The coprecipitation of strontium,magnesium, sodium,potassium and chloride ions with gypsum. An experimental study

The coprecipitation of Sr²⁺, Mg²⁺, Na⁺, K⁺ and Cl^? into gypsum was studied as a function of temperature, brine concentration and growth rate. The concentrations of the studied cations in the gypsum increase with growth rate (kinetic effect), with a tendency to reach a limiting value at high growth rates. The partition coefficients of Sr tend to increase with brine concentration and decrease with temperature. The partition coefficients of the other cations also decrease with temperature but depend only very slightly on brine concentration. The concentrations of coprecipitated chloride are negligibly small.The coprecipitation behavior is explained in terms of the relation between the rate of desorption of the coprecipitating ions from the surface of the growing crystal, and the rate of growth. The studied cations may substitute for Ca²⁺ in its normal lattice sites and/or reside in interstitial positions among the structural water molecules. The relative amount of foreign cations occupying interstitial positions increases with increasing growth rate.The elucidation of the behavior of coprecipitated ions in gypsum given here forms a basis for the utilization of these ions as geochemical indicators for the environment of deposition of gypsum. These indicators may help in reconstructing important parameters such as temperature, brine concentration and growth rate.     

Mechanisms for anhydrite and gypsum formation in the Kuroko massive sulfide–sulfate deposits,north Japan

The Sr, Ba, and rare earth elements (REEs) concentrations and Sr isotopic composition of anhydrite and gypsum have been determined for samples from the Matsumine, Shakanai, and Hanaoka Kuroko-type massive sulfide–sulfate deposits of northern Japan to evaluate the mechanisms of sekko (anhydrite and gypsum) ore formation. The Sr isotopic compositions of the samples fall in the range of 0.7077–0.7087, intermediate between that for middle Miocene (13–15 Ma) seawater (0.7088) (Peterman et al., Geochim Cosmochim Acta, 34:105–120, 1970) and that for country rocks (e.g., 0.7030–0.7050) (Shuto, Assn Geol Collab Japan Monograph 18:91–105, 1974). The Kuroko anhydrite samples exhibit two types of chondrite-normalized REE patterns: one with a decrease from light REEs (LREEs) to heavy REEs (HREEs) (type I), and another with a LREE-depleted pattern (type II). Based on the Sr content and isotopic ratio (assuming an Sr/Ca (mM/M) of 8.7 for seawater), anhydrite is considered to have formed by mixing of preheated seawater with a hydrothermal solution of Sr/Ca (mM/M) = ca. 0.59–1.36 under the condition in which the partition coefficient (Kd) ranges between ca. 0.5 and 0.7. This results in the formation of anhydrite with higher Sr content with an Sr isotopic value close to that of seawater under seawater-dominant conditions. Larger crystals of type II anhydrite are partly replaced by smaller ones, indicating that anhydrite dissolution and recrystallization occurred after or during the formation of sekko ore. Gypsum, which partially replaces anhydrite in the Kuroko deposits, also exhibits two distinct chondrite-normalized REE patterns. Because LREEs are likely to be more readily mobilized during dissolution and recrystallization, it is hypothesized that LREEs are leached from type I anhydrite, resulting in the formation of type II anhydrite with LREE-depleted profiles.     

Strontium distribution and celestite occurrence in Zechstein (Upper Permian) anhydrites of West Poland

The previous study showed that the Zechstein (Upper Permian) anhydrites have about 0.2% strontium with a remarkably small sample scatter. Our study of three lower Zechstein anhydrite units (Lower Anhydrite, Upper Anhydrite and Basal Anhydrite) from West Poland indicate that although often the Sr content is 0.1–0.2%, there are common deviations. In particular, a considerable part (28%) of the studied samples is characterized by lower values (<0.1%), and on the other hand ca. 15% of samples are Sr-enriched, and in those samples celestite was recorded. Particular anhydrite levels differ especially in the frequency of samples showing great Sr content. The greatest variation was found in the Lower Anhydrite. This agrees well with the conclusion derived from the sedimentological studies indicating that there was the greatest differentiation of depositional environments during the deposition of the Lower Anhydrite. The Sr content is a good indicator of brine concentration during the gypsum precipitation and it seems that the subsequent gypsum–anhydrite transformation itself does not affect the strontium distribution. The histograms of Sr content in the Basal Anhydrite indicate a slightly higher brine concentration than it was during the Lower Anhydrite deposition, and the latter in turn was higher than brine concentration during the Upper Anhydrite sedimentation. Celestite veins are clearly diagenetic in origin. The form of celestite occurrence and the increased strontium content (1% or more) indicate an additional source of ions that occurred outside the anhydrite series. In the case of the Lower Anhydrite, the supposed additional source of Sr was related to aragonite-to-calcite transition and squeezing of CaCl₂ brines from reefs into anhydrite series due to increased pressure. For the Basal Anhydrite this source could be related to brines derived from the Older Halite deposits.     

