The history of the Earth system is a story of change. Some changes are gradual and benign, but others, especially
those associated with catastrophic mass extinction, are relatively abrupt and destructive. What sets one group
apart from the other? Here, I hypothesize that perturbations of Earth’s carbon cycle lead to mass extinction if they
exceed either a critical rate at long time scales or a critical size at short time scales. By analyzing 31 carbon isotopic
events during the past 542 million years, I identify the critical rate with a limit imposed by mass conservation.
Identification of the crossover time scale separating fast from slow events then yields the critical size. The modern
critical size for the marine carbon cycle is roughly similar to the mass of carbon that human activities will likely
have added to the oceans by the year 2100.
SCIENCE ADVANCES RESEARCH ARTICLE
Table 1. Event
per mil (%o) and de
Event name
Abbreviation
Date[Ma] 810) 81(tenv) Ar tenv[]M
Ediacaran-Cambrian
Ed
541.00
2.50
4.00
-6.50
2.000
032
2.302
Nemakit-Daldynian -Tommotian
NDT
524.36
5.00
0.982
0.41
1.450
Cambrian Spice
Spice
4.30
1.30
-3.00
1.000
0.12
End-Ordovician
Ord
445.80
4.90
-0.70
560
0.230
0.42
0.344
Silurian mulde
Mul
428.20
1.00
0.260
Silurian lau
423.50
7.00
1.00
-6.00
0.500
030
0.538
Frasnian-Famennian
372.20
-1.50
1.540
311
Tournaisian
T
351.55
3.50
1.510
Mid-Capitanian
C
262.45
4.00
-5.00
0.500
027
0.480
End-Permian
PT
251.94
4.00
-1.50
5.50
0.060
1.13
0243
rly triassic
251.22
2.00
0.250
0.26
0228
Triassic-Jurassic
T
201.64
0.050
0.087
Toarcian
Toar
182.60
2.10
0.15
Aptian
Apt
120.21
2.95
1.15
0.047
0.26
0.043
Albian-Cenomanian
100.50
0.110
0030
Mid-Cenomanian
mcn
95.90
3.10
-0.85
0.138
0.038
Cenomanian-Turonian
94.20
5.30
1.60
0.553
0.07
0.135
retaceous-Paleogene
198
0.026
Early late Paleocene
ELPE
58.9
3.48
3.07
0.42
0.039
0.11
0.015
Paleocene-Eocene thermal maximum
PETM
190
0.80
2.70
0.083
0.41
0.121
Eocene thermal Maximum 2
ETM2
53.70
-1.12
0.045
0.28
0.045
Eocene Hyperthermal H2
H2
53.60
0.033
0.19
0.023
Eocene Hyperthermal 12
53.20
1.56
0.040
0.023
Eocene Hyperthermal 11
53.10
1.56
0.84
0.72
0.040
0.19
0.028
Eocene thermal Maximum 3
ETM3
52.50
0.20
-0.60
-0.80
0.037
0.24
0.032
Eocene-Oligocene boundary
33.50
1.60
1.00
0.60
0.430
0.03
Miocene Climatic Optimum
MCO1
1690
1.44
0.50
0.028
0.18
0018
Miocene Climatic Optimum 2
MCO2
16.40
0.76
0.022
0.028
Miocene Climatic Optimum 3
MCO3
1600
1.67
-0.66
0.032
021
0.024
Miocene Climatic Optimum 4
MCO4
1560
2.17
-0.60
0.029
0.022
Last glacial maximum -to-Holocene
LGMH
0.02
0.11
0.45
0.34
0.018
0.20
0013
did: Fig 3A shows that the upper envelope of event size M decreases The time scale of critical events appears to have declined since the
with time. To understand this evolution, note that Eq 5 predicts that early Triassic(250 Ma) by about one order of magnitude, to about 20
changes in the size of critical events, for which o=dc, derive directly to 30 ky since the Miocene(16 Ma). The smaller time scale is similar
from changes in teny. Figure 3B shows that this time scale--which to the -10-ky time scale of the modern oceans homeostatic response
should be roughly equivalent to the damping time--decreases toward to a change in pH(22-25). The time scale's decrease since the Triassic
the present
is consistent with the evolutionary expansion of the modern biological
Rothman, Sci. Adv. 2017; 3: e1700906 20 September 2017
3of12
SCIENCE ADVANCES RESEARCH ARTICLE
Mass extinction
A
Othe
1士1 per mil
●Edi
Log 1.5
●Lau
●ord
Log 1.5
Mass extinct
our
Other
●Toar●Mul
● Spice
●PETM
10
2
B
●TJ
●cT
●FF
●HT●Apt
alen cn
●i1
A
10
士Log15
Event duration Teny year
● Mass extinction
±Log15
● Other
-500-400-300-200-1000
Date [My
10
Fig 3. Evolution of size and time scale. (A)Dimensionless mass perturbation M
●Tour
Am/m*as a function of the geologic age of the event. The relative absence of smaller
● Spice
events in the deeper past likely derives from poor data and a lack of interest. The
●ord
●FF
absence of large events in the more recent past, however cannot be explained by this
bias. B)Time scale teny of critical events (events falling within the error bars of the Q
●Mul
straight line in Fig 2B)as a function of geologic age. Error bars( Materials and methods
●P
are guides for interpretation
≈101
●TJ
●KT
●oi1
●
iable after the introduction of the deep-sea carbonate sink (26, 27, 30, 33)
They also identify the crossover time scale tx with the homeostat time o
●ELPE
●LGMH
B/ Scale, implying tx 10 ky(22-25)in modern oceans
With these results in hand, the modern critical size Mc of an asymp
101
10
totically fast perturbation of the marine carbon cycle now follows. First,
Dimensionless duration cTenv 2To
insertion of M(Oc, Tenv) from Eq 5 into Eq 2 provides the critical rate
rc=c/2to. equation 3 then predicts
Fig. 2. Depictions of the size and time scale of carbon isotopic events. (A)Mag
nitude of the isotopic shift Ar=81(Tenv)-81(0)as a function of its duration of time
teny.(B)Dimensionless mass perturbation M=Am/'m* as a function of the di
