https://doi​.org/10.1130/G48825.

Manuscript received 13 January 2021

Revised manuscript received 2 March 2021
Manuscript accepted 16 March 2021

© 2021 Geological Society of America. For permission to copy, contact editing@geosociety.org.

Published online 17 May 2021

Revisiting stepwise ocean oxygenation with authigenic barium

enrichments in marine mudrocks
Guang-Yi Wei1*, Hong-Fei Ling1*, Graham A. Shields2, Simon V. Hohl3, Tao Yang1, Yi-Bo Lin1 and Feifei Zhang1
1
 tate Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University,
S
Nanjing 210023, China
2
Department of Earth Sciences, University College London, Gower Street, London WC1E 6BT, UK
3
State Key Laboratory of Marine Geology, School of Ocean and Earth Sciences, Tongji University, Shanghai 200092, China

ABSTRACT maximum constraint on the extents of global

There are current debates around the extent of global ocean oxygenation, particularly anoxic or euxinic seafloor. Further constraints on
from the late Neoproterozoic to the early Paleozoic, based on analyses of various geochemical the extent of global ocean oxygenation cannot be
indices. We present a temporal trend in excess barium (Baexcess) contents in marine organic- directly acquired based on these metal proxies.
rich mudrocks (ORMs) to provide an independent constraint on global ocean redox evolu- For modern fully oxidized ocean basins,
tion. The absence of remarkable Baexcess enrichments in Precambrian (>ca. 541 Ma) ORMs with Ba-limited conditions, excess barium
suggests limited authigenic Ba formation in oxygen- and sulfate-deficient oceans. By contrast, (Baexcess) accumulations in marine sediments are
in the Paleozoic, particularly the early Cambrian, ORMs are marked by significant Baexcess ­commonly linked to the formation of BaSO4-
enrichments, corresponding to substantial increases in the marine sulfate reservoir and oxy- supersaturated “microenvironments” in organic
genation level. Analogous to modern sediments, the Mesozoic and Cenozoic ORMs exhibit no matter linked to shallow-marine export produc-
prominent Baexcess enrichments. We suggest that variations in Baexcess concentrations of ORMs tivity (e.g., Bishop, 1988; Dymond et al., 1992;
through time are linked to secular changes in the marine dissolved Ba reservoir associated Paytan and Griffith, 2007; Martinez-Ruiz et al.,
with elevated marine sulfate levels and global ocean oxygenation. Further, unlike Mo, U, 2019). However, more systematic analyses of
and Re abundances, significant Baexcess enrichments in ORMs indicate that the overall ocean modern marine sediments deposited in different
oxygenation level in the early Paleozoic was substantially lower than at present. redox environments challenged the use of Baexcess
as a reliable proxy for paleo-productivity on a
INTRODUCTION seafloor redox, based on the principle that burial more global scale (Schoepfer et al., 2015). In
Earth’s 4.5-billion-year history is character- fluxes of these elements into ORMs are primar- particular, predominantly O2-deficient oceans
ized by a stepwise increase in atmospheric and ily determined by their ocean concentrations, of the Precambrian may have had a more exten-
oceanic oxygen levels, with two major steps rec- which are in turn related to global marine redox sive dissolved Ba reservoir in deep waters (cf.
ognized in the geologic record: the Great Oxida- states (Scott et al., 2008; Partin et al., 2013; Falkner et al., 1993; Crockford et al., 2019).
tion Event (GOE) between 2.4 and 2.1 Ga, and Reinhard et al., 2013; Sheen et al., 2018). Secu- At such times, the water column’s sulfate con-
the Neoproterozoic Oxygenation Event (NOE) lar changes in Mo, U, and Re concentrations in tents, rather than Ba concentrations, may have
between 0.8 and 0.55 Ga (Holland, 2006; Lyons ORMs have consistently supported the inference played a first-order control in Baexcess accumula-
et al., 2014; Knoll and Nowak, 2017). Multiple of stepwise increases in marine oxygen levels tion in ancient marine sediments (Torres et al.,
redox proxies have been used to track the long- throughout Earth’s history (Fig. 1) (Scott et al., 1996). Although Ba is not a redox-sensitive ele-
term redox evolution of Earth’s atmosphere 2008; Partin et al., 2013; Sheen et al., 2018). ment, the removal of Ba from the water column
and ocean (see reviews in Canfield [2005], Significantly elevated Mo, U, and Re enrich- is intrinsically linked to marine sulfate levels,
Och and Shields-Zhou [2012], and Tostevin ments through the NOE highlight that marine associated with global oceanic redox states and
and Mills [2020]), among which the concen- Mo, U, and Re reservoirs were potentially com- pyrite burial fluxes. In this view, Ba enrichments
trations of redox-sensitive metals (RSMs) in parable to those in the modern ocean as a result in ancient sediments depend on co-evolution of
marine organic-rich mudrocks provided insights of progressive ocean oxygenation. However, the dissolved Ba and sulfate reservoirs in the ancient
into temporal changes in marine redox states sizes of marine Mo, U, and Re reservoirs may oceans. In this study, we present Ba concentra-
(Robbins et al., 2016; Algeo and Li, 2020). not be linearly related to the dissolved O2 con- tions of ORMs from the Archean to the modern
Enrichments of Mo, U, Re, and Cr in marine centration of global seawater. Although large times, aiming to provide new insights into the
organic-rich mudrocks (ORMs, defined by hav- dissolved RSM reservoirs imply modern-sized extent of global ocean oxygenation throughout
ing a total organic carbon content of >0.4 wt%) global anoxic or euxinic seafloor sinks (Partin the Earth’s history. Combining with the esti-
have been used to reconstruct trends in global et al., 2013; Reinhard et al., 2013; Sheen et al., mated marine sulfate concentrations, we use
2018), this does not require modern-like dis- authigenic Ba concentrations in ORMs to recon-
*E-mails: guangyiwei@nju.edu.cn; hfling@nju. solved O2 concentrations. In this view, Mo, U, struct the long-term evolution of the marine dis-
edu.cn and Re enrichments in ORMs only provide a solved Ba reservoir and further constrain the

