Determination of SO4β1 for yttrium and the rare earth elements at I = 0.66 m and t = 25°C—implications for YREE solution speciation in sulfate-rich waters

We present a complete set of stability constants (_SO4β₁) for the monosulfato-complexes of yttrium and the rare earth elements (YREE), except Pm, at I = 0.66 m and t = 25°C, where _SO4β₁ = [MSO₄⁺] × [M³⁺]⁻¹[SO₄²⁻]⁻¹ (M ≡ YREE and brackets indicate free ion concentrations on the molal scale). Stability constants were determined by investigating the solubility of BaSO₄ in concentrated aqueous solutions of MCl₃. This is the first complete set to be published in more than 30 years.The resulting _SO4β₁ pattern is very similar in shape to one reported by de Carvalho and Choppin (1967a) (I = 2 mol/L; t = 25°C) that has been largely ignored. Stability constants vary little between La and Sm, but display a weak maximum at Eu. Between Eu and Lu, _SO4β₁ decreases by 0.2 log units, substantially exceeding the ±0.02 log unit average analytical precision. The stability constant for Y is approximately equal to that for Er. Our _SO4β₁ pattern is consequently distinctly different from the consensus pattern, based on a single data set from 1954, which is essentially flat, with a range of only 0.07 log units between the lowest and highest _SO4β₁ values within the lanthanide series (excluding Y).Values of _SO4β₁ obtained in this work, in conjunction with the ion-pairing model of Millero and Schreiber (1982), allow prediction of _SO4β₁ between 0 and 1 m ionic strength. These results are used to assess both the absolute and relative extent of YREE sulfate complexation in acidic, sulfate-rich waters.     

Microbial dissolution of calcite at T = 28 °C and ambient pCO2

This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species (Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO₂ over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH₄⁺ as an N source, and H₂PO₄⁻ as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H₂O-CO₂-CaCO₃ system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH₄⁺ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H₂CO₃ generated by dissolution of atmospheric CO₂ (H₂CO₃ + CaCO₃ → Ca²⁺ + 2HCO₃⁻) and H⁺ released during NH₄⁺ uptake (H⁺ + CaCO₃ → Ca²⁺ + HCO₃⁻). Reaction with H₂CO₃ and H⁺ supplied ∼45% and 55% of the total Ca²⁺ and ∼60% and 40% of the total HCO₃⁻, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH₄⁺ was ∼2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H₂CO₃. In lactate bearing reactors, most H⁺ generated by NH₄⁺ uptake reacted with HCO₃⁻ produced by lactate oxidation to yield CO₂ and H₂O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H₂CO₃ at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH₄⁺ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.     

Comparative geochemistries of Pd and Pt:: Formation of mixed hydroxychloro and chlorocarbonato-complexes in seawater

Comparative observations of Pd^II and Pt^II hydrolysis in chloride solutions indicate that [PdCl₃OH²⁻]/[PdCl42−] and [PtCl₃OH²⁻]/[PtCl42−] concentration ratios in salinity 35 seawater (S = 35) are smaller than one at a typical surface ocean pH (∼8.2), and are larger than one at pH = 8.2 when S < 10. The hydrolysis behaviors of PdCl42− and PtCl42− are very similar. In 0.5 M NaCl at 25°C the hydrolysis constant for both elements, written in the form β₁ = [MCl₃OH²⁻][Cl⁻][H⁺][MCl42−]⁻¹, is logβ1*=−8.97. Between ionic strengths 0.3 M and 1.0 M for Pd^II and between 0.1 M and 1.0 M for Pt^II, log β₁ is within approximately 0.1 units of the value appropriate to 0.5 M NaCl. This small dependence of PdCl42− and PtCl42− hydrolysis constants on ionic strength is consistent with predictions based on expected activity coefficient behavior.Carbonate is observed to complex PdCl42− significantly, but to a smaller extent than OH⁻ under conditions appropriate to seawater. Complexation of PtCl42− by CO32− was observed in this work but the rate of complexation was too slow to allow equilibrium observations. The principal dissimilarity between the chemistries of Pd^II and Pt^II in our investigation was the sharp contrast in observed Pd^II and Pt^II reaction rates. Differences in reaction kinetics may cause fractionation of Pd^II and Pt^II in the environment. The speciation of Pt^II, unlike Pd^II, is likely to be based on chemical environments experienced by Pt^II over a period of days, and perhaps weeks.     

