Abstract
The dynamics of the carbon cycle across different timescales is crucial for understanding past and present global climate changes. Following the Permian–Triassic boundary mass extinction (PTBME), the carbon cycle changed profoundly during the following 5.4 Myr, with magnitudes of changes comparable to those of the Precambrian. In pace with the successive cycles of the carbon budget, the recovery of the marine nekton underwent several evolutionary diversification and extinction cycles accompanied by eustatic sea-level changes and profound ecological reorganization of land plants, all indicative of climatic changes. Additional eruptive bursts of the Siberian Large Igneous Province (SLIP) are traditionally called upon as a plausible trigger for these climatic oscillations but firm evidence for coeval SLIP volcanism is still lacking. Based on new precise and accurate U-Pb zircon ages, we establish a high-resolution temporal calibration of the biggest positive carbon isotope excursion (CIE) spanning about 600 kyr in the late Smithian. The age of the Smithian-Spathian boundary (SSB) is established between 249.29 ± 0.06 and 249.11 ± 0.09 Ma. Our oldest U-Pb zircon ages indicate no overlap in time between the middle Smithian onset of the thermal maximum and the youngest available U-Pb zircon ages from SLIP volcanism. The constructed time line also indicates a duration of the global unconformity at the SSB that is compatible with glacio-eustatism. Potential cooling mechanisms such as a volcanic winter, the biological pump and the cessation of volcanism are discussed in the light of this new time line. In the low latitudes, the onset of the positive CIE remarkably predates the temperature drop by some 100 to 125 kyr. However, as long as the magnitude of such offset – if any – is unknown for the high latitudes, relations between the CIE and the cooling will remain an open question associated with largest Triassic extinction of the nekton.
Introduction
Following the Permian–Triassic boundary mass extinction (PTBME), and as a consequence of volcanic activity of the Siberian Large Igneous Province (SLIP), the global carbon cycle entered a protracted disequilibrium state (Payne et al., 2004; ) spanning the entire Early Triassic. Prior to the SLIP, the carbon cycle was stable and controlled by a combination of local mechanisms distributed in time and space around Earth at the time () excluding any consistent overriding and common control as was the case for the Early Triassic. This abrupt change of carbon cycle dynamics points to the crucial role of volatiles emitted from the SLIP in the disruption of the Late Permian equilibrium state. Based on the age of the Permian-Triassic boundary (PTB; ; ) and of the early-middle Anisian boundary (Ovtcharova et al., 2015) this unstable state persisted for at least 5.4 Myr before waning during the middle Anisian. Until a new equilibrium state was restored during the Anisian, the recovery of the marine benthos lingered, thus markedly differing from the diversification-extinction crises of the nekton (Orchard, 2007; ) that were alternating with the ecological crises of terrestrial plants (). The low competition within the shelly benthos most likely contributed to this delay (). Diversified bivalve communities returned in the middle Anisian () while coral reefs diversity was not restored to levels equivalent to that of the late Permian diversity until the Ladinian (Stanley, 2003), i.e., about 6 Myr after resumption of a stable carbon cycle. Of paramount importance is to reconstruct the relative timing of the global excursion of the carbon cycle, of successive diversification-extinction cycles of the nekton, intercalated ecological swaps of land plants punctuated by fern spikes, of eustatic sea-level change, carbonate crises and deposition of black shales dominated by terrestrial organic matter (OM) on shelves, and of climate change.
Here we reconstruct the timing of the largest positive carbon isotope excursion (CIE) of the Early Triassic during the late Smithian and basal Spathian (Payne et al., 2004; ). The magnitude of the associated Smithian-Spathian Boundary (SSB) extinction even surpassed that of the PTBME for the nekton and was the largest throughout the entire Triassic. High-precision U-Pb dating techniques (chemical abrasion, isotope dilution, thermal ionization mass spectrometry, and CA-ID-TIMS) are applied to single zircon crystals of volcanic ash beds intercalated with fossil-rich marine sediments in four sections of the Luolou Fm. (Nanpanjiang Basin, South China; Figures 1A, 2), herewith achieving a temporal resolution of the stratigraphic record at the 100 kyr level. Here we use a Bayesian age depth model to calibrate the duration of the CIE, of the black shale deposition, of the global SSB unconformity, and the age for the onset of cooling in low latitudes. This model permits (i) to detect hiatuses and changing sedimentation rate that both influence the shape and amplitude of the CIE, (ii) to exclude a volcanic winter as a cooling mechanism, and (iii) to evaluate other alternative cooling mechanisms such as CO2 drawdown by silicate weathering or by the biological pump in the hypothetical frame of the cessation of a middle Smithian SLIP volcanic episode.
