Environmental and biological controls on elemental (Mg/Ca, Sr/Ca and Mn/Ca) ratios in shells of the king scallop Pecten maximus

The relationship between potential elemental proxies (Mg/Ca, Sr/Ca and Mn/Ca ratios) and environmental factors was investigated for the bivalve Pecten maximus in a detailed field study undertaken in the Menai Strait, Wales, U.K. An age model constructed for each shell by comparison of measured and predicted oxygen-isotope ratios allowed comparison on a calendar time scale of shell elemental data with environmental variables, as well as estimation of shell growth rates. The seasonal variation of shell Mn/Ca ratios followed a similar pattern to one previously described for dissolved Mn²⁺ in the Menai Strait, although further calibration work is needed to validate such a relationship. Shell Sr/Ca ratios unexpectedly were found to co-vary most significantly with calcification temperature, whilst shell Mg/Ca ratios were the next most significant control. The temporal variation in the factors that control shell Sr/Ca ratios strongly suggest the former observation most likely to be the result of a secondary influence on shell Sr/Ca ratios by kinetic effects, the latter driven by seasonal variation in shell growth rate that is in turn influenced in part by seawater temperature. P. maximus shell Mg/Ca ratio to calcification temperature relationships exhibit an inverse correlation during autumn to early spring (October to March-April) and a positive correlation from late spring through summer (May-June to September). No clear explanation is evident for the former trend, but the similarity of the records from the three shells analysed indicate that it is a real signal and not a spurious observation. These observations confirm that application of the Mg/Ca proxy in P. maximus shells remains problematic, even for seasonal or absolute temperature reconstructions. For the range of calcification temperatures of 5-19 °C, our shell Mg/Ca ratios in P. maximus are approximately one-fourth those in inorganic calcite, half those in the bivalve Pinna nobilis, twice those in the bivalve Mytilus trossulus, and four to five times higher than Mg/Ca ratios in planktonic and benthonic foraminifera. Our findings further support observations that Mg/Ca ratios in bivalve shell calcite are an unreliable temperature proxy, as well as substantial taxon- and species-specific variation in Mg incorporation into bivalves and other calcifying organisms, with profound implications for the application of this geochemical proxy to the bivalve fossil record.     

Calcification rate influence on trace element concentrations in aragonitic bivalve shells: Evidences and mechanisms

Trace elements in calcareous organisms have been widely used for paleoclimatic studies. However, the factors controlling their incorporation into mollusc shells are still unclear. We studied here the Sr, Mg, Ba and Mn serial records in the shells of two aragonitic marine bivalve species: Mesodesma donacium and Chione subrugosa from the Peruvian Coast. The elemental concentrations were compared to local temperature and salinity records. The relationships with crystal growth rate G were investigated thanks to well defined periodic growth structures providing a precise shell chronology. Our results show that for both species, environmental parameters only have minor influence, whereas crystal growth rate strongly influences trace elements concentrations, especially for Sr (explaining up to 74% of the variance). The relationship between G and Sr/Ca exhibits variability among the shells as well as inside the shells. For a same growth rate value, Sr/Ca values are higher in more curved shell sections, and the growth rate influence is stronger as well. We show that intercellular and Ca²⁺-pump pathways cannot support the calcification Ca²⁺ flux, leading us to propose an alternative mechanism for ionic transport through the calcifying mantle, implying a major role for calcium channels on mantle epithelial cell membranes. In this new calcification model, Sr/Ca shell ratios is determined by Ca²⁺-channel selectivity against Sr²⁺, which depends (i) on the electrochemical potential imposed by the crystallisation process and (ii) on the Ca²⁺-channel density per surface unit on mantle epithelia.     

Barium uptake into the shells of the common mussel (Mytilus edulis) and the potential for estuarine paleo-chemistry reconstruction

