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Ocean acidification may have severe consequences for marine ecosystems; however, assessing its future impact is difficult because laboratory experiments and field observations are limited by their reduced ecologic complexity and sample period, respectively. In contrast, the geological record contains long-term evidence for a variety of global environmental perturbations, including ocean acidification plus their associated biotic responses. We review events exhibiting evidence for elevated atmospheric CO2, global warming, and ocean acidification over the past ~300 million years of Earth’s history, some with contemporaneous extinction or evolutionary turnover among marine calcifiers. Although similarities exist, no past event perfectly parallels future projections in terms of disrupting the balance of ocean carbonate chemistry—a consequence of the unprecedented rapidity of CO2 release currently taking place.
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DOI: 10.1126/science.1208277
, 1058 (2012);335 Science et al.Bärbel Hönisch
The Geological Record of Ocean Acidification
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The Geological Record of
Ocean Acidification
rbel Hönisch,
*Andy Ridgwell,
Daniela N. Schmidt,
Ellen Thomas,
Samantha J. Gibbs,
Appy Sluijs,
Richard Zeebe,
Lee Kump,
Rowan C. Martindale,
Sarah E. Greene,
Wolfgang Kiessling,
Justin Ries,
James C. Zachos,
Dana L. Royer,
Stephen Barker,
Thomas M. Marchitto Jr.,
Ryan Moyer,
Carles Pelejero,
Patrizia Ziveri,
Gavin L. Foster,
Branwen Williams
Ocean acidification may have severe consequences for marine ecosystems; however, assessing
its future impact is difficult because laboratory experiments and field observations are limited by
their reduced ecologic complexity and sample period, respectively. In contrast, the geological
record contains long-term evidence for a variety of global environmental perturbations, including
ocean acidification plus their associated biotic responses. We review events exhibiting evidence
for elevated atmospheric CO
, global warming, and ocean acidification over the past ~300 million
years of Earths history, some with contemporaneous extinction or evolutionary turnover among
marine calcifiers. Although similarities exist, no past event perfectly parallels future projections
in terms of disrupting the balance of ocean carbonate chemistrya consequence of the
unprecedented rapidity of CO
release currently taking place.
The geological record is imprinted with nu-
merous examples of biotic responses to
natural perturbations in global carbon cy-
cling and climate change (Fig. 1), some of which
could have been caused by large-scale ocean
acidification. By reconstructing past changes in
marine environmental conditions, we can test hy-
potheses for the causes and effects of future-
relevant stressors such as ocean acidification on
ecosystems (1). However, for the fossil record to
be of direct utility in assessing future ecosystem
impacts, the occurrence and extent of past ocean
acidification must be unambiguously identified.
In recent years, a variety of trace-element and
isotopic tools have become available that can be
applied to infer past seawater carbonate chemis-
try. For instance, the boron isotopic composition
B) of marine carbonates reflects changes in
seawater pH, the trace element (such as B, U, and
Zn)to-calcium ratio of benthic and planktic for-
aminifer shells records ambient [CO
], and the
stable carbon isotopic composition (d
C) of or-
ganic molecules (alkenones) can be used to es-
timate surface ocean aqueous [CO
Because direct ocean geochemical proxy
observations are still relatively scarce, past ocean
acidification is often inferred from a decrease in
the accumulation and preservation of CaCO
marine sediments, potentially indicated by an in-
creased degree of fragmentation of foraminiferal
shells (3). However, it is difficult to distinguish
between the original calcification responses to
chemical changes in the surface ocean and post-
mortem conditions at the sea floor. For instance,
planktic calcifiers may secrete heavier or lighter
shells (4), but that signal may be modified at the
sea floor through dissolution or overgrowth after
deposition (5,6). This duality can introduce con-
troversy over the identification of causes and
effects, the drivers of biological change, and
Lamont-Doherty Earth Observatory of Columbia University,
Palisades, NY 10964, USA.
School of Geographical Sciences,
University of Bristol, Bristol BS8 1SS, UK.
School of Earth
ment of Geology and Geophysics, Yale University, New Haven,
CT 06520, USA.
Department of Earth and Environmental
Sciences, Wesleyan University, Middletown, CT 06459, USA.
Ocean and Earth Science, National Oceanography Centre
Southampton, University of Southampton, Southampton SO14
3ZH, UK.
Department of Earth Sciences, Utrecht University,
3584 CD Utrecht, Netherlands.
School of Ocean and Earth
Science and Technology, Department of Oceanography, Uni-
versity of Hawaii at Manoa, Honolulu, HI 96822, USA.
ment of Geosciences, Pennsylvania State University, University
Park, PA 16802, USA.
Department of Earth Sciences, Uni-
versity of Southern California (USC), Los Angeles, CA 90089,
Museum für Naturkunde at Humboldt University, 10115
Berlin, Germany.
Department of Marine Sciences, University
of North CarolinaChapel Hill, NC 27599, USA.
Earth and
Planetary Sciences Department, University of California Santa
Cruz, CA 95064, USA.
School of Earth and Ocean Sciences,
Cardiff University, Cardiff CF10 3AT, UK.
Department of Geo-
logical Sciences and Institute of Arctic and Alpine Research,
University of Colorado, Boulder, CO 80309, USA.
University of
South Florida St. Petersburg, Department of Environmental
Science, Policy, and Geography, St. Petersburg, FL 33701, USA.
Institució Catalana de Recerca i Estudis Avançats and Depart-
ment of Marine Biology and Oceanography, Consejo Superior
de Investigaciones Científicas, 08003 Barcelona, Catalonia, Spain.
Institute of Environmental Science and Technology, Universitat
Autònoma de Barcelona, 01893 Barcelona, Spain.
ment of Earth Sciences, Vrije Universiteit, 1081HV Amsterdam,
W. M. Keck Science Department of Claremont
McKenna College, Pitzer College, and Scripps College, Claremont,
CA 91711, USA.
*To whom correspondence should be addressed. E-mail:
Deglaciation PETM Toarcian
asteroid impact
mass extinction
mass extinction
0 100 Time (My) 200 300
Shallow reef
Fig. 1. Idealized diversity trajectories of the calcareous and organic fossil lineages discussed in the text.
Extinction and radiation suggest events of major environmental change throughout the past 300 My.
Calcareous plankton is shown in black, calcareous benthos in blue, and organic fossils in green, and the
line thickness indicates relative and smoothed species richness. Highlighted events (vertical red lines)
have been associated with potential ocean acidification events (Fig. 4). Calcareous organisms were not
uniformly affected at all times, suggesting the importance of synergistic environmental factors to ex-
tinction, adaptation, and evolution as well as different sensitivity due to physiological factors. Iden-
tification of a paleo-ocean acidification event therefore requires independent geochemical evidence
for ocean chemistry changes. Images of organisms are exemplary. References and further information
on the displayed organisms are available in the supporting online material.
on November 19, 2012www.sciencemag.orgDownloaded from
whether past intervals of ocean acidification
are characterized by environmental conditions
relevant for the near future. Coeval changes in
ocean circulation will also introduce regional
biases in proxy records and hence affect global
Here, we review the factors controlling ocean
acidification, describe evidence for the occurrence
of ocean acidification events in the past, and dis-
cuss the potential as well as weaknesses of the
geological record in helping us predict future eco-
system changes.
Is Ocean Acidification Primarily a
pH-Decline Phenomenon?
