ADSORPTION ON HYDROUS OXIDES I. OXALATE AND BENZOATE ON GOETHITE

The adsorption of oxalic acid on synthetic goethite (α-FeOOH) was studied using adsorption isotherms. Infrared spectra were obtained for goethite-oxalate complexes at several points on the isotherms. On a goethite preparation with a phosphate sorption capacity of 200|μmolg^?1 the amounts of oxalate strongly adsorbed varied from near zero at pH 8 to about l00μmolg^?1 at pH 4 and below. At pH 3.4, the first l00μmolg^?1 of oxalic acid added was strongly adsorbed as a binuclear complex (FeOOC–COOFe), replacing two singly-coordinated OH groups by ligand exchange. At higher concentrations a further 200 μrnol g^?1 of oxalic acid formed a monodentate complex (FeOOC–COOH) so that more oxalate could be accommodated. Benzoic acid was weakly adsorbed on goethite with one benzoate oxygen replacing one singly-coordinated OH. The other oxygen of the COO group fitted into the goethite surface so that the benzene ring was at a high angle to the (100) face.     

ADSORPTION ON HYDROUS OXIDES: II. OXALATE, BENZOATE AND PHOSPHATE ON GIBBSITE

Adsorption isotherms, the infrared spectra of adsorbed species, and the amount of hydroxyl released when oxalate is adsorbed, all indicate that adsorption of oxalate, benzoate and phosphate at low solution concentrations occurs only on A1(OH)(H₂ O) sites exposed on edge faces of the platy gibbsite crystals studied. This is confirmed by the finding that the vibrations of surface hydroxyl groups on the principal plate faces are unaffected when excess oxalate is present, and further supported by the low affinity for oxalate of imogolite, a tubular mineral with a very large gibbsite-like surface, but with a very low concentration of edge sites. Infrared spectra indicate that oxalate is adsorbed in bidentate form. Near neutrality and at low solution concentrations, gibbsite adsorbs more oxalate than does goethite of comparable surface area.     

New infrared band assignments for the arsenate ion adsorbed on synthetic goethite (α-FeOOH)

Infrared spectroscopy was used to show that arsenate is adsorbed on the surface of synthetic goethite (α-FeOOH) as the acidic HAsO₄²- ion, replacing singly coordinated surface OH groups. In this respect, arsenate is analogous to phosphate, but its larger size apparently causes it to interact more strongly with some of the OH groups that remain on the surface. This has suggested an alternative assignment for the absorption bands of these OH groups.     

ADSORPTION OF SELENITE, PHOSPHATE AND SULPHATE ON HYDROUS ALUMINA

Selenite was adsorbed on a positively charged hydrous alumina at a solution pH of 5.0, and the OH ^? released and changes in the surface charge were measured. The adsorption isotherm levelled off at high concentrations suggesting a definite adsorption maximum. The OH^? released yielded a curvilinear relationship of increasing slope with the selenite adsorbed. The positive charge on the alumina surface was neutralized by the adsorbed selenite and the net charge became close to zero as the adsorption of selenite was near maximum. The molar ratio of the ligands (OH^?+ OH₂) displaced over selenite adsorbed was more than one at surface saturations of <0.5, but it was approaching one with increasing adsorption of selenite. The results are explained in terms of preferential adsorption of divalent (SeO²₃^?) and monovalent (HSeO^?₃ selenite on a highly positively and less positively charged surface respectively, in agreement with the VSC^? VSP model of Bowden et al. (1973; 1977). The supply of SeO²₃^? for adsorption is considered to be favoured by an expected lower H activity in solution adjacent to the positively charged surface than that in the bulk solution. A general discussion is given on the ligand exchange adsorption of selenite, phosphate and sulphate on hydrous alumina.     

ADSORPTION ON HYDROUS OXIDES. III. FULVIC ACID AND HUMIC ACID ON GOETHITE, GIBBSITE AND IMOGOLITE

Adsorption isotherms were obtained for fulvic and humic acids on synthetic gibbsite and goethite and on a natural imogolite. The results were interpreted with the help of spectra of the adsorption complexes, and measurements of hydroxyl displaced. The mechanism of adsorption involved ligand exchange with the surface hydroxyl groups and hydrogen bonding. The hydroxyl groups displaced included singly coordinated species on the (100) face of goethite and on the edge faces of gibbsite. The doubly coordinated hydroxyl groups on the (001) face of gibbsite were not replaced, and this face adsorbed only un-ionized fulvic acid probably by a hydrogen bonding mechanism. Imogolite adsorbed most fulvic acid because of its high porosity. Only isolated places on its surface reacted with fulvic acid to form carboxylate groups.     

