Reconstruction of palaeosalinity using carbon isotopes and benthic associations: a comparison

Carbon and oxygen isotopes were determined on 40 recrystallized shells of Late Jurassic bivalves from the Lusitanian Basin of Portugal. In contrast with the oxygen isotopes, which exhibited considerable diagenetic distortion, the carbon isotopes are thought to preserve a record of the salinity of the Jurassic marginal marine seas in which these bivalves lived. The reconstructed palaeosalinities range from 35%o (euhaline) to 5% (oligohaline). Comparing these values with the palaeosalinity reconstructed from a palaeoecological analysis of 17 stratigraphic levels within the basin, the independently derived values agree in most cases. Strongly differing values are explained as being due to biotic factors and to diagenetic distortion of the isotopic signal; they are less likely to be due to smallscale time-averaging or insufficient microstratigraphic sampling. On the whole, the carbon isotope analyses are thought to produce reasonable palaeosalinity values, although data from infaunal, originally aragonitic bivalves appear to be less reliable than those from epifaunal bivalves with a predominantly or exclusively calcitic shell. As diagenetic alteration of the carbon isotope signal is, however, unpredictable and biotic effects on the isotopic composition are insufficiently known, palaeosalinity reconstructions based on stable isotope data should be supported by palaeoecological data.     

The isotopic composition of oxygen and carbon in the subfossil mollusc shells of the Baltic Sea as an indicator of palaeosalinity

The carbon (δ¹³ C) and oxygen (δ¹⁸O) isotopic composistion in mollusc shells in mainly determined by the isotopic composition of water and dissolved bicarbonate. The δ¹⁸O values of water show a good correlation with the salinity of the Baltic. This correlation served as a basis for reconstructing palaeosalinity and for stratifying the marine sediments according to the δ¹⁸O values of the carbonate skeletons of subfossil shells. The δ¹³C values in shells are mainly determined by the isotopic composition of land-originating bicarbonate, especially in the carbonate skeleton of Lymnaea balthica , which inhabits the immediate coastal zone. According to the δ¹⁸O data, salinity in the investigated area (the coastal area of W and NW Estonia) was highest (about 9–11%) during the Littorina stage. The Limnae a stage had, in general, a salinity similar to the contemporary one, but during some phases possibly exceeding it by 2–3%.     

Nd and Sr isotope compositions in modern and fossil bones - Proxies for vertebrate provenance and taphonomy

Rare earth elements (REE), while not essential for the physiologic functions of animals, are ingested and incorporated in ppb concentrations in bones and teeth. Nd isotope compositions of modern bones of animals from isotopically distinct habitats demonstrate that the ¹⁴³Nd/¹⁴⁴Nd of the apatite can be used as a fingerprint for bedrock geology or ambient water mass. This potentially allows the provenance and migration of extant vertebrates to be traced, similar to the use of Sr isotopes. Although REE may be enriched by up to 5 orders of magnitude during diagenesis and recrystallization of bone apatite, in vivo¹⁴³Nd/¹⁴⁴Nd may be preserved in the inner cortex of fossil bones or enamel. However, tracking the provenance of ancient or extinct vertebrates is possible only for well-preserved archeological and paleontological skeletal remains with in vivo-like Nd contents at the ppb-level. Intra-bone and -tooth REE analysis can be used to screen for appropriate areas. Large intra-bone Nd concentration gradients of 10¹-10³ are often measured. Nd concentrations in the inner bone cortex increase over timescales of millions of years, while bone rims may be enriched over millenial timescales. Nevertheless, ε_Nd values are often similar within one ε_Nd unit within a single bone. Larger intra-bone differences in specimens may either reflect a partial preservation of in vivo values or changing ε_Nd values of the diagenetic fluid during fossilization. However, most fossil specimens and the outer rims of bones will record taphonomic ¹⁴³Nd/¹⁴⁴Nd incorporated post mortem during diagenesis. Unlike REE patterns, ¹⁴³Nd/¹⁴⁴Nd are not biased by fractionation processes during REE-uptake into the apatite crystal lattice, hence the ε_Nd value is an important tracer for taphonomy and reworking. Bones and teeth from autochthonous fossil assemblages have small variations of ±1 ε_Nd unit only. In contrast, fossil bones and teeth from over 20 different marine and terrestrial fossil sites have a total range of ε_Nd values from -13.0 to 4.9 (n = 80), often matching the composition of the embedding sediment. This implies that the surrounding sediment is the source of Nd in the fossil bones and that the specimens of this study seem not to have been reworked. Differences in ε_Nd values between skeletal remains and embedding sediment may either indicate reworking of fossils and/or a REE-uptake from a diagenetic fluid with non-sediment derived ε_Nd values. The latter often applies to fossil shark teeth, which may preserve paleo-seawater values. Complementary to ε_Nd values, ⁸⁷Sr/⁸⁶Sr can help to further constrain the fossil provenance and reworking.     

