Fossil Brachiopod Shells Research Articles

Diagenetic and Biological Overprints in Geochemical Signatures of the Gigantoproductus Tertiary Layer (Brachiopoda): Assessing the Paleoclimatic Interpretation

Variations in the geochemical signatures of fossil brachiopod shells may be due to diagenesis and/or biological processes (i.e., 'vital effects'). It is critical to characterise them in order to identify reliable shell areas suitable for paleoclimate studies. This investigation contributes to an in-depth understanding of geochemical variations in Gigantoproductus sp. shells (SW Spain, Serpukhovian age), throwing light onto the Late Paleozoic Ice Age interpretation. Microstructural, crystallographic, cathodoluminescence and geochemical (minor and trace elements, δ18O, δ13C, and strontium isotopes) characterisations have been performed on the tertiary layer of the ventral valve, to assess the preservation state. Poorly preserved areas exhibit microstructural and geochemical changes such as recrystallisation, fracturing and higher Mn and Fe enrichment. Moreover, these areas have a higher dispersion of ⁸⁶Sr, ⁸⁷Sr, δ18O and δ13C than well-preserved areas. Three structural regions have been identified in well-preserved areas of the ventral valve by differences in valve curvature and thickness, such as the umbonal and thick and thin regions. These regions have different proportions of Mg, S, Na, δ18O, and δ13C, which are interpreted as 'vital effects' and probably related to growth-rate differences during shell growth. The Gigantoproductus tertiary layer seems the most suitable for paleoclimate studies, because it retains the original microstructure and geochemical composition.

Reassessment of ocean paleotemperatures during the Late Ordovician

Abstract The Late Ordovician is a paradox, with a greenhouse climate shifting to an icehouse climate during a time of presumably high CO2 levels. We used clumped isotope (Δ47) microanalysis of fossil brachiopod shells to determine paleotemperatures of North America (Cincinnati Arch) during the Katian (453–443 Ma). Microanalyses of fossil brachiopods yielded a right-skewed distribution of clumped isotope temperatures [T(Δ47)] ranging from 25 °C to 55 °C with a mode of 32 °C and a mean of 36 °C. To test the impact of Δ47 reordering (reequilibration of 13C-18O bonding) at burial temperatures on T(Δ47), we applied a Monte Carlo simulation to a Δ47 reordering model based on the burial history. Because the reordering simulation indicated partial reordering, we used the simulation results to back-calculate T(Δ47) and correct the reordering effect. Correcting for reordering decreased the mean T(Δ47) by only ~1 °C, to 35 °C, and did not change the mode (32 °C). These temperatures are lower than those of previous studies, but still suggest that the Late Ordovician climate of the Cincinnati Arch was warmer than the modern subtropical seas. However, carbonate facies in these strata argue for upwelling of cool water; thus, typical subtropical surface waters may have been as warm as 35 °C approaching the Hirnantian glaciation. Seawater δ18O values derived from back-calculated T(Δ47) and brachiopod δ18O values average −0.3‰ ± 0.6‰ relative to Vienna standard mean ocean water (VSMOW), consistent with the value expected for subtropical surface waters in a greenhouse Earth, assuming a constant seawater-δ18O model.

Permian–Triassic mass extinction pulses driven by major marine carbon cycle perturbations

