Introduction
Planetary differentiation has led to two fundamental types of crust on Earth: (1) continental, which tend
to survive over long periods acquiring ancient rock records and evolved compositions; and (2) oceanic,
which tend to be juvenile and rapidly recycled by subduction (Campbell and Taylor, 1983). According to
standard models, continental crust is primarily formed by fluid flux melting in the mantle wedge above
subducting hydrated oceanic plates as they are recycled into the mantle. This is then followed by
fractional crystallization of mantle-derived magmas and/or partial melting of preexisting crustal
lithologies (Hawkesworth and Kemp, 2006; Moyen et al., 2021). Collectively, these “distillation”
processes have led to the development of a more felsic crust with a significant enrichment of
incompatible elements, such as rubidium and strontium, with respect to the mantle as Earth has aged
(Veizer, 1989; McDermott and Hawkesworth, 1990). However, the questions of how the continental crust has
evolved chemically over time and how it has influenced Earth’s oceans and atmosphere remain as
fundamental unresolved problems.
Earth’s present oceans have a uniform Sr isotopic composition (87Sr/86Sr = 0.7092)
that primarily reflects the balance between radiogenic Sr input from weathering of the continents and
unradiogenic Sr input from hydrothermal alteration of oceanic crust (Veizer and Mackenzie, 2014).
Although 87Sr/86Sr ratios in marine carbonates are better documented for
Phanerozoic versus Precambrian marine limestones, oceanic 87Sr/86Sr ratios appear
to have departed from mantle values as early as ca. 2.8 Ga (Shields and Veizer, 2002) (Fig. 1A). This
transition has been interpreted to mark a change from mantle- to river-buffered oceans as the continents
rose and hydrothermal circulation of oceanic crust decreased as heat dissipated from Earth with time
(Veizer and Mackenzie, 2014). 87Sr/86Sr ratios have subsequently risen in
association with the differentiation of the crust, with rapid increases during two principal intervals
in the Precambrian, namely in the Paleoproterozoic and Neoproterozoic (Shields and Veizer, 2002) (Fig.
1A). Identifying potential drivers for these shifts in marine 87Sr/86Sr ratios
during the Precambrian is of widespread interest because of possible links to major perturbations in the
global carbon cycle and hypothetical connections to changes in tectonism, climate, and
atmospheric-oceanic oxygenation (Shields, 2007; Campbell and Allen, 2008; Sobolev and Brown, 2019).
Figure
1
(A)
87Sr/
86Sr evolution of seawater from marine limestones and fossils with
respect to the mantle contribution (Shields and Veizer, 2002). Red data points are poorly constrained in
age (greater than ± 50 Ma). (B) Normalized marine
87Sr/
86Sr evolution from Shields
(2007) with respect to kernel density estimate plot and histogram (Vermeesch, 2012) of cumulative U-Pb
age data (
n = 24,190) for the global compilation of detrital zircons analyzed in this study.
Emergence of paired high dT/dP-intermediate dT/dP metamorphism and widespread ultrahigh-pressure (UHP)
and blueschist metamorphism (cold subduction) from Brown and Johnson (2018), and Wilson cycle onset from
Shirey and Richardson (2011).
The average Sr isotopic composition of the present oceanic crust is relatively uniform (~0.703), but the
Sr isotopic composition of today’s continental crust (~0.73 on average) is spatially highly variable
(~0.703 to >0.73) due to a heterogeneous rock record that includes juvenile and ancient, evolved
crustal components (Veizer and Mackenzie, 2014). The average Sr isotopic composition of today’s rivers
(~0.711) reflects a balance of the weathering of such sources on a global scale (Veizer and Mackenzie,
2014), but the dynamic nature of the solid Earth has likely led to changes in the proportion of
radiogenic rocks being weathered on Earth’s surface over time. This notion is supported by recent
analyses of a global detrital zircon database, which have led to the conclusion that, at least for the
past 1.0 Ga, increases in the 87Sr/86Sr ratios recorded in marine limestones
generally coincide with decreases in the εHf composition of zircons produced by increased
magmatic reworking of preexisting radiogenic crust (Bataille et al., 2017). Decreases in zircon
εHf have been found to correlate with increases in whole-rock 87Sr/86Sr
ratios (Bataille et al., 2017). Increases in oceanic 87Sr/86Sr ratios have,
therefore, been linked to the production, and weathering, of extensive felsic igneous rocks along
convergent margins involving subduction or collisions (Bataille et al., 2017). A plausible causal link
exists because such rocks tend to be eroded rapidly due to their high elevations above sea level in
proximity to oceans (Milliman and Syvitski, 1992).