Comparative Scavenging of Yttrium and the Rare Earth Elements in Seawater: Competitive Influences of Solution and Surface Chemistry

Distribution coefficients were obtained for yttrium and the rare earth elements (YREEs) in aqueous solutions containing freshly precipitated hydroxides of trivalent cations (Fe³⁺, Al³⁺, Ga³⁺, and In³⁺). Observed patterns of log _i K _S–, where _i K _S = [MS _i ][M³⁺]^?1[S _i ]^?1, [MS _i ] is the concentration of a sorbed YREE, [M³⁺] is the concentration of a free hydrated YREE ion, and [S _i] is the concentration of a sorptive solid substrate (Fe(III), Al, Ga, In)– exhibited similarities to patterns of YREE solution complexation constants with hydroxide (_OH β ₁) and fluoride (_F β ₁), but also distinct differences. The log _i K _S pattern for YREE sorption on Al hydroxide precipitates is very similar to the pattern of YREE hydroxide stability constants (log_OH β ₁) in solution. Linear free-energy relationships between log _i K _S and log_OH β ₁ showed excellent correlation for YREE sorption on Al hydroxide precipitates, good correlation for YREE sorption on Ga or In hydroxide precipitates, yet poor correlation for YREE sorption on Fe(III) hydroxide precipitates. Whereas the correlation between log _i K _S and log_F β ₁ was generally poor, patterns of log( _i K _S/_F β ₁) displayed substantially increased smoothness compared to patterns of log _i K _S. This indicates that the conspicuous sequence of inflections along the YREE series in the patterns of log _i K _S and log_F β ₁ is very similar, particularly for In and Fe(III) hydroxide precipitates. While the log _i K _S patterns obtained with Fe(III) hydroxide precipitates in this work are quite distinct from those obtained with Al, Ga, and In hydroxide precipitates, they are in good agreement with patterns of YREE sorption on ferric oxyhydroxide precipitates reported by others. Furthermore, our log _i K _S patterns for Fe(III) hydroxide precipitates bear a striking resemblance to predicted log _i K _S patterns for natural surfaces that are based on YREE solution chemistry and shale-normalized YREE concentrations in seawater. Yttrium exhibits an itinerant behavior among the REEs: sorption of Y on Fe(III) hydroxide precipitates is intermediate to that of La and Ce, while for Al hydroxide precipitates Y sorption is similar to that of Eu. This behavior of Y can be rationalized from the propensities of different YREEs for covalent vs. ionic interactions. The relatively high shale-normalized concentration of Y in seawater can be explained in terms of primarily covalent YREE interactions with scavenging particulate matter, whereby Y behaves as a light REE, and primarily ionic interactions with solution ligands, whereby Y behaves as a heavy REE.     

Oxidation of iron (II) nanomolar with H2O2 in seawater

The oxidation of Fe(II) with H₂O₂ at nanomolar levels in seawater have been studied using an UV-Vis spectrophotometric system equipped with a long liquid waveguide capillary flow cell. The effect of pH (6.5 to 8.2), H₂O₂ (7.2 × 10⁻⁸ M to 5.2 × 10⁻⁷ M), HCO₃⁻ (2.05 mM to 4.05 mM) and Fe(II) (5 nM to 500 nM) as a function of temperature (3 to 35 °C) on the oxidation of Fe(II) are presented. The oxidation rate is linearly related to the pH with a slope of 0.89 ± 0.01 independent of the concentration of HCO₃⁻. A kinetic model for the reaction has been developed to consider the interactions of Fe(II) with the major ions in seawater. The model has been used to examine the effect of pH, concentrations of Fe(II), H₂O₂ and HCO₃⁻ as a function of temperature. FeOH⁺ is the most important contributing species to the overall rate of oxidation from pH 6 to pH 8. At a pH higher than 8, the Fe(OH)₂ and Fe(CO₃)₂²⁻ species contribute over 20% to the rates. Model results show that when the concentration of O₂ is two orders of magnitude higher than the concentration of H₂O₂, the oxidation with O₂ also needs to be considered. The rate constants for the five most kinetically active species (Fe²⁺, FeOH⁺, Fe(OH)₂, FeCO₃, Fe(CO₃)₂²⁻) in seawater as a function of temperature have been determined. The kinetic model is also valid in pure water with different concentrations of HCO₃⁻ and the conditions found in fresh waters.     

