Rock Coatings (Developments in Earth Surface Processes 6)

Developments in Earth Surface Procc!-.ses 6

ROCK COATINGS

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Chapter 10 MANGANIFEROUS

ROCK

VARNISH

"Now, if these black cmsts were formed by a slow decomposition of the granitic rock, under the double influence of humidity and the tropical sun, how is it to be conceived that these oxides are spread so uniformly over the whole surface of the stony masses, and are not more abundant round a crystal of mica or hornblende than on the feldspar and milky quartz?" yon Humboldt (1812, p. 245)

I0.I.

Introduction

Rock varnish is a dark coating that is characterized by clay minerals cemented to rock surfaces by oxides and hydroxides of manganese and iron. The term "desert varnish" is also common, because these accretions are particularly noticeable in arid regions. Although paper thin, rock varnish can completely alter the appearance of a landscape (Figure 10.1).

Figure 10.1. These images show how rock vamish can completely alter the color of a landscape. The upper photograph is of the Gebel Zuweira range in the southern Sinai Peninsula, where rock varnish turns light-colored granites and into ebony. The middle view shows how even a patchy cover of ~30~m-thick vamish progressively darkens older debris flows on the Black Mountains in southern Death VaUey. The lower p~cture, taken from Hoover Dam, Arizona/Nevada, reveals visual impact by subtraction; note the ~oathtub ring' where the vamish has been chemically eroded by the waters of Lake Mead.

Rock Varnish

Rock varnish is the most studied of all rock coatings. In the last two hundred years, there have only been two monograph-length treatments of rock coatings, and both have addressed rock varnish. The first analyzed blackened rocks in the Egyptian Desert and along the Nile (Lucas, 1905). The second characterized the interaction between case hardening crusts, manganiferous rock varnishes, polishes from eolian abrasion, and weathering rinds in North Africa (Haberland, 1975). The number of papers written about rock varnish exceeds all other rock coatings combined. Hence, you will find that this chapter is the most detailed. I divide literature discussions in this chapter into three eras of rock varnish research. The first is prior to World War II. The second rests between World War II and the first dissertations written about rock comings, in this case rock varnish (Bard, 1979; Potter, 1979). The third era extends to the present, where an increasing number of students have chosen to conduct thesis and dissertation research on different aspects of rock varnish (Anderson, 1995; Bard, 1979; Best, 1989; Dorn, 1980; Dom, 1985; Elvidge, 1979; Liu, 1994; Perry, 1979; Potter, 1979; Spatz, 1988). Rather than jump straight into the details of the rock coating, the literature on rock varnish is sufficiently extensive to warrant an evaluation of how the field has evolved over time. Research problems in the field of rock varnish have changed little since Alexander von Humboldt (1812) initiated the scholarly study of black coatings on rocks. He was concerned with its composition being dominated by manganese, whether it was extemaUy applied (his preferred hypothesis) or derived from the host rock, spatial distribution (along rivers and in deserts), controls on why it remains the same minimal thickness, relationship to the environment, and its possible role in human illness. Since von Humboldt accurately dismissed native concerns about the role of rock varnish on human sickness, the role of varnish on health is the only topic explored by von Humboldt that has not burgeoned into a substantial literature. In the 'early years' of varnish research prior to World War II, several researchers drew justification for their studies from the unsolved problems isolated by von Humboldt (1804) and reiterated by Charles Darwin (Darwin, 1897). The main debate rested on whether rock varnish derived from the weathering products of the underlying rock, or from externally-applied material. Based on the chemical analyses of Lucas (1905) and the model of Linck (1901), the majority of researchers concluded that varnish derived from capillary solutions drawn from the rock and evaporated on the surface. An emerging focus of research in archaeology, and to a lesser extent geomorphology, was over varnish as an indicator of antiquity. In the 'middle years' of research between World War II and the late 1970's when the field matured to the point where dissertations and theses were written, there was a gradual improvement in the precision of chemical measurements, more concern over the use of varnish as an indicator of exposure age, exploration of a biological origin by culturing, and debates over the optimal climate for varnish formation. However, there were no major shifts in the nature of research problems. "Desert varnish" was thought to have its origins in the underlying rock. The great enhancement of manganese was thought by most, but not all, to occur by the greater mobility of manganese as compared to iron. Substantial shifts in research focus, methodology, and schools of thought occurred in the 'modem period' of research, heralded by dissertations and theses in the latter half of the 1970's. Probably the most important finding was that the bulk of varnish was composed of clay minerals (Haberland, 1975; Potter, 1979; Potter and Rossman, 1977). A consensus was also reached, on the basis of more spatially precise electron microscope and electron microprobe data, that varnish was an external accretion and that

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varnish was found in virtually all terrestrial weathering environments. Although there has been a great expansion of researchers advocating a microbial explanation for Mnenhancement in varnish, a consensus on varnish genesis has not been reached. The trend towards specialization in science in general was felt in rock varnish over the last two decades, as the research problems asked by most investigators narrowed in focus to new applications of different analytical techniques and to very specific issues of varnish characteristics. In addition, there has been an expansion in funding to investigate the dating of rock varnish, which resulted in a wave of publications assessing its usefulness as an indicator of antiquity. The focus of this chapter is like the others in section two of this book: to provide an understanding of the state-of-the-art knowledge on a rock coating in order to set up section three of the book, where I attempt to promote a more general understanding of the geography rock coatings. Section 10.2 of this chapter details the characteristics of this ubiquitous rock coating, and section 10.3 integrates abiotic and biotic explanations to develop a new model to explain the genesis of rock varnish. 10.2. Characteristics 10.2.1. Environmental Settings: Desert Varnish or Rock Varnish? There are two dominant English-language terms for manganese-iron rock coatings with a clay matrix, desert varnish and rock varnish. Desert varnish (Merrill, 1898) is older than rock varnish (Dora and Oberlander, 1981b; Krumbein and Jens, 1981). And while the use of rock varnish has increased in recent years, desert varnish is still in widespread use (e.g., Cremaschi, 1996). A search of the Intemet, for example, will see more hits for desert varnish than rock varnish. The basic question raised in this section is whether the term "desert varnish" is a misnomer, simply because this rock coating is found in a wide variety of settings other than deserts. 10.2.1.1. Perspectives Prior to Worm War H

As in today's literature, there were three general opinions on the distribution of manganese-iron films on rocks. One group simply kept their observations limited to arid regions, often with concomitant opinions about the importance of the harsh sunlight or heat of the desert. These researchers noted the presence of rock varnish in Australian (Basedow, 1914; Moulden, 1905; Talbot, 1910; Woodward, 1914), North American (Blake, 1855; Blake, 1858; Bryan, 1922; Gilbert, 1875; Loew, 1876; Stevenson, 1881; Walther, 1892), and Saharan-Arabian Deserts (Ball, 1916; Blanck et al., 1926; Linck, 1901; National-Geographic-Society, 1924; Walther, 1891). Another group noted that black coatings on rocks had a global distribution in a variety of environments from deserts to glaciers, that these coatings were similar in character next to glaciers, on quartzite boulders in Washington D.C., on the banks of tropical rivers, and other types of Mn-Fe accumulations such as in laterites and deep-sea nodules (Ball, 1903; Boussingault, 1882; Brandes, 1901; Knaust, 1930; Lucas, 1905; Merrill, 1906; Polynov, 1937; Zahn, 1929). For example, the dark coatings found in the Egyptian Desert were felt to be similar to those found at the Cataracts of the Nile (Roziere 1813, cited by Linck, 1930, p. 243; Lucas, 1905). Linck brought this perspective together (1930) and argued with many examples that "Schutzrinden" had a

Rock Varnish

global distribution; it occurred in deserts from around the globe, adjacent to streams, in tropical soils, near glaciers, and on virtually all rock types. There were some, however, that acknowledged the ubiquitous occurrence of manganese-iron coatings in a variety of environments, but considered the black coatings in deserts to be different. Many were persuaded by Walther (1891, 1912) who argued that the black coatings on banks of tropical rivers are not associated with desert films, since they are produced without the aid of tropical climate or flowing water.

10.2.1.2. Perspectives in the Middle Years

After World War II, many geomorphologists considered the "desert varnish" in drylands to be a unique phenomenon (Blackwelder, 1954; Daveau, 1966; Lukashev, 1970; Peel, 1960). These views were promoted in introductory and specialty textbooks (Heizer and Baumhoff, 1962; Longwell et al., 1950; Muller and Oberlander, 1978; Oilier, 1984). Black Mn-Fe coatings called "desert varnish" were also recognized a wide variety of environments, including: alpine (Glazovskaya, 1968; HOllerman, 1963; Hooke et al., 1969; Hunt, 1954; Klute and Krasser, 1940; Krumbein, 1969; Scheffer et al., 1963), riverine (Blackwelder, 1948; Hunt, 1954), Arctic (Btidel, 1960; Cailleux, 1967; Krumbein, 1969; Rapp, 1960; Skarland and Giddings, 1948; Washburn, 1969b), Antarctic (Glazovskaya, 1958; Glazovskaya, 1971; Markov, 1960; Markov et al., 1970; McGraw, 1967; Skarland and Giddings, 1948; Taubert, 1956; Tedrow and Ugolini, 1966; Ugolini, 1970), littoral (Hooke et al., 1969), and humid mid-lattitude settings (Hooke et al., 1969; Hunt, 1954; Kelly, 1956; Krumbein, 1969; Tricart and Cailleaux, 1964). Hunt (1954) and Engel and Sharp (1958) argued that since manganese-iron coatings are best developed in arid regions, the phenomenon deserves the name "desert varnish" (Engel and Sharp, 1958; Hunt, 1954; Hunt and Mabey, 1966). Krumbein (1969), in contrast, suggested the term "iron-manganese crusts" be substituted to reflect its more global distribution. The term rock varnish was suggested later (Dora and Oberlander, 198 lb; Krumbein and Jens, 1981).

10.2.1.3. Notion of an Ideal Climate of Formation

There was a debate over the role of climate on varnish formation, clearly associated with the foregoing question. The debate has largely died out, although the issue has not been resolved. The discussion was polarized between those believing varnish forms best in deserts, and those believing that varnishes seen in deserts are relicts of a former "pluvial" (wetter) climate. The most common opinion was that the optimum climatic conditions for "desert varnish" formation occur in deserts, where varnish is currently thought to be forming: in the Mojave Desert (Denny, 1965; Engel, 1957; Engel and Sharp, 1958; Hildreth, 1976; Hooke et al., 1969), the Great Basin (Hooke et al., 1969; Lakin et al., 1963; Springer, 1958), the Negev Desert (Krumbein, 1969), Thar Desert in India (Allchin et al., 1978), Libya (Glennie, 1970, p. 20), Australian drylands (Hills et al., 1966; Twidale, 1968), Atacama Desert (Klute and Krasser, 1940; McGinnies et al., 1968), the

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Egyptian Pyramids (Blackwelder, 1948; Emery, 1960; Iskander, 1952), and other locales in Africa (Clark, 1954; Daveau, 1966; Glennie, 1970; Scheffer et al., 1963). Sometimes, climatic conditions were specified. Engel (1957) and Engel and Sharp (1958) observed varnished cobbles in a dirt road in the Mojave Desert that was about 25-years-old at the time of study. As a consequence, they proposed that mean annual precipitation of under 4 inches (10 cm), and hot temperatures after wetting, represents the "optimum" conditions for varnish formation. Grant et al. (1968, p. 44) argued that dust storms, followed by rain and high temperatures, favor varnish development. Altithermal climates favored black manganese-rich varnishes (Glennie, 1970, p. 19; Hayden, 1976, p. 277; Allen, 1978). Other investigators believed that frequent moistening increased rates of varnish formation (Goodwin, 1960; Klute and Krasser, 1940; Turner, 1963), and that the black (manganese-rich) varnish now found in deserts formed more rapidly and extensively in prior "pluvial" (wet) periods (Capot-Rey, 1965; Hunt, 1954; Hunt, 1961; Hunt, 1974; Hunt, 1975; Hunt and Mabey, 1966; Passarge, 1955; Tricart and Cailleaux, 1964). Hayden (1976, p. 278) felt that orange-bottom varnish has a pluvial origin. Varnish is thought to be forming currently on: fiver boulders between high and lower water stages (Hunt, 1954; Potter, 1979), cliffs over which seepage flows (Engel and Sharp, 1958; Hunt, 1954; Hunt, 1961; Hunt, 1972; Smith, 1978; Supplee et al., 1971), in more moist microenvironments (Turner, 1963), alpine settings (Engel and Sharp, 1958; Glazovskaya, 1968; H011erman, 1963; Klute and Krasser, 1940; Krumbein, 1969), Arctic and Antarctic environments (Btidel, 1960; Ugolini, 1970; Washburn, 1969b), semi-arid locales such as the Sahel (Tricart and Cailleaux, 1964). The explanation for requiring moisture was that the metals enhanced in varnish required transport by water (Butzer and Hansen, 1968; Hunt, 1954; Hunt, 1961; Supplee et al., 1971). Klute and Krasser (1940) argued that the poor varnish in the Atacama desert, compared with excellent varnish in the Patagonian Pampa and European Alps, indicates the importance of frequent wetting. As long as the rock surface is free of vegetation, frequent wetting was felt to assist in the penetration of water in stones that contained iron and manganese on moraines in the Alps. This explained rapid formation of varnish (coveting 10% of rocks) on moraines deposition ninety years earlier in the 1850's. The English language debate over the climate of varnish formation was probably best formulated in the writings of Charles Hunt (1954, 1961, 1974) and Celeste Engel and Robert Sharp (1958). Whereas Hunt (1954) argued that varnishing was a product of past pluvial periods, Engel and Sharp (1958) noted varnish formation within 25 years in the Mojave Desert; they also pointed to dendritic growth forms and the coalescence of black spots indicative of contemporary varnish formation. Engel and Sharp (1958) advocated a steady-state model, where the state of varnish was a balance between formative and destructive processes. Varnishes are so abundant in deserts, just because varnishforming processes are more important than varnish-destroying processes. Hunt (1961, p. B 194-B195) responded: "Engel and Sharp (1958, p. 515-516) overemphasize such a locality---one where they infer varnish has been deposited in 25 years. But the total record indicates clearly that such deposition is highly localized and exceptional. Were it otherwise, buildings and other surfaces, artificial and natural, that are as old as 25 years should generally be darkly stained."

Engel and Sharp's (1958) conclusion that varnish can form in 25 years has been extensively cited (Cooke and Warren, 1973; Fairbridge, 1968a; Goudie and Wilkinson, 1977; Hem, 1964), and sometimes with a critical eye (Mabbutt, 1977). Later studies (Dorn and Oberlander, 1982; Elvidge, 1982) revealed that the Mojave road construction

Rock Varnish

site was a case of a reformed desert pavement. Some of the cobbles had abrasion marks made by the road construction equipment, and varnish had not reformed in these marks by 1980 (Dora and Oberlander, 1982); however, the cobbles thrust into the soil by road formation did reappear. The up thrusting process, in part responsible for pavement reformation (Springer, 1958), was not recognized when Engel (1957) conducted the original field work. An issue in this debate revolves around the interpretation that past climate could be inferred by studying the health of varnish at a site; the occurrence of flaking varnish, circular blisters, and isolated patches of varnish on a largely unvarnished surface could indicate that varnish was not forming at present and was in a state of deterioriation (Clements and Clements, 1953; Demangeot, 1971; Engel, 1957; Engel and Sharp, 1958; Grant et al., 1968; Hildreth, 1976; Hunt and Mabey, 1966). Daveau (1966) argued that much varnish in North Africa was relict. Still others argued the varnish in northwestern Australia formed in the more arid, last full-glacial period (Clarke, 1977). Some used varnish to interpret paleoclimates on the basis of coatings on buried artifacts (Clark, 1950). Caution was also urged in the use of the occurrence of desert varnish as an indicator of past aridity, because "desert varnish" existed in a variety of environments (Cailleaux, 1969; Krumbein, 1969; Krumbein, 1971; Mabbutt, 1977). Uncertainty over the role of climate was mirrored in a minor disagreement over the role of aspect. Observations in the Mojave Desert (Engel and Sharp, 1958) suggested there was no consistent variation related to aspect; rather the stability of the underlying rock is more important (Engel and Sharp, 1958). Engel (1957) observed that entire desert mountain ranges, miles long and thousands of feet high were "completely" coated with "desert varnish". In contrast, aspect was thought to influence varnish development in southern Africa (Goodwin, 1960). Turner (1963, p. 14-15) concurred for Glen Canyon in the Colorado Plateau. "Petroglyphs that are shaded all year around do not have patina. Petroglyphs of the same style, with some parts shaded part of the time and some sunlit, vary in patina, although almost always the sunlit designs have more patina than the partially shaded designs (Turner, 1963, p. 14-15)."

10.2.1.4. Environmental Context

There is no debate in the current literature over the environment where desert varnish or rock varnish occurs. There now appears to be a widespread acceptance that the same phenomenon can be found in a wide variety of environmental settings (Table 10.1). Concomitantly but unfortunately, dialog over the climate most favorable for varnish growth has also been dropped from the literature in the last two decades. This issue, however, has not been resolved. Rock varnish is known to grow all over rock surfaces within decades in some settings (Dorn and Meek, 1995; Dora and Oberlander, 1982; Klute and Krasser, 1940), while in other places only spot coverage grows after a few thousand years (Blackwelder, 1948; Dorn and Oberlander, 1982). Figure 10.2 presents a tentative model to explain rapid growth in places of abundant moisture, but where competing organisms are unable to grow.

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Table 10.1. Environments where rock varnish has been observed. Where Found Artifacts Fractures in rocks Geologic Settings Ground Figures Ground-line Historical Surfaces Littoral Petroglyphs Springs

References (Toplyn, 1988) (Dom and Oberlander, 1982; Engel and Sharp, 1958) (Dom and Dickinson, 1989; Marchant et al., 1996) (Clarkson, 1994; von Wedhof, 1989) (Engel and Sharp, 1958; Hooke et al., 1969) (Iskander, 1952) (Hooke et al., 1969) (Bard, 1979; Bard et al., 1978) (Frugal and Sharp, 1958; Hunt, 1954; Hunt, 1961; Hunt, 1972; Supplee et al., 1971) (Lucas, 1905) see also http://minerals'gps'caltech'edu/files/varnish/river-v'gif (Dora and Obedander, 1982) (Bucldey, 1989; Hunt, 1954) (Boussingault, 1882; Phaup, 1932) (Glazovskaya, 1958; Glazovskaya, 1971; Markov, 1960; Markov et al., 197~ Taubert, 1956) (Glazovskiy, 1985; H611erman, 1963; WhaUey, 1984) (Jahn and Maneck, 1991; Washburn, 1969b) (Walther, 1912; White, 1990) (Klute and Krasser, 1940; Linck, 1930) (Krumbein, 1969; Tricart and Cailleaux, 1964) (Linck, 1930; Whalley et al., 1990)

Streams, exoreic Streams, periglacial Streams, temperate Streams, tropical Subaerial Antarctic Subaerial, alpine Subaerial, Arctic Subaerial, deserts Subaerial, periglacial Subaerial, temperate Subglacial

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Figure 10.2. Generalized model of rates of rock vamish formation, where moisture abundance promotes growth, but only so long as acid-producing lithobionts are uncommon.

Rock Varnish

The model in Figure 10.2 is based on case studies and a general understanding of biotic processes of manganese fixation and biochemical erosion. The slowest varnishing takes place in the harshest deserts where moisture limits manganese enhancement by biotic agencies. Moderate growth rates are found in deserts like the Negev and Mojave; competing lithobionts can grow, but generally only in the wettest microenvironments. The most rapid varnishing takes place where moisture is readily available but other lithobionts have not yet started to grow, for example proglacial streams or rock fractures. Places of rapid lithobiontic growth, like microcolonial fungi central Australia, are places of rapid varnishing and rapid varnish erosion. I note, however, that this model has not been subject to rigorous attempts at falsification.

10.2.2. Physical-Chemical Characteristics 10.2.2.1. Thickness

The thickness of varnishes found in deserts is generally less than 100 micrometers (Cooke et al., 1993; Daveau, 1959; Daveau, 1966; Engel, 1957; Engel and Sharp, 1958; Hayden, 1976; Hildreth, 1976; Hooke et al., 1969; Hunt and Mabey, 1966; Karlov, 1961; Mabbutt, 1977; Marshall, 1962; Scheffer et al., 1963). However, the reader should keep in mind that these individuals sampled prominent examples of rock varnish. When I instituted a 'random' sampling of 30 rock varnishes along a transect one meter in length at the classic 'Salt Springs' site, Mojave Desert, of Engel and Sharp (1958), varnish thickness averaged 24 ktm with a standard deviation of 14 ~tm. The thickest true rock varnish that I have ever observed reached ~600 micrometers; it developed on a chert of the Providence Mountains, Mojave Desert, eastern California. There are reports of varnishes up to 7 millimeters thick (Klute and Krasser, 1940; Krumbein, 1969; Peel, 1960; Rogers, 1966; Tricart and Cailleaux, 1964). The writing of these papers, however, could be interpreted to indicate that these measurements may be on the combined thickness of weathering finds and the overlying rock varnish. Unlike the uniform thickness of tropical fiver varnishes reported by von Humboldt (1804) and Darwin (1897), the "thickness and character of varnish can change sharply even within one locality...In some deserts virtually all rock surfaces are covered with varnish; in others, varnish is absent (Cooke and Warren, 1973, p. 87-88)." Varnish is thickest in protected places (along rock crevices, hollows in the rock, depressions, pits, etc.), on fine grained igneous rocks, on rough or porous landforms without a soil cover, and on rocks rich in iron and manganese (Blackwelder, 1954; Cooke et al., 1993; Daveau, 1959; Daveau, 1966; Engel, 1957; Engel and Sharp, 1958; Hooke et al., 1969; Hunt and Mabey, 1966; Krumbein, 1969; Mabbutt, 1977; Scheffer et al., 1963; Washburn, 1969b).

10.2.2.2. Color

For the most part, opinions on the source of the color of rock varnish has not changed. There is agreement that "the tapestries that are blue-black in color are formed by the manganese, and those that are red are formed by iron" (Supplee et al., 1971, p. 7).

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Figure 10.3. Typical appearance of rock varnish seen in the field, where the darkest (blackest) varnishes a r e enriched in manganese in the surface layers and orange vamishes are not. A. Black vamish growing on quartzite from Salt Springs, Mojave Dese~ the width of the frame is ~10 cm. B. Dusky-brownvamish, growing on a quartzite boulder of Pleistocene shoreline of Searles Lake, Califomia. C. Black (upper rock surface) and orange (surface that the rock hammer rests on) varnishes. The orange varnish is an iron film from a rock crevice position (see Type III iron film in Chapter 9) growing on a rhyodacite lithology from Rainbow Basin, Mojave Desert. D. Orange varnish (Type III iron film) from the underside of a granodiorite cobble in a desert pavement from Mesa, Arizona the width of the frame is ~14 on.

Turner (1963, p. 14) added concerns over the role of varnish thickness and the influence of the host rock, noting that "color is considered to be a function of patina depth." Studying the northern Karroo in South Africa, Goodwin (1960, p. 308) also added the perspective that other rock coatings could influence the appearance of varnish, in that "droppings from perching birds (there are no trees) affect this dark skin of epidaphic patination, rotting and bleaching the slightly glazed dark varnish to a mat, pale russet brown."

10.2.2.3. She en A noted and sometimes conspicuous characteristic of some black varnish is its sheen (Figure 10.4). The shiny appearance has been attributed to eolian polishing with dust (Garner, 1974; Goudie and Wilkinson, 1977; Grant et al., 1968; Hunt, 1954; Klute and Krasser, 1940) and sand blasting (Begole, 1973; Supplee et al., 1971; Turtle, 1983). Eolian abrasion, however, readily removes rock varnish (Laity, 1995) and is not important in creating its sheen. Other alternative explanations for the sheen of varnish have been noted in the literature. These include a thin coating of goethite (Kelly, 1956), the metabolic products of cyanobacteria (Scheffer et al., 1963), and exposure to the sun because shadowed surfaces and varnishes formed in rock crevices had dull varnishes (Engel and Sharp, 1958). While these factors may be important, I favor the importance of a smooth or lamellate surface micromorphology (Krumbein, 1969) in combination with manganese enrichment at the very surface of the varnish (Dora and Oberlander, 1982).

Rock Varnish

Figure 10.4. Shiny vamish can be found in different locations, but the most common is at the ground line. Shiny ground-line band vamishes can be found on cobbles in desert pavements or where soil covers bedrock, a s in this case on basalt at Dry Falls of the Owens River, eastern Califomia.

10.2.2.4. Mineralogy Varnish minerals were originally reported to be amorphous (Engel, 1957; Engel and Sharp, 1958; Hildreth, 1976; Hooke et al., 1969; Mabbutt, 1977), with a streak that is dark brown (Engel and Sharp, 1958). Some thought that goethite (Kelly, 1956; Scheffer et al., 1963) and ferric chamosite (Washburn, 1969b) were important components. Seminal research conducted with inflared spectroscopy, X-ray diffraction and electron microscopy at the California Institute of Technology revealed that the bulk of rock varnish is composed of clay minerals (Potter, 1979; Potter and Rossman, 1977). Clay minerals typically comprise 60% to 70% of rock varnish by weight. The major clays are illite, montmorillonite, mixed-layer illite-montmorillonite, kaolinite (usually a minor constituent, but in some cases a major), and chlorite. The dominance of clay minerals distinguishes rock varnish from manganese-rich heavy metal skins (see chapter 8). Clays are a very minor part of heavy-metal skins, whereas clays are vital to the structure and formation of rock varnish. Electron microscopy exemplifies that clays dominate the structure of varnish; this can be seen as a new layer of varnish is laid down (Figure 10.5) and it can be seen by layered structure seen in cross-sections (Figure 10.6). Clay minerals are cemented to the host rock by oxides of manganese and iron (Potter, 1979; Potter and Rossman, 1977; Potter and Rossman, 1978; Potter and Rossman, 1979a; Potter and Rossman, 1979c). Birnessite is the dominant manganese mineral in black varnish, and hematite is a major iron oxide in both black and orange varnish. Figure 10.7 presents one of the largest Mn-crystals I have seen on or in rock varnish; they may be the radiating rods of birnessite. Figure 10.8 illustrates a large hematite grain. Most of the iron and manganese oxides that cements clay minerals together (Potter, 1979; Potter and Rossman, 1979a) are much smaller - - on the order of nanometers as seen in High Resolution Transmission Electron Microscopy.

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Figure 10.5. Secondary electron image of clay minerals accreting on rock varnish on Hanaupah Canyon Fan, eastem California. Note how the individual clay platelets overlap as they cement onto the surface.

Figure 10.6. High resolution transmission electron microscopy image of the parallel structure imposed by clay minerals. The top of the varnish is to the left. Note that the scale bar is in nanometers, so the image is a cross-section of perhaps ten of platelets in Figure 10.5 The sample is from Hanaupah Canyon Fan, Death Valley and was prepared by A. Overson.

