Influences of organic matter and calcification rate on trace elements in aragonitic estuarine bivalve shells

A suite of elements (B, Na, Mg, S, K, Ca, V, Mn, Cr, Sr, and Ba) was measured in aragonitic shells of the estuarine bivalve Corbula amurensis, the Asian clam, using the Sensitive High-Resolution Ion MicroProbe with Reverse Geometry (SHRIMP RG). Our initial intent was to explore potential geochemical proxy relationships between shell chemistry and salinity (freshwater inflow) in northern San Francisco Bay (SFB). In the course of this study we observed variations in shell trace element to calcium ([M]/Ca) ratios that could only be attributed to internal biological processes. This paper discusses the nature and sources of internal trace element variability in C. amurensis shells related to the shell organic fraction and shell calcification rates. The average organic content of whole C. amurensis shells is 19%. After treating whole powdered shells with an oxidative cleaning procedure to remove organic matter, shells contained on average 33% less total Mg and 78% less total Mn. Within our analytical uncertainty, Sr and Ba contents were unchanged by the removal of organic matter. These results show that aragonitic C. amurensis shells have a large component of non-lattice-bound Mg and Mn that probably contribute to the dissimilarity of [M]/Ca profiles among five same-sized shells. Non-lattice-bound trace elements could complicate the development and application of geochemical proxy relationships in bivalve shells. Because B, Ba and Sr occur exclusively in shell aragonite, they are good candidates for external proxy relationships. [M]/Ca ratios were significantly different in prismatic and nacreous aragonite and in two valves of the same shell that had different crystal growth rates. Some part of these differences can be attributed to non-lattice-bound trace elements associated with the organic fraction. The differences in [M]/Ca ratios were also consistent with the calcification rate-dependent ion transport model developed by Carré et al. [Carré M., Bentaleb I., Bruguier O., Ordinola E., Barrett N. T. and Fontugne M. (2006) Calcification rate influence on trace element concentrations in aragonitic bivalve shells: evidences and mechanisms. Geochim. Cosmochim. Acta70, 4906-4920] which predicts that [M]/Ca ratios increase as calcification rates increase and Ca²⁺ channel specificity decreases. This result, in combination with the possibility that there were ontogenetic variations in growth rates among individuals younger than 2 years, underscores the need to develop an independent age model for C. amurensis shells. If growth-rate effects on lattice-bound [M]/Ca ratios can be constrained, it may yet be possible to develop high-resolution geochemical proxies for external solution chemistry in low-salinity regions of SFB.     

Boron isotope geochemistry of Paleozoic brachiopod calcite: Implications for a secular change in the boron isotope geochemistry of seawater over the Phanerozoic

Boron isotope composition of marine carbonates has been proposed as a paleo-pH proxy and potential tool to reconstruct atmospheric pCO₂. The precise knowledge of the boron isotopic composition of ancient seawater represents the fundamental prerequisite for any paleo-pH reconstruction. This contribution presents boron isotope values for Silurian to Permian brachiopod calcite that might be used to reconstruct pH or boron isotope composition of past oceans. All brachiopod shells were screened for diagenetic recrystallization by means of cathodoluminescence microscopy, trace element geochemistry (B, Fe, Mn, Sr) as well as SEM. Only nonluminescent shells revealing well-preserved microstructures, high strontium and boron concentrations as well as low iron and manganese contents were accepted for boron isotope analysis. The boron isotope ratios of Silurian, Devonian, Pennsylvanian and Permian brachiopod calcite range from 6.8 to 11.0‰, 7.3 to 14.9‰, 12.4 to 15.8‰ and 10.1 to 11.7‰, respectively. These δ¹¹B values are significantly lower in comparison to δ¹¹B values of modern biogenic carbonates and indicate that the Paleozoic oceans were depleted in ¹¹B by up to 10‰. Box modeling of the boron geochemical cycle suggests that the significant depletion of ¹¹B in the oceanic reservoir may have been initiated by an enhanced continental boron discharge. Our data support the earlier made conclusion that boron isotopes may not be used in the geological past as reliable paleo-pH proxy unless the boron isotopic composition of ancient oceans can be constrained by further studies.     