The current rate of anthropogenic CO
leads to a surface ocean environment charac-
terized not only by elevated dissolved CO
decreased pH (7) but, critically, decreased satura-
tion with respect to calcium carbonate (CaCO
a compound widely used by marine organisms
for the construction of their shells and skeletons
(8). In contrast, slower rates of CO
release lead
to a different balance of carbonate chemistry
changes and a smaller seawater CaCO
response, which may induce differential biotic
response or even no response at all, invalidating a
direct analog. The reason for a smaller saturation
response to slow CO
release is that the alkalinity
released by rock weathering on land must ulti-
mately be balanced by the preservation and burial
of CaCO
in marine sediments (Fig. 2), which
itself is controlled by the calcium carbonate sat-
uration state of the ocean (9). Hence, CaCO
saturation is ultimately regulated primarily by
weathering on long time scales, not atmospheric
partial pressure of CO
). While weathering
itself is related to atmospheric PCO
(10), it is
related much more weakly than ocean pH, which
allows pH and CaCO
saturation to be almost
completely decoupled for slowly increasing at-
mospheric PCO
Using a global carbon cycle model (2), we
show the progressive coupling between CaCO
saturation and pH as the rate of CO
increases and sources (weathering) and sinks
burial) of alkalinity are no longer ba-
lanced. For rapid century-scale and thus future-
relevant increases in atmospheric PCO
, both
surface ocean pH and saturation state decline in
tandem (Fig. 3). The projected decrease in ocean
surface saturation statehere, with respect to
aragonite (W
)is an order of magnitude
larger for a rapid CO
increase than for a slow
[100 thousand years (ky)] CO
increase. Ulti-
mately, saturation recovers while the pH remains
suppressed, reflecting how changes in the oce-
anic concentrations of dissolved inorganic carbon
(DIC) and alkalinity make it possible to have
simultaneously both high CO
and high carbon-
ate ion concentration saturation ([CO
], which
controls saturation), but with the relatively greater
increase in [CO
] causing lower pH. The key to
unlocking the geological record of ocean acid-
ification is hence to distinguish between long-
term steady states and transient changes. We use
the term ocean acidification eventfor time in-
tervals in Earths history that involve both a re-
duction in ocean pH and a substantial lowering
of CaCO
saturation, implying a time scale on
the order of 10,000 years and shorter (Fig. 3).
Indications of Paleo-Ocean Acidification
With these criteria in mind, we review (in reverse
chronological order) the intervals in Earthshistory
for which ocean acidification has been hypothe-
sized, along with the evidence for independent
geochemical and biotic changes. We confine this
review to the past ~300 million years (My) be-
cause the earlier Phanerozoic (and beyond) lacks
the pelagic calcifiers that not only provide key
proxy information but also create the strong deep-
sea carbonate (and hence atmospheric PCO
) buf-
fer that characterizes the modern Earth system
(9). Our criteria for identifying potentially future-
relevant past ocean acidification are (i) massive
release, (ii) pH decline, and (iii) saturation
decline. We also discuss evidence for the time
scale of CO
release, as well as for global warming.
Events are given a similarity index that is based
on available geochemical data (table S1) and are
indicated in Fig. 4A.
Late Pleistocene deglacial transitions. The
last deglaciation is the best documented past event
associated with a substantive (30%) CO
189 to 265 matm between 17.8 to 11.6 ky before
+ H2OH
++ HCO3
Atmosphere [850]
Ocean [38000]
biosphere [2000]
Fossil fuel CO2 emissions (8.5)
Emissions from land use change (1.0)
CO2 uptake (2.0)
Net CO2 dissolution (2.3)
Net CO2 fixation (10)
CaCO3 dissolution (0.6)
water column
CaCO3 dissolution (0.4)
sea floor
Shallow water
Corg burial (0.1)
Shallow water
CaC O3 burial (0.1)
Low temperature basaltic alteration
Carbonate (0.1)
Kerogen (0.1)
Calcification (1.1)
Deep sea
CaCO3 burial (0.1)
Corg oxidation (9.9)
Corg oxidation (0.1)
Reservoir inventory
values [PgC]
Processes leading to
ocean acidification
and/or reduction of
CaCO3 saturation and
their approximate
fluxes (PgC yr-1)
Processes leading to
ocean alkalinization
and/or CaCO3
and their approximate
fluxes (PgC yr-1)
Surface sediments
Fossil fuels . . . . . .
Shales . . . . . . . . . . . . .
Mantle . . . . . . . . . . . . .
Carbonate rocks . . . .
Fig. 2. When CO
dissolves in seawater, it reacts with water to form carbonic
acid, which then dissociates to bicarbonate, carbonate, and hydrogen ions. The
higher concentration of hydrogen ions makes seawater acidic, but this process
is buffered on long time scales by the interplay of seawater, seafloor carbonate
sediments, and weathering on land. Shown are the major pathways of reduced
carbon (black) and of alkalinity (yellow). Processes leading to ocean acid-
ification and/or reduction of CaCO
saturation are indicated in red, and pro-
cesses leading to ocean alkalinization and/or CaCO
saturation increases are
indicated in blue. Anthropogenic perturbations are marked in italics. Ap-
proximate fluxes are printed in parentheses (PgC year
), whereas reservoir
inventory values are shown in brackets [PgC]. Natural carbon cycle fluxes are
from (70); anthropogenic fluxes for 2008 are from (57), which for the land
sink is significantly above its 19902000 average of 2.6 PgC year
due to the
2008 La Niña state (8). SCIENCE VOL 335 2 MARCH 2012 1059
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the present (B.P.) (11). Boron isotope estimates
from planktic foraminifers show a 0.15 T0.05
unit decrease in sea surface pH (12) across the
deglacial transitionan average rate of decline
of ~0.002 units per 100 years compared with the
current rate of more than 0.1 units per 100 years
(table S1). Planktic foraminiferal shell weights
decreased by 40 to 50% (4), and coccolith mass
decreased by ~25% (13). In the deep ocean,
changes in carbonate preserva-
tion (14), pH [from foraminiferal
B(15)] and [CO
foraminiferal B/Ca and Zn/Ca
(16,17)] differed between ocean
basins, reflecting covarying
changes in deep-water circula-
tion and an internal carbon shift
within the ocean. The regional
nature of these variations high-
lights the general need for careful
evaluation of regional versus glob-
al effects in paleo-studies.
OligocenePliocene. The cli-
mate of the Oligocene to Plio-
cene [34 to 2.6 million years ago
(Ma)] contains intervals of ele-
vated temperature and modest
deviations of atmospheric PCO
from modern values (Fig. 4). Of
particular interest has been the
Pliocene warm period [3.29 to
2.97 Ma (18,19)], which is char-
acterized by global surface tem-
peratures estimated to be ~2.5°C
higher than today (19), atmospher-
ic PCO
between 330 to 400 matm
(Fig. 4C) (18,20), and sea surface
~0.06 to 0.11 units lower
(18) than the preindustrial. Eco-
logical responses to the warming
include migration of tropical for-
aminifer species toward the poles
(21), but there are no documented
calcification responses or increased
nannoplankton extinction rates
(22). The early to middle Miocene
(23 to 11 Ma) and Oligocene (34
to 23 Ma) were also character-
ized periods of elevated temper-
atures and slightly higher PCO
compared with preindustrial val-
ues (Fig. 4C) but, because of their
long duration, were not associ-
ated with changes in CaCO
uration (Fig. 3C).
