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The present study aimed to investigate the genesis and characteristics of some of the world-famous agate deposits in the state of Chihuahua, Mexico (Rancho Coyamito, Ojo Laguna, Moctezuma, Huevos del Diablo, Agua Nueva). Geochemical and textural studies of host rocks showed that all the studied deposits are related to the same rock type within the geological unit of Rancho el Agate andesite, a quartz-free latite that shows clear indications of magma mixing. As a result of their large-scale distribution and various differentiation processes, as well as transport separation, different textures and local chemical differences between rocks of different localities can be observed. These differences have also influenced the properties of SiO2 mineralization in the rocks. The mixing of near-surface fluids from rock alterations with magmatic hydrothermal solutions led to the accumulation of various elements in the SiO2 matrix of the agates, which were, on the one hand, mobilized during secondary rock alteration (Fe, U, Ca, K, Al, Si) and, on the other hand, transported with magmatic fluids (Zn, Sb, Si, Zr, Cr). Different generations of chalcedony indicate a multi-stage formation as well as multiple cycles of filling the cavities with fluids. The hydrothermal fluids are presumably related to the residual solutions of a rhyolitic volcanism, which followed the latitic extrusions in the area and probably caused the formation of polymetallic ore deposits in the Chihuahua area. The enrichment of highly immobile elements indicates the involvement of volatile fluids in the agate formation. The vivid colors of the agates are almost exclusively due to various mineral inclusions, which consist mainly of iron compounds.

Agates in Paleocene/Eocene tuffs from El Picado/Los Indios, Cuba were investigated to characterize the mineral composition of the agates and to provide data for the reconstruction of agate forming processes. The volcanic host rocks are strongly altered and fractured and contain numerous fissures and veins mineralized by quartz and chalcedony. These features indicate secondary alteration and silicification processes during tectonic activities that may have also resulted in the formation of massive agates. Local accumulation of manganese oxides/hydroxides, as well as uranium (uranyl-silicate complexes), in the agates confirm their contemporaneous supply with SiO2 and the origin of the silica-bearing solutions from the alteration processes. The mineral composition of the agates is characterized by abnormal high bulk contents of opal-CT (>6 wt%) and moganite (>16 wt%) besides alpha-quartz. The presence of these elevated amounts of “immature” silica phases emphasize that agate formation runs through several structural states of SiO2 with amorphous silica as the first solid phase. A remarkable feature of the agates is a heterogeneous distribution of moganite within the silica matrix revealed by micro-Raman mapping. The intensity ratio of the main symmetric stretching-bending vibrations (A1 modes) of alpha-quartz at 465 cm−1 and moganite at 502 cm−1, respectively, was used to depict the abundance of moganite in the silica matrix. The zoned distribution of moganite and variations in the microtexture and porosity of the agates indicate a multi-phase deposition of SiO2 under varying physico-chemical conditions and a discontinuous silica supply.

Agate—a spectacular form of SiO2 and a famous gemstone—is commonly characterized as banded chalcedony. In detail, chalcedony layers in agates can be intergrown or intercalated with macrocrystalline quartz, quartzine, opal-A, opal-CT, cristobalite and/or moganite. In addition, agates often contain considerable amounts of mineral inclusions and water as both interstitial molecular H2O and silanol groups. Most agate occurrences worldwide are related to SiO2-rich (rhyolites, rhyodacites) and SiO2-poor (andesites, basalts) volcanic rocks, but can also be formed as hydrothermal vein varieties or as silica accumulation during diagenesis in sedimentary rocks. It is assumed that the supply of silica for agate formation is often associated with late- or post-volcanic alteration of the volcanic host rocks. Evidence can be found in association with typical secondary minerals such as clay minerals, zeolites or iron oxides/hydroxides, frequent pseudomorphs (e.g., after carbonates or sulfates) as well as the chemical composition of the agates. For instance, elements of the volcanic rock matrix (Al, Ca, Fe, Na, K) are enriched, but extraordinary high contents of Ge (>90 ppm), B (>40 ppm) and U (>20 ppm) have also been detected. Calculations based on fluid inclusion and oxygen isotope studies point to a range between 20 and 230 °C for agate formation temperatures. The accumulation and condensation of silicic acid result in the formation of silica sols and proposed amorphous silica as precursors for the development of the typical agate micro-structure. The process of crystallisation often starts with spherulitic growth of chalcedony continuing into chalcedony fibers. High concentrations of lattice defects (oxygen and silicon vacancies, silanol groups) detected by cathodoluminescence (CL) and electron paramagnetic resonance (EPR) spectroscopy indicate a rapid crystallisation via an amorphous silica precursor under non-equilibrium conditions. It is assumed that the formation of the typical agate microstructure is governed by processes of self-organization. The resulting differences in crystallite size, porosity, kind of silica phase and incorporated color pigments finally cause the characteristic agate banding and colors.

