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    Microstructural and geochemical investigations on Late Cretaceous archosaur teeth from Alberta, Canada Herve Bockerens! Laboratoire de biogéochinie isotopique, Université de Paris VI (Plerre et Marie Curie), C. P. 120, 4, Place Jussieu, F-75252 Paris Cédex 05, France Donato B. BRINKMAN Royal Tyrrell Museum of Palaeontology, P.O. Box 7500, Drumheller, AB TOI OY0, Canada Yannicke Daven Laboratoire de pétrologie sédimentaire et paléonologie, Centre national de la recherche scientifique, Unité de recherche associge n® 722, bévimene 504, Université Paris XI, F-91405 Orsay Cedex, France Anpré Maniorr Laboratoire de biogéochimle isotopique, Université de Paris VI (Pierre et Marie Curie), C. P. 120, 4, Place Jussiew, F-75252 Paris Cédex 05, France Received July 29, 193 Revision accepted February 25, 1994 Microstructural and chemical composition studies on fossil reptile teth from Upper Cretaceous localities of Alberta, Canada, show that the quality of preservation exhibits great variability within a formation, as well as within a locality oF even a single tooth. The chemical composition of fossil ename! is close to that of modern enaimel, whereas the chemical com positions of fossil and madern dentine ace vety different. It seems that fossil enamel may have rettined some paleodistary information in its chemical composition, whereas deatine, as well as bone, likely did not. Paleodietary interpretations may thus be drawn from the chemical composition of some elements in woth enamel, sch as strontium, but more studies on rece. reptiles are urged for comparisn. Des études de microstructures et de compositions chimiques sur des dents de reptiles fosiles provenant de focalités du Cr6- lac€ supérieur dAlbera, Canada, monteent que l qualité de la préservation présente une importante varabilité au sein dune Formation, mais aussi dans une localité et méme &'intérieur d'une dent. La composition chimique de mail fossileest proche e celle de I"émail actuel, tandis que les compositions chimiques de la dentine fossil et moderne sont bien différentes. It semble que Iérail fossile ait pu conserver certaines informations sur les paléo-régimes alimentaires cans sa composition chi- ‘migue, alors que ce n'est probablement pas le cas pour le dentine et pour es. Des interpretations de paléo-régimes alimens Can, Bah Se. 3, 785-792 1954 Introduction | Palacoenvironmental reconstructions use two main types of | data, The first one is based on comparison between the geo- graphic distributions of fossil and recent taxa, The second one is the chemical and (or) isotopic compositions of biogenic mineralized tissues (e.g., Toots and Voorhies 1965). This lat- | > ter approach has received considerable attention in the past three decades, but to be valid, it depends on the assumption cy that the bone and tooth chemical composition is devoid of post- ‘mortem diagenetic alteration. Some criteria for the preserva- tion of isotopic composition on fossil organic matter have been sated (DeNiro 1985; DeNiro and Weiner 1988; Bocherens et al. 19912), but in most papers concerned with the chemical composition of vertebrate fossils, no mention is made of alter- ations. There is general agreement that phosphatic tissues are stable. However, recent studies have shown that Sr contents Of fossil bones can be changed by diagenetic processes (Bosz ‘and Hampel 1978; Sillen 1988; Schoeninger 1989), as well as oxygen isotopic composition of bone phosphate (Kolodny and Boaz 1993). Enamel is considered to be an extremely hard "Present address: Geophysical Laboratory, Carnepie Institution of Washington, 5251 Broad Branch Road N.W., Washington, DC 20015-1305, U.S.A, sa Co? oi laires peuvent ttre établies& partir de la composition chimique de certains éléments ccomplémentares sur des reptiles actuels sont nécessaires pour établi des comparsisons. ‘que le strontium, mais des études crystalline tissue, lacking in impurities; it is assumed that this, dense tissue is much less sensitive to diagenetic processes then bone or dentine. This seems to be actually true for carbon iso- topic composition in mammal samples that are several million years old (Lee-Thorp and van der Merwe 1987; Quade et al 1992). Diagenetic changes in dentine and enamel have not been studied, even in mammals. Multielement analyses of fos- sil reptilian enamel and dentine have shown that major and ‘minor elemental contents frequently are changed (Dauphin 1989, 1991) In spite of the abundance of literature about paleodiets, only 4 few studies have been devoted to elucidating the conse- quences of diagenesis. Many reconstructions of paleodiets are bbased on prehistoric or historic human bones. It must be noted that the burial processes of these human “fossils” are very different from those of reptiles or mammals in nature. More over, one or two chemical elements are analyzed, in