Effect of $$\hbox {CO}_2$$ solubility on dissolution rate of calcite in saline aquifers for temperature range of 50–100 $$^{\circ } \hbox {C}$$∘C and pressures up to 600 bar: alterations of fractures geometry in carbonate rocks by $$\hbox {CO}_2$$-acidified brines

An empirical model is developed to predict the dissolution rate of calcite in saline solutions that are saturated with respect to dissolved \(\hbox {CO}_2\) over a broad range of both subcritical and supercritical conditions. The focus is on determining the rate of calcite dissolution within a temperature range of 50–100 \(^\circ \hbox {C}\) and pressures up to 600 bar, relevant for \(\hbox {CO}_2\) sequestration in saline aquifers. A general reaction kinetic model is used that is based on the extension of the standard Arrhenius equation with an added, solubility-dependent, pH term to account for the saturated concentration of dissolved \(\hbox {CO}_2\). On the basis of this kinetic model, a new rate equation is obtained using multi-parameter, nonlinear regression of experimental data to determine the dissolution of calcite as a function of temperature, pressure and salinity. Different models for the activity coefficient of \(\hbox {CO}_2\) dissolved in saline solutions are accounted for. The new rate equation helps us obtain good agreement with experimental data, and it is applied to study the geochemically induced alterations of fracture geometry due to calcite dissolution.     

Conditions of the formation of thermomineral waters in the Talysh fold zone of the Lesser Caucasus (Azerbaijan) based on isotope-geochemical data (3Не/4Не, $${\delta ^{13}}{C_{c{o_2}}},{\delta ^{13}}{C_{c{h_4}}},{\delta ^{15}}{N_{{N_2}}}{,^{87}}Sr{/^{86}}Sr,\delta {D_{{H_2}O}},and{\delta ^{18}}{O_{{H_2}O}}$$)

It is shown that the gas and water phases of the thermal nitrogen–methane waters in the Talysh fold zone of the Lesser Caucasus mountain system contain helium and strontium with mantle isotope signatures (³Не/⁴Не from 200 × 10^–8 to 401 × 10^–8 and ⁸⁷Sr/⁸⁶Sr from 0.70490 to 0.70562). At the same time, clear signs of the mantle component in other gases (nitrogen, methane, and carbon dioxide) are absent. The δ¹⁵N value in nitrogen varies from +0.3 to +1.7‰, methane is mainly characterized by δ¹³C from–57.4 to–38.0‰, while δ¹³C(CО₂) varies from–24.4 to–11.3‰. An increase of the CО₂ content is accompanied by the decrease of δ¹³C in CО₂, against the background of increasing SO₄ content in the salt composition of waters. This indicates a microbial nature of CO₂ in the studied gases. Thus, the presence of mantle helium and strontium in the thermal waters is likely related to their leaching from the Pleogene–Neogene host volcanic rocks. The studies of the oxygen and hydrogen isotope composition in water revealed quite different mechanisms for the formation of cold and thermal waters of the region. The cold waters are mainly fed by local infiltration, whereas the feeding of thermal nitrogen–methane waters is strongly provided by transit atmogenic waters (>50%), which are formed in the mountain ranges at altitudes no less than 1600 m and spaced at 20–40 km or more from the thermal discharge sites.     

Modified Peierls–Nabarro dislocation equation for $$ \left\langle {\text{110}} \right\rangle {\{ 1\bar{1}0\} } $$ dissociated superdislocations in perovskite CaSiO3

In the paper, we investigate the core width of superpartials and dissociated width of the 〈110〉{1–10} superdislocations in CaSiO₃ perovskite under pressures of 30 and 100 GPa by using the modified P–N dislocation equation. Our results show that when taking into account the discrete effect correction, core width of superpartials and dissociated width become much wider, and both of them increase significantly with the increase of the superdislocation angle. Furthermore, it is found that the dissociated width and core width of superpartials are determined by value of the unstable stacking fault energy and antiphase boundary energy, which are independent of the position of unstable stacking energy. Interestingly, the Peierls stress of superpartials can be predicted by using the variational method to solve the modified P–N dislocation equation.     