The Permian/Triassic boundary approximately 251.9 million years ago marked the most severe environmental crisis identified in the geological record, which dictated the onwards course for the evolution of life. Magmatism from Siberian Traps is thought to have played an important role, but the causational trigger and its feedbacks are yet to be fully understood. Here we present a new boron-isotope-derived seawater pH record from fossil brachiopod shells deposited on the Tethys shelf that demonstrates a substantial decline in seawater pH coeval with the onset of the mass extinction in the latest Permian. Combined with carbon isotope data, our results are integrated in a geochemical model that resolves the carbon cycle dynamics as well as the ocean redox conditions and nitrogen isotope turnover. We find that the initial ocean acidification was intimately linked to a large pulse of carbon degassing from the Siberian sill intrusions. We unravel the consequences of the greenhouse effect on the marine environment, and show how elevated sea surface temperatures, export production and nutrient input driven by increased rates of chemical weathering gave rise to widespread deoxygenation and sporadic sulfide poisoning of the oceans in the earliest Triassic. Our findings enable us to assemble a consistent biogeochemical reconstruction of the mechanisms that resulted in the largest Phanerozoic mass extinction. The end-Permian mass extinction was linked with ocean acidification due to carbon degassing associated with Siberian Trap emplacement, according to boron isotopes from fossil shells and reconstruction of the carbon cycle.

The effects of meteoric diagenesis on the geochemical composition and microstructure of Pliocene fossil Terebratalia coreanica and Laqueus rubellus brachiopod shells from northeastern Japan

Stable carbon (δ13C) and oxygen isotope (δ18O) compositions of fossil brachiopod shells can be used to interpret paleoclimatic and paleoceanographic conditions. However, the initial isotopic composition of the living shells might be modified by diagenetic alteration. To assess the degree of this modification, we analyzed δ13C and δ18O and three common indicators of alteration in shells: minor element (manganese (Mn), iron (Fe), and strontium (Sr)) concentrations; cathodoluminescence (CL)/non-luminescence; and the shell microstructure of fossil Terebratalia coreanica and Laqueus rubellus (rhynchonellate brachiopod) shells from an exposure of conglomerates of the Tentokuji Formation (Pliocene, 3.85–2.75 Ma) in northeastern Japan. Two indices were used to quantify the preservation state of shell microstructure: the altered fiber ratio (AFR) and the altered fiber and puncta-filling cement ratio (AF-PCR). We qualified the degree of luminescence by measuring the mean cathodoluminescence index (MCLI), defined as the mean R values in a particular area of a CL image with RGB colors. The δ13C and δ18O values were negatively correlated with AFR or AF-PCR and MCLI. The sampling spots with high Mn and Fe concentrations also exhibited relatively low δ13C and δ18O. The δ13C and δ18O were more strongly correlated with Mn concentration than with Fe concentration. Therefore, of the three minor elements examined in this study, Mn concentration is the most reliable indicator of meteoric diagenesis in the studied shells. Unlike Mn and Fe concentrations, Sr concentrations in the modern and fossil brachiopod shells were similar, with overlapping ranges. This indicates that Sr concentration is not likely to be a good indicator of diagenetic alteration in the studied shells. Our study provides further evidence that multiple criteria should be applied and cross-checked when assessing diagenetic alteration of brachiopod shells.

Assessing the biomineralization processes in the shell layers of modern brachiopods from oxygen isotopic composition and elemental ratios: Implications for their use as paleoenvironmental proxies

Fossil brachiopod shells are often used as valuable archives to reconstruct paleoenvironmental conditions in deep time. However, biomineralization processes can impact their fidelity as geochemical proxies. Brachiopod shells comprise an outer primary layer, a secondary fibrous layer and sometimes, a tertiary columnar layer. Therefore, it is essential to assess the potential effects of the biomineralization processes in each of the different shell microstructures of modern brachiopods. This study analyses the oxygen isotopic composition together with Li/Ca, Na/Ca Mg/Ca and Sr/Ca data at high spatial (20-50 μm) resolution in seven modern brachiopod species, focusing on differences between the primary, secondary and tertiary layers. In all studied species, δ18O values of the outer primary layer are consistently out of equilibrium with seawater. Also, this shell layer is enriched in Li, Na, Mg and Sr. Contrary to the primary layer, the innermost secondary layer is near or at oxygen isotopic and elemental equilibrium with ambient seawater. The columnar tertiary shell layer, if present, has the least variable and the heaviest oxygen isotopic composition, within the range of equilibrium values with seawater. This tertiary layer, however, is depleted in minor and trace elements relative to the other shell layers. Thus, the tertiary layer is more suitable for oxygen isotopic studies, whereas the innermost secondary layer of the most mature parts of the shell is the best target in two-layered shells. While we do not observe any clear interspecific relationships between Mg/Ca and Sr/Ca ratios, on one hand, and environmental parameters such as temperature, salinity and pH, on the other hand, there is a positive interspecific relationship between Na/Ca and salinity and a negative interspecific relationship between Li/Ca and temperature, suggesting their potential use as proxies of physicochemical parameters of seawater.