bone only, not generally in dentine or enamel. Another problem is the analytical method. Bones and teeth are not compact tis- sues. They have numerous cavities (large ones such as medul- lary cavities in bone, or small, such as dentinal tubular) and these cavities are often filled with secondary minerals or sedi- ‘ments. Bulk analytical methods such as atomic absorption are ‘quantitatively precise, but hard tissues (bone or dentine) and 786 (CAN. 1, BARTH SC VOL, 31, 1904 sediment are counted together. The comparison of the results dof chemical studies performed on bulk material and on local- ized points on porous structures such as dinosaur eggshells has shown the importance of the differences between the two methods (Dauphin and Jaeger 1990). Finally, the variability of the diagenetic alterations in various taxa in a given fossili- ferous site is not yet known, Because of the abundance of dinosaur teeth in the Late Cretaceous of Alberta, and because carbon and nitrogen iso- topic abundances in fossil bone organic matter from this area have been used to investigate the possibility of reconstructing the food webs of these animals (Bocherens et al. 1991b; ‘Ostrom et al. 1990; Bocherens 1992), we have used dinosaur teeth to try to answer some questions about the effects of dia~ ‘genetic process on chemical composition, Teeth, like bone, are mineralized tissues with 2 carbonate hydroxylapatite ‘mineral fraction and an organic fraction but teeth comprise two different tissues, One of them, enamel, is structurally very different from bone, whereas the other one, dentine, is very similar to bone, Comparison of the evolution of these two ti sues during diagenesis under the same external conditions may bbe a fruitful approach for the study of diagenesis effects on the ‘geochemical parameters. Previous studies Microstructures Both prismatic and aprismatic enamel is present in reptiles (Schmidt and Keil 1971; Cooper and Poole 1973; Grine etal. 1979; Dauphin 1984; Buffetaut etal. 1986a, 1986; Carlson and Bartels 1986; Dauphin 1987, 1988). The dentine of recent Crocodylia is orthodentine type, which consists of regular parallel tubules, perpendicular to the outer surface and to the growth layers. In fossil Reptilia, only orthodentine has been observed. Chemical composition The chemical composition of the teeth of recent and fossil Repiilia is still not well known, Recent crocodylian teeth have been studied (Dauphin 1989), and the salient data are summa- rized in Table 1. P and Ca contents show a better linear corre- lation in dentine than in enamel. Ca and Mg are sometimes correlated, just as P and Mg. Th fossil Crocodylia of various sites (Dauphin 1989, 1991), tecth are generally entiched in Fe, whereas Mg is removed from the dentine. Na and Fe, and sometimes P, are good dis- ciminants for enamel and dentine in a tooth. The diagenetic processes tend to make uniform the composition of dentine and enamel ‘Some data on the chemical composition of noncrocodylian fossil teeth are available (Dauphin 1991). In these teeth (Thecodontia, Saurischia, and Omnithischia), P and Ca con- tents of dentine and enamel become similar. Diagenetic changes are greater than the primary differences between herbivorous and carnivorous taxa, in spite of a good microstructural pres- ervation. Fossil enamel is enriched in Ca, S, Fe, and Sr. Chemical composition and paleodiets Problems of diagenesis have been discussed by some authors, but few of them refer to the natural recent contents of hard tissues (Dauphin and Denys 1988, 1992a; Dauphin 1989), Moreover, they are based on chemical contents of bone, rarely teeth, and only on mammalian material. The question of the stability of Sr (and other elements) throughout the diagenetic processes has never been fully resolved. Accord ing to Toots and Voorhies (1965), Wyckoff, and Doberenz (1968), Parker and Tooths (1974, 1980), Schoeninger (1979), Lambert et al. (1982, 1983), and Hancock et al. (1987), the Sr content is not affected by’diagenesis. On the contrary, the ‘Sr content of fossil bone is affected by diagenetic processes, according to Boaz and Hampel (1978), Lambert et al. (1979), Sillen (1981), and Schoeninger et al, (1984). We may note in passing that there are similar discussions about Mg, Cu, and Zn (Lambert et al, 1982, 1983, 1985; Byrne and Parris 1987). Williams (1989) noticed that many elements are not distributed homogeneously in bones. Moreover, minerals are precipitated in pores and canals. In rocent mammals, Sr contents are higher in herbivorous than in carnivorous snimals. Experimental data have shown that the differences in bone Sr levels are related to the diet Sr levels Price et al. 1986). However, data of various authors differ. In herbivorous mammals, 100Sr/Ca varies from 0.115, to 0.327 (Sillen 1988), but according to Byrne and Parris (1987), 100Sr/Ca is equal to 0.038 in Cervidae. In fossil or