Removal of trace elements from landfill leachate by calcite precipitation

Spontaneous precipitation of secondary calcite (CaCO₃) has been observed in 25 samples of landfill leachate-polluted stream waters. During the 6-month precipitation experiment, the formation of calcite acts as a principal trace-element scavenging process. The concentrations of Fe, Sr, Ba and Mn and other trace elements in solution significantly decreased as calcite formed during the experiments. The PHREEQC-2 geochemical code indicated high supersaturation of the initial leachate-polluted waters with respect to calcite. The chemical/mineralogical study (SEM/EDS, XRD, ICP MS) revealed that this newly formed calcite contains considerable amounts of metals and metalloids removed from solution. Such a geochemical process can be considered to be important for spontaneous decontamination in landfill-affected environments (stream sediments, soils) or landfill technical facilities (settling basins). This removal takes place especially during dry periods with low rain precipitation, when the landfill waters exhibit both higher alkalinity and higher trace element concentrations.     

Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions

A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R_p) to the gross forward precipitation rate (R_f), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R_p has been experimentally measured under varying conditions, but the magnitude of R_f is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R_f can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R_b or k_b), since at equilibrium R_f = R_b, and R_p = 0. Hence it can be inferred that R_f ≈ R_p + R_b. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R_p (=R_f − R_b) ? R_b. For precipitation rates high enough that R_p ? R_b, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R_p ≈ R_b for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R_f for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R_p. Allowing R_b to vary as , consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R_b is constant. This model can account for most of the experimental data in the literature on the dependence of ⁴⁴Ca/⁴⁰Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for ¹⁸O/¹⁶O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R_b on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.     

Sorption and catalytic oxidation of Fe(II) at the surface of calcite

The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO₃Fe⁺ and >CO₃FeCO₃H⁰. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t_1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t_1/2 = 41 ± 1 min and t_1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO₃FeCO₃H⁰, for which the species specific rate constant was estimated.     

An experimentally verified model for calcite precipitation in veins

Calcite is commonly found as a vein-filling mineral in rocks. However, the factors controlling its deposition are complex and not well understood in quantitative terms. In order to advance our understanding of the processes involved, we have refined the model for calcium carbonate mass transport in subsurface carbonate rocks of Morse and Mackenzie (1993) and developed a new experimental technique to test it. This technique uses a flow-through reactor that simulates a vein opening. Agreement was observed between model predictions and experimental observations for the deposition of calcite in synthetic veins. The influences of surface area to solution volume ratio, solution saturation state with respect to calcite, and flow velocity were well predicted by the model.

The model predicts that in order to have a fairly uniform deposition of calcite within a vein, solution flow must be quite rapid (tens to thousands of cm h⁻¹) or the solution must be only slightly supersaturated with respect to calcite. A low degree of solution supersaturation demands what may be unreasonably large volumes of solution flow to achieve vein filling for the vein configuration we have studied.     

Hyperfiltration-induced precipitation of calcite

Hyperfiltration is sometimes cited as a mechanism to explain high degrees of calcite cementation at shale/sandstone contacts. To test this cementation mechanism, a series of experiments were performed in which solutions undersaturated with respect to calcite were hydraulically forced through a Ca-bentonite at different flow rates. Calcite precipitate was observed on the bentonite membrane from hyperfiltrated stock solutions having initial calcite saturation indices of 0.91 and 0.59. Supersaturation conditions at the clay's high-pressure interface are likely provided by establishment of a concentration polarization layer.In the subsurface, the driving force for hyperfiltration is a differential hydraulic pressure gradient acting across a shale membrane. This hydraulically-induced flux of solution causes a build-up of solute at the shale's high-pressure interface to levels that may exceed saturation indices of common cementing minerals like calcite. Although the source of the hydraulic pressure is likely due to compaction within the sedimentary pile, directional flow constraints suggest that hyperfiltration-induced precipitation of calcite occurs at sand/shale boundaries away from areas of active compaction.     

