Kathleen A. Campbell

Trace metal chemistry and silicification of microorganisms in geothermal sinter, Taupo Volcanic Zone, New Zealand

Abstract As part of a pilot study investigating the role of microorganisms in the immobilisation of As, Sb, B, Tl and Hg, the inorganic geochemistry of seven different active sinter deposits and their contact fluids were characterised. A comprehensive series of sequential extractions for a suite of trace elements was carried out on siliceous sinter and a mixed silica-carbonate sinter. The extractions showed whether metals were loosely exchangeable or bound to carbonate, oxide, organic or crystalline fractions. Hyperthermophilic microbial communities associated with sinters deposited from high temperature (92–94°C) fluids at a variety of geothermal sources were investigated using SEM. The rapidity and style of silicification of the hyperthermophiles can be correlated with the dissolved silica content of the fluid. Although high concentrations of Hg and Tl were found associated with the organic fraction of the sinters, there was no evidence to suggest that any of the heavy metals were associated preferentially with the hyperthermophiles at the high temperature (92–94°C) ends of the terrestrial thermal spring ecosystems studied.

A LATE DEVONIAN HYDROCARBON-SEEP DEPOSIT DOMINATED BY DIMERELLOID BRACHIOPODS, MOROCCO

Abstract A spectacular carbonate deposit from the western Meseta of Morocco consists of microbial and brachiopod limestones. The small, meter-sized Famennian limestone blocks are embedded in Carboniferous shales, implying later displacement. Primary deposition of the limestones apparently occurred below the depth limit of phototrophic organisms. The brachiopods belong to the genus Dzieduszyckia within the rhynchonellide superfamily Dimerelloidea. They occur in fantastic abundance, in a low-diversity faunal assemblage. The microbial limestones contain fossilized threadlike microorganisms of unknown affiliation. The enormous accumulation of brachiopods on the Famennian seafloor is best explained by the former existence of a seep. Crude oil was a major component of the seepage fluids, as indicated by the occurrence of pyrobitumen (metamorphosed petroleum) and δ13Ccarbonate values as low as −12‰, akin to the isotopic composition of carbonates forming at modern oil seeps. The lowest δ13C values in the Dzieduszyckia deposit are found for a carbonate phase referred to as banded/botryoidal cement. It is a fibrous, low-Mg calcite cement in the form of isopachous rims and botryoids that precipitated directly on and within brachiopod shells. The microbial limestones predominantly consist of this phase and therefore can be classified as cement framestones. Reticulate patterns of botryoidal aggregates and an elevated Sr content agree with an aragonite precursor of the banded/botryoidal cement. The interpretation of the Dzieduszyckia deposit as seep related supports the hypothesis that Paleozoic and Mesozoic members of the rhynchonellide superfamily Dimerelloidea were a lineage long associated with seeps that survived from Late Devonian to Early Cretaceous time.

Recognition of a Mio-Pliocene cold seep setting from the northeast Pacific convergent margin, Washington, U.S.A.

A fossil methane seep community is preserved in marine strata of the Mio-Pliocene Quinault Formation, southwestern Washington. Quinault sediments were deposited unconformably on a middle Miocene accretionary complex, the Hoh rocks assemblage; both units are now accreted to the continental margin, uplifted, and exposed in coastal seaclifs along the western Olympic Peninsula. The Hoh accretionary complex was probably the source of methane-rich fluids to the proposed Quinault paleoseep, which comprises approximately 15 m vertically by 75 m horizontally of an extensive outcrop of mid-shelf depth deposited sandstones and siltstone

Biosignatures on Mars: What, Where, and How? Implications for the Search for Martian Life.

Abstract The search for traces of life is one of the principal objectives of Mars exploration. Central to this objective is the concept of habitability, the set of conditions that allows the appearance of life and successful establishment of microorganisms in any one location. While environmental conditions may have been conducive to the appearance of life early in martian history, habitable conditions were always heterogeneous on a spatial scale and in a geological time frame. This “punctuated” scenario of habitability would have had important consequences for the evolution of martian life, as well as for the presence and preservation of traces of life at a specific landing site. We hypothesize that, given the lack of long-term, continuous habitability, if martian life developed, it was (and may still be) chemotrophic and anaerobic. Obtaining nutrition from the same kinds of sources as early terrestrial chemotrophic life and living in the same kinds of environments, the fossilized traces of the latter serve as useful proxies for understanding the potential distribution of martian chemotrophs and their fossilized traces. Thus, comparison with analog, anaerobic, volcanic terrestrial environments (Early Archean >3.5–3.33 Ga) shows that the fossil remains of chemotrophs in such environments were common, although sparsely distributed, except in the vicinity of hydrothermal activity where nutrients were readily available. Moreover, the traces of these kinds of microorganisms can be well preserved, provided that they are rapidly mineralized and that the sediments in which they occur are rapidly cemented. We evaluate the biogenicity of these signatures by comparing them to possible abiotic features. Finally, we discuss the implications of different scenarios for life on Mars for detection by in situ exploration, ranging from its non-appearance, through preserved traces of life, to the presence of living microorganisms. Key Words: Mars—Early Earth—Anaerobic chemotrophs—Biosignatures—Astrobiology missions to Mars. Astrobiology 15, 998–1029.

