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Sedimentary Geology 440 (2022) 106254

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Sedimentary Geology

journal homepage: www.elsevier.com/locate/sedgeo

Unravelling the fabrics preserved inside early diagenetic concretions:


Insights for the distribution, accumulation and preservation of
organic-rich mud in the interior of epicontinental basins
Germán Otharán a,⁎, Carlos Zavala a,b, Juergen Schieber c, Daniela Olivera a,d, Marcelo Martínez a,d, Pablo Díaz d,
Zalmai Yawar c, Luis Agüero d
a
Geology Department, Universidad Nacional del Sur, Av. Alem 1253, Cuerpo B´ - 2do Piso, B8000ICN Bahía Blanca, Buenos Aires Province, Argentina
b
GCS Argentina, Molina Campos 150, B8002CYD Bahía Blanca, Buenos Aires Province, Argentina
c
Department of Earth and Atmospheric Sciences, Indiana University, Bloomington, IN 47405, USA
d
Instituto Geológico del Sur (INGEOSUR), Universidad Nacional del Sur - Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Av. Alem 1253, cuerpo B´-1° Piso,
B8000ICN Bahía Blanca, Buenos Aires, Argentina

a r t i c l e i n f o a b s t r a c t

Article history: Fine-grained sedimentary rocks generally undergo severe mechanical compaction during burial, which compli-
Received 6 August 2022 cates the recognition of primary mudstone fabrics and associated sedimentary features. Early diagenetic concre-
Received in revised form 3 September 2022 tions, however, provide a rare glimpse of primary fabrics because cement filling the pore space prevents the
Accepted 5 September 2022
collapse of original grain arrangements. Hand specimens of concretions collected from the basal condensed sec-
Available online 9 September 2022
tion of the Late Jurassic-Early Cretaceous Vaca Muerta Formation (Neuquén Basin, Argentina), allow for analysis
Editor: Dr. Brian Jones of sedimentary processes responsible for the dispersal, accumulation and burial of organic carbon-rich sediment
in an epicontinental sea. Representative samples from central basin depositional localities were examined by op-
tical, scanning electron microscopy and energy dispersive X-ray spectroscopy. Petrographic observations were
Keywords: complemented with palynological and organic geochemical analyses. Close examination of uncompacted fabrics
Condensed sections reveals a significantly more complex and dynamic depositional scenario than previously assumed (suspension
Carbonate concretions settling). Although many of the component grains in the studied samples were originally delivered to the
Bottom currents sediment–water interface by suspension settling processes (i.e., marine snow, hypopycnal plumes, pumice
Composite particles
rafts), there is substantial evidence of episodic sedimentation controlled by punctuated events of seafloor distur-
Organic matter preservation
bance and erosion. The common presence of muddy intraclasts indicate that the seafloor was frequently
reworked by bottom currents that caused the widespread distribution of organic carbon-rich sediment across
distal basin depositional environments. Bottom current circulation supplied oxygen to the sediment–water inter-
face and created suitable conditions for benthic life, contravening the assumption of bottom water anoxia as a
prerequisite for organic carbon preservation. The excellent preservation state of freshwater algae (Pediastrum
complex) suggests that organic matter contained inside mud composite particles can travel long distances before
being deposited in distal depositional settings. Encapsulation protects organic components from mechanical/bio-
genic degradation and provides an anoxic microenvironment for preventing the oxidation of the organic matter
contained inside of mud composite grains. The study shows that organic carbon encapsulation may be an impor-
tant mechanism for organic carbon preservation in relatively energetic and non-anoxic settings, calling for a crit-
ical reappraisal of the processes responsible for the sequestration of organic carbon from the biosphere and its
long-term storage in organic-rich mudstone successions.
© 2022 Elsevier B.V. All rights reserved.

1. Introduction

⁎ Corresponding author. Fine-grained sedimentary rocks (grain size <62.5 μm), including
E-mail addresses: german.otharan@uns.edu.ar (G. Otharán), mudstone and shale, constitute at least two thirds of the sedimentary
czavala@gcsargentina.com (C. Zavala), jschiebe@indiana.edu (J. Schieber),
daniela.olivera@uns.edu.ar (D. Olivera), marcelo.martinez@uns.edu.ar (M. Martínez),
rock record (e.g., Schieber, 1998a; Potter et al., 2005). However, when
pabesdiaz@ingeosur-conicet.gob.ar (P. Díaz), zyawar@indiana.edu (Z. Yawar), compared to sandstone and carbonate deposits, they remain a poorly
luisaguero@ingeosur-conicet.gob.ar (L. Agüero). understood group of sedimentary rocks (e.g., Schieber and Zimmerle,

https://doi.org/10.1016/j.sedgeo.2022.106254
0037-0738/© 2022 Elsevier B.V. All rights reserved.
G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

1998; Macquaker and Gawthorpe, 1993; Aplin and Macquaker, 2011). In dependent on specific microbial-mediated redox reactions that supply
hand specimen, mudstone appears to be featureless and homogeneous the mineralizing solutes for precipitation (Irwin et al., 1977; Hudson,
relative to other rock types and, except for the presence of laminae, it 1978; Scotchman, 1989, 1991; Macquaker and Gawthorpe, 1993). In ad-
rarely exhibits readily visible grain size variations or textural attributes. dition, the precipitation of early diagenetic cements requires diffusive
Studies based on the hand-specimen appearance of mudstone, com- transport of oxidants and labile organic matter to the reaction sites,
bined with geochemical proxies (e.g., Dean et al., 1986; Schlanger et al., and enough time so that a sufficient volume of cements can accumulate
1987; Dean and Arthur, 1989; Sageman et al., 2003; Algeo and Maynard, on pore spaces (Raiswell, 1988; Aplin and Macquaker, 1993, 2011;
2004; Dean, 2007; Wilson and Schieber, 2017a), have long nurtured the Raiswell and Fisher, 2000; Macquaker et al., 2014). Because of this,
belief that organic‑carbon-rich rocks were typically deposited in organic carbon-rich mud deposited during periods of very low net sed-
low energy environments that were characterized by long term (105– iment accumulation rates is particularly prone to enrichment in early
106 years) persistence of anoxic bottom waters and sediment delivery diagenetic cements (Raiswell, 1971; Schlanger and Douglas, 1974;
to the seafloor via continuous settling of discrete particles from Dix and Mullins, 1988; Raiswell, 1988; Macquaker and Gawthorpe,
suspension. This long held paradigm was challenged by studies of mod- 1993; Aplin and Macquaker, 2011; Lazar et al., 2015a). This is particu-
ern shelf and coastal marine environments that documented mud larly the case for condensed sections that mark periods of maximum
deposition in the presence of wave and tidal activity (e.g., Nittrouer relative sea-level rise and maximum transgression (Macquaker, 1994;
and Sternberg, 1981; Rine and Ginsburg, 1985). Also, petrographic Macquaker and Gawthorpe, 1993; Macquaker and Taylor, 1996).
studies (O'Brien and Slatt, 1990; Bennett et al., 1991; Macquaker and Early diagenetic carbonate concretions, formed close to the
Gawthorpe, 1993; Macquaker, 1994; Macquaker and Taylor, 1996; sediment–water interface, can provide a glimpse of primary, or at
Schieber, 1994, 1998b, 1999; Wilson and Schieber, 2016; Wilson et al., least less distorted, depositional fabrics (Curtis et al., 2000; Lash and
2020) show mudstone to be much more heterogeneous and feature- Blood, 2004). The cement passively infills the pore space (Lippmann,
rich than previously assumed. Stacked successions of very thin 1955; Raiswell, 1971), preventing the destruction of original grain ar-
(<10 μm) beds (sensu Campbell, 1967) are common and point to rangements as burial proceeds (Weeks, 1953; Clifton, 1957; Westphal
successions of discrete depositional events, rather than to a continu- et al., 2000). Investigation of these uncompacted fabrics within concre-
ous rain of dispersed particles. Textural analyses (Macquaker and tions allows the evaluation of the mechanisms responsible for mud
Gawthorpe, 1993; Macquaker, 1994; Wetzel and Uchman, 1998; transport and deposition in otherwise highly compacted successions
Lobza and Schieber, 1999; Schieber, 2003; Wilson et al., 2021) as where the primary fabrics may be much more cryptic. Concretions
well as recent laboratory experiments (Schieber and Wilson, 2021) also provide a window into the early modification of the organic matter
and observations of the benthic boundary layer in modern settings in hydrocarbon source rocks (Curtis et al., 2000).
(Dashtgard et al., 2015) also show that primary depositional fabrics In Argentina, the excellent outcrops of the Upper Jurassic – Lower
in mudstone are commonly degraded by bioturbation, indicating Cretaceous Vaca Muerta Formation along the Neuquén Basin thrust-
that the impact of bottom water anoxia has been overestimated, and fold belt are a natural laboratory to study the sedimentological pro-
and that organic carbon-rich mudstone can accumulate under mod- cesses that control organic carbon accumulation and preservation in
erately oxygenated conditions that support benthic life. In addition, mudstone-dominated successions. At central basin depositional locali-
direct insights from experiments in laboratory flumes (Schieber ties, the basal interval of the Vaca Muerta Formation is composed of
et al., 2007; Schieber and Southard, 2009; Schieber, 2011) and recent organic carbon-rich mudstone and commonly exhibits multiple hori-
oceanographic observations (Macquaker et al., 2010a; Denommee zons with large carbonate concretions. Given the shift in depositional
et al., 2016) point to the critical role of advective sediment transport paradigms that emphasize deposition of organic-rich mud under ener-
processes in mud dispersal and accumulation (Schieber, 2016a; getic conditions in environments that support benthic life, it is now nec-
Wilson and Schieber, 2014, 2017b; Lazar et al., 2015a; Smith et al., essary to re-evaluate the processes responsible for the preservation of
2019). large volumes of organic carbon in distal depositional environments.
Collectively, these observations show that depositional environ- Such setting are characterized by sedimentation rates that are com-
ments of mud can be substantially more energetic and dynamic than monly so low as to cause oxidation of the organic components that
previously presumed, and suggest that a reappraisal of depositional lead to concretionary cements.
models is in order for a good interpretation of many organic carbon-
rich mudstone deposits. Nonetheless, parsing mudstone depositional 1.2. Purpose of study
processes is challenging because mudstone: (1) is typically dark-
colored and fine-grained; (2) can appear homogeneous and feature- One aim of this paper is to advance the understanding of primary
less at initial inspection (e.g., Schieber, 2003); (3) is severely affected fabrics preserved inside early diagenetic carbonate concretions. The
by weathering, which severely degrades most textural attributes concretions: (1) provide important information about the mechanisms
(Macquaker et al., 2010b); and (4) is severely affected by mechanical responsible for the delivery, dispersal, accumulation and preservation
compaction that generates planar fabrics and obscure the recogni- of organic carbon-rich mud in basinal settings; (2) account for the
tion of primary sedimentary structures (Schieber et al., 2010; Plint difference in provenance between sediment deposited at central
et al., 2012; Schieber and Bennett, 2013). Compaction also affects basin depositional areas; (3) facilitate the recognition of different
primary grain arrangements, especially in mudstone enriched in types of originally water-rich aggregate grains; and (4) give insights
water-rich aggregates (e.g., floccules, intraclasts, fecal pellets) that about the early diagenetic processes that occur in originally organic
are generally flattened and deformed as burial proceeds (Schieber carbon-rich mud prior to compaction. An understanding of the sedi-
et al., 2010; Schieber, 2016b; Li and Schieber, 2018). mentary processes that control organic matter distribution, accumu-
lation, and diagenesis in the interior of epicontinental basins allows
1.1. Carbonate concretions for prediction of the areal extent and stratigraphic distribution of or-
ganic carbon-rich mudstone that has favorable petrophysical prop-
In the early stages of mud deposition, and prior to any significant erties for development of unconventional hydrocarbon reservoirs.
compaction, a series of rapid, biologically driven, diagenetic reactions
can result in highly cemented intervals that form either continuous 2. Geologic setting
beds or discontinuous, localized concretionary horizons (Raiswell,
1971; Curtis, 1987; Macquaker, 1994; Selles-Martinez, 1996; Curtis The Neuquén Basin is an important oil-bearing basin located in the
et al., 2000; Westphal et al., 2000). Early cements are generally Andean foothills in west-central Argentina (32°–40° S). It is a back-arc

