LETTERS Warm saline intermediate waters in the Cretaceous tropical Atlantic Ocean OLIVER FRIEDRICH1,2 *, JOCHEN ERBACHER1 , KAZUYOSHI MORIYA2 , PAUL A. WILSON2 AND HENNING KUHNERT3 1 Bundesanstalt für Geowissenschaften, Stilleweg 2, 30655 Hannover, Germany National Oceanography Centre, University of Southampton, European Way, Southampton SO14 3ZH, UK 3 Center for Marine Environmental Sciences, Universität Bremen, Klagenfurter Strasse, 28359 Bremen, Germany * e-mail: [email protected] 2 Published online: 30 May 2008; doi:10.1038/ngeo217 During the mid-Cretaceous period, the global subsurface oceans were relatively warm, but the origins of the high temperatures are debated. One hypothesis suggests that high sea levels and the continental configuration allowed high-salinity waters in lowlatitude epicontinental shelf seas to sink and form deep-water masses1–3 . In another scenario, surface waters in high-latitude regions, the modern area of deep-water formation, were warmed through greenhouse forcing4 , which then propagated through deep-water circulation. Here, we use oxygen isotopes and Mg/Ca ratios from benthic foraminifera to reconstruct intermediatewater conditions in the tropical proto-Atlantic Ocean from 97 to 92 Myr ago. According to our reconstruction, intermediate-water temperatures ranged between 20 and 25 ◦ C, the warmest ever documented for depths of 500–1,000 m. Our record also reveals intervals of high-salinity conditions, which we suggest reflect an influx of saline water derived from epicontinental seas around the tropical proto-North Atlantic Ocean. Although derived from only one site, our data indicate the existence of warm, saline intermediate waters in this silled basin. This combination of warm saline intermediate waters and restricted palaeogeography probably acted as preconditioning factors for the prolonged period of anoxia and black-shale formation in the equatorial proto-North Atlantic Ocean during the Cretaceous period. The middle of the Cretaceous period (∼120–80 Myr ago) is widely interpreted to represent the best example of a long-lived greenhouse interval from the entire geological record with high global temperatures deep-ocean temperatures at least 10 ◦ C warmer than today5 , high atmospheric carbon dioxide levels6 and minimal7 , possibly transient8 , continental ice budgets. Characteristic of this greenhouse interval is the deposition of abundant organic-rich sediments in the geological record, many of them finely laminated and well known as some of the world’s most important petroleum source rocks. Some of these black shales are widely, if not globally, distributed. Among the global Oceanic Anoxic Events (OAEs), OAE 2 is the most prominent, lasting approximately 500 kyr and falling during the interval of peak sustained global warmth of the past 150 Myr (refs 5,9). It is associated with significant turnover within numerous biotic groups, and a prominent carbon isotope increase in marine records10,11 . Other black shales are mainly present in the Atlantic–Tethyan realm and recent results show that the equatorial proto-North Atlantic was, for some reason, particularly prone to anoxia with black-shale deposition at Demerara Rise spanning over 20 Myr of Albian to Santonian time11 . Numerous studies have focused on the origin of OAEs and the cause of mid-Cretaceous warmth. However, with the exception of some modelling experiments, comparatively few studies have concentrated on the issue of water-mass formation and ocean circulation during this peak greenhouse interval. Furthermore, most palaeoceanographic studies of the mid-Cretaceous are limited9,12 by problems of diagenetic alteration of carbonate sediments and calcareous microfossils and/or extremely low sampling resolution. Thus, controversy has developed regarding the importance of ocean circulation mode to the question of the warmth of the Cretaceous world. The hypothesis of a mode of water-mass formation and oceanic circulation, to some extent driven by or at least influenced by the sinking of warm, saline