Rock Varnish

Figure 10.7. Secondary electron image of radiating crystals that are rich in manganese, according to energy-dispersive X-ray analyses. The radiating form is from a broken inner surface of rock varnish from Undoolya Gap, central Australia and it could be bimessite (Chukhrov et al., 1980).

Figure 10.8. High resolution transmission electron microscopy image of hematite, identified by electron diffraction. The sample is from Hanaupah Canyon Fan, Death Valley and was prepared by A. Overson.

Submicroscopic fragments of detrital minerals are trapped by the clay minerals. The presence of detrital grains was first inferred, based on anomalous Fe and Mn electron microprobe measurements in the lower "subordinate" layer of the varnish (Hooke et al., 1969). Upon closer examination, detrital minerals are common in subaerial rock varnishes. Quartz (Potter, 1979), calcite, titanomagnetites, feldspars (Dorn, 1986; Dorn

197

198

Chapter 10

et al., 1990), and barium sulfate (Krinsley and Manley, 1989) have been noted. Figure 10.9 exemplifies different perspectives on detrital minerals, trapped within rock varnish as the clays are cemented by Mn-Fe oxides.

Figure 10.9. Views of detrital minerals, trapped in rock varnish as clays are cemented by Mn-Fe oxides. The abbreviations are on the imagery for the different type of imagery are HRTEMfor high resolution transmission electron microscopy;SE for secondaryelectrons, and BSE for backscattered electrons.

10.2.2.5. Chemistry The analytical chemist Celeste Engel (1957) completed the first M.S. thesis research on rock varnish, and then teamed up with Robert Sharp to write a seminal paper on the chemistry of rock varnish in the Mojave Desert (Engel and Sharp, 1958). Although Engel and Sharp realized the potential for some contamination by the underlying rock, scraping varnish was done with great care to minimize the influence of the rock. The principle elements and oxides in "desert varnish" were determined to be O, H, Si, A1, Fe, Mn with the major oxides of SiO2, A1203, H20, Fe203, and MnO (Engel, 1957; Engel and Sharp, 1958). Like Lucas (1905), a major effort was spent on comparing the chemistry of the rock and varnish, with the elements most enriched in varnish relative to the rock being Mn>H20>Fe>P. Enrichment ratios (varnish:rock) varied from 66 to 292 for Mn, 2 to 66 for Fe, and 13 to 60 for H20 (Engel, 1957; Engel and Sharp, 1958). The essential "problem" of varnish formation, identified originally by von Humboldt (1812), and reiterated by Engel and Sharp (1958) was how to explain the great enrichment in Mn over Fe, relative to the underlying rock. Varnish Mn:Fe ratios

Rock Varnish

varied from 20, in contrast with ratios of 1:60 in the earth's crust (Engel, 1957; Engel and Sharp, 1958; Glazovskaya, 1968; Glazovskaya, 1971; Hooke et al., 1969; Hunt and Mabey, 1966; Krumbein, 1969; Lakin et al., 1963; Scheffer et al., 1963). Varnish is a 'kitchen soup' of heterogeneous constituents. The inherent heterogeneity became abundantly clear in the minor elements. In order of decreasing concentration, these are: Ca, Mg, Na, K, Ti, and P (Engel, 1957; Engel and Sharp, 1958; Glazovskaya, 1968; Hooke et al., 1969; Marshall, 1962). Like Mn, minor elements could vary considerably (0.5 - 1.5%) from place to place in bulk samples (Engel and Sharp, 1958), and microprobe analyses showed even greater variation with measurements as high as 16.2% (Hooke et al., 1969, p. 283). Ba, and Sr were the most abundant trace elements, with Cu, Ni, Zr, Pb, V, Co, La, Y, B, Cr, Sc, and Yb found in all varnishes in order of decreasing concentration (Engel and Sharp, 1958). U was enriched in varnish more than twenty times, as compared to the underlying rock (Marshall, 1962). Negev varnishes may be rich in Cu and Co (Evenari et al., 1971). The elements Cd, W, Ag, Nb, Sn, Ga, Mo, and Zn were found in some, but not all varnishes (Engel and Sharp, 1958; Lakin et al., 1963). High ambient levels of Cu, B, Ar, and Sb were reflected in higher concentrations of these elements in varnishes from those areas, suggestive that varnish could be useful as a geochemical prospecting tool (Lakin et al., 1963). An electron microprobe examination (Hooke et al., 1969) provided the first definitive data on the chemistry of varnish, because contamination from the underlying rock could be ruled out by using micron-sized beams. In varnishes from Deep Springs Valley and Death Valley, eastern California, Mn and Fe usually increased outward from the rock into the varnish. CaO and MgO usually decreased outward. When A1203, K20, and FeO were in abundance in the rock, they decreased outward from the rock into the varnish. When these oxides were in low concentrations in the rock, they increased in abundance in the varnish. In all samples, MnO increased in an outward direction from the rock. TiO2 was correlated with FeO. With the acquisition of more and more precise chemical data, there has been the realization that the chemical composition of the varnish varies greatly at all spatial scales: from micron to micron within a single depth profile or chemical transect, between locations on the same rock, between different rocks from the same area and between different areas (Dom et al., 1990; Dora et al., 1992a; Dorn and Krinsley, 1991; Dorn and Oberlander, 1982; Dragovich, 1988a; Dragovich, 1988b; Dragovich, 1993a; Duerden et al., 1986; Engel and Sharp, 1958; Glazovskaya, 1968; Hooke et al., 1969; Krinsley and Anderson, 1989; Kfinsley and Dora, 1991; Krumbein, 1969; Lakin et al., 1963; O'Hara et al., 1989; O'Hara et al., 1990). There is also considerably chemical variability. In some places, trace elements like barium may reach minor element proportions. In other places, barium is below the limit of detection. In some places, fragments of organic matter are commonly mixed in and underneath varnish; in other places, organic matter is lacking altogether. The spatial heterogeneity of varnish chemistry can be illustrated through chemical analyses and visually. Table 10.2 presents the bulk elemental chemistry of rock varnishes in deserts. Although several milligrams were measured together to average internal heterogeneity, there is still a lot of variability in the chemistry of varnish in different places and in different geomorphic positions. The chemical variability is not limited to desert regions. Table 10.3 demonstrates both the intrasite and intersite variability. Manganese and silica show the highest variability, since these are major constituents and they are negatively correlated. However, all constituents show place-to-place and intrasite variability that often exceeds 25%. Consider the chemistry of stream varnish in Virginia (Table 10.4). Intersite

199

200

Chapter 10

variability for manganese ranges from 30% to 50% by weight. Although lower in abundance, the ranges from other elements are greater. Calcium, for example, ranges from 1.6% to 7.9%. The larger conclusion is that non-desert rock varnishes have a chemistry similar to desert rock varnishes, and that they display considerable variability. The variability in the constituents of subaerial varnishes can be considered from the perspective of different places in the world (Table 10.5) and from different places within a localized region (Table 10.6). These results reveal that intrasite variation displayed in Table 10.5 is similar t6 intersite variation displayed in Table 10.6. Furthermore, averaging many different electron microprobe measurements averaged together yields a general compositional picture similar to bulk chemical analyses (Table 10.2) (Engel and Sharp, 1958; Lakin et al., 1963).

Table 10.2. Examples of elemental variation exhibited in bulk chemical analyses of rock varnishes found in desert regions. SITE:

POSITION: Na Mg AI Si P S K Ca Ti Mn Fe Ni Cu Zn Rb Sr Zr Ba Fb

Salt TrailFan, Manix Makanak Sinai Petroglyph Ingenio, Ayers Peru Rock, Springs, D e a t h Lake, a Till, Peninsula, South Mojave Valley Mojave Hawai'i Egypt Australia Desert Australia Desert* Desert Unknown Former Rock Fracture 0.25** bid*** 4.4 0.14 25.84 23.74 37.49 39.09 1.61 0.49 na 0.7 2.35 3.45 0.8 4.87 0.74 1.52 11.77 10.87 14.5 13.47 na 0.13 na 0.12 na 0.27 na bid na bid na 0.29 0.25 0.85 na bid

> lm Above Soil 1.1 3.44 25.77 32.35 1.15 0.3 2.11 1.35 0.84 12.47 18.09 bid 0.22 0.3 0.25 0.21 0.22 0.19 0.74

With Silica Skin 0.62 1.98 21.13 29.77 0.69 0.2 3.3 4.89 0.73 13.6 21.13 bid 0.33 0.49 bid bid bid 0.16 0.98

>lm Above Soil 0.28 1.5 22.94 32.81 bid bid 2.42 2.91 0.68 11.97 22.94 bid 0.25 0.42 bid 0.42 bid 0.18 0.27

> 1m Above Soil 0.17 1.21 22.81 33.34 0.53 bid 2.79 2.18 0.65 21.7 13.26 bid 0.44 0.44 bid bid bid 0.14 0.34

At Soil Surface na**** 2.11 20.45 45.88 0.53 1.13 2.91 6.22 0.85 4.94 12.03 bid 0.04 0.16 bid 0.11 bid 2.42 0.22

From Rock Fracture na 1.58 28.77 35.69 bid bld 2.11 1.45 1.19 11.91 16.57 bid bid bid bid bld bid 0.73 bid i

i

* Results are normalized to 100% ** Measurements by PIXE (Cahill, 1986), except for the Salt Springs sample which were analyzed by electron microprobe (Potter and Rossman, 1979a). *** Below limit of detection **** Not available

201

Rock Varnish

Table 10.3 Analyses of rock varnishes in non-desert environments. Measurements were made with the electron microprobe. The saprolite sample (data from Weaver, 1978) had a water content of 11.95%. The Icelandic varnish came from a subsurface position (data from Douglas, 1987), but the other analyses were on subaerial varnishes or varnishes exposed to water flow. Ave (n) refers to the number of electron microprobe analyses averaged. SD refers to the standard deviation. Table abbreviations are as follows: nm, not measured; nr, not reported; and bid, below limit of detection. Site

Na20 MgO AI20 3 SiO2 P205 SO3 K20 CaO TiO2 MnO Fe20 3 BaO Total

Saprolite

nr

0

21.51 25.64nr

nr

0.67 0

Iceland

0.23

0.66

27.18 25.400.04

nr

0.26

1.73 1.47 9.90

1 . 2 6 14.76 18.67 4.08 0.10

0.92

1.04 0.55 16.34 21.00 1.66 80.37

0.39

Lake Louis Ave bid (reservoir) (5) shoreline, SD bid Wyoming

Mt. Van Ave bid Valkenburg (49) Antarctica SD bid

2.33

622

0.33 1.22 5.41

66.73

10.51 nr

77.39

0.79

0.07

0.34 0.12

1.86 16.36 21.98 2.50

0.24

1.16 1.92 1.09 20.15 11.05 1.90 80.20

0.66

0.38

0.63

1.83

7.04 0.90

0.31

11.58 3.45

1.15

5.37

1.17 3.24

29.309.45

0 . 8 3 1.39 4.22 0.26 31.39 0.98

0.37

82.65

020

2.18

11.15 3.97

029

0.15

2.96

PopoAjie River, Wyoming

Ave 0.11 1 . 0 4 5.27 (10) SD 0.26 0,29 2 2 5

28.92 9.78

1.31 1.39 10.20 0.15 25.00 1.57

0.70

85.42

11.24 3.44

0.55

029

0.54

3.37

Boulder, Sky Lake, TienShan, China

Ave 0.30 1.85 13.62 23.51 nm (211) SD 0 . 2 3 0.39 2 . 6 1 5.02 nm

nm

1.82 1.47 0.73 19.83 10.89 1.76 75.78

nm

0.35 0.36

Ave 0.04 (9) SD 0.13

031

1.62

5.87

2.90

321

3.71

r~g, So.

1.14

0_52 5.79

nr

0.49 8.63

0.83

0.10 10.30 0.84

0.32 5.30

2.09

0.56

12.02

Table 10.4. Energy dispersive semi-quantitative analyses of rock varnish in streams in Virginia, normalized to 100% (Robinson, 1993). Elements below the limit of detection (-0.8%) are listed as nd. Values are elemental weight percent. Stream War Branch Goodwin Creek Elk Run Elk Run

N a i

1.1 0.4 0.7 0.2

Mg 0.4 0.3 3.0 0.3

A1 10.4 4.7 11.6 10.8

Si 14.6 22.2 15.8 23.5

i

K nd 0.7 nd 1.5

Ca 4.4 3.7 1.6 7.9

Mn 43.3 50.2 43.8 30.1

Fe 25.8 17.8 23.5 25.7

Chapter 10

202

Table 10.5. Averages and standard deviations of electron microprobe analyses of rock varnishes from different desert regions: New South Wales in Australia (Dragovich, 1988b); Nasca line in Peru; alluvial fan in Tunisia (White et al., 1996); the Takla Makan desert in western China; and the Sonoran Desert in Arizona (Perry, 1979). Ave (n) refers to the number of electron microprobe analyses averaged. SD refers to the standard deviation; nr means not reported. Site

Na2OMgO A1203 SiO2 P205 SO3 K20 CaO TiO2 MnO Fe20 3 BaO Total

New South Wales

Ave 0.60 1.25 23.38 28.73 2.28 0 . 1 7 1.11 1.09 0.87 15.14 15.01 (~0) SD 0 . 3 5 0.10 1.41 5 . 0 3 0 . 4 3 0 . 0 5 0.31 0.49 0.23 7.75 2.00

Nasca line Peru

Ave 0.12 0.86 17.65 21.08 1.61 0 . 1 2 1.53 1.00 0.50 15.34 21.66 1.68 83.14 (10) SD 0 . 0 5 0.34 1.82 1.89 0.71 0 . 1 0 0.38 0.49 0.33 8.21 12.40 0 . 7 3 3.31

Alluvial Ave 0.22 2.05 12.36 24.83 0.47 1.35 1.40 1.10 0.71 16.05 8.51 fan (10) Tunisia SD 0.20 0.37 1 . 4 0 4 . 3 0 0 . 3 0 0 . 8 6 0.50 0.45 0.23 2.31 0.75 Takla Makan China

0.70 90.57 0.35 2.54

4.88 73.92 1.19 5.17

Ave 0.08 1.99 16.14 23.42 1.55 0 . 0 3 1.42 1.57 0.56 17.39 14.06 1 . 0 0 79.22 (25) SD 0 . 0 5 0.55 1 . 5 4 3 . 1 3 0 . 3 3 0 . 0 4 0.37 0.20 0.13 5.10 1.58 0.27 4.37

Sonoran Ave 0.21 2.48 23.19 30.95 1.25 0 . 1 7 1.76 0.94 0.62 11.55 19.00 Desert (8) Arizona SD 0 . 0 8 0.55 2 . 7 1 5 . 2 4 0 . 1 7 0 . 0 3 0.37 0.25 0.14 9.41 4.67

nr

92.11

nr

2.23 i

9

Table 10.6. Averages and standard deviations of electron microprobe analyses of rock varnishes within four regions. This table is characterized by samples coming from different geomorphic surfaces in a region: for Bishop Creek, samples came from 156 different places from glacial moraines; for Death Valley, 300 locations from alluvial fans; for the Mojave Desert, 100 petroglyphs; for South Australia, 20 alluvial fan boulders. Site

Na20 MgO A1203 SiO2 P205 SO3 K20 CaO TiO2 MnO Fe20 3 BaO Total

Bishop Ave 0 . 0 9 1 . 0 6 13.54 21.45 2.13 0.15 0.96 1.03 0.79 16.99 15.91 0.26 74.37 Creek (156) California SD 0.22 0 . 6 1 2 . 9 6 7 . 8 4 0.96 0.21 0.58 0.34 0.36 14.33 3.26 0 . 2 7 6.18 Death Ave 0.29 Valley (300) California SD 0.23

1.61 16.77 20.81 2.01 0.20 1.34 1.22 0.62 14.44 12.16 0.65 72.12 0 . 6 0 2 . 7 3 4 . 2 5 0.73 0.24 0.34 0.52 0.57 8.30 2 . 7 2

Mojave Ave 0 . 2 3 0 . 8 1 11.26 33.69 1.12 0.17 1.08 1.11 0.50 23.07 7.73 Desert (115) Califomia SD 0.45 0.61 7 . 7 4 23.55 0.89 0.21 0.75 0.66 0.56 18.13 5.87 Olary Ave 0.16 South (100) Australia SD 0.39

0.66

8.68

0 . 6 2 81.38 0 . 5 9 9.57

1.55 16.80 26.35 2.15 0.06 1.15 0.86 0.68 16.18 14.70 0.50

81.15

0 . 5 5 1 . 9 6 7 . 6 6 0.39 0.12 0.35 0.39 0.24 6.87 2 . 8 8 0 . 2 5 3.88

203

Rock Varnish

The most detailed work on the trace element chemistry of varnish was done with the aid of neutron activation (Bard, 1979; Bard et al., 1978). Varnishes were scraped from andesite boulders and petroglyphs on shorelines of Pyramid Lake, Nevada. Table 10.7 exemplifies data obtained in the dissertation of James Bard. Most of the trace elements found in rock varnish are highly correlated with the abundance of manganese. This is likely because of the scavenging ability of manganese oxides (Filipek et al., 1981; Jenne, 1968; Loganathan and Burau, 1973; Robinson, 1981; Saeki et al., 1995). Silicon is not measured by neutron activation, but microprobe measurements indicate that silica is inversely proportional to manganese, and its co-associated elements: Ca, V, As, U, Ba, Sm, La, Lu, W, Mo, Co, Sc, Sb, Th, Zn, Ce, Yb and Nd.

Table 10.7. Neutron activation analyses for a rock varnish at Eetza Mountain, near Fallon, Nevada (Bard, 1979).

Element

Surface Layer 2nd 'i~ayer

3rd Layer

4th Layer

5th Layer

8.34 5.4 2.36 0.65 21751 7.28 250 14.86 52.5 12.72 5621 17.96 111.83 0.82 37.47 6.82 81.62 19.12 2.28 2.08 41.1 28.34 22 18 2.07 186 4.22 342.2 3.38 0.45 6.53 103.8

9.03 7.0 2.38 0.44 18601 7.07 200 11.50 48.8 11.71 5200 16.19 101.48 0.80 29.24 8.15 73.24 19.02 1.99 1.62 43.6 24.45 49 13 1.83 192 3.9 300.1 3.15 0.43 5.95 91.4

8.6 4.9 2.43 0.29 17771 6.99 246 16.82 44.4 11.27 4896 15.23 94.32 0.71 26.15 6.74 70.45 18.75 2.08 1.59 39.5 22.31 46 25 1.78 182 3.68 283.8 3.19 0.41 5.64 86.1

i

AI % Ca % Na % Ti % Mn ppm Fe % V ppm Dy ppm As ppm U ppm Ba ppm Sm plma La ppm Lu ppm W ppm Mo ppm Co ppm Sc ppm Cs ppm Sb ppm Cr ppm Th ppm Ni ppm Rb ppm Tb ppm Zn ppm Eu ppm Ce ppm Hf ppm Ta ppm Yb ppm Nd ppm

8.95 5.7 2.18 0.42 22651 7.53 280 16.04 60.7 13.76 5777 20.34 126.58 1.01 44.1 11.54 94.12 20.59 2.59 2.57 50.1 36.39 53 23 2.29 200 4.67 417.9 3.4 0.44 7.42 116.9

8.7 5.4 2.35 0.44 21751 7.5 276 17.13 64 13.36 5715 19.16 119.28 0.92 38.21 7.5 85.87 19.95 1.84 2.45 42.2 32.32 44 25 2.15 209 4.46 377.6 3.36 0.43 6.91 110

204

Chapter 10

Some generalizations can be made from the above chemical analyses. 1) Silica and aluminum, taken together, comprise the bulk of rock varnish. This is consistent with clays being the dominant mineralogy. 2) Manganese and iron oxides comprise one-quarter to one-third of rock varnish. However, there is a tremendous amount of point-to-point variability in their abundance; clays are high when oxides are in lower abundance. 3) The minor elements display variable patterns. Generally, Mg, K, and Ca are correlated with clays in cation-exchange positions and not with manganese. Ba is often correlated with S in barium sulfates (Cremaschi, 1996; Dorn et al., 1990; O'Hara et al., 1989). In other cases, both Ba and Ca are correlated with Mn (Reneau et al., 1992). P is sometimes correlated with iron and sometimes with Mn. Ti can be correlated with Fe in titanomagnetite detrital grains, but more often Ti is not well correlated with any major element. 4) The trace elements are generally correlated with Mn abundance, and sometimes with Fe. 5) Because varnish is porous, contains water, carbon, and a great number of trace elements, electron microprobe measurements typically have total measurements that are far less than 100%. These generalizations, in summary, do not greatly alter the fundamental findings in the seminal work of Engel and Sharp (1958). An alternative perspective on the chemistry of rock varnish is to examine the larger picture, literally. When rock varnishes are ground down very thin, it is possible to see through normally opaque layers. When viewed in cross-section with an optical microscope, there are orange, yellow and black layers. Orange and yellow layers are not enriched in manganese and black layers are manganese-rich (Perry, 1979; Perry and Adams, 1978). Figure 10.10 is an example of layers that can be found in rock varnish.

Figure 10.10. Optical ultra thin section of rock varnish from Galena Canyon alluvial fan, Death Valley. The rock varnish is about 200 I.tm in thickness. The dark layers appear black under a microscope. The gray layers are mostly orange, but the lightest gray layers are yellow. This thin section was prepared by Liu (1994).

Originally, only two layers were recognized in many varnishes: a bottom layer rich in iron and a top layer rich in manganese (Engel, 1957; Hunt and Mabey, 1966; Krumbein, 1969). I believe that this is a relatively common sequence that is produced

Rock Varnish

by the opening of rock crevices. Iron films grow in closed rock crevices (chapter 9); as the crevice opens, manganese-rich black varnishes grow over orange, iron films - - all in the rock fracture. When the varnish is truly subaerial in its genesis, the type of layering pattern seen is much more complex, like those reported by Liu and Dorn (1996) and seen in Figure 10.10. There is often a much more complex story in the layering of rock varnishes, spearheaded by the research of Tanzhuo Liu (Liu, 1994; Liu et al., 1997; Liu and Dorn, 1996). Liu explains the three colors seen in cross-sections. Yellow colors form during hyper-arid intervals and are the richest in clay minerals, iron, and tend to be enriched in C1. Orange colors form during arid periods; they can have manganese enrichment of a few percent. Black layers accrete during semi-arid periods in regions that are now deserts and are greatly enriched in manganese over one hundred times above adjacent dust, soil and rock material. Liu's visual work reveals that layering patterns are consistent within a particular region (e.g. Death Valley, California, the Dead Sea, western China, Patagonia), and that these layering patterns may also correlate with larger-scale climatic changes. Chemical variability in rock varnish can also be mapped with X-rays (Figure 10.11). X-ray mapping confirms earlier findings that the optical layers correlate with chemistry (Dom, 1990; Perry and Adams, 1978).

Figure 10.11 X-ray mapping of a thin section of rock vamish from Death Valley, courtesy of Tanzhuo Liu. White indicates the highest concentrations. Note, for example, that the uppermost layer (the Holocene) is rich in Si, A1, Mg and CI, but is not enhanced in Mn.

The great chemical variability reported in rock varnishes may be in part from different layers being analyzed. There is also considerable evidence to indicate that great chemical variability occurs from the analysis of different places in varnishes that are not well layered (Dora and Krinsley, 1991; Krinsley and Dora, 1991; Liu, 1994).

205

206

Chapter 10

10.2.2.6. Micromorphology Interest in the form of rock varnish began with the use of scanning electron microscopes (SEM). While optical microscopy had been used to examine varnishes in cross-section (Haberland, 1975; Hunt, 1961; Lucas, 1905; Perry and Adams, 1978), the characterization of varnish morphology began in earnest with SEM. The first observations of varnish indicated a fiat, smooth micromorphology. Krumbein (1969, p. 353) characterized "desert varnish" as having a "lamellate structure...whose particle size is almost extremely small..." Figure 10.12 and 10.13 exemplify this morphology, certainly the most common in arid settings.

Figure 10.12. Secondary electron image of lamellate rock varnish on the high shoreline of Lake Lisan, a paleolake of the Dead Sea, Israel. Note the subparallel accretion of clay particles on the varnish surface.

Figure 10.13. Secondary electron image of lamellate rock varnish on a debris cone of Death Valley, Califomia Note how the clays impose a lameUate structure in cross-section, as first noticed by Potter and Rossman (1977).

Rock Varnish

Subsurface varnish formed in saprolite fractures surfaces in the southeastern United States have a fiat, clay-oriented fabric (Weaver, 1978). Potter (1979, p. 172-173) similarly characterized Mojave Desert varnish as flat with "a coherent fabric due to clay minerals oriented roughly parallel to the rock surface. Perry (1979, p. 15) observed that microlaminations in cross-sections can be "traced laterally for several millimeters" in these smooth varnishes. Whalley and colleagues observed similar textures in Afghanistan, Norway, and Tunisia (Smith and Whalley, 1988; Whalley, 1983; WhaUey, 1984; WhaUey et al., 1990). "Dendrite-type structures" (Perry, 1979, p. 23) were noted on an Idaho varnish; this is essentially a tongue of a newer layer of Krumbein-texture varnish with a longer length than width. Rougher surface micromorphologies also occur. Perry (1979, p. 20-21) documented the occurrence of "botryoidal growth-structures" that are "mound-like" and "enlarge, coalesce, and are succeeded by new mounds as varnish accretes." Botryoids vary in height from "a few micrometers to as much as 40 micrometers (Perry, 1979, p. 20)." Figures 10.14, 10.15, and 10.16 exemplify botryoidal varnishes.

Figure 10.14 Secondary electron image of botryoidal rock vamish at the North Summit of Mt. Ellen, Henry Mountains, Utah. The sample was collected by J. Bendix.

Figure 10.15 Secondary electron image of botryoidal rock vamish at Point of Rocks Picnic Area, Davis Mountains, west Texas.

207

208

Chapter 10

Figure 10.16. Botryoidal varnishes from Kitt Peak, Arizona, seen in two perspectives. The view on the left shows the topography by secondary electrons. The view on the right shows these structures from the bottom upwards with backscattered electrons.

Other, less common, morphologies occur. "Looped structures" were seen on varnish from Stoddard Wells in the.Mojave Desert (Perry, 1979, p. 22); this term described sinuous and anastomotosing micron-scale fibers that have the appearance of montmorillonite (Robert and Tessier, 1992). Smoothed-mounds were also noted at Stoddard Wells in the Mojave Desert (Perry, 1979, p. 24): "This sample was collected from a stone pavement where prevalent winds may cause wind-abrasion and subsequent polishing of the varnish surface." A "wrinkled coat" micromorphology was noted by Whalley (1983, p. 208) that was felt to be a primary depositional features, perhaps related to dehydration. Also, micron-scale "protuberances," some of which are enriched in Mn or Fe rich, are on top of the wrinkles. The vast majority of rock varnishes have micromorphologies that range between lamellate and botryoidal. A number of factors can influence micromorphology, including clay content, manganese abundance, epilithic organisms, morphology of the underlying rock, varnish thickness, eolian abrasion, proximity to soil, and other microenvironmental factors (Dorn, 1985; Dorn, 1986). Figure 10.17 exemplifies the importance of local controls on varrtish form that may be only a few microns apart. The microenvironmental effect seen in Figure 10.17 is consistent with what is known about lamellate varnish. The clay minerals in the rock fracture impose more of a layered structure than the botryoidal varnishes seen on a surface where clays can be washed off with precipitation There also appears to be a general regional correlation between micromorphology and vegetation abundance. Abundant vegetation correlates with micromorphologies that are botryoidal, whereas less vegetation cover is associated with lamellate structures (Dorn, 1985; Dorn, 1986). This is probably because dust is less common in humid regions, and manganese-rich botryoidal centers are able to grow in discrete clusters. In contrast, areas of less vegetation contain more dust. According to this interpretation, clays overwhelm and literally bury tendencies towards nucleation of manganese around discrete clusters.

