Oceanic Anoxic Event 2 (OAE2) occurred at the Cenomanian/Turonian boundary (~ 94 Ma) in the mid-Cretaceous during super-hot-house conditions, characterised by high atmospheric CO2 and exceptionally high sea levels1. It was one of several periods of widespread ocean anoxia during the Mesozoic2, and was coupled with deposition of organic-rich shales, marine extinctions2,3 and terrestrial vegetation changes4. It is often expressed in the sedimentary record as a short-lived negative δ13C carbon isotope excursion (CIE)5 followed by a broad positive CIE in bulk organic matter (~ 5‰) and carbonate (2–3‰), although organic carbon isotopes do not always mirror carbonate trends6. The Mid-Cenomanian Event (MCE) is a smaller-scale, short-term anoxic event that occurred ~ 96.5 Ma, with a positive δ13C excursion ~ 1‰7,8, and a shift in foraminiferal, radiolarian, and calcareous nannofossil assemblages9,10. Initiation of OAE2 warming is thought to have enhanced nutrient cycling and stimulated high productivity, explaining the deposition of organic-rich material, the broad positive CIE, and the expansion of oxygen minimum zones (OMZs) due to enhanced decomposition within the water column11. This mechanism may also apply to the MCE but the event has hitherto been less comprehensively studied.
One mechanism proposed to have initiated OAE climate change is large-scale volcanism. During the Cretaceous there were several active Large Igneous Provinces (LIPs), including the Caribbean (CLIP; ~95–83 Ma and ~ 81–71 Ma), High Arctic (HALIP; ~130–90 Ma), and Kerguelen (~ 122–90 Ma) (Fig. 1). Each of these LIPs have major eruptive phase timings compatible with OAE2 and MCE initiation, although precise correlation between volcanism and these perturbations is under debate12–14. The evidence traditionally used to infer volcanism during OAE2 is sedimentary shifts in osmium (Os) isotopes, with many sections worldwide found to exhibit a characteristic negative Osi (187Os/188Os) shift from radiogenic (continental weathering) to unradiogenic (hydrothermal alteration and/or weathering of juvenile crust) values, and an increase in sedimentary Os concentrations6,11, 15–17. Over OAE2, negative Osi shifts are variable between sites, and sometimes occurred in multiple pulses immediately prior to and within the event in the Western Interior Seaway (WIS), (proto-)North Atlantic Ocean, Tethys Ocean, European Epicontinental Sea, (proto-)South Atlantic Ocean, and the Pacific Ocean6,11,16,18. Identifying the precise OAE2 onset is critical to the debate but remains challenging in many records, particularly those without both carbonate and organic carbon isotope stratigraphy. High concentrations of Os in the WIS18 and Canadian High Arctic19 occur shortly after the initiation of a major phase of HALIP volcanism dated to ~ 94 Ma13, potentially linking it with OAE218. Other studies suggest that the CLIP was the trigger for OAE220,21, based on higher Os concentrations and large initial Osi excursions in the southern WIS adjacent to the Caribbean, compared to sites in the Western Pacific and the central WIS6.
Sedimentary Hg is potentially a more direct proxy than Os isotopes for LIPs21,25, 28–30 as it is produced in large quantities by volcanism (accounting for 20–40% of modern natural Hg atmospheric emissions31), and exhibits a short residence time in the atmosphere (< 1 year32) and oceans (decades to centuries33). The short timeframe of atmospheric mixing may allow for globally preserved heterogenous signals from massive subaerial volcanic Hg emissions, whilst submarine volcanism sourced from hydrothermal vents or expelled fluids from reactions between mafic rocks and seawater may cause more regional marine Hg signals21,28. After atmospheric emission, precipitation and dust-fall removes Hg, which is either deposited directly into the ocean, or first on land where it is cycled through organic matter and clay and later released into oceans via riverine transport21. Following marine emission, Hg is likely to remain within ocean water, either staying proximal to the source or transported distally with ocean currents. Modelling suggests the majority of Hg is sequestered in sediments within < 1 kyr34. The relatively modest OAE2 increases in Hg and Hg relative to total organic carbon (Hg/TOC) – the material on which Hg is primarily adsorbed29 – in the WIS and (proto-)North Atlantic is surprising if OAE2 was triggered by the nearby CLIP21. Furthermore, the magnitude of Hg/TOC values from OAE2 sections in the Tethys Ocean indicate no evidence for significant volcanic-related excess Hg25. MCE initiation is understudied, and no consensus on LIP involvement has yet been reached21,35,36.
