低分子有机酸对土壤氟吸附的影响

用等温平衡吸附法研究了柠檬酸，草酸对砂姜黑土和潮土氟吸附的影响，提出了有机酸影响氟吸附的可能机理，实验结果表明，有机酸对土壤氟吸附有较大的影响：（1）当有机酸处理低浓度时，土壤氟吸附量随浓度升高而增加；高浓度时，土壤氟吸附量随有机酸浓度升高而降低；（2）在有机酸存在条件下，土壤氟的吸附量与平衡氟浓度间呈极显著的直线正相关或负相关。     

有机酸对潮褐土和红壤吸附Cu(Ⅱ)的影响及其机制

采用吸附平衡法,研究了有机酸(草酸、柠檬酸)对潮褐土和红壤吸附Cu2+的影响及机制.结果表明,潮褐土、红壤对Cu2+吸附明显有异,潮褐土对Cu2+吸附量是红壤对Cu2+吸附量的5倍多.潮褐土对Cu2+的竞争吸附率随有机酸浓度升高而降低,当草酸、柠檬酸浓度为10 mmol(L-1时,Cu2+吸附率均分别比对照的降低40%和70%以上.在低浓度条件下,红壤对Cu2+的竞争吸附率随有机酸浓度的提高而增加,当草酸、柠檬酸浓度分别超过1 mmol(L-1和0.05 mmol(L-1时,又随有机酸浓度的升高而降低.两种土壤对Cu2+次级吸附率随有机酸浓度升高而变化的规律与竞争吸附的一致.在相同有机酸浓度下,土壤对Cu2+的次级吸附率均比竞争吸附率的高.     

有机酸对潮褐土和红壤吸附Cu(II)的影响及其机制

采用吸附平衡法,研究了有机酸(草酸、柠檬酸)对潮褐土和红壤吸附Cu2+的影响及机制。结果表明,潮褐土、红壤对Cu2+吸附明显有异,潮褐土对Cu2+吸附量是红壤对Cu2+吸附量的5倍多。潮褐土对Cu2+的竞争吸附率随有机酸浓度升高而降低,当草酸、柠檬酸浓度为10 mmolL-1时,Cu2+吸附率均分别比对照的降低40%和70%以上。在低浓度条件下,红壤对Cu2+的竞争吸附率随有机酸浓度的提高而增加,当草酸、柠檬酸浓度分别超过1 mmolL-1和0.05 mmolL-1时,又随有机酸浓度的升高而降低。两种土壤对Cu2+次级吸附率随有机酸浓度升高而变化的规律与竞争吸附的一致。在相同有机酸浓度下,土壤对Cu2+的次级吸附率均比竞争吸附率的高。     

表面活性剂对柴油在土壤中吸附的影响

通过静态吸附实验,研究土壤对十二烷基苯磺酸钠(LAS)和十六烷基三甲基溴化铵(CTAB)的吸附行为,探讨表面活性剂对柴油吸附的影响.结果表明,土壤对LAS和CTAB的吸附等温线均为非线性,其吸附能力的大小顺序为:轻壤土>轻粘土>中壤土>砂壤土>重壤土>紧砂土.同一土壤中,CTAB的吸附量大于LAS的吸附量.LAS和CTAB均利于柴油在土壤表面的解吸,且LAS的解吸效果更好.柴油的吸附量随LAS浓度的升高而降低.当CTAB的浓度小于临界胶束浓度CMC时,吸附量随CTAB浓度的升高而升高,当CTAB的浓度等于或大于临界胶束浓度(CMC)时,吸附量随CTAB浓度的升高而降低.     

