铝(氢)氧化物对有机酸和磷酸根的竞争吸附研究

研究了磷 /草酸浓度比 (Cp/Cox)、草酸 (OX)与磷 (P)加入顺序、多种有机酸共存等条件下铝 (氢 )氧化物 (Al(OH)x)对有机酸和磷的吸附量变化。结果表明 :磷浓度一定时 ,随Cp/Cox减小 ,Al(OH)x吸附磷量降低 ,吸附OX量增高 ,吸附阴离子总量一般随浓度升高而增加 ;Cp/Cox相同时 ,5种加入方式吸P顺序为P/OX P -OX OX +P OX -P OX/P ;Cp/Cox不同时 ,Al (OH)x吸附配位体的总量也相应变化 ;几种有机酸共存时 ,Al(OH)x对体系中的各种阴离子均有吸附 ,且相互影响和制约 ,总吸附量取决于离子种类和浓度 ,3种有机酸影响P吸附量的顺序为柠檬酸 (CA) 草酸 (OX) 酒石酸 (Tar) ;Al (OH)x加磷后随平衡时间延长 ,先吸附的OX和CA对吸附P量的影响逐渐减弱 ,它们的相对亲合力越来越成为主导因素。     

有机肥(物)对土壤中磷的活化作用及机理研究──Ⅱ.有机肥(物)分解产生的有机酸及其对不同形态磷的活化作用

通过有机肥在不同土壤水分状况下分解产生的有机酸种类和数量检测、各种有机酸对不同磷酸盐的溶磷试验,对有机肥活化土壤磷的机理进行了研究。结果表明,无论在好气或淹水条件下,猪粪、稻草和纤维素均能明显增加土壤中有机酸含量,其作用为猪粪＞稻草＞纤维素;7种检出的有机酸对不同形态人工合成磷酸盐的溶磷能力为：草酸和乙酸对钙磷的溶磷均有一定效果,多数有机酸对铝磷的溶磷效果均不错,而柠檬酸对铁磷的溶磷效果最好。柠檬酸虽数量不及其它有机酸,但在有机肥活化土壤磷中所起的作用是最大的。铁磷在有机肥活化磷中的贡献较其它形态无机磷大。     

有机肥(物)对土壤中磷的活化作用及机理研究──Ⅱ.有机肥(物)分解产生的有机酸及其对不同形态磷的活化作用

通过有机肥在不同土壤水分状况下分解产生的有机酸种类和数量检测、各种有机酸对不同磷酸盐的溶磷试验,对有机肥活化土壤磷的机理进行了研究。结果表明,无论在好气或淹水条件下,猪粪、稻草和纤维素均能明显增加土壤中有机酸含量,其作用为猪粪＞稻草＞纤维素;7种检出的有机酸对不同形态人工合成磷酸盐的溶磷能力为:草酸和乙酸对钙磷的溶磷均有一定效果,多数有机酸对铝磷的溶磷效果均不错,而柠檬酸对铁磷的溶磷效果最好。柠檬酸虽数量不及其它有机酸,但在有机肥活化土壤磷中所起的作用是最大的。铁磷在有机肥活化磷中的贡献较其它形态无机磷大。     

针铁矿和针铁矿—胡敏酸复合体对Se(Ⅳ)吸附机制

研究了针铁矿和针铁矿—胡敏酸复合体对Se(Ⅳ)的吸附机制。结果表明:针铁矿和复合体对Se(Ⅳ)的最大吸附容量分别为0.202 mmol g-1和0.159 mmol g-1。针铁矿的等温吸附数据适合用Langmuir模型拟合,而Freundlich模型更适合描述复合体的等温吸附过程。针铁矿的等电点(IEP)在7.0附近,复合体的IEP3.0;当p H=4.0时,它们的表面电位分别为46.6 m V和-40.5 m V。X—射线光电子能谱(XPS)分析显示,针铁矿和复合体表面Fe2p3/2的电子结合能(B.E.)分别为711.4e V和711.5 e V,复合体表面C1s的B.E.值为284.8 e V。初始p H=4.0时,样品与Se(Ⅳ)相互作用后的主要变化体现在:(1)针铁矿和复合体的悬浮液p H分别升高至4.4和4.2,表面电位分别降低了39.08 m V和升高了1.8 m V;(2)针铁矿表面Fe(Ⅲ)的B.E.值降低了0.4 e V,但吸附态Se(Ⅳ)的B.E.值无明显变化;(3)复合体表面Fe(Ⅲ)的B.E.值降低了0.3 e V,表面C-O中C的B.E.值由285.7 e V升高至286.5e V,吸附态Se(Ⅳ)的B.E.值升高了0.6 e V。针铁矿和复合体吸附Se(Ⅳ)的主要机制包括表面配合反应(复合体表面铁羟基与HSe O3-之间存在双齿配位)、静电引力、氢键等作用。此外,复合体表面吸附态Se(Ⅳ)同时与针铁矿和胡敏酸发生了作用,形成了针铁矿—Se(Ⅳ)—胡敏酸三元体。     