Element partitioning during precipitation of aragonite from seawater: A framework for understanding paleoproxies

This study presents the results from precipitation experiments carried out to investigate the partitioning of the alkaline earth cations Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ between abiogenic aragonite and seawater as a function of temperature. Experiments were carried out at 5 to 75 °C, using the protocol of Kinsman and Holland [Kinsman, D.J.J., Holland, H.D., 1969. The coprecipitation of cations with CaCO₃ IV. The coprecipitation of Sr²⁺ with aragonite between 16 and 96 °C. Geochim. Cosmochim. Acta33, 1-17.] The concentrations of Mg Sr and Ba were determined in the fluid from each experiment by inductively coupled plasma-mass spectrometry, and in individual aragonite grains by secondary ion mass spectrometry. The experimentally produced aragonite grains are enriched in trace components (“impurities”) relative to the concentrations expected from crystal-fluid equilibrium, indicating that kinetic processes are controlling element distribution. Our data are not consistent with fractionations produced kinetically in a boundary layer adjacent to the growing crystal because Sr²⁺, a compatible element, is enriched rather than depleted in the aragonite. Element compatibilities, and the systematic change in partitioning with temperature, can be explained by the process of surface entrapment proposed by Watson and Liang [Watson, E.B., Liang, Y., 1995. A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am. Mineral.80, 1179-1187] and Watson [Watson, E.B., 1996. Surface enrichment and trace-element uptake during crystal growth. Geochim. Cosmochim. Acta60, 5013-5020; Watson, E.B., 2004. A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals. Geochim. Cosmochim. Acta68, 1473-1488]. This process is thought to operate in regimes where the competition between crystal growth rate and diffusivity in the near-surface region limits the extent to which the solid can achieve partitioning equilibrium with the fluid. A comparison of the skeletal composition of Diploria labyrinthiformis (brain coral) collected on Bermuda with results from precipitation calculations carried out using our experimentally determined partition coefficients indicate that the fluid from which coral skeleton precipitates has a Sr/Ca ratio comparable to that of seawater, but is depleted in Mg and Ba, and that there are seasonal fluctuations in the mass fraction of aragonite precipitated from the calcifying fluid (“precipitation efficiency”). The combined effects of surface entrapment during aragonite growth and seasonal fluctuations in “precipitation efficiency” likely forms the basis for the temperature information recorded in the aragonite skeletons of Scleractinian corals.     

Environmental significance of C/C and O/O ratios of modern land-snail shells from the southern great plains of North America

¹³C/¹²C and ¹⁸O/¹⁶O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ¹⁸O values (PDB scale) ranged from −4.1‰ to 1.2‰, while δ¹³C values ranged from −13.2‰ to 0.0‰. δ¹⁸O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ¹⁸O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ¹⁸O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ¹³C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ¹³C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C₃, C₄) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the “neighborhood” scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.     

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

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

Paleoenvironment of the Folsom archaeological site, New Mexico, USA, approximately 10,500 C yr B.P. as inferred from the stable isotope composition of fossil land snail shells

Well-preserved aragonitic land snail shells (Vallonia) from late Pleistocene Eolian sediment in the Folsom archaeological site in New Mexico exhibit an overall decrease of δ¹⁸O_PDB from maximum values of +2.7‰ (more positive than modern) to younger samples with lower average values of about −3.6‰ (within the modern range). The age of the samples (approximately 10,500 ¹⁴C yr B.P.) suggests that the decrease in δ¹⁸O may manifest climatic changes associated with the Younger Dryas. Some combination of increased relative humidity and cooler temperatures with decreased δ¹⁸O of precipitation during the times of snail activity can explain the decrease in shell δ¹⁸O. A well-known Paleoindian bison kill occurred at the Folsom site during this inferred environmental transition.Average δ¹³C values of the aragonite shells of the fossil Vallonia range from −7.3 to −6.0‰ among different archaeological levels and are not as negative as modern values. This suggests that the proportion of C₄ vegetation at the Folsom site approximately 10,500 ¹⁴C yr B.P. was greater than at present; a result which is consistent with other evidence for higher proportions of C₄ plants in the region at that time.     

