Complexation of Cu2+ and Pb2+ by peat and humic acid

The binding of metal to humic substances is problematical. The approaches for studying metal binding to organic matter are briefly reviewed. Ion-selective electrodes (Cu²⁺ and Pb²⁺) were used to measure metal complexation by a whole peat and an extracted humic acid (HA) fraction. Scatchard plots and calculation of incremental formation constants were used to obtain values for the binding constants for the metals onto both peat and HA. Both the peat and the humic acid had a larger maximum binding capacity for Pb²⁺ than for Cu²⁺ (e.g. at pH = 5 HA gave 0·188 mmol Cu²⁺ g^?1 and 0·564 mmol Pb²⁺ g^?1: peat gave 0·111 mmol Cu²⁺ g^?1 and 0·391 mmol Pb²⁺ g^?1). Overall, the humic acid had a larger metal binding capacity, suggesting that extraction caused conformational or chemical changes. The binding constants (K₁) for Cu²⁺ increased with increasing pH in both peat and humic acid, and were larger in the peat at any given pH (e.g. at pH = 5 HA gave log K₁= 2·63, and peat gave log K¹= 4·47 for Cu²⁺). The values for Pb²⁺ showed little change with pH or between peat and humic acid (e.g. at pH = 5 HA gave log K¹= 3·03 and peat gave log K¹= 3·00 for Pb²⁺). In the peat, Cu²⁺ may be more able to bind in a 2:1 stoichiometric arrangement, resulting in greater stability but smaller binding capacity, whereas Pb²⁺ binds predominantly in a 1:1 arrangement, with more metal being bound less strongly. Whole peat is considered to be more appropriate than an extracted humic acid fraction for the study of heavy metal binding in organic soils, as this is the material with which metals introduced into an organic soil would interact under natural conditions.     

KINETICS OF ION EXCHANGE IN SOIL ORGANIC MATTER. IV. ADSORPTION AND DESORPTION OF Pb2+, Cu2+, Cd2+, Zn2+ AND Ca2+ BY PEAT

The equilibria as well as the rates of adsorption and desorption of the ions Pb²⁺, Cu²⁺, Cd²⁺, Zn²⁺, and Ca²⁺ by soil organic matter were determined in batch experiments as a function of the amount of metal ions added to an aqueous suspension of HCl-washed peat. Simultaneous determination of the metal ions and hydrogen ions in the solution by atomic absorption spectrophotometry and pH-measurements showed that the adsorption of one divalent metal ion by peat was coupled with the release of two hydrogen ions. Since this equivalent ion-exchange process causes a corresponding increase of the electric conductivity of the solution, the rates of the adsorption and desorption processes were determined by an immersed conductivity electrode. The distribution coefficients show that the selective order for the metal adsorption by peat is Pb²⁺ > Cu²⁺ > Cd²⁺≌ Zn²⁺ > Ca²⁺ in the pH range of 3·5 to 4·5. The slope of -2, as observed in a double logarithmic plot of the distribution coefficients versus the total solution concentration confirms the equivalence of the ion-exchange process of divalent metal ions for monovalent H₃O⁺ -ions in peat. The absolute rates of adsorption, as well as the rates for the fractional attainment of the equilibrium, increase with increasing amounts of metal ions added. This behaviour is also observed for the subsequent desorption of the metal ions by H₃O⁺-ions. At a given amount of metal ions added, the absolute rates of adsorption decrease in the order Pb²⁺ > Cu²⁺ > Cd²⁺ > Zn²⁺ > Ca²⁺, while the rates for the fractional attainment of the equilibrium decrease in the order Ca²⁺ > Zn²⁺≌ Cd²⁺ > Pb²⁺ > Cu²⁺. The half times for adsorption and desorption were in the range of 5 to 15 sec.     

Formation constants of cu2+ complexes with humic and fulvic acids

Formation constants for Cu²⁺ complexes with humic and fulvic acids were determined by a modification of the well-known Bjerrum potentiometric titration method. Highly stable complexes were formed with formation constants of the order of those observed for synthetic polycarboxylic acids. Overall formation constants for a two-step process (B₂) ranged from 2.5 · 10^?4 to 7.9 · 10^?3.     

