The chemistry of orthophosphate uptake from seawater on to calcite and aragonite

The chemistry of orthophosphate uptake from synthetic seawater onto the surfaces of synthetic calcite, aragonite and low-magnesium biogenic calcite has been studied, in order to elucidate the kinetics of the process (generally believed to be the major control of dissolved reactive phosphate in carbonate-rich marine sediments). Our results differ from those obtained by others, who have studied orthophosphate uptake in low ionic strength solutions and at much higher supersaturations relative to apatite.In both ‘free drift’ and chemostat experiments, Mg and F have only a minor effect on the reaction rate. Even at constant solution composition the rate of orthophosphate uptake was found to decrease by 10⁶ over a two week period. The data from the ‘free drift’ experiments can be fitted to the Elovich equation. This indicates that the kinetics observed for this reaction can be explained by an exponential decrease in available surface reaction sites and/or a linear increase in the activation energy associated with chemisorption as the reaction proceeds.     

Americium interaction with calcite and aragonite surfaces in seawater

Observations of the distribution of ²⁴¹Am in the marine environment indicate that Am has a high affinity for solid surfaces. The adsorption of Am onto calcite and aragonite surfaces from seawater and related solutions has been studied, in order to establish the interaction of Am with a major component of many marine sediments. Results indicate that Am is rapidly and strongly adsorbed. This occurs even when both dissolved Am concentrations and solid to solution ratios are low. The minimum value for $\text{K}{}_{\mathrm{D}}$ determined is 2 × 10⁵. Measurements of reaction kinetics established that Am is adsorbed from seawater at 40 times the rate per unit surface area on synthetic aragonite that it is on synthetic calcite. Approximately 15% of the difference is attributable to epitaxial influences, with the remainder being due to enhanced site competition by Mg on calcite relative to aragonite. The adsorption rate is first order with respect to Am concentration, but follows approximately the square root of the solid surface area to solution volume ratio.Adsorption rate of Am on biogenic aragonite and Mg-calcites are, within a given particle size range, close to equal. It is not possible to normalize these adsorption rates to surface area due to the differing microporous structure of biogenic carbonates. The Am adsorption rates on a shallow water calcium carbonate-rich sediment gave results which were predicted from, its mineralogie mixture of components.     

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.     

Calcite and aragonite precipitation from seawater solutions of various salinities: Precipitation rates and overgrowth compositions

The reaction rate and composition of calcite and aragonite overgrowths precipitated from seawater solutions of various salinities (i.e. S=5, 15, 25, 35, 44) were determined at 25°C and 10^−2.5-atm. CO₂ partial pressure using a constant disequilibrium seeded technique. The rate data were fitted to an empirical rate law of the form:

logR=n(ω_{c(or a)}-1)+logk

where n is the empirical reaction order; and k is the rate constant. Calcite precipitation rates in seawater solutions do not vary appreciably as a result of salinity variations over the range investigated, while those for aragonite show an increase in going from the higher (i.e. S=35, 44) to the lower (i.e. S=5, 15, 25) salinity range. This study also confirms previously published findings that above a given saturation state (i.e. Ω_c>/2.6) aragonite precipitates more rapidly than calcite at 25°C.

The incorporation of Sr²⁺ in aragonite and Mg²⁺ in calcite overgrowths are independent of the precipitation rate. The partition coefficient of Sr²⁺ in aragonite is approximately equal to unity and is unaffected by salinity variations between 5 and 44. However, the Mg²⁺ partition coefficient in calcite, increases with decreasing salinity of the parent seawater solutions, possibly as a result of variations in the sulfate content of the solutions and solids.

The experimental results were discussed in the context of a number of geological environments.     

An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures

To determine oxygen isotope fractionation between aragonite and water, aragonite was slowly precipitated from Ca(HCO₃)₂ solution at 0 to 50°C in the presence of Mg²⁺ or SO₄²⁻. The phase compositions and morphologies of synthetic minerals were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The effects of aragonite precipitation rate and excess dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution on oxygen isotope fractionation between aragonite and water were investigated. For the CaCO₃ minerals slowly precipitated by the CaCO₃ or NaHCO₃ dissolution method at 0 to 50°C, the XRD and SEM analyses show that the rate of aragonite precipitation increased with temperature. Correspondingly, oxygen isotope fractionations between aragonite and water deviated progressively farther from equilibrium. Additionally, an excess of dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution results in an increase in apparent oxygen isotope fractionations. As a consequence, the experimentally determined oxygen isotope fractionations at 50°C indicate disequilibrium, whereas the relatively lower fractionation values obtained at 0 and 25°C from the solution with less dissolved CO₂ gas and low precipitation rates indicate a closer approach to equilibrium. Combining the lower values at 0 and 25°C with previous data derived from a two-step overgrowth technique at 50 and 70°C, a fractionation equation for the aragonite-water system at 0 to 70°C is obtained as follows:

     

Deep-sea coral aragonite as a recorder for the neodymium isotopic composition of seawater

Deep-sea corals have been shown to be useful archives of rapid changes in ocean chemistry during the last glacial cycle. Their aragonitic skeleton can be absolutely dated by U-Th data, freeing radiocarbon to be used as a water-mass proxy. For certain species of deep-sea corals, the growth rate allows time resolution that is comparable to ice cores. An additional proxy is needed to exploit this opportunity and turn radiocarbon data into rates of ocean overturning in the past.Neodymium isotopes in seawater can serve as a quasi-conservative water-mass tracer and initial results indicate that deep-sea corals may be reliable archives of seawater Nd isotopes. Here we present a systematic study exploring Nd isotopes as a water-mass proxy in deep-sea coral aragonite. We investigated five different genera of modern deep-sea corals (Caryophyllia, Desmophyllum, Enallopsamia, Flabellum, Lophelia), from global locations covering a large potential range of Nd isotopic compositions. Comparison with ambient seawater measurements yields excellent agreement and suggests that deep-sea corals are reliable archives for seawater Nd isotopes.A parallel study of Nd concentrations in these corals yields distribution coefficients for Nd between seawater and coral aragonite of 1-10, omitting one particular genus (Enallopsamia). The corals and seawater did however not come from exactly the same location, and further investigations are needed to reach robust conclusions on the incorporation of Nd into deep-sea coral aragonite.Lastly, we studied the viability of extracting the Nd isotope signal from fossil deep-sea corals by carrying out stepwise cleaning experiments. Our results show that physical removal of the ferromanganese coating and chemical pre-cleaning have the highest impact on Nd concentrations, but that oxidative/reductive cleaning is also needed to acquire a seawater Nd isotope signal.     

Calcite and aragonite saturation States of Kamaran strait surface seawater, Yemen: summer time

Surface seawater samples from Kamaran Strait of Yemen were collected for physical and chemical parameter determinations. This work reports the results of air and surface seawater temperature, salinity, pH, and total alkalinity measurements. The air temperature ranged from 29.9°C to 36.5°C with an average value of 31.5?±?1.5°C, whereas the seawater surface temperature ranged from 34.0°C to 36.0°C with a mean value of 34.5?±?0.5°C. The salinity was observed to be high, ranging from 38.03 to 38.81 with an average value of 38.45?±?0.22. The pH ranged from 7.74 to 8.27 with a mean value of 8.11?±?0.10. The total alkalinity was found to range from 2.3860 to 2.5000 meq L^?1 with an average value of 2.4288?±?0.0351 meq L^?1. The result of the study showed that there was a negative correlation between the pH and surface seawater temperature and salinity. The surface seawater of the Kamaran Strait was found to be several fold supersaturated with respect to calcium carbonate. The measured percent degree of saturation ranged from 454% to 668% with respect to calcite and from 246% to 361% with respect to aragonite. The lowest value of supersaturation with respect to both calcite and aragonite were found in front of as-Salif port, where human and developmental activities are intensively increased. The visual inspection of coral reefs distribution and their intensity were obviously observed in areas of high value of supersaturation with respect to both minerals, high transparency of seawater column, and low human activities. Further studies are needed to investigate the occurrence, distribution, and mineralogy of corals and the effects of physical and chemical parameters upon their growth in the region.     