In this study we test if calcite shells of the common mussel, Mytilus edulis, contain barium in proportion to the water in which they grew. Similar to all bivalves analyzed to date, the [Ba/Ca]_shell profiles are characterized by a relatively flat background [Ba/Ca]_shell, interrupted by sharp [Ba/Ca]_shell peaks. Previous studies have focused on these [Ba/Ca]_shell peaks, but not on the background [Ba/Ca]_shell. We show that in both laboratory and field experiments, there is a direct relationship between the background [Ba/Ca]_shell and [Ba/Ca]_water in M. edulis shells. The laboratory and field data provided background Ba/Ca partition coefficients (D_Ba) of 0.10 ± 0.02 and 0.071 ± 0.001, respectively. This range is slightly higher than the D_Ba previously determined for inorganic calcite, and slightly lower than foraminiferal calcite. These data suggest that M. edulis shells can be used as an indicator of [Ba/Ca]_water, and therefore, fossil or archaeological M. edulis shells could be used to extend knowledge of estuarine dissolved Ba throughputs back in time. Moreover, considering the inverse relationship between [Ba/Ca]_water and salinity, background [Ba/Ca]_shell data could be used as an estuary specific indicator of salinity. The cause of the [Ba/Ca]_shell peaks is more confusing, both the laboratory and field experiments indicate that they cannot be used as a direct proxy of [Ba/Ca]_water or phytoplankton production, but may possibly be caused by barite ingestion.     

A strong temperature effect on U/Ca in planktonic foraminiferal carbonates

Three planktonic foraminiferal species Globigerina bulloides, Neogloboquadrina pachyderma (d), and Globorotalia inflata collected from core-tops spanning 35° to 65°N in the North Atlantic were used for U/Ca and Mg/Ca and foraminiferal shell weight analyses. Except for U/Ca in G. bulloides calcified under warm conditions (>∼13 °C), U/Ca ratios in all three studied species increase with decreasing latitude and show strong positive correlations with Mg/Ca ratios. A dissolution effect on planktonic U/Ca is suggested by decreased shell weight and U/Ca and Mg/Ca ratios for shells from very deep water depth (>4.4 km) along the latitudinal transect. G. bulloides from down core samples in the North Atlantic show low U/Ca ratios during the last glacial and high ratios during the Holocene, similar to the Mg/Ca evolution trend. In general, our data indicate that the U incorporation into planktonic foraminiferal carbonates is strongly influenced by calcification temperature, although U/Ca in G. bulloides may be affected by seawater carbonate ion concentration under warm conditions and/or other factors.     

Mg/Ca, Sr/Ca, and stable isotopes in modern and Holocene Protothaca staminea shells from a northern California coastal upwelling region

This study explores the potential of intertidal Protothaca staminea shells as high-resolution geochemical archives of environmental change in a coastal upwelling region. Mg/Ca and Sr/Ca ratios were analyzed by excimer laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) at sub-weekly temporal resolution in shells growing ∼1 mm per month. Growth patterns of a modern P. staminea shell from Humboldt Bay, California, collected in December 1999 made it possible to infer a lifespan from 1993 to 1998. Growth hiatuses in the shell may have excluded records of extreme events. Mg/Ca ratios appeared to be partly controlled by water temperature; the correlation coefficient between temperature and Mg/Ca was r = 0.71 in one of four growth increments. Significant year-to-year differences in the sensitivity of Mg/Ca to temperature in P. staminea could not be explained, however. Sr/Ca ratios appeared to be more closely related to shell growth rate. Oxygen isotopes, measured at 2-week temporal resolution in the same shell, did not show a clear relation to local temperature in summer, possibly because temperatures were higher and less variable at the King Salmon mudflat, where the shell was collected, than in the main channel of Humboldt Bay, where water properties were monitored. Negative shell δ¹³C values (<−0.5‰) marked spring and summer coastal upwelling events.The Mg contents of P. staminea midden shells dated to ∼3 ka and ∼9 ka were significantly lower than in the modern shell. This may have resulted from degradation of a Mg-rich shell organic matrix and precluded quantitative interpretation of the older high-resolution records. Elevated δ¹³C values in the ∼3 ka shell suggested that the individual grew in highly productive or stratified environment, such as a shallow coastal embayment or lagoon.     

