Phosphate alters the compositional characteristics of humic acid adsorbed onto goethite

Journal of Soils and Sediments - The adsorption of organic matter and phosphate on minerals is a common natural process that has an important impact on the migration and burial of carbon and...     

Interactions of allophane with humic acid and cations

Allophanic soils are known to accumulate organic matter, but the underlying mechanism is not well understood. Here we have investigated the sorption of humic acid (HA) by an allophanic clay in the presence of varied concentrations of either CaCl₂ or NaCl as background electrolytes. Both the HA and the clay were separated from New Zealand soils. Much more HA was sorbed in CaCl₂ than in NaCl of the same ionic strength. Apparently Ca²⁺ ions were more effective than Na⁺ ions in screening the negative charge on HA. In CaCl₂ the HA molecule might also assume a more compact configuration than in NaCl. In the presence of CaCl₂ sorption increased, reached a maximum, and then declined as the concentration of HA in solution was increased. This behaviour was not observed in NaCl where sorption showed a gradual and steady increase with HA concentration. We propose that ligand exchange occurs between the surface hydroxyl groups of allophane and the carboxylate groups of HA. As a result, the allophane–HA complex acquires negative charges, requiring the co‐sorption of extraneous cations (Ca²⁺ or Na⁺) for charge balance. The Ca²⁺ co‐sorbed can attract more HA to the complex possibly by a cation‐bridging mechanism, giving rise to a maximum in sorption. The decline in sorption beyond the maximum may be ascribed to a decrease in the concentration of free Ca²⁺ ions through binding to HA molecules in solution. The increase in supernatant pH may be attributed to a ligand exchange reaction between the surface hydroxyls of allophane and the carboxylate groups of HA, and proton binding to the allophane–HA complex.     

Observations and modelling of the reactions of 10 metals with goethite: adsorption and diffusion processes

A sample of goethite was mixed for periods which ranged from 2 hours to 8 weeks with solutions of dilute nitrate salts of Pb, Hg, Cd, Zn, Cu, Ni, Co, Mn, Cr and Al. The amount of sorption after each period was measured for an appropriate pH range for each metal. The sorption behaviour was characterized both by using characteristics of the sorption curves such as the pH at which half of the added metal was sorbed (pH₅₀) and by fitting a model in which sorption was mainly characterized by an affinity constant and by a diffusion constant. Initial sorption, whether characterized by the pH₅₀ or by the affinity constant, was closely correlated with the appropriate dissociation constants of the metals. The greater the affinity of the metals for hydroxide ions, the greater their affinity for the goethite surface. The metals differed in the rate at which they continued to react with the goethite. Lead had the slowest continuing reaction, cobalt the fastest. The continuing reaction was due to diffusion into the particles. It was characterized by the fitted diffusion constant and by the change with time in the pH₅₀. For seven of the eight divalent metals, these were correlated with the ionic radius of the metals: the larger the radius, the slower the reaction. For Al and Cr, rates were slower than would be expected from the ionic radii and we suggest this shows that these ions react as the larger M(OH)²⁺ ions. The behaviour of Ni was consistent with oxidation of the surface species and diffusion of Ni(OH)²⁺ ions. The continuing reaction was similar to that observed when metal ions react with soils and suggests that their reaction with iron oxides is important in soils. The results also show that studies in which sorption is measured at only one period of reaction are incomplete and the application of equilibrium models to such results is misleading.     