subfossil carnivores, 100Sr/Ca ranges between 0.063 and 0.097, and between 0.089 and 0.126 in herbivores (Sillen 1981), but reaches 0.403 in some carnivores and 0.415 in herbivores of the Omo site (Sillen 1986) Comparatively litle work has been done in diet reconstruc- tion studies using other chemical elements and statistical and multivariate analysis. According to Parker et al. (1974), Lambert et al. (1985), Byrne and Parris (1987), and Hancock et al. (1989), Na is affected by diagenesis; but Na is stable according to Lambert et al. (1982). In spite of some altere- tions, Na should be useful for dietary reconstruction (Lambert etal. 1985; Byrne and Perris 1987). Zn has also been consid- ered a “good disoriminant"” element (Byrne and Parris 1987). From the data oblained on some fossil reptilian teeth, @ direct use of the chemical composition of fossil hard tissues to reconstruct paleodiets is difficult (Dauphin 1991). Marine animals (fishes and molluscs) tend to have higher concentra- tions of Sr (Byrne and Parris 1987), since ingestion of seafood tends to increase the Sr/Ca ratio. Material and methods Material Recent teeth are from Crocodylus acutus (America), Croco- dylus cataphractus (West Aftica), Crocodylus palustris (Asia), Alligator mississippiensis (North America), and Paleosuchus trigonatus (South America). Crocodylus acutus is found near rivers and lakes, and sometimes along the coastal areas, and P. trigonatus is found near small tropical rivers (Alcala and Dy-Lincco 1990). The adult animals are terrestrial; when they are older than 10 years, they are found 500 1000 m from the river. The two species feed on small mammals, snakes, birds, ‘and aquatic turtles, C. acurus feeding also on some aquatic invertebrates and fishes, and P. trigonatus on very few fishes and aquatie molluses. Cracadylus cataphractus is found near the coastal region and near rivers or lakes, Its diet is not well known, It is thought that the adult animals feed on fishes, snakes, frogs, and shrimps, because of their narrow snout. Crocodylus palustris is found in aquatic zones and feeds on insects, frogs, mammals, birds, and some fishes. Alligator mississippiensis is found in lakes or marshes as well as in ‘marine and brackish zones. Is diet is composed of turtles, gas~ tropods, fishes, birds, mammals, and insects (Pooley 1990). Fossil teeth come from three Late Cretaceous Canadian sites: DOCHERENS EF AL 78s i Taute 1. Chemical contents (in pp) of Fossil enamel and dentine Grove Thet Thott Alb? Hagt* Geer Cert® Cer? Cor* CARN HERB FOS & Coo Enamel rn O 8 Nom 7153 9677 8350 7119 — 730 7398 7583-7509 062 7443-7752 12880 ek erate itsine atlero| joa 1030 2357 1524 2540 1190 aT. S116 Mgm 707553383706. TOD 933 IS SH« | 587166. SA co 480464 aka Sor 915,503 S43. 236 Som 360 4139 4717 337 — 1299 380327 © 3961 443 897926 52 782 Ts Fem 7080 707 9333 2081 — 27503211 2912 1982 4800 2721 2711 923 © 162 © 6} O73 | TaD so 1MO 1282 © 958 4078528 1:982 34 sem 187680 20 50075-6315 RM] ia a0) erst 0 Odes sea salto ase 2081 255 zm 7 AT oS 1080201150. 280 « 1002 Sil im 765 140 2186-78325. tsS. 782,527 884 Mom 530 767,220 awit © 18 0 BH as 409 454304 2693653025708 Cee ast 0, = 62s) sae oral rose 100) 017 719 «3423S 267 si0 5364831092 24s 28a Am 7 m0 62 310 GIL 750 55H, 7087067051117 kee cate a0 612120) S00 ee a8 oe ori arora 12) ez isG Pm 173.540 166013 185517 177019 — 180360 198 O44 144.053 137573 175.472 165.003 170237 173 367 ¢ 4821 7391 13500 5 844 11548 7047 1443121709 8110 28981 20481 6 034 Cam 385.053 343 900 390275 365256 | — 363 590 406 344. 309 650 313.573 363 621 348 289.355 955 334 127 @ 10098 18547 27638 11376 20014 20371 28920 33.080 19794 45 835 33.697 20176 Dentine Ge eee ea a ig ee Nem S417 6507 4667 4783 5.162 4640 6270 5353 $242 5467 5333 5383, 3.808, j 158° 1693" 25387 133° “1989 1993-2454 1556 1176 Toll S81 980 T Mg m 587793750 7919299501045 «BD «1100 730 S77? «GIT a 4560763} 954 T3755] a8 8S SBS SE ee 0d) soe eas no cess) sas plots) isasl st staal! si @ 496 16s 568427495964 66053. 3991 Be2««1:252«1:360 9 Fem 4357 1314 7425 7556 8595 10185 8550 3.980 17667 S158 9787 7730 6a7 Br 00 i ce ee ee ei Sr m 1006 436 4832851203001 1671000 «48710861822 « 8 6D 517M 1305 2405 1330-19103? 38B Zo m 481 1216 4837811812] 36054] D8] @ 71193 509521785 3021588 TOL?) ioe Oe ee ee ae « 2% 011322981799 1203 58381171126 08d? Clom 39g 60 saz SHR 5857 48015931650 4710188091917 « e449 SI 38553203379 SLB]. 2210 Alm 650 1100 1283 556 90S GHOL'107= 758997 ak Ts 4 o 28 a3 56770 GT S03 MGS 21S 2674S 200188 Pm 158659 146 107 165 133 164343 170-219 165 995 175 $00 127753 47 317 158 563. 