低分子量有机酸对可变电荷土壤中铝吸附的影响

铝毒是酸性土壤上植物生长不良的主要限制因素,铝的生物毒性与铝离子的化学形态有密切的关系[1, 2],而铝的化学形态又受包括低分子量有机酸在内的多种因素的影响[3, 4].低分子量有机酸是土壤中广泛存在的一类非常活泼的物质,植物在生长过程中其根系会不断分泌出各种有机酸,植物残体分解过程中和土壤微生物代谢过程中均会产生有机酸[5, 6].一些有机酸阴离子可以被可变电荷土壤吸附,并影响土壤的某些表面化学性质;另一方面某些有机酸阴离子能够与铝形成稳定的络合物从而改变铝离子在溶液中的存在形态,这两方面的原因都有可能对可变电荷土壤中铝的吸附产生影响.     

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。     

低分子量有机酸对土壤中铝的化学行为的影响

本文从Al在土壤中的水解-沉淀、吸附-解吸、活化、迁移、降低毒性以及对含Al矿物的表面性质的影响等方面综述了低分子量有机酸对Al的化学行为的影响,并提出了今后需要进一步加强研究的一些方面。     

低分子量有机酸对可变电荷土壤和矿物表面化学性质的影响

低分子量有机酸是土壤中广泛存在的,它们参与土壤中许多化学过程,在营养元素活化、解铝毒和矿物风化等方面发挥重要作用。本文综述了可变电荷土壤和矿物对低分子量有机酸的吸附及这类有机酸对土壤的表面电荷、动电性质和土壤吸附无机阴、阳离子的影响,为从事相关研究工作的同志提供参考。     

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。     

几种低分子量有机酸淋溶对土壤pH和交换性铝的影响

采用原状土柱进行模拟淋溶实验,比较研究了模拟酸雨和几种低分子量有机酸对红壤pH和交换性Al的影响。结果表明,与去离子水CK相比,pH3.5和pH4.5模拟酸雨淋洗后0~10cm土层pH分别降低了0.27、0.44和0.08、0.18个单位,土壤交换性Al含量分别增加了4.43%和2.38%;而10~50cm土层pH没有显著变化。柠檬酸、苹果酸和草酸淋洗后0~10cm土层pH比模拟酸雨淋洗后高0~0.3个单位,土壤交换性Al含量则要低0.08~0.75cmol/kg。与模拟酸雨相比,100μmol/L柠檬酸、苹果酸和草酸淋洗后10~50cm土层pH降低幅度基本上<0.1个单位,交换性Al含量增加了6.99%~12.82%;而10mmol/L柠檬酸、苹果酸和草酸淋洗后10~50cm土层pH降低幅度达0.02~0.83个单位,交换性Al含量增加了22.45%~34.66%。这意味着低分子量有机酸或许比酸雨在加速土壤酸化方面有更大的威胁。     

低分子量有机酸对土壤磷释放动力学的影响

模拟植物在缺磷条件下,根系所分泌的有机酸种类和数量,用流动法研究了柠檬酸,苹果酸,草酸和酒石酸对土壤磷释放的影响。结果表明：有机酸能明显促进土壤中磷的释放,不同有机酸对石灰性土壤活化能力大小的次序为草酸≥柠檬酸〉苹果酸〉酒石酸;而对酸性土壤磷的释放量与Ｆｅ＋Ａｌ释放量之间呈极 相关,有机酸活化土壤磷能力大小的次序为柠檬酸〉草酸〉酒石酸〉苹果酸。     

低分子量有机酸对砖红壤表面电荷的影响

本文研究了4种低分子量有机酸对砖红壤表面电荷性质的影响,结果表明存在于体系中的有机酸增加了表面负电荷量,同时减少表面正电荷的量。在低有机酸加入量下,有机酸对正电荷的影响程度比其对负电荷的影响程度大得多。4种酸对土壤表面电荷影响的大小顺序为:柠檬酸>苹果酸>草酸>醋酸。有机酸对表面电荷的影响随体系pH而变化,它们对正电荷的影响程序随pH的增加而减小,而对负电荷的的影响呈相反的变化趋势。有机酸主要通过其阴离子在土壤表面的吸附来影响土壤的表面电荷性质。     

氧化土和老成土中自然产生的有机酸对磷的活化

Citric and malic acids at concentrations of 0.1,1.0,10,and 100 mmol/L were added to three Ultisols and one Oxisol,The amount of P in solution increased with increasing organic acid concentrations,while the amount of Fe-and Al-bound P decreased.This result suggested that naturally occurring products of organicmatter decomposition could increase the P availability to plants in soils where there is a relatively large pool of Fe-and Al-bound P.The interactions between citric and malic acids at the above concentrations,and p added at rates of 10,20,40,and 80mg/kg were determined.At zero levels of organic acids,all added P became either labile or bound ,and greater proportions remained soluble as the concentration of orgaic acids increased,which suggested that organic acids reduced fixation of dissolved P in Fe-and AL-rich soils .Agricultural practices which increase organic matter input on P-deficient acid soild could decrease P deficiency,This would be important in many tropical and subtropical regions where these soils are common,and where the costs of fertilizers and lime are relatively high.     