恒电荷土壤胶体对Cu2+ 、Pb2+ 的静电吸附与专性吸附特征

供试土壤胶体对Cu2 、Pb2 的吸附强度用pH50 值表示 ,其大小次序为 :土 >黄绵土、黑垆土 >黄褐土。离子强度实验和表面络合反应机制证明恒电荷土壤胶体对Cu2 、Pb2 的吸附含有专性吸附 ,n值可作为判断专性吸附与静电吸附比例的特征值 ,低pH值时 ,以水解 -络合吸附为主 ;高pH值时 ,以水解 -络合与沉淀吸附为主。静电吸附和专性吸附的比例与pH有关 ,各土壤胶体专性吸附百分数大小为 :黄褐土 >土 >黑垆土 >黄绵土。不同土壤胶体在同一介质中对Cu2 、Pb2 的固有络合常数logKintM 值及固有络合ΔG m 负值大小次序与吸附强度大小一致。在定pH定浓条件下 ,考虑离子之间的相互作用时 ,土壤胶体对重金属离子的吸附过程可用BDM等温式描述。供试土壤胶体对Cu2 、Pb2 专性吸附ΔG m 的大小与固有络合ΔG m 接近且大小次序也一致。     

Stability constants of complexes of metals with humic and fulvic acids under non-acid-conditions

Stability constants of complexes of four divalent metal ions viz. Cu²⁺, Zn²⁺, Mn²⁺ and Ca²⁺ with humic (HA) and fulvic acids (FA) at pH values of 7 and 8 were determined. The log K (logarithm of the stability constant) ranged from 3.09 to 7.77 and from 2.22 to 5.98 for metal-humic and metal fulvic acid complexes, respectively. Sequentially, the order of stability constants were as follows: Cu> Ca> Mn> Zn and Cu> Ca> Zn> Mn for metal -HA and metal-FA complexes, respectively, indicating a higher degree of complexation with Cu metal ion.     

Physicochemical simulation of the ion exchange between humus acids and cations of different valencies

An approximate calculation was made for the ion exchange of black humic acids and the related fulvic acids with the cations H⁺, K⁺, Na⁺, Ca²⁺, Mg²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe³⁺, and Al³⁺. The calculation was based on the method of physicochemical simulation, the concepts of the chemical potentials of the elements, the experimental study of the equilibriums, and the determination of the activity coefficients of the monoionic forms of humus acids. Because of the presence of different functional groups, humus acids are considered as two-phase systems with specific activity coefficients for the monoionic forms of these acids in each phase. Examples of experimental studies and practical calculations of ion-exchange equilibriums in wide ranges of humus and solution cationic compositions were compared. Although the proposed approaches require perfecting, they can be used for solving practical problems and controlling equilibriums at the experimental stage.     

Effect of the particle-size distribution on the adsorption of copper, lead, and zinc by Chernozemic soils of Rostov oblast

The parameters of adsorption of Cu²⁺, Pb²⁺, and Zn²⁺ cations by soils and their particle-size fractions were studied. The adsorption of metals by soils and the strength of their fixation on the surface of soil particles under both mono- and polyelement contamination decreased with the decreasing proportion of fine fractions in the soil. The adsorption capacity of the Lower Don chernozems for Cu²⁺, Pb²⁺, and Zn²⁺ depending on the particle-size distribution decreased in the following sequence: clay loamy ordinary chernozem ∼ clay loamy southern chernozem > loamy southern chernozem > loamy sandy southern chernozem. According to the parameters of the adsorption by the different particle-size fractions (C _max and k), the heavy metal cations form a sequence analogous to that obtained for the entire soils: Cu²⁺ ≥ Pb²⁺ > Zn²⁺. The parameters of the heavy metal adsorption by similar particle-size fractions separated from different soils decreased in the following order: clay loamy chernozem > loamy chernozem > loamy sandy chernozem. The analysis of the changes in the parameters of the Cu²⁺, Pb²⁺, and Zn²⁺ adsorption by soils and their particlesize fractions showed that the extensive adsorption characteristic, namely, the maximum adsorption (C _max), was a less sensitive parameter characterizing the soil than the intensive characteristic of the process—the adsorption equilibrium constant (k).     