Kinetic mechanism of oxygen isotope disequilibrium in precipitated witherite and aragonite at low temperatures: an experimental study

To study what dictates oxygen isotope equilibrium fractionation between inorganic carbonate and water during carbonate precipitation from aqueous solutions, a direct precipitation approach was used to synthesize witherite, and an overgrowth technique was used to synthesize aragonite. The experiments were conducted at 50 and 70°C by one- and two-step approaches, respectively, with a difference in the time of oxygen isotope exchange between dissolved carbonate and water before carbonate precipitation. The two-step approach involved sufficient time to achieve oxygen isotope equilibrium between dissolved carbonate and water, whereas the one-step approach did not. The measured witherite-water fractionations are systematically lower than the aragonite-water fractionations regardless of exchange time between dissolved carbonate and water, pointing to cation effect on oxygen isotope partitioning between the barium and calcium carbonates when precipitating them from the solutions. The two-step approach experiments provide the equilibrium fractionations between the precipitated carbonates and water, whereas the one-step experiments do not. The present experiments show that approaching equilibrium oxygen isotope fractionation between precipitated carbonate and water proceeds via the following two processes:

1.

Oxygen isotope exchange between [CO₃]²⁻ and H₂O:

(1)     

甘南沼泽沉积脂类生物标志化合物的组成特征

较为系统地分析了寒冷潮湿高原气候条件下形成的沼泽泥炭中脂类化合物，研究了它们的组成，来源和成岩过程，结果表明，正构烷烃，正构烯烃，正构脂肪酸，直链烷基酮和直链烷基醇都由长链组分所构成，这些长链组分来自草本植物，并且得到它们单体碳同位素证据的支持，丰富的奥利烯醇和羽扇烷醇均起源于陆源高等植物，存在很少报道过的一系列藿醇化合物，它们起源于细菌，甾酮和甾醇都以C29组分为主，C28和C29组分主要来自高等植物，而27组分则具有一个细菌源。无奇偶优势的短链正构烷烃，细菌起源的脂肪酸（C14，C15，异构和不饱和脂肪酸），直链烷基－2－酮，藿类和一些甾酮的存在，都说明在这种沉积环境中沉积有机质已经历了强烈改造作用。甾烯酮和甾烯醇分别向它们烷烃的化学和生物化学转化也十分明显。     

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.     

The solubility of aragonite in seawater—I. Effect of pH and water chemistry at one atmosphere

The effect of water chemistry on the solubility of aragonite in seawater has been defined experimentally as a series of apparent solubility products measured with respect to pH at one atmosphere.The dominant control of the apparent solubility product of aragonite is the carbonate ion concentration, and this is primarily a function of pH. In the light of this fact, we have reconciled our data with 81 other reported values of aragonite solubility by simply examining the water chemistry of the waters in which they were determined.     

Solubility of aragonite in seawater—II. Effect of pressure on the onset and maintenance of dissolution

The apparent solubility product (K'_sp) of aragonite in a variety of seawater compositions has been determined at pressures from 0 to 1019 atm and a nomogram developed to allow the determination of the K'_sp when the apparent ion product (AIP) at one atmosphere and the collection depth of a water sample are known.This nomogram provides a basis from which the onset of aragonite dissolution can be determined for conditions representative of aragonite sedimentation through the changing water masses of the open ocean.     

Elasticity of single-crystal aragonite by Brillouin spectroscopy

The elastic constants of natural single-crystal aragonite (CaCO₃) have been measured by Brillouin spectroscopy at ambient conditions. The elastic constants C₁₁, C₂₂, C₃₃, C₄₄, C₅₅, C₆₆, C₁₂, C₁₃ and C₂₃ are 171.1±1.0, 110.1±0.9, 98.4±1.2, 39.3±0.6, 24.2±0.4, 40.2±0.6, 60.3±1.0, 27.8±1.6 and 41.9±2.0 GPa, respectively, for aragonite. The linear compressibilities of the a-, b- and c-axis for aragonite at ambient conditions were derived from our measured data to be 3.0±0.2, 4.2±0.2 and 7.3±0.6×10^–3 GPa^–1, respectively. The aggregate bulk and shear moduli for aragonite using the Voigt-Reuss-Hill (VRH) scheme are thus calculated to be 68.9±1.4 and 35.8±0.2 GPa, respectively. The value of bulk modulus is in remarkable contrast to the literature value of 46.9 GPa measured almost a century ago. Our new datum, however, is closer to that derived from recent atomistic simulation and static compression studies.     