A model for the distribution of trace elements between calcite and dolomite

A crystal-growth model is proposed, which allows ions of a trace element to enter the Ca and Mg sites of dolomite in proportion to the size of the ions relative to that of Ca and Mg ions, and which assigns equal portions of the trace element to the Ca site of dolomite and the Ca site of associated calcite. The model produces calcite/dolomite distribution coefficients of 0.79 for Mn and 0.43 for Fe, which may be compared with 0.85 and 0.28 as observed in marble, and a distribution coefficient of 2.0 for Sr and Ba, which may be compared with observed values of 2.3 for Sr and 1.8 for Ba.     

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

The rate of Cd²⁺ sorption by calcite was determined as a function of pH and Mg²⁺ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO₃. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca²⁺ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd²⁺ sorption decrease with increasing pH or with increasing Mg²⁺. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer.A model is presented which is consistent with the rates of Cd²⁺ sorption and Ca²⁺ isotopic exchange. In the model, the first step in Cd²⁺ sorption involves a fast adsorption reaction that is followed by diffusion of Cd²⁺ into a surface layer of hydrated CaCO₃ that overlies crystalline calcite. Desorption of Cd²⁺ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO₃, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution.     

Sorption and desorption of arsenate and arsenite on calcite

The adsorption and desorption of arsenate (As(V)) and arsenite (As(III)) on calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic concentrations were kept low (<33 μM) to avoid surface precipitation. The results show that little or no arsenite sorbs on calcite within 24 h at an initial As concentration of 0.67 μM. In contrast, arsenate sorbs readily and quickly on calcite. Likewise, desorption of arsenate from calcite is fast and complete within hours, indicating that arsenate is not readily incorporated into the calcite crystal lattice. The degree of arsenate sorption depends on the solution chemistry. Sorption increases with decreasing alkalinity, indicating a competition for sorption sites between arsenate and (bi)carbonate. pH also affects the sorption behavior, likely in response to changes in arsenate speciation or protonation/deprotonation of the adsorbing arsenate ion. Finally, sorption is influenced by the ionic strength, possibly due to electrostatic effects. The sorption of arsenate on calcite was modeled successfully using a surface complexation model comprising strong and weak sites. In the model, the adsorbing arsenate species were and . The model was able to correctly predict the adsorption of arsenate in the wide range of calcite-equilibrated solutions used in the batch experiments and to describe the non-linear shape of the sorption isotherms. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not sorb on calcite, will dominate and, hence, As will be highly mobile. In contrast, when conditions are oxidizing, arsenate is the predominant species and, because arsenate adsorbs strongly on calcite, As mobility will be significantly retarded. The estimated retardation factors for arsenate in carbonate aquifers range from 25 to 200.     

Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3 h) and low concentrations of phosphate (?50 μM). Sorption of phosphate on calcite was studied in 11 different calcite-equilibrated solutions that varied in pH, P_CO2, ionic strength and activity of Ca²⁺, and . Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2-3 h while desorption is complete in less than 0.5 h. The reversibility of the sorption process indicates that phosphate is not incorporated into the calcite crystal lattice under our experimental conditions. Precipitation of phosphate-containing phases does not seem to take place in systems with ?50 μM total phosphate, in spite of a high degree of super-saturation with respect to hydroxyapatite (SI_HAP ? 7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the activity decreases (at constant pH) and as pH increases (at constant activity). The primary effect of ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. The experimental results were modeled satisfactorily using the constant capacitance model with >CaPO₄Ca⁰ and either >CaHPO₄Ca⁺ or > as the adsorbed surface species. Generally the model captures the variation in phosphate adsorption onto calcite as a function of solution composition, though it was necessary to include two types of sorption sites (strong and weak) in the model to reproduce the convex shape of the sorption isotherms.     

Toward a conceptual model of the calcite surface: hydration,hydrolysis, and surface potential