PaleoceneEocene. Evidence
for rapid carbon injection asso-
ciated with the PaleoceneEocene
Thermal Maximum (PETM, 56
Ma) as well as a number of smaller
transient global warming events
(hyperthermals) during the late
Paleocene and early Eocene (58
to 51 Ma) comes primarily from
observations of large [up to 4
per mil ()] negative d
associated with pronounced decreases in calci-
um carbonate preservation (24). Depending on
the assumed source, rate, and magnitude of CO
release (25),a0.25to0.45unitdeclineinsurface
seawater pH is possible, with a reduction in mean
surface ocean aragonite saturation from W=3
downto1.5to2(1). The calcite compensation
depth (CCD) (8)roseby~2kmtoshallowerthan
1.5 km in places (24) (compared with >4 km
today). Although a pH decrease or PCO
remains to be confirmed by geochemical proxies
for any of the hyperthermal events, the amount
of carbon injected can be modeled on the basis
of consistent carbonate d
C and CCD changes,
yielding between ~2000 and 6000 PgC for the
onset of the PETM (26,27). However, as with the
last glacial transition, deep sea geochemistry ap-
pears strongly modulated by regional ocean cir-
culation changes (28), which adds an additional
layer of complexity to global extrapolation and
highlights the importance of adequate spatial cov-
erage of the data.
PETM sediments record the largest extinction
among deep-sea benthic foraminifers of the past
75 My (29), and a major change in trace fossils
indicates a disruption of the macrobenthic com-
munity (30). However, the covariation of ocean
acidification, warming, and corresponding oxygen
depletion (fig. S2) (23) precludes the attribution of
this extinction to a single cause (1,29). In shallow
water environments, a gradual shift from calcar-
eous red algae and corals to larger benthic foramin-
ifers as dominant calcifiers started in the Paleocene
and was completed at the PETM with the collapse
of coralgal reefs and larger benthic foraminiferal
turnover (31). This event is recognized as one of
the four major metazoan reef crises of the past
300My(Fig.1)(32). In marginal marine settings,
coccolithophore (33) and dinoflagellate cyst (34)
assemblages display changes in species compo-
sition, but these are interpreted to reflect sensitiv-
ity to temperature, salinity stratification, and/or
nutrient availability (34,35), not necessarily acid-
ification (fig. S2). In the open ocean, the occur-
rence of deformities in some species of calcareous
nannoplankton has been described (36), but de-
spite a strong change in assemblages, there is no
bias in extinction or diversification in favor of
or against less or more calcified planktic spe-
cies (37).
Cretaceous and Cretaceous-Paleogene. The
well-known mass extinction at 65 Ma is gener-
ally accepted to have been triggered by a large
asteroid impact (38). In addition to potential ter-
restrial biomass or fossil carbon burning, the im-
pact may have caused the emission of SO
vaporized gypsum deposits at the impact site
and/or nitric acid aerosols produced by shock
heating of the atmosphere, which could have led
to acid rain and hence potentially to rapid acid-
ification of the surface ocean (38). Although
planktic calcifiers exhibited elevated rates of ex-
tinction and reduced production (22,39), reef
corals did not experience a major extinction (32),
and benthic foraminifers were not affected in ei-
ther shallow or deep waters (29). Because mul-
tiple environmental changes covaried and proxy
data for marine carbonate chemistry are not yet
available, unambiguous attribution of the planktic
extinctions to any one driver such as ocean acid-
ification is currently not possible.
The earlier Cretaceous (K) (Fig. 4A) is gen-
erally a time of massive chalk deposition (mainly
Time (years)
1 10 100 1,000 10,000 100,000
Mean ocean
Mean ocean
Mean ocean
surface pH
Mean surface pHSWS
Time to a doubling of P
8.1 8.0 7.9
Rising CO
Fig. 3. The trajectories of mean ocean surface pH and aragonite
saturation (W
)becomeprogressivelydecoupled as the rate of
atmospheric PCO
change increases. The four panels show the results
of a series of experiments in an Earth system model (2). (A) Prescribed
linear increases of atmospheric PCO
(on a log
scale) from ×1 to ×2
preindustrial CO
, with the different model experiments spanning
a range of time scales (but experiencing the same ultimate CO
change). (B) Evolution of mean surface pH in response to rising CO
(C) Evolution of mean surface W
.(D) A cross-plot illustrating
how W
is progressively decoupled from pH as the rate of PCO
increase slows, with future-relevant rate of PCO
increase showing a
diagonal trajectory from top left to bottom right, whereas slow PCO
increases result in an almost horizontal trajectory toward lower pH
with very little saturation change. All plots are color-coded from red
(fast)toblue(slow). These model results include both climate
and long-term (silicate) weathering feedback. See (2)andfig.S1for
the role of these and other feedbacks.
on November 19, 2012www.sciencemag.orgDownloaded from
in the form of nannofossil calcite),
as well as one of elevated PCO
(Fig. 4B) and lower pH (Fig. 4D).
This association can be miscon-
ceived as evidence that marine
calcification will not be impaired
under conditions of low pH in the
future. However, this reasoning is
invalid because extended periods
of high PCO
(Fig. 4B) do not nec-
essarily result in a suppressed sea-
water calcite saturation state (Fig. 3)
(1,40), which exerts an impor-
tant control on organismscalcifi-
cation (41).
Cretaceous and Jurassic oce-
anic anoxic events. The Mesozoic
oceanic anoxic events (OAEs) (in
particular, OAE 2 ~93 Ma, OAE1a
~120 Ma, and Toarcian OAE ~183
Ma) were intervals during which
the oceans oxygen minimum and
deep anoxic zones expanded mark-
edly (42). The onsets of these OAEs
have been linked to the emplace-
ment of large igneous provinces,
degassing large amounts of CO
and associated environmental con-
sequences of warming, lower oxy-
gen solubility, and possibly ocean
acidification (42). Some of the
Cretaceous OAEs were associated
with turnover in plankton commu-
nities (43). Deformities and some
minor size reduction in coccoliths,
as well as a massive increase in
the abundance of heavily calcified
nannoconids, have been observed
(44,45). However, similar to more
recent events, there is difficulty in
unequivocally attributing observa-
tions to surface water acidification
given the covariation of environ-
mental changes (46).
Because most old sea floor
(~180 Ma or older) is subducted,
the sedimentary record of the
Toarcian OAE is now restricted to former con-
tinentalmargins. Sedimentary organic and inor-
ganic carbon deposits display initially negative,
followed by positive d
C excursions, which is
consistent with an influx of CO
into the at-
mosphere followed by organic carbon burial
(42). The negative isotopic transition occurs in
distinct negative d
C shifts, each estimated to
occur in less than 20 ky (47) and possibly in as
little as 650 years (48). The Toarcian OAE is
associated with a reef crisis that was particularly
selective against corals and hypercalcifying
sponges (animals with a large skeletal-to
organic biomass ratio) (Fig. 4B) (32) and with a
decrease in nannoplankton flux (49). Again,
these observations could have been a response
to any one or combination of a number of dif-
ferent contemporaneous environmental changes.
TriassicJurassic. The TriassicJurassic (T/J)
mass extinction is linked to the coeval emplace-
ment of the Central Atlantic Magmatic Province
(50). Proxy records across the T/J boundary
(~200 Ma) suggest a doubling of atmospheric
over as little as 20 ky (51,52), although
the absolute PCO
estimates differ greatly between
proxies, with leaf stomata suggesting an increase
from 700 to 2000 matm, whereas pedogenic car-
bonates indicate an increase from 2000 to 4400
matm (Fig. 4C) (2). Decreased carbonate satura-
tion is inferred from reduced pelagic carbonate
accumulation in shelf sediments (53), although
shallow water carbonate deposition can vary in
response to many parameters, not only acidifica-
tion. A calcification crisis amongst hypercalcify-
ing taxa is inferred for this period (Fig. 4B), with
reefs and scleractinian corals experiencing a near-
total collapse (32). However, the observation that
tropical species were more affected than extra-
tropical species suggests that global warming may
have been an important contributor or even dom-
inant cause of this extinction (32).