FIGURE 1
FIGURE 2

Field photographs of the Smithian-Spathian boundary (SSB); white lines indicate the position of the boundary between units Vb and Va; (A) Qiakong section; topmost part of Daye Fm visible in lower left corner (person for scale); (B) Laren section; (C) Lilong section; (D) close-up of the Laren section, typical facies of unit IVb, with laminated black shale and rare, thin intervening gray limestone (Anasibirites multiformis/Xenoceltites pauciradiatus Zone); (E) Laren section, close-up view of the boundary between units IVb and Va; and (F) Laren section, ash layer CHIN10, note positive grading within the ash layer; for (E) and (F) hammer for scale.
Materials and Methods
Mineral Separation and CA-ID-TIMS U-Pb Dating
Detailed U-Pb age determinations were carried out on single zircon grains from volcanic ash beds of four sedimentary sections (Figure 1B); Laren (GPS coordinates 24°36′25.30″N 106°52′40.70″E); Shanggang (24°48′44.40″N 106°32′31.90″E); Lilong (24°54′25.69″N 106°32′30.37″E); and Qiakong (25°51′26.38″N 107°18′32.09″E). Zircon was recovered from each ash layer by crushing, milling and sieving to <250 μm prior gravity separation (Wifley Table), Frantz magnetic separation, and heavy-liquid separation using methylene iodide. From some ash layers zircon crystals were selected and mounted in epoxy resin and polished to reveal internal growth textures, followed by cathodo-luminescence (CL) imaging using a JEOL JSM7001F thermal field emission scanning electron microscope (SEM) at the University of Geneva (Supplementary Figure S4; CL images provided on request). CL images were used to select zircon crystals without inherited cores, major cracks, inclusions or disturbed zoning prior chemical abrasion. Selected zircon were annealed for 48 h at 900°C and washed several times with 3 N HNO3 in 3 ml Savillex beakers before the partial dissolution for 18 h at180°C in 40% HF and trace HNO3 in a pressurized Parr vessel containing fifteen 200 μl microcapsules, in order to minimize the effects of post-crystallization loss of radiogenic lead (Mattinson, 2005). Zircon grains of the Shanggang section were partially dissolved for only 12 h at 210°C. The chemically abraded zircon crystals were transferred in 3 ml Savillex vials and cleaned with 3 N HNO3 before fluxing overnight at 80°C on a hotplate in 6 N HCl. Zircon were washed again several times in 3 N HNO3. Single zircon crystals were loaded into clean 200 μl microcapsules, spiked with ∼4–6 mg of the EARTHTIME 202Pb–205Pb–233U–235U tracer solution (
In this study we re-dated two ash layers from Laren previously dated by
Age Depth Model
The age depth-model was obtained by the “rbacon” code (
Carbon Isotopes and Oxygen Isotope Measurements of Carbonates
High-resolution sampling was carried out in Qiakong, Shanggan, and Laren (Figure 1 and Supplementary Table S3) sections for stable isotope measurements (C and O) of bulk micrite (δ13Ccarb, δ18Ocarb). Samples were carefully cleaned, cut and drilled with a diamond-tipped drill to produce a fine powder. Carbonate carbon and oxygen isotopes compositions (δ13Ccarb and δ18Ocarb) were performed at the Institute of Earth Surface Dynamics, University of Lausanne with a GasBench II connected to a Thermoquest Finnigan DeltaPlus XL mass spectrometer, using a He-carrier gas system according to a method adapted after Spötl and Vennemann (2003). For calcite, a reaction temperature of 70°C was used and samples were reacted for 1 h. In-house standards of calcite were treated in the same way run interspersed with the samples in the same sequence. Samples were normalized using the in-house Carrara Marble standard calibrated against δ13C and δ18O values of NBS-19 (+1.95 and -2.20‰, respectively, relative to VPDB). External reproducibility for the analyses estimated from replicate analyses of the in-house standard (n = 8 per run of 32 samples) was better than ±0.08‰ for δ13C and ± 0.1‰ for δ18O values. The results are expressed in the δ-notation [δ = (R1/R2-1) × 1000] where R1 is the 13C/12C or 18O/16O ratio in the sample and R2 is the corresponding ratio of the standard V-PDB, in parts per thousand (‰).