Ba, Ra, Th, and U in marine mollusc shells and the potential of Ra/Ba dating of Holocene marine carbonate shells

The geochemistry of Ba, Ra, Th, and U and the potential of using ²²⁶Ra/Ba ratios as an alternative dating method are explored in modern and Holocene marine mollusc shells. Five modern shells of the Antarctic scallop Adamussium colbecki collected from the present day beach and six radiocarbon dated specimens from Holocene beach terraces of the Ross Sea region (Antarctic) between 700 and 6100 calibrated yr BP old have been analysed by mass spectrometry. In clean shells ²²⁶Ra concentrations and ²²⁶Ra/Ba ratios show a clear decrease with increasing age, suggesting the possibility of ²²⁶Ra dating. Limiting factors for such dating are Ba and ²²⁶Ra present in surface contaminants, and ingrowth of ²²⁶Ra from U present within the shell. Surface contamination is difficult to clean off entirely, but moderate levels of residual contamination can be corrected using ²³²Th. Sub-samples from the same shell with different proportions of contamination form a mixing line in a ²²⁶Ra/Ba-²³²Th/Ba graph, and the ²²⁶Ra/Ba of the pure shell can be derived from the intercept on the ²²⁶Ra/Ba axis. Contaminant corrected ²²⁶Ra/Ba ratios of late-Holocene ¹⁴C-dated samples fall close to that expected from simple ²²⁶Ra excess decay from seawater ²²⁶Ra/Ba values. ²²⁶Ra ingrowth from U incorporated into the shell during the lifetime of the mollusc can be corrected for. However, the unknown timing of post mortem U uptake into the shell makes a correction for ²²⁶Ra ingrowth from secondary U difficult to achieve. In the A. colbecki shells, ²²⁶Ra ingrowth from such secondary U becomes significant only when ages exceed ∼2500 yr. In younger shells, ²²⁶Ra/Ba ratios corrected for surface contamination provide chronological information. If evidence for a constant oceanic relationship between ²²⁶Ra and Ba in the ocean can be confirmed for that time scale, the ²²⁶Ra/Ba chronometer may enable the reconstruction of variability in sea surface ¹⁴C reservoir ages from mollusc shells and allow its use as a paleoceanographic tracer.     

A review on bivalve shell,a tool for reconstruction of paleo-climate and paleo-environment

Environmental information can be extracted from bivalve shell geochemistry. In this review, the latest research progress and the existing problems as well as the focus of future research on stable oxygen and carbon isotopic composition and trace elemental ratios of bivalve shell were investigated. Oxygen isotopic signatures of bivalve shell have been proved precipitate in equilibrium with their host water and used as a robust tool to reconstruct ancient water temperature. In order to reconstruct quantitative paleo-temperature information, the future research on bivalve shell oxygen isotope should combine with the study of ancient water oxygen isotope. Metabolic effect pre- vents the direct application of stable carbon isotopic composition of bivalve shell from extracting dissolved inorganic carbon information. The contribution of metabolic carbon to bivalve shell is species specific. Stable carbon isotopic composition of dissolved inorganic carbon could be reconstructed if the metabolic contribution could be accounted for. Explore ways to remove contribution of metabolic effects to bivalve shell is the future focus of the research. There is no consensus on the effect of temperature on bivalve trace element ratios, which may be also species spe- cific, each proxy should ideally be validated and calibrated for each species before being used to interpret past climate and environmental conditions. Future research needs to pay attention to the bivalve shell biomineralization process, which controlled bivalve shell trace element ratios. Cultivation experiment is an important way to obtain the relevant conclusions.     

Li/Ca in multiple species of benthic and planktonic foraminifera: thermocline, latitudinal, and glacial-interglacial variation

Li/Ca ratios were measured in planktonic and benthic foraminifera from a variety of hydrographic settings to investigate the factors influencing lithium incorporation into foraminiferal tests including temperature, dissolution, pressure, and interspecies differences. Down-core measurements of planktonic (Orbulina universa, Globigerinoides ruber, and Globigerinoides sacculifer) and benthic foraminifera (calcitic Cibicides wuellerstorfi and aragonitic Hoeglandina elegans) show a systematic variation in Li/Ca with δ¹⁸O through the last glacial-interglacial transition. All species examined exhibit an increase in Li/Ca between 14 to 50% from the Holocene to the last glacial maximum. Li/Ca generally increases with decreasing temperature as seen in a latitudinal transect of planktonic O. universa and down-slope benthic species along the Bahama Bank margins. Postdepositional dissolution possibly causes a decrease in planktonic foraminiferal Li/Ca along the Sierra Leone Rise, and increased water depth causes a decrease in benthic foraminiferal Li/Ca in the deep Caribbean. However, none of these effects are sufficient to account for the observed glacial-interglacial changes. Physiological factors such as calcification rate may affect the Li/Ca content of foraminiferal calcite. The calcification rate in turn may be a function of carbonate ion concentration of ambient ocean water. This work shows that incorporation of lithium by foraminifera appears to be influenced by factors other than seawater composition and does not appear to be dominated by changes in temperature, dissolution, or pressure. We hypothesize that the consistent increase in foraminiferal Li/Ca during the last glacial maximum may be linked to changes in seawater carbonate ion concentration. Important parameters to be tested include calcification rate and foraminiferal test size and weight. If foraminiferal Li/Ca is dominantly controlled by calcification rate as a function of seawater carbonate ion concentration, then Li/Ca may act as a proxy of past atmospheric CO₂.     