Stable isotope fractionation between mollusc shells and marine waters from Martinique Island

Forty-nine aragonitic and calcitic shells from 14 species of marine tropical molluscs (Bivalvia, Gastropoda, Polyplacophora) and ambient waters from Martinique have been analyzed for their carbon and oxygen isotope compositions. Mineralogy of shells was systematically determined by Raman spectroscopy that reveals composite shell structures and early processes of diagenetic alteration. In mangrove, brackish waters result from the mixing between 89±1% of seawater and 11±1% of freshwater, a hydrological budget quantified by both oxygen isotope and salinity mass balance calculations. Mollusc shells from the mangrove environment (S=31‰; δ¹⁸O=0.5‰) are characterized by mean δ¹³C values (−1.2‰) lower than those (+2.6‰) living in the open sea (S=35‰; δ¹⁸O=1‰). These low carbon isotope compositions result from the oxidation of organic matter into bicarbonate ions used in the building of mollusc shells. The oxygen isotope compositions of the studied mollusc species are mainly controlled by the temperature and composition of seawater whereas the role of the so-called “vital effects” is negligible. Contrasting with carbon isotopes, variability in the δ¹⁸O values among and within species of mollusc shells is very low (1σ=0.15) for a given littoral environment. Using ambient temperatures of seawater (28-30 °C), oxygen isotope fractionations between all studied living species and environmental waters match those extrapolated from the fractionation equation established for molluscs by Grossman and Ku [Chem. Geol., Isot. Geosci. Sect. 59 (1986) 59] in the range 3-20 °C. By analyzing calcite and aragonite layers from the same shell or by comparing shells from different species living in the same environment, there is no evidence that oxygen isotope fractionation between aragonite and water differs from that between calcite and water. On the basis of these results, we conclude that the oxygen isotope compositions of shells from most fossil mollusc species are suitable to estimate past seawater temperatures at any paleolatitude.     

微量元素分布揭示腕足化石壳体原始信息保存现状

以产于四川龙门山地区泥盆系观雾山组的有铰纲腕足化石Ｉｎｄｅｐｅｎｄａｔｒｙｐａ ｌｅｍｍａ Ｃｈｅｎ为研究对象,利用激光熔样等离子质谱（ＬＡ－ＩＣＰ－ＭＳ）对其壳体棱柱层中Ｆｅ、Ｍｇ、Ｍｎ、Ｎａ、Ｂａ和Ｓｒ六种微量元素进行了就位分析。它们在壳体横切面中的对称分布特征总体上与壳体增生方式和过程相一致,表明壳体的绝大部分未经成岩作用的改造。与常用的结构判据、阴极发光判据和微量元素含量判据相比较,微量元     

腕足壳体与碳酸盐岩全岩中碳、氧、锶同位素差异

利用碳酸盐岩中的地球化学信息反演是研究地质历史时期古环境、古气候变化的一种常用手段.上世纪八十年代前,学术界一直将碳酸盐岩全岩样品作为研究对象.近年来,腕足化石壳体引起了科学家的注意,认为相比碳酸盐岩全岩样品,腕足壳体能更为完好地保存原始的地球化学信息.研究通过对比四川龙门山泥盆纪腕足化石和碳酸盐岩全岩样品中碳、氧、锶同位素(黄思静、卢长武等人数据),发现腕足化石中氧同位素明显高于碳酸盐岩全岩;但碳、锶同位素基本一致.上述结果表明:相比腕足化石,碳酸盐岩全岩样品蕴含的地球化学信息虽有所差异,但在大多数情况下,尤其是缺乏腕足化石的时期,碳酸盐岩全岩蕴含的地球化学信息照样可以反演地质历史时期的古环境变化,尤其是碳、锶同位素.     