Raman investigation of the pigment families in recent and fossil brachiopod shells.

Shells of the three subphyla of extant and extinct representatives of the phylum Brachiopoda display coloured patterns with diverse shapes and at different degrees. These colourations are readily visible in natural light but are best revealed under UV light for the fossils concerned. To identify these pigments, Raman spectroscopy has been used for the first time on brachiopod shells. The widespread identified pigments belong to the carotenoid family, best represented in all the animal kingdom, the second one concerns the melanin/melanin-like pigments and, surprisingly, additional molecules of the cytochrome family are revealed for the first time in one of the brachiopod shells studied. The putative functions of shell pigmentation, still under debate, are discussed.

A SAMPLING STRATEGY FOR RECENT AND FOSSIL BRACHIOPODS: SELECTING THE OPTIMAL SHELL SEGMENT FOR GEOCHEMICAL ANALYSES

Recent and fossil brachiopod shells have a long record as biomineral archives for (palaeo)climatic and (palaeo)environmental reconstructions, as they lack or exhibit limited vital effects in their calcite shell and generally are quite resistant to diagenetic alteration. Despite this, only few studies address the issue of identifying the best or optimal part of the shell for geochemical analyses. We investigated the link between ontogeny and geochemical signatures recorded in different parts of the shell. To reach this aim, we analysed the elemental (Ca, Mg, Sr, Na) and stable isotope (δ18O, δ13C) compositions of five recent brachiopod species (Magellania venosa, Liothyrella uva, Aerothyris kerguelensis, Liothyrella neozelanica and Gryphus vitreus), spanning broad geographical and environmental ranges (Chile, Antarctica, Indian Ocean, New Zealand and Italy) and having different shell layer successions (two-layer and three-layer shells). We observed similar patterns in the ventral and dorsal valves of these two groups, but different ontogenetic trends by the two- and three-layer shells in their trace element and stable isotope records. Our investigation led us to conclude that the optimal region to sample for geochemical and isotope analyses is the middle part of the mid-section of the shell, avoiding the primary layer, posterior and anterior parts as well as the outermost part of the secondary layer in recent brachiopods. Also, the outermost and innermost rims of shells should be avoided due to diagenetic impacts on fossil brachiopods.

Paleoceanographic conditions at approximately 20 and 70 ka recorded in Kikaithyris hanzawai (Brachiopoda) shells

The δ13C and δ18O values of fossil brachiopod shells have been widely used as paleoenvironmental proxies. In this study, we investigated intrashell and intraspecific variations in the isotopic and minor element concentrations of well-preserved shells of the brachiopod Kikaithyris hanzawai (Yabe) from the last glacial period (∼20ka [Last Glacial Maximum; LGM] and ∼70ka [Marine Isotope Stage 4; MIS4]), collected in the Central Ryukyus, and used these data to estimate the paleoceanographic conditions (seawater temperature, concentration of dissolved inorganic carbon [DIC], and δ13C value of DIC [δ13CDIC]). The δ13C and δ18O profiles along the maximum growth axis, obtained from the inner shell surface, show three distinct intervals, corresponding to changes in shell morphology. These results suggest that the bulk isotopic compositions of brachiopods with complex shell morphologies are unsuitable for paleoenvironmental reconstructions. Nevertheless, there exists a specific shell portion with relatively small intrashell and intraspecific variations. The past seawater temperatures derived from the δ18O values of this portion are consistent with the alkenone- and planktic foraminiferal Mg/Ca-based past seawater temperatures reported in previous studies. The past δ13CDIC values estimated from the δ13C values of the specific shell portion are within the range of the past δ13CDIC values calculated from known atmospheric and oceanographic parameters. The past DIC concentrations reconstructed from the brachiopod-based δ13CDIC values are lower than the present concentrations in the East China Sea, which can be explained by low partial pressure of CO2 during the last glacial period. These results indicate that the δ13C and δ18O values obtained from K. hanzawai shells are potential paleoenvironmental indicators. The intrashell and intraspecific variations in the K. hanzawai shells are different for each minor element. Some anomalously high Mn and Fe concentrations in the shells are probably caused by metabolic factor(s), not by meteoric diagenesis. This suggests that the minor element concentrations are useful but not perfect for distinguishing diagenetically altered and unaltered portions of the shells of K. hanzawai in the studied succession.