156.957 157.671 89 140 g 4058 27621 7665 4747 120397789 118M 9889 S748 8789 19.216 14.639 16 980 Cam 328.937 315.271 355 125 354 761 367 443 342 905 371 130 294.959 293.375 338524 301 957 329300 138 893 : g 91 42669 18819-7345 19841 16-417 23-454 7724 16031 19.764 57967 43-442 29 152 Noras: Da on reset Cronyn (Gros) ave bean aed. Cr, fowl rosa The, theropods Al, Aerio Had, aoa; Cx, comlopen CARN, cumnivoros fos; HERB, herbivorous oss; FOS, ll fa; R Cre, cent crocodiles inate samples rom uth River Foran, * ie 2s simples om Sleveile RR Grade; *, indents sample from Horseshoe Canyon Formation, A yepresete tenure of pons alec ine case of inv! sampes (Cro, The, Alb, Had, Cer the mube finvsl nthe cae of CARN, HERD, FOS, andR Cave. oh, avenge oto uncer, (D Teath of certopsids, hadrosaurids, and theropods come _brate bone bed (Ebesth 1990). This kind of site contains @ ftom various localities in the Judith River Formation (formerly concentration of small (<50 mum), well-sried, multigen ‘Oldman Formation, Campanian) in Alberta, (2) Teeth of ceratopsids, hadrosaurids, theropods, and eroe- “odylians come from Steveville RR Grade (BB 102), near Dinosaur Provincial Park (Judith River Formation) and were collected in 1989 (by H.B. and D.B.). This site is located at “the western end of Dinosaur Provincial Park, south-central [Ge Alberta, From 2 taphonomic point of view, itis a microverte- vertebrate remains dominated mostly by fish scales, champ- sosaur vertebrae, turtle plates, and crocodile and dinosaur ele- ments (Brinkman 1990). External morphology is often fairly well preserved. These sites probably represent waterlain, mechanical accumulations of resistant skeletal components. ‘These elements may have been submitted to prolonged periods Of subaerial or subaqueous exposure before burial. Turtle and 786 (GAN. J BARTH SCI. VOL. 3, 1984 ‘erocodile bones ftom this site have yielded organic matter, and were chosen: C. acinus and P.trigonatus. They were added as the amino acid composition ofthis organic matter suggests thet additional individuals, two individuals, for dentine, two for at least part of it originates from bone collagen (Bocherens enamel. Thus they are figured on the graphs but are. not 1992) included in the analyses. The chemical content of teeth is given {G) One premaxilla tooth of Albertosaurus comes from the in pats per million. Because all the elements are not included Horsethiet Canyon, Drumbeller area, Alberta (Horseshoe in the analysis (the sum of chemical content differs from 100% Canyon Formation, lower Mazstrichtian. for each individual), the usual calculation mode of principal- pe ‘component analysis can be used Microstructures Observations ‘The outer surface and fractures of teeth were observed with scanaing electron microscope (Philips 50S; URA n° 623, Uni- versité de Paris XI, Orsay). Some were etched with various acids (dilute HCI, formic acid, or HyPO,). Polished and etched sections were also used. The etching treatment is used to get cleaner broken surfaces. It does not interfere with the chemical analyses and does not generate artifacts. Microstructures Enamel The outer surface of the enamel of some recent specimens of A. mississippiensis shows a prismatic structure (Dauphin 1984) (Fig. 1a). Prism diameter is about 5—6 ym. A slight etching reveals the horizontal growth layers. The mean thick: ‘ness ofthe enamel is 25 ym in recent erocodilians. The enamel Chemical composition Of the crocodile teeth of Steveville RR Grade does not show ‘We are concerned here with the state of preservation of the prismatic structure (Fig. 16). The outer surface is relatively two tissue’ present in teeth, enamel and dentine, so the Joca- smooth, whereas the vertical sections show a growth striation tion of the chemical analyses must be known. parallel to the outer surface. The enamel fibres are clearly visi- f ‘Teeth ate embedded in araldte. They are then polished with ble, The maximum thickness is 30 um. diamond pastes and cleaned by ultrasonic treatment. A slight The thickness of the enamel of theropod teeth réaches etching, using 5% formic acid for 15 s at 20°C, reveals the 200 um (Dauphin 1987, 1988), but the maximum observed structural details of enamel and dentine. The specimens were thickness in Steveville RR Grade specimens is lower than ‘coated in a vacuum evaporator with carbon. 100 um, Neither prisms nor distinct growth lines are visible ‘Teeth were transferred to a Philips SOS scanning electron _in the Steveville RR Grade theropods (Fig. 1c). On other microscope with Link energy-dispersive X-ray microanaly- specimens from Alberta, prismatic structures are sometimes sis system (AN 10000) (URA n° 723, Université de Paris XI, preserved, with secondary lacunae between the prisms. The Orsay): The use of the ZPB method (peak:to background) enamel. of Albertosaurus is $5-um thick; for.comparison,, the, allowed us to study rough surfaces. Because of the etching, the enamel of Tarbosaurus (Upper Cretaceous of Gobi) is about positions of the analyzed points with respect to the structural 90 am (Dauphin 1988). Prismatic units are absent in Alberto~ features are precisely known. At lenst 10 microprobe analyses saurus, but horizontal growth