Enamel diagenesis at South African Australopith sites: Implications for paleoecological reconstruction with trace elements

Elemental ratio data from archaeological and paleontological bone have often been used for paleoecological reconstruction, but recent studies have shown that, even when solubility profiling techniques are employed in an attempt to recover biogenic signals, bone is an unreliable material. As a result, there has been renewed interest in using enamel for such studies, as it is known to be less susceptible to diagenesis. Nevertheless, enamel is not immune from diagenetic processes, and several studies have suggested that paleoecologically relevant elements may be altered in fossil enamel. Here, we investigate Sr, Ba, Zn, and Pb compositions of enamel from South African karstic cave sites in an effort to ascertain whether or not this material provides reliable paleoecological information. We compared enamel data for mammals from three fossil sites aged 1.8-3.0 Ma, all of which are on dolomites, with data from modern mammals living on dolomitic and granitic substrates. Sr/Ca and Ba/Ca are about three times higher in enamel from modern mammals on granites than those living on dolomites, stressing the need for geologically appropriate modern/fossil comparisons. After pretreatment with dilute acid, we found no evidence of increased Sr/Ca, Ba/Ca, or Pb/Ca in fossil enamel. In contrast, Zn/Ca increased by over five times at one site (Makapansgat), but much more subtly elsewhere. Ecological patterning in Sr/Ca, Ba/Ca, and Sr/Ba ratios was also retained in fossil enamel. This study suggests that Sr/Ca, Ba/Ca, and Pb/Ca data likely preserve paleoecological information from these sites, but also demonstrates that geologically similar sites can differ in the degree to which they impart certain elements (Zn in this case) to fossils. Thus, screening is probably necessary on a site-by-site basis. Lastly, further investigation of elemental distributions in modern foodwebs is necessary before elemental ratio analysis can become a common tool for paleoecological reconstruction.     

Effects of diagenesis on paleoclimate reconstructions from modern and young fossil corals

The integrity of coral-based reconstructions of past climate variability depends on a comprehensive knowledge of the effects of post-depositional alteration on coral skeletal geochemistry. Here we combine millimeter-scale and micro-scale coral Sr/Ca data, scanning electron microscopy (SEM) images, and X-ray diffraction with previously published δ¹⁸O records to investigate the effects of submarine and subaerial diagenesis on paleoclimate reconstructions in modern and young sub-fossil corals from the central tropical Pacific. In a 40-year-old modern coral, we find secondary aragonite is associated with relatively high coral δ¹⁸O and Sr/Ca, equivalent to sea-surface temperature (SST) artifacts as large as −3 and −5 °C, respectively. Secondary aragonite observed in a 350-year-old fossil coral is associated with relatively high δ¹⁸O and Sr/Ca, resulting in apparent paleo-SST offsets of up to −2 and −4 °C, respectively. Secondary Ion Mass Spectrometry (SIMS) analyses of secondary aragonite yield Sr/Ca ratios ranging from 10.78 to 12.39 mmol/mol, significantly higher compared to 9.15 ± 0.37 mmol/mol measured in more pristine sections of the same fossil coral. Widespread dissolution and secondary calcite observed in a 750-year-old fossil coral is associated with relatively low δ¹⁸O and Sr/Ca. SIMS Sr/Ca measurements of the secondary calcite (1.96-9.74 mmol/mol) are significantly lower and more variable than Sr/Ca values from more pristine portions of the same fossil coral (8.22 ± 0.13 mmol/mol). Our results indicate that while diagenesis has a much larger impact on Sr/Ca-based paleoclimate reconstructions than δ¹⁸O-based reconstructions at our site, SIMS analyses of relatively pristine skeletal elements in an altered coral may provide robust estimates of Sr/Ca which can be used to derive paleo-SSTs.     

