Ca isotopes in carbonate sediment and pore fluid from ODP Site 807A: The Ca(aq)-calcite equilibrium fractionation factor and calcite recrystallization rates in Pleistocene sediments

The calcium isotopic compositions (δ⁴⁴Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (α_s−f) between calcite and dissolved Ca²⁺ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of α_s−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ⁴⁴Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.     

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.     

Formation and evolution of carbonate chimneys at the Lost City Hydrothermal Field

The Lost City Hydrothermal Field at 30°N, near the Mid-Atlantic Ridge, is an off-axis, moderate temperature, high-pH (9-10.8), serpentinite-hosted vent system. The field is hosted on ∼1.5 Ma crust, near the summit of the Atlantis Massif. Within the field, actively venting carbonate chimneys tower up to 60 m above the seafloor, making them the tallest vent structures known. The chemistry of the chimneys and vent fluids is controlled by serpentinization reactions between seawater and underlying peridotite. Mixing of <40-91 °C calcium-rich vent fluids with seawater results in the precipitation of variable mixtures of aragonite, calcite, and brucite. The resultant deposits range from tall, graceful pinnacles to fragile flanges and delicate precipitates that grow outward from fissures in the bedrock. In this study, mineralogy, petrographic analyses, major and trace element concentrations, and Sr isotopic compositions are used to propose a model for the growth and chemical evolution of carbonate chimneys in a serpentinite-hosted environment. Our results show that nascent chimneys are characterized by a porous, interlacing network of aragonite, and brucite minerals that form extremely fragile structures. The chemistry of these young deposits is characterized by ∼10 wt% Ca and up to 27 wt% Mg, extremely low trace metal concentrations, and ⁸⁷Sr/⁸⁶Sr isotope ratios near 0.70760. During aging of the chimneys, progressive reactions with seawater result in the dissolution of brucite, the conversion of aragonite to calcite, and infilling of pore spaces with calcite. The oldest chimneys are dominated by calcite, with bulk rock values of up to 36 wt% Ca and <1 wt% Mg. These older structures contain higher concentrations of trace metals (e.g., Mn and Ti), and have Sr isotope ratios near seawater values (0.70908). Exposed ultramafic rocks are prevalent along the Mid-Atlantic, Arctic, and Indian Ocean ridge networks and it is likely that other Lost City-type systems exist.     

Mg fractionation in crustose coralline algae: Geochemical, biological, and sedimentological implications of secular variation in the Mg/Ca ratio of seawater

The Mg/Ca ratio of seawater has varied significantly throughout the Phanerozoic Eon, primarily as a function of the rate of ocean crust production. Specimens of the crustose coralline alga Neogoniolithon sp. were grown in artificial seawaters encompassing the range of Mg/Ca ratios shown to have existed throughout the Phanerozoic. Significantly, the coralline algae’s skeletal Mg/Ca ratio varied in lockstep with the Mg/Ca ratio of the artificial seawater. Specimens grown in seawater treatments formulated with identical Mg/Ca ratios but differing absolute concentrations of Mg and Ca exhibited no significant differences in skeletal Mg/Ca ratios, thereby emphasizing the importance of the ambient Mg/Ca ratio, and not the absolute concentration of Mg, in determining the Mg/Ca ratio of coralline algal calcite. Specimens grown in seawater of the lowest molar Mg/Ca ratio (mMg/Ca = 1.0) actually changed their skeletal mineralogy from high-Mg (skeletal mMg/Ca > 0.04) to low-Mg calcite (skeletal mMg/Ca < 0.04), suggesting that ancient calcitic red algae, which exhibit morphologies and modes of calcification comparable to Neogoniolithon sp., would have produced low-Mg calcite from the middle Cambrian to middle Mississippian and during the middle to Late Cretaceous, when oceanic mMg/Ca approached unity. By influencing the original Mg content of carbonate facies in which these algae have been ubiquitous, this condition has significant implications for the geochemistry and diagenesis of algal limestones throughout most of the Phanerozoic. The crustose coralline algae’s precipitation of high-Mg calcite from seawater that favors the abiotic precipitation of aragonite indicates that these algae dictate the precipitation of the calcitic polymorph of CaCO₃. However, the algae’s nearly abiotic pattern of Mg fractionation in their skeletal calcite suggests that their biomineralogical control is limited to polymorph specification and is generally ineffectual in the regulation of skeletal Mg incorporation. Therefore, the Mg/Ca ratio of well-preserved fossils of crustose coralline algae, when corrected for the effect of seawater temperature, may be an archive of oceanic Mg/Ca throughout the Phanerozoic. Magnesium fractionation algorithms that model algal skeletal Mg/Ca as a function of seawater Mg/Ca and temperature are presented herein. The results of this study support the empirical fossil evidence that secular variation of oceanic Mg/Ca has caused the mineralogy and skeletal chemistry of many calcifying marine organisms to change significantly over geologic time.     