layers are well developed in the. ‘were made at Various locations on individual tissues in most outer part of the enamel (Fig. 14). of the samples. For the purpose of this study the mean values Only some patches of enamel are preserved in the hadro~ of analyses for within samples are used as the representative saurid teeth, and these are without visible prisms. variable for the sample. The electron beam is focused to 100 ‘The maximum thickness in ceratopsian enamel is about ‘of 200 nm, during 60 or 100 s, voltage being 15 kV. The stan- 200 am (Dauphin 1987, 1988). An ornamentation of rounded dard was cobalt tubercles is preserved in the Steveville RR Grade teeth. The tubercles are more pronounced on the crests of the teeth than. palevare ate La in the intercrestal zone. They are not regularly elongated and Geochemical data obtained from enamel and dentine can be nisTota\ cine. TD Oe al, 1988), represented by points in hyperdimensional space. Principal” The maximum observed thickness is 285 wm. Prismatic units component analysis is then used to drop the hyperdimensionsl ng prow layers are not visible Figs. Le, 1. Some coratop- space into a lowerdimensional space with minimum loss of Sian gpccimens of Alberta show double growth layers information, The chemical contents of enamel and dentine were computed with principal-component analysis, based on _Dentine correlation matrix (STATITCF program). The variables include The dentine of the Steveville RR Grade crocodile is ortho- the chemical elements, and the individuals are dentine and dentine, the tubules of which have been secondarily filled enamel, the fossil tissues, Aimong the recent teeth, two species (Fig. 1g). Tio, 1 Mirostuares of rest and fol pian teth, (=) Outer surface ofthe enamel of Aligatormisisppienss (recent) showing the pisate pattern, CP 166 ALS. (8) Vertical section in te enamel ofthe Stvevile RR Grade creole tooth. Some horizontal growth lines ae vse: TMP 691222, HPO, 10%, 75», 20°C. %1995, (2) Vereal section in the enamel of Stevevile RK Grade theropod I toh miher prismatic pater ror grosth line are present. TMP 89-122-6, HyPO, 10%, 60s, 20°C, x1230. (Vertical setion of te ovierenormel prt oft frontal teth of Albertosauras, showing growth lines. TMP 89-128-20 (16900), HsPOx 10%, 79s, 20°C. %2200. (© Oster ornamentation on acre afe ceratopsianfoth (Seveile RR Grae), TMP 89-1224, HyPO, 10%, 6's, 20°C, x60. (7) Vera Sexo in ceatupran toot; enamel doesnot show prismatic nt or groweh nes, Same species as fn). 235, (2) Longitudinal polishes tnd eched section in the dentine ofthe Stevvile RR Grade crocodile. The ules ofthe orhodentine ace secondly file, Same specimen tin). 495, () Oblique smtin inthe orthodentine, the tbules of which are wf. Same specimen a in (2). 2320, (9 Oblgue section in be onhodentne of a Stevevile BR Grade theropod tooth, The tabuls are secondarily filed. Same specimen asin 8). 1005. (Oblique {ction nthe orhocentine aa frontal ooh ofAerosaus, showing te eglar emp tubules, Same specimen asin (2). 1005. Vertical fection in the onhodentne ofa badrosarid toot; the wbles ofthe dentine are empty. TMP 89-1227, HPO, 10%, 80s, 20°C, 1010, {0,Odigue Seton of the dentine of eertopian tooth, with empty tbules. See specimen asin (@), 4370 DOCHERENS ET A. 787 788 (CAN. 1 EARTH SCL. VOL. 3, 1954 ‘Taste 2. Weight ratio (1000 for Se!Ca, Mg/Ca, and ZniCa) in fos and recent teeth Enamel Dentine Taxon CaP StiCa_ MgiCa Zn/Ca CaP SriCa My/Ca_Zn/Ca Crot* 2.05 053 199 218 207 305 178146 Thee 207 198 1st 246 216 138 251 3.85 Thee ri he) (ey oe Alb 206 198185216 0052.23 2.23 Hace = 5 LD aig 2 253 3.08 cer ling: a0) 922 297) ork aia) | 27) 3.70) Cert 205 221 230 495 21d 242-281 LST cer 2i5 024 218 210 184 497 3.66 1.53 Ce 228 0 240 055 (199 341 3.75 048 ©. acu. eg arto Oe os) lise) 1G) | sale 57.70) C ea Im = 656 265 152 052 5.22 10:16 © pal 190 1.65 O41 «4.05 157 3.08 4427.36 A. ms. LR 17S 145 3.92 LOL 45.95 27.55 138.47 Pig pe eae 029 sa) ise cist 408i 10.88 HERBF om 213 102 2.20 264 201 352 325 1.89 o O12 0.8 O21 184 013 106 053 136 CARNE m 2.07 088 163 229 218 171 223 240 co 0.02 0.8 046 036 004 120 031 107 FOS om 2.10 095 191 247 208 252 268 © 2.17 ¢ 008 078 O45 124 O11 143 065 115 RodM om 1.69 152 5:56 573 150 346 2345 9.81 @ 003 118 109 144 O12 324 1274 © 2.97 Rodi om 179 168 436-229 «157 S52 5489 5.18 7 003 48 0.62 057 008 395 18.15 1.68 ‘ores: @ aeut, Crocodplus aout; C. cate, Crocodsla caaphracts; C. pal, Crocodglus als 4. mi ligation missssipplenss, 1 Paleosucha irigonaus; HERB F_ herbivorous fosils; CARN F, carivorose foes; Rod M, recent rodeat molar, Rod , recent rent incisor. Otter abbrevions atin Table 1 In some cases, the tubules of the theropod orthodentine are empty (Pig. 1h) In other specimens, the tubules were cas, and the intetubular dentine is partially dissolved (Fig. 1). The dentinal tubules of Alberiosaurus from the Horseshoe Canyon Formation are