ABSTRACT The Monterey Formation and related formations in California have long been the subject of field and laboratory studies on silica diagenesis. Biogenic or amorphous silica (opal-A) alters to a more-ordered opal-CT and eventually to the crystalline end member, quartz, with increasing burial depth and temperature. Low-pressure nitrogen sorption serves as an indicator of silica alteration by detecting the nanometer-scale pore structures associated with opal-CT while excluding contributions from larger pores. To apply this method, calibrations with known compositions are not required, sample preparation and measurements are straightforward, hazardous waste is not generated (as with mercury porosimetry), and subtle changes in silica phase are readily detected. Nitrogen desorption isotherms, collected on mini cores (~0.8 cm diameter × 1 cm) after outgassing at 50 °C and processed using the Barrett-Joyner-Halenda method, provide nanometer-scale pore throat size distributions (nPSD), pore volumes (nPV), and surface areas (nSA). A scatter plot of nPV and nSA reveals two distinct trends. Samples with more nSA per unit volume contain opal-CT, either in transition from opal-A or completely converted. The other nSA trend consists of opal-A and quartz samples in the small nSA and nPV range, whereas samples with small nSA and large nPV also contain opal-CT and are in transition to quartz. These distinct trends are also apparent in the nPSD. Samples with more nSA exhibit a peak between 4 and 10 nm, whereas samples with less nSA have a broad peak between 10 and 100 nm if they contain opal-CT. Images collected via scanning electron microscopy reveal that opal-CT morphologies account for these differences.

ABSTRACT An evaluation of an integrated data set collected over the past 12 years designed to identify the parameters controlling reservoir quality and production properties in organic, siliceous mudrocks reveals the key diagenetic processes affecting the development of brittleness in siliceous mudrocks. This work was motivated by the failure of early efforts to correlate brittleness to x-ray diffraction (XRD) mineralogy. The outcome of this analysis has been the recognition of two, often overlapping, pathways to brittleness that are determined at the time of deposition by the relative proportions of clay, detrital quartz, and biogenic silica present in the original sediment and are later affected by burial history. One pathway begins with a phyllosilicate–mud-dominated sediment, and the other begins with a sediment containing common or abundant biogenic silica (opal-A). Both pathways are characterized by compactional porosity loss and both eventually include the generation of authigenic quartz cement; however, the source of that authigenic quartz is different between the two pathways. The authigenic quartz that characterizes the first pathway is developed from the illitization of smectite and is precipitated as a cement within the argillaceous matrix. This authigenic quartz is detectable along with the detrital quartz by XRD analysis. All other factors being equal, the volume of brittle, authigenic quartz cement derived from the alteration of smectite is proportional to the volume of original clay. As a result, the effectiveness of this cement to increase the brittleness of the rock may be impacted by the presence of the ductile clays. In the alternate pathway, authigenic quartz is derived from the transformation of biogenic opal-A and is independent of the amount of clay. Much of the XRD quartz volume in rocks derived from biogenic–silica-rich sediment that contained little or no detrital quartz will comprise a brittle, authigenic cement.

Over recent decades, numerous studies have highlighted the importance of opal, chalcedony and quartz varieties, chiefly in volcanic, but also in metamorphic and sedimentary environments. The focus is to define accurately their structures, composition and properties, as well as to identify the factors controlling the formation and the ageing of different forms of silica. In the field of archaeological sciences efficient discriminants are the bases from which the origin and provenance of materials may be traced. Substantial efforts were made in the attempt to combine geochemical, mineralogical, petrographic and geological features with archaeological and archaeometric information. However the results show that data integration is complicated, and several unanswered questions remain. On the one hand, archaeological research has focused on technological and ethnographic aspects, mainly concerning use-wear and heat-treatment studies. Mineralogical characterization has often been limited to the identification of the material, frequently by Raman microspectroscopy alone. On the other hand, the Earth sciences have provided basic mineralogical, crystal-chemical and geological knowledge, but failed to provide a systematic data collection of sources and their geochemistry. As a consequence, large gaps persist in the identification of archaeological opals, chalcedonies and quartz varieties, and in the geographic mapping of possible sources. In this context, the present review aims to summarize the current academic debate on such issues, possibly to encourage further work in the field. After a brief introduction to terminology, the structure of opals, their colours and properties are discussed, followed by an introduction to silica dissolution/precipitation and opal-formation processes. The next section reviews the information available on use of opals and provenance from historical sources, mainly Pliny the Elder, followed by a short list of ancient and modern opal supply areas, together with a (necessarily incomplete) summary of the geological and geochemical information. The discussion then encompasses chalcedony, agate and chalcedony varieties (carnelian, sard, onyx, sardonyx, chrysoprase, Cr-chalcedony, ‘gem silica’ or ‘chrysocolla chalcedony’ and heliotrope), following the same scheme as was adopted for opals. Terminology, distinguishing features, formation conditions, information derived from Pliny’s books, past and current supply areas and, finally, archaeometric provenance issues are addressed for each type of material. As for chalcedony, a comprehensive note on moganite has been included. The next section focuses on chert, flint and jasper. Given the large amount of materials available on this topic, the present review must necessarily be considered introductory and partial. The discussion aims to provide useful indications on how to distinguish chert from flint and chert from jasper; secondly, the information provided by Pliny and the archaeometric state of the art on these materials is reviewed. The last section examines quartz varieties: hyaline quartz (rock crystal), milky quartz, smoky quartz, rose and pink quartz, amethyst, citrine, prasiolite and blue quartz. An exhaustive mineralogical discussion on quartz is beyond the scope of this review; conversely a review of the historical information is provided, together with a brief list of major supply areas, a summary of the archaeometric studies performed on these materials, as well as an indication of the geological literature which can be used proficiently for provenance studies.

Abstract Oligo-Miocene (‘Maikopian’) deposits are considered the main source rocks in the Black Sea area, although only a few source-rock data are available. Geochemical logs from nine wells are used together with age constraints provided by calcareous nannoplankton, well and seismic data to determine vertical and lateral changes of the source potential. Oligocene rocks overlie Eocene deposits with a major unconformity on the western Black Sea shelf in Bulgaria. A west–east-trending erosional structure (the Kaliakra canyon) developed during Lower Oligocene time and was filled with Oligo-Miocene deposits. Potential source rocks are present in different stratigraphic units, but the most prolific intervals accumulated during time intervals when the isolation of the Paratethys resulted in oxygen-depleted, brackish environments with high bioproductivity. These include Lower Solenovian rocks related to blooms of calcareous nannoplankton, which form an extensive layer outside the Kaliakra canyon. This unit hosts a good potential to generate oil and gas. Diatom-rich, very good oil-prone source rocks accumulated during a second isolation event in the Kozakhurian. Thick sections of these diatom-rich rocks occur within the canyon and are present in thin layers outside of it. High productivity of siliceous organisms is attributed to upwelling within the canyon. All studied units are thermally immature on the shelf.