The Holocene fossil marine macrofauna of the Vestfold Hills, East Antarctica

The Holocene (< 10,000 years old) fossil marine macrofauna (molluscs, polychaetes, mammals and birds) of the Vestfold Hills, Antarctica (68°30'S, 78°00'E) is described. All species are extant, with circumantarctic or wider distributions and wide depth ranges. At Heidemann Bay, Pleistocene-age (> 30 ky old) shell fragments occur in a Holocene moraine. These are interpreted as being glacially reworked fossil shells. Holocene benthic estuarine and coastal molluses and serpulid worm tubes are abundant on the flanks of terraces above saline and hypersaline lakes. Extensive radiocarbon dating gives a chronology of these deposits which were not synchronous. Mummies of seals and penguins, which are concentrated on the shores of the saline lakes and scattered across the Hills, are of no use in dating geomorphological events. Marine fossils in moraines are difficult to interpret because they can be glacially-transported live or fossil shells, or deposited after wind transport. The fossil fauna has such a wide ecological range that it indicates only in general terms that for part of the Pleistocene and most of the Holocene, climatic conditions were broadly similar to the present.     

A review of Macoma balthica (L) as a stratigraphic marker in the Pleistocene sediments of the southern North Sea Basin

The first occurrence and presence of the bivalve Macoma balthica in the Pleistocene shallow marine sediments (Crags) of East Anglia has long been used to characterise the youngest “Weybourne” or “Wroxham” Crag Formation of Early to early Middle Pleistocene age. A review of recent work on the morphological variation and genetic lineages of living populations of the species and of work on fossil discoveries in East Greenland suggests that the current palaeontological species definition is too narrow, that the species arrived in the Atlantic about 2.4 Ma and much earlier than is envisaged from the studies of the North Sea Basin, and that there were several trans-Arctic migrations of the species during the Pleistocene. This paper reviews these findings and concludes that: (i) detailed morphometric analyses of fossil Macoma species from the Crag need to be undertaken and the species definitions comprehensively reviewed to take account of the morphological and genetic variation seen in modern populations; (ii) detailed morphometric analysis of modern M. balthica should be undertaken and tied to the different genetic lineages, and (iii) the current palaeontological definition of Macoma balthica should not be relied on as the basis for a First Appearance Datum (FAD) in the Southern North Sea basin.     

The stratigraphical significance of deer species in the cromer forest-bed formation

Deer species provide a valuable biostratigraphical tool through Cromer Forest-bed times, due particularly to species turnover between the Early and early Middle Pleistocene. This study is based on the reidentification of 348 fossil antlers. The provenance of most large mammal fossils from the CF-bF, collected over 150 years, was recorded only by the nearest coastal village. None the less, analysis of the cervid taxa by these ‘localities’ reveals interesting patterns. The fauna of the West Runton Freshwater Bed is of early Middle Pleistocene complexion, and that from the foreshore at East Runton is of Early Pleistocene. Pure or nearly pure early Middle Pleistocene assemblages also occur at Kessingland-Pakefield and at Trimingham. At Overstrand, Sidestrand, Mundesley, Bacton and Happisburgh, there is a mixture of Early and early Middle Pleistocene elements. Analysis of Savin's data shows that fossils of earlier species were generally found further down the beach than those of later ones. Late nineteenth century geological surveys, made when bone collecting was at its peak, give additional information about fossil horizons, which in several cases can be related to modern stratigraphical units. Most Early Pleistocene large-mammal bones came from Pastonian conglomerates, in contrast to small-mammal and molluscan assemblages mostly extracted from Pre-Pastonian Crag. However, the diversity of Early Pleistocene CF-bF cervid species in comparison with continental faunas, and their pattern of distribution between sites, suggests they may span more than one chronostratigraphic stage. Early Middle Pleistocene assemblages came from strata now referred to the Cromerian, and the differing proportions of taxa between sites provide limited evidence of time-transgression.     