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

basin that developed during the Mesozoic on the western margin sandstone deposits (Leanza et al., 2003; Otharán et al., 2020; Naipauer
of Gondwana (Mosquera et al., 2011). The basin has a northwest– et al., 2020).
southeast elongated shape, covers >160,000 km2 (Vergani et al., The Vaca Muerta Formation is part of a shallowing-upward marine
1995), and has a sedimentary infill of at least 7000 m of siliciclastic, sedimentary succession known as the Vaca Muerta–Quintuco system
carbonate, and evaporite deposits that accumulated in a wide range of (Veiga and Spalletti, 2007; see also Kietzmann et al., 2014, 2016).
continental and marine depositional environments (Fig. 1). Although The Vaca Muerta–Quintuco (VM-Q) system is a mixed carbonate–
it has been studied in depth due to its importance as an oil-bearing siliciclastic depositional system that consists of multiple prograding
basin, previous studies have historically focused on conventional clastic subaqueous clinoforms that accumulated between the early Tithonian
reservoirs (Schiuma et al., 2002). Growing hydrocarbon production and the early Valanginian (González et al., 2018). The lowermost inter-
from unconventional reservoirs, however, has inspired recent studies val of the VM-Q system is a transgressive deposit with a basal con-
of the sedimentary details of finer grained intervals (e.g., González densed section that accumulated during a period of high productivity
et al., 2018). of organic carbon and a high sea-level that led to reduced siliciclastic
input (U1, Early–Middle Tithonian). These deposits accumulated as
2.1. Depositional framework of the Vaca Muerta Formation the bottomsets of gentle-dipping clinoforms in a low gradient (0.2°–
0.3°; Minisini et al., 2020; Reijenstein et al., 2020) mixed ramp system
The Vaca Muerta Formation (Weaver, 1931) constitutes a thick (up to (Fig. 2), and represent the main source-rock interval of the Vaca Muerta
1400 m; Otharán et al., 2020) and widely distributed (>120,000 km2; Formation (6–8 wt% TOC, max. 15 wt% TOC; González et al., 2018).
Leanza et al., 1977) stratigraphic unit that accumulated during the Historically, organic carbon-rich mudstone have been interpreted as
Late Jurassic to Early Cretaceous in the Neuquén Basin (Groeber, strata deposited below storm wave base in a low-energy basin to
1946; Leanza, 1973). This unit is mainly composed of organic outer ramp environment with bottom water that was prone to persis-
carbon-rich mudstone (avg. 3.2 wt% TOC, max. ~15 % TOC; Brisson tent anoxia during prolonged periods of time (Mitchum and Uliana,
et al., 2020) alternating with thin volcaniclastic layers (Minisini 1985; Legarreta and Uliana, 1991; Spalletti et al., 1999, 2000, 2014;
et al., 2020), limestone (Kietzmann et al., 2014, 2016) and minor Zeller et al., 2015). In this model, sediment is initially delivered to the

Fig. 1. Geologic map and generalized stratigraphic column of the Neuquén Basin (modified after Zavala et al., 2006).

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 2. Vaca Muerta-Quintuco depositional system (early Tithonian-early Valanginian). Paleogeographic maps based on Legarreta and Uliana (1991); shelf-breaks following Dominguez
and Catuneanu (2017); seismic cross-section from González et al. (2018). The location of the studied localities is also indicated (1. Mulichinco creek; 2. Neuquén river).

sediment–water interface by continuous rain of discrete particles from 3. Materials and methods
an overlying water column with elevated primary production of organic
matter (Kietzmann et al., 2014, 2016). In this case, local rates of sedi- Concretions were collected from outcrops of the Vaca Muerta
ment accumulation and the balance of inputs to the inner basin are Formation in Neuquén province, west-central Argentina (Fig. 2). Hand
such that the materials derived from primary production are neither specimens of concretions were selected on the basis of macroscopic
diluted significantly by other components nor oxidized before being primary sedimentary features on weathered surfaces (Fig. 3). More
buried, promoting an optimal preservation of the organic matter than 50 samples were taken back to the laboratory, slabbed perpendic-
(Veiga and Orchuela, 1989). ular to bedding with a rock saw (Sorrento CLI 350), and polished with
During the late Tithonian–early Valanginian (U2-U6), a gradual in- grinding wheels of successively finer grit sizes. High-resolution images
crease in the supply of siliciclastic and carbonate sediment from the of the polished slabs were acquired using a Samsung SCX-4729FW flat-
southern and eastern margin (Mitchum and Uliana, 1985; Legarreta bed scanner and contrast was enhanced with Adobe Photoshop CC for
and Uliana, 1991) resulted in the NW progradation of increasingly examination of small-scale (cm- to mm-scale) sedimentary and
steeper clinoforms (Fig. 2). Consequently, the VM-Q system gradually biogenic features. The most representative samples were selected for
evolved into a distally steepened mixed ramp, characterized by a well- further petrographic, palynological, and organic geochemistry studies.
defined shelf break that divided the inner ramp (topset) from outer
ramp and distal basin environments (bottomset) (Mitchum and 3.1. Studied interval
Uliana, 1985; González et al., 2018). During this stage, the progressive
reduction in accommodation space in shallow-marine environments The studied carbonate (CaCO3) concretions are stratigraphically
favored the basinward shift of the marginal calcareous mud belt via confined to laterally persistent horizons located within the lowermost
muddy underflows, and resulted in clinoform growth and progradation ~100 m of the Vaca Muerta Formation. Samples were collected from
(Fig. 2). Some of the potential processes for cross-shelf transport of the organic-rich condensed section located at the base of this unit in
sediment in the VM-Q system include storm-driven underflows central basin depositional localities. Concretionary horizons show a
(Kietzmann et al., 2014, 2016), wave–current enhanced sediment- vertical stratigraphic recurrence varying from <1.5 m to ~4 m. They al-
gravity flows (Otharán, 2020; Minisini et al., 2020), bottom currents ternate with strongly compacted organic carbon-rich (avg. 4 wt% TOC)
(Otharán, 2020; Minisini et al., 2020; Paz et al., 2022), as well as turbid- (Otharán et al., 2020) calcareous mudstone with bedding-parallel fi-
ity currents and muddy hyperpycnal flows (Paz et al., 2019; Otharán brous veins (<1–5 cm) (see also Ravier et al., 2020) and thin interbeds
et al., 2020; Capelli et al., 2021). (<1–7 cm) of volcaniclastic layers (Fig. 3A). Concretions are generally

