pH对土壤吸持磷酸根的影响及其原因

本文选择了浙江、江苏15个性质变化范围较大的土壤样品,研究在两种支持电解质、不同pH条件下对磷酸根的吸持反应。结果表明,加碱提高强酸性土壤的pH值,导致交换性铝的水解和羟基铝聚合物的生成,增加对磷的吸持。磷酸根同酸性土壤的反应,可促进交换性铝的水解,释放出H⁺,降低体系的pH。在CaCl₂介质中,当pH>6时,可能有磷酸钙类盐形成,使溶液中磷浓度显著降低。有机质对土壤吸持磷有重要影响。在低pH下有机质通过与Al³⁺形成络合物,阻碍溶液中A1³⁺的水解,并与磷酸根竞争羟基铝化合物表面的反应点位,从而降低酸性土壤对磷酸根的吸附量。     

水稻根尖细胞原生质膜表面电势对不同氮形态、 铝和pH的响应

相对于NO_3~--N,NH_4~+-N可以缓解植物铝毒害,但其机制还不清楚。铝在细胞膜表面的吸附量受细胞膜表面电势影响,直接影响到铝毒害。本文采用酶解法提取水稻根尖原生质体,研究了原生质膜表面zeta(ξ)电势对NH_4~+N、NO_3~--N、铝和pH的响应。结果表明,不管是否加铝,NH_4~+-N和NO_3~--N本身并不显著影响原生质膜表面ξ电势,但是加铝和降低pH均可以去极化原生质膜表面ξ电势。水稻吸收NH_4~+-N一般降低生长介质pH,吸收NO_3~--N升高生长介质pH。因此,NH_4~+-N缓解水稻铝毒的原因,不是因为NH_4~+-N本身去极化了细胞膜表面电势,而是因为水稻吸收NH_4~+-N降低了介质pH,去极化了细胞膜表面电势,从而可能降低了铝在水稻根尖表面的吸附。     

硫酸铝对苏打盐碱土吸附氟的影响研究

采用平衡振荡法,通过加入不同比例的铝、氟来研究硫酸铝对苏打盐碱土吸附氟的影响。结果表明:苏打盐碱土加入硫酸铝以后,能够缩短对氟的吸附平衡时间,并且随着铝用量的增加和吸附时间的延长,氟的吸附量呈增加,而解吸率呈降低的趋势;其中1︰1铝氟摩尔比处理的吸附量高达640.45 mg/kg,为不施铝处理的6.5倍,但是其解吸率最低,为24.7%,为对照处理的0.3倍。这与Al3+和F–络合形成不同比的铝氟配合物,Al3+水解后降低土壤溶液pH,并形成羟基铝,进而与盐碱土中的蒙脱石形成聚合羟基铝–蒙脱石复合体有关。因此,铝的存在可以增加苏打盐碱土对氟的吸附,降低解吸率,进而减小氟在该土中的迁移,降低其生物有效性。     

模拟酸雨对赤红壤磷素及Ca2+，Al3+，Fe2+淋失特征的影响

本研究通过室内土柱试验,研究了不同强度和持续时间的模拟酸雨淋溶下,赤红壤磷素淋失量及部分阳离子（Ca2+、Al3+、Fe2+）的释放程度和特征。结果表明:经pH 2.0、pH 3.0、pH 4.0、pH 5.0模拟酸雨持续淋溶 34 d后,淋溶液pH值变化并不明显（＞0.05 ）,而对Ca2+、Fe2+的溶出有显著的促进作用,Ca2+、Al3+、Fe2+ 溶出量均随 pH 值的降低而升高,Al3+ 和 Fe2+ 淋失量在pH 2.0时均有骤增现象。随淋溶时间的增加,土壤可溶态磷的淋失量表现为先增加后逐渐降低;随着pH值的降低,土壤磷淋失总量也表现为先增加后降低,pH4.0的酸雨有助于促进土壤磷的释放,pH＜4.0时土壤磷的淋失减少。相关分析发现淋溶液中磷淋失总量与Al3+和Fe2+溶出量均呈显著负相关（r1=0.6531, r2=0.5107）,和Ca2+总溶出量相关关系不显著（r3=0.1287）,表明高强度酸雨降低了土壤磷淋失量可能与酸雨作用导致活性铁、铝的大量释放,增加了磷的活性吸附点位,从而增加了对磷酸根离子配位吸附与固定有关。     