Organic Geochemistry and Palynofacies
The characterization and quantification of preserved OM were performed on powdered whole rock samples at the Institute of Earth Sciences of the University of Lausanne, Switzerland, using a Rock-Eval 6 and following the method described by
Results
Biochronology
Accuracy of biochronological ages is of uttermost importance in constructing a reliable and robust frame in time and space for the biotic and abiotic events associated with the end-Smithian extinction. This goal has been facing two major obstacles. Firstly, the traditional use of conodont interval zones whose bases are defined by first occurrences (FO) of index species and whose tops are defined by the base of the next zone. These continuous zones assume that the FO of index species are synchronous, which is more the exception than the rule. Secondly, the incompleteness of the record, which has been generally overlooked but which opens a window in terms of global eustatic sea-level changes. Triassic ammonoid biochronology hinges on the principle of discontinuous and mutually exclusive maximal associations zones, which is an approach also shared by the more elaborate Unitary Association zones (UAZs;
Ammonoid zones based on maximal associations are here updated and new conodont Unitary Association Zones for the Nanpanjiang Basin are presented in Figure 1B. The most complete succession of ammonoid zones of the Luolou Fm. is documented in Laren (
Carbon Isotope Compositions and Organic Matter Contents
Carbon isotope variations in middle Smithian to early Spathian carbonates obtained from the four studied sections (Figure 1) are consistent and synchronous with other SSB sections worldwide as established by ammonoid biochronological control. The four analyzed sections yield a spike-shaped positive CIE peaking either slightly below or at the boundary between the black shales (Unit IVb) and the nodular limestone (Unit Va). The particular shape of his CIE is known from almost all low latitude SSB sections and its variable amplitude suggests truncation of the CIE peak, thus pointing to a global hiatus (
Carbon isotope compositions of organic carbon, Rock-Eval, TOC, and palynofacies analyses from Qiakong are presented in Supplementary Material, Supplementary Figure S3 and Supplementary Table S4, and provide evidence for the nature of the OM. Absence of major change in the composition of the OM supports the primary origin of the carbon isotope compositional changes. The parallel trend between organic and carbonate δ13C values suggests that variations within the carbon cycle were equilibrated over the atmosphere, linking the organic records to the inorganic records. Rock-Eval analyses plot within the fields of kerogen type II and III and point to a dominantly terrestrial origin of OM. The mature late Smithian OM is dominated by woody particles (both translucent and opaque) in this shelf setting, with a weak upward increasing trend, indicating a preeminent terrestrial origin. This late Smithian OM may conceivably be reworked from older strata or result from bacterial decomposition. The black shale unit is also accompanied by a reduction of the biogenic carbonate fraction in the sediment, suggesting a carbonate crisis on shelves.
U/Pb Geochronology of Zircon From Volcanic Ash Beds
Zircon U/Pb dates were analyzed from volcanic ash beds of all four sedimentary sections shown in Figure 1B. The complete data set can be found in Supplementary Table S1, and is shown in Figure 3. The choice of the relevant zircon dates for the calculation of the mean age is an essential and somewhat non-objective step. Below, we are giving our best estimates for the depositional age of a give ash layer, on the basis of the youngest cluster of zircon dates, after removal of some clear outliers from radiogenic lead loss. This “best estimate” age is compared to the age of the youngest zircon (lead loss outliers removed) and the mean age estimated from the maximum number of samples that still satisfy the statistical criteria of Wendt and Carl (1991) in Supplementary Table S5. Computing age-depth models with these different selection approaches will give an indication of the error introduced by this subjective choice (see below).
FIGURE 3

206Pb/238U single-grain zircon analyses of volcanic ash layers from sections Qiakong, Laren Shanggang, and Lilong. MSWD = mean square of weighted deviates. Horizontal bars: single-grain zircon analysis (2σ error). Weighted mean ages are calculated from grains marked in black, analyses marked in gray are excluded from the weighted mean age calculation. Vertical bar: weighted mean age and 2σ error (x = internal, y = external uncertainty including tracer calibration, z = external uncertainty including tracer calibration, and 238U decay constant uncertainty).