waters in low-latitudinal regions with extreme net evaporation is deeply rooted in the palaeoceanographic literature about the Cretaceous period and the early Cenozoic era1–3 . Numerical circulation model experiments for a restricted Atlantic basin during the Albian have simulated formation of warm, saline intermediate- to deep-water masses along the northern coastlines of South America and Africa13 . Similarly, δ18 O data from Albian and Cenomanian molluscs and radiaxial fibrous calcite cements have been interpreted to record warm, saline water masses originating from the ancestral Gulf of Mexico14 . Yet the nonlinearity of the equation of state for sea water means that the sensitivity of density to changes in salinity is small at high temperatures. Furthermore, other model experiments conclude4 that the global picture of water-mass formation must be dominated by sinking at high latitudes, and further petro-geochemical analysis15 of molluscs and marine cements calls into question the δ18 O-based interpretations of the Gulf of Mexico data because of diagenetic alteration. To investigate the hydrography of the low-latitude proto-North Atlantic, we generated stable isotope records in glassy9 foraminiferal calcite (see the Methods section) from over 100 m of black shales recovered from Ocean Drilling Program sites 1258 and 1260 at Demerara rise, which have present water depths of 3,192 m and 2,549 m respectively (Supplementary Information, Fig. S1). On the basis of seismic stratigraphy and sediment composition, these sites record the history of intermediate waters during the Cenomanian age (palaeodepths of ∼1,000 m at site 1258 and ∼500 m at site 1260 (refs 16,17)). We generated a chronology nature geoscience VOL 1 JULY 2008 www.nature.com/naturegeoscience © 2008 Macmillan Publishers Limited. All rights reserved. 453 LETTERS Age (Myr) Stage –30 δ 13 Corg (‰ VPDB) –28 –26 –24 δ 18 Ocarb (‰ VPDB) –22 –5 –4 –3 –2 –1 0 92.5 Turonian 92.0 5 93.0 93.5 OAE 2 4 94.0 94.5 3 95.5 Cenomanian 95.0 MCE Decreasing benthic foraminiferal abundances and diversities 96.0 2 96.5 Site 1258 1 97.0 Site 1260 –30 –28 –26 –24 δ13 Corg (‰ VPDB) –22 36 32 28 24 20 Palaeotemperature (°C) 16 12 Figure 1 δ 18 O for planktic (black) and benthic foraminifera of sites 1258 (orange) and 1260 (red). See the Methods section for palaeotemperature calculation. δ 13 Corg partly from ref. 11. Planktic foraminifera: Hedbergella delrioensis (open black circles, site 1258); benthic foraminifera (site 1258, this study and ref. 7; site 1260, this study): Bolivina anambra (horizontal crosses), B. cf. incrassata (open downward triangles), Gavelinella dakotensis (open squares), G. intermedia (diagonal crosses), Gavelinella spp. (asterisks), Lenticulina spp. (open upward triangles), Neobulimina albertensis (circles), Osangularia schloenbachi (open diamonds) Praebulimina prolixa (filled diamonds), Tappanina sp. 1 (filled squares), mixed benthics (filled downward triangles). Grey fields: 90% of data around interval mean. MCE: Middle Cenomanian event. for these sequences using new and published11 organic carbon isotope (δ13 Corg ) data together with a recently published calcareous nannofossil biostratigraphy18 (Fig. 1). Our benthic oxygen isotope record is of much higher resolution than any previously published data set for the mid-Cretaceous and indicates that intermediate waters at Demerara Rise were extremely warm throughout the Early and Middle Cenomanian (Fig. 1, Supplementary Information, Fig. S2). Assuming reasonable, conservative estimates for seawater δ18 O (see the Methods section), we estimate intermediate-water temperatures for Demerara Rise between 20 and 25 ◦ C—the warmest yet reported from well-preserved benthic foraminiferal 454 calcite of the mid-Cretaceous and far exceeding today’s water temperatures at comparable depths (4–7 ◦ C (ref. 19)). Our benthic oxygen isotope record exhibits noticeable stratigraphic structure and these data fall into five time intervals on this basis (Fig. 1). During the first of these intervals (∼97.3–96.5 Myr), benthic δ18 O shows a relatively narrow spread about a mean of about −2.25h Vienna PeeDee Belemnite (VPDB). The mean benthic δ18 O in interval 2 (∼96.5–95.5 Myr) is only slightly higher but the spread of data is noticeably wider, especially at site 1258 (Fig. 1). For interval 3 (∼95.5–94 Myr), mean benthic δ18 O is noticeably higher than for any other part of our record with nature geoscience VOL 1 JULY 2008 www.nature.com/naturegeoscience © 2008 Macmillan Publishers Limited. All rights reserved. LETTERS Site 1258 Site 1260 Age (Myr) 94.4 0 Benthics (n × 10 3 /g) 1 δ 18O benthic (‰ VPDB) 2 –3 δ 18O benthic (‰ VPDB) Benthics (n × 10 3 /g) –2 –1 0 1 2 –3 –2 –1 Tappanina sp.1 94.6 B. anambra B. cf. incrassata 94.8 3 Mixed benthics 95.0 95.2 95.4 95.6 P. prolixa G. dakotensis G. intermedia 95.8 96.0 2 N. albertensis 96.2 96.4 Figure 2 Benthic foraminiferal abundances and δ 18 O values of sites 1258 and 1260 for the time interval between 94.4 and 96.4 Myr. Abundances as individuals per gram dried sediment. Intervals 2 and 3 and isotopic markers are the same as in Fig. 1. the lowest values recorded in interval 4 on the run up to OAE 2. Benthic δ18 O values in the remainder of our record (interval 5) show a narrow spread about a mean of about 2.0h VPDB. The data comprising this record do not come from a single species, but the sample-to-sample consistency and the similar values recorded by different taxa in the same samples indicate that the variability seen cannot be attributed to taxon-dependent isotopic offsets (Fig. 2). Instead, we interpret the changes in our record (Fig. 1) to indicate real environmental signals. These signals are large and require substantial shifts in the δ18 O of sea water and/or temperature of Cretaceous sea water. For example, the shift in mean benthic δ18 O across the interval 2/3 boundary requires an increase in seawater δ18 O of about 1h or a cooling of about 4 ◦ C. Similarly, within interval 2 at site 1258, particularly well-defined, high-amplitude variations in benthic δ18 O are seen on a timescale of about 100 kyr that require changes in intermediate-water δ18 O of about 2–2.5h or of temperature by about 8 ◦ C. Despite these pronounced changes in our benthic record, very little variation is seen in our accompanying planktic record (Fig. 1). This observation indicates7 that the benthic δ18 O record cannot be explained in terms of whole-ocean changes in seawater δ18 O (for example, due to glaciation), but leaves the origin of the large changes in benthic δ18 O unexplained. To help decipher the origin of the large changes in benthic δ18 O seen in our records, we have generated faunal records for the key time intervals (top of 2, base of 3, Fig. 2). This data set reveals large shifts in benthic foraminiferal abundance within the late stages of interval 2 and a rapid decline to near-zero abundance on the run up to the interval 2/3 boundary (Fig. 2). This transition is slightly earlier and sharper in the deeper site (1258). We interpret the high-amplitude changes in abundance within interval 2 to reflect a combination of changes in food availability and oxygenation at the sea floor. Yet, changes in food availability cannot have contributed to the marked decline in foraminiferal abundance near the interval 2/3 boundary because this would require a total loss of productivity—something that is inconsistent with the high total organic carbon content of these sediments. Thus, this signal must predominantly reflect decreased sea-floor oxygenation. These changes in faunal abundance occur in tandem with pronounced shifts in benthic δ18 O, where low abundances are coincident with high benthic δ18 O and vice versa, and this relationship is particularly clear at the deeper site (site 1258, Fig. 2). The sign of this relationship points to pronounced increases in local seawater δ18 O and salinity (not cooling) as the cause of the high benthic δ18 O intervals because benthic foraminiferal assemblages are relatively insensitive to temperature. To test our interpretation