Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein

Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature.     

Biomineralization in bryozoans: present,past and future

Many animal phyla have the physiological ability to produce biomineralized skeletons with functional roles that have been shaped by natural selection for more than 500 million years. Among these are bryozoans, a moderately diverse phylum of aquatic invertebrates with a rich fossil record and importance today as bioconstructors in some shallow‐water marine habitats. Biomineralizational patterns and, especially, processes are poorly understood in bryozoans but are conventionally believed to be similar to those of the related lophotrochozoan phyla Brachiopoda and Mollusca. However, bryozoan skeletons are more intricate than those of these two phyla. Calcareous skeletons have been acquired independently in two bryozoan clades – Stenolaemata in the Ordovician and Cheilostomata in the Jurassic – providing an evolutionary replicate. This review aims to highlight the importance of biomineralization in bryozoans and focuses on their skeletal ultrastructures, mineralogy and chemistry, the roles of organic components, the evolutionary history of bimineralization in bryozoans with respect to changes in seawater chemistry, and the impact of contemporary global changes, especially ocean acidification, on bryozoan skeletons. Bryozoan skeletons are constructed from three different wall types (exterior, interior and compound) differing in the presence/absence and location of organic cuticular layers. Skeletal ultrastructures can be classified into wall‐parallel (i.e. laminated) and wall‐perpendicular (i.e. prismatic) fabrics, the latter apparently found in only one of the two biomineralizing clades (Cheilostomata), which is also the only clade to biomineralize aragonite. A plethora of ultrastructural fabrics can be recognized and most occur in combination with other fabrics to constitute a fabric suite. The proportion of aragonitic and bimineralic bryozoans, as well as the Mg content of bryozoan skeletons, show a latitudinal increase into the warmer waters of the tropics. Responses of bryozoan mineralogy and skeletal thickness to oscillations between calcite and aragonite seas through geological time are equivocal. Field and laboratory studies of living bryozoans have shown that predicted future changes in pH (ocean acidification) combined with global warming are likely to have detrimental effects on calcification, growth rate and production of polymorphic zooids for defence and reproduction, although some species exhibit reasonable levels of resilience. Some key questions about bryozoan biomineralization that need to be addressed are identified.     

Calcite and aragonite distributions in the skeletons of bimineralic bryozoans as revealed by Raman spectroscopy

Abstract. Bryozoans are among a diverse range of invertebrates capable of secreting calcium carbonate skeletons. Relatively little is known about biomineralization in bryozoans, despite the importance of understanding biomineralization processes for nanotechnology and the threats imposed by ocean acidification on organisms having calcareous skeletons. Ten species of cheilostome bryozoans that are reported to have bimineralic skeletons of calcite and aragonite are studied here using Raman spectroscopy. This technique allowed identification of the two mineral phases at submicron spatial resolution, allowing the distributions of calcite and aragonite within bryozoan skeletons to be determined with unprecedented precision. Confirming previous findings based on the use of chemical stains, most of the bimineralic species analyzed exhibited a calcitic skeletal framework, composed of basal, vertical, and inner frontal walls, having aragonite deposited subsequently onto the outer surfaces of the frontal walls. In one species ( Odontionella cyclops ), aragonite formed the superstructure above the autozooids, and in two others, traces of aragonite were detected on the undersides of the frontal shields. Using Raman spectroscopy, it was possible for the first time to determine the mineralogy of small-scale structures, including orificial rims, condyles and hinge teeth, avicularian pivotal bars and rostra, and ascopore rims and sieve plates. Even when surrounded by aragonitic frontal shields, these structures were found typically to be calcitic, the two exceptions being the aragonitic avicularia of Stylopoma inchoans and O. cyclops . Unexpectedly, the first-formed part of the basal wall at the distalmost growing edge of Pentapora foliacea was found to consist mainly of aragonite. This may point to a precursory phase of biomineralization comparable with the unusual mineralogies identified previously in the earliest-formed skeletons of members of some other invertebrate phyla.     