The impact of salinity on the Mg/Ca and Sr/Ca ratio in the benthic foraminifera Ammonia tepida: Results from culture experiments

Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ¹⁸O signal measured on the same material, to calculate the δ¹⁸O_w, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor D_Sr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in D_Mg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The D_Sr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.     

Response of the coccolithophores Emiliania huxleyi and Coccolithus braarudii to changing seawater Mg and Ca concentrations: Mg/Ca, Sr/Ca ratios and δCa, δMg of coccolith calcite

Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ^44/40Ca and Δ^26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L⁻¹, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2σ) independent of species. Partition coefficient of Mg²⁺ increased with increasing seawater Ca²⁺ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr²⁺ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ^26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ^26/24Mg (by >+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.     

Application of calcite Mg partitioning functions to the reconstruction of paleocean Mg/Ca

Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca)^H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates.These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., “aragonite seas”) and lowest when seawater Mg/Ca was low (e.g., “calcite seas”). It follows that, during times of “calcite seas” when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites.     

Controls on ostracod valve geochemistry, Part 1: Variations of environmental parameters in ostracod (micro-)habitats

The variations of environmental conditions (T°, pH, δ¹³C_DIC, [DIC], δ¹⁸O, Mg/Ca, and Sr/Ca) of ostracod habitats were examined to determine the controls of environmental parameters on the chemical and isotopic composition of ostracod valves. Results of a one-year monitoring of environmental parameters at five sites, with depths of between 2 and 70 m, in Lake Geneva indicate that in littoral to sub-littoral zones (2, 5, and 13 m), the chemical composition of bottom water varies seasonally in concert with changes in temperature and photosynthetic activity. An increase of temperature and photosynthetic activity leads to an increase in δ¹³C values of DIC and to precipitation of authigenic calcite, which results in a concomitant increase of Mg/Ca and Sr/Ca ratios of water. In deeper sites (33 and 70 m), the composition of bottom water remains constant throughout the year and isotopic values and trace element contents are similar to those of deep water within the lake. The chemical composition of interstitial pore water also does not reflect seasonal variations but is controlled by calcite dissolution, aerobic respiration, anaerobic respiration with reduction of sulphate and/or nitrate, and methanogenesis that may occur in the sediment pores. Relative influence of each of these factors on the pore water geochemistry depends on sediment thickness and texture, oxygen content in bottom as well as pore water. Variations of chemical compositions of the ostracod valves of this study vary according to the specific ecology of the ostracod species analysed, that is its life-cycle and its (micro-)habitat. Littoral species have compositions that are related to the seasonal variations of temperature, δ¹³C values of DIC, and of Mg/Ca and Sr/Ca ratios of water. In contrast, the compositions of profundal species are largely controlled by variations of pore fluids along sediment depth profiles according to the specific depth preference of the species. The control on the geochemistry of sub-littoral species is a combination of controls for the littoral and profundal species as well as the specific ecology of the species.     

Palaeoenvironmental records from fossil corals: The effects of submarine diagenesis on temperature and climate estimates

