Authigenic quartz and albite in Devonian limestones: origin and significance

Euhedral quartz and albite crystals are common in Devonian (Givetian-Frasnian) shallow-marine shelf carbonates from the Belgian Ardennes. Several features such as morphology, the presence of carbonate inclusions, inversion temperatures and occurrence in the insoluble residues of stylolitic surfaces indicate that these crystals have developed authigenically. Oxygen isotope ratios point to an intermediate deep burial realm of origin at temperatures of 60–90°C. The predominance of illite and the almost total absence of smectite clay minerals is interpreted as an indication that illitization produced the silica needed for authigenesis. The mineral composition of inclusions indicates that the carbonate host rock must have consisted of low-Mg calcite already at the time of authigenesis. These inclusions represent an earlier diagenetic stage than the present carbonate rock, since they were protected from further diagenetic alteration by the surrounding quartz. The calcite inclusions display a higher Sr/Ca and Mg/Ca ratio than the carbonate host-rock. Because neomorphic diagenesis of the carbonate continued after silicate authigenesis, the contents of Mg and Sr in the calcite of the host carbonate are even lower. The authigenic feldspar mineralogy seems to be determined by the composition of the host-sediment.     

Diagenesis of the Newark Rift Basin, Eastern North America

Late Triassic nonmarine strata in the Newark Rift Basin, eastern North America, accumulated in a subsiding half-graben prior to opening of the Atlantic Ocean. These strata consist, in ascending order, of the Stockton, Lockatong, and Passaic formations. Although different in specific lithology, these formations all exhibit diagenetic fabrics dominated by authigenic albite and analcime. These same minerals have a similar presence in Late Triassic (Newark Supergroup) strata of other rift-related basins to the north, suggesting that related authigenesis is not simply a result of local diagenetic factors. The basal deposit, the Stockton Formation, is composed of fluvial sandstones and overbank mudstones, with nodular pedogenic calcite (calcrete). During burial, original micrite was first recrystallized into sparry calcite and then later subjected to partial replacement by authigenic albite, which is also present as overgrowths and void fillings in overbank mudstones. The Lockatong Formation contains organic-rich shales, carbonates, and evaporative mudstones deposited under cyclic conditions in laterally extensive lacustrine environments. Analcime comprises up to 40% of these strata by volume, occurring within the matrix, as a replacement of original carbonates and evaporites, and as fillings in macrovoids. The overlying Passaic Formation is made up of massive red mudstones, evaporites, and local calcareous lacustrine sequences. Evaporites are replaced by coarse-grained anhydrite together with some authigenic albite. A central question concerns the source for the Na, Si, and Al required for albite and analcime authigenesis. It is suggested that, in addition to alteration of primary siliciclastic material, sodium in particular was supplied in two ways: (1) from high concentrations in original evaporative brines and groundwaters (Lockatong and Passaic formations); and (2) from dissolution of associated sodium-bearing evaporites (Lockatong and Passaic Formation) during diagenesis. It is proposed here that basin-sourced, Na-enriched brines circulated through the section over time. As albite is more stable at elevated temperatures relative to analcime, it developed in the lowermost strata of the basin (Stockton Formation). Analcime is more prevalent in the overlying Lockatong Formation.     