五台山土壤水稳性团聚体Ca—SOC和Fe(Al)—SOC分布特征

以五台山垂直带土壤为研究对象,按照垂直分布从高到低依次对亚高山草甸土(A)、山地草甸土(B)、棕壤(C)、淋溶褐土(D)和石灰性褐土(E)进行采集,研究土壤本身及各土壤2,2~0.25,0.25~0.053,0.053mm水稳性团聚体钙键合有机碳(Ca—SOC)和铁铝键合有机碳(Fe(Al)—SOC)的分布特征。结果表明:从A到E,各土壤Ca—SOC的含量没有明显变化趋势,而Fe(Al)—SOC的含量呈先升高后降低的趋势。随着团聚体粒径的减小,A的Ca—SOC和Fe(Al)—SOC含量变化趋势相反(前者先升高后降低,后者先降低后升高),B的Ca—SOC和Fe(Al)—SOC含量呈先降低后升高的趋势,D的Ca—SOC和Fe(Al)—SOC含量变化趋势与B相反,表现为先升高后降低;此外,C的Ca—SOC和Fe(Al)—SOC含量逐渐减小,而E的Ca—SOC和Fe(Al)—SOC含量逐渐增加。相关性分析表明,各土壤及2mm团聚体Fe(Al)—SOC与土壤有机碳含量之间呈显著正相关,相关系数分别为r土壤=0.898(P0.05),r2mm=0.978(P0.01)。各土壤及团聚体中Fe(Al)—SOC的含量明显大于Ca—SOC的含量,而且2~0.25mm和0.25~0.053mm团聚体Ca—SOC和Fe(Al)—SOC含量间都呈显著正相关。因此,五台山各土壤铁铝键的键合能力以及铁铝复合体的稳定性均高于Ca—SOC,且土壤和各级团聚体Fe(Al)—SOC的含量及分配比例明显高于Ca—SOC。     

湖南两个小流域土壤中铝和铁的形态分布及其相关性研究

分别在湖南的郴州和长沙选定两小流域(SZY 和 LKS),从小流域规模分析了酸雨频降区两小流域土壤的主要理化特性和土壤 Al、Fe 形态。结果表明:在小流域 SZY 土壤中,各种形态的 Al、Fe 含量均高于小流域 LKS 土壤中对应形态的 Al、Fe 含量;在同一剖面, 各种形态的 Al、Fe 含量有表土高于底土的趋势。两小流域土壤中,除 Feox外各种形态的 Al、Fe 均与土壤有机质呈正相关,酸沉降能影响 Al、Fe 形态的转化和淋溶。酸沉降影响 Al、Fe 的溶出可能是通过形成可溶性的有机物-Al、Fe 的复合物而从难溶性 Al、Fe 转化而来。土壤中各种形态的 Al 与对应形态的 Fe 呈线性正相关,酸沉降增加了毒性元素 Al 的溶出,同时也可能增加营养元素 Fe 的有效性。     

被锰、铁和铝固定的磷的性质的比较研究

An experiment was conducted to examine the role of Mn in P fixation through comparing with Al and Fe.Hydroxides and oxides of Al,Fe and Mn were prepared in lab under opened and closed conditions to react with phosphate,The newly formed Mn hydroxide showed the strongest P-fixing ability,even several times higher than Fe hydroxide ,but became the lowest rapidly due to ageing when exposed to air,Mn oxide showed the lowest P-fixing ability,Therefore,a sound consideration on P fixation should be based on both quantities and P-fixing abilities of the compounds of Fe,Al and Mn,The importance of Mn on P availability should receive more attention especially under oxidation-reduction dynamic conditions.     

