The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from human activities. Broad interrelationships among these processes and their effects can be discerned by application of principles of chemical thermodynamics. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium, including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the Earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural freshwater. The ways in which solutes are taken up or precipitated and the amounts present in solution are influenced by many environmental factors, especially climate, structure and position of rock strata, and biochemical effects associated with life cycles of plants and animals, both microscopic and macroscopic. Taken together and in application with the further influence of the general circulation of all water in the hydrologic cycle, the chemical principles and environmental factors form a basis for the developing science of natural-water chemistry. Fundamental data used in the determination of water quality are obtained by the chemical analysis of water samples in the laboratory or onsite sensing of chemical properties in the field. Sampling is complicated by changes in the composition of moving water and by the effects of particulate suspended material. Some constituents are unstable and require onsite determination or sample preservation. Most of the constituents determined are reported in gravimetric units, usually milligrams per liter or milliequivalents

Study and Interpretation of the Chemical Characteristics of Natural Water

Nitrogen—Inorganic Forms

Most soils contain inorganic nitrogen (N) in the form of ammonium (NHt) and nitrate (NO)"). Nitrite (NOz) also may be present, but the amount is usually too small to warrant its determination, except in cases where NHt or NHt-forming fertilizers are applied to neutral or alkaline soils. Several other forms of inorganic N have been proposed as intermediates during microbial transformations of N in soils, including hydroxylamine (NH20H), hyponitrous acid (H2N20 2), and nitramide (NH2N02), but these compounds are thermodynamically unstable and have not been detected in soil. Until the 1950s, inorganic N was believed to account for <2% of total soil N, on the assumption that NHt and NO)" are completely recovered by extracting soil with a neutral salt solution. The validity of this assumption was challenged by the finding that some soils contain NHt in a form that is not extracted by exchange with other cations (e.g., Rodrigues, 1954; Dhariwal & Stevenson, 1958; Stevenson & Dhariwal, 1959; Bremner & Harada, 1959; Bremner, 1959; Schachtschabel, 1960, 1961; Young, 1962), and by estimates that the proportion of soil N in this form can exceed 50% for some subsurface soils (Stevenson & Dhariwal, 1959; Young, 1962). In such cases, NHt is said to be fixed, and fixed NHt has subsequently been defined as the NHt in soil that cannot be replaced by a neutral potassium salt solution (SSSA, 1987), such as 1 or 2 M KCI or 0.5 M K2S04, in contrast to exchangeable NHt, which is extractable at room temperature with such a solution. Existing information indicates that fixed NHt occurs largely, if not entirely, between the layers of 2: I-type clay minerals, particularly vermiculite and illite (hydrous mica), and that fixation results from entrapment of NHt in ditrigonal voids in the exposed surfaces upon contraction of the clay lattice (Nommik & Vahtras, 1982). The term, nonexchangeable NHt, has been used by Bremner (1965) and Keeney and Nelson (1982) in previous editions of this publication as a more precise alternative to fixed NHt. The same term is used in the present treatment, with specific reference to NHt determined by the method described in "Determination of Nonexchangeable Ammonium," which involves digestion with an HF-HCI solution following treatment of the soil with alkaline KOBr to remove exchangeable NHt and labile organic-N compounds.

Nitrogen - inorganic forms.

Dissimilatory Fe(III) and Mn(IV) reduction.

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

Uranium solution-mineral equilibria at low temperatures with applications to sedimentary ore deposits

Stable carbon isotope ratios and the existence of a gas phase in the evolution of carbonate ground waters

The geochemistry of some carbonate ground waters in central Pennsylvania

Solubility products of amorphous ferric arsenate and crystalline scorodite (FeAsO4 · 2H2O) and their application to arsenic behavior in buried mine tailings

Donald Langmuir

Papers

Uranium solution-mineral equilibria at low temperatures with applications to sedimentary ore deposits

Stable carbon isotope ratios and the existence of a gas phase in the evolution of carbonate ground waters

The geochemistry of some carbonate ground waters in central Pennsylvania

Solubility products of amorphous ferric arsenate and crystalline scorodite (FeAsO4 · 2H2O) and their application to arsenic behavior in buried mine tailings

Dissociation constants of calcite and CaHC03+ from 0 to 50°C