THE PRESENT STATUS OF ZIRCON

Saxena (1966a) proposed that zircon could be authigenic and low-grade metamorphic, as well as magmatic in origin. He questioned the mechanical and chemical stability of zircon, the use of crystal morphology in correlation, and the use of roundness as a criterion of detrital origin. In so doing, he challenged the role of zircon in problems of stratigraphy, pedogenesis, and sedimentary, igneous, and metamorphic petrology. SAXENA'S(1966a, b) evidence for authigenic and low-grade metamorphic zircon is unconvincing, since conventional explanations adequately encompass his obser- vations, and do not conflict with established knowledge of zircon behaviour. During weathering, authigenesis, and metamorphism, zircon is shown to conform with the concepts that: (1) its removal and transport in solution is minimal, (2) zircon formation during authigenesis and low-grade metamorphism is insignificant. Rare occurrences of hydrozircon confirm this paucity of authigenic zirconium minerals. At high metamorphic grades zircon-transformation is favoured by the “wet” metasomatic processes of the amphibolite facies and impaired by the “dryness” of the granulite facies. The occurrence of zircon transformation in the granulite facies may also be prevented by incorporation of zirconium in the lattice of newly-formed pyroxene. Release of this zirconium during diaphthoresis of pyroxene-bearing granulites could give rise to new zircon. The formation of zircon during authigenesis, and its formation and transfor- mation during low-grade metamorphism, would diversify initially homogeneous assemblages; but Saxena has failed to prove that either process does in fact occur. It is contended that, since the positive correlation of zircon assemblages from co-eval sedimentary and metamorphic rocks of the Kingsbridge area is opposed to Saxena's views regarding the origin and behaviour of zircon, the roles of authigenesis in the formation of zircon, and of low-grade metamorphism in its formation and transformation, are insignificant or non-existent.     

Discrete clay diagenesis in a very low-permeable sequence constrained by an isotopic (K–Ar and Rb–Sr) study

Multimethod analyses of several size fractions of clays were used to reconstruct the diagenetic history of the shallow buried claystones within the Paris Basin. A systematic decrease occurred in K-Ar dates relative to the decrease in size of the clay fractions, signifying higher amounts of newly formed clay material in the finer fractions. We suggest that the authigenic clay minerals occurring in the fine fractions had an Al-montmorillonite composition. By assuming that the isotopic K-Ar and Rb-Sr dates obtained on a bentonite layer in the sedimentary sequence stand for pure, authigenic clay minerals, one may interpret all K-Ar dates as mixtures of one authigenic and two detrital end-members. The results imply that a period of low sea level favoured diagenetic smectite-type clay formation about 10-15 million years after deposition of the sediments. Signatures of limited-scale chemical and isotopic homogenisation mean that the rock volumes affected by the diagenetic modifications had to be quite limited. The study of clay minerals extracted from some stylolites further suggests that any overpressure related to the origin of stylolites had no effect on clay authigenesis.     

Possible accumulation of authigenic, expandable-type clay minerals in the substructure of tuttle creek dam, Kansas, U.S.A.

A preliminary review of the literature indicates that the chemistry of the water from relief wells south of Tuttle Creek Dam (T.C.D.) is favorable for the formation of authigenic montmorillonitic and mixed-layer clays whereas the chemistry of the waters of Tuttle Creek Reservoir (T.C.R.) indicates only kaolinite as a possible authigenic phase. The montmorillonitic and mixed-layer clays are very undesirable in a dam's structure due to their ion exchange capacity and swellability-compressibility; both factors can possibly shorten the life of an earthfill dam.

Further study indicates that the water chemistry of the relief wells is close to that for many of the wells in the Blue River Valley and Kansas River Valley from below the dam and that this criterion alone cannot be used to answer the critical question of authigenesis. Clay mineralogic study coupled with a Rb-Sr geochronologic study indicates that, despite some real differences in the types of clays found in both T.C.R. and T.C.D., an allogenic origin for the clays is probable. This refutes the idea that the dam is being weakened by authigenic clay deposition, but more chemical date are needed to confirm the Rb-Sr work.     