The solubility of calcite and aragonite in seawater of 35%. salinity at 25°C and atmospheric pressure

The solubilities of synthetic, natural and biogenic aragonite and calcite, in natural seawater of 35%. salinity at 25°C and 1 atm pressure, were measured using a closed system technique. Equilibration times ranged up to several months. The apparent solubility constant determined for calcite of 4.39(±0.20) × 10^?7 mol² kg^?2 is in good agreement with other recent solubility measurements and is constant after 5 days equilibration. When we measured aragonite solubility we observed that it decreased with increasing time of equilibration. The value of 6.65(±0.12) × 10^?7 mol² kg^?2, determined for equilibration times in excess of 2 months, is significantly less than that found in other recent measurements, which employed equilibration times of only a few hours to days. No statistically significant difference was found among the synthetic, natural and biogenic material. Solid to solution ratio, contamination of aragonite with up to 10 wt% calcite and recycling of the aragonite made no statistically significant difference in solubility when long equilibration times were used.Measured apparent solubility constants of aragonite and calcite are respectively 22( ± 3)% and 20( ± 2)% less than apparent solubility constants calculated from thermodynamic equilibrium constants and seawater total activity coefficients. These large differences in measured and calculated apparent solubility constants may be the result of the formation of surface layers of lower solubility than the bulk solid.     

Compositional variations and morphological evolution in platinum beach placers, southern New Zealand

Morphologies of placer platinum group minerals (PGM) are more variable and resistant to modification during transport than placer gold grains. This study documents morphological evolution of PGM placer grains during up to 120 km of transport in beach placers after river transport from inferred sources up to 200 km inland. PGM morphological changes are calibrated with changes in morphology of associated placer gold. Most of the PGM are Pt-Fe alloy and have been fed into the beach placer system from a large river at the western end of the beaches on the south coast of New Zealand. The incoming fluvial PGM suite includes Os, Ir and Ru alloys which may have been derived from distal ophiolitic sources. More proximal sources have Ural-Alaskan affinities and these contributed cooperite and braggite, or sperrylite, locally, as well as Pt-Fe alloy grains. Some PGM may have been recycled through Cretaceous-Quaternary fluvial sediments before entering the modern placer system. Recycled placer PGM grains have also been derived from elevated Quaternary beaches near the coastline. PGM grains entering beach placers have rough surfaces, with remnants of crystal faces, and these evolve to smooth flakes with progressive long-shore transport. PGM flakes have slightly thickened rims caused by impacts by saltating sand on windy beaches, and the most distal beach placers contain flakes with incipient toroidal shapes. These PGM incipient toroids are poorly developed compared to accompanying well-formed toroidal gold that has developed in nearly all beach placers, including those on elevated Quaternary beaches. Typical PGM and gold placer grain size decreases with increasing distance of transport, from fluvial grain size of 400–1,000 to ～200 microns on the most distal beaches, accompanied by eastward loss of equant PGM grains and associated increase in proportion of flakes. Although net transport distance is ～120 km in the beach placer complex, frequent aeolian transport of grains from beach to dunes and subsequent recycling by storm surges substantially increased total transport distance in a dynamic windy tectonic environment.     

青岛地区晚白垩世基性脉岩中麻粒岩捕虏体的成分特征及其温压条件

青岛地区晚白垩世基性脉岩中含有两类麻粒岩捕虏体,富辉石麻粒岩和富长石麻粒岩.富辉石麻粒岩的主要矿物组合为Opx＋Cpx＋Pl,具有细粒变晶结构;富长石麻粒岩主要矿物组合为Pl＋OpX＋Cpx十Q或Pl＋Opx/Cpx＋Q,具有中粗粒粒状变晶结构.麻粒岩捕虏体中辉石的Mg#较低（＜66）,普通辉石具有富Na贫Ca的特征,与岩浆底侵作用形成的麻粒岩特征接近.二辉石温度计的计算结果显示这些麻粒岩捕虏体的麻粒岩相变质平衡温度在847～910℃之间.结合富长石麻粒岩的地质压力计的计算结果（0.99～1.17GPa）和地温梯度推测出的＂岩石学＂Moho面深度在33～36公里之间,与＂地震＂Moho面深度基本一致.麻粒岩捕虏体中普通辉石的矿物成分和该地区活跃的岩浆活动暗示青岛地区下地壳麻粒岩不同于典型的古老下地壳麻粒岩地体或捕虏体.他们的形成可能是华北克拉通古老麻粒岩与岩浆底侵作用相互作用的结果.