Boron in siliceous materials as a paleosalinity indicator1

The ¹⁰B(n, α)⁷Li nuclear reaction has been used with alpha-sensitive plastic track detectors to determine boron concentrations in siliceous live-collected and fossil sponge spicules. This radiographic technique allows B determinations with 5–6% uncertainties on objects 20–25 μm in diameter and for concentrations as low as 0.5 ppm. Boron concentrations in spicules from different specimens from the same location agreed to within 10% when the spicules were not: (1) smaller than 20 μm in diameter, (2) from dictyonine skeletons, (3) the extremely large root-like spicules found in some soft substrate hexactinellids, or (4) microscleres. These criteria also applied to spicules found in sediment samples. Spicules from live-collected sponges exhibited a taxonomy-independent correlation of B concentrations with water salinity for samples from regions of low water temperature and high productivity. Measured concentrations ranged from nearly 0 ppm B (freshwater sponges) to 500–700 ppm (marine sponges), with intermediate values for brackish-water specimens. However, spicules from tropical, low-productivity marine locations contained markedly less boron than spicules from temperate, high-productivity regions. Thus, water temperature and/or food supply also seem to influence B concentrations. Pleistocene spicules from deep-sea cores contained less boron than was expected in comparison with live-collected spicules based on present water temperatures and nutrient supplies, but B concentrations did not vary with depth in the cores. Infrared spectroscopy, electron microprobe analysis and visual inspection revealed no evidence for chemical or mineralogic alteration. It is not clear whether the lower B concentrations of the Pleistocene samples are the result of diagenetic processes or the as yet undefined effects of differences in food supply and/or environmental conditions.     

Models of diffusion-limited uptake of trace elements in fossils and rates of fossilization

Many fossils are assumed to take up trace elements by a process of combined diffusion plus adsorption (DA), yet in principle composition profiles can be explained by several different diffusion-limited processes, including diffusion plus reaction or recrystallization (DR) and double-medium diffusion (DMD). The DA and DMD models are supported by REE and U composition profiles across fossil teeth, measured by laser-ablation ICP-MS, that show error-function - like diffusion profiles into enamel from the dentine-enamel interface and concentrations in the interior of enamel that are at original biogenic levels or higher. Published composition and age profiles in some Pleistocene bones may be better explained by a DR model. All three diffusion models imply linear behavior between age and distance squared, vastly simplifying U-series dating methods for Pleistocene fossils. Modeled uptake rates for fossil teeth yield a strict minimum bound on durations of about one decade to one century. The similarity of diffusion profiles in teeth, irrespective of depositional ages ranging from ∼30 ka to >30 Ma, implies that uptake occurred quickly, with a maximum duration of a few tens of kyr for typical fossil enamel; faster uptake is implied for typical fossil bone and dentine. Disparities in these uptake estimates compared to some archeological bone may reflect sampling and preservation bias for paleontological vs. archeological materials.     

Intensified mid-Holocene Asian monsoon recorded in corals from Kikai Island, subtropical northwestern Pacific

Coupled records of Sr/Ca and oxygen isotope ratios (δ¹⁸O) of coral skeletons have been used to produce quantitative estimates of paleo-sea surface temperature (SST) and δ¹⁸O of surface seawater that can in some cases be converted to sea surface salinity (SSS). Two fossil corals from Kikai Island in the subtropical northwestern Pacific, a location affected by East Asian summer and winter monsoons, were analyzed to investigate differences between mid-Holocene and present-day SST and SSS. At 6180 cal yr BP, SSTs were roughly the same as today, both in summer and winter; δ¹⁸O_seawater and SSS values were higher both in summer (+ 0.5‰, +1.1 psu) and in winter (+ 0.2‰, + 0.6 psu) than modern values. At 7010 cal yr BP, SSTs were slightly cooler both in summer and winter (−0.8 and −0.6 °C), whereas δ¹⁸O_seawater and SSS had higher values in summer (+ 0.3‰, + 0.6 psu) and in winter (+ 0.8‰, + 1.9 psu) than present-day values. These results are consistent with other marine records for the mid-Holocene of the low and midlatitudes in the northwestern Pacific. Such regional conditions indicate that the East Asian summer and winter monsoons were more intense in the mid-Holocene, which was likely a function of the mid-Holocene insolation regime.     

