有机污染物污染土壤的植物修复

综述了植物修复土壤有机污染物污染的机理及应用等的研究进展状况，提出了未来植物修复的研究重点。     

六种有机污染物对土壤微生物的影响

为排除实验误差的干扰，得出较为可靠的分析，本文用数理统计中“方差分析”方法研究了苯乙烯、间-二氯苯、邻-二氯苯、氯苯、邻苯二甲酸二丁酯、十六烷等六种有机污染物对自行分离鉴定的褐球固氮细菌（Azotobacter chroococcum）、纤维单胞菌（ Cellulomonas sp.)以及土壤中放线菌、霉菌、酵母菌的影响。结果表明，邻苯二甲酸二丁酯在10ppm、50ppm 两种浓度均使纤维单胞菌无一存活，其它五种污染物在两种受试浓度对土壤微生物效应各不相同。有的无显著影响，有的刺激土壤中霉菌，有的使酵母菌数量增加，有的则有一定的抑制作用。     

有机修饰塿土对苯胺的吸附

以十六烷基三甲基溴化铵(CTMAB)单一修饰和CTMAB+十二烷基磺酸钠(SDS)混合修饰塿土耕层和粘化层土样,从吸附实验和热力学角度研究修饰土样对苯胺的吸附特征和机理。结果表明,供试土样对苯胺吸附均呈现100CB>50CB>120CS>CK的高低顺序,耕层修饰后对苯胺的平衡吸附量增大了4.5￣8.57倍,粘化层土样增大了6.0￣18.33倍;温度为40℃时耕层未修饰土样对苯胺的吸附量高于粘化层未修饰土样,20℃时则低于粘化层原土土样,而修饰土样则均呈现粘化层修饰土样对苯胺的吸附高于塿土耕层修饰土样的结果;耕层土样随温度升高苯胺平衡吸附量升高,而粘化层土样则表现出降温有利于苯胺吸附的现象,修饰剂对土样的修饰对苯胺的吸附具有"感温钝化"效应;Henry模型适用于描述苯胺的吸附;修饰土样对苯胺的吸附自由能变均为ΔG<0,属于自发反应,粘化层各土样对苯胺吸附为放热熵减过程,吸附自发性由焓减控制,耕层各土样对苯胺吸附为吸热熵增过程,其吸附自发过程为熵增控制过程;疏水吸附是修饰土样对苯胺吸附的主要机理,但修饰剂对于土壤表面的修饰是不均匀修饰,粘化层土样以物理吸附机制为主,耕层土样则存在化学吸附的机制。     

挥发性有机污染物在土壤中的运移机制与模型

挥发性有机污染物在土壤多孔介质中有三种可能的存在状态：溶于水中、挥发为气体及吸附于固体颗粒。挥发性有机污染物在水、气、固体颗粒三相间的物质交换与分配是决定其运移的重要因素，在相间物质交换为平衡的条件下，可用阻滞系数来表示其影响，污染物与土壤固体颗粒间的非平衡吸附解吸是相间交换中影响污染物运移的最重要的机制，由于天然土壤具有固有的不均质性，必须用多个反应系数才能准确描述污染物与固体颗粒间的非平衡吸附解吸。     

苯胺在有机修饰黏化层塿土中的吸附动力学

以不同比例十六烷基三甲基溴化铵单一修饰(CB)和十六烷基三甲基溴化铵+十二烷基磺酸钠混合修饰(CB+SDS,简称CS)(土娄)土黏化层土样,采用批处理法通过不同的速度参数研究了修饰土样对苯胺的吸附动力学特征。结果表明,有机修饰能够显著加快土黏化层土样对苯胺的吸附速度、温度的升高可使起始吸附速度加快,但对其他各项速度参数影响不显著;苯胺吸附速度随添加浓度的增大而增大;在20℃和40℃下,总吸附速度Vt、起始吸附速度V0.5、快速吸附速度Vf在低苯胺添加浓度下,总体上不同比例修饰土样对苯胺的吸附速度差异均不显著,而在高苯胺添加浓度下,在5%显著性水平上均具有CB100%修饰土(100CB)>CB50%比例修饰土(50CB)≈CB100%+SDS20%修饰土(120CS)>原土(CK)的高低顺序;苯胺的吸附反应呈现快速反应和慢速反应两个阶段,总吸附反应以快速吸附反应为主,修饰土样快速反应和慢速反应的转折时间(tc)均在3h以内;修饰土样中有机相对苯胺的疏水分配吸附是快速吸附的主要机制,具有吸附质浓度驱动的特征;慢速吸附主要发生在未被修饰的原始土样表面,机制比较复杂。     