Here, we measure Hg and Hg/TOC at two high palaeolatitude (~ 60°S) sites in the Mentelle Basin37 – located relatively close to the Kerguelen LIP (Fig. 1) – over OAE2 and the MCE in order to constrain the possible source and timing of large volcanic episodes. International Ocean Discovery Program (IODP) Sites U1516 and U1513 contain expanded Cenomanian sections in a relatively deep water bathyal setting37, ideal for Hg analysis. To compare volcanic pulses with regional and global environmental changes, we stratigraphically constrain OAE2 and the MCE within an existing biostratigraphic framework using δ13C on bulk rock carbonate, TOC, and single species of benthic foraminifera, and then constrain environmental changes with δ13C and δ18O, benthic foraminiferal assemblages, and other published productivity proxies. We find higher Hg and Hg/TOC values associated with OAE2 initiation than in Caribbean records, indicating volcanic activity near the Mentelle Basin, such as the Kerguelen LIP. Based on Hg/TOC pulse timings, we suggest volcanic emissions played a significant role in triggering changes in the climate and carbon cycle, as well as regulating the phases of OAE2. In contrast, there is little evidence that the MCE began with a volcanic event near the Mentelle Basin. We infer high productivity and possible upwelling throughout OAE2, based on benthic foraminiferal assemblages and bulk sediment isotopes, similar to Northern Hemisphere records21,35,36.
Mentelle Basin OAEs
We correlate Sites U1513 and U1516 (Fig. 2; Supplementary Fig. 1) with new tie points (A–I) using a combination of δ13C(carbonate), δ13C(organic), Natural Gamma Radiation (NGR), TOC, XRF-Ca counts, and published nannofossil and foraminifera datums ranging from Albian to Turonian (Methods). The sites are ~ 40 km apart and record similar environmental and palaeoceanographic histories. Both are characterised by a broad transition from alternations of (nannofossil-rich) claystones and chalks with relatively higher TOC in the Albian and Cenomanian, punctuated by rare and thin organic-rich shales, to chalk and nannofossil-rich clay in the Turonian with lower TOC. Both the MCE and OAE2 are clearly defined by positive excursions in δ13C and NGR (Fig. 3).
As 13C(carbonate) and 13C(organic) records do not exhibit the clear characteristic long-term positive CIE often defining OAE2, due in part to a low carbonate horizon and likely changing sources of bulk material, we constructed a composite benthic foraminiferal isotope record for Site U1516 (Fig. 3) using individual species and correcting for species-specific offsets (Methods, Supplementary Data 1, Supplementary Fig. 2). 13C(benthic) and 18O(benthic) composite curves reflect bottom water values, and broadly support 13C(carbonate) as most likely dominated by a surface water signal from mixed nannofossil and planktonic foraminifera. A notable and clear initial negative 13C(carbonate) ‘pulse’ of ~ 0.75‰ at U1513 and U1516 (tie point F in Fig. 2, phase A in Fig. 3) is also present in OAE2 records from Tibet and Japan, and is taken to mark the onset of OAE25,41. This is followed by the OAE2 ‘build-up’ phase B, a positive CIE which is only partly present due to very low carbonate (from tie point G). The peak CIE is not recorded at either site due low carbonate, but above this interval (from tie point H) elevated 13C(benthic) clearly indicates the OAE2 ‘plateau’ phase C, in contrast to the rapid decline in 13C(carbonate). This is supported by nannofossil biostratigraphy38, as E. octopetalus first occurrence (FO) and Q. gartnerii FO are in OAE2 phase C at sites on Kerguelen Plateau and Eastbourne25, UK (Fig. 3). The offset of 13C(carbonate) from δ13C(benthic) may be due to a change in the composition of the bulk carbonate (e.g., nannofossil assemblage shift) or change in surface water mass. A gradual decline of 13C in both bulk and benthic foraminiferal records shows the start of the ‘recovery’ phase D.
