邻苯二甲酸和水杨酸在可变电荷土壤中的吸附行为

研究了2种低分子量有机酸邻苯二甲酸和水杨酸在2种代表性可变电荷土壤红壤和砖红壤中的吸附行为。结果表明,可变电荷土壤对有机酸的吸附容量较大,对邻苯二甲酸的吸附亲和力大于对水杨酸的亲和力,在砖红壤中2种有机酸的吸附量大于在红壤中的,这与土壤的游离铁、铝氧化物的含量一致。土壤氧化铁在有机酸吸附中起着重要作用,粘土矿物如高岭石对有机酸的吸附量很小。有机酸的吸附涉及专性吸附和静电吸附2种机制,并以前者为主。当pH小于4.5时,pH的改变对有机酸的吸附影响不大;当pH大于4.5时,有机酸的吸附量随pH的增加而减小。     

Adsorption of phthalic acid and salicylic acid by two variable charge soils as influenced by sulphate and phosphate

Low‐molecular‐weight (LMW) organic acids exist widely in soils, especially in the rhizosphere, and the adsorption of these acids may affect their reactions in soils. The adsorption behaviour of phthalic acid and salicylic acid by two variable charge soils (a Rhodic Ferralsol and a Haplic Acrisol) was investigated. Both soils exhibited great adsorption capacity for these organic acids, with a greater affinity for phthalic acid. The Rhodic Ferralsol adsorbed more organic acids of both kinds than the Haplic Acrisol, which was consistent with the content of iron and aluminum oxides in the two soils. The iron oxides in these soils played a significant role in adsorption of the organic acids, whilst the soil aluminosilicate minerals, such as kaolinite, showed a small adsorption capacity. The presence of phosphate and sulphate caused a decrease in the adsorption of both organic acids because of their competition with them for sorption sites. The phosphate showed a bigger inhibition on the adsorption than sulphate as a result of a greater amount of phosphate adsorbed by the soils. The adsorption of both organic acids was affected by pH only slightly at pH < 4.5. However, the adsorption decreased with the increase in pH at pH > 4.5. A similar trend was observed for the phosphate system, but the opposite was seen for the sulphate system. This suggests that the inhibition of sulphate on the adsorption of the organic acids decreased with the increase in pH, because the adsorption of sulphate decreased strongly with increasing pH.     

用土柱淋溶实验研究水杨酸对酸性土壤铝迁移的影响

选择2种可变电荷土壤和1种酸性恒电荷土壤用土柱淋溶实验研究了水杨酸对土壤铝迁移的影响。结果表明，不同土壤由于矿物组成的差异，它们对有机酸的吸附容量有很大的不同，因此有机酸对不同土壤中铝的迁移有不同的影响。富铁土游离氧化铁的含量低于铁铝土，它对有机酸的吸附量也低于铁铝土的，因此在淋溶实验初期，有机酸对铝迁移的影响较小，在淋溶实验后期，由于土壤对有机酸的吸附达饱和状态，有机酸对铝的迁移表现出很强的促进作用，特别在有机酸初始浓度较高的情况下。铁铝土含有大量铁、铝氧化物，对有机酸有很高的吸附容量，有机酸对这类土壤铝迁移的影响很小。淋溶土对有机酸的吸附量很小，当有机酸的初始浓度较高时，淋溶实验开始后不久，有机酸就对铝的迁移表现出明显的促进作用。实验结果还表明，铝的迁移还与体系pH有关，低pH条件有利于土壤铝的溶解和迁移。     

氧化还原条件下有机物料对酸性土壤pH、铁形态和铜吸附解吸的影响

研究了添加有机物料对水稻土、红壤和砖红壤在干湿交替一次以后土壤pH、铁的形态和对铜吸附解吸行为的影响。结果表明,添加有机物料使得土壤pH升高,且随着有机物料加入量的增加而升高。与对照相比,添加有机物料可使水稻土、红壤和砖红壤的pH分别上升1.55、0.8和1.33个pH单位。红壤和砖红壤中无定形氧化铁含量增加,而水稻土中变化不大。在铜的平衡浓度为0.2 mmol/L时,添加有机物料培养可使水稻土、红壤和砖红壤铜的吸附量分别增加6.7、10.3和3.6 mmol/kg。     

