Palaeogeography, Palaeoclimatology, Palaeoecologv 105 (1993): 235-243 235 Elsevier Science Publishers B.V., Amsterdam Thermal excursions in the ocean at the Cretaceous-Tertiary boundary (northern Morocco): 6 sO record of phosphatic fish debris C. L6cuyer a, P. Grandjean b, J.R. O'Neil b, H. Cappetta c and F. Martineau a aLaboratoire de GOochimie Isotopique, GOosciences Rennes, UPR 4661 CNRS, UniversitO de Rennes I, 35042 Rennes codex, France hStable Isotope Laboratory, Department of Geological Sciences, University (~/Michigan, 1006 C.C. Little Building, Ann Arbor MI 48109-1063, USA ¢Laboratoire de PalOontologie, Place EugOne Bataillon, UniversitO de Montpellier H, 34060 Montpellier, France (Received November 24, 1992; revised and accepted May 27, 1993) ABSTRACT C. Lecuyer, P. Grandjean, J.R. O'Neil, H. Cappetta and F. Martineau, 1993. Thermal excursions in the ocean at the Cretaceous-Tertiary boundary (northern Morocco): c~lsO record of phosphatic fish debris. Palaeogeogr., Palaeoclimatol., Palaeoecol., 105: 235-243. High precision oxygen isotope analyses were made of phosphate extracted from 17 samples of nektonic and benthic fish debris sampled across the stratigraphic Cretaceous-Tertiary boundary in northern Morocco. A refinement of the silver phos- phate method was used to isolate phosphate from biogenic materials. Measured ~180 values of 18.6-20.5%o are interpreted as reflecting high-resolution thermal variations that affected the ocean water column of the western Tethys. The warm (27°C) water masses that characterized Maastrichtian times underwent rapid cooling and stabilized at an average temperature of 19°C during the Dano-Montian and Thanetian. This period of constant and cool temperature was followed by a relatively rapid but more gradual warming to about 25°C achieved in the Middle Ypresian. Significant small shifts in 6180 values between nektonic and benthic fauna recorded only during the stages of rapid warming or cooling may correspond to averaged thermal differences within the water column that developed in response to global climatic changes. The indicated temperature distribution could have been caused by thermal changes in the atmosphere rather than some signal carried by deep ocean currents. The oxygen isotope data coupled with previous measurements of REE and eNd~TIon the same samples support the suggestion that paleo-Pacific westward currents progressed as far as the northwestern part of the African platform at the end of the Cretaceous period. Introduction changes in the temperature of surface or bottom waters of the ocean can be examined in detail and There is increasing interest in the study of global possibly elucidated. The temperature may vary at changes and its effect on terrestrial and marine any location in the ocean as a result of (1) global environments. Most paleoclimatic information has warming or cooling, (2) changes in ocean circula- been derived from the study of exceptional features tion patterns as a result of Earth-scale climatic that are preserved in the geologic record and variations, or (3) changes in circulation patterns exposed in a geographically restricted area. as a result of regional tectonic events. Conclusions concerning climate can be drawn only One of the most spectacular examples of global if the area under examination is free of strong change occurred at the Cretaceous-Tertiary regional control. While the ultimate cause of global boundary, a time characterized by major faunal change is a matter of great debate, the role and extinctions and large-scale climatic variations importance of immediate second-order effects like (Alvarez et al., 1980; Shackleton, 1985; Officer 0031-0182/93/$06.00 ~ 1993 -- Elsevier Science Publishers B.V. All rights reserved. 236 C. LECUYER ET AL. et al., 1987; Keller, 1989). We have made measure- rounding shelves. Phosphate samples collected in ments of the oxygen isotope compositions of phos- northern Morocco and Israel, however, appear to phatic fish remains from the Cretaceous-Tertiary have recorded deep-water REE characteristics and section in northern Morocco in an attempt to were not subjected to regional controls. The geo- understand the causes of oceanic thermal varia- chemical data for these materials suggest that deep tions that may have occurred around this time cold water from the North Atlantic or other water period. The usefulness of oxygen isotope composi- from the eastern Tethys with a strong negative Ce tions of natural phosphates for paleothermometry anomaly and a eNd(T) value of ~ --5 flushed out has been well documented (e.g. Longinelli and shallow epicontinental seawater as early as the Nuti, 1973; Kolodny et al., 1983; Shemesh et al., Middle Cretaceous. 