Quaternary coral reefs of the Red Sea coast, Egypt: diagenetic sequence, isotopes and trace metals contamination

This study focuses on the diagenetic sequence under marine and meteoric conditions as well as isotopes and trace metals contamination in Quseir and Gebel Zeit areas along the Egyptian Red Sea coast through a series of modern and fossil corals, Porites lutea and Favites pentagona. The diagenetic sequence begins with deposition of thin fringes of syntaxial aragonite and micritic high-magnesian calcite in the modern corals to completely altered Porites and partially altered Favites to low-magnesium calcite in the oldest Pleistocene unit. Average δ¹⁸O and δ¹³C values of Pleistocene corals in the two studied areas were lower than those of modern corals. Values of modern corals and lower fossil unit indicated coralline limestone, while those of middle and upper fossil units indicated fresh water influences. Average values of trace metals in modern corals were higher than those of Pleistocene counterpart except for Mn. Modern coral samples recorded enrichment in the average values of Pb, Zn, and Mn at Quseir area and enrichment in Co, Cu, and Ni at Gebel Zeit area. This may be attributed mostly to different tourist activities, landfill due to increase urbanization and nearby of Quseir area from the old phosphate harbor at El Hamrawin area, as well as oil exploration and production activities in the Gulf of Suez area. Also, results indicated that most samples of Porites have high concentration of trace metals than in Favites, especially in Cu, Zn, Mn, and Pb. This may due to high amounts of intergranular porosity and high total surface area of Porites in contrast to Favites.     

The isotopic composition of Tertiary carbonates from the Mainz Basin: an example of isotopic fractionations in 'closed basins'

The carbon and oxygen isotopic composition of seventy-nine samples of biogenic carbonates from the Mainz Basin Tertiary (Oligocene and Lower Miocene) was analysed. Most samples were mollusc shells still consisting of aragonite. Assuming only small temperature effects, salinity trends derived from isotope data are consistent with palaeontological results from the region: a salinity cycle ranging from fresh water-brackish (Lower Oligocene) towards marine (Middle Oligocene) and brackish-fresh water (Upper Oligocene) was found. Within the Lower Miocene, a trend of decreasing salinities is suggested. Though the isotopic salinity trends coincide rather well with palaeontological salinities, the absolute oxygen isotope ratios indicate an unusual isotopic environment enriched in ¹⁸O. Isotope fractionation is explained by evaporation of a closed basin (Rupelton excluded) with fresh water influx from surrounding land areas in a subtropical climate. Enrichment in ¹⁸O by repeated evaporation processes is paralleled by increasing concentration of Sr. Increasing fresh water influx during the Oligocene is due to climatic changes with a trend of more humid conditions towards the younger rock strata.     

Mineralogical and geochemical compositions of modern bivalve shells from the Mediterranean coast of Egypt

The stable isotopic composition (¹³C and ¹⁸O) and elemental (Sr and Mg) of marine molluscs are presented for Carditacea and Solenacea shells collected off the Mediterranean coast of Egypt. Based on shell microstructures and mineralogy, the bivalve shells are preserved in their original mineralogy and chemistry.The Sr and Mg concentrations of the bivalve shells have mean values of 1960 ppm and 226 ppm respectively. The stable isotopic composition generally show high values of ¹⁸O and ¹³C. The ¹⁸O values range from +0.1 to –1.8 PDB and most shells are highly enriched in¹³C; averaging +2.5 PDB. These elemental and isotopic signatures are analogous to modern marine bivalves from other localities.The oxygen and carbon isotopes, together with the calculated temperatures, suggest that the aragonitic bivalve shells were precipitated in isotopic equilibrium from warm marine waters.     