Sedimentary Hg reflects Kerguelan LIP activity
Both absolute Hg concentrations and Hg/TOC from Sites U1513 and U1516 (Fig. 2) show significant pulsed enrichments (Hg > 150 ppb and Hg/TOC > 200 ppb/wt%) broadly mirroring one another in association with the lead-up to and early OAE2, compared to low baseline values in the Albian and lower Cenomanian (Hg ~ 50 ppb and Hg/TOC < 100 ppb/wt%). An episode of elevated but minor single-point spikes occurs in the lead-up to OAE2 (above tie point E), a significant long-lived Hg/TOC spike is present during the negative 13C ‘pulse’ (tie point F in Fig. 2, ‘i’ in Fig. 4), and a second major spike occurs just after the onset of the low carbonate horizon (tie point G in Fig. 2, ‘ii’ in Fig. 4). We conclude these Hg pulses originated predominantly from volcanic activity rather than transported terrigenous material common in marginal settings34, or from buried redox fronts25; as our sites were in deep water distal to the shoreline37, there is no correlation between Hg and proxies for terrigenous input42 (εNd and K/Al; Supplementary Fig. 4), and no turbiditic sedimentary features are reported37. Furthermore, although recent work has suggested euxinic conditions can result in the overprinting of sedimentary Hg25, we report a lack of isorenieratene indicating no photic zone euxinia (Supplementary Fig. 5), and benthic foraminiferal assemblages indicative of oxic environments below the OAE2 low carbonate interval (Fig. 5). Hg measurements across possible anoxic episodes such as TOC spikes (lower in the low carbonate interval) may therefore be taken as minimum values.
Southern WIS and Demerara Rise records over OAE2 show relatively low Hg (mostly < 100 ppb) and Hg/TOC elevations (mostly < 50 ppb/wt%) (Fig. 4)21,25, suggesting a Southern Hemisphere volcanic source for the Mentelle Basin spikes. The high Hg/TOC values are more similar to records spanning the end-Triassic Central Atlantic Magmatic Province and OAE1d30,44 (> 200 ppb/wt%) which, when coupled with their stratigraphic appearance at the beginning of OAE2, point to a nearby volcanic source capable of triggering global climate change such as the Kerguelen LIP (Fig. 1). This LIP was volcanically active for > 32 myr and although precise dating is relatively limited, recent 40Ar/39Ar dating shows an active eruptive phase of the Central Kerguelen Plateau at 92.8 ± 1.5 Ma14. The Hg/TOC record from nearby Kerguelen Plateau Ocean Drilling Program Site 1138 shows higher values than North Atlantic sites, but is missing the critical OAE2 onset interval due to a hiatus24,25 where we might expect elevated Hg (Fig. 4). Hiatuses are perhaps unsurprising as uplift likely occurred during eruptive phases, and the Kerguelen Plateau was largely subaerial with pyroclastic deposits evidencing explosive subaerial volcanism in the Late Cretaceous45.
Estimating the submarine versus subaerial proportion of Kerguelen Plateau flood basalts is difficult, although extensive evidence exists for both45. Volcanic activity associated with the Hg and Hg/TOC spikes across OAE in the Mentelle Basin may have been largely marine-based due to the stronger local signal, although the modest increases in Hg/TOC in Atlantic records21 may indicate a partial atmospheric signature. The tholeiitic basalts are thought to have contained significant quantities of sulfur45, and by implication Hg31 and, similar to CLIP, have Pb isotope values14,45 similar to those measured across OAE2 in central Italy46. The high latitude position of Kerguelen would have allowed injection of gasses and ash directly into the stratosphere, promoting the global influence of atmospheric volatiles45. Palaeo-currents likely influenced the spread of Hg within the ocean basin, and thus the concentration of volcanically-derived Hg in sediments proximal to the source. The palaeogeography of the Cenomanian/Turonian prevented deep water flow between the proto-Indian Ocean and the proto-South Atlantic, the Pacific and the northern Tethys, and restricted intermediate depth currents connecting these regions (Fig. 1)47,48. Based on modelled reconstructions of Cretaceous ocean currents, intermediate water may have had a net eastward flow from the Kerguelen Plateau providing a plausible pathway for marine Hg to enter the Mentelle Basin48.
Evolution of Cenomanian volcanism
There are slightly elevated levels of Hg and Hg/TOC in the lower part of the MCE, relative to background values, at both Mentelle Basin sites (Fig. 2). Although these changes are small (~ 50–100 ppb/wt%), they are similar to those found in other sites that capture the MCE in the proto-North Atlantic and WIS21. In the Mentelle Basin Hg and Hg/TOC values are slightly elevated at the onset of the MCE CIE, before dropping to background levels mid-way through. However, this is in contrast to records from the Maverick Basin (southern WIS) and Demerara Rise (proto-North Atlantic), where elevated Hg/TOC values occur mid-way through the CIE21. Despite an absence of low Osi values, indicating volcanism may not have been the primary driver8, 12–14, our Hg records suggest volcanism may have had a role in triggering the MCE, although the source was likely distal to the Mentelle Basin.