The thermodynamics of the I \overline{1} –P \overline{1} phase transition in Ca-rich plagioclase from an assessment of the spontaneous strain

In-situ powder diffraction measurements between 90 and 935?K on four anorthite-rich plagioclase samples (An₁₀₀, An₉₆Ab₄, An₈₉Ab₁₁ and An₇₈Ab₂₂) were used to determine the detailed evolution of these samples through the $I \overline{1} $ – $P \overline{1} $ phase transition. The c-type reflections indicative of $P \overline{1} $ symmetry were detected only in An₁₀₀, An₉₆Ab₄, whereas deviations in the evolution of the unit-cell parameters with temperature were observed in all samples, most prominently in the β unit-cell angle. The c-type reflections disappear at ~510 and ~425?K in An₁₀₀ and An₉₆Ab₄ respectively, and their intensity decreases according to a tricritical trend $ I^{2} \propto \left( {T - T_{\text{c}} } \right) $ . The cell parameter changes were used to determine the spontaneous strains arising from the transition which were modelled with Landau theory, allowing for low-temperature quantum saturation, in order to determine the thermodynamic behaviour. In An₁₀₀ tricritical behaviour was observed [T _c?=?512.7(4)?K; θ_s?=?394(4)] in good agreement with previous studies, and the c-type superlattice reflections indicative of $P \overline{1} $ symmetry persist up to the T _c determined from the spontaneous strain, and then disappear. The evolution of the spontaneous strain in An₉₆Ab₄ is tricritical at low temperatures [T _c?=?459(1) K, θ_s?=?396(5)] up to the temperature of disappearance of c-type reflections, but becomes second order beyond ~440?K. In An₈₉Ab₁₁ the strain displays second-order behaviour throughout [T _c?=?500(1) and θ_s?=?212(5)], and the c-type reflections are not detected in the powder diffraction patterns at any temperature. The apparent discrepancy between the absence of c-type reflections in temperature ranges where the cell parameters display significant spontaneous strain is resolved through consideration of the sizes of the anti-phase domains within the crystals. It is deduced that the tricritical phase transition occurs in well-ordered crystals with large domains in which the behavior of individual domains is dominant (i.e. in pure anorthite) or where the $P \overline{1} $ distortions within the domains are large enough to dominate the structural coherency strains between the domains. When both the magnitude of the $P \overline{1} $ pattern of displacements of the tetrahedral framework become smaller and the influence of the structural coherency between anti-phase domains becomes significant, the thermodynamic behavior becomes 2nd-order in character, the c-type reflections disappear, and the orientation of the spontaneous strain changes.     

The solubility of [4H]Si defects in α-quartz and their role in the formation of molecular water and related weakening on heating

The nature of the solubility of water as [4H]_Si defects in quartz, and their role in providing a source of molecular water on heating, is investigated. Existing ab inito energy calculations on the incorporation of water in quartz are used to show that energetically 4H for Si substitution is likely to constitute the most prevalent mode of water uptake on the atomic scale in quartz under equilibrium conditions, and that the planar defects previously observed by a number of different authors by electron microscopy in wet quartz are likely to be planar rafts of aggregated [4H]_Si defects which are formed on supersaturation. These new conclusions call into question the previous identification of the planar defects as high pressure water clusters and require that their role in the production of molecular water in the context of recent theories of hydrolytic weakening be re-assessed. Accordingly the existing ab initio results have been used to establish the characteristics of the phase diagram for the system quartz-water in the temperature and pressure range of interest in hydrolytic weakening. Additional electron-optical experiments on wet quartz show that, on annealing at temperature in the electron microscope, similar planar defects develop in wet quartz by a diffusion process. In the context of existing theories of hydrolytic weakening it is now proposed that the conversion of [4H]_Si defects to molecular water, where this is dictated by the equilibrium phase diagram, leads to a relatively large increase in volume and to the appearance of the bubbles of free water and the nucleation of associated prismatic dislocation loops of Burgers vector b=1/3 a $\langle 11\bar 20\rangle $ as previously observed. Ultimately the development of these loops leads to dislocation-induced plasticity.     

