Trace metal–humate interactions. I. Experimental determination of conditional stability constants     

《Applied Geochemistry》2000,15(7):953-973

The enhancement of mobility of radionuclides in the geosphere through complexation by humic substances is a source of uncertainty in performance assessment of radioactive waste repositories. Only very few data sets are available which are relevant for performance assessment of an underground repository for radioactive waste. Using the equilibrium dialysis-ligand exchange method developed at the Paul Scherrer Institut, conditional stability constants for the formation of complexes of Aldrich humic acid with Ca²⁺, NpO₂⁺, Co²⁺, Ni²⁺, UO₂²⁺ and Eu³⁺ and complexes of Laurentian soil- and Suwannee River fulvic acid with Co²⁺, UO₂²⁺ and Eu³⁺ were measured. pH was varied between 5 and 10 and ionic strength between 0.02 and 0.2 M. The data are presented as equilibrium coefficients that are free from any model assumptions. The equilibrium coefficients increased in the order Ca²⁺≅NpO₂⁺<Co²⁺< Ni²⁺<UO₂²⁺< Eu³⁺. The quality of the data is assessed in an extended discussion of statistical and systematical errors, and by a critical ‘rereview’ of the auxiliary stability constants used for the calculation of the equilibrium coefficients. An approximate overall uncertainty of 0.5 log-units is estimated for the stability data reported. The conditional stability constants were found to increase markedly with increasing pH in the case of Co²⁺, UO₂²⁺ and Eu³⁺. For Ni²⁺, Ca²⁺ and NpO₂⁺ this effect was less pronounced. For all metal ions tested, the influence of ionic strength was of less importance, and the conditional stability constants did not show a significant dependence on the type of humic substances investigated.  相似文献   

Hydro-chemical analysis and ionic flux of meltwater runoff from Khangri Glacier,West Kameng,Arunachal Himalaya,India     

Harish Bisht  Prakash Chandra Arya  Kireet Kumar 《Environmental Earth Sciences》2018,77(16):598

The detailed hydro-chemical study of meltwater draining from Khangri glacier Arunachal Pradesh has been carried out to evaluate the major ion chemistry and weathering processes in the drainage basin. The investigative results shows that the meltwater is almost neutral to slightly acidic in nature with Mg–HCO₃-dominated hydro-chemical facies. In glacial meltwater, Ca^+?2 is the most dominated cation followed by Mg⁺², Na⁺, and K⁺, while HCO₃^? is the most dominant anion followed by SO₄^2?, NO₃^?, and Cl^?. The dominant cations such as Ca⁺² and Mg⁺² show a good relation with the minerals abundance of the rocks. Calcite (CaCO₃) and biotite [K(Mg,Fe)₃AlSi₃O₁₀(F,OH)₂] are the most abundant minerals in the deformed carbonate-rich metasedimentary rocks near to the snout with some K feldspar (KAlSi₃O₈) and quartz (SiO₂). This suggests Ca⁺² have definitely entered into the water due to the dissolution of calcite and Ca feldspar (CaAl₂Si₂O₈), while one of the source of Mg⁺² is biotite. Na feldspar (NaAlSi₃O₈) has contributed towards the availability of sodium ion, while potassium ion is derived from the chemical weathering of K feldspar and biotite. The chemical weathering is the foremost mechanism controlling the hydro-chemistry of the Khangri glacier because of the least anthropogenic interferences. The mineralogy of surrounding rocks is studied to understand better, the rock–water interaction processes, and their contribution towards ionic concentration of meltwater. The meltwater discharge and individual ion flux of the catchment area have also been calculated, to determine the ionic denudation rate for the ablation season. The high elemental ratio of (Ca?+?Mg)/(Na?+?K) (7.91?±?0.39 mg/l) and low elemental ratio of (Na?+?K)/total cations (0.11?±?0.004) indicate that the chemical composition of meltwater is mainly controlled by carbonate weathering and moderately by silicate weathering. The scatter plot result between (Ca?+?Mg) and total cations confirms that carbonate weathering is a major source of dissolved ions in Khangri glacier meltwater. In addition, the statistical analysis was also used to determine the correlation between physical parameters of glacier meltwater which controlled the solute dynamics.  相似文献   

Complexation of Pb(II) by Chloride Ions in Aqueous Solutions     

Robert H. Byrne  Wensheng Yao  Yanxin Luo  Frank J. Millero 《Aquatic Geochemistry》2010,16(3):325-335