不同pH、电解质浓度条件下草酸对针铁矿吸附Cd(II)的影响及机制

用吸附平衡法研究了不同草酸浓度、体系pH对针铁矿 (G)吸附Cd2+的影响与机制以及电解质 (KNO3)浓度对针铁矿、草酸化针铁矿 (G+40 )吸附Cd2+的影响差别及原因。结果表明 ,低浓度草酸 (1mmolL-1 )促进Cd2+的吸附 ;高浓度草酸 (1mmolL-1/sup )抑制Cd2+的吸附。已吸附在针铁矿表面的草酸对Cd2+ 吸附的影响与液相中草酸的影响不同 ,这主要与草酸引起的针铁矿表面电荷性质的变化、草酸在固液两相间的分配、草酸与Cd2+的配合作用和竞争作用有关。电解质 (KNO3)浓度对针铁矿和草酸化针铁矿吸附Cd2+的影响明显不同 ,随KNO3 浓度的提高 ,针铁矿的Cd吸附率由 44.5%增至 95%以上 ,而草酸化针铁矿吸附率由 29%降至6.2% ,这主要决定于二者的电荷零点 (PZC)和体系pH变化的不同。     

Differentiation between adsorbed and precipitated sulphate in soils and at micro-sites of soil aggregates by sulphur K-edge XANES

To investigate the potential of synchrotron‐based X‐ray Absorption Near‐Edge Structure spectroscopy (XANES) at the sulphur (S) K‐edge for a discrimination of adsorbed and precipitated sulphate in soils and soil particles, XANES spectra of ionic sulphate compounds and Al/Fe hydroxy sulphate minerals were compared with spectra of SO₄^2? adsorbed to ferrihydrite, goethite, haematite, gibbsite or allophane. Ionic sulphate and hydroxy sulphate precipitates had broader white‐lines (WL) at 2482.5 eV (full width at half maximum (FWHM) of edge‐normalized spectra, 2.4–4.2 eV; Al hydroxy sulphates, 3.0 eV) than SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (FWHM, 1.8–2.4 eV). The ratio of the white‐line (WL) height to the height of the post‐edge feature at 2499 eV (WL/PEF) was larger for SO₄^2? adsorbed to Al/Fe oxyhydroxides or allophane (8.1–11.9) than for Al/Fe hydroxy sulphates and ionic sulphates (3.9–5.7). The WL/PEF ratio of edge‐normalized S K‐edge XANES spectra can be used to distinguish adsorbed from precipitated SO₄^2? in soils and also at microsites of soil particles. The contribution of adsorbed and precipitated SO₄^2? to the total SO₄^2? pool can be roughly quantified. Adsorbed ester sulphate may result in overestimation of precipitated SO₄^2?. The spectra of most soils could be fitted by linear combination fitting (LCF), yielding a similar partitioning between adsorbed and precipitated SO₄^2? as an evaluation of the WL/PEF ratio. The SO₄^2? pool of German forest soils on silicate parent material in most cases was strongly dominated by adsorbed SO₄^2?; however, in three German forest soils subject to elevated atmospheric S deposition, a considerable portion of the SO₄^2? pool was precipitated SO₄^2?, most likely Al hydroxy sulphate. The same is true for Nicaraguan Eutric and Vitric Andosols subject to high volcanogenic S input. In the subsoil of the Vitric Andosol, adsorbed SO₄^2? and Al hydroxy sulphate coexist on a micron scale.     

ADSORPTION OF THE HERBICIDE 2,4-D ON GOETHITE

Adsorption, of the herbicide 2,4-Dichlorophenoxyacetic acid (2,4-D) on an iron oxide, goethite, was studied in aqueous suspensions as a function of solution pH, ionic strength of the medium, and initial 2,4-D concentration. The 2,4-D anion was reversibly adsorbed on positively charged goethite surfaces, maximum adsorption being observed near the pK_a of 2,4-D (2.73) and at low ionic strength. Within certain levels of adsorption (5–22 mg 2,4-D adsorbed/g goethite) the complex became hydrophobic and floated to the liquid surface. This flotation effect disappeared on further adsorption. It is suggested that adsorbed 2,4-D anions are orientated with their hydro-phobic aromatic ends directed towards the solution, the carboxyl groups being weakly bound to positive sites on the oxide surface. At high levels of adsorption, some of the anions are orientated in the opposite direction by π–π interaction, with the first adsorbed layer and the surface reverts to its hydrophilic nature.     