几种电解质对土壤吸附Cu2+的影响

采用平衡吸附法研究了潮褐土、红壤对Cu^2 的等温吸附以及不同pH和电解质对土壤吸附Cu^2 的影响。结果表明，(1)土壤对Cu^2 的吸附量随平衡溶液中Cu^2 浓度增加而增加，潮褐土CuCu^2 最大吸附量明显比红壤的高，约是红壤的4—5倍。(2)体系pH显著影响土壤对Cu^2 的吸附，随pH升高Cu^2 吸附率增加，基本呈S形曲线变化。(3)随体系电解质浓度的增加，土壤对Cu^2 吸附率的变化趋势因土壤性质及体系中电解质种类、浓度的不同而不同。随KNO3浓度提高，土壤Cu^2 吸附率降低。KCl、KH2PO4对潮褐土吸附Cu^2 的影响与红壤的有些不同，低浓度KCl、KH2PO4抑制潮褐土对Cu^2 的吸附，高浓度KCl、KH2PO4促进潮褐土对Cu^2 的吸附，面对红壤。KCl降低Cu^2 的吸附率，KH2PO4提高Cu^2 的吸附率，但随KH2PO4浓度的提高，其提高幅度逐渐减弱。     

铁、铝氧化物和土壤对苄嘧磺隆的吸附

用平衡吸附法研究了苄嘧磺隆在两种土壤(广州赤红壤、湖南红壤)和两种人工合成氧化物(针铁矿、铝氧化物)中的吸附,以及pH对吸附的影响.结果表明:(1)用Langmuir,Freundlich和Temkin等温方程描述供试样品对苄嘧磺隆的吸附,其中Freundlich吸附等温方程拟合的结果较佳.在苄嘧磺隆的实验浓度范围内和一定的pH条件下,吸附苄嘧磺隆的量随其浓度的升高而增加,其顺序为:铝氧化物＞湖南红壤＞针铁矿＞广州赤红壤.(2)苄嘧磺隆在供试样品中的吸附量随溶液pH值的升高而减小.     

不同磷含量和秸秆添加量对褐土镉吸附解吸的影响

采用室内培养的方法,通过人为添加不同量的玉米干秸秆和磷,研究不同含磷量土壤对镉吸附解吸影响,以探讨磷—镉在土壤中的交互作用机制。结果表明,不同含磷量的土壤对不同质量浓度锌镉吸附解吸时,在低质量浓度镉（Cd3）条件下,土壤对镉的吸附量随磷质量分数的增加先升高后降低,解吸量随着土壤中磷质量分数的增加先升高后降低再升高;而在高质量浓度镉（Cd30）条件下,土壤对镉的吸附量随磷质量分数的增加逐渐升高,在相同磷水平下,随外加锌质量浓度的增加,镉的吸附量明显降低,而解吸量则逐渐升高。不同秸秆量土壤对不同质量浓度镉吸附解吸时,在Cd3条件下,土壤对镉的吸附量随秸秆加入量的增加先升高后降低,而在同一质量分数磷情况下,吸附量逐渐下降;土壤对镉的解吸量在磷质量分数为120 mg·kg^-1（P2）时最低,而后随着磷质量分数的增加而增加。在同一质量分数磷水平情况下,随着秸秆添加量的增加,土壤对镉的解吸量逐渐增加。而在Cd30条件下,土壤对镉的吸附量逐渐增加,在同一磷水平情况下,土壤对镉的吸附情况是低量秸秆（C1）〉高量秸秆（C2）,但在磷质量分数为240 mg·kg^-1（P3）水平下,不添加秸秆（C0）情况时镉的吸附量最大,而后降低。土壤对镉的解吸量随着磷含量的增加而增加。在同一磷水平情况下,随着秸秆添加量的增加,土壤对镉的解吸量逐渐增加。     