Coral Ba/Ca molar ratios as a proxy of precipitation in the northern Yucatan Peninsula,Mexico

The Yucatan Peninsula consists of a karstic terrain that allows the aquifer to directly recharge from rainfall. Due to the various dissolution/precipitation reactions occurring during groundwater flow, the groundwater discharge in the coastal zone becomes a source of trace elements including Ba. The aim of this study was to use the coralline Ba/Ca record as a proxy of precipitation under the consideration that rainfall rates vary at inter-annual time scales. Annual Ba/Ca ratios, both the total content (Ba/Ca_TC) and the Ca-substitutive fraction (Ba/Ca_CaF), were quantified in a 52-a old coral colony of Montastraea annularis from the Punta Nizuc Reef, Mexican Caribbean. Average Ba/Ca_TC (5.90 ± 0.56 μmol/mol) was ∼20% higher than Ba/Ca_CaF (4.85 ± 0.33 μmol/mol) indicating that Ba is also incorporated in other fractions. Correlation between annual precipitation and Ba/Ca_TC time-series is significant (r = 0.77, p < 0.05), allowing the use of the Ba/Ca_TC ratio as a proxy of precipitation, and hence, enabling the reconstruction of precipitation patterns through time. Likewise, the Ba/Ca_CaF ratio can be used for the reconstruction of dissolved Ba in coastal seawater.     

Nanostructure, composition and mechanisms of bivalve shell growth

Freshwater and marine cultured pearls form via identical processes to the shells of bivalves and can therefore serve as models for the biomineralization of bivalve shells in general. Their nanostructure consists of membrane-coated granules (vesicles) which contain amorphous calcium carbonate (ACC) at the beginning of the biomineralization sequence, preceding the crystallization of aragonite and vaterite. In contrast to the commonly accepted view, crystallization of ACC occurs rapidly and within the granular nano-compartments mediated by organic molecules much earlier than platelet formation. The interlamellar organic sheets in nacre that form the platelet structure of nacre themselves form by self-organization after the crystallization process of CaCO₃ is completed and, thus, cannot serve as a nucleation template for aragonite. Pores in the organic sheets are postulated to be a result of this process rather than to represent the pathways for CaCO₃ through pre-existing interlamellar sheets. The amorphous phase has the highest concentrations of Mg (5.8 mol%), Mn (6.6 mol%), S (4.7 mol%) and P (1 mol%) of the three CaCO₃-polymorphs. Mg/Ca and Mn/Ca ratios are found to decrease in the order ACC > vaterite > aragonite, corresponding to decreasing organic content in the different phases. This, as well as an observed enrichment of Mg in the organic-rich growth-banding of the pearls, suggests an at least partially organic speciation of Mg and Mn in bivalves and may be responsible for the observed physiological influence on Mg/Ca and Mn/Ca ratios in bivalves as a proxy for environmental parameters.     

Aspartic acid racemization dating of Holocene brachiopods and bivalves from the southern Brazilian shelf, South Atlantic

The extent of racemization of aspartic acid (Asp) has been used to estimate the ages of 9 shells of the epifaunal calcitic brachiopod Bouchardia rosea and 9 shells of the infaunal aragonitic bivalve Semele casali. Both taxa were collected concurrently from the same sites at depths of 10 m and 30 m off the coast of Brazil. Asp D/L values show an excellent correlation with radiocarbon age at both sites and for both taxa (r²_{Site 9 B. rosea} = 0.97, r²_{Site 1 B. rosea} = 0.997, r²_{Site 9 S. casali} = 0.9998, r²_{Site 1 S. casali} = 0.93). The Asp ratios plotted against reservoir-corrected AMS radiocarbon ages over the time span of multiple millennia can thus be used to develop reliable and precise geochronologies not only for aragonitic mollusks (widely used for dating previously), but also for calcitic brachiopods. At each collection site, Bouchardia specimens display consistently higher D/L values than specimens of Semele. Thermal differences between sites are also notable and in agreement with theoretical expectations, as extents of racemization for both taxa are greater at the warmer, shallower site than at the cooler, deeper one. In late Holocene marine settings, concurrent time series of aragonitic and calcitic shells can be assembled using Asp racemization dating, and parallel multi-centennial to multi-millennial records can be developed simultaneously for multiple biomineral systems.     