THE SPECIFIC ADSORPTION OF DIVALENT Cd, Co, Cu, Pb, AND Zn ON GOETHITE

The specific adsorption of divalent Cd, Co, Cu, Pb, and Zn on goethite is measured as a function of pH. For each mole of heavy metal adsorbed approximately two moles of H+ ions are displaced from the interface. Using these results the heavy metal adsorption data are expressed as functions of the solution concentrations of both H+ and metal ions, and the interfacial reaction is described by the equation, ₂SH+M²⁺= S₂M+₂H⁺. The adsorption data are consistent with an electrochemical model of the simultaneous adsorption of H⁺ ions and divalent metal ions on to the oxide. The intrinsic affinities of the metal ions for the oxide surface increase in the order, Cd < Co < Zn < Pb < Cu. However, besides the affinity of the metal ion for the surface, the adsorption curves are considered to be influenced by surface charge, the adsorption density of the metal ions and their size. The analysis of the data in terms of H⁺ and M²⁺ ion adsorption is considered to be complementary to the hydrolysis model for heavy metal adsorption.     

Interactive effect between sulfate and selenate on glutathione pool in garden rocket (Eruca sativa L.) leaves

Garden rocket (Eruca sativa L.) plants grown in sand culture were irrigated with normal 1/10 Hoagland's medium [low sulfate (SO₄^2?)] or with double SO₄^2? concentration (high SO₄^2?), each supplemented with 0, 2, 10 ppm SeO₄^2? as sodium selenate for 30 days. Increasing SO₄^2? concentration in the nutrient medium diminished SeO₄^2? uptake, foliar hydrogen peroxide (H₂O₂), and MDA via enhancing the glutathione pool and their enzyme activities. These results showed that increasing SO₄^2?/SeO₄^2? ratio in nutrient medium of rocket plants played an important role in selenate detoxification.     

Studies on Adsorption Characteristics of Al-Free and Al-Substituted Goethite for Heavy Metal Ion Cr(VI)

In the present paper, α-FeOOH and α-Fe(Al)OOH were prepared, and the adsorption of Cr(VI) on the two samples was investigated. The influence of pH, initial concentration, and some anions such as SO₄ ^2?, H₂PO₄ ^?, C₂O₄ ^2?, CO₃ ^2?, and SiO₃ ^2? on the adsorption of Cr(VI) on α-FeOOH and α-Fe(Al)OOH was studied by batch techniques. The results show that the adsorption capacity of Cr(VI) on α-Fe(Al)OOH increases with the introduction of aluminum, but decreases with the increase of pH. The adsorption irreversibility of Cr(VI) on α-Fe(Al)OOH is much higher than that on pure α-FeOOH. The adsorbed Cr(VI) species mainly exists in the form of *Fe(wk)-OHCrO₄ ^2? on the surface of the samples. With the presence of SiO₃ ^2?, CO₃ ^2?, C₂O₄ ^2?, SO₄ ^2?, and H₂PO₄ ^?, the binding of Cr(VI) is inhibited by different degree. The inhibition of those anions is larger in the pure goethite than that in the Al-substituted goethite system. After Al was introduced into α-FeOOH, Cr(VI) ions are preferentially adsorbed on Al sites rather than Fe sites on α-Fe(Al)OOH.     

Sulphate sorption by variable charge soils

The sorption of sulphate (SO^2?₄) by three variable charge soils from the Canary Islands (Spain) was studied. Sulphate sorption decreased with increasing pH. Only negligible amounts of SO^2?₄ were sorbed above pH 6.5. When the soils were washed with an indifferent electrolyte (0.01 M KCl), more SO^2?₄ was recovered than had been sorbed. This indicated a release of native SO^2?₄ Sulphate replaced hydroxyl ions (OH) and co-ordinated H₂O molecules, as well as very small amounts of silicate (Si). No measurable amount of phosphate (P) was released. On average hydroxyl release accounted for 50% of SO^2?₄ sorbed, the rest being accounted for by the increase in negative charge as measured by K⁺ adsorption. The results presented here are consistent with the sorption of SO^2?₄ through a ligand exchange mechanism, but in a different plane of sorption to that of phosphate.     

Adsorption of selenite to goethite in a flow-through reaction chamber

Adsorption of selenite on goethites in NaCl and Na₂SO₄ solutions was performed in a newly designed flow-through reaction chamber as well as in a traditional batch system. Six goethites with different morphologies were used as adsorbents. For the experiments the goethite was placed in the chamber prior to flushing with the salts. Introduction of the NaCl and Na₂SO₄ solutions only, and in combination with selenite, resulted in different responses with respect to the pH. The pH changes were explained by means of anion-binding energies, with Cl^? 4^2? 3^2?. Neither the morphological characteristics of the adsorbents nor the electrolyte anion influenced the amount and the rate of selenite adsorption, The mixing mode in the reactor chamber affected the selenite adsorption density, as indicated by higher densities in the batch experiments.     

