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ABSTRACT

Kinetic barriers inhibit quartz nucleation and growth at lower temperatures (<50°C [<122°F]). Thus, under ordinary geothermal gradients, the formation of authigenic quartz in fine-grained systems is preceded inevitably by the early stages of compaction. Nucleation sites for quartz precipitation and the abundance and sizes of pores into which quartz cement can be emplaced are limited by the compactional state at the time of precipitation. The two main types of grain alteration that are proposed to yield authigenic quartz, dissolution of biogenic opal and illitization of smectite, occur in different temperature ranges and contrasting compactional regimes. This chapter summarizes petrographic observations on quartz components (grains and cement) by high-resolution cathodoluminescence (CL) and X-ray elemental mapping in 11 mudrock units ranging in age from Ordovician to Oligocene. The amounts of quartz cement observed provide constraints on the sources of silica for the formation of authigenic quartz and mass and volume balances of silica generation and precipitation in mudrock diagenesis.

The size (1–3 μm), spatial distribution, and abundance (typically 30–40% of rock volume) of authigenic microquartz that arise from the biogenic opal pathway are consistent with the compactional state of mud in the temperature range of the opal-A to opal-CT transition. Mudrocks that are clearly cemented by authigenic microquartz contain a volume of quartz in excess of amounts potentially generated by illitization (up to about 13% of rock volume). In the absence of abundant biogenic silica and consequent early cementation that inhibits compaction, the most common mudrock in the temperature range of illitization (>~80°C [>~176°F]) have few available nucleation surfaces for quartz precipitation and little available pore space (mostly nanometer scale) to accommodate pore-filling crystal growth. Sites for higher temperature quartz precipitation, synchronous with illitization, are mostly restricted to localized packing flaws at contacts between silt-size particles and constitute a trivial volume of the rock. Thus, tarls tend to feature diagenesis dominated by compaction that dramatically reduces pore space prior to the onset of significant reactions of the grain component such as albitization and illitization. The absence of discernible cementation in most deep basinal mudrocks raises the possibility that mechanical compaction persists as a mechanism of porosity decline to greater depths in mud than in sand.

INTRODUCTION

A genetic link between illitization of smectite and precipitation of quartz cement, in sandstones (e.g., Gluyas and Coleman, 1992; Lynch et al., 1997) and mudstones (e.g., Hinch, 1980; Peltonen et al., 2009; Thyberg et al., 2010), has been postulated for over a half-century (Towe, 1962). The higher ratio of Si to Al in the tetrahedral sites of smectite group minerals as compared with similar sites in illite inspired the notion that replacement of smectite by illite during burial diagenesis should yield excess dissolved Si that could subsequently be sequestered as authigenic quartz (Lynch et al., 1997). The recent availability of cathodoluminescence (CL) and other compositional imaging on scanning electron microscopes has provided a wealth of information on the distribution of authigenic quartz in mudrocks (Milliken, 1994a; Milliken et al., 2012a, 2016; Fishman et al., 2015; Buckman et al., 2017; Dowey and Taylor, 2017; Milliken and Olson, 2017). This chapter reviews and summarizes these observations on quartz types in mudrocks (mudstone, shale) that have reached thermal maturity associated with development of prominent quartz cement in sandstones. The paragenesis and volumetric amounts of quartz cement reported for these thermally mature mudrocks can be used to place constraints on the reactions that mobilize and precipitate silica.

BACKGROUND

Petrology of Authigenic Quartz

Quartz cement in sandstone can be readily detected and quantified using light microscopy (McBride, 1989), although CL imaging can refine such observation and measurements (Sippel, 1968; Houseknecht, 1991; Evans et al., 1994). In mudrock (mudstone, shale), however, the detection of authigenic quartz is far more challenging because of the intrinsically small size of the intergranular spaces available for cement emplacement (generally <1 μm; Milliken and Day-Stirrat, 2013). Studies that measure quartz content or quartz properties based on bulk measures, such as quantitative X-ray diffraction, elemental analysis by X-ray fluorescence, or oxygen isotopic analysis, may be used to infer the presence of authigenic quartz in mudrocks but cannot directly ascertain its abundance or type (e.g., cement, grain replacement, or fracture fill). Studies that document the presence of quartz cement based only upon spectroscopic characterization of quartz CL emission (Thyberg et al., 2009; Thyberg and Jarhren, 2011) incorporate uncertainties related to the overlapping CL character of authigenic and detrital quartz (Sprunt et al., 1978; Ramseyer et al., 1988; Hogg et al., 1992; Boggs et al., 2002; Bernet and Bassett, 2005). Most silt-size detrital quartz in mudrock displays low-level reddish luminescence that possibly relates to the derivation of many silt particles from low-rank pelitic metamorphic rocks (Sprunt et al., 1978; Blatt, 1987). In addition to the common red/brown CL colors of detrital metamorphic quartz, authigenic quartz displays diverse CL colors that overlap those of detrital grains (Ramseyer et al., 1988; Rezaee and Tingate, 1997), and thus, spectroscopy alone cannot be used to specify quartz type. CL imaging overcomes this uncertainty by providing a clear view of the spatial distribution of differently luminescing quartz types, allowing recognition of quartz components as detrital grains of either extrabasinal or intrabasinal origin, grain replacement, fracture fill, and intergranular cement (Milliken, 1994b; Milliken et al., 2012a).

A key facet of authigenic quartz distribution concerns the impact of kinetic limitations on quartz nucleation and growth (Walderhaug, 1996). Authigenic quartz formed at low temperature (<50°C [<122°F]) is generally associated with elevated silica concentrations that approach the fields of opal saturation, in many cases yielding petrographic forms of quartz such as chert and chalcedony (Kastner and Gieskes, 1983; Thiry et al., 1988). In addition to rare overgrowths on detrital quartz grains, low-temperature quartz, for example in silcretes, displays diverse petrographic forms such as equant microcrystalline intergrowths (chert), chalcedony of many types, and minutely zoned quartz overgrowths, which occur as both pore-filling (cements) and replacement (Thiry et al., 1988; Abdel-Wahab et al., 1998; Alexandre et al., 2004; Haddad et al., 2006).

