有机酸根与铝氧化物表面吸附磷的解吸

研究了有机酸根离子与合成铝氧化物表面吸附磷解吸的相互关系。结果表明:（1）有有机酸时比无有机酸时吸附的磷具有更高的解吸率,无草酸且加磷pH为4时,0.01molL-1KCI对磷的解吸率最低,草酸与磷共存且pH为6时磷的解吸率最高;（2）高浓度有机酸可解吸低浓度有机酸难解吸的磷,草酸难解吸的磷可为等浓度的柠檬酸极解吸;（3）不同浓度草酸和柠檬酸对铝-草酸复合物吸附磷的解吸率比对Al（OH)x的低,而对铝-柠檬酸复合物吸附磷的解吸率则比对Al（OH）x的高;（4）柠檬酸对铝-磷复合物中磷的解吸量随柠檬酸浓度升高而增大。这些结果证明,有机酸对铝氧化物吸附磷的解吸机理包括配位交换和溶解,有机酸可促进磷的解吸,提高磷的有效性。     

铝(氢)氧化物对有机酸和磷酸根的竞争吸附研究

研究了磷 /草酸浓度比 (Cp/Cox)、草酸 (OX)与磷 (P)加入顺序、多种有机酸共存等条件下铝 (氢 )氧化物 (Al(OH)x)对有机酸和磷的吸附量变化。结果表明 :磷浓度一定时 ,随Cp/Cox减小 ,Al(OH)x吸附磷量降低 ,吸附OX量增高 ,吸附阴离子总量一般随浓度升高而增加 ;Cp/Cox相同时 ,5种加入方式吸P顺序为P/OX P -OX OX +P OX -P OX/P ;Cp/Cox不同时 ,Al (OH)x吸附配位体的总量也相应变化 ;几种有机酸共存时 ,Al(OH)x对体系中的各种阴离子均有吸附 ,且相互影响和制约 ,总吸附量取决于离子种类和浓度 ,3种有机酸影响P吸附量的顺序为柠檬酸 (CA) 草酸 (OX) 酒石酸 (Tar) ;Al (OH)x加磷后随平衡时间延长 ,先吸附的OX和CA对吸附P量的影响逐渐减弱 ,它们的相对亲合力越来越成为主导因素。     

有机阴离子对磷酸根吸附的影响

在中性条件下,低浓度的柠檬酸、草酸、酒石酸和胡敏酸阴离子都能显著降低针铁矿、非晶氧化铝、高岭石和红壤对磷酸根的吸附,尤其在低磷吸附饱和度下效果更好。有机阴离子抑制磷酸根吸附的能力因有机酸的种类和性质、以及固相的表面特性而异。有机阴离子存在下吸附的磷酸根具有较高的同位素³²P交换活性和解吸率。测定了吸附平衡溶液中铁和铝的浓度。结果表明,在实验条件下(pH 7.0),即使较高浓度的有机酸根(10^-2mol)也只能溶解极少量的铁和铝。有机阴离子络溶作用不足以说明固相吸附磷能力的显著下降。可见,有机阴离子降低磷酸根吸附的机制主要是竞争专性吸附。有机阴离子占据了一部分高亲和力的吸附位,从而降低了土壤固相吸附磷的量,增加了吸附态磷的活性。     

低分子量有机酸对红壤无机磷活化的作用

采用室内模拟试验研究了低分子量有机酸,如草酸、柠檬酸、酒石酸和苹果酸在红壤无机磷活化中的作用。结果表明,相同浓度下,有机酸活化土壤磷的能力为柠檬酸酒石酸苹果酸。低浓度(0.5mmolL-1)时,草酸活化能力最小;高浓度(≥5mmolL-1)时,其活化能力最大。对同一种有机酸而言,土壤各无机磷形态活化量均随pH的升高而降低;且在同一酸度下,其活化量以铝磷(Al-P)为最多,铁磷(Fe-P)和钙磷(Ca-P)次之,闭蓄态磷(O-P)则最少。有机酸活化土壤无机磷酸盐应该是质子酸效应和有机酸阴离子络合效应共同作用的结果,且与磷酸盐的溶度积常数密切相关。研究结果对根系土壤无机磷素循环研究有着重要的意义。     

不同有机酸对石灰性土壤磷的活化效应及机理

【目的】添加低分子量有机酸是活化土壤难溶性磷有效途径。比较研究几种低分子量有机酸及其组合对土壤磷的活化性能,为土壤磷的高效利用提供依据。【方法】低磷和高磷石灰性土壤选自新疆石河子,设置5个低分子有机酸添加处理：草酸、柠檬酸、黄腐酸、柠檬酸+草酸、草酸+柠檬酸+黄腐酸处理,和一个0.01mmol/L KCl对照。采用吸附平衡实验法测定土壤磷的吸附量;采用土壤吸附动力学实验法测定土壤磷的解吸动力学。采用常规和灭菌土壤培养方法,通过连续浸提法研究低分子有机酸及其组合对磷组分动态转化的影响和pH对磷的活化效应。【结果】Langmuir与Elovich模型均可较好地拟合土壤对磷的吸附热力学(R²=0.852～0.994)与吸附动力学过程(R²=0.882～0.975)。低磷土壤的最大吸附量(Q_max)、最大缓冲容量(MBC)、吸附力常数(K_L)和吸附速率(b)均高于高磷土壤,表明低磷土壤对磷的吸附更强。低分子量有机酸添加均降低了Q_max、MBC和b。草酸对Q_max和...     

