Geochemistry of Early Toarcian carbonates

The Early Toarcian was characterized by two large perturbations to the carbon cycle: a positive trend associated with increased organic matter burial and ocean anoxia, and a pronounced negative carbon isotope excursion (CIE). We contrast the geochemical evolution in the carbonate phases of two successions: one from the Paris Basin (Sancerre core, comprising black shales), the other from the Lusitanian Basin (Peniche section with very minor lithological expression of bottom water anoxia). Our aim was to identify whether these carbon cycle perturbations were related, and differentiate between the common (global) versus regional expressions of the biogeochemical response and ocean chemistry. Our results highlight contrasts in timing of different phases of anoxia in both locations through the widely documented negative CIE. Widespread anoxic conditions were not a necessary prerequisite for generating a pronounced CIE, as required by the recycling (so-called "Küspert") model. The production of carbonate simultaneously dropped during the d13C negative shift in both locations, likely in response to lowered seawater saturation rate induced by substantial absorption of CO2 from the atmosphere. The recovery interval was accompanied by a rapid reestablishment of seawater alkalinity, and primary and carbonate productivity in epicontinental seas, as evidenced by high d13C and Sr/Ca, in contrast with the more open ocean regime in the Lusitanian Basin. Our results confirm that parallels can be draw between the ocean productivity response and feedback during the Toarcian CIE and the PETM. Both events are characterized by ocean acidification and reduced pelagic calcification followed by a peak in nearshore coccolith productivity, which could have helped the recovery from the perturbation.

Stable isotopic composition and carbonate concentrations of sediments of the Cretaceous/Paleogene boundary in the Antarctic

Stable isotopic records across the Cretaceous/Paleogene (K/P) boundary in Maud Rise Holes 689B and 690C indicate that significant climatic changes occurred during the latest Cretaceous, beginning approximately 500 k.y. prior to the mass extinction event and the enrichment of iridium at the K/P boundary (66.4 Ma). An oxygen isotopic decrease of ~0.7 per mil - ~1.0 per mil is recorded in the Late Cretaceous planktonic and benthic foraminifers between 66.9 and 66.6 Ma. The negative isotope excursion was followed by a positive excursion of similar magnitude between 66.6 Ma (latest Cretaceous) and ~66.3 Ma (earliest Paleocene). No other isotopic excursions of this magnitude are recorded in the planktonic and benthic microfossil records 1.0 m.y prior to, and for 2.0 m.y following the mass extinction event at the K/P boundary. The magnitude and duration of these isotopic excursions were similar to those at the Paleocene/Eocene and Eocene/Oligocene boundaries. A major d13C excursion occurred 200 k.y. prior to the boundary, involving a positive shift in planktonic and benthic d13C of ~0.5 per mil - 0.75 per mil. Similar changes observed in other deep-sea sequences indicate that this reflected a global change in d13C of the oceanic total dissolved carbon (TDC) reservoir. The magnitude of this inferred carbon reservoir change and its association with high latitude surface-water temperature changes recorded in the d18O records implies that it was linked to global climate change through feedback loops in the carbon cycle. At the K/P boundary, the surface-to-deep water d13C gradient is reduced by approximately 0.6 per mil - ~0.2 per mil. However, unlike sequences elsewhere, the planktonic-benthic d13C gradient (Delta d13C) was not eliminated in the Antarctic. The surface-to-deep water gradient was re-established gradually during the 400 k.y. following the mass extinction. Full recovery of the Delta d13C occurred by ~60.0 Ma. In addition to the reduced vertical d13C gradient across the K/P boundary, there was a negative excursion in both planktonic and benthic d13C beginning approximately 100 k.y. after the boundary (66.3 Ma). This excursion resulted in benthic d13C values in the early Paleogene that were similar to those in the pre-K/P boundary intervals. This negative shift appears to reflect a change in the d13C of the oceanic TDC reservoir shift that may have resulted from reduced carbon burial and/or increased carbon flux to the oceans. Any model that attempts to explain the demise of the oceanic plankton at the end of the Cretaceous should consider the oceanic environmental changes that were occurring prior to the massive extinction event.

