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SDAS 2002 Vol 81 Proceedings of the South Dakota Academy of Science,Vol. 81 (2002) 161 RARE EARTH ELEMENT SIGNATURES OF FOSSIL VERTEBRATES COMPARED WITH LITHOSTRATIGRAPHIC SUBDIVISIONS OF THE UPPER CRETACEOUS PIERRE SHALE, CENTRAL SOUTH DAKOTA Doreena Patrick Department of Geology Temple University Philadelphia, PA 19122 James E. Martin Museum of Geology South Dakota School of Mines and Technology, Rapid City, South Dakota 57701 D.C. Parris Natural History Bureau New Jersey State Museum Trenton, NJ 08625 D.E. Grandstaff Department of Geology Temple University Philadelphia, PA 19122 Keywords Rare earth elements, Pierre Shale, South Dakota, mosasaur, Verendrye, Cre- taceous, Hornerstown, Sharon Springs, paleoenvironments, New Jersey ABSTRACT Rare earth elements were measured in mosasaur bones collected from five members (Sharon Springs, Gregory, Crow Creek, DeGrey, and Verendrye) of the upper Cretaceous Pierre Shale at localities near the Missouri River in Brule, Buffalo, Hughes and Hyde counties. Fossils from each member of the Pierre Shale have different REE signatures. Signatures of fossils from individual mem- bers may be distinctive over wide areas; fossils from the Verendrye Member have REE signatures that are consistent over 250 square kilometers. Fossils from the Sharon Springs Member have distinctive REE signatures that may be further subdivided into three superposed groups that correspond with the upper, mid- dle, and lower Sharon Springs Member. Because REE signatures may differ 162 Proceedings of the South Dakota Academy of Science,Vol. 81 (2002) among stratigraphic units, fossil bones eroded from their stratigraphic context may be assigned to their proper depositional unit based on REE signature com- parisons. We interpret changes in REE signatures among members as resulting from differences in mixing between two end members: oxygenated and anoxic sea- waters. If differences in mixing are interpreted as depth differences, the lower Sharon Springs Member was deposited in deep, anoxic water. Water depths de- crease in the middle and upper Sharon Springs, but the overlying Gregory Member was deposited in shallow water. The overlying Crow Creek, DeGrey, and Verendrye members were then deposited in progressively deeper marine waters, but not as deep as the lower Sharon Springs. These interpretations are generally consistent with those based on faunal diversity and eustatic sea lev- el curves. REE signatures in fossils from the Campanian Verendrye Member were al- so compared with those of similar fossils from the Maastrichtian Navesink For- mation of New Jersey. Although the signatures differ, they are sufficiently sim- ilar so as to indicate similar degrees of mixing of oxygenated and anoxic deep waters and suggest similar water depths. INTRODUCTION REE concentrations and neodymium isotopes in fossil bones and teeth have been used to infer paleo-redox conditions in marine waters (Wright et al., 1987), detect reworking of fossils (e.g., Trueman and Benton, 1997; Trueman, 1999; Staron et al., 2001), and to accomplish or test paleoenvironmental (Gi- rard and Albarède, 1996; Reynard et al., 1999) and paleogeographic recon- structions (Wright et al., 2002). Many of these and other studies have examined stratigraphic variations of REE and have attempted to infer paleoenvironmen- tal or paleoredox conditions and their variations in time and space as well as chemical nature and origin of water masses producing those signatures. The total Rare Earth Element concentrations (ΣREE) in modern bones and teeth are generally less than 20 ppm (Chenery et al., 1996; Staron et al., 2001; Patrick et al., 2001). However, ΣREE in fossil bones may be greater than 1,000 to 10,000 ppm (e.g., Arrhenius et al., 1957, and Table 1). Therefore, more than ca. 95% of REE in fossil bone is diagenetically incorporated into bone post mortem. Because most REE are introduced post mortem, REE signatures in fos- sils do not reflect the diet, trophic level, or phylogenetic position of the or- ganism. Different osteological materials from a single organism may have dif- ferent concentrations of REE; however, the signatures in all of the bones are essentially the same within analytical error (Patrick et al., 2001, in preparation). Research indicates that REE and possibly other