In fluids well below the saturation state of opal and at higher temperatures (>50°C [>122°F]), quartz nucleation and growth display Arrhenius behavior (Walderhaug, 1994a, b, 1996), complicated by the necessity of clean surfaces on preexisting quartz as nucleation sites (Cecil and Heald, 1971; Heald and Larese, 1974; Paxton et al., 1990; Pittman et al., 1992; Jahren and Ramm, 2000). The sluggishness of quartz nucleation and growth, even at relatively elevated temperatures (<200°C [<392°F]), results in subsurface fluids that are generally supersaturated with respect to quartz (Land, 1997), further evidenced by the failure of silica geothermometry in this temperature range (Land and Macpherson, 1992a). An additional factor in quartz precipitation concerns crystallographic controls (Lander et al., 2008) that retard the growth rate once the slowest growing crystal faces dominate the crystal surface. In the case of very small nucleation surfaces (as in mudrocks), the slowest growth rates may dominate over most of the crystal growth history.

Volumetrics of Smectite Illitization

In diagenetic systems, a given chemical reaction generally can be formulated in a variety of ways, depending on factors such as solute concentrations, pH, Eh, and the combination of minerals assumed to participate as sources and sinks of reactants. An often-ignored aspect of reaction formulation concerns the petrographic implications as expressed by the molar volumes of solid reactants. Here, the specific petrographic (volumetric) aspects of chemical reactions are of interest for establishing constraints on depth and timing. The progress of pore space modifications in compaction of mud is at least partially known (e.g., Velde, 1996) and places limits on the volumes of diagenetic minerals that can be emplaced into those spaces at different times in the burial history.

The illitization of smectite is, volumetrically speaking, the most significant reaction in the sedimentary portion of the crust as it involves the most volumetrically significant detrital mineral (smectite) in the volumetrically dominant mudrocks (Lynch, 1997; Lynch et al., 1997). Numerous studies over the past 50 years have attributed authigenic quartz in sandstones (e.g., Lynch et al., 1997) and mudrocks (e.g., Hinch, 1980; Peltonen et al., 2009; Thyberg et al., 2010) to Si mobilized by illitization. Whether or not authigenic quartz related to illitization precipitates in close proximity to the reacting clay minerals has significant implications for the evolution of porosity, permeability, and mechanical rock properties in mudrocks as well as for the mass balance of material transfer between mudrocks and sandstones.

The volumetrics of smectite illitization vary tremendously in different formulations of the reaction. Table 1 reports an example of smectitic and illitic mixed-layer illite/smectite compositions determined by extraction and analysis of the pure mineral phases from Gulf of Mexico mudrocks by separation of the <0.1 μm (Lynch, 1997; Table 1). Use of end-members representing a fuller range of known compositions on the smectite to illite spectrum (e.g., Środoń and McCarty, 2008; Środoń et al., 2009) yields elemental balances (for both imports and exports) that are more extreme than the ones presented in Table 2. The compositional end-members used here were chosen because they are associated in a known basinal setting across a well-documented smectite to illite transition and provide a relatively conservative estimate of elemental change (Table 2, Figure 1) in mudrocks associated with quartz-cemented sandstones.

Figure 1.

Elemental balances for Si and Al in illite reaction models (Table 2). Vertical lighter blue line indicates Al balance. Horizontal darker blue line indicates Si balance. None of the modeled reactions can simultaneously balance Al and Si.

Figure 1.

Elemental balances for Si and Al in illite reaction models (Table 2). Vertical lighter blue line indicates Al balance. Horizontal darker blue line indicates Si balance. None of the modeled reactions can simultaneously balance Al and Si.

Table 1.

Molar compositions and properties of minerals used for modeling reported in Table 2.

MineralElement (Formula Moles)Molecular WeightDensity2Molar Volume2
 KNaMgFeAlSiOHg/molg/cm3cm3/mol
Smectite10.120.250.410.221.533.88122745.002.76269.93
Illite10.650.080.200.142.273.41122783.002.80279.64
K-feldspar1.00   1.003.008 278.262.55109.12
Quartz     1.00  60.072.6522.67
MineralElement (Formula Moles)Molecular WeightDensity2Molar Volume2
 KNaMgFeAlSiOHg/molg/cm3cm3/mol
Smectite10.120.250.410.221.533.88122745.002.76269.93
Illite10.650.080.200.142.273.41122783.002.80279.64
K-feldspar1.00   1.003.008 278.262.55109.12
Quartz     1.00  60.072.6522.67
1

Lynch, 1997.

2

Środoń et al., 2009.

Table 2.

Material balances in illitization.

BalanceIllite GeneratedK-feldspar ConsumedKNaMgFeAlSiOHQuartz/illiteK-Feldspar/illite% quartz in Whole-rock with 50% Illite
 molesmolesmolesmolesmolesmolesmolesmolesmolesmolesVolume RatioVolume RatioVolume %
Smectite K0.180.000.000.240.370.191.113.259.781.631.43 71.4
1 mole smectite: 1 mole illite1.000.00−0.530.170.210.08−0.740.47000.06 2.9
Molar with K-feldspar1.000.5300.170.210.08−0.212.064.2400.170.388.3
Smectite Al0.670.00−0.320.200.280.130.001.583.910.650.19 9.5
Al with K-feldspar0.670.320.000.200.280.130.182.135.380.650.260.1912.8
Smectite Si1.140.00−0.620.160.180.06−1.050.00−1.65−0.280.00 0.0
Si with K-feldspar1.140.620.000.160.180.06−0.431.863.31−0.280.130.396.6
BalanceIllite GeneratedK-feldspar ConsumedKNaMgFeAlSiOHQuartz/illiteK-Feldspar/illite% quartz in Whole-rock with 50% Illite
 molesmolesmolesmolesmolesmolesmolesmolesmolesmolesVolume RatioVolume RatioVolume %
Smectite K0.180.000.000.240.370.191.113.259.781.631.43 71.4
1 mole smectite: 1 mole illite1.000.00−0.530.170.210.08−0.740.47000.06 2.9
Molar with K-feldspar1.000.5300.170.210.08−0.212.064.2400.170.388.3
Smectite Al0.670.00−0.320.200.280.130.001.583.910.650.19 9.5
Al with K-feldspar0.670.320.000.200.280.130.182.135.380.650.260.1912.8
Smectite Si1.140.00−0.620.160.180.06−1.050.00−1.65−0.280.00 0.0
Si with K-feldspar1.140.620.000.160.180.06−0.431.863.31−0.280.130.396.6