Stable carbon and oxygen isotope ratios of bulk sediment from DSDP Hole 62-463 (Appendix A)

In order to elucidate early Aptian marine paleotemperature evolution across the period of enhanced organic carbon (Corg)-burial [Oceanic Anoxic Event (OAE) 1a], stable isotope analyses were performed on pelagic limestones at Deep Sea Drilling Project Site 463, central Pacific Ocean. The delta18O data exhibit a distinct anomaly by ~-2? spanning the OAE 1a interval (i.e., a ~6 m-thick, phytoplanktonic Corg-rich unit constrained by magneto-, bio- and delta13C stratigraphy). Elucidation of paleotemperature significance of the delta18O shift is made by taking account of recent Sr/Ca evidence at the same section, which revealed that geochemical signals in carbonate-poor lithologies are relatively unaltered against burial diagenesis. By discriminating delta18O values from carbonate-poor samples (CaCO3 contents=5-30 wt.%), it appears that an abrupt rise in seasurface temperatures (SSTs) by 8 °C (=-1.7? shift in delta18O) occurred immediately before OAE 1a, whereas a cooling mode likely prevailed during the peak Corg-burial. In terms of its stratigraphic relationship as to the Corg-rich interval and to a pronounced negative delta13C excursion, as well as its timescale, the observed SST rise resembles those associated with the Paleocene-Eocene thermal maximum and, more strikingly, Jurassic Toarcian OAE. This observation is consistent with the hypothesis that these paleoenvironmental events were driven by a common causal mechanism, which was likely initiated by the greenhouse effect via massive release of CH4 or CO2 from the isotopically-light carbon reservoir and terminated by a negative productivity feedback.

Susceptibility measurements at Gubbio sections

The complex interplay between extraterrestrial events and earth-bound processes that triggered one of the greatest biological crises of the Phanerozoic requires a high resolution timescale. Detailed magnetic susceptibility measurements at the Contessa Highway and Bottaccione sections (Italy) span the Cretaceous-Paleogene boundary and reveal clear orbital signatures in the sedimentary record. Identification of precession and 405 kyr eccentricity cycles allows an estimate of 324+/-40 kyr for the duration of the Maastrichtian part of Chron C29r. We present in the same high resolution time frame sites in Spain and the North and South Atlantic and bio-horizons, biotic changes, stable isotopic excursions and the decrease in Osmium isotopes recorded in these sections. The onset of 187 Os/ 188 Os decrease coincides with the d13 C negative excursion K-PgE1, thus suggesting a first pulse in Deccan volcanism at 66.64 Ma. The K-PgE3 d13 C negative excursion is possibly the expression of a second pulse at 66.26 Ma. Late Maastrichtian d13 C negative excursions are of low intensity and span durations of one to two eccentricity cycles, whereas early Danian excursions are brief (about 30 kyr) and acute. In Biotic response to late Maastrichtian perturbations occurred with a delay of ca. 200 kyr after the beginning of K-PgE1 shortly before K-PgE3. The biotic perturbation could be thus either a delayed response to K-PgE1, or a direct response to K-PgE3, and possibly, a threshold response to the stepwise buildup of CO2 atmospheric injections. No delay is evident in response to early Danian hyperthermal events. These differences suggest that short-lived, volcanically-derived environmental perturbations were buffered within the stable late Maastrichtian oceanic realm whereas they were amplified by the more sensitive and highly disturbed early Danian oceanic ecosystem.

Beryllium concentrations and deposition rates in ODP holes from the north Atlantic

Increases in the production rate of cosmogenic radionuclides associated with geomagnetic excursions have been used as global tie-points for correlation between records of past climate from marine and terrestrial archives. We have investigated the relative timing of variations in 10Be production rate and the corresponding palaeomagnetic signal during one of the largest Pleistocene excursions, the Iceland Basin (IB) event (ca. 190 kyr), as recorded in two marine sediment cores (ODP Sites 1063 and 983) with high sedimentation rates. Variations in 10Be production rate during the excursion were estimated by use of 230Thxs normalized 10Be deposition rates and authigenic 10Be/9Be. Resulting 10Be production rates are compared with high-resolution records of geomagnetic field behaviour acquired from the same discrete samples. We find no evidence for a significant lock-in depth of the palaeomagnetic signal in these high sedimentation-rate cores. Apparent lock-in depths in other cores may sometimes be the result of lower sample resolution. Our results also indicate that the period of increased 10Be production during the IB excursion lasted longer and, most likely, started earlier than the corresponding palaeomagnetic anomaly, in accordance with previous observations that polarity transitions occur after periods of reduced geomagnetic field intensity prior to the transition. The lack of evidence in this study for a significant palaeomagnetic lock-in depth suggests that there is no systematic offset between the 10Be signal and palaeomagnetic anomalies associated with excursions and reversals, with significance for the global correlation of climate records from different archives.

