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。     

几种低分子量有机酸淋溶对土壤铝、硅及盐基离子淋失的影响

采用50cm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Al、Si及盐基离子淋失的影响。结果表明,模拟酸雨淋洗后土壤中有极少量的Al和一定量的Si及盐基离子淋出。与去离子水对照相比,pH3.5和pH4.5模拟酸雨处理Si的淋出总量分别增加了6.52%和3.26%;K 、Na 、Ca2 和Mg2 等盐基离子淋出量增加了2.41%~96.80%。100μmol/L的柠檬酸、苹果酸和草酸处理Al、Si的淋出量与模拟酸雨处理相差不大,而10mmol/L的柠檬酸、苹果酸和草酸处理则比模拟酸雨处理有显著的增加。有机酸淋洗后淋出液中各盐基离子含量均要高于模拟酸雨处理,盐基离子淋出总量是模拟酸雨处理的1.58~9.27倍。实验结果说明低分子量有机酸在酸化土壤方面比酸雨有更大的威胁。由于盐基离子的大量淋失,模拟酸雨和有机酸淋洗后淋出液pH均要高于原淋洗液pH。     

模拟酸雨和几种低分子量有机酸淋溶对土壤交换性盐基的影响

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交换性盐基的影响。结果表明:与去离子水对照相比,pH 3．5和pH 4．5模拟酸雨淋洗后,0-20 cm土层土壤交换性K 、Na 、 Ca2 和Mg2 含量增加了5．19％-14．65％,而这种增加主要发生在10-20 cm土层。100 μmol／L和10 mmol／L的柠檬酸、苹果酸和草酸淋洗后,0-20 cm土层土壤交换性K 、Na 、Ca2 和Mg2 含量与模拟酸雨淋洗后的结果相差不大,有的层次甚至还要稍低;而在20-50 cm土层则增加了10．42％-96.41％。有机酸淋洗后,土壤交换性盐基的增加受矿物溶解和盐基迁移两方面的影响,而下层的增加可能主要是盐基迁移的影响,由此可见有机酸或许加快了盐基离子向下迁移的速度和土壤酸化过程。     

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。     

低分子量有机酸对石灰性土壤磷素形态转化及有效性的影响

采用室内培养和化学分析的方法研究了几种低分子量有机酸对石灰性土壤中磷的活化作用。结果表明:供试有机酸通过溶解、螯合等作用均能不同程度地促进合成磷酸盐的磷素释放。活化DCP、ODP、Fe-P、A l-P的能力依次为柠檬酸>草酸>苹果酸>酒石酸>乙酸;活化FA的能力是草酸>柠檬酸>苹果酸>酒石酸>乙酸。同种有机酸作浸提剂时,有机酸浓度越高磷酸盐中磷素释放量也越大。施加各种有机酸可以不同程度地降低土壤中Fe-P、A l-P和Ca10-P,增加Ca2-P、Ca8-P和O-P含量,总的趋势是促进土壤中植物难以利用的无机磷形态向有效性较高的形态转化。这种促进作用大小顺序为草酸>柠檬酸>酒石酸。     

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。     

淋溶条件下低分子量有机酸对淋出液及三峡库区典型土壤性质的影响

[目的]研究低分子量有机酸(草酸、柠檬酸、酒石酸)作用下淋出液及土壤(紫色潮土和灰棕紫泥)性质的变化,以期为三峡库区的环境管理提供参考和科学依据。[方法]采用间歇式土柱模拟试验进行研究。[结果]高浓度低分子量有机酸(≥50mmol/L)能够破坏灰棕紫泥的酸碱缓冲体系,当草酸、柠檬酸和酒石酸浓度≥50mmol/L时,灰棕紫泥土壤pH值均从8左右降到了4.11以下;而紫色潮土的缓冲性能较强,经淋溶后土壤pH值变化不大,仍然维持在6.84~8.71左右,与空白处理差异性不显著。另外,灰棕紫泥淋出液电导率变化较紫色潮土明显,高浓度低分子量有机酸处理下,灰棕紫泥淋出液电导率最高值达到了34.400mS;灰棕紫泥在3种低分子量有机酸淋洗下淋溶出离子量的大小顺序为:柠檬酸酒石酸草酸。[结论]低分子量有机酸的酸解作用和络合作用是影响淋出液pH值、淋出液电导率和土壤pH值变化的主要原因,并能够参与紫色潮土和灰棕紫泥的化学和生物化学过程。低分子量有机酸的存在对三峡库区水环境恶化存在一定的风险。     

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。     

休耕轮作对黑土酸化的影响

通过长期定位试验,在吉林省德惠市采集休耕轮作的土壤样品,研究休耕轮作对土壤pH值及土壤交换性H+、Al3+的影响;休耕轮作对土壤阳离子交换性能的影响;休耕轮作的土壤pH值与各相关理化性状的相关性;休耕轮作对土壤缓冲性能的影响以及对酸化速率的影响.结果表明:(1)土壤经过休耕轮作后,土壤酸化得到缓解,土壤交换性酸(交换性H+和交换性Al3+)呈下降的趋势,土壤pH随着交换性酸的降低而升高;交换性H+和交换性Al3+含量随土壤有机质含量的增加而减小.(2)休耕轮作措施能够增加土壤中阳离子交换量及盐基饱和度;(3)土壤pH与各盐基阳离子的相关性大小依次为Ca2+＞ Na+＞ K+＞Mg2+,并且交换性Ca2+含量最多,占盐基总量的89％～95％,对盐基饱和度贡献最大;(4)休耕轮作措施能够增加土壤的酸碱缓冲容量,休耕轮作后的土壤最高酸碱缓冲容量是长期连作土壤酸碱缓冲容量的2倍以上,从而增强了土壤对酸碱的缓冲性能,并且降低了土壤的酸化速率.     