CITATION: Wei, G.-Y., et al., 2021, Revisiting stepwise ocean oxygenation with authigenic barium enrichments in marine mudrocks: Geology, v. 49, p. 1059–1063,
https://doi.org/10.1130/G48825.1

Geological Society of America | GEOLOGY | Volume 49 | Number 9 | www.gsapubs.org 1059

Downloaded from http://pubs.geoscienceworld.org/gsa/geology/article-pdf/49/9/1059/5387113/g48825.1.pdf

by Southern University of Science and Technology of China user
 ian Volcanic Observatory) standards. We also
A compiled a literature database of Ba concentra-
tions and associated Al and total organic carbon
(TOC) contents in ORMs through geological
time. Because barite ore–bearing rocks associ-
ated with local hydrothermal or burial diagenetic
processes can exhibit extreme Ba enrichments
unrelated to global oceanic dissolved Ba con-
centrations, they were excluded from our data-
base and are not discussed further on. We also
chose the typical samples from the early Cam-
B brian for scanning electron microscopy (SEM)
observations in order to better constrain the sit-
ing and origin of particulate Ba in ancient ORMs
(Figs. S2 and S3 in the Supplemental Material1).
Authigenic Ba concentrations of analyzed
and literature marine sediments (i.e., non-detri-
tal particulate Ba, defined as Baexcess) were cal-
culated using the following:

 Ba 
 Ba  detritus =   ×  Al  bulk , (1)
 Al  detritus
C
 Ba  excess =  Ba  bulk −  Ba  detritus. (2)

The Ba/Al ratios of the detrital component

were derived from the average upper continental
crust (UCC) (AlUCC = 8.15%, BaUCC = 624 ppm)
(Rudnick and Gao, 2014). Temporal trends in
Baexcess enrichment in ORMs through the geo-
logical time are presented in Figure 2.

