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.     

Effect of low-molecular-weight organic acids on Cl- adsorption by variable charge soils

Low-molecular-weight (LMW) organic acids exist widely in soils and have been implicated in many soil processes.The objective of the present paper was to evaluate effect of two LMW organic acids, citric acid and oxalic acid, on Cl^- adsorption by three variable charge soils, a latosol, a lateritic red soil and a red soil, using a batch method. The results showed that the presence of citric acid and oxalic acid led to a decrease in Cl- adsorption with larger decreases for citric acid. Among the different soils Cl- adsorption in the lateritic red soil and the red soil was more affected by both the LMW organic acids than that in the latosol.     

有机酸和质子对淹水水稻土非交换性铵释放的影响

In a model experiment, which imitated the rhizosphere of rice, the effect of organic acids (oxalic acid, citric acid) and protons on the release of non-exchangeable NH4^ and the resin adsorption of N was studied in a paddy soil, typical for Zhejiang Province, China. Oxalic and citric acids under low pH conditions, in combination with proton secretion, favored the mobilization of NH4^ ions and increased resin adsorption of N. The release of non-exchangeable NH4^ was associated with less formation of iron oxides. These could coat clay minerals and thus hinder the diffusion of NH4^ ions out of the interlayer. Protons enhanced the release of NH4^ , and then they could enter the wedge zones of the clay minerals and displace non-exchangeable NH4^ ions.     

低分子量有机酸对促进可变电荷土壤中铝溶解的影响

Low-molecular-weight （LMW） organic acids exist widely in soils and play an important role in soil processes such as mineral weathering, nutrient mobilization and A1 detoxification. In this research, a batch experiment was conducted to examine the effects of LMW organic acids on dissolution of aluminum in two variably charged soils, an Ultisol and an Oxisol. The results showed that the LMW organic acids enhanced the dissolution of A1 in the two investigated soils in the following order： citric 〉 oxalic 〉 malonic 〉 malic 〉 tartaric 〉 salicylic 〉 lactic 〉 maleic. This was generally in agreement with the magnitude of the stability constants for the Al-organic complexes. The effects of LMW organic acids on Al dissolution were greater in the Ultisol than in the Oxisol as compared to their controls. Also, the accelerating effects of citric and oxalic acids on dissolution of A1 increased with an increase in pH, while the effects of lactic and salicylic acids decreased. Additionally, when the organic acid concentration was less than 0.2 mmol L-I, the dissolution of A1 changed Iittle with increase in acid concentration. However, when the organic acid concentration was greater than 0.2 mmol L^-1,the dissolution of A1 increased with increase in acid concentration. In addition to the acid first dissociation constant and stability constant of Al-organic complexes, the promoting effects of LMW organic acids on dissolution of A1 were also related to their sorption-desorption equilibrium in the soils.     

Effect of Oxalic and Citric Acids on Zinc Release Kinetic in Two Calcareous Soils

Rate of zinc (Zn) release from solid to solution phase by organic acids can influence Zn availability in calcareous soils. The objective of the present study was to investigate the effect of different concentrations (1.1, 2.2, and 3.3 mM) of oxalic acid and citric acid on the kinetic release of Zn from two calcareous soils from Eastern Iran. The two organic acids showed significant difference in Zn release from studied soils. Cumulative Zn release during 72 h ranged from 5.85 to 10.4 mg kg^?1 in soil 1 and ranged from 8.7 to 16.9 mg kg^?1 in soil 2 using different concentrations of oxalic acid. The amount of cumulative Zn release after 72 h in soil 1 ranged from 13.65 to 28.77 mg kg^?1 and from 17.63 to 23.13 mg kg^?1 when different concentrations of citric acid was used. In general, Citric acid released 38% more Zn from soils than oxalic acid. The release of Zn from soils increased with citric acid concentration but decreased with increasing of oxalic acid concentrations in the solution. The simplified Elovich equation best described Zn release as a function of time (r² = 0.93 and SE = 0.78). From the present study, Zn release from soils can be limited by the higher concentration of oxalic acid, while citric acid is suitable for enhancing soil lability of Zn.     