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     

活性氧化铈／介孔分子筛除氟剂对环境水体的脱氟行为研究

通过浸渍－共沉淀法，在SiMCM-41分子筛表面负载氧化铈，制备出对水体中氟离子具有特效选择吸附作用的新型除氟材料，研究了表面负载量、溶液的pH值和温度等对氟离子在除氟剂表面吸附的影响。并就氟离子在除氟剂表面吸附动力学、吸附等温线和吸附机理进行了探讨。     

酸铝胁迫下4个速生桉优良无性系的生长反应

采用砂土培育法研究不同的酸铝处理对几种桉树优良无性系（巨尾桉9号、巨尾桉12号、尾叶桉4号、韦赤桉3号）幼苗生长及膜透性等变化的影响。试验设: pH 3.0＋0 mg/L Al3+、 pH 3.0＋120 mg/L Al3+、 pH 4.0＋0 mg/L Al3+、 pH 4.0＋120 mg/L Al3+、 pH 4.8＋0 mg/L Al3+5个处理。结果表明,不同酸铝处理对4个桉树优良无性系形态、生长指标、含水率、叶绿素含量、质膜透性和脯氨酸含量等都产生不同的影响。与对照（pH 4.8＋0 mg/L Al3+）相比,pH 3.0＋120 mg/L Al3+处理对桉树幼苗的生长产生的抑制作用明显,叶、芽皱缩、变形,苗高、地径以及各器官含水率降低,质膜透性和叶绿素含量下降,桉树幼苗累积较多的脯氨酸。其中,巨尾桉广林9号对酸铝逆境的抗性优于其它3个无性系。4个桉树优良无性系抗酸铝逆境的能力强弱依次为: 巨尾桉9号巨尾桉12号 韦赤桉3号尾叶桉4号。因此,选育耐酸铝桉树无性系品系是改善南方富铝化酸性土壤林地生产力的重要策略之一。     

Zn改性Sr/γ-Al2O3表面吸附甲醇活化羟基的分子模拟

为明确Zn原子掺杂强化Sr/γ-Al2O3对吸附甲醇效果的影响,进而提高生物柴油产率,该研究基于密度泛函理论,在Sr单原子掺杂的基础上建立了Sr-Zn双原子掺杂γ-Al2O3(110)表面模型,通过计算掺杂能得到了最稳定催化剂表面;优化模拟了甲醇吸附于催化剂表面的吸附构型,并计算相应的吸附能。模拟结果表明,Sr原子倾向于替换Al3c-1和Al4c-2配位铝,Zn原子倾向与替换Al4c-4配位铝,此时催化剂表面掺杂能最小,其值为945.00 kJ/mol;Zn原子掺杂Sr/γ-Al2O3(110)表面时,甲醇吸附催化剂表面的吸附能绝对值增加,其吸附能值为?305.60 kJ/mol,甲醇上氧原子得电子数增加,羟基上氢原子与催化剂表面成键效果更好。Zn原子掺杂强化Sr/γ-Al2O3催化剂吸附甲醇的稳定性得到强化,有利于后续生物柴油的合成。研究结果可为促进生物柴油的发展、有效调整农业结构、减少化石燃料的燃烧提供理论参考。     

铵态氮/硝态氮对水稻铝吸收的影响及其机制研究

选用两个水稻品种武运粳7号（耐铝品种）和扬稻6号（铝敏感品种）作为实验材料,利用水培试验,通过长期和短期处理相结合的方式研究了NH4+-N和NO3--N对水稻Al吸收的影响及其作用机制。结果表明,与NH4+-N相比,NO3--N促进了水稻对Al的吸收。而且随着NO3--N浓度的提高,水稻根中Al含量显著增加,随着NH4+-N浓度的提高,水稻根中Al含量显著降低。这些结果表明NH4+-N和NO3--N对水稻Al吸收的影响具有浓度效应。当向Al溶液添加pH缓冲剂后,NH4+-N和NO3--N对根尖Al累积的影响变小,表明NH4+-N和NO3--N处理下溶液pH的变化可能是NH4+-N和NO3--N对水稻Al吸收影响不同的一个原因。     