膏岩三轴压缩试验及高温相变特征研究

采用伺服刚性试验机对天然膏岩开展三轴压缩试验,研究了温度及围压对膏岩强度及变形特性的影响。结果表明,膏岩在不同围压下均具有良好的塑性流动特性,加载后无明显的剪切破坏面,而是出现明显的侧向膨胀。根据三轴试验结果,利用摩尔-库仑定律得到了膏岩的强度准则及抗剪强度参数。升高温度导致膏岩强度降低,且高温下石膏发生晶型转变,从二水石膏脱水转变为半水石膏,利用扫描电镜和X衍射对此过程进行了研究。脱水过程导致瞬间孔隙应力增加,膏岩破坏特性由延性转变为脆性。随着持续加载,破裂断面逐渐愈合。膏岩显著的塑性流动能力及快速的裂隙愈合能力对于天然气盖层的封闭稳定性具有重要意义。     

The dehydration process of gypsum under high pressure

The effects of pressure on the dehydration of gypsum materials were investigated up to 633 K and 25 GPa by using Raman spectroscopy and synchrotron X-ray diffraction with an externally heated diamond anvil cell. At 2.5 GPa, gypsum starts to dehydrate around 428 K, by forming bassanite, CaSO₄ hemihydrate, which completely dehydrates to γ-anhydrite at 488 K. All the sulphate modes decrease linearly between 293 and 427 K with temperature coefficients ranging from −0.119 to −0.021 cm⁻¹ K⁻¹, where an abrupt change in the ν₃ mode and in the OH-stretching region indicates the beginning of dehydration. Increasing the temperature to 488 K, the OH-stretching modes completely disappear, marking the complete dehydration and formation of γ-anhydrite. Moreover, the sample changes from transparent to opaque to transparent again during the dehydration sequence gypsum-bassanite-γ-anhydrite, which irreversibly transforms to β-anhydrite form at 593 K. These data compared with the dehydration temperature at room pressure indicate that the dehydration temperature increases with pressure with a ΔP/ΔT slope equal to 230 bar/K. Synchrotron X-ray diffraction experiments show similar values of temperature and pressure for the first appearance of bassanite. Evidence of phase transition from β-anhydrite structure to the monazite type was observed at about 2 GPa under cold compression. On the other hand at the same pressure (2 GPa and 633 K), β-anhydrite was found, indicating a positive Clausis-Clayperon slope of the transition. This transformation is completely reversible as showed by the Raman spectra on the sample recovered after phase transition.     

Gypsum: a review of its role in the deterioration of building materials

The deterioration of buildings and monuments by gypsum is the result of crystallization cycles of this salt. Although gypsum can dehydrate to a hemihydrate, the mineral bassanite, and to an anhydrate, the mineral anhydrite, this reaction occurs in nature on a geological time scale and therefore it is unlikely to occur when gypsum is found on and in building materials. The CaSO₄–H₂O system appears deceptively simple, however there are still discrepancies between the experimental and thermodynamically calculated data. The reason for the latter can be attributed to the slow crystallization kinetics of anhydrite. Apart from this, the large numbers of studies carried out on this system have focused on industrially important metastable phases, such as the hemihydrate and soluble anhydrite. The paper presents a review of the studies dealing with the phase equilibria of the CaSO₄–H₂O system as well as the influence of other salts on the solubility of gypsum. It tries to glean out the relevant information that will serve to explain the deterioration observed on building materials by the crystallization of gypsum and thus allows developing improved conservation methods.     

