蒙山茶园土壤组分对铝吸附解吸热力学特征的影响

采用间歇法和振荡平衡法,通过实验室模拟,研究了蒙山茶园土壤(紫色土和黄壤)原土及各粒级组分对铝吸附解吸的热力学特征,并分析土壤有机质、游离氧化铁和CEC对其吸附解吸的影响。结果表明:(1)不同土壤原土及各粒级组分对铝的吸附量都随铝离子浓度的增大而增加,且各粒级土壤对铝的吸附量不同,表现为土壤颗粒比表面越大,有机质、游离氧化铁和CEC越高,其吸附量越大。紫色土原土及各粒级组分对铝的等温吸附过程用Freundlich方程描述最佳,说明紫色土对铝的吸附是多层吸附;而黄壤原土及各粒级组分对铝的等温吸附过程则用Langmuir方程描述最佳,说明黄壤对铝的吸附以单层吸附为主。(2)紫色土原土及各粒级组分对铝的解吸率表现出以下关系:粗砂粒原土细砂粒粉粒粘粒,黄壤原土及各粒级组分对铝的解吸率则表现出以下关系:细砂粒粗砂粒原土粉粒粘粒,两者解吸率的大小关系均与其有机质及游离氧化铁相反,表明两种土壤的原土及各粒级组分中有机质和游离氧化铁越高,其专性吸附率就越高,从而解吸率越小,说明土壤有机质和游离氧化铁影响土壤对铝的固持能力。(3)土壤最大吸附量与有机质、游离氧化铁含量和CEC都表现出显著或极显著的正相关关系,而其最大解吸率也均与有机质、游离氧化铁含量和CEC表现出显著或极显著的负相关关系。     

活化过硫酸钠氧化土壤对挥发性有机污染物吸附特性的影响

活化过硫酸钠(Sodium persulfate,SPS)氧化技术是一种新型的土壤修复技术。为了更科学地评价化学氧化处理后土壤的环境风险,本文通过亚铁离子活化过硫酸钠法对有机质(Organic matter,OM)含量存在显著差别的两种土壤进行氧化处理,比较了活化过硫酸钠氧化前后两种土壤样品对3种挥发性有机污染物的吸附特性。结果表明,亚铁活化的SPS能够氧化土壤中腐殖酸和胡敏素类的有机质。对OM含量较高的1号土,SPS氧化对有机质的去除率为71.9%。而对OM含量较低的2号土,SPS氧化对有机质的去除率为49.9%。1号土样对3种挥发性有机物的吸附以分配作用为主,氧化后的1号土样对3种物质的吸附机制不变,但吸附量有所增加;2号土样对3种挥发性有机污染物的吸附有一定的非线性,而氧化后的2号土样对3种物质的吸附线性特征增强。吸附数据用对数形式的Freundlich方程拟合得到分配系数lg Kf值,比较有机碳标化后的分配系数lg Kfoc,氧化后的土壤有机质对3种挥发性有机污染物的吸附特性有所提高。分析表明,SPS氧化了有机质中较多的极性组分(如羧基及羟基等),从而使处理后的土壤中有机质的非极性增强,强化了对非极性化合物的吸附。     

名山河流域黄壤组分对微团聚体吸附解吸镉的影响

选取名山河流域4种土地利用方式（林地、水田、茶园、旱地）的黄壤为研究对象,采用平衡液等温吸附法和NH4OAC、EDTA溶液解吸法,研究土壤组分（有机质、游离氧化铁）对微团聚体吸附解吸Cd2＋的影响。结果表明：去除土壤组分前后,原土及各粒径微团聚体对Cd2＋的吸附量均随Cd2＋初始浓度增大而增大,吸附量均按以下次序递减：（〈0.002mm）〉2～0.25mm〉原土〉0.053～0.002mm〉0.25～0.053mm,与有机质、游离氧化铁、CEC呈极显著正相关。吸附减少量大小关系为：去除有机质〉去除游离氧化铁,有机质的贡献率大于游离氧化铁。Freundlich方程拟合效果最佳,达到极显著水平,分布系数Kd值与Cd2＋初始浓度呈曲线负相关。NH4OAC解吸率随原吸附Cd2＋初始浓度增大而增大,以最大解吸率计,递减规律为：0.25～0.053mm〉0.053～0.002mm〉原土〉2～0.25mm〉（〈0.002mm）;EDTA解吸率随原吸附Cd2＋初始浓度增大而减小,递减规律与NH4OAC解吸率相反。去除土壤组分后,NH4OAC解吸率上升,EDTA解吸率下降,茶园与旱地黄壤非解吸率减小,林地与水田黄壤非解吸率增大。去除土壤组分后,非专性吸附与吸附总量呈极显著正相关,专性吸附与吸附总量呈极显著负相关。     

