红壤中低分子量有机酸的吸附动力学

低分子量有机酸在土壤中广泛存在尤其是在根际土壤中,其主要来源于动植物残体的分解、微生物的代谢、植物根系的分泌和土壤中有机物的转化等。由于羧基的强络合作用,低分子量有机酸一旦进入土壤将很快被土壤吸附,影响土壤的表面电荷性质和动电性质,进而影响其在土壤中的作用。关于低     

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.     

Effect of carboxylic and thiol ligands (oxalate, cysteine) on the kinetics of desorption of Hg(II) from kaolinite

Sorption and desorption of Hg(II) on clay minerals can impact the biogeochemical cycle and bio-uptake of Hg in the environment. We studied the kinetics of the desorption of Hg(II) from kaolinite as affected by oxalate and cysteine, representing the ligands with carboxylic and thiol groups of different affinities for Hg(II). The effects of pH (3, 5, and 7), ligand concentration (0.25 and 1.0?mM), and temperature (15??C, 25??C, and 35??C) on the Hg(II) desorption were investigated through desorption kinetics. Our study showed that the Hg(II) desorption was pH dependent. In the absence of any organic ligand, >90% of the previously adsorbed Hg(II) desorbed at pH?3 within 2?h, compared to <10% at pH?7. Similar results were observed in the presence of oxalate, showing that it hardly affected the Hg(II) desorption. Cysteine inhibited the Hg(II) desorption significantly at all the pH tested, especially in the first 80?min with the desorption less than 20%, but the inhibition of the desorption appeared to be less prominent afterwards. The effect of the ligand concentration on the Hg(II) desorption was small, especially in the presence of oxalate. The effect of temperature on the Hg(II) desorption was nearly insignificant. The effect of the organic acids on the Hg(II) sorption and desorption is explained by the formation of the ternary surface complexes involving the mineral, ligand, and Hg(II). The competition for Hg(II) between the cysteine molecules adsorbed on the particle surfaces and in the solution phase probably can also affect the Hg(II) desorption.     

Studies on Selective Uptake Behavior of Hg(II) and Pb(II) by Functionalized Poly(Ethylene Terephthalate) Fiber with 4-Vinyl Pyridine/2-Hydroxyethylmethacrylate

The adsorption behavior of 4-vinyl pyridine and 2-hydroxyethylmethacrylate grafted poly(ethylene terephthalate) fiber toward the Hg(II) and Pb(II) ions in aqueous solutions was studied by a batch equilibration technique. The influence of the treatment time was considered as well as the pH of the solution, the initial metal ions concentration, the graft yield, and the temperature. Such parameters as the adsorption kinetics, the adsorption isotherm, and the desorption time were further studied. Maximum adsorption occurred at pH 3 and pH 6 for Hg(II) and Pb(II), respectively. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for heavy metal ions. The adsorption data is a good fit with Freundlich isotherm. Desorption studies indicated that the maximum percent recovery of Hg(II) and Pb(II) was 93.4% and 76.3%, respectively with 1 M HNO₃.     

低分子量有机酸对高岭石中铝释放的影响

选择了几种土壤中可能存在的低分子量脂肪羧酸 ,研究了它们对高岭石中铝释放的影响。结果表明 ,有机酸可以通过络合作用促进高岭石中铝的释放。几种有机酸对体系中可溶性铝影响的大小顺序为 :草酸 >柠檬酸 >丙二酸 >苹果酸 >乳酸。草酸、柠檬酸和乳酸对可溶性铝释放的促进作用随体系pH的升高而减小 ,其中草酸体系中可溶性铝随pH的变化幅度最大。在苹果酸体系中 ,可溶性铝随pH的升高而稍有增加。体系中的可溶性铝随有机酸浓度的增加而增加 ,而交换性铝随柠檬酸浓度的增加而减少 ,先随苹果酸浓度增加而增加 ,然后又逐渐减少。与对照相比 ,柠檬酸和草酸使交换性铝的量减小 ,苹果酸和乳酸在低pH下使交换性铝明显增加 ,而苹果酸在较高pH下使交换性铝减少。有机酸影响释放出的铝在固液相间的分配比 ,苹果酸在低pH下使体系中释放出的大部分铝以交换性形态存在 ,而在较高pH下 ,大部分铝以可溶形态存在。在草酸体系中 ,释放出铝的大部分都以可溶形态存在。不同有机酸的不同表现与体系中铝的溶解平衡、铝的吸附 -解吸平衡、有机酸的吸附 -解吸平衡、有机酸的离解平衡和铝与有机酸的络合 -离解平衡有关。     