ptx
mensionless time scale p tenv/2to for each of the events depicted in(A). The
straight(identity) line denotes the equality predicted by eq 5 when p=oc
0.23+0.07. Event abbreviations are defined in table 1. error bars (materials
0.0082±0.0041
and Methods)are guides for interpretation
where, as a guide, a total uncertainty of +% is assumed. The mod
ern oceans contain about 38,000 Pg C; the critical dimensional mass
pump beginning approximately 220 Ma(26, 27), corresponding to the is therefore about 310+ 155 Pg C
earliest observations of coccolithophores and associated calcareous ph
From 1850 to the present, human activities have resulted in the
toplankton in the fossil record(28, 29). As the biological pump addition of about 155 25 Pg c to the oceans(34). Projections for
strengthened, the export of precipitated calcium carbonate from surface further carbon uptake depend strongly on the trajectory of fossil
waters to deep ocean sediments increased, leading to growth of the deep- emissions and land use, among other factors (34, 35). Figure 4 com
sea sedimentary carbonate reservoir(26, 27, 30). When ph decreases in pares the critical mass to the present accumulation and four projec
modern oceans, dissolution of sedimentary carbonate minerals is one of tions to 2100 obtained from coupled climate-carbon cycle models
the principal processes via which these disturbances are damped (31, 32). (34 ). The strictest emission scenario results in oceanic carbon uptake
Because this mechanism strengthened over the last 220 My, critical per- whose mean falls just below the critical mass; at the other extreme,
turbations of the marine carbon cycle would have become shorter in time the mean model uptake is about 74% greater than critical. Although the
and smaller in magnitude, but not necessarily less dangerous, because uncertainty of each prediction in Fig. 4 is considerable, all scenarios
their maximum flux would have remained c These observations are for cumulative uptake at the century s end either exceed or are com-
each consistent with the suggestion that the carbon cycle became less var- mensurate with the threshold for catastrophic change
Rothman, Sci. Adv. 2017; 3: e1700906 20 September 2017
SCIENCE ADVANCES RESEARCH ARTICLE
600
the initial disturbance System-wide instability may then follow. Because
RCP8.5
500
the critical rate rc bounds qualitatively different dynamical regimes, per-
RCP6.0
turbation that exceed re (at time scales much greater than tx) suggest
RCP4.5
such unstable evolution The carbon cycle thus becomes one of many
a 300F RCP264
environmental stressors, and an array of causes is naturally implicated
Multiple causes may also be responsible for a sixth extinction
当200
(1, 42). However, the anthropogenic disturbance of the carbon cycle
100
merits its own appraisal. If an anomalous flux greater than M/x brings
the carbon cycle past a stability threshold at time scales much greater
than tx 10 years, then the instantaneous addition of an anomalous
ig. 4. Cumulative modern ocean uptake of carbon since 1850, up to the mass greater than Mc will excite similar behavior. The existence of these
Fi
present (green)and projected to 2100(blue), compared to the predicted crit. thresholds is this paper's central hypothesis. If they exist, one would
ical mass of 310 Pg c(solid red line) and an assumed uncertainty of +%
dashed red lines). Projections (34)are given for four representative concentra
expect that an instability resulting from an impulsive addition of co2
tion pathway scenarios RCPx, where x represents the radiative forcing, in units of would play out over a time scale with the same order of magnitude as
W/m, deriving from accumulated emissions in the year 2100(35). At the extreme
the damping time scale tx. The upshot is that an unstable trajectory
ends of the projections, RCP26 represents the range of lowest-emission scenarios would reach its maximum extent roughly 10 years after the threshold is
in the scientific literature, and RCP85 represents the high range of nonclimate breached. But how that process plays out remains unknown
olie
oS Of the two intermediate path
RCP4.5
emission pathway resulting from many climate policies found in the literature,
whereas RCP60 is representative of most scenarios without limitations on emis- MATERIALS AND METHODS
sions (35). The present cumulative uptake is obtained by adding 6 years of an The event database
annual uptake rate of 2.3 Pg C year(34) to the 2011 total of Ciais et al.(34)
After a brief discussion of possible sources of error this section sum
marizes how each event has been identified and quantified. Geological
paleoenvironmental, and paleobiological context is also given, as are
DISCUSSION
relevant references. All data, including the identification of abbrevia-
The value of the empirical results in Figs. 2 and 3 lies not in any indi- tions, are provided in Table 1
vidual data points but rather in their collective trends. The following When multiple observations are used to compute a mean, the sam