柠檬酸对蒙山茶园土壤微团聚体吸附-解吸Cu2+的影响

以蒙山茶园土为对象,运用平衡液吸附法以及NaNO3溶液解吸法探讨了柠檬酸对原土及各粒径土壤微团聚体吸附-解吸Cu2+的特性,以期明确柠檬酸对土壤吸附解吸铜的过程中产生的影响。结果表明,加入柠檬酸后,随着Cu2+浓度的增加,原土和各粒径土壤微团聚体对Cu2+的吸附有所增加,吸附量大小顺序为:(0.002mm)(0.053~0.002)mm原土(2~0.25)mm(0.25~0.053)mm,与土壤微团聚体中游离氧化铁、阳离子交换量以及有机质含量大小顺序一致;柠檬酸对Cu2+的吸附既有促进作用又有抑制作用,低浓度(0~1mmol/L)的柠檬酸促进土壤微团聚体对Cu2+的吸附,而高浓度(1mmol/L)的柠檬酸则降低其吸附,吸附量在柠檬酸浓度为0.5mmol/L时达到最大;Langmuir、Freundlich、Temkin 3种方程对其等温吸附过程的拟合均达到了极显著水平(p0.01),其中以Langmuir方程的拟合效果最佳,说明加入柠檬酸后的原土及各粒径土壤微团聚体对Cu2+的吸附以单层吸附为主;随着铜浓度的上升,土壤微团聚体对Cu2+的易解吸率不断增加,柠檬酸的进一步加入使得土壤微团聚体对Cu2+的解吸率上升,而解吸大小顺序与吸附顺序相反。     

名山县蒙山茶园土壤各粒级组分对K~+吸附-解吸特征的影响

以名山县蒙山茶园紫色土为对象,用物理方法将蒙山茶园紫色土分成粒径大小不同的土壤组分(≤0.002mm,0.02～0.002mm,0.2～0.02mm,2～0.2mm),分别通过动力学和热力学方法研究它们对K+的吸附-解吸行为。结果表明:紫色土不同粒级组分对K+的吸附量表现为小于0.002mm>0.02～0.002mm>原土>0.2～0.02mm>2～0.2mm,而解吸量则呈相反的规律。用Elovich方程、双常数方程、抛物线扩散方程及一级扩散方程分别对K+的吸附-解吸动力学数据进行拟合,并用Langmuir、Freundlich和Temkin热力学方程对等温吸附过程进行拟合。原土及各粒级组分K+的吸附量均随K+初始浓度的增大而增大,但各粒级组分吸附量大小关系各不相同,K+均向最小粒径富集。运用动力学方法,原土和各粒径组分对K+的吸附特性均用Elovich吸附方程拟合最佳,原土和各粒级组分对K+的解吸特性均用Elovich解吸方程拟合效果最佳。运用热力学方法,原土和土壤各粒级组分以及分别去除有机质和游离氧化铁后对K+的吸附特性均用Freundlich吸附方程拟合效果最佳,原土和土壤各粒级组分以及分别去除有机质和游离氧化铁后对K+的解吸特性均用Freundlich吸附方程拟合效果最佳。     