D EXCESS Ba ENRICHMENT IN ORMS

THROUGH GEOLOGICAL TIME
Dissolved Ba in the modern oceans is
­commonly sourced from continental weathering,
along with a relatively small flux of hydrother-
mal fluids, and is scavenged by the formation
and subsequent burial of particulate Ba (i.e., dis-
crete micrometer-sized barite) (Dickens et al.,
2003). Modern pelagic sediments typically have
significantly low Baexcess concentrations due to
low dissolved Ba concentrations and BaSO4-
undersaturated conditions of deep seawater
(Bridgestock et al., 2018). Given the high ­sulfate
concentration (∼29 mM) in modern fully oxi-
dized oceans, particulate Ba accumulations in the
Figure 1. Compilations of Mo, U, and Re concentrations in organic-rich mudrocks (A–C), cor- sediments are dominated by the limited dissolved
responding to evolution of Earth’s atmospheric oxygen content and key biological innovation Ba availability in the water column (<∼100 nM)
events through the Precambrian (D). PAL—present atmospheric level. Red lines in A–C denote (Martinez-Ruiz et al., 2019). Analogous to mod-
average values for Archaean, early Proterozoic (only for B), mid-Proterozoic, and Neoprotero- ern marine sediments, the Cenozoic and Mesozoic
zoic–Phanerozoic data (data from Scott et al., 2008; Partin et al., 2013; Sheen et al., 2018). Panel
D is modified from Lyons et al. (2014) and Knoll and Nowak (2017, and references therein). The ORMs consistently show low Baexcess concentra-
faded red curve represents a classical, two-step model of atmospheric oxygenation; the blue tions (<∼3500 ppm), demonstrating presumably
curve shows an emerging model from Lyons et al. (2014). The arrows denote possible “whiffs” of BaSO4-undersaturated conditions of the coeval
oxygen in the Archaean. GOE—Great Oxidation Event; NOE—Neoproterozoic Oxygenation Event. seawater. By contrast, the Paleozoic ORMs are
characterized by significant Baexcess enrichments
global ocean oxygenation level in the critical spectrometer at the State Key Laboratory for (as much as 10,000–20,000 ppm), suggesting
geological periods. Mineral Deposits Research, Nanjing University
(China). The long-term reproducibility of the
METHODS measurements was better than 5% in this study,
1
Supplemental Material. Supplemental methods,
Figures S1–S5, and data sources. Please visit https://
New major and trace element data in this based on duplicated analyses of IAPSO (Inter- doi​ . org/10.1130/GEOL.S.14470863 to access
study were obtained using a Thermo Finnigan national Association for Physical Sciences of the the supplemental material, and contact editing@
Element XR inductively coupled plasma mass Ocean) seawater and BHVO-2 (Basalt, Hawai- geosociety.org with any questions.

1060 www.gsapubs.org | Volume 49 | Number 9 | GEOLOGY | Geological Society of America

Downloaded from http://pubs.geoscienceworld.org/gsa/geology/article-pdf/49/9/1059/5387113/g48825.1.pdf