picture emerges. Carbon isotopic events rarely exceed a maximum iso- ple SD, the unaveraged observations, or both are noted in the events
topic shift that grows roughly like the logarithm of their time scale. This description. However, these quantities only indicate the variability of
upper bound appears related to the minimum rate--zero-at which or- a particular set of observations rather than an estimate of the obser
ganic carbon can be immobilized as rock. Events outside this limit result
ational error. As with any compilation of isotopic data [for example
from a fundamental disturbance of the carbon cycle, possibly related to Hayes et al. (43)], inadequate sampling may be a more significant
unstable dynamics, mass extinction, or both
problem. Here, it takes two forms: the sheer paucity of observations,
These conclusions follow from analyzing all isotopic events the and biases deriving from not only the original investigators-who
same way. Exceptions are, however, expected. For example, four events may favor larger isotopic excursions-but also the needs of the present
(Ediacaran-Cambrian, Nemakit-Daldynian-Tommotian, Paleocene- compilation, which favors carbon isotopic studies associated with strong
Eocene Thermal Maximum, and Miocene Climatic Optimum 2)un- geochronological constraints. An additional source of error derives
accompanied by mass extinction exceed the upper error bar of the from incompleteness of the sedimentary record. For example, a hiatus 52
critical rate. If, say, these events were driven by dissociation of methane in sediment deposition, or erosion after deposition, may make the true
hydrates [for example, (36)] rather than respired organic carbon, the carbon isotopic minimum effectively unavailable to the modern observer, 8
isotopic composition of the perturbative flux would be much lighter thereby leading to an underestimate of A
(about%0). The estimated size of these events would then drop The ideal geochronological control would provide absolute dates
by more than 50%, and they would each lie below the critical line. This at the initiation and termination of isotopic excursions. Only one
observation may help explain the Paleocene-Eocene Thermal Maximums event in the database-at the Ediacaran-Cambrian boundary-meets
modest biotic impact. The Frasnian-Famennian extinction provides this standard. Among the others, all but l of the 18 events extending
another exception. Supposing that it is indeed a mass extinction, its from the Toarcian(182 Ma) to the Miocene(16 Ma) are timed by as
presence well below the critical line illustrates an important point: Mass trochronology, including, in some cases, information obtained fron
extinctions need not be caused by disruptions of the carbon cycle(2). isotope geochronology. The duration of five of the older, pre-Jurassic
Modern investigations of mass extinctions often emphasize a plural- events is determined from at least two dates provided by u-pb geo
ity of causes. Erwins"complex web of causality"(8, 37)addresses chronology that bracket less than twice the accumulation of sediment
how a combination of volcanism, climate change, marine anoxia, meth- deriving from the event itself; a sixth event(end-Permian)comes close
ane release, and other environmental stressors may have contributed to this standard
to the end-Permian extinction. Recent studies of the end-Cretaceous The remaining pre-Quaternary events are timed by biostratigraphy
extinction consider massive volcanism(38)in addition to a bolide impact with reference to the Geologic Time Scale ( 44) their time scales are there
(39). Flood basalt eruptions are also clearly associated with the end- fore the most poorly constrained. Two of them, the end-Ordovician and
Triassic(40 )and end-Permian(15)extinctions, but their contribution Frasnian-Famennian events, are among the Big Five mass extinctions
to CO2 levels is ostensibly modest(41). Evidently, the carbon cycle both A third mass extinction-the end-Triassic-is constrained by both
indicates and excites Earth system change. These dual roles merge, how- isotope geochronology and astrochronology, but these constraints
ever, if external perturbations cause the cycle to respond by magnifying are not directly associated with the carbonate-carbon isotope excursion
Rothman, Sci. Adv. 2017; 3: e1700906 20 September 2017
SCIENCE ADVANCES RESEARCH ARTICLE
If these three mass extinction events and the other four events with poor 260 ky as shown by crameret al (66), the gotland excursion correlates
temporal constraints( Cambrian Spice, Tournaisian, mid-Capitanian, well with observations in the West Midlands, England, with the West
and Albian-Cenomanian)are removed from the database, the trends Midlands excursion having a magnitude of about 4%o and the Gotland
in Figs. 2 and 3 remain intact and no new trends api
ear
excursion about 2%0, a range that is consistent with other observations
