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Section 1. General Perspectives ............................ 1 Chapter 1. Introduction .................................. 2 1.1. Focus and Organization of Book ............................. 2 1.2. Awareness of Rock Coatings ............................... 4 1.3. Nomenclature ......................................... 11 1.4. Historical Perspective on Major Research Threads ................. 16 Chapter 2. Paradigms and Methods in Rock Coating Research... 19 2.1. Alternative Perspectives ................................... 19 2.2. Adopting the Paradigm of Landscape Geochemistry ................... 20 2.2.1. Adjudicating Competing Hypotheses ......................... 20 2.2.2. Introduction to Landscape Geochemistry ..................... 20 2.2.2.1. The Development of Landscape Geochemistry in Soviet Geography ............................... 20 2.2.2.2 Landscape Geochemistry Outside of Russia/Soviet Union ....... 21 2.2.2.3. Fundaments of Landscape Geochemistry .................. 22 2.2.3. Rock Coatings as a Part of the Geochemical Landscape ........... 24 2.3. Methods Used in Original Data Gathering ....................... 27 2.3.1. Field Collection ..................................... 27 2.3.2. Preparation of Polished Cross-sections and Ultrathin Sections ....... 29 2.3.3. Secondary Electron Microscopy ........................... 29 2.3.4. Backscattered Electron Microscopy ....................... 30 2.3.5. X-Ray Spectrometry .......... .. ......... ............ 30 2.3.5.1. X-Ray Images ....................................... 31 2.3.5.2. Energy Dispersive Spectrometry ....................... 31 2.3.5.3. Wavelength Dispersive Spectrometry .......... 31 2.3.5.4. Detection of Organic Matter .......... .......... 31 2.3.6. Admission of Bias ............................. 32 Section 2. Different Rock Coatings .......................... 33 Chapter 3. Anthropogenic Pigments .........................34 3.1. Introduction ........................................... 34 3.2. Prehistoric Rock Pigments ................................. 34 3.3. Historic Rock Painting ................................... 36 3.3.1. Coatings to Change Appearances .......................... 36 3.3.2. Coatings to Preserve Stone .............................. 38 3.3.3. Coatings to Preserve Landscape Aesthetics .................... 38 Chapter 4. Lithobiontic Coatings .......................... 41 4.1. Introduction ........................................... 41 4.2. Different Types of Lithobiontic Coatings....................... 43 4.2.1. Bacteria ........................................... 43 4.2.2. Cyanobacteria ...................................... 48 4.2.3. Fungi ............................................ 49 4.2.4. Algae ............................................ 56 4.2.5. Lichens ........................................... 57 4.2.6. Higher Plants ................................ .... 60 4.3. Controls on Distributions .................................. 61 4.4. Impact of Lithobiontic Coatings ............................. 63 4.4.1. On Organic Remains .................................. 63 4.4.2. On Rock Weathering .................................. 64 4.4.3. On Other Rock Coatings ............................ .. 65 Chapter 5. Carbonate Crusts ......... ................ 67 5.1. Introduction ........................................... 67 5.2. Freshwater Deposits ...................................... 67 5.3. Marine Littoral ......................................... 70 5.4. Pedogenic ............................................ 72 5.5. Subaerial Rock Faces ..................................... 79 5.6. Carbonate Crusts and Greenhouse Warming ...................... 83 Chapter 6. Case Hardening Agents ......................... 85 6.1. Introduction ......................................... 85 6.2. Characteristics .................... .................... 86 6.2.1. Environmental Settings .............................. 86 6.2.1.1. Subaerial Desert Exposures ....................... .. 86 6.2.1.2. Subsurface Origins ................................ 87 6.2.1.3. Associated with Carved Rock ......................... 88 6.2.1.4. Tropics ........................................ 91 6.2.1.5 Temperate Environments .....;......... .......... ... 94 6.2.1.6. Arctic and Alpine Environments ....... ................ 95 6.2.2. Composition .............. . .................... 96 6.2.2.1. Material Added to Weathering Rind ...... ............... 96 6.2.2.2. Rock Coatings as Case Hardening Agents ................. 101 6.2.2.3. Fused Rock as a Case Hardening Agent ................... 104 6.2.3. Rates of Formation ................................... 105 6.3. Origin .............................................. 106 Chapter 7. Dust Films ................................... 108 7.1. Introduction ........................................... 108 7.2. Characteristics ... ..................................... 