Rock Varnish

Figure 10.17. Secondary electron image of two different side-by-side vamish morphologies collected from the Poverty Hills, Owens Valley, eastem Califomia. The lamellate varnish on the right side of the micrograph formed in a rock crevice. In contrast, the botryoidal forms on the left side grew in a subaerial environment. The scale bar is 4 microns.

10.2.2.7. Textures Seen in Cross-Section

Rock varnish cross-sections have different appearances depending upon the technique used, including light transmitted through thin sections (see section 10.2.2.5; Engel and Sharp, 1958; Haberland, 1975; Hume, 1925; Hunt, 1954; Laudermilk, 1931; Liu, 1994; Lucas, 1905; Perry, 1979), secondary electrons (Dorn, 1984; Dorn, 1986; Perry, 1979), backscattered electrons (Haberland, 1975; Krinsley and Dorn, 1991; Krinsley et al., 1990; Krinsley and Manley, 1989; Nagy et al., 1991; Raymond et al., 1992; Raymond et al., 1989; Reneau et al., 1992), and transmitted electrons (Krinsley et al., 1995; Raymond et al., 1992). This section explores how varnishes appear in cross section when viewed by different types of electron microscopy. Figure 10.18 compares images made by backscattered, secondary, and transmitted electrons, Backscattered electrons show an overall layering pattern, with secondary electrons revealing that the layers are broken up into overlapping subparallel structures. At very high resolution, seen with transmission electron microscopy, these layers are in turn composed of even smaller subparallel units that are mixture of clays and oxides. The clay minerals impose the lamellate structure seen at the resolution of secondary electrons and resolved with high resolution transmission electron microscopy. High resolution transmission electron microscopy, conducted in collaboration with Dr. David Krinsley (Krinsley and Dorn, 1995), has revealed that clay minerals gradually weather in place. Figure 10.19 shows imagery of clay minerals at different scales. The lattice structures are gradually breaking apart as manganese and iron oxides mobilize and reprecipitate between the lattice structures. This creates 'monolayers' at the scale of nanometer (Robert and Tessier, 1992). Figure 10.19 is organized at different spatial scales, from lower resolution in the upper left to very high resolution in the lower

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fight. All o f the images show that the regular lattice spacing of clay minerals is disturbed by weathering within the varnish. A classic question in rock varnish is whether or not rock varnish derives from the underlying rock. This question was resolved in the late 1970s when scanning electron microscope imagery shows distinct boundaries between the rock and the overlying rock varnish (Allen, 1978; Perry, 1979; Perry and Adams, 1978; Potter and Rossman, 1977). Many images presented throughout this chapter reinforce the idea that rock coatings are accretions. Figure 10.20 shows that there is a clear contact for rock varnish even at the scale of n a n o m e l e r ~ _

Figure 10.18. Different types of electron microscope imagery from Death Valley imagery in row A, Antarctica in row B, and Peru in row C. The backscattered electron (left column) and secondary electron (middle column) imagery provides different perspectives on the samples. The HRTEM imagery (right column) yields much more detailed information. The secondary images are of samples mechanically broken, and the varnish/rock contact (arrows) was determined with the aid of energy dispersive X-ray analyses; these varnishes were coUected a few millimeters away from the section imaged by both BSE and HRTEM. The BSE imagery shows the complete section before ion milling prepared the sample for examination with HRTEM; the double arrow in the middle of the BSE image of Antarctic varnish 031) shows the location of an angular unconformity. The scale bar is in micrometers.

Rock Varnish

Figure 10.19. Weathering of clay minerals in samples from Hawai'i (A,G,K,M), Antarctica (B,D,F,L,N), Peru (C,I), and Death Valley (E,H,J,O) as revealed by transmission electron microscopy imagery with scale bars in nanometers. Images A and B illustrate areas where the organized lattices of mixed-layer illite-montmorillonite clays are starting to separate--highlighted by the arrows. Image B shows a transition in an illite grain from more (left) to less (right) organized material. Images C and D illustrate the migration of granular-textured material into clay minerals, highlighted in image C with an arrow. In image D, the granular material runs from upper left to lower fight and the splitting clays rest on top (between arrows). The arrows in images E-L illustrate the separation of clay minerals into mono-layers (Robert and Tessier, 1992). In some cases, mono-layers feather in the middle of a clay pod (E,F,H). In G, the arrow highlights separation at the contact between two less-weathered clays; the darker grain below the arrow is too thick to be electron transparent. The tip of a clay mineral is starting to separate into mono-layers at about the position of the arrow in image I. The arrows in images J and K exemplify the ubiquitous wavy texture from spalling' along the individual 001 planes. Images L-O illustrate regular lattice spacing juxtaposed against more chaotic textures, all within a single pod. In L, the arrows highlight places where laminae separate and develop an amorphous character. Lattice spacing on the left side of M, lower part of N and left side of O is consistent with iUite and textural interstratified clay (Banfield and Eggleton, 1988; Mall and Komameni, 1989; Robert et al., 1990); the opposite sides illustrate a more disorganized pattern of clay weathering and areas of amorphous (less crystallized) textures.

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Figure 10.20. TEM imagery reveals a clean contact between rock and vamish from (A) Nazca, Peru (B) Antarctica (C) Death Valley (D) Kaho'olawe Island, Hawari. Open arrows indicate the contact. The dark arrow in D shows an ambiguous contact, probably because the rock rests overlying the varnish (or visa versa) in the TEM foil. As in all TEM imagery, the scale bars are in nanometers.

10.2.2.8. Post-Depositional Modification Post-depositional modification is where the varnish changes after it is originally laid down. Probably the most important post-depositional modification is the leaching of cations from rock varnish. Cation exchange (CE) in soils occurs with smectites, hydrous mica, chlorite, interstratified minerals, kaolinite, oxides and hydroxides and organic compounds (Talibudeen, 1981; Tucker, 1983); all of these are found in rock varnish. In addition, both Mn- and Fe-oxides can serve as cation-exchange complexes (Jenne, 1968). Hence, it should not be surprising that rock varnish experiences cation exchange. High resolution transmission electron microscopy reveals that the vast majority of varnish consists of submicron-sized grains (Figure 10.18, Figure 10.19, Figure 10.20). Consequently, large surface areas are available for CE. Little is known about the rates and kinetics of adsorption in natural environments, however, especially in environments like rock varnish; it is clear, however, that CE processes go on as solutions pass through submicron-sized and micron-scale pores. Clay minerals develop a negative charge and attract cations to exchange positions because of isomorphous substitution. A1 (III) in octahedral layers and Si (IV) in tetrahedral sheets are replaced by ions of smaller valence, for example Mg (II), Fe (II),

Rock Varnish

Zn (II) and Ni (II) (Goulding and Talibudeen, 1980). In order to keep electronuetrality, exchangeable cations are attracted. These charge-compensating cations are found in clays within interlayer positions (e.g., smectites), in structural holes, on fracture surfaces, where interlayers are disturbed by hydration or a foreign cation and on external surfaces (Talibudeen, 1981). The mixed-layer illite-montmorillonite clays, for example, have a stronger preference for K, Rb and Cs due to the match of cation size and structural holes in minerals (Brown et al., 1978). Visual (Dorn and Krinsley, 1991; Krinsley et al., 1990; Liu, 1994; Liu et al., 1997; Liu and Dora, 1996) and chemical evidence (Dorn, 1989; Dragovich, 1997; Glazovskiy, 1985; Pineda et al., 1990; Whitley and Annegard, 1994; Whitney and Harrington, 1993; Zhang et al., 1990) all point to cation leaching as an important process in rock varnish. However, arguments have been made that cation-leaching does not occur in rock varnish (Reneau et al., 1990; Reneau et al., 1992). Yet, the evidence for postdepositional modification by leaching is too strong to ignore; it includes layers in rock varnish are interrupted by pockets of chaotic structure (Figure 10.21), and the redeposition of the leached material (Figure 10.22) that cannot be explained without cation leaching.

Figure 10. 21. Backscattered electron image of rock varnish growing on Starvation Canyon Fan, Death Valley. Note how even layering is broken in the upper right hand part of the varnish (arrow). In addition, there are pockets of micron-scale leaching in the lower layer.

There has long been an interest in rock varnish as an agent of case hardening of soft rocks or weathered substrates (Butzer and Hansen, 1968; Daveau, 1966; Demangeot, 1971; Karlov, 1961; Kiersch, 1950; Oberlander, 1977; Peel, 1960; Tricart, 1972; Tricart and Cailleaux, 1964; Wilhelmy, 1964). Chapter 6 presented clear evidence that some of the material leached out of the rock varnish reprecipitates within the underlying host rock, promoting case hardening.

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Figure 10.22. Post-depositional modification of varnish from (A,C) Antarctica and (B,D) Death Valley. The upper imagery is by HRTEM with scale bars in manometers. The lower imagery is by BSE (scale bars in micrometers) is of a different section, collected a few millimeters away from the high resolution transmission electron microscope section. The arrows in B shows where the 'tube' of reprecipitated varnish is covered and re-emerges from undemeath the layered varnish. The arrows in C and D highlight tubes of mostly reprecipitated Mn-Fe (measured by energy and wavelength dispersive X-ray spectrometry).

10.2.3. Classification of Rock Varnish 10.2.3.1. Prior Perspectives on Classification Rock varnish (or "desert varnish" or "patina") means different things to different investigators. Most frequently, these terms are applied to dark coatings on rocks, typically 20 1/5 to 1/66, 1/12 to 1/20 1/10 to 1/16 1/8 to 1/12 1/4 to 1/6 1/2 to 1/4 1/7 1/lto 1/2 ,

,

Rock Varnish

An early explanation for the origin of rock varnish involved the deposition of pollen (White, 1924). Pollen remains, however, are only infrequently seen directly incorporated into rock varnish (Figure 10.28).

Figure 10.28. Scanning electron micrograph of an oak pollen grain being incorporated into rock varnish. Fungal filaments surround the pollen grain.

It may be that some of the enrichment in rock varnish could be from manganese having a source in biological materials, that are then reworked by heterotrophic organisms. For example, the microcolonial fungi that are abundant on rock surfaces (Dragovich, 1993a; Staley et al., 1983; Staley et al., 1982) are heterotrophs and may obtain nutrients in part from pollen and other organic deposits. In summary, plant remains show the greatest enrichment of manganese of all of the potential sources. Regardless of the source of the manganese, however, mobilization of divalent maganese is needed to move the cation from source to sink. Then, another mechanism(s) is needed to stabilize manganese by oxidation to Mn (IV).

10.3.3. New Polygenetic Model of Varnish Formation This section presents a new model for rock varnish formation, where both biotic and abiotic processes are involved. The three key ingredients in both rock varnish and this model involve clay minerals, biotic enhancement of manganese, and to a lesser extent the enhancement of iron. Hence, this section first explores the nature of clay minerals in rock varnish. Then, I turn to an exploration of manganese enhancement. Lastly, these components are synthesized in this new polygenetic model.

10.3.2.1. Clay Minerals at the Building Block Level

Clay mineral weathering is ubiquitous in rock varnish (Figure 10.19). The clay minerals (illite, smectite, interstratified illite-smectite, chlorite) which compose the

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bulk of varnish (Potter, 1979; Potter and Rossman, 1977) also weather. The clay minerals start out as 'pods' with regular lattice spacings and coatings (Robert and Terce, 1989), Then, clays begin to feather into mono-layers (Robert and Tessier, 1992). These mono-layers are separated by nanometer-sized possible unit-cells that are similar in appearance to some biomineralized iron (Mann et al., 1993; Robert and Terce, 1989) and manganese (Kuznetsov, 1970; Mackenzie et al., 1971; Mulder, 1972; Perfirev et al., 1965; Vojak, 1984). Evidence for clay-mineral weathering can be found in Figure 10.19. At lower magnifications, detrital grains of clays appear to split at the edges; the splitting process is sometimes associated with the migration of darker material--presumably migrating Mn, Fe that should be more resistant to electron beam (arrow in Figure 10.19A). Figure 10.19B shows transition in an illite grain from organized (left) to more disorganized (fight) as the grain weathers; regular lattice spacings split in association with possible bacterial textures (granular areas, discussed later). A typical pattern is found in Figure 10.19C, where there are 5-6 discrete layers that may have started out as different detrital grains (along with granular bacterial texture, discussed later); however, within each layer even lattice spacing is a rarity; wavy mono-layers dominate. At higher magnification in Figure 10.19, within a single 'pod-detritar clay mineral grain (Figure 10.19D-6F), there is evidence of irregular lattice spacing, indicating separation and the development of mono-layers (arrows in Figure 10.19E-I)~ essentially 001 planes of exfoliation (Robert and Tessier, 1992). In many cases, the feathering is associated with granular textures (of possible bacterial origin, discussed later), as in Figure 10.19D. Consider the arrow in Figure 10.19G, which shows the splitting of the upper illite grain associated with nanometer-sized unit-cells, while the material on the fight side is so disorganized lattice spacing cannot be discerned; the darker grain on the lower left is too thick to be electron transparent. The lower part of Figure 10.19J shows regular spacing, while the upper part shows wavy monolayers and abundant nanometer-sized unit-cells. The monolayers (wavy lines) in Figure 10.19K consist almost entirely of connected unit-cells. At the highest magnifications used (Figure 10.19L-O), disorganized wavy layers rest next to regularly spaced lattice fringes (with spacing that is consistent with illite, smectite, chlorite, and interstratified clay~textural interstratification) (Banfield and Eggleton, 1988; Mall and Komarneni, 1989; Robert et al., 1990). The juxtaposition of organized versus wavy layers may be 'born' when varnish is initially deposited, or it may be a product of gradual in situ diagenesis; however, some in situ diagenesis seems probable given the long times involved. However, the feathering of the clay minerals in rock varnish is a new observation and a key element in its growth.

10.3.2.2. Manganese Enhancement

The general consensus over abiotic vs. abiotic mechanisms of manganese enhancement has largely shifted in the last few decades towards microbial models of genesis. This is true for several reasons: (1) the pH conditions on manganese-rich varnishes in deserts (Dora, 1990) are not high enough to oxidize manganese by inorganic processes (Uren and Leeper, 1978); (2) the rock surfaces that do change local pH conditions (e.g., adjacent to lichens) lack varnish (Dora and Oberlander, 1982; Dragovich, 1986b);

Rock Varnish

(3) fixation of Mn by clay minerals (EI-Demerdashe et al., 1982; Reddy, 1973; Reddy and Perkins, 1976) yield Mn concentrations orders of magnitude below values found in rock varnish; (4) the distribution of incipient rock varnish as millimeter-scale patches is suggestive of biological colonization, while a chemical process would yield a more uniform deposit (Dorn and Oberlander, 1982); (5) rock varnish occurs in acidic environments that do not experience high enough pH values to oxidize Mn (Dorn and Oberlander, 1982; Douglas, 1987; Krumbein, 1969); (6) organic matter is common as a trace compound within rock varnish (Dorn and DeNiro, 1985; Merrill, 1898); (7) manganese-rich varnishes are less common in hyper-arid/hyper-alkaline regions (Jones, 1991); (8) varnish grows rapidly in periglacial and riverine environments (Dorn and Oberlander, 1982; Klute and Krasser, 1940) which do not have sufficient alkalinity or high enough pH values to oxidize Mn, but there is a slow rate of varnish growth in deserts that do experience these fluctuations (Dorn and Oberlander, 1982; Whalley, 1983); (9) no laboratory experiment has yet produced Mn-rich varnish with Eh-pH fluctuations; (10) experimentation reveals that Mn-rich varnish is not produced abiofically (Jones, 1991); and (11) a number of studies have concluded that biological agents of manganese enhancement grow on rock surfaces and can explain the great enhancement of manganese in rock varnish (Dora and Oberlander, 1981a; Dora and Obeflander, 1981b; Dora and Oberlander, 1982; Drake et al., 1993; Francis, 1921; Grote and Krumbein, 1992; Grote and Krumbein, 1993; Ha-mung, 1968; Hungate et al., 1987; Jones, 1991; Krumbein, 1969; Krumbein, 1971; Krumbein and Jens, 1981; Nagy et al., 1991; Palmer et al., 1985; Rahm, 1974; Staley et al., 1991; Taylor-George et al., 1983). At the same time, abiotic arguments have not gone away (Elvidge and Collet, 1981; Engel and Sharp, 1958; Hooke et al., 1969; Moore and Elvidge, 1982; Smith and Whalley, 1988). These models rely on the greater mobility of manganese over iron where small pH~h fluctuations dissolve Mn but not Fe (Krauskopf, 1957). The Mn released by slightly acidic precipitation, is then fixed in clays after evaporation or change in pH. I would like to emphasize two key points in favor of abiotic arguments. First, very few examples of fossilized Mn-oxidizing microorganisms have been reportexl (Dora and Meek, 1995; Smith and Whalley, 1988). Fungal remains have been occasionally seen buffed within rock varnish (Dragovich, 1993a; Nobbs and Dora, 1993; Taylor-George et al., 1983), but these are not enriched in manganese. In other biotically-generated coatings, fossilized remains are common (Beveridge and Fyfe, 1985; Ferris et al., 1986; Konhauser et al., 1994; Schultze-Lam et al., 1996). Second, abiotic genesis could produce the forms observed with high resolution transmission electron microscopy (Figure 10.19): nanometer-scale crystals of Mn and Fe exfoliating clay minerals along 001 planes (cf. Robert and Tessier, 1992: 86). This is not to say that microbial fossils or casts of fossils encrusted in manganese are completely lacking. They do occur (Figure 10.29, Figure 10.30 and Figure 10.31), but they are rare (Dora and Meek, 1995). More commonly, there are granular forms that may be the decayed remnants of bacteria.

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Figure 10.29. Backscattered electron micrograph of Mn-rich rod-shaped bacterial casts in rock varnish from Kaho'olawe, Hawai'i.

Figure 10.30. Backscattered Oeft) and transmission electron (righ0 micrographs of cocci-forms, encmsted with manganese, in a rock varnishes from Marie Byrd Land, Antarctica. The underlying rock is quartz. The bright cell walls in backscatter are likely composed of granular deposits seen in the TEM image. Images were from the same sample, but not the same thin section.

Figure 10.31. Possible bacterial remains visible with transmission electron microscopy, from Antarctica. According to focused-beam (~1-2gin) qualitative EDS analyses the areas around this object shows great enrichments in Mn. Note how the center of the cocci-like object is brighter than the surrounding material, because the electron beam is less transparent where the walls of a sphere begin to turn.

245

Rock Varnish

Granular forms are very common in four samples examined with transmission electron microscopy (Figure 10.32). These granular forms are conformal with clay minerals). Some have an oval shape, but most are linear. The granular texture is not usually found with clay minerals, but similar granular forms are associated with iron coatings on clays (Robert and Terce, 1989) and with biogenic manganese precipitates (Kuznetsov, 1970; Mackenzie et al., 1971; Mulder, 1972; Perfirev et al., 1965; Vojak, 1984). Granular features also line the edges of bacterial casts (Figure 10.30).

............

L

"

Figure 10.32. These micrographs show a transition between granular-textured material to nanometer-sized 'dot clusters', with samples from Death Valley (A,F,I), Hawai'i (B, H,G), Peru (C,E), and Antarctica (D). The scale bars are in manometers. Granular textures (A-C) may be a stage in the re-mobilization of Mn-Fe from cell-waU fragments. It is possible that the next step is a transition towards a mixture of granular textures and "dusters of dots" (F,I), followed by just dot clusters (D,E,G,H).

In the next section I propose a mdoel where these granular forms are the products of the dissolution and reprecipitation of manganese and iron in bacterial cell walls. Some manganese and iron removed from the bacterial casts is leached from the varnish into the host rock to reprecipitate in the weathering rind and aid in case hardening (chapter 6). However, some of the manganese and iron is redistributed within the clay minerals as unit cells, that in turn weather clay minerals into mono-layers.

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10.3.2.3. How Rock Varnish Grows

The initial manganese enhancement of manganese, and to a lesser extent iron, in rock varnish is most likely through the activity of bacteria, followed by abiotic processes. The first step is the concentration of manganese (and iron) on the cells walls of bacteria (Figure 10.29, Figure 10.30, Figure 10.31, Figure 10.32). There may also be some enhancement through the deposition and remobilization of organic remains on rock surfaces (Table 10.11). The second step is the mobilization of divalent manganese away from these cell walls. This could occur immediately after Mn-enhancement; or it could occur thousands of years later. Figure 10.32 shows the gradual break-down of biomineralized Mn-Fe from cells that are thoroughly encrusted (Figure 10.30). As these cell encrustations degrade, the oxides are remobilized as nanometer-scale unit cells (dots in Figure 10.19 and Figure 10.32). The granular material has a high surface/volume ratio, which in turn facilitates further dissolution, mobilization and reprecipitation. The third step is the movement of manganese unit cells into clay minerals. Potter and Rossman (1979a: 93) and Potter (1979:174-175) argued for this step without the benefit of supporting HRTEM imagery: "Clay is more than a passive contaminant in vamish. In some instances it may serve as a medium for capillary movement of varnishing solutions. Deposition of the manganese and iron oxides within the clay matrix might then cement the clay layer. The clay may aid in deposition, lnite is known to fix manganese under the pH and Eh conditions at which varnish forms (Reddy and Perkins, 1976)...the hexagonal arrangement of the oxygens in either the tetrahedral or octahedral layers of the clay minerals could form a suitable template for crystallization of the layered structures of bimessite. The average 0-0 distance of the tetrahedral layer is 3.00/~ in iUitemontmoriUonite mixed-layered clays, which differs only 3.4 percent from the 2.90/~ distance of the hexagonally closed-packed oxygens in bimessite..."

Bimessite can "appear as thin laths up to 0.3 I.tm long" (see Figure 10.7) or "as very minute (tens of Angstrom units) laths, which are coiled bent, or twisted so that they look like filaments (Chukhrov et al., 1980, p. 348-9)." Perry (1979) reported that small particles in rock varnish show a hexagonal net of spot reflections in electron diffraction. This would be consistent with the bimessite mineralogy found in infrared studies (Potter and Rossman, 1979a). The weathering of clays, the development of monolayers, and the occurrence of nanometer-sized dots in and amongst the monolayers (Figure 10.19) is fully consistent with Potter and Rossman's (1977) model where clay minerals cement Mn-Fe oxides to rock surfaces. Potter (1979, p. 174-7) wrote: "...the clay and oxide phases may be mutually dependent: the clay depending on the oxides for resistance to erosion; the oxides dependent on the clay for transport and deposition."

The only steps missing in the Cal Tech model involve the processes by which Mn (and Fe) are microbially enhanced, and then released to cement clays to the rock surface. Thus, bacterial remnants in the form of decayed cell walls and redistributed manganese and iron comprise a significant portion of total varnish volume, even if only a few of the bacteria themselves have survived diagenesis. A large uncertainty in this model concerns iron. Iron is not concentrated above crustal levels in many varnishes, while in other the enhancement can be five-fold. It is possible that some enhancement is through the concomitant concentration of iron, that occurs along with manganese (Dorn and Oberlander, 1982), or separately (Adams et al., 1992). It is possible that some of the granular morphologies include iron. Certainly

Rock Varnish

iron is the key cementing agent in Type III iron films (see chapter 9) and iron likely assists in varnish cementation. In summary, I believe that rock varnish is a by product of the weathering of bacterial casts and the weathering of clay minerals. Clay minerals will not form rock varnish by themselves. Dust films, silica glaze and other rock coatings may result from clays, but not rock varnish. Similarly, bacterially-enhanced manganese will not form rock varnish by itself; heavy-metal skins will result instead. Rock varnish grows only where and when the nanometer-scale decayed remnants of bacterial casts maneuver in between the broken and decayed fragments of clay minerals.

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Chapter 11 NITRATES

AND OTHER

UNCOMMON

ROCK

COATINGS

The theory of knowledge which I wish to propose is a largely Darwinian theory of the growth of knowledge. From the arr,oeba to Einstein, the growth of knowledge is always the same: we try to solve our problems, and to obtain, by a process of elimination, something approaching adequacy in our tentative solutions. (Popper, 1979, p. 261)

11.1. Introduction This chapter focuses on rock coatings that are relatively uncommon. Phosphates, nitrates, halite, and sulfates are rarely reported as coatings on rocks at the earth's surface. But before I get into trouble with those who study "duricrusts", it is important distinguish the term "crust" as it is used in the soils and geomorphic literature from rock coatings. Duricrusts refer to salts that are concentrated in meter-thick layers in a near-surface locations. Terms like calcrete, salcrete and gypcrete are used to describe geomorphologicaUy resistant crusts (Watson, 1989), and caliche is used to describe nitrate duricrusts in the Atacama desert (Ericksen, 1981; Ericksen, 1983). Yet, duricrusts and duricretes are not rock coatings. They are subsurface phenomena that can be exposed at the surface under certain circumstances. The literature on phosphates, nitrates, chlorides, and sulfates is extensive. The literature on phosphates is concentrated geological settings. Papers on nitrate, chloride and sulfate salts tend to focus on their occurrence in playas, their role as geomorphic agents, and as components of deserts soils. Despite the extensive literature on these raw materials, the vast majority of the discussion has nothing to do their accretion as coatings on rocks. The organization of this chapter is to discuss in turn phosphate skins, nitrate crusts, salt crusts, and gypsum crusts. In each section, my focus is to synthesize relevant information on rock coatings from the broader literature. In some cases, I have provided supplementary data from original studies. Lastly, I offer an explanation for the limited distribution of these rock coatings.