有机酸对几种土壤胶体吸附解吸镉离子的影响

用平衡法研究了有机酸对土壤胶体吸附 解吸Cd2 的影响。结果表明 ,黄棕壤、红壤、砖红壤胶体Cd2 最大吸附容量 (Qm)分别为 4 3 7、16 8、1 5 8mmolkg-1。在加入Cd2 浓度相同的条件下 ,土壤胶体Cd2 吸附量随有机酸浓度的升高呈峰形曲线变化。当有机酸与Cd2 共存时 (竞争吸附 ) ,低浓度的草酸 (小于0 5～ 2mmolL-1)或柠檬酸 (小于 0 0 2 5～ 0 2mmolL-1)提高Cd2 吸附量 ,高浓度的草酸或柠檬酸能降低Cd2 吸附量。吸附有机酸后的土壤胶体 (次级吸附 )对Cd2 次级吸附量的影响与竞争吸附一致 ,但两者的Cd2 吸附量变化幅度不一样。这是由于两种吸附体系液相中有机酸残留浓度不同所致。土壤胶体吸附态Cd2 的解吸结果表明 ,草酸浓度不仅影响Cd2 的总解吸量、总解吸率 ,还影响土壤胶体表面KNO3 解吸态与DTPA解吸态Cd2 的分配比例     

铝胁迫下萹蓄与饭豆根系有机酸分泌特性比较

以蓄和饭豆为试验材料,从对Al胁迫的响应时间、蛋白质合成抑制剂的影响、体内有机酸含量变化及阴离子通道抑制剂的影响等方面,比较研究了Al诱导根系分泌有机酸的差异,以进一步明确铝(Al)诱导植物根系有机酸分泌的过程。结果表明,萹蓄根系在Al胁迫后30.min内分泌出草酸,而Al胁迫至少4.h后饭豆根系才开始分泌柠檬酸;蛋白质合成抑制剂环己亚酰胺(Cycloheximide,CHM)不影响萹蓄根系草酸的分泌,但抑制了84%Al诱导的饭豆根系柠檬酸的分泌,表明前者不需要新蛋白质的诱导合成,却是后者所必需的。Al处理不改变萹蓄根尖草酸的含量,但明显提高了饭豆根尖柠檬酸的含量;阴离子通道抑制剂苯甲酰甲醛(Phenylglyoxal,PG)和蒽-9-羧酸(Anthrancene-9-carboxylic.acid,A-9-C)分别有效抑制Al诱导萹蓄根系草酸的分泌及饭豆根系柠檬酸的分泌,再次证明两者有机酸的分泌是通过某种被Al所诱导或激活的阴离子通道所实现的。     

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。     

低分子量有机酸对可变电荷土壤铝活化动力学的影响

从动力学角度研究了几种低分子量有机酸对2种酸性土壤中铝的活化和活化铝在土壤固/液相之间分配的影响。结果表明:对于络合能力弱的醋酸和乳酸,主要通过质子作用活化铝,且活化作用明显小于盐酸。而络合能力较强的苹果酸、草酸和柠檬酸,主要通过络合作用促进铝的释放,且这种作用随有机酸根阴离子络合能力的增强而增加。在氧化铁含量较高的砖红壤中,苹果酸、草酸和柠檬酸通过专性吸附增加土壤表面负电荷,从而增加土壤交换态铝;但在氧化铁含量较低的红壤中,草酸和柠檬酸主要通过形成可溶性铝络合物降低交换态铝。活化铝在土壤固/液相间的分配主要决定于溶液中有机阴离子与土壤固相表面对铝离子的竞争。醋酸和乳酸活化的铝主要以交换态铝存在;而草酸和柠檬酸活化的铝主要以有机酸-铝络合物存在于溶液中,特别是在氧化铁低的红壤中,这将促进铝在土壤-水体中的迁移。     

低分子量有机酸对石灰性土壤磷吸附动力学的影响

根据植物在缺磷胁迫下,根系分泌的有机酸种类的数量,用流动法研究了柠檬酸、苹果酸、草酸和酒石酸对石灰性土壤磷吸附动力学的影响。结果表明：有机酸均能明显降低土壤对磷的吸附,不同有机酸降低磷吸附的能力大小的次序为草酸≥柠檬酸〉苹果酸≥酒石酸。     