松辽盆地南部HX井上白垩统青山口组黑色泥岩的矿物组成与自生微晶石英成因

泥质岩的矿物组成和成岩作用是制约其作为CO₂地质封存的盖层封闭能力和作为页岩气储层具易压裂性质的重要原因。通过地球化学分析、X-射线衍射分析和扫描电镜观测及能谱测定,确定了松辽盆地南部HX井上白垩统青山口组泥岩的矿物组成,识别出了蒙皂石转变伊利石反应过程中形成的亚微米级自生微晶石英。研究表明：HX井上白垩统青山口组泥岩的母岩岩石类型和风化效应一致,泥岩主要由黏土矿物、钠长石和石英组成,钾长石少量;黏土矿物以伊利石/蒙皂石混层为主,其次为绿泥石;脆性矿物（钠长石、石英和钾长石）的平均质量分数为44.43%,黏土矿物平均质量分数为54.26%。蒙皂石转变伊利石反应过程中形成的亚微米级微晶石英单晶呈自形－半自形粒状,集合体呈巢状,分布于伊利石/蒙皂石混层黏土矿物的微孔隙中。以伊利石/蒙皂石混层矿物为主、且存在一定量的自生微晶石英的泥岩盖层（例如HX井青山口组泥岩）将有助于注入CO₂的长期封存。HX井青山口组泥岩中的脆性矿物含量符合工业价值页岩气的储层标准,而黏土矿物含量则相差较多。     

K–Ar dating of authigenic minerals in siliciclastic sequences: an example from the south Sanfranciscana Basin (Western Minas Gerais,Brazil)

K–Ar dating was applied on authigenic potassic minerals which are abundant in sandstones from the south of the Sanfranciscana Basin, Western Minas Gerais State, central Brazil. The Quintinos Member fluvial sandstones (Três Barras Formation, Areado Group) contain significant amounts of authigenic K‐feldspar as microcrystals of adularia and sanidine habits. The ages of these microcrystals cluster into three groups: 106.1 ± 2.2, 89.9 ± 1.9 and 88.8 ± 1.8 Ma (from Albian to Coniacian). The older age of 106.1 ± 2.2 Ma was obtained from the coarse fraction analysed (10–20 µm) that can contain a mixture of detrital potassic minerals (K‐feldspar, muscovite, biotite and illite) and different authigenesis of K‐feldspar (overgrowths and microcrystals). Thus, only the younger ages were interpreted as precipitation of K‐feldspar microcrystals during the Late Cretaceous into the Quintinos Member sandstones. Moreover, these ages can document the formation of microcrystals within a few million years after deposition of the sandstones. The ages of authigenic illite from the Capacete Formation epiclastic sandstones (Mata da Corda Group) range from 88.5 ± 1.9 to 71.5 ± 1.9 Ma (Coniacian–Campanian). These results suggest the timing of the illitization event in these sandstones as well as a synchrony with K‐feldspar authigenesis in the Quintinos Member sandstones. These results are well constrained and are in agreement with stratigraphic, biostratigraphic and radiometric ages previously reported for the Sanfranciscana Basin. Copyright © 2014 John Wiley & Sons, Ltd.     

Sr and Ar isotope studies of detrital smectites from the Atlantic Ocean (D.S.D.P., Legs 43, 48 and 50)

Mineralogical, morphological and isotopic (RbSr and KAr) determinations were made on some detrital smectites of Palaeocene and Cenomanian ages from D.S.D.P. drillings in the Atlantic Ocean. These minerals are not inert in their depositional environment; authigenic laths grow on detrital sheets with sharp borders. This authigenesis could occur slightly after deposition in a closed system, for some of these smectites. It has been tentatively quantified by the RbSr and KAr isotopic methods, which seem also well suited to evaluate the chemical extent of this authigenesis. At least, no preferential loss of ⁴⁰Ar vs. ⁸⁷Sr could be detected in the minerals, even in those which are smaller than 0.2 μm.     