11.2. Phosphate Skins Phosphate rock coatings occur in a wide variety of geological contexts, for example copper phosphate cornetite in mines (Nriagu, 1984, p. 31), aluminum phosphates in hydrothermal settings (Nriagu, 1984, p. 129), calcium-aluminum phosphates in pegmatites (Nriagu, 1984, p. 129), in coal seams (Ward et al., 1996) and other geological settings (Zanin, 1989). These same coatings can be seen at the earth's surface when they are exposed by natural erosion and anthropogenic activity. The focus

Uncommon Rock Coatings

here, however, rests on rock coatings formed near or at the earth's surface--not in geological deposits. Phosphorus is the tenth most common element in the earth's crust (Parker, 1967). Phosphate most often combines with iron (ferrous or ferric), aluminum, calcium and manganese to form a wide variety of phosphate minerals (Nriagu, 1984). The largest deposits of commercially mined phosphates are marine in origin (Cook, 1984), but both organic and inorganic phosphates are common components of soils (Mulder and van Veen, 1968; Shang et al., 1992). In general, phosphorus accumulates in alkaline and acidic environments and accumulates in neutral environments mainly as apatite (Zanin, 1989). One of the most common types of phosphate skins forming in today's terrestrial weathering environment can be found on relatively dry coral reef islands (Zanin, 1989, p. 341), largely through the interaction of guano with calcium carbonate in the coral (Fosberg, 1957; Hutchinson, 1950). While most of this phosphate exists as 'phosphate rock' and not as rock coatings, recent deposits "consists normally as a thin (0.1mm) fringe of multilaminar phosphatic cement (carbonate-hydroxy-fluor-apatite) enveloping unaltered sand-sized skeletal grains (Stoddart and Scoffin, 1983), p. 396)." In some cases, the guano-derived phosphate skins may also form in crenitic environments (Trueman, 1965). Guano-derived phosphate skins can be found in drylands (MacLeod et al., 1995). Kestral guano started out as iron, magnesium and calcium phosphates. Upon interaction with calcium carbonate, a calcium pyrophosphate evolved that was more stable than the original guano. Figure 11.1 illustrates the appearance of a typical phosphate skin found on desert rocks, derived from guano deposits of an unknown origin. A preliminary radiocarbon ages for a guano collected from a tafoni in Papago Park, Phoenix, Arizona, ran was about 1300 radiocarbon years, making correlations with contemporary bird occupation difficult. Phosphate skins can incorporate eolian detritus (Figure 11.2). My selected observations indicate that phosphate skins can reach thicknesses of at least 0.5 mm. Electron microprobe analyses of the relatively pure sections of the Papago Park phosphate skin reveals that the much of the coating is phosphorus. The second most common measured element is sodium, which may be a sodium nitrate (Table 11.1).

Figure 11.1. Phosphate skin in Joshua Figure 11.2. Backscattered electron microprobe image of Tree National Monument. The white phosphate skin formed in tafoni of Papago Park, Arizona. The skin originated as a guano deposit within darker detrital grains are quartz, indicating that eolian the tafoni hollow. Mobilization and materials can be trapped by phosphate skins. The bright subsequent reprecipitation resulted in the detrital mineral is hornblende. Electron microprobe deposition of this phosphate skin. measurements (Table 11.1) were made in a transect in the area where the phosphate skin lacked the abundant detritus.

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250

Not all phosphate skins necessarily derive from guano, and not all are white. Dusky red coatings (Munsell 2.5YR 3/2) are fairly common on the granodiorite pediment boulders in the Apple Valley area of the Mojave Desert, California. These coatings are typically 2000 microbasins examined within a 320 km 2 area in Death Valley (Liu and Dom, 1996). The general stratigraphy is shown on Figure 15.2. Mean vamish thickness is 401am (a), 501am (b) 50~tm (c) 50pro- (d), 80~tm (e), 601am (t3, 120lain (g), 80~m (h).

Chapter 15

348

Unit Laminae 1

IlQI~

Tm'minal Pligstoce~ (-tLouo-I1,ooo!

Last Ola~al Period (unit starts -55, 0001uid Chris around 21,000)

5

Last (unit star~ ~ i 3o, oo0)

~ 300, 0 0 0

~arO

15.2. Idealized sequence of varnish layering units (LU) in Death Valley from (Liu, 1994).

349

Geographical Variations

.6

N

.18

.3 Sample site and number

iii

0

i

1 km

36~

/

Figure 15.3. Location of sampling sites for ultra-thin section on Warm Springs Alluvial Fan, southem Death VaLley, from Liu (1994).

Chapter 15

350

!

! LU-2+ 1

~LU-3 ~LU-4

~LU-5 ~LU-6

~LU-7 ~LU-8 >_LU-8 0 ........... 1 km

3.6~ Figure 15.4. Map of Warm Springs Alluvial Fan, southem Death Valley, based on the layering patterns seen in rock varnishes, from Liu (1994). The mapping units are the oldest layering seen in thin section. LU >8 is the oldest, because varnishes on this portion of the alluvial fan have the most complicated layering. LU 1+2 is a combination of varnishes with only the simplest (youngest) layering patterns.

~

.

Figure 15.5. Aerial photograph of Warm Springs Alluvial Fan, southern Death Valley. The view looks to the southwest.

Geographical Variations

15.2.2 Generalization of Field Observations The first regional map of the distribution of a rock coating was presented for Arizona (Elvidge and Moore, 1979). Elvidge (1979) used initial field observations to develop a correlation between the distribution of rock varnish and a combination of soil alkalinity, annual precipitation and vegetation. Then, using maps of these environmental factors, Elvidge field checked the initial predictive relationship and developed a general map to correspond with vegetation patterns (Figure 15.6).

Figure 15.6. Map of the distribution of rock vamish in Arizona, southwestern United States, modified from Elvidge and Collet (1981).

Elvidge (1979) and Elvidge and Collet (1981) concluded that varnish is best developed in the most arid, alkaline and dusty parts of Arizona, in the "Sonoran Zone" of saguaro and other succulent vegetation. They felt that the second best area of varnish development is in the high desert of the Colorado Plateau, the "Plateau Zone" that is dry and has alkaline soils. The third best area of varnish formation is the Eroded Sonoran Zone where rock varnish is patchy in distribution and often eroding. Upland areas of the state were mapped as having no rock varnish because of the abundance of moisture and vegetation. The lithobiontic coatings in Israel were mapped in a similar fashion (Figure 4.35) (Danin, 1986). Relationships between lithobionts, lithology and climate identified seen in the field, in coordination with laboratory observations, were generalized to the entire country using previously mapped environmental parameters. Correlating rock coatings with established environmental parameters to produce a generalized map is certainly not a new approach in cartography. It yields first-order approximations. For example, living in Arizona, I find Elvidge's map reasonable at first glance. I only disagree with the interpretation of varnish erosion; rock varnish forms in all areas of the state and areas identified as experiencing 'varnish erosion' are actually experiencing erosion of the host rock. The flaw in this general approach is that it admittedly misses a tremendous amount of internal variability that exists in an environmental region. A key question I address later in this chapter is whether the internal variability in rock coating distribution in each environmental region is so great to prevent the use of these types of cartographic short-cuts.

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15.2.3 Remotely Sensed Imagery The third strategy used to map rock comings in the literature is satellite or airborne imagery. In remote sensing an attempt is made to learn about the surface characteristics of specific areas. These 'training sites' are then used to understand the reflectance or emission of areas not yet studied on the ground. The Pixel sizes used are at best a few square meters and more typically tens of meters across. Hence, spectra are treated statistically to extract the relevant information (White et al., 1997). Remote sensing has not been used to map rock coatings, with a few exceptions (e.g., White et al., 1997), but rather to map the geology of surfaces. The interest in rock coatings in the geologically-oriented remote-sensing community is because rock coatings influence the reflectance signature of the geology (Abrams et al., 1991; Adams et al., 1982; Anderson, 1995; Best, 1989; Bothorol et al., 1984; Clayton, 1989; Daily et al., 1979; Elvidge and Collet, 1981; Farr, 1981; Gaddis et al., 1990; Lyon, 1990; Rivard et al., 1992; Salisbury and D'Aria, 1992; Schaber et al., 1976; Shipman and Adams, 1987; Spatz et al., 1989; Sultan et al., 1987; White, 1993a; Wood et al., 1989). This effort is to extract the influence of the rock coating, all in order to obtain more accurate information about the underlying geology, not rock comings. Relationships between rock coatings and geology are complex. First, there are a plethora of rock coatings; however, most research on remote sensing only considers one or at most two of these different coatings. Second, spectral changes involve complex interactions between rock coatings and erosion. Consider Figure 15.7, where Hanaupah Canyon Alluvial Fan in Death Valley darkens and lightens with time and with the exposure of calcrete. In other words, there is a 'bell curve' for the reflectance of alluvialfan surfaces. This general model of lightening over time, based on calcrete, cannot even be applied to adjacent alluvial fans. Immediately to the North, Death Valley Canyon Alluvial Fan undergoes the same spectral change of darkening and then lightening, but the lightening on the older units has to do with the instability of the host rock, not with the exposure of calcrete. The oldest surfaces on Death Valley Canyon Alluvial fan have clasts that have undergone granular disintegration, leaving meter-sized circles (Figure 15.8).

Figure 15.7. SPOT image of Hanaupah Canyon alluvial fan in Death Valley, along with a general model of surface evolution. For a few thousand years, the surface has a 'bar and swale' topography that is rough. In comparison with other surfaces, there is high albedo because of the paucity of rock varnish. After about ten thousand years, the topography changes to a smooth desert pavement that darkens as it varnishes. After about a hundred thousand years, gullies erode into the flat pavement and these surfaces round into baUenas. The general albedo does not simply darken with more varnishing; rather, it darken with varnishing and then lightens with the weathering of rocks and with the exposure of calcrete crusts in the ballenas.

BEandChm~el . . . . . . -v~/-r

Smo(ratPavnt~eat Iacisr Pavement

Geographical Variations

llmCr'~,,~

Figure 15.8. Aerial photograph and ground view of an older surface on Death Valley Canyon alluvial fan. The lighter colored surfaces are the oldest, but they are the lightest because of the breakdown of the host rock into grus; the arrow on the aerial photograph indicates the approximate position of the ground photograph.

The most informed use of remote sensing to study rock coatings and geomorphology has been in Tunisia (White, 1990; White, 1993a; White, 1993b; White et al., 1996; White and Walden, 1994; White et al., 1997). An understanding of field characteristics, laboratory work, and a clear sense of geomorphic relationships were combined to interpret the remotely sensed data. In essence, the strategy combines three scales of information: micron-scale insight from laboratory studies; meter-scale insights from field observations; and kilometer-scale integration through remote sensing - - but all the while with a firm understanding on the processes of rock coating development. Consider the following: "Iron coatings have a less significant effect on host rock spectral reflectance characteristics, due largely to the thin, discontinuous coating relative to manganeserich rock vamishes...Iron-rich rock coatings do not preclude recognition of the host rock lithology from remotely sensed spectral reflectance measurements. Manganese-rich rock varnishes do, however, preclude such recognition, by obscuring the underlying host rock lithology...Because of their more pronounced spectral reflectance characteristics, manganese-rich rock varnishes are likely to be more suitable for deriving geomorphological information, such as mapping geomorphological surfaces of different ages from remotely sensed data (White, 1990, p. 32)."

The distinction of White's work does not rest in working with the most expensive and highest resolution imagery, but rather in an awareness of the interplay between geomorphic conditions and different types of rock coatings, including iron films, rock varnish, gypsum crusts, in addition to an awareness of the distinction between these and weathering rinds. Complexities have been similarly appreciated where biotic rock coatings have been the focus of the remote sensing study. Maps of lithobiontic coatings have been made with the aid of remotely-sensed imagery (Kokaly et al., 1997). Again, this research effort is different from the aforementioned geologic studies, because the focus rests on the lithobiontic coatings (see chapter 4), not on the underlying rock. The end product is a lithobiontic map (Figure 15.09) for cryptogamic crusts in a portion of Arches National Park.

353

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Chapter 15

Arches National Park MierobiotieSoilsMap USOSmbandmap 80% "micro" 20% "vr 72% "micro" 10% ",and" 18% "ve~"

~O1%

"micro"

~% "sand" 16% "v~..

40% "micro" 2,1)% "Salad"

40% "veg"

20~& "micro" ~g0~ "sand" 1oo% t|~d04 BB m

Note: "sa~"- sand,or rock

gok.ly, Clark,and Swayzr 1993

Figure 15.9. This figure illustrates the approximate aerial coverage of the cryptogamic crusts and black lichens (labeled as micro for microbiotic) in a portion of Arches National Park (Kokaly et al., 1997). 1992 AVIRIS remotely sensed imagery were calibrated against laboratory reference spectra to create this map to the north of Wolfe Range and Delicate Arch. The Pixels are 17 meters This image is adapted from Kokaly et al. (1997).

Excellent rock coatings maps, such as Figure 15.9, could be made with remote sensing, but only if there is a clear understanding of the wide variety of rock coatings that are integrated into the individual Pixels. Inaccurate maps are easy to make without interactive feedbacks between micron-scale laboratory data, millimeter- to meter-scale field insights, and remote sensing. This is because rock coatings are not scale invariant. The rock coatings seen with the microscope show great variability from place to place on a boulder, over a landform, and throughout a region (Figure 15.10). Although Death Valley is normally thought to be dominated by rock varnish, meter-long transects sampled across bare rock surfaces for all geomorphic units reveal a coverage of rock varnish of 19% (with a standard deviation of 35%). When only alluvial fans units are considered, varnish coverage averages 24+31%, with the most consistent varnish cover on latest Pleistocene alluvial fan units at 35+22%. The aerial coverage of other rock coatings, including silica glaze, carbonate crusts, iron films, oxalate-rich crusts and lithobionts, exceeds rock varnish by a factor of two. The significance of this issue is that Death Valley is frequently used as a field training site for dozens of remote sensing studies by NASA-funded scientists. Literally tens of millions of dollars have been spent investigating Death Valley with remote sensing, where rock varnish has been an integral part of the research; yet, these studies have all ignored the heterogeneity in rock coatings. These studies have blithely assumed that the only coating is rock varnish. My point is simple. Before the influence of rock coatings can be decoupled from the host rock, rock-coating heterogeneity must be understood at all scales. Maps of lithology and rock coatings may be inaccurate simply because of an incorrect assumption of coating homogeneity. Fortunately, this assumption is not made in all research at the interface of rock coatings and remote sensing (e.g., White, 1990; Kokaly et al., 1997).

Geographical Variations

Figure 15.10. Optical view of rock coatings at different scales reveals vastly different perspectives. The lower right optical microscope view of dark rock vamish on granodiorite (~1 mm wide), was sampled from a -70 cm-wlde boulder flower left), on a smooth desert pavement on Hanaupah Canyon alluvial fan (arrow, upper fight), shown by the box in the SPOT satellite image of Death Valley (upper left frame ~100 km wide).

15.3 Case Study in Regional Variability: Himalayan Transect In order to give the reader a feel for the variety of rock coatings that exist side-byside, all within mapping units used to generalize field observations and certainly within the scale of single Pixels, I present a case study of the variety of rock coatings seen in a large region. Regional sampling offer a means evaluating variations at different scales. Samples are analyzed in the laboratory at the micron to millimeter scale. Samples are collected in the field at the millimeter to meter scale, with sites kilometers apart. The purpose of this section of chapter 15 is to analyze the geographical variability of rock coatings across a region. In the process I will illustrate that it would be very easy to produce inaccurate maps by oversimplifying the realities of rock coatings in a region. This section explores in greater detail the nature of rock coatings found on the two different sides of the "Roof of the World" (Bishop, 1962): the moist and glaciated Khumbu of Nepal and drylands of the West Kunlun in the Tibetan Plateau. The Himalayan Ranges and Tibetan Plateau expose one of the world's greatest expanses of what G.K. Gilbert (1877) characterized as weathering-limited landscapes,

355

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Chapter 15

where the rate of land surface lowering is limited by the rate of weathering. In other words, rock is seen at the surface because erosional processes are faster than weathering. Relatively little is known about the nature of rock coatings in the Himalayan Mountains and Tibet. Working in the Karakoram, visual changes in rock varnish was used as a method to estimate landform age (Derbyshire et al., 1984). Cation-ratio dating has been used to date rock varnish in the Pamirs (Glazovskiy, 1985). High concentrations of bacteria, algae, and fungi grow on varnish in the Tien Shan at ~4200 m (Parfenova and Yarilova, 1965). Others have noted a similarity between rock varnishes in the Greater Himal and warm deserts (Dora, 1991; Kalvoda, 1984; Kalvoda, 1992; Whalley, 1983; Whalley, 1984). To the north of the Tibetan Plateau in inland low deserts, Chinese scientists have explored the nature (Zhu et al., 1985) and cationratio (Zhang et al., 1990) of rock varnish.

15.3.1. Study Areas The glaciated Khumbu region of Nepal rests on the south side of Mount Everest (Figures 15.11). The climate of the Khumbu is greatly influenced by monsoonal circulation patterns and mountain climatology; it has a dry winter and wet summer (Inouye, 1976). Precipitation peaks during early afternoon on glaciers and highlands in the monsoon season, and later in the evening in lower valley locales (Higuchi et al., 1982). Valley wind systems are important in the transportation of sensible heat and water vapor, in both the monsoon and winter season (Ohata et al., 1981). The geomorphic, soils, hydrologic, and biogeographic systems of the Khumbu are influenced by the region's present and past climate (Biiumler et al., 1991; Haffner, 1972). During the last glacial maxima, rock glaciers were active (Jakob, 1992) and glaciers extended down the Imja Khola valley at least to Namche Bazar at 3440 m (Heuberger and Weingartner, 1985), and perhaps as far as Lukla at about 2500 m (Fushimi, 1980), in contrast to present glacial termini reaching around 5000 m (Fushimi et al., 1979). The last major advance was in the Little Ice Age during the 16th century (Fushimi, 1980). The proglacial landscape is still adapting to glacially steepened valley slopes with concomitant hazards of mass wasting, fluvial erosion, and jokulhaup processes. Lithologies in the area include gneiss, leucogranites, and the metasedimentary Everest seres above 8200 m (e.g., limestone, phyllite, quartzite, marble, schist) (Rochette et al., 1994; Vuichard, 1986). Rock coatings in the Khumbu were collected in an altitude transect from several different environmental settings (Figure 15.11): gneiss cobbles on the surface of solifluction lobes on Kala Pattar at about 5400 m; supraglacial quartzite clasts on the surface of the Khumbu Glacier at about 5250 m (Figure 15.12 and 15.13); glacially polished gneiss clasts at the terminus of the Khumbu Glacier at about 4900 m; gneiss avalanche boulders beneath Pokalde at about 4600 m; gneiss clasts on the surface of the Tshola rock glacier at about 4500 m (Figure 15.14); leucogranites stream-side cobbles of the Imja Khola River at about 4(X)0 m near Pangboche; and a faced (during construction) gneiss cobble in a 10-year-old wall (when collected) in Namche Bazar at -3400 m. Although these samples do not represent the complete variety of rock coatings in the Khumbu region, they exemplify some of the more noticeable rock coatings.

Geographical Variations

0

I

1

2 km

I

'86*50

I

~s

\

Pumon

~t

~

.,~-'~'v-~,~.,.,,,,,

.".g

~ Keda l ~ r /

fQ Dugla

357

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~

9

k,~....,...

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Mount

Sampling Sites 9 PoK~le 1 K~

Q D mgboche

l~r

2 Khumbu OMcier Surface 3 Khumbu Glacier Terminus 4 TsholaRock Glacier Surface 5 Talus Boulder 6 Imja Khola Stxuam-side Boulder 7 Namche Bazar Faced Well

./ 9 Arna Dabl~an

Figure 15.11. Map of sampling sites in the Khurnbu region, Nepal.

Figure 15.12. Surface of Khumbu Glacier below the Kala Pattar. The Everest base camp is usually located in the upper left hand side of the photograph. The individual seracs in the ice fall are tens of meters high.

Figure 15.13. Clast in supraglacial melt water on Khumbu glacier -5250 m, collected from the far lower left comer of 4.11. The normally white quartzite is coated by rock varnish.

358

Chapter 15

Figure 15.14. Tshola rock glacier. A sample was collected from the surface of the rock glacier about 100 m above the outwash plain of the Khumbu Glacier in the foreground.

The other end of the environmental transect is in the Ashikule Basin, resting in one of the driest sections of the Tibetan Plateau, on the north side of the west Kunlun Mountains (Figure 15.15). Only a little climatological data exist for this area (Derbyshire et al., 1991). Present day precipitation totals probably rest between 300 mm and 800 mm; in the West Kunlun, however, the ratio of precipitation received on the north and south-facing slopes is 1:5, suggesting that the Ashikule Basin is in the lower end of this range. Present-day climatic snowlines in the area are ~5600 m; and mean monthly temperatures during the warmest summer months probably range from -2~ to +2~ (Yafeng et al., 1992). Snowlines lowered during the Pleistocene, but only by about 200-300 m in the West Kunlun Mountains. This relatively small depression is probably due to the extreme aridity of the area (Yafeng et al., 1992). The latest Pleistocene glacier receded from its terminal position about ~14,000 to 15,000 years ago in the West Kunlun Mountains, where it extended to 5300 m, and about 6.5 km away from the present glacial terminus of the Congce Glacier (Yafeng et al., 1992). The geomorphology of the Ashikule Basin is dominated by the Akesu volcanic field, which consists of potassium-rich lava flows and cinder cones that range in age from ~70 ka to ,-540 ka. Two saline lakes are situated in the Basin: Ashikule and Urukele. Periglacial features such as rock streams also mantle the steeper slopes of the surrounding hills. It is difficult to understate the extent to which eolian processes influence the Ashikule Basin. Loess mantles all lava flows, burying much of the topography. The isotope geochemistry of loess in the region suggests an origin in the adjacent Tarim Basin (Liu et al., 1994) There is also widespread evidence for eolian abrasion of the lava flow surfaces. As will be discussed later, ventifact surfaces do display rock coatings, suggesting that eolian abrasion is episodic. Analyses of the loess indicate that there is a high content of both carbonate and sulfate minerals w perhaps derived from some local sources of deflation of the Ashikule and Urukele saline lakes. Rock coatings in the Ashikule Basin were collected by T. Liu from different microenvironmental settings (Figure 15.15), all at about the same altitude of ~47004800 m. They have the sample designation of AKB in figure captions for this section. The collection sites are: bombs on rims of volcanic cones (Figure 15.16), and constructional surfaces of lava flows (Figure 15.17); outcrops that have been subject to eolian abrasion (Figure 15.18); beach ridges of Urukele Lake (Figure 15.19); rock streams on hillsides of the Ashikule Basin (Figure 15.20); Pleistocene moraines of the West Kunlun Mountains; and a fiver terrace adjacent to the Pulu River.

359

Geographical Variations

0

10

20 km

. b"~.'m ,~,,,,,

--" ~ - ~ . , , . ~ h bAtg . ,~,.'?~~huangKaru'~

"36 ~ N

Karata~, . . . . . . . . .

l),thr

Urukele I... ~ ' ~

69~

'

Mtn~

Figure 15.15. Sample sites in Ashikule Basin, Tibet.

Figure 15.16. Ahishan cone in the background with the salt playa of Urekele Lake in the foreground. Photo courtesy of Tanzhuo Liu.

Figure 15.17. Surface of lava flow from Ashisan volcano. The lens cap provides scale. Photo courtesy of Tanzhuo Liu.

Figure 15.18. Surface of Ashishan lava flow that has been subjected to loess deposition and eolian abrasion that reset the development of rock coatings. The rock hammer provides scale. Photo courtesy of Tanzhuo Liu.

360

Chapter 15

Figure 15.19. Beach ridges of Urukele Lake. Photo courtesy of Tanzhuo Liu.

Figure 15.20. Rock streams on hiUslopes on the southeast side of the Ashikule Basin. Photo courtesy of Tanzhuo Liu.

15.3.2. Rock Coatings in the Khumbu The first part of this section gives the reader a feel for the micron-scale characteristics and variety of rock coatings found in the Khumbu in a transect from the Kala Pattar at 5400 m to Pangboche at about 4000 m (Figure 15.11). The second part of this section generalizes some o f the field and the laboratory insights on Khumbu rock coatings. Table 15.1 presents the electron microprobe data for all of the Khumbu rock coatings. Solifluction lobes and turf-bank terraces on the Kala Pattar (--5400 m) contain gneiss clasts with dark brown rock coatings. Figure 15.21a reveals that these coatings are mostly iron films (Table 15.1a) that precipitate in weaknesses defined by foliations in the gneiss. Although these iron skins may be found at the surface, they probably develop first in the fractures and are exposed by spalling. These iron films were similar to those found on the gneiss clasts on the surface of the Tshola rock glacier (Figure 15.14) at about 4500m (Figure 15.21f).