Li,Sr, Mg,and Na in foraminiferal calcite shells from laboratory culture,sediment traps,and sediment cores

Constant-temperature laboratory culture experiments of the planktonic foraminiferal species Globigerinoides sacculifer (Brady) suggest that the ratios of Li and Sr to Ca in the shells are a function of these ratios in the culture solutions. $\text{Mg}\text{Ca}$ and $\text{Na}\text{Ca}$ in the shells did not vary with changes of these ratios in the culture solution. These are the first direct determinations of the relationship between foraminiferal shell chemistry and solution composition.The possibility of temperature dependence for the minor elemental composition of foraminiferal shells was also investigated in the laboratory and by analysis of several planktonic and one benthic foraminiferal species from sediment trap and sediment core samples. The $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios in the natural samples roughly correlate with calcification temperature, whereas differences in the Li/Ca ratios are small and not systematically related to temperature. However, laboratory culture experiments at 20°C and 30°C showed no variation in the $\text{Li}\text{Ca}$, $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios with calcification temperature for the planktonic foraminifera G. sacculifer and Orbulina universa. Therefore, observed differences in the $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios for the sediment trap and core foraminiferal samples cannot be ascribed to direct effects of calcification temperature, but may be due to some other environmental factor which is correlated with temperature.     

The impact of solution chemistry on Mytilus edulis calcite and aragonite

Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.     

Source of trace element variability in Great Barrier Reef corals affected by the Burdekin flood plumes

Massive corals in the Great Barrier Reef, analyzed at high-resolution for Sr/Ca (thermal ionization mass spectrometry) and trace elements such as Ba and Mn (laser ablation inductively coupled plasma mass spectrometry), can provide continuous proxy records of dissolved seawater concentrations, as well as sea surface temperature (SST). A 10-yr record (1989 to 1998) from Pandora Reef, an inshore reef regularly impacted by the freshwater plumes of the Burdekin River, is compared with an overlapping record from a midshelf reef, away from runoff influences. Surface seawater samples, taken away from river plumes, show little variability for Sr/Ca (8484 ± 10 μmol/mol) and Ba (33.7 ± 0.7 nmol/kg). Discrete Ba/Ca peaks in the inshore coral coincide with flood events. The magnitude of this Ba/Ca enrichment is most likely controlled by the amount of suspended sediments delivered to the estuary, which remains difficult to monitor. The maximum flow rate at peak river discharge is used here as a proxy for the sediment load and is shown to be strongly correlated with coral Ba/Ca (r = 0.97). After the wet summer of 1991, the coral Ba/Ca flood peak is followed by a plateau that lingers for several months after dissipation of plume waters, signifying an additional flux of Ba that may originate from submarine groundwater seeps and/or mangrove reservoirs. Both Mn and Y are enriched by a factor of ∼5 in inshore relative to midshelf corals. Mn/Ca ratios show a seasonal cycle that follows SST (r = 0.7), not river discharge, with an additional high variability in summer suggesting a link with biological activity. P and Cd show no significant seasonal variation and are at a low level at both inshore and midreef locations. However, leaching experiments suggest that part of the coral P is not lattice bound.     

Calcium isotope fractionation in modern scleractinian corals

The ⁴⁴Ca/⁴⁰Ca ratios of cultured (Acropora sp.) and open ocean (Pavona clavus, Porites sp.) tropical reef corals are positively correlated with growth temperature. The slope of the temperature-fractionation relation is similar to inorganic aragonite precipitates. However, δ^44/40Ca of the coral aragonite is offset from inorganic and sclerosponge aragonite by about +0.5‰. This offset can neither be explained by the very fast, biologically controlled calcification of scleractinian corals, nor as a consequence of calcification from a partly closed volume of fluid. As corals actively transport calcium through several cell layers to the site of calcification, the most likely explanation for the offset is a biologically induced fractionation. Our results indicate a limited use of Ca isotopes in scleractinian corals as temperature proxy.     