Lead chloride formation constants at 25°C were derived from analysis of previous spectrophotometrically generated observations of lead speciation in a variety of aqueous solutions (HClO₄–HCl and NaCl–NaClO₄ mixtures, and solutions of MgCl₂ and CaCl₂). Specific interaction theory analysis of these formation constants produced coherent estimates of (a) PbCl⁺, \textPbCl₂⁰ {\text{PbCl}}_{2}^{0} , and PbCl₃⁻ formation constants at zero ionic strength, and (b) well-defined depictions of the dependence of these formation constants on ionic strength. Accompanying examination of a recent IUPAC critical assessment of lead formation constants, in conjunction with the spectrophotometrically generated formation constants presented in this study, revealed significant differences among various subsets of the IUPAC critically selected data. It was found that these differences could be substantially reduced through reanalysis of the formation constant data of one of the subsets. The resulting revised lead chloride formation constants are in good agreement with the formation constants derived from the earlier spectrophotometrically generated data. Combining these data sets provides an improved characterization of lead chloride complexation over a wide range of ionic strengths:

log \text Cl b 1 = 1. 4 9 1- 2.0 4 I 1/ 2 ( 1+ 1. 5 I 1/ 2 ) - 1 + 0. 2 3 8 I log \text Cl b 2 = 2.0 6 2- 3.0 6 I 1/ 2 ( 1+ 1. 5 I 1/ 2 ) - 1 + 0. 3 6 9 I log \text Cl b 3 = 1. 8 9 9- 3.0 6 I 1/ 2 ( 1+ 1. 5 I 1/ 2 ) - 1 + 0. 4 3 9 I. \begin{gathered} {\log}\,{}_{\text{ Cl}} \beta_{ 1} = 1. 4 9 1- 2.0 4\,I^{ 1/ 2} \left( { 1+ 1. 5\,I^{ 1/ 2} } \right)^{ - 1} +\,0. 2 3 8\,I \hfill \\ {\log}\,{}_{\text{ Cl}} \beta_{ 2} = 2.0 6 2- 3.0 6\,I^{ 1/ 2} \left( { 1+ 1. 5\,I^{ 1/ 2} } \right)^{ - 1} +\,0. 3 6 9\,I \hfill \\ {\log}\,{}_{\text{ Cl}} \beta_{ 3} = 1. 8 9 9- 3.0 6\,I^{ 1/ 2} \left( { 1+ 1. 5\,I^{ 1/ 2} } \right)^{ - 1} +\,0. 4 3 9\,I. \hfill \\ \end{gathered}  相似文献    17. Arsenic-bearing carbonate waters: Geochemical and thermodynamic analysis of their genesis,transformation of arsenic migration species,and models for the genesis of hydrogenic as sulfide mineralization      S. R. Krainov  B. N. Ryzhenko  E. V. Cherkasova 《Geochemistry International》2007,45(12):1235-1257 Analysis of hydrogeochemical materials on As distribution in CO2-bearing (carbonate) waters in various regions and the thermodynamic simulation of geochemical processes in rock-CO2-bearing water systems made it possible to constrain the optimal conditions for As transfer from rocks into carbonate waters and the accumulation of this element in the waters. The problem was solved with regard for the various rates of As transitions from rocks to water: (a) high rates of As transitions from rocks in compliance with the ion exchange mechanism and (b) low rates of As transitions from rocks in compliance with the mechanism involving the decomposition of As-bearing minerals. Various mechanisms of As extraction from rocks result in the compositional diversity of the aqueous phase and various As migration species in CO2-bearing waters, which, in turn, control the equilibrium concentration levels of this element. The principally important boundary conditions of As enrichment in CO2-bearing waters are high \(P_{CO_2 } \) and R/W ratios in the geochemical systems, a preliminary increase in the Cl concentration in the CO2-bearing waters, and the origin of these waters at high-density heat fluxes. As migration species were simulated for the model solutions and real carbonate waters of various geochemical types, and it is demonstrated that the predominant As species are oxygen-bearing HAsO 2 0 , and AsO 2 ? at a subordinate role of the sulfide HAs2S 4 2? , and As2S 4 2? — species even at high Σ S2? in the system. Two models of the genesis of solid As sulfides in CO2-bearing waters are analyzed: (1) with oxygen-bearing species (HAsO 2 0 , and AsO 2 ? ), which occur most widely, and (2) with sulfide species (As2S 4 2? , HAs2S 4 ? , and As4S 7 2? ), which occur not as widely.  