Modelling the geochemical cycle of boron: Implications for the long-term δ11B evolution of seawater and oceanic crust

The boron geochemical cycle has been simulated using a time-dependent geochemical box model that was coupled to a one-dimension model of seawater–oceanic crust interactions. Boron elemental and isotopic compositions of oceanic rocks as a function of depth were calculated by mass balance, using the temperature and porosity profiles of the crust as well as the available experimental and empirical distribution coefficients and fractionation factors between mineral and water. Ranges of boron elemental and isotopic variations of seawater were calculated for crust–seawater interactions that take place from the ridge-axis to the off-axis closure of the hydrothermal system. The present-day δ¹¹B of seawater (40‰) could represent a steady-state value. However, depending on crustal permeability, lifetime of water–rock interactions, and expansion rate of the oceanic ridge, the δ¹¹B of seawater may vary from 30‰ to 50‰ at the 10 million year scale.Some boron isotope compositions of Cretaceous biogenic carbonates and ophiolitic serpentinites from Oman are comparable to modern rock samples, suggesting that the δ¹¹B of Cretaceous seawater was close to the present-day value. Low δ¹¹B values of some biogenic carbonates cannot be attributed to low pH values of past seawater, but more probably to δ¹¹B variations of seawater or diagenetic alteration by crustal aqueous fluids. Boron isotope composition of hydrothermally altered serpentines could be considered as a promising proxy of the seawater composition.     

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.     

Radiocarbon Ages Constraints on the Origin and Shedding of Bank-Top Sediment in the Bahamas during the Holocene

Great quantities of fine-sized aragonite needles are produced in the shallow waters that cover the tops of the Bahama Banks and then exported to the bank margins where they accumulate with shells of pelagic organisms. To better understand these processes, we investigated Holocene-aged sediments in a core from the southwestern margin of Little Bahama Bank. The aragonite content of the sediments, ??¹⁸O of planktonic foraminifera shells, and radiocarbon ages of aragonite-rich <63 ??m sediments and coexisting planktonic foraminifera shells were determined. Sediment deposition was rapid overall, and a significant increase in deposition rate occurred 3,500?C4,000 years ago, shortly after rising sea level flooded the bank top with seawater and caused a dramatic increase in the shallow water area where aragonite production occurred. During the latest Holocene when high deposition rates minimize effects of bioturbation, aragonite-rich <63 ??m sediments are 400?C600 years older than coexisting foraminifera. This difference indicates the net age of aragonite when it was exported from the bank top. It is consistent with expectations of the ??hip-hop??n?? model (Morse et al. in Geochimica et Cosmochimica Acta 67: 2819?C2826, 2003) whereby aragonite needles on the bank top, formed initially by biologic or other processes, continue to grow for hundreds of years via precipitation of epitaxial carbonate cement from seawater. Earlier in the Holocene, when sea level was lower and the top of Little Bahama Bank was subaerially exposed, the deposition rate and aragonite content of the sediments were less, and the aragonite-rich <63 ??m sediments are about 1,000 years younger than coexisting foraminifera. This age difference can be explained by downward mixing of latest-Holocene <63 ??m material into older early-Holocene sediments.     

Re-evaluating boron speciation in biogenic calcite and aragonite using B MAS NMR

Understanding the partitioning of aqueous boron species into marine carbonates is critical for constraining the boron isotope system for use as a marine pH proxy. Previous studies have assumed that boron was incorporated into carbonate through the preferential uptake of tetrahedral borate B(OH)₄⁻. In this study we revisit this assumption through a detailed solid state ¹¹B magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopic study of boron speciation in biogenic and hydrothermal carbonates. Our new results contrast with those of the only previous NMR study of carbonates insofar as we observe both trigonal and tetrahedral coordinated boron in almost equal abundances in our biogenic calcite and aragonite samples. In addition, we observe no strict dependency of boron coordination on carbonate crystal structure. These NMR observations coupled with our earlier re-evaluation of the magnitude of boron isotope fractionation between aqueous species suggest that controls on boron isotope composition in marine carbonates, and hence the pH proxy, are more complex that previously suggested.     