Temperature limits for preservation of primary calcite clumped isotope paleotemperatures

Solid-state reordering of C–O bonds in the calcite lattice can alter the clumped isotope composition of paleotemperature archives such as fossil brachiopod shells without inducing significant changes in shell microstructure and trace element concentrations, metrics commonly used to gauge preservation quality. To correctly interpret the paleoenvironmental significance of clumped isotope-derived paleotemperatures, it is necessary to understand the temperature–time domain in which solid-state C–O bond reordering is important. We address this question using a combination of laboratory and natural geological experiments on Paleozoic brachiopod shells. The laboratory experiments involve heating fossil brachiopod calcite at different temperatures and times to directly observe rates of 13C–18O bond reordering. The resulting Arrhenius parameters are indistinguishable from values previously determined for an optical calcite with similar trace element compositions. We develop an alternative kinetic model for reordering that accounts for non-first-order reaction progress observed during the initial several hundred minutes of laboratory heating experiments, and show that the simplified first-order approximation model (Passey and Henkes, 2012) predicts reaction progress equally well for temperatures and timescales relevant to sedimentary basins. We evaluate our laboratory-based rate predictions by studying brachiopod calcite from several sedimentary basins with independently constrained burial temperature histories. Specifically, we use the laboratory-derived Arrhenius parameters to predict the evolution of brachiopod calcite clumped isotope compositions during successive one million-year time steps reflecting the burial and exhumation temperature paths of each basin. While this exercise is limited by the relatively large uncertainties in the temperature histories of these basins, we find general correspondence, within error, between predicted and observed clumped isotope values. We present simplified temperature–time diagrams for calcite showing domains where primary clumped isotope compositions will be preserved, partially reordered, and fully reordered. In conclusion, calcite samples dwelling at ∼100°C or lower for 106–108 year timescales should not be affected by solid-state C–O bond reordering.

Shell structure, patterns and trends of oxygen and carbon stable isotopes in modern brachiopod shells