Phosphate sorption by natural hematites

Iron (hydr)oxides are active phosphate sorbents in soils and sediments, but no information exists on phosphate (P) sorption by natural hematites. In this study, we characterized the chemical, mineralogical and P-sorption properties of 14 hematite-rich natural materials of different origins. Phosphate sorption was described by a modified Freundlich equation including a time term. Phosphate sorbed at 1d at an equilibrium concentration of 1 mg P dm^?3 ranged widely (0.2–1.7 μmol m^?2). After 1 d, hematites showed a marked slow sorption. At 75 d, and an equilibrium concentration of 6mg P dm^?3, the total amount of P sorbed ranged between 0.8 and 4.1 μmol mp^?2. Phosphate-sorption capacity was influenced by the morphology of the coherently scattering domains: the shorter the domains in the crystallographic c relative to the a direction, the lower the P-sorption capacity. This has been observed by other authors in synthetic hematites and agrees with the idea that the prismatic faces, which have singly co-ordinated Fe-OH groups, are more active in P-sorption than other faces. The average P sorption capacity of hematites was similar to that of natural goethites (2.6 μmol P m^?2) but, in contrast to these, variability among samples was high. In comparison with goethites, hematites show slower sorption and lower affinity for phosphate.     

Dispersion of humic allophane soils with supersonic vibration

The difficulties in dispersing volcanic ash soils of Japan and New Zealand have been considered to be due to the association or aggregation of allophane (3, 5, 7–10). In particular, MIYAZAWA (9) has obtained evidence that stable microaggregates of Humic Allophane soils derived from volcanic ash have been formed by dehydration of allophane. Recently, several investigators (2, 4, 6, 8, 9, 12) have pointed out that ultrasonic vibration is effective in dispersing the fine particles of soils. With respect to the applicability of supersonic vibration to the particle-size distribution analysis of Humic Allophane soils, MIYAZAWA (9) stated that the maximum dispersion, as measured by the clay content, was obtained only with supersonic vibration using an acidic medium. KOBO and OBA (8) reported that calgon (sodium hexametaphosphate) as a dispersing agent was successfully applicable to most Humic Allophane soils, but the use of HCI was necessary for some highly allophanic subsoils, and that the effect of supersonic vibration on dispersion of the soils is attributed to the breakdown of aggregates larger than 20 microns in diameter. They also recommended a mixture of 10g of soil and 50 ml of water and 20 min. exposure for a supersonic vibrator (10 Kc, 300 W). With respect to the applicability of vibration treatment in the particle-size distribution analysis of Humic Allophane soils containing volcanic glasses in abundance, some apprehension may be entertained about the breakdown of primary minerals, especially of volcanic glasses (9, 10).     

Specific gravity of allophane and volcanic ash soils determined with a pycnometer

The determination of the specific gravity of allophane is an interesting and important problem, but it is no exaggeration to say that we have no satisfactory answer to this question in spite of numerous studies. In this note, the specific gravities of allophane, weathered pumices and volcanic ash soil were determined with a pycnometer, and the values compared with those of the other clay minerals and non-volcanic ash soils.     

Adsorption of xanthan polymer on allophane and effect on the changes in colloidal stability of allophane by heavy metal ions

The influence of divalent cations at concentrations of 10^-6.0 to 10^-4.0 M on the colloidal stability of partially deflocculated allophane by gum xanthan (GX) polysaccharide at pH 6.5 was investigated at two GX concentrations. Experiment in the presence of 10^-2.0 g L^-1 GX showed that the stability decreased by the addition of divalent cations and the effect of the decrease due to the cationic species was evident in a higher concentration range, i.e., 10^-5.0 to 10^-4.0 M. The order of the effect was Pb >Zn > Cd > Mg. Experiment in a 10^-4.5 g L^-1 GX solution revealed that (i) the stability increased by the addition of heavy metal cations at 10^-5.0 M (the order of the effect was Pb > Zn > Cd) and decreased at a concentration above 10^-4.5 M, (ii) whereas the stability decreased by the addition of Mg ion. The striking difference in the stability behavior due to the difference between the two GX-concentrations was attributed to the (i) degree of GX-adsorption (and hence negative charge from the carboxyl group in GX) onto allophane based on the electrophoretic mobility, (ii) complexation of heavy metal cations by organic ligand (carboxyl group) in GX which was adsorbed onto allophane, and (iii) surface complexation by heavy metal cations and hydroxyl groups on allophane. The results were discussed in relation to the characteristics of the particles of allophane, viz., (i) polymer-coated soft particles, and (ii) semi-soft particles on which the rigid (hard) surface of allophane substantially remained.     

