Bridget Y. Lynne

Baking black opal in the desert sun: The importance of silica in desert varnish

Desert varnish, a widespread black manganese-rich rock coating, contains labile organic compounds, but a mechanism for its formation and for their preservation remains unproven. Using Raman spectroscopy, X-ray diffraction, and scanning transmission electron microscopy, we analyzed varnish and found amorphous hydrated silica (opal) and the silica mineral moganite, similar to findings we have reported from siliceous hot-spring deposits. We suggest that the slow dissolution of silica from anhydrous and hydrous minerals, and its subsequent gelling, condensation, and hardening, provides a simple explanation of a formation mechanism for desert varnish and silica glazes and the incorporation of organic material from local environments. These chemical signatures, sequestered in silica, provide valuable information about terrestrial and extraterrestrial paleoenvironments.

Tracking crystallinity in siliceous hot-spring deposits

Siliceous hot spring deposits (sinters) entrap paleoenvironmentally significant components and are used as extreme-environment analogs in the search for early Earth and extraterrestrial life. However, sinters undergo a series of textural and mineralogical changes during diagenesis that can modify and overprint original environmental signals. For ancient hydrothermal settings including those close to the dawn of life, these transformations have long since occurred, so that study of diagenetic processes and effects is best undertaken in much younger deposits still undergoing change. Three young sinters preserve the entire diagenetic sequence of silica phases, from opal-A to quartz. The 6000 to ∼ 11,500 years BP ± 70 years sinter at Steamboat Springs, Nevada, the ∼ 1600 - 1900 ± 160 years BP Opal Mound sinter at Roosevelt Hot Springs, Utah, and the ∼ 456 ± 35 years BP deposit at Sinter Island, Taupo Volcanic Zone, New Zealand, provide an opportunity to track crystallographic, mineralogic and morphologic transitions of sinter diagenesis using standard and new analytical approaches. Worldwide, sinter forms from cooling, alkali chloride waters as noncrystalline opal-A, transforming first into noncrystalline opal-A/CT, then paracrystalline opal-CT ± moganite, paracrystalline opal-C, and eventually to microcrystalline quartz. In this study, these changes were identified by the novel and combined application of electron backscatter diffraction, X-ray powder diffraction, and scanning electron and optical microscopy techniques. We show that mineralogical changes precede morphological and accompanied crystallographic transformations. During this modification, silica particles grow and shrink several times from the micron- to nano-meter scales via dissolution, reprecipitation and recrystallization, and diagenesis follows the Ostwald Step rule. All deposits followed nearly identical diagenetic pathways, with time as the only variable in the march toward physicochemically stable quartz crystals. Diagenesis alters original environmental signatures trapped within sinters. After five silica phase changes, filamentous microfossils are modified but still remain recognizable within sinter from the Opal Mound and Steamboat Springs deposits, and during the opal-A to opal-CT silica phase transformations at Sinter Island. Therefore, delineating diagenetic components and how they affect sinters is necessary to accurately identify biosignals from ancient hot-spring deposits.

Acceleration of sinter diagenesis in an active fumarole, Taupo volcanic zone, New Zealand

Siliceous sinters form where nearly neutral pH, alkali chloride waters discharge at the surface (100 C). They may preserve biogenic and abiogenic material and therefore archive paleoenvironmental settings. Freshly precipitated sinters undergo diagenesis through a five-step series of silica mineral phase changes, from opal-A to opal-A/CT to opal-CT to opal-C to quartz. Transformation rates vary among sinters because postde- positional conditions can accelerate or retard diagenesis, meanwhile preserving or destroy- ing biosignals. We monitored alteration and diagenesis of newly precipitated, filamentous microbe-rich sinter during a two-year field experiment, where sinter was suspended inside a fumarole at Orakei Korako, Taupo volcanic zone, New Zealand. Patchy and complex diagenesis resulted from changes in environmental conditions, including variations in tem- perature, pH, and the intermittent deposition of sulfur. Throughout the experiment, opal- A was dissolved by acidic steam condensate, and reprecipitated locally. Quartz crystals grew on the sinter surface within 21 weeks. Previous reports of transformation rates from opal to quartz are on the order of thousands of years in duration. Thus, our results show that fumarolic overprinting accelerates diagenesis. Microbial preservation was not favor- able because primary filamentous fabrics were obscured by deposition of opal-A micro- spheres, smooth silica infill, and sulfur. If ancient hydrothermal systems were among the likely places where early life flourished, it is necessary to distinguish between depositional features and those inherited during diagenesis. This near-real time experiment enabled observations on environmental controls of diagenetic change in silica minerals and illus- trated the variability of conditions that can occur in nature during this complex process.

Making silica rock coatings in the lab: synthetic desert varnish

Desert varnish and silica rock coatings have perplexed investigators since Humboldt and Darwin. They are found in arid regions and deserts on Earth but the mechanism of their formation remains challenging (see Perry et al. this volume). One method of researching this is to investigate natural coatings, but another way is to attempt to produce coatings in vitro. Sugars, amino acids, and silicic acid, as well as other organic and (bio)organic compounds add to the complexity of naturally forming rock coatings. In the lab we reduced the complexity of the natural components and produced hard, silica coatings on basaltic chips obtained from the Mojave Desert. Sodium silicate solution was poured over the rocks and continuously exposed to heat and/or UV light. Upon evaporation the solutions were replenished. Experiments were performed at various pHs. The micro-deposits formed were analyzed using optical, SEM-EDAX, and electron microprobe. The coatings formed are similar in hardness and composition to silica glazes found on basalts in Hawaii as well as natural desert varnish found in US southwest deserts. Thermodynamic mechanisms are presented showing the theoretical mechanisms for overcoming energy barriers that allow amorphous silica to condense into hard coatings. This is the first time synthetic silica glazes that resemble natural coatings in hardness and chemical composition have been successfully reproduced in the laboratory, and helps to support an inorganic mechanism of formation of desert varnish as well as manganese-deficient silica glazes.