Table 15.1. Electron microprobe analyses of rock coatings in the Khumbu of Nepal. Values in oxide weight percent. Totals do not reach 100% due to porosity, water, and content of organic matter. Transects correspond to lines in indicated figures. ,

9

n

,,, i

i

9

,,,

_

Section a. Iron films

Sample from Kala Pattar (see Figure 15.2l a) TRANSECT: Na20

Left to Right

0.22 0.21 0.28

MgO A1203 Si02

P205

S03 K20

CaO Ti02 MnO FeO BaO

Total

0 . 0 4 4 . 0 2 3 . 2 6 4.18 0.79 0.22 0.06 0.00 0.00 63.17 0.00 75.96 0 . 0 2 4 . 3 0 2 . 9 7 3 . 4 0 1.29 0.19 0.10 0.00 0.00 62.99 0.00 77.03 0 . 0 5 4.51 2 . 8 4 4.09 1.90 0.29 0.12 0.00 0.00 59.07 0.00 75.26

Samole from Khumbu dacier, where iron skin is under silica daze (Figure 15.21b~ TRANSECT: Na20

Top to Bottom

0.00 0.00 0.00

MgO A1203 Si02

P205

S03 K20

CaO Ti02 MnO FeO BaO

Total

5.01 5 . 3 0 7 . 5 2 0.22 0.64 0.00 0.16 0.00 0.15 60.57 0.00 79.57 6 . 3 3 8 . 0 9 8.01 0 . 3 7 0.60 0.00 0.20 0.00 0.19 59.00 0.00 82.79 5 . 3 2 6 . 7 7 9 . 0 6 0 . 5 0 0.55 0.00 0.22 0.00 0.28 57.17 0.00 79.87

Sample from Tshola rock glacier (Figure 15.21f) TRANSECT: Na20

Left to Right

0.19 0.15 0.09

MgO A1203 Si02

P205

S03 K20

CaO Ti02 MnO FeO BaO

Total

0 . 1 1 2 . 1 7 4 . 0 9 3.17 1.03 0.30 0.10 0.00 0.00 69.01 0.00 80.17 0 . 1 9 2 . 0 9 4 . 1 9 2 . 4 0 0.99 0.27 0.12 0.00 0.00 68.18 0.00 78.58 0 . 2 4 1.97 3 . 7 7 3.88 1.44 0.19 0.12 0.00 0.00 67.46 0.00 79.16

Geographical Variations

361

Section b: Silica glaze Sample from Khumbu glacier, where silica glaze is above iron skin (Figure 15.13b) TRANSECT: Na20 MgO A1203 Si02 P205 S03 K20 CaO Ti02 MnO Top 0.03 0.43 6.93 52.41 1.24 0.02 0.25 0.06 1.57 0.00 to 0.00 0.45 6.72 62.33 1 . 3 7 0.02 0.12 0.11 1 . 3 3 0.05 Bottom 0.03 0.41 4.75 56.61 1.26 0.02 0.11 0.03 0.75 0.04 0.01 0.28 6.08 59.84 1.24 0.07 0.24 0.04 0.73 0.10 0.08 0.18 5.26 56.61 1.40 0.05 0.23 0.04 0.68 0.00

FeO 7.19 5.24 4.17 4.23 3.56

BaO 0.02 0.06 0.00 0.06 0.01

Total 70.15 77.80 68.18 72.92 68.10

Section c: Phosphate Skin Sample from avalanche boulder beneath Pokalde (Figure TRANSECT: Na20 MgO A1203 Si02 P205 S03 Right 0.00 0.00 2.02 1.04 1.45 0.21 (bright) 0.00 0.00 1.60 1.14 1.30 0.32 through 0.51 0.15 25.17 18.10 25.82 0.21 dark to 0.48 0.19 22.04 13.17 26.70 0.17 Left 0.33 0.22 21.90 20.11 25.07 0.16 (speckled) 0.45 0.15 20.71 18.10 30.62 0.27 0.40 0.25 30.27 12.20 27.40 0.17 0.13 0.36 18.88 14.08 25.54 0.26 0.14 0.37 19.04 11.59 26.36 0.33

15.23c) K20 CaO 0.00 0.38 0.00 0.41 0.44 7.36 0.32 7.52 0.41 6.74 0.29 6.50 0.44 7.39 0.15 3.96 0.50 4.33

Ti02 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.40 0.98

MnO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

FeO 74.70 79.07 1.77 2.36 1.96 1.22 2.20 19.07 18.71

BaO 0.00 0.00 0.25 0.23 0.15 0.19 0.00 0.20 0.12

Total 79.80 83.84 79.78 73.18 77.05 78.50 80.82 83.03 82.47

Section d: Rock Varnish Samvle from Namche Bazar rock wall (Figure 18,21d) TRANSECT: Na20 MgO AI203 Si02 P205 S03 Top 0.00 0.32 5.71 12.46 2.98 1 . 2 7 to 0.03 0.38 7.67 14.79 3.71 1 . 4 5 Bottom 0.20 0.33 8.75 10.93 3.07 1.20 0.00 0.48 6.97 11.95 3.14 1 . 1 5 0.13 0.48 9.67 10.10 3.53 1.70

K20 2.33 2.45 2.43 2.42 2.42

CaO 1.01 1.08 1.68 1.65 1.41

Ti02 0.42 0.42 0.43 0.42 0.45

MnO 35.53 36.75 40.16 48.19 36.84

FeO 13.98 13.73 13.58 14.12 14.08

BaO 1.28 1.97 1.09 1.30 1.37

Total 77.29 84.43 83.85 91.79 82.05

Sample from Imja Khola stre.aln-sidr boulder ffigure 15.22) TRANSECT: Na20 MgO A1203 Si02 P205 S03 K20 Top 0.15 0.22 9.17 6.00 0.77 0.07 0.64 to 0.13 0.26 6.11 7.17 0.71 0.08 0.55 Bt~Itma 0.12 0.31 9.07 10.60 0.80 0.00 0.50 0.12 0.44 8.18 9.66 0.82 0.00 0.61 0.11 0.51 7.88 9.90 0.88 0.00 0.49

CaO 0.50 0.57 0.49 0.33 0.56

Ti02 0.51 0.52 0.47 0.39 0.40

MnO 42.17 43.09 40.68 37.65 38.38

FeO 8.51 8.37 9.19 8.66 8.10

BaO 1.50 1.44 1.39 1.10 1.22

Total 70.21 69.00 73.62 67.96 68.43

Section e: Oxalate Crusts Sample from Namche Bazar rock wall (Figure 1~.23c) TRANSECT: Na20 MgO A1203 Si02 P205 S03 Top 0.00 1.44 0.13 0.04 0.05 0.27 to 0.00 1.30 0.14 0.05 0.05 0.29 Bottom 0.00 1.50 0.18 0.06 0.08 0.24 0.11 1.60 2.14 3.61 0.06 0.29 0.13 1.81 3.22 5.26 0.07 0.21 0.09 1.55 3.37 4.89 0.09 0.22 0.15 1.90 3.49 6.00 0.10 0.25 0.10 1.55 4.20 5.48 0.06 0.26

CaO 55.21 54.27 50.86 59.17 49.28 50.48 52.22 57.30

Ti02 0.00 0.00 0.00 0.05 0.06 0.07 0.05 0.00

MnO 1.80 2.20 0.10 0.16 0.90 2.00 1.56 1.12

FeO 0.00 0.00 0.05 0.07 0.05 0.06 0.07 0.00

BaO 0.25 0.32 0.00 0.00 0.15 0.33 0.25 0.18

Total 59.19 58.62 53.07 67.37 61.34 63.37 66.31 70.50

K20 0.00 0.00 0.00 0.11 0.20 0.22 0.27 0.25

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Chapter 15

Quartzite clasts on the surface of the Khumbu Glacier at about 5250 m (Figure 15.13) have coatings of silica glaze, sometimes interbedded with iron films (Figure 15.21b; Table 15.1b). The appearance of the coating was a clear glossy glaze with an orange tint. Although the silica glaze is an accretion on the underlying rock, there was a clear preference of silica glaze for quartzite clasts on the glacier. These same quartzite clasts also have dark coatings of manganiferous rock varnish (Figure 15.22; Table 15.1d). A similar botryoidal micromorphology is found in stream coatings on leucogranite cobbles along the Imja Khola River near Pangboche at -4000 m.

At the terminus of the Khumbu Glacier at about 4900 m, glacially polished gneiss sometimes has an orange hue. Examination by both BSE and secondary electrons reveals that this "polish" is actually a combination of glacial polish and an extremely thin iron-rich silica glaze (Figure 15.21e). Subglacial rock coatings have been noted previously (Whalley et al., 1990). However, these shiny boulders give the appearance of true glacial polish, at least to the naked eye, and the rock coatings are much thinner than any subglacial rock coatings described previously. Gneiss avalanche boulders beneath Pokalde at about 4600 m have dark coatings of phosphate crusts, sometimes capped by iron hydroxides (Figure 15.21c; Table 15.1c). In places the iron and phosphates are mixed together in an iron phosphate, perhaps strengite (FePO4.2H20). Faced rocks in a wall in the town of Namche Bazar at ,-3400 built about 10 years prior to the time of collection, had two distinct types of rock coatings: manganiferous rock varnish (Figure 15.21d; Table 15.1d) and crusts of calcium oxalate (Figure 15.23). The calcium oxalate crusts on the wall illustrate different stages of development. Figure 15.23a shows a live crustose lichen with white dots of calcium oxalate in the outer section. After the lichen dies, the calcium oxalate apparently undergoes a diagenesis to a granular texture that rests on the rock surface, or a previous rock coating (Figure 15.23b). Older calcium oxalates on the wall have two types of textures: granular and porous; or distinctive layering. These two types of oxalate-rich crusts can interlayer at the scale of microns (Table 15.1e; Figures 15.23c and 15.23d). Different Khumbu rock coatings affect the general landscape, but differently at different scales. The most discernible effect is to darken the appearance of a mountain face (Figure 14.4). All of the inorganic rock coatings, except silica glaze, generally darken a rock's appearance. In addition, lithobiontic rock coatings are common on Khumbu rock surfaces, including lichens, fungi, algae, cyanobacteria, moss and bacterial mats. These organic films often have a dark pigment (Fletcher et al., 1985), perhaps to provide protection against ultraviolet radiation (Vincent and Roy, 1993). Iron skins appear to be most prevalent in locally acidic environments. For example, the pH of soil samples in contact with ten cobbles on the Kala Pattar averaged 4.3+ 1.2. Other iron skins were found on rock surfaces exposed to spring water exiting from bog environments with Sphagnum spp.; acidiphilous iron bacteria may be important in iron precipitation (Nealson, 1983) in these environments. Microenvironmental settings appear to control the distribution of rock coatings. The most dominant type of rock coating in the Khumbu are lithobiontic coatings, where the growth of lichens, moss, algae, cyanobacteria, fungi, and bacteria are determined by biogeographic controls. The second most common rock coating are oxalate-rich crusts; these occur most commonly adjacent to crustose lichens. The third and fourth most abundant coating are rock varnish and manganese heavy-metal skins that grow where water flow occurs seasonally over rocks. In fourth place are iron films in places where acidic waters flow over rocks. The distribution of silica glazes and phosphate films are

Geographical Variations

much more limited, and I could not determine even a speculative environmental control on the distribution of these coatings.

Figure 15.21. Different rock coatings seen in cross-section, from the Khumbu of Nepal. Scale bar in microns. All images are taken with backscattered electrons except the right image in Figure 15.21e which shows topography with secondary electrons. a. Stringers of iron hydroxides precipitate within fractures in gneiss collected from the Kala Pattar (-5400 m). The thickest iron films are found at the surface and underneath some gneiss. As the iron mobilizes and reprecipitates in the fractures, it mechanically weathers the gneiss. b. Silica glaze precipitated on a quartzite clast resting on the surface of the Khumbu glacier (-5250 m). The bright material underneath the silica glaze on the left side of the image is an iron film. The dark spaces are pore spaces in the quartzite weathering rind. c. Phosphate crust on an avalanche boulder on the slope beneath Pokalde, at about 4600 m. The brighter material is a pocket of iron oxides that interdigitates with the less bright phosphate. d. Manganiferous rock varnish on a gneiss cobble that was faced about 10 years before collection, from the village of Namche Bazar at -3400 m. e. Backscatter (left) and secondary electron (right) views of a glacially polished boulder at the terminus of the Khumbu Glacier at about 4900 m. The BSE image reveals that the polish is a different material than the underlying gneissic quartz grain. The coating is less than a micron thick, which is less than the spot size of the electron microprobe. Qualitative EDS analysis that includes both the underlying material (quartz) and the 'polish' reveals that it is an iron-rich silica glaze that contains four elements that are below the limit of detectmn in the underlying rock (iron, aluminum, calcium, and manganese). f. An iron film on gneiss clast on the surface of the Tshola rock glacier (-4500 m) is remobilizing and is precipitating 'stringers' within the host clast.

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Figure 15.22. Secondary electron images of manganiferous rock varnish with a botryoidal micromorphology. The left image shows a cross-section of the botryoidal varnish on top of a gneissic rock found on the surface of the Khumbu glacier on quartzite boulders. The fight image shows a granitic stream-side cobble along the Imja Khola River at about 4000 m near Pangboche. The full length of the dots is indicated in microns. See Table 15. ld for the chemical composition measured in a polished cross-section.

Figure 15.23. Oxalate growing on faced gneiss cobbles on 10-year-old wall in Namche Bazar. Scale bar in microns. All images by BSE. a. Live lichen, showing bright oxalate dots in the crustose portion. The oxalate gives the tissue mechanical strength. b. Granular calcium oxalate resting on the gneiss rock, and in this case next to manganiferous rock varnish (brighter). c. Calcium oxalate crust with an outer porous layer and an inner lamellate layer. d. Close-up of the laminae in the box shown in Figure 15.23C.

Geographical Variations

Rock coatings in the Khumbu appear to grow and erode on time scales from years to centuries. Faced stone used to construct house walls have well-developed manganiferous rock varnish and calcium oxalate-rich crusts. Stream boulders that are abraded each melt season develop manganiferous rock varnish the following low-flow period. Boulders on Little Ice Age moraines (Fushimi, 1980) display several cycles of coating development and boulder spaUing. For example, rock varnish forms on polished surfaces that have inset spalls coated by oxalate-rich crusts, that are in turn eroded by inset spalls and the formation of more oxalate-rich crust. Rapid formation of rock coatings is undoubtedly tied to the moist climate, combined with an abundance of bare rock surfaces. In contrast, rapid rates of coating erosion may also be tied to abundant moisture which promotes acidity and concomitant chemical erosion, along with more rapid boulder spalling.

15.3.3. Rock Coatings in Ashikule Basin, West Kunlun Mountains A variety of rock coatings were found in this cold, dry, and dusty portion of the Tibetan Plateau: rock varnish, silica glaze, oxalate-rich crusts, phosphate films, carbonate crusts, dust films, and sulfate crusts (BaSO4, CaSO4). The most common rock coatings are silica glaze, rock varnish, and dust films. The other types of coatings are much less abundant. Several rock coatings play a role in breaking apart clasts, through a process that is often called salt weathering, a term that is in part a misnomer in this case. Sulfates were found on the sides of fractures in all volcanic samples (Figures 15.24a,b). Barite plays a role in the brecciation of grains (Figure 15.24a), while gypsum spreads fractures by precipitating along joint walls (Figure 15.24b). Carbonate is also found along rock fractures by itself (Figure 15.24d), or precipitated on top of gypsum (Figure 15.24b). Deflation of salts from shorelines of saline lakes likely provides the raw ingredients. On the volcanics, rock varnish is best developed in cracks, where it can be seen separating breaking-off pieces from the main rock (Figure 15.24f). Dust along the sides of crevices probably assists in the opening of joints (Figure 15.24c). In a few samples, phosphates films were found in the narrowest part of the rock crevice (Figure 15.24e). The abundance of loess on the landscape is reflected in the nature of the rock coatings. The surfaces of many rocks are coated with a thin film of dust (Figure 15.25a,b). This dust is then cemented to the rock surface in silica glazes (Figure 15.25c). Dust may also be an important source of silica in glazes that are deposited from solution (Figure 15.25d). The vast majority of subaerial rock varnishes are extremely thin (Figure 15.26d), even though they can appear visually well developed to the naked eye. Thin varnishes, however, often encapsulate thicker deposits of loess deposited in rock-surface depressions (Figure 15.26e, 15.26f, 15.26g). Dust pieces are also incorporated into thicker varnishes (Figure 15.26h). One of the most unusual aspects of Tibetan varnish is the interdigitation of varnish and phosphate films, even at the micron scale (e.g., Figure 15.26c). In order to assess the source of the manganese in the rock varnish (Table 15.2f-1), the dust attached to the volcanics in the Ashikule Basin was analyzed in situ (Table 15.2a) and gently scraped from each sample. The scraped material was homogenized in a flux of lithium metaborate, polished, and analyzed with a 1001am beam with the electron

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m i c r o p r o b e . T h e c o n t e n t o f M n O a v e r a g e d 0 . 1 1 % with a s t a n d a r d d e v i a t i o n o f 0 . 0 8 % . T h e c o n t e n t o f F e O w a s m u c h larger, 5.13_+2.52%. T h e p H o f the d u s t w a s 8.8+0.7.

Figure 15.24. Different types of rock coatings originate in rock fractures in the Ashikule basin. All images are by BSE. Scale bars are in microns. a. Barite (bright material at top of image) precipitated on and appears to be causing a brecciation of the underlying plagioclase (darker) minerals on the wall of a fracture. The sample is from AKB-93-1, a volcanic bomb at the rim of Ashishan volcano. b. A fracture waU has a sequence of gypsum (darker inner material) and calcium carbonate (brighter outer material), from sample AKB-93-5, a sloped surface of the west lava flow of Ashishan volcano. c. Dust accumulating on the wall of a fracture, in sample AKB-93-2, the northeast lava flow of the Ashishan volcano. The line indicates the location of an electron microprobe transect (Table 15.2a) that runs from loose dust to particles cemented by crack varnish. d. Calcium carbonate deposited along a joint fracture of sample AKB-93-7, from the south lava flow from the Ulukeshan cone. The line locates a probe transect (Table 15.2b). e. Iron phosphate found at the base of a rock fracture in AKB-93-23, a lava flow of Migongshan volcano. The line locates a probe transect (Table 15.2c). f. Rock varnish can be seen on the surface and penetrating and opening a rock crevice, from sample AKB-93-21, a lava flow from the Daheishan cone.

367

G e o g r a p h i c a l Variations

Table 15.2. Electron microprobe analyses of rock coatings in the Ashikule Basin of the West Kunlun Mountains, Tibet. Values in oxide weight percent. Totals do not reach 100% due to porosity, water, and content of organic matter. Transects correspond to lines in indicated figures. 9

i

9

i

Section a. Adhered dust and crack varnish (Figure 15.24c) TRANSECT: Na20 MgO AI203 Si02 P205 S03 1(20 CaO Ti02 MnO FeO BaO Top to Bottom

0.44 0.47 0.90 0.23 0.94 0.51 0.77 0.22 0.16 0.49

1.47 1.25 1.65 0.49 0.85 0.81 1.57 1.43 0.90 1.32

0.45 0.45 0.35 0.22 0.15 0.13 0.22 0.30 0.22 0.27

0.12 0.17 0.43 0.08 2.19 3.14 6.25 7.48 9.87 9.80

5.43 6.18 8.30 8.07 19.66 15.74 24.48 23.01 27.44 22.98

0.23 0.21 0.23 0.06 0.21 0.42 6.17 3.68 1.70 0.21

Total 77.19 63.71 62.49 89.27 88.48 88.81 94.51 81.19 95.06 95.86

CaO 3.10 0.72 20.60 0.30 1.70 0.10 56.82 3 . 5 3 2.00 19.09 0 . 5 7 1.57 0.17 52.01 0.95 20.71 18.08 0.00 0 . 1 2 1.22 48.04

Ti02 0.00 0.07 0.47

MnO 0.05 0.00 0.00

FeO 2.13 1.36 1.74

BaO 0.00 0.00 0.27

Total 85.68 80.57 98.38

1.64 4.26 1.94 1.11 1.19 1.24 1.76 2.11 2.16 1.86

14.19 17.87 12.79 7.80 9.58 10.18 15.59 12.19 16.84 16.91

50.49 30.51 33.80 69.64 52.46 54.38 31.77 25.74 30.51 36.97

0.21 0.11 0.27 0.00 0.09 0.09 0.16 0.00 0.07 0.14

0.50 0.30 0.22 0.17 0.12 0.27 3.72 2.42 1.17 0.60

2.02 1.93 1.61 1.40 1.04 1.90 2.05 2.61 4.02 4.31

Section b. Calcium carbonate crust (Figure 15.24d) TRANSECT: Na20 MgO AI203 Si02 P205 S03 K20 Top to Bottom

0.16 0.20 6.78

Section c. Phosphate film (Figure 15.24e) TRANSECT: Na20 MgO A1203 Si02 P205 Top to Bottom

0.88 0.80 0.68 0.75 0.67

0.19 0.21 0.29 0.35 0.40

29.44 30.84 30.04 29.09 32.07

S03 0.23 0.23 0.22 0.21 0.23

K20 0.16 0.06 0.14 0.15 0.16

CaO 8.26 8.67 9.08 8.28 7.69

Ti02 0.00 0.00 0.00 0.00 0.10

MnO 0.00 0.00 0.00 0.00 0.00

FeO 2.30 2.02 2.01 1.94 1.85

BaO 0.00 0.00 0.00 0.00 0.00

Total 76.27 76.92 77.31 75.82 80.75

P205 S03 49.88 0 . 1 9 0.71 47.26 0 . 3 1 0.83 45.99 0 . 3 1 1.06 6 2 . 0 7 1 . 5 2 0.33 63.49 1 . 6 2 0 . 2 9 5 9 . 8 3 1 . 4 9 0.18

K20 2.44 2.16 2.16 0.24 0.18 0.25

CaO 3.03 3.14 3.55 2.17 1.96 1.80

Ti02 0.14 0.23 0.21 0.10 0.13 0.09

MnO 0.00 0.00 0.00 0.22 0.24 0.20

FeO 6.45 4.14 7.19 1.51 1.30 1.97

BaO 0.67 0.70 0.83 0.20 0.19 0.15

Total 84.00 79.26 80.49 74.21 76.03 74.62

K20 0.00 0.00 0.00 0.00 0.00 0.00

CaO 1.03 1.22 1.20 1.09 1.55 1.43

Ti02 0.00 0.00 0.00 0.00 0.00 0.00

MnO 0.00 0.00 0.00 0.00 0.130 0.00

FeO 0.24 0.26 0.30 0.67 0.78 1.02

BaO 0.00 0.00 0.00 0.00 0.00 0.00

Total 92.68 93.46 90.54 86.18 90.15 89.70

3.46 2.00 2.17 2.57 2.48

31.35 32.09 32.68 32.48 35.10

Section d. Silica glaze (Figure 15.25c) TRANSECT: Na20 MgO A1203 Si02 Left to Right

0.67 0.55 0.94 0.18 0.33 0,19

3.64 2.94 2.07 0.45 0.60 1.17

16.18 17.00 16.18 5.22 5.70 7.30

Section e. Silica glaze (Figure 15225d) TRANSECT: Na20 MgO A1203 Si02 Top to Bottom

0.13 0.12 0.15 0.20 0.23 0.19

0.00 0.00 0.00 0.00 0.00 0.00

5.91 5.48 6.29 4.94 6.90 4.06

85.24 86.14 82.34 78.90 80.29 82.55

P205 0.13 0.24 0.26 0.38 0.40 0.45

S03 0.00 0.00 0.00 0.00 0.00 0.00

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Chapter 15

Section L Rock varnish and phosphate (Figure 15.26b) TRANSECT: Na20 MgO Al203 Si02 P205 S03 K20 Left to Right

0.00 2.97 0.22 4.39 0.00 0.00 0.07 0.70 2.32 0.36 0.43 1.31 0.24 0.00 0.00

2.55 1.72 2.12 1.16 1.14 2.84 0.23 2.04 0.93 0.20 3.52 1.29 2.95 4.15 0.66

12.38 9.41 11.85 13.96 10.28 12.23 1.23 12.43 9.50 1.72 13.89 11.36 18.48 1.80 3.29

27.38 34.25 28.18 43.94 22.93 26.25 82.94 34.57 53.36 93.47 31.56 47.15 36.99 13.37 56.59

13.22 10.38 14.09 4.90 18.95 11.46 2.52 12.90 9.85 0.62 11.18 9.81 7.88 25.16 11.57

0.57 0.82 0.17 0.75 0.85 0.20 0.35 0.75 0.20 0.00 0.50 0.00 0.27 0.72 1.07

2.11 0.72 1.82 1.33 1.79 2.75 0.14 1.40 1.02 0.19 1.52 1.25 4.30 0.40 1.01

CaO 18.65 15.34 21.18 12.05 23.56 14.58 2.71 18.75 14.89 1.36 16.94 16.69 10.40 34.81 14.12

Ti02 0.90 0.20 0.70 0.38 0.30 0.25 0.05 0.77 0.15 0.03 0.52 0.38 0.23 0.10 0.22

MnO 1.92 1.34 1.32 0.83 1.14 6.35 0.21 1.34 0.28 0.04 0.58 0.54 1.46 1.64 0.49

FeO 9.31 16.23 8.24 5.06 4.89 11.14 0.51 7.28 3.10 0.39 15.68 6.26 6.35 2.44 1.47

BaO 0.60 1.38 0.36 1.22 0.95 1.33 0.16 0.61 0.10 0.00 0.00 0.07 0.30 0.55 1.41

Section g. Rock varnish and phosphate film (Figure 15. 26c) LEFTTr. Na20 MgO A1203 Si02 P205 S03 K20 CaO Ti02 MnO FeO BaO

Total 89.59 94.76 90.25 89.97 86.78 89.38 91.12 93.54 95.70 98.38 96.32 96.11 89.85 85.14 91.90

Top to Bouom

0.00 0.00 0.00 0.00 0.00 0.00 0.00

2.49 1.14 0.48 0.53 4.00 2.29 2.84

9.66 6.82 2.40 2.12 11.36 11.81 2.44

16.84 13.50 5.69 3.87 22.68 21.35 10.91

14.02 21.52 27.41 21.13 17.32 5.16 27.20

0.32 0.27 0.17 0.00 0.15 3.25 1.05

1.41 1.29 0.52 0.47 2.14 1.84 0.45

18.44 36.16 48.02 21.25 21.60 7.09 37.01

0.33 0.40 0.00 22.07 0.20 0.32 0.10

9.80 1.32 0.58 8.78 0.92 11.39 0.99

18.94 4.19 1.59 18.58 11.50 17.64 3.52

0.63 0.21 0.09 0.15 0.09 5.73 0.50

Total 92.88 86.82 86.95 98.95 91.96 87.87 87.01

RIGHTTr. Top to Bottom

0.05 0.00 0.00 0.00 0.00 0.00 0.00

2.52 1.56 2.49 0.41 0.40 2.17 2.75

13.74 6.20 10.01 2.06 2.38 10.60 1.78

26.53 73.94 19.60 4.39 17.71 20.30 8.49

8.11 1.42 19.89 21.72 23.76 6.71 24.98

0.00 0.10 0.20 0.20 0.32 0.00 1.02

2.22 1.65 1.52 0.37 0.51 1.61 0.35

11.77 2.08 26.71 28.02 40.83 8.27 36.38

0.50 2.00 0.08 0.05 0.28 0.35 0.10

6.46 0.19 0.94 8.58 0.43 13.12 1.82

13.25 2.10 6.23 11.40 1.10 18.84 4.96

0.94 0.51 0.13 0.15 0.09 1.94 0.95

86.09 91.75 87.80 77.35 87.81 83.91 83.58

Section h. Rock varnish and phosphate (Figure 15.26d) TRANSECT Na20 MgO AI203 Si02 P205 S03 K20 CaO Ti02 MnO FeO BaO Top to Bottom

0.00 0.00 0.00 0.00 0.23 0.00 1.46 0.11 0.00 0.00 0.00 0.00

3.08 2.92 3.56 1.94 2.19 2.50 1.69 1.33 3.37 2.01 2.21 2.07

14.44 12.43 10.45 10.45 11.51 9.26 11.24 9.18 11.94 11.13 11.71 10.22

26.76 23.98 37.57 23.47 27.88 36.43 34.47 37.35 26.83 19.40 24.13 19.10

5.11 13.34 10.98 11.14 15.01 12.28 13.79 13.11 13.73 14.23 13.24 18.40

0.10 1.95 7.08 3.67 8.26 15.57 0.98 0.12 2.76 19.73 0.83 1.54 10.92 0.20 0.15 1.39 18.57 0.65 1 . 4 2 6.72 0.36 0.00 1.72 17.03 15.40 0.75 5.86 0.58 0.57 1.86 23.45 0.28 0.44 6.49 0.90 0.37 1.54 18.96 0.35 0.46 6.53 0.45 0.30 1.39 20.09 0.25 0.46 5.18 0.23 0.10 2.37 19.60 0.83 0.89 4.83 0.45 0.25 1.71 20.22 0.52 2.49 8.85 0.46 0.17 1.73 20.48 0.47 4.93 12.47 0.71 0.30 2.00 18.81 0.52 4.53 11.81 0.71 0.05 1.43 27.05 0.32 2.81 8.64 0.40

Total 87.00 88.77 91.82 88.34 90.81 89.13 90.55 90.15 90.37 87.73 89.97 90.49

Geographical Variations Section i. Rock varnish (Figure 15.26e) TRANSECT Na20 MgO A1203 Si02 P205 UpperRight 0.20 3.28 11.90 24.67 1.79 to

Lower Left

0.20 0.00 0.16 5.36 2.72 4.11 3.55

3.12 3.02 2.55 1.43 2.57 2.32 3.18

11.79 11.41 11.19 14.27 9.94 11.58 11.41

22.89 22.19 21.80 61.18 41.65 52.69 53.36

CaO 3.65 4.06 4.46 4.45 4.76 11.75 8.68 8.30

Ti02 0.42 0.32 0.70 0.53 1.15 1.90 1.10 0.97

MnO 15.71 16.35 15.70 13.76 0.25 1.54 0.62 0.53

FeO 18.52 18.37 19.64 24.68 6.41 18.64 9.29 10.25

BaO 1.92 2.18 2.39 2.22 0.23 0.36 0.23 0.21

CaO 0.95 1.11 20.37 0.22 1.75 8.70 0.55 1.63 20.61 0.22 0.46 38.24 0.00 0.40 10.58