低分子有机酸/盐对森林暗棕壤铁的释放效应

模拟森林凋落物淋洗液中草酸/草酸盐和柠檬酸/柠檬酸盐的浓度范围,设计了不同浓度草酸/草酸盐和柠檬酸/柠檬酸盐溶液一次性浸提和多次连续浸提等系列实验,结果表明,草酸/草酸盐和柠檬酸/柠檬酸盐对暗棕壤铁具有活化作用,活化作用大小因有机酸/盐种类、浓度和土壤性质而异。随着低分子有机酸/盐浓度的增加,A1层和B层暗棕壤活化释放的铁也逐渐增多。pH 5.16的低分子有机盐溶液对A1层和B层暗棕壤铁的活化作用强于同浓度的相应低分子有机酸,即柠檬酸盐>柠檬酸,草酸盐>草酸,因此推断草酸盐和柠檬酸盐溶液促进暗棕壤铁活化释放的机理主要在于低分子有机酸阴离子的配位反应。柠檬酸/柠檬酸盐对A1层和B层暗棕壤铁的活化作用强于同浓度的草酸/草酸盐,即柠檬酸>草酸,柠檬酸盐>草酸盐,这主要与柠檬酸对铁较强的络合能力及较大的离解常数有关。A1层与B层相比,草酸/草酸盐和柠檬酸/柠檬酸盐均对B层暗棕壤释放的铁量较高。另外,低分子有机酸对暗棕壤铁的释放并不是一次就能完成的,第一次以后的连续4次浸提仍源源不断释放出数量可观的铁。     

Heavy Metal Release from Some Industrial Wastes: Influence of Organic and Inorganic Acids, Clay Minerals, and Nanoparticles

Knowledge about heavy metal release from industrial solid wastes(ISWs) is crucial for better management of their environmental risks. This study was conducted to investigate the effect of organic and inorganic acids, clay minerals, and nanoparticles(NPs) on the release of heavy metals from sugar factory waste, ceramic factory waste, leather factory waste, and stone cutting waste. The influence of the extractants on heavy metal release from these ISWs was in the following descending order: citric acid oxalic acid nitric acid≥ sulfuric acid Ca Cl2. Addition of clay minerals and NPs as adsorbents decreased heavy metal release, which was significantly lower in NP-treated wastes than in the clay mineral-treated wastes. On the other hand, the presence of organic and inorganic acids increased heavy metal adsorption by NPs and clay minerals. These results suggest that NPs can be applied successfully in waste remediation,and organic and inorganic acids play an important role in the removal of heavy metals from the studied adsorbents.     

Citric acid enhances the mobilization of organic phosphorus in subtropical and tropical forest soils

Low-molecular-weight organic acids are considered to be effective in the release of inorganic phosphorus (P) but their effectiveness to mobilize organic P is not well understood. The aim of this study was to examine the role of three common organic acids (maleic, oxalic, and citric acids) in mobilizing organic P in forest soils. Soil samples tested in this study were collected from either native or plantation forests in subtropical and tropical Australia with 16–87% of soil total P being in organic form. At a concentration of 10 mM organic acid kg^?1 soil, all three organic acids did not enhance the release of inorganic P as compared with water, whereas the three organic acids displayed different capacities in mobilizing organic P. Citric acid significantly enhanced the solubilization of organic P by 34.7% as compared with water; whereas no significant differences were observed in the mobilization of organic P among maleic acid, oxalic acids, and water. The amount of organic P solubilized by citric acid was not correlated with soil pH but increased with increasing soil organic P as the values were below 200 mg kg.^?1 The possible mechanisms of the effective mobilization of organic P by citric acid were discussed. Our results implied that organic P might play an important role in P nutrition of plants in subtropical and tropical forests due to its substantial proportion in soil P and the effective mobilization by organic acids.     

Citric acid influence on soil phosphorus availability

Citric acid is a low-molecular-weight organic acid exuded by the plant roots. Organic anions derived from this acid compete for phosphorus (P) adsorption sites in clay minerals. The objective was to evaluate the P availability by application of P and citric acid tothe soil. For this purpose, an experiment in green house was conducted at the rates of 0, 45, 90, and 180 mg dm^?3 P in Entisol and 0, 100, 200, and 400 mg dm^?3 P in Oxisol, combined with 0, 0.5, 1.0, and 2.0 mg dm^?3 citric acid in pot. In the Entisol, 115 mg dm^?3 of P and 0.7 mg dm^?3 of citric acid resulted in maximum corn growth. However, in the Oxisol, the estimated rates were 299 mg dm^?3 of P and 1.3 mg dm^?3 of acid citric. Citric acid use in Entisol and Oxisol increased P availability of corn plants.     