The geochemistry of coral skeletons may reflect seawater conditions at the time of deposition and the analysis of fossil skeletons offers a method to reconstruct past climate. However the precipitation of cements in the primary coral skeleton during diagenesis may significantly affect bulk skeletal geochemistry. We used secondary ion mass spectrometry (SIMS) to measure Sr, Mg, B, U and Ba concentrations in primary coral aragonite and aragonite and calcite cements in fossil Porites corals from submerged reefs around the Hawaiian Islands. Cement and primary coral geochemistry were significantly different in all corals. We estimate the effects of cement inclusion on climate estimates from drilled coral samples, which combine cements and primary coral aragonite. Secondary 1% calcite or ∼2% aragonite cement contamination significantly affects Sr/Ca SST estimates by +1 °C and −0.4 to −0.9 °C, respectively. Cement inclusion also significantly affects Mg/Ca, B/Ca and U/Ca SST estimates in some corals. X-ray diffraction (XRD) will not detect secondary aragonite cements and significant calcite contamination may be below the limit of detection (∼1%) of the technique. Thorough petrographic examination of fossils is therefore essential to confirm that they are pristine before bulk drilled samples are analysed. To confirm that the geochemistry of the original coral structures is not affected by the precipitation of cements in adjacent pore spaces we analysed the primary coral aragonite in cemented and uncemented areas of the skeleton. Sr/Ca, B/Ca and U/Ca of primary coral aragonite is not affected by the presence of cements in adjacent interskeletal pore spaces i.e. the coral structures maintain their original composition and selective SIMS analysis of these structures offers a route to the reconstruction of accurate SSTs from altered coral skeletons. However, Mg/Ca and Ba/Ca of primary coral aragonite are significantly higher in parts of skeletons infilled with high Mg calcite cement. We hypothesise this reflects cement infilling of intraskeletal pore spaces in the primary coral structure.     

Calcite dissolution kinetics in Na-Ca-Mg-Cl brines

Sedimentary basins can contain close to 20% by volume of pore fluids commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of migration, dispersive mixing, or anthropogenic injection of CO₂. This study measured calcite dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (50-200 g L⁻¹ TDS). The dissolution rate dependency on brine composition, pCO₂ (0.1-1 bar), and temperature (25.0-82.5 °C) was modeled using the empirical rate equation

R=k(1-Ω)ⁿ     

Search for the proverbial mantle osmium sources to the oceans: Hydrothermal alteration of mid-ocean ridge basalt

We present Os and Sr isotopes and Mg, Os, and Sr concentrations for ridge-crest high-temperature and diffuse hydrothermal fluids, plume fluids and ridge-flank warm spring fluids from the Juan de Fuca Ridge. The data are used to evaluate the extent to which (1) the high- and low-temperature hydrothermal alteration of mid-ocean ridge basalts (MORBs) provides Os to the deep oceans, and (2) hydrothermal contributions of non-radiogenic Os and Sr to the oceans are coupled. The Os and Sr isotopic ratios of the high-temperature fluids (265-353 °C) are dominated by basalts (¹⁸⁷Os/¹⁸⁸Os = 0.2; ⁸⁷Sr/⁸⁶Sr = 0.704) but the concentrations of these elements are buffered approximately at their seawater values. The ¹⁸⁷Os/¹⁸⁸Os of the hydrothermal plume fluids collected ∼1 m above the orifice of Hulk vent is close to the seawater value (=1.05). The low-temperature diffuse fluids (10-40 °C) associated with ridge-crest high-temperature hydrothermal systems on average have [Os] = 31 fmol kg⁻¹, ¹⁸⁷Os/¹⁸⁸Os = 0.9 and [Sr] = 86 μmol kg⁻¹, ⁸⁷Sr/⁸⁶Sr = 0.709. They appear to result from mixing of a high-temperature fluid and a seawater component. The ridge-flank warm spring fluids (10-62 °C) on average yield [Os] = 22 fmol kg⁻¹, ¹⁸⁷Os/¹⁸⁸Os = 0.8 and [Sr] = 115 μmol kg⁻¹, ⁸⁷Sr/⁸⁶Sr = 0.708. The data are consistent with isotopic exchange of Os and Sr between basalt and circulating seawater during low-temperature hydrothermal alteration. The average Sr concentration in these fluids appears to be similar to seawater and consistent with previous studies. In comparison, the average Os concentration is less than seawater by more than a factor of two. If these data are representative they indicate that low-temperature alteration of MORB does not provide adequate non-radiogenic Os and that another source of mantle Os to the oceans must be investigated. At present, the magnitude of non-radiogenic Sr contribution via low-temperature seawater alteration is not well constrained. If non-radiogenic Sr to the oceans is predominantly from the alteration of MORB, our data suggest that there must be a different source of non-radiogenic Os and that the Os and Sr isotope systems in the oceans are decoupled.     