Ti02 0.27 0.42 0.47 0.08 0.03

MnO 2.16 11.26 4.34 3.20 0.17

FeO 4.53 14.54 11.85 5.52 3.33

BaO Total 1.47 93.36 1.62 86.10 0.60 85.41 0.32 78.46 0.09 92.56

CaO Ti02 MnO 1.70 0.02 1.48 3.65 0.38 18.76 1.92 0.00 1.53 3.79 0.32 20.25 1.74 0.12 1.55 4.04 0.50 19.70 2.41 0.07 1.69 4.58 0.77 17.64 2.61 0.25 1.76 4.86 0.60 13.08 0.69 12.06 0.25 12.88 0.50 2.83 0.00 35.07 0.00 36.78 0.00 0.00 0.00 31.11 0.00 33.11 0.00 0.00

FeO 17.86 17.19 17.67 19.03 21.45 2.82 0.13 0.14

BaO 2.05 2.32 2.37 2.17 1.65 0.33 0.40 0.45

Total 80.46 81.05 81.65 83.28 83.02 82.98 79.88 74.09

FeO 0.04 6.23 0.04 0.06 0.01 0.09

BaO 0.00 0.02 0.00 0.06 0.00 0.00

Total 93.87 81.72 73.76 76.09 84.35 82.43

2.25 2.41 2.98 0.32 2.50 2.20 1.86

S03 0.40 0.45 0.12 0.15 0.00 0.00 0.17 0.00

K20 1.86 1.69 1.66 1.73 4.25 2.16 3.34 3.02

Section J. Rock varnish and phosphate (Figure 15.26g) TRANSECT Na20 MgO A1203 Si02 P205 S03 K20 Top to Bottom

1.11 0.00 0.00 0.00 5.34

1.31 2.69 1.79 0.60 0.23

10.17 33.69 11.98 25.89 10.64 19.00 2.91 5.16 20.67 49.31

369

16.22 7.03 13.93 21.75 2.41

Section k. Rock varnish on sulfate (Figure 15.26i) TRANSECT Na20 MgO A1203 Si02 P205 S03 K20 Top to Bottom

0.05 0.16 0.07 0.12 0.24 0.53 0.94 1.00

3.02 2.84 2.95 3.05 3.40 2.12 0.00 0.00

10.52 10.90 10.32 11.15 10.83 1.51 1.05 2.11

20.97 19.83 20.62 20.60 22.29 46.46 5.51 6.17

Section !. Calcium oxalate and silica glaze (Figure 15.28a) TRANSECT Na20 MgO A1203 Si02 P205 S03 K20 Upper Left 0.84 0.35 3.14 88.40 0.00 0.00 0.23 to

Lower Right

0.31 0.95 0.16 0.07 1.23

5.75 6.01 2.75 5.46 4.74

8.16 9.46 4.33 1.44 7.90

6.49 12.12 12.66 60.53 45.97

0.00 0.02 0.00 0.16 0.09

0.00 0.00 0.72 1.07 1.25

0.40 0.05 0.28 0.05 0.46

CaO 0.87 53.1 45.11 55.07 15.53 20.67

Ti02 0.00 1.18 0.00 0.00 0.03 0.03

MnO 0.00 0.08 0.00 0.00 0.00 0.00

Total 84.32 83.67 83.70 86.20 99.61 95.73 96.33 96.64

The amount of manganese found in the varnish is about 100 times more than in the loess. Therefore, at least 100 times the varnishes weight in loess must come in contact with the rock surface, somehow chemically release the Mn, which is then reprecipitated on the rock surface. Because the lava flows have been exposed to loess deposition for more than 70,000 years (F.M. Phillips, personal communication, 1995), far more loess has come in contact with the rock surfaces than is necessary to provide enough Mn for the varnish. In other words, the source of the Mn is not a problem. Rather the uncertainty rests in the process by which the manganese is concentrated. The pH values of the dust are far too high to have manganese released from the dust (Mulder, 1972; Schweisfurth et al., 1980; van Veen, 1972). In order to release the Mn, it must be transformed to the mobile divalent state, which might occur with the natural acidity associated with rain/snow. The dissolved Mn could then be reprecipitated on the rock surface by either: (1) evaporation of the moisture; (2) a change in pH when the solution comes in contact with another loess particle; or (3) microbial oxidation and fixation of manganese.

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Figure 15.25. Dust and sihca glaze on rock surfaces. All images are by BSE. Scale bars are in microns. a. A top-down view of dust on surface of AKB-93-2, from the northeast Ashisan flow. The pattern of cracking is similar to mud cracks. The dark gray areas may be remnants of desiccated fungal hyphae. b. A cross-sectional view of the same sample as Fig. 25a, where a splitting biotite grain is enveloped by loosely adhered dust. The dust may enhance weathering by storing capillary water. c. Two types of silica glaze on AKB-93-8, the east lava flow from the Yishan cone. The glaze on the left is composed of mostly loess particles cemented by silica glaze, where as the glaze on the right is composed of mostly silica glaze. The reason for the discontinuity is not clear. The line indicates the location of a probe transect (Table 15.2d). d. Silica glaze formed on AKB-93-5, the west flow of the Ashisan cone. This silica glaze is comparatively unusual, because it does not contain pieces of dust detritus. Instead, the sihca glaze appears to be reprecipitated in laminae, probably from solutions. Also, a perpendicular fracture split the silica glaze (and the underlying rock), before the most recent depositional level. The line locates the probe transect (Table 15.2e).

A bacterial hypothesis for the enhancement of manganese from loess is favored by in situ microscopic observations. Manganese-concentrating bacteria occur on Tibetan varnishes (Figure 15.27a), and they are also found within the varnishes (Figure 15.27b). The bright dots in Figure 15.27a are greatly enriched in Mn, when examined by EDS spots ~ll.tm in diameter. They are the fight size for cocci that precipitate manganese on cell walls (cf. (Ferris et al., 1987b; Greene and Madgwick, 1991). Bright rims around the bacteria in Figure 15.27b are smaller than the ~llam spot size of EDS, but analyses centered on the bacteria reveal high peaks in Mn. Since brightness in BSE is from higher atomic number, it is reasonable that the Mn is associated with the cell walls. A careful examination of Figure 15.27b reveals smaller cocci-shaped features, perhaps the desiccated remains of bacterial casts. Although calcium oxalate crusts are far less common in the Ashikule Basin than in Nepal, they do occur on lava flow surfaces in association with silica glaze (Figure 15.28a,d; Table 15.2m) and lichens (Figure 15.28b,c). In one case, a calcium carbonate crust formed over a calcium oxalate-rich crust (Figure 15.28d).

Geographical Variations

Figure 15.26. Examples of rock vamishes found in the Ashikule Basin, imaged by BSE. Scale bars are in microns a. The rock vamish currently on the surface started in a rock fracture; its progressive growth separates grains from the rock (upper left), from AKB-92-23, southeast flow of the Migongshan volcano. b. A thin rock vamish on the surface (left) is much better developed in a rock fracture. The line indicates the probe transect (Table 15.20. The sample is from AKB-93-8, the east flow of Yishan volcano. c. The interdigitation of varnish and silica glaze is seen here on a very fine scale. The lines indicate the electron microprobe transects (Table 15.2g), from AKB-93-2. d. This is one the thickest vamishes found on the subaerial surfaces of the volcanics in the Ashikule Basin. The line indicates probe transect (Table 15.2h), from AKB-93-1, a bomb on rim of Ashishan volcano. e. Rock vamish formed on top of silica glaze, from AKB-93-8, east flow of Yishan volcano. The line indicates a probe transect (Table 15.2i). f. Varnish cementing dust deposits accumulate in a depression in sample from AKB-93-21, south flow of Daheishan volcano. g. Close-up of the rock varnish in the center of Figure 26f. The line indicates the probe transect (Table 15.2j). h. Rock varnish developed on a glacial moraine from the West Kunlun Mountains. The porous zones are areas of cation leaching where capillary water flows through the varnish. Also note the large detrital grains of dust. The sample is from AKB-93-11, Yishan dome rhyolite. i. Rock varnish formed on top of a sulfate crest. The sample came from a crack vamish, from AKB93-8, east flow of Yishan volcano. The line indicates probe transect (Table 15.2k).

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Fi.gure 15.27. Manganese-concentrating bacteria found in the Ashikule Basin, Tibet. Scale bars are in microns. a. BSE image of the surface of varnish on AKB-93-6, the west flow of the Ashishan volcano. The sample was first subjected to etching by HF fumes to remove the very surface layer of dust, very gently washed with deionized water, and carbon coated. b. BSE image of cross-section of varnish from AKB-93-6, the west flow of the Ashishan volcano.

15.3.4. Discussion and Conclusion The rock coatings on the roof of the world can be placed in a broader context in different ways. For the general physical geographer trying to understand spatial variations in the natural landscape, there is an asymmetry in rock coatings that reflects the entire physical geography system. For the geomorphologist with an eye on the weathering system, rock coatings are a secondary weathering product and a positive feedback on rock weathering. For the purposes of this chapter, the transect across the roof of the world illustrates a serious flaw in attempts to map geographical variability in rock coatings.

15.3.4.1 Asymmetry in Rock Coatings and Landscape Aesthetics Rock coatings are ubiquitous in both the cool and wet Khumbu of Nepal and the cold and dry West Kunlun Mountains of Tibet. Coatings are even found on rocks resting on the surfaces of active glaciers. Uncoated 'bare' rock is seen only where the rate of erosion exceeds the rate of coating, for example in Nepal in places of frequent avalanching. Although rock coatings are ubiquitous in both settings, they reflect the

Geographical Variations

very different physical geography systems on opposite sides of the highest topography on Earth.

Figure 15.28. Calcium oxalate crests in Ashikule Basin, Tibet. The scale bars are in microns a. and c. Lichens, oxalate, and silica glaze, from AKB-93-8 Yishan volcano lava flow. Figure 15.28a presents a view of backscattered electrons, where the lichens appear black; in 15.28c, the lichens are visible. The line in 15.28a indicates the location of a probe transect (Table 15.21). The darker areas in BSE are silica glaze. b. Speckled texture of calcium oxalate on AKB-93-1 next to a lichen, from the Ashishan volcano. d. Superposition of calcium carbonate (brighter outside rim), on oxalate crust (mixed with dark threads of silica glaze), all on top of a basal layer of dark silica glaze, now on the surface of AKB-93-21, the south lava flow from the Daheishan volcano.

There are similarities and differences in rock coatings in the two contrasting study areas. Rock varnish, silica glaze, calcium oxalate crusts, and phosphate films occur in both areas. At the same time, these same coatings display differences. For example, Khumbu rock varnish is intermediate between clay-rich varnish (chapter 10) and clayabsent manganese heavy-metal films (chapter 8); it has much more manganese, fewer clay minerals, and is most common where water flows. Tibetan varnish is more geographically widespread, and interfingers with silica glaze and phosphates, but is extremely thin. Silica glaze is also much more widespread in Tibet. Calcium oxalate is much more geographically restricted in Tibet. For example, on the Ashikule Basin lava flows it occurs next to small patches of lichens, and it interdigitates with silica glaze. The wet and geomorphically active Khumbu is a young landscape, with slope and fluvial processes still adjusting to the retreat of the 16th Century Little Ice Age glaciers. Lithobionts (moss, algae, lichens, fungi, cyanobacteria) tend to form first on moistened surfaces. Dark coatings of calcium oxalate (whewellite) form streaks downflow from organic coatings or plants. Dark films of iron hydroxides are found in the Khumbu where acidic waters support acid-loving iron bacteria (cf. Nealson 1983). Manganiferous rock varnishes occur in the most xeric settings and on stream-side boulders. The net aesthetic effect is to darken the landscape by masking rock minerals with low albedo coatings, which increases the visual contrast between ephemeral snow and the rocky landscape.

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In a West Kunlun, Tibetan, landscape almost devoid of vegetation with lower relief, rock coatings play a more obvious role in defining the landscape aesthetics. High albedo tan-colored loess is everywhere, drowning the microtopography. Although the slower-growing dark manganiferous rock varnish is much thinner in Tibet than in Nepal, it is ubiquitous and provides a strong visual contrast to the loess. Dark colors come from rock varnish, and varnish is interdigitates with silica glaze and phosphate films.

15.3.4.2. Comparison with Rock Coatings in Other Geographic Settings The objective of this section is to compare the chemical and textural aspects of Khumbu and Tibetan rock coatings with rock coatings in other geographic settings.

15.3.4.2.1. Iron Films The ability of bacteria genera such as Leptothrix, Thiobacillus, and Gallionella to oxidize iron in acidic to neutral waters is well known (Aristovskaya, 1975; Chukhrov et al., 1973; Mallard, 1981; Nealson, 1983). Although I did not attempt to culture microorganism, bacteria-like forms were seen with the aid of electron microscopy on the surface of iron skins in Nepal. Because iron skins are associated with acidic drainage and iron is geochemically mobile in its divalent state, bacterial oxidation and fixation is required for the presence of iron skins. Iron films are common near nivation patches (e.g., Cailleux 1967), especially where snow melt moves through Sphagnum moss and waters have low pH values. One less appreciated aspect of iron films is that precipitation of iron helps create silt-sized rock fragments, in a fashion similar to the observations of iron skins from Karkevagge, Northern Scandinavia (Dixon et al., 1995) and Antarctica (Hayashi, 1989). Thus, the glacial flour load of alpine systems may be due, in part, to the weathering of rocks by iron films. Iron is present in Khumbu coatings at concentrations greater than 55% (measured as FeO). Aluminum and silica are the next most common elements, and their abundance appears inversely correlated with the amount of phosphorus and sulfur. Unfortunately, there are not enough analyses globally to determine if the iron films in the Khumbu (Table 15.1a) are typical of iron films in similar environmental settings.

15.3.4.2.2. Silica Glaze Deposits of amorphous silica, mixed with aluminum and iron, are found in virtually every terrestrial environment including: coastal sea cliffs (Mottershead and Pye, 1994), tropical rivers (Alexandre and Lequarre, 1978), subaerial tropical rock surfaces (Curtiss et al., 1985), subtropical deserts (Fisk, 1971), Antarctica (Weed and Norton, 1991), and temperate humid settings (Dorn and Meek, 1995; Robinson and Williams, 1987). The silica glazes analyzed from the Khumbu and West Kunlun Mountains are similar to those found elsewhere. The distinctive morphological and chemical break between rock and coating reflects an external origin (Figures 15.21b, 15.25c,d, 15.28d). Amorphous silica is the main constituent (over half SIO2), with lesser amounts of aluminum (5 to -20% A1203) and iron (1 to ~ 10% FeO). Textures range from those rich in detritus (Figure 15.25c, 15.26e) to even compositions indicative of deposition from solutions (Figure 15.21b, 15.25d). The interdigitation of silica glaze and other

Geographical Variations

rock coatings (Figure 15.21b, 15.26e) occurs elsewhere, for example, South Africa (Butzer et al., 1979) and Hawai'i (Dora et al., 1992a).

15.3.4.2.3. Dust Films

Dust particles attach to rock surfaces in deserts (Hobbs, 1917; Rivard et al., 1992). In Tibet, loess that comes to rest on rock surfaces (Figure 15.25a,b) is cemented to more permanently by rock varnish (Figure 15.24c, 15.26f, h), silica glaze (Figure 15.25c, 15.26e), carbonates (Figure 15.24d), sulfates (Figure 15.26i), and probably oxalates (Figure 15.28b).

15.3.4.2.4. Carbonate and Sulfate Crusts

Sulfate (barite, gypsum) and carbonate crusts rock coatings on Tibetan volcanics probably started as deposits in rock crevices with raw material coming from the deflation of sulfate salts along lake margins. However, gypsum crusts in Antarctica are precipitated as snow sublimates (Hayashi, 1989), a process that could also occur in the Ashikule basin. Sulfate and carbonate occur together in Figure 15.24b, which also occurs in coastal deserts such as the Namib (Goudie, 1972) and Baja California (Conca and Rossman, 1985). The origin of exposed carbonate and gypsum is complex, however, and must be considered on a case-by-case basis (Watson, 1985; Watson, 1992; White, 1993b). Hence, these comparisons are speculative.

15.3.4.2.5. Oxalate-Rich Crusts

Oxalates-rich crusts are much more abundant crusts than many had previously thought. Whewellite (CaC204.H20), a calcium oxalate, is probably the most common mineral in rock-surface settings (Lewin and Charola, 1981; Russ et al., 1994; Zfik and Sk~ila, 1993), although oxalates occur with other cations such as iron (humboldtine) and magnesium (glushinskite). Many oxalates derive from lichens (Del Monte et al., 1987a; Wilson et al., 1980), but they may also come from plants (Lewin and Charola, 1981). Oxalate crusts in Nepal and Tibet appear to derive from lichens. Figure 15.23, all from one wall in Namche Bazar, shows a possible sequence of diagenesis to form oxalate-rich crusts: from speckled Ca-oxalate within live crustose lichens (Figure 15.23a); to granular textured crusts immediately adjacent to lichens (Figure 15.23b); and finally to more massive oxalate (Figure 15.23c,d). The few oxalates found in the Ashikule Basin were found only immediately adjacent to lichens. Calcium-oxalate crusts may include other constituents in variable amounts, for example gypsum, clays, and quartz from eolian sources (Russ et al., 1994). The most common co-constituent in the Khumbu and West Kunlun oxalates is silica-aluminum in the laminar section in Figures 15.23c,d and Figure 15.28a; these elements probably derive from clay minerals. The granular section in Figure 15.23c, however, does not contain A1-Si (Table 15.1e) all while the magnesium content remains constant, suggesting the magnesium has an origin different than clays. The Khumbu oxalate

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also contains a few percent of a Mn-Ba mineral - - perhaps romanechite (Table 15. le), a constituent that has not been reported in other oxalate crusts. 15.3.4.2.7. Phosphate Skins Phosphate skins are poorly researched, especially as rock coatings in alpine environments. Those observed here (Figures 15.21c, 15.24e, 15.26c) are unlike those reported previously in alpine regions. One phosphate skin in Tibet (Figure 15.24e; Table 15.2c) appears to be an aluminum-phosphate, with a chemistry consistent with a Ca-millisite 0~licoteaux and Lucas, 1984; Nriagu, 1984). The chemistry of phosphate that interdigitates rock varnish (Figure 15.26b-Table 15.2f; Figure 15.26c-Table 15.2g; Figure 15.26d-Table 15.2h; Figure 15.26g-Table 15.2j ) is consistent with an apatite (Nriagu, 1984). The phosphate skin in Figure 15.21c, from the Khumbu, has three BSE textures: an upper iron skin; a middle darker section; and a speckled bottom texture. The chemistry of the middle texture is similar to the Table 15.2c in Tibet, perhaps a Ca-millisite. The chemistry of the lower left end of the transect (area with bright speckles) could represent a combination of Ca-millisite and a Fe-P mineral, which could be strengite (FePO4.2H20). The Khumbu phosphate accretion (Figure 15.21c) may relate to iron phosphate films seen in the Arctic (Konhauser et al., 1994) that are produced by bacteria. Iron is present in variable amounts (Table 15.1c). Bacteria (not seen in the BSE images) may be involved in Khumbu phosphate precipitation (Lucas and Pr6v6t, 1981), since bacteria are present on the surface and qualitative EDS spot analyses on these bacteria reveal high P peaks.

15.3.4.2.8. Rock Varnish The varnishes in the Khumbu and West Kunlun Mountains are generally similar to varnishes elsewhere in chemistry in that they are characterized by clay minerals that are cemented to the rock by iron and manganese hydroxides. Their texture indicates that they form as an accretion on top of the underlying rock. The Khumbu varnishes have more hydroxides and less clay (Table 15.1d) than Tibetan (Table 15.2a, 2f-j) and other varnishes (Dorn et al., 1992a). The most common type of Khumbu varnish is found adjacent to running water. This is consistent with Mn-rich rock coatings found along water courses in other alpine settings (Cailleux, 1967; Dora and Obedander, 1982; HOllerman, 1963). West Kunlun varnishes are different from most varnishes found elsewhere in that they interdigitate with phosphates, probably an apatite (Figure 15.26b-Table 15.2f; Figure 15.26c-Table 15.2g; Figure 15.26d-Table 15.2h; Figure 15.26g-Table 15.2j), and sulfates (Figure 15.26i-Table 15.2k). The West Kunlun environment is dry enough and has a high enough pH to preserve well-layered varnishes that record climatic changes. The age of the volcanics is old enough to record climatic changes in varnishes elsewhere. However, varnishes with distinctive layering does not occur in the thin subaerial varnishes on the volcanics. In contrast, West Kunlun varnishes are best developed in a crevice positions, where Mn correlates with Ba, suggesting a Ba-Mn m i n e r a l - perhaps romanechite.

Geographical Variations

The lack of layering on the volcanics could be due external or internal factors. The external factors that might preclude the development of layers be: (1) weathering that exposes rock crevices (Figure 15.24); and (2) eolian abrasion that resets the varnish clock. For example, Figure 15.27b displays fossilized bacteria that have been shaved in half by wind abrasion. While evidence for wind abrasion can be found in the field (T. Liu, personal communication, 1996), the wind abrasion has not been enough to completely abrade off the fossilized bacteria or remove pahoehoe surface textures. Therefore, the eolian abrasion appears to be, at the least, episodic. It may also be that intrinsic varnish-forming factors preclude the development of layers on Akesu volcanics. One possibility may be that subaerial varnish formation that is too slow to record climatic fluctuations. The most likely explanation for the lack of layering is interdigitation with other types of coatings that occurs in a discontinuous fashion. Consider the abundance of phosphate within varnish. The phosphate (Figure 15.26b-Table 15.2f; Figure 15.26c-Table 15.2g; Figure 15.26dTable 15.2h; Figure 15.26g-Table 15.2j) occurs in lenses, as does the silica glaze. Hence, a continuous layering pattern that might record climatic changes does not get a chance to develop. The only setting where layered varnishes, similar to those that occur in warm deserts, have been found is on boulders on glacial moraines of the West Kunlun Mountains (Figure 15.26h).

15.3.4.3. Role of Himal-Tibet Rock Coatings in the Weathering System Rock coatings are not viewed as integrated part of the earth's system in any scientific literature. The typical treatment in physical geography or physical geology books is to add an unconnected section on 'rock varnish' in 'desert landforms'. A more appropriate placement would be within 'weathering and soils', for rock coatings are at the same time a secondary weathering product, and an example of a positive feedback in rock weathering. Weathering breaks down rocks formed at higher temperatures and pressures into products more in equilibrium with conditions found at the earth's surface. All types of rock coatings exemplify this concept. Whether a manganiferous rock varnish, a crust of calcium oxalate, or a glaze of amorphous silica, new mineral assemblages have formed. And these assemblages have distinctive spatial patterns that reflect geographical variability at the atmosphere-biosphere-lithosphere-hydrosphere interface on rock surfaces. A relatively unexplored aspect of rock coatings, well illustrated in both the Khumbu and Tibetan plateau, is their ability to aid in rock weathering by enhancing preexisting rock weaknesses. The rock weathering promoted by rock coatings is a combination of both mechanical and chemical processes. Iron skins in Nepal, for example, form on the surface and within a rock. They can range in color from bright red to a dark brownblack. Iron skins that occur within a rock are deposited from solutions along grain boundaries and joints. The precipitation further widens the fracture. When the next remobilization and reprecipitation event occurs, the solutions move further into the cracks, which in turn splits them further. Images from Nepal (Figure 15.21a,15.21f) are similar to those seen in K~il'kevagge, Northern Scandinavia (Dixon et al., 1995). Several different rock coatings in Ashikule Basin of the West Kunlun Mountains exemplify a positive feedback in that new weathering products further accelerate the breakdown of rocks (Figure 15.24). Dust moves into rock crevices by mechanical transport (Villa et al., 1995) (Figure 1.5.24c). The dust may aid in the widening of

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fractures even further by storing capillary water to be subsequently frozen, which in turn increases the dust flux. Other rock coatings appear to be aggressive in breaking off and enveloping pieces of rock from the crevice sides (see carbonate in Figure 15.24d). Sulfates can brecciate rock walls (Figure 15.24a). The growth of rock varnish in cracks can split fractures as well (Figure 15.240. Chapter 6 emphasized the protective role of rock coatings. These observations, in contrast, indicate that rock coatings can exert an erosional influence. This is a particularly important point in rock conservation efforts. The possible erosional influence of rock coatings is not limited to what has been observed in Nepal and Tibet. Because many rock coatings are dark, they have a low albedo and experience increased temperatures. Thus, they may promote enhanced thermal expansion of minerals. The thermal coefficients of expansion and contraction for the rock coatings may be substantially different from the underlying rock. In this way, rock coatings formed in fractures may increase the friability of the weathering find. A case in point is in Petra in Jordan, where Paradise (1993b, 1995) found that the calcite cement in the host rock expands and contracts at a different rate than the surrounding quartz grains, thus explaining more rapid rates of erosion associated. Although Paradise (1993b, 1995) studied erosion of the rock material, carbonate crusts and other rock coatings could potentially have a similar effect.

15.3.4.4. Implications for Understanding Geographical Variations in Rock Coatings I do not think it is possible to produce an accurate map showing the geographical variability in Himal-Tibetan rock coatings. Too much heterogeneity exists at all spatial scales. Coatings interdigitate at the scale of microns and millimeters. Different rock coatings are found side-by-side at the scale of meters. My experience in the transect discussed in this section, and elsewhere in the world, is that heterogeneity is the rule. While it is possible to map variable characteristics of a single rock coating over an area, it is not possible to generate meaningful mapping units of different types of rock coatings where the graphical scale of the map is in kilometers.