Boron isotopic constraints on the source of Hawaiian shield lavas

Boron isotopic compositions of lavas from three representative Hawaiian shield volcanoes (Kilauea, Mauna Loa, and Koolau) were analyzed by thermal ionization mass spectrometry. The boron isotopic composition of each sample was analyzed twice, once with and once without acid leaching to evaluate the effect of posteruptive boron contamination. Our acid-leaching procedure dissolved glass, olivine, secondary zeolite, and adsorbed boron; this dissolved boron was completely removed from the residue, which was comprised of plagioclase, pyroxenes, and newly formed amorphous silica. We confirmed that an appropriate acid-leaching process can eliminate adsorbed and incorporated boron contamination from all submarine samples without modifying the original ¹¹B/¹⁰B ratio. On the other hand, when the sample was weathered, i.e., the olivine had an iddingsite rim, ¹¹B/¹⁰B of the acid-resistant minerals are also modified, thus it is impossible to get the preeruptive ¹¹B/¹⁰B value from the weathered samples. Through this elimination and evaluation procedure of posteruptive contamination, preeruptive δ¹¹B values for the shield lavas are −4.5 to −5.4‰ for Koolau (N = 8), −3.6 to −4.6‰ for Kilauea (N = 11), and −3.0 to −3.8‰ for Mauna Loa (N = 6).Historical Kilauea lavas show a systematic temporal trend for B content and Nb/B coupled with other radiogenic isotopic ratios and trace element ratios, at constant δ¹¹B, indicating little or no assimilation of crustal materials in these lavas. Uncorrelated B content and δ¹¹B in Koolau and Mauna Loa lavas may also indicate little or no effect of crustal assimilation in these lavas. The source of KEA-component (identical to the so-called Kea end member in Hawaiian lavas) of the Hawaiian source mantle, represented by Kilauea, should be derived from lower part of subducted oceanic crust or refractory peridotite in the recycled subducted slab. The systematic trend from Kilauea to Koolau—decreasing δ¹¹B coupled with decreasing εNd as well as increasing ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb—is consistent with involvement of subducted sediment components in the EMK(enriched Makapuu)-component, represented by Makapuu-stage of Koolau lavas.     

Stable carbon isotopes in freshwater mussel shells: Environmental record or marker for metabolic activity?

Mussel shells have been used in a number of paleoecological and environmental studies. The interpretation of stable carbon isotopic composition of shell material is still controversial. The carbon for shell carbonate precipitation can either be derived from ambient dissolved inorganic carbon (DIC), with shells recording environmental signals, or from metabolic CO₂, with the potential to disguise environmental signals. To gain insight into this question, we investigated four nearly 100-yr long-term records of aragonite shells from an extant freshwater bivalve species, the endangered freshwater pearl mussel (Margaritifera margaritifera L.). Single growth increments of the outer prismatic and the inner nacreous zones were successfully and easily separated with a simple heat treatment for chronological analyses of δ¹³C in single layers of each zone. Autocorrelation and semivariance statistical methods reveal that mussels show distinct individual signal patterns, which extend up to 25 yr. Signal patterns are reliably reproduced with replicate samples from defined layers within one shell and show similar patterns with a slight offset for inner nacreous and outer prismatic layers for individual animals. Mussels exposed to the same environmental conditions exhibit distinct and contradictory signature patterns, which do not match between individuals. This observation can only be explained by strong metabolic influences on shell precipitation. Environmental changes in pH, temperature, electric conductivity and atmospheric carbon signature had no or little (<5%) influence, whereas body tissue protein and body tissue δ¹³C signatures negatively correlated with the youngest produced shell δ¹³C signatures, indicating that respiration causes a preferential loss of light isotopes from body mass and an inverse enrichment in shell aragonite. Hence, the shells of the freshwater pearl mussel yield a long-term record of metabolic activity, whereas the use of δ¹³C in these shells as recorder for environmental signals is questionable. This may also be true for shells from other species, for which metabolic carbon incorporation has been acknowledged.     