Endolithic biodegradation of cool-water skeletal carbonates on Scott shelf, northwestern Vancouver Island, Canada

Biodegradation of shell material is widespread in the cool-water skeletal carbonate deposits on Scott shelf, northwestern Vancouver Island, and is especially evident in the large aragonitic bivalves, Glycymeris and Humilaria, major primary sediment contributors. Ten types of endolithic microborings have been identified in the shells, including representatives of green algae (e.g., Ostreobium quekettii), blue-green algae (e.g., Plectonema terebrans, ?Scytonema sp.), fungi, bacteria and clionid sponges, as well as macroborings of phoronids, polychaetes and naticid gatropods. Microcrystalline carbonate is not precipitated in vacated bores. Boring physically weakens the shells, rendering them more prone to mechanical abrasion during sediment transport and bioturbation, and to biological abrasion by grazing benthos. Tumbling experiments demonstrate that the rate of carbonate mud production is much greater for bored as compared to fresh bivalve shells, and that mud production rates decrease with tumbling time because most endolithic microborings are confined to the periphery of grains. Boring also increases significantly the porosity and surface area of skeletal grains, and destroys their organic matrix, making them susceptible to maceration and dissolution on cool-water shelves. Fostered by the generally low rates of carbonate production and accumulation, many aragonitic bivalve shells on Scott shelf have become thoroughly degraded through a combination of endolithic microboring, maceration and dissolution within about 1000 years in ambient sea water. In geologic terms, such selective taphonomic loss of skeletal material may be considerable in ancient temperate-shelf limestones and should be evaluated when interpreting their paleoecology and paleoenvironments.     

A continuous multi-millennial record of surficial bivalve mollusk shells from the São Paulo Bight,Brazilian shelf

To evaluate the potential of using surficial shell accumulations for paleoenvironmental studies, an extensive time series of individually dated specimens of the marine infaunal bivalve mollusk Semele casali was assembled using amino acid racemization (AAR) ratios (n = 270) calibrated against radiocarbon ages (n = 32). The shells were collected from surface sediments at multiple sites across a sediment-starved shelf in the shallow sub-tropical São Paulo Bight (São Paulo State, Brazil). The resulting ¹⁴C-calibrated AAR time series, one of the largest AAR datasets compiled to date, ranges from modern to 10,307 cal yr BP, is right skewed, and represents a remarkably complete time series: the completeness of the Holocene record is 66% at 250-yr binning resolution and 81% at 500-yr binning resolution. Extensive time-averaging is observed for all sites across the sampled bathymetric range indicating long water depth-invariant survival of carbonate shells at the sediment surface with low net sedimentation rates. Benthic organisms collected from active depositional surfaces can provide multi-millennial time series of biomineral records and serve as a source of geochemical proxy data for reconstructing environmental and climatic trends throughout the Holocene at centennial resolution. Surface sediments can contain time-rich shell accumulations that record the entire Holocene, not just the present.     

柴西上干柴沟组中上段介壳微量元素古环境古气候意义

介壳微量元素具有重要的沉积古环境古气候意义,结合介壳微量元素含量变化特征和介壳化石组合生态环境特征可得到柴达木盆地西部上干柴沟组中上段更为详尽的古环境古气候演化特征。柴达木盆地西部上干柴沟组中上段介壳微量元素比值Sr/Ca、Ba/Ca、U/Ca及元素Sr、Ba、U在A阶段（28.35~26.42 Ma）值较低,B阶段（26.42~23.08 Ma）值整体较高,段末值有所下降,C阶段（23.08~22.33 Ma）值明显上升,Mn/Ca和Mn值变化大致相反。A阶段Sr/Ca和Sr均值（分别为0.002 278、37.76×10-9）较低,B阶段均值（分别为0.003 347、41.46×10-9）较高,C阶段二者均值（分别为0.003 346、56.06×10-9）也较高,Ba/Ca、U/Ca、B、U有着类似的平均值变化特征,Mn/Ca和Mn值有着相反的平均值变化特征。同时相应各阶段介壳化石组合有所不同。通过介壳微量元素变化及化石组合特征,结合同期深海氧同位素及前人研究成果表明,上干柴沟组中上段柴西古湖古环境古气候演化特征为: A阶段,盐度较低和还原性较强,水位较高,气候相对温暖润湿;B阶段,整体盐度较高和氧化性较强,水位较浅,气候整体炎热干旱,段末气候干旱程度降低;C阶段,盐度和氧化性增高,湖水变浅,气候向冷干演化,响应了早中新世中国西北内陆干旱化。该地区该时段古气候主要受全球气候演化和青藏高原隆升的影响,与副特提斯海西退也有一定关系。     