Although smectite group minerals and illite have certain similarities of crystalline structure, their compositions are far from stoichiometric equivalency. Thus, the reaction of smectite to illite cannot be written as a closed-system reaction for all elements. The reaction mechanism in the process of illitization remains unclear but is generally regarded to proceed as a dissolution of detrital smectite accompanied by precipitation of authigenic crystals of mixed-layer illite/smectite (Ahn and Peacor, 1986) that contain ever greater proportions of illite layers as temperature increases (Hower et al., 1976; Lynch, 1997). The overall reaction between the starting smectite and the final illite-rich illite/smectite (referred to as “illite” below) can be balanced on any particular element present in both minerals. The reaction can also be written based on molar or volumetric balances. Table 2 does not present all possible reaction balances but rather focuses on four particular variants: (1) 1:1 molar balance between smectite and illite (similar to a volume balance because the molar volumes of smectite and illite are similar1); (2) balance on the major interlayer cation K; (3) balance on the relatively immobile Al; and (4) Si balance. Molar, Al, and Si balance are further examined with detrital K-feldspar as a balancing source for K. Balances for Al, Si, and the major interlayer cation are the main focus of this analysis, although the implications for Na, Mg, and Fe can also be examined in Table 2. Reaction balances relative to potential consumption or evolution of H+ (weathering vs. reverse weathering reactions; Milliken, 2004), Cl (charge balance; Hanor, 1997), and H2O dissociation (Seewald, 2003) are potentially important aspects of the illitization chemical system that are beyond the scope of this analysis.

A reaction balance based on K can be soundly rejected based on the indicated volumetrics (Table 2). The amount of K in the starting smectite composition can only generate 0.18 moles of illite, leading to an immense loss in the total clay volume that is not consistent with observed compaction in sedimentary basins. In the case of K-conservation, there is so little illite precipitated that the molar balances for other elements become strongly positive. In the case of Si, an excess is generated sufficient to precipitate an amount of authigenic quartz 1.4 times greater than the volume of the final illite volume, a clearly absurd result given mudrock compositions in which clay mineral volume generally exceeds quartz volume. This extreme imbalance highlights the reasoning employed by several authors with respect to the substantial K-import that is needed to accomplish illitization (Awwiller, 1993; Land et al., 1997; Lynch, 1997; Van de Kamp, 2008). It is unrealistic to consider elemental balance in illitization without including the participation of dissolving K-feldspar.

Balancing the reaction on Al not only is appealing in terms of minimizing the elemental transfer of a relatively immobile element but also leads to a reduction in the volume of clay, corresponding to around 0.67 moles of illite for every mole of smectite dissolved. This volume loss is the basis of previously leveled criticisms of this “cannibalization” formulation of the reaction (cf., Boles and Franks, 1979; Awwiller, 1993). Balancing the clay reaction on Si leads to an increase in clay volume and also increases the imbalance with respect to K. Adding the requisite amount of K to balance the Si-neutral reaction leads finally to a total reaction with excess Si. Thus, Si excess is a feature of any illitization formulation, although the excess Si does not necessarily originate only from the clay. A molar balance for the reaction yields an outcome that is intermediate between Al- and Si-balance reactions (Figure 1).

As mentioned above, K-feldspar participation in illitization is nontrivial. The amount of K-feldspar required ranges from 38 to 39% (molar- and Si-balanced reactions) to 19% of the illite volume (Al-balanced reaction). K-feldspar content in shallow Gulf of Mexico mudrocks averages around 3–5% (Awwiller, 1992; Land et al., 1997; Lynch, 1997), thus requiring import of K derived from dissolution of detrital K-feldspar in associated sandstones and perhaps from deeper crustal sources as well (Van de Kamp, 2008).

Silica excess generated by the K-feldspar-balanced reaction formulations, if precipitated as authigenic quartz entirely within the mudrocks, creates a quartz volume that ranges from 13 to 17% (molar and Si-balanced reactions) to around 26% (Al-balanced reaction) of the illite volume. In a mudrock containing 50% illitic clay by volume (typical of Gulf of Mexico mudrocks; Awwiller, 1992; Land et al., 1997; Lynch, 1997), this would correspond to an authigenic quartz content in the range of 6.5–13% of the total rock volume. Lesser volumes of authigenic quartz would result if the Si excess from illitization were partially distributed into other authigenic silicates or exported from the mudrock to sandstone. A component of detrital illite or illitic mixed-layer clay within the modeled 50% illite content would also be associated with lesser Si release. X-ray diffraction studies show that detrital clay mineral assemblages in early burial are often mixed, including pure smectite, disordered illite-smectite (McCarty et al., 2008, 2009; Lanson et al., 2009), and detrital illite (e.g., Grathoff et al., 1998; Aldega and Eberl, 2005).

SAMPLES AND METHODS

This chapter utilizes petrographic results from previous studies by the author and co-authors (Milliken, 1994a, 2013, 2014; Land and Milliken, 2000; Day-Stirrat et al., 2010; Milliken et al., 2012a, b, 2016; Milliken and Olson, 2017) as well as new data from unpublished work (Tables 3, 4). Methodologies for observation of quartz types, particularly energy-dispersive spectroscopy for X-ray elemental mapping (EDS mapping) and CL imaging, are described in Milliken and Olson (2017) and Milliken et al. (2017). All of the images were obtained from polished thin sections and combine signals from EDS and CL with secondary electron images to improve edge sharpness. Quantification of authigenic quartz (Table 4) follows the image tracing methods of Milliken and Olson (2017). Terms for compositional classification of mudrock, based on the primary detrital grain assemblage, follows the terminology of Milliken (2014): tarl (terrigenous argillaceous mudrock) dominated by extrabasinal detritus and containing little biogenic component; carl (calcareous argillaceous) and sarl (siliceous argillaceous) containing significant amounts of intrabasinal biogenic debris (generally >25 vol. %).

Table 3.

Formations studied.