有机酸对铝氧化物吸附磷的影响

以存在不同配位阴离子 (硫酸根、磷酸根、草酸根、柠檬酸根 )时合成的铝氧化物为对象 ,用平衡吸附法研究了草酸、柠檬酸等的浓度和 pH对铝氧化物吸附磷的影响 ,并讨论有机酸影响磷吸附的机制。结果表明 :六种合成铝氧化物的最大吸磷量 (Xm)介于 0.189～ 0.838mmol/g ,以Al(OH)x的吸磷量最高 ,铝 柠檬酸复合物 (Al-CA)的吸磷量最低 ;有机酸浓度升高时 ,铝氧化物的吸磷量降低 ,且柠檬酸的影响程度高于草酸 ;先加 pH为 2的草酸或酒石酸 ,Al(OH)x对磷的次级吸附量最低 ,而有机酸pH为 3时 ,Al(OH)x对磷的次级吸附量达最高 ,有机酸溶液 pH由 4增至 9,铝氧化物吸磷量变化不大或逐渐降低。有机酸与磷混合加入同单加磷相比 ,pH 3时差异较小 ,pH 4～ 6时差异最显著 ,pH 7～ 8时又减小 ;有机酸降低铝氧化物吸磷量的机理包括酸性溶解和络合竞争两方面 ,在 pH 2时以前者为主 ,pH 3～ 9时以后者为主 ,且铝氧化物表面的吸附点位对供试配位阴离子都是亲合的     

不同pH下有机酸对针铁矿和膨润土吸附Cd2+、Pb2+的影响

用平衡吸附法研究了不同pH下,三种有机酸(乙酸、酒石酸和柠檬酸)对针铁矿和膨润土等温吸附Cd2 、Pb2 的影响。结果表明:在加入的Cd2 、Pb2 浓度分别小于0.2 mmol L-1和4.0 mmol L-1时,针铁矿和膨润土吸附平衡体系的pH随加入重金属浓度的增加而降低,膨润土体系的pH降低更明显。在有机酸作用下,pH对针铁矿和膨润土吸附Cd2 、Pb2 的影响差异显著。3酒石酸>乙酸,其对膨润土吸附的影响差异不明显。     

镉与柠檬酸、EDTA在几种典型土壤中交互作用的研究

采用批平衡实验方法研究了镉在青黑土 (IB)、黄棕壤 (YB)和红壤 (R)三种土壤上的吸附和解吸过程以及吸附介质酸度、共存有机酸等对此过程的影响。结果表明 :柠檬酸、EDTA的存在明显降低了镉在黄棕壤和青黑土上的吸附 ,同时镉解吸率较在硝酸钠体系要小 ,有机物的存在增加了土壤中镉的相对非饱和吸附点位。而在红壤上有机物的存在对镉的影响则随介质pH的改变而发生显著变化。酸性条件下 ,有机物的存在增加镉在红壤上的吸附 ,而随pH的增加 ,有机物减少镉的吸附。同时镉在硝酸钠体系中的解吸率随总吸附量的增加而呈现峰形的变化规律。土壤类型变化显著影响镉与有机物之间的交互作用过程     

甘草根瘤菌CCNWGX035的抗逆特性及结瘤特征研究

Thirty-nine rhizobial isolates were isolated from the root nodules of Glycyrrhiza uralensis and Glyeyrrhiza glabra, growing in the arid and semiarid regions of northwestern China, to test their taxonomic position and stress tolerance and to select one promising putative inoeulant strain for further studies. On the basis of 113 physiological and biochemical characteristics, the isolates were clustered into three groups. One isolate CCNWGX035 was found to have high tolerance to NaC1, pH, and temperature. By sequencing the 16S rDNA, isolate CCNWGX035 was placed in genus Mesorhizobium. Nodulation tests demonstrated that the isolate not only formed nitrogen-fixing nodules on its original host plant Glyeyrrhiza glabra, but also on Sophora vieiifolia, Lotus cornieulatus, Trifolium repens, Melilotus suaveolens, and Sophora alopecuroides. On the basis of sequence analysis of the nodA gene, isolate CCNWGX035 was closely related to strains of the genus Mesorhizobium, exhibiting some novel characteristics of root nodule bacteria.     