EVOLUTION OF ZIRCONS IN SEDIMENTARY AND METAMORPHIC ROCKS

Zircons have been studied in the sedimentary rocks of the Sparagmite Group (Eocambrian) and their metamorphic associates from the Trondheim area and the adjacent regions in Norway and Sweden. The majority of zircon population (type B) has been formed in the sediments by authigenesis. Another authigenic associate is rutile. The authigenic zircons have irregular, round and ellipsoidal habits. In metamorphic rocks the same grains show a greater tendency of euhedrism, forming drum-like crystals with acute (331) pyramids and short prisms. Authigenic zircons are usually clear and transparent but some grains may show cloudy appearance. A few other grains (type A) with different habit and many inclusions appear to be of detritai nature. Dissolution of a metamictized zircon population in the source rock is possible in many ways. An important possibility is the dissolution of zircons in alkaline solution. Carbonated lime-rich waters or other acidic solutions could be equally effective. Zirconates, so formed, are transported to the basin of deposition as colloidal particles or as ionic complexes. The authigenic process is visualized as a deposition of the zirconates by adsorption or by precipitation as zirconium hydroxide, possibly due to change in the Eh and pH in the environment. The hydrated oxide subsequently reacts with silica to form metastable hydrozircon. In course of time hydrozircon dehydrates and becomes a normal zircon. Numerous growths have been noted and are classified genetically into (l) late authigenic growths, and (2) growths syngenetic with metamorphism. The shape of the host grain usually controls the final shape of the overgrown grain. There is some effect of metamorphism on the morphology of the authigenic zircons. In view of the characters of the newly generated zircons, the use of shape, size, zoning and such other parameters of zircons in petrogenetic problems, has to be retested to ensure its reliability. Rather than being a mineral of igneous derivation only, zircon is from three parentages: igneous, authigenic and metamorphic. It is argued that the persistence of the authigenic zircons should be greatest because of very low concentration of radioactive elements.     

Strate—bound Anorthites in the Dachang Sn—Polymetallic Ore Field,Guangxi,China

From the petrological study of ore-hosting focks which contain large anorthits crystals and the occurrence and chemical composition of anorthites and related minerals,the authors consider that the large anorthite crystals are of authigenic origin. The distribution characteristics of anorthites,i.e.,they are distributed along the bedding and structurally weak zones but not restricted to synsedimentary slump structures,and the relationship for some elements between anorthites and other minerals indicate that anorthites have resulted from reaction of circulating alkaline solutions rich in Al and Si with carbonated during the Indosinian orogeny.The results of this work suggest that the association of authigenic anorthites with bedded orebodies in the Dachang ore field may be the evidence that the mineralization is related to circulating underground hot waters.     

Crystallization of alkalic feldspar phenocrysts and origin of perthites in granitoids (as in certain intrusives in Northeast USSR)

Magmatic origin of large (up to 5 cm) phenocrysts of K-feldspar is indicated by mineralogical, chemical, and roentgenometric-structural analysis of the crystals. Perthites are found to be metasomatic products of replacement of plagioclase by K-feldspar. This reaction is accompanied by albitization of plagioclase and then by growth of albite after feldspar, in cleavage planes and elsewhere, or by spot-segregations of albite in places formerly occupied by plagioclase. — V.P. Sokoloff     

Diagenetic mineral development within the Upper Jurassic Haynesville-Bossier Shale,USA

Despite recent advances, diagenetic processes in fine-grained sediments are still relatively poorly understood. Key questions still to be resolved include the types of diagenetic minerals present in mudstones and the extent of element mobility in these low permeability systems. This study utilizes data from the Haynesville-Bossier Shale, USA, to analyze lithologies, discriminate authigenic phases and identify mobile elements during diagenesis. It has implications for understanding how authigenic minerals develop and the sources of those authigenic minerals in fine-grained sediments. On the basis of grain-size and mineralogy five lithologies are designated: (i) silica-rich argillaceous mudstones; (ii) argillaceous siliceous mudstones; (iii) mixed siliceous mudstones; (iv) mixed mudstones; and (v) authigenically-dominated mudstones. The diagenetic development of the Haynesville-Bossier Shale can be divided into early and late diagenesis. Ferroan and non-ferroan dolomite, framboidal pyrite and bioclast pore-filling kaolinite and calcite grain replacements and cements all formed during early diagenesis. Late diagenetic mineral phases include illite formed by the illitization of smectite, replacive and displacive chlorite, calcite-replacive albite, quartz-replacive calcite and replacive and/or displacive quartz. The presence of extensive late diagenetic mineral precipitates indicates that there was a degree of element mobility on at least the local scale. Aluminium present in albite is most likely to have resulted from the illitization of smectite. Quartz overgrowths probably resulted from illitization and the pressure dissolution at quartz silt grain boundaries. Externally, hydrothermal fluids resulting from regional-scale igneous activity appear to have played a role in the formation of chlorite and possibly albite. The work indicates that extensive mineral development and element mobility occurred during late diagenesis.     