察尔汉盐湖的半水石膏及其成因分析

本文对自然界极为少见、产于青海柴达木盆地的半水石膏的矿物特征进行了详细研究,并引用实际资料及理论依据,对其成因进行了探讨。     

马海盆地深部孔隙卤水矿床水化学特征及成因

通过数理统计、聚类以及离子特征系数等分析方法,对柴达木马海盆地的深部砂砾石层孔隙卤水水化学特征进行了分析。卤水离子浓度空间分布特征表现为pH、Cl^-、TDS和Na+浓度值变化范围较小,分布均匀,而K^+、Rb^+以及Br^-、Mg^2+、Li^+、Sr^2+、I^-、B2O3、Ca^2+、Cs^+、NO3^-、SO4^2-等离子浓度分布不均匀,差异显著;Cl^-、TDS、Na^+、K^+、Mg^2+和Li^+与SO4^2-聚为一个亚类,表明卤水演化过程中有酸性液体的参与;K^+含量自西向东有增大的趋势,与Mg^2+和Li^+的变化具有相关性;离子特征系数反映出蒸发残余及盐岩溶解的多源性特征。研究区水化学类型为单一的氯化钠型,这种单一的物源可能与推测的更新统下伏盐岩层有关。     

Anhydrite–gypsum transition in the argillites of flooded salt workings in eastern France

This study aims at understanding the physico-chemical interactions between the saturated brine and the rocks enclosing the underground salt workings in Lorraine (eastern France). These anhydrite-rich and argillaceous rocks were characterized in terms of mineralogy, micro-texture and connected porosity. Then, the two main lithofacies, massive anhydrite and anhydrite-rich argillite, were immersed in brine during more than 1 year. During this batch experiment, the argillites were affected by macroscopic splitting, contrarily to the massive anhydrite. Micro-texture and brine chemical analyses clearly show the swelling due to the hydration of anhydrite into gypsum inside the argillites, whereas hydration occurs superficially on the massive anhydrite, due to its very low permeability. Anhydrite–gypsum transformation is promoted by the presence of dissolved strontium and potassium in saturated brine. The low activity of water in saturated brine does not allow the clay fraction to swell significantly during the experiment. Thus, the expansion resulting from the hydration of anhydrite into gypsum might be responsible of the splitting of argillite in a saturated brine environment. The superficial anhydrite hydration on massive anhydrite can be explained by the low amount of connected porosity (less than 1%).     

Das geochemische Verhalten des Strontiums bei der Genese und Diagenese von Ca-Karbonat- und Ca-Sulfat-Mineralen

Experimental partioning of Sr between solutions, aragonite, calcite, gypsum and anhydrite show that the isomorphous replacement of Ca²⁺ by Sr²⁺ can be described as a linear function. The constants of the distributions are used to calculate primary Sr-contents of the various Ca-carbonates and Ca-sulfates precipitated from seawater and to estimate the point of precipitation of celestite. Comparism of these data with actual Sr-contents in sediments and sedimentary rocks show that in most cases gypsum has to be considered as the primary precipitate. Anhydrite in general is formed by diagenetic alteration of gypsum. The average Sr-content of gypsum rocks make it very probable that the Sr-concentration of seawater has stayed virtually unchanged since the end of Mesozoic. Sr-contents of carbonate rocks show that most of the limestones have been altered diagenetically. The distribution of Sr within the various sedimentary units of the earth's crust make it very probable that this alteration occurred in a system open to pore solutions.     

Circumgranular bassanite in a gypsum crust from eastern Algeria – a potential palaeosurface indicator

Detrital sand grains are surrounded by thin bassanite coatings in the upper part of a coarse-crystalline gypsum crust from the Algerian Sahara. The bassanite developed by topotactic replacement of the surrounding gypsum in the absence of a liquid phase. Heating experiments using a gypsum crystal with sand inclusions produced similar patterns and textures. In one experiment, bassanite developed around quartz and carbonate grains but not along the sides of the heated gypsum crystal. This is the result of differences in heat capacity between gypsum, quartz and calcite. Bassanite formation in the crust from Algeria was not controlled by differences in thermal properties. Instead, the bassanite apparently formed under conditions of thermal equilibrium. The occurrence of bassanite as circumgranular coatings in the crust is interpreted as being related to the availability of submicroscopic space along the contact between the gypsum cement and the enclosed sand grains. The presence of coatings of this type, or derived relict features, is a potential criterion for the recognition of palaeosurfaces.     