Polycrystalline apatite synthesized by hydrothermal replacement of calcium carbonates

Aragonite and calcite single crystals can be readily transformed into polycrystalline hydroxyapatite pseudomorphs by hydrothermal treatment in a (NH₄)₂HPO₄ solution. Scanning electron microscopy of the reaction products showed that the transformation of aragonite to apatite is characterised by the formation of a sharp interface between the two phases and by the development of intracrystalline porosity in the hydroxyapatite phase. In addition, electron backscattered diffraction (EBSD) imaging showed that the c-axis of apatite is predominantly oriented perpendicular to the reaction front with no crystallographic relationship to the aragonite lattice. However, the Ca isotopic composition of the parent aragonite, measured by thermal ionization mass spectrometry was inherited by the apatite product.Hydrothermal experiments conducted with use of phosphate solutions prepared with water enriched in ¹⁸O (97%) further revealed that the ¹⁸O from the solution is incorporated in the product apatite, as measured by micro-Raman spectroscopy. Monitoring the distribution of ¹⁸O with Raman spectroscopy was possible because the incorporation of ¹⁸O in the PO₄ group of apatite generates four new Raman bands at 945.8, 932, 919.7 and 908.8 cm⁻¹, in addition to the ν₁(PO₄) symmetric stretching band of apatite located at 962 cm⁻¹, which can be assigned to four ¹⁸O-bearing PO₄ species. The relative intensities of these bands reflect the ¹⁸O content in the PO₄ group of the apatite product. By using equilibrated and non-equilibrated solutions, with respect to the ¹⁸O distribution between aqueous phosphate and water, we could show that the concentration of ¹⁸O in the apatite product is linked to the degree of ¹⁸O equilibration in the solution. The textural and chemical observations are indicative of a coupled mechanism of aragonite dissolution and apatite precipitation taking place at a moving reaction interface.     

The distribution of strontium in limestones on Barbuda, West Indies

The Sr²⁺ content of Barbudan limestones is proportional to the aragonite content. The Sr²⁺ content of calcite which has replaced aragonite varies from 3000 p.p.m. in the youngest limestones to 50 p.p.m., average values are approximately 300 p.p.m. The (mSr²⁺/mCa²⁺)_L ratios from well waters within the limestone fall within the predicted values assuming K^Sr_C～0·1. The high (mSr²⁺/mCa)²⁺_L ratios expected by a lower value of K^Sr_C do not occur. The build up of (mSr²⁺/mCa²⁺)_L ratios seen in waters from Barbados is not seen in the well waters from Barbuda. The Sr²⁺ content of calcite is generally lower than is seen in Barbados, but similar to that seen in parts of the Miami Oolite. Diagenesis of aragonite in Barbudan limestones is probably occurring in a more open system than in Barbados.     

A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates

The boron isotope-pH technique is founded on a theoretical model of carbonate δ¹¹B variation with pH that assumes that the boron isotopic composition of carbonates mirrors the boron isotopic composition of borate in solution (δ¹¹B_carb = δ¹¹B_borate). Knowledge of the fractionation factor for isotope exchange between boric acid and borate in solution (α_4-3), the equilibrium constant for the dissociation of boric acid (pK_B*), as well as the isotopic composition of boron in seawater (δ¹¹B_sw) are required parameters of the model.The available data suggests that both the value of α_4-3 and the history of δ¹¹B_sw are poorly constrained. However, if one assumes that δ¹¹B_carb = δ¹¹B_borate, an empirical value for α_4-3 can be estimated from the results of inorganic carbonate precipitation experiments. This exercise yields an α_4-3 value of ∼0.974 in accordance with recent theoretical estimates, but substantially deviates from the theoretical value of 0.981 often used to estimate paleo-ocean pH. Re-evaluation of ocean pH using an α_4-3 value of 0.974 and published foraminiferal δ¹¹B values for the Cenozoic yield pH estimates that are relatively invariant, but unrealistically high (∼8.4-8.6). Uncertainty increases as foraminiferal ‘vital effects’ are considered and different models for secular changes in seawater δ¹¹B are applied.The inability to capture realistic ocean pH possibly reflects on our understanding of the isotopic relationship between carbonate and borate, as well as the mechanism of boron incorporation in carbonates. Given the current understanding of boron systematics, pH values estimated using this technique have considerable uncertainty, particularly when reconstructions exceed the residence time of boron in the ocean.     