Influence of allophane and organic matter contents on surface properties of Andosols

The aim of this study was to use nitrogen gas adsorption to study the complex surface properties of a wide range of Andosol Ah and Bw horizons; N₂ gas adsorption not only provides specific surface area, SSA, but it also yields complementary information about micropore volume and hydrophilic and/or hydrophobic surface properties. Total SSAs were positively related to micropore SSA which was, in its turn, positively interrelated to the dimensionless parameter C of the Brunauer‐Emmett‐Teller (BET) equation (micropore N₂ filling) and microporous allophane content. The more allophanic the Andosol horizon sample, the larger were its total, micropore and mesopore SSAs. On the other hand, strong negative exponential relationships were obtained between either total or micropore or mesopore SSA and soil organic carbon content, with a SSA threshold at an organic carbon content of c. 8–10%, the SSAs being extremely small at larger organic carbon content values. Both SSA_BET and C_BET decreased non‐linearly as a function of the organic C/allophane ratio, with either a SSA_BET or a C_BET threshold at an organic C/allophane ratio value of 3–5, above which both SSA_BET and C_BET were very small (mostly the aluandic Andosol Ah horizons). The more the soil allophanes are assumed to be coated, the more hydrophobic the soil surfaces become and the smaller both SSA_BET and C_BET become; nitrogen gas has a permanent quadrupole moment and therefore acts as a polar probe when surfaces are sufficiently hydrophobic. The antagonistic roles played by allophanes and organic matter in both the SSAs and the values of the dimensionless parameter C in the BET equation were also highlighted by (i) multiple linear regressions between the SSAs and both allophane and organic carbon contents and (ii) principal‐component analysis of SSA_BET, C_BET and soil constituent (allophane, ferrihydrite and organic C) contents.     

Retention of Ni,Zn and Cd by Si-associated goethite

Synthetic goethite used to study the effects of reaction time and temperature on the pH-dependent sorption of Ni, Zn and Cd was associated with amorphous silica. Ni interacted with dissolved Si and formed a Ni/Si precipitate on the goethite surface. Individual metals added at a concentration of 0.5 μmol g^?1 and sorbed during a reaction period of 504 hours (21 days) at 35°C were extracted by 0.7 M HNO₃ for 14 days. At the end of this period 11,28 and 40 percent of Ni, Cd and Zn, respectively, were not extracted whereas 20 percent of the total Fe content of the goethite and 39 percent of the associated Si were dissolved. During the sorption process metals became immobilized in the goethite particles. This effect can be related to a diffusion of metal ions into micropores. A total mobilization of sorbed metals can only be achieved by a complete dissolution of the goethite. The strong fixation of Ni, Zn and Cd by goethite suggests that additions of this Fe oxide could be used to ameliorate highly contaminated sludges or soils.     

Mechanism of inhibitory effect of allophane and montmorillonite on some enzymes

It is well established that the presence of clay in an enzyme-substrate system may reduce the activity of enzymes (1-3,5,6,8,11-14). This inhibition by the clay would be principally caused by the adsorption of enzyme and/or substrate on the clay particle. In the previous papers (1–3), the activity of some enzymes was found to be inhibited in various degrees by clays. The enzyme appears to be adsorbed on the clay particle in various ways according to the nature of adsorbate as well as adsorbent. This suggests that the enzyme is adsorbed by the clay so as not to combine with the substrate, or that the adsorbed enzyme molecule has a configuration different from that of a free enzyme molecule, reducing the activity of the enzyme.     

Fe(III)-EDDHA and -EDDHMA sorption on Ca-montmorillonite, ferrihydrite, and peat.