that much of the structure in our benthic δ18 O record within intervals 2 and 3 reflects pronounced changes in local seawater δ18 O, which reflects salinity rather than temperature, we measured Mg/Ca ratios in benthic foraminiferal calcite, which are a proxy for calcification temperature. Although the foraminiferal calcite in our samples is extremely well preserved, the tests are small in size and rare in many samples (Figs 1,2). Therefore, it was not possible to generate a high-resolution record using conventional techniques. Instead, we measured Mg/Ca ratios in a small subset of samples using a laser-ablation method (Table 1). This limited data set cannot be used to evaluate shortterm environmental change, and absolute temperatures cannot be calculated with accuracy because of the uncertainty associated with the Mg/Ca ratio of Cretaceous sea water20 and species-specific Mg partitioning between sea water and foraminiferal calcite. However, the data available show only modest variation with the highest Mg/Ca ratios indicated for interval 3—a pattern consistent with the interpretation that the comparatively high benthic δ18 O values during interval 3 are attributable to the local incursion of warm high-δ18 O, high-salinity waters (rather than colder waters). To assess the probable mechanism of formation of the postulated high-δ18 O, high-salinity waters, it is important to consider the tectonic configuration of the Atlantic Ocean during the mid-Cretaceous. During the Late Cenomanian, the central North Atlantic was an isolated basin (see Supplementary Information, Fig. S1) with limited exchange of intermediate and deep waters occurring with adjacent basins. Connection to the Tethys Ocean was restricted by continental terranes21 , the Equatorial Atlantic nature geoscience VOL 1 JULY 2008 www.nature.com/naturegeoscience © 2008 Macmillan Publishers Limited. All rights reserved. 455 LETTERS Table 1 Comparison of Mg/Ca with δ 18 O for three distinct intervals. (Depth in metre composite depth (mcd), age in million years (Myr), Mg/Ca ratios and δ 18 O data versus VPDB. Interval numbers refer to those shown in Fig. 1; s.d., standard deviation; n of ind., number of measured individuals; holes, number of individual holes ablated; B. anambra, Bolivina anambra ; N. albertensis, Neobulimina albertensis.) Depth (mcd) Age (Myr) Mg/Ca species Mg/Ca n of ind. Mg/Ca holes Mg/Ca sample mean Mg/Ca sample s.d. δ 18 O sample (h) 417.25 417.6 439.375 440.11 467.67 468.32 92.58 92.65 94.83 94.89 96.96 97.00 B. anambra B. anambra B. anambra B. anambra N. albertensis N. albertensis 3 3 5 5 5 5 6 10 18 16 21 23 5.84 8.82 11.13 9.12 8.20 10.22 2.19 1.98 3.36 1.99 2.46 3.19 −2.69 −1.88 −1.13 −1.06 −2.15 −2.09 Gateway and the Caribbean Gateway allowed exchange of only surface waters22,23 , whereas connection to the Arctic Ocean was blocked until the opening of the Greenland–Iceland–Norwegian Sea during the Oligocene epoch24 . Hence, the intermediate- to deep-water masses of the central Atlantic Ocean at this time would have been formed locally within the basin. One mode of water-mass formation within the basin must presumably have involved winter cooling at the highest latitudes available. Tectonic reconstructions, however, show that the basin extended only to the mid-latitudes (∼40–45◦ N, Supplementary Information, Fig. S1). On the basis of brachiopod δ18 O data and observed latitudinal gradients in the preservation of organic material in the Atlantic Ocean, Cenomanian southwestern European shelf seas are proposed as a potential source region contributing to protoNorth Atlantic intermediate and deep waters25 . Our data suggest the operation of an extra mode of water-mass formation—lowlatitude evaporation-led modification of waters in epicontinental basins and/or on shelf areas. Our sites can be excluded as a source for this type of water formation owing to the increased gradient between planktic and benthic foraminiferal calcite during interval 3 relative to 2 and 4. More likely source regions for the proposed highsaline