Detrital and authigenic(?) baddeleyite (ZrO2) in ferromanganese nodules of Central Indian Ocean Basin

Occurrence of baddeleyite (ZrO2) which is a rare mineral has been recorded in ferromanganese nodules of Central Indian Ocean Basin (CIOB). The mineral occurs either as independent isolated sub-rounded to elliptical grains or in clusters forming fine subhedral crystals (<3 mm) within ferromanganese concretionary growth bands. The mode of occurrence, textural features and chemistry of the mineral suggest detrital and possibly an authigenic origin for baddeleyite. For authigenic origin it is proposed that zirconium might have got released either from the terrigenous sediments or the altered seafloor rocks forming halogen complexes and subsequently it has re-precipitated in the form of baddeleyite within manganese nodules under oxic to sub-oxic conditions.     

Authigenie gypsum in deep-sea manganese nodules

Gypsum crystals of authigenic origin have been found in manganese nodules of the deep-sea sediment surface (4500-5500 m water depth) from the Central Pacific Ocean.     

Sedimentary K-Ar signatures in clay fractions from Mesozoic marine shelf environments in Israel

The K-Ar system in clay fractions from shallow marine carbonate shelf environments was investigated on silicate fractions (clay minerals, feldspar) separated from 20 Lower Jurassic to Upper Cretaceous sedimentary rocks, deposited in the southern Tethys ocean. The range of lithologies investigated included dolomite and chalk [IR (insoluble residue)<10%], marl, shale (IR= 70–85%) and sandstone (IR>90%). The results show that K-bearing clay fractions often have K-Ar ages similar to the suggested age of deposition, which means either supply of land-derived authigenic K-bearing clays or synsedimentary diagenetic authigenesis, or both. This K-Ar synsedimentary signal is recorded in clay fractions from the whole range of studied lithologies and stratigraphic units. Among the clay minerals, the synsedimentary K-Ar signature was recorded and retained in illite/smectite of the <2-um and <0.2-um fractions. A prominent synsedimentary signature is found in K-feldspars, from shaly and especially from calcareous rocks, which is substantiated by their authigenic origin based on idiomorphic crystal morphology and their limited size distribution (4–10 um). Post-depositional closure of the K-Ar system is indicated by ages up to 15 Ma younger than the stratigraphic age in different lithologies from dispersed localities. A distinct late diagenetic (20–25 Ma younger) event is recorded in the formation of authigenic K-feldspar within Upper Cretaceous chalk and shale. In the IR and >10-um fractions the K-Ar ages reflect the contribution of detrital mica and feldspar which accompanies the kaolinite-dominated samples. The overall results differ considerably from K-Ar age patterns observed in deep-sea sediments, a difference which may be connected with the occurrence of brines in these shelf deposits. The findings indicate the potential in the K-Ar dating of fine IR fractions of marine shelf sediments in terms of geochronological-stratigraphic and palaeogeographical aspects as well as in the petrology of clay minerals themselves.     