PermianTriassic. The PermoTriassic (P/T)
mass extinction (252.3 Ma) was the most severe
of the Phanerozoic Era and coincided, at least in
part, with one of the largest known continental
eruptions, the Siberian trap basalts. Recent es-
timates for the total CO
release put it at ~13,000
to 43,000 PgC in 20 to 400 ky (5456)an an-
nual carbon release of ~0.1 to 1 PgC [compared
with 9.9 PgC in 2008 (57)]. There is some obser-
vational evidence for carbonate dissolution in
shelf settings (54), but its interpretation is again
debated (58). There is abundant evidence for
ocean anoxia, photic zone euxinia (enrichment in
Fig. 4. Compilation of data-based
[(B) and (C)] and model-reconstructed
[(C) and (D)] indicators of global
carbon cycle evolution over the
past 300 My together with candi-
date ocean acidification events (A).
(A) Summarization of the degree to
which events (table S1) have some
similarity to modern ocean acidifica-
tion. The similarity index (table S1)
is color-coded, where red indicates
3/most similar, orange indicates
2/partly similar, and yellow indicates
1/unlike. (B)Proxy-reconstructed
atmospheric PCO
(2) grouped by
proxy: yellow circles indicate paleo-
sol d
C, light blue squares indicate
marine phytoplankton d
C, red
triangles indicate stomatal indices/
ratios, dark blue inverted triangles
indicate planktic foraminiferal d
green five-pointed stars indicate
liverwort d
C, purple six-pointed
stars indicate sodium carbonates,
with 10-My averages shown by gray
bars. For plotting convenience, es-
timates exceeding 3000 matm are not
shown [primarily paleosol d
the uppermost Triassic/lowermost
Jurassic (2)]. (C) Ocean Mg/Ca ratios
(red triangles, left axis), reconstructed
from fluid inclusions (2) and echino-
derm fossil carbonate [red squares
(71)] together with the Phanerozoic
seawater model of (72) (red line).
Also shown (blue circles, right axis)
is [Ca
] from fluid inclusions (2)
and models [blue line (72)]. (D)
Model-reconstructed changes in
mean ocean surface pH at 20-My
intervals [black line (73)].
Time (millions of years before present)
1000 200 300
perturbation events
0200 300
Mg/Ca (mol mol
] (mol mol
K J Tr P
oarcian OAE
End Cretaceous
OAE 1a
Deglacial transitions
Cenozoic Mesozoic Paleozoic
Modern (pre-industrial)
Band estimates
up to ~5000 µatm
at 201 Ma
Mean ocean
surface pH
SWS SCIENCE VOL 335 2 MARCH 2012 1061
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hydrogen sulfide) (59), and strong warming (54),
but no direct proxy evidence for pH or carbonate
ion changes. Knoll et al.(59) inferred the prefer-
ential survival of taxa with anatomical and phys-
iological features that should confer resilience
to reduced carbonate saturation state and hyper-
capnia (high CO
in blood) and preferential ex-
tinction of taxa that lacked these traits, such as
reef builders (32).
Is There a Geologic Analog for the Future?
A number of past ocean carbon-cycle perturbation
events share many of the characteristics of an-
thropogenic ocean acidification (Fig. 4 and table
S1), with the notable exception of the estimated
rates of CO
release. In the general absence of
direct proxy evidence for lower pH and reduced
saturation before the Pliocene, global carbon cycle
models can be used to infer the magnitude of
carbon release by fitting observed changes in the
C of calcium carbonates and organic remnants
(60). However, as well as needing information on
the source and isotopic composition of the added
carbon, the time scale of d
C change is critically
important to the estimation of CO
fluxes (25).
Because of the lack of open-ocean sediments and
increasingly poor temporal and spatial resolution
of the geological record further back in time, it is
difficult to place adequate constraints on the
duration and rate of CO
release. Radiometric
dating techniques are not accurate enough to
identify Mesozoic intervals of 10-ky duration,
although orbital spectral analysis of highly
resolved isotope and/or sedimentological records
can help to partly overcome thisfor example,
if a d
C excursion is shorter or longer than one
precession cycle [21 ky (51)]. Even for the well-
studied PETM, the duration of the main phase
of this carbon injection is still debated (35,61),
and model-inferred peak rates of 1PgCper
year (26,61) could potentially be an underestimate.
Additional complications arise because car-
bon may not have been released at a uniform rate
and, in the extreme, may have occurred in the
form of rapid pulses. In such cases, the assump-
tion of an average emissions rate throughout
the entire duration of the pulsed release will fail
to capture the potential for episodes of intense
acidification. For instance, although the total
duration of the CO
release from the T/Jage
Central Atlantic Magmatic Province was esti-
mated to be ~600 ky, pulses as short as ~20 ky
have been suggested (51,62). Similarly, the main
phase of OAE1a (excluding the recovery inter-
val) was ~150 ky (45) and hence too slow for
carbonate saturation to be significantly affected
(Fig. 3), but major volcanic eruptions and thus
rapid CO
release could potentially have produced
future-relevant perturbations in the carbon cycle.
Substantially improved chronologies and higher-
resolution records are needed to refine estimates
of rate.
Given current knowledge of the past 300 My
of Earths history (Fig. 4 and table S1), the PETM
and associated hyperthermal events, the T/J, and
potentially the P/T all stand out as having excel-
lent potential as analog events, although the T/J
and P/T are much more poorly constrained be-
cause of the absence of deep-sea carbonate de-
posits. OAEs may also be relevant but were
associated with less severe volcanism (CO
lease) than were the older events (P/T and T/J).
The last deglacial transition, although charac-
terized by temperature and CO
-increase, is two
orders of magnitude slower than current anthro-
pogenic change. It is also thought to largely rep-
resent a redistribution of carbon within the ocean
and to the atmosphere and terrestrial biosphere
and hence did not have as potent and globally
uniform an acidification effect as an input from
geological reserves. Because of the decoupling
between pH and saturation on long time scales
(Fig. 3), extended intervals of elevated PCO
as the middle Miocene, Oligocene, and Cretaceous
can be firmly ruled out as future-relevant analogs.
What Are the Perspectives for Using the Geological
Record to Project Global Change?
Only rapid or pulsed CO
release events can
provide direct future-relevant information. As-
sessment of such events critically depends on
independent geochemical quantification of the
associated changes in the carbonate system, spe-
cifically seawater-pH and CaCO
saturation. Geo-
chemical proxy estimates are not yet available
for the Cretaceous and beyond and need to be
obtained to verify whether ocean acidification
did indeed happen. This is challenging, because
in addition to the potential for increasing post-
depositional alteration and reduced stratigraphic
exposure, uncertainty over the chemical and iso-
topic composition of seawater increases and lim-
its our interpretation of these proxies (63,64).
Future studies will have to improve and expand
geochemical estimates and their uncertainties of
surface and deep-ocean carbonate chemistry as-
sociated with carbonate dissolution and ecolog-
ical changes. This includes finding new archives
to study the secular evolution of seawater chem-
istry but also the laboratory study of living proxy
carriers under conditions mimicking past seawater
chemistry. An unfortunate aspect of the geolog-
ical record, however, is the lack of deep-sea car-
bonates in the Early Jurassic and beyond, which
further reduces our ability to reconstruct the car-
bonate chemistry of those older events.