Because of a recent increase in interest in the properties of the calcite surface, there has also been an increase in activity toward development of mathematical models to describe calcite’s surface behaviour, particularly with respect to adsorption and precipitation. For a mathematical model to be realistic, it must be based on a sound conceptual model of atomic structure at the interface. New observations from high resolution techniques have been combined with previously published data to resolve the apparent conflict with results from electrokinetic studies and to present a picture of what the calcite surface probably looks like at the atomic scale.In ultra-high vacuum (10⁻¹⁰ mbar), a cleaved surface remains unreacted for at least an hour, but the unreacted surface does not remain as a termination of the bulk structure. X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and atomic force microscopy (AFM) show that the outer-most atomic layer relaxes and the surface slightly restructures. In air, dangling bonds are satisfied by hydrolysed water. XPS and time-of-flight secondary ion mass spectrometry (TOF-SIMS) reveal the presence of adsorbed OH and H. In AFM images, the features so typical of calcite, namely, alternate-row offset, pairing and height difference, as well as the consistent dependence of these features on the force and direction of tip scanning, are best explained by OH filling of the vacant O sites created during cleavage on the Ca octahedra. Thus there is solid evidence to indicate the presence of OH and H chemi-sorbed at the termination of the bulk calcite structure.Wet chemical studies, however, show that calcite’s pH_pzc (zero point of charge) varies with sample history and solution composition. Electrophoretic mobility measurements indicate that the potential-determining ions are not H⁺ and OH⁻, but rather Ca²⁺ and CO₃²⁻ (or HCO₃⁻ or H₂CO₃⁰). This apparent conflict is resolved by a slight modification of the electrical double layer (EDL) model. At the bulk termination, hydrolysis species are chemi-bonded. At the Stern layer, adsorption attaches Ca²⁺ and CO₃²⁻ (or other carbonate species), but the hydrolysis layer keeps them in outer-sphere coordination to the surface. With dehydration, loss of the hydrolysis species results in direct contact between adsorbed ions and the bulk termination, therefore, inner-sphere sorption is equivalent to extension of the three dimensional bulk network, which is precipitation. Attachment of ions with size and charge compatible with Ca and CO₃ likewise results in coprecipitation and solid–solution formation.     

Thermodynamic model for sorption of bivalent heavy metals on calcite in natural-technogenic environments

Approaches to the construction of thermodynamic models for sorption of trace-element cations on carbonates are considered. To calculate thermodynamic equilibria by the method of Gibbs free-energy minimization, the existing database of reaction constants and thermodynamic potentials was extended. Different types of models are illustrated by the example of precipitation of Cd, Cu, Pb, and Zn from the water of a drainage stream flowing out of the impoundment of barite-polymetallic ore-dressing wastes. It is shown that the mobility of metals in such cases can be controlled by their sorption by calcite present in bottom sediments and suspension. Any approach can be successfully applied to both the modeling of experimental data on cation sorption and the prediction of the ecologo-geochemical situation in the districts of dressing works.     

The influence of picocyanobacterial photosynthesis on calcite precipitation

This study assessed the role of picocyanobacterial photosynthesis in the induction of calcite precipitation. It aimed at establishing whether photosynthetic uptake of bicarbonate by Synechoccoccus cells leads to calcite nucleation. The precipitation of calcite was initiated by addition of previously washed cyanobacterial cells of Synechococcus strain PCC 7942 to solutions of calcium carbonate at different saturation levels with respect to calcite. Precipitation experiments were performed under controlled laboratory conditions in two set-ups: one in which photosynthesis was inhibited using a herbicide called Diuron and the other one in which photosynthesis was taking place. During the experiments, a pH meter monitored the pH and ion selective electrodes monitored concentrations of carbonate and calcium ions. The morphology of the precipitated crystals was analysed using Scanning Electron Microscopy. When the kinetics of calcium carbonate nucleation by the Synechococcus cells were compared for the two sets of experiments, there were very little differences. In fact, the induction times for precipitation reactions with photosynthesis were shorter due to the uptake of carbon dioxide. It is therefore, concluded that photosynthesis does not directly influence the nucleation of calcite at the surface of Synechococcus cells with sufficient supply of carbon dioxide, i.e. cells took up carbon dioxide and not bicarbonate. The microscopic observations, however, provided some evidence that picocyanobacterial cell walls act as a template for calcite nucleation.     

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO₂H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation $\text{Y =}\text{100}\text{[1 + exp ? (A + BX)]}$, where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.     