吐温类表面活性剂在黑龙江黑土中的吸附特性研究

采用平衡振荡法,研究黑龙江黑土对吐温类非离子表面活性剂(Tween20、Tween40、Tween60和Tween80)的吸附特征及影响因素。结果表明,在试验浓度范围内,吐温类表面活性剂在黑土上的吸附随着平衡质量浓度的增加而增加;各表面活性剂的吸附等温线均呈"S"型,可用Freundlich吸附模型来描述;在同一平衡质量浓度下,Tween20和Tween40在黑土中的吸附量高于Tween60和Tween80的吸附量;有机质含量高的土壤S1对表面活性剂吸附能力高于有机质含量低的土壤S2。通过H2O2氧化去除黑土中的有机质后,对表面活性剂的吸附量与原土相比变化不大,表明土壤矿物质和有机质都是吸附表面活性剂的重要成分。黑土对Tween80的吸附量随着温度的增加而增加,但随着体系pH值的增加而呈现逐渐下降的趋势。     

有机质含量对石灰性黄潮土和砂姜黑土磷吸附–解吸特性的影响

通过往土壤中添加不同量小麦秸秆,经好气培养1年后,获得不同有机质含量梯度的系列土壤,研究有机质含量对石灰性黄潮土和砂姜黑土磷（P）相关吸附参数和不同水土比下解吸溶液P浓度的影响。结果表明,Langmuir方程能够较好地拟合不同有机质含量的两种土壤对P的等温吸附曲线,拟合度均达到显著（P 0.05）或极显著（P 0.01）水平。黄潮土和砂姜黑土P最大吸附量（Xm）、吸附结合能常数（K）、最大缓冲容量（MBC）、吸附饱和度（DPS）及相同水土比下P解吸溶液浓度与有机碳含量间均呈显著或极显著的二次抛物线关系。抛物线拐点之前,随有机质含量的提高,P的吸附能力增强,解吸能力降低;拐点之后,吸附能力降低,解吸能力增强。各水土比条件下,P解吸溶液浓度与Xm、K、MBC呈显著或极显著负相关,与DPS呈显著或极显著正相关。随有机质含量的提高,土壤P植物有效性和P流失风险呈先降低后增强的抛物线趋势;土壤供P缓冲能力则先增强后降低。砂姜黑土Xm、K、MBC均明显高于黄潮土,DPS明显低于黄潮土;且其抛物线拐点滞后,拐点横坐标有机碳含量明显高于黄潮土。不同有机质含量的解吸曲线较黄潮土排列紧密;砂姜黑土黏粒含量、碳酸钙含量明显高于黄潮土,全P和Olsen-P含量明显低于黄潮土,这可能是影响两种石灰性土壤P吸附–解吸特性差别的主要原因。     

土壤中黑碳对农药敌草隆的吸附-解吸迟滞行为研究

采用批处理振荡法和连续稀释法分别测定了敌草隆在人工添加黑碳土壤和自然形成的不同有机质和黑碳含量的土壤中的吸附一解吸行为。吸附结果表明，人工添加黑碳的土壤对敌草隆的吸附强度和吸附容量以及吸附等温线的非线性均随土壤黑碳添加浓度的增加而逐步增大；自然土壤的吸附容量和吸附强度随土壤总有机质含量增加而增加，但吸附等温线的非线性则与土壤中黑碳对有机质的相对含量有关，黑碳比例越高，等温线非线性越大。解吸实验结果表明，无论是人工添加黑碳的土壤还是自然土壤，对敌草隆的解吸迟滞作用均随土壤黑碳含量增高而愈明显。     