The growth in volatile renewable energy (RE) generation is accompanied by an increasing network load and an increasing demand for storage units. Household storage systems and micro power plants, in particular, represent an uncertainty factor for distribution networks, as well as transmission networks. Due to missing data exchanges, transmission system operators cannot take into account the impact of household storage systems in their network load and generation forecasts. Thus, neglecting the increasing number of household storage systems leads to increasing forecast inaccuracies. To consider the impact of the storage systems on forecasting, this paper presents a new approach to calculate a substation-specific storage forecast, which includes both substation-specific RE generation and load forecasts. For the storage forecast, storage systems and micro power plants are assigned to substations. Based on their aggregated behavior, the impact on the forecasted RE generation and load is determined. The load and generation are forecasted by combining several optimization approaches to minimize the forecasting errors. The concept is validated using data from the German transmission system operator, 50 Hertz Transmission GmbH. This investigation demonstrates the significance of using a battery storage forecast with an integrated load and generation forecast.

The morphology, chemical, and mineralogical composition of subsurface filamentous fabrics (SFF) from the Deccan Volcanic Province (DVP) were investigated to determine the origin of these spectacular aggregates. SFF occur in a wide variety of morphologies ranging from pseudo-stalactites to irregular fabrics and are classified as SFFIr (irregular) or SFFMa (matted). The SFF samples exhibit a thread-like (or filament-like) center from which mineral precipitation starts to form the final macroscopic morphologies. Detailed investigations revealed organic material (fungal chitin) in the innermost filamentous core, which may have acted as an initial nucleus for the mineralization processes. The morphometric characteristics of certain filamentous fabrics are very similar to those of microbial filaments and the fabrics formed from them but are clearly distinct from similar types of non-biological precipitates (fibrous minerals, speleothems, and “chemical gardens”). These features indicate that the filamentous cores might be products of microbial communities that were active in the basaltic cavities. The SFF cross-sections display similar concentric layers of the mineral succession and reach thicknesses of several centimeters with spectacular lengths up to 100 cm and constant diameters. The typical mineralization sequence points to temporal variation in the chemical composition of the mineralizing fluids from Fe(Mg)-rich (Fe-oxides/-hydroxides, Fe-rich sheet silicates such as celadonite and di-/tri-smectite) to Ca-dominated (Ca-rich zeolites) and finally pure SiO2 (opal-CT, chalcedony, and macro-crystalline quartz). Assuming biological activity at least during the early mineralization processes, circumneutral pH conditions and maximum temperatures of 100–120 °C were supposed. The formation of filamentous cores including Fe-bearing phyllosilicates probably occurred near the surface after cooling of the lava, where the elements necessary for mineral formation (i.e., Si, Mg, Al, Fe) were released during alteration of the volcanic host rocks by percolating fluids.

The study of the oldest surviving rock suites is crucial for understanding the processes that shaped the early Earth and formed an environment suitable for life. The metasedimentary and metavolcanic rocks of the early Archean Isua supracrustal belt contain abundant apatite, the geochemical signatures of which may help decipher ancient environmental conditions. However, previous research has shown that secondary processes, including amphibolite-facies metamorphism, have reset the original hydrogen isotope composition (δD) of apatite from the Isua belt; therefore, δD values are not indicative of primary conditions in the Archean. Here, we report the first in situ chlorine isotope (δ37Cl) analyses by Secondary Ion Mass Spectrometry (SIMS) from Isua apatite, which we combine with information from transmission electron microscopy, cathodoluminescence imaging, and spectroscopy, documenting the micron-scale internal features of apatite crystals. The determined δ37ClSMOC values (chlorine isotope ratios vs. standard mean ocean chloride) fall within a range from −0.8‱ to 1.6‱, with the most extreme values recorded by two banded iron formation samples. Our results show that δ37Cl values cannot uniquely document primary signatures of apatite crystals, but the results are nonetheless helpful for assessing the extent of secondary overprint.