empty (Fig. 1) Tn the dentine of a given hadrosaur tooth, some tubules are empty, whereas others are secondarily filled (Fig. 14) The tubules of the orthodentine of ceratopsian teeth are emply (Fig. 10. Chemical composition “The salient features ofthe chemical contents of enamel and dentine are summarized in Tables 1 and 2 and Figs, 2 and 3 Data of recent Crocodylia (R Croc in tables) and some mam- mals (codes) have been added. The rodent data chosen in this paper are typical of those measured on a large sampling of modern rodents (Dauphin and Denys 19925). Enamel (Tables 1, 2; Fig. 3) in recent specimens is charac- terized by high P and Ca contents (Table 1), and a weight ratio of CalP of 1.93 (Table 2). Nais rather high. The average P content of fosil enamel (Fig. 3) is similar to that of recent ‘enamel, but the average Ca content is somewhat higher. Ca/P is higher than that in the recent enamel. Na content is lower than that in recent Crocodylia, Iti the same for Mg and Al, ‘but Fe is higher. ‘The dentine (Tables 1, 2; Fig. 3) of recent Crocodylia shows ower P and Ca contents’ with regard to the recent enamel (Table 1). The weight ratio Ca/P is lower than that of the recent enamel (Table 2). The recent dentine is rich in Mg and S. The fossil dentine samples (Fig. 3) are enriched in P and Ca, and the average Ca/P ratio is equal to that of the fossil enamel. The loss of Mg and Cl is clear, whereas Na and Fe ‘increase in fossil dentines. In fossils, Sr and S contents increase or decrease according to the specimens. “Multivariate analysis of fossil specimens shows that axis 1 accounts for 30.4% of the total variation, axis 2 for 23.9%, and axis 3 for 12.9%. The specimens are sorted along axis | ‘according to their contents in Ca, P, and Zn (Fig. 3); they are sorted according to their contents in Mn and Fe, opposed to Na contents, along axis 2. The dentine and enamel of two recent cracodilians have been added as supplementary individ- uals. The diagram shows clearly that dentine is more altered than enamel, Recent dentine and enamel are well separated, whereas fossil dentine and enamel are not so well separated. ‘The enrichment of fossil dentine in P, Ca, and Na is clear, Discussion Structural and chemical preservation Diagenetic changes ‘The comparison between recent and fossil teeth shows that diagenetic changes have occurred, although the extent differs in dentine and enamel. For example, Na content is bigher in recent enémel than in fossil enamel, but Na content is higher in fossil dentine than in recent dentine. Mg content is high in recent teeth, low in fossil teeth. Not only the elemental content changes but also the ratios. The mechanism, rate, and predict ability of these changes are poorly understood. BOCHERENS EF AL 789 “Reo E Ree 0 Fos © SFos D i : Na Mg S Fe Sr Zn Ma Cl AY Roo D Fos D 000 evo E sooo § sco 2 roof \, of Na Mg 8 Fe Sr Zn Mn Gl foc & Fos E ty 5 120004 8 e000, e000 Bob Nee ees Na No § Fo Sr 2n wn Cl Al ‘Abundance (po Mo cl Al Na Mg S Fe Sr Zn Fig. 2. Comparison of chemical content of mean fossil and eecent tissues (in ppm). Fos B, fossil enamel; Fos D, fossil dentine; Rec D, recent dentine; Rec B, recent enamel ‘High Ca, P, and Zn contants 2High Mn and Fo contents 3:High Na contonts See, Sent, Fossil dentine Fic, 3. Prineipel-component analysis based on chemical content. Th individuals re sorted along the axis | (30.4% of the total variation) sczording to their Ca, P, and Zn contents; they are sored slong axis 2 (23.9% cf the total variation) according to their contents in Ma and Fe, opposed to Na contents Comparison berween enamel and dentine From Table 2 and Fig, 3; itis clear that there is much more similarity between recent'and fossil enamel than between recent and fossil dentine. Mg, Sr, Za, Mn, Cl, and Al amounts are very similar in fossil and recent enamel, whereas there is 4 depletion in Na and an enrichment in $ and Fe in fossil enamel when compared with modern enamel. On the other hand, the chemical composition of fossil dentine is clearly Gifferent from that of modern dentine, especially for Mg (strongly depleted in the fossil) and Fe (more than 10 times higher in fossil than in modern dentine). Chemical composi- tion in fossil dentine and enamel appears more similar than between modern dentine and enamel. This better stability of chemical composition in enamel relative to dentine is consis- "0 (CAN. 2. EARTH SCI. VOL. 31, 198 tent with results on carbon isotopic composition in bone, den- tine, and enamel in late Cenozoic fossil mammals (Lee-Thorp and van dec Merwe 1987), Variability ‘The examination of the microstructures of recent and fossil teeth allows us to understand the observed variability in the chemical changes. Enamel is a compact tissue, except for the presence of some tubules, Dentine is a porous tissue, with very humerous small tubules. It is covered on its outer face by tenamel, but the