Laren
Five ash layers from Laren were sampled from the latest Smithian to the early Spathian. Twenty-two zircon grains of ash layer CHIN10 were analyzed. Ash layer CHIN10 is a prominent, dm thick, coarse-grained volcanic ash layer thinning upward, which is interbedded within the marly limestone ca. 8 m above the SSB. This ash layer within the Luolou Fm. has a very large lateral distribution throughout Guangxi and southern Guizhou. Long prismatic zircon without any prominent feature or inheritance yielded the youngest U-Pb ages. A subset of zircon grains has significantly older 206Pb/238U ages (up to 1013 Ma), and exhibits sector zoning and/or xenocrystic cores (Supplementary Figure S4). Finally, three grains were considered to calculate the best estimate 206Pb/238U date of 248.853 ± 0.086/0.11/0.29 Ma 2σ (MSWD = 0.51; X/Y/Z error notation according to Schoene et al., 2010). Sample 230214AT is located at the lithological boundary between the nodular and wavy limestone 15 cm below ash layer CHIN10. Zircons are short to long prismatic. Sixteen grains were dated, the youngest three yield a final 206Pb/238U age of 248.86 ± 0.23/0.33/0.35 Ma 2σ (MSWD = 0.06, n = 3). Nine grains of ash layer 230214BT (2.75 m below CHIN10) were analyzed, the best estimate is a 206Pb/238U date of 248.97 ± 0.16/0.16/0.31 Ma 2σ (MSWD = 0.89, n = 3). Six grains of ash layer LAR206 (0.5 m below the base of the nodular limestone) were dated, three grains yielding the best estimate 206Pb/238U date of 249.35 ± 0.13/0.15/0.30 Ma 2σ (MSWD = 0.079, n = 3). Eight grains of CHIN40 were analyzed, four of which yielded a best estimate 206Pb/238U date of 250.647 ± 0.064/0.09/0.28 Ma 2σ (MSWD = 0.84, n = 4).
Shanggang
Five ash layers were sampled from the middle-late Smithian to the early Spathian. Ash layer SHA301T is ca. 8.4 m above the base of the nodular limestone, at the top of Unit Vb. Six grains were analyzed, four of them yielding a best estimate 206Pb/238U date of 248.86 ± 0.11/0.13/0.30 Ma 2σ (MSWD = 0.21, n = 4) for the ash layer deposition. Ash layer SHA306T is located ca. 2.7 m above the base of the nodular limestone, yielding a variety short to long prismatic zircon grains. The age of six grains was determined, of which five yielded a best estimate 206Pb/238U date of 249.071 ± 0.092/0.11/0.29 Ma 2σ (MSWD = 0.66, n = 5). Because of low angle faulting the topmost 0.6 m of the black shale below the nodular limestone are crushed. Ash layer SHA359T is located ca. 0.8 m below the base of the nodular limestone. Six grains were dated yielding a best estimate 206Pb/238U date of 249.33 ± 0.10/0.12/0.29 Ma 2σ (MSWD = 0.25, n = 6). Ash layer SHA339T is ca. 5.8 m below the base of the nodular limestone. Six long prismatic zircon grains were analyzed yielding a best estimate 206Pb/238U date of 249.74 ± 0.12/0.13/0.30 Ma 2σ (MSWD = 0.62, n = 6). Ash layer SHA303T is ca. 9.3 m below the base of the nodular limestone. The age of eight long-prismatic zircon grains was determined, seven of them yielding a best estimate 206Pb/238U date of 250.116 ± 0.085/0.11/0.29 Ma 2σ (MSWD = 1.1, n = 8).