Nevertheless, the unknown errors in the observations render quan-(65, 66). I therefore estimated the magnitude to be 3+ 1%0
titative error analysis infeasible The representative error bars for A M, Silurian Lau event, 423 Ma
and teny in Figs. 2 and 3 are instead guides for interpretation
A significant global positive carbon isotopic excursion known as the
The following list proceeds from the oldest to the youngest event. " Lau Event occurs in the Ludlow Epoch of the Silurian(65, 67-72)
Ediacaran-Cambrian boundary 541 Ma
The excursion typically peaks at 6 to 8%0[for example, Lehnert et al
The magnitude and duration of this negative isotopic excursion derive (71), though values as small as 3 to 4%0 and as high as 10 to 11%0
from the Oman carbon isotope data of Amthor et al. (45)and the U-Pb have been observed in North America (68)and Sweden(70), respective
geochronology of Bowring et al. (46). Other data from Morocco, Siberia, ly. Given that uncertainty, I adopted a conservative mean peak value of
Mongolia, and China(47, 48)suggest global consistency. The absence of 7%0. The negative downswing after the peak typically bottoms out at
the Ediacaran biota in the Cambrian has led to the suggestion that the about 1%00, resulting in a typical total negative shift of about 6%0
Ediacaran biota vanished by mass extinction at the end of the Ediacaran, Cramer et al. (72) have recently bracketed the duration of the excursion
possibly related to the environmental event signaled by this excursion by U-Pb geochronology, finding that it must be less than about 1. 17 My
(45, 49-52). However, gradual extinction coupled with permanent Following their analysis, I took the upswing and downswing to be
environmental changes unfavorable to preservation of the Ediacaran roughly symmetric, each occupying about one-half of an approximately
biota may also be possible(53)
million-year interval, implying that the duration of the downswing is
Nemakit-Daldynian-Tommotian boundary 525 Ma
bout 500 ky
Both the carbon isotopic excursion and the u-Pb dates establishing Frasnian-Famennian boundary 372 Ma
the duration of this Early Cambrian event are from the Moroccan data The boundary between the Frasnian and Famennian stages in the Late
of Maloofet aL (47, 54); data from Siberia, Mongolia, and China con- Devonian is associated with one of the Big Five mass extinctions(5, 6)
firm its global nature(47, 48). No mass extinction has been associated But the drop in diversity at the boundary is thought to be a consequence
with this interval. However, diversity(number of genera) and disparity of a lack of originations rather than an elevated extinction rate(19, 20)
(number of classes)sharply increase in the Tommotian, primarily be- The boundary is associated with a global positive carbon isotopic excur
cause of the rise of small shelly fossils(55). The Nemakit-Daldynian- sion, known as the Upper Kellwasser Event(73). The magnitude and Q
Tommotian boundary is also associated with a transition from seawater duration of the excursion are taken from the compilation of european
chemistry that favored aragonite precipitation to seawater favoring cal- Devonian data of Buggisch and Joachimski(74)
cite precipitation(47, 56)
Tournaisian event, 352 Ma
Cambrian Spice, n497 Ma
Buggisch et al (75) presented carbon isotopic data from Belgium, g
The duration and magnitude of this late Cambrian event also known Ireland, france, western Canada, and the western United States that
as the Steptoean positive carbon isotope excursion, are taken from the collectively exhibit a pronounced positive isotopic excursion in the
Australian data of Saltzman et al. (57). The event has also been found in Tournaisian stage of the Carboniferous. Using their biostratigraphic
North America, China, Kazakhstan, and Sweden(58, 59). The initiation time scale, I estimated the duration of the negative limb of the excursion 9
of this positive isotopic excursion coincides with an extinction of trilo- to be 1.51 My; the magnitude of the excursion in their compilation is
bites(58)
about35‰
End-Ordovician event, v446 Ma
Mid-Capitanian event, 262 Ma
The latest stage of the Ordovician-the Hirnantian-simultaneously A mass extinction in the Capitanian Stage of the Middle Permian is as
exhibits a positive isotopic excursion and one of the big Five mass sociated with a negative isotopic excursion of carbonate carbon of about
extinctions. I estimated the magnitude of the negative limb of the 5%0 over about 500 ky(76, 77). Observations of the event in south China oo
excursion from data obtained at Vinni Creek and Monitor Range, suggest that the extinction event coincides with the initiation of Emeishan
Nevada(60), Copenhagen Canyon, Nevada(61), Blackstone Range, volcanism(78)and the onset of the excursion(76)
Yukon(60), Wangjiawan, south China(62), the Kardla drill core, Estonia End-Permian extinction, -252 Ma
(63),and Anticosti Island, Quebec(64). The seven data sets yield a mean The end-Permian extinction is considered the most severe of the Bi