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 3. Early diagenetic carbonate (CaCO3) concretions. A) Overview of large, bedding-parallel oblate concretions located at the lowermost interval of the Vaca Muerta Formation (see also
Fig. 1). Concretions are enclosed by a succession of differentially compacted, thin-bedded organic-rich mudstones, bedding parallel fibrous calcite veins and ash beds. B) Laminated
mudstone fabrics; a 14 cm-length pen for scale. Note the presence of sharp and irregular, erosional surfaces (e). C) Irregular erosional surface. D) Scours and sharp boundaries related
to erosional surfaces. E) Internal lamina truncations and subtle erosional surfaces; a 20 mm-diameter coin for scale. F) Low-angle, current-ripple cross-lamination developed on top of
an erosional surface.

oblate ellipsoids up to 2 m in diameter and 0.7 m thick that are oriented the analysis of the overall composition and distinctive characteristics
parallel to bedding. The horizontal distance between adjacent concre- of the microfacies preserved in early diagenetic concretionary horizons,
tions fluctuates from 20 cm to >1 m. Locally, individual concretions and on the identification of various composite particles. The term
merge laterally into sheet-like (stratiform) carbonate bodies. “composite particle” is hereafter used to refer to aggregate grains
composed of a mixture of multiple clay- to silt-sized mineral grains
3.2. Petrographic analysis (sensu Li and Schieber, 2018). Detailed petrographic examination of
thin sections in both plane-polarized light and cross-polarized light
A total of 18 thin sections (2.5 × 4 cm, 25–30 μm thick) and 20 argon was conducted using a Zeiss Photo 2 petrographic light microscope.
ion-milled samples (up to 12 mm in diameter) were prepared, all cut Ion-milled samples were studied using a FEI Quanta 400 scanning
perpendicular to bedding. The petrographic examination focused on electron microscope (SEM) in both backscatter electron and

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

secondary electron modes. The SEM was operated at 15 kV, at a The palynological slides are stored at the repository of the Instituto
working distance of ~10 mm. Energy dispersive X-ray spectroscopy Geológico del Sur-Universidad Nacional del Sur, Bahía Blanca,
(EDS) was used to determine the mineral components of individual Argentina. They are labeled by catalog numbers preceded by the abbre-
grains. Because no coating was applied to samples, the SEM was op- viations UNSP (Universidad Nacional del Sur, Palynology) and VM (Vaca
erated in low vacuum mode with water vapor as a quench gas. This Muerta Formation). Specimen locations are referenced with England
mode of operation has the added benefit of differential charge Finder coordinates.
buildup on the specimen surface, which enables charge contrast imag-
ing (CCI; Griffin, 2000) and allows for the imaging of very subtle but im- 3.4. Organic geochemistry
portant compositional differences between particles and cements. High
magnification (<5 μm) CCI in secondary electron mode under the SEM Twenty-two samples were powdered with an agate mortar and
was critical for the identification of composite particles as discrete enti- pestle, and approximately 60 mg of sediment was weighed and
ties that were not (or barely) captured in backscattered electron images subsequently pyrolyzed with a Rock-Eval VI apparatus following the
because there is little compositional contrast between such particles procedure of Behar et al. (2001). The measurements were carried out
(they consist mostly of calcite) and the carbonate (calcite) cement at Y-TEC Laboratories (La Plata, Argentina), and the performance of
that surrounds them (cf. Li and Schieber, 2018; Schieber et al., 2019; the instrument was checked every ten samples and validated with
Li et al., 2021). Mudstone lithofacies were described using the nomen- standard values of IFP 160 000 (S/N1 5-081840).
clature scheme broadly proposed by Macquaker and Adams (2003)
and Lazar et al. (2015b). 4. Results

3.3. Palynofacies analysis Concretions show sharp, irregular micro-erosional surfaces (Fig. 3B,
C), micro-scours (Fig. 3D) and convolute laminae (Fig. 3A, E) at bedding
Fifteen palynological samples were prepared and examined in detail. bounding surfaces, as well as subtle lamina truncations (Fig. 3E)
The physical and chemical extraction of the palynological matter and gently-dipping cross lamination (Fig. 3F). Textural analyses of
(PM) was performed following standard non-oxidative techniques polished slabs and thin sections show that samples are organized into
(Volkheimer and Melendi, 1976; Tyson, 1995). Detailed palynological stacked successions of very thin beds (ranging in thickness from <1 to
examinations were conducted using a transmitted light microscope 30 mm). These mudstone deposits show four main lithofacies types
(Olympus BX40). Additionally, the preservation state of the PM was (Fig. 4): (1) carbonate-rich fine sandstone (CfS); (2) carbonate- and
analyzed with a reflected fluorescence light microscope (RFL; Olympus silt-bearing sandy mudstone (CSsM); (3) silt-dominated coarse mud-
BH2). The description of the organic particles was carried out stone (ScM); and (4) carbonate-rich medium mudstone (CmM).
following the terminology proposed by Batten (1983, 1996), Tyson The intergranular space between primary components is filled with
(1995), and Oboh-Ikuenobe and de Villiers (2003). For the evaluation cloudy, finely crystalline carbonate cement. Under secondary electron
of the total PM, at least 500 particles per sample were counted using a mode in the SEM, a bright, homogeneous microspar cement composed
×40 lens. The counts were performed considering two major categories of a dense mosaic of anhedral crystals (<20 μm) is recognized. The
(Table 1): (1) structured organic matter (i.e., palynomorphs, translu- EDS energy spectra suggests that the microspar cement is mainly com-
cent, and opaque phytoclasts); and (2) structureless organic matter posed of non-ferroan calcite. The studied samples are characterized by a
(i.e., amorphous organic matter: AOM). The palynofacies (i.e., the differ- low organic carbon content (0.10–1.37 wt% TOC), with an average value
ent assemblage types of PM) were defined according to those counts. of 0.44 wt% TOC (Table 2). Most of the samples display <0.50 wt% TOC,

Table 1
Classification of the palynological organic matter recognized in the samples analyzed in this study.