Qiakong
The sample collection from the Qiakong section is composed of six thin ash layers that do not show signs of post-depositional lateral transport. Twelve long prismatic (∼200 μm) zircon of ash layer QIA13T are analyzed (ca. 14 m above the base of the nodular limestone). Zircon displays no inheritance at the resolution we are able to achieve. The youngest grain yielding a 206Pb/238U date of 247.83 ± 0.17 Ma was excluded from the final age calculation due to suspected loss of radiogenic lead. The best estimate 206Pb/238U date of QIA13T is 248.250 ± 0.065/0.091/0.28 Ma 2σ (MSWD = 1.2, n = 3). Sample QIA12T is located at the lithological boundary between the nodular limestone (unit Vb) and the overlying fine laminated marly limestone (unit Vc) and could possibly correlate with ash layer 230214AT in the Laren section as well as with SHA301T in the Shanggang section (Figure 1). Nine long prismatic zircon grains from QIA12T (∼200 μm) were analyzed. The youngest cluster of three grains yield a 206Pb/238U age of 248.893 ± 0.069/0.094/0.28 Ma 2σ (MSWD = 0.56, n = 3). Eleven zircon grains of ash layer QIA11T (ca. 6.3 m above the nodular limestone) were analyzed zircon are exceptionally low in radiogenic lead. The best estimate 206Pb/238U was calculated on the basis of the two youngest grains at 248.95 ± 0.49/0.50/0.57 Ma 2σ (MSWD = 0.0056; n = 2). The lithological boundary between the black shale and the nodular limestone is bracketed by ash layers QIA9T (206Pb/238U = 249.110 ± 0.088/0.11/0.29 Ma 2σ; MSWD = 1.8, n = 7) and QIA07T (206Pb/238U = 249.292 ± 0.063/0.091/0.28 Ma 2σ; MSWD = 0.36, n = 4), which are considered to be representative of zircon crystallization and ash bed deposition. Both younger zircon of ash layer QIA9T (206Pb/238U = 246.40 ± 0.018 Ma) and QIA07T (206Pb/238U = 248.58 ± 0.22 Ma), respectively, most likely suffered from a small amount of lead loss and were excluded from the age calculation. QIA3T is a reddish thin layered ash bed occurring 4 m below the base of the nodular limestone (Figure 1B). Twelve grains have 206Pb/238U dates from 253.4 ± 1.8 Ma to 371.1 ± 4.2 Ma, which are all considered to be inherited and are excluded from the age model. These grains of Triassic to Permian age are evidently reworked into the late Smithian black shale.
Lilong
Ash layer LIL508 is a thin ash bed occurring within the black shale ca. 0.5 m below the base of the nodular limestone. Zircons are short to long prismatic (ca. <100 μm). Twelve grains were measured, yielding dispersed 206Pb/238U dates over an age range from 249.56 ± 0.26 Ma to 263.38 ± 0.36 Ma. Therefore, all these grains are of detrital origin and are excluded from the age model. Interestingly, QIA3T, and LIL508 are the only two samples containing reworked zircon grains and are from unit Vb, providing another line of evidence that the black shale was deposited during a lowered based level accompanied by erosion in the hinterland.
Age-Depth Model
The stratigraphic position of each ash bed and the selected mean ages of the youngest cluster of zircon dates were used to calculate separate age-depth models for Qiakong, Laren, and Shanggang (Figure 4). The model of each section reveals an increase of sedimentation rate across the SSB and the presence of a hiatus at or near the top of the late Smithian black shale. Based on the ammonoid biochronological definition, the SSB is within the interval of separation between GXZ and TAZ (since NZ is missing in South China) in the topmost part of unit IVb, which is bracketed by ashes QIA07T (249.292 ± 0.063 Ma) and QIA09T (249.110 ± 0.088 Ma). The shortest estimate for the duration of the SSB gap in the most expanded Qiakong section derived from the age depth model is of 64 ± 104 kyr, a figure well within the range of Cretaceous “cold snaps,” and ephemeral ice sheets (Miller et al., 2005). The base of the TAZ is considered equivalent to the base of the nodular limestone (Figure 1B) and therefore yields a minimum estimate for the age of the SSB (249.167 ± 0.087 Ma; Figure 4). Calculating age-depth models on the base of (i) youngest zircon date of each sample, and (ii) minimum cluster at maximum acceptable MSWD value (see above) yields average age estimates of 249.133 ± 0.132 Ma and 249.263 ± 0.101 Ma, respectively, for the SSB. The three approaches thus yield coincident SSB model age estimates within their respective uncertainties.
FIGURE 4

Bayesian “rbacon” age models for Qiakong Laren and Shanggang. The red line represents the model mean age with its error envelope at 95% confidence interval in gray. Data are reported as Th-corrected 206Pb/238U ages with 2σ internal uncertainty. Two groups of ash layers yielded ages that overlap within error, thus allowing the positioning of two time-lines: a first line including QIA07T, LAR206T, and SHA359T at the top of the late Smithian Unit IVb, and a second line linking QIA12T, CHIN10, and SHA301T of late early Spathian age at the lower boundary of Unit Vc. The position and age of the “Black Band Marker,” an isochronous 10–15 cm thick shale layer 1.0 to 3.5 meters above the boundary between units Va and Vb in Qiakong (Figure 1) is indicated as well. The base of the nodular limestone rests upon an unconformity and is interpolated from all three sections at an age of 249.167 ± 0.087 Ma.