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。     

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。     

红壤中低分子量有机酸的吸附特征

应用平衡法研究了红壤对草酸、柠檬酸、酒石酸和苹果酸的吸附行为。结果表明:红壤对有机酸的吸附量随着有机酸平衡溶液浓度的增加而增加,有机酸种类不同,吸附量也不同。有机酸在红壤中的吸附行为均可以很好地用Langmuir、Freundlich和Temkim方程描述,其中以Langmuir方程的拟合效果最好。红壤对有机酸均具有较高的吸附率,在0.5～20mmolL-1初始浓度范围内,草酸、柠檬酸、酒石酸和苹果酸的吸附率最大分别可达89.2%、77.5%、67.4%和47.1%。红壤对柠檬酸、酒石酸和苹果酸的吸附率均随着有机酸初始浓度的增加先急剧下降(<5mmolL-1),之后缓慢下降至趋于平稳;草酸的吸附率则随着初始浓度的增加而增加,在3mmolL-1左右时达到最大,随后降低至趋于平稳。     

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     

有机酸和磷对两种污染土壤铅的释放作用研究

用土壤培养和化学浸提法研究了不同低分子量有机酸和磷对污染土壤中铅释放的影响。结果表明,随有机酸浓度增加,铅污染红壤、棕壤中可溶出铅量均增加。当供试有机酸浓度≥1mmol·L-1时,相同浓度有机酸溶出铅量为柠檬酸〉乙酸〉草酸;当有机酸浓度≤0.5mmol·L-1时,溶出铅量为草酸〉柠檬酸〉乙酸。将2g·kg-1磷及50mmol·kg-1有机酸与铅污染红壤以不同方式混合后,柠檬酸处理的溶出铅比率（在污染土壤中加入P、有机酸后溶出铅含量与单加有机酸溶出铅含量之比）为66%（先加有机酸再加磷）、58%（有机酸与磷同时加入）、70%（先加磷再加有机酸）,草酸处理（方式同上）的溶出铅比率为90%、89%、94%,乙酸处理（方式同上）的为10%、8%、10%。铅污染棕壤上,以上处理的溶出铅比率分别为106.46%、104.43%、105.19%（柠檬酸）;43%、48%、58%（草酸）;38%、42%、55%（乙酸）。供试条件下,红壤最低溶出铅比率低于棕壤。     

大豆和小麦对矿物钾的活化作用研究

大豆、春小麦均能有效地活化利用白云母、钾长石中的结构性钾,结构钾释放量为19.53mg kg-1~45.46mg kg-1。春小麦和大豆根系分泌的有机酸主要为草酸、酒石酸和柠檬酸,其次为乳酸、乙酸和苹果酸。草酸溶液酸性较强,络合能力也强,其活化钾的能力最强。苹果酸、酒石酸、柠檬酸、乙酸和乳酸亦可有效地促进白云母和钾长石的分解,但活化土壤钾的能力比较低。低分子量有机酸作用下矿物钾的释放是酸性水解和络合溶解双重作用的结果。草酸、酒石酸、柠檬酸是影响大豆、春小麦吸收利用矿物钾的主要低分子量有机酸。     

The effect of low-molecular-weight organic acids and inorganic phosphorus concentration on the determination of soil phosphorus by the molybdenum blue reaction

Low-molecular-weight organic acids play an important role in the mobilization of soil phosphorus (P). The molybdate blue colorimetric method, based on the formation of P molybdenum blue compound, is commonly used for analysis of phosphate in soil and environmental samples. However, some organic acids can act as a ligand to bond with molybdenum acid, which subsequently interfere with the colorimetric reaction. The recoveries of P were inhibited by the addition of oxalic (>2 mM) and citric acids (>3 mM) both in standard P solutions and soil extracts, but formic and maleic acids did not interfere with the P determination. The inhibition of oxalic and citric acids on P recovery remained even at higher level of P (up to 100 μg P 100 ml⁻¹) though such interferences decreased by increasing P concentration. Comparison between oxalic and citric acids revealed the more pronounced interference by the addition of oxalic acid. The results suggested that the interference of organic acids with P determination is related to the types of organic acids and the ratio of organic acid ligands to P anions in the solutions. Thus, analysis of P using the molybdate blue colorimetric method should be undertaken cautiously in the presence of relative strong ligands like oxalic and citric acids.     