老冲积黄壤微团聚体对As(Ⅴ)与P竞争吸附—解吸特性

土壤微团聚体是土壤的最基本结构单元,不同粒径微团聚体的理化性质的差异不同使得重金属离子在各粒径微团聚体中的吸附—解吸能力大小不同。以名山河流域老冲积黄壤为研究对象,将其划分为4个粒径(2~0.25mm,0.25~0.053mm,0.053~0.002mm,0.002mm)。采用批培养法研究原土及不同粒径微团聚体对As(Ⅴ)与P的竞争吸附—解吸特性。结果表明:原土及不同粒径微团聚体对As(Ⅴ)、P的吸附—解吸特性相似,等温吸附均符合Langmuir和Freundlich方程,但Langmuir方程拟合效果最佳;动力学吸附均符合伪一级方程和伪二级方程,但伪二级方程拟合效果更好。原土及各粒径微团聚体对As(Ⅴ)、P的吸附均以专性吸附为主,非专性吸附为辅。原土及不同粒径微团聚体对As(Ⅴ)、P的最大吸附量不仅与粒径大小有关,与土壤有机质、CEC、游离氧化铁含量呈正相关。由于0.002mm粒径的土壤比表面积大,有机质、CEC、游离氧化铁含量高,故其对As(Ⅴ)、P有最大吸附能力和最高初始吸附速率。As(Ⅴ)、P在各粒径微团聚体上解吸量与其吸附量呈指数关系。当As(Ⅴ)与P共存时,明显互相抑制对方的吸附,促进对方的解吸。As(Ⅴ)与P在0.002mm粒径土壤中存在的竞争吸附—解吸能力最小。     

萘和p,p′-DDE在典型包气带介质上的吸附动力学及吸附-解吸特征

选取3种典型包气带土壤为吸附剂,萘和p,p′-DDE为吸附质,研究了其吸附动力学特征及吸附解吸规律。实验结果显示,初始浓度越大,吸附到达平衡所需时间就越短。数据拟合结果表明,单一级次的动力学方程难以描述两种吸附质的吸附动力学特征,分析认为土壤对有机污染物的吸附过程不是单一反应,而是有机污染物在无机矿物、无定型有机碳和凝聚型有机碳上同时进行吸附反应的复合结果。萘与p,p′-DDE的吸附、解吸过程均表现出非线性,Freundlich方程的吸附指数n在不同程度上偏离1;两种污染物在土样中的吸附过程不完全可逆,Kow、初始浓度以及土壤有机碳含量（fo）c的差异都影响其在土壤不同组分上的吸附百分比,进而影响解吸率。萘更多地吸附在无机矿物表面及无定型有机碳上,随着初始浓度的增大（37.7~780.9μg.L-1）,解吸率可从10%左右增至近85%;而当初始浓度为37.7μg.L-1时,随foc的增大（0.01%~0.65%）,解吸率由12.39%降至3.90%。p,p′-DDE则更多地吸附在凝聚型有机碳上,解吸率随浓度的变化（11.0~275.1μg.L-1）仅在1%~5%内波动,当初始浓度为11.0μg.L-1时,解吸率随foc的增大由4.49%降至1.06%。两者解吸率都和foc呈负相关关系。     

Sorption of naphthalene derivatives on to soils from a long-term field experiment: a particle size fractionation and extraction study

The present work investigates the impact of site management on the retention of organic compounds in soil in a long‐term field experiment and focuses on the role of particle size fractions. Specifically, we studied the influence of long‐term farming practices on the soil’s ability to adsorb five hydrophobic organic compounds (HOCs), specifically naphthalene derivatives (naphthalene, 1‐naphthol, 1‐naphthylamine, 1‐hydroxy‐2‐naphthoic acid, 1,4‐naphthoquinone). We examined the sorption on soil and its particle‐size fractions with varying amounts and origins of organic matter in soil amended with farmyard manure and mineral fertilizers over more than 40 years. The soil organic matter had no significant impact on the sorption behaviour of the HOCs. Adsorption on the clay and silt fraction provided a deeper insight into the mechanisms and indicates a strong affinity with adsorption sites of the mineral phase. Naphthalene derivatives with hydrogen atoms in their functional groups adsorbed more strongly than other compounds on to soils containing smaller amounts of organic carbon. Desorption experiments with five organic extractants showed partitioning models for HOCs between extractant and soil surface. Only in experiments with the most polar extractant, formamide, did we observe an influence of the compound’s functional groups on the desorption mechanisms. Column experiments with a HPLC‐system and on‐line UV‐detection proved to be a satisfactory alternative to batch experiments. This approach should enable investigations of adsorption with larger numbers of compounds and soils at the same time.     