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。     

低分子量有机酸类物质对红壤和黑土磷有效性的影响

在20℃恒温培养条件下,研究低分子量有机酸类的钠钙盐(LA)和低分子量有机酸类与混合氨基酸的钠钙盐(LAA)不同用量水平对红壤和黑土磷有效性的影响。研究表明,两种低分子量有机酸类混合物在各不同水平下均能显著提高红壤和黑土磷有效性;随着培养的进行,添加有LA、LAA的各处理对红壤和黑土中磷有效性均有明显提高。无论是LA或LAA,红壤中以半量处理对提高磷有效性作用效果更为明显,而黑土中则以LAA作用效果更好,且以常量LAA处理的效果最好,常量LA和LAA处理间差异显著。在添加磷肥的基础上,与不加有机酸物质处理(CKp)相比,添加常量LA、LAA和半量LA(0.5 LA)、LAA(0.5 LAA)处理,在红壤中磷固定率平均值分别降低10.5%、22.3%和11.3%、19.4%;在黑土中分别降低8.6%、10.6%和14.1%、11.8%。LA和LAA对降低红壤和黑土磷固定率效果显著,红壤以半量处理的效果较好,黑土则以常量LAA处理效果最好。     

电解质对酸性土壤铝的溶解及铝形态在土壤溶液中的分布的影响

KCl, CaCl₂, NH₄Cl, NaCl, K₂SO₄ and KF solutions were used for studying the effects of cations and anions on the dissolution of aluminum and the distribution of aluminum forms respectively. Power of exchanging and releasing aluminum of four kinds of cations was in the decreasing order Ca²⁺ >K⁺ >NH₄⁺ >Na⁺. The dissolution of aluminum increased with the cation concentration. The adsorption affinity of various soils for aluminum was different. The aluminum in the soil with a stronger adsorption affinity was difficult to be exchanged and released by cations. The Al-F complexes were main species of inorganic aluminum at a low concentration of cations, while Al³⁺ became major species of inorganic aluminum at a high concentration of cations. The results on the effect of anions indicated that the concentrations of total aluminum, three kinds of inorganic aluminum (Al³⁺, Al-F and Al-OH complexes) and organic aluminum complexes (Al-OM) when SO₄^2- was added into soil suspension were lower than those when Cl^- was added. The dissolution of aluminum from soils and the distribution of aluminum forms in solution were affected by the adsorption of F^- on the soil. For soils with strong affinity for F^-, the concentrations of the three inorganic aluminum species in soil solution after addition of F^- were lower than those after addition of Cl^-; but for soils with weak affinity for F^-, the concentrations of Al³⁺ and Al-OM were lower and the concentrations of Al-F complexes and total inorganic aluminum after addition of F^- were higher than those after addition of Cl^-. The increase of F^- concentration in soil solution accelerated the dissolution of aluminum from soils.     

有机物料对淹水土壤中施入的镉形态的影响

The effect of three organic materials(rice straw,Chinese milk vetch and pig manure)on the fractionation of cadmium added into two soils(a red soil and a fluvo-aquic soil) was studied using submerged incubation experiment.The organic materials increased soil soild organic carbon(SOC),pH value,the concentration of active Si in all the treatments and active Fe and Mn in some treatments.Accumulated SOC caused directly the increase of Cd bound to solid organic matter and consequently the decrease of exchangeable Cd.Higher active Si and pH,as well as lower Eh,were also responsible for the reduction of exchangeable Cd.Cd bound to mn oxide was positively correlated with pH values and rose significantly after one-month incubation,but decreased after three-month incubation.Cd bound to amporphous Fe oxide increased with the incubation time,but was not affected significantly by adding organic materials.     

外源低分子量有机酸对碳酸钙预处理的酸性土壤中活性铝钙镁影响的研究

通过在所研究的第四纪红黏土发育的红壤中混入CaCO3,研究在pH缓冲体系中外加低分子量有机酸对土壤中Al、Ca和Mg的影响。结果表明:无论加CaCO3与否,在pH 4.5的条件下外源草酸、柠檬酸、苹果酸的加入均使土壤可溶性Al显著提高,交换性Al显著下降和交换性Ca显著升高;加入CaCO3的情况下,3种有机酸处理的交换性Mg均显著提高。3种有机酸促进Al溶解能力的大小顺序为:柠檬酸>草酸>苹果酸,这一结果与有机酸和Al形成络合物的稳定常数大小一致。另一方面,3种有机酸处理下,CaCO3预处理均引起可溶性Al的显著升高和交换性Al的下降。双因素方差分析表明,有机酸通过络合作用或沉淀作用对可溶性和交换性Al、Ca和Mg均具有绝对的影响优势,CaCO3仅对可溶性和交换性Al、交换性Ca有显著影响,由于实验中pH缓冲体系的控制,这种影响主要通过Al与Ca、Mg的竞争交换作用实现。总体来说,外源低分子量有机酸的加入使土壤活性Al显著升高,活性Ca、Mg略有升高,有机酸在酸性土壤中的作用需从有机酸溶解阳离子的角度进一步评价。     