Coprecipitation of radionuclides with calcite: estimation of partition coefficients based on a review of laboratory investigations and geochemical data

Coprecipitation of radionuclides with secondary solids is currently neglected in safety assessments for radioactive waste repositories, although this process is thought to be important in limiting radionuclide solution concentrations. This paper provides a systematic review of laboratory data on metal coprecipitation with calcite, presented in the form of phenomenological partition coefficients. The aim of this investigation is to provide a consistent set of parameter values for the quantitative modelling of radionuclide coprecipitation with calcite, which will be the dominant alteration product in cementitious repositories accessed by carbonate-rich groundwater.From the data reviewed, empirical correlations have been derived that relate experimentally determined partition coefficients (λ_Me) to measurable chemical properties of the coprecipitated metals (ionic radii and sorption parameters of the incorporated trace metals, solubility products of the pure metal carbonates). These correlations have then been used to predict the partition coefficients of radionuclides for which no laboratory data exist.Such predictions indicate that the actinides will partition strongly into calcite under reducing conditions (λ_Me ∼200–1000 for trivalent, λ_Me ∼20–200 for tetravalent actinides). Nickel(II) incorporation will be moderate (λ_Me ∼1–10), while incorporation of ions like U(VI), Cs(I), Sr(II) and Ra(II) in calcite will be weak (λ_Me<1).In spite of substantial uncertainties, the estimated partition coefficients are sufficiently accurate to allow a semi-quantitative evaluation of the effect of radionuclide coprecipitation with calcite in limiting radionuclide solution concentrations in well characterised repository environments.     

Formation and chemical evolution of magnesium chloride brines by evaporite dissolution processes—Implications for evaporite geochemistry

The evolution of magnesium chloride brines with high bromide contents via a multistage reaction and dissolution process has been studied in brine seeps of a German potash mine. The observed chemical trends and phase equilibria can be modeled and interpreted in terms of a NaCl solution (cap rock brine) infiltrating into a potash zone characterized by the metamorphic mineral assemblage kieserite + sylvite + halite + anhydrite. Establishment of a persistent, stable equilibrium assemblage and constant fluid composition in the invariant point IP1 of the six component (Na-K-Mg-Ca-Cl-SO₄-H₂O) system of oceanic salts is prevented by the perpetually renewed input of NaCl-brine and by the intermittent exposure of incompatible kieserite. Instead, the solutions develop towards the metastable invariant point IP1(gy), with the mineral assemblage carnallite + polyhalite + sylvite + halite + gypsum, where gypsum takes the place of anhydrite (stage I). The temporary exposure of kieserite and the ensuing formation of polyhalite effectively buffer the solutions along the metastable polyhalite phase boundary during stages II and III. Eventually, in stage IV, polyhalite becomes depleted and admixture of more NaCl brine leads to low sulfate solution compositions, which are now only constrained by carnallite + sylvite + halite, and the once hexary system degenerates to a quaternary one (Na-K-Mg-Cl-H₂O) in point E. Bromide in brines shows equilibrium partitioning with respect to the wall rock minerals. The pattern of evolving brine compositions may serve as a model for similar brine occurrences, which in some cases may have been misinterpreted as remains of fossil, highly concentrated and chemically modified seawater. Similar magnesium chloride brines of salt lakes (e.g., Dead Sea, Dabusun Lake) show subtle differences and are constrained by fewer mineral equilibria (more degrees of freedom), and their low sulfate contents are due to gypsum precipitation, driven by calcium chloride input from dolomitization reactions. Finally, the observed reaction sequence is generalized, and a model for the formation of magnesium sulfate depleted, chloride-type potash salts and bischofite deposits by leaching of sulfate-type evaporites is proposed.     