108 7.2.1. Environmental Settings .................................. 108 7.2.2. Composition ... .................................... 112 7.2.3. Rates of Formation ................................... 115 7.3. Origin ................................................... 117 Chapter 8. Heavy Metal Skins ............................. 120 8.1. Introduction ........................................... 120 8.2. Manganese Skins ....................................... 120 8.2.1. Environmental Settings ................................ 121 8.2.2. Composition ....................................... 122 8.2.2.1. Mineralogy ..................................... 122 8.2.2.2. Chemistry ................... ............... 122 8.2.2.3. Scavenging of Other Heavy Metals ..................... 130 8.2.2.4. Rates of Formation ................................ 130 8.2.2.5. Morphology ................ ................... 130 8.2.3. Origin .............................. ...... 132 8.2.3.1. Biotic Hypotheses ................................. 132 8.2.3.2. Abiotic Hypotheses ................................ 134 8.2.3.3. Combination of Biotic and Abiotic Formation .............. 134 8.3. Heavy metal skins as a mix of natural and anthropogenic factors ....... 135 8.3.1. Introduction ....................................... 135 8.3.2. Lead-enriched Heavy Metal Skins .......................... 136 8.3.3. Copper and Other Heavy Metal Skins ............... ............. 138 8.3.4. Patina, Metal Corrosion and Rock Coatings ................... 141 Chapter 9. Iron Films .................................... 144 9.1. Introduction .......................................... 144 9.2. Characteristics .................... ..................... 146 9.2.1. Environmental Settings ................................ 146 9.2.1.1. Artifacts ................... ........... ....... 146 9.2.1.2. Fractures in Rocks ............................... 147 9.2.1.3. Grain Coating on Sand ....... ................ 151 9.2.1.4. Springs ..................................... 153 9.2.1.5. Streams .... ................................ 153 9.2.1.6. Subaerial Rock Surfaces ............................. 155 9.2.1.7. Underside of Rocks ............................. 159 9.2.1.8. Iron Films Interdigitated With Other Rock Coatings .......... 160 9.2.2. Composition ............... ....................... 163 9.2.2.1. Mineralogy ....... . ................ ........... 164 9.2.2.2. Type I Iron Films ................................. 164 9.2.2.3. Type II Iron Films ................................ 169 9.2.2.4. Type III Iron Films ................................ 171 9.2.2.5 Heavy Metal Scavenging ........................... 178 9.2.3. Information on Rates of Formation ......................... 178 9.3. Origin ........................... 180 9.3.1. Source of the Iron .................................... 180 9.3.2. Abiotic Genesis ................................... .. 181 9.3.3. Biotic Genesis ...................................... 182 9.3.4. General Models ............................ .... 184 Chapter 10. Manganiferous Rock Varnish .................... 186 10.1. Introduction ..................................... 186 10.2. Characteristics ................................ ..... 188 10.2.1. Environmental Settings: Desert Varnish or Rock Varnish? ......... 188 10.2.1.1. Perspectives Prior to World War II ..................... 188 10.2.1.2. Perspectives in the Middle Years ...................... 189 10.2.1.3. Notion of an Ideal Climate of Formation ................ 189 10.2.1.4. Environmental Context ............................ 191 10.2.2. Physical-Chemical Characteristics ......................... 193 10.2.2.1. Thickness ..................................... 193 10.2.2.2. Color ........................................ 193 10.2.2.3. Sheen .................................. .. 194 10.2.2.4. Mineralogy ........... ......................... 195 10.2.2.5. Chemistry .................... ............ 198 10.2.2.6. Micromorphology ......... ................ ......... 206 10.2.2.7. Textures Seen in Cross-Section ....................... 209 10.2.2.8. Post-Depositional Modification ...................... 212 10.2.3. Classification of Rock Varnish .......................... 214 10.2.3.1. Prior Perspectives on Classification .................... 214 10.2.3.2. Why Classify Rock Varnish? ........................ 215 10.2.3.3. Color/Chemistry Differences ......................... 216 10.2.3.4. Geomorphic Differences ............................ 216 10.2.3.5. Microscopic Distinctions ........................... 217 10.2.3.6. Dangers of Misidentification ......................... 218 10.2.3.7. Dangers of Instituting a Bad Classification ................ 221 10.2.3.8. A Tiered Classification for Rock Varnish ................. .... 222 10.2.4. Rates of Formation .................................. 224 10.2.4.1. Observations Prior to World War II .................... 224 10.2.4.2. Observations from World War II to the First Dissertation ...... 