CO2 concentration and stable isotope ratios of three Antarctic ice cores covering the period from 149.4 - 1.5 kyr before 1950

We present new d13C measurements of atmospheric CO2 covering the last glacial/interglacial cycle, complementing previous records covering Terminations I and II. Most prominent in the new record is a significant depletion in d13C(atm) of 0.5 permil occurring during marine isotope stage (MIS) 4, followed by an enrichment of the same magnitude at the beginning of MIS 3. Such a significant excursion in the record is otherwise only observed at glacial terminations, suggesting that similar processes were at play, such as changing sea surface temperatures, changes in marine biological export in the Southern Ocean (SO) due to variations in aeolian iron fluxes, changes in the Atlantic meridional overturning circulation, upwelling of deep water in the SO, and long-term trends in terrestrial carbon storage. Based on previous modeling studies, we propose constraints on some of these processes during specific time intervals. The decrease in d13C(atm) at the end of MIS 4 starting approximately 64 kyr B.P. was accompanied by increasing [CO2]. This period is also marked by a decrease in aeolian iron flux to the SO, followed by an increase in SO upwelling during Heinrich event 6, indicating that it is likely that a large amount of d13C-depleted carbon was transferred to the deep oceans previously, i.e., at the onset of MIS 4. Apart from the upwelling event at the end of MIS 4 (and potentially smaller events during Heinrich events in MIS 3), upwelling of deep water in the SO remained reduced until the last glacial termination, whereupon a second pulse of isotopically light carbon was released into the atmosphere.

Iron speciation and magnetic susceptibility in bottom sediments of the Black Sea, Core SMG91-903

12 cores of Late Pleistocene - Holocene deposits were studied. They were collected by gravity cores on the continental slope and in the deep-water part of the Black Sea within the Adler-Tuapse polygon. In four of them in New Euxinian deposits at the base of a packet of hydrotroilite laminae paleomagnetic anomalies likely resulting from the Gothenburg magnetic excursion occur. Comparison with results of similar studies in the western Black Sea, where the Gothenburg magnetic excursion was previously found, let to validate stratigraphic synchronism of the hydrotroilite horizon in the eastern and western parts of the Black Sea and to confirm the authors' views about peculiarities of paleogeographical development of the Black Sea basin in the Late Pleistocene - Holocene.

Paleomagnetic and beryllium isotope record of West Equatorial Pacific sediments

The reliability of paleomagnetic records as proxies of the geomagnetic field intensity is still a matter of controversy since volcanic materials hardly provide continuous records, and marine sediments are suspected to carry a remanence biased by post-depositional realignments and/or by overprints. Such long standing debate emphasizes the need for the development of methods independent from paleomagnetism to decipher geomagnetic intensity variations. High resolution measurements of authigenic 10Be/9Be along with a detailed sedimentary record of directional and relative paleointensity variations evidence, over the 0.6-1.3 Ma time interval, frequent and recurrent excursions or short events in the late Matuyama and the early Brunhes epochs, among which two Brunhes-Matuyama reversal precursors and an intra-Jaramillo excursion. The results of this study confirm the idea of a highly unstable geomagnetic field as suggested by paleomagnetic evidences.

Long-term biogenic particle fluxes in the Bering Sea and the central subarctic Pacific Ocean