inner pulpal cavity allows exchange of ele- ‘ments with surrounding sediment and groundwaters. The vari ability of microstructural preservation of dentine in the fossil teeth is clear. In hadrosaur dentine, some areas are devoid of mineralization in the tubules, whereas other areas exhibit important mineralizations in the same tooth. Te-we consider the Steveville RR grade locality, great varia tions in the pattern of microstructural changes can be seen, ranging from empty tubules to heavy mineralization. The same kind of heterogeneity in organic matter preservation in one Iocality has been noticed from amino acid composition (Wyck- #1972; Davidson et al. 1978; Bocherens et al. 1991a, Bocherens 1992). Paleodietary interpretation of Sr values ‘To investigate whether the chemical composition is pre~ served in a fossil sample, we compare the content in one ele- ‘ment with that in a modeta equivalent as well as the chemical contents between fossil samples, which are expected to present characteristic variations according to ecological or dietary characters. Sr is interesting in this regard because of its behavior in trophic webs. Its concentration decreases at each trophic level; thus it is expected to be lower in carnivores than. in herbivores (Blias etal. 1982). The reference data on Sr con- tents and diets are based on mammals (Schoeninger 1989). (Our analysis of recent rodent teeth fall into the range given for herbivores by Sillen (1000Sr/Ca between 0.89 and 3.27; Sillen 1981, 1988), and is consistent with the herbivorous diet of these rodents (Table 2). Thus the ability to know mammal diet from energy-dispersive spectroscopic analyses is good. Results fon recent reptilian teeth, however, are somewhat different Five reptilian samples have been studied (Dauphin 1989); the 41000Sr/Ca ratio of crocodilians falls into the range of herbi ‘vorous mammals (Sillen 1981, 1988), except for the dentine of C. cataphractus (Table 2), The comparison of the rates of tooth replacement in mammals and reptiles may explain the chemical difference. The life of a tooth in A. mississippiensis is only 2 years. Through tetracycline labelling, it was deter- mined that incremental lines in alligator dentine are daily depositional features (Erickson 1991). Such lines are found in dinosaurs, but their periodicity is not yet known. Moreover, the type of insertion of a reptilian tooth in the jaw differs from that of mammals, ‘The turnover of the chemical contents and the physiology of these two taxa are different. It seems that if ‘we want to use Sr as dietary indicator, a new calibration is necessary for herbivorous and carnivorous reptiles. Similar problems of calibration between reptiles and mammals occur forthe other elements used as dietary indicators. According to Byrne and Parris (1987), bone Na contents are higher in carni- vores than in herbivores. This difference is found for enamel if we compare. recent crocodile teeth and rodent molar and incisor (Dauphin and Denys 19922). ‘The same is not true for dentine, but Na/Ca (LOO0Na/Ca, weight ratio) in enamel and dentine of recent crocodiles is higher than the ratios for rodents. Bone Zn contents is higher in car herbivores (Byrne and Parris 1987). Zn content of recent crocodile enamel is between those of rodent incisor and molar enamel. Zn contents of dentine are similar in crocodiles and rodents, All the dentine Zn/Ca ratios (1000Zn/Ca, weight ratio) of crocodiles are higher than those of rodents. The range ‘of Zn/Ca in crocodilian teeth is similar to that of rodent teeth (Table 2), and higher then the data of Byrne and Parris (1987) It is thus difficult to infer conclusions about diet from direct comparison of tooth chemical composition of modern reptilian carnivores, such as erocodiles, with that of modern herbivor- ‘ous mammals, such as rodents Considering only the Steveville RR Grade samples, the Sr amount in enamel and dentine is lower for theropod (carni- vore) than for ceratopsian and hadrosaur (both most likely herbivores, Norman 1985). Nonetheless, the crocodile shows much higher Sr in dentine than in enamel and its dentine is the ‘most mineralized of the analyzed specimens. Albertosaurus from Horseshoe Canyon Formation has very low Sr, in enamel ‘as well as in dentine, and this dinosaur was a carnivore (Norman 1985). ‘A constant problem when dealing with fossil reptiles, and especially with dinosaurs, is the lack of recent ecological ref- erences for comparison, We thus urge new work on recent herbivore and carnivore reptiles in the same ecosystem. Comparison of the different geochemical methods for paleo- dietary investigations in dinosaurs ‘Three geochemical methods on bone, dentine, and enamel may be used for paleodietary investigations in dinosaurs: chemical analyses, isotopic biogeochemistry of carbon and nitrogen in fossil organic matter, and isotopic biogeochemistty of carbon in carbonate