有机酸作用下黄壤无机纳米微粒对Cd~(2+)吸附动力学特性

为探究有机酸对镉在纳米粒级土壤上的有效性及其形态的影响,基于超声—离心—冻融法,应用到四川省名山河流域老冲积黄壤中,获得纳米微粒(≤100 nm),分别研究不同分子量有机酸(柠檬酸、富里酸、EDTA)及其组合(柠檬酸+EDTA、柠檬酸+富里酸、富里酸+EDTA)对土壤纳米微粒吸附Cd~(2+)动力学特性的影响。结果表明,土壤纳米微粒对Cd~(2+)的动力学吸附量大小关系表现为:柠檬酸+EDTA富里酸柠檬酸+富里酸柠檬酸富里酸+EDTAEDTA。总的来看,EDTA的抑制作用最强,最能降低土壤纳米微粒对Cd~(2+)的吸附。     

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.     

Verringerung der Phosphatsorption durch Zusatz organischer Verbindungen zu Böden in Abhängigkeit vom pH-Wert

Reduction of Phosphate sorption in soils by some organic compounds as dependent on pH 3 soils of pH 4.1, 5.9, and 7.1 were treated with aqueous solutions (at 3 concentrations) of 37 organic compounds (organic acids, phenolics, uronic acids, sugars); following an equilibration with ³²P-diammonium phosphate the recovery of ³²P was measured in the soil extract. All tested compounds did not show any effects at a concentration of 0.1 mg/g soil. Sugars, uronic acids, 2-keto-D-gluconic acid and most amino acids (with the exception of Glu, Asp, Cys, Phe which raised the recovery of ³²P by 2 to 3%) were ineffective even at the highest rate (10 mg/g soil). Aromatic acids and phenolics increased the recovery to a greater extent (highest increases with gallic acid: 8 to 11% depending on the soil). Effects were greatest with aliphatic acids like citric acid (45 to 48%), isocitric acid (8 to 64%), malic acid (12 to 57%), and malonic acid (8 to 38%). Only these four acids as well as ascorbic and isoascorbic acid markedly increased the recovery of ³²P even at a concentration of 1 mg/g soil. The effects of these acids (with the exception of malonic acid) decreased with increasing soil pH. By adding HCl to the soil in controls, it could be shown that the increased recovery rates of ³²P were not caused by the decrease in pH.     

低分子量有机酸对红壤磷酸单酯酶活性的影响

采用室内模拟试验研究了低分子量有机酸(柠檬酸、草酸、苹果酸、酒石酸)对红壤磷酸单酯酶活性的影响。结果表明,低浓度有机酸(<1μmol g-1)对磷酸单酯酶活性有促进作用,且促进作用大小依次为柠檬酸≈草酸>苹果酸>酒石酸;而高浓度有机酸(>5μmol g-1)则为抑制作用,且抑制作用大小依次为柠檬酸>草酸>苹果酸>酒石酸。当体系pH趋向酶促反应最佳pH时,磷酸单酯酶活性增强;反之,当体系pH远离酶促反应最佳pH时,磷酸单酯酶活性减弱。有机酸根一方面通过羧基的辅助作用提高磷酸单酯酶活性;另一方面通过释放土壤A l3+、Fe3+等金属离子,对土壤磷酸单酯酶活性有一定的抑制作用。     

有机酸对针铁矿和膨润土吸附Cd2+、Pb2+的影响

用平衡吸附法研究了不同浓度的有机酸（乙酸、酒石酸和柠檬酸）对针铁矿和膨润土吸附Cd^2＋、Pb^2＋的影响。结果表明：（1）低浓度（〈0．6mmolL^-1）有机酸促进供试矿物吸附Cd^2＋和Pb^2＋，随着有机酸浓度增加，吸附逐渐被抑制。高浓度（〉1．0mmolL^-1）有机酸对Pb^2＋吸附的抑制作用比对Cd^2＋的强。有机酸浓度的变化对针铁矿Cd^2＋、Pb^2＋吸附率的影响大于对膨润土的。（2）不同Cd^2＋浓度下，有机酸对膨润土Cd^2＋吸附强度的影响大于针铁矿。加入高浓度Cd^2＋（8．0mmolL^-1）时，低浓度有机酸对膨润土吸附Cd^2＋的促进作用比加入低浓度Cd^2＋（0．4mmolL^-1）时明显，高浓度有机酸对膨润土吸附Cd^2＋的抑制作用与低浓度Cd^2＋时相近。（3）低浓度有机酸（〈0．6mmolL^-1）时，酒石酸、柠檬酸对针铁矿吸附Cd^2＋的促进作用大于乙酸，而它们对膨润土吸附Cd^2＋的促进作用相似；在三种有机酸高浓度（〉1．0mmol L^-1）时，针铁矿对Cd^2＋的吸附都趋于稳定，而柠檬酸对膨润土吸附Cd^2＋的抑制作用比乙酸和酒石酸的明显。不同种类有机酸下，矿物对Pb^2＋吸附率大小的变化基本一致。     