Seawater Mg/Ca controls polymorph mineralogy of microbial CaCO3: a potential proxy for calcite-aragonite seas in Precambrian time

A previously published hydrothermal brine-river water mixing model driven by ocean crust production suggests that the molar Mg/Ca ratio of seawater (mMg/Ca(sw)) has varied significantly (approximately 1.0-5.2) over Precambrian time, resulting in six intervals of aragonite-favouring seas (mMg/Ca(sw) > 2) and five intervals of calcite-favouring seas (mMg/Ca(sw) < 2) since the Late Archaean. To evaluate the viability of microbial carbonates as mineralogical proxy for Precambrian calcite-aragonite seas, calcifying microbial marine biofilms were cultured in experimental seawaters formulated over the range of Mg/Ca ratios believed to have characterized Precambrian seawater. Biofilms cultured in experimental aragonite seawater (mMg/Ca(sw) = 5.2) precipitated primarily aragonite with lesser amounts of high-Mg calcite (mMg/Ca(calcite) = 0.16), while biofilms cultured in experimental calcite seawater (mMg/Ca(sw) = 1.5) precipitated exclusively lower magnesian calcite (mMg/Ca(calcite) = 0.06). Furthermore, Mg/Ca(calcite )varied proportionally with Mg/Ca(sw). This nearly abiotic mineralogical response of the biofilm CaCO3 to altered Mg/Ca(sw) is consistent with the assertion that biofilm calcification proceeds more through the elevation of , via metabolic removal of CO2 and/or H+, than through the elevation of Ca2+, which would alter the Mg/Ca ratio of the biofilm's calcifying fluid causing its pattern of CaCO3 polymorph precipitation (aragonite vs. calcite; Mg-incorporation in calcite) to deviate from that of abiotic calcification. If previous assertions are correct that the physicochemical properties of Precambrian seawater were such that Mg/Ca(sw) was the primary variable influencing CaCO3 polymorph mineralogy, then the observed response of the biofilms' CaCO3 polymorph mineralogy to variations in Mg/Ca(sw), combined with the ubiquity of such microbial carbonates in Precambrian strata, suggests that the original polymorph mineralogy and Mg/Ca(calcite )of well-preserved microbial carbonates may be an archive of calcite-aragonite seas throughout Precambrian time. These results invite a systematic evaluation of microbial carbonate primary mineralogy to empirically constrain Precambrian seawater Mg/Ca.     

Shell mineralogical trends in epifaunal Mesozoic bivalves and their relationship to seawater chemistry and atmospheric carbon dioxide concentration

The Late Triassic-Early Jurassic change from aragonite- to calcite-facilitating conditions in the oceans, which was caused by a decrease of the Mg²⁺/Ca²⁺ ratio of seawater in combination with an increase of the partial pressure of carbon dioxide, also affected the shell mineralogy of epifaunal bivalves. In the “calcite sea” of the Jurassic and Cretaceous, the most diverse and abundant families of epifaunal bivalves had largely calcitic shells. Some of them, such as the Inoceramidae, acquired this shell mineralogy earlier in Earth's history but did not significantly diversify until the onset of “calcite sea” conditions. Others, however, replaced aragonite by calcite in their shell at the beginning of the Jurassic, as shown for the Ostreidae, Gryphaeidae, Pectinidae, Plicatulidae, and Buchiidae. In these families, replacement of aragonite by calcite took place in the middle and inner layer of the shell and was not associated with changes in morphology and life habit. It is therefore proposed that lower metabolic costs rather than higher resistance against dissolution or advantageous physical properties triggered the calcite expansion in their shells. This explanation fits well the observation that clades of thin-shelled bivalves were less affected by the change of seawater chemistry. Thick-shelled clades, by contrast, may suffer a severe decline in diversity until they adapt their shell mineralogy, as demonstrated by the Hippuritoida: The diversity of the Megalodontoidea, which failed to adapt their shell mineralogy to “calcite sea” conditions, dramatically decreased at the end of the Triassic, whereas their descendents became dominant carbonate producers during the Late Mesozoic after they acquired a calcitic outer shell layer in the Late Jurassic. These examples indicate that changes in the seawater chemistry and in the partial pressure of carbon dioxide are factors that influence the diversity of carbonate-secreting animals, and, as in the case of the decline of the Megalodontoidea, may contribute to mass extinctions.     