Contribution of {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} and 13CTDIC Evaluation to the Identification of CO2 Sources in Volcanic Groundwater Systems: Influence of Hydrometeorological Conditions and Lava Flow Morphologies—Application to the Argnat Basin (Chaîne des Puys, Massif Central, France)

Mineralization of groundwater in volcanic aquifers is partly acquired through silicates weathering. This alteration depends on the dissolution of atmospheric, biogenic, or mantellic gaseous CO₂ whose contributions may depend on substratum geology, surface features, and lava flow hydrological functionings. Investigations of $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC (total dissolved inorganic carbon) on various spatiotemporal scales in the unsaturated and saturated zones of volcanic flows of the Argnat basin (French Massif Central) have been carried out to identify the carbon sources in the system. Mantellic sources are related to faults promoting CO₂ uplift from the mantle to the saturated zone. The contribution of this source is counterbalanced by infiltration of water through the unsaturated zone, accompanied by dissolution of soil CO₂ or even atmospheric CO₂ during cold periods. Monitoring and modeling of δ¹³C_TDIC in the unsaturated zone shows that both $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC are controlled by air temperature which influences soil respiration and soil-atmosphere CO₂ exchanges. The internal geometry of volcanic lava flows controls water patterns from the unsaturated zone to saturated zone and thus may explain δ¹³C heterogeneity in the saturated zone at the basin scale.     

Lazurite: Validation as a Mineral Species with the Formula Na7Ca(Al6Si6O24)(SO4) $${\text{S}}_{3}^{{\bullet - }}$$ ⋅H2O and New Data

Geology of Ore Deposits - The status of lazurite as a valid mineral species has been confirmed. The neotype specimen from the Malaya Bystraya gem lazurite deposit, Baikal Lake area has been studied...     

Thermodynamic behaviour of the high-temperature P\bar 1{\text{-}}I\bar 1 phase transition along the CaAl2Si2O8–SrAl2Si2O8 join

In situ high-temperature synchrotron radiation powder diffraction patterns were taken from room temperature to T = 740°C from synthetic feldspars along the join CaAl₂Si₂O₈–SrAl₂Si₂O₈ (An–SrF). Three samples of composition An₉₅SrF₅, An₉₀SrF₁₀ and An₈₅SrF₁₅ were investigated, and the evolution of cell parameters with T was determined by Rietveld analysis of powder X-ray diffraction patterns. The high-temperature $P\bar 1{\text{-}}I\bar 1$ phase transition, previously observed with T _c = 241°C in anorthite, was found in An₉₅SrF₅, An₉₀SrF₁₀ and An₈₅SrF₁₅ feldspars at T _c = 233(5)°, 195(2)° and 174(2)°C respectively. The transition was revealed by the disappearance of critical reflections and variations in the rate of change of cell parameters with temperature. A significant, although small (between 0.0025 and 0.0012 at room temperature), spontaneous strain could be measured, allowing the thermodynamic behaviour of the transition to be modelled. A second-order trend for An₉₀SrF₁₀ and An₈₅SrF₁₅ [β = 0.504(7) and 0.505(7) respectively] or nearly second-order for An₉₅SrF₅[β = 0.458(4)] was observed in contrast with tricritical behaviour of end member anorthite. An extrapolation of the T _c versus composition to room temperature indicates that the critical composition for the $P\bar 1$ phase is An₆₀SrF₄₀.     