trace elements are incorporat- ed within 3,000 to 10,000 years after deposition (Grandstaff et al., 2001; Patrick et al., 2001, in preparation; Millard and Hedges, 1995, 1996) during early dia- genetic recrystallization of the bone apatite. After incorporation into the osteo- logical material, the REE signature in fossils is apparently stable and serves as a record of depositional or early diagenetic conditions (Wright et al., 1987; Proceedings of the South Dakota Academy ofScience,Vol.Proceedings oftheSouthDakota 81(2002) 163 Table 1. REE in fossils from selected members of the Pierre Shale. Number Specimen Unit Latitude Longitude La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu (degree N) (degree W) 72 Tylosaurine Lower Sh Spr 43.7012 99.4012 9.31 18.18 3.11 19.15 4.60 1.06 4.15 0.49 2.50 0.40 0.92 0.11 0.74 0.09 56 Tylosaur (?) Lower Sh Spr 43.6967 99.4119 13.86 23.23 3.65 19.98 4.79 1.11 4.10 0.47 2.38 0.37 0.86 0.11 0.67 0.08 65 Mosasaur Middle Sh Spr 43.7669 99.4326 10.04 19.64 3.34 19.14 4.74 1.12 4.45 0.54 2.73 0.42 0.94 0.11 1.29 0.11 53 Tylosaur Upper Sh Spr 43.7782 99.4298 12.04 13.24 1.78 15.42 3.51 0.75 3.73 0.55 4.25 1.00 3.26 0.49 3.44 0.54 62 Mosasaur Upper Sh Spr 43.7811 99.3989 47.79 44.32 1.64 6.59 1.37 0.58 3.58 0.31 2.17 0.48 1.86 0.24 1.46 0.31 64 Mosasaur Gregory * * 4953.2 4987.5 469.9 1932.2 328.0 113.0 731.7 123.3 1060.4 321.8 1176.7 184.3 1251.5 221.6 59 Mosasaur Crow Creek * * 469.9 825.6 22.82 73.49 13.57 7.47 40.25 3.61 25.71 7.62 28.43 4.61 30.32 5.34 60 Mosasaur DeGrey * * 172.2 269.2 17.57 69.06 14.97 4.15 23.50 3.36 25.49 6.63 21.47 3.06 18.53 3.30 1 Plioplatycarpus Verendrye 43.9335 99.5119 - 214.7 31.27 128.2 27.70 6.20 34.94 5.40 36.04 7.95 23.09 3.24 20.31 3.24 2 Plioplatycarpus Verendrye 43.9335 99.5119 - 55.70 8.11 32.67 7.34 1.70 9.43 1.50 9.92 2.20 6.67 0.98 5.94 0.98 3 Plioplatycarpus Verendrye 43.9335 99.5119 - 161.1 21.70 85.56 17.56 4.29 25.05 3.89 26.50 6.31 19.30 2.78 17.43 2.85 5 Plioplatycarpus Verendrye 43.9335 99.5119 - 42.68 5.91 23.55 4.62 1.13 6.51 1.02 6.95 1.65 5.04 0.71 4.51 0.76 21 Plioplatycarpus Verendrye 43.9035 99.5384 - 50.84 7.47 28.31 6.27 1.50 8.19 1.31 8.64 1.92 5.79 0.83 5.19 0.87 36 Plioplatycarpus Verendrye 43.9035 99.5384 257.2 422.3 53.60 221.1 48.59 11.25 61.65 8.80 61.08 13.32 40.26 5.71 35.85 5.56 33 Plioplatycarpus Verendrye 44.1841 99.7289 214.4 354.4 46.22 194.0 41.45 9.38 51.96 7.53 51.22 11.35 34.41 4.87 30.62 4.74 34 Plioplatycarpus Verendrye 44.1841 99.7289 184.7 291.4 37.29 168.3 35.63 8.30 46.63 6.74 47.45 10.35 31.65 4.58 30.35 4.68 35 Plioplatycarpus Verendrye 44.1841 99.7289 208.0 318.3 40.04 164.8 34.22 8.13 46.23 6.97 49.40 10.86 33.47 4.78 31.36 4.85 REE concentrations in ppm, * South Dakota School of Mines and Technology Specimen, primary Latitude and Longitude data not available, - Not determined, Sh Spr = Sharon Springs Member 164 Proceedings of the South Dakota Academy of Science,Vol. 81 (2002) Henderson et al., 1983; Trueman, 1999). REE signatures in fossils from differ- ent stratigraphic units may differ, providing unique "fingerprints" of variations in their depositional or early diagenetic environments. In this paper we present results of a preliminary study of REEs in mosasaur fossils from five Campanian members (Sharon Springs, Gregory, Crow Creek, DeGrey, and Verendrye) from the lower part of the upper Cretaceous (Cam- panian to Maastrichtian) Pierre Shale at localities near the Missouri River in Brule, Buffalo, Hughes and Hyde counties, central South Dakota. This study was conducted to determine whether REE signatures in vertebrate fossils vary stratigraphically from one member to another in the Pierre Shale. We have al- so investigated whether REE signatures are similar laterally within in a single member. Where REE in fossils differ stratigraphically they may be used to dis- tinguish fossils from different units. Because the REE signatures reflect the orig- inal composition and source of water masses from which the REE were incor- porated, we have attempted to draw inferences about paleoenvironmental con- ditions and the sources of marine waters in this part of the Western Interior Seaway. We introduce the use of ternary diagrams for interpreting variations of REE signatures in fossils and their paleoenvironmental implications.
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