New constraints on the last aragonite–calcite sea transition from early Jurassic ooids

Calcite and aragonite seas are commonly distinguished based on the prevailing primary mineralogy of ooids and carbonate cements over time. Secular oscillations of these seas are usually attributed to changes in ocean chemistry and paleoclimate. While the veracity of such oscillations has been verified by independent data and modeling approaches, the timing of the transition from one ocean state to the other remains poorly resolved. Here, the timing of the last aragonite–calcite sea transition is estimated by assessing the preservation of Early Jurassic ooids from the Trento Platform in northern Italy. Point counting of ooid-bearing limestones from four distinct stratigraphic levels provides a contrasting pattern: Hettangian and Sinemurian ooids are all poorly preserved and were probably predominantly originally aragonitic, whereas Pliensbachian and Toarcian ooids are excellently preserved, suggesting a primary calcitic mineralogy. Although calcitic ooids may have already been common in the Late Triassic, it is proposed that the last aragonite–calcite sea transition occurred in the Early Jurassic between the Sinemurian and Pliensbachian, at least in this subtropical region. Therefore, the selective extinction of aragonite-secreting organisms at the end-Triassic mass extinction cannot be attributed to secular changes in ocean chemistry.     

Carbonate mineralogy of a tropical bryozoan biota and its vulnerability to ocean acidification

Decreasing pH levels in the world’s oceans are widely recognized as a threat to marine life. Bryozoans are among several phyla that produce calcium carbonate skeletons potentially affected by ocean acidification (OA). Depending on species, bryozoan skeletons can consist of calcite, aragonite or have a bimineralic combination of these two minerals. Aragonite is generally more soluble in seawater than calcite, making aragonitic species more vulnerable to OA. Here, for the first time we use Raman spectroscopy to determine the mineral composition of a tropical bryozoan biota. Compared with bryozoan biotas from higher latitudes in which calcite predominates, aragonite was found to occur in a much higher proportion of the 22 cheilostome bryozoan species collected from the shorelines of Penang and Langkawi in Malaysia, where 46% of species are calcitic, 41% aragonitic and 13% bimineralic. All but one of the aragonitic or bimineralic species belong to the ascophorans, whereas calcitic skeletons characterized most of the anascans, many of which are primitive ‘weedy’ malacostegines. These results suggest a relatively high vulnerability of tropical bryozoan faunas to OA, with the weedier taxa likely to be least impacted.     

Perspectives in coral reef hydrodynamics

Knowledge of skeletogenesis in scleractinian corals is central to reconstructing past ocean and climate histories, assessing and counteracting future climate and ocean acidification impacts upon coral reefs, and determining the taxonomy and evolutionary path of the Scleractinia. To better understand skeletogenesis and mineralogy in extant scleractinian corals, we have investigated the nature of the initial calcium carbonate skeleton deposited by newly settling coral recruits. Settling Acropora millepora larvae were sampled daily for 10 days from initial attachment, and the carbonate mineralogy of their newly deposited skeletons was investigated. Bulk analyses using Raman and infrared spectroscopic methods revealed that the skeletons were predominantly comprised of aragonite, with no evidence of calcite or an amorphous precursor phase, although presence of the latter cannot be discounted. Sensitive selected area electron diffraction analyses of sub-micron areas of skeletal regions further consolidated these data. These findings help to address the uncertainty surrounding reported differences in carbonate mineralogy between larval and adult extant coral skeletons by indicating that skeletons of new coral recruits share the same aragonitic mineralogy as those of their mature counterparts. In this respect, we can expect that skeletogenesis in both larval and mature growth stages of scleractinian corals will be similarly affected by ocean acidification and predicted environmental changes.     

Variations in primary aragonite, calcite, and clay in fine-grained calcareous rhythmites of Cambrian to Jurassic age— an environmental archive?

Limestone-marl alternations represent a common type of fine-grained calcareous rhythmites during the entire Phanerozoic. Their diagenetic overprint, however, obliterates their value for palaeoenvironmental interpretations. The original mineralogical composition of the carbonate fraction (aragonite, high-Mg calcite, low-Mg calcite) would potentially yield important information on palaeoenvironmental conditions: for example shallow-water carbonate factories are usually characterised by extensive aragonite production, whereas pelagic carbonate production is dominated by calcitic organisms. Therefore, a reconstruction of the pre-diagenetic mineralogical composition of limestone-marl precursors would be desirable. A particularly conspicuous attribute of fine-grained calcareous rhythmites is the intercalation of two rock types that have undergone two entirely different diagenetic pathways (“differential diagenesis”). As indicated by earlier petrography work, in the interlayers selective aragonite dissolution has taken place, and the dissolved aragonite provided the cement for the limestones. Primary aragonite usually is not preserved in diagenetically mature fine-grained limestones. However, in a recently published paper a method is proposed to quantify the primary mineralogical composition of the precursor sediments of a fine-grained calcareous rhythmite. Here we apply this method to several published data sets from sections of Cambrian to Jurassic age. We try to answer the following questions: Where does the aragonite come from, especially during times of “calcite seas”? What is the impact of the enhanced pelagic carbonate production since the Late Jurassic on the formation of limestone-marl alternations? How much dissolved aragonite is lost to sea water during early marine burial diagenesis, i.e. how closed is the diagenetic system? As demonstrated for the five examples shown here, the new method for reconstructing primary mineralogy potentially provides insight into ancient depositional environments, surface productivity, and ocean chemistry.     