Effects of Organic Anions on Phosphate Adsorption and Desorption from Variable—Charge Clay Minerals and Soil

Effects of citrate and tartrate on phosphate adsorption and desorption from kaolinite,goethite,amorphous Al-oxide and Ultisol were studied.P adsorption was significantly decreased as the concentration of the organic anions increased from 10^-5 to 10^-1 M.At 0.1 M and pH 7.0,tartrate decreased P adsorption by 27.6%-50.6% and citrate by 37.9-80.4%,depending on the kinds of adsorbent.Little Al and/or Fe were detected in the equilibrium solutions,even at the highest concentration of the organic anions.Effects of the organic anions on phosphate adsorption follow essentially the competitive adsorption mechanism.The selectivity coefficients for competitive adsorption can be used to compare the effectiveness of different organic anions in reducing P adsorption under given gonditions. Phosphate desorption was increased by 3 to 100 times in the presence of 0.001 M citrate or tartrate compared to that in 0.02 M KCl solution alone.However,for all the soil and clay minerals studied the amount of P desorbed by citrate or tartrate was generally lower than or close to that of isotopically exchangeable P.The effect of organic anions on phosphate desorption arises primarily from ligand exchange.     

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.     

Effect of acid deposition on the displacement of Al(III) in soils

This study represents an assessment of some of the key factors influencing the mobility of Al(III) and its displacement in acid soils. This assessment is based on the effect of pH and other solution variables on the solubility of Al(III) and its complex formation with OH^?, F^? and organic ligands (fulvates and humates). Above all, the adsorption behavior of Al(III) on iron(III) (hydr)oxides and on SiO₂ on one hand, and the adsorption of organic acids and of humic substances on mineral surfaces on the other hand was investigated. Adsorption is interpreted in terms of surface complex formation equilibria; the mass law constants derived permit the modeling of adsorption as a function of solution variables. It is illustrated that the distribution of oxides and hydroxides in the soil profile affects the pH buffering, determines the mobility of the organic acids while the mobility of Al(III) is primarily governed by the formation and dissolution of Al(III) (hydr)oxides.     

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.     

Competitive adsorption between phosphate and carboxylic acids: quantitative effects and molecular mechanisms

The competitive adsorption at the water‐goethite interface between phosphate and a carboxylic acid, either oxalate, citrate, 1,2,3,4‐butanetetracarboxylic acid (BTCA), mellitate or Suwannee River Standard Fulvic Acid 1S101F (FA), was investigated over a wide pH range (3–9) by means of batch experiments and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. The quantitative results from the competitive adsorption measurements show that the efficiency of the organic acids in competing with phosphate was in the order oxalate < citrate < BTCA ≅ FA < mellitate. Oxalate showed no detectable effect, whereas the effect in the mellitate system was strong, and the aggregative results indicate that an increasing number of carboxylic groups favours competitive ability towards phosphate. The infrared spectroscopic results show conclusively that competition for goethite surface sites between carboxylic acids and phosphate is not a ligand‐exchange reaction between inner‐sphere surface complexes. Instead, ligands capable of multiple H‐bonding interactions are required to out‐compete and desorb surface complexes of phosphate. The fact that partially protonated organic acids are the most efficient emphasizes the importance of both H‐accepting carboxylate groups and H‐donating carboxylic acid groups for the competitive effect.     

Desferrioxamine-B promoted dissolution of an Oxisol and the effect of low-molecular-weight organic acids

This study was conducted to quantify the adsorption of desferrioxamine-B (DFO-B), a commercial trihydroxamate siderophore, onto an Oxisol and particularly examine the DFO-B-promoted soil dissolution in the presence of two small organic acids (citric and oxalic acids). Adsorption of DFO-B to Oxisol was rapid, and the adsorption isotherms yielded maximum surface concentrations of 9.59 μmol g^?1 at pH 5.0, much lower than the soil cation exchange capacity. After reaching the maximum concentration within several minutes, the DFO-B adsorption to the soil subsequently decreased and attained a steady state, followed by a slight increase at the end of the reaction. Release of Fe, Mn, and Al from the soil was greatly enhanced in the presence of DFO-B. No competitive or synergic effect between the DFO-B and citric or oxalic acids was found on dissolution of Al- or Fe-containing minerals. However, a synergic effect between DFO-B and citric acid on dissolution of Mn-containing minerals was found, and a slight competitive effect of oxalic acid on release of Mn promoted by DFO-B was observed. These results can enhance our understanding on the role of siderophores in soils dissolution and weathering as well as the release of nutrient elements in the presence of low-molecular-weight organic acids.