Organic anion-to-acid ratio influences pH change of soils differing in initial pH

Purpose

This study aimed to investigate the effect of initial soil pH and organic anion-to-acid ratio on changes in soil pH.

Materials and methods

Two soils (Podosol and Tenosol) along with two carboxylic acids (malic and citric acid) and their anions (sodium malate and citrate), commonly found in plant residues, were used in this study. Stock solutions of either malic acid and disodium malate or citric acid and trisodium citrate were added to pre-incubated soils at anion-to-acid ratios of 0:100, 10:90, 25:75, 50:50, 75:25, 90:10, 100:0 and at 0.25 g C kg^?1 soil. Soils were adjusted to 80 % field capacity and mixed thoroughly, and three replicates of 50 g of each soil were transferred into individual plastic cores and incubated at 25 °C in the dark for 30 days. Soil pH, respiration, NH₄ ⁺, and NO₃ ^? were determined.

Results and discussion

Soil pH increased linearly with increasing organic anion-to-acid ratio. The addition of organic anions to soil resulted in net alkalinisation. However, the addition of organic acids immediately decreased soil pH. During subsequent incubation, soil pH increased when the organic anions were decomposed. Alkalinity generation was lower in the Podosol (initial pH 4.5) than in the Tenosol (initial pH 6.2), and was proportional to anion-to-acid ratio across all the treatments. Cumulative CO₂-C release was approximately three times lower in the Podosol than the Tenosol at day 2 due to lower microbial activity in the low-pH Podosol.

Conclusions

Increasing anion-to-acid ratio of organic compounds increased soil pH. Increases in soil pH were mainly attributed to direct chemical reactions and decomposition of organic anions. Low pH decreased the amount of alkalinity generated by addition of organic compounds due to incomplete decomposition of the added compounds. This study implies that organic anion-to-acid ratio in plant residues plays an important role in soil pH change.     

Model organic compounds differ in their effects on pH changes of two soils differing in initial pH

The mechanisms by which organic materials affect soil pH are not fully understood. This study for the first time compared the short-term effect of various model organic compounds on pH change of two soils differing in initial pH (Podosol of pH 4.4 and Tenosol of pH 6.1). Eight organic compounds, representing common compounds in plant residues, were selected based on the number and type of chemical functional groups. The addition of organic acids (acetic, malic, citric, and benzoic acid) reduced soil pH immediately due to H⁺ dissociation. The magnitude of pH decrease depended on the rate of application, degree of dissociation of the acids, and initial soil pH. During a subsequent incubation, pH was slowly restored as these compounds were decomposed. The degree to which pH was restored was reduced with increasing addition rate. The production of H⁺ ions was increased with increasing rate of acid addition and decreased over time. When potassium citrate (organic anion) was added, soil pH increased due to H⁺ consumption upon decomposition. Compounds with amine groups (glucosamine hydrochloride) and less easily decomposable compounds (phenol) did not significantly alter pH during 16-day shaking. Changes in pH after glucose addition were relatively small compared with other compounds and were not expected because hydroxyl chemical groups of glucose are neutral. The present study demonstrated that the addition of model organic compounds to soil caused soil pH to increase, decrease, or remains unaffected. The extent and direction of pH change was dependent on the chemical functional group, addition rate, decomposition, and the initial soil pH.     

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.     

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.     

添加有机酸对土壤镉形态转化及苋菜镉积累的影响

植物根系分泌的低分子量有机酸能够与土壤中的镉形成镉–有机酸复合体,从而影响根际镉的移动性。本文通过添加有机酸对土壤镉形态转化的研究,阐明有机酸与镉生物积累的关系。采用盆栽试验及土壤培养等方法,研究了添加苹果酸、柠檬酸对赤红壤和黄棕壤中镉的形态转化以及超积累型苋菜天星米镉生物积累的影响。结果表明,与Cd 25 mg/kg处理比较,Cd 25 mg/kg＋苹果酸、Cd 25mg/kg＋柠檬酸处理对苋菜生物量未产生影响,但显著增加苋菜根系及地上部镉含量;添加苹果酸、柠檬酸处理显著降低土壤专性吸附态Cd含量,却显著增加了交换态Cd、碳酸盐结合态Cd和有机结合态Cd含量。说明添加苹果酸、柠檬酸还能够通过影响土壤镉形态转化而促进苋菜对镉的积累。     