Time-series sediment traps were deployed for five consecutive years in two distinctively different subarctic marine environments. The centrally located subarctic pelagic Station SA (49°N, 174°W; water depth 5406 m) was simultaneously studied along with the marginal sea Station AB (53.5°N, 177°W; water depth 3788 m) in the Aleutian Basin of the Bering Sea. A mooring system was tethered to the sea-floor with a PARFLUX type trap with 13 sample bottles, which was placed at 600 m above the sea-floor at each of the two stations. Sampling intervals were synchronized at the stations, and they were generally set for 20 days during highly productive seasons, spring through fall, and 56 days during winter months of low productivity. Total mass fluxes, which consisted of mainly biogenic phases, were significantly greater at the marginal sea Station AB than at the pelagic Station SA for the first four years and moderately greater for the last year of the observations. This reflects the generally recognized higher productivity in the Bering Sea. Temporal excursion patterns of the mass fluxes at the two stations generally were in parallel, implying that temporal changes in their biological productivity are strongly governed by a large-scale seasonal climatic variability over the region rather than local phenomena. The primary reason for the difference in total mass flux at the two stations stems mainly from varying contributions of siliceous and calcareous planktonic assemblages. A significantly higher opal contribution at Station AB than at Station SA was mainly due to diatoms. Diatom fluxes at the marginal sea station were about twice those observed at the pelagic station, resulting in a very high opal contribution at Station AB. In contrast to the opal fluxes, CaCO3 fluxes at Station AB were slightly lower than at Station SA. The ratios of Corg/Cinorg were usually significantly greater than one in both regions, suggesting that preferentially greater organic carbon from cytoplasm than skeletal inorganic carbon was exported from the surface layers. Such a process, known as the biological pump, leads to a carbon sink which effectively lowers p CO2 in the surface layers and then allows a net flux of atmospheric CO2 into the surface layer. The efficiency of the biological pump is greater in the Bering Sea than at the open-ocean station.

Mineralogical (bulk rock and clay fraction) and stable isotope composition (d13C, d18O) of Aptian deposits of the Bir Oum Ali succession, central Tunisia

Alternations between siliciclastic, carbonate and evaporitic sedimentary systems, as recorded in the Aptian mixed succession of southern Tunisia, reflect profound palaeoceanographic and palaeoclimatic changes in this area of the southern Tethyan margin. The evolution from Urgonian-type carbonates (Berrani Formation, lower Aptian) at the base of the series, to intervals dominated by gypsum or detrital deposits in the remainder of the Aptian is thought to result from the interplay between climate change and tectonic activity that affected North Africa. Based on the evolution of clay mineral assemblages, the early Aptian is interpreted as having been dominated by slightly humid conditions, since smectitic minerals are observed. Near the early to late Aptian boundary, the onset of a gypsiferous sedimentation is associated with the appearance of palygorskite and sepiolite, which supports the installation of arid conditions in this area of the southern Tethyan margin. The evaporitic sedimentation may have also been promoted by the peculiar tectonic setting of the Bir Oum Ali area during the Aptian, where local subsidence may have been tectonically enhanced linked to the opening of northern and central Atlantic. Stress associated with the west and central African rift systems may have triggered the development of NW-SE, hemi-graben structures. Uplifted areas may have constituted potential new sources for clastic material that has been subsequently deposited during the late Aptian. Chemostratigraphic (d13C) correlation of the Bir Oum Ali succession with other peri-Tethyan regions complements biostratigraphic findings, and indicates that a potential expression of the Oceanic Anoxic Event (OAE) 1a may be preserved in this area of Tunisia. Although the characteristic negative spike at the base of this event is not recognized in the present study, a subsequent, large positive excursion with d13C values is of similar amplitude and absolute values to that reported from other peri-Tethyan regions, thus supporting the identification of isotopic segments C4-C7 of the OAE1a. The absence of the negative spike may be linked to either non preservation or non deposition: the OAE1a occurred in a global transgressive context, and since the Bir Oum Ali region was located in the innermost part of the southern Tethyan margin during most of the Aptian, stratigraphic hiatuses may have been longer than in other regions of the Tethys. This emphasizes the importance of integrating several stratigraphic disciplines (bio-, chemo- and sequence stratigraphy) when performing long-distance correlation.

Alkenone stable carbon isotopes, carbonate stable carbon and oxygen isotopes, planktic foraminifera boron isotopes and atmospheric CO2 calculations and box model results from Ras il-Pellegrin section, Malta