五氯苯酚在矿物表面吸附——实验、表面反应模式及其环境意义

利用批量平衡技术研究了石英、高岭石、伊利石、蒙脱石和铁氧化物对五氯苯酚(PCP)吸附的pH关系等温线和浓度关系等温线,发现所有矿物的pH关系等温线都表现出典型的峰形曲线特征,峰位在pH=5～6之间,依矿物不同而不同。基于矿物表面羟基位化合态和PCP的化合态考虑,提出一种包含表面络合反应和表面静电吸附反应的模式,对pH关系等温线计算拟合发现有很好的相关性。模式计算还表明,石英和层状硅酸盐矿物对PCP吸附以表面络合反应为主,而氧化铁矿物则包含表面络合反应和表面静电吸附反应,但以后者占主导,其反应平衡常数比前者大1～3个数量级。高岭石和氧化铁矿物的浓度吸附等温线可用Langmuir方程很好拟合,最大吸附量的大小顺序是赤铁矿>纤铁矿>针铁矿>高岭石>石英>蒙脱石≈伊利石,并可以用矿物表面羟基位浓度和反应机制加以解释。PCP在矿物表面可观的吸附量说明矿物表面吸附对憎水性可离解有机化合物(HIOCs)在天然水相体系和沉积中的迁移转化过程起着相当重要的作用。     

Effects of seed material and solution composition on calcite precipitation

We studied the effects of seed material and solution composition on calcite crystal precipitation using a pH-stat system. The seed materials investigated included quartz, dolomite, two calcites with different particle size and specific surface area, and two dried precipitates from precipitative softening water treatment plants. Our results indicated that, of the seed materials examined, only calcite had the ability to initiate calcite precipitation in a solution with a degree of supersaturation of 5.3 over a period of two hours, and that the precipitation rate was proportional to the available surface area of the seed. For different solution compositions with the same degree of supersaturation, the calcite precipitation rate increased with increasing carbonate/calcium ratio, which contradicts the generally accepted empirical rate expression that the degree of supersaturation is the sole factor controlling precipitation kinetics. By applying a surface complexation model, the surface concentrations of two species, >CO₃⁻ and >CaCO₃⁻, appear to be responsible for catalyzing calcite precipitation.     

Sorption of inorganic 14C on to calcite,montmorillonite and soil

Although ¹⁴C occurs naturally, it is also a waste product of the nuclear industry, and can be important because of its long half-life, high mobility as an anion, and ready incorporation into biota. Some aqueous inorganic species are anionic with migration minimally retarded by most geological and soil materials. Substantial retardation is expected when calcite is present, but there are few data to quantify this effect. The present study measured partition coefficient values, R_d (concentration on solids divided by concentration in liquids), of 8–85 l kg⁻¹ for a series of calcite materials and for a carbonated soil. In contrast, R_d was zero for montmorillonite. The series of calcite materials varied in particle size. In order to investigate the effects of particle size, dissolution and degassing of ¹⁴C and ¹²C were monitored as pH was slowly decreased. The change in pH with addition of acid was strongly affected by particle size, as expected, but there was no systematic effect of particle size on the relative dissolution rates of ¹⁴C vs ¹²C, or on R_d. Apparently, surface area was not a limiting factor in the interaction of ¹⁴C with these materials. The ¹⁴C in soil behaved most like the very fine calcite, indicating that the specific surface of the soil carbonate was similar to that of the very fine calcite.     

Inhibition of calcite precipitation by orthophosphate: Speciation and thermodynamic considerations

The inhibition of heterogeneous calcite precipitation by orthophosphate was investigated under four different solution compositions using a pH-stat system. The system composition was designed to maintain a constant degree of supersaturation with respect to calcite, but with different carbonate/calcium ratios and pH values during precipitation. Inhibition in the presence of orthophosphate was found to be more effective at lower carbonate/calcium ratios and lower pH values. With the assumption that the calcite precipitation rate is proportional to the surface concentration of active crystal-growth sites, the reduction in the rate of calcite precipitation by phosphate can be explained by a Langmuir adsorption model using a conditional equilibrium constant and total phosphate concentration. Through a detailed analysis of chemical speciation in the solution phase and calcite surface speciation using chemical equilibrium computer modeling, the “conditional” equilibrium constants obtained at different solution compositions were found to converge to a single “non-conditional” value if only was considered in the adsorption reaction. This suggests that is the responsible species for inhibition of calcite precipitation because it adsorbs to the surface and blocks the active crystal-growth sites. The standard enthalpy change (ΔH⁰) and standard entropy change (TΔS⁰) of the adsorption reaction, determined by experiments performed from 15 to 45 °C, were 58.5 and 98.3 kJ/mol, respectively. The high positive values of the standard enthalpy change and the standard entropy change suggest that the adsorption reaction is an endothermic reaction, chemisorptive in nature, and driven by the entropy change, most likely resulting from the dehydration process that accompanies the adsorption of onto the calcite surface.     