waters would have been the contemporaneous epicontinental seas of northern South America and northern Africa. Many were the sites of contemporaneous evaporite formation (see Supplementary Information, Fig. S1). Some of the Cretaceous shelf areas closest to Demerara Rise are well known to have become marginal anoxic basins accumulating vast deposits of organic-carbon-rich sediments during intervals of sea-level high stand. Sedimentological and palynofloral data from, for example, eastern Venezuela, point to semi-arid climate conditions, which are proposed to result in high salinities and low oxygen contents in shallow shelf areas26 . It seems probable that the main reason for the extreme warmth of the Cretaceous ocean interior was the warmth of surface waters at mid- to high-latitude sites of deep convection4,25 . But our data show that high-δ18 O, high-salinity water masses existed at least sporadically over Demerara Rise during the Late Cenomanian. Data of this type from one locality cannot be used to determine the regional extent or global significance of such water masses. However, the mid-Cretaceous was a time of extremely high eustatic sea levels27 resulting in vast epicontinental seas during the Cenomanian and Turonian—potentially favourable locales for the sporadic formation of low-latitude warm and saline water masses akin to those that form today during the summer on the Bahama Bank complex28 , with potential implications for our understanding of ocean circulation in a greenhouse world. We interpret the existence of warm saline waters at depth on Demerara Rise to the unique plate tectonic configuration of the mid-Cretaceous proto-North Atlantic, the extremely high sea levels and the greenhouse climate of the Cenomanian. We postulate that delivery of these dense water masses acted, together with 456 Interval number Mg/Ca interval mean δ 18 O interval mean (h) δ 18 O interval s.d. 5 7.33 −1.97 0.35 3 10.13 −1.56 0.52 1 9.21 −2.56 0.35 the restricted and silled nature of the basin, to precondition the region in favour of anoxia, helping to explain the exceptionally long history of laminated black shale and ultimately hydrocarbon source rock formation. METHODS AGE MODEL We use the numerical ages of ref. 29. Tie points are the beginning of the carbon isotope excursion paralleling the Middle Cenomanian event (lower part Acanthoceras rhotomagense and upper part Cunningtoniceras inerme ammonite zone25 ; 95.7 Myr), the last occurrence of the nannofossil marker Corollithion kennedyi18 (94.1 Myr) and the initiation of the OAE 2 positive carbon isotope excursion, estimated as ∼300 kyr before the Cenomanian/Turonian boundary (93.8 Myr (ref. 25)). At site 1258, a sharp decline of carbon isotope values in the uppermost part of OAE 2 points to the existence of a short-term hiatus11 . Accordingly, our Turonian data from site 1258 are plotted against age by correlating the carbon isotope values to site 1260. ISOTOPE AND Mg/Ca MEASUREMENTS AND PALAEOTEMPERATURE RECONSTRUCTION Foraminiferal tests from Demerara Rise are generally extremely well preserved (‘glassy’), lacking internal cements and recrystallization9 (see Supplementary Information, Fig. S3). A few intervals including most parts of the OAE 2, however, show significant calcite infilling of the shells. Tests from these intervals are not used in this study. The small numbers of individuals and shifts in assemblages made it necessary to generate species-specific records using multiple taxa (see Supplementary Information, Tables). Different habitat effects are believed to explain a part of the strong scattering in our data. Furthermore, it is possible that the mechanism of changes in the bottom-water mass, as proposed in this study, also operated on short timescales influencing the benthic oxygen isotope values. Hence, we focus mainly on the long-term changes of the stable isotope record. Stable isotope measurements were obtained from single taxon separates using between 5 and 50 individuals mainly from the fractions 63–125 µm and 125–250 