Chemical compositions of mussels and clams from the Tangyin and Yonaguni Knoll IV hydrothermal fields in the southwestern Okinawa Trough

Studies of the chemical characteristics of mussels and clams in seafloor hydrothermal fields are important for understanding mass fluxes and elemental partitioning from hydrothermal vents into the biosphere, metal bioaccumulation of seafloor hydrothermal ecosystems, and the sources and sinks of biogeochemical and fluid cycles. We are the first to measure the mineral, major, trace and rare earth element, and carbon and oxygen isotope compositions of mussels (Bathymodiolus platifrons) and clams (Conchocele bisecta) from the Tangyin and Yonaguni Knoll IV hydrothermal fields in the southwestern Okinawa Trough. Mineralogical analysis shows that the carbonate shells of the mussel and clam samples are mainly composed of calcite and aragonite. Metal elements exhibit linear correlations in the shells (e.g., V and U) and tissues (e.g., Li and Rb) of the mussels and clams, suggesting that not all positive correlations of elements in tissues are inherited by the shells. V/As, Ca/Sr, and Fe/Cr ratios in the mussels and clams are close to those in the seawater, indicating that element ratios of seawater might be inherited by the mussels and clams. In addition, the Fe/Cr ratio of the shells of both mussels and clams can be used to trace the local seawater composition.The total LREE concentrations of mussel and clam tissue samples are higher than those of the mussel and clam shell samples, are similar to the hydrothermal fluids, exhibit LREE enrichment (La_CN/Nd_CN ratios = 1.86-32.1), and no or only slightly negative Eu anomalies, indicating that benthic animals are a sink of LREEs from hydrothermal fluids, and that the Eu/Eu* ratios of fluids change when fluids are incorporated into the tissues of the mussels and clams. In addition, the δ¹³C values of mussel shell samples are heavier than those of the clam shell samples in the hydrothermal field, indicating that more than one carbon source may be involved in defining the δ¹³C compositions of the shells. The majority of the δ¹⁸O values of clam shell samples fall in the range of δ¹⁸O values of the mussel shell samples, and are close to the hydrothermal fluid δ¹⁸O_H2O values, implying that the δ¹⁸O values of mussel and clam shell carbonate is influenced by the hydrothermal environment (magmatic water and fluid dilution with seawater).     

Li/Ca ratios of ostracod shells at Lake Qinghai, NE Tibetan Plateau, China: a potential temperature indicator

Acquiring continuous and high-resolution natural records in recent 2,000?years is the hot issue in the palaeoclimate research. Recent studies revealed that Li/Ca and Mg/Li ratio of carbonate is a potential tracer of past environmental changes in the oceans, and is seldom applied for palaeoclimate reconstruction in lakes. To make full understanding of the potential of Li/Ca ratios of carbonates in lakes, Li/Ca ratios of monospecific ostracod shell Eucypris inflate with similar size in the lacustrine sediment core from Lake Qinghai, NE Tibetan Plateau have been analysed for the first time. Single species can effectively avoid the interspecies effects. In combination with the sedimentation rate that existed, data derived from ²¹⁰Pb and ¹³⁷Cs, downcore variations of Li/Ca ratios of ostracod shells during the past 800?years in Lake Qinghai have been reconstructed successfully. By comparing Li/Ca ratios and temperature inferred from meteorological records and tree ring widths in Dulan and Qilianshan in adjacent regions, Li/Ca ratios of ostracod shells negatively correlate with temperature. Higher temperature corresponds with lower Li/Ca ratios, and vice versa, indicating that Li/Ca ratio of ostracod shells is an effective indicator for temperature variations. Therefore, ongoing in-depth investigation using Li/Ca ratios of carbonates in more lakes to further reveal its palaeotemperature implications would be deserved.