The bracketed age of the SBB is at marked variance with the ca. 1 Myr younger age derived from astronomical tuning (Li et al., 2016a, b). Omission of stratigraphic gaps and the utilization of interval zones defined by frequently diachronous first appearance of index conodont species provide potential explanations for this younger age. Interestingly, this divergence in the age of the SSB decreases when astronomical tuning is based on carbon isotope composition (
FIGURE 5

Durations of the hiatus, of the carbon isotope excursion (CIE) and age of the early Spathian “Black Band marker.” Color code: pink represents the part of the CIE in the Qiakong section that is missing in Laren and Shanggang; blue: duration of preserved carbon excursion in Laren and Shanggang; white: duration between onset of nodular limestone and black shale marker; and purple: duration of pre-CIE black shale deposition in Qiakong. The Black Band Marker provides an independent isochronous time line. 206Pb/238U single-grain zircon ages of dated ash layers are indicated, for sample numbers see Figure 1.
FIGURE 6

Conceptual model for the timeframe of the subsequent five-phase evolution of global climate, sea-level and ammonoid diversity from the mid-Smithian to basal Spathian, relating the carbon isotope record of this study to δ18OphosN (
Equipped with this calibration, the time compatibility of two cooling feedback mechanisms, i.e., silicate weathering and marine organic carbon cycling, can now be quantitatively evaluated. The results of these calculations are summarized in Table 1. Feedback mechanisms could conceivably account for some or all of the late Smithian cooling. Such assessments rest on the unwarranted assumption that the excess of atmospheric CO2 originated from a volumetrically important middle Smithian eruptive burst of the SLIP.
TABLE 1
| A) volcanic emission | ||||||||||
| Siberian traps emission PTB | CIE (total; ‰) | dcf (‰) | dci (‰) | dce (‰) | Mf (Gt) | Mi (Gt) | Me (Gt) | Eruption duration (a) | Gt/a | |
| −4.92 | −1.32 | 3.6 | −9.9 | 129,000 | 82,000 (2) | 47,000 (1) | 500,000 | 0.09 | ||
| B) Burial of organic carbon | ||||||||||
| Drawdown of atmospheric C by burial of organic carbon (600 ka CIE) | CIE (total; ‰) | dcf (‰) | dci (‰) | dcb (‰) | Mf (Gt) | Mi (Gt) | Mb (Gt) | |||
| 6.13 | 4.03 | −2.1 | −27 | 103,500 | 129,000 | −25,500 | ||||
| Drawdown Rate Gt/a | Phase duration (a) | Missing Gt | Total atmospheric C drawdown Gt | |||||||
| Missing atmospheric C due to hiatus | −0.051 | 64,000 | −3264 | −28,764 | ||||||
| C drawdown needed before initiation positive CIE | 135,000 | −6885 | −6885 | |||||||
| Total C drawdown | −35,649 | |||||||||
| C) Weathering of SLIP Basalts | ||||||||||
| Literature values | C consumption rate of SLIP area | C consumption rate of SLIP area in 600 ka | ||||||||
| annual ave. T | Mol C/km2/a | km2 | mol/a | Time (a) | mol in 600 ka | g C | Gt C | |||
| Columbia Plateau (3) | 7.4°C | 370,000 | 2,500,000 | 9.3E + 11 | 600,000 | 5.6E + 17 | 6.7E + 18 | 6660 | ||
| Deccan Traps (3) | 27°C | 1,260,000 | 2,500,000 | 3.2E + 12 | 600,000 | 1.9E + 18 | 2.3E + 19 | 22,680 | ||
| Mt. Cameroon (3) | 25.6°C | 3,440,000 | 2,500,000 | 8.6E + 12 | 600,000 | 5.2E + 18 | 6.2E + 19 | 61,920 | ||
| Java (3) | 24.8°C | 6,410,000 | 2,500,000 | 1.6E + 13 | 600,000 | 9.6E + 18 | 1.2E + 20 | 115,380 | ||
| SLIP (1)* | 2,500,000 | 6.3E + 12 | 600,000 | 3.8E + 18 | 4.5E + 19 | 45,360 | ||||
Mass balance calculations.