Radiation-induced defects in euclase: formation of O<Superscript>−</Superscript> hole and Ti<Superscript>3+</Superscript> electron centers

Irradiation techniques are often applied to gem minerals for color enhancement purposes. Natural green, blue and colorless specimens of rare gemological quality euclase, BeAlSiO₄(OH), from Brazil were irradiated with gamma rays in the dose range from 10 to 500 kGy. Although the colors of the different specimens were not strongly influenced, two different irradiation-induced paramagnetic defect centers were found by electron paramagnetic resonance (EPR). The first one is an O⁻ hole center interacting with one Al neighbor and the second is a Ti³⁺ electron center. The EPR angular rotation patterns of both irradiation-induced defects were measured and analyzed. The results suggest that O⁻ hole centers are formed by dissociation of the hydroxyl ions, similar as in topaz crystals. In euclase the OH⁻ ions interconnect distorted Al octahedra and Be tetrahedra in O₅ positions. During irradiation, the electrons are captured by titanium ions (Ti⁴⁺ + e⁻), leading to the formation of paramagnetic Ti³⁺ ions. From the EPR rotation patterns it is clear that these ions substitute for Al ions. The spin Hamiltonian parameters of the irradiation-induced defects are analyzed and compared to similar defect centers in other mineral specimens. Thermal annealing experiments show that the O⁻ hole centers and Ti³⁺ electron centers are directly connected through the radiation process.     

Experimental determination of activity-composition relations in Ni2SiO4− Mg2SiO4 and Co2SiO4-Mg2SiO4 olivine solid solutions at 1200 K and 0.1 MPa and 1573 K and 0.5 GPa

Activity-composition relations in the olivine solid solutions Ni₂SiO₄⁻ -Mg₂SiO₄ and Co₂SiO₄-Mg₂SiO₄ have been determined at 1200 K and 0.1 MPa and at 1573 K and 0.5 GPa by equilibration with the corresponding oxide solutions. Both olivine solutions show small positive deviations from ideal (two site) mixing, which, within the limits of accuracy of the method, may be described by the simple regular solution model with parameters W_Ni+Mg^ol= 0.35 ± 1.0 kJ/g-atom and W_Co-Mg^ol = 1.37 ± 0.9 kJ/g-atom. The requirements of internal consistency between the two systems also show that the recent determination by Brousse et al. (1984) of the enthalpy of formation of Mg₂SiO₄is to be preferred over earlier work, and that their value is also probably more accurate than the uncertainty in their own measurements indicates; activities in the NiO-MgO system are close to ideal.     

Phase states of hydrous–hydrocarbon fluids at elevated and high temperatures and pressures: Study of the forms and maximal depths of oil occurrence in the Earth’s interior

Based on synthetic fluid inclusions in quartz grown at 240–490°C and 7–150 MPa in aqueous–oil solutions, the behavior, composition, and phase states of liquid, gaseous, and solid hydrocarbons (HC) were studied. Investigations were performed using common and fluorescent microscopy, microthermometry, local common and high-temperature IR Fourier spectroscopy, Raman spectroscopy, chromatography, and X-ray and microprobe analysis. The data obtained allowed us to understand the influence of thermobaric conditions and volume proportions of the oil, aqueous, and gaseous phases on the composition, phase state, and behavior of hydrous–hydrocarbon fluids and estimate the forms and probable maximal depths of the origin of oil in the Earth’s interior.     

NH4-bearing micas in poly-metamorphic Alpuj��rride micaschists and gneisses from the central zone of the Betic Cordillera (Spain): tectono-metamorphic and crystal-chemical constraints