低分子量有机酸对可变电荷土壤吸附性氟解吸的影响

低分子量有机酸可增加可变电荷土壤中吸附性F的解吸,4种有机酸对F解吸影响的大小顺序为:草酸>丙二酸>柠檬酸>苹果酸。有机酸对F解吸的增加作用随有机酸浓度的增加和pH的升高而增加。有机酸可以通过两种机制来增加F的解吸量,一是有机酸阴离子与F对土壤表面吸附位的竞争作用;另一机制是有机酸通过促进土壤氧化铝的溶解来增加F的解吸量。从短程反应看,第一种机制是主要的。     

Phytotoxicity of organic acids as influenced by montmorillonite,hydroxy‐Al montmorillonite and phosphate fertilization

Abstract

The germination and growth of wheat seedlings were studied at pH 5.5 in liquid growth media with organic acids in concentrations ranging from 800 to 1200 ppm, before and after interaction of the organic acids with montmorillonite and hydroxy‐Al montmorillonite. Germination was not affected by the organic acids, but subsequent growth was dependent on the kind and concentration of organic acid in the growth medium. Acetic acid was more inhibitory than citric acid. Gallic acid polymerized at pH 5.5 and was phytotoxic at 1200 ppm. Interaction of organic acids with montmorillonite and hydroxy‐Al montmorillonite reduced the concentration of organic acids in solution by adsorption. Despite this reduction in concentration the phytotoxicity of the growth media was enhanced after the interaction. This was caused by the dissolution of surface Al and the effect was more pronounced in cases where hydroxy‐Al interlayered montmorillonite was the adsorbent. Additions of P as KH₂PO₄ alleviated the phytotoxicity of organic acids but not the associated Al toxicity. The amount of P lost by adsorption or precipitation was dependent on the form of Al in the growth media.     

Sulfate adsorption by variable charge soils: Effect of low-molecular-weight organic acids

Sulfate (SO₄ ^2–) movement and transport in soils has received considerable attention in recent years. In most soils, SO₄ ^2– coexists with a variety of natural organic compounds, especially organic acids. Studies were conducted to assess the effect of low-molecular-weight organic acids (eight aliphatic and five aromatic acids) on SO₄ ^2– adsorption by variable charge soils from Chile and Costa Rica. The effects of type of organic acid, pH, type of soil, and organic acid concentration were investigated. In one experiment, a 1.0 g soil sample was equilibrated with 25 ml 0, 0.5, 1.0, 2.0, 4.0, or 6.0 mM K₂SO₄ in 1 mM NaCl in the presence or absence of 5 mM citric acid. In the second set of experiments, the adsorption of 2 mM SO₄ ^2– in soils at pH 4 or pH 5 in the presence or absence of one of 13 organic acids at a concentration of 2 mM or 5 mM was studied. Results showed that citric acid significantly decreased SO₄ ^2– adsorption by the two soils. Sulfate adsorption decreased with increasing pH of the equilibrium solution. Aliphatic acids, with the exception of cis-aconitic acid, decreased the amount of SO₄ ^2– adsorbed by the two soils, with oxalic, tartaric, and citric acid showing the greatest effect. The differences in pH values of the equilibrium solutions in the presence and absence of organic acids were significantly, but negatively, correlated with the amount of SO₄ ^2– adsorbed, suggesting chemisorption of SO₄ ^2– and the release of hydroxide ions. The ionization fraction values of the organic acids at the equilibrium pH were correlated with the amounts of SO₄ ^2– adsorbed, suggesting that the protonation of surface hydroxyl groups of the mineral phase increased as the strength of the ionization of the acid increased, thus creating more positively charged surfaces. Received: 12 February 1997     