Chemical speciation of trace metals at the air-sea interface: The application of an equilibrium model

Air-sea interfacial solutions have characteristically high concentrations of trace metals, microorganisms, organic compounds, and solids relative to bulk solutions. The potential for the chemical interaction of an array of trace metals in the interfacial regions with complexing organic ligands and adsorbing solid surfaces has been evaluated through the use of an equilibrium computer model. Computations suggest that higher interfacial accumulations of copper and lead may occur relative to cadmium and mercury. These results are found to be generally compatible with available field data describing trace metal interfacial accumulation. The forms of metals found to be partitioned between bulk and interfacial solutions are consistent with the hypothesis that solid surface adsorption and dissolved organic complexation reactions bring about metal enrichment at the surface microlayer.     

The Marl Slate: a model for the precipitation of calcite, dolomite and sulphides in a newly formed anoxic sea

Detailed studies of a new, complete Marl Slate core in South Yorkshire have provided information on isotopic (δ¹³C, δ¹⁸O, δ³⁴S) and geochemical variations (trace elements and C/S ratio) which enable the formulation of a model for carbonate and sulphide precipitation in the Late Permian Zechstein Sea. Calcite and dolomite are intimately associated; the fine lamination, organic character and absence of benthos in the sediments are indicative of anoxic conditions. Lithologically the core can be divided into a lower, predominantly sapropelic Marl Slate (2 m) and an upper Transition Zone (0·65 m) of alternating sapropel and calcite-rich and dolomite-rich carbonates. C/S ratios are 2·22 for the Marl Slate and 1·72 for the Transition Zone respectively, both characteristic of anoxic environments. δ¹⁸O in the carbonates shows a large and systematic variation closely mirrored by variations in calcite/dolomite ratio. The results suggest a fractionation factor equivalent to a depletion of 3·8% for ¹⁸O and 1·5% for ¹³C in calcite. The δ³⁴S values of pyrite are isotopically light (mean value = - 32·7%) suggesting a fractionation factor for the Marl Slate of almost 44%, typical of anoxic basins. The results are related to stratification in the early Zechstein Sea. Calcite was precipitated in oxic upper layers above the halocline. Below the oxic/anoxic boundary framboidal pyrite was precipitated, resulting in lower sulphate concentration and elevated Mg/Ca ratio (due to calcite precipitation). As a result of this, dolomite formation occurred below the oxic/anoxic interface, within the anoxic water column and in bottom sediments. Variations in calcite/dolomite ratios, and isotopic variations, are thus explained by fluctuations in the relative level of the oxic/anoxic boundary in the Zechstein Sea.     

The kinetics of calcite precipitation from a high salinity water

Calcium carbonate is one of the most common and important scale-forming minerals in oilfield produced water, but the kinetics of CaCO₃ precipitation has been ignored in most scale prediction models because of the lack of reliable precipitation rate model. There are none in the open literature for oilfield conditions (temperature > 100°C, pressure > 200 bar and salinity > 0.5 mol kg− 1). In this work the kinetics of calcite (CaCO₃) precipitation from high salinity waters (up to 2 mol kg⁻¹) have been studied by a pH-free-drift method in a closed water system. This method. is much easier to operate than the often used steady-state method. The experimental results indicate that the calcite precipitation rate is not only affected by the solution CaCO₃ saturation level, but also by the solution pH, ionic strength and the concentration ratios of Ca to HCO₃₋ ions (C_Ca²⁺/C_HCO3⁻). When the concentration ratios of Ca to HCO₃⁻ ions are close to their chemical stoichiometric ratio of 0.5, the calcite growth from a supersaturated solution is believed to be surface reaction controlled. However, at higher C_Ca²⁺C_HCO3⁻ ratios, the transportation of the lattice ions to calcite crystal surface has to be considered.