Major Categories Source


categories

Structured Palynomorphs Sporomorphs Spores Reproductive structures Pteridophyte and Briophyte


Pollen grains Gymnosperms
Organic-walled microplankton Fresh-water algae Cholorophyte algae
Acritarchs Organic-walled marine microplankton
Prasinophytes
Dinocysts
Zoomorphs Palynoforaminifera Benthic foraminifera
Bacterial remains Filaments, sheaths and coccoids Cyanobacteria
Phytoclasts Translucent Tracheids with pits Higher plant debris
Tracheids without pits
Other woody remains
Membranes
Cuticles
Tissues
Brown-black fragments
Yellow-brown fragments
Degraded fragments
Opaque Blade-shape
Equidimensional
Charcoal
Structureless Amorphous organic matter (AOM) Fibrous Mainly derived from degradation of macrophyte tissues
Granular Phytoplankton or bacterially derived (“AOM” sensu
Tyson, 1995)
Spongy Mainly derived from degradation of continental algae
Membraneous (Batten, 1983)
Gelified Microbial reworking of terrestrial fragments (sensu
Pacton et al., 2011)
Resins Natural products of higher plants

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 4. Overview of the main mudstone lithofacies recognized in polished samples of concretions. A) Carbonate-rich fine sandstones (CfS facies) sharply overlain by cross-laminated car-
bonate- and silt-bearing sandy mudstones (CSsM facies). The CSsM facies is downlapping onto a scoured surface (e) and is sharply overlain by structureless, carbonate-rich medium mud-
stones (CmM facies). Note the similarity between CmM and CfS (carbonate-rich fine sandstones) facies at macroscopic scale. Soft-sediment deformation structures are evident subjacent to
the erosional surface (white triangles). B) Examples of the CSsM facies showing continuous, planar parallel lamination truncated by a scoured surface followed by gentle-dipping cross-
laminated mudstones. Towards the top of the image, the CSsM facies is overlain by silt-dominated coarse mudstones (ScM facies). C) Stacked succession of thin-bedded mudstones. In-
dividual beds exhibit sharp erosional bases and burrow mottled tops (white arrows). The ScM facies is enriched in pyrite (Py) and commonly exhibit soft-sediment deformation structures
(white triangles). D) Stacked succession of thin bedded mudstones comprising a range of mudstone lithofacies. Note the presence of very thin (< 0.1 mm), discontinuous, non-parallel silt
laminae within the CfS facies (yellow triangles). E) Lamina truncations within the CSsM facies. Soft-sediment deformation structures are evident underneath the erosional surface (white
triangles). F) ScM facies overlain by CfS facies. Note the presence of composite grains (cg) and internal lamina truncations (yellow triangles). The primary lamination of the CfS facies is
partially overprinted by diminutive burrow mottles (white arrows). G) Subtle lamina truncations (yellow triangles) and erosional features (e) within the CfS facies. H) Plane polarized light
image illustrating in detail the erosional boundary shown in C (between the ScM and the CmM facies). Note the presence of some borrow mottles within the ScM facies (white arrows).
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

five samples exhibit TOC values ranging between 0.50 and 1.00 wt%, and 4.1. Carbonate-rich fine sandstone (CfS)
only two samples exceed 1.00 wt% TOC (Fig. 5). Palynological evidence
shows that amorphous organic matter (AOM) represents >52 % of the This facies consists of superimposed calcareous mud laminae
total organic content (Fig. 6). that are largely composed of dark-colored, sand-sized (100–350 μm)

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Table 2 within the CfS facies, and subordinate numbers of silt-sized feldspar
Organic geochemistry statistics from Rock Eval 6 Pyrolisis Analysis. clasts typically appear as dispersed, isolated grains (Fig. 7B).
Facies TOC S2 Tmax HI OI

(wt%) (mg HC/g rock) (°C) (mg HC/g TOC) (mg CO2/g TOC) 4.1.2. Palynofacies analysis
CSsM Avg 0.50 0.24 379 47 54 The palynofacies of the CfS facies shows high frequencies of AOM,
Max 0.70 0.61 415 110 103 varying from 80.4 up to 95.6 %. Some samples exhibit a predomi-
Min 0.29 0.04 339 14 27 nance of granular type AOM, although others present high values of
CfS Avg 0.69 0.11 377 20 30
granular to spongy types (Fig. 6). The second most important group
Max 1.37 0.16 412 41 42
Min 0.29 0.07 342 9 10 of palynomorphs is the opaque phytoclasts, mainly the blade-shape
ScM Avg 0.18 0.12 434 76 93 forms (2–11.6 %). Palynomorphs, mostly of continental origin, are
Max 0.25 0.16 608 120 140 present in all samples but in low concentrations, reaching up to 3 %
Min 0.10 0.07 364 29 43
of the total organic content. They are principally represented
CmM Avg 0.29 0.09 404 34 39
Max 0.34 0.10 407 43 48
by cheirolepidiacean (Fig. 10A, B) and bisaccate pollen grains and
Min 0.21 0.09 399 26 34 continental algae (Botryoccocus spp.). Marine components (i.e.,
tasmanacean algae, Fig. 10G, H) are present only in the UNSPVM5252
sample, along with filaments of cyanobacteria. In general, the sam-
ples are non-fluorescent under RFL, except for isolated jellified
composite particles (Fig. 7), including two different types: (1) muddy
AOM masses and filamentous forms. Framboidal and/or euhedral py-
intraclasts (Fig. 8) and (2) fecal pellets (Fig. 9). Composite particles
rite is common in all samples.
have point contacts and exhibit a similar packing to the microfabrics
recently described in the Cretaceous Carlile Formation (Laycock et al.,
2017), as well as those recognized in modern deposits from the South- 4.1.3. Organic geochemistry
west Louisiana subaqueous delta (Denommee et al., 2016). Out of a total of seven analyzed samples, four samples exhibit TOC
CfS beds typically exhibit sharp, irregular, scoured bases and con- values >0.50 wt%, but only two exceed 1.00 wt% TOC (Fig. 5A), which
formable tops, and range in thickness from <5 mm up to ~30 mm. are the highest TOC values registered in this study (1.02 and 1.37 wt%
Due to its overall calcitic composition, the recognition of primary lami- COT). In addition, the CfS samples show the lowest HI and OI, varying
nation within the CfS facies can be challenging (Fig. 4D). In places, from 9 to 41 mg HC/g TOC and from 10 to 42 mg CO2/g TOC, respectively
however, the CfS facies shows intercalated non-parallel, very thin (Table 2). All the samples show S2 peaks <0.20 mg HC/g rock
(<0.1 mm) laminae of volcaniclastic silt. Such thin silt layers are very (0.07–0.16 mg HC/g rock), and thus Tmax values (342–412 °C) were
helpful in recognizing subtle lamina truncations within the CfS facies not considered.
(Fig. 4F, G). Locally, they are partially disrupted by cryptic bioturbation
and diminutive horizontal burrows related to the burrowing activity
of benthic meiofauna (Fig. 4F).
4.2. Carbonate- and silt-bearing sandy mudstone (CSsM)
4.1.1. Types of grains and cements
The mudstone consist of very thin beds (<10 to ~30 mm) with
Composite particles are the main constituents of the CfS facies
sharp, scoured bases overlain by finely laminated sandy to coarse mud-
(Fig. 7). Muddy intraclasts are subangular to subrounded dark brown-
stone (Fig. 4A, B). Mudstone beds show continuous, planar- to curved,
ish, clay-rich aggregates with a grain size ranging between 200 and
nonparallel lamination with gently dipping cross-lamination (Fig. 4A,
350 μm (Fig. 8A, B). The interior of mud intraclasts is filled with detrital
B), as well as continuous- to discontinuous-planar, parallel lamination
clay (Fig. 8C, D) and fine-silt-sized feldspar and minor quartz grains.
(Fig. 4C, D). Cross-laminated fabrics commonly downlap onto sharp,
Small amounts of coccolith debris has been also identified in the in-
scoured bedding surfaces. Also, soft-sediment deformation structures
terior of muddy intraclasts. Intragranular cements filling the original
are relatively common at bed boundaries (Fig. 4A, E).
pore space of muddy intraclasts include small, micritic calcite crys-
Petrographic examination of the CSsM facies shows thin, sharp-
tals (<3 μm, Fig. 8C), authigenic clay, and subordinate microquartz
based lamina-sets that consist of intercalated silt-rich laminae and
(<2 μm, Fig. 8C, D). In EDS, Ca is the highest peak (calcite cement).
calcareous (micritic) muddy laminae (Fig. 11A, B). Micro-scale load
Subordinate peaks are Si, Al, K and Na, which are associated with de-
structures are common at the boundary between muddy laminae
trital clay and silt-sized grains.
and overlying silt layers (Fig. 11).
Fecal pellets are subrounded to rounded, pale brown, carbonate-rich
aggregates (Fig. 9A). Such particles exhibit an elliptical to elongate
shape, and generally are smaller than clay-rich muddy intraclasts 4.2.1. Types of grains and cements
(70–230 μm; Fig. 9B). Under high magnification in the SEM, fecal pellets Silt-rich laminae are 0.1 to 1.2 mm thick and pinch-out laterally
are predominantly composed of phytoplankton debris, more specifi- over a distance of a few centimeters (Fig. 11C). They are mainly com-
cally coccoliths (Fig. 9C, D). Coccolith remains are easily missed because posed of fine silt to very fine sand-sized, volcanic-sourced idiomor-
they are of the same composition as the surrounding cement, but in sec- phic microlites (<100 μm, following Murphy et al., 2000) and
ondary SEM mode they are readily visible (Fig. 9C, D) because of charge microphenocrysts (100–300 μm) of plagioclase, K-feldspar, and
contrast effects (CCI). In cases, the interiors of fecal pellets were affected quartz grains (Fig. 11D, E). They also include a minor amount of vol-
by an intense diagenetic overprint (recrystallization of carbonate re- canic rock fragments. Silt-rich laminae are typically more cemented
mains of coccolithophores), making the differentiation of fecal pellets by calcite than calcareous muddy laminae (Fig. 11D).
from other composite particles challenging. In comparison with clay- Calcareous mud laminae are dark-colored and 0.2 to 2 mm thick.
rich, muddy intraclasts, fecal pellets show a higher peak of Ca in the Mud laminae typically show a microfabric supported by sand-sized
EDS, possibly because of their higher primary carbonate content. (70–250 μm) composite particles that in cases are hard to differentiate
There are minor peaks of Si and Al, which could be in response to diage- from the enclosing calcareous mud matrix (Fig. 11C, D). Composite par-
netic quartz and admixed clay. Carbonate remains of coccolithophores ticles include muddy intraclasts and fecal pellets with similar petro-
in the interior of fecal pellets are generally strongly recrystallized. In ad- graphic attributes as those ones described in the CfS facies. Calcareous
dition, biogenic grains, including calcified radiolarians (both nasselaria muddy laminae also contain 50 to ~200 μm diameter biogenic particles
and spumellaria) and benthic foraminifera are relatively common (i.e., calcified radiolarians, forams, ostracods).