The effectiveness of Fe chelates as Fe sources and carriers in soil can be severely limited by the adsorption of Fe chelates or chelating agents in the solid phase. To study this phenomenon, well-characterized peat, Ca-montmorillonite, and ferrihydrite were used as model compounds, and the adsorption of Fe-EDDHA and Fe-EDDHMA chelates were studied. Sorption isotherms for the meso and racemic isomers of these chelates on the soil materials are described. The variability of sorption with pH in peat and ferrihydrite was also determined because both have variable surface charge at different pH values. In montmorillonite, at low concentrations, the retention of Fe from the Fe-EDDHMA chelate is greater than the one of the Fe-EDDHA chelate. As well as the concentration increased, the inverse situation occurs. The behavior of both meso and racemic isomers of chelates in contact with Ca-montmorillonite is similar. The Fe-meso-EDDHA isomer was highly adsorbed on ferrihydrite, but the racemic isomer is not significantly retained by this oxide. For Fe-EDDHMA isomers, the racemic isomer was more retained by the oxide, but a small sorption of the racemic isomer was also observed. Results suggest that Fe-EDDHA chelates were more retained in peat than Fe-EDDHMA chelates. The most retained isomer of Fe-EDDHA was the meso isomer. For Fe-EDDHMA, the adsorption was very low for both racemic and meso isomers.     

Interaction of copper and zinc with allophane and organic matter in the B horizon of an Andosol

Andosols developed on basaltic material are naturally rich in metals. Organic matter and allophane, the key colloids of these soils, have a strong affinity for trace metals, but are intimately mixed so that speciation of trace metal is difficult to determine. We used three complementary approaches, namely physical fractionation, chemical extraction and potentiometric measurement, to distinguish them. Physical particle-size separations and chemical selective dissolution of allophanes and organic matter were combined to demonstrate relations between the occurrence of colloids and contents of Cu and Zn in an andic B horizon. About 22% of total soil Cu and 7% of total soil Zn were present in the < 5-μm fraction, associated with organic or amorphous mineral constituents. To support this association further, the affinity of soil colloids for Cu and Zn in a mimicked system was demonstrated. An Al-rich allophane was synthesized, and a portion of the organic matter was extracted from the clay fraction, and their reactivities towards Cu²⁺ or Zn²⁺ were studied by potentiometry. The two metallic cations displayed specific affinity towards allophane or soluble organic matter. Furthermore, the behaviour of copper and zinc in the ternary system, allophane + soluble organic matter + trace element, revealed a synergy in the surface complexation. The use of these three speciation approaches highlighted the linkage between metals and constituents, and showed how important the colloidal constituents are in the behaviour of Cu and Zn in Andosols.     

Weathering and allophane neoformation in soils developed on volcanic ash in the Azores

On Faial and Pico islands (Azores), we studied two profiles on basaltic pyroclasts that contain buried horizons, and we focussed on petrography, micropedology and mineralogy. Emphasis was given to weathering of the lapilli and ashes, and the neoformation of allophane. A combination of optical studies, in situ chemical analyses, X‐ray diffraction and infrared spectroscopy of clay fractions revealed that allophane is present both in the micromass of the groundmass, in alteromorphs after lapilli or pumice, and in clay coatings. Whereas most studies describe allophane as a colloidal fraction formed by the congruent and total dissolution of the ashes, this study shows evidence for the formation of allophane alteromorphs, due to leaching of Si and cations, with preservation of the original shapes of the tephra. The allophane alteromorphs often display optical characteristics that resemble those of palagonite. Increasing alteration is observed through three steps: (i) hydration of the glass associated with strong cation and Si leaching, (ii) allophane hypocoatings, and (iii) allophane alteromorphs with development of intragrain bridges. The chemical signature of the alteromorphs varies from a pure alumino‐silicate at one extreme to an Fe(Ti) enriched alumino‐silicate at the other. Between those two extremes, the colour grades from yellow to dark orange, with microzonations. An Al‐rich allophane composition is associated with gibbsite in the EUR6‐Pico profile, whereas at the base of the EUR5‐Faial profile, Si‐rich allophane is associated with halloysite. Some variations of the palaeo‐environment are also suggested by strong iron segregation observed with various secondary phases (ferrihydrite, haematite, iddingsite).     