低硒土壤中75Se的形态转化

用⁷⁵SeO₂水溶液分别按0.131ppm和1.631ppm比例处理暗棕色森林土。用这种土壤盆栽的小麦含Se分别为0.023ppm和0.493ppm。小麦收获之后,对土壤残留的⁷⁵Se用不同的提取剂连续进行化学分级,⁷⁵Se的各种形态按其占土壤总Se的百分比大小排序为:同位素交换态Se>NH₄OH可提态Se>HNO₃可提态Se>HCl可提态硒>水溶态Se>K₂SO₄可提态硒。土壤残留⁷⁵Se主要以NaHSeO₃同位素交换态存在,其量占土壤总硒28%,NH₄OH可提态Se次之,占20%;水溶态Se较少,仅6-7%。以SeO₃^-2形式加入土壤的⁷⁵Se被土壤紧密吸附。     

几种氧化铁的离子吸附特性研究

氧化铁是土壤中常见的氧化物,其中较为普遍的是针铁矿和赤铁矿,在某些土壤中也含有纤铁矿和无定形氧化铁.它们通常以极小的颗粒单独存在,或以胶膜状包裹在其它矿物颗粒的外面,有较大的比表面积,易受环境的影响,因此具有较高的活性,并对许多土壤的物理化学性质产生重要的影响.某些重金属离子和某些污染物进入土壤后的动向和行为也深受土壤中氧化铁的影响.     

Mechanism of sulphate adsorption by two tropical SoilS

The mechanism of sulphate (SO₄) adsorption was investigated using two highly-weathered soils with contrasting surface-charge characteristics (one with a net negative charge and the other with a net positive charge). The addition of SO₄ caused a release of OH and increased the adsorption of cations, in keeping with the widely-held view that SO₄ is chemisorbed by replacing -OH and -OH₂ ligands. On the other hand, adsorbed SO₄ was completely recovered by washing with an indifferent electrolyte solution (1 M KC1), an extractant which is usually taken to be specific for ‘exchangeable’ ions. The amounts of SO, adsorbed were several times higher than those of non-specifically adsorbed Cl. It is suggested that the experimental observations can be interpreted in terms of a model in which SO₄ adsorbs in a plane closer to the surface than monovalent anions (e.g. in the Stern layer). The consequence of higher counter-ion valence and proximity to the surface is that additional positive charge is induced onto the surface by OH release. Charge reversal in the diffuse layer allows more cations to be adsorbed. This type of adsorption may involve forces other than the purely electrostatic but, in contrast to chemisorption, the adsorbed anion does not become chemically coordinated to the surface metal atoms.     

水钠锰矿(Birnessite)对Mn2+持留机理的研究

本试验研究了一种合成水钠锰矿对Mn²⁺的持留机理和Mn²⁺被吸附后的去向,并进一步探讨了三种锰盐溶液(MnSO₄,MN(NO₃)₂和MnCl₂)对水钠锰矿晶体结构变化的影响。.试验结果表明,水钠锰矿对MN²⁺离子的吸附包括专性吸附和非专性吸附。随着吸附后的老化过程,吸附在矿物表面的锰逐渐扩散到晶格内,其置换性随之降低。.在MnSO₄,Mn(NO₃)₂和MnCl₂溶液中,水钠锰矿最终转化成六方锰矿(Nsutite),一种比水钠锰矿更稳定,结晶更好的晶体。MnSO₄溶液在加入水钠锰矿后pH值比其它两种溶液高,除生成六方锰矿外还形成大量拉锰矿(Ramsdellite)。随着生成新矿物的老化,最初被吸附的Mn被固定在晶格内而失去其置换性和生物有效性。     

华南红壤的交换性碱和交换性酸

本文提出了一个同时测定土壤的交换性酸和交换性碱的简易方法。将土壤的交换性酸和交换性碱区分为:Na-交换性酸、Ba-交换性酸和SO₄-交换性碱、F-交换性碱。用推荐的方法,在野外对华南地区由不同母质发育的砖红壤、赤红壤、红壤等10个剖面进行了测定。结果表明,红壤类土壤含有相当量的交换性碱,但其数量比交换性酸少。酸性母质发育的土壤的交换性酸和交换性碱量大于由基性岩发育的土壤者。红壤的交换性酸和碱的量随电性盐浓度的增高而增大,浓度大于0.1N后,数量基本不变。