UnitLocationAgeGrain AssemblagesPetrographic Studies
Abundant and Pervasive Authigenic Microquartz:(General Abundance)
Mowry FormationPowder River Basin, Wyoming, USACretaceousSiliceous mudrock (original sarl?)Milliken and Olson, 2017
Woodford FormationPermian Basin, Texas, USADevonianSiliceous mudrock (original sarl?)Longman et al., 2018 (this volume); and this study
Locally Abundant Authigenic Microquartz in Overall Mixed Grain Assemblages:
Eagle Ford FormationMaverick Basin, Texas, USACretaceousCarl>sarl>tarlPommer and Milliken, 2015; Milliken et al., 2016
Vaca Muerta FormationNeuquen Basin, ArgentinaJurassicTarl>carl>sarlThis study
Barnett ShaleFort Worth Basin, Texas, USAMississippianTarl=sarl>carlMilliken et al., 2012a, b, 2019
Bakken FormationWilliston Basin, North Dakota, USADevonianTarl>sarl>carlThis study
unnamed unitBaltic Basin, Poland and LithuaniaSilurianTarl>>carl>sarlMilliken et al., 2018; and this study
Longmaxi FormationSichuan Basin, ChinaOrdovicianTarl>sarl>carlThis study
Generally Lacking Authigenic Microquartz:
Frio FormationGulf of Mexico Basin, Texas, USAOligoceneTarlMilliken, 1994a
Wilcox FormationGulf of Mexico Basin, Texas, USAPaleoceneTarlDay-Stirrat et al., 2010
Yanchang FormationOrdos Basin, ChinaTriassicTarlMilliken et al., 2017; Loucks et al., 2017; Ko et al., 2017
UnitLocationAgeGrain AssemblagesPetrographic Studies
Abundant and Pervasive Authigenic Microquartz:(General Abundance)
Mowry FormationPowder River Basin, Wyoming, USACretaceousSiliceous mudrock (original sarl?)Milliken and Olson, 2017
Woodford FormationPermian Basin, Texas, USADevonianSiliceous mudrock (original sarl?)Longman et al., 2018 (this volume); and this study
Locally Abundant Authigenic Microquartz in Overall Mixed Grain Assemblages:
Eagle Ford FormationMaverick Basin, Texas, USACretaceousCarl>sarl>tarlPommer and Milliken, 2015; Milliken et al., 2016
Vaca Muerta FormationNeuquen Basin, ArgentinaJurassicTarl>carl>sarlThis study
Barnett ShaleFort Worth Basin, Texas, USAMississippianTarl=sarl>carlMilliken et al., 2012a, b, 2019
Bakken FormationWilliston Basin, North Dakota, USADevonianTarl>sarl>carlThis study
unnamed unitBaltic Basin, Poland and LithuaniaSilurianTarl>>carl>sarlMilliken et al., 2018; and this study
Longmaxi FormationSichuan Basin, ChinaOrdovicianTarl>sarl>carlThis study
Generally Lacking Authigenic Microquartz:
Frio FormationGulf of Mexico Basin, Texas, USAOligoceneTarlMilliken, 1994a
Wilcox FormationGulf of Mexico Basin, Texas, USAPaleoceneTarlDay-Stirrat et al., 2010
Yanchang FormationOrdos Basin, ChinaTriassicTarlMilliken et al., 2017; Loucks et al., 2017; Ko et al., 2017
Table 4.

Authigenic quartz volumes in the matrix of cemented clay-dominated mudrocks.

Siliceous MudrocksDepthImaged AreaMicrocrystalline Quartz CementPyriteSilt-sized GrainsMatrix (Clay-Sized Grains + Pores)Matrix+CmtCmt/Total Matrix
 mμm2vol. %vol. %vol. %vol. %vol. % 
Barnett Shale2678356435.40.523.240.976.30.46
Woodford Formation3508722446.81.622.329.376.10.61
Unnamed; Baltic Basin2671103435.40.79.754.389.70.40
Vaca Muerta Formation33641074525.20.040.334.559.70.42
Mowry Formation*2570–34812288441.01.415.239.680.60.51
   36.8 22.139.776.50.48
Siliceous MudrocksDepthImaged AreaMicrocrystalline Quartz CementPyriteSilt-sized GrainsMatrix (Clay-Sized Grains + Pores)Matrix+CmtCmt/Total Matrix
 mμm2vol. %vol. %vol. %vol. %vol. % 
Barnett Shale2678356435.40.523.240.976.30.46
Woodford Formation3508722446.81.622.329.376.10.61
Unnamed; Baltic Basin2671103435.40.79.754.389.70.40
Vaca Muerta Formation33641074525.20.040.334.559.70.42
Mowry Formation*2570–34812288441.01.415.239.680.60.51
   36.8 22.139.776.50.48
*

Average of five samples from Milliken and Olson, 2017.

Mudrocks described here share an important textural distinction from mudrocks in general. The silt content (2–62.5 μm) is typically in the range of 10–20 vol. %. The larger silt particles range in size up to around 30 μm, but the median size of the silt is generally smaller than “sortable silt” (~10 μm; McCave et al., 1995). Thus, silt-size particles in the mudrocks, dominantly composed of quartz and feldspar, are generally surrounded by clay-size particles composed dominantly of clay minerals and do not form a framework of touching silt-size quartz/feldspar grains. Even the larger silt particles in these mudstones tend to be isolated grains surrounded by clay-size particles and have not been sorted into layers of concentrated silt. This contrasts with local layers of sorted coarser silt that occur in these rock units, which, though technically “mudstone” by virtue of being dominated by particles <62 μm, have fabric arrangements, starting porosity, and grain surfaces more in common with sorted sandstones. The mudrocks with fabric dominated by clay-size particles and unsorted silt correspond to the volumetrically dominant mudrock types in the rock units considered for this review (Table 3), and this chapter addresses the broad question of the nature of cementation in the clay-rich portions (in the textural meaning of “clay-size”) of these fine, unsorted mudstones.

PETROGRAPHIC OBSERVATIONS

Authigenic quartz in mudrocks takes many forms including grain replacement of a variety of detrital components (mainly fossils), fillings within anomalously large pores, and fracture fills (Milliken et al., 2012a, b, 2016, 2017; Milliken, 2013; Milliken and Olson, 2017). All of these forms of authigenic silica are particularly abundant in mudrock units that, at the time of deposition, contained primary detrital biogenic silica (opal-A) in the form of radiolaria and sponge spicules, an association also noted by other authors (e.g., Cressman, 1962; Fishman et al., 2015; Zhao et al., 2017). In these same mudrocks dull-luminescing authigenic microquartz is also commonly observed as small (1–3 μm) equant crystals that occur singly and as clusters distributed more or less uniformly through the clay-size matrix (Figure 2). At the margins of quartz silt particles, the microquartz is intergrown with small (generally around 1 μm) rims of quartz overgrowth cement (Figure 2). Where present, the total volume of this microquartz generally approaches 40% of the volume of the matrix (Table 4), and, if pore-filling, places a constraint on the porosity at the time of silica emplacement (Milliken and Olson, 2017). In rare instances, particularly within anomalously large pores, the dull-luminescing microquartz has thin outer zones of brighter luminescing red or blue quartz (Figure 3), suggesting multiple stages in the history of quartz emplacement that corresponded to contrasting states in fluid chemistry or quartz growth rate.