不同浓度柠檬酸溶液中石灰性紫色土微团聚体对Pb~(2+)的吸附解吸特性变化

铅(Pb~(2+))因溶解度较小,易在土壤中长期滞留,从而造成严重的土壤铅污染。柠檬酸(Citric Acid)作为植物根系分泌的典型天然有机酸,含有大量羧基功能团和活性点位,影响着土壤中重金属的吸附和解吸。为深入了解柠檬酸输入土壤后,Pb~(2+)在土壤中的积累与迁移规律,以石灰性紫色土为研究对象,通过模拟试验,采用平衡液吸附法及柠檬酸、HCl解吸法,研究了不同浓度柠檬酸溶液中石灰性紫色土及各粒径微团聚体对Pb~(2+)的吸附-解吸特性。结果表明:在不同浓度柠檬酸溶液中,石灰性紫色土全土及各粒径微团聚体对Pb~(2+)的吸附量随其初始浓度增大而增加,各粒径间吸附量大小顺序为:(0.002 mm)2~0.25 mm全土0.053~0.002 mm0.25 mm~0.053 mm;柠檬酸浓度在0~1 mmol·L~(-1)范围内,石灰性紫色土全土及各粒径微微团聚体对Pb~(2+)的吸附量明显上升,1~100 mmol·L~(-1)范围内吸附量下降,低浓度的柠檬酸能够有效促进全土及各粒径微团聚体对Pb~(2+)的吸附,高浓度柠檬酸则起抑制作用,降低土壤对Pb~(2+)的吸附量;Freundlich方程对等温吸附过程的拟合达到极显著水平(R2=0.985-0.999),全土和不同粒径微团聚体对Pb~(2+)的吸附为不均匀表面的多层吸附;易解吸率随初始Pb~(2+)质量浓度上升而不断增大,难解吸率不断下降,加入柠檬酸后,易解吸率进一步上升,且随柠檬酸浓度升高而增大。研究柠檬酸溶液中石灰性紫色土对Pb~(2+)的吸附-解吸特性,能够有效预测石灰性紫色土区域重金属的环境效应,对农业环境安全调控具有重要意义。     

可变电荷土壤和恒电荷土壤Cl-吸附特性的研究

对不同浓度KCl和不同pH下，3种可变电荷土壤和4种恒电荷土壤Cl-吸附量进行了测定。结果表明，土壤Cl-吸附量随平衡Cl-浓度C（e）增加而增大，恒电荷土壤呈线性，可变电荷土壤在添加Cl-0.5~5.0mmol/L下，符合Langmuir吸附等温式。同一浓度下的Cl-吸附量及其随浓度增加的速率均为砖红壤>红壤>赤红壤>黄棕壤>棕壤、暗棕壤和黑土，与这些土壤所带正电荷量顺序相一致。Langmuir方程K值较小且几种土壤差异不大。恒电荷土壤对Cl-的吸附量很小，在浓度较低时常出现负吸附，其吸附机理可能更多的是与K+吸附时的同时吸附。7种土壤Cl-吸附量均随pH增加而降低，但降低强度可变电荷土壤远大于恒电荷土壤。     

石灰性褐土中柠檬酸对土壤Cu(Ⅱ)、Cd(Ⅱ)吸附-解吸的影响

通过室内培养和吸附-解吸实验,研究了不同柠檬酸含量土壤对Cu2+、Cd2+吸附-解吸的影响.结果表明,土壤对Cu2+的吸附量随加入柠檬酸量的增加而明显增加,达到峰值后(柠檬酸含量为0.5 mmol.kg-1),吸附量随柠檬酸含量的增加而下降,即Cu2+的吸附曲线呈峰型.在低柠檬酸含量时,土壤对Cu2+的吸附量受Cd2+浓度影响较小,但随柠檬酸含量的增加,在低铜浓度处理(Cu2+浓度为600 mg·L-1,Cu600)下,土壤对Cu2+的吸附量随Cd2+浓度的增大而增大,但在高浓度铜处理(Cu2+浓度为1000 mg·L-1,Cu1000)下,土壤对Cu2+的吸附量随Cd2+浓度的增加而减少.Cu2+的解吸量随柠檬酸含量的增加而总体上降低;相同柠檬酸含量下,Cu600处理下,Cd2+浓度为10 mg·L-1(Cd10)条件下Cu2+解吸量明显低于无Cd2+(Cd0)和Cd2+浓度为1 mg·L-1(Cd1)条件下.而Cu1000处理下,Cd2+的浓度对Cu2+解吸量的影响较小.Cd2+吸附量随柠檬酸含量的增加无明显变化,但随Cu2+浓度的增加下降明显,其中无Cu2+处理Cd2+吸附量极显著地高于Cu600和Cu1000处理,而Cu600和Cu1000处理间差异不显著,且土壤对Cd2+的吸附随镉添加量增加而增加;Cd2+的解吸量随柠檬酸含量的增加先增大后保持稳定,在柠檬酸含量为0.5 mmol.kg-1时达到最大,Cu600处理的Cd2+的解吸量显著地高于Cu1000处理.     