by Southern University of Science and Technology of China user

B table [see footnote 1]).
A the late Neoproterozoic
more efficient trapping of Ba from the water
column compared to the modern ocean. The
Baexcess concentrations of the Precambrian ORMs
(>ca. 541 Ma) are low overall (<4000 ppm),
except for several high values in the Paleopro-
terozoic (ca. 1.8 Ga) (as much as 10,000 ppm).
For Neoproterozoic and Paleozoic ORMs, the
lack of appreciable relationships of Babulk and
Baexcess to Al concentrations suggests no effects
of continental detrital inputs on Ba accumu-
lations in paleo-marine sediments (Figs. S5A
and S5B).
For modern marine settings, clear correla-
tions between accumulation rates of Baexcess
and those of organic carbon were observed
only in specific environments (e.g., the equato-
rial Pacific), challenging the use of Baexcess as
a widely reliable proxy for paleo-productivity
(Schoepfer et al., 2015). In this study, the lack
of any appreciable correlations between Babulk
or Baexcess and TOC contents is observed in the
Neoproterozoic and Paleozoic ORMs, especially
in samples with notably high Babulk and Baexcess
concentrations (Figs. S5C and S5D). Notably
high Baexcess signals can be found in samples
with either high or low TOC contents. In these
contexts, we suggest that instead of marine pro-
ductivity, oceanic sulfate concentrations associ-
ated with ocean oxygenation levels may have
played a first-order control on significant Baexcess
accumulations in the late Neoproterozoic and
Paleozoic ORMs (cf. Wei and Algeo, 2020).
The Precambrian oceans show inconspicuous
Baexcess enrichments in ORMs, presumably due
to pervasive deep-marine anoxia and limited
sulfate concentrations (Canfield and Farquhar,
2009; Kah et al., 2004; Reinhard et al., 2013;
Planavsky et al., 2014). However, some Paleo-
proterozoic ORMs (ca. 1.8 Ga) reveal relatively
Geological Society of America | GEOLOGY | Volume 49 | Number 9 | www.gsapubs.org
Downloaded from http://pubs.geoscienceworld.org/gsa/geology/article-pdf/49/9/1059/5387113/g48825.1.pdf
by Southern University of Science and Technology of China user
high Baexcess, likely implying a transient increase
in marine sulfate reservoir following the GOE
(Poulton et al., 2004; Planavsky et al., 2012).
The onset of significant Baexcess enrichments in
ORMs occurred during the late Neoprotero-
zoic through the early Cambrian (ca. 520 Ma)
interval, which is marked by extreme Baexcess
enrichments in ORMs (Fig. 2A), corresponding
to substantially elevated marine sulfate levels
during this period (Kah et al., 2004; Canfield and
Farquhar, 2009; Algeo et al., 2015). High Baex-
cess enrichments in ORMs persisted through the
Paleozoic, suggesting the protracted existence
of a large dissolved Ba reservoir in the Paleo-
zoic oceans. By contrast, no appreciable Baexcess
enrichments are recognized in the Mesozoic and
Cenozoic ORMs, coincident with the inception
of a resiliently oxygenated ocean and rise to
current marine sulfate concentrations since the
Mesozoic (Algeo et al., 2015; Lu et al., 2018).
LONG-TERM EVOLUTION OF THE
MARINE DISSOLVED Ba RESERVOIR
AND GLOBAL OCEAN OXYGENATION