Desorption kinetics of arsenate adsorbed on Al (oxy)hydroxides formed under the influence of tannic acid

Although, much research has been done on arsenate adsorption by Al (oxy)hydroxides, relatively little is known about the kinetics of arsenate desorption from these (oxy)hydroxides, especially those formed in the presence of organic acids. The desorption kinetics of arsenate adsorbed on Al (oxy)hydroxides, formed under the influence of tannic acid, was investigated using 0.1 and 0.5 mM phosphate at pH 5.5 and an ionic strength of 0.01 M at 298 and 318 K. The kinetic data expressed as the mole fraction of the arsenate remaining adsorbed on the Al (oxy)hydroxides after different desorption periods indicated multiple rate characteristics; a fast reaction period from 0.083 to 3 h and a slow reaction period from 3 to 24 h. The second-order rate equation of the six kinetic models tested was chosen to compare the desorption rate of arsenate. The rate constants of arsenate desorption from the Al (oxy)hydroxides formed at different tannate/Al molar ratios (MRs) followed the order: tannate/Al MR of 0 > tannate/Al MR of 0.1 > tannate/Al MR of 0.01 > tannate/Al MR of 0.001 in the fast reaction period, and tannate/Al MR of 0.1 > tannate/Al MR of 0 > tannate/Al MR of 0.01 > tannate/Al MR of 0.001 in the slow reaction period both in 0.1 and 0.5 mM phosphate systems. The data indicate that the Al (oxy)hydroxides formed in the presence of small amounts of tannic acid (tannate/Al MR = 0.001 and 0.01) had a higher adsorption affinity for arsenate and resulted in slower desorption rates of the adsorbed arsenate compared with the Al (oxy)hydroxides formed in the absence of tannic acid. This is ascribed to the tannate-induced structural perturbation, development of microporosity, enhanced specific surface area, and reactivity of the Al precipitates. As the tannate/Al MR increased from 0.001 to 0.1, the rate constants of arsenate desorption steadily increased. This was attributed to the decrease in the point of zero salt effect (PZSE) of the Al precipitates with the increase of the tannate/Al MR and the resultant electrostatic repulsion from coprecipitated tannate which would weaken the binding of arsenate on the Al precipitates. The effect of temperature on the desorption rate of arsenate, which was governed by the activation energy and the pre-exponential factor (collision frequency), varied with the nature of the Al precipitates. The findings obtained in the present study indicate that the relative effects of tannate-induced structural perturbation, enhanced specific surface area, decreased PZSE, and development of micropore structure in the Al (oxy)hydroxides determine the overall impact of tannate on the kinetics of arsenate desorption from these Al (oxy)hydroxides.     

红壤中铝、锰和铁在酸雨作用下的释放特征

酸雨作用下红壤中Al、Mn和Fe的释放大多具有阶段性特征,旦土壤不同,其阶段性特征存在明显的差异。多数情况下同一土壤中Al和Fe的阶段性释放特征较为相似。3种元素累积释放量(Q)随淋溶量(H)的变化符合二次模型:Q=A B1H B2H2。经过9150～10650mm的酸雨淋溶以后,与对照(pH5.6)相比,pH4.5的酸雨使Al累积释放量增加8.16%～87.49%,Mn增加-4.29%～24.75%,Fe增加5.78%～86.03%;pH3.5的酸雨使Al累积释放量增加68.59%～158.60%,Mn增加26.11%～205.53%,Fe增加8.48%～138.88%。3种元素对酸雨的敏感性依次是:Al>Fe>Mn。其累积释放量在不同土壤之间表现出基本一致的特点:Al和Mn的释放量较为接近,且远远大于Fe的释放量。     

浓度与pH互作下表没食子儿茶素没食子酸脂（EGCG）对黄壤Al、Fe、Mn迁移的影响

对淋溶环境下黄壤的Al、Fe、Mn浓度进行分析,探讨浓度与pH互作下表没食子儿茶素没食子酸脂(EGCG)对黄壤Al、Fe、Mn迁移的影响。采用二因素四水平完全随机试验,用48个不同浓度和pH组合的EGCG溶液对黄壤进行间歇淋溶,测定淋出液中Al、Fe、Mn浓度,分析黄壤Al、Fe、Mn迁移总量和迁移过程。结果表明,黄壤Al、Fe、Mn迁移总量在浓度与pH互作下均有显著差异;高浓度(5.00mmol/L)高pH(5.5)EGCG溶液有利于Al和Fe的迁移,迁移总量分别为180.24mg/L和41.15mg/L;而EGCG溶液在高浓度(5.00mmol/L)低pH(3.5)时有利于Mn的迁移,其迁移总量为4.50mg/L;Al、Fe、Mn迁移总量在浓度与pH互作下主要表现为AlFeMn。随着淋溶的进行,淋出液中Al和Mn浓度在中后期(大致在第8次取样后)均逐渐降低;但随着中、高浓度(1.00,5.00mmol/L)高pH(5.5)、高浓度(5.00mmol/L)中pH(4.5)的EGCG溶液淋溶的进行,淋出液Fe浓度先增加后降低;当EGCG浓度与低pH(3.5)互作时,淋出液Fe浓度随淋溶的进行整体呈现明显的升高趋势。EGCG溶液的淋溶对土壤Al/Mn毒的治理有一定效果,且淋溶前期的效果更明显,但EGCG溶液不具备同时经济高效治理土壤Al/Mn毒的优势。     

