Grand Canyon

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1002/2016TC004166

Constraints on a Late Cretaceous uplift, denudation, and incision of the Grand Canyon region, southwestern Colorado Plateau, USA, from U-Pb dating of lacustrine limestone

Hydrocarbons, native sulfur, Mississippi Valley-type (MVT) deposits, and sulfuric acid karst in the Delaware Basin, southeastern New Mexico, and west Texas, USA, are all genetically related through a series of sulfur redox reactions. The relationship began with hydrocarbons in the basin that reacted with sulfate ions from evaporite rock to produce isotopically light (δ34S = -22 to -12) H2S and bioepigenetic limestone (castiles). This light H2S was then oxidized at the redox interface to produce economic native sulfur deposits (δ34S = -15 to +9) in the castiles, paleokarst, and along graben-boundary faults. This isotopically light H2S also migrated from the basin into its margins to accumulate in structural (anticlinal) and stratigraphic (Yates siltstone) traps, where it formed MVT deposits within the zone of reduction (δ34S = -15 to +7). Later in time, in th zone of oxidation, this H2S reacted with oxygenated water to produce sulfuric acid, which dissolved the caves (e.g., Carlsbad Cavern and Lechuguilla Cave, Guadalupe Mountains). Massive gypsum blocks on the floors of the caves (δ34S = -25 to +4) were formed as a result of this reaction. The H2S also produced istopically light cave sulfur (δ34S = -24 to -15), which is now slowly oxidizing to gypsum in the presence of vadose drip water.

Sulfur redox reactions: Hydrocarbons, native sulfur, Mississippi Valley-type deposits, and sulfuric acid karst in the Delaware Basin, New Mexico and Texas

Carol A. Hill

Papers

Cave Minerals of the World

Sulfuric acid speleogenesis of Carlsbad Cavern and its relationship to hydrocarbons, Delaware Basin, New Mexico and Texas

Age and Evolution of the Grand Canyon Revealed by U-Pb Dating of Water Table-Type Speleothems

Constraints on a Late Cretaceous uplift, denudation, and incision of the Grand Canyon region, southwestern Colorado Plateau, USA, from U-Pb dating of lacustrine limestone

Sulfur redox reactions: Hydrocarbons, native sulfur, Mississippi Valley-type deposits, and sulfuric acid karst in the Delaware Basin, New Mexico and Texas