In each time interval, the ORMs may exhibit
either high or low Baexcess contents (Fig. 2), likely
controlled by short-time-scale changes in marine
redox state or depositional condition. How-
ever, the secular trend in Baexcess enrichments
in ORMs throughout the Neoproterozoic and
Phanerozoic is closely related to temporal evo-
lution of the marine sulfate reservoir (Fig. 2;
also see Wei and Algeo, 2020). An increase in
marine sulfate concentration accelerates the
consumption of dissolved Ba in the ocean via
barite precipitation. Thus, the Baexcess abundance
in ORMs is determined by the relative sizes of
marine sulfate and Ba reservoirs. We further
qualitatively estimate changes in seawater Ba
Figure 2. (A) Temporal
trends in excess barium
(Baexcess) enrichment in
organic-rich mudrocks
(data sources are pre-
sented in the Supplemental
Blue circles denote data
before the Neoproterozoic;
gray circles, data from the
Neoproterozoic to Paleo-
zoic; tan circles, data from
the Mesozoic and Ceno-
zoic. Brown bars indicate
temporal distribution of
bedded barite deposits
(Jewell, 2000). (B) Evo-
lution of marine sulfate
concentrations (blue line)
(with 2σ error bars, blue
shaded area) throughout
and Phanerozoic, modified
from Algeo et al. (2015).
O-S—Ordovician-Silurian;
P-T—Permian-Triassic;
PETM—Paleocene–Eocene
Thermal Maximum.
concentrations throughout the Neoproterozoic
and Phanerozoic based on the calculation of
marine barite saturation (Fig. 3). The presum-
ably BaSO4-undersaturated conditions in the
early Neoproterozoic oceans, demonstrated by
nonexistent Baexcess enrichments in ORMs, may
have facilitated accumulation of a notable dis-
solved Ba inventory from continental weather-
ing or hydrothermal fluids. The marine dissolved
Ba reservoir during the early Neoproterozoic
was likely three orders of magnitude larger than
that of the modern ocean (Fig. 3). The inception
of BaSO4-supersaturated oceans in the late Neo-
proterozoic led to an overall decrease in marine
dissolved Ba concentrations; nevertheless, the
pervasive BaSO4-supersaturated conditions of
the Paleozoic ocean required an oceanic Ba res-
ervoir at least an order of magnitude larger than
that of the modern ocean (Fig. 3). The Mesozoic
and Cenozoic oceans, characterized by BaSO4-
undersaturated conditions, more likely had low
dissolved Ba concentrations, close to that of the
modern ocean (Fig. 3).
Modern anoxic basins (e.g., Black Sea;
Framvaren Fjord, southern Norway) consis-
tently show notably higher dissolved Ba con-
centrations in deep seawater (280–460 nM)
relative to the global pelagic ocean (<100 nM)
(Falkner et al., 1993) due to remobilization
of barites following sulfate reduction in sedi-
ment pore waters (e.g., Schoepfer et al., 2015).
In some oxygen-depleted continental margins
(e.g., Peru margin), the recycled Ba can dif-
fuse upward and reprecipitate as a diagenetic
barite front across the sulfate-sulfide transition
zone in the sediment piles (Torres et al., 1996).
Once the bottom waters are pervasively barite
supersaturated, successive barite accumulations
in sediment piles are not likely quantitatively
1061