降水酸度对马尾松根际环境中铝形态的影响

为了探明降水酸度对植物根际环境中铝形态的影响,以马尾松为例,采用根箱栽培、配制不同pH值的模拟酸雨以室外模拟酸雨喷淋法研究马尾松根际及非根际土壤中铝形态的特征及规律.研究结果表明:酸雨对土壤中铝化合物具有溶蚀作用,可促进土壤里活性铝离子(Al3+)溶出,并且酸雨pH值越低,活性铝离子累积溶出量越大,溶出的铝所形成的铝形态在马尾松根际土壤与非根际土壤以及根际不同土层之间存在一定差异,马尾松根际pH值和根系分泌物协同影响铝形态的动态变化.根际土壤中有机铝结合态含量增加.交换态铝含量则稍稍下降.     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究 Ⅰ.共存离子对NO3-吸附的影响

研究了我国典型3种可变电荷土壤和4种恒电荷土壤在陪伴阳离子分别为K+、Na+、Ca2+时和1mmolL-1KCl、K2SO4支持电解质中NO-3的吸附.结果表明,NO-3吸附量随pH的增加而减小.在添加相同浓度NO-3时,3种可变电荷土壤对NO-3的吸附量顺序为Ca(NO3)2＞KNO3＞NaNO3＞KNO3+KCl＞KNO3+K2SO4;在初始NO-3浓度0.5～5mmolL-1的范围内,吸附量随浓度变化的关系符合Langmuir等温吸附式.由此求出与NO-3吸附结合能有关的常数(K)在不同共存离子存在下数值较小且差异不大,因此认为不同陪伴阳离子和不同伴随阴离子对NO-3吸附的电性机理影响不大,只是改变了土壤表面的正电荷数量从而使吸附量发生变化.4种恒电荷土壤对NO-3的吸附量通常很小,其中在Ca(NO3)2介质中较在其他介质中稍大,最大吸附量仅为1.5mmolkg-1左右,约为可变电荷土壤的1/10,且在浓度较低时常观察到负吸附.     

阴离子对可变电荷土壤吸附铜离子的影响机理

根据NO-3、Cl-和SO24-对可变电荷土壤和恒电荷土壤吸附Cu2+的影响的比较,探讨了阴离子对可变电荷土壤吸附Cu2+的影响机理。结果表明,当3种阴离子的浓度相同时,在SO24-体系中铁质砖红壤对Cu2+的吸附率较在NO3-和Cl-体系中大得多,而在浓度相同的3种阴离子体系中,黄棕壤对Cu2+的吸附率相差不大。在离子强度相近的NaCl体系中,砖红壤对Cu2+的吸附率相近。在3种阴离子体系中,随着pH升高,砖红壤对Cu2+的吸附率均增大;但在NO-3体系和Cl-体系中Cu2+的吸附率相近;而在SO24-体系中Cu2+的吸附率最大。随着Na2SO4浓度的增大,铁质砖红壤和砖红壤对Cu2+的吸附率减小。但在0.005 mol L-1和0.05 mol L-1Na2SO4体系中,Cu2+的吸附率大于在不含Na2SO4的体系中者。而在0.5 mol L-1Na2SO4体系中,Cu2+吸附率小于在不含Na2SO4体系中者。在3种浓度的Na2SO4体系中,黄棕壤对Cu2+的吸附率均小于在不含Na2SO4体系中者。总之,阴离子可通过离子强度、专性吸附和形成离子对影响土壤对Cu2+的吸附。在可变电荷土壤中,阴离子对Cu2+吸附的影响机理较在恒电荷土壤中复杂得多。     