excursion of 5.6+.9%0. Each data set except for Copenhagen canyon Five(8). a significant negative isotopic excursion occurs at the time
has been correlated to graptolite zones by gorjan et al (62). By estimating of the extinction, just below the Permian-Triassic boundary. Korte
the fraction of the persculptus and extraordinarius zones in which the and Kozur (16) reviewed observations of the excursion in 40 localities
excursion occurs at each site and estimating those time intervals from worldwide and concluded that the excursion ranged from 4 to 7%0; I
Gradstein et aL. (44), I found that the negative limb of the excursion lasted therefore took the magnitude of the excursion to be at the center of that
approximately 230 ky
distribution(5.5%0). The 60-ky duration of the excursion derives from
Silurian mulde event, n428 Ma
the well-studied section at meishan, south China, where cao et al. (79)
A sequence of two positive excursions, known as the Mulde event," have provided high-resolution carbon isotopic data and U-Pb geo-
occurs in the Homerian stage of the Silurian, during a period of grap- chronology provides strong constraints on the time scale(9)
tolite extinctions known as the Big Crisis(65). The event is apparently Early Triassic, 251 Ma
global(65). Cramer et al.(66) have recently bracketed the earlier of the Several significant isotopic excursions of unknown origin follow the
two excursions between two U-Pb dates obtained in Gotland, Sweden. end-Permian extinction(80-83). Galfetti et al. (83)provided carbon
I focused on the negative downswing, which occupies somewhat more isotopic data tied to U-Pb geochronology from the Loulou Formation,
than half of the dated interval, and estimated its duration to be about northwest Guanxi, south China. The only temporally constrained
Rothman, Sci. Adv. 2017; 3: e1700906 20 September 2017
SCIENCE ADVANCES RESEARCH ARTICLE
negative isotopic shift occurs in a negative excursion that begins ap- Program(ODP) Site 1050 at Blake Nose, western North Atlantic, as
proximately 251. 22 Ma(83)in the mid-Smithian and declines approx- presented by Ando et al. (108). When plotted using the time scale of
imately 3. 5%0 over approximately 250 ky
Huber et al.(109), the odp data show an unambiguous 0.7%o negative
One of the Big Five extinctions, the end-Triassic event is temporally Mid-Cenomanian event, 95.9 Mg oximately 110 ky
Triassic-Jurassic boundary, w201 Ma
excursion across the boundary over apt
associated with the emplacement of the Central Atlantic magmatic The mid-Cenomanian positive carbon isotopic excursion has been
province(40 ). Geochemically, the most well-studied section is at St. clearly observed in European sections(107), the North Atlantic(110)
Audries Bay in southwest England, where the extinction interval coin- western North America(111), and elsewhere. My analysis follows from
cides with a rapid fall and subsequent rise of the isotopic composition of the correlation of the"English Chalk" reference carbonate curve(107)
organic matter( 84)that lasts 20 to 40 ky according to astrochronology to carbon isotopic data from the Cretaceous Western Interior Seaway of
(85). This so-called initial excursion in organic carbon is widely observed North America(111, 112). I used the time scale of Eldrett et al.(112),
(86). However, its significance for understanding the evolution of marine which is based on a combination of astrochronology and u-Pb geo
dissolved inorganic carbon is unclear(86,87), partly because it may be chronology. As indicated in figure 1l of Eldrett et al(112), the negative
associated with observed changes in flora(87)-and therefore variations swing of the excursion begins at about 96.5 Ma, followed by a decline of
in the organic matter itself-and partly because inorganic isotopic com- about 0.85%0 over roughly 138 ky
positions need not track organic isotopic compositions(43 ). There are Cenomanian-Turonian boundary event, m94. 2 Ma
unfortunately few well-resolved isotopic studies of carbonate carbon as- Otherwise known as oceanic anoxic event 2, the positive isotopic
sociated with the end-Triassic event(88-93). These carbonate studies excursion at the Cenomanian-Turonian boundary is probably the
also reveal a negative excursion associated with the extinction, but it most widely observed of the Cretaceous isotopic events(107, 111, 112)
is often unclear if they represent the initial excursion"or the later As for the mid-Cenomanian event, my estimate of the time scale and
120-ky-long main excursion seen in organic carbon(84, 85). A recent magnitude of the Cenomanian-Turonian event follows from the cor
review(94) cautions that diagenetic alteration may have corrupted car- relation of the English Chalk reference carbonate curve(107)to car
bonate data, yet a careful study of lithological effects at an Italian section bon isotopic data from the Cretaceous Western Interior Seaway of
suggests that the carbonate excursion may indeed be primary (87). An North America(111, 112). i took the initiation of the event to be 3