ocean. White star indicates Ba concentration of the modern Black Sea deep water (SO4 con-
centration is zero). Dashed areas represent ranges of SO4 and Ba concentrations in ancient
oceans through geological time.
exhausted via sulfate reduction in sediment
pore waters during the early diagenesis, partly
attributed to the formation of barite fronts in
the upper sediment profile. In this view, sul-
fate reduction in sediment pore waters may not
hamper the preservation of average high Baexcess
signals in ancient rocks, which also accounts
for ORMs deposited in strongly anoxic settings
still containing notably high Baexcess signals (e.g.,
early Cambrian black shales) (Fig. S4). Addi-
tionally, although increased continental or sub-
marine weathering and hydrothermal inputs of
Ba may have supplied additional Ba to a local
depositional system or pelagic ocean (Dickens
et al., 2003), such processes more likely occur
on a several-million-year time scale. Long-term
evolution of the marine dissolved Ba reservoir
throughout geological time cannot result solely
from rapid changes in its source fluxes. More-
over, significant particulate Ba accumulation
in ORMs originated from the late Ediacaran to
the early Cambrian when chemical weathering
intensity was relatively low before the coloniza-
tion of land plants (e.g., Dahl and Arens, 2020).
Accordingly, chemical weathering accelerated
by land plants could not have been a first-order
control on marine authigenic particulate Ba for-
mation in the late Paleozoic.
In conclusion, secular changes in Ba contents
of ORMs dominantly corresponded to long-term
global ocean redox evolution. Persistent BaSO4-
undersaturated conditions in the Precambrian
oceans facilitated substantial accumulations of
dissolved Ba in the seawater until marine sul-
fate concentrations approached a level where
the saturation index was high enough for BaSO4
precipitation. Hence, the lack of any appreciable
Baexcess enrichments in ORMs suggests perva-
sive marine anoxia before the NOE. By contrast,
significant Baexcess enrichments in ORMs from
the late Neoproterozoic to the Paleozoic mark
1062
Downloaded from http://pubs.geoscienceworld.org/gsa/geology/article-pdf/49/9/1059/5387113/g48825.1.pdf
by Southern University of Science and Technology of China user
Figure 3. Barite saturation
index (ratios between the
activity products of free
Ba and SO 4 ions and
the solubility product of
barite) as a function of SO4
concentrations (mmol/L)
and Ba concentrations
(μmol/L) of the oceans
and a qualitative evalua-
tion of Ba concentrations
from the Neoproterozoic
to present-day oceans.
Diagonal dashed line
represents the value of 1
for the barite saturation
index, corresponding to
the threshold for BaSO4-
saturated conditions.
Gray arrow denotes the
range of SO4 and Ba con-
centrations in the modern
a significant rise in global ocean oxygenation
and elevated marine dissolved sulfate concentra-
tions. However, the persistence of a large marine
dissolved Ba reservoir through the Paleozoic,
supported by ubiquitous Baexcess enrichments in
ORMs and widespread bedded barite deposits
(Fig. 2) (Jewell, 2000), indicates that the NOE
was relatively modest and that the baseline of
the Paleozoic ocean oxygen level was markedly
lower than that of the modern ocean. Traced
by Baexcess enrichments, the stabilization of a
resiliently oxygenated ocean should be much
later than previously inferred via Mo, U, and
Re enrichments in ORMs. A persistently and
resiliently oxygenated ocean was more likely
not established until the Mesozoic, in line with
the published records of I/Ca ratios in marine
carbonates (Lu et al., 2018).
ACKNOWLEDGMENTS
This study was funded by the Strategic Priority
Research Program(B) of the Chinese Academy of
Sciences (grant XDB26000000) and the National Nat-
ural Science Foundation of China (grants 42002002,
41872002, 41661134048). We are grateful to editor
Chris Clark, Thomas Algeo, and an anonymous
reviewer for their constructive reviews.
REFERENCES CITED
Algeo, T.J., and Li, C., 2020, Redox classification
and calibration of redox thresholds in sedimen-