µm. Measurements were carried out using a Finnigan MAT 251 mass spectrometer at the Leibniz-Labor (Kiel, Germany), coupled online to the Carbo-Kiel device I for automated CO2 preparation. External precision is better than 0.07h. The data are given in the usual δ-notation and refer to the VPDB standard as established using the NBS20 carbonate isotope standard. Palaeotemperature calculations are based on equations (1) of ref. 30, assuming a δ18 Ow of Late Cretaceous sea water of −1.0hSMOW for an ice-free world31 and that the foraminiferal calcite was formed in isotopic equilibrium with Cretaceous sea water. This universal application of the mean value for δw is appropriate for deep waters (and thus for most of the presented data), but will lead to an underestimation of SSTs calculated from planktic foraminiferal δ18 O values due to latitudinal gradients for δw of the surface ocean9 . Mg/Ca measurements were carried out using a New Wave UP 193 solid-state laser ablation system with 193 nm wavelength, coupled to a Finnigan Element 2 sector field inductively coupled plasma mass spectrometer at the University of Bremen. The calibrations are based on the NIST 612 glass standard reference material. For each sample, the final Mg/Ca ratio was calculated by averaging the measurements of all ablated holes from all specimens (maximum of five specimens per sample and five holes per specimen, see Table 1 for number of ablated holes). The relative standard deviation for Mg/Ca based on 10 measurements on the NIST 612 was 4.5%; the standard error of the nature geoscience VOL 1 JULY 2008 www.nature.com/naturegeoscience © 2008 Macmillan Publishers Limited. All rights reserved. LETTERS average was 1.4%. The latter value gives an estimate of the precision of the foraminiferal Mg/Ca data. On the basis of the uncertain Mg/Ca of Cenomanian sea water, possible temporal changes in seawater Mg/Ca composition and the unknown relation between ambient water temperature and the Mg/Ca of extinct foraminifera, we refrain from calculating palaeotemperatures based on this proxy and discuss inferred changes in only relative temperature. 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Density cascading: off-shelf sediment transport, evidence and implications, Bahama Banks. J. Sedim. Res. 65, 45–56 (1995). 29. Hardenbol, J. et al. Mesozoic and Cenozoic sequence chronostratigraphic framework of European basins. SEPM Spec. Publ. 60, 3–13 (1998). 30. Bemis, B. E., Spero, H. J., Bijma, J. & Lea, D. W. Reevaluation of the oxygen isotopic composition of planktonic foraminifera: Experimental results and revised paleotemperature equations. Paleoceanography 13, 150–160 (1998). 31. Shackleton, N. J. & Kennett, J. P. Paleotemperature history of the Cenozoic and the initiation of Antarctic glaciation: oxygen and carbon isotope analysis in DSDP sites 277, 279, and 280. DSDP Init. Rep. 29, 743–755 (1975). Supplementary Information accompanies this paper on www.nature.com/naturegeoscience. Acknowledgements We are grateful to the Leg 207 Shipboard Scientific Party, W. Hale, N. Westphal, K. Noeske and S. Feller. D. Panten, N. Andersen and H. Erlenkeuser are thanked for measuring stable isotopes. Our paper benefited from discussions with H. Brumsack, A. Forster, P. Hardas, A. Hetzel, J. Mutterlose, R. Norris and P. Sexton. This research used samples provided by the Ocean Drilling Program. ODP is sponsored by the US National Science Foundation and participating countries under the management of Joint Oceanographic Institutions. Financial support for this study was provided by the German Research Foundation (to O.F., J.E. and H.K.), KAKENHI (to K.M.) and UK ODP NERC (to P.A.W.). Author information Reprints and permission information is available online at http://npg.nature.com/reprintsandpermissions. Correspondence and requests for materials should be addressed to O.F. nature geoscience VOL 1 JULY 2008 www.nature.com/naturegeoscience © 2008 Macmillan Publishers Limited. All rights reserved. 457
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