Figure 2.

CL images of mudrocks with abundant authigenic microquartz. Yellow ovals indicate regions of microquartz (higher relief and better polish) distributed in clay mineral matrix (lower relief and poor polish). Yellow arrows indicate microquartz that is distributed as overgrowths on detrital quartz grains. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. py = pyrite framboids; ab = detrital albite; c = detrital calcite. All compositions were confirmed by EDS elemental mapping. (A) Barnett Shale. (B) Upper Bakken Formation. (C) Woodford Formation. (D) Silurian of Baltic Basin. (E) Vaca Muerta Formation. (F) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 2.

CL images of mudrocks with abundant authigenic microquartz. Yellow ovals indicate regions of microquartz (higher relief and better polish) distributed in clay mineral matrix (lower relief and poor polish). Yellow arrows indicate microquartz that is distributed as overgrowths on detrital quartz grains. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. py = pyrite framboids; ab = detrital albite; c = detrital calcite. All compositions were confirmed by EDS elemental mapping. (A) Barnett Shale. (B) Upper Bakken Formation. (C) Woodford Formation. (D) Silurian of Baltic Basin. (E) Vaca Muerta Formation. (F) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 3.

CL images of small crystals of brighter luminescing and zoned authigenic quartz lining cavities within dark-luminescing silicified skeletal fragments (yellow arrows). (A) Barnett Shale. (B) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 3.

CL images of small crystals of brighter luminescing and zoned authigenic quartz lining cavities within dark-luminescing silicified skeletal fragments (yellow arrows). (A) Barnett Shale. (B) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

In mudrocks that lack abundant primary biogenic silica, the volume of authigenic microquartz is essentially nil (Figure 4; Table 4). Careful inspection reveals minute amounts (much less than 1% of rock volume) of authigenic quartz associated with packing flaws at rare contacts between quartz silt particles (Figure 5). In associated layers containing a touching framework of coarser silt and very fine sand, intergranular quartz overgrowth cement can be observed similar to the observations reported by Dowey and Taylor (2017; their figures 5–7; p. 20–21).

Figure 4.

CL images of mudrocks lacking authigenic microquartz. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite; dolo = detrital dolomite. All compositions were confirmed by EDS elemental mapping. (A) Wilcox Formation. (B) Barnett Shale. (C) Barnett Shale. (D) Yanchang Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 4.

CL images of mudrocks lacking authigenic microquartz. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite; dolo = detrital dolomite. All compositions were confirmed by EDS elemental mapping. (A) Wilcox Formation. (B) Barnett Shale. (C) Barnett Shale. (D) Yanchang Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 5.

CL images of mudrocks with small amounts of quartz cement at grain contacts (yellow arrows). Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite. All compositions were confirmed by EDS elemental mapping. (A) Yanchang Formation. (B) Vaca Muerta Formation. (C) Yanchang Formation. (D) Wilcox Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 5.

CL images of mudrocks with small amounts of quartz cement at grain contacts (yellow arrows). Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite. All compositions were confirmed by EDS elemental mapping. (A) Yanchang Formation. (B) Vaca Muerta Formation. (C) Yanchang Formation. (D) Wilcox Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

The contrasting petrographic character between mudrocks with and without quartz cement can be equally recognized in X-ray elemental maps made by EDS (Figure 6).

Figure 6.

EDS elemental maps of mudrocks with abundant microquartz cement (A and B) contrasted with mudrocks lacking authigenic microquartz (C and D). Quartz is red, albite is aqua, K-feldspar is brighter yellow, calcite is blue, detrital clay is darker yellow, pyrite is bright gray, and organic matter is black. (A) Mowry Formation. (B) Woodford Formation. (C) Yanchang Formation. (D) Longmaxi Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 6.

EDS elemental maps of mudrocks with abundant microquartz cement (A and B) contrasted with mudrocks lacking authigenic microquartz (C and D). Quartz is red, albite is aqua, K-feldspar is brighter yellow, calcite is blue, detrital clay is darker yellow, pyrite is bright gray, and organic matter is black. (A) Mowry Formation. (B) Woodford Formation. (C) Yanchang Formation. (D) Longmaxi Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

DISCUSSION

Elemental Balances

Images such as shown in Figures 2, 4, 6 demonstrate a stark petrographic contrast between mudrocks that do and do not contain authigenic microquartz that is amenable to quantification. The siliceous mudrock units in Table 1 that contain abundant microquartz have mostly experienced thermal histories sufficient to induce illitization. However, a comparison of data in Tables 2, 4 reveals that, in the samples that contain authigenic quartz, the volume of microquartz (Table 4) substantially exceeds the amount that could be generated in any formulation of illitization (Table 2). It is possible that the very minor amounts of later precipitating and brighter luminescing quartz observed locally in these rocks (less than 1% of rock volume; Figure 5) may be related to a later episode of feldspar dissolution and illitization.

It seems clear that a local material balance within the thermally mature illitized tarls (Figures 4, 5) cannot be achieved within the detrital smectite-detrital K-feldspar-authigenic illite-authigenic quartz system of the local mudrock. The vanishingly small amounts of authigenic quartz observed in most deep mudrocks demand that either Si is not generated during illitization (unlikely based on plausible reaction balances), that it is sequestered within the mudrocks in minerals other than quartz, or, alternatively, exported from the mudrock. Other possible authigenic silicates of volumetric significance that are observed to increase with depth in mudrocks are chlorite and albite (Milliken, 1992; Awwiller, 1993). Together with the generally lower activation energies of authigenic clays (around 25 kJ/mole; Meunier, 2005) as compared with quartz (>50 kJ/mole; Bennett, 1991; Gratz and Bird, 1993; Rimstidt, 2015), the abundance of clay surfaces in fine-grained rocks enhance the likelihood that clay mineral precipitation will be preferred over quartz precipitation. A complete balancing of elements among all dissolving and precipitating phases within mudrocks and sandstones is beyond the scope of this chapter; however, the volumetric analysis of illitization together with the presented petrographic observations provide important constraints for full analysis of the scale of system closure.