Experimental studies of oxygen isotope fractionation in the carbonic acid system at 15°, 25°, and 40°C

In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO₃⁻ and CO₃²⁻ concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO₃⁻, CO₃²⁻, and CO_2(aq)) were investigated at 15°, 25°, and 40°C. To investigate oxygen isotope exchange between HCO₃⁻, CO₃²⁻, and H₂O, NaHCO₃ solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl₂ was added to the NaHCO₃ solutions. This resulted in immediate BaCO₃ precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon (DIC). Data from experiments at 15°, 25°, and 40°C (1 atm) show that the oxygen isotope fractionation between HCO₃⁻ and H₂O as a function of temperature is governed by the equation:

     

Copper(II) carbonate complexation in seawater

Cupric carbonate and cupric bicarbonate complexation constants were determined in natural seawater and in a variety of synthetic media. The formation constants of CuHCO₃⁺, CuCO₃⁰ and Cu(CO₃)₂^2? at 25°C and zero ionic strength are: log β_H⁰ = 1.8, log β₁⁰ = 6.82 and log β⁰₂ = 10.6. Formation constants of these species appropriate to 0.7 molar ionic strength and 25°C are log β_H ～- 1, log β₁ = 5.73, log β₂ = 9.3. Our results indicate that the inorganic speciation scheme of Cu(II) in seawater is dominated by CuCO₃⁰ and that the ternary species, CuCO₃OH^?, is of substantial importance.     

Stability of YREE complexes with the trihydroxamate siderophore desferrioxamine B at seawater ionic strength

Organic complexation of yttrium and the rare earth elements (YREEs), although generally believed to be important, is an understudied aspect of YREE solution speciation in the open ocean. We report the first series of stability constants for complexes of YREEs (except Ce and Pm) with the trihydroxamate siderophore desferrioxamine B (DFOB), representing a class of small organic ligands that have an extraordinary selectivity for Fe(III) and are found in surface seawater at low-picomolar concentrations. Constants were measured by potentiometric titration of DFOB (pH 3-10) in the presence of single YREEs, in simple media at seawater ionic strength (NaClO₄ or NaCl, I = 0.7 M). Under these circumstances, the terminal amine of DFOB does not deprotonate. The four acid dissociation constants of the siderophore were determined separately by potentiometric titration of DFOB alone.Values for the bidentate (log β₁), tetradentate (log β₂), and hexadentate (log β₃) complexes of La-Lu range from 4.88 to 6.53, 7.70 to 11.27, and 10.09 to 15.19, respectively, while Y falls between Gd and Tb in each case. Linear free-energy relations of the three stability constants with the first YREE hydrolysis constant, log , yield regression coefficients of >0.97. On the other hand, plots of the constants vs. the radius of the inner hydration sphere display an increasing deviation from linearity for the lightest REEs (La > Pr > Nd). This may signify steric constraints in DFOB folding around bulkier cations, a larger mismatch in coordination number, or a substantial degree of covalence in the YREE-hydroxamate bond.Complexes of the YREEs with DFOB are many orders of magnitude more stable than those with carbonate, the dominant inorganic YREE ligand in seawater. Speciation modeling with MINEQL indicates that, for an average seawater composition, the hexadentate complex could constitute as much as 28% of dissolved Lu at free DFOB concentrations as low as 10⁻¹³ M. Such conditions might occur when DFOB or other siderophores are present in excess over metals for which they have high affinity, like Fe(III) and Co(III), for example during plankton blooms. Even if it turns out that trihydroxamate siderophores are not the dominant organic YREE ligand in seawater, our results establish a benchmark for producing effects on YREE solution speciation comparable to that of DFOB: the free concentration of any weaker organic ligand L must exceed that of DFOB by a factor β₃/_Lβ₁, assuming its first order complex is formed in greatest abundance.     