Effects of organic acids on Cd adsorption and desorption by two anthropic soils

The objective of this experiment was to study the effects of malic, tartaric, oxalic, and citric acid on the adsorption and desorption characteristics of Cd by two typical anthropic soils (lou soil and irrigation-silted soil) in North-west China. Cadmium adsorption and desorption were studied under a range of temperatures (25°C, 30°C, 35°C, 40°C), organic acid concentrations (0.5–5.0 mmol·L^-1), and pH values (2–8). The results showed that the Cd adsorption capacity of the lou soil was significantly greater than that of the irrigation-silted soil. Generally, Cd adsorption increased as the temperature increased. In the presence of NaNO₃, the adsorption of Cd was endothermic with ΔH values of 31.365 kJ·mol^-1 for lou soil and 28.278?kJ·mol^-1 for irrigation-silted soil. The endothermic reaction indicated that H bonds were the main driving force for Cd adsorption in both soils. However, different concentrations of organic acids showed various influences on the two soils. In the presence of citric acid, chemical adsorption and van der Waals interactions were the main driving forces for Cd adsorption rather than H bonds. Although the types of organic acids and soil properties were different, the effects of the organic acids on the adsorption and desorption of Cd were similar in the two soils. The adsorption percentage of Cd generally decreased as organic acid concentrations increased. In contrast, the adsorption percentage increased as the pH of the initial solution increased. The exception was that adsorption percentage of Cd increased slightly as oxalic acid concentrations increased. In contrast, the desorption percentage of Cd increased with increasing concentrations of organic acids but decreased as the initial solution pH increased.     

Effect of low molecular weight organic acids on adsorption and desorption of fluoride on variable charge soils

The effect of four low molecular weight organic acids on F⁻ adsorption by two variable charge soils was investigated using a batch method. The organic acids reduced F⁻ adsorption through competition by the acids with F⁻ for sorption sites. Oxalic and malonic acids, both of which have simpler chemical structures, were more effective than citric or malic acid. The effect of organic acids on F⁻ adsorption was more prominent at higher pH values and with larger amounts of the organic acids. The desorption study showed that the organic acids enhanced the desorption of F⁻ adsorbed by the soils. In the control and malic acid systems, desorption increased sharply with decreasing pH, while in the oxalic acid system, desorption rose slightly with decreasing pH. Desorption also increased with increasing amount of organic acid added. There are two possible mechanisms for the effect of the organic acids on F⁻ adsorption and desorption: (1)␣competition of the organic acids with F⁻ for adsorption sites and (2) dissolution of the adsorbents, especially dissolution of soil Al.     

有机酸对珠江三角洲水稻土镉解吸行为的影响

用批平衡实验方法,研究了3种有机酸及其两两混合酸在一系列pH值梯度下(pH3~7)对珠江三角洲沉积型水稻土镉(Cd)解吸的影响.结果表明,只有柠檬酸及含柠檬酸的混合酸在较低酸度区(pH>5)可以显著促进Cd的解吸,这一效应与浓度成正相关,而苹果酸、草酸及二者的混合酸在所试验酸度范围均促进了Cd吸附,特别是草酸,促进作用随浓度的升高而增强.在较低pH区(pH<5),苹果酸最有利于Cd解吸,在高pH区(pH≥5),柠檬酸最有利于Cd解吸,草酸的Cd解吸能力最低.混合有机酸交互作用不显著,对Cd解吸的影响约等于各个单独酸的作用之和,但在一些酸度条件下,可存在颉颃作用.图3表2参22     

不同pH下低分子量有机酸对黄壤中铝活化的影响

用一次平衡的方法研究了不同pH下低分子量有机酸对黄壤中铝活化的影响.结果表明,低分子量有机酸体系可以通过质子和有机酸阴离子两个因素促进黄壤中铝的活化.当pH>4.3时,有机酸通过络合作用促进铝溶解的大小顺序为:柠檬酸>草酸>水杨酸>乳酸,与有机酸和铝形成络合物的稳定常数大小一致.有机酸阴离子可以通过自身的吸附增加土壤交换态铝的量,但质子作用对黄壤交换态铝的活化比有机酸阴离子的吸附起着更为重要的作用,随pH值的降低这种趋势更加明显.有机酸对交换态铝的活化作用随pH值的降低而增加.低分子量有机酸活化的铝主要分布在土壤表面的交换位上,但在柠檬酸和草酸体系中,当pH值分别大于4.40和4.55时,活化铝主要分布在土壤溶液中.     