The sensitivity of ocean chemistry to CO
lease, and the relationship between induced pH
and PCO
changes, vary through time and further
complicate the picture. For instance, seawater
calcium and magnesium ion concentrations were
different in the past (Fig. 4C). This alters the oceans
carbonate ion buffering capacity and hence sen-
sitivity of the Earth system to carbon perturbation
(65) because all other things being equal, higher
ambient Ca
concentrations means that a lower
carbonate ion concentration is required to achieve
the same saturation and hence balance weathering.
Varying seawater Mg/Ca ratios may potentially
also affect the mineralogy of marine calcifiers,
where the more soluble high-Mg calcite predom-
inated Neogene reefs and reefs during the Per-
mian through Early Jurassic, and more resistant
low-Mg calcite predominated during the Late
Jurassic through Paleogene (66). Thus, on this
mineralogical basis the response of marine cal-
cifiers to ocean acidification and seawater geo-
chemistry during the P/T and T/J would arguably
be closer to the modern than, for example, dur-
ing the PETM (67). Improved estimates of past
seawaterMg/Ca composition are necessary to
better evaluate all of this.
Although we have concentrated on the pros-
pects for extracting information from the geo-
logical record concerning the impact of ocean
acidification, we must question whether it really
is necessary to isolate its effect on marine orga-
nisms from other covarying factors (68). In par-
ticular, consequences of increasing atmospheric
will also be associated with warming in the
surface ocean and a decrease in dissolved oxy-
gen concentration (69). Massive carbon release,
whether future or past, will hence share the same
combination and sign of environmental changes.
The strength of the geological record therefore
lies in revealing past coupled warming and ocean
acidification (and deoxygenation) events as an
integratedanalog, with future and past events
sharing the same combination and sign of en-
vironmental changes. However, in additionally
driving a strong decline in calcium carbonate sat-
uration alongside pH, the current rate of (mainly
fossil fuel) CO
release stands out as capable of
driving a combination and magnitude of ocean
geochemical changes potentially unparalleled
in at least the last ~300 My of Earth history,
raising the possibility that we are entering an
unknown territory of marine ecosystem change.
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Acknowledgments: Funding for the Workshop on Paleocean
Acidification and Carbon Cycle Perturbation Eventswas
provided by NSF OCE 10-32374 and Past Global Changes
(PAGES). We thank the workshop participants for stimulating
discussions and contributions to this manuscript, and the USC
Wrigley Institute on Catalina Island for hosting the workshop.
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initiated the workshop and supported it at all stages. This
work is a contribution to the European Project on Ocean
Acidification(EPOCA). Data presented in Fig. 4 are
presented in tables S2 and S3 (2).
Supporting Online Material
SOM Text
Figs. S1 to S3
Tables S1 to S3
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CORRECTIONS & CLarifiCations
Post date 16 March 2012
on November 19, 2012www.sciencemag.orgDownloaded from
... This was followed by increased continental weathering and increased fluxes of nutrients and alkalinity to seawater, resulting in increased organic carbon burial that may have additionally been facilitated by high seawater temperature due to the CO 2 greenhouse effect of LIP volcanism (e.g. Schlanger and Jenkyns, 1976;Jenkyns, 1980;Erba, 1994;Weissert et al., 1998;Zeebe, 2001;Erba et al., 2010;Hönisch et al., 2012;Föllmi, 2012;Bauer et al., 2017;Jenkyns, 2018;Adloff et al., 2020;Matsumoto et al., 2022). These environmental perturbations caused the demise of northern Tethyan carbonate platforms, while microbial carbonates apparently became more abundant in central and southern Tethys, as postulated for Bacinella-rich carbonates that are abundant before and after OAE 1a (e.g. ...
... A decrease in seawater carbonate saturation has been discussed previously for OAE 1a (Weissert and Erba, 2004;Erba et al., 2010;Gibbs et al., 2011;Hönisch et al., 2012). However, it requires the injection of CO 2 on time scales sufficiently short to prevent the dynamics of the lysocline to maintain carbonate saturation, i.e. during less than 50 kyr (Zeebe, 2001;Hönisch et al., 2012). ...
... A decrease in seawater carbonate saturation has been discussed previously for OAE 1a (Weissert and Erba, 2004;Erba et al., 2010;Gibbs et al., 2011;Hönisch et al., 2012). However, it requires the injection of CO 2 on time scales sufficiently short to prevent the dynamics of the lysocline to maintain carbonate saturation, i.e. during less than 50 kyr (Zeebe, 2001;Hönisch et al., 2012). Geochemical modeling based on carbon and osmium isotope data for the negative CIE implies that a short-lived (50 kyr) increase of volcanic CO 2 emission by a factor of 6-10 will cause measurable acidification-related results, but not carbonate undersaturation (Bauer et al., 2017). ...
Full-text available
We report the first high-resolution sedimentological and geochemical record of the negative carbon-isotope excursion (CIE) at the onset of the early Aptian oceanic anoxic event (OAE) 1a from a carbonate-ramp depositional environment, analysed from a well core from c. 2500 m depth, 100 km offshore Abu Dhabi, United Arab Emirates. Time-series analysis of stable oxygen isotope values and concentrations of Si, Al, and Ti resulted in durations of the C3 and C4 segments of the CIE that support relative completeness of the C3 segment and high sediment preservation rates of c. 13 cm/kyr of the studied sedimentary sequence. Stable oxygen-isotope ratios of bulk carbonates are interpreted to indicate two episodes of cooling, separated by rapid warming during the peak of the negative CIE. The contributions of diagenesis and seawater pH on the bulk oxygen-isotope record will have affected the palaeoclimatic signal and are critically discussed. A major shift in oxygen isotope values at the peak of the negative CIE in the C3 segment coincides with relatively carbonate-poor, marly deposits, time-equivalent with other, global evidence for a reduction of carbonate saturation of sea-surface water. According to our chemo- and cyclostratigraphic calibration, this episode of low carbonate saturation of seawater reflects a pulse of major volcanic CO2 release from the Ontong-Java large igneous province that was sufficiently short to have escaped internal buffering by the dynamics of the ocean lysocline.
... Recent studies on the present-day global change, particularly increasing temperature and ocean acidification linked to the massive release of greenhouse gasses to the atmosphere due to anthropogenic activities, are progressively demanding detailed analyses of events of similar magnitude throughout the Earth history (Ridgwell and Schmidt, 2010;Gattuso and Hansson, 2011;Hönisch et al., 2012;Hansen et al., 2013;Lunt et al., 2013;Zeebe and Zachos, 2013;Burke et al., 2018;Haynes and Hönisch, 2020). One of the targets is to analyze the effects of these global processes on marine calcified biota in the geological record to model and compare with the predicted biological changes for the future. ...
... One of the targets is to analyze the effects of these global processes on marine calcified biota in the geological record to model and compare with the predicted biological changes for the future. The Paleocene/Eocene thermal maximum (PETM) is a spike-like thermal event (Kennett and Stott, 1991;Thomas and Shackleton, 1996), at which researchers are looking as an ancient analogue to understand the ongoing biotic changes (Zeebe and Westbroek, 2003;Sluijs et al., 2007;Ridgwell and Schmidt, 2010;McInerney and Wing, 2011;Zeebe and Ridgwell, 2011;Hönisch et al., 2012;Zeebe, 2012;Norris et al., 2013;Zeebe and Zachos, 2013;Mudelsee et al., 2014;Haynes and Hönisch, 2020). ...