Calcite precipitation and dissolution of biogenic aragonite in shallow Ordovician calcite seas

The Ordovician was a time of extensive and pervasive low-magnesium calcite (LMC) precipitation on shallow marine sea floors. The evidence comes from field study (extensive hardgrounds and other early cementation fabrics in shallow-water carbonate sequences) and petrography (large volumes of marine calcite cement in grainstones). Contemporaneous sea-floor events, particularly relationships with boring and encrusting organisms and reworking in sequences of intraformational conglomerates, confirm the early timing of such LMC cementation, and also of widespread associated aragonite dissolution. Local evidence points to the dissolved aragonite as a significant source of the calcite cement. This scenario, and the fabrics that provide the evidence for it, are likely to be pointers to other times in the stratigraphic record when LMC was the predominant shallow marine precipitate (Calcite Sea times). The combination of rapid calcite precipitation and aragonite dissolution at a time early in the Phanerozoic when many major invertebrate groups were becoming established may have acted as an influence on the evolution of both their skeletal mineralogy and their ecology.     

Mineralogy of Arctic bryozoan skeletons in a global context

Bryozoans are major carbonate producers in some ancient and Recent benthic environments, including parts of the Arctic Ocean. Seventy-six species of bryozoans from within the Arctic Circle have been studied using XRD to determine their carbonate mineralogies and the Mg content of the calcite. The majority of species were found to be calcitic, only four having bimineralic skeletons that combined calcite and aragonite, and none being entirely aragonitic. In almost all species, the calcite was of the low- (<4 mol% MgCO₃) or intermediate-Mg (4–11.99 mol% MgCO₃) varieties. Previous regional studies of bryozoan biomineralogy have found higher proportions of bimineralic and/or aragonitic species in New Zealand and the Mediterranean, with a greater number of calcitic species employing intermediate- and high-Mg calcite. The Antarctic bryozoan fauna, however, has a similar mineralogical composition to the Arctic. The lesser solubility of low-Mg calcite compared to both Mg calcite and aragonite in cold polar waters is most likely responsible for this latitudinal pattern. However, it is unknown to what extent environmental factors drive the pattern directly through eliciting an ecophenotypic response from the bryozoans concerned or the pattern reflects genetic adaptations by particular bryozoan clades.     

Aragonite shells are more ancient than calcite ones in bivalves: new evidence based on omics

Two calcium carbonate crystal polymorphs, aragonite and calcite, are the main inorganic components of mollusk shells. Some fossil evidences suggest that aragonite shell is more ancient than calcite shell for the Bivalvia. But, the molecular biology evidence for the above deduction is absent. In this study, we searched for homologs of bivalve aragonite-related and calcite-related shell proteins in the oyster genome, and found that no homologs of calcite-related shell protein but some homologs of aragonite-related shell proteins in the oyster genome. We explained the results as the new evidence to support that aragonite shells are more ancient than calcite shells in bivalves combined the published biogeological and seawater chemistry data.     

Mg and Ca isotope fractionation during CaCO3 biomineralisation

The natural variation of Mg and Ca stable isotopes of carbonates has been determined in carbonate skeletons of perforate foraminifera and reef coral together with Mg/Ca ratios to assess the influence of biomineralisation processes. The results for coral aragonite suggest its formation, in terms of stable isotope behaviour, approximates to inorganic precipitation from a seawater reservoir. In contrast, results for foraminifera calcite suggest a marked biological control on Mg isotope ratios presumably related to its low Mg content compared with seawater. The bearing of these observations on the use of Mg and Ca isotopes as proxies in paleoceanography is considered.     