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 5. Programmed pyrolysis data discriminated by lithofacies types. A) Kerogen quality diagram (S2 versus total organic carbon). B) Pseudo–van Krevelen diagram (Hydrogen Index
versus Oxygen Index). C) Kerogen type and maturity diagram (HI versus Tmax).

4.2.2. Palynofacies analysis colour (i.e., UNSPVM5256/57). Pyrite is a common component of all
The CSsM's palynofacies is characterized by the highest values of palynological samples from the CSsM facies, and is very abundant in
AOM, which ranges from 76 % up to 97 %. Granular AOM is dominant the UNSPVM5254/56/57 samples.
(Fig. 6). The second most abundant type is the phytoclasts, especially
the opaque blade-shaped forms (0.7–13.7 %). Palynomorphs are the 4.2.3. Organic geochemistry
least abundant in all studied samples (up to 1.3 %), and are mainly rep- The samples belonging to the CSsM facies (n = 6) have an organic
resented by continental freshwater- to brackish-algae (Botryoccocus carbon content between 0.29 and 0.70 wt% TOC, where half of the
spp., Fig. 10E, F). Sheaths of cyanobacteria are present in UNSPVM5251, samples exceed the average value of 0.50 wt%. The HI ranges from 14
and marine palynomorphs are present sample UNSPVM5253 (i.e., to 110 mg HC/g TOC (HI avg. = 47 mg HC/g TOC). The OI fluctuates
dinocysts and palynoforaminifera, Fig. 10I, J). In general, the samples between 27 and 103 mg CO2/g TOC (OI avg. = 54 mg CO2/g TOC).
are non-fluorescent under RFL, except for isolated particles. Only two The S2 peaks vary between 0.04 and 0.61 mg HC/g rock (S2 avg. =
samples show moderate fluorescence of the AOM to the greenish yellow 0.24 mg HC/g rock). Tmax values are relatively low (339–415 °C). It is

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 6. Composite chart showing the frequency distribution of the different categories of PM recognized in the studied palynological samples of the Vaca Muerta Formation (based on
counts of at least 500 particles per sample). The colour bars refer to the four main lithofacies types recognized in this study: CSsM facies (light brown), CfS facies (dark brown), ScM facies
(light violet) and CmM facies (dark grey); black-filled circles indicate the presence of PM. (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)

worth mentioning that in samples with S2 peaks of <0.20 mg, HC/g rock parallel wavy lamination style (Fig. 4C, D). The primary fabric of the ScM
Tmax values were not calculated, since they are often inaccurate facies is commonly disrupted by horizontal burrows related to the activ-
(Peters, 1986). Only two samples among the CSsM facies present reli- ity of deposit-feeding organisms (Fig. 12A).
able Tmax values (341 °C and 339 °C).
4.3.1. Types of grains and cements
4.3. Silt-dominated coarse mudstone (ScM) Silt and sand grains are mostly quartz and feldspar from a volcanic
source (Fig. 12B), and additional grains include volcanic rock fragments
This facies is mainly composed of coarse silt- to fine sand-sized par- (Fig. 12C) and occasionally abundant, cuspate- and platy-shaped
ticles organized into sharp- to erosive-based, diffusely laminated beds devitrified (argillized) shards (Fig. 12D). Two different types of volcanic
ranging from ~1 to 25 mm in thickness (Fig. 4C, F, H). Soft-sediment de- rock fragments (VRF, sensu Li and Schieber, 2018) were identified, in-
formation structures are relatively common and impart a discontinuous, cluding: (1) altered (argillized, smectite-dominated) volcanic ash

Fig. 7. Secondary electron images of the CfS facies. A) Overview of the overall fabric of the CfS facies, mainly composed of sand-sized composite grains. B) Sand-sized aggregate grains,
bioclastic particles (e.g., calcitized radiolaria, foraminifera) and dispersed silt-sized feldspar clasts (F). C, D) Different types of composite grains within the CfS facies, including fecal pellets
(P) and muddy intraclasts (ic). The intergranular porosity between mud aggregate grains is infilled with finely crystalline calcite cement (ca).

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 8. Plane polarized light and secondary electron images showing petrographic characteristics of muddy intraclasts. A) Cross-polarized light image illustrating medium-sand-sized
(300 × 150 μm), subrounded muddy intraclast (ic). Note the high contrast of this muddy intraclast regarding to the surrounding microspar carbonate matrix. B) Secondary electron image
showing a clay-rich muddy intraclast (ic) surrounded by microcrystalline calcite cement (ca). Silt-sized feldspar grains (F) are also recognized. C) Secondary light image illustrating the
interior of the muddy intraclast show in B. This composite particle is mainly composed of detrital clays. The intersticial space between clays is filled with euhedral, micron-sized calcite
crystals (ca). Diagenetic quartz is also present (Q). Note the disruption caused by the precipitation of calcite crystals in the interstitial space, producing an important displacement of the
original arrangements between clay minerals as they grow. D) Secondary light image showing detrital clays (cl), calcite cement (ca) and diagenetic quartz (Q).

fragments (similar to type 1 VRF of Li and Schieber, 2018); and the highest HI (29–120 mg HC/g TOC) and OI (43–140 mg CO2/g TOC,
(2) lathwork lithic fragments (Fig. 12C), commonly showing an inter- Fig. 5B), whereas S2 peaks vary from 0.07 to 0.16 mg HC/g rock, fairly
growth and pseudomorphic volcanic texture, mainly composed of ad- below the cut-off value for evaluating the Tmax, which are relatively
mixtures of plagioclase, K-feldspar and some quartz microlites low (364–413 °C), except for one sample presenting a Tmax value of
surrounded by altered volcanic glass (type 2 VRF, Li and Schieber, 608 °C (Fig. 5C).
2018). The ScM facies contains subordinate amounts of bioclastic grains,
such as tests of calcified radiolarians, benthic and planktonic foraminif- 4.4. Carbonate-rich medium mudstone (CmM)
era, as well as small, hollow, commonly micritic-walled calcispheres.
This facies typically has abundant pyrite content, manifested as large, This facies consists of 20 to 30 mm thick beds with conformable
euhedral pyrite crystals concentrated along bedding and lamina sur- bases and tops. The mudstone has a structureless, homogenized
faces (Fig. 4C, F). (cryptobioturbated) fabric (Fig. 4A, C, E) enriched in biogenic grains
(Figs. 4H, 8A, B), including planktonic and benthic microfossils, as well
4.3.2. Palynofacies analysis as remains of thin-shelled bivalves and disarticulated valves of ostracods.
The palynofacies type of the ScM facies is characterized by In thin sections, diminutive horizontal burrows are clearly visible.
the highest percentages of both phytoclasts and palynomorphs in all Such burrows are circular-to oval shaped, and typically filled with
studied samples. The phytoclasts are mainly opaque particles (13.5– clay, minor amounts of dispersed fine silt debris, and small tests of ben-
31.2 %), and blade-shaped forms are predominant (Fig. 10). In the thic foraminifera and calcified radiolaria. The bioturbation intensity is
UNSPVM5260 and UNSPVM5266 samples, the bacterial and algal generally higher close to the upper boundary of CmM layers. Here,
palynomorphs (sheaths, filaments and coccoids of cyanobacteria and there are small burrows (Fig. 4C) and biodeformational structures
Botryoccocus colonies, respectively) are dominant. The UNSPVM5261 (Fig. 4A, E) related to the burrowing activity of benthic organisms capa-
sample shows the highest palynomorph diversity within all studied ble of “swimming” through soupy muddy substrates (mantle and swirl
samples. This palynofacies includes cheirolepidiacean and bisaccate sensu Lobza and Schieber, 1999; see also Schieber, 2003).
pollen grains, prasinophyte algae, dinocysts (cf. Aptea notialis), and
palynoforaminifera. The AOM is manly represented by granular and 4.4.1. Types of grains and cements
granular- to spongy-types. In general, the organic matter is non- The planktonic fauna is comprised of abundant calcified radiolarians
fluorescent except for isolated particles. Pyrite is common in all sam- (Fig. 13A) and some globigerinid foraminifers, whereas benthic organ-
ples, and some have very high concentrations (i.e., UNSPVM5258/66). isms include small (<0.6 mm sensu Flügel, 2010), single-chambered fo-
raminiferal tests as well as larger, agglutinated orbitolinid foraminifers
4.3.3. Organic geochemistry (Fig. 13B); minor ostracods have been also recognized. Clay floccules
The samples belonging to the ScM facies (n = 6) record the lowest are also relatively common and consist of 30 to 50 μm diameter,
TOC values (0.10–0.25 wt%; avg. = 0.18 wt%). These samples display subrounded to rounded, clay-rich, black aggregates (Fig. 14A). They