不同NaNO_3浓度下可变电荷土壤铜离子解吸率的分配及影响因素

研究了江西红壤和昆明铁质砖红壤在去离子水中和在0.1molL-1NaNO3溶液中吸附铜离子后,依次在包括去离子水在内,浓度由低到高的NaNO3溶液中解吸时,铜离子解吸率在不同吸附pH段的分配规律。结果表明,随着吸附pH的升高,可在去离子水中解吸的铜离子解吸率变化规律与在NaNO3溶液中者完全不同。在所研究的吸附pH范围内,大致以吸附pH3.7~4.0为界,低于此值时,吸附性铜离子基本以在去离子水中解吸为主,反之则基本为交换性解吸。土壤中氧化铁含量和吸附时溶液的NaNO3浓度越高,则能被交换解吸的铜离子所占总解吸率的比例越低。其原因与不同pH段各种铜离子吸附态在不同吸附条件下的比例分配以及解吸对体系pH的影响有关。     

Adsorption and Desorption of Copper in Pasture Soils

Abstract

Copper (Cu) is bound strongly to organic matter, oxides of iron (Fe) and manganese (Mn), and clay minerals in soils. To investigate the relative contribution of different soil components in the sorption of Cu, sorption was measured after the removal of various other soil components; organic matter and aluminum (Al) and Fe oxides are important in Cu adsorption. Both adsorption and desorption of Cu at various pH values were also measured by using diverse pasture soils. The differences in the sorption of Cu between the soils are attributed to the differences in the chemical characteristics of the soils. Copper sorption, as measured by the Freundlich equation sorption constants [potassium (K) and nitrogen (N)], was strongly correlated with soil properties, such as silt content, organic carbon, and soil pH. The relative importance of organic matter and oxides on Cu adsorption decreased and increased, respectively, with increasing solution Cu concentrations. In all soils, Cu sorption increased with increasing pH, but the solution Cu concentration decreased with increasing soil pH. The cumulative amounts of native and added soil Cu desorbed from two contrasting soils (Manawatu and Ngamoka) during desorption periods showed that the differences in the desorbability of Cu were a result of differences in the physico‐chemical properties of the soil matrix. This finding suggests that soil organic matter complexes of Cu added through fertilizer, resulted in decreased desorption. The proportions of added Cu desorbed during 10 desorption periods were low, ranging from 2.5% in the 24‐h to 6% in the 2‐h desorption periods. The desorption of Cu decreased with increasing soil pH. The irreversible retention of Cu might be the result of complex formation with Cu at high pH.     

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。     

恒电荷土壤及可变电荷土壤与离子间相互作用的研究Ⅲ Cu2+和Zn2+的吸附特征

研究了3种典型可变电荷土壤和4种典型恒电荷土壤在不同pH和不同浓度下单纯及共存体系中Cu2 和Zn2 的吸附及其影响因素。结果表明,两类土壤对Cu2 或Zn2 的吸附量均随平衡浓度增加而增大,符合Langmuir吸附等温式;当Cu2 、Zn2 浓度一定时,pH升高使Cu2 、Zn2 吸附量增大,但当pH >5时,Cu2 、Zn2 吸附量随pH变化甚微,出现一个接近最大吸附量的“平台”。当添加Cu2 、Zn2 浓度相同,但二种离子的总浓度不同时,平衡液的Cu2 /Zn2 浓度比均小于1,说明两类土壤对Cu2 的吸附选择性大于Zn2 ,且这种趋势不因pH和离子浓度而改变。当Cu2 、Zn2 共存时,使可变电荷土壤的Zn2 吸附量减小约70 % ,是恒电荷土壤降低量的约1.5倍;可变电荷土壤吸附一个Cu2 或Zn2 时所释放H 的平均数,明显大于恒电荷土壤者,说明可变电荷土壤对Cu2 及Zn2 的吸附中专性吸附的比例较恒电荷土壤大     

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。     

不同浓度铜离子土壤的吸附-解吸行为——兼论弱专性吸附态的存在

研究了三种可变电荷土壤和两种恒电荷土壤不同铜离子浓度条件下的吸附-解吸行为。结果表明,不同铜离子浓度下土壤的pH-Cu2+吸附率曲线均在低pH段出现会合,且随着铜离子浓度升高,pH-Cu2+吸附率曲线有向右偏移的趋势。证实了可变电荷土壤中吸附性铜离子可被去离子水解吸,并存在解吸峰现象。针对解吸前后吸附体系pH值的变化研究结果显示,吸附时体系pH低于5.0时,解吸后pH上升;而吸附体系pH高于5.0时,解吸后pH下降,表明pH5.0可能是土壤吸附铜离子机理发生变化的又一个转折点。本文还对专性吸附中弱吸附态的存在和形成原因进行了初步探讨。     