线性和非线性方法估计单宁酸共存下形成的无定形铝氧化物上菲的吸附等温线参数比较

采用批实验研究了菲在单宁酸干扰下形成的不同晶形铝氧化物上的吸附现象,并用不同的吸附等温线方程对吸附平衡数据进行了拟合,重点比较了线性和非线性回归方法估计吸附等温线参数的差异。结果表明:菲在各种晶形的铝氧化物上都有明显的吸附,但并不是完全随着单宁酸含量和结晶度的变化而规律性变化。吸附平衡数据以Langmuir、Redlich-Peterson和Dubinin-Radushkevich吸附等温方程,用不同的回归方法估计的等温线参数值均有显著性差异。线性回归得到的参数有不确定性,表明用线性回归来判断吸附等温线能否对吸附平衡数据进行最优拟合是不可靠的。相反,非线性回归能较好地确定菲在不同晶形铝氧化物上的最佳吸附等温线及相应参数。采用R2和χ2共同检验发现,菲在4种不同结晶度(单宁酸与铝的摩尔比(MR)=0,10-3,10-2,10-1)铝氧化物上的最佳吸附等温线方程并不尽相同,分别为Freundlich,Freundlich,Dubinin-Radushkevich和Freundlich,反映了各种晶形的铝氧化物的表面异质性。修正的Freundlich方程比较不同晶形铝氧化物对菲的相对吸附容量顺序为:MR=10-3MR=10-2MR=0MR=10-1。由此,认为菲在无定形铝氧化物上的吸附是熵驱动的结果。     

灭菌土壤玉米一花生混作对花生铁营养的影响研究

盆栽试验研究灭菌土壤玉米 花生混作对花生植株Fe营养与根际土壤有效铁的影响结果表明 ,玉米 花生混作可显著提高花生新叶叶绿素及活性铁含量 ,下针初期可增加花生地上部全Fe含量和根际土壤活性铁含量 ,混作在改善花生Fe营养过程中始终起主导作用 ;而灭菌土壤处理则仅在花生生长早期有利于改善其Fe营养状况     

Partial replacement of Fe(o,o‐EDDHA) by humic substances for Fe nutrition and fruit quality of citrus

The most widely used Iron (Fe) fertilizer in calcareous soils is the synthetic chelate Fe(o,o‐EDDHA). However, humic substances are occasionally combined with Fe chelates in drip irrigation systems in order to lower costs. We investigated the effect of various mixtures of Fe(o,o‐EDDHA) and a commercially available humic substance on Fe availability in a calcareous soil from Murcia, Spain (in vitro experiment) and on leaf Fe content and fruit‐quality attributes of Citrus macrophylla (field experiment). In the in vitro experiment, a calcareous soil was incubated for 15 d with solutions of sole Fe(o,o‐EDDHA) and humic substance and of a mixture of humic substance and Fe(o,o‐EDDHA) to determine the dynamics of available Fe. While the mixture did not significantly increase the available soil Fe, it did decrease the rate of Fe retention in the surface soil compared to sole Fe(o,o‐EDDHA). In the field experiment, the substitution in the application solution of 67% of Fe(o,o‐EDDHA) by commercial humic substance increased leaf P in lemon trees from 0.19% with sole Fe(o,o‐EDDHA) to 0.30% and leaf Fe from 94 mg kg^–1 to 115 mg kg^–1. Some quality parameters like vitamin C content and peel thickness were also improved with a partial substitution of Fe(o,o‐EDDHA) by humic substances. We conclude that a partial substitution of commercial Fe chelates by humic substance can improve crop Fe uptake and may thus be economically attractive. The underlying physiological mechanisms and ecological implications require further studies.