Biogenic Accumulations of Uranium in Recent Seas

The objective of this study is to determine the geochemical role of molluscs in the distribution of uranium in the marine ecosystem. Biogeochemical studies are carried out on recent mollusc shells from the Caspian Sea, Sea of Japan, Sea of Marmara, Aegean Sea, Black Sea, Mediterranean Sea, Baltic Sea, and Indian Ocean, which differ from each other in terms of physical, chemical, geographic, and geochemical characteristics. In this study, nine Gastropoda and fifty-four Pelecypoda shells of different species are analyzed to document variations of uranium in seasonal layers, which were formed by the seasonal carbonate-organic phase of molluscs during their entire lives. Shell used in this study principally comprises three layers: upper (outer) prismatic, middle prismatic, and inner (mother-of-pearl) layers. In addition, when possible, the head, the middle, and the lower parts of the shells are used for analyses separately. Also, the biological accumulation rate values for each different mollusc species rel     

Preservation of the shell matrix protein dermatopontin in 1500 year old land snail fossils from the Bonin islands

Organic molecules such as proteins can be preserved in certain fossils. The bulk properties of fossil proteins of both vertebrates and invertebrates have been studied for over half a century. Named proteins have so far been identified, however, only in vertebrate fossils, such as collagen from mammoth bones. Using immunological assays, we examined 1500 year old fossils of the extinct land snail Mandarina luhuana from the Bonin islands for the presence of dermatopontin, a molluscan shell matrix protein. First, we examined the shell microstructure and mineralogy of the fossil shells using scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) in order to estimate the extent of diagenetic alteration. The results suggest that the original microstructure and mineralogy of the shells are preserved. Antiserum raised against the Type-1 dermatopontin fragment of the living land snail Euhadra brandtii showed significant immunological reactivity with the extracts from the fossil shells of M. luhuana. Immunological binding curves drawn for the shell extracts of extant M. aureola and the extinct M. luhuana confirmed the presence of dermatopontin in the fossil shells and provided an estimate that about 75–98% of the original dermatopontin was lost from the M. luhuana fossils. This is the first report of a named protein being identified in invertebrate fossils.     

Timescales and mechanisms of REE and Hf uptake in fossil bones

Rare earth element (REE) patterns of fossil bones and teeth are widely used as proxies for provenance, taphonomy, and palaeoenvironment. In order to investigate if fossil bones behave as closed systems over geologic time, REE profiles were analysed by LA-ICPMS along cross sections of 54 bones from various well-characterised and well-dated settings. These include terrestrial and marine diagenetic environments, covering Early Triassic to Holocene ages. In general, all fossil bones exhibit the highest REE concentrations at the outer rim, gradually decreasing by up to four orders of magnitude toward the inner bone cortex. Intra-bone REE concentration gradients decrease significantly from Quaternary via Tertiary to Mesozoic specimens, suggesting long term REE uptake and open system behaviour of fossil bone. This view is further corroborated by ¹⁷⁶Lu-¹⁷⁶Hf dating of selected samples, all yielding significantly younger ages than the known chronostratigraphic ages. Hence, there is clear evidence for long term open system behaviour of fossil bones with respect to REE, which is in marked contrast to currently accepted models suggesting that REE uptake is only early diagenetic. Although unexpected, statistically significant four to seven point isochrons are observed for four fossil dinosaur bone samples and one Upper Triassic Mastodonsaurus tooth with MSWDs ranging from 0.083 to 4.5. Notably, mobility of Lu alone cannot account for the observed age patterns. Assuming constant Lu uptake rates over time, the radiometric ages should only be as low as half of the chronostratigraphic age. However, a six-point isochron defined by subsamples of a single Upper Triassic Mastodonsaurus tooth yields an age of 65.2 ± 1.1 Ma (MSWD = 0.68), much younger than half of the stratigraphic age (ca. 234 Ma). Hence, Hf must also undergo late diagenetic exchange. Likely mechanisms to account for the presence of statistically meaningful isochrons as well as for the late diagenetic exchange of both REE and Hf are diffusion, adsorption, and dissolution-reprecipitation processes.