Legend: dcf: final C isotope composition, dci: initial C isotope composition, dce: average isotope composition of emitted C (magmatic, sedimentary), dcb: C isotope composition of buried organic matter, Mf: final mass of C, Mi: mass of atmospheric C initially present Me: mass of erupted C, Mb: mass of buried C, Gt: gigatons, Sobolev et al. (2011); Payne et al. (2004),
Discussion
Mechanisms of CO2 Removal From the Atmosphere
Silicate Weathering
The weathering of large subaerial exposures of basaltic flows emplaced during the activity of Large Igneous Provinces can act as an efficient CO2 sink during times of warm and humid climate. We adopt present-day CO2 consumption rates of basaltic provinces from
Burial of Organic Carbon, the “Biological Pump”
In the following, we assess how much carbon has to be removed from the atmosphere by the biological pump in order to generate a positive CIE with an amplitude of 6‰. Mass balance calculations (Table 1B) yield a drawdown of 25,500 Gt C (Ma) from the atmosphere to be stored in the sedimentary sink. This buried amount is approximately half of the ∼47,000 Gt C that was injected into the atmosphere during the main eruptive event of the SLIP (Sobolev et al., 2011; Me in Table 1A), a value used here for our Smithian case. Hence, it leaves the final atmospheric C reservoir with an excess of 103,500 Gt C (Mf in Table 1B). The 64 ± 104 kyr long hiatus at the top of black shales in Qiakong is equivalent to about 3264 Gt C missing from the budget, which must be added to the 25,500 Gt C estimate for the preserved part of the drawdown (Mb in Table 1B), thus yielding a grand total of ca. 29,000 Gt C for the entire late Smithian. This calculation suggests that the biological pump alone was not able to remove more than ca. 30% of the total atmospheric C and thus was not sufficient for eliciting a late Smithian cooling of 7–8°C on the northern Indian margin (
Implications for Triassic Climate Models
A Timeline for the CIE and Temperature Around the SSB
The calibrated succession of climatic upheavals around the SSB is subdivided into five phases, summarized in Figure 6. The 622 ± 137 kyr long late Smithian positive CIE is best defined in the most complete Qiakong section (Figure 1B). It encompasses the time interval between the end of the middle Smithian negative peak marking the exit from the global thermal maximum (Phase 1), and the positive peak at the base of the Spathian (Phase 5). In Qiakong, the precise timing of the SSB and of Phase 4 are blurred by a gap including the NZ ammonite zone, which is included within the global glacio-eustatic hiatus straddling the boundary. The massive and protracted burial of OM during the late Smithian cooling is considered the cause of a global increase of δ13C in marine carbonates. The total shift in δ13C between Phase 1 and 5 is of +6‰, thus yielding an average rate of change of approximately +1‰ per 100 kyr. The comparably smaller +4‰ CIE that followed the negative end-Permian peak in deep water and continuous sections (
Reasons for C Cycle Instability
Payne and Kump (2007) explained the unstable global C cycle during the Early Triassic with recurrent injections of volcanogenic (at δ13C = -5‰) and thermogenic C from OM sources (at δ13C = -25‰), augmented by associated feedback mechanisms (Svensen et al., 2009, 2015). Among the latter, we may identify variations of global temperature and latitudinal temperature gradient, marine anoxia, burial of organic carbon, weathering and riverine C, P input into the oceans, and sea-level oscillations. Exact timing established for the SLIP activity (
Arguments for a Cold Latest Smithian
A late Smithian cooling (starting with the GXZ) in the low latitudes is supported by several independent lines of evidence. Biogeographic distribution of conodonts indicates that cold-water forms (segminiplanate taxa) became unusually abundant within shallow tropical waters (Leu et al., 2019). Following the middle Smithian spore spike of global scope, the ecological recovery of terrestrial plants already started during the late Smithian (
A Volcanic Origin for the Middle-Early Late Smithian Thermal Maximum?
A recent string of studies investigating geochemical proxies across the end-Smithian extinction (Lyu et al., 2019; Shen et al., 2019; Song et al., 2019; Stebbins et al., 2019a, b; Zhang et al., 2019) all revolve around the scenario of a volcanogenic origin for the middle to early late Smithian thermal maximum. All these works also proposed cessation of volcanism as the primary trigger for the latest Smithian and basal Spathian cooling. Below, we address exclusively key points pertaining to volcanism indicators and timing.