This study investigates δ 13C and δ 18O variations in the shells of modern brachiopods representing all extant groups of calcite-precipitating brachiopods, collected live from 8 locations. SEM examinations determined the ultrastructural characteristics of each species prior to isotope analyses. δ 13C and δ 18O analyses of shell carbonate were carried out with samples representing disparate morphological features and ultrastructural shell layers of both ventral and dorsal valves. Generally, δ 18O values from the fibrous secondary or prismatic tertiary shell layers of the articulated Terebratulida and Rhynchonellida species were in oxygen isotopic equilibrium with ambient seawater. Isotopic temperatures extrapolated from these values are close to measured annual mean seawater temperatures. δ 18O values were relatively unaffected by shell specialisation. The only exception was Antarctic species Liothyrella uva, which did not have a complete tertiary shell layer typical of this genus and had δ 18O values of the innermost layer strongly correlated with δ 13C and mostly not in oxygen isotopic equilibrium with ambient seawater. With the exception of the rhynchonellid Notosaria nigricans, the outer primary layer material was depleted in δ 13C and δ 18O and highly variable. Inclusion of this material even as part of a whole shell sample could lead to misinterpretation of seawater temperature, therefore only fossil secondary layer material should be used. The anomalous articulated thecideidine brachiopod Thecidellina barretti is composed of mainly primary shell material and was not in oxygen isotope equilibrium. δ 18O values from the laminar secondary layer material of the inarticulated Craniida are highly variable. Therefore, these species are not recommended for use as palaeoenvironmental proxies. This study suggests caution when employing fossil brachiopod shells with similar ultrastructures to modern craniid and thecideidine brachiopods. The carbon isotope composition is highly variable in all of the brachiopods studied. Analysis of samples from specialised regions of the secondary shell layer show a pattern of depletion in 13C relative to non-specialised secondary material. The carbon isotope variability is independent of δ 18O and is repeated in most of the articulated species regardless of geographical location. This is possibly a vital effect produced by metabolic prioritisation.

Ontogenetic trace element distribution in brachiopod shells: an indicator of original seawater chemistry

Articulated fossil brachiopod shells have been used extensively to extract primary chemical information of Phanerozoic seawater. Despite the selection of well-preserved shells using trace element, microstructure and cathodoluminescence criteria, there are still concerns as to whether the selected brachiopod shells do indeed contain original seawater signals. Analyzed in-situ by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LAICPMS), Sr, Na, Mg, Mn, B and Ba distribute symmetrically in shell transects of the modern brachiopods Magellania flavescens and Terebratulina septentrionalis. Symmetry of the trace element distribution pattern is considered an intrinsic and original ontogenetic property of the brachiopod shell chemistry. The trace element distribution is symmetrical in a well-preserved shell of the Devonian brachiopod Independatrypa lemma, indicating that the selected shell by the conventional criteria has preserved its original seawater signal for 400 Ma. In another specimen of I. lemma that is considered diagenetically altered, trace element concentrations are asymmetrically distributed in the shell. The agreement between the distribution criteria and the conventional methods indicates the latter can be used to select brachiopod shells with original seawater chemistry. The average element concentration in the whole shell of unaltered brachiopods should be a reflection of the seawater chemistry, while its change in different part of a shell reflects ontogenetic effect, and its high frequent fluctuations in a transect are results of changes in environmental parameters with seasonal or annual characteristics.

Use of stable oxygen isotope determinations from brachiopod shells in palaeoenvironmental reconstruction

Stable oxygen isotope analyses were obtained from fossil brachiopod shells from a shallow marine deposit of Upper Pleistocene age (approximately 80 ka) in New Zealand as part of a palaeoenvironmental investigation. Bulk analyses of entire shells of Calloria inconspicua yielded highly variable results (a range of 2.30‰), rendering these data of limited use as palaeoenvironmental proxies. Attempts to obtain consistent oxygen isotope values by removing areas of the brachiopod shell thought to be prone to oxygen isotope disequilibrium effects (‘vital effects’) revealed that the matching anterior portions of ventral and dorsal valves from the same individual (which were secreted at the same time) also yielded different oxygen isotope ratios. The dorsal valve δ 18O values were higher and less variable than those obtained from the ventral valve of the same individual. The investigation was then extended to living representatives of the same species from a similar shallow water habitat from the South Island of New Zealand. The pattern of dorsal valves yielding higher and less variable oxygen isotope values than matching areas of the ventral valves was repeated in seven out of eight individuals investigated, although there was considerable variation in the absolute values from specimen to specimen. Contrary to common practice therefore, it seems that in this species it is the much thinner and lighter dorsal valve that provides a more consistent isotopic measurement. If converted into absolute temperature estimates, the dorsal valve measurements correspond to a temperature midway between the mean and maximum annual temperature experienced by this species in its present-day habitat, which may make it acceptable as a palaeoenvironmental indicator. The high level of variation between individuals (including an inferred temperature from one ventral valve above the mean maximum temperature experienced) indicates that a range of individuals needs to be investigated in any palaeoenvironmental investigation to avoid misleading interpretations. However, intra- and inter-specimen variation in isotopic composition may provide valuable palaeobiological information on growth rates, metabolism and possibly also pathological conditions in the past.