有机酸对污染土壤中镉释放的影响

There is limited information on the release behavior of heavy metals from natural soils by organic acids. Thus, cadmium release, due to two organic acids (tartrate and citrate) that are common in the rhizosphere, from soils polluted by metal smelters or tailings and soils artificially contaminated by adding Cd were analyzed. The presence of tartrate or citrate at a low concentration (≤ 6 mmol L^-1 for tartrate and ≤ 0.5 mmol L^-1 for citrate) inhibited Cd release, whereas the presence of organic acids in high concentrations (≥ 2 mmol L^-1 for citrate and ≥ 15 mmol L^-1 for tartrate) apparently promoted Cd release. Under the same conditions, the Cd release in naturally polluted soils was less than that of artificially contaminated soils. Additionally, as the initial pH rose from 2 to 8 in the presence of citrate, a sequential valley and then peak appeared in the Cd release curve, while in the presence of tartrate the Cd release steadily decreased. In addition, Cd release was clearly enhanced as the electrolyte concentration of KNO₃ or KCl increased in the presence of 2 mmol L^-1 tartrate. Moreover, a higher desorption of Cd was shown with the KCl electrolyte compared to KNO₃ for the same concentration levels. This implied that the bioavailability of heavy metals could be promoted with the addition of suitable types and concentrations of organic acids as well as reasonable field conditions.     

Prediction of Polycyclic Aromatic Hydrocarbon Bioaccessibility to Earthworms in Spiked Soils by Composite Extraction with Hydroxypropyl-β-Cyclodextrin and Organic Acids

Traditional exhaustive extraction methods often overestimate the risk of polycyclic aromatic hydrocarbon(PAH) bioaccessibility to biota. Therefore, reliable assessment methods need to be established. In this study, a composite extraction with hydroxypropyl-β-cyclodextrin(HPCD) and three low-molecular-weight organic acids, oxalic acid(OA), malic acid(MA), and citric acid(CA), was used to predict the PAH bioaccessibility to earthworms, subjecting to two soils(red soil and yellow soil) spiked with selected PAHs,phenanthrene, pyrene, chrysene, benzo(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, and benzo(a)pyrene. For both soils,concentrations of PAHs by composite extraction using HPCD-OA(R~2= 0.89–0.92, slope = 1.89–2.03; n = 35), HPCD-MA(R~2=0.92–0.96, slope = 1.43–1.67; n = 35), and HPCD-CA(R~2= 0.92–0.96, slope = 1.26–1.56; n = 35) were significantly correlated with PAH accumulation in the Eisenia fetida earthworms. Moreover, the HPCD-CA-and HPCD-MA-extracted PAH concentrations were closer to the earthworm-accumulated PAH concentration than the extraction using just HPCD. The results indicated that the composite extraction could improve the prediction of PAH bioaccessibility, and therefore can serve as a reliable chemical method to predict PAH bioaccessibility to earthworms in contaminated soils.     

有机物料对酸性红壤铝毒的缓解效应

利用盆栽试验研究了施用不等量稻草对酸性红壤旱耕地铝毒的缓解效应。结果表明,添加不等量的秸秆碳(C)后,土壤pH值显著提高,土壤交换性铝和吸附态羟基铝的含量则明显降低,土壤有机络合态铝的含量也呈增加趋势。添加铝盐并不影响秸秆碳对降低土壤交换性铝和吸附态羟基铝含量的作用。在本研究中,土壤pH值与土壤交换性铝和土壤吸附态羟基铝均呈显著负相关,方程分别为y=-2193.9x+11545,R2=0.9798**,y=-655.34x+9748,R2=0.7837**。土壤交换性铝和吸附态羟基铝与玉米主根长,地上部磷、钾含量均呈显著负相关,是抑制玉米吸收养分的主要限制因素,土壤吸附态羟基铝是次于交换性铝的又一活性较大的铝化合物。     

铵、钾同时存在时, 土壤对铵的优先吸附

The water stability of aggregates in various size classes separated from 18 samples of red soils under different managements, and the mechanisms responsible for the formation of water-stable soil aggregates were studied. The results showed that the water stability of soil aggregates declined with increasing size, especially for the low organic matter soils. Organic matter plays a key role in the formation of water-stable soil aggregates. The larger the soil aggregate size, the greater the impact of organic matter on the water stability of soil aggregates. Removal of organic matter markedly disintegrated the large water-stable aggregates (> 2.0 mm) and increased the small ones (< 0.25-0.5mm) to some extent, whereas removal of free iron(aluminium) oxides considerably destroyed aggregates of all sizes, especially the < 0.25-0.5 mm classes. The contents of organic matter in water-stable aggregates increased with aggregate sizes. It is concluded from this study that small water-stable aggregates (< 0.25-0.5 mm) were chiefly cemented by Fe and Al oxides whilst the large ones (> 2.0 mm) were mainly glued up by organic matter. Both free oxides and organic matter contribute to the formation and water stability of aggregates in red soils.