Flood basalts of the Deccan Volcanic Province erupted between about 67.5 to 60.5 Ma ago and reached a thickness of up to 3500 m. The main part consists of compound and simple lava flows with a tholeiitic composition erupted within 500,000 years at about 65 Ma. Within the compound lava flows, vesicles and cavities are frequent. They are filled by secondary minerals partly of well development and large size. This study presents data on the secondary mineralization including detailed field descriptions, optical, cathodoluminescence and SEM microscopy, X-ray diffractometry, fluid inclusions, C and O isotope analyses, and Rb-Sr and K-Ar geochronology. The investigations indicate a multistage precipitation sequence with three main stages. During stage I clay minerals and subsurface filamentous fabrics (SFFs), of probably biogenic origin, formed after the lava flows cooled down near to the Earth’s surface. In stage II, first an assemblage of calcite (I) and zeolite (I) (including mordenite, heulandite, and stilbite) as well as plagioclase was overgrown by chalcedony, and finally a second calcite (II) and zeolite (II) generation developed by burial metamorphism by subsequent lava flows. Stage III is characterized by precipitation of a third calcite (III) generation together with powellite and apophyllite from late hydrothermal fluids. Rb-Sr and K-Ar ages of apophyllite indicate a large time span for stage III. Apophyllite formed within different time intervals from the Paleogene to the early Miocene even within individual lava flows at certain localities. From the Savda/Jalgaon quarry complex, ages cluster at 44−48 Ma and 25−28 Ma, whereas those from the Nashik area are 55−58 Ma and 21−23 Ma, respectively.

Quartz and other silica minerals make up 12. [...]

The occurrence and formation of silicified wood from five late Paleozoic basins in Central Europe was investigated. Fossil wood from diverse geological settings was studied using field observations, taphonomic determinations as well as mineralogical analyses (polarizing microscopy, cathodoluminescence (CL) microscopy and spectroscopy). The results indicate that silicification is either a monophase or multiphase process under varying physico-chemical conditions. In particular, CL studies revealed complex processes of silica accumulation and crystallization. The CL characteristics of quartz phases in silicified wood can mostly be related to blue (390 and 440 nm), yellow (580 nm), and red (650 nm) emission bands, which may appear in different combinations and varying intensity ratios. Yellow CL is typical for initial silicification, reflecting quick precipitation under oxygen-deficient conditions caused by initial decay of the organic material. Blue CL is predominantly of secondary origin, resulting from replacement of precursor phases by a secondary hydrothermal quartz generation or subsequent silicification of wood. The red CL can be related to a lattice defect (non-bridging oxygen hole center—NBOHC).

We performed a detailed analysis of hydrothermal quartz at the Mokrsko gold deposit (Čelina, Mokrsko-East, and Mokrsko-West deposits). Twenty-one samples were studied by scanning electron microscopy cathodoluminescence (CL) imagining, CL emission spectra and trace elements were measured on six selected samples. Four quartz growth generations Q1 to Q4 were described. Homogeneous early blue CL Q1 with initial emission spectra at 380 and 500 nm was observed at the Čelina deposit with typical titanium concentrations in the range of 20–50 ppm. Hydrothermal quartz at Mokrsko-West, which also includes early Q1, late subhedral faces of yellow CL Q2, and microfissures of greenish CL Q3 (both 570 nm), is characterized by titanium depletion. The titanium concentration is comparable to previous studies of crystallization temperatures proving titanium concentration in quartz as a good geothermal indicator. Q4, developed in microfissures only at Čelina, has no visual CL effect. Mokrsko-West is specific in comparison to Mokrsko-East and Čelina by germanium enrichments in hydrothermal quartz (up to 17 ppm) and the presence of fluorite. Tectonic (sheeted veinlets system, regional tectonic setting) and geochemical (germanium in quartz, the presence of fluorite) characteristics of the quartz veins link the late mineralization stages at the Mokrsko-West deposit to the temporally related Blatná intrusive suite.