Rate-controlled calcium isotope fractionation in synthetic calcite

The isotopic composition of Ca (Δ⁴⁴Ca/⁴⁰Ca) in calcite crystals has been determined relative to that in the parent solutions by TIMS using a double spike. Solutions were exposed to an atmosphere of NH₃ and CO₂, provided by the decomposition of (NH₄)₂CO₃, following the procedure developed by previous workers. Alkalinity, pH and concentrations of CO₃²⁻, HCO₃⁻, and CO₂ in solution were determined. The procedures permitted us to determine Δ(⁴⁴Ca/⁴⁰Ca) over a range of pH conditions, with the associated ranges of alkalinity. Two solutions with greatly different Ca concentrations were used, but, in all cases, the condition [Ca²⁺]>>[CO₃²⁻] was met. A wide range in Δ(⁴⁴Ca/⁴⁰Ca) was found for the calcite crystals, extending from 0.04 ± 0.13‰ to −1.34 ± 0.15‰, generally anti-correlating with the amount of Ca removed from the solution. The results show that Δ(⁴⁴Ca/⁴⁰Ca) is a linear function of the saturation state of the solution with respect to calcite (Ω). The two parameters are very well correlated over a wide range in Ω for each solution with a given [Ca]. The linear correlation extended from Δ(⁴⁴Ca/⁴⁰Ca) = −1.34 ± 0.15‰ to 0.04 ± 0.13‰, with the slopes directly dependent on [Ca]. Solutions, which were vigorously stirred, showed a much smaller range in Δ(⁴⁴Ca/⁴⁰Ca) and gave values of −0.42 ± 0.14‰, with the largest effect at low Ω. It is concluded that the diffusive flow of CO₃²⁻ into the immediate neighborhood of the crystal-solution interface is the rate-controlling mechanism and that diffusive transport of Ca²⁺ is not a significant factor. The data are simply explained by the assumptions that: a) the immediate interface of the crystal and the solution is at equilibrium with Δ(⁴⁴Ca/⁴⁰Ca) ∼ −1.5 ± 0.25‰; and b) diffusive inflow of CO₃²⁻ causes supersaturation, thus precipitating Ca from the regions exterior to the narrow zone of equilibrium. The result is that Δ(⁴⁴Ca/⁴⁰Ca) is a monotonically increasing (from negative values to zero) function of Ω. We consider this model to be a plausible explanation of most of the available data reported in the literature. The well-resolved but small and regular isotope fractionation shifts in Ca are thus not related to the diffusion of very large hydrated Ca complexes, but rather due to the ready availability of Ca in the general neighborhood of the crystal-solution interface. The largest isotopic shift which occurs as a small equilibrium effect is then subdued by supersaturation precipitation for solutions where [Ca²⁺]>>[CO₃²⁻] + [HCO₃⁻]. It is shown that there is a clear temperature dependence of the net isotopic shifts that is simply due to changes in Ω due to the equilibrium “constants” dependence on temperature, which changes the degree of saturation and hence the amount of isotopically unequilibrated Ca precipitated. The effects that are found in natural samples, therefore, will be dependent on the degree of diffusive inflow of carbonate species at or around the crystal-liquid interface in the particular precipitating system, thus limiting the equilibrium effect.     