Increases in the 87Sr/86Sr ratios recorded in marine limestones have recently been
shown to correlate with changes in zircon trace element ratios indicative of increased crustal reworking
and thickness recorded in Neoproterozoic to Triassic sandstones from Antarctica (Paulsen et al., 2020).
Increases in crustal thickness lead to increases in continental elevation (mountain building), which has
in turn been associated with increased Sr runoff into Earth’s oceans (Edmond, 1992; Richter et al.,
1992; Raymo and Ruddiman, 1992; Shields, 2007). Therefore, the record of increases in crustal
assimilation and thickness from Antarctica may point to significant, punctuated releases of Sr from the
continental reservoir. This represents a potentially important suite of coupled processes operating
outside of the steady-state, and hence warrants investigation on a global scale.
This study integrates detrital zircon U-Pb age and trace element proxies for an exceptionally large
global detrital zircon data set (n = 24,206) from samples derived from Earth’s major
continental landmasses to develop a better understanding of the petrotectonic evolution of continental
crust through time and its potential link to the 87Sr/86Sr evolution of Earth’s
oceans (see Supplemental Material1 for data, sources, and methods). The cumulative zircon age
distribution binned in 0.1-Gyr age intervals in Figure 1B shows a series of age peaks similar to other
global U-Pb detrital zircon age data sets (Campbell and Allen, 2008). The majority of zircons in this
data set (Th/U >0.1) are expected to be derived from felsic igneous rocks formed along convergent
margins, which represent the primary source for zircons within the geologic record (Lee and Bachmann,
2014).
Patterns of Crustal Reworking
Thorium is an incompatible element that becomes enriched relative to other elements as continental crust
matures (McLennan and Taylor, 1980). Therefore, increases in Th/Yb ratios in zircon should correlate
with increases in the production of evolved felsic rocks associated with magmatic recycling of older
radiogenic crust (Barth et al., 2013). Monte Carlo bootstrap resampling of the trace element record (to
minimize the effect of sampling bias presented by zircon age peaks) shows that increased Th/Yb ratios
are generally associated with two principal periods in the Precambrian since 3.0 Ga (Fig. 2A). The
results suggest a higher proportion of magmas characterized by increased assimilation of radiogenic
crust at 2.5–1.9 Ga and 0.7–0.5 Ga. Igneous zircon Th contents may be influenced by the presence of rare
accessory phases (e.g., allanite) that compete to incorporate Th during crystallization (Kirkland et
al., 2015). However, this pattern is also recognized on a global scale in the zircon Hf isotope record,
the isotopic value of which is primarily controlled by the amount of crustal recycling in magmas.
εHf-age values from a separate large detrital zircon data set (n = 70,656) show that
significant negative deviations of εHf values correlate with these Th/Yb peaks (Fig. 2B). The
87Sr/86Sr isotope curve shown in Figures 2A–2B, which is normalized to model
87Sr/86Sr ratios of the global river and mantle inputs, shows increases that
post-date the peaks in crustal assimilation indicated by zircon Th/Yb and εHf values—a time
lag that may in part reflect processes such as weathering and erosion. The zircon trace element data
are, therefore, consistent with the hypothesis that increases in the proportion of evolved magmas along
convergent margins have had an important influence on radiogenic Sr input into Earth’s oceans during
these time intervals.
Figure
2
(A) Average Th/Yb (crustal input proxy); (B)
εHf (crustal input proxy; note axis reversal);
and (C) Yb/Gd (crustal thickness proxy) with their 95% confidence envelopes determined by Monte Carlo
bootstrap resampling of zircons in 0.1-Gyr time brackets compared to normalized marine
87Sr/
86Sr evolution.
εHf data from Puetz and Condie (2019). Age of
“boring billion” from Holland (2006). UHP—ultrahigh-pressure.