In situ stabilization of arsenic in soil with organoclay, organozeolite, birnessite, goethite and lanthanum-doped magnetic biochar

Arsenic (As) is a known carcinogen and naturally occurring semi-metal in soils and in the Earth''s crust. Contamination of soils and water with As poses a serious threat to millions of people worldwide due to its health hazards and toxicological properties. Hence, devising novel and efficient methods for remediation of contaminated areas has attracted a great deal of interest across the globe. In this study, we investigated the usefulness of synthetic birnessite, goethite, hexadecylpyridinium chloride-modified montmorillonite (HDPC-M), hexadecylpyridinium bromide-modified zeolite (HDPB-Z), and lanthanum (La)-doped magnetic biochar produced from eucalyptus bark (La-Euchar) as adsorbents at 10% dosage for As stabilization in a soil spiked with 1 000 mg kg^-1 As. The effectiveness of the above adsorbents in As immobilization in soil was assessed using single-step extractions with 2 mol L^-1 HNO₃ and deionized water, the simplified bioaccessibility extraction test (SBET) method, and sequential extraction with the modified Community Bureau of Reference (BCR) method. Application of the adsorbents shifted the exchangeable fraction of As to more recalcitrant fractions and dramatically reduced the exchangeable fraction by 6%-99% and the extractable amounts with HNO₃, deionized water, and SBET method by 30%-92%, 17%-95%, and 12%-90%, respectively, compared to the unamended control. The immobilizing effects of adsorbents on As decreased in the sequence of birnessite > La-Euchar > goethite > HDPB-Z > HDPC-M. Birnessite exhibited great affinity for As and drastically reduced As extractability by more than 90% in all single extractions. The results revealed that HDPC-M, HDPB-Z, La-Euchar, birnessite, and goethite are promising immobilizing agents for in situ stabilization of As in terrestrial environments.     

磷酸盐在水铁矿及水铁矿-胡敏酸复合体表面的吸附

The adsorption of phosphate onto ferrihydrite (FH) and two FH-humic acid (HA) complexes, obtained by co-precipitating FH with low (FH-HA1) and relatively high amounts of humic acid (FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanism of phosphate adsorption onto two soil compositions. The isoelectric point (IEP) and the specific surface area (SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower pH, and the increase in the ionic strength promoted phosphate adsorption at a higher pH. However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower pH and increased the adsorption at a higher pH.     

有机酸对高岭石, 针铁矿和水铝英石吸附镉的影响

Effects of organic acids （oxalic, acetic, and citric） on adsorption characteristics of Cadmium （Cd） on soil clay minerals （kaolinite, goethite, and bayerite） were studied under different concentrations and different pH values. Although the types of organic acids and minerals were different, the effects of the organic acids on the adsorption of Cd on the minerals were similar, i.e., the amount of adsorbed Cd with an initial solution pH of 5.0 and initial Cd concentration of 35 mg L^-1 increased with increasing concentration of the organic acid in solution at lower concentrations, and decreased at higher concentrations. The percentage of Cd adsorbed on the minerals in the presence of the organic acids increased considerably with increasing pH of the solution. Meanwhile, different Cd adsorption in the presence of the organic acids, due to different properties on both organic acids and clay minerals, on kaolinite, goethite, or bayerite for different pHs or organic acid concentrations was found.     

高岭石,蒙脱石和针铁矿对泥炭腐殖酸的吸附和分离

Sorption of humic acid (HA) on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants (HOCs) and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite (1:1 clay), montmorillonite (2:1 clay), and goethite (iron oxide) for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and solid state ¹³C nuclear magnetic resonance spectroscopy (NMR). The mineral-HA complexes were characterized by DRIFT. Polarity index [(N+O)/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aliphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aliphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceous fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the mineral-HA complexes. ¹³C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction was observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.     