important additional problem is the need to estimate the time scale of at the positive peak labeled B in figure ll of Eldrett et al(112)
the carbonate excursion. The data of clemence et al.(92) provide a so- and found that the ensuing negative excursion declines by 1.60%0
lution to these problems. In their analysis of inorganic and organic car in roughly 553 ky
bonate at the Tiefengraben section in the Austrian Alps, they found an Cretaceous-Paleogene extinction, 65.5 Ma
initial 2%0 negative excursion in carbonate that extended to the second The end-Cretaceous negative isotopic excursion is associated with
significant minimum in their organic data(92), which in turn correlates one of the Big Five extinctions (5), widely known for the extinction
reasonably well with the astrochronologically calibrated organic data at of dinosaurs and the Alvarez impact hypothesis(39). Its temporal
St. Audries Bay(85). Their initial carbonate excursion was then association with the eruption of the massive deccan volcanic province
ound to last approximately 50 ky [which included one precessional in India is less widely known(38). I obtained the magnitude and time o
cycle of the pre-recovery interval identified by Ruhl et al. (85). This scale of the carbon isotopic event from the deep-sea bulk carbon iso
2.0%o shift is also consistent with isotopic analyses of carbonate in pris- topic data obtained at ODP Sites 1210 (Northwest Pacific)and 1262
tine oysters located near St. Audries Bay(91)
(South Atlantic), as presented by Alegret et al.(113)using an orbitally
Toarcian oceanic anoxic event, w183 Ma
tuned time scale(114) i took the initiation and termination of the
The early Toarcian oceanic anoxic event(95)is widely observed in approximately 1. 15 +0.03%o(the mean of 1. 16 and 1. 13%0)negative 3
Europe as a negative excursion in the isotopic composition of carbonate isotopic excursion at each site to be where values of &1 begin to change a
(96-99) To estimate its magnitude and duration, I used the high-resolution by at least 0. 1%0, resulting in a mean event duration of roughly 26 ky
carbonate record of Hesselbo et al. (96)obtained at Peniche(Portugal). (the average of 8.5 and 44 ky)
The astrochronology of Suan et al. (97) found a duration of 150 ky(their Early late Paleocene event, 58.9 Ma
interval Cl)for the negative isotopic excursion, which is consistent with Also known as the mid-Paleocene biotic event, this negative excursion is
the subsequent analysis of Huang and Hesselbo(100). Using this chro- synchronous with dissolution of carbonate and changes in the orga
nology, recent U-Pb dating by Burgess et al. (101) found that the intru- nization of benthic and planktonic ecosystems(115, 116). The mag-
sive magmatism associated with the Ferrar large igneous province is nitude and time scale of this negative excursion are taken from the
synchronous with the negative excursion
high-resolution bulk isotopic record of Littler et al. (115)
Aptian oceanic anoxic event, w 120 Ma
Paleocene- Eocene thermal maximum 55.5M
The negative isotopic excursion associated with the aptian oceanic The negative isotopic excursion of the Paleocene-Eocene Thermal Max
anoxic event has been observed worldwide in open ocean records of imum is perhaps the most studied carbon isotopic event in Earth history
carbonate carbon(102-105). My estimate of the magnitude and duration (11), in large part because of its association with significant climate
of the excursion derived from the astrochronology of malinverno et al. warming and clear evidence of ocean acidification( 10). The event is also
(106) performed on the carbonate record of Erba et al. (103). The negative associated with a significant extinction of benthic foraminifera(12)
excursion spans the interval C3 originally identified by Menegatti et al. however, other groups of benthic and planktic microfossils show little
(102)] and lasts approximately 47 ky
or no extinction(11). The time scales of the isotopic excursion of bulk
Albian-Cenomanian boundary, 100 Ma
carbonate in two deep-sea cores, from ODP Site 1266 on the Walvis
This complex carbon isotope event occurred near the Albian-Cenomanian Ridge in the South atlantic and OdP Site 690 in the Weddell Sea
boundary (mid-Cretaceous)in several European sections(107). Here, Southern Ocean, have each been estimated independently by identifica-
I focused on the carbon isotopic data obtained at Ocean Drilling tion of orbital cycles(117)and the estimation of sedimentation rates
Rothman, Sci. Adv. 2017; 3: e1700906 20 September 2017
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SCIENCE ADVANCES RESEARCH ARTICLE
om the concentration of He(118, 119). The mean of the resulting negative isotopic excursion, which I designated Miocene Climatic Op
four estimates [corresponding to the cumulative time between the onset timum 1, that has also been identified in lower-resolution records from
of the excursion and the termination of its core"as summarized in three other sites, elsewhere in the pacific and in the Southern ocean