Uptake of fluoride by aragonite

The uptake of F by aragonite is attributed to the ion-exchange process, in which one CO₃^2? ion in the structure is replaced by two F^? ions. Under the equilibrium condition at 15° C and 1 atm., the partition of F between aragonite and aqueous solution is described by:

$\text{log}\text{(}\text{[}\text{F}\text{]}\text{a}{}_{\mathrm{<mtext>F</mtext>}}\text{)=1.95 + 0.54}\text{log}\text{a}{}_{\mathrm{<mtext>Ca</mtext>}}$

were [F] denotes the F content of aragonite in mol/g, and a_F and a_Ca are the aqueous activities of F^? and Ca²⁺, respectively. The equation was successfully applied to estimating the F content of marine aragonite.     

细纹灰尖巴蜗牛壳体氧同位素组成的季节性变化

陆生蜗牛壳体碳酸盐氧同位素组成,理论上取决于壳体生长季节的降水 18O丰度、温度和湿度,对揭示古气候和古环境变化具有巨大的潜力。然而,同一地区不同属种的蜗牛生长季节存在一定的差异,因此,了解不同季节生长的蜗牛壳体氧同位素特征,是其成为重建古气候、古环境变化的工具的关键。为了进一步阐明降水氧同位素组成和气候月际变化对蜗牛壳体 18O的影响,分别对从江苏镇江逐月采集的现生细纹灰尖巴蜗牛(Bradybaena ravida redfieldi)进行了整体壳体及壳口文石氧同位素组成的分析,结果表明： 1)不同月份采集的样品壳口的 δ18O 值变化较大,从－1.92‰至－6.79‰,幅度达4.87‰,其中,4～6月采集的样品 δ18O 值较正,平均 －2.40±0.42‰,7～9月采集的样品明显偏负,平均 －6.41±0.34‰; 2)整个壳体的 δ18O 值差别不大,平均 －2.61±0.47‰,与 4～6月壳口 δ18O 平均值相近; 3)不同月份蜗牛壳口 δ18O 值呈现出与当地的降水氧同位素组成、温度和大气相对湿度等相似的季节性变化模式,其中降水氧同位素组成对壳口 δ18O 变化的影响是主要的。这些特征说明,蜗牛壳体碳酸盐氧同位素组成受其生长时的环境因素(降水 18O丰度,温度和相对湿度)控制,对于中国夏季风影响地区来说,春季生长的蜗牛壳体相对富集 18O,而夏季生长的壳体 18O相对贫化。换句话说,根据蜗牛壳体碳酸盐氧同位素组成能够推测壳体主要生长季节,或降水 18O丰度及气候温湿程度的特征。对于B.ravida redfieldi来说,氧同位素组成显示了壳体主要生长时期为春季的特征。     

Controlling factors of the δ 11B-pH proxy and its research direction

Significant boron isotope fractionation occurs in nature (?70 ‰ to +75 ‰) due to the high geochemical reactivity of boron and the large relative mass difference between ¹⁰B and ¹¹B. Since the 1990s, reconstruction of ancient seawater pH using the isotopic composition of boron in bio-carbonates (δ ¹¹B_carb), and then calculation of the past pCO₂ have become important issues for the international isotope geochemistry community, and are called the δ ¹¹B-pH proxy. Although many achievements have been made by this proxy, various aspects of boron systematics require rigorous evaluation. Based on the previous researches, mechanism of boron isotope fractionation, variation of boron isotope (δ ¹¹B) in nature (especially in bio-carbonates) and controlling factors of the δ ¹¹B-pH proxy, such as the dissociation constant of B(OH)₃ in seawater (pK_a), the δ ¹¹B of seawater (δ ¹¹B_SW), the boron isotopic fractionation factor between B(OH) ₄ ^? and B(OH)₃ (α _4–3), and the incorporated species of boron into bio-carbonates, are reviewed in detail and the research directions of this proxy are proposed. Generally, the controversy about pK_a, δ ¹¹B_sw, and α _4–3 is relatively less, but whether boron incorporated into bio-carbonates only in the form of B(OH) ₄ ^? remains doubtful. In the future, it is required that the physicochemical processes that control boron incorporation into carbonates be rigorously characterized and that the related chemical and isotopic fractionation be quantified. It is also necessary and important to establish a “best-fit empirically equation” between δ ¹¹B_carb and pH of seawater based on the precipitation experiments of inorganic or culture experiments of corals or foraminifera. In addition, extended application of the δ ¹¹B-pH proxy to the earlier part of the Phanerozoic relying on the Brachiopods is worthy of studying. Like other geochemical indicators, there are limiting factors of δ ¹¹B; however, it remains a very powerful tool in the reconstruction of past seawater pH at present.     