Effect of Organic Acids on Heavy-Metal Uptake and Growth of Canola Grown in Contaminated Soil

Heavy-metal pollution of soils causes many environmental, animal, and human health problems. Phytoextraction of heavy metals from contaminated soils is an effective and economic technique. Humic acids are naturally occurring phenol body polymerisates, which form chelate compounds with heavy metals. In the present study the influence of soil- applied humic, citric, and malic acids on the lead (Pb), cadmium (Cd), and chromium (Cr) uptake from a contaminated soil by canola plant was examined in a greenhouse experiment. The experiment was arranged in factorial design based on randomized complete blocks with three replications. The factors of experiment included three organic acids (humic, citric, and malic acid) as first factor and five concentrations [0, 0.001, 0.002, 0.003, and 0.004 (v/v)] as second factor. The results showed that increase in organic acid concentration significantly increased heavy-metal uptake by canola plant, which accumulated heavy metals in different parts of the plant. In addition, crop growth representing by plant height and plant dry weight as well as seed production significantly decreased. Based on these results, canola can be considered as effective crop for phytoextraction of heavy metals from contaminated soils.     

低分子量有机酸对石灰性土壤有机磷组成及有效性的影响

为探索提高土壤磷素有效性的途径,采用室内培养的方法,研究不同有机酸对土壤速效磷含量及有机磷组分的影响。结果表明,添加有机酸后土壤速效磷含量发生显著变化,其中草酸处理下土壤速效磷含量显著高于其他处理,而柠檬酸和苹果酸对土壤速效磷含量具有抑制作用,其活化量为负值;随着培养时间的延长,速效磷含量缓慢降低。速效磷含量随着草酸浓度的升高而升高,随着苹果酸、柠檬酸浓度的升高而降低;有机酸处理后,土壤活性、中活性、中稳性有机磷升高,高稳性有机磷降低,这说明有机酸能促进土壤有机磷由有效性低的形态逐步向有效性高的形态转化,其中草酸的作用效果总体上较柠檬酸和苹果酸强。     

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。     

Organic acid behaviour in a calcareous soil implications for rhizosphere nutrient cycling

Calcareous soils are frequently characterized by the low bioavailability of plant nutrients. Consequently, many vascular plant species are unable to successfully colonize calcareous sites and the floristic composition of calcareous and acid silicate soils has been shown to differ markedly. The root exudation of oxalate and citrate has been suggested to play a pivotal role in same nutrient acquisition mechanisms operating in calcareous soils. The aim of this study was therefore to investigate the nutrient extraction efficiency of three individual organic acids commonly identified in root exudates, i.e. citric, malic and oxalic acid. Our results clearly demonstrate the context dependent nature of nutrient release by organic acids. The degree of P extraction was highly dependent on which organic acid was added, their concentration and pH, and their contact time with the soil. P is generally more efficiently extracted by organic acids at a high pH and follows the series oxalate>citrate>malate. The opposite relationship between pH and extraction efficiency was apparent for most other cations examined (e.g. Zn, Fe), which are more efficiently extracted by organic acids at low pH. A serious constraint to the ecological importance of organic acid exudation in response to P deficiency is, however, their very low P mobilization efficiency. For every mol of soil P mobilized, 1000 mol of organic acid has to be added. It can, however, be speculated that in a calcareous soil with extremely low P concentrations it is still beneficial to the plants to exude organic acids in spite of the seemingly high costs in terms of carbon.     