低分子量有机酸对促进可变电荷土壤中铝溶解的影响

Low-molecular-weight （LMW） organic acids exist widely in soils and play an important role in soil processes such as mineral weathering, nutrient mobilization and A1 detoxification. In this research, a batch experiment was conducted to examine the effects of LMW organic acids on dissolution of aluminum in two variably charged soils, an Ultisol and an Oxisol. The results showed that the LMW organic acids enhanced the dissolution of A1 in the two investigated soils in the following order： citric 〉 oxalic 〉 malonic 〉 malic 〉 tartaric 〉 salicylic 〉 lactic 〉 maleic. This was generally in agreement with the magnitude of the stability constants for the Al-organic complexes. The effects of LMW organic acids on Al dissolution were greater in the Ultisol than in the Oxisol as compared to their controls. Also, the accelerating effects of citric and oxalic acids on dissolution of A1 increased with an increase in pH, while the effects of lactic and salicylic acids decreased. Additionally, when the organic acid concentration was less than 0.2 mmol L-I, the dissolution of A1 changed Iittle with increase in acid concentration. However, when the organic acid concentration was greater than 0.2 mmol L^-1,the dissolution of A1 increased with increase in acid concentration. In addition to the acid first dissociation constant and stability constant of Al-organic complexes, the promoting effects of LMW organic acids on dissolution of A1 were also related to their sorption-desorption equilibrium in the soils.     

离子强度和pH对可变电荷土壤与铜离子相互作用的影响

研究了离子强度和pH对可变电荷土壤表面电荷与铜离子吸附的影响。作为对照 ,也研究了它们对恒电荷土壤黄棕壤的有关性质的影响。结果表明 ,随pH升高 ,土壤的表面负电荷增加 ,正电荷减少。对于可变电荷土壤 ,可出现电荷零点 (pH0 )。随pH升高 ,土壤对Cu2 的吸附量增大。随着离子强度增大 ,恒电荷土壤对Cu2 的吸附百分率明显降低 ,可变电荷土壤对Cu2 离子的吸附百分率也降低 ,但降低的幅度比恒电荷土壤者小得多。土壤中氧化铁的含量越高 ,降低的幅度越小。对于含 2 1 %左右游离氧化铁的铁质砖红壤 ,即使支持电解质NaNO3的浓度高达 1molL- 1,对Cu2 的吸附仍然几乎没有影响。从离子强度和pH与土壤表面电荷和铜离子吸附的关系 ,可以推测在土壤对铜离子的吸附中 ,既存在电性吸附 ,又存在专性吸附。在可变电荷土壤对铜离子的吸附中 ,专性吸附较为重要     

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。     

有机酸对土壤中镉的解吸及影响因素

研究了酒石酸和柠檬酸对两种不同处理土壤 (镉质土和污染土 )中Cd的解吸行为 ,探讨了介质pH值、支持电解质等对其解吸镉质土和污染土中Cd的影响。结果表明 ,随有机酸浓度升高 ,柠檬酸和酒石酸对镉质土和污染土中Cd的解吸率呈先降低后升高变化 ,出现一波谷 ,波谷位置与有机酸和土壤类型有关。当解吸液起始pH值由 2升至 8时 ,柠檬酸对镉质土和污染土中Cd的解吸率呈降低—升高—降低的变化 ,先后出现一波谷和一波峰 ,且柠檬酸浓度高时变化趋势尤为明显 ;而酒石酸对镉质土和污染土中Cd的解吸率则一直降低。解吸液中支持电解质浓度提高 ,酒石酸对镉质土和污染土中Cd的解吸率增大 ,且以KCl为支持电解质时的解吸率要高于KNO3。     

Oxalic Acid Effect on Potassium Release from Typical Rice Soils of Kashmir

Batch experiments were employed to examine the influence of oxalic acid on release kinetics of potassium (K) from soils along with adsorption and desorption of soil K⁺. The soils used were three rice soils from high-, mid-, and low-altitude zones. The results showed that soil K extracted using 0.2 mol L^–1 oxalic acid was similar to that of 1 mol L^–1 boiling nitric acid (HNO₃). The relation between K release (y) and concentrations of oxalic acid (c) could be best described as y = a + b log c, whereas the best-fit kinetic equation of K release was y = a + b √t. The K release for soils was in the order Bonbagh > Ganasthan > Kreeri. An oxalic acid solution with low pH was able to release more K. Oxalic acid decreased soil K⁺ adsorption and increased desorption, the effect of which tended to be greater at lower pH.     