Ion exchange properties of humus acids

Ion exchange equilibriums in a complex of brown humic acids (HAs) and related fulvic acids (FAs) with cations (H⁺, K⁺, Na⁺, Ca²⁺, Mg²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe³⁺, and Al³⁺) have been studied, and the activity coefficients of the acid monoionic forms have been determined. The composition of the stoichiometric cell in the system of black and brown HAs and related FAs in a leached chernozem of the Ob’ region has been calculated with consideration for the earlier studies of the ion exchange properties of black HAs and related FAs. It has been shown that hydrogen, calcium, magnesium, aluminum, and iron are the major components in the exchange complex of humus acids in the leached chernozem with the other cations being of subordinate importance. In spite of some differences between the analytical and calculated compositions of the humus acids, the results of the calculations can be considered satisfactory. They indicate that calculations are feasible for such complex objects as soils, and their accuracy will improve with the expansion of the experimental studies. The physicochemical simulation of the transformation of the humus acid composition under different acid-base conditions shows that the contents of most cations decrease under alkalization, and hydroxides or carbonates become the most stable forms of these cations. Under the acidification of solutions, the binding of alkaline and alkaline-earth elements by humus acids decreases and the adsorption of iron and aluminum by humus acids increases.     

Comparative analysis of mono- and polyelement adsorption of copper,lead, and zinc by an ordinary chernozem from nitrate and acetate solutions

Isotherms of mono- and polyelement adsorption of Cu²⁺, Pb²⁺, and Zn²⁺ by an ordinary chernozem were described by the Langmuir equation. The values of the adsorption constant k decreased in the range Cu²⁺ > Pb²⁺ ≫ Zn²⁺ for the monoelement adsorption from nitrate and acetate salt solutions, Cu²⁺ > Pb²⁺ > Zn²⁺ for the polyelement adsorption from nitrate solutions, and Pb²⁺ > Cu²⁺ ≫ Zn²⁺ for the polyelement adsorption from acetate solutions. The maximum adsorption (C _{max, ∞}) of individual cations at the polyelement contamination was always lower than at the monoelement contamination because of the mutual competition. At the same time, the values of k for the polyelement adsorption were higher than those for the monoelement adsorption because heavy metals (HMs) interact with most of the specific adsorption centers. It was shown that the ratio between the content of exchangeable cations displaced from the soil exchangeable complex (SEC) into the solution and the content of adsorbed HMs decreased with the increasing concentration of adsorbed HMs. These values could be higher (for Cu²⁺), equal, or lower than 1 (for Pb²⁺ and Zn²⁺). In the former case, this was due to the dissolution of readily soluble salts at low HM concentrations in the SEC. In the latter case, this was related to the adsorption of associated HMs and the formation of new phases localized on the surface of soil particles at high HM concentrations in the SEC.     

Interactions between montmorillonite and fulvic acid

The isotherms at 20°C for the adsorption of ¹⁴C-labelled fulvic acid from aqueous solutions by montmorillonite containing different exchangeable cations, have been determined. Below a concentration of 0.45 mg/ml and at near neutral pH, all samples give linear isotherms, the slope of which increases in the order Ba²⁺ < Ca²⁺ < Zn²⁺ < La³⁺ < Al³⁺ <Cu²⁺ < Fe³⁺. In the absence of interlayer expansion, the shape of the isotherms is interpreted in terms of solute entry into intercrystalline pores within a clay domain. The affinity of fulvic acid for the clay surface is related to the ionic potential or polarising power of the exchangeable cation. It is inferred that fulvic acid adsorbs by hydrogen bonding between an anionic group of the acid and a water molecule in the primary hydration shell of the saturating cation. Comparison of the data with those for the humic acid extracted from the same organic matter source, indicates that secondary interactions between adsorbed molecules or directly with the montmorillonite surface, contribute to the overall affinity. With samples saturated with Al³⁺, Fe³⁺, and Cu²⁺ ions, part of the adsorbed fulvic acid may also be attached to the clay by a complexation reaction involving the metals as such, or when they exist as polyhydroxy compounds at the mineral surface.     

Specific and non-specific adsorption of inorganic ions

The authors reported that the relative bonding strength between ligand of soil colloid surface and cations could be obtained easily by the measurement of MCSA, and that the MCSA corresponded to the constant of Langmuir's adsorption isotherm equation.