table 1 of Murphy et al.(119) is 83+ 23 ky. I obtained the magnitude (127). i obtained the magnitude(0.5%o)and time scale(28 ky) from
of the isotopic excursion, 2.7 1.1%0, from the mean of 33 published the bulk carbonate record. The event is synchronous with shoaling of
analyses of bulk Paleocene-Eocene Thermal Maximum carbonates re- the carbonate compensation depth(CCD)
viewed by McInerney and Wing(11). The initial value of the excursion Miocene Climatic Optimum 2 16.4 Ma
was obtained similarly (11). Although these averages lack prejudice, Holbourn et al.(127) identified three other Miocene Climatic Opti
they may nevertheless underestimate the excursions size(120)and mum negative excursions, which I designated Miocene Climatic Op
overestimate its time scale(121)
timum 2 to Miocene Climatic Optimum 4, during which 81 decreases
Eocene thermal Maximum 2, m53.7 Ma
sharply and the CCD appears to shoal. Using the same high-resolution
The Eocene is punctuated by several"hyperthermal events, each repre- record as for Miocene Climatic Optimum 1, I found that Miocene
sented by a negative excursion in the isotopic composition of carbonate Climatic Optimum 2 has a time scale of 22 ky and a magnitude of
carbon and dissolution of deep-sea marine carbonates Eocene Thermal 0.76%0
Maximum 2, one such event, follows the Paleocene-Eocene Thermal Miocene Climatic Optimum 3, M16.0 Ma
Maximum (also known as Eocene Thermal Maximum 1)by roughly See Miocene Climatic Optimum 2. For Miocene Climatic Optimum 3, I
2 My My estimate of the magnitude of Eocene Thermal Maximum 2 found a time scale of 32 ky and a magnitude of 0.66%0 This event also
derived from averaging estimates from four high-resolution bulk isotopic appears in the records of OdP Site 1146 in the western Pacific Ocean
records presented by Stap et al. (122). The records derive from ODP Sites (128)and ODP Site U1338 in the eastern equatorial Pacific (129)
1262, 126, 1265, and 1267, corresponding to paleowater depths ranging Miocene Climatic Optimum 4, M15.6 Ma
from about 1500 to 3600 m(122); the shallowest site yields an excursion See Miocene Climatic Optimum 2. For Miocene Climatic Optimum 4,
of about 1.5%0, Whereas the others are each about 1.0%0(122), yielding the excursion has a magnitude of 0.6%0 and a time scale of 29 ky
a mean of 1.13+0.25%0. The time scale is about 45 ky
Last Glacial Maximum-to-Holocene deglacial-0021 M
Eocene Hyperthermal H2, 53.6 Ma
Using a compilation of 480 records of benthic foraminiferal carbon iso- 3
The magnitude and time scale of this Eocene hyperthermal event come tope analyses, Peterson et al. (130)estimat
Increase
from ODP Sites 1263, 1265, and 1267. Following Stap et al. (122), I took the isotopic composition of dissolved inorganic carbon of 0.34+0.19%0
the excursion of bulk carbon isotopes to be about 0.6%0 and the time from the last glacial maximum to the holocene. i took the time scale to
scale to be about 3 3 ky
be 18 ky, given their Last Glacial Maximum averages over 19 to 23 ky
Eocene Hyperthermal, M53.2 Ma
and Holocene averages over 0 to 6 ky. This is the only positive isotopic
I obtained the magnitude(0.72%0)and time scale (41 ky)of this eocene shift in the database in which the magnitude and time scale derive from
hyperthermal event from the high-resolution bulk carbon isotopic the upswing for the others, such as the Ordovician, the calculations cor
record of Littler et al. (115), which derives from ODP Site 1262
respond to the ensuing downshift
Eocene Hyperthermal 12,M53.1 Ma
This Eocene hyperthermal follows Eocene Hyperthermal ll by about The boundary value problem
100 ky. Using the same source(115)as for Eocene Hyperthermal Il, The boundary value problem derives from a model of the global carbon
I found an excursion of about 0.61%0 and a time scale of 40 ky
isotopic system presented by rothman et al. (131, 132). This model
Eocene thermal Maximum 3, 52.5 Ma
partitions carbon into two reservoirs. The inorganic reservoir contains
I estimated the magnitude and time scale of this hyperthermal event from a mass m of carbon with isotopic composition dj the organic reservoir 2
the high-resolution benthic carbon isotopic record of lauretano et al. contains carbon of isotopic composition 8. In the phanerozoic, the
(123), obtained at ODP Sites 1262 and 1263. The two records are similar,, isotopic composition of the organic reservoir typically equilibrates 8
yielding an excursion of about 0.8%0 and a time scale of about 37 ky. with respect to inputs and outputs at time scales much faster than
Early oligocene Event, 33.5 Ma
the inorganic reservoir(131). The evolution of 8 is then described
The positive carbon isotopic excursion just above the Eocene-Oligocene by equation 8 of Rothman et al. (132)
boundary is associated with the initiation of permanent cenozoic
ice sheets on Antarctica(124-126). I focused on the negative down
swing to lighter isotopic compositions that followed. The time scale
=(61-8)+b2e
(8)