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 9. Cross polarized light and secondary electron images illustrating fecal pellets. A) Cross-polarized light image showing carbonate-rich fecal pellets (P). B) Secondary light image of a
rounded fecal pellet. The fecal pellet is surrounded by a fine-grained matrix cemented by microcrystalline calcite cement (ca). Minor fine-silt-sized feldspar (F) grains are recognized
within the matrix. C) Secondary light image showing the interior of a carbonate-rich fecal pellet mainly composed of phytoplankton-derived material, most commonly coccolithophore
remains (co). D) Secondary light image showing the interior of a strongly carbonate-cemented fecal pellet. Note the blurry aspect of coccolith debris (co) caused by the recrystallization of
primary components and pervasive microcrystalline calcite (ca) cementation during diagenesis. Other diagenetic products are quartz (Q) and clays (cl).

are typically are disseminated within the CmM facies along with 5. Discussion
fecal pellets and other biogenic particles (Fig. 14B). Under high mag-
nification in the SEM, the interiors of presumed clay floccules typi- In distal marine settings, condensed sections composed of organic
cally show detrital clay arranged in an open mesh-like fabric with carbon-rich mudstone would traditionally be assumed to represent
intervening calcite cement (Fig. 14C, D). Detrital mica also is locally long, more or less uninterrupted, periods of quiescence and sediment
a common constituent of clay floccules. The original pore space be- starvation dominated by background sedimentation in stagnant bottom
tween clay flakes is predominantly filled with microcrystalline cal- waters. However, close examination of uncompacted fabrics preserved
cite cement (Fig. 14D), and in places with subordinated amounts of inside early diagenetic concretions from the Vaca Muerta Formation re-
diagenetic quartz. veals a significantly more complex and dynamic depositional scenario.
Lesser amounts of dispersed, fine-silt-sized grains (mostly quartz Importantly, concretions provide a record of the primary fabric and
and K-feldspar), detrital mica (Fig. 13D), amorphous organic matter constituent particles of some of the fine-grained facies that build up
(Fig. 13C) and plant debris (phytoclasts) are in cases common in the condensed sections. Component grains in these concretion-hosted
CmM facies. mudstone deposits show that sediment was delivered to the basin
from multiple sources, including detrital and volcaniclastic inputs, in ad-
dition to sediment produced within the basin (see also Milliken et al.,
4.4.2. Palynofacies analysis 2019). The details of the lithofacies described here demonstrates that,
The palynofacies type of the CmM facies (UNSPVM5255 sample) re- even at distal depositional settings, episodes of seafloor disturbance
cords ~76 %, mainly granular, AOM. The phytoclasts group roughly con- and erosion are very common in epicontinental basins, at least during
stitutes 20 % of the total organic spectrum, largely represented by periods of sediment starvation characterized by a dramatic decrease in
opaque blade-shaped particles. The palynomorph group makes up sediment flux to the basin. Also, the presence of diminutive trace fossils
4.60 %. Freshwater algae (Pediastrum complex) and palynoforaminifera indicates that these environments are probably stressed and oxygen-
are also present. In general, the PM is non-fluorescent, except for the deficient, perhaps dysoxic or even suboxic, but not completely anoxic.
algal content.
5.1. Primary delivery of organic carbon-rich sediment to the seafloor

4.4.3. Organic geochemistry The detailed facies analysis of concretion samples from the Vaca
The samples from the CmM facies (n = 3) have an average TOC Muerta Formation suggest that primary delivery of fine-grained sedi-
value of 0.29 wt%, and a range between 0.21 and 0.34 wt% (Fig. 5A). ment to the seafloor occurred mainly by: (i) hemipelagic rain of mate-
The HI fluctuates from 26 to 43 mg HC/g TOC, whereas the OI ranges rial with a biological origin (marine snow); (ii) episodic input of
from 34 to 48 mg CO2/g TOC. The S2 values vary by ~0.09 mgHC/g extrabasinal components by wind-borne pumice rafts and dilute
rock, so Tmax values are not fairly consistent (399–407 °C). buoyant plumes; and (iii) gravity and storm-driven underflows.

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Fig. 10. Selected palynomorphs and palynofacies types from the studied concretionary samples of the Vaca Muerta Formation. A) Classopollis spp. within the CfS facies. Euhedral pyrite
crystals are recognized in the interior of this pollen grain (red arrows) (UNSPVM5265: D37/4). B) Classopollis torosus (Reissinger) Balme within the ScM facies; spongy AOM is also present
(red arrow) (UNSPVM5261: M29/4). C) Pediastrum sp. recognized in the CmM facies (UNSPVM5255: B30/1). D, E) Botryococcus sp. cf. B. braunii within the CSsM facies; the red arrow in-
dicates a cup with “growth rings” in a simple unbranched compound colony; the black arrow points out to the cup's cavity that once held the autospores remains (UNSPVM5251: C24/1).
E) RFL photomicrograph. F, G) Tasmanites spp. in the CfS facies (UNSPVM5252: S20/0). G) RFL photomicrograph. H) cf. Aptea notialis Quattrocchio and Sarjeant within the ScM facies; ven-
tral view, lacking the operculum (UNSPVM5261: H23/2). I) Palynoforaminifera identified in the CSsM facies (UNSPVM5253: B34/0). J) Cyanobacteria remains in the ScM facies, including
coccoid cells (red arrows) and filaments (black arrow) (UNSPVM5260: B35/3). K, L) Filament of cyanobacteria in the CfS facies (UNSPVM5252: X14/4). L) RFL photomicrograph. M,
N) Sheath of cyanobacteria recognized in the CSsM facies (UNSPVM5251: P26/1). N) RFL photomicrograph. O) Blade-shaped opaque phytoclasts (red arrows) and pyrite framboids
(black arrows) in the CfS facies (UNSPVM5252: T8/1). P) Spongy AOM within the CfS facies (UNSPVM5262: O1/2). Q) Charcoal (red arrow) within the CfS facies (UNSPVM5262: O22/
0). R) Granular AOM mass (red arrow) within the CSsM facies (UNSPVM5251: U52/2). S) Gelified AOM (red arrow) and granular AOM (black arrow) within the CSsM facies
(UNSPVM5256: O29/0). T) Pyrite framboids (red arrow) and dark granular AOM mass (red arrow) within the CSsM facies (UNSPVM5254: L28/3). Scale bars width represent 10 μm. E
and J photomicrographs were taken with differential interference contrast (DIC) illumination. (For interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)

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Fig. 11. CSsM facies. The CSsM facies consist of thin laminasets composed of an alternation between silt-rich laminae and calcareous muddy laminae enriched in composite grains.
A) Continuous, planar-to curved, nonparallel lamination defining gentle-dipping cross-lamination. Muddy laminae are mainly composed of sand-sized composite grains and minor
bioclastic particles, such as calcitized radiolaria (ra) and forams (fo). B) Continuous, planar parallel-lamination defined by the alternation between silt-rich and muddy laminae. Note
the variation in thickness of individual silt and muddy layers among this laminaset. C) Gentle-dipping cross-lamination defined by the alternation of non-parallel, silt-rich lenticular lam-
inae and muddy laminae. Note the lateral pinch-out of the central silt-rich lamina. D) secondary electron image and E) backscattered electron image illustrating a silt-rich layer (S) within
calcareous muddy laminae (M) enriched in sand-sized composite grains. Aggregate grains are evident in secondary electron images, but they are undistinguishable in backscattered mode.
Silt-rich layers are mainly composed of idiomorphic, volcanic-sourced feldspar and quartz grains and are better cemented by calcite than the enclosing clay-rich laminae. Note the presence
of small-scale load structures related to the density contrast induced by silt-rich laminae over the subjacent muddy laminae (white arrows in D).