水铁矿对磷的吸附及胶体态磷迁移能力预测

土壤中流失的磷进入水体容易引起富营养化污染。目前对于铁矿物胶体结合态磷在土壤孔隙介质中的稳定性和迁移能力的认识还存在不足。本研究采用吸附试验,考察水铁矿对磷的吸附特征以及pH、离子强度和胡敏酸对磷在液相、水铁矿胶体和水铁矿固体上分布的影响;通过DLVO理论,预测水铁矿胶体结合态磷的稳定性和迁移能力。结果表明,假二级动力学模型(R~2=0.964)更适合用于描述磷在水铁矿上的吸附过程,磷在水铁矿上的吸附受液膜扩散、内部扩散和化学吸附等过程控制。Freundlich模型(R2=0.970)对等温吸附的拟合效果好,说明水铁矿对磷的吸附为多层吸附过程。从Langmuir模型参数可知,水铁矿对磷的最大理论吸附量为22.55mg·g~(-1)。水铁矿对磷的吸附能力随pH的升高而降低,随离子强度的升高而升高。然而,低离子强度和高pH有利于反应体系中水铁矿胶体的释放。无论胡敏酸是否存在,在碱性且离子强度不高(1～10mmol·L~(-1))的条件下,有约5%～20%的磷会与水铁矿胶体结合,且这些磷-水铁矿胶体之间的静电斥力较大。根据DLVO理论计算可知,这些带负电荷的胶体之间稳定性较好,在土壤中有一定迁移能力。在实际农业活动中,磷肥的过量施用可能会使大量的磷酸根离子吸附在铁矿物上,促进土壤孔隙水中形成稳定的、带负电的铁矿物胶体,这种磷-铁矿物复合胶体的迁移很可能成为磷迁移的另一种形式。本研究结果可为胶体促进下磷淋失风险评估提供理论和数据支撑。     

Irreversibility of sulfate sorption on goethite and hematite

Sulfate ion adsorption and desorption experiments carried out on synthetic goethite and hematite and natural hematite show adsorption to be a highly irreversible reaction. All oxides showed an increase in sulfate ion adsorption with decrease in pH. Only a small fraction of sorbed sulfate was desorbable after 48 hr, and only at a pH of 3. Extreme irreversibility of sulfate sorption on these common soil minerals suggests that adsorbed sulfate is more immobile in watersheds than previously considered and that recovery models which inherently assume reversibility may need to be modified.     

Effect of organic acids on the adsorption of copper,lead, and zinc by goethite

The adsorption of Cu, Pb, and Zn by synthetic goethite was studied in the absence and presence of oxalic, citric, and glutamic acids at different pH values. It was shown that, in the absence of an acid, the content of adsorbed metals increased with the increasing pH. The content of adsorbed cations at constant pH values decreased in the sequence: Cu > Pb > Zn. The simultaneous addition of metal cations and organic acids to the goethite suspension increased the content of the adsorbed elements. The oxalic and citric acids had similar effects on the adsorption of copper and lead in the studied pH range. The metal: acid concentration ratios significantly affected the adsorption of the heavy metals by goethite. An increase in the metal adsorption was observed to a certain metal: acid ratio, which was followed by a gradual decrease. The adsorption of the metals by goethite also depended on the properties of the metal cations and the organic ligands. The observed tendencies were attributed to the complexation of heavy metals with organic acid anions and the simultaneous sorption of acids at positively charged sites on the goethite surface with the formation of mineral-organic compounds, which significantly modified the surface properties of the mineral. The study of the effect of increasing lead concentrations in the solution on the copper adsorption by goethite in the absence, in the presence, and at the addition of an oxalic acid solution to the goethite suspension one hour before the beginning of the experiment showed that lead decreased the adsorption of copper in all the treatments. The possible mechanisms of the processes occurring in the system were considered.