15.4. Concluding Perspectives Anytime a specialized monograph in the natural sciences is written, it is necessarily filled with the sort of detail that a specialist desires. And yet, I had hoped to weave into the detail three general themes of broader interest. My first general goal is to alter your perception of the geography of rock coatings. Rock coatings are one of the least appreciated aspects of rocky landscapes, but these skin-deep accretions are one of the most important agents in defining the color and texture of bare-rock landscapes. The color of many of the world's famous natural rock landmarks is not due to the rock, but the rock coatings. Ayers Rock, Australia, is naturally ivory, but it has an orange appearance due to the growth of iron films (Figure 14.9). The Nazca lines of Peru are noticeable from the air because stones with manganiferous varnish have been pushed to the side (Clarkson, 1990; Silverman, 1990). When the world television audience focused on the 1996 Summer Olympic Games, Stone Mountain, Georgia, was viewed in televised 'shorts', and its coloration is controlled by films of iron, crusts of calcium oxalate, and glazes of silica (Figure 6.15). Bare rocks around the world are covered by lichens (Sharnoff, 1994), including the walls of Milford Sound in New Zealand and Easter Island giant sculptures. I hope that the

Geographical Variations

reader realizes by now that, in fact, there are very few rocky landscapes whose appearance is not altered by natural rock coatings. My second goal is to bring together in one place and synthesize the literature on rock coatings. Ever since von Humboldt (1812) initiated the scholarly study of rock coatings, the diaspora in scholarship in the natural sciences has been mirrored in the burgeoning literature on rock coatings. The reality is that researchers interested in rock coatings come from many different disciplines and publish in places that are rarely encountered by scientists in other fields. By writing the first book on rock coatings, and by integrating these different literatures, I hope to encourage a cross-fertilization of ideas in different fields studying the same phenomenon. My third goal is to promote the development of theory. Right now, the vast majority of research on rock coatings has been the gathering of empirical data. Yet much of the history of natural science has been the search for generalizations to order the chaos of data on the natural world. Thus, I advocate the perspective of landscape geochemistry as a general paradigm to understand rock coatings in a cohesive intellectual fashion. Using landscape geochemistry, I present a general model to interpret the geography of rock coatings. The usefulness of landscape geochemistry and the proposed hierarchical model will be measured in the future: by how well it helps us to understand geochemical pollution; how to best preserve stone monuments; how to estimate the ages of rock surfaces; and more generally, how it aids the interpretation of natural biogeochemical systems at the earth's surface. It was disappointing that I could not meet my third goal more completely. I was able to present only a cursory explanation for the geography of rock coatings. The fault may be mine; biogeochemical patterns may be patently clear to a more perceptive scholar. Yet, I have come to realize that understanding the geography of rock coatings will require an integration of information at different scales. Available methods of data acquisition are simply inappropriate for making jumps in scale, between micron-scale electron microscope imagery and remotely sensed Pixels on the order of meters. Existing efforts to map rock coatings are laudable, but only a few examples exist of researchers who base their general maps on micron-scale knowledge. There has been no effort to generalize microscopic information at the milleter scale, which will be necessary to make the leap to meter scale airborne and satellite data. I challenge future researchers to understand the complexity found at microns, millimeters, and meters all before trends are mapped at the scale of kilometers. It is only by studying rock coatings at different scales that researchers will be able to use different spectacles to understand this complex and ubiquitous aspect of our planet's surface.

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~p

418

Geographical Index

Geographical Index

Acropolis, Greece, 224 Afghanistan, 207 Africa, 1, 34, 35, 79, 86, 91, 92, 187, 190, 191,194, 227, 288, 292, 375 Agra, India 5, 111 Akesu volcanic field, Tibet, 80, 283,358 Alaska, U.S.A, 57 Alice Springs, Australia 109 Antarctica, 25, 34, 46, 57, 87, 95, 101,102, 136, 145, 147, 156, 157, 181,182, 183, 184, 201, 210, 211,212, 214, 238, 244, 245,255, 264, 269, 278, 287, 288, 292, 293,310, 332, 374, 375 Apple Valley, Califomia, U.S.A., 250, 251 Arches National Park, Utah, U.S.A. 353,354 Arctic, 3, 60, 63, 79, 95, 121,147, 157, 164, 189, 190, 192, 251, 267,376 Argentina, 286 Arizona State University, Arizona, U.S.A. 72, 300, 301,313 Ashikule Basin, Tibet 358, 359, 360, 365, 366, 370, 371,372, 373,375,377 Ashishan Volcano, Tibet, 359, 366, 371,372, 373 Atacama Desert, 61, 108, 175, 189, 190, 248, 255, 256, 259, 261, 312 Atlas Mountains, Morocco, 297, 329 Ayers Rock, Australia 2, 6, 179, 200, 330, 378 Baffin Island, Canada, 95 Baja Califomia, Mexico 61, 175, 264, 375 Beacon Valley, Antarctica 184, 293 Bear River, Sierra Nevada, Califomia, U.S.A. 95, 96, 97, 156 Belfast, 258, 265 Berkeley, California, U.S.A. 131, 218

Bighorn Basin, Wyoming, U.S.A. 310 Bishop Creek, Califomia, U.S.A. 103,202, 227, 229, 230, 286 Bishop Tuff, Califomia, U.S.A. 50, 51, 87, 105, 106, 107,255 Black Hills, U.S.A. 65, 271,273 Brazil, 18 Calico Early Man Site, Califomia, U.S.A. 219 Canadian Rockies, 227 Canyon de CheUy, Colorado Plateau, U.S.A. 9, 325, 345 central Australia, 108, 159, 193, 197,305 Central Valley, California, U.S.A., 258 Chad, 92 Chile, 108, 110, 255, 256, 259, 260, 312 China, 175, 201,202, 205 Cima Volcanic Field, Mojave Desert, California, U.S.A., 36, 274 C6a, Portugal 161,169, 288,298, 314,331,332 Colorado Plateau, U.S.A., 8, 60, 191,238, 277, 293,324, 339, 351 Colorado River, U.S.A., 56, 78, 139, 226, 289, 297,310, 331 Columbia Plateau, U.S.A. 43 Conejo Volcanics, Califomia, U.S.A. 286 Coso Volcanic Field, California, U.S.A., 218, 226, 334 Crater Flat, southern Nevada, U.S.A. 170, 172, 173, 174 Cyprus, 146, 181,264 Dana Plateau, Sierra Nevada, Califomia, U.S.A. 125, 131, 148 Daylight Pass, Nevada, U.S.A. 150 Dead Sea, Israel, 44, 205, 206, 257, 258, 261 Death Valley National Monument, Califomia-Nevada, U.S.A.,, 7, 13, 39, 40, 53, 74, 75, 77, 104, 114, 157, 158, 159, 171, 176, 177, 186, 196, 197, 199,

Geographical Index 200, 202, 204, 205,206, 210, 211,212, 213,214, 220, 225, 226, 230, 231,245,259, 264, 310, 346, 347,348, 349, 350, 352,353, 354, 355 Egypt, 1, 17, 79, 86, 111, 143, 178, 200, 233, 235, 282 England, 87, 94, 101, 106, 286, 302 Europe, 234, 266, 269 Fontana, Califomia, 166, 167 France, 94, 130, 134, 238,286 Galena Canyon, Death Valley, California, U.S.A. 177, 204 Gettysburg, Pennsylvania, U.S.A., 127, 128 Gold Beach, Oregon, U.S.A. 292 Grand Canyon, Arizona, U.S.A. 2, 331 Great Basin, U.S.A., 189 Great Britain, 8 Green Island, Australia 70 Greenland, 95, 136, 147, 152, 157, 164 Haifa, Israel, 73 Haleakala, Hawai'i, U.S.A., 14, 285,303, 311 Henry Mountains, Utah, U.S.A., 207,326 Hoover Dam, U.S.A. 186 Hualalai, Hawai'i., 51, 58, 296, 306, 307, 312, 314, 315, 316 Iceland, 153, 171,201 Idaho, U.S.A., 207 Israel, 42, 59, 61, 62, 66, 73, 86, 117, 143, 175, 180,206, 257, 258,261,302, 351 Italy, 50, 138,255,264 Iztacc~uatl Volcano, Mexico, 162, 171,172, 176, 252, 253, 303, 304, 307, 308,314, 316 Jewel Cave, South Dakota, U.S.A., 126 Joshua Tree National Monument, U.S.A., 45, 249, 330 Judean Hills, West Bank, 59 Kakadu, Australia, 268, 282 K~irkevagge, Scandinavia, 79, 80, 81,147, 154, 168, 169, 183, 332,374,377 Kentucky, U.S.A., 133,254, 255 Khumbu, Nepal, 2, 115, 116, 123, 124, 129, 156, 302,303, 327, 355,356, 357,358,360, 361, 362,363, 364, 365,372, 373, 374,375,376,377 Kileaua, Hawai'i, 295 Kitt Peak, Arizona, U.S.A., 13,208 Lake Bonneville, Utah, U.S.A., 72, 235 Lake Lisan, Israel-Jordan, 44, 206, 257

419 Lake Ransom Canyon, Texas, U.S.A., 76 Lake Roosevelt, Arizona, U.S.A., 54 Legend Rock, Wyoming, U.S.A. 37, 310 Libya, 189, 282 Maine, U.S.A. 130 Malawi, 310 Mammoth Hot Springs, Yellowstone National Park, U.S.A., 153 Marie Byrd Land, Antarctica, 244 Mars, 7, 8,26, 112, 121,144,280, 321,322 Maui, Hawai'i, 14, 92, 93,284, 285, 311 Mauna Kea, Hawai'i, 12, 284, 285, 294, 302, 303,306, 314, 315, 316 Mauna Ulu, Hawai'i, 92, 94, 295 Mauritania, 238 McDowell Mountains, Arizona, U.S.A., 6 Medicine Lodge, Wyoming, 90 Mediterranean, 49, 94, 339 Mesa, Arizona, U.S.A. 104, 194 Mexico, 17, 139, 162, 171,172, 176, 227, 240, 252, 253, 303, 304, 307, 308, 314, 316, 341, 342 Migongshan Volcano, Tibet, 366, 371 Mintum, Scotland, 61 Mojave Desert, 50, 52, 57, 81, 82, 103, 105, 146, 151,160, 164, 171,180, 189, 190, 191,193, 194, 198, 200, 202, 207, 208, 217, 219, 225,234, 238, 250, 251 Mono Basin, Califomia, U.S.A., 87, 105, 106, 275 Morocco, 94, 238, 281,286, 310, 331 Mt. Van Valkenburg, Antarctica, 46, 201 Namib Desert, 61, 157, 164, 263, 375 Nasca, Peru, 4, 78, 79, 176, 202, 261,327, 328, 339,345 Negev Desert, Israel, 45, 59, 61, 117, 118, 143, 189,225, 238, 239 New Guinea, 153 New South Wales, Australia, 202, 269,282, 294, 302 New York, U.S.A., 130 Norway, 62, 207 Oakland, California, U.S.A., 142 OgaUala Formation, West Texas, U.S.A. 73 Olary Province, Australia, 55, 289 Orinoco, Venezuela, 11, 17, 18 Owens Valley, California, U.S.A. 209,227 Pakistan, 86

420

Palm Springs, Califomia, U.S.A., 102 Papago Park, Phoenix, Arizona, U.S.A., 113, 118, 166, 167, 168, 249, 250 Paran, Israel, 86 Parker Dunes, Arizona, U.S.A., 152, 171,172, 249 Patagonia, Argentina, 175,205 Peru, 5, 78, 79, 175, 176, 200, 202, 210, 211,212, 245,257, 259, 260, 261,283, 289, 310, 327, 328,339, 345, 378 Petra, Jordan, 2, 5, 91, 92, 97, 101, 158, 159, 266, 289, 327, 328, 345,378 Petrified Forest National Park, Arizona, U.S.A.,, 39, 91 Phoenix, Arizona, U.S.A., 39, 54, 83, 113, 166, 167, 168, 249 Pikes Peak, Colorado, U.S.A., 87, 95 Pisgah Crater, Mojave Desert, California, U.S.A. 50 Poverty Hills, Califomia, U.S.A. 209 Providence Mountains, Califomia, U.S.A., 82, 193 Puerto Rico, 80 Punta CabaUos, Peru, 257,259, 260 Pyramid Lake, Nevada, U.S.A., 68, 69, 74, 159, 203 Pyramids, Egypt, 190, 225, 282 Queen Creek, Arizona, U.S.A., 139, 140 Queensland, Australia, U.S.A., 35, 70, 123, 124, 132, 176, 178, 235,269, 282, 318 Rainbow Basin, Califomia, U.S.A., 194 Red Fort, India, 5 Rogue River, Oregon, U.S.A. 292 Russia, 21 Sahara Desert, 157, 159, 170, 182, 238,282 Sahel, 190 Salt Springs, Mojave Desert, Califomia, U.S.A. 193, 194, 200 San Francisco Peaks Volcanic Field, Arizona, U.S.A., 58 San Pedro River, Arizona, U.S.A., 141 Santa Monica Mountains, Califomia, U.S.A., 14, 286, 287 Searles Lake, Califomia, U.S.A., 160, 194, 227,228 Sedona, Arizona, U.S.A., 99, 100, 112,113 Shoshone, California, U.S.A., 174, 175 Sierra Nevada, California, U.S.A., 95, 96, 97, 103,125, 131, 148, 154, 155, 156, 281,286, 343 Sierra Pinacate, Mexico, 227

GeographicalIndex Silver Lake, Mojave Desert, California, U.S.A., 151,160, 161,219 Sinai Peninsula, Egypt,, 8, 10, 17, 71,108, 109, 186, 200, 251, 283,284 Snake River Plain, U.S.A., 283 Sonoran Desert, southwestern North America, 103, 111, 159, 166, 202, 351 South Africa, 34, 79, 194, 227,292, 375 South Australia, 4, 46, 55, 81,99, 157,200, 202, 265,289 South Mountain Park, Arizona, U.S.A., 53 southeastem Colorado, U.S.A., 85 southern Nevada, U.S.A., 79, 88, 97, 112, 114, 163, 172,255 SP Crater, Arizona, U.S.A. 58, 104, 105 Spain, 146, 168, 271 Spitzbergen, 225 Starvation Canyon, California, U.S.A., 104, 213 Stone Mountain, Georgia, U.S.A., 94, 95, 97, 150, 251,252, 286, 308, 309, 378 Sunflower, Arizona, U.S.A., 47, 48, 50, 52 Superior, Arizona, U.S.A., 140 Superstition Mountains, Arizona, U.S.A., 269 Susquehanna River, northeastem U.S.A., 138 Sweden, 88, 154 Taj Mahal, India, 111 Tassili, Sahara Desert, 35 Tempe Butte, Arizona, U.S.A., 72, 75, 76, 115 Thar Desert, India, 111, 189 Thasos, Greece, 56, 101,269 Thiel Mountains, Antarctica, 156 Tibet, 8, 10,37, 80, 110,253,356, 359, 366, 372, 373,374, 375, 376, 377, 378 Tien Shan Mountains, 201,238, 356 Tikal, Guatemala, 289, 291 Tunisia, 157, 183,202, 207,262, 263,266, 353 United Kingdom, 112, 122, 123, 130,286 Urekele Lake, Tibet, 359 Utah, U.S.A., 72, 91,201,207,235, 293,326 Valley of Fire, southern Nevada, U.S.A., 79, 97, 105 Van Horn, west Texas, U.S.A., 78 Venice, Italy, 138, 254 Ventura, California, U.S.A., 136, 137 Venus, 84, 122 Vermont, U.S.A., 13, 164, 165,272, 273 Victoria Land, Antarctica, 184, 293

Geographical Index Virginia, U.S.A. 122, 130, 137, 138, 142, 199, 201 Warm Springs, Death Valley, California, U.S.A., 53,346, 349, 350 West Kunlun Mountains, Tibet, 8, 10, 80, 110, 253, 283,355, 358,365, 366, 371,372, 374, 375,376, 377 West Texas, U.S.A., 45, 270, 271, 272 Wharton HiM, Australia, 4, 289 White Mountains, Nevada, U.S.A. 148 Wind River Mountains, Wyoming, U.S.A., 8, 11, 97, 98, 149 Wyoming, 8, 11, 37, 64, 65, 88, 89, 90, 97, 98, 129, 149, 153, 201,271,273,310, 339 Yemen, 261 Yishan Volcano, Tibet,, 370, 371, 373 Yosemite National Park, Califomia, U.S.A., 8, 10, 97, 98, 327

421

422

Subject Index

Subject Index

Abiotic, 67, 70, 106, 134, 180, 181, 183,184, 185, 188,239,241, 242,243, 246, 266, 276, 285, 318 Abrasion, 151,152, 187, 191,194, 208, 218, 221,223,280, 282, 338, 358, 359, 377 Acid, 24, 38, 45, 78, 122, 132, 155, 164, 181, 182, 192,223,231, 232, 234, 235,276, 280, 317, 319, 320, 325, 336, 337, 339, 373 Acid drainage, 122, 336, 337 Acid precipitation, 339 Adsorb, 137, 152, 178 Aesthetic, 38, 345,373 Age, 64, 105, 150, 151,165, 187, 218,219, 220, 221,225, 226, 227,228, 231,272, 313, 314, 316, 332, 356, 358,376 Algae, 10, 15, 48, 49, 56, 57, 60, 64, 70, 71,101, 112, 124, 133,235, 238, 239, 240, 327, 330, 337, 342, 356, 362, 373 Alkaline, 24, 25, 181,218, 239, 243,249, 266, 280,317, 333, 337,339,351 Alluvial fan, 7, 13, 71, 75, 77, 78, 104, 170, 172, 173,174, 177, 202, 204, 220, 224, 225, 264, 346, 350, 352, 353,354, 355 Alpine, 3, 11, 60, 63,147, 155, 189, 190, 192, 225, 274, 374, 376 Alumina glaze, 14, 295, 311, 312, 313,321 Amorphous, 5, 15, 26, 90, 92, 100, 119, 153, 154, 181,195, 211, 239, 279, 280, 281,282, 283, 284, 287, 288, 293,297, 298, 300, 310, 317, 318,319, 374, 377 Anthropogenic, 15, 19, 26, 33, 34, 35, 37, 48, 56, 59, 120, 127, 135, 136, 139, 217,223, 254, 262,270, 300, 326, 327, 335, 336 Apatite, 15,249, 251,254, 266, 376 Aquatic, 56, 141, 180, 181, 183, 184, 185, 323 Arid, 7, 24, 26, 60, 72, 78, 85, 102, 112, 115, 152, 164, 175, 182, 183,186, 188, 189, 190, 191,

205, 206, 233,237, 243, 256, 259, 264, 266, 269, 274, 277, 279, 281,286, 289, 329, 335, 339,351 Arsenic, 65, 139, 178, 334 Artifact, 305, 313, 346 Artificial, 39, 40, 190, 222, 324 Backscauer, 148, 244, 272, 291, 295,296, 306, 308, 311 Bacteria, 41, 43, 44, 45, 46, 48, 54, 63, 70, 71, 80, 81,121,126, 133, 145, 153, 154, 181,182, 183, 184, 216, 218,238, 239, 246, 251,255,267,316, 318, 322,337, 340, 342,356, 362, 370, 372, 373,374, 376, 377 Barite, 38, 375 Barium, 15, 38, 174, 198, 199,204, 295,296, 297 Basalt, 14, 28, 43, 50, 58, 88, 90, 92, 93, 115, 175, 195, 215, 218,221,274, 285,302, 336 Bauxite, 310 Beachrock, 70, 71 Best looking, 218, 219 Bias, 3, 27,272,340 Biofilm, 15, 41, 43, 45, 49,223 Biogeochemical, 2, 20, 22, 24, 26, 27, 132, 135, 143,215,216, 217,219, 222, 223,224, 324, 335,336, 339, 341,342, 344, 345,379 Biogeochemical barrier, 132, 143, 216, 324, 335, 336, 339, 341, 344 Biogeochemistry, 223 Biological origin, 47, 61,181,184, 187 Biorind, 48, 57 Biotite, 35, 102, 145, 156, 180,286, 370 Bimessite, 129, 195, 197, 246 Black, 4, 8, 13, 15, 16, 17, 18, 27, 42, 49, 50, 52, 60, 64, 82, 90, 93, 99, 100, 110, 122, 123, 125, 132, 145, 147, 153, 154, 160, 161,163, 168, 174, 175, 176, 182, 184, 186, 187, 188, 189, 190, 193, 194, 195, 204, 205,214, 215, 216, 222, 223,

Subject Index 224, 225, 227, 231,232, 234, 235,238, 265,268, 272, 282, 286, 293,296, 330, 331,334, 340, 354, 373,377 Bog, 362 Bronze, 141 Budding bacteria, 44, 45, 322 Building, 6,38, 47, 82, 107, 110, 112, 256, 258,265,266, 327, 340 Cadmium, 139, 178, 339 Calcite, 35, 79, 86, 91, 107, 108, 112, 197, 264, 271,288, 292, 378 Calcium, 3, 5, 9, 10, 15, 38, 40, 48, 49, 65, 67, 70, 72, 73, 74, 78, 79, 80, 82, 83, 88, 89, 91, 97, 101,107, 111,248,249,251, 254, 255, 262, 264, 265, 266, 269,270, 271,272,273, 274, 275,276, 293,300, 319, 338, 342, 362, 363,364, 365, 366, 370, 373, 375,377,378 Calcrete, 15, 72, 73, 74, 75, 76, 77, 78, 79, 248,332, 352 Caliche, 248, 256 Capillary, 79, 101,181,187,232, 233,234, 235,236, 238, 246, 256, 266, 370, 371,378 Carbon dioxide, 26, 38, 61, 70, 73, 84, 181,232, 279 Carbonate, 15, 33, 35, 38, 48, 49, 59, 65, 67, 68, 70, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 90, 91, 97, 101,107, 111,117, 153, 182,223,249, 266, 269, 281,292, 300, 329, 332, 339, 354, 358, 365, 366, 367,373, 375, 378 Carbonic acid, 38, 234 Case hardening, 79, 85, 86, 87, 88, 89, 91, 92, 95, 96, 97, 100, 101,103, 104, 105, 106, 107, 114, 158, 187,213,223, 245, 287,289, 329, 330 Cast, 46 Cataract, 15, 16 Cation exchange, 212 Cave, 61,126, 216, 223,254, 255 Cell, 43, 46, 183, 184, 244, 245, 246, 251,370 Chamosite, 195 Charcoal, 35, 101,265,271,289, 290, 316 Chemolithotrophic, 153,322 Chert, 28, 45, 149, 193,282 Chlorite, 195, 212,242 Clay mineral, 46, 48, 86, 91, 97, 99, 112, 120, 122, 135, 145, 149, 151,152, 157, 159, 160, 164, 171,176, 177, 178, 180, 181, 186, 187, 195, 196, 197, 205, 207,208, 209, 211,214, 218, 222,241,242,243,245, 246, 247,251,271,300, 310, 335, 373,375, 376 Climate, 21, 59, 61, 87, 106, 108, 159, 180, 187, 189, 190, 191,

423

214, 215, 232, 256, 264, 266, 272,335, 339, 351,356, 365 Coast, 71, 73, 158,257, 302 Cobalt, 130, 138 Cocci bacteria, 45, 47, 126, 183, 184, 244, 318, 370 Cold spring, 153 Color, 2, 6, 8, 11, 15, 35, 39, 61, 88, 138, 141,144, 145, 147, 148, 149, 150, 152, 153,154, 156, 157, 159, 161,164, 175, 176, 178, 179, 180, 186, 193, 194, 214, 216, 220, .221,222, 232, 239,251,286, 311,321,330, 345,377, 378 Compete, 331,334, 341,342, 343 Competition, 65,135,324, 334, 339, 340 Complexing, 49, 310, 316, 317 Copper, 14, 15, 35, 120, 136, 138, 139, 140, 141,143,178, 248, 275,335 Coral, 70, 249 Core softening, 86, 101,102, 107, 329 Corrosion, 135,136, 141,142, 143 Crack, 157, 174, 215,216, 217, 218,219, 220, 222,224, 366, 367 Crenitic, 223,249 Crevice, 63, 111, 147, 149, 160, 161,164, 174, 175, 194, 205, 209,218, 219,222,224, 330, 336, 339, 365,366, 376, 378 Cryptogamic, 60, 255, 354 Cultural, 5, 6, 11,225,275 Culturing, 44, 187,222, 318 Cyanobacteria, 10, 15, 48, 49, 60, 61, 65, 70, 71,194, 216, 221, 238,362, 373 Date, 275, 313, 325,356 Dating, 130, 180, 188, 215,218, 219,220, 272, 314, 316, 356 Degradation, 11, 219 Dehydration, 208 Desert, 1, 5, 14, 15, 16, 28, 39, 44, 53, 56, 57, 76, 77, 78, 79, 101,108, 111,138, 143, 149, 151,156, 157, 158, 159, 160, 162, 164, 170, 171,172, 173, 174, 180, 181,182, 183, 186, 188, 189, 190, 191,194, 195, 198, 199, 200, 201,202, 206, 214, 215, 216, 217,219, 220, 223,224, 226, 227, 231,232, 233,234, 235, 236, 237, 238, 239,248, 249, 251,255, 262, 269,282, 288, 296, 305, 310, 321,326, 329, 332,334, 337, 339, 351,352, 355,377 Desert glaze, 296 Desert P7avement,5, 28, 56, 57, 76, ,78, 143, 159, 162, 164, 172, 173, 174, 180, 182, 191, 194, 195, 215,216, 217,219, 220, 223,224, 234, 251,282, 288, 305, 310, 339, 352, 355 Desert varnish, 14, 16, 39, 101, 156, 164, 181,186, 188, 189,

424

191,198, 206, 214, 220, 226, 227,233, 235,236, 238, 321, 329 Diagenesis, 38, 63, 73, 111, 180, 242,246, 254, 265,268, 362, 375 Diapir, 261 Differential, 86, 96, 97, 102, 227 Diffusion, 141 Dissolution, 78, 90, 93, 101,102, 184, 239, 245,246, 264, 267, 269, 280, 285,299, 317 Dissolve, 78, 79, 84, 165, 181,231, 232,233, 243,254, 260, 266, 279, 280, 317, 324, 334, 335, 338, 369 Dolerite, 145, 156, 184, 232 Dolomite, 15, 28, 79, 80, 81, 82, 84, 302 Dune, 151,152, 280 Duricrust, 75, 76, 321 Dust, 13, 33, 73, 90, 108, 109, 11O, 111,112, 113, 114, 115, 116, 117, 118, 119, 135, 138, 139, 169, 190, 194, 205,208, 216, 217,221,222, 224,234, 236, 239, 240, 253,275,276, 280, 281,284, 317,320, 321,324, 329,335, 336, 337,339, 344, 365,366, 367, 369,370, 371, 372,378 Dust film, 33, 90, 108, 109, 110, 111,112, 113, 114, 115, 116, 117, 118, 119, 138, 139,253, 321,324, 329, 336, 365 Earth figure, 162, 289 Ecosystem, 323 Efflorescence, 15, 79, 255, 256, 257,258, 259, 262, 266, 276 Eh, 24, 132, 134, 153, 181,243, 246, 336 Engraving, 4, 221,223,289 Environment, 3, 11, 16, 18, 20, 24, 26, 28, 48, 57, 63, 76, 78, 79, 101,107, 112, 120, 122, 135, 136, 143, 144, 145, 147, 153, 157, 162, 164, 180, 181,187, 191,209, 214, 215,216, 217, 219,221,222,223,227, 237, 249,266, 267,268,274, 275, 277,278, 279, 281,282, 310, 332,333, 335, 337,339, 344, 345,374,376 Environmental change, 14, 26, 135, 337,338, 339, 346 Eolian, 107, 111,141,180, 187, 194, 208, 218, 221,223,249, 259, 275, 281,282,324, 338, 358,359, 375, 377 Epoxy, 28, 29, 109, 113,115 Erosion, 3, 26, 28, 38, 41, 58, 59, 64, 73, 75, 76, 79, 85, 87, 90, 91, 92, 93, 95, 96, 101,102, 106, 108, 110, 111,117, 121, 127, 158, 160, 179, 193, 215, 219, 223, 224, 225,246, 248, 252,262, 273,279, 281,282, 289, 316, 324, 326, 327, 328, 329,330, 332, 333,334, 336,