History of carbonate ion concentration over the last 100 million years

Instead of having been more or less constant, as once assumed, it is now apparent that the major ion chemistry of the oceans has varied substantially over time. For instance, independent lines of evidence suggest that calcium concentration ([Ca²⁺]) has approximately halved and magnesium concentration ([Mg²⁺]) approximately doubled over the last 100 million years. On the other hand, the calcite compensation depth, and hence the CaCO₃ saturation, has varied little over the last 100 My as documented in deep sea sediments. We combine these pieces of evidence to develop a proxy for seawater carbonate ion concentration ([CO₃²⁻]) over this period of time. From the calcite saturation state (which is proportional to the product of [Ca²⁺] times [CO₃²⁻], but also affected by [Mg²⁺]), we can calculate seawater [CO₃²⁻]. Our results show that [CO₃²⁻] has nearly quadrupled since the Cretaceous. Furthermore, by combining our [CO₃²⁻] proxy with other carbonate system proxies, we provide calculations of the entire seawater carbonate system and atmospheric CO₂. Based on this, reconstructed atmospheric CO₂ is relatively low in the Miocene but high in the Eocene. Finally, we make a strong case that seawater pH has increased over the last 100 My.     

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle,USA

This study investigated the potential for the uranium mineral carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO₂. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO₄ + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2mCa⁺² > mHCO₃⁻ + 2mCO₃⁻²) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa⁺² < mHCO₃^- + 2mCO₃⁻²) carnotite saturation was not achieved. In systems open to CO_2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO₂ ranging from 10^−3.5 to 10^−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO₂ equal to 10^−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO₂.     

Determination of carbon fractionation factor between aqueous carbonate and CO2(g) in two-direction isotope equilibration

The experiments were conducted in the open CO₂ system to find out the equilibrium fractionation between the carbonate ion and CO₂(g). The existence of isotopic equilibrium was checked using the two-direction approach by passing the CO₂−N₂ gases with different δ¹³C compositions (− 1.5‰ and − 23‰) through the carbonate solution with δ¹³C = − 4.2‰. The Δ_{CO3T²⁻−CO2(g)} equilibrium fractionation is given as 6.03 ± 0.17‰ at 25 °C. Discussion is provided about the significance of carbonate complexing in determination of Δ_{CO3T²⁻−CO2(g)} and Δ_{HCO3T⁻−CO2(g)} fractionations. Finally, an isotope numerical model of flow and kinetics of hydration and dehydroxylation is built to predict the isotopic behaviour of the system with time.     

Speciation of rare earth elements in natural terrestrial waters: assessing the role of dissolved organic matter from the modeling approach

Humic Ion-Binding Model V, which focuses on metal complexation with humic and fulvic acids, was modified to assess the role of dissolved natural organic matter in the speciation of rare earth elements (REEs) in natural terrestrial waters. Intrinsic equilibrium constants for cation-proton exchange with humic substances (i.e., pK_MHA for type A sites, consisting mainly of carboxylic acids), required by the model for each REE, were initially estimated using linear free-energy relationships between the first hydrolysis constants and stability constants for REE metal complexation with lactic and acetic acid. pK_MHA values were further refined by comparison of calculated Model V “fits” to published data sets describing complexation of Eu, Tb, and Dy with humic substances. A subroutine that allows for the simultaneous evaluation of REE complexation with inorganic ligands (e.g., Cl⁻, F⁻, OH⁻, SO₄²⁻, CO₃²⁻, PO₄³⁻), incorporating recently determined stability constants for REE complexes with these ligands, was also linked to Model V. Humic Ion-Binding Model V’s ability to predict REE speciation with natural organic matter in natural waters was evaluated by comparing model results to “speciation” data determined previously with ultrafiltration techniques (i.e., organic acid-rich waters of the Nsimi-Zoetele catchment, Cameroon; dilute, circumneutral-pH waters of the Tamagawa River, Japan, and the Kalix River, northern Sweden). The model predictions compare well with the ultrafiltration studies, especially for the heavy REEs in circumneutral-pH river waters. Subsequent application of the model to world average river water predicts that organic matter complexes are the dominant form of dissolved REEs in bulk river waters draining the continents. Holding major solute, minor solute, and REE concentrations of world average river water constant while varying pH, the model suggests that organic matter complexes would dominate La, Eu, and Lu speciation within the pH ranges of 5.4 to 7.9, 4.8 to 7.3, and 4.9 to 6.9, respectively. For acidic waters, the model predicts that the free metal ion (Ln³⁺) and sulfate complexes (LnSO₄⁺) dominate, whereas in alkaline waters, carbonate complexes (LnCO₃⁺ + Ln[CO₃]₂⁻) are predicted to out-compete humic substances for dissolved REEs. Application of the modified Model V to a “model” groundwater suggests that natural organic matter complexes of REEs are insignificant. However, groundwaters with higher dissolved organic carbon concentrations than the “model” groundwater (i.e., >0.7 mg/L) would exhibit greater fractions of each REE complexed with organic matter. Sensitively analysis indicates that increasing ionic strength can weaken humate-REE interactions, and increasing the concentration of competitive cations such as Fe(III) and Al can lead to a decrease in the amount of REEs bound to dissolved organic matter.     