The relative bonding strength of cations with respect to kaolinitic soil clay at pH 6 was, Cr³⁺>Fe³⁺, Al³⁺>Ga⁸⁺>Cu⁸⁺>Pb²⁺>Y³⁺, La³⁺>Mn²⁺>Ni²⁺, Co²⁺> Zn²⁺>Sr²⁺, Mg²⁺>NH⁴⁺, K⁺, and with respect to colloid with humus coating, Y³⁺, La³⁺>Pb²⁺>Cu²⁺, and the other orders were same.

The solubility of cations in soil colloid aqueous dispersion system was calculated from the values of MCSAs, and considered as follows, Y³⁺, La³⁺, Cu³⁺, Pb³⁺, Mn²⁺, Ni²⁺, CO²⁺: concentration in soil solution and soil geochemical mobility may be regulated by the specific adsorption reaction, Zn²⁺, Mg²⁺, Sr²⁺, K⁺, NH⁴⁺: concentration in soil solution and soil geochemical mobility may be regulated by the non-specific adsorption reaction, but at neutral to alkaline condition, Zn²⁺ and Mg²⁺ may specifically adsorb on soil, clays, Fe³⁺, Cr³⁺, Al³⁺, Ga³⁺: concentration in soil solution and soil geochemical mobility may be regulated by the solubility of their oxide hydrates.     

Formation of metal-humic acid complexes by titration and their characterization by differential thermal analysis and infrared spectroscopy

Humic acid (HA) extracted from a Eustis loamy sand (Psammentic Paleudult, Red Yellow Podzolic soil) was flocculated by titration with Al³⁺-, Fe³⁺-, Cu²⁺-, Zn²⁺-, Mn²⁺-, Ba²⁺-, Ca²⁺-, and Mn²⁺-chloride solutions, respectively, to determine possible development of metal-HA complexes, as reported by Flaig et al. (1975), and Tiurin and Kononova (1962). Titration was conducted with HA solutions with an initial pH 11.5 or 7.0. The results indicated that the cations used, except Mg²⁺, yielded insoluble complexes with HA, irrespective of initial pH. After titration, the pH of the metal-HA flocs was 6.0–7.0, which was expected in view of the presence of cation exchange and buffering capacity of HA compounds. More complex formation through electrovalent and covalent bonding by COO^? and phenolic OH groups of the HA molecule was only attained by the use of HA solutions with pH 11.5. On the other hand, less complex formation occurred by the use of HA solutions with an initial pH 7.0, through electrovalent bonding by COO^? groups. Differential thermal analysis (d.t.a.) curves of HA showed shifts in temperatures of the main decomposition peak as a result of flocculation with the different metals. Based on the type of the cations involved, the metal-humic acid flocs could be listed in the following decreasing order of thermal stability: Al³⁺ = Zn²⁺ = Mg²⁺ ≥ HA > Ca²⁺ > Ba²⁺ > Fe³⁺ > Cu²⁺ > Mn²⁺. A systematic relationship could not be found indicating that trivalent ions resulted in the formation of thermally less stable metal-humic acid flocs than divalent ions, as has been reported for HA-metal complexes. Physical mixtures of HA and metal hydroxides exhibited d.t.a. features resembling those of original (nontreated) HA, but not those of the HA-metal flocs.Infrared spectroscopy revealed increased absorption for COO^? vibrations at 1620 and 1400cm^?1 in spectrograms of metal-HA flocs compared to that of original humic acid, a phenomenon explained by many authors to be caused by bonding of the metal ions in hydrated form to the carboxyl or phenolic hydroxyl groups or both of the humic acid molecule. HA-flocs formed from solutions with an initial pH 11.5 had identical i.r. spectra compared with those formed from solutions with an initial pH 7.0.     

Adsorption features of Cu(II), Pb(II), and Zn(II) by an ordinary chernozem from nitrate,chloride, acetate,and sulfate solutions