Remediation of Metal-Contaminated Soil by Organic Metabolites from Fungi II—Metal Redistribution

Exudation of low molecular weight organic acids by fungi was studied in a project focusing on bioremediation of metal-contaminated soils. The production of acids (mainly oxalic and citric acid) as a response to nutrient variations and presence of metals has recently been reported (Arwidsson et al. 2009). A significant release of metals was observed and was related not only to the production of organic acids but also to the resulting pH decrease in the systems. The processes governing the release and redistribution of metals in the soil–water fungus system were the focus of the present continuation of the project, based on observations of Aspergillus niger, Penicillium bilaiae, and a Penicillium sp. The release of lead was 12% from the soil with the second highest initial load (1,600 mg kg^?1), while the release of copper was 90% from the same soil (140 mg kg^?1). The dominating mechanism behind the release and subsequent redistribution was the change in pH, going from near neutral to values in the range 2.1–5.9, reflecting the production of organic acids. For some of the systems, the formation of soluble complexes is indicated (copper, at intermediate pH) which favors the metal release. Iron is assumed to play a key role since the amount of secondary iron in the soils is higher than the total load of secondary heavy metals. It can be assumed that most of the heavy metals are initially associated with iron-rich phases through adsorption or coprecipitation. These phases can be dissolved, or associated metals can be desorbed, by a decrease in pH. It would be feasible to further develop a process in technical scale for remediation of metal-contaminated soil, based on microbial metabolite production leading to formation of soluble metal complexes, notably with copper.     

Influence of low-molecular-weight organic acids on the solubilization of phosphates

A range of low-molecular-weight organic acids were identified in rhizosphere soil, leaf litter, and poultry manure compost. Laboratory and greenhouse experiments were carried out to examine the effects of seven low-molecular-weight organic acids on phosphate adsorption by soils, and the solubilization and plant uptake of P from soil pre-incubated with monocalcium phosphate and North Carolina phosphate rock. Acetic, formic, lactic (monocarboxylic), malic, tartaric, oxalic (dicarboxylic), and citric (tricarboxylic) acids were used in the study. The addition of organic acids decreased the adsorption of P by soils in the order tricarboxylic acid>dicarboxylic acid>monocarboxylic acid. The decreases in P adsorption with organic acid addition increased with an increase in the stability constant of the organic acid for Al (logK _Al). Organic acids extracted greater amounts of P from soils meubated with both monocalcium phosphate and phosphate rock than water did. Although more phosphate was extracted by the organic acids from monocalcium phosphate — than from phosphate rock — treated soils in absolute terms, when the results were expressed as a percentage of dissolved phosphate there was little difference between the two fertilizers. The amount of P extracted by the organic acids from both fertilizers increased with an increase in logK _Al values. The addition of oxalic and citric acids increased the dry matter yield of ryegrass and the uptake of P in soils treated with both fertilizers. The agronomic effectiveness of both fertilizers increased in the presence of organic acids and the increase was greater with the phosphate rock than with the monocalcium phosphate. The results indicated that organic acids increase the availability of P in soils mainly through both decreased adsorption of P and increased solubilization of P compounds.     

温度和水土比对红壤吸附低分子量有机酸的影响

通过一次平衡法考察了温度和水土比对红壤吸附草酸、柠檬酸、酒石酸和苹果酸的影响。结果表明,有机酸的吸附量、最大吸附量（Sm）及吸附亲和力常数（K）均随温度的升高而增加,随着水土比的增加而降低。温度和水土比变化对有机酸吸附的影响程度因有机酸种类而异,影响程度大小与土壤对有机酸的吸附亲和力（K）大小顺序相反。45℃ 时,土壤对草酸、柠檬酸、酒石酸和苹果酸的吸附量分别是 25℃ 时的 1.19、1.22、1.24 和 1.28 倍;100:1 水土比条件下,草酸、柠檬酸、酒石酸和苹果酸的吸附量分别较 10:1 水土比条件下减少了 48.3%、54.9%、63.5% 和 76.1%。