tary systems: Geochimica et Cosmochimica
Acta, v. 287, p. 8–26, https://doi​.org/10.1016/​
j.gca.2020.01.055.
Algeo, T.J., Luo, G.M., Song, H.Y., Lyons, T.W., and
Canfield, D.E., 2015, Reconstruction of secu-
lar variation in seawater sulfate concentrations:
Biogeosciences, v. 12, p. 2131–2151, https://doi​
.org/10.5194/bg-12-2131-2015.
Bishop, J.K.B., 1988, The barite-opal-organic car-
bon association in oceanic particulate mat-
ter: Nature, v. 332, p. 341–343, https://doi​
.org/10.1038/332341a0.
Bridgestock, L., Hsieh, Y.-T., Porcelli, D., Homoky,
W.B., Bryan, A., and Henderson, G.M., 2018,
www.gsapubs.org | Volume 49 | Number 9 | GEOLOGY | Geological Society of America
Controls on the barium isotope compositions
of marine sediments: Earth and Planetary Sci-
ence Letters, v. 481, p. 101–110, https://doi​
.org/10.1016/​j.epsl.2017.10.019.
Canfield, D.E., 2005, The early history of
atmospheric oxygen: Homage to Robert A.
Garrels: Annual Review of Earth and Planetary
Sciences, v. 33, p. 1–36, https://doi.​ org/10.1146/​
annurev.earth.33.092203.122711.
Canfield, D.E., and Farquhar, J., 2009, Animal evolu-
tion, bioturbation, and the sulfate concentration
of the oceans: Proceedings of the National Acad-
emy of Sciences of the United States of Ameri-
ca, v. 106, p. 8123–8127, https://doi​.org/10.1073/
pnas.0902037106.
Crockford, P.W., et al., 2019, Barium-isotopic con-
straints on the origin of post-Marinoan barites:
Earth and Planetary Science Letters, v. 519, p. 234–
244, https://doi​.org/10.1016/​j.epsl.2019.05.018.
Dahl, T.W., and Arens, S.K.M., 2020, The impacts
of land plant evolution on Earth’s climate and
oxygenation state—An interdisciplinary review:
Chemical Geology, v. 547, 119665, https://doi​
.org/10.1016/​j.chemgeo.2020.119665.
Dickens, G.R., Fewless, T., Thomas, E., and Bralower,
T.J., 2003, Excess barite accumulation during the
Paleocene-Eocene Thermal Maximum: Massive
input of dissolved barium from seafloor gas hy-
drate reservoirs, in Wing, S.L., et al., eds., Causes
and Consequences of Globally Warm Climates
in the Early Paleogene: Geological Society of
America Special Paper 369, p. 11–23, https://doi​
.org/10.1130/0-8137-2369-8.11.
Dymond, J., Suess, E., and Lyle, M., 1992, Barium in
deep-sea sediment: A geochemical proxy for pa-
leoproductivity: Paleoceanography, v. 7, p. 163–
181, https://doi​.org/10.1029/92PA00181.
Falkner, K.K., Klinkhammer, G.P., Bowers, T.S.,
Todd, J.F., Lewis, B.L., Landing, W.M., and
Edmond, J.M., 1993, The behavior of barium
in anoxic marine waters: Geochimica et Cos-
mochimica Acta, v. 57, p. 537–554, https://doi​
.org/10.1016/0016-7037(93)90366-5.
Holland, H.D., 2006, The oxygenation of the atmo-
sphere and oceans: Philosophical Transactions of
the Royal Society: Series B, Biological Scienc-
es, v. 361, p. 903–915, https://doi​.org/10.1098/
rstb.2006.1838.
Jewell, P.W., 2000, Bedded barite in the geologic
record, in Glenn, C.R. et al., eds., Marine Au-
thigenesis: From Global to Microbial: SEPM
(Society for Sedimentary Geology) Special Pub-
lication 66, p. 147–161, https://doi​.org/10.2110/
pec.00.66.0147.
Kah, L.C., Lyons, T.W., and Frank, T.D., 2004, Low
marine sulphate and protracted oxygenation of
the Proterozoic biosphere: Nature, v. 431, p. 834–
838, https://doi​.org/10.1038/nature02974.
Knoll, A.H., and Nowak, M.A., 2017, The timetable
of evolution: Science Advances, v. 3, e1603076,
https://doi​.org/10.1126/sciadv.1603076.
Lu, W., et al., 2018, Late inception of a resiliently
oxygenated upper ocean: Science, v. 361, p. 174–
177, https://doi​.org/10.1126/science.aar5372.
Lyons, T.W., Reinhard, C.T., and Planavsky, N.J.,
2014, The rise of oxygen in Earth’s early ocean
and atmosphere: Nature, v. 506, p. 307–315,
https://doi​.org/10.1038/nature13068.
Martinez-Ruiz, F., Paytan, A., Gonzalez-Muñoz,
M.T., Jroundi, F., Abad, M.M., Lam, P.J., Bishop,
J.K.B., Horner, T.J., Morton, P.L., and Kastner,
M., 2019, Barite formation in the ocean: Ori-
gin of amorphous and crystalline precipitates:
Chemical Geology, v. 511, p. 441–451, https://
doi​.org/10.1016/​j.chemgeo.2018.09.011.
Och, L.M., and Shields-Zhou, G.A., 2012, The Neo-