Patterns of Crustal Thickening
Increases in magmatic reworking of preexisting radiogenic crust should occur associated with thermal
maximums as the crust thickens (DeCelles et al., 2009). Garnet is a mineral found in crustal magmas that
is highly sensitive to pressure and incorporates heavy rare earth element (HREE)+Yb relative to other
trace elements (Ducea et al., 2015). Therefore, changes in Yb/Gd ratios in zircon, for example, are
thought to correlate with changes in the crustal thickness during magmatism (Barth et al., 2013). The
trace element record retained within the zircon data shows that the lowest Yb/Gd ratios in the data set
(Fig. 2C) correlate well with the Paleoproterozoic and Neoproterozoic Th/Yb and εHf peaks.
These crustal thickness patterns are similar to those presented recently based on La/Yb ratios for a
global compilation of 5587 detrital zircons (Balica et al., 2020). In particular, both analyses show
Paleoproterozoic and Neoproterozoic peaks in crustal thickness that are separated by an intervening
interval from ca. 1.8 Ga to 0.8 Ga during a period of environmental stasis known as the “boring billion”
(Holland, 2006). The trace element data are therefore consistent with increased assimilation of
radiogenic crust during periods of increased crustal thickness along convergent margins. Increases in
crustal thickness are in turn associated with mountain building driven by tectonic shortening along
Earth’s major convergent plate boundaries involving advancing states of subduction and collisions. Thus,
the patterns in the zircon trace element data are also consistent with the hypothesis that increases in
the proportion of radiogenic rocks (e.g., older basement) uplifted and exposed along convergent margins
have had an important influence on radiogenic Sr input into Earth’s oceans (Richter et al., 1992).
Crustal Thickness and Sr Flux
Geologists have long recognized that the widespread generation of continental topographic relief, which
increases the overall surface area and potential energy, should correlate with increases in sedimentary
flux into Earth’s oceans. Analysis of Phanerozoic sedimentary rock records suggests that increasing
sedimentary flux correlates with increases in 87Sr/86Sr ratios in marine
limestones (Hay et al., 2001). Detrital zircon age peaks have been attributed to increases in
sedimentary flux associated with widespread continental collisions and convergent margin magmatism
(Campbell and Allen, 2008; McKenzie et al., 2016). However, other authors have favored increases in
preservation for these age peaks (Hawkesworth et al., 2009), and zircon abundance does not always
correlate with increases in 87Sr/86Sr ratios in Earth’s oceans over time (Fig.
1B).
Increases in sedimentary flux derived from weathering of a greater proportion of elevated continental
crust should, however, occur associated with an increase in flysch deposition. Flysch successions
include interbedded graywackes and shales rich in quartz and feldspars, which, when water-saturated, are
fertile sources for the generation of S-type granites (Collins and Richards, 2008; Zhu et al., 2020).
Thus, S-type granite production may serve as a proxy for previous intervals of increased flysch
deposition. We identified zircons that are likely to have been derived from S-type granite using the
trace element discrimination procedure of Zhu et al. (2020), wherein S-type granites typically have
elevated phosphorus concentrations relative to I-type granites because apatite
[Ca5(PO4)3(OH,F,Cl)] crystallization is suppressed in the S-type
magmas. To test the hypothesis that the peaks in crustal thickness were associated with an increase in
S-type granites, we integrated S-type zircons identified within our data set with those found through an
examination of zircons from 52 of Earth’s major rivers (Zhu et al., 2020). Peaks in S-type zircon
percentages overlap or even postdate the latter stage of increases in crustal thickness identified here
(Fig. 3A). Thus, increasing radiogenic Sr input into Earth’s oceans appears to be related to (1) the
weathering of a greater proportion of radiogenic rocks produced and exposed as the crust thickened
during the Paleoproterozoic and Neoproterozoic time intervals, and (2) concomitant increases in
continental weathering and sedimentary flux into the oceans.