The high proportions of material originated in surface waters rec- accumulated by suspension settling (e.g., Kietzmann et al., 2011,
ognized in the CmM facies (e.g., coccolith-rich fecal pellets, tests of 2016; Minisini et al., 2020). The homogenized fabric of the CmM facies
radiolarians and foraminifers) can be presumed to have traveled to suggests that shortly after deposition this facies was disrupted by
the seabed as a hemipelagic rain of organic detritus (marine snow) the burrowing activity of benthic meiofauna (e.g., agglutinated forami-
from the overlying water column (e.g., Alldredge and Cohen, 1987; nifera), contravening the assumption of stagnant and anoxic bottom
Alldredge and Silver, 1988; Macquaker et al., 2010b). Subordinate waters.
amounts of silt-sized particles, detrital mica, plant debris, and fresh- The ScM facies is here linked to two different depositional processes.
water algae might have arrived at these distal depositional sites by (1) Wind-borne volcanic ash was directly sourced from the Andean oro-
hypopycnal plumes. Clay-rich floccules could have been supplied genic belt during pulses of intense volcanic activity. It was originally de-
by dilute buoyant river plumes that sporadically reached distal, basinal posited by suspension settling from floating pumice rafts, and then
environments. Clay flocculation would have enhanced the gravitational subject to reworking by bottom currents. (2) Volcanic particles derived
settling of detrital mud through the water column to the seafloor (Lamb from the erosion of ash-fall deposits exposed in the volcanic highlands
et al., 2020). Additionally, the local presence of bioclastic remains of located in western margin of the basin, carried by rivers to the ocean.
thin-shelled bivalves and disarticulated valves of ostracods within the The relatively high proportion of blade-shaped opaque particles sug-
CmM facies suggests that some material was probably sourced from gests that volcanic highlands were vegetated and supplied plant debris
shallow-water environments during strong storm events, and then to the basin, likely transported by density-driven underflows for long

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 12. ScM facies. A) Plane polarized light image illustrating the ScM facies, characterized by a homogenized fabric with abundant pyrite content. Note the presence of clay-filled burrows
(white-dashed). B) Backscattered image showing sand-sized volcanic-sourced feldspar grains and euhedral pyrite crystal masses. Some feldspars are partially replaced by authigenic clays.
C) Backscattered image of a lathwork volcanic-rock fragment (VRF) showing an intergrowth texture dominated by plagioclase microlites and interstitial glass. It is worth noting the pres-
ence of small (<5 μm) pyrite framboids in the upper left of the photomicrograph. Also, micron-sized crystals of pyrite are evident inside the VRF. D) Secondary electron image of altered
(devitrified) volcanic shards mainly composed of authigenic clays.

distances until they reached distal depositional settings (cf. Lamb et al., Honjo, 1980; Honjo et al., 1984; Harris, 1994), and excreted coccolith
2008; Rutman et al., 2021). debris in pellets that settled to the sediment–water interface (Cuomo
and Bartholomew, 1991). After being deposited by suspension settling,
5.2. Winnowing, erosion and redistribution of organic-rich mud fecal pellets and planktonic fauna sourced from the photic zone
(e.g., radiolaria, globose forams, ostracods) were intermittently
The CSsM and CfS facies typically show microfabrics suggesting winnowed by bottom currents, transported in bedload with muddy
that depositional processes were dominated by bottom-traction trans- intraclasts and other biogenic constituents sourced from the benthos
port, possibly associated with muddy underflows. The microfabric of (e.g., benthic forams), and finally deposited as laminated mudstone
these facies strongly suggests that current-generated ripple trains deposits (see also Birgenheier et al., 2017; Li and Schieber, 2018;
migrated as discrete entities over the seabed (Fig. 15), supporting the Schieber et al., 2019).
narrative of non-stagnant bottom waters. More specifically, petro-
graphic evidence points to sedimentation under generally and episodic 5.3. Early diagenesis and burial
erosive scouring and reworking by bottom currents. The presence of
cyanobacterial remains within the CSsM facies indicates that bottom Concretions contain important information about early diagenetic
currents were strong enough to rework and erode firm substrates colo- reactions and mineralization that occurs close to the sediment–water
nized by microbial mats in shallow-water environments, and then interface in distal marine settings, and thus they are very important
transport fragments to basinal settings prior to burial. The recognition for understanding the processes that promote natural carbon sequestra-
of freshwater algae (i.e., Botryococcus) within the CSsM facies reinforces tion from the biosphere to the lithosphere.
the idea of seafloor erosion and organic carbon transport from continen- The primary fabrics and the abundance of intergranular carbonate ce-
tal and/or shallow-water environments towards distal depositional set- ments establish that the growth of the concretions studied here occurred
tings. Furthermore, the mud intraclasts in the CSsM and CfS facies are in high porosity mud prior to compaction, during periods of very low net
here interpreted as the recycled products of recently deposited beds, sediment accumulation rates (e.g., Raiswell, 1988). Cementation oc-
likely originated through the erosion of surficial, water-saturated curred prior to significant burial, because otherwise mud intraclasts
mud by bottom currents (Schieber et al., 2010). Shallow-buried would have been flattened, producing a lenticular shale fabric (Schieber
mud was sufficiently cohesive to resist disaggregation during erosion et al., 2010). It is assumed here that shortly after deposition the pores
and subsequent bedload transport, abrasion and collisions (e.g., of mud intraclasts were filled with calcite cement as concretion nucle-
Schieber et al., 2010; Plint, 2014; Li and Schieber, 2018; Li et al., 2021). ation was initiated. Because these cements were early, i.e., before com-
High magnification CCI in secondary electron mode under the SEM paction, they occupied most of the primary pore space of the muddy
revealed that in addition to mud intraclasts, aggregate-rich laminae sediment (e.g., Lippmann, 1955; Raiswell, 1971), with minimal displace-
also contain fecal pellets produced by planktonic feeders (e.g., copepods) ment of the original grain arrangements. The common presence of non-
that selectively fed on coccolithophores in the photic zone (Hattin, 1975; ferroan calcite cement and pyrite suggests that cement precipitation

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 13. CmM facies. A) Plane polarized light image illustrating a sharp contact separating the CmM facies from the subjacent CSsM facies. The CmM facies show a homogenized fabric
enriched in dark-colored silt-sized composite particles and bioclastic grains, including calcified radiolarians and small remains of thin-shelled bivalves. In addition, fine-silt-sized quartz
grains are recognized. B) Cross polarized light image showing an agglutinated benthic foraminifer (fo), abundant calcified radiolarians (ra) and minor fecal pellets (P). C) Plane polarized
light image illustrating calcified radiolarian (ra) and dark-colored aggregates within an overall structureless clay-rich matrix with dispersed silt-sized quartz grains (Q). D) Backscattered
electron image of the CmM facies showing calcified radiolarians (white dashed), silt-sized quartz grains (Q) and detrital mica (m). Note the presence of small (<5 μm) disseminated pyrite
crystals and framboids.