The origin and significance of groundwater-seepage gypsum from Bristol Dry Lake, California, USA

Gypsum and anhydrite fabrics observed in trenches and deep (500 m) cores from Bristol Dry Lake, California, USA, exhibit a vertical alignment of crystals similar to the fabric seen in bottom-nucleated brine pond gypsum. However, geochemical and sedimentological evidence indicate that the gypsum formed in Bristol Dry Lake precipitated displacively within the sediment where groundwater saturated with respect to gypsum recharges around the playa margin (groundwater-seepage gypsum). Evidence for displacive growth of gypsum is: (i) the geometry of the deposit, (ii) stable isotopic data and the water chemistry of the brine, and (iii) inclusions of matrix which follow twin planes and completely surround crystals as they grow. The bulk of the gypsum precipitated in the playa occurs around the edges of the playa in the playamargin facies and completely rings the lake. Sulphate concentrations in the groundwater increase toward the gypsum zone in the playa margin. Basinward of this zone, sulphate concentrations decrease sharply to trace element levels in the basin centre brine. Authigenic gypsum is rare in the centre of the playa. Stable (δ¹⁸O values measured for gypsum waters of crystallization (GWC) are similar to the values calculated for groundwater in the playa margin and alluvial fan sediments (?– 6%0), whereas measured brine δ¹⁸O values range from + 0·5 to + 3·7%0. Deuterium values measured for groundwater are ?– 70%0, GWC are ?– 60 to – 65%0 and brine values are ?– 57%0. The geometry of the deposit and the chemical data suggest that the water precipitating the gypsum is more closely associated with the groundwater than the brine. However, some mixing between groundwater and brine is likely. Within 100 m of the surface, the gypsum dehydrates to anhydrite, although the same vertically aligned fabric is retained through the diagenetic process. The similarity of displacive vertically aligned gypsum and anhydrite fabrics seen in Bristol Dry Lake to subaqueously deposited gypsum in modern brine ponds indicates that the criteria used to define subaqueous fabrics must be better constrained.     

四川盆地三叠系杂卤石形成条件的实验研究

四川盆地三叠系杂卤石有很大一部分产于硬石膏层中,与硬石膏互层。在许多杂卤石产出层位,缺失钾镁盐甚至石盐等易溶盐类。上述现象用已有的研究资料难以解释。本文通过100多个实验点的平衡实验,研究了35℃ K—Na—Mg—Ca—SO_4—Cl—H_2O六元海水体系中,NaCl及K、Mg盐均不饱和条件下杂卤石形成的可能性。与饱和溶液相比,不饱和溶液中杂卤石稳定区收缩。但在饱和溶液被稀释将近1倍时,杂卤石仍有一定的稳定范围。 在实验研究的基础上分析了四川盆地三叠系含杂卤石剖面的成因。由于成盐期卤水频繁地被淡化,形成“石膏——石盐+钾镁盐——石膏”沉积韵律。成岩作用中盐层遭受来自石膏层的水的溶滤。在石膏层较厚,盐层较薄的层段,石盐和钾镁盐可被全部溶掉,形成对NaCl及K、Mg盐均不饱和的液体。当这种对易溶盐类不饱和的液体进入膏层,部分K、Mg组分就能与CaSO_4结合生成杂卤石被保留下来,形成现在所看到的“硬石膏一杂卤石——硬石膏”剖面。     

Mineral equilibria in a six-component seawater system,Na-K-Mg-Ca-SO4-Cl-H2O,at 25°C

Phase relations in the 6-component system Na-K-Mg-Ca-SO₄-Cl-H₂O have been calculated for halite saturation, 25°C and 1 atm pressure. Using a Jänecke projection with the apices Ca-Mg-K₂-SO₄, 27 stable invariant points have been located which are connected by 69 univariant curves. Polyhalite is the only quaternary solid, but anhydrite occupies the bulk of the interior tetrahedral space. Consequently, 24 of the invariant points lie very close to the Ca-free base, Mg-K₂-SO₄. The remaining three points involve tachyhydrite and/or antarcticite. All points but two (20,27) represent peritectic conditions. Metastable equilibria have been calculated for the Ca-free system and yield relations corresponding to the solar diagram.Seawater lies in the subspace anhydrite-halite-carnallite-kieserite-bischofite (point 20) and its evaporation has been discussed for conditions of equilibrium and fractional crystallization. After gypsum is converted to anhydrite, halite precipitates. The next phase, under equilibrium conditions, is glauberite, crystallizing at the expense of anhydrite. Continued evaporation leads to glauberite resorption and eventual replacement by polyhalite. Then follow the magnesium sulfates epsomite, hexahydrite and kieserite, which are joined by carnallite. Polyhalite is replaced by anhydrite and bischoflte is added at the final invariant condition. Kainite does not appear as a primary phase under equilibrium conditions, but it is an important phase during fractional crystallization, where Ca-phases are not allowed to back-react with the brine.Up to the appearance of glauberite, thickness ratios of halite: anhydrite couplets (equilibrium or fractionation) can vary from 0 to 7, the relative amount of halite increasing with more intense evaporation. During evaporation, the activity of H₂O decreases from 0.98 (seawater) to 0.34 (final invariant brine). The data provided can be used to evaluate the effects of mineral precipitation, evaporation and brine mixing for a wide variety of natural brines.     

Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998     

Correlated trace element “vital effects” in tropical corals: A new geochemical tool for probing biomineralization

Micron-scale variations in the trace-element (TE) composition of tropical coral skeletons were measured using laser-ablation ICP-MS (LA-ICP-MS) as part of an investigation into the chemical processes underlying paleoenvrionmental proxy reconstructions. Fluctuations in B, Mg, Sr, Ba and U were measured at high spatial resolution in two Porites corals from the Great Barrier Reef (Australia), and the fine-scale fluctuations (< ∼1.0 mm) were compared with seasonal TE cycles in a third coral. Fine-scale TE variations were found to have a large amplitude over distances corresponding to less than 1 month growth. Variations were quasi-periodic and appeared to have characteristic wavelengths on weekly (6-7 d) and monthly (28 d) scales, although periodicity was not continuous and variations could not be matched either within or between individual corallites. Fine-scale variations between Mg, Sr and U were significantly correlated with each other (Sr and U are positively correlated, but negatively correlated with Mg). This 3D correlation “vector” has the same slope as the seasonal-scale Mg, Sr and U correlations, suggesting that the same chemical/biologic biomineralization process mediates trace element variations at both timescales. Importantly, the fine-scale variations are too large to be caused directly by daily to monthly fluctuations in sea-surface temperature. This means that seasonal variations in these elements cannot reflect purely inorganic temperature-dependent coprecipitation. Models of physicochemical calcification were developed to test whether changes in calcification rate could explain the trace-element correlations. The calculations show that increases in calcification rate will result in correlated decreases in all TE/Ca ratios. The models reproduce the Sr partition coefficient, trace-element correlation slopes, and amplitude of fine-scale variations for an average calcifying pH of 8.5, varying by ±0.2 pH units. The models, however, predict U partition coefficients which are too low, and cannot reproduce the negative correlation between Mg and the other trace elements, which may be caused by crystallographic factors.     

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.     

Evaporative evolution of a Na–Cl–NO<Subscript>3</Subscript>–K–Ca–SO<Subscript>4</Subscript>–Mg–Si brine at 95 °C: Experiments and modeling relevant to Yucca Mountain,Nevada

A synthetic Topopah Spring Tuff water representative of one type of pore water at Yucca Mountain, NV was evaporated at 95°C in a series of experiments to determine the geochemical controls for brines that may form on, and possibly impact upon the long-term integrity of waste containers and drip shields at the designated high-level, nuclear-waste repository. Solution chemistry, condensed vapor chemistry, and precipitate mineralogy were used to identify important chemical divides and to validate geochemical calculations of evaporating water chemistry using a high temperature Pitzer thermodynamic database. The water evolved toward a complex "sulfate type" brine that contained about 45 mol % Na, 40 mol % Cl, 9 mol % NO₃, 5 mol % K, and less than 1 mol % each of SO₄, Ca, Mg, ∑CO₂(aq), F, and Si. All measured ions in the condensed vapor phase were below detection limits. The mineral precipitates identified were halite, anhydrite, bassanite, niter, and nitratine. Trends in the solution composition and identification of CaSO₄ solids suggest that fluorite, carbonate, sulfate, and magnesium-silicate precipitation control the aqueous solution composition of sulfate type waters by removing fluoride, calcium, and magnesium during the early stages of evaporation. In most cases, the high temperature Pitzer database, used by EQ3/6 geochemical code, sufficiently predicts water composition and mineral precipitation during evaporation. Predicted solution compositions are generally within a factor of 2 of the experimental values. The model predicts that sepiolite, bassanite, amorphous silica, calcite, halite, and brucite are the solubility controlling mineral phases.