Crystallographic data for authigenic phillipsite from manganese nodules

Microscopic phillipsite crystals occur as elongated prisms that extend outward from the walls of interstitial cavities in manganese nodules from the southern Argentine Basin. X-ray diffraction data and unit cell dimensions indicate that these authigenic crystals correspond to those phillipsites which form from alteration of palagonitic materials on the ocean floor. Textural features of the nodules indicate that the phillipsite crystals were more likely deposited during the growth history of the nodules, thus suggesting a relationship between the crystals and the nodules themselves in terms of mode of origin.     

Authigenic albite in carbonate rocks – a tracer for deep-burial brine migration?

Euhedral, post-depositional albite from the Eastern and Western Alps, the western Carpathians and some Greek islands was examined petrographically and geochemically to gain insights into the nature of feldspar reactions in carbonate rocks. This study focuses on coarsely crystalline, homogeneously nucleated albite in order to avoid problems related to the presence of inseparable detrital material in fine-grained albite varieties. All albite samples show a very restricted compositional variability and are typically ≥ 99 mol% Ab component. Unit-cell parameters determined by Rietveld analysis are slightly more variable than previously accepted, but confirm high Al–Si ordering characteristic of low albite. The oxygen isotopic composition of albite ranges from + 19·4‰ to + 28·3‰ VSMOW. There is no direct relationship between the δ¹⁸O value and the inferred temperature of albite formation, nor is there one with stoichiometry. The coarse crystal size (up to several millimetres in diameter), petrographic evidence showing albite cross-cutting stylolites, greater abundance of albite in carbonate rocks subject to high-grade diagenetic or weak metamorphic overprinting and available fluid inclusion data suggest that albite precipitation is favoured at higher temperatures in carbonates than in sandstones. Pore fluids were invariably brines, as suggested by the inferred high positive δ¹⁸O_fluid values, the common association of albite-bearing carbonates and evaporites and reports of saline fluid inclusions in albite. The presence of authigenic albite may thus be a useful tracer of palaeobrine–carbonate reactions, particularly in deep-burial and incipient metamorphic settings.     

The contribution of authigenic feldspars to the geochemical balance of alkali metals

About 5 per cent of all feldspars in sediments are authigenic. This amounts to 0·94 per cent of the total sedimentary mass. At least 2.1 × 10¹⁸ kg Na and 3.4 × 10¹⁸kg K have been removed from sea water by reconstitution of authigenic feldspars in the total mass of surviving sediments. Consequently, 9.3 × 10¹⁹ moles CO₂ have been released by the formation of authigenic albite and 8.8 × 10¹⁹ moles CO₂ by the formation of authigenic K-feldspar.     

Über die Verteilung und Neubildung der nichtkarbonatischen Mineralkomponenten der Oberkreide aus der Umgebung von Hannover

Comparative investigations were made on the non-carbonate components of calcareous sediments of the upper chalk formation of the Hanover region.The mineral composition of the residues insoluble in 0.5 n HC1 has first been determined optically and by X-ray photographs and described. The quantitative analysis of the components contained was effected by microscopic counting using the phase contrast method up to the grain size of 2 u, and for the clay fractions proper by X-ray phase analyses.In addition to the minor components (feldspars, biotite, pyrite, marcasite, glauconite, heavy minerals and mikro-fossils) the residues contain quartz, muscovite, illite, montmorillonite and kaolinite.The calcareous sediments of the upper senon formation are specially characterized by the occurrence of authigenic heulandite crystals which could be analysed and described here for the first time. Moreover secondary crystallization of quartz, turmaline and albite could be observed in all the samples analysed.     

EVOLUTION OF ZIRCONS IN SEDIMENTARY AND METAMORPHIC ROCKS: A REPLY

In a discussion Kalsbeek (1967) suggests that my idea of an authigenic origin of zircons seems to be the result of mis-identification of authigenic titaniferous minerals as zircon. Kalsbeek appears to have formed this opinion firstly because he sees all the crystals (Saxena , 1966a, plate IV) as zircons. I never mentioned this. Since 70% of the matrix in the sandstones consists of such aggregate, the very idea of having so much zircon in the rock would be fantastic and absurd.