Tarls are the volumetrically dominant mudrocks, forming the greater proportion of mudrocks in the thick sedimentary successions of continental margins as well as in many nonmarine basins (Milliken, 2014). Smectite is generally an abundant or even dominant detrital clay mineral in the mudrocks of such settings (e.g., Hower et al., 1976; Allison et al., 2003; Underwood, 2018). The lack of observable quartz cementation in all of the tarls examined has significant implications for constraining elemental mobility in the upper crust. Additional observations are warranted given that mudrocks of tarl composition may display widely differing burial and pore-pressure histories that lead to contrasting porosity evolution. However, none of the thermally mature tarl mudrocks available to the author have displayed more than trivial quartz cementation at rare grain contacts.

Taking the minimum illitization case (K-feldspar, Si balance) that generates an amount of quartz equal to 6.6% of the volume of mudrock, a transfer of that silica to adjacent sandstone (assuming sandstones are 30% of the basinal volume) would yield 15% authigenic quartz in the sandstone. This amount exceeds observed amounts of quartz cement in deep basinal sandstone and suggests that, again, a simple mineralogical system of illite/quartz diagenesis is inadequate as a model. This is especially true in view of the possibility that quartz cementation in sandstone can also be effectively balanced on internal feldspar dissolution alone (Land and Macpherson, 1992b) requiring no silica input from mudrocks. Authigenic minerals other than illite and quartz need to be incorporated in the overall balance before the scale of system closure for Si mobility can be determined. The long-standing consensus that attributes a genetic connection between quartz cementation (in both mudrocks and sandstones) and Si released from illitization deserves re-examination because the local elemental balance during illitization in most mudrocks does not appear to involve significant quartz precipitation.

Implications for Compaction

The timing of authigenic quartz emplacement can be partially constrained by pore volumes at different stages of compaction. In general, porosity in excess of 40 vol. % is only observed in muds buried to less than about 0.5 km (e.g., Fowler et al., 1985; Velde, 1996; Long et al., 2011). Thus, the timing of any massive authigenic quartz emplacement is interpreted as occurring early in the burial history through a silica mobilization pathway related to alteration of opaline biogenic debris (Isaacs, 1981, 1982; Kastner and Gieskes, 1983), as previously discussed in Milliken and Olson (2017). Microbial mediation is likely an important factor for overcoming kinetic barriers in this early silica mobilization and precipitation pathway (Birnbaum and Wireman, 1984; Westall et al., 1995; Perry, 2003; Ramseyer et al., 2013; Longman et al., 2018).

Lynch (1997) reports that the major progress of the illitization reaction in the Frio Formation of South Texas occurs in the range of 2–4 km (1.2–2.5 mi) burial under a geothermal gradient in the range of 25–30°C/km (77–86°F/0.6 mi). Studies reporting mudrock porosity across this depth range generally indicate a decline from around 20% to around 10% (Hinch, 1980; Fowler et al., 1985; Velde, 1996; Hunt et al., 1998; Day-Stirrat et al., 2008; Yang and Aplin, 2010), although a strong porosity trend correlated specifically with illitization has not been documented. The sizes of pores in this depth range may be quite small (Aplin et al., 2006), presenting barriers to nucleation and growth of crystals (Emmanuel et al., 2010).

Although some amount of submicron authigenic quartz distributed through the clay-size matrix in the tarls (Figures 4, 5) cannot be definitively ruled out based on petrographic observation, an amount of this material corresponding to several percent of the clay-size volume seems unlikely to have completely escaped observation. Furthermore, quartz content in submicron size separates is reported to be low in <1 μm separates (Awwiller, 1993) and undetectable in <0.1 μm separates (Lynch, 1997). Although a decline from 20 to 10 vol. % represents a pore volume sufficient to host the amounts of quartz cementation suggested by Table 2, there is no evidence that such amounts of quartz cement are present in typical mudrocks buried to this depth range (Figure 4). Thus, any porosity decline observed across the depth range of illitization is unlikely to be caused by pore-filling cementation.

Although the depth of compactional stabilization in rigid grain sand is well-established (Paxton et al., 2002), there is great uncertainty concerning the depth distribution of different mechanisms of porosity decline in muds. Porosity decline in muds is seldom partitioned between the effects of true compaction (bulk volume loss arising from rearrangement of sedimentary particles) and cementation (pore-filling mineral precipitation) (Giles et al., 1998). The general notion of “chemical compaction” that presumably comes to dominate pore loss in the deep basin (Bjorlykke and Hoeg, 1997) subsumes various chemical and chemical/mechanical mechanisms of porosity loss, encompassing such disparate mechanisms as pore-filling cementation (Ramdhan and Goulty, 2011), pressure dissolution (Vernik, 1997) and crystal realignment during recrystallization (Goulty et al., 2012). An alternative model of deep basinal porosity decline in mudrocks has been proposed, based on the persistent correlation of deep mudrock porosity with pressure, suggesting that mechanical compaction alone continues to dominate pore loss in deep basins (Goulty et al., 2016). The absence of detectable cementation in illitized tarls reported here supports a model of continuing dominance of mechanical compaction in the depth range of illitization. The suggestion of Goulty et al. (2016) that deep basinal mudrock porosity loss continues to be dominated by grain-to-grain interaction between clay particles is consistent with the observation that no nonclay pore-filling, grain-binding precipitates appear in the zone of illitization. Compactional stabilization of mud may occur much more deeply than in sand.

SUMMARY

Mudrocks that contain abundant biogenic silica at deposition are prone to relatively early and low-temperature cementation by microquartz. Where present, the volume of this early authigenic quartz typically exceeds the amount of silica that can be attributed to illitization of smectite. In mudrocks lacking a significant biogenic grain component, thermal maturation in the zone of illitization is not accompanied by the appearance of detectable authigenic quartz. Thus, the Si released by illitization must be taken up by authigenic phases other than quartz within the mudrock or exported to associated sandstones. In the absence of significant cementation, pore loss through mechanical compaction may proceed in mudrocks across the burial zone of illitization.

ACKNOWLEDGMENTS

This chapter is dedicated to colleague and friend Leo Lynch (deceased), who inspired me to think about the issues addressed in this chapter. This research summarizes results from several decades of support from NSF’s EAR and IODP programs, DOE basic energy sciences (BES), the Mudrock Systems Research Laboratory (MSRL), several individual petroleum companies, and the Jackson School of Geosciences. Mark Longman (QEP Resources) provided the samples of Woodford Shale. Doug McCarty provided helpful discussion of clay mineral bulk properties and Sally Sutton and Ruarri Day-Stirrat are thanked for reading an early version of the manuscript. David Budd and an anonymous reviewer kindly provided constructive suggestions that improved the chapter. Publication of this chapter is authorized by the Director, Bureau of Economic Geology.