Quartz of metamorphic rocks from the Kaoko belt (Namibia) representing metamorphic zones from greenshist to granulite facies were investigated by cathodoluminescence (CL) microscopy and spectroscopy to characterize their CL properties. The samples cover P-T conditions from the garnet zone (500 ± 30 °C, 9 ± 1 kbar) up to the garnet-cordierite-sillimanite-K-feldspar zone (750 ± 30 °C, 4.0–5.5 kbar). Quartz from 10 different localities and metamorphic environments exclusively exhibits blue CL. The observed CL colors and spectra seem to be more or less independent of the metamorphic grade of the host rocks, but are determined by the regional geological conditions. Quartz from different localities of the garnet-cordierite-sillimanite-K-feldspar zone shows a dominant 450 nm emission band similar to quartz from igneous rocks, which might be related to recrystallization processes. In contrast, quartz from different metamorphic zones in the western part of the central Kaoko zone (garnet, staurolite, kyanite, and kyanite-sillimanite-muscovite zone) is characterized by a heterogeneous blue-green CL and a dominant 500 nm emission band that strongly decreases in intensity under electron irradiation. Such CL characteristics are typical for quartz of pegmatitic and/or hydrothermal origin and indicate the participation of fluids during neoformation of quartz during metamorphism.

Gaseous and liquid fluids in agates (banded chalcedony—SiO2) of different localities were investigated systematically by thermogravimetry-mass-spectrometry within a temperature range from 25 to 1450 °C, for the first time. Chalcedony and macrocrystalline quartz from twelve agate samples were investigated, from Germany (Schlottwitz, St. Egidien, Chemnitz and Zwickau), Brazil (Rio Grande do Sul), Scotland (Ayrshire) and the USA (Montana). They originate from mafic and felsic volcanic rocks as well as hydrothermal and sedimentary environments. The results were evaluated regarding compounds of hydrogen with fluorine, chlorine, nitrogen, carbon and sulphur. Additionally, oxygen compounds were recognized with hydrogen, fluorine, nitrogen, sulphur and carbon. The nature of the compounds was identified based on their mass-charge-ratio and the intensity ratios of the associated fragments. Due to interferences of different compounds with the same mass-charge-ratio, only H2O, HF, NO, S, SO, CO3—as well as several hydrocarbon compounds (for example CO32− or CO)—could be properly identified. The main degassing temperatures were detected at around 500 and 1000 °C. Generally, a difference between quartz and chalcedony regarding the composition of their fluids could not be found. The results indicate a silica source for the agate formation from aqueous solutions but also a possible role of fluorine compounds. Additionally, CO2 and other fluids were involved in the alteration of volcanic rocks and the mobilization and transport of SiO2.

Quartz samples of different origin from 10 localities in the Southern Ural region, Russia have been investigated to characterize their trace element compositions and defect structures. The analytical combination of cathodoluminescence (CL) microscopy and spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and trace-element analysis by inductively coupled plasma mass spectrometry (ICP-MS) revealed that almost all investigated quartz samples showed very low concentrations of trace elements (cumulative concentrations of

The 1895 discovery of a petrified tree near Clover Creek in south-central Idaho, USA, attracted worldwide attention and resulted in the naming of a new species of ancient oak, Quercinium pliocaenicum Schuster. For more than a century, the discovery has largely been forgotten, even though specimens reside in reputable museums. Reinvestigation of the locality in 2014/2015 resulted in newly-collected specimens and a wealth of new data. Optical microscopy confirms the cellular anatomy used for the original taxonomic study. X-ray diffraction, scanning electron microscopy, energy-dispersive electron spectroscopy, Raman spectroscopy and cathodoluminescence microscopy reveal details of the mineralization, showing the presence of opal-CT as the primary component, with chalcedony as a lesser constituent. This mineralogy suggests petrifaction occurred in at least two stages, beginning with opalization of cellular tissue, leaving open vessels that became filled with chalcedony during a later mineralization episode. Clover Creek oak represents relict flora growing in a wetter climate before the uplift of the Cascade Range created a rain shadow that caused profound desertification of the inland Pacific Northwest.