The effect of Cl^?,SO ₄ ^2? , CH₃COO^?, and NO ₃ ^? anions on the adsorption of copper, lead, and zinc by an ordinary chernozem has been studied. The effect of the anions on the adsorption of Cu²⁺, Pb²⁺, Zn²⁺ ions is significant but uncertain. It has been shown that the attendant anions affect the shape of the adsorption isotherms, which are described by the Langmuir, Freundlich, or Henri equations. The constants of the adsorption from a nitrate solution calculated from the Langmuir equation (K _L) decrease in the following order: Cu²⁺ > Pb²⁺ >> Zn²⁺. The values of the maximum adsorption (C _max) decrease in the following order: Cu²⁺ ≥ Zn²⁺ > Pb²⁺ for acetate solutions and in the series Pb²⁺ > Zn²⁺ ≥ Cu²⁺ for nitrate solutions. The values of the Henry constants (K _H) calculated for the adsorption of the same cations from chloride solutions decrease in the same order as the values of K _L. The CH₃COO^? anion has the highest effect on the constant values. The NO ₃ ^? and Cl^? anions “switch their places” depending on the attendant cation, but their effect is always lower than that of the acetate anion. The values of C _max for copper and zinc are most affected by the CH₃COO^? anion, and the adsorption of zinc is most affected by the Cl^? and NO ₃ ^? anions. The assessment of the mobility of the adsorbed cations from the extraction with ammonium acetate (pH 4.8) has shown that the content of the desorbed metals is always lower than the content of the adsorbed cations and varies from 0.025 to 83%. According to their mobility, the adsorbed metals form the following order: Zn²⁺ > Pb²⁺ > Cu²⁺. The effect of the attendant anions on the extractability of the adsorbed cations decreases in the following order: chlorides > sulfates > acetates > nitrates.     

Chelating–Ultrafiltration Treatment of Some Heavy Metal Ions in Aqueous Solutions by Crosslinking Carboxymethyl Modified Cornstarch

Crosslinking carboxymethyl starch (CCMS) powder of degree of substitution (DS) 0.43–0.59 was prepared by the process of two steps of alkali addition synthesis. The technique of powder coupling with ultrafiltration was used to absorb Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺, and Cd²⁺ from aqueous solutions. FTIR was used to demonstrate the successfully grafting of carboxymethyl groups, and the technique of microwave plasma torch atomic emission spectrometer was applied in rapid determination of the aforementioned heavy metals ions. The results revealed that the removal sequence of heavy metal ions followed the order of Pb²⁺>Cu²⁺>Cd²⁺>Zn²⁺>Ni²⁺. By assistant of diethylene triamine penlaacetic acid, the quaternary system of Pb²⁺/Ni ²⁺/Cd²⁺/Cu²⁺ mixture solution could have the ideal separation. Besides, the influence of pH, ζ potential, DS value, and membranes molecular weight cut-off on removal of 20 mg L⁻¹ Pb²⁺ or Ni²⁺ was also investigated.     

应用穆斯堡尔(Mössbauer)谱学方法研究Fe+++, Fe++与胡敏酸结合的性质

本文应用穆斯堡尔谱学方法,研究了在不同pH条件下Fe⁺⁺⁺,Fe⁺⁺与胡敏酸结合的性质。计算机拟合的pH3.0⁵⁷Fe-胡敏酸络合物泥浆的穆斯堡尔谱和参数表明,三对四极双峰(图1,AA',BB',CC')是合理的。在pH3.0 Fe⁺⁺⁺以高自旋态存在,它和胡敏酸的结合多于一种环境类型。在pH1.0的⁵⁷Fe-胡敏酸络合物中,观察到了Fe⁺⁺⁺的穆斯堡尔谱信号,但没有Fe⁺⁺的信号,在这个样品离心分离出的液体部分检测到了加入量的59.7%的铁,表明在pH1.0时相当数量的Fe⁺⁺⁺被胡敏酸还原成Fe⁺⁺,Fe⁺⁺并不与胡敏酸牢固结合。在30伏电析过的⁵⁷Fe-胡敏酸络合物样品中(pH2.8)出现了Fe⁺⁺⁺,Fe⁺⁺的穆斯堡尔谱,这一结果指示出,在电析过程中由于⁵⁷Fe⁺⁺⁺-胡敏酸络合物悬浮液pH的降低,一部分Fe⁺⁺⁺还原成Fe⁺⁺,在pH2.8相当数量的Fe⁺⁺与胡敏酸牢固结合。根据在80K记录的穆斯堡尔谱,在pH1—3的范围出现了磁有序成份,但在室温记录的穆斯堡尔谱没有磁分裂。     