proterozoic oxygenation event: Environmental
 perturbations and biogeochemical cycling: Earth-
Science Reviews, v. 110, p. 26–57, https://doi​
.org/10.1016/​j.earscirev.2011.09.004.
Partin, C.A., et al., 2013, Large-scale fluctuations in
Precambrian atmospheric and oceanic oxygen
levels from the record of U in shales: Earth and
Planetary Science Letters, v. 369–370, p. 284–
293, https://doi​.org/10.1016/​j.epsl.2013.03.031.
Paytan, A., and Griffith, E.M., 2007, Marine barite:
Recorder of variations in ocean export productiv-
ity: Deep-Sea Research: Part II, Topical Studies
in Oceanography, v. 54, p. 687–705, https://doi​
.org/10.1016/​j.dsr2.2007.01.007.
Planavsky, N.J., Bekker, A., Hofmann, A., Owens,
J.D., and Lyons, T.W., 2012, Sulfur record of ris-
ing and falling marine oxygen and sulfate lev-
els during the Lomagundi event: Proceedings of
the National Academy of Sciences of the United
States of America, v. 109, p. 18,300–18,305,
https://doi​.org/10.1073/pnas.1120387109.
Planavsky, N.J., Reinhard, C.T., Wang, X., Thomson,
D., McGoldrick, P., Rainbird, R.H., Johnson, T.,
Fischer, W.W., and Lyons, T.W., 2014, Low mid-
Proterozoic atmospheric oxygen levels and the
delayed rise of animals: Science, v. 346, p. 635–
638, https://doi​.org/10.1126/science.1258410.
Poulton, S.W., Fralick, P.W., and Canfield, D.E., 2004,
The transition to a sulphidic ocean ∼1.84 billion
Geological Society of America | GEOLOGY | Volume 49 | Number 9 | www.gsapubs.org
Downloaded from http://pubs.geoscienceworld.org/gsa/geology/article-pdf/49/9/1059/5387113/g48825.1.pdf
by Southern University of Science and Technology of China user
years ago: Nature, v. 431, p. 173–177, https://doi​
.org/10.1038/nature02912.
Reinhard, C.T., Planavsky, N.J., Robbins, L.J., Partin,
C.A., Gill, B.C., Lalonde, S.V., Bekker, A., Kon-
hauser, K.O., and Lyons, T.W., 2013, Proterozoic
ocean redox and biogeochemical stasis: Proceed-
ings of the National Academy of Sciences of the
United States of America, v. 110, p. 5357–5362,
https://doi​.org/10.1073/pnas.1208622110.
Robbins, L.J., et al., 2016, Trace elements at the intersec-
tion of marine biological and geochemical evolu-
tion: Earth-Science Reviews, v. 163, p. 323–348,
https://doi​.org/10.1016/​j.earscirev.2016.10.013.
Rudnick, R.L., and Gao, S., 2014, Composition of the
continental crust, in Rudnick, R.L., ed., Treatise
on Geochemistry (second edition), Volume 4: The
Crust: Amsterdam, Elsevier Science, p. 1–51,
https://doi​ . org/10.1016/B978-0-08-095975-
7.00301-6.
Schoepfer, S.D., Shen, J., Wei, H., Tyson, R.V., Ingall,
E., and Algeo, T.J., 2015, Total organic carbon,
organic phosphorus, and biogenic barium fluxes
as proxies for paleomarine productivity: Earth-
Science Reviews, v. 149, p. 23–52, https://doi​
.org/10.1016/​j.earscirev.2014.08.017.
Scott, C., Lyons, T.W., Bekker, A., Shen, Y., Poul-
ton, S.W., Chu, X., and Anbar, A.D., 2008, Trac-
ing the stepwise oxygenation of the Proterozoic
ocean: Nature, v. 452, p. 456–459, https://doi​
.org/10.1038/nature06811.
Sheen, A.I., Kendall, B., Reinhard, C.T., Creaser, R.A.,
Lyons, T.W., Bekker, A., Poulton, S.W., and An-
bar, A.D., 2018, A model for the oceanic mass
balance of rhenium and implications for the ex-
tent of Proterozoic ocean anoxia: Geochimica et
Cosmochimica Acta, v. 227, p. 75–95, https://doi​
.org/10.1016/​j.gca.2018.01.036.
Torres, M.E., Brumsack, H.J., Bohrmann, G., and
Emeis, K.C., 1996, Barite fronts in continental
margin sediments: A new look at barium remo-
bilization in the zone of sulfate reduction and
formation of heavy barites in diagenetic fronts:
Chemical Geology, v. 127, p. 125–139, https://
doi​.org/10.1016/0009-2541(95)00090-9.
Tostevin, R., and Mills, B.J.W., 2020, Reconciling
proxy records and models of Earth’s oxygen-
ation during the Neoproterozoic and Palaeozo-
ic: Interface Focus, v. 10, 20190137, https://doi​
.org/10.1098/rsfs.2019.0137.
Wei, W., and Algeo, T.J., 2020, Secular variation in
the elemental composition of marine shales since
840 Ma: Tectonic and seawater influences: Geo-
chimica et Cosmochimica Acta, v. 287, p. 367–
390, https://doi​.org/10.1016/​j.gca.2020.01.033.
Printed in USA
1063