ADSORPTION-DESORPTION CHARACTERISTICS OF HIGH LEVELS OF COPPER IN SOIL CLAY FRACTIONS

Copper adsorption and desorption under acid conditions by soil clay fractions separated from Vertisol, Planosol and Gleyic Acrisol has been studied in 0.01 M Ca(NO₃)₂. A Freundlich equation was appropriate to describe Cu adsorption. Within the range of 150 to 2600 mg of copper per kg of soil clay fraction the proportions of Cu not displaced during 5 successive 48-hour desorptions with 0.01 M Ca(NO₃)₂ decreased with increasing adsorption density and at the lower pHs. The proportions ranged from as high as 0.98 in th case of the Vertisol clay (pH 5.3) to as low as 0.12 (88% desorption) in the Planosol clay (pH 4.5). Measurement of separation factors (ga Cu/Ca) showed that the preference of the clay surface for Cu over Ca decreased in the order: Gleyic Acrisol > Planosol > Vertisol. A considerable amount of sorbed copper could be solubilized by decreasing pH values to 4 when in the Planosol clay 39% was desorbed and 45% was desorbed in the Gleyic Acrisol clay.     

Glyphosate adsorption on synthetic allophanes and halloysite: Effects of pH and mineral properties

Background

Glyphosate (GLP) is a widely used herbicide with possible adverse effects on human health and the environment. In soils, GLP strongly adsorbs on clay-sized minerals, depending on pH, the amount of organic carbon, as well as the contents and properties of Al and Fe oxyhydroxides and clay minerals. Many clay-sized minerals have already been investigated regarding GLP adsorption behavior, but information on minerals commonly found in volcanic soils is still lacking.

Aim

The aim of this study was to investigate for the first time the pH-dependent adsorption of GLP on allophane and halloysite, typical minerals found in volcanic soils.

Methods

GLP adsorption was studied in batch experiments at three pH values (5, 6, and 7). Synthetic allophanes with two different initial Al:Si ratios (1.4 and 1.8) and a halloysite were used as adsorbents.

Results

The adsorption capacity (AC) increased with rising Al:Si ratio and decreasing pH. The AC of allophane was significantly higher than that of halloysite. GLP adsorption on allophane was larger than that reported for other clay minerals and Al and Fe oxyhydroxides, especially at low pH. The AC of halloysite was higher than reported for most other clay minerals.

Conclusion

Different mineral formation pathways in volcanic soils, notably the formation of halloysite versus allophanes, strongly affect the soils’ retention capacity for GLP. The high AC of allophanes may induce the low mobility of GLP in allophane-containing soils. Long-term use of GLP may accumulate the herbicide in these soils with potential effects on biodiversity and ecosystem services.     

Lead ion adsorption on montmorillonite–Al hydroxide polymer systems

Clay–Al hydroxide polymer systems (CAlHO) can bind heavy metals effectively. Their adsorption behaviour depends on the type of metal. We studied the dependence of Al‐loading and pH on the adsorption of Pb to Na‐saturated montmorillonite–Al hydroxide polymer systems. The available binding sites on the Al hydroxide polymers (AlHO) had a strong affinity for Pb ions, whereas a minor amount of Pb was bound to the clay surface. The pH had a pronounced effect on the Pb binding to the AlHO. At pH 6.0, AlHO effectively adsorbed Pb. The amount of Pb adsorbed to the AlHO, expressed per mole Al, increased with increasing amount of AlHO fixed. Lead bound to the AlHO could easily be removed by exchange and is therefore reversibly bound to the AlHO. Probably, Pb is outer‐sphere bound to the AlHO and an electrostatic bonding mechanism is involved. At pH 5.0 there was almost no adsorption of Pb to the AlHO, and the adsorption of Pb to the clay surface was limited because Al³⁺ ions competed with Pb²⁺ for exchangeable sites. At pH 6.6 and relatively large Pb concentrations, separate precipitates of Pb(OH)₂ and Al(OH)₃ were formed. Results from experiments in pure clay systems suggest that the Pb(OH)₂ precipitate was present as positively charged Pb polymers.     

Mechanisms of fixation and release of ammonium in paddy soils after flooding. IV. Significance of oxygen secretion from rice roots on the availability of non-exchangeable ammonium – a model experiment

In a model experiment the effect of O₂ secretion from imitated rice roots on the availability of non-exchangeable NH₄⁺ and N uptake by imitated roots under flooding conditions was investigated. O₂ secretion favoured the mobilization of non-exchangeable NH₄⁺ and increased N uptake by increasing the uptake of NO₃^--N. O₂ secretion resulted in a significant decrease in the concentration of exchangeable NH₄⁺ due to nitrification and in a lower pH of the rhizosphere. The protons are derived from the oxidation of Fe²⁺. In contrast, coating of clay minerals with Fe oxides, which is promoted by O₂ secretion and formation of free Fe oxides in the rhizosphere, may hinder the release of non-exchangeable NH₄⁺.     