Full-text available
During the Paleocene/Eocene Thermal Maximum, ~55.6 Ma, the Earth experienced the warmest event of the last 66 Ma due to a massive release of CO2. This event lasted for ~100 thousands of years with the consequent ocean acidification (estimated pH = 7.8-7.6). In this paper, we analyze the effects of this global environmental shift on coralline algal assemblages in the Campo and Serraduy sections, in the south-central Pyrenees (Huesca, N Spain), where the PETM is recorded within coastal-to-shallow marine carbonate and siliciclastic deposits. In both sections, coralline algae occur mostly as fragments, although rhodoliths and crusts coating other organisms are also frequent. Rhodoliths occur either dispersed or locally forming dense concentrations (rhodolith beds). Distichoplax biserialis and geniculate forms (mostly Jania nummulitica) of the order Corallinales dominated the algal assemblages followed by Sporolithales and Hapalidiales. Other representatives of Corallinales, namely Spongites, Lithoporella as well as Neogoniolithon, Karpathia, and Hydrolithon, are less abundant. Species composition does not change throughout the Paleocene/Eocene boundary but the relative abundance of coralline algae as components of the carbonate sediments underwent a reduction. They were abundant during the late Thanetian but became rare during the early Ypresian. This abundance decrease is due to a drastic change in the local paleoenvironmental conditions immediately after the boundary. A hardground at the top of the Thanetian carbonates was followed by continental sedimentation. After that, marine sedimentation resumed in shallow, very restricted lagoon and peritidal settings, where muddy carbonates rich in benthic foraminifera, e.g., milioliids (with abundant Alveolina) and soritids, and eventually stromatolites were deposited. These initial restricted conditions were unfavorable for coralline algae. Adverse conditions continued to the end of the study sections although coralline algae reappeared and were locally frequent in some beds, where they occurred associated with corals. In Serraduy, the marine reflooding was also accompanied by significant terrigenous supply, precluding algal development. Therefore, the observed changes in coralline algal assemblages during the PETM in the Pyrenees were most likely related to local paleoenvironmental shifts rather than to global oceanic or atmospheric alterations.
... However, the scale, pace and effects of climatic changes are comparable between these two time intervals. Rapid warming often brings about changes in other environmental factors such as ocean acidification, hypoxia etc., which have been noticed in the Recent and are also recorded from the early Eocene (e.g., Zachos et al. 2005;Sluijs et al. 2009;Hönisch et al. 2012;Ivany et al. 2018;Willard et al. 2019). The differences in climatic conditions between the present-day high-latitude Patagonia, Argentina and the tropical western India of the Ypresian are significant. ...
Full-text available
Facultative monogamy in an early Eocene brooding oyster and its evolutionary implications KALYAN HALDER and ANIKET MITRA Halder, K. and Mitra, A. 2021. Facultative monogamy in an early Eocene brooding oyster and its evolutionary implications. Acta Palaeontologica Polonica 66 (3): 647-662. Dwarf males of Ostrea jibananandai sp. nov. from the lower Eocene rocks of the Cambay Basin, western India, are found attached inside the anterior end of the hinge of large females. Commonly, one male is found inside a female shell. Equivalent associations are known in the extant oyster Ostrea puelchana and the Neogene "Cubitostrea" alvarezii from Argentina. This association increases successful fertilization of eggs by reducing sperm loss in these spermcasting/brood-ing oysters. The sperms, released into water, are normally brought in with the inhalant water current before fertilization inside the body of the female in brooding oysters. This male-female association reduces the uncertainty involved in fertilization because sperms are released directly inside the female shell. The phenomenon is christened here as facultative monogamy. With this discovery, its evolution in oysters is pushed back more than 40 myr to over 54 Ma. Facultative mo-nogamy evolved only in these three species over its long history in spite of its obvious advantages. Facultative monogamy reduces evolutionary flexibility by decreasing phenotypic variability. It is argued here that the phenomenon evolved by trading off morphological variability in favour of successful fertilization in response to environmental perturbations that tend to disrupt sperm transport in open water. Rapid global warming is hypothesized to potentially cause environmental perturbation, because two of the three cases of facultative monogamy in oysters, Eocene O. jibananandai sp. nov. and Recent O. puelchana, occurred at the early stages of hyperthermal events. K ey w o r d s : Bivalvia, Ostrea, internal fertilization, global warming, spermcasting, Eocene, Cambay Basin, India. Kalyan Halder [] and Aniket Mitra [],
... The marine system is intimately linked to these climatic changes. Oceanic CO 2 uptake leads to ocean acidification that, when combined with additional temperature and pollution stresses, may lead to marine ecosystem destabilization (Sabine et al., 2004;National Research Council, 2010;Riebesell and Tortell, 2011;Honisch et al., 2012). In addition to managing the climate crisis, an additional focus should be placed on maintaining ocean health and services. ...
Full-text available
In addition to reducing carbon dioxide (CO2) emissions, actively removing CO2 from the atmosphere is widely considered necessary to keep global warming well below 2°C. Ocean Alkalinity Enhancement (OAE) describes a suite of such CO2 removal processes that all involve enhancing the buffering capacity of seawater. In theory, OAE both stores carbon and offsets ocean acidification. In practice, the response of the marine biogeochemical system to OAE must be demonstrably negligible, or at least manageable, before it can be deployed at scale. We tested the OAE response of two natural seawater mixed layer microbial communities in the North Atlantic Subtropical Gyre, one at the Western gyre boundary, and one in the middle of the gyre. We conducted 4-day microcosm incubation experiments at sea, spiked with three increasing amounts of alkaline sodium salts and a 13C-bicarbonate tracer at constant pCO2. We then measured a suite of dissolved and particulate parameters to constrain the chemical and biological response to these additions. Microbial communities demonstrated occasionally measurable, but mostly negligible, responses to alkalinity enhancement. Neither site showed a significant increase in biologically produced CaCO3, even at extreme alkalinity loadings of +2,000 μmol kg−1. At the gyre boundary, alkalinity enhancement did not significantly impact net primary production rates. In contrast, net primary production in the central gyre decreased by ~30% in response to alkalinity enhancement. The central gyre incubations demonstrated a shift toward smaller particle size classes, suggesting that OAE may impact community composition and/or aggregation/disaggregation processes. In terms of chemical effects, we identify equilibration of seawater pCO2, inorganic CaCO3 precipitation, and immediate effects during mixing of alkaline solutions with seawater, as important considerations for developing experimental OAE methodologies, and for practical OAE deployment. These initial results underscore the importance of performing more studies of OAE in diverse marine environments, and the need to investigate the coupling between OAE, inorganic processes, and microbial community composition.
... They show, for example, that coral recruits exposed to ambient (i.e., non-acidified) pH conditions have less variability in internal skeletal structure amongst individuals than when they are exposed to acidified conditions. Over geological timescales, OA has been shown to have impacted marine calcifiers in as wide a range of ways [25] as has been reported for modern-day calcifiers exposed to acidification in controlled laboratory experiments [5]. Pomar and coauthors (this issue) [26] reflect on calcareous biomineralization throughout the last 3.7 Ga of Earth history under highly variable atmospheric and seawater chemistry conditions. ...
It is well known that the increasing partial pressure of atmospheric CO2 (pCO2) is reducing surface ocean pH, a process known as ocean acidification (OA) [...]