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.     

Loblolly pine plant community structure and soil solution aluminum,organic acids,calcium, magnesium,and pH

Abstract

Vegetative cover may influence soil chemical properties by producing organic acids that can modify the toxicity are responsible for high levels of nontoxic soil solution aluminum (Al). This study was conducted to determine the effect of loblolly pine (Pinus taeda L.) plant community structure, i.e., differing vegetative covers, on exchangeable cation distribution, and soil solution concentration of aluminum (Al) and organic acids. Soil was sampled were taken from 8‐year‐old forest plots with differing plant community structure (herbaceous‐hardwood‐pine, herbaceous‐pine, hardwood‐pine, and pine only), and measured for exchangeable cations. Soil solution extracts were analyzed for Al, organic acids, and the major cations and anions. There were significant differences in exchangeable Al, and calcium (Ca) among communities. Soil pH was highest in the herbaceous‐pine community, while other communities did not differ in soil pH. Oxalic, citric, malic, and succinic acids were detected in soil solution for all communities, but did not differ significantly among communities. Calculated Al activity was less than those determined by the 8‐hydroxy quinoline (15 sec) method. For these conditions, calculated Al activities did not change by accounting for the Ca‐ and magnesium (Mg)‐organic acid complex. The Al activities found were similar to previous reported levels that were considered nontoxic.     

Changes in aluminum pools of andisols due to soil acidification

Abstract

Aluminum concentrations in soil solutions are not only controlled by inorganic clay minerals but also by organically bound aluminum. The objective of this study was to determine which pools contribute to Al dissolution. Soil samples were taken at various distances from tree trunks and at various depths at the Rolling Land Laboratory (RLL), Hachioji, Tokyo. Selective dissolution techniques were used to analyze the changes in pools of solid-phase aluminum. Soil pH values around Hinoki cypresses were in the aluminum buffer range. Exchangeable aluminum contents in soils under Hinoki cypresses were 104 mmol_c kg-^?1 on the average. This value was similar to that of the cation exchange capacity (CEC) of Andisols at RLL at a soil pH of 4. The relationship between the soil pH and exchangeable, organically bound, and amorphous aluminum pools showed that dissolved aluminum ions in the soil solution were primarily derived from the amorphous Al pool. Dissolved aluminum ions were substituted with base cations of soils, resulting in the increase of the content of exchangeable Al and/or the formation of complexes with organic matter which increased the proportion of organically bound Al pools. Increase in the proportion of organically bound Al pools indicated the importance of complexation with soil organic matter for controlling the aluminum concentration in the soil solution.     

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.     

Interlayer materials of partially interlayered vermiculites in Dystrochrepts derived from Tertiary sediments

Interlayer materials of partially interlayered vermiculites (PIV) in 15 Dystrochrepts derived from Tertiary sediments were analysed by dissolution with hot 1/3M sodium citrate or 0.15 M oxalate-oxalic acid in combination with XRD and IR spectroscopy. Both the citrate and oxalate treatments dissolved Al from all soil clays. The dissolution of Al by the citrate treatment paralleled the dissolution of Si and the interlayer collapse of PIV, whereas that by the oxalate treatment did not, indicating that the interlayer materials contain not only Al but Si. The materials dissolved by the citrate treatment had a molar Si/Al ratio ranging from 0.72 to 0.24 that decreased with the increasing interlayering of PIV. Differential IR spectroscopy indicated the dissolution of aluminosilicates possibly having Si-O, Al-OH and Si-O-Al bonds, but not Si-O-Si bonds. The extent of interlayering of PIV showed a good correlation with the amount of Al dissolved by the citrate treatment and increased with increasing soil pH (H₂O) from 4.5 to 5.2 and with decreasing exchangeable Al in soil.
Formation of a hydroxy-Al sheet partially bonded with Si-tetrahedra was suggested as a possible model of the interlayer structure of PIV. The differences between PIV in the studied Inceptisols and other soils are discussed.     

Comparing the effects of paper pulp and lime additions to acid tropical soils using batch experiments

Paper mill residuals may beneficially be used to improve the fertility of tropical acid soils. The effects of paper pulp on soil pH, exchangeable Al and soil solution composition of three acid tropical soils were compared with the effects of equivalent rates of lime in two batch experiments. Paper pulp was more effective than lime in increasing soil pH. However, both amendments were equally effective in decreasing exchangeable Al. Paper pulp and lime similarly influenced the composition of the soil solution by increasing soil solution pH, dissolved organic carbon, inorganic carbon, NO₃, SO₄, Ca and Mg. The supply of nitrate by the soil, however, was reduced in paper pulp treatments compared to lime treatments. Nitrate had a major role in controlling nutrient concentrations in the soil solution. Reduced NO₃ concentrations in paper pulp treated soils compared to limed soils could therefore result in lower nutrient availability and limited losses by leaching.     

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