Seawater temperature proxies based on DSr, DMg, and DU from culture experiments using the branching coral Porites cylindrica

In order to investigate the incorporation of Sr, Mg, and U into coral skeletons and its temperature dependency, we performed a culture experiment in which specimens of the branching coral (Porites cylindrica) were grown for 1 month at three seawater temperatures (22, 26, and 30 °C). The results of this study showed that the linear extension rate of P. cylindrica has little effect on the skeletal Sr/Ca, Mg/Ca, and U/Ca ratios. The following temperature equations were derived: Sr/Ca (mmol/mol) = 10.214(±0.229) − 0.0642(±0.00897) × T (°C) (r² = 0.59, p < 0.05); Mg/Ca (mmol/mol) = 1.973(±0.302) + 0.1002(±0.0118) × T (°C) (r² = 0.67, p < 0.05); and U/Ca (μmol/mol) = 1.488(±0.0484) − 0.0212(±0.00189) × T (°C) (r² = 0.78, p < 0.05). We calculated the distribution coefficient (D) of Sr, Mg, and U relative to seawater temperature and compared the results with previous data from massive Porites corals. The seawater temperature proxies based on D calibrations of P. cylindrica established in this study are generally similar to those for massive Porites corals, despite a difference in the slope of D_U calibration. The calibration sensitivity of D_Sr, D_Mg, and D_U to seawater temperature change during the experiment was 0.64%/°C, 1.93%/°C, and 1.97%/°C, respectively. These results suggest that the skeletal Sr/Ca ratio (and possibly the Mg/Ca and/or U/Ca ratio) of the branching coral P. cylindrica can be used as a potential paleothermometer.     

Seasonal dripwater Mg/Ca and Sr/Ca variations driven by cave ventilation: Implications for and modeling of speleothem paleoclimate records

A 4-year study in a central Texas cave quantifies multiple mechanisms that control dripwater composition and how these mechanisms vary at different drip sites. We monitored cave-air compositions, in situ calcite growth, dripwater composition and drip rate every 4-6 weeks. Three groups of drip sites are delineated (Groups 1-3) based on geochemical variations in dripwater composition. Quantitative modeling of mineral-solution reactions within the host carbonate rock and cave environments is used to identify mechanisms that can account for variations in dripwater compositions. The covariation of Mg/Ca (and Sr/Ca) and Sr isotopes is key in delineating whether Mg/Ca and Sr/Ca variations are dictated by water-rock interaction (i.e., calcite or dolomite recrystallization) or prior calcite precipitation (PCP). Group 1 dripwater compositions reflects a narrow range of the extent of water-rock interaction followed by varying amounts of prior calcite precipitation (PCP). Group 2 dripwater compositions are controlled by varying amounts of water-rock interaction with little to no PCP influence. Group 3 dripwater compositions are dictated by variable extents of both water-rock interaction and PCP. Group 1 drip sites show seasonal variations in dripwater Mg/Ca and Sr/Ca, whereas the other drip sites do not. In contrast to the findings of most previous dripwater Mg/Ca-Sr/Ca studies, these seasonal variations (at Group 1 drip sites) are independent of changes in water flux (i.e., rainfall and/or drip rate), and instead significantly correlate with changes in cave-air CO₂ concentrations. These results are consistent with lower cave-air CO₂, related to cool season ventilation of the cave atmosphere, enhancing calcite precipitation and leading to dripwater geochemical evolution via PCP. Group 1 dripwater Mg/Ca and Sr/Ca seasonality and evidence for PCP as a mechanism that can account for that seasonality, have two implications for many other regions where seasonal ventilation of caves is likely: (1) speleothem trace-element records may provide seasonal signals, and (2) such records may be biased toward recording climate conditions during the season when calcite is depositing. Additionally, we use our results to construct a forward model that illustrates the types of speleothem Mg/Ca and Sr/Ca variations that would result from varying controls on dripwater compositions. The model provides a basis for interpreting paleo-dripwater controls from high frequency Mg/Ca and Sr/Ca variations for speleothems from caves at which long term monitoring studies are not feasible.     