Jurassic and Cretaceous Gastropods from Hydrocarbon Seeps in Forearc Basin and Accretionary Prism Settings, California

Fourteen gastropod species from 16 Mesozoic hydrocarbon seep carbonate deposits of the Great Valley Group and Franciscan Complex in California are described. Two genera are new: Bathypurpurinopsis has a fusiform shell with a siphonal fold, and variable Paskentana has turbiniform or littoriniform shells with spiral and/or scaly sculpture and convex or shouldered whorls. Due to the lack of data on shell microstructure and protoconch morphology, many of our taxonomic assignments have to remain tentative at present. Species that are described as new include: Hokkaidoconcha bilirata, H. morenoensis, H. tehamaensis (Hokkaidoconchidae), Abyssochrysos? giganteum (Abyssochrysidae?), Paskentana globosa, P. berryessaensis, and Bathypurpurinopsis stantoni (Abyssochrysoidea, family uncertain). The total fauna represents a mixed bag of taxa that were: (i) widely distributed during the late Mesozoic (Amberleya); (ii) restricted to late Mesozoic seep carbonates in California (Atresius, Bathypurpurinopsis, Paskentana); and (iii) members of seep/deep-sea groups with a long stratigraphic range (abyssochrysids, hokkaidoconchids).

The mineralogy, texture and significance of silica derived from alteration by steam condensate in three New Zealand geothermal fields

Abstract Opaline silica residue accumulates on the surface and in the near surface of the Te Kopia, Tikitere and Rotokawa geothermal fields, where rhyolitic tuffs are attacked by steam condensate, made acid (pH 2-3) by sulphuric acid produced by oxidation of H2S that accompanies steam discharge. Silica residue is one product of this alteration process that also yields kaolinite, sulphur, sulphide and aluminous sulphates, including alunite and alunogen, as pH, Eh and available moisture fluctuate across the field surface. Coagulation of colloidal polymeric silica or, possibly, direct deposition of monomeric silica can occur from the acid solutions of the digested country rock, depending on pH, concentration, temperature and the presence and concentration of other species. As with silica sinter, the first-formed silica phase consists of disordered opal-A microspheroids, commonly 0.1-5 μm in diameter. These coalesce and become overgrown by further opaline silica to yield a mass resembling gelatinous ‘frog spawn’ that lines cavities and envelops surfaces. This mass is the principle component of botryoidal, transparent to translucent hyalite that comprises much residue. Following deposition, this juvenile residue may crystallize to opal-CT lepispheres, 1-3 μm across and, subsequently, to chalcedonic quartz. Both the opal-A and opal-CT of the New Zealand residues are more disordered than those occurring in typical moderate- to low-temperature sinters. The opaline silica of silica residues enjoys a reaction relationship with both kaolinite and aluminium sulphates, including alunite and alunogen. These phases and the silica precipitate continuously and undergo dissolution at the surface of all three localities. The precise pathway followed depends upon the prevailing surface conditions, including humidity, pH, Eh, and Al and K activities. As Al is flushed from the system, the ultimate stage of alteration that may result is the dissolution of the silica itself in acidified rainwater, fogdrip or further steam condensate.

Silicifying Biofilm Exopolymers on a Hot-Spring Microstromatolite: Templating Nanometer-Thick Laminae

Exopolymeric substances (EPS) are an integral component of microbial biofilms; however, few studies have addressed their silicification and preservation in hot-spring deposits. Through comparative analyses with the use of a range of microscopy techniques, we identified abundant EPS significant to the textural development of spicular, microstromatolitic, siliceous sinter at Champagne Pool, Waiotapu, New Zealand. Examination of biofilms coating sinter surfaces by confocal laser scanning microscopy (CLSM), environmental scanning electron microscopy (ESEM), cryo-scanning electron microscopy (cryo-SEM), and transmission electron microscopy (TEM) revealed contraction of the gelatinous EPS matrix into films (approximately 10 nm thick) or fibrillar structures, which is common in conventional SEM analyses and analogous to products of naturally occurring desiccation. Silicification of fibrillar EPS contributed to the formation of filamentous sinter. Matrix surfaces or dehydrated films templated sinter laminae (nanometers to microns thick) that, in places, preserved fenestral voids beneath. Laminae of similar thickness are, in general, common to spicular geyserites. This is the first report to demonstrate EPS templation of siliceous stromatolite laminae. Considering the ubiquity of biofilms on surfaces in hot-spring environments, EPS silicification studies are likely to be important to a better understanding of the origins of laminae in other modern and ancient stromatolitic sinters, and EPS potentially may serve as biosignatures in extraterrestrial rocks.

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.

Jurassic geothermal landscapes and fossil ecosystems at San Agustín, Patagonia, Argentina

Abstract: An extensive, well-preserved, Late Jurassic (c. 150 Ma) geothermal system at San Agustín farm in the Deseado Massif, Patagonia, Argentina, is described. This deposit, along with others previously known from the same region, partially fills a considerable gap between Cenozoic and scattered Palaeozoic hot spring localities reported worldwide. The San Agustín deposit is novel because it represents a large (1.4 km2) and nearly complete geothermal landscape. Siliceous hot spring facies, both subaerial and subaqueous, are exposed side by side in their original spatial and geological context, set amongst intrusive rhyolite domes and fluviolacustrine sediments. The Jurassic hot springs have preserved an entire local ecosystem containing microbes, arthropods, gastropods and plants exhibiting Lagerstätten-style preservation. Plant preservation, in particular, ranges from decayed litter, to seedling sprouts, and to dense stands in life orientation with intact anatomy. The San Agustín deposit shares some ecological, taphonomic and sedimentological characteristics with modern hot springs. As it formed in a pre-angiosperm world, it is akin to the famous hot spring-related Devonian Rhynie cherts of Scotland. It differs in having excellent exposure, and thus will probably contribute to a better understanding of biosignal preservation in extreme environments in the geological record.

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.