Adsorption of pentachlorophenol by soils

The adsorption studies using soils various in the species of clay minerals and organic matter content indicate:

1) That apparent adsorption occurs to the greatest extent on the strong acid soil system compared to the moderate acid soil system, regardless of the species of clay mineral and organic matter content. And there is no adsorption on the slightly acid or neutral soil system.

2) The apparent adsorption involves adsorption of molecules and/or anions and precipitation of molecules in the micell and the external liquid phase.

3) The magnitude of adsorption occurs in the decreasing order of humus-allophanic, allophanic, montmorillonitic, and halloysitic soils.

4) The major factor governing the magnitude of apparent adsorption is pH.     

STUDIES ON SOIL COPPER

Adsorption isotherms were determined for the specific adsorption of copper by soils and soil constituents. Adsorption was found to conform to the Langmuir equation. The Langmuir constants, a (adsorption maximum) and b (bonding term), were calculated. Soils were found to have specific adsorption maxima at pH 5.5 of between 340 and 5780 μg g^?1, and a multiple regression analysis revealed that organic matter and free manganese oxides were the dominant constituents contributing towards specific adsorption. Adsorption maxima for soil constituents followed the order manganese oxides > organic matter > iron oxides > clay minerals, which supported the findings for whole soils. The cation exchange capacities (non-specific adsorption) of the test soils were found to be far greater than the specific adsorption maxima. However, evidence suggests that, for the relatively small amounts of copper normally present in soils, specific adsorption is the more important process in controlling the concentration of copper in the soil solution.     

Evaluation of arsenite sorption in Spanish soils

Abstract

Arsenite sorption was studied at different temperatures (30,40, and 50°C) to investigate processes that remove arsenite from soil solution (adsorption or precipitation), and if adsorption was taking place, how many sites were involved in this process, and their nature. Adsorption was the only reaction reducing levels of soluble arsenite in the two alkaline soils used in this experiment, Jijona and Agost; however, arsenite precipitation occurred in an acidic substrate (pH 4.0), Galicia soil. Iron (Fe) oxides and clay minerals were the soil components controlling arsenite sorption in the Jijona soil (pH 7.9 and high levels of Fe oxides). Calcite and clay minerals were the inorganic constituents involved in arsenite sorption in the Agost soil (pH 8.0 and high levels of CaCO₃). Arsenite sorption was an endothermic and non‐spontaneous process. The fact that the higher the temperature, the higher the arsenite sorption, however, was likely due to an increase in the diffusion rate.     

Comparison of the adsorption of maize root mucilage and polygalacturonic acid on montmorillonite homoionic to divalent lead and cadmium

Summary Root mucilage material (RM) was isolated from maize plants grown in the field, and its affinity to montmorillonite (M) homoionic to Pb²⁺ and Cd²⁺ was compared with that of a commercial polygalacturonic acid (PGA). Adsorption isotherms of the commercial and natural materials on the two clay systems were compared in unbuffered systems at pH 3 and pH 6. Adsorption of PGA occurred only at pH 3, and was higher on M-Pb than on M-Cd. In contrast, the adsorption of RM was higher on M-Cd than on M-Pb. Total amounts of RM adsorbed at pH 3 were about 3 times lower on M-Cd and 20 times lower on M-Pb than the respective amounts of PGA adsorbed at the same pH. Polygalacturonic acid had a high content of relatively well dissociated (pKa = 3.5) carboxylic groups, and adsorbed on the clay surface at pH values lower than its pKa. At pH 6, the dissociation of the acid groups favoured its solubility, and the metal cations were then probably displaced by ion exchange. The lower affinity of RM to the clay materials was related to its average molecular weight, which was lower than that of PGA, and to its water solubility, which was higher than that of PGA. The low pH dependence of the adsorption of RM was related to its lower carboxylic acidity and higher content in hydroxyl and amino groups.