Sorption and desorption of selenium in different soils of the mediterranean area

Abstract

The adsorption of selenium (Se) in the selenate form and its desorption by phosphate in four soils with different physiochemical properties were studied in the laboratory. To determine adsorption isotherms for selenate 25 mL of solutions containing 1 to 100 ppm of Se were added to 2.5 g of soil. Desorption isotherms were determined by resuspending the samples in phosphate solution. The selenate sorption process was adequately described by the Freundlich equation. In pine forest and woodland soils, characterized by the highest organic matter content and cation exchange capacity (CEC) values, the isotherms were classified as L type, since the amount of Se sorbed appeared to move towards saturation. The organic matter content played the most important part in the adsorption of Se, while pH appeared to have a small effect on the ability of the soil to adsorb Se. The high CaCO₃ content of the pine forest soil may have contributed in increasing the Se adsorption notwithstanding the high pH value. The cultivated and arable soils showed a reduced sorption capacity. The sorption could be described by an S type curve. At low concentrations of Se the affinity of the solid phase was less than that of the liquid phase. By increasing the concentration of Se in solution, the affinity of the solid phase increased and the sorption was favored. Selenate desorption by water was negligible, whereas the amount of Se desorbed by phosphate varied among the different soils. The desorption experiments indicated that a significant portion of the sorbed Se was irreversibly retained. This suggests the existence of linkages which allow the release of Se in the soil solution only after physico‐chemical variation such as exchange with phosphate ions.     

Response of sorption processes of MCPA to the amount and origin of organic matter in a long-term field experiment

Changes in farming practices over long times can affect the sorption behaviour of MCPA ((4‐chloro‐2‐methylphenoxy)acetic acid). We studied the adsorption–desorption mechanisms of MCPA on soil with varied amounts and origins of soil organic matter obtained from a long‐term field experiment with various organic amendments. The origin of the soil organic matter seems to be crucial for the sorption behaviour of MCPA. Samples of soil amended with sewage sludge sorbed MCPA more strongly than the soil under any other treatment. Peat‐amended soil was second followed by soil receiving animal manure, green manure, mineral fertilizer without N and the fallowed soil. Both the carbon content and the origin of the organic matter are important for the sorption. A decrease of carbon content of a soil does not necessarily imply a reduction of sorption capacity for polar organic acids such as MCPA. Nevertheless, our adsorption–desorption experiments suggest that with decreasing carbon content the role of mineral sorption mechanisms could become more pronounced. Our results showed that interactions of soil organic matter and soil minerals distinctly influence adsorption properties for MCPA.     

Sorption of dissolved organic nitrogen by acid subsoil horizons and individual mineral phases

Dissolved organic matter is important in translocation and export of nutrients from forest ecosystems. Its mobility in soil is restricted by sorption to mineral surfaces which depends on its chemical properties. Carboxyl and hydroxyl groups form strong bondings to mineral surfaces, whereas the role of N‐containing functional groups in the sorption process is less well understood. We examined in laboratory experiments the binding of dissolved organic matter from the forest floor to amorphous Al(OH)₃, goethite, kaolinite, and illite and to subsoils in order to compare the sorption and desorption of dissolved organic C with that of dissolved organic N. The mineral samples were equilibrated with acidic solutions of organic matter at pH 4. In the equilibrium solutions organic C and N and their contribution to two operationally defined fractions, namely the so‐called hydrophilic and hydrophobic fractions, were determined. We measured neutral and acidic amino sugars to discover the nature of the binding of organic N. Within the hydrophilic and hydrophobic fractions, the sorption and desorption of organic C and N did not differ, indicating that there was no preferential binding of N‐containing compounds. The hydrophilic fraction contained more N and sorbed less than the hydrophobic fraction, and so the overall retention of organic N by the mineral phases and subsoils was smaller than that of organic C. Among the amino sugar compounds, muramic acid was preferentially removed from the solution, whereas the neutral amino sugars were sorbed similar to organic C. The results suggest that the sorption of N‐containing compounds is favoured by acidic groups and not by amino groups.     