The content and distribution of NH₄-bearing micas in micaschists and paragneisses of the Alpujárride complex (Betic Cordillera, Spain) are interpreted on the basis of textures, metamorphic history and crystal-chemical constraints. NH₄ is present in important amounts in early micas, recording their older diagenetic-to-metamorphic history. NH₄ was inherited by micas formed in successive metamorphic events. At similar metamorphic grade, annite is enriched in NH₄ relative to muscovite with a fractionation of 4:1. Maximum NH₄ contents were estimated in golden annite from medium-grade schists and in retrogressive annite-chlorite mixed-layers (~1.0?wt.%). A Ti-NH₄ avoidance gives rise to associated chemical changes, such as the enrichment in Mg and in ^VIAl. These data suggest that NH₄ can be a decisive factor in chemical equilibrium and element partitioning between coexisting phases, thus affecting to the commonly used thermobarometers. Estimation of the P-T conditions from texturally different muscovite-annite pairs reveals the superposition of several stages of mica growth, under different geothermal gradients.     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999     

Single-crystal EPR study of three radiation-induced defects (Al–O2 3?, Ti3+ and W5+) in stishovite

Single-crystal electron paramagnetic resonance spectra of electron-irradiated stishovite, measured at temperatures from 3.5 to 294?K, reveal three S?=?1/2 radiation-induced defects: an aluminum-associated oxygen hole center and two nd ¹ centers (Ti³⁺ and W⁵⁺). The aluminum-associated oxygen hole center, characterized by an orthorhombic site symmetry, coaxial matrices of the electronic Zeeman g, nuclear hyperfine A(²⁷Al) and nuclear quadrupole P(²⁷Al), and the orientation of the g-minimum axis along an O–O direction and those of the unique A(²⁷Al) and P(²⁷Al) axes perpendicular to the O–O direction, is an Al–O₂ ^3? center, with the unpaired electron equally distributed on two equatorial oxygen atoms of a substitutional Al³⁺ ion at the octahedral Si site. Fully optimized Al-doped structure, theoretical ²⁷Al nuclear hyperfine and quadrupole coupling constants and directions, and 3D spin densities from periodic hybrid density functional theory calculations provide further support for this structural model. Spin Hamiltonian parameters of the Ti³⁺ and W⁵⁺ centers, which are confirmed by their diagnostic ⁴⁷Ti, ⁴⁹Ti and ¹⁸³W hyperfine structures, arise from electron trapping on substitutional Ti⁴⁺ and W⁶⁺ ions at the octahedral Si site.     

Provenance and reconnaissance study of detrital zircons of the Palaeozoic Cape Supergroup in South Africa: revealing the interaction of the Kalahari and R��o de la Plata cratons

In order to facilitate the understanding of the geological evolution of the Kalahari Craton and its relation to South America, the provenance of the first large-scale cratonic cover sequence of the craton, namely the Ordovician to Carboniferous Cape Supergroup was studied through geochemical analyses of the siliciclastics, and age determinations of detrital zircon. The Cape Supergroup comprises mainly quartz-arenites and a Hirnantian tillite in the basal Table Mountain Group, subgreywackes and mudrocks in the overlying Bokkeveld Group, while siltstones, interbedded shales and quartz-arenites are typical for the Witteberg Group at the top of the Cape Supergroup. Palaeocurrent analyses indicate transport of sediment mainly from northerly directions, off the interior of the Kalahari Craton with subordinate transport from a westerly source in the southwestern part of the basin near Cape Town. Geochemical provenance data suggest mainly sources from passive to active continental margin settings. The reconnaissance study of detrital zircons reveals a major contribution of Mesoproterozoic sources throughout the basin, reflecting the dominance of the Namaqua-Natal Metamorphic Belt, situated immediately north of the preserved strata of Cape Supergroup, as a source with Archaean-aged zircons being extremely rare. We interpret the Namaqua-Natal Metamorphic Belt to have been a large morphological divide at the time of deposition of the Cape Supergroup that prevented input of detrital zircons from the interior early Archaean Kaapvaal cratonic block of the Kalahari Craton. Neoproterozoic and Cambrian zircons are abundant and reflect the basement geology of the outcrops of Cape strata. Exposures close to Cape Town must have received sediment from a cratonic fragment that was situated off the Kalahari Craton to the west and that has subsequently drifted away. This cratonic fragment predominantly supplied Meso- to Neoproterozoic, and Cambrian-aged zircon grains in addition to minor Silurian to Lower Devonian zircons and very rare Archaean (2.5?Ga) and late Palaeoproterozoic (1.8-2.0?Ga) ones. No Siluro-Devonian source has yet been identified on the Kalahari Craton, but there are indications for such a source in southern Patagonia. Palaeozoic successions in eastern Argentina carry a similar detrital zircon population to that found here, including evidence of a Silurian to Lower Devonian magmatic event. The Kalahari and Río de la Plata Cratons were thus in all likelihood in close proximity until at least the Carboniferous.     