The development of a permanent, stable ice sheet in East Antarctica happened during the middle Miocene, about 14 million years (Myr) ago. The middle Miocene therefore represents one of the distinct phases of rapid change in the transition from the "greenhouse" of the early Eocene to the "icehouse" of the present day. Carbonate carbon isotope records of the period immediately following the main stage of ice sheet development reveal a major perturbation in the carbon system, represented by the positive d13C excursion known as carbon maximum 6 ("M6"), which has traditionally been interpreted as reflecting increased burial of organic matter and atmospheric pCO2 drawdown. More recently, it has been suggested that the d13C excursion records a negative feedback resulting from the reduction of silicate weathering and an increase in atmospheric pCO2. Here we present high-resolution multi-proxy (alkenone carbon and foraminiferal boron isotope) records of atmospheric carbon dioxide and sea surface temperature across CM6. Similar to previously published records spanning this interval, our records document a world of generally low (~300 ppm) atmospheric pCO2 at a time generally accepted to be much warmer than today. Crucially, they also reveal a pCO2 decrease with associated cooling, which demonstrates that the carbon burial hypothesis for CM6 is feasible and could have acted as a positive feedback on global cooling.

Stable carbon and oxygen isotope ratios of foraminifera from Cretaceous and Paleocene sediments

Detailed analysis of over 200 samples of uppermost Cretaceous and Paleocene sediments from Atlantic Ocean DSDP Sites 384, 86, 95, 152, 144, 20C, 21, 356, 357, and 329 provides new information on the temperature stratification of Paleocene planktonic foraminifera, the temperature and carbon isotopic changes across the Cretaceous/Tertiary boundary, and the fluctuating temperature and carbon isotopic records through the Paleocene ~64.5-54 m.y.). There was a significant temperature rise across the Cretaceous/Tertiary boundary both at the surface and in deep waters of the Atlantic Ocean. This temperature rise occurred before the basal Tertiary 'Globigerina' eugubina Zone, so that in the oldest Paleocene sample yet analyzed from the deep sea (Site 356) temperatures are already three degrees higher at the bottom and at the surface than in the Cretaceous. The temperature rise across the boundaryis more pronounced on the bottom and in samples from higher latitudes. Accompanying the temperature rise across the boundary there is a significant shift in the carbon isotope profile. In the basal Paleocene the foraminifera of the surface zone demonstrate very negative carbon isotope values (unlike in the Cretaceous of today's ocean), while deeper dwelling species have more positive values which then decrease to the bottom. The unusual carbon isotope gradients persist through the first three million years of the Paleocene until towards the top of planktonic foraminiferal Zone P.1 (G. trinidadensis Zone) the foraminifera record a profile more positive at the surface and decreasing towards the bottom (as in today's ocean). During the Paleocene there are two noteworthy rises in surface water temperature; the first around 62-61 m.y. (G. trinidadensis Zone), and the second near the base of the Globorotalia angulata Zone, 60-59 m.y. At this time surface temperatures at low to mid latitudes reached values near 25°C, while at mid-latitude Site 384 temperature highs near 22°C were registered. At a sample spacing of around one per million years, we have only produced some of the detail of these temperature fluctuations. The later Paleocene is generally cooler and there do not seem to be any large variations either through time or latitude. Middle-latitude sites average temperatures near 15°C at the surface, while high lower latitude site temperatures range near 18°C. The most salient feature of the bottom temperature record (based on multispecific samples) through the Paleocene is its lack of fluctuations. There is an overall temperature range of 5°C at these intermediate depth sites (paleodepth estimates between 1500 and 3000 m). Higher values near 13°C accompany the surface temperature peaks around 62 and 60 m.y., while low values near 8°C occur in Zone P.2 (61-60 m.y.). We detected no change in bottom temperature across the paleocene/Eocene boundary in the few samples studied so far. While there are several fluctuations in the carbon isotope values through the early Paleocene, the general trend is one of increasingly positive values at the surface and at depth. This trend culminates in the late Paleocene (upper Zone P.4, about 56-57 m.y.) with a major excursion in the carbon isotope values. At low latitudes the range between the surface and the deepest planktonic foraminifera is a delta13C of 4 per mil as compared with a range of 2 per mil today. The carbon values drop off slightly, but remain strongly positive through the remainder of the Paleocene at most sites. Accompanying the carbon isotope excursion at Site 384 is a productivity increase and a proposed rise in the CCD.