Diagenetic effects on the distribution of uranium in live and Holocene corals from the Gulf of Aqaba

We investigated the effects of diagenetic alteration (dissolution, secondary aragonite precipitation and pore filling) on the distribution of U in live and Holocene coral skeletons. For this, we drilled into large Porites lutea coral-heads growing in the Nature Reserve Reef (NRR), northern Gulf of Aqaba, a site close to the Marine Biology Laboratory, Elat, Israel, and sampled the core material and porewater from the drill-hole. In addition, we sampled Holocene corals and beachrock aragonite cements from a pit opened in a reef buried under the laboratory grounds. We measured the concentration and isotopic composition of U in the coral skeletal aragonite, aragonite cements, coral porewater and open NRR and Gulf of Aqaba waters.Uranium concentration in secondary aragonite filling the skeletal pores is significantly higher than in primary biogenic aragonite (17.3 ± 0.6 compared to 11.9 ± 0.3 nmol · g⁻¹, respectively). This concentration difference reflects the closed system incorporation of uranyl tri-carbonate into biogenic aragonite with a U/Ca bulk distribution coefficient (K_D) of unity, versus the open system incorporation into secondary aragonite with K_D of 2.4. The implication of this result is that continuous precipitation of secondary aragonite over ∼1000 yr of reef submergence would reduce the coral porosity by 5% and can produce an apparent lowering of the calculated U/Ca - SST by ∼1°C and apparent age rejuvenation effect of 7%, with no measurable effect on the calculated initial U isotopic composition.All modern and some Holocene corals (with and without aragonite cement) from Elat yielded uniform δ²³⁴U = 144 ± 5, similar to the Gulf of Aqaba and modern ocean values. Elevated δ²³⁴U values of ∼180 were measured only in mid-Holocene corals (∼5000 yr) from the buried reef. The values can reflect the interaction of the coral skeleton with ²³⁴U-enriched ground-seawater that washes the adjacent granitic basement rocks.We conclude that pore filling by secondary aragonite during reef submergence can produce small but measurable effects on the U/Ca thermometry and the U-Th ages. This emphasizes the critical importance of using pristine corals where the original mineralogy and porosity are preserved in paleooceanographic tracing and dating.     

Aragonite relic preservation in Jurassic calcite-replaced bivalves

Shells of the aragonite bivalve Neomiodon (Great Estuarine Group, Jurassic, Scotland) replaced by coarse neomorphic calcite contain oriented relics of the original aragonite ultrastructure. The presence of these relics in such old altered shells, as well as the high Sr content of the replacement calcite, indicate that the process of calcite replacement of aragonite is not a cumulative slow process involving repeated alteration events, but rather a rapid, one-step process. Aragonite relics, once encased in neomorphic spar, will survive as unequivocal evidence of original aragonite mineralogy, barring total remobilization of the enclosing stable calcite, a generally unlikely event. The retention of this residual aragonite and high-Sr calcite supports recent isotopic studies which suggest that the multiple phases of alteration (‘recrystallization’) invoked in earlier literature are unlikely events in the diagenesis of most undolomitized limestones. Retention of aragonite relics appears to be independent of whether alteration occurs in shallow meteoric or, as in the case of our Neomiodon material, deeper burial environments. Pseudopleochroism of the replaced Neomiodon shells appears to be due to organic, largely graphitic, relics, not to the aragonite relics.