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。     

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     

有机酸对活化土壤中镉和小麦吸收镉的影响

向土壤中加入外源有机酸,研究有机酸对活化土壤中镉的作用和小麦吸收镉的影响。结果表明：有机酸对土壤中镉有一定的活化能力,对镉活化能力强弱顺序为ＥＤＴＡ〉缺铁小麦根分泌物〉柠檬酸〉苹果酸〉水。但ＥＤＴＡ却降低了小麦地上部镉的含量,缺铁小麦根分泌物明显增加了小麦地上部镉含量。与对照相比,柠檬酸和苹果酸对小麦地上部的镉含量有一定的促进作用,也增加了小麦地上部镉含量。     

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     

Sorption of organic acids in acid soils and its implications in the rhizosphere

Organic acids have been implicated in many soil-forming and rhizosphere processes, but their fate in soil is poorly understood. We examined the sorption of four simple short-chain organic acids (citric, oxalic, malic and acetic) in five acid soils and on synthetic iron hydroxide (ferrihydrite). The results for both soils and ferrihydrite indicated that the sorption depended on concentration in the following order of strength: phosphate >> oxalate > citrate > malate >> acetate. The sorption reactions in soil were shown to be little influenced by pH, whereas for ferrihydrite, sorption of all ligands increased strongly with decreasing pH. The sorption of organic anions onto ferrihydrite was influenced to a lesser extent by the presence of metal cations in solution. From the results we calculated that when organic acids enter solution they rapidly become sorbed onto the soil's exchange complex (> 80% within 10 min), and we believe that this sorption will greatly diminish their effectiveness to mobilize nutrients from the rhizosphere.     

有机酸培养时间和种类对煤矸石碎屑组成及速效养分的影响

为研究有机酸添加后煤矸石碎屑组成及其速效养分变化,以淮南潘集矿区为研究区域,选取矿区内多处煤矸石山上大块煤矸石人工破碎后作为供试材料,向其中添加10 mmol/L低分子量有机酸和腐殖酸水溶液,恒温培养120 d,在不同培养阶段取出部分样品测定煤矸石碎屑颗粒组成、EC、pH和速效养分等指标。结果表明,有机酸的添加总体上促进了煤矸石碎屑颗粒的细化。其中,黏粒平均增幅达81.90%,极细砂增幅在42%以上,粉粒和极粗砂粒含量平均下降幅度分别为21.05%、62.34%。有机酸添加有助于煤矸石碎屑颗粒基质结构向好的方向发展,并且以柠檬酸和腐殖酸效果最好。培养后的各处理pH值、电导率、速效养分对有机酸种类和培养时间的响应存在显著差异。有机酸添加后,酒石酸、草酸和腐殖酸处理pH均上升较大,平均pH值分别为7.69、7.75和7.71,显著大于对照处理(P<0.05),达到微碱性水平。除苹果酸处理外,其他处理的pH随培养时间的变化表现“N”型特征。电导率的变化与pH值变化正好相反,以苹果酸处理上升最大,比培养前增幅达146.78%;有机酸添加极大促进了煤矸石碎屑碱解氮(AN)和速效磷(AP)的释放,前者以苹果酸效果较好(释放量最大为CK的1.56倍和培养前的13.03倍),后者以柠檬酸效果较好(释放量最大为培养前的2.56倍和CK的3.39倍)。随着培养时间延长,碱解氮和速效磷释放量均逐渐增加;水分浸润和有机酸溶液添加均在前期表现一定抑制煤矸石碎屑颗粒速效钾(AK)释放的作用,后期逐渐表现一定促进释放的作用,但各有机酸处理之间差异不显著。有机酸对煤矸石山生态修复肯有一定积极作用。     