Effects of seawater carbonate ion concentration and temperature on shell U, Mg, and Sr in cultured planktonic foraminifera

We investigate the sensitivity of U/Ca, Mg/Ca, and Sr/Ca to changes in seawater [CO₃²⁻] and temperature in calcite produced by the two planktonic foraminifera species, Orbulina universa and Globigerina bulloides, in laboratory culture experiments. Our results demonstrate that at constant temperature, U/Ca in O. universa decreases by 25 ± 7% per 100 μmol [CO₃²⁻] kg⁻¹, as seawater [CO₃²⁻] increases from 110 to 470 μmol kg⁻¹. Results from G. bulloides suggest a similar relationship, but U/Ca is consistently offset by ∼+40% at the same environmental [CO₃²⁻]. In O. universa, U/Ca is insensitive to temperature between 15°C and 25°C. Applying the O. universa relationship to three U/Ca records from a related species, Globigerinoides sacculifer, we estimate that Caribbean and tropical Atlantic [CO₃²⁻] was 110 ± 70 μmol kg⁻¹ and 80 ± 40 μmol kg⁻¹ higher, respectively, during the last glacial period relative to the Holocene. This result is consistent with estimates of the glacial-interglacial change in surface water [CO₃²⁻] based on both modeling and on boron isotope pH estimates. In settings where the addition of U by diagenetic processes is not a factor, down-core records of foraminiferal U/Ca have potential to provide information about changes in the ocean’s carbonate concentration.Below ambient pH (pH < 8.2), Mg/Ca decreased by 7 ± 5% (O. universa) to 16 ± 6% (G. bulloides) per 0.1 unit increase in pH. Above ambient pH, the change in Mg/Ca was not significant for either species. This result suggests that Mg/Ca-based paleotemperature estimates for the Quaternary, during which surface-ocean pH has been at or above modern levels, have not been biased by variations in surface-water pH. Sr/Ca increased linearly by 1.6 ± 0.4% per 0.1 unit increase in pH. Shell Mg/Ca increased exponentially with temperature in O. universa, where Mg/Ca = 0.85 exp (0.096*T), whereas the change in Sr/Ca with temperature was within the reproducibility of replicate measurements.     

Chemical and isotopic constraints on water/rock interactions at the Lost City hydrothermal field, 30°N Mid-Atlantic Ridge

Low temperature vent fluids (<91 °C) issuing from the ultramafic-hosted hydrothermal system at Lost City, 30°N Mid-Atlantic Ridge, are enriched in dissolved volatiles (H₂,CH₄) while attaining elevated pH values, indicative of the serpentization processes that govern water/rock interactions deep in the oceanic crust. Here, we present a series of theoretical models to evaluate the extent of hydrothermal alteration and assess the effect of cooling on the systematics of pH-controlled B aqueous species. Peridotite-seawater equilibria calculations indicate that the mineral assemblage composed of diopside, brucite and chrysotile likely dictates fluid pH at moderate temperature serpentinization processes (<300 °C), by imposing constraints on the aCa⁺⁺/a²H⁺ ratios and the activity of dissolved SiO₂. Based on Sr abundances and the ⁸⁷Sr/⁸⁶Sr isotope ratios of vent fluids reported from Lost City, estimated water/rock mass ratios (w/r = 2-4) are consistent with published models involving dissolved CO₂ and alkane concentrations. Combining the reported δ¹⁸O values of vent fluids (0.7‰) with such w/r mass ratios, allows us to bracket subseafloor reaction temperatures in the vicinity of 250 °C. These estimates are in agreement with previous theoretical studies supporting extensive conductive heat loss within the upflow zones. Experimental studies on peridotite-seawater alteration suggest that fluid pH increases during cooling which then rapidly enhances boron removal from solution and incorporation into secondary phases, providing an explanation for the highly depleted dissolved boron concentrations measured in the low temperature but alkaline Lost City vent fluids. Finally, to account for the depleted ¹¹B composition (δ¹¹B ∼25-30‰) of vent fluids relative to seawater, isotopic fractionation between tetrahedrally coordinated aqueous boron species with BO₃-bearing mineral sites (e.g. in calcite, brucite) is proposed.     

Experimental and natural early diagenetic mobility of Sr and Mg in biogenic carbonates

Ammonium acetate dissolution experiments were performed on shell material of the modern bivalves, Crassostrea virginica (calcite) and Mercenaria mercenaria (aragonite). Their purpose was to determine the order of preferential dissolution of Sr, Mg and Ca; these results subsequently were compared with Sr, Mg and Ca data from other Recent as well as ancient mollusks.Results from these experiments suggest the following relative order of abundance of readily exchangeable Mg and Sr in biogenic carbonates: Mg(arag) > Mg(calc) > Sr(calc) > Sr(arag). It is apparent that incongruent dissolution of minerals with different solubilities cannot entirely explain the observed dissolution patterns for Sr, Mg and Ca in these biogenic carbonates. Secular changes in whole shell Mg and Sr concentrations for Recent and unrecrystallized fossil mollusks suggest an order of “ionic mobility” in diagenesis identical to the order of abundance for readily exchangeable ions found in the NH₄Ac dissolution experiments. It is concluded that this “ionic mobility” is due to a post mortem, early diagenetic (pre-recrystallization) approach to equilibrium with the surrounding chemical environment.     