Crystallization behavior of Na2SO4–MgSO4 salt mixtures in sandstone and comparison to single salt behavior

We report on the crystallization behavior and the salt weathering potential of Na₂SO₄, MgSO₄ and an equimolar mixture of these salts in natural rock and porous stone. Geochemical modeling of the phase diagram of the ternary Na₂SO₄–MgSO₄–H₂O system was used to determine the equilibrium pathways during wetting (or deliquescence) of incongruently soluble minerals and evaporation of mixed electrolyte solutions. Model calculations include stable and metastable solubilities of the various hydrated states of the single salts and the double salts Na₂Mg(SO₄)₂·4H₂O (bloedite), Na₂Mg(SO₄)₂·5H₂O (konyaite), Na₁₂Mg₇(SO₄)₁₃·15H₂O (loeweite) and Na₆Mg(SO₄)₄ (vanthoffite). In situ Raman spectroscopy was used to study the phase transformations during wetting of pure MgSO₄·H₂O (kieserite) and of the incongruently soluble salts bloedite and konyaite. Dissolution of kieserite leads to high supersaturation resulting in crystallization of higher hydrated phases, i.e. MgSO₄·7H₂O (epsomite) and MgSO₄·6H₂O (hexahydrite). This confirms the high damage potential of magnesium sulfate in salt damage of building materials. The dissolution of the incongruently soluble double salts leads to supersaturation with respect to Na₂SO₄·10H₂O (mirabilite). However, the supersaturation was insufficient for mirabilite nucleation. The damage potential of the two single salts and an equimolar salt mixture was tested in wetting–drying experiments with porous sandstone. While the high damage potential of the single salts is confirmed, it appears that the supersaturation achieved during wetting of the double salts at room temperature is not sufficient to generate high crystallization pressures. In contrast, very high damage potentials of the double salts were found in experiments at low temperature under high salt load.1     

The solubility control of rare earth elements in natural terrestrial waters and the significance of PO 4 3− and CO 3 2− in limiting dissolved rare earth concentrations: A review of recent information

Rare earth element (REE) concentrations in alkaline lakes, circumneutral pH groundwaters, and an acidic freshwater lake were determined along with the free carbonate, free phosphate, and free sulfate ion concentrations. These parameters were used to evaluate the saturation state of these waters with respect to REE phosphate and carbonate precipitates. Our activity product estimates indicate that the alkaline lake waters and groundwaters are approximately saturated with respect to the REE phosphate precipitates but are significantly undersaturated with respect to REE carbonate and sulfate precipitates. On the other hand, the acidic lake waters are undersaturated with respect to REE sulfate, carbonate, and phosphate precipitates. Although carbonate complexes tend to dominate the speciation of the REEs in neutral and alkaline waters, our results indicate that REE phosphate precipitates are also important in controlling REE behavior. More specifically, elevated carbonate ion concentrations in neutral to alkaline natural waters tend to enhance dissolved REE concentrations through the formation of stable REE-carbonate complexes whereas phosphate ions tend to lead to the removal of the REEs from solution in these waters by the formation of REE-phosphate salts. Removal of REEs by precipitation as phosphate phases in the acid lake (pH=3.6) is inconsequential, however, due to extremely low [PO ₄ ^3– ] _F concentrations (i.e., 10^–23 mol/kg).