and isotopic change are derived from the high-resolution data col
lected at ODP Site 1218, using the astrochronological time scale where ji is the flux of carbon of isotopic composition 8; into the surface
presented by Coxallet al (125). The negative shift extends over rough- carbon cycle(deriving typically from volcanism and continental
ly 0.6+0.1%o during a period of about 430+ 100 ky. The three ODp weathering), b2 is the burial flux of organic carbon out of the surface
records presented by Zachos and Kump(126)are consistent with cycle, and e=81-82 is the isotopic fractionation between inorganic
these estimate
and organic carbon
Miocene Climatic Optimum 1, w16.9 Ma
Suppose now that a new source of carbon with isotopic composition
Holbourn et al. (127) provided high-resolution carbon isotopic records 8, flows into the carbon cycle with flux ji, and that the burial flux b2
spanning most of the Miocene Climatic Optimum, a period of warm increases by an amount b2 while e remains constant. Equation 8 then
climates ranging from 17.0 to 14.7 Ma that interrupted the longer-term becomes
trend of Cenozoic cooling The records are obtained from Integrated
ODP Site U1337 in the eastern equatorial Pacific Ocean, at a paleowater
ds
depth of 3500 to 4000 m. The Miocene Climatic Optimum began with a
m方(6-861)+j1(61-8)+(b2+b2)e
Rothman, Sci. Adv. 2017; 3: e1700906 20 September 2017
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SCIENCE ADVANCES RESEARCH ARTICLE
where ji, 8i, and b, represent unperturbed quantities that satisfy the The normalized mass perturbation evolves as
steady-state relation
dM
9)
0=(81-81)+b2E
(10)
hich is obtained by taking the derivative of both sides of Eq. 13 and
where 8, is the steady-state isotopic composition of the inorganic reser- using Eqs. 15 to 17. Finally, the derivative of Eq 4 in the main text pro-
voir Subtraction of Eq. 10 from Eq 9 then yields
rides the evolution of the normalized flux perturbation
dt
(61-81)+j(6-81)+b2E
dJ
Here, 8 is set to the average isotopic composition of Phanerozoic or-
ganic carbon(-27 8%0(21)]. Consequently, the terms in Eq. ll pro- The differential equations 18 to 20 describe changes in the isotopic
portional toji andb, are practically indistinguishable so that a positive composition of marine inorganic carbon in response to the normalized
perturbation of the input flux is equivalent to a negative perturbation of flux(t). The first term in parentheses in Eq 18 encodes the tendency of
the burial flux. I therefore set b2=0 and reinterpreted ji as representa- 81 to relax back to the initial value 81, and the second term describes the
tive of any perturbation of the flux to the inorganic reservoir that carries forcing of the system out of steady state by injection of carbon with iso-
the isotopic composition of organic matter
topic composition 8. Because o is unknown, the solution of this system 2
Further simplifications follow by reexpressing the remaining terms requires not only three initial conditions but also one end condition:
in Eq. 1l using variables defined in the main text. First, recall that the
mass m is decomposed into an unperturbed component m* and a per-
turbation Am according to
1(0)=81
M(0)=0
J(0)=0
where, by definition,
61(τeny)=81+△r
24
△m(t)=Jo(t)dt
(13)
Equations 18 to 24 constitute the complete boundary value problem
The solution for o, which is obtained numerically, provides the evolu
Substitution of Eq. 12 into Eq 9 and division of both sides by m* then tion of 8(t) that matches its observed initial and final states while re- 9
vilas, for
b2=0
maining consistent with Eqs. 18 to 20
81)+m*(8-61)(14)Equation 17 shows that the turnover time to equals the mass m*of in
organic carbon in the oceans divided by the input flux ji In steady state,
the latter is equal to the rate at which carbon is immobilized in marine
Recall also the definitions of the normalized mass perturbation
sediments. The modern preindustrial reservoir of dissolved inorganic oo
carbon is about 38,000 Pg(133). Sedimentary organic carbon and car-
M=△m/m米
15
bonate carbon are immobilized in sediments at the total preindustrial
size by the sequestration rate, one obtains to 140 ng the reservoir
rate of approximately 0. 28 Pg year(134, 135). By dividing the reservoir
the normalized input flux
Krissansen-Totton et al(21) have recently provided a comprehen
sive analysis of the evolution of the organic burial fraction through ge
J=jill
(16
ologic time, commonly designated as f. Their study of the phanerozoic
portion of the record largely derives from an earlier analysis of Hayes et al
(43); both studies findf-0 23, which this paper assigns to pc Hayes et al
and the turnover time
(43)compute in a series of contiguous intervals throughout the Phan-
erozoic, obtaining a sequence f. The root mean square(rms)fluctuation
to =m
(17) of the fis is 0.037. The error assigned to pe is twice the rms fluctuation
Inserting each of these expressions into Eq. 14, one obtains
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