支持电解质浓度对磷酸根在可变电荷土壤表面吸附和解吸的影响

研究了离子强度对2种可变电荷土壤中磷酸根吸附和解吸的影响。结果表明,当pH分别大于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度的增加而增加;当pH分别小于3.7和4.0时,红壤和砖红壤对磷酸根的吸附量随离子强度呈相反的变化趋势。电解质主要通过改变离子专性吸附面上的电位来影响磷酸根的吸附。Zeta电位的测定结果表明,当pH大于土壤胶体的等电点(IEP)时,吸附面上电位为负值,且随离子强度增加数值减小,对磷酸根的排斥力减小,土壤表面对磷酸根的吸附量增加;当pH小于IEP时,吸附面上的电位为正值,它随离子强度增加而减小,不利于磷酸根的吸附。解吸实验的结果表明,吸附于可变电荷土壤表面的磷酸根在去离子水中的解吸量高于0.1 mol L-1NaNO3体系中的解吸量。这同样由于电解质浓度对土壤表面吸附面上的电位的影响所致。     

Adsorption and desorption of triasulfuron by soil

The adsorption and desorption of the herbicide triasulfuron [2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide] by three soils, soil organic matter (H(+) and Ca(2+)-saturated), and an amorphous iron oxide were studied. Adsorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the adsorption in all of the systems. Indeed, the adsorption on soils was negatively correlated with pH. The highest level of adsorption was measured on soils with low pH and high organic carbon content. Moreover, it was found that humic acid is more effective in the adsorption compared with calcium humate (the pH values of the suspensions being 3.5 and 6, respectively). Experiments on amorphous iron oxide confirmed the pH dependence. Desorption was hysteretic on soils having high organic carbon content.     

配位体交换在减慢由酸雨造成的可变电荷土壤酸化速度中的意义

For the purpose of evaluating the role of ligand exchange of sulfate ions in retarding the rate of acidification of variable charge soils,the changes in pH after the addition of different amounts of HNO3 or H2SO4 to representative soils of China were measured .A difference between pH changes caused by the two kinds of acids was observed only for variable charge soils and kaolinite,but not for constant charge soils and bentonite,The larger the proportion of H2SO4 in the HNO3-H2SO4 mixture,the lower the calculated H^ ion activities remained in the suspension.The difference in H^ ion activities between H2SO4 systems and HNO3 systems was larger for soils with a low base-saturation(BS) percentage than those with a high BS percentage.The removal of free iron oxides from the soil led to a decrease in the difference,while the coating of Fe2O3 on a bentonite resulted in a remarkable appearance of the difference.The effect of ligand exchange on the acidity status of the soil varied with the soil type.Surface soils with a high organic matter content showed a less pronounced effect of ligand exchange than subsoils did.It was estimated that when acid rain chiefly containing H2SO4 was deposited on variable charge soils the acidification rate might be slower by 20%-40% than that when the acid rain chiefly contained HNO3 for soils with a high organic matter content,and that the rate might be half of that caused by HNO3 for soils with a low organic matter content,especially for latosols.     

模拟酸雨对荔枝果园土壤磷素等温吸附与解吸特性的影响

采用等温吸附试验方法研究了模拟酸雨对荔枝果园土壤磷的吸附与解吸特性的影响。试验结果表明,不同处理间土壤对磷的最大吸附量(Xm)为pH2.5>pH4.5>CK=pH6.5,其中pH2.5的酸雨淋溶处理对磷的最大吸附量(Xm)与其它处理间差异显著;土壤吸附磷的解吸量(Xd)分别与相应的吸附量(X)和原平衡溶液浓度(C)呈显著的指数相关和线性相关,随着土壤对吸附量的增加,土壤磷的解吸量呈指数增长。     

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.