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1
The molar volume of expandable smectite varies tremendously for different hydration states. The smectite molar volume used here, calculated from reported densities and molecular weights (Srodoń and McCarty, 2008; Środoń et al., 2009), is based upon a dehydrated smectite because the focus is upon an understanding of the potential quartz volume relative to the final nonexpandable clay volume. A full assessment of bulk volume change in the sediment as a whole across the burial history would necessarily include an assessment of smectite dehydration, but changes in water volume do not enter into an assessment of Si mobility.

Figures & Tables

Figure 1.

Elemental balances for Si and Al in illite reaction models (Table 2). Vertical lighter blue line indicates Al balance. Horizontal darker blue line indicates Si balance. None of the modeled reactions can simultaneously balance Al and Si.

Figure 1.

Elemental balances for Si and Al in illite reaction models (Table 2). Vertical lighter blue line indicates Al balance. Horizontal darker blue line indicates Si balance. None of the modeled reactions can simultaneously balance Al and Si.

Figure 2.

CL images of mudrocks with abundant authigenic microquartz. Yellow ovals indicate regions of microquartz (higher relief and better polish) distributed in clay mineral matrix (lower relief and poor polish). Yellow arrows indicate microquartz that is distributed as overgrowths on detrital quartz grains. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. py = pyrite framboids; ab = detrital albite; c = detrital calcite. All compositions were confirmed by EDS elemental mapping. (A) Barnett Shale. (B) Upper Bakken Formation. (C) Woodford Formation. (D) Silurian of Baltic Basin. (E) Vaca Muerta Formation. (F) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 2.

CL images of mudrocks with abundant authigenic microquartz. Yellow ovals indicate regions of microquartz (higher relief and better polish) distributed in clay mineral matrix (lower relief and poor polish). Yellow arrows indicate microquartz that is distributed as overgrowths on detrital quartz grains. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. py = pyrite framboids; ab = detrital albite; c = detrital calcite. All compositions were confirmed by EDS elemental mapping. (A) Barnett Shale. (B) Upper Bakken Formation. (C) Woodford Formation. (D) Silurian of Baltic Basin. (E) Vaca Muerta Formation. (F) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 3.

CL images of small crystals of brighter luminescing and zoned authigenic quartz lining cavities within dark-luminescing silicified skeletal fragments (yellow arrows). (A) Barnett Shale. (B) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 3.

CL images of small crystals of brighter luminescing and zoned authigenic quartz lining cavities within dark-luminescing silicified skeletal fragments (yellow arrows). (A) Barnett Shale. (B) Mowry Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 4.

CL images of mudrocks lacking authigenic microquartz. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite; dolo = detrital dolomite. All compositions were confirmed by EDS elemental mapping. (A) Wilcox Formation. (B) Barnett Shale. (C) Barnett Shale. (D) Yanchang Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 4.

CL images of mudrocks lacking authigenic microquartz. Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite; dolo = detrital dolomite. All compositions were confirmed by EDS elemental mapping. (A) Wilcox Formation. (B) Barnett Shale. (C) Barnett Shale. (D) Yanchang Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 5.

CL images of mudrocks with small amounts of quartz cement at grain contacts (yellow arrows). Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite. All compositions were confirmed by EDS elemental mapping. (A) Yanchang Formation. (B) Vaca Muerta Formation. (C) Yanchang Formation. (D) Wilcox Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 5.

CL images of mudrocks with small amounts of quartz cement at grain contacts (yellow arrows). Detrital quartz is angular, has variable cathodoluminescence color and intensity, and ranges in size from coarse clay to silt. ab = detrital albite. All compositions were confirmed by EDS elemental mapping. (A) Yanchang Formation. (B) Vaca Muerta Formation. (C) Yanchang Formation. (D) Wilcox Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 6.

EDS elemental maps of mudrocks with abundant microquartz cement (A and B) contrasted with mudrocks lacking authigenic microquartz (C and D). Quartz is red, albite is aqua, K-feldspar is brighter yellow, calcite is blue, detrital clay is darker yellow, pyrite is bright gray, and organic matter is black. (A) Mowry Formation. (B) Woodford Formation. (C) Yanchang Formation. (D) Longmaxi Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Figure 6.

EDS elemental maps of mudrocks with abundant microquartz cement (A and B) contrasted with mudrocks lacking authigenic microquartz (C and D). Quartz is red, albite is aqua, K-feldspar is brighter yellow, calcite is blue, detrital clay is darker yellow, pyrite is bright gray, and organic matter is black. (A) Mowry Formation. (B) Woodford Formation. (C) Yanchang Formation. (D) Longmaxi Formation. Table 3 reports further mineralogical details for each stratigraphic unit.

Table 1.

Molar compositions and properties of minerals used for modeling reported in Table 2.

MineralElement (Formula Moles)Molecular WeightDensity2Molar Volume2
 KNaMgFeAlSiOHg/molg/cm3cm3/mol
Smectite10.120.250.410.221.533.88122745.002.76269.93
Illite10.650.080.200.142.273.41122783.002.80279.64
K-feldspar1.00   1.003.008 278.262.55109.12
Quartz     1.00  60.072.6522.67
MineralElement (Formula Moles)Molecular WeightDensity2Molar Volume2
 KNaMgFeAlSiOHg/molg/cm3cm3/mol
Smectite10.120.250.410.221.533.88122745.002.76269.93
Illite10.650.080.200.142.273.41122783.002.80279.64
K-feldspar1.00   1.003.008 278.262.55109.12
Quartz     1.00  60.072.6522.67
1

Lynch, 1997.

2

Środoń et al., 2009.

Table 2.

Material balances in illitization.