相似文献    18. The effect of cobalt ion on nucleation of calcium-carbonate polymorphs      David M. Barber  Philip G. Malone  Robert J. Larson 《Chemical Geology》1975,16(3):239-241 Cobalt, like Mg, may cause the precipitation of aragonite rather than calcite in aqueous solutions due to the adsorption and crystal poisoning of calcite by a hydrated ion. Solutions containing NaCl and CaCl2, having the ionic strength and Ca content of seawater (35‰ salinity), were spiked with known amounts of CoCl2. Calcium carbonate was precipitated by the addition of 0.7 ml of 1 M Na2CO3. All experimental runs were made at 25°C, and all products were examined by X-ray diffraction. At low concentrations of Co (< 5·?4M) calcite and vaterite formed. At concentrations from 5·10?4 M to 2·10?3M, the products consisted of combinations of calcite and vaterite; aragonite and calcite; aragonite and vaterite; calcite, vaterite and aragonite. In solutions of 3·10?3M CoCl2, most precipitates were aragonite with only one sample containing a small amount of calcite. All precipitates from 5·10?3M CoCl2 solutions either contained aragonite or were amorphous. Solutions with concentrations of 1 · 10?2M CoCl2 produced only amorphous precipitates. All precipitates contained an amorphous violet phase, assumed to be basic cobaltous carbonate (2CoCO3·Co(OH)2·H2O).  相似文献    19. Dissolution Kinetics of Calcite in NaCl–CaCl2–MgCl2 Brines at 25 °C and 1 bar pCO2      Dwight K. Gledhill  John W. Morse 《Aquatic Geochemistry》2004,10(1-2):171-190 Calcite dissolution rates were measured as a function of saturation state in NaCl–CaCl2–MgCl2 solutions at 1 bar (0.1 MPa) pCO2 and 25 °C. Rates measured in phosphate- and sulfate-free pseudo-seawater (Ca2+:Mg2+= 0.2, I= 0.7) were compared with those in synthetic brines. The brines were prepared by co-varying calcium and magnesium (Ca2+:Mg2+= 0.9; 2.0; 2.8; 3.1; 4.8; 5.8) along with ionic strength (I= 0.9; 1.1; 1.6; 2.1; 3.0; 3.7; 4.4 m) to yield solutions approximating those of subsurface formation waters. The rate data were modeled using the equation, R = k(1 ? Omega;) n , where k is the empirical rate constant, n describes the order of the reaction and ω is saturation state. For rates measured in the pseudo-seawater, n= 1.5 and k= 4.7 × 10?2 mol m?2 hr?1. In general, rates were not significantly faster in the synthetic brines (n= 1.4 ± 0.2 and k= 5.0 ± 7 × 10?2 mol m?2 hr?1). The rate coefficients agree within experimental error indicating that they are independent of ionic strength and Ca2+:Mg2+ over a broad range of brine compositions. These findings have important application to reaction-transport modeling because carbonate bearing saline reservoirs have been identified as potential repositories for CO2 sequestration.  相似文献    20. Groundwater quality on the territory of Kikinda municipality (Vojvodina,Serbia)      Nenad Marić  Sanja Mrazovac Kurilić  Ivan Matić  Stanko Sorajić  Jelena Zarić 《Environmental Earth Sciences》2014,72(2):525-534 This paper provides insight into the quality of groundwater used for public water supply on the territory of Kikinda municipality (Vojvodina, Serbia) and main processes which control it. The following parameters were measured: color, turbidity, pH, KMnO4 consumption, TDS, EC, NH4 +, Cl?, NO2 ?, NO3 ?, Fe, Mn, total hardness, Ca2+, Mg2+, SO4 2+, HCO3 ?, K+, Na+, As. The correlations and ratios among parameters that define the chemical composition were determined aiming to identify main processes that control the formation of the chemical composition of the analyzed waters. Groundwater from 11 analyzed sources is Na–HCO3 type. Intense color and elevated organic matter content of these waters originate from humic substances. The importance of organic matter decay is assumed by positive correlation between organic matter content and TDS, HCO3 content. There is no evidence that groundwater chemistry is determined by the depth of captured aquifer interval. The main processes that control the chemistry of all analyzed water are cation exchange and feldspar weathering.  相似文献