THERMODYNAMICS AND THERMOCHEMISTRY OF THE EXCHANGE REACTION BETWEEN NH4+ AND Mn2+ IN A MONTMORILLONITE CLAY

The exchange reaction between NH₄⁺ and Mn³⁺ was studied on a montmorillonite clay at several temperatures and different ionic strengths. Manganese was preferred to ammonium; this preference increased with the temperature and dilution of the dialysate. Comparison with published data concerning exchanges involving NH₄⁺ and the alkaline-earths showed that in the sequence of increasing selectivity: Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺, Mn²+ lies between Mg²⁺ and Ca²⁺. The enthalpy change was measured calorimetrically and calculated by application of the van't Hoff law to the temperature coefficient of the equilibrium constants. Both values were in good agreement. The excellent recoveries of Mn²⁺ at the end of the exchange reaction and the constancy of the cation exchange capacity over the whole range of surface composition ruled out the possibility of significant adsorption in the MnOH⁺ form. The behaviour of manganese was very similar to that of the alkaline-earth cations.     

Ca2+和CaM对苹果果实Ca2+-ATPase,SOD和PEA活性的影响

采用45Ca2+ 示踪等方法研究苹果果肉质膜微囊Ca2+ ATPase与Ca2+ 运输之间的关系 ,在Ca2+ 和CaM激活剂和抑制剂存在条件下培养果实圆片 ,探索Ca2+-ATPase ,SOD和PEA活性受Ca2+和 (或 )CaM调控的可能性。结果表明 ,存在于质膜上的Ca2+-ATPase并受载体A23187刺激而活性增加 ,Ca2+-ATPase活性与Ca2+运输依抑制剂EB浓度增加而下降 ,二者变化趋势十分一致 ,从而证实了Ca2+-ATPase推动苹果果肉质膜微囊Ca2+的主动运输。果肉质膜微囊Ca2+-ATPase同时受到Ca2+和CaM调节 ,而SOD和PEA活性仅受Ca2+ 的调节 ,而与CaM无关。     

Removal of Copper,Lead, Methylene Green 5, and Acid Red 1 by Saccharide-Derived Spherical Biochar Prepared at Low Calcination Temperatures: Adsorption Kinetics,Isotherms, and Thermodynamics

Spherical biochar derived from saccharides (glucose, sucrose, and xylose) was prepared through two steps: pre-hydrothermal carbonization at 190 °C and calcination at low temperatures (200–325 °C). The spherical biochar was characterized by Brunauer–Emmett–Teller (BET) surface area analysis, Fourier transform infrared spectroscopy, zeta potential, scanning and transmission electron microscopies, and X-ray diffraction. The result indicated that the spherical biochar exhibited low S _BET (15–22 m²/g), but abundant superficial active oxygen-containing functional groups. The spherical biochar possessed a negatively charged surface within solution pH 2.0–11. The adsorption process of Pb²⁺, Cu²⁺, and methylene green 5 (MG5) was strongly dependent on the solution pH and reached fast equilibrium at approximately 60 min. The maximum Langmuir adsorption capacity (Q°_max) exhibited the following order: glucose-biochar > sucrose-biochar > xylose-biochar prepared at 300 °C. The selective adsorption order of glucose-biochar was Cu²⁺ (0.894 mmol/g) > Pb²⁺ (0.848 mmol/g) > MG5 (0.334 mmol/g). The electrostatic attraction played a determining role in the adsorption mechanism of pollutant cations. The adsorption of anionic dye (acid red 1) on the spherical biochar was negligible because of electrostatic repulsion. The spherical biochar can serve as a newer and promising adsorbent to remove toxic pollutant cations from water media.     

The H+/M2+ exchange stoichiometry of calcium and zinc adsorption by ferrihydrite

The specific adsorption of Ca²⁺ and Zn²⁺ by ferrihydrite results in the net release of H⁺. The rate and H⁺/M²⁺ exchange stoichiometry of this reaction were monitored with a pH-stat. A rapid reaction of less than 6 min was followed by a slower reaction which continued at a diminishing rate for at least 2 days. Adsorption of Ca²⁺ at pH 7.8 and Zn²⁺ at pH 5.4 resulted in the net release of 0.92 and 1.70 mol H⁺/mol M²⁺ adsorbed, respectively. For Zn²⁺ adsorption, this stoichiometry was shown to be independent of pH. These estimates agree well with independent estimates based on the pH dependence of adsorption. The difference between the Ca²⁺ and Zn²⁺ stoichiometries was related to the differing acidity of the –OH₂ ligands attached to the adsorbed ions.