低分子量有机酸对可变电荷土壤吸附铝的影响机制

通过吸附性铝的解吸实验研究了低分子量有机酸对三种可变电荷土壤(2种砖红壤和1种赤红壤)吸附铝的影响机制，结果表明，柠檬酸、苹果酸和酒石酸等带有3个及3个以上活性官能团的有机酸在低pH条件下可以通过形成土壤一有机酸一铝三元表面络合物和增加土壤的表面负电荷两种机制显著增加土壤对铝离子的吸附量，但以前一种影响机制为主。乳酸、水杨酸、草酸和丙二酸等带有2个活性官能团的有机酸仅通过改变土壤的表面负电荷影响铝的吸附。土壤氧化铁是土壤吸附有机酸的主要载体，当用化学方法将土壤中的氧化铁除去后，有机酸对铝吸附的影响变小。在pH5．0时有机酸主要通过形成可溶性有机铝络合物减小土壤对铝的吸附，但有机酸的存在增加了Al^3 在吸附性铝中所占的比例，导致铝的解吸率增加。土壤中大量氧化铁的存在使其即使在低pH下也能对铝离子发生专性吸附，导致吸附性铝的解吸率减小。     

重金属-柠檬酸-针铁矿三元体系的表面络合模型研究

根际环境产生的柠檬酸等小分子有机酸可能影响重金属的溶出效应.本文研究了4种重金属Cd、Pb、Cu、Ni及柠檬酸在针铁矿表面的三元体系吸附行为,结果发现柠檬酸促进了4种重金属酸性条件下在针铁矿表面的吸附量,而Cu、Ni促进了柠檬酸碱性条件下的吸附.结合红外光谱图发现,重金属-柠檬酸-针铁矿主要存在以下2种三元体系形态,即以柠檬酸为"桥键"的≡Fe2CitMe形态和以重金属为"桥键"的(≡FeOH)2MeCit形态.采用电荷分配-多位点表面配合(CD-MUSIC)模型成功预测了的三元体系重金属及柠檬酸在针铁矿表面的吸附行为,模型结果发现柠檬酸的存在显著改变了重金属的吸附形态,其中≡Fe2CitMe为Cd、Pb、Ni三元体系中酸性条件下的主要形态,(≡FeOH)2CuCit为Cu的主要形态.研究补充完善了根际环境的土壤形态模型数据库,为预测重金属的溶出及生物有效性的模型研究提供了基础数据.     

Effects of organic matter on the specific adsorption of heavy metals by soil

The adsorption of heavy metals on soil from the Neihu Landfill Site in Taipei City was investigated in order to assess the groundwater pollution problems. The effects of soil organic matter and the behaviors of organic complexing ligands like EDTA and humic acid to the overall adsorption process were studied and discussed. For explaining the results, the pH value of soil system and the properties of the soil/aqueous interface were chosen as two significant and interacted factors for discussion. The concept of the specific adsorption mechanism was also demonstrated and discussed. The results showed that the complexing ligands existing in soil liquid phase have more influences than natural organic matter does. The competitive sequences of different organic matter contents indicated that organic functional sites preferentially bind with Cu and Cd. The presence of EDTA and humic acid which formed ligandlike complexes will reduce Cd adsorption efficiency. These effects will induce mobility and the fate of heavy metals in soils, such as bioavailability.     