Phylomineralogy of the Coralline red algae: Correlation of skeletal mineralogy with molecular phylogeny

The coralline algae in the orders Corallinales and Sporolithales (subclass Corallinophycidae), with their high degree of mineralogical variability, pose a challenge to projections regarding mineralogy and response to ocean acidification. Here we relate skeletal carbonate mineralogy to a well-established phylogenetic framework and draw inferences about the effects of future changes in sea-water chemistry on these calcified red algae. A collection of 191 coralline algal specimens from New Zealand, representing 13 genera and 28 species, included members of three families: Corallinaceae, Hapalidiaceae, and Sporolithaceae. While most skeletal specimens were entirely calcitic (range: 73–100 wt.% calcite, mean 97 wt.% calcite, std dev = 5, n = 172), a considerable number contained at least some aragonite. Mg in calcite ranged from 10.5 to 16.4 wt.% MgCO₃, with a mean of 13.1 wt.% MgCO₃ (std dev = 1.1, n = 172). The genera Mesophyllum and Lithophyllum were especially variable. Growth habit, too, was related to mineralogy: geniculate coralline algae do not generally contain any aragonite. Mg content varied among coralline families: the Corallinaceae had the highest Mg content, followed by the Sporolithaceae and the Hapalidiaceae. Despite the significant differences among families, variation and overlap prevent the use of carbonate mineralogy as a taxonomic character in the coralline algae. Latitude (as a proxy for water temperature) had only a slight relationship to Mg content in coralline algae, contrary to trends observed in other biomineralising taxa. Temperate magnesium calcites, like those produced by coralline algae, are particularly vulnerable to ocean acidification. Changes in biomineralisation or species distribution may occur over the next few decades, particularly to species producing high-Mg calcite, as pH and CO₂ dynamics change in coastal temperate oceans.     

Shell Growth in the Marine Environment: Approaches to the Problem of Marginal Calcification

Although marine waters are usually found to be supersaturatedwith respect to both calcite and aragonite, natural precipitationof these carbonate minerals is very restricted. This is apparentlydue to the occupancy and effective removal of lattice sitesby random organic molecules present in natural seawater. Despite this, many marine organisms build external shells orskeletons of calcium carbonate, utilizing various ingeniousmethods to prevent seawater contamination at the growing shellmargin. The periostracum, which apparently evolved as an aidto marginal calcification, has undergone numerous modificationsserving important secondary functions inspecialized groups.     

Shell microstructure and mineralogy of the Littorinidae: ecological and evolutionary significance

An examination of the shell microstructure and mineralogy of species from 30 of the 32 genera and subgenera of the gastropod family Littorinidae shows that most species have a shell consisting of layers of aragonitic crossed-lamellar structure, with minor variations in some taxa. However, Pellilitorina, Risellopsis and most species of Littorina have partly or entirely calcitic shells. In Pellilitorina the shell is made entirely of calcitic crossed-foliated structure, while in the other two genera there is only an outer calcitic layer of irregular-prismatic structure. A cladistic analysis shows that the calcitic layers have been independently evolved in at least three clades. The calcite is found only in the outermost layers of the shell and in species inhabiting cooler waters of both northern and southern hemispheres. Calcium carbonate is more soluble in cold than warm water and, of the two polymorphs, calcite is about 35% less soluble than aragonite. We suggest that calcitic shell layers are an adaptation of high latitude littorinids to resist shell dissolution.     

Effect of end-Triassic CO<Subscript>2</Subscript> maximum on carbonate sedimentation and marine mass extinction

Correlation of stratigraphic sections from different continents suggests a worldwide interruption of carbonate sedimentation at the Triassic–Jurassic boundary, which coincided with one of the most catastrophic mass extinctions in the Phanerozoic. Both events are linked by a vulcanogenic maximum of carbon dioxide, which led to a temporary undersaturation of sea water with respect to aragonite and calcite and a corresponding suppression of carbonate sedimentation including non-preservation of calcareous skeletons. Besides the frequently cited climatic effect of enhanced carbon dioxide, lowering the saturation state of sea water with respect to calcium carbonate was an additional driving force of the end-Triassic mass extinction, which chiefly affected organisms with thick aragonitic or high-magnesium calcitic skeletons. Replacement of aragonite by calcite, as found in the shells of epifaunal bivalves, was an evolutionary response to this condition.     