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and ⁸⁷Sr/⁸⁶Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q_h), based on Cl mass balances, vary from 0.06 to 0.22 m yr⁻¹, resulting in fluid residence times in the terraces of 10-24 yrs.As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO₃ > HCO₃ > SO₄ reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute ⁸⁷Sr/⁸⁶Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and ⁸⁷Sr/⁸⁶Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate.Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R_solute are estimated from linear Na and Si pore weathering gradients b_solute such that

     

Trace/minor element:calcium ratios in cultured benthic foraminifera. Part II: Ontogenetic variation

Ontogenetic (developmental stage) measurements of Mg/Ca and Sr/Ca were made on the benthic foraminifer Bulimina aculeata, which were cultured under controlled physicochemical conditions of temperature, pH, alkalinity, salinity, and trace- and minor-element concentrations. We utilized two methods of ontogenetic sampling—whole specimens progressively increasing in length and laser microdissection of a single specimen with subsequent analysis of dissected portions. A novel high-resolution laser-microdissection (HRLM) method allowed for precise (10 μm) cuts of the foraminiferal tests (shells) along the geometrically complex sutures distinguishing individual chambers. This new microdissection method limited sample loss and cross-contamination between foraminiferal chambers. Little or no variation in D_Sr was observed at different foraminiferal developmental stages. Conversely, D_Mg was enriched during a mid-developmental stage of whole-specimen samples (150-225 μm D_Mg = 1.6 × 10⁻³) compared to earlier and later stages (<150 μm, >225 μm D_Mg = 8.3 × 10⁻⁴). Further analysis of HRLM ontogenetic samples showed a larger, age-dependent D_Mg signature variation. This increase in shell Mg/Ca may contribute substantially to the measured inter-individual variability in Mg/Ca temperature prediction for cultured B. aculeata. Due to relatively large Mg/Ca inter- and intra-individual variability, measuring similar-size foraminiferal samples may improve the precision of paleotemperature prediction. Additionally, partial dissolution of the highest ontogenetically Mg-enriched calcite (D_Mg = 1.3 × 10⁻²-1.6 × 10⁻²) may occur in undersaturated bottom-water environments or during reductive cleaning procedures. Thus, the calcite phases remaining after partial dissolution by either natural or laboratory cleaning processes may not accurately represent the calcification environment.     

The use of O,H, B,Sr and S isotopes for tracing the origin of dissolved boron in groundwater in Central Macedonia,Greece

The groundwater B concentration in Mesozoic karst, Neogene and alluvial aquifers in the West part of Chalkidiki province in Central Macedonia, Greece reaches 6.45 mg L⁻¹, which exceeds the limit of 1 mg L⁻¹, set by the European Union for drinking water. The high B contents have been detected in this area, not only near the shoreline, where seawater intrusion occurs, but also in the inland part of the basin. Multi isotope (²H, ¹⁸O, ³⁴S, ¹⁸O_(SO4), ¹¹B, ⁸⁷Sr/⁸⁶Sr) data from borehole and thermal water springs allow identification of the possible B sources. The B dissolved in groundwater in the Chalkidiki area is mainly geogenic. The low δ¹¹B values, 0–1‰, similar to those of thermal fluids from continental geothermal fields, and the low Cl/B ratio compared to seawater both indicate a geothermal origin for B and reflect deep circulation and interaction with igneous rocks. The ⁸⁷Sr/⁸⁶Sr ratio also indicates that the deep-aquifer granodiorite is the predominant rock source of Sr, while the shallow limestone unit has negligible effects on the dissolved Sr budget in these thermal karst waters which O and H isotopes show to be of meteoric origin. The main source of high B in borehole water is mainly mixing with B-rich geothermal water. The mixing between geothermal water and water from the Neogene aquifer is also reflected by isotopic contents of SO₄.     

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.