225 10.2.4.3. Calculating Rates of Formation ......................... 227 10.3. Origin .............................................. 231 10.3.1. Framing the Issues Historically ........ .................. 231 10.3.1. Debate Prior to World War II .......................... 231 10.3.1.1. Internal Origin ............................. . 231 10.3.1.2. External Origin ............................... 233 10.3.1.3. Biological Origin .............................. 234 10.3.1.4. Polygenetic Origin ............................. 235 10.3.2. Debate from World War II to the First Dissertation ........... 236 10.3.2.1. Internal Origin ................................ 236 10.3.2.2. External Origin ............................. . 237 10.3.2.3. Both Internal and External....................... 237 10.3.2.4. Manganese Enhancement by Chemical Processes........ 237 10.3.2.5. Manganese Enhancement by Biotic Processes ........... 237 10.3.2. Source of the Manganese ......................... 239 10.3.3. New Polygenetic Model of Varnish Formation ................ 241 10.3.2.1. Clay Minerals at the Building Block Level............. 241 10.3.2.2. Manganese Enhancement......................... 242 10.3.2.3. How Rock Varnish Grows .................... 246 Chapter 11. Nitrates and Other Uncommon Rock Coatings ...... 248 11.1. Introduction ......................................... 248 11.2. Phosphate Skins ..................................... . 248 11.3. Nitrate Crusts ......................................... 254 11.4. Salt Crusts ........................................... 256 11.5. Sulphate Crusts ...............................262 11.6 Why these Rock Coatings have a Limited Distribution .............. 266 Chapter 12. Oxalate-rich Crusts ............................ 268 12.1. Introduction .......................................... 268 12.2. Characteristics .........................................269 12.2.1. Environmental Settings ................................269 12.2.2. Composition ...................................... 270 12.2.3. Rates of Formation .................................. 272 12.3. Origin .............................................. 275 13.2.1.11. Silica Glazes Interdigitated With Other Rock Coatinf 13.2.2. Composition ............................... 13.2.2.1 Type I. Homogeneous Amorphous Silica Glaze ..... 13.2.2.2. Type II. Detrital-rich Silica Glaze .............. 13.2.2.3. Type III. Alumina-Iron-rich Silica Glaze .......... 13.2.2.4. Type IV. Alumina-rich Silica Glaze ............. 13.2.2.5. Type V. Iron-rich Silica Glaze ................ 13.2.2.6. Type VI. Alumina Glaze .................... 13.2.3. Rates of Formation ........................... 13.3. Origin ..................................... 13.3.1. Source of the Silica ........................... 13.3.2. Abiotic Genesis ............................. 13.3.3. Biotic Genesis .............................. 13.3.4. General Models ............................. 13.4. Speculation on Iron Films on Mars ................... Section 3. Synthesis .............................. Chapter 14. General Model of Rock Coating Developmer 14.1 Introduction .................................. 14.2 Landscape Geochemical Hierarchy of Controls ........... 14.2.1. First-Order Processes: Geomorphic Controls .......... 14.2.1.1. Exposure of Bare Rock ..................... 14.2.1.2. Stability of Rock Surfaces ................... 14.2.1.3. The Role of Rock Type .................... 14.2.2. Second-Order Processes: Inheritance from a Subsurface Pos 14.2.3. Third-Order Processes: Habitability for Lithobionts ..... 14.2.4. Fourth-Order Processes: Transport Pathways ............ 14.2.5. Fifth-Order Processes: Biogeochemical Barriers ........ 14.2.6. A consideration for the dynamic .................. 14.3. The Hierarchical Model as an Interpretive Tool ........... Chapter 15. Analyzing Geographical Variations in Rock 15.1 Introduction ................................... 15.2. Different Approaches to Map Regional Geographical Variabilit 15.2.1 Generalization of Micron-Scale Analyses ............ 15.2.2 Generalization of Field Observations ............... 15.2.3 Remotely Sensed Imagery ...................... 15.3.4.2. Role of Rock Coatings in the Weathering System ..... 15.3.4.2.1. Iron Films ........................... 15.3.4.2.2. Silica Glaze .......................... 15.3.4.2.3. Dust Films ........................... 15.3.4.2.4. Carbonate and Sulfate Crusts ............ 15.3.4.2.5. Oxalate-Rich Crusts ......... ....... 15.3.4.2.7. Phosphate Skins ....................... 15.3.4.2.8. Rock Varnish ......................... 15.3.4.3. Comparison with Rock Coatings in Other Geographic Se 15.3.4.4. Implications for Understanding Geographical Variations ii Rock Coatings .................................. 15.4. Concluding Perspectives ............................ References .............................. Geographical Index ................................. Subject Index .....................................