Adsorption of mercury compounds by tropical soils II. Effect of soil: Solution ratio,ionic strength,pH, and organic matter

Mercury adsorbed from HgCl₂ and 2-methoxy-ethylmercury chloride (Aretan) solutions by three contrasting soils showed a dependence on soil: solution ratio and initial Hg concentration in soil solution. Changing the soil solution ratio from 1: 10 to 1 : 100 but keeping the initial concentration constant resulted in an increase in Hg adsorption from both Hg compounds. A similar change in soil: solution ratio accompanied by a decrease in initial concentration, on the other hand, resulted in decrease in Hg adsorption. Upon manipulating of the pH of the surface soils, adsorption of HgCl₂ at 100 mg Hg L^?1 concentration increased from about 701 :o over 95 mg Hg kg^?1 when pH was raised from 5.0 to 8.0. Precipitation of Hg may also have contributed to this trend. Aretan adsorption by these soils, on the other hand, changed little with change in pH. Removal of organic matter from soil resulted in large reductions of Hg adsorbed, as much as 95 % from the HgCl₂ solutions, but only up to 31 % from Aretan solutions. This suggests that organic matter in soil played a mayor role in the adsorption of inorganic Hg whereas the soils' mineral fractions were involved more in the adsorption of the organic Hg compound.     

Effect of Low Molecular Weight Organic Anions on Adsorption of Aluminum by Variable Charge Soils

To examine the effect of organic anions on adsorption of Al by variable charge soils at different pH values, the adsorption by three soils in the presence of three low-molecular-weight aliphatic carboxylic acids was investigated. The results showed that the effect depended on pH, the type of organic anions and their concentration. The presence of citrate and oxalate led to an increase in the adsorption of Al at low pH and low concentration of organic anions, with citrate showing a stronger effect than oxalate. For example, the maximum increments of Al adsorption in the presence of citrate were 131.9, 104.8 and 32.9% in the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively, whereas in the presence of oxalate it was 36.1% in the Rhodic Ferralsol. At high pH or high concentration of organic anions, they showed an inhibiting effect on the adsorption of Al. For example, citrate caused the increase in Al adsorption by 164.0, 131.0 and 61.0% at pH3.85 and the decrease in Al adsorption by 15.2, 19.5 and 45.6% at pH 4.8 for the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively. In the citrate and oxalate systems, the adsorption of Al increased with the increase in the concentration of organic anions, reaching a maximum values at about 0.4 mmol L^?1, and then decreased. When the concentration of organic anions was higher than about 1.0 mmol L^?1, both citrate and oxalate inhibited the adsorption of Al. The ability of organic anions in increasing the adsorption at low pH and decreasing the adsorption at high pH followed the same order: citrate > oxalate > acetate. The increase of Al adsorption at low pH is caused by the increase in soil negative surface charge as a result of the adsorption of organic anions by variable charge soils, while the decrease of Al adsorption at high pH and high concentration of organic anions is related to the competition of organic ligands for aluminum ions with soil surface. After the removal of free iron oxides from the soil, Al adsorption decreased in the presence of citrate, the anion species most strongly adsorbed by variable charge soils and complexed with aluminum ions. For example, for the Rhodic Ferralsol and the Ferric Acrisol, the removal of free iron oxides caused a decrease in the adsorption of Al in the presence of citrate at pH4.4 by 26.2 and 21.9%, respectively.     

镉在胡敏酸上的吸附动力学和热力学研究

采用镉离子选择电极研究了镉在胡敏酸上的吸附特征。实验结果表明 ,胡敏酸对镉的等温吸附规律与介质pH有关。当pH为 3 0 0和 3 50时符合Freundlich方程 ,当pH在 4 0 0～ 6 50之间更好地符合Langmuir方程 ;在pH为 3 0 0～ 6 50之间 ,吸附量与pH成显著正相关。温度升高吸附量降低 ,吸附热与反应介质的pH有关 ,pH升高 ,吸附反应放热增加 ;胡敏酸对镉的吸附作用力随介质pH改变发生较大变化 ,当pH为6 50时主要为配位基交换作用。胡敏酸对镉的吸附含有部分不释放氢的静电吸附 ,其吸附反应动力学用Elovich方程拟合效果较好