Smithian weak mercury anomalies from a diverse array of sections form a central argument in support of volcanism. These anomalies were causally related to the middle Smithian –early late Smithian thermal maximum by Shen et al. (2019). The modest magnitude of these Smithian anomalies stands in marked contrast with that associated to the PTBME, which is contemporaneous with the main eruptive phase of the Siberian LIP. Unlike the PTBME anomaly, Smithian weak Hg/TOC anomalies do not appear to be synchronous but are scattered throughout middle and late Smithian times. Therefore, clear evidence for substantial middle Smithian volcanism that would lead to a thermal maximum is still wanted (see section “discussion” in
Although the upper boundary of the Siberian Traps is an erosional one, no SLIP ages (
Expanding on the volcanic hypothesis, Shen et al. (2019) then related the cooling documented across the SSB to the cessation of volcanism. However, younger Hg/TOC anomalies of comparable amplitude during the Spathian were also recorded from the same sections studied by these authors, thus undermining a direct control of Smithian and Spathian climatic changes by volcanism, even if assuming that Smithian, and Spathian weak Hg/TOC anomalies are a reliable proxy for volcanism. Additional volcanic bursts of the SLIP have long been invoked as the usual ad hoc suspect controlling Early Triassic climatic changes (e.g., Ovtcharova et al., 2006) but no clear mercury anomaly nor U-Pb ages support this hypothesis.
The offset between the inception of the positive CIE and the onset of the cooling amounts to 100 to 125 ky in the low latitude (see Figure 6). However, no such data are available for the high latitude. Therefore, it is not yet possible to establish if the cooling was synchronous or not across the entire range of latitude, as the CIE apparently was. As long as the latitudinal pattern of temperature change remains unknown, feedbacks between temperature and the carbon cycle during the Smithian and Spathian cannot be objectively addressed at a global scale.
Conclusion
The high-resolution timeline proposed in this study allows detailed understanding of the sequence of environmental and biological changes during a 2 Myr long period across the SSB. Our model summarized in Figure 6 proposes links between (i) global temperature, (ii) sea-level variations, (iii) variation in terrestrial and marine bio-productivity, and of burial of organic carbon, (iv) weathering intensity, continental runoff and precipitation of inorganic carbon, and eventually (v) evolutionary crises and diversification pulses of marine biota. Silicate weathering alone is shown to be a quantitatively plausible mechanism explaining the late Smithian global cooling. Although the burial of organic carbon (the “biological pump”) must have partly contributed to the cooling, it cannot explain the late Smithian cooling if considered as the sole mechanism. We also point out that a volcanic origin of the immediately preceding thermal maximum still lacks robust evidence, a consequence of which is that volcanic forcing of Early Triassic climate remains an ad hoc and weak explanation.
Statements
Data availability statement
All data are contained in Table 1 and Supplementary Tables S1–S5. Background data, metadata, CL images of dated zircon crystals, and further analytical protocols not contained in the methods section are available on request from the authors.
Author contributions
HB and US designed the research. HB, ML, BB, and NG collected the field data and the samples. PW carried out the U-Pb geochronology work. TV, BB, ML, ES-H, and NG collected the other data. All authors contributed the data interpretation. PW, HB, and US wrote the manuscript with the help of all other authors.
Funding
This study was supported through the Swiss National Science Foundation grant numbers 156424 and 182007 (US), and 160055 (HB).
Acknowledgments
All authors thank the Geneva and Zürich groups for technical support, especially Maria Ovtcharova for invaluable support in U/Pb analytics and Thierry Adatte for RockEval analyses. Ji Cheng and Kuang Guodun are deeply thanked for their long-term help in the field. The final version of this work benefited from constructive and helpful reviews by TA and SB, as well as by the Frontiers editor MC.
Conflict of interest
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.
Supplementary material
The Supplementary Material for this article can be found online at: https://www.frontiersin.org/articles/10.3389/feart.2020.00196/full#supplementary-material
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Summary
Keywords
Early Triassic, Smithian-Spathian boundary, U-Pb geochronology, carbon cycle, carbon isotopes, biochronology, Bayesian age-depth model
Citation
Widmann P, Bucher H, Leu M, Vennemann T, Bagherpour B, Schneebeli-Hermann E, Goudemand N and Schaltegger U (2020) Dynamics of the Largest Carbon Isotope Excursion During the Early Triassic Biotic Recovery. Front. Earth Sci. 8:196. doi: 10.3389/feart.2020.00196
Received
21 February 2020
Accepted
15 May 2020
Published
09 June 2020
Volume
8 - 2020
Edited by
Michael Andrew Clare, University of Southampton, United Kingdom
Reviewed by
Thomas Algeo, University of Cincinnati, United States; Seth Burgess, California Volcano Observatory (CalVO), USGS, United States
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© 2020 Widmann, Bucher, Leu, Vennemann, Bagherpour, Schneebeli-Hermann, Goudemand and Schaltegger.
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*Correspondence: Urs Schaltegger, urs.schaltegger@unige.ch
This article was submitted to Sedimentology, Stratigraphy and Diagenesis, a section of the journal Frontiers in Earth Science
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