Geological investigation of a section at Kulyumbe river in Siberia

An integrated, high-resolution chemostratigraphic (C, O and Sr isotopes) and magnetostratigraphic study through the upper Middle Cambrian - lowermost Ordovician shallow-marine carbonates of the northwestern margin of the Siberian Platform is reported. The interval was analysed at the Kulyumbe section, which is exposed along the Kulyumbe River: an eastern tributary of the Enisej River. It comprises the upper Ust'-Brus, Labaz, Orakta, Kulyumbe, Ujgur, and lower Iltyk formations and includes the Steptoean positive carbon isotopic excursion (SPICE) studied here in detail from upper Cambrian carbonates of the Siberian Platform for the first time. The peak of the excursion, showing d13C positive values as high as +4.6? and least-altered 87Sr/86Sr ratios of 0.70909, is reported herein from the Yurakhian Horizon of the Kulyumbe Formation. The stratigraphic position of the SPICE excursion does not support traditional correlation of the boundary between the Orakta and Labaz formations at Kulyumbe River with its supposedly equivalent level in Australia, Laurentia, South China, and Kazakhstan, where the Glyptagnostus stolidotus and G. reticulatus biozones are known to immediately precede the SPICE excursion and span the Middle-Upper Cambrian boundary. The Cambrian-Ordovician boundary is probably situated in the middle Nyajan Horizon of the Iltyk Formation, in which carbon isotope values show a local maximum below a decrease in the upper part of the Nyajan Horizon, attributed herein to the Tremadocian. A refined magnetic polarity sequence shows that the geomagnetic reversal frequency was very high during the Middle Cambrian at 5-10 reversals per Ma, assuming a total duration of ~10 Ma and up to 100 magnetic intervals in the Middle Cambrian. By contrast, the sequence attributed herein to the Upper Cambrian on chemostratigraphic grounds contains only 10-11 magnetic intervals. Preprint in Open Access hdl:10013/epic.30209.d001

(Table S1) Carbon and oxygen isotope values, and Mn and Sr concentrations of Early Jurassic sediments

For much of the Mesozoic record there has been an inconclusive debate on the possible global significance of isotopic proxies for environmental change and of sequence stratigraphic depositional sequences. We present a carbon and oxygen isotope and elemental record for part of the Early Jurassic based on marine benthic and nektobenthic molluscs and brachiopods from the shallow marine succession of the Cleveland Basin, UK. The invertebrate isotope record is supplemented with carbon isotope data from fossil wood, which samples atmospheric carbon. New data elucidate two major global carbon isotope events, a negative excursion of ~2 per mil at the Sinemurian-Pliensbachian boundary, and a positive excursion of ~2 per mil in the Late Pliensbachian. The Sinemurian-Pliensbachian boundary event is similar to the slightly younger Toarcian Oceanic Anoxic Event and is characterized by deposition of relatively deepwater organic-rich shale. The Late Pliensbachian strata by contrast are characterized by shallow marine deposition. Oxygen isotope data imply cooling locally for both events. However, because deeper water conditions characterize the Sinemurian-Pliensbachian boundary in the Cleveland Basin the temperature drop is likely of local significance; in contrast a cool Late Pliensbachian shallow seafloor agrees with previous inference of partial icehouse conditions. Both the large-scale, long-term and small-scale, short-duration isotopic cycles occurred in concert with relative sea level changes documented previously from sequence stratigraphy. Isotope events and the sea level cycles are concluded to reflect processes of global significance, supporting the idea of an Early Jurassic in which cyclic swings from icehouse to greenhouse and super greenhouse conditions occurred at timescales from 1 to 10 Ma.

Öate Cretaceous to early Paleogene nutrient and paleoproductivity records of ODP Leg 171 sites

We evaluate phosphorus (P) and biogenic barium (bio-Ba) as nutrient burial and export productivity indicators for the Late Cretaceous and early Paleogene, combining these with calcium carbonate (CaCO3), organic carbon (C), and bulk CaCO3 C isotopes (d13C). Sample ages span 36-71 Ma (~1 sample/0.5 m.y.) for a depth transect of sites in the western North Atlantic (Blake Nose, Ocean Drilling Program Leg 171B, Sites 1052, 1051, and 1050). We use a multitracer approach including redox conditions to investigate export productivity surrounding the global Paleocene d13C maximum (~57 Ma). Reducing conditions render most of the bio-Ba record not useful for export productivity interpretations. P and organic C records indicate that regional nutrient and organic C burial were high at ~61 and ~69 Ma, and low during the Paleocene d13C maximum, a time of proposed global high relative organic C burial. Observed organic C burial changes at Blake Nose cannot explain this C isotope excursion.