hydroxylapatite. All these measure- ‘ments give valuable information on living animals but these. values may be altered by diagenesis and thus become unreli- able, Here we give comments on the use of these methods con- ‘cerning their applications on dinosaur material, and conclude thatthe most promising method is isotopic analyses on organic ‘matter, although new developments in extraction and purifica- tion are needed, Chemical analyses As we have seen inthis stady, there is a possibility that some of the chemical analyses of Late Cretaceous fossil enamel may siill have paleodietary information, but bone and dentine are very likely altered by diagenesis. Isotopic biogeochemistry of organic matter (Of the three geochemical methods discussed here, this is the ‘only one where it is possible to check the preservation of in vivo information of the extracted material without comparison ‘with recent equivalents, Indeed, it has been established chat preservation of collagen-like amino acid composition in organic matter extracted from bone or dentine means preservation Of isotopic values, at least for Pleistocene mammals up 10 ~1000 ke old (DeNiro 1985; DeNiro and Weiner 1988; Bocherens etal. 1991a; Bocherens 1992). The crucial point is the extraction of organic matter with collagen-like amino acid composition from dinosaur material. As early as the middle of the 1960's, Heller (1965) presented collagen-like amino acid ‘composition for organic matter from an ichthyosaur vertebra, from Lias e from Holzmaden. Wyckoff (1972) and Davidson etal. (1978) published promising amino acid compositions for dinosaur and crocodile material from different Mesozoic BOCHERENS ET AL, 1 localities. Dinosaur and other reptile specimens from Late Cretaceous localities, including localities in the Judith River Formation, have yielded organic matter with some collagen characteristics (Ostrom et al. 1990; Bocherens et al. 19915; Bocherens. 1992) but the preservation of original isotopic values as still to be demonstrated. More powerful laboratory methods will probably allow extraction of organic matter suit- able for isotopic analysis from some ofthese promising samples. Fossil dentine is sometimes claimed to preserve its collagen better than does bone (Righy and Getty 1984; Masters 1987) but other results show that collagen is sometimes better pre~ served in bone than in dentine of the same fossil specimen Bocherens 1992). Enamel may preserve organic matter but in very low amounts (Glimcher et al. 1990) and this organic mat- ter is poorly known, even in recent samples. Nevertheless, comparison with modem equivalents remains necessary for the ecological interpretation of isotopic values Isotopic biogeochemistry of carbonate hydroxylapatite ‘The carbon isotopic abundances are not preserved in the inorganic phase of mammal bone and dentine a few millions | of years old (Lee-Thorp and van der Merwe 1987; Koch et al, in press); thus itis unlikely that they are preserved in the much ‘older dinosaurs. In mammal tooth enamel, isotopic values are preserved several tens of millions years, and are used to recon struct paleoenvironments of Cenozoic mammals (Quade etal 1992; Cerlng etal. 1993). The thinness ofthe enamel (typi- cally ess than $00 ym) of dinosaurs and other reptiles limits the usefulness of this approach to these animals, although some measurements of carbon isotopic abundancs in Permian ‘Therapsid teth with thicker enamel have been used for strati- ‘raphic correlations (Thackeray etal. 1990) Conetusions From the results of this study, it appears that the quality of the preservation presents great variability within a formation, as well as within a locality or even a single tooth. The chemi- cal composition is very different between fossil and modern dentine, It seems that fossil enamel may have retained some ppaleodietary information in its chemical composition, whereas dentine, as well as bone, likely did not. Paleodietary interpre- tations may thus be drawn from the chemical composition of some elements, sich as strontium, but more studies on recent reptiles are urged for comparison. Multi-elemental studies in fossil enamel, connected with isotopic studies on indigenous bone or dentine organic matter, may finally provide valuable information on the trophic position of some dinosaur groups ‘in Mesozoic ecosystems Acknowledgments ‘We thank Noreen Tuross for critical review of this manu- script. We are also indebted to the Université de Paris VI (Pierre et Marie Curie) and Naturalia et Biologia for providing travelling funds for collecting samples in Canada. (Alcala, A.C., and Dy-Liacco, M.TLS. 1990. H alligators et eaimans, Bordas, Montrouge, France, pp. 136155. Boez, N.T., and Hampel, J. 1978. Strontium content of fossil tooth ‘enamel and diet of early hominids. Journal of Paleontology, 52: 2 928-933,

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