铬在土壤中的吸附解吸研究进展

对铬在土壤中的吸附解吸研究进行了综述,土壤中铬的吸附解吸机理包括非专性吸附(离子交换吸附)、专性吸附以及物理表面吸附,分别对pH、氧化还原电位、土壤组分(土壤矿物和有机质)、竞争离子以及离子强度等因素对铬吸附解吸的影响作了论述。文章进一步描述了土壤中铬吸附解吸的数学模型Freundlich方程、Langmuir方程、一级动力学模型、金属-腐殖酸模型(one-sitemodel)和表面络合模型-扩散层模型(DLM)等的研究情况,并对今后的研究方向进行了探讨。     

对硝基氯苯在土壤和腐殖酸上的长期吸附与多步解吸的研究

采用批量平衡实验法研究了对硝基氯苯（p-NCB）在土壤和腐殖酸上的长期吸附和多步解吸,比较了连续的多步解吸与一步解吸的差异。结果表明,随着吸附时间的增加吸附量均会有所增加,随吸附时间增加吸附等温线的非线性增强。p-NCB在液相和固相上的初始浓度对吸附速率有一定影响,低浓度比高浓度时达到平衡的速率要低。对于两种受试土壤,两次解吸得到的等温线均无法与吸附等温线重合,表现出很强的吸附不可逆性。而尽管p-NCB在腐殖酸上表现出明显的非线性吸附（n = 0.794）,但4次解吸后所得到的平衡位点与吸附所得的平衡位点基本落在同一条直线上,对数坐标下进行线性拟合的相关系数（R2）可达0.988,说明吸附过程是完全可逆的。     

阿特拉津对绿麦隆吸附-解吸作用的影响

采用批平衡实验,研究绿麦隆在单一及复合污染体系中的吸附-解吸行为。结果表明,无论是单一体系还是复合体系,吸附等温线均可用Freundlich模型进行良好的拟合。随着阿特拉津浓度的增加,土壤对绿麦隆的吸附作用降低,表明绿麦隆和阿特拉津之间存在竞争吸附,这可能与土壤的有机质类型和绿麦隆、阿特拉津的性质、结构有关。解吸实验表明,随着阿特拉津的浓度增加,绿麦隆的解吸作用增加。吸附过程的拟合指数n值大于解吸过程的对应值,即绿麦隆在不同体系中的解吸作用均存在一定的滞后性。应用Freundlich解吸等温线参数对吸附-解吸等温线的滞后作用进行量化,CT、（CT＋0.5AT）、（CT＋1AT）和（CT＋2AT）处理解吸等温线的滞后系数ω分别为165.200,146.132,94.534和85.945,即随阿特拉津浓度增加,绿麦隆解吸等温线的滞后性降低。     

Effect of liming on hexazinone sorption and desorption behavior in various soils

Liming is a practice commonly used to modify soil acidity, neutralize aluminum, and increase calcium and magnesium in the soil. Liming can change herbicide retention processes and consequently weed control and potential environmental contamination. The effects of liming on the sorption and desorption of hexazinone in different soils were evaluated. Samples from seven Brazilian soils were collected and separated into two subsamples, with and without limestone incubation. Hexazinone was quantified using ultra high-performance liquid chromatography. The sorption and desorption coefficients were determined in soils using Freundlich isotherms. Increasing the pH did not alter the sorption kinetics of hexazinone in the same soil class. The shortest sorption time of hexazinone occurred in soils with higher organic matter (OM) and clay content. Liming reduced the sorption and increased the desorption of hexazinone in the soils, which was caused by the increase in pH and reduction of OM content. Although the application of limestone increased desorption, the rate at which this process occurred was less than the sorption rate of hexazinone in most cases. In alkaline soils, the recommended dose of hexazinone for pre-emergence application should be low to avoid leaching and reduce the contamination of groundwater resources.     

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.