Solubility and equilibrium constants of lead in carbonate solutions (25°C,I = 0.3 mol dm−3)

The solubilities of PbCO₃(s), 2PbCO₂·Pb(OH)₂(s), and of 3PbCO₃ 2Pb(OH)₂(s) have been studied at 25°C ± 0.1°C in solutions of the constant ionic strength I = 0.3 mol/dm³, consisting primarily of sodium perchlorate. A few experiments with hydrocerussite were performed in solutions of 0.1 M KNO₃. The concentrations of lead and hydrogen ions have been determined in solution in contact with the solid phase. From experimental data the following values for equilibrium constants are obtained: log [Pb²⁺]·pCO₂·[H⁺]^?2 = 5.20log [Pb²⁺]·pCO^0.67₂·[H⁺]^?2 = 6.80log [Pb₂₊]³·[CO^2?₃]²·[OH^?]² = ?44.08 (and ?44.8 forI = 0.1 M)log [PbCO⁰₃]·[Pb²⁺]^?1·[CO^2?₃]^?1 = 5.40log [Pb(CO₃)^2?₂]·[Pb₂₊]^?1·[CO^2?₃]^?2 = 8.86 The data indicate that hydrocerussite is the most stable solid phase in natural waters. Comparison with the literature and needs for further research are also presented.     

Chemical and isotopic characteristics of fluids along the Cameroon Volcanic Line, Cameroon

Results of the chemical and isotopic analysis of the water and gases discharged from volcanic crater lakes and soda springs located along the Cameroon Volcanic Line were used to characterize and infer their genetic relationships. Variations in the solute compositions of the waters indicate the dominant influence of silicate hydrolysis. Na⁺ (40–95%) constitutes the major cation in the springs while Fe²⁺ + Mg²⁺ (70%) dominate in the CO₂-rich lakes. The principal anion is HCO₃ (>90%), except in the coastal springs where Cl-predominates. Lakes Nyos and Monoun have FeMgCaHCO₃⁻ type signatures; the soda springs are essentially NaHCO₃⁻ type, while all other lakes show similar ionic compositions to dilute surface waters. Dissolved gases show essentially CO₂ (>90%), with small amounts of Ar and N₂, while CH₄ constitutes the principal component in the non-gassy lakes. Active volcanic gases are generally absent, except in the Lobe spring with detectable H₂S. Stable isotope ratio evidence indicates that the bicarbonate waters are essentially of meteoric origin. CO₂ (δ¹³C = −2 to −8%₀ and He (³He/⁴He = 1 to 5.6R_a) infer a mantle contribution to the total CO₂. CH₄ has a biogenic source, while Ar and N₂ are essentially atmospheric in origin, but mixing is quite common.     

Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China: Evidence from Formation Water and Natural Gas Geochemistry

<正>Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin(CUTB) show that gas invasion at the late stage is accompanied by an increase of the contents of H_2S and CO_2 in natural gas,by the forming of the high total dissolved solids formation water,by an increase of the content of HCO_3~-,relative to Cl~-,by an increase of the 2nd family ions(Ca~(2+),Mg~(2+),Sr~(2+) and Ba~(2+)) and by a decrease of the content of SO_4~(2-),relative to Cl~-.The above phenomena can be explained only by way of thermochemical sulfate reduction(TSR).TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula:ΣCH+CaSO_4+H-_2O→H_2S+CO_2+CaCO_3.(1) Dissolved SO_4~(2-) in the formation water is consumed in the above reaction,when H_2S and CO_2 are generated,resulting in a decrease of SO_4~(2-) in the formation water and an increase of both H_2S and CO_2 in the natural gas.If formation water exists, the generated CO_2 will go on reacting with the carbonate to form bicarbonate,which can be dissolved in the formation water,thus resulting in the enrichment of Ca~(2+) and HCO_3~-.The above reaction can be described by the following equation:CO_2+H_2O+CaCO_3→Ca~(2+)+2HCO_3~-.The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃,which is the minimum for TSR to occur.At the same time,dolomitization,which might be a direct result of TSR,has been found in both the Cambrian and the lower Ordovician.The above evidence indicates that TSR is in an active reaction,providing a novel way to reevaluate the exploration potentials of natural gas in this district.     

Comparison of two potential strategies of planktonic foraminifera for house building: Mg or H removal?

Marine organisms must possess strategies enabling them to initiate calcite precipitation despite the unfavorable conditions for inorganic precipitation in surface seawater. These strategies are poorly understood. Here we compare two potential strategies of marine calcifyers to manipulate seawater chemistry in order to initiate calcite precipitation: Removal of Mg²⁺ and H⁺ ions from seawater solutions. An experimental setup was used to monitor the onset of inorganic precipitation on seed crystals as a function of the Mg²⁺ concentration and pH in artificial seawater. We focused on precipitation rates typical for biogenic calcification in planktonic foraminifera (∼10⁻³ mol m⁻² h⁻¹) and time scales typical for the initiation of calcification in these organisms (minutes to hours). We find that the carbonate ion concentration has to increase by a factor of ∼13 when [Mg²⁺] increases from 0 to 53 mmol kg⁻¹ in order to maintain a typical biogenic precipitation rate. Model calculations for the energy requirement for various scenarios of Mg²⁺ and H⁺ removal including Ca²⁺ exchange and CO₂ diffusion are presented. We conclude that the more cost-effective strategy to initiate calcite precipitation in foraminifera is H⁺ removal, rather than Mg²⁺ removal.     

CO2 and sulfuric acid controls of weathering and river water composition

Reactions of CO₂ with carbonate and silicate minerals in continental sediments and upper part of the crystalline crust produce HCO₃⁻ in river and ground waters. H₂SO₄ formed by the oxidation of pyrite and reacting with carbonates may produce CO₂ or HCO₃⁻. The ratio, ψ, of atmospheric or soil CO₂ consumed in weathering to HCO₃⁻ produced depends on the mix of CO₂ and H₂SO₄, and the proportions of the carbonates and silicates in the source rock. An average sediment has a CO₂ uptake potential of ψ = 0.61. The potential increases by inclusion of the crystalline crust in the weathering source rock. A mineral dissolution model for an average river gives ψ = 0.68 to 0.72 that is within the range of ψ = 0.63 to 0.75, reported by other investigators using other methods. These results translate into the CO₂ weathering flux of 20 to 24 × 10¹²mol/yr.     

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO₂ consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO₂ consumption to silicate weathering than methods utilizing Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and ⁸⁷Sr/⁸⁶Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (P_CO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca²⁺-Mg²⁺-HCO₃⁻ waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca²⁺ and Sr²⁺, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and P_CO2 gradients in the Himalaya.The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO₂. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg²⁺, Ca²⁺, and HCO₃⁻ mass balances support interpretations of preferential Ca²⁺ removal by calcite precipitation. On the basis of patterns of saturation state and P_CO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca²⁺ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca²⁺ during riverine transport brings the Ca/Sr and ⁸⁷Sr/⁸⁶Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr²⁺ budget and suggest that the conventional application of two-component Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations has overestimated silicate-derived Sr²⁺ and HCO₃⁻ fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.