Calcareous nannofossil distribution, environmental magnetism, and geochemical data provide stratigraphic evidence concerning the paleoceanographic changes across the lower/middle Albian and the Oceanic Anoxic Event 1b (OAE1b, Kilian Level) at South Atlantic Ocean. In this study, we analyzed samples from the sedimentary records at Deep Sea Drilling Project (DSDP) Site 364, Kwanza Basin, Angola. This section is associated with the initial phases of evolution of the South Atlantic Ocean, characterized by the deposition of extensive evaporite layers under restricted marine conditions, which were preserved in many sedimentary basins of the Brazilian and African continental margins. The open marine conditions that followed this period are recorded in the sequences of limestones interbedded with organic matter-rich black shales. In the Kwanza Basin, Site 364 contains a well-preserved sedimentary record of these post-salt sequences. In this study, we address the Lower Cretaceous sedimentary records at Site 364 from a paleoceanographic perspective, investigating the influence of OAE1b and local paleoenvironmental conditions. Our data analysis indicates a progressive reduction in hypersaline conditions during the lower/middle Albian. In these conditions, five paleoceanographic intervals (PIs) were described, which show different evidence of dysoxia/anoxia and salinity fluctuations, euxinic intervals, surface-water temperature changes, and hydrothermal activity signals, as well as possible ocean acidification episodes. These paleoceanographic conditions at Site 364 are associated with a stratified thermocline composed of warm surface-water from the North Atlantic (Western Tethys) and cool deep-water incursions from the Austral Atlantic, which strongly affected the composition of the calcareous nannofossil assemblages. We propose that the lower/middle Albian paleogeographic and paleoceanographic conditions observed in the Kwanza Basin were likely related not only to local events linked to the early development of the South Atlantic, but also to the OAE1b - Kilian Level recognized in several basins from around the world.
Microfossils have a ubiquitous and well‐studied fossil record with temporally and spatially fluctuating diversity, but how this arises and how major events affect speciation and extinction is uncertain. We present one of the first applications of PyRate to a micropalaeontological global occurrence dataset, reconstructing diversification rates within a Bayesian framework from the Mesozoic to the Neogene in four microfossil groups: planktic foraminiferans, calcareous nannofossils, radiolarians and diatoms. Calcareous and siliceous groups demonstrate opposed but inconsistent responses in diversification. Radiolarian origination increases from c. 104 Ma, maintaining high rates into the Cenozoic. Calcareous microfossil diversification rates significantly declines across the Cretaceous–Palaeogene boundary, while rates in siliceous microfossil groups remain stable until the Paleocene–Eocene transition. Diversification rates in the Cenozoic are largely stable in calcareous groups, whereas the Palaeogene is a turbulent time for diatoms. Diversification fluctuations are driven by climate change and fluctuations in sea surface temperatures, leading to different responses in the groups generating calcareous or siliceous microfossils. Extinctions are apparently induced by changes in anoxia, acidification and stratification; speciation tends to be associated with upwelling, productivity and ocean circulation. These results invite further micropalaeontological quantitative analysis and study of the effects of major transitions in the fossil record. Despite extensive occurrence data, regional diversification events were not recovered; neither were some global events. These unexpected results show the need to consider multiple spatiotemporal levels of diversity and diversification analyses and imply that occurrence datasets of different clades may be more appropriate for testing some hypotheses than others.
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The Paleocene‐Eocene Thermal Maximum (PETM) is associated with major extinctions in the deep ocean, and significant paleogeographic and ecological changes in surface ocean and terrestrial environments. However, the impact of the associated environmental change on shelf biota is less well understood. Here, we present a new PETM record of a low paleolatitude shallow‐marine carbonate platform from Meghalaya, NE India (eastern Tethys). The biotic assemblage was distinctly different to other Tethyan PETM records dominated by larger benthic foraminifera and calcareous algae both in the Paleocene and Eocene. A change in taxa and forms indicating deeper waters with a concurrent decrease in abundance of shallow water algae suggests a sea‐level rise during the onset of the PETM. The record is lacking the ecological change from corals to larger foraminiferal assemblages and the Lockhartia dominance, characteristic of several other sections in the Tethys. Comparison with a global circulation model (GCM) indicates high regional temperatures in the Thanetian which may have excluded corals from the region. Furthermore, the regional circulation pattern is isolating the site from the wider Paratethys. Our study highlights the need for a diverse global perspective on shallow‐marine response to the PETM and the strength of coupling data to global climate models for interpretation.
Crustose coralline algae (CCA) are a group of calcifying red macroalgae crucial to tropical coral reefs because they form crusts that cement together the reef framework1. Previous research into the responses of CCA to ocean warming (OW) and ocean acidification (OA) have found reductions in calcification rates and survival2,3, with magnitude of effect being species-specific. Responses of CCA to OW and OA could be linked to evolutionary divergence time and/or their underlying molecular biology, the role of either being unknown in CCA. Here we show Sporolithon durum, a species from an earlier diverged lineage that exhibits low sensitivity to climate stressors, had little change in metabolic performance and did not significantly alter the expression of any genes when exposed to temperature and pH perturbations. In contrast, Porolithon onkodes, a species from a recently diverged lineage, reduced photosynthetic rates and had over 400 significantly differentially expressed genes in response to experimental treatments, with differential regulation of genes relating to physiological processes. We suggest earlier diverged CCA may be resistant to OW and OA conditions predicted for 2100, whereas taxa from more recently diverged lineages with demonstrated high sensitivity to climate stressors may have limited ability for acclimatisation.
The Triassic–Jurassic transition, which is here broadly defined as extending from the Late Triassic through the Early Jurassic (~237 Ma to 174 Ma), was an important interval in Earth history. The end-Triassic mass extinction (ETME), at ~201 Ma, ranks among the ‘Big Five’ Phanerozoic mass extinctions. It largely completed the shift from the ‘Paleozoic Evolutionary Fauna’ to the ‘Modern Evolutionary Fauna’ that had been initiated by the end-Permian mass extinction, and may have contributed to the ‘Mesozoic Marine Revolution’ and rise of dinosaurs to dominance in terrestrial environments. In addition, the Triassic–Jurassic transition encompasses a second-order mass extinction during the early Toarcian oceanic anoxic event (T-OAE), at ~181 Ma. The ETME was triggered by Central Atlantic Magmatic Province (CAMP) magmatism, and the T-OAE by Karoo-Ferrar Large Igneous Province (KFLIP) magmatism, both associated with the stepwise disintegration of the Pangean supercontinent. These events led to major changes in continental and marine habitats, including climatic warming, ocean acidification, and widespread watermass anoxia, that produced a cascade of lethal environmental stresses. This article undertakes a review of the ETME and T-OAE mass extinctions, the large igneous province eruptions that triggered those biotic events, and the web of environmental changes that linked them together.
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[1] A simple model of the CaCO3 saturation state of the ocean is presented. It can be solved analytically and is intended to identify the fundamental controls on ocean carbonate ion concentration. It should also attract researchers unfamiliar with complex biogeochemical models. Despite its limitations, the model-calculated CaCO3 saturation state of today's ocean agrees well with observations. In general, the model reveals three distinctly different modes of operation: The “Strangelove Ocean” of high supersaturation which is dominated by inorganic CaCO3 precipitation, (2) the “Neritan Ocean” of indefinite saturation dominated by biogenic shallow-water CaCO3 precipitation, and (3) the “Cretan Ocean” of low saturation dominated by biogenic pelagic CaCO3 precipitation. In the latter mode, the deep ocean [CO32−] is remarkably stable, provided that the biogenic production of CaCO3 exceeds the riverine flux of Ca2+ and CO32−. This explains the overall constancy of the saturation state of the ocean documented over the last 100 Ma. The model is then used to address diverse questions. One important result is that the recovery of the oceanic carbonate chemistry from fossil fuel neutralization in the future will be accelerated due to expected reduced biogenic calcification.