No vital effect on δ 18O and δ 13C values of fossil brachiopod shells, Middle Devonian of China

Biogenic fractionation (vital effect) of carbon and oxygen isotopes during metabolism is ubiquitous among marine organisms. Whether there is vital effect on the isotopic compositions of fossil brachiopods represents one of the most controversial issues in the carbonate stable isotope geochemistry. Furthermore, the problem involves not only the feasibility of the utilization of fossil brachiopod shells as analysis samples for obtaining the original carbon and oxygen isotopic compositions of carbonates, but also the credibility of the data and conclusions already achieved in the study field. With fossil brachiopods from Middle Devonian of China, this study investigates the vital effect by comparisons of δ 18O and δ 13C between the fossils of the same original living environment and the shell’s preservation at levels of species, genus, and family. No systematic differences of δ 18O and δ 13C between fossils were found, which led to the conclusion that no detectable vital effect occurred in the fossil brachiopod shells. The argument that the fossil brachiopod possibly has biogenic fractionation with the stable isotopes of carbon and oxygen resulted likely from studies of fossils that are different in the original living environment or the state of preservation.

δ 18O and REE contents of phosphatic brachiopods: a comparison between modern and lower Paleozoic populations

δ 18O values of both carbonate (18.7–25.1‰) and phosphate (15.1–16.7‰) components of the francolite from the fossil brachiopod shells are interpreted as the result of a partial resetting of pristine isotopic compositions. The similarity of hat-shape REE patterns of some lower Ordovician linguloids with those of extant littoral specimens suggests the preservation of a 500 Myr-old record of REE marine chemistry. In agreement with the known paleogeography, the phosphatic brachiopods have been deposited in a coastal environment under shallow and oxygenated marine waters. However, the contents and distribution of REE in some strongly altered brachiopod shells reveal an alteration of the original negative Ce anomalies and both Nd and Sm enrichments that transformed the initial hat-shape patterns of linguloids into strongly convex or bell-shape patterns.

The isotopic record of ocean chemistry and diagenesis preserved in non-luminescent brachiopods from Mississippian carbonate rocks, Illinois and Missouri

Fossil brachiopod shells are commonly used as a faithful record of the chemical and isotopic composition of the ancient ocean water in which they grew, owing to their stable mineralogy and their presence in marine strata throughout Phanerozoic time. The utility of these fossils for preserving ocean-water compositions is evaluated through analyses of multiple specimens that grew in contemporaneous sea water at individual stratigraphic horizons in the Mississippian-age Burlington-Keokuk Formation of mid-continent North America. Significant variations in Sr, C, and O isotopic compositions are observed in contemporaneous, non-luminescent shells, indicating that apparently pristine brachiopod shell material has been altered by post-depositional processes of diagenesis. The least-altered compositions at each horizon are used to estimate secular variations of 87 Sr/ 86 Sr in Early Mississippian ocean water. The estimated rates of change of ocean-water 87 Sr/ 86 Sr are comparable in magnitude to the rapid Sr isotopic changes documented for Cenozoic ocean water, for which high-frequency glacial cycles are inferred as a driving mechanism. The rigorous assessment of diagenetic effects on the isotopic signatures of marine phases is requisite for the advancement of high-resolution reconstructions of paleo-ocean chemistry.