Figure
3
(A) Average Yb/Gd (crustal thickness proxy) compared to the percentage of S-type zircons with its 95%
confidence envelope. (B) Th/Yb (crustal input proxy) compared to a global compilation of ages versus
temperature/pressure (
T/P) (°C/GPa) of high dT/dP (granulite−ultrahigh temperature [UHP])
(red); intermediate dT/dP (eclogite−high-pressure granulite) (purple); and low dT/dP (high-pressure−UHP)
metamorphism (blue) from Brown and Johnson (2018). (C) U/Yb (crustal input and fluid input proxy)
compared to a global compilation of passive margin abundance from Bradley (2008). Tenure of
supercontinent/cratons from Bradley (2011), increases in atmospheric oxygen, early “whiffs” of oxygen
(green arrows) and intervening boring billion from Holland (2006) and Lyons et al. (2014), and snowball
Earth glaciations adapted from Sobolev and Brown (2019). Supercontinent/craton abbreviations: K—Kenor;
Su—Superia; Sc—Sclavia; N—Nuna; R—Rodina; G—Gondwana; P—Pangea. NOE—Neoproterozoic oxygenation event;
GOE—Great oxygenation event.
The results reviewed above provide important confirmation that increases in Sr recorded in marine
carbonates correlate with first-order changes in convergent margin tectonism over time (Bataille et al.,
2017; Gernon et al., 2021). Increasing 87Sr/86Sr ratios in Cenozoic marine
limestones have been associated with decreases in unradiogenic Sr flux related to lower seafloor
spreading rates (Van Der Meer et al., 2014) and cooler ocean temperatures (Coogan and Dosso, 2015),
suggesting that the cause of increased 87Sr/86Sr ratios in the oceans may be
multifactorial. The ancient ocean crust record is in large part lost due to subduction (Scholl and von
Huene, 2009), but our results suggest that increases in 87Sr/86Sr ratios in oceans
have been strongly influenced by a continental component. If the increases in the proportion of
radiogenic sources and sedimentary flux represent a coupled suite of processes as we contend, then they
raise the question as to why convergent margin tectonism changed during these time periods. Insight into
this issue comes from an examination of modeling and other proxy data sets to which we now turn.
Supercontinent Patterns and Sr Flux
Modeling studies suggest that supercontinent tenures should be marked by elevated temperatures in the
underlying subcontinental mantle with convergent margins in retreating states with arcs on thinner crust
in outboard locations with respect to the continents (Lenardic et al., 2011; Lee et al., 2013; Lenardic,
2016). Temporal considerations based on multiple proxy data sets suggest that the lows in crustal
recycling and thickness identified in the zircon proxy data overlap with the tenure of supercontinents
over Earth’s history (Figs. 3A–3B) (Bradley, 2011). For example, the low in crustal recycling and
thickness during the boring billion correlates with the tenure of Nuna during a period dominated by high
dT/dP metamorphism (Fig. 3B) and higher thermal gradients (Brown and Johnson, 2018). This pattern may
reflect supercontinent insulation of the mantle (Brown and Johnson, 2018) associated with the
development of hot back-arc environments (Hyndman et al., 2005) and a greater proportion of convergent
margins in retreating states with arcs on thinner crust in outboard localities (Roberts, 2013; Paulsen
et al., 2020; Tang et al., 2021).
Supercontinent break-up, by contrast, should lead to a release of potential energy stored in the
underlying mantle (Lenardic, 2016). Thermal release of the mantle induces changes in the geodynamic
state of the leading edge of continents by driving them into advancing compressional states of
subduction and collisions involving arcs and continental blocks that favor crustal thickening (Lee et
al., 2013). Increases in crustal recycling and thickness identified in the zircon proxy data correlate
with an increase in passive margin abundance (Bradley, 2008) (Fig. 3C). These increases around the
Proterozoic-Phanerozoic time interval also correlate with a decrease in thermal gradients of high dT/dP
metamorphism (Brown and Johnson, 2018). Collectively, these patterns are consistent with supercontinent
break-up driving a greater proportion of convergent margins into compressional advancing states and
collisions with magmatism in thicker crust. High 87Sr/86Sr ratios in oceans during
these periods are presumably due to increases in the proportion of exposed radiogenic sources and
sedimentary flux from the continents associated with a reorganization of riverine drainage networks.