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The late Paleozoic deglaciation is the vegetated Earth’s only recorded icehouse-to-greenhouse transition, yet the climate dynamics remain enigmatic. By using the stable isotopic compositions of soil-formed minerals, fossil-plant matter, and shallow-water brachiopods, we estimated atmospheric partial pressure of carbon dioxide (pCO2) and tropical marine surface temperatures during this climate transition. Comparison to southern Gondwanan glacial records documents covariance between inferred shifts in pCO2, temperature, and ice volume consistent with greenhouse gas forcing of climate. Major restructuring of paleotropical flora in western Euramerica occurred in step with climate and pCO2 shifts, illustrating the biotic impact associated with past CO2-forced turnover to a permanent ice-free world.
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We have extended the GENIE-1 Earth system model to include a representation of sedimentary stratigraphy and the preservation of biogenic carbonates delivered to the ocean floor. This has enabled us to take a novel approach in diagnosing modern marine carbon cycling: assimilating observation of the calcium carbonate (CaCO3) content of deep-sea sediments with an ensemble Kalman filter. The resulting calibrated model predicts a mean surface sediment content (32.5 wt%) close to the observed value (34.8 wt%), and a global burial rate of CaCO3 in deep sea sediments of 0.121 PgC yr-1, in line with recent budget estimates of 0.10-0.14 PgC yr-1. We employ the GENIE-1 model in quantifying the multimillennial-scale fate of fossil fuel CO2 emitted to the atmosphere. In the absence of any interaction between ocean and sediments, an equilibrium partitioning of CO2 is reached within ˜1000 years of emissions ceasing, with 34% (645 ppm) remaining in the atmosphere out of a total fossil fuel burn of 4173 PgC. An additional 12% of CO2 emissions (223 ppm) are sequestered as bicarbonate ions (HCO3-) by reaction with deep-sea carbonates ("seafloor CaCO3 neutralization") on a timescale of ˜1.7 ka. Excess of carbonate weathering on land over deep-sea burial results in a further net transformation of 14% of CO2 emissions (261 ppm) into HCO3- ("terrestrial CaCO3 neutralization") on a timescale of ˜8.3 ka. We have also assessed the importance of a changing climate in modulating the stabilization of atmospheric CO2 through ocean-sediment interaction. Increased ocean stratification suppresses particulate organic carbon export, which in turn enhances seafloor CaCO3 preservation. The resulting reduction in the sequestration of fossil fuel CO2 represents a new positive feedback on millennial-scale climate change.
In the Hartford basin, caliche calcites in fluvial mudstones and stones have isotopic compositions (δ 13C = -7.3 to -3.8‰ PDB; δ 18O = -8.0 to -5.6‰ PDB) that reflect paleosol processes during climatic conditions that varied from warm and dry in Late Triassic time to relatively cooler and probably wetter in the Early Jurassic. Isotopic compositions of caliche calcites in redbeds in the Fundy basin indicate a parallel climate change from Late Triassic to Early Jurassic time, but also that the climate was relatively hotter and probably drier over the entire interval, as compared to the Hartford basin. -Authors
▪ Abstract Developments in plant physiology since the 1980s have led to the realization that fossil plants archive both the isotopic composition of atmospheric CO2 and its concentration, both critical integrators of carbon cycle processes through geologic time. These two carbon cycle signals can be read by analyzing the stable carbon isotope composition (δ13C) of fossilized terrestrial organic matter and by determining the stomatal characters of well-preserved fossil leaves, respectively. We critically evaluate the use of fossil plants in this way at abrupt climatic boundaries associated with mass extinctions and during times of extreme global warmth. Particular emphasis is placed on evaluating the potential to extract a quantitative estimate of the δ13C of atmospheric CO2 because of the key role it plays in understanding the carbon cycle. We critically discuss the use of stomatal index and stomatal ratios for reconstructing atmospheric CO2 levels, especially the need for adequate replication, and present...
Planktic Foraminifera are an extremely abundant, important and successful group of marine protists. They are particularly useful in reconstructing past environments and for biostratigraphic dating. Despite their importance, the origin of the group is uncertain. Previous work has suggested that they evolved from a benthic ancestor during the Triassic or, perhaps, the Mid-Jurassic (?Bajocian), but a reason for their origination has remained unclear. Here, we present evidence from the Toarcian (early Jurassic) of NW Europe that the origin of the planktic Foraminifera may have been one of the results of the early Toarcian oceanic anoxic event. This event appears to have been associated with a massive dissociation of gas hydrates and other, perhaps related, water chemistry changes.
Permian waning of the low-latitude Alleghenian/Variscan/Hercynian orogenesis led to a long collisional orogeny gap that cut down the availability of chemically weatherable fresh silicate rock resulting in a high-CO2 atmosphere and global warming. The correspondingly reduced delivery of nutrients to the biosphere caused further increases in CO2 and warming. Melting of polar ice curtailed sinking of O2- and nutrient-rich cold brines while pole-to-equator thermal gradients weakened. Wind shear and associated wind-driven upwelling lessened, further diminishing productivity and carbon burial. As the Earth warmed, dry climates expanded to mid-latitudes, causing latitudinal expansion of the Ferrel circulation cell at the expense of the polar cell. Increased coastal evaporation generated O2- and nutrient-deficient warm saline bottom water (WSBW) and delivered it to a weakly circulating deep ocean. Warm, deep currents delivered ever more heat to high latitudes until polar sinking of cold water was replaced by upwelling WSBW. With the loss of polar sinking, the ocean was rapidly filled with WSBW that became increasingly anoxic and finally euxinic by the end of the Permian. Rapid incursion of WSBW could have produced ∼20 m of thermal expansion of the oceans, generating the well-documented marine transgression that flooded embayments in dry, hot Pangaean mid-latitudes. The flooding further increased WSBW production and anoxia, and brought that anoxic water onto the shelves. Release of CO2 from the Siberian traps and methane from clathrates below the warming ocean bottom sharply enhanced the already strong greenhouse. Increasingly frequent and powerful cyclonic storms mined upwelling high-latitude heat and released it to the atmosphere. That heat, trapped by overlying clouds of its own making, suggests complete breakdown of the dry polar cell. Resulting rapid and intense polar warming caused or contributed to extinction of the remaining latest Permian coal forests that could not migrate any farther poleward because of light limitations. Loss of water stored by the forests led to aquifer drainage, adding another ∼5 m to the transgression. Non-peat-forming vegetation survived at the newly moist poles. Climate feedback from the coal-forest extinction further intensified warmth, contributing to delayed biotic recovery that generally did not begin until mid-Triassic, but appears to have resumed first at high latitudes late in the Early Triassic. Current quantitative models fail to generate high-latitude warmth and so do not produce the chain of events we outline in this paper. Future quantitative modeling addressing factors such as polar cloudiness, increased poleward heat transport by deep water and its upwelling by cyclonic storms, and sustainable mid-latitude sinking of warm brines to promote anoxia, warming, and thermal expansion of deep water may more closely simulate conditions indicated by geological and paleontological data.