Os records over OAE2 are somewhat different from Hg/TOC records (Fig. 4), in part due to their geographic separation and sedimentary weathering inputs, and in part due to the much longer ocean residence time for Os (~ 10 kyr)49. It is also challenging to correlate precisely between sites because biostratigraphy has some uncertainty on short timescales, and the characteristic CIE used to define the OAE2 onset is usually measured on bulk sediment. Indeed, 13C(organic) and 13C(carbonate) records commonly diverge from one another with the former exhibiting a delayed or absent positive CIE (e.g., Mentelle Basin, Tibet, Vocantian Basin; Fig. 4), whilst important sites from the WIS are based solely on 13C(organic). A recent study used 13C(organic) to correlate an early Osi shift in the WIS site Iona-1 as evidence for CLIP activity6, but we note alternative correlations exist18. Furthermore, it is likely that successive Kerguelen LIP eruptive phases released varying relative proportions of Os and Hg, as considerable geochemical variability is detected between different eruptive phases due to changes in relative melt incorporation of plume, continental and oceanic crust45. The numerous Hg/TOC pulses between tie points E and F (Fig. 2) document early volcanic activity, and although this is not recorded in Os isotopes from U151650 (possibly due to low resolution), precursor negative Osi excursions do occur in Tibet, the WIS, and Japan6,16,51 (Fig. 4). This precursor OAE2 volcanism was likely relatively minor as it occurred before major climate changes associated with OAE2, whilst Hg ‘spike i’ was relatively major as it is more stratigraphically extensive (multiple data points at both sites, Fig. 2), occurs at the beginning of the Osi excursion in U1516 (Fig. 4), and is associated with the initial negative 13C ‘pulse’ of OAE2 phase A (Figs. 2–4). A similar sharp negative shift has also been documented in England52, the southeast North Atlantic53, the western Pacific54 and the WIS55, and has been suggested as linked to LIP-related carbon release5.
Volcanism-induced palaeoenvironmental change over OAE2
Kerguelen LIP carbon release45 likely caused ocean warming, which in the Cretaceous may have disrupted the thermocline, triggering upwelling nutrient-rich waters to sustain enhanced productivity56. Between 478–474 m in U1516 (Fig. 6), the dominance of opportunistic planktonic foraminifera Microhedbergella has been interpreted as signifying enhanced nutrient runoff and likely upwelling38, and our benthic foraminiferal assemblage data supports changing organic carbon flux with varying infaunal/high productivity species ranging from 5–40%. To test for upwelling, we calculated the difference between measured 13C(organic) and 13C(carbonate) values in the same sample (Δ13C) as a proxy for relative changes in surface ocean CO257. Our data shows a gradual and sustained divergence (increased Δ13C) in the lead up to and early OAE2 phases A and B (Fig. 6), supporting enhanced upwelling bringing CO2-rich water to the surface, and/or increasing atmospheric CO258, possibly linked to volcanism.
The second significant Hg and Hg/TOC ‘spike II’ (Fig. 4, 6) occurs near the base of the low carbonate interval, and likely identifies a significant episode of LIP volcanism due to its association with severe environmental change in the Mentelle Basin (e.g., ocean acidification50 and an enhanced hydrological cycle59), and a pulse in Os with low Osi values in U1516 likely global in nature (Fig. 4). Enhanced productivity (TOC spikes, biogenic silica50, radiolarians)38 (Fig. 6) occurred with enhanced upwelling (further decreasing 13C(organic)) (Fig. 2). Above the low carbonate interval (OAE phase C), benthic foraminiferal assemblages contain a greater proportion of infaunal/high productivity species, increasing % CaCO3, and high productivity Microhedbergella and “Globigerinellioides”38, despite the presence of organic poor sediments. Due to low TOC, Hg data are absent, except one point in U1516 which suggests possible further episodes of volcanism through phases B / C (Fig. 6); this is supported by Os and Osi pulses that occur above the low carbonate interval, suggested as from Kerguelen volcanism50.
Our work highlights the utility of using multiple volcanic proxies in diagnosing causal mechanisms for past global warming events, and the critical importance of measuring species-specific isotopes in refining global OAE correlations. Future study of Kerguelen Plateau eruptive phases, Hg isotopes and earth system modelling will provide insights into LIP emissions and climate interactions, and identification of past tipping points within the climate system.