低分子量有机酸对土壤磷活化影响的研究

研究两种低分子量有机酸（柠檬酸和苹果酸）对土壤磷活化影响,并用修正的Hedley法测定土壤磷活化前后磷组分的变化。结果表明,低分子量有机酸能持续活化土壤磷,活化强度随低分子量有机酸浓度的增大而增强,并且柠檬酸活化土壤磷的能力强于苹果酸。低分子量有机酸能促进作物有效态无机磷组分（H2O-P和NaHCO3-Pi）的释放;同时还促进有机磷组分（NaHCO3-Po和NaOH-Po）的矿化。在低分子量有机酸浓度达到0.5 mmol/L以上时,其对土壤磷组分的活化量的顺序为:NaOH-Pi HCl-P NaHCO3-Pi H2O-P,即铁铝结合态磷 钙结合态磷 作物有效态磷。低分子量有机酸活化土壤磷的过程中伴有大量铁、铝释放,且铁或铝的释放量与磷活化量之间显著正相关（P0.05）。说明铁、铝结合态磷是低分子量有机酸活化土壤磷的主要磷源,并且其活化机制可能与铁、铝结合态磷的螯合溶解有关。     

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。     

Rapid intrinsic rates of amino acid biodegradation in soils are unaffected by agricultural management strategy

Amino acids represent one of the largest inputs of dissolved organic nitrogen to soil and consequently they constitute a major component of the organic N cycle. The effect of agricultural management on the rate of amino acid turnover in soil, however, remains largely unknown. The aim of this study was to evaluate in long-term field experiments the effect of fertilizer addition (N, P and K), grazing, pH manipulation (lime addition), vegetation cover and shifts (grassland versus arable) and drainage on the mineralization of ¹⁴C-labelled amino acids in agricultural topsoils. Our results showed that the intrinsic rate of amino acid mineralization was rapid for all management regimes, irrespective of the tested soil type. The average (±SEM) half-life of the amino acids in all soils (n=155) was calculated to be 2.3±0.5 h. The relative amount of amino acid-C partitioned into respiration (25% of total C) versus biomass production (75% of total C) was also unaffected by management strategy. The rate of amino acid mineralization was shown to be slightly sensitive to soil pH, peaking at around pH_(2CaCl) 5.0 with an approximate twofold reduction at the pH extremes (pH 3.8 and 6.4). We conclude that management regime has little effect on the intrinsic rate of amino acid mineralization in agricultural soils. We propose therefore that total microbial activity rather than microbial diversity or community structure is likely to be the key determinant governing amino acid turnover in agricultural soils.     

单一及复合有机酸对土壤中镉形态的影响研究

为寻找可行的强化重金属污染土壤植物修复的方法,研究了柠檬酸与复合有机酸(苹果酸+柠檬酸)对土壤中重金属Cd各形态的影响。结果表明,对于不同污染程度的CdⅠ~CdⅣ土壤,单一与复合添加有机酸均能有效活化土壤中重金属Cd;当复合添加2.5 mmol kg-1苹果酸+7.5 mmol kg-1柠檬酸时土壤中最具活性的可交换态Cd百分含量增长率显著高于单一添加10 mmol kg-1柠檬酸时的增长率。     

Competition for amino acids between wheat roots and rhizosphere microorganisms and the role of amino acids in plant N acquisition

The direct uptake of organic nitrogen compounds from the soil solution by plant roots has been hypothesised to constitute a significant source of N to the plant particularly in N limiting ecosystems. The experiments undertaken here were designed to test whether wheat roots could out-compete the rhizosphere microflora for a pulse addition of organic N in the form of three contrasting amino acids, namely lysine, glycine and glutamate. Amino acids were added at a concentration reflecting reported soil solution concentrations (100 μM) and the uptake into either plant biomass or respiration or microbial biomass and respiration determined over a 24 h chase period. The results showed that the plant roots could only capture on average 6% of the added amino acid with the remainder captured by the microbial biomass. We therefore present direct in vivo evidence to support earlier work which has hypothesised that organic N may be of only limited consequence in high input agricultural systems. We suggest that this is a result of the higher concentrations of NO₃⁻ in agricultural soil solutions, the slow movement of amino acids in soil relative to NO₃⁻, the rapid turnover of amino acids by soil microorganisms, and the poor competitive ability of plant roots to capture amino acids from the soil solution.