1983; Luz et al., 1984; Karhu and Epstein, 1986). In the present study we integrate the REE and Thus if well-preserved marine fish remains (teeth Nd isotope database with oxygen isotope analysis and bones) are available for analysis, it may be of the same phosphates and then address the possible to determine paleotemperatures of past following questions: (1) can thermal variations in oceans (Kolodny and Raab, 1988). In addition, the ancient water column be identified? (2) are REE contents and eNd values of such fish remains such thermal variations caused by introduction of provide an effective means of elucidating circula- an exotic deep water from the North Atlantic or tion patterns of ancient ocean water masses Tethys or rather by a global thermal change in the (Grandjean et al., 1987; 1988). atmosphere?, and (3) is there a regional climatic Shark and ray teeth from a section in northern correlation with the Eastern Tethys where samples Morocco were selected for this study because: (1) from Israel and Jordan have previously provided Northern Morocco was situated between the paleotemperatures for Cretaceous to Eocene Atlantic Ocean and the Tethys Sea in a region waters (Kolodny and Raab, 1988). where tectonic processes operative in the past are of great geologic interest and are relatively well- Analytical procedures understood through the time span under investiga- tion (Scotese et al., 1988; Bardossy and Dercourt, The Ag3PO 4 method 1990). (2) Splits of the same samples examined for REE contents and Nd isotope ratios by Grandjean Phosphatic oxygen in biogenic materials appears et al. (1988) were available for oxygen isotope to form in isotopic equilibrium with body fluids analysis. (3) The samples provide a very good time and, after the death of the animals, to be relatively resolution from Lower Maastrichtian to Upper resistant to oxygen isotope exchange with environ- Ypresian. (4) The combination of oxygen isotope mental fluids, especially during apatite recrystalli- data with the results of Grandjean et al. (1988) zation at the sediment-water interface (Luz and should provide a powerful geochemical tool to Kolodny, 1989). The first method of isolating the gain insight into the direction, amplitude and phosphate radical from fossil phosphatic materials origin of thermal variations of the oceans during for oxygen isotope analysis was published by this time interval. Tudge (1960) and modified successively by Grandjean et al. (1988) suggested that REE Longinelli (1965, 1966), Longinelli and Nuti contents and Nd isotope compositions of seawater (1973), Longinelli et al. (1976) and Kolodny et al. from continental shelves and platforms result (1983). This is a laborious method involving the largely from regionally controlled diagenetic fluxes. precipitation of a hygroscopic, low-temperature They proposed, furthermore, that the weak Ce form of BiPO4 after six days of wet chemistry. anomalies measured in modern phosphates are a The method presented here is a refinement of the reflection of the isolation of these materials from Ag3PO4 technique developed by Crowson et al. deep oceanic waters and that the Nd isotope (1992) and was selected because (1) the Ag3PO 4 compositions of phosphates are the same as those procedure is far less time-consuming than the of average labile sedimentary Nd from the sur- BiPO4 method, (2) measurements can be per- THE CRETACEOUS TERTIARY BOUNDARY (NORTHERN MOROCCO): 01~O RECORD OF PHOSPHATIC FISH DEBRIS 237 formed easily on natural samples as small as 15 mg regular addition of a few drops of DDW. The or less, (3) the Ag3PO4 crystals are stable and non- crystals are then collected on a millipore filter, hygroscopic, and (4) oxygen can be extracted washed three times with DDW and air dried at quantitatively from AgaPO 4 using BrF5 in a con- 60°C. The Ag3PO4 crystals produced this way are ventional silicate extraction line and the isotopic quite pure by the criterion that no contaminants measurements are reproducible with low standard were detected using either SEM or X-ray diffrac- deviations. tion analysis. After washing in distilled water, the samples are crushed in a stainless steel mortar and ground with Fluorination procedure and mass spectrometry an agate mortar and pestle. After dissolution of 15 30 mg of powdered sample in 2M HF at 2YC Aliquots of between 12 and 15 mg of Ag3PO 4 for 24 hours, the CaF 2 that precipitates is sepa- crystals are weighed into nickel reaction vessels rated from the phosphate solution by centrifu- and degassed 4 hours at room temperature and an gation. The CaF 2 precipitate is rinsed three times additional 4 hours at 150 200°C. This degassing using double deionized water (DDW) and the rinse procedure assures that atmospheric water is effi- water added to the phosphate solution which is ciently desorbed from the samples. A 5/1 mole finally neutralized with a 2M KOH solution. excess of BrF5 is reacted with the samples at 600°C Before use, the AmberliteTM-IRA-400(OH) ion for 12 hours. Chemical yields of near 100% were exchange resin is flushed with several liters of obtained routinely at the University of Michigan DDW to eliminate chloride and avoid precipitation and replicate analyses at the University of Rennes of AgC1. A 2-ml aliquot of cleaned resin is then (n= 25) of the NBS 120c Florida phosphate added along with the neutralized solution to a standard were very reproducible at a 6180 value polypropylene tube.