Chloroacetic acids in environmental processes

The fate of chloroacetic acids (CAA) in forest soils was studied using radio-indicator methods. We showed that chloroacetic acids are both microbially degraded and simultaneously formed by chloroperoxidase-mediated chlorination of acetic and humic acids. The degree of biodegradation of chloroacetic acids in soil depends on their concentration. Dichloroacetic acid (DCA) is degraded faster than trichloroacetic acid (TCA). Chlorination of acetic acid led to a fast formation of dichloroacetic acid, whereas chlorination of humic acids gave rise to trichloroacetic acid. Both processes lead to a steady state in soil, participate in the chlorine cycle and possibly also in decomposition of organic matter in forest ecosystems.     

The determination of fluoride in water in the presence of organic acids and iron using a fluoride-selective electrode

Surface waters in Scotland, notably from upland catchment areas, are commonly enriched in iron and organic acids. This study investigated the impact of these species on the direct potentiometric determination of fluoride using a fluoride-selective electrode. As the electrode technique is commonly used to monitor the fluoride content of potable waters, it is important that these effects are evaluated if such waters are to be fluoridated. The determination method used was that defined by Nicholson (1983) and Nicholson and Duff (1981) to minimise errors. This employs the TISAB III-TAC buffer system with the following composition (in 1L): 58.0 g sodium chloride, 57.0 mL glacial acetic acid, 4.0 g CDTA, 243.0 g tri-ammonium citrate adjusted to pH 5.4 with 10 M sodium hydroxide. Experimental solutions of fluoride with organic acid or iron were prepared, and the effect on fluoride concentration determined for each combination. Concentrations used: fluoride: 0.1, 1.0 mg L⁻¹; humic acid: 5, 10, 100, 1000, 10,000 mg L⁻¹; oxalic acid: 5, 10, 100, 1000, 10,000 mg L⁻¹; iron(III): 1, 10, 100, 500 mg L⁻¹; Humic acid (HA) concentrations had no impact on the determination of fluoride at the 1.0 mg L⁻¹ level. However, with 0.1 mg L⁻¹; F⁻, an increase in the apparent fluoride concentration was observed when HA > 1,000 mg L⁻¹; this increased with increasing HA content to a maximum of ∼600%. Oxalic acid (OA) generally had no impact on the fluoride determinations at the 1.0 mg L⁻¹; level, but at an OA concentration of 10,000 mg L⁻¹; fluoride concentrations were reduced by ∼50%. At 0.1 mg L⁻¹ F⁻, increasing OA concentrations produce a steady increase in the fluoride concentration of up to 200% with 1,000 mg L⁻¹; OA, greater OA contents produce a fall in the fluoride content. Iron had no effect on the fluoride determinations at both the 0.1 and 1.0 mg L⁻¹ levels. The causes of the apparent increases in fluoride concentration have not been determined, although fluoride contamination by the reagents has been ruled-out. However, the results demonstrate that the defined method and buffer system is suitable for the determination of fluoride in the presence of iron and organic acids at naturally occurring levels, and that fluoride will not be masked from detection.     

Strong adsorption of DNA molecules on humic acids

Analysing soil microbial communities is often hampered by DNA adsorption on soil organic compounds such as humic acids. However the role of humic acids in DNA adsorption and stability in soils remains controversial. To characterize DNA–humic acid interactions, we studied DNA adsorption on two commercially available humic acids and a soil humic acid extracted from an Andosol. Desorption of the adsorbed DNA using 4 different solutions—distilled water, 0.1 M NaCl, 0.1 M sodium phosphate buffer (pH 6.0), and 1% sodium dodecyl sulfate solution—was also studied to understand the mechanism of DNA adsorption on humic acids. Here, we show that humic acids play an important role in DNA adsorption to soils. DNA molecules were adsorbed on the humic acids, with adsorption increasing proportionally with the DNA concentrations in the solution. The adsorption on all humic acid samples was fitted with Freundlich equation, and the parameters obtained from the equation indicated a high affinity between the humic acids and DNA molecules. The total amount of DNA desorbed by the 4 solutions was less than 2% of the total DNA adsorbed on all the humic acids. The results demonstrate that DNA molecules are able to bind strongly to humic acids by ligand binding, hydrophobic interaction, aggregation, or precipitation.