Subject Index 337,338, 341,343,351,352, 356, 365, 372, 378 Euendolith, 41, 49, 53, 54, 58, 61 Evaporation, 70, 71, 73, 75, 79, 83, 91,107, 139, 140, 181,227, 233,236, 243,256, 257, 262, 264, 266, 282, 317,320, 369 Evaporite, 12, 83, 256, 261,262 Feedback, 84, 340, 372, 377 Feldspar, 13, 14, 17, 40, 95, 113, 115, 116, 136, 142, 147, 151, 152, 155, 164, 186, 251,282, 283,284 Ferrihydrate, 35 Ferruginous, 17, 101,157 Filament, 29, 50, 74, 133 Filamentous, 44, 49, 50, 51, 52, 133, 221 Fissure, 114 Flood, 19 Fluvial, 101,102, 138,219,223, 260,313, 356, 373 Fossil, 64, 70, 84, 135 Fracture, 3, 76, 80, 109, 111, 117, 131,137, 147, 160, 166, 205, 208,213, 217,220, 274, 332, 366, 370, 371,377 Freshwater, 56, 67, 68, 84, 134 Fungal, 50, 51, 54, 58, 73, 74, 239, 269, 291, 318, 327,370 Fungi, 10, 15,28,42, 49,50,51,52, 53, 54, 55, 60, 81, 83, 92, 93, 183,193, 216, 221,238, 239, 241,266, 290, 291, 315, 327, 330, 332, 334, 340, 342, 356, 362,373 Fuse, 104, 233 Gasoline, 136, 137, 138, 139 Genesis, 19,33, 48, 75, 118, 119, 153,182, 183, 184, 188, 205, 231,232, 236, 239,242, 243, 278,280, 285, 294, 317, 318, 335 Geography, 2, 3, 16, 20, 21, 22, 24, 32, 43,107, 144, 188, 236, 266, 269, 294, 323,324, 345, 372, 373, 377, 378,379 Geology, 2, 3, 21, 80, 144, 164, 236, 352, 377 Geomorphic, 24, 26, 28, 102, 158, 199,202, 214, 216, 217, 218, 219, 220, 221,222, 223, 224, 225,248, 259, 326, 327, 329, 343,345, 353,354, 356 Geomorphology, 2, 26, 108, 151, 187,217, 346, 353,358 Gibber, 282, 305 Glacial, 61, 95, 96, 97, 103, 11O, 115, 121,162, 191,202,223, 227,229, 230, 264, 275, 283, 284, 286, 303,304, 307, 308, 313,314, 327, 343,356, 358, 362, 371,374, 377 Glacial polish, 95, 96, 97, 162, 284, 314,343,362 Glaciated, 12, 26, 96, 314, 355,356

Subject Index Glacier, 112, 129, 179, 217, 283, 303,356, 357, 358,360, 362, 363,364 Glass, 29, 105, 112, 281 Gnamma, 60, 92, 93, 102 Gneiss, 232, 274, 276, 288, 356, 360, 362, 363,364 Gobi, 283 Goethite, 35, 134, 146, 153, 154, 159, 164, 182, 194, 195 Graffiti, 34, 36, 37, 39 Grain coating, 3, 152, 157, 164 Green, 3, 35, 48, 56, 57, 141,240 Greenhouse, 83, 84 Ground water, 17, 74, 75, 134, 181, 234, 255, 256, 258,262, 275, 317,321,337 Grus, 103,353 Guano, 61, 101,249,250, 254, 256, 335 Gullies, 75, 76, 77, 78, 352 Gypcrete, 79, 248, 262 Gypsum, 35, 38, 57, 78, 79, 248, 258,259, 261,262,263, 264, 265,266, 270, 271,335, 339, 353,365, 366, 375 Gypsum crust, 79, 248, 258,262, 264, 265, 353,375 Halite, 248, 257,258, 260, 261, 271,335 Hardness, 91, 102, 105, 107, 117 Heat, 18, 57, 188, 234, 236, 356 Heavy metal, 15, 32, 33, 34, 56, 111,120, 121,130, 135, 136, 138, 139, 141,142, 143, 178, 195,227, 271,272,277, 329, 339,342 Heavy metal skin, 32, 33, 34, 120, 121,135, 136, 138, 139, 142, 143,195, 227,271,277, 329, 342 Hematite, 35, 134, 145, 149, 151, 154, 157, 159, 164, 195, 197, 277 Heterogeneity, 21, 199, 215, 217, 354,378 Heterogeneous, 27, 163, 168, 180, 199 Hierarchy, 324, 326, 337 HiUslope, 61, 109, 326 Homblende, 17, 186, 249 Hot spring, 153, 280 Humid, 48, 87, 102, 106, 111,130, 138, 145, 148, 159, 182, 189, 208, 227, 264, 269, 286, 308, 329, 330, 374 Humus, 235 Hydration, 213 Hydrochloric acid, 132, 231,235 Hydrofluoric acid, 45 Hydrothermal, 107, 153,223,248, 268,280 Hydroxide, 35, 38, 39, 138, 153, 178 Hyphae, 44, 45, 49, 50, 51, 58, 238, 269, 318, 370 Ignimbrite, 153

425

IUite, 164, 195,211,213, 241,242, 246 Induration, 87, 101,105, 107 Infrared, 35, 195, 220, 239, 246, 270 Instability, 316, 352 Interdigitate, 35, 79, 129, 171,173, 270, 289, 311, 341,376, 378 Interfinger, 160, 169, 277,292 Intermittent, 97, 98, 125, 131,147, 148, 149, 342 Intertidal, 122, 130, 134 Iron, 1, 3, 6, 8, 14, 15, 17, 18, 24, 35, 36, 39, 45, 46, 48, 49, 50, 51, 65, 80, 87, 88, 91, 92, 94, 95, 96, 97, 98, 99, 101,106, 107, 112, 120, 122, 123, 127, 128, 132, 134, 135, 136, 137, 138, 139, 141,142, 143, 144, 145, 146, 147, 148, 149, 150, 151,152, 153, 154, 155, 156, 157, 158, 159, 160, 161,162, 163, 164, 165, 166, 167, 168, 169, 170, 171,172, 173, 174, 175, 176, 177, 178, 179, 180, 181,182, 183, 184, 185, 186, 187,188, 189, 190, 193, 194, 195,204, 205,209, 214, 216, 220, 222, 223,227,232, 233, 234, 235, 236, 237,238, 239, 240, 241,242, 243,245, 246, 249, 251,252, 253,254, 267, 277,280, 281,282,284, 286, 287,288, 289, 291,292, 295, 296, 298, 299, 301,302, 303, 304, 305, 309, 310, 312, 313, 318,319, 320, 321,322, 324, 325,327, 329, 330, 331,332, 333,334, 336, 337,338, 339, 341,342, 343,344, 353, 354, 360, 361,362, 363,373, 374, 375,376,378 Iron bacteria, 183,337,362, 373 Iron films, 1, 3, 6, 94, 97, 98, 99, 134, 137, 143, 144, 145, 146, 147, 148, 149, 150, 151,152, 153,154, 155, 156, 157, 158, 159, 160, 161,162, 163, 164, 165,166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181,182, 183, 184, 185, 188, 205,247, 286, 287,289, 292, 310, 318, 321, 322,324, 325, 327,329, 330, 331,332, 333,336, 337, 338, 339,341,343,353,354, 360, 361,362, 363,374, 378 Iron phosphate, 15, 251,252,253, 254, 267, 362,376 Jarosite, 181, 182 Joint, 64, 76, 87, 88, 89, 90, 91, 106, 117, 160, 219, 285,286, 310, 311,330, 331,332,343, 365, 366 Kaolinite, 35, 97, 107, 108, 112, 114, 115, 195,212 Karst, 67,260

426

Lake, 68, 261,262, 338, 375 Lamellate, 131, 194, 206, 208, 209, 364 Laminar, 72, 75, 76, 130, 375 Lamination, 169, 184 Landscape geochemistry, 1, 2, 20, 21, 22, 24, 25, 26, 27, 32, 67, 266, 318, 324, 379 Laterite, 24 Lava, 51, 58, 67, 80, 81, 88, 92, 102, 253, 285,296, 297, 306, 307,309, 311,312,313, 314, 358, 359, 366, 369, 370, 373 Lava tube, 67, 81 Leaching, 28, 40, 106, 165,212, 213,219, 229, 237,256, 261, 371 Lead, 15, 24, 26, 35, 47, 107, 110, 120, 130, 136, 137, 138, 139, 178 Lichen, 15, 58, 59, 60, 62, 63, 78, 82, 132, 235, 238,239, 275, 276, 338, 362, 364, 373 Light, 6, 15, 29, 31, 57, 63, 64, 108, 117, 176, 186,209,220,234, 239,252, 270, 308, 331,334 Limestone, 15, 38, 42, 48, 56, 57, 58, 59, 80, 82, 84, 86, 118, 140, 146, 181,225,232, 233, 257,264, 265,269, 275, 329, 356 Limonite, 156, 164 Lithobiont, 327,331 Littoral, 3, 17, 18, 70, 71,130, 189, 216,223 Loess, 8, 28, 108, 261,358, 359, 365,369, 370, 374, 375 Lunar, 112, 121 Magnesium, 15, 40, 80, 81, 82, 83, 249,263, 265,270, 271,275, 300, 375 Magnetite, 35, 136, 138, 156, 164, 233 Manganese, 6, 15, 16, 17, 18, 24, 35, 39, 40, 44, 45, 46, 47, 48, 49, 50, 51, 64, 65, 96, 99, 107, 120, 121,122, 123, 124, 125, 126, 127, 128, 129, 130, 131,132, 133, 134, 138, 142, 143,148, 150, 153, 154, 160, 161,166, 170, 174, 175, 176, 182, 183, 186, 187, 188, 189, 190, 193, 194, 195, 197, 200, 203,204, 205,208,209, 214, 215,216, 218, 219, 220, 221, 222, 223, 224, 227,232, 233, 234, 235, 236, 237,238, 239, 240, 241,242, 243,244, 245, 246, 247, 249, 271,272, 273, 274, 277, 295, 297,299, 318, 324, 325, 334, 335,336, 337, 338,339, 340, 341,342, 353, 362,363, 365,369,370, 373, 376 Marble, 49, 50, 69, 111,138, 224, 264, 265, 275,356 Marine, 3, 26, 67, 70, 84, 115, 121, 249,258, 259, 260 Mat, 15, 39, 74, 194, 213

Subject Index Mica, 17, 186, 212, 288 Microcolonial, 28, 50, 53, 54, 55, 83,183,193, 241,315,334 Migration, 20, 21, 22, 23, 24, 26, 139, 141,211,216, 222, 224, 242,257, 263,266, 318, 335, 337,345 MiUisite, 376 Mineral, 14, 26, 40, 41, 43, 44, 48, 65, 97, 112, 116, 117, 134, 152, 156, 157, 160, 181, 182, 195, 211,241,242,249, 251, 254, 268, 270, 275,284, 287, 316, 319, 321,322,329, 338, 375,376, 377 Mixing, 77, 134, 238,337 Model, 2, 100, 109, 111,184, 185, 187, 188, 190, 191,192, 193, 232,238, 241,246, 256, 257, 263,266, 276, 317, 319, 323, 324, 340, 341,343,344, 345, 352,379 Montmorillonite, 164, 195,208, 211,213,246 Monument, 41,254, 255 Moraine, 103, 110, 129, 184, 229, 253,293, 371 Morphology, 47, 50, 206, 208, 269 Moss, 15, 56, 60, 70, 330, 331,334, 362,373, 374 Nitrate, 15, 223, 248, 249, 254, 255, 256,335 Nomenclature, 14, 16, 144 Ocean, 19, 108, 135 Olivine, 84, 115, 117,215,311 Opal, 281,289 Orange, 6, 8, 15, 92, 98, 144, 145, 151,153, 154, 157, 158, 159, 160, 161, 164, 171,172, 173, 174, 175, 176, 178, 179, 180, 190, 194, 195, 204, 205, 215, 222,223, 224, 268,330, 362, 378 Organic acid, 43, 48, 78, 182, 184, 223,276 Organic matter, 31, 35, 54, 63, 124, 126, 127, 128, 129, 135, 160, 184, 199, 232, 234, 243, 250, 265, 271,286, 299, 300, 302, 307,311,312, 315,316, 317, 334, 341,360, 367 Origin, 2, 16, 27, 34, 47, 61, 106, 107, 117, 123,132, 136, 155, 180, 181,184, 187, 190, 215, 231,232, 233,234, 235, 236, 239,241,242, 249,261,268, 275,276, 317,323,344, 358, 374,375 Orthoclase, 35, 113, 115, 116, 142, 152,283 Oxalate, 5, 9, 1O, 13, 15, 54, 59, 65, 79, 88, 89, 94, 101, 107, 129, 179,215, 221,223,252, 268, 269,270, 271,272,273,274, 275,276, 277,278,286, 292, 293, 318, 325,327,328, 329, 332,335, 338, 339,341,342,

Subject Index 354, 362, 364, 365,369, 370, 373,375, 377, 378 Oxalic acid, 276 Oxidation, 48, 132, 141,144, 153, 157, 164, 181,182, 183, 218, 233,236, 238, 241,337, 369, 374 Oxide, 15, 17, 18, 35, 36, 91,106, 113, 121,134, 136, 137, 138, 139, 140, 152, 153, 157, 159, 163,171,181,195,233,238, 246, 294, 297, 300, 309, 310, 311,312, 320, 360, 366 Paint, 15, 34, 35, 37, 39, 135,324 Paradigm, 1, 20, 21, 22, 24, 27, 32, 65,219, 220, 379 Patina, 14, 15, 16, 27, 141, 159, 191,194, 214, 220, 225, 226, 234, 288, 313 Pavement, 5, 28, 56, 57, 77, 78, 159, 162, 172, 173, 174, 182, 191,194, 208, 215, 216, 219, 223,224, 234, 251, 281,282, 288,289, 305,310, 339, 352, 355 Pediment, 104, 250, 251, 261 Pedogenic, 67, 72, 73, 76, 77, 135, 281,282, 319, 337 Periglacial, 26, 79, 192, 243 Petroglyph, 4, 8, 35, 36, 37, 54, 88, 89, 91, 99, 150, 161,221, 265, 271,289, 291,298, 304, 310 pH, 24, 29, 73, 114, 132, 134, 135, 145, 153, 181,183,218, 223, 238, 242, 243,246, 319, 336, 337,339, 362, 369, 374, 376 Phosphate, 10, 15, 35, 65, 94, 101, 111,136, 223,248, 249, 250, 251,252, 253,254, 266, 319, 362,363, 365,366, 367, 368, 369, 373, 374, 376, 377 Pigment, 35, 36, 136, 223, 270, 362 Plagioclase, 14, 40, 84, 109, 116, 134, 136, 148, 149, 155, 251, 252,253, 284, 286, 287, 366 Plant, 18, 41, 60, 135, 166, 167, 235, 241,258, 300 Playa, 255, 359 Point source, 135 Polish, 30, 95, 96, 97, 162,223, 284, 288, 314, 317, 343,362, 363 Pore, 42, 57, 58, 60, 63, 72, 75, 80, 90, 92, 95, 99, 100, 101,139, 141, 148, 156, 280, 287, 292, 298,363 Potassium, 15, 40, 113, 115, 152, 178, 181,182,255,271,335, 358 Precipitation, 15, 24, 28, 38, 41, 44, 48, 49, 53, 59, 65, 70, 71, 73, 75, 78, 79, 115, 121,134, 138, 146, 152, 153, 154, 181, 190, 208, 233,236, 238, 239, 240, 243, 251,254, 256, 257, 258,259, 260, 262, 263, 264, 265,266, 275, 290, 291, 317, 318,319, 321,335,337, 338,

427

339, 340, 351,358,362, 374, 376,377 Prehistoric, 19, 34, 35,285 Preservation, 8, 38, 88, 95, 184, 232,338 Pyrite, 181,325 Quartz, 17, 28, 35, 43, 50, 52, 54, 57, 58, 89, 92, 112, 116, 139, 143, 147, 148, 149, 150, 151, 154, 164, 165, 185, 186, 225, 233,236, 239, 244, 249, 259, 265,271,272,275,280, 285, 292,293, 308, 329,338, 363, 375,378 Quartzite, 95, 96, 97, 110, 114, 139, 140, 149, 150, 156, 175, 176, 188, 194, 230, 233,259, 260, 269, 303, 339, 356, 357, 362, 363,364 Rate, 23, 26, 62, 65, 157, 180, 225, 228,230, 231,243,256, 257, 274, 313, 319, 325,326, 327, 328, 329, 330, 334, 335, 336, 342,356, 372, 378 Rate of growth, 334 Red, 6, 8, 15, 35, 49, 85, 99, 145, 146, 148, 149, 151,153, 154, 155, 157, 158, 159, 171,174, 178,232, 250, 251,256, 278, 286,288, 291,311,321,377 Reddening, 152, 155, 180 Redox, 26, 135, 181 Reg, 45 Regolith, 3, 127, 128, 130, 131 Remote sensing, 2, 7, 26, 157, 262, 284, 352, 353,354 Reprecipitate, 209, 245 Reprecipitation, 24, 143, 181,229, 245,246, 249, 285,377 Review, 2, 33, 35, 63, 67, 144, 238, 268 Rhyolite, 107, 218,275,371 River, 11, 17, 56, 107, 115, 158, 190, 192, 193,214, 224, 231, 232,233, 234, 260, 292, 297, 326, 334, 338,358 Road, 6, 26, 190, 225, 326, 327 Road cut, 39, 128, 131,137, 138, 326 Rock art, 36, 59, 61, 106, 226, 268, 269, 270, 314 Rock shelter, 15, 85, 101,250, 254, 255, 318, 336 Rock vamish, 1, 3, 4, 5, 6, 7, 8, 9, 10, 13, 15, 16, 28, 31, 37, 39, 44, 45, 46, 47, 51, 53, 54, 55, 64, 65, 66, 77, 79, 81, 82, 87, 88, 91, 92, 93, 94, 98, 99, 100, 101,102, 103,104, 118, 120, 122, 124, 127, 130, 136, 138, 139, 144, 146, 149, 150, 153, 156, 157, 160, 161,162, 163,170, 175, 176, 177, 178, 179, 182, 186, 187, 188, 189, 191,192, 193, 194, 195, 196, 197, 198, 199, 200, 201,202, 203,204, 205,206, 207, 208, 210, 212, 213,214, 215, 216,

428

217,218,220,221,222,223, 224,226,227,228,230,231, 233,234,235,236,237,238, 239,241,242,243,244,246, 247,269,271,277,288,289, 292,293,299,318,322,324, 325,327,328,329,330,331, 332,334,335,338,339,342, 346,350,351,352,353,354, 355,356,357,362,363,364, 365,371,373,374,375,376, 377,378 Rod bacteria, 45, 46, 126, 244 Rust, 142, 144, 164 Salcrete, 15,248 SMine, 43,81,233,256,258,266 S~inelake, 358,365 SMtcrust, 248,256,257,259,260, 261 SMt weathering, 43,259,365 Samplepmpa~tion, 315 Sand, 17,60,145,151,152,157, 164,171,172,194,249,262, 265,280,281,310,317 Sandstone, 9,28,37,42,64,65,70, 79,85,88,89,91,97,100, 102,103,107,112,157,159, 224,225,232,234,254,255, 257,265,269,273,277,282, 287,288,310,318,325,329, 330,331,332,338,339,342 Saprohte, 201,207 S~dli~,7, 152,167,352,355 Scale, 1, 26, 30, 46, 47, 50, 58, 59, 60, 61, 65, 66, 72, 75, 76, 78, 79, 87, 105, 110, 117, 156, 157,176,182,196,205,208, 209,210,211,212,213,214, 220,221,222,228,229,243, 245,246,247,257,271,274, 280,284,302,307,319,341, 345,346,353,354,355,359, 360,362,365,371,373,378, 379 Scavenging, 130, 178, 203 Schist, 80,81,147,151,154,156, 160,161,168,169,327,331, 356 S.eason, 19,91,111,113,235,344, 356,365 Secondary, 13,29,30,31,50,52, 54,74,106,107,152,178, 198,208,209,210,265,271, 291,296,314,315,343,362, 363,372,377 Sec~te, 43,48,49,50,64,318,338 Sediment, 108,115,136,138,231 Seepage, 190,254,255,262,317 Sheen, 194,292 Silica, 1,3,5,8,9,10,15,24,31, 33,34,35,36,38,40,64,65, 80,86,87,88,89,90,92,93, 94,97,99,100,101,102, 107,111,113,118,119,122, 123,127,128,130,139,141, 150,152,153,154,155,157, 161,162,163,164,169,170, 171,173,174,179,184,185, 199,203,215,223,247,250,

Subject Index 251,252,265,271,275,279, 280,281,282,283,284,285, 286,287,288,289,290,291, 292,293,294,295,296,297, 298,299,300,301,302,303, 304,305,306,307,308,309, 310,311,313,314,315,316, 317,318,319,320,321,322, 324,325,329,330,331,332, 334,336,337,339,341,342, 343,344,354,360,361,362, 363,365,369,370,371,373, 374, 375, 377, 378 Silica glaze, 1, 3, 8, 9, 10, 33, 34, 35, 36, 64, 65, 80, 86, 88, 89, 90,92,93,94,101,102,118, 119,123,139,141,153,154, 155,157,161,162,169,179, 185,215,223,247,252,265, 271,275,279,281,282,283, 284,285,286,287,288,289, 290,291,292,293,294,295, 296,297,298,299,300,301, 302,303,304,305,306,307, 308,309,310,311,313,314, 315,316,317,318,319,320, 321,322,324,325,329,330, 331,332,334,336,339,341, 342,343,344,354,360,361, 362,363,365,369,370,371, 373,374, 375,377 Silicate, 3, 26, 84, 106, 140, 269, 279,288, 317, 319, 321,329, 337 Silicic acid, 280, 319, 320 Silt, 5, 15, 60, 110, 135, 151,374 Slope, 21, 61, 68, 114, 129,259, 305,327, 335,336, 341,363, 373 Smectite, 241,242 Sodium, 15, 39, 79, 135,232,249, 250, 255, 256, 257,258, 259, 263,300 Soil, 17, 20, 21, 28, 48, 60, 72, 73, 75, 76, 77, 78, 81, 84, 104, 109, 118, 135, 141,152, 159, 169, 173, 180, 181,182, 185, 191,193, 195,205,208, 216, 217,218, 219, 220, 221,223, 224, 234, 236, 237,239, 255, 256, 262, 266, 279, 281,285, 287,294, 310, 317,326, 328, 333,335, 336, 337, 351,362 Soiling of buildings, 11, 15, 110 Solution, 1, 17, 39, 106, 164, 181, 232,233, 234, 236, 237, 238, 239,257, 262,266,275, 317, 319,337, 342,365,369 Soot, 101 Spatial, 2, 21, 22, 31, 87, 187, 199, 209,222, 321,345,346, 372, 377,378 Spring, 67, 122, 134, 216, 362 Stability, 11, 39, 79, 102, 103, 157, 158, 191,313,314, 326, 327, 335,338, 342 Stable, 20, 24, 25, 26, 28, 35, 40, 157, 181,221,249,266, 276, 279,332, 334, 342

Subject Index Steel, 18, 135, 141,142, 166, 167, 300 Stone conservation, 11, 38, 107, 254, 268, 289 Streaks, 8, 9, 10, 99, 141,157,252, 277,324, 325,342, 345, 373 Stream, 18, 56, 67, 105, 122, 123, 124, 125, 130, 131,132, 134, 138, 139, 148, 149, 153, 155, 158, 176, 181,199, 292, 326, 337,356, 361,362, 364, 373 Strengite, 251,362, 376 Stromatolite, 47, 65, 70, 183 Subaerial, 26, 28, 67, 75, 76, 78, 79, 81, 84, 88, 109, 135, 145, 150, 155, 157, 158, 162, 163, 164, 169, 170, 172, 175, 179, 180, 181, 183, 184, 197, 200, 201,205, 209, 214, 215, 216, 217,218, 219, 220, 221,222, 223,224, 235,264, 266, 281, 286, 287, 310, 330, 332, 336, 344, 365, 371,374, 376, 377 Sublimation, 264 Subsurface, 3, 24, 43, 72, 75, 76, 87, 106, 117, 150, 162, 163, 179, 184,201,216,217,248, 257,262, 266, 281,327, 329, 330, 331,332, 333,334, 342, 343 Succession, 57, 63, 65,338 Sulfate crust, 262, 264, 265, 365, 371 Sulfuric acid, 181,232, 325 Tafoni, 87, 101,106, 113,249, 282 Tailings, 135 Talus, 67, 68, 69, 75, 86 Temperate, 94, 102, 145, 148, 157, 192,269, 286, 308,374 Thickness, 17, 18,29, 43, 73, 110, 132, 157, 159, 169, 173, 176, 187,193, 194, 204, 208, 220, 224, 228, 229,230, 231,235, 250, 254, 264, 284, 313, 347 Till, 314, 315, 343 Toxic, 120, 135, 178 Transmission, 45, 46, 153, 196, 197, 198, 209, 211,212,214, 243, 244, 245, 280 Transport, 29, 108, 109, 135, 141, 151,152, 190, 219, 221,239, 246, 262, 322, 326, 327, 342, 343,377 Travertine, 15, 67, 338 Tuff, 87, 269 Tundra, 60 Ultrathin, 29 Underside, 57, 164, 172, 173, 180, 194, 223, 334 Unstable, 103, 157,218, 313,316, 319,327 Uranium, 120, 130 Urban, 11, 34, 36, 81, 82, 110, 112, 113, 119, 135, 139, 146, 168, 180, 264, 265, 329

429

Volcanic, 12, 58, 80, 105, 153,253, 274, 275, 280, 281,283, 317, 358,365, 366 Volcanic ash, 275,283, 317 Water flow, 38, 76, 97, 98, 99, 126, 135, 153, 155, 166, 201,216, 223,269, 273,277,286, 307, 331,335, 336, 337, 341,342, 362, 371,373 Water repellent, 38 Weathering, 1, 2, 3, 5, 11, 12, 13, 14, 17, 24, 25, 26, 38, 41, 43, 48, 57, 58, 59, 60, 63, 64, 65, 79, 84, 86, 87, 91, 92, 93, 94, 95, 96, 97, 99, 101,102, 104, 106, 107, 110, 122, 135, 139, 142, 144, 145, 146, 147, 151, 155, 156, 157, 158, 166, 180, 181,182, 187, 188, 193, 210, 211,215, 216, 218,219, 220, 228,232, 233,236, 237, 238, 239, 241,242, 245,246, 247, 249, 259, 265,266, 267, 275, 278,279, 281,282,286, 287, 314, 315, 316, 317,318, 319, 325,326, 327, 334, 336, 338, 341,342, 345, 353,356, 363, 365,370, 372, 374, 377, 378 Weathering find, 1, 12, 13, 57, 58, 92, 94, 95, 96, 99, 101, 104, 106, 156, 158, 166, 187, 193, 233,236, 245,265,286, 287, 314, 315, 316, 317,334, 353, 363,378 Wetland, 216 Zinc, 15, 130, 138, 139, 140, 142, 178,339