Intracrystalline biomolecules in Recent and fossil brachiopod shells - the biochemistry of shell coloration

The study of fossil biomolecules requires not only well preserved fossil samples, but abundant Recent material so that reference points can be established. Ideally it would also be possible to study the in situ decay of organic molecules in samples of different geological ages, and hence determine how degradation proceeds with time. The shells of brachiopods fulfill both these criteria, containing up to 1% organic components entombed within their shells, which are composed of highly stable, low magnesium calcite, that survives well in the fossil record for hundreds of millions of years.This particular study has concentrated on Plio-Pleistocene brachiopods from New Zealand. These fossils are the ancestors of living species, and hence it is possible to investigate intracrystalline biomolecules in modern day shells, as well as the degradation products of such biomolecules in fossil shells of the same species.Three of the species investigated have bright red shells in life, and during the study it became clear that this coloration was caused by a carotenoprotein which was embedded within, rather than around, the calcite fibres of the brachiopod shell. Carotenoproteins are composite molecules composed of a protein and a prosthetic carotenoid group. The protein has been characterised by hplc (high performance liquid chromatography) and SDS PAGE (sodium dodecylsulphate polyacrylamide gel electrophoresis), and the amino acids at the N-termini have been sequenced, demonstrating that this is a small protein which has a molecular weight of 6.5 kDa and is identical in all 3 species.At least two different types of carotenoids were detected after initial purification, and these were characterised using direct probe mass spectra, and hplc/mass spectra. Using these techniques the two carotenoids have been tentatively identified as canthaxanthin and the mono acetylenic analogue of asthaxanthin.In addition to the carotenoproteins, the calcite crystals of recent brachiopod shells contain lipids (carboxylic acids) and carbohydrates, which were characterised by gas chromatography (GC) and gas chromatography/mass spectrometry analyses (GC/MS).Fossil brachiopod shells could be distinguished from recent shells due to their lack of unsaturated acids and smaller amounts of carboxylic acids present. However there was no trend of decreasing quantities of fatty acid with increasing age.The presence of organic molecules such as carotenoproteins, lipids and carbohydrates within calcite crystals poses two questions. Firstly, are these compounds merely wastes metabolic products and are deposited within the shell during growth or, secondly, do they play an important role in the process of biomineralisation? At present these questions remain largely unanswered, because at present only the function of the carotenoprotein has been determined from the spectrum of biomolecules present within the shell (and the carotenoprotein may have other functions apart from coloration).

Macromolecules in brachiopod shells: characterization and diagenesis

An immunological investigation was conducted of soluble intra-crystalline macromolecules isolated from living and fossil brachiopod shells, which had previously been used for an immunologically based study of phylogeny (serotaxonomy). The soluble intra-crystalline macromolecules comprised 0.03% by weight of the extant shell material. Bulk analysis and gel electrophoresis indicated that the organic material is predominantly glycoprotein, and contains up to 30% by weight carbohydrate. Treatment of the macromolecules with periodate and proteinase K revealed that antibodies were raised predominantly against the carbohydrate moieties. Using a specially adapted dot blot immunobinding assay (DIBA) the decay in immunological signal over geological time was determined. Pleistocene shells have lost between 99 and 99.9% of immunological reactivity, and original antigenic determinants form a declining proportion of total organic matter. It is suggested that condensation reactions between amino acids and sugars account for the rapid destruction of determinants; this has important implications for the direction of future studies on fossil macromolecules. □Serotaxonomy, biomolecular palaeontology, glycoproteins, melanoidins, brachiopods.

Biogeochemistry of brachiopod intracrystalline molecules

Brachiopods contain both proteins and lipids within the biocrystals of their shell. One intracrystalline chromoprotein causes red shell coloration, whereas the other molecules may be involved with biomineralization, may strengthen the biocrystal, or may simply have been inadvertently engulfed by calcite during shell growth. Evidence is presented which suggests that at least some of the breakdown products of indigeneous intracrystalline molecules can be recovered from the biocrystals of fossil brachiopod shells. Investigations of the remains of these intracrystalline molecules in fossils have geological application in fields such as environmental reconstruction, isotopic determinations, taxonomy and the interpretation of colour in extinct organisms.