How corals made rocks through the ages

Hard, or stony, corals make rocks that can, on geological time scales, lead to the formation of massive reefs in shallow tropical and subtropical seas. In both historical and contemporary oceans, reef‐building corals retain information about the marine environment in their skeletons, which is an organic–inorganic composite material. The elemental and isotopic composition of their skeletons is frequently used to reconstruct the environmental history of Earth's oceans over time, including temperature, pH, and salinity. Interpretation of this information requires knowledge of how the organisms formed their skeletons. The basic mechanism of formation of calcium carbonate skeleton in stony corals has been studied for decades. While some researchers consider coral skeletons as mainly passive recorders of ocean conditions, it has become increasingly clear that biological processes play key roles in the biomineralization mechanism. Understanding the role of the animal in living stony coral biomineralization and how it evolved has profound implications for interpreting environmental signatures in fossil corals to understand past ocean conditions. Here we review historical hypotheses and discuss the present understanding of how corals evolved and how their skeletons changed over geological time. We specifically explain how biological processes, particularly those occurring at the subcellular level, critically control the formation of calcium carbonate structures. We examine the different models that address the current debate including the tissue–skeleton interface, skeletal organic matrix, and biomineralization pathways. Finally, we consider how understanding the biological control of coral biomineralization is critical to informing future models of coral vulnerability to inevitable global change, particularly increasing ocean acidification.     

Composition of the early Oligocene ocean from coral stable isotope and elemental chemistry

A sectioned and polished specimen of the coral Archohelia vicksburgensis from the early Oligocene Byram Formation (～30 Ma) near Vicksburg, Mississippi, reveals 12 prominent annual growth bands. Stable oxygen isotopic compositions of 77 growth‐band‐parallel microsamples of original aragonite exhibit well‐constrained fluctuations that range between ?2.0 and ?4.8. Variation in δ¹⁸O of coral carbonate reflects seasonal variation in temperature ranging from 12 to 24 °C about a mean of 18 °C. These values are consistent with those derived from a bivalve and a fish otolith from the same unit, each using independently derived palaeotemperature equations. Mg/Ca and Sr/Ca ratios were determined for 40 additional samples spanning five of the 12 annual bands. Palaeotemperatures calculated using elemental‐ratio thermometers calibrated on modern corals are consistently lower; mean temperature from Mg/Ca ratios are 12.5 ± 1 °C while those from Sr/Ca are 5.8 ± 2.2 °C. Assuming that δ¹⁸O‐derived temperatures are correct, relationships between temperature and elemental ratio for corals growing in today's ocean can be used to estimate Oligocene palaeoseawater Mg/Ca and Sr/Ca ratios. Calculations indicate that early Oligocene seawater Mg/Ca was ～81% (4.2 mol mol^?1) and Sr/Ca ～109% (9.9 mmol mol^?1) of modern values. Oligocene seawater with this degree of Mg depletion and Sr enrichment is in good agreement with that expected during the Palaeogene transition from ‘calcite’ to ‘aragonite’ seas. Lower Oligocene Mg/Ca probably reflects a decrease toward the present day in sea‐floor hydrothermal activity and concomitant decrease in scavenging of magnesium from seawater. Elevated Sr/Ca ratio may record lesser amounts of Oligocene aragonite precipitation and a correspondingly lower flux of strontium into the sedimentary carbonate reservoir than today.     

Selective solution of macroinvertebrate calcareous hard parts: a laboratory study

Ten suites of 16 common types of invertebrate hard parts were placed in acid baths for 24 hours to determine relative rates and common styles of dissolution. Skeletal mineralogies included aragonite and both high-magnesium and low-magnesium calcite. Hard parts included barnacle cxoskelctons, cchinoid tests, gastropod opercula and gastropod and bivalve shells. Calcitic barnacle plates dissolved most rapidly, aragonitic and high magnesium calcitic hard parts showed intermediate rates, and the calcitic shells of the oyster dissolved at the lowest rate. The surface area to weight ratio of the hard parts correlated ( r =0.650) significantly with the hard part's rate of dissolution. Skeletal remains with a high surface area to weight ratio dissolved faster than those with a low surface area to weight ratio. Skeletal porosity and mineralogy appeared to be responsible for additional variation in the rate of dissolution. The effect of the surface area to weight ratio is sufficient to overcome the effect of mineralogy. Dense, compact aragonitic hard parts can persist longer than porous, thin calcitic remains. Typical features associated with skeletal degradation include development of chalky textures, thinning of distal margins, surface etching and formation of holes in bivalve muscle scars. Such features may aid in the recognition of partial dissolution of skeletal remains in the rock record. □ Taphonomy, paleoecology, fossil-diagenesis.