The correlations between the zircon proxy data and processes involving subduction outlined above warrants
an examination of the U/Yb ratio in the zircon data set. The U/Yb ratio in zircon has been used as a
proxy for crustal reworking (Verdel et al., 2021) but may also reflect the amount of subducting slab
fluid addition in magmas, because U is a fluid-mobile large-ion lithophile element (LILE; K, Sr, Rb, Cs,
Ba, Pb, U) extracted from slabs, and is, therefore, enriched relative to HREE such as Yb (Barth et al.,
2013). U/Yb increases correlate with the increases in crustal assimilation and thickness we have
identified (Fig. 3C), consistent with a higher amount of crustal recycling and flux of subduction fluid
along a greater proportion of convergent margins during these periods. We, therefore, conclude that the
increases in riverine Sr input into Earth’s oceans were related to geodynamic changes in convergent
margin networks, which were required to accommodate the birth and maturation of new ocean basins created
by supercontinent break-up and dispersal. These episodes were associated with increased weathering and
erosion of radiogenic rocks along convergent margins and greater expanses of uplifted, higher-elevation
radiogenic crust found along the leading edges of continents. Increases in riverine Sr were likely
amplified by the exhumation of continental crust associated with rifting (DeLucia et al., 2018), which
is consistent with the general thesis supported here, that increases in riverine Sr are primarily driven
by tectonism induced by global changes in plate margin networks. Increasing
87Sr/86Sr compositions in Cenozoic marine sediments have also been associated with
glaciation (Palmer and Elderfield, 1985). Snowball Earth deglaciation likely contributed to the
Paleoproterozoic and Neoproterozoic Sr excursions (Sobolev and Brown, 2019), but the data reviewed here
suggest that tectonism played a major role. Collectively, the balance of these processes is likely
recorded in today’s continental rock record by the great unconformities at the Precambrian-Phanerozoic
and Archean-Proterozoic boundaries (Windley, 1984; Peters and Gaines, 2012).
Broader Implications
Our results suggest that increases in 87Sr/86Sr ratios in oceans occur when a
greater proportion of continental crust is thick and high, leading to increases in evolved felsic
magmatism, radiogenic basement exposure, and riverine sedimentary flux. From a broader perspective, the
results raise the important question of whether solid Earth processes play a fundamental role in
modulating global climate and atmospheric oxygenation over geologic time scales. If the correlations
outlined above are representative of a global tectonic pattern as we contend, then the generation of
continental relief highlights the introduction of a significant silicate weathering sink associated with
the drawdown of CO2 and associated transition into periods of global glaciation (Hoffman and
Schrag, 2002) (Fig. 3). Uplift associated with convergent margin tectonism may therefore have further
enhanced CO2 drawdown associated with the exhumation and weathering of rocks associated with
continental rifting and dispersal (Donnadieu et al., 2004; DeLucia et al., 2018). Continental uplift has
also been previously postulated to be linked to steps in oxygenation of Earth’s atmosphere during the
Paleoproterozoic and Neoproterozoic through enhanced erosion and nutrient supply to the oceans, as well
as changes in the proportion of subaerial volcanism (Campbell and Allen, 2008; Gaillard et al., 2011)
(Fig. 3B). Oxygenation may have fostered the decrease of CH4, a potent greenhouse gas
(Fakhraee et al., 2019), while uplifts along convergent margins promoted nascent glaciation in cooler,
high-elevation habitats, providing further feedback (albedo) for a runaway global glaciation. The
ultimate drivers for these important steps in Earth’s evolution are controversial and likely involved a
complex set of variables and inextricably linked feedbacks. However, in general terms, potential links
between the solid Earth and the evolution of its climate, atmosphere, and oceans are highlighted by
recent modeling that suggests that global climate may ultimately be modulated by changes in outgassing
and weathering sinks associated with mantle thermal states during the assembly and break-up of
supercontinents (Jellinek et al., 2020). While the oceans have played a fundamental role in the
geochemical evolution of the continents (Campbell and Taylor, 1983), the continents have, in turn,
shaped the oceans and perhaps major evolutionary steps in Earth’s global climate and the oxygenation of
its ocean-atmosphere system.
Acknowledgments
We thank Jay Chapman and two anonymous reviewers for comments that improved this manuscript. This work
was supported by the Faculty Development Program at the University of Wisconsin, Oshkosh.
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