was linked to microbial degradation processes of organic matter that oc- organic matter in surface waters. The enrichment in TOC content regis-
curred close to the sediment–water interface (Curtis, 1987; Ritger et al., tered in the basal condensed section of the Vaca Muerta Formation (up
1987; Paull et al., 1992; Canfield, 1994; Von Rad et al., 1996). Diagenetic to 15 % TOC, Brisson et al., 2020) may have resulted from (i) an increase
pyrite formed due to bacterial sulfate reduction in carbonaceous sedi- in primary productivity related to episodes of high volcanic activity that
ment beneath a dysoxic or even oxygenated water column (Goldhaber supplied large amounts of volcanic ash enriched in nutrients (e.g., N,
et al., 1977), an interpretation consistent with the prevalence of large P, K, Si, Fe) to surface waters (Yang et al., 2021), and/or (ii) enhanced
euhedral grains (Wilkin et al., 1996), a lack of framboidal pyrite (Blood fertilization and phytoplankton blooms associated with upwelling of
et al., 2019), and the common presence of diminutive burrow mottles nutrient-rich deep-water masses (e.g., Smith and Bustin, 1998).
and disrupted fabrics. The activity of microbial communities near the Condensation and enhanced primary productivity are not sufficient
sediment–water interface probably resulted in the breakdown of labile to explain the origin of organic-rich condensed sections. Preservation
organic components (Liu et al., 2021), reducing TOC, S2 peaks, and HI is also a key factor for the development of organic carbon-rich mud-
values during the early stages of diagenesis. Sulfate-reducing bacte- stone (Bohacs et al., 2005). After primary deposition, active degradation
ria selectively destroyed a more hydrogen-rich component of the by aerobic and anaerobic processes acting nearby the sediment-water
primary organic matter mixture (Littke, 1993), leaving residual interface results in <1 % of the photosynthesized organic matter
organic compounds mainly represented by indigestible, refractory retained and buried in sediment (Middelburg and Meysman, 2007).
organic matter (type III-IV, Fig. 5). Collectively, our data suggest Organic carbon remineralization is attenuated in environments charac-
that concretions plausibly formed within or just above the sulfate terized by anoxic/euxinic bottom water conditions, although many an-
reduction zone (Irwin et al., 1977) (Fig. 15), where oxygen replen- cient organic carbon-rich mudstone successions shows that organic
ishment by diffusion processes becomes increasingly more difficult, carbon accumulation and preservation does not necessarily require
resulting in oxygen-depleted interstitial waters (Potter et al., 2005; the presence of stagnant bottom waters and sustained anoxic/euxinic
Milliken and Day-Stirrat, 2013). conditions (Schieber, 2003; Macquaker et al., 2010b; Ghadeer and
Macquaker, 2012). The processes responsible for the preservation of
5.4. Condensation, enhanced productivity and organic carbon preservation significant amounts of organic carbon in condensed sections developed
under suboxic/dysoxic depositional settings are not yet comprehen-
The sedimentary rock record shows that organic carbon enrichment sively understood (Hartnett et al., 1998; Moodley et al., 2005; Könitzer
in distal marine environments is typically enhanced during periods of et al., 2014).
very low net sediment accumulation rates (<100 cm/kyr) that contrib- Although microbial degradation processes destroyed most of the or-
ute to organic matter concentration in condensed intervals (e.g., ganic matter that supplied the mineralizing solutes for carbonate precip-
Sageman et al., 2003). Also, organic‑carbon-rich intervals are typically itation and concretion growth, the palynological samples studied here
associated with periods of high nutrient influx that promote the prolif- surprisingly exhibit important clues for understanding the mechanisms
eration of primary producers and enhance primary productivity of that promote organic carbon preservation in condensed intervals. Out

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G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 14. Plane polarized light and secondary electron micrographs illustrating clay floccules. A) Plane polarized light image of clay-rich floccules (Fl), calcified radiolarians (R), silt-sized
quartz grains (Q) and plant debris (Ph) within the CmM facies. B) Secondary light image showing fecal pellets (P) and clay floccules (Fl) within the CmM facies. C) Secondary light
image showing detrital clays (cl) adhered one another in the interior of a clay-rich floccule. D) Secondary light image showing the interior of a round-shaped, clay-rich floccule highly
cemented with microcrystalline calcite.

of the total palynological matter, granular AOM is the most important or- 6. Conclusion
ganic matter type. Granular AOM sensu Pacton et al. (2011) is a microbial
product characterized by a heterogeneous fluorescence, i.e., material with This study demonstrates that early diagenetic carbonate concretions
strong fluorescence (bacterial bodies) surrounded by weaker fluorescent can provide important clues for understanding the depositional setting
extracellular polymeric substances (EPS), and it is commonly associated and early diagenetic history of organic‑carbon-rich mudstone that make
with bacterial filaments. EPS is generated by microbes and eukaryotic up condensed sections. The close examination of uncompacted fabrics
phytoplankton as (1) secretions of biofilms that secure attachment and preserved inside early diagenetic concretions from the Vaca Muerta
enhance their local environment, and/or (2) metabolic-excess waste Formation reveals a significantly more complex and dynamic deposi-
products (Decho and Gutierrez, 2017). Importantly, EPS can encapsulate tional scenario than previously assumed (suspension settling para-
organic and inorganic materials in small aggregates of particulate organic digm). Although component grains in the studied dataset include
matter forming marine snow, establishing localized anoxic conditions, abundant material originally delivered to the sediment–water interface
even in the presence of an oxygenated water column (Decho and by suspension settling processes (i.e., marine snow, hypopycnal plumes,
Gutierrez, 2017; Martínez et al., 2018a, 2018b). This process is associated pumice rafts), there is substantial evidence of episodic sedimentation
with an oxygen gradient that leads to an increase of anoxia towards the controlled by episodic events of seafloor disturbance and erosion.
interior of the aggregates (Alldredge and Cohen, 1987; Alldredge and The architecture of the lithofacies described here demonstrates
Silver, 1988; Ploug et al., 1997; Ploug, 2008; Decho and Gutierrez, 2017). that, even at basinal settings, the seafloor was frequently disturbed
The great abundance of mud composite particles within the by bottom current activity. Bottom currents were strong enough to
facies described here strongly support the idea that organic carbon en- sweep the seabed and intermittently erode it, resulting in the
capsulation could be an important mechanism for organic carbon pres- recycling of hemipelagic mud in the form of muddy intraclasts that
ervation in relatively energetic and non-anoxic distal depositional were transported in bedload together with biogenic components
environments (Macquaker et al., 2010b). Besides creating an anoxic and volcanic-sourced particles derived from the reworking of
microenvironment that prevents the oxidation of the organic matter volcaniclastic deposits. As a result of bottom-traction transport, rip-
contained inside of the aggregates (e.g., Ghadeer and Macquaker, ple trains migrated over the seabed and were deposited along with
2012), encapsulation also protects organic components from (1) degra- suspended sediment. The winnowing of the seafloor by swift bottom
dation and abrasion during transport, and (2) feeding microorganisms currents is an important mechanism for the widespread distribution
(see also Yu et al., 2009). The excellent preservation state of freshwater of organic carbon-rich sediment from the periphery to the interior of
algae (Pediastrum complex) suggests that organic matter contained epicontinental basins, especially during periods of low net sediment
inside mud composite particles can travel long distances before accumulation rates and condensation of organic carbon on the sea-
being deposited in distal depositional settings. After settling to the floor under minimal input of detrital clay and silt.
sediment–water interface, these particles can be also subject to Although microbial degradation processes destroyed most of the
reworking and bottom-traction transport by bottom currents re- organic content record, the concretions studied here represent a
sponsible for organic carbon redistribution in basinal settings. unique dataset for understanding the mechanisms that promote

17
G. Otharán, C. Zavala, J. Schieber et al. Sedimentary Geology 440 (2022) 106254

Fig. 15. Diagram illustrating the processes that control the delivery, dispersal, accumulation and diagenesis of organic carbon-rich sediment in the interior of epicontinental basins during
periods of sediment starvation. During such periods of very low net sediment accumulation rates, a condensed flux of biogenic material to the seafloor under minimal input of detrital clay
and silt lead to a significant delivery of organic carbon to the seafloor, however, only a small fraction of the OM is preserved due to intensive remineralization by microbial-mediated re-
actions that increase the alkalinity of the environment and supply the mineralizing solutes for early cementation and concretion nucleation at shallow burial depths.

organic carbon preservation in condensed intervals. The microfabrics in- Acknowledgements


dicate that bottom water layers were not persistently anoxic, and in fact
bottom current circulation supplied oxygen to the sediment–water inter- The authors deeply acknowledge the National Scientific and
face and created suitable conditions for benthic life, contravening the as- Technical Research Council (CONICET), the Geology Department of
sumption of bottom water anoxia as a prerequisite for organic carbon Universidad Nacional del Sur (UNS), the Indiana University Department
preservation in condensed sections. The excellent preservation state of of Earth and Atmospheric Sciences and Y-TEC S.A. for supporting field
freshwater algae (Pediastrum complex) strongly suggest that encapsula- activities, sample preparation and analyses. The authors are especially
tion could be an important mechanism for organic carbon preservation grateful to Dr. J.H.S. Macquaker, Dr. L.P. Birgenheier and Dr. P. Pedersen
in relatively energetic and non-anoxic distal depositional environments. for their valuable comments and suggestions on a previous version of
Besides creating an anoxic microenvironment that prevents the oxidation this manuscript. Special thanks to Dr. B. Jones, Dr. R.D. Wilson and Dr.
of the organic matter contained inside of the aggregates, encapsulation P.M. Myrow for their professionalism and commitment to improve the
also protected organic components from feeding microorganisms and quality of this manuscript. The authors also want to express thanks to
degradation and abrasion during transport. F. Brea and C. Selva for performing the organic geochemical analyses.
The dataset presented in this study provides evidence that organic M. Arcuri , M. Di Meglio , A. Zorzano , A. Torresi and M. Fantín contrib-
matter contained inside mud composite particles is capable of traveling uted with interesting discussions about the mechanisms responsible
for long distances before being accumulated and buried in distal deposi- for the delivery, accumulation and preservation of organic-rich mud in
tional settings, calling for a critical reappraisal of the processes that con- epicontinental basins.
trol organic carbon preservation in epicontinental seas.

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