BalanceIllite GeneratedK-feldspar ConsumedKNaMgFeAlSiOHQuartz/illiteK-Feldspar/illite% quartz in Whole-rock with 50% Illite
 molesmolesmolesmolesmolesmolesmolesmolesmolesmolesVolume RatioVolume RatioVolume %
Smectite K0.180.000.000.240.370.191.113.259.781.631.43 71.4
1 mole smectite: 1 mole illite1.000.00−0.530.170.210.08−0.740.47000.06 2.9
Molar with K-feldspar1.000.5300.170.210.08−0.212.064.2400.170.388.3
Smectite Al0.670.00−0.320.200.280.130.001.583.910.650.19 9.5
Al with K-feldspar0.670.320.000.200.280.130.182.135.380.650.260.1912.8
Smectite Si1.140.00−0.620.160.180.06−1.050.00−1.65−0.280.00 0.0
Si with K-feldspar1.140.620.000.160.180.06−0.431.863.31−0.280.130.396.6
BalanceIllite GeneratedK-feldspar ConsumedKNaMgFeAlSiOHQuartz/illiteK-Feldspar/illite% quartz in Whole-rock with 50% Illite
 molesmolesmolesmolesmolesmolesmolesmolesmolesmolesVolume RatioVolume RatioVolume %
Smectite K0.180.000.000.240.370.191.113.259.781.631.43 71.4
1 mole smectite: 1 mole illite1.000.00−0.530.170.210.08−0.740.47000.06 2.9
Molar with K-feldspar1.000.5300.170.210.08−0.212.064.2400.170.388.3
Smectite Al0.670.00−0.320.200.280.130.001.583.910.650.19 9.5
Al with K-feldspar0.670.320.000.200.280.130.182.135.380.650.260.1912.8
Smectite Si1.140.00−0.620.160.180.06−1.050.00−1.65−0.280.00 0.0
Si with K-feldspar1.140.620.000.160.180.06−0.431.863.31−0.280.130.396.6
Table 3.

Formations studied.

UnitLocationAgeGrain AssemblagesPetrographic Studies
Abundant and Pervasive Authigenic Microquartz:(General Abundance)
Mowry FormationPowder River Basin, Wyoming, USACretaceousSiliceous mudrock (original sarl?)Milliken and Olson, 2017
Woodford FormationPermian Basin, Texas, USADevonianSiliceous mudrock (original sarl?)Longman et al., 2018 (this volume); and this study
Locally Abundant Authigenic Microquartz in Overall Mixed Grain Assemblages:
Eagle Ford FormationMaverick Basin, Texas, USACretaceousCarl>sarl>tarlPommer and Milliken, 2015; Milliken et al., 2016
Vaca Muerta FormationNeuquen Basin, ArgentinaJurassicTarl>carl>sarlThis study
Barnett ShaleFort Worth Basin, Texas, USAMississippianTarl=sarl>carlMilliken et al., 2012a, b, 2019
Bakken FormationWilliston Basin, North Dakota, USADevonianTarl>sarl>carlThis study
unnamed unitBaltic Basin, Poland and LithuaniaSilurianTarl>>carl>sarlMilliken et al., 2018; and this study
Longmaxi FormationSichuan Basin, ChinaOrdovicianTarl>sarl>carlThis study
Generally Lacking Authigenic Microquartz:
Frio FormationGulf of Mexico Basin, Texas, USAOligoceneTarlMilliken, 1994a
Wilcox FormationGulf of Mexico Basin, Texas, USAPaleoceneTarlDay-Stirrat et al., 2010
Yanchang FormationOrdos Basin, ChinaTriassicTarlMilliken et al., 2017; Loucks et al., 2017; Ko et al., 2017
UnitLocationAgeGrain AssemblagesPetrographic Studies
Abundant and Pervasive Authigenic Microquartz:(General Abundance)
Mowry FormationPowder River Basin, Wyoming, USACretaceousSiliceous mudrock (original sarl?)Milliken and Olson, 2017
Woodford FormationPermian Basin, Texas, USADevonianSiliceous mudrock (original sarl?)Longman et al., 2018 (this volume); and this study
Locally Abundant Authigenic Microquartz in Overall Mixed Grain Assemblages:
Eagle Ford FormationMaverick Basin, Texas, USACretaceousCarl>sarl>tarlPommer and Milliken, 2015; Milliken et al., 2016
Vaca Muerta FormationNeuquen Basin, ArgentinaJurassicTarl>carl>sarlThis study
Barnett ShaleFort Worth Basin, Texas, USAMississippianTarl=sarl>carlMilliken et al., 2012a, b, 2019
Bakken FormationWilliston Basin, North Dakota, USADevonianTarl>sarl>carlThis study
unnamed unitBaltic Basin, Poland and LithuaniaSilurianTarl>>carl>sarlMilliken et al., 2018; and this study
Longmaxi FormationSichuan Basin, ChinaOrdovicianTarl>sarl>carlThis study
Generally Lacking Authigenic Microquartz:
Frio FormationGulf of Mexico Basin, Texas, USAOligoceneTarlMilliken, 1994a
Wilcox FormationGulf of Mexico Basin, Texas, USAPaleoceneTarlDay-Stirrat et al., 2010
Yanchang FormationOrdos Basin, ChinaTriassicTarlMilliken et al., 2017; Loucks et al., 2017; Ko et al., 2017
Table 4.

Authigenic quartz volumes in the matrix of cemented clay-dominated mudrocks.

Siliceous MudrocksDepthImaged AreaMicrocrystalline Quartz CementPyriteSilt-sized GrainsMatrix (Clay-Sized Grains + Pores)Matrix+CmtCmt/Total Matrix
 mμm2vol. %vol. %vol. %vol. %vol. % 
Barnett Shale2678356435.40.523.240.976.30.46
Woodford Formation3508722446.81.622.329.376.10.61
Unnamed; Baltic Basin2671103435.40.79.754.389.70.40
Vaca Muerta Formation33641074525.20.040.334.559.70.42
Mowry Formation*2570–34812288441.01.415.239.680.60.51
   36.8 22.139.776.50.48
Siliceous MudrocksDepthImaged AreaMicrocrystalline Quartz CementPyriteSilt-sized GrainsMatrix (Clay-Sized Grains + Pores)Matrix+CmtCmt/Total Matrix
 mμm2vol. %vol. %vol. %vol. %vol. % 
Barnett Shale2678356435.40.523.240.976.30.46
Woodford Formation3508722446.81.622.329.376.10.61
Unnamed; Baltic Basin2671103435.40.79.754.389.70.40
Vaca Muerta Formation33641074525.20.040.334.559.70.42
Mowry Formation*2570–34812288441.01.415.239.680.60.51
   36.8 22.139.776.50.48
*

Average of five samples from Milliken and Olson, 2017.

Contents

GeoRef

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