植物修复技术及其在环境保护中的应用

阐述了植物修复技术的含义,即利用植物去修复和消除有机毒物和无机毒物引起的土壤环境污染,介绍了对有机污染物修复的方法：（１）根收获,（２）叶表挥发,（３）植物降解;对无机污染物修复的方法;（１）收获生物量或将污染物进行生物挥发从而将污染物将出土体,（２）将污染物转变成为无生物活性的形态收获生物量对于回收某些贵重金属是很有价值的。基因工程技术以及农业技术的综合运用可以更好地促进植物修复的效果。     

两种土壤中邻苯二胺对铜离子吸附—解吸平衡影响的研究

采用室内测试方法，研究了低浓度的外源铜离子在两种不同性质土壤中的吸附、解吸过程及其受邻苯二胺的影响。结果发现，外源铜离子在红壤中的吸附随pH的变化明显变化，而在黑土中的吸附则随pH变化改变较小，吸附在红壤中的铜较吸附在黑土中的铜更易于解吸，有机物邻苯二胺对铜在两种土壤中的吸附和解吸过程产生了明显影响。酸性条件下邻苯二胺的存在增加了红壤对铜的吸附量，但同时也增加了铜的解吸百分数。而邻苯二胺基本不改变铜在黑土中的表观吸附量，但显著影响铜的解吸百分数。     

微塑料对典型污染物吸附解吸的研究进展

近些年来,环境中的微塑料污染引起了全世界的广泛关注。微塑料具有比表面积大、吸附力强等特点,其易与环境中的典型污染物(如有机污染物和重金属)相互作用,改变这些污染物的环境行为。明确微塑料对有机污染物和重金属的吸附解吸作用过程和机制,对于明确有机污染物和重金属的环境行为及毒性效应的相应变化具有重要的意义。本文系统综述了微塑料对有机污染物和重金属吸附解吸作用的研究进展,着重从微塑料性质(类型、形貌特征、表面官能团、极性、吸附位点、结晶度、老化程度)、污染物性质(表面官能团、疏水性、极性、浓度、形态等)以及环境因素(温度、pH、盐度、离子强度、表面活性剂、微生物膜)3个方面,系统分析了微塑料对典型污染物吸附解吸的作用过程和机理。微塑料对有机污染物和重金属的吸附解吸主要受表面吸附、孔隙填充、络合作用以及疏水作用等的影响。微塑料对污染物的吸附动力学绝大部分符合动力学(准)二级模型,部分符合一级动力学;吸附等温线基本符合Frendlich模型、Langmuir模型和Henry模型,部分符合线性模型和复合模型。未来应加强微塑料对一些新型污染物吸附解吸方面的研究工作,进一步明确微塑料与典型污染物之间相互作用的过程和机理,并建立相关的数据库和模型。希望为后续的微塑料吸附解吸典型污染物的相关研究提供借鉴与参考,也为科学地认识微塑料的环境行为提供依据。     

生物质炭对有机污染物的吸附及机理研究进展

生物质炭是一种利用废弃生物质材料在缺氧或厌氧环境中热化学转换制备的多孔级富碳固体材料。因其吸附能力强,制备原料来源广泛,生产成本低且环境友好等优点受到学术界越来越多的关注。探究生物质炭对有机污染物的吸附机理和规律,对于评估其环境行为和应用价值至关重要。着重综述了目前研究报道的生物质炭吸附有机污染物的吸附机理,包括分配作用、表面吸附作用和孔隙截留等。一般低温生物质炭对非极性有机物的吸附机制以分配作用为主,这种非竞争性吸附机理可以解释高浓度有机污染物在生物质炭上的吸附过程。表面吸附是一种非线性竞争性吸附作用,是有机污染物在生物质炭表面有效吸附位点上形成静电作用或通过氢键、离子建、π-π相互作用等结合的过程。孔隙截留是另一种生物质炭固定有机污染物的微观机制,有机污染物在孔隙内部的分配和吸附也是生物质炭吸附能力的重要体现。而在实际复杂的污染环境中,各类生物质炭对有机污染物的吸附过程需要多种机制共同解释。此外,本文对吸附机制的影响因素进行了分析和总结,生物质炭自身理化特性决定了其应用价值,生物质炭的性质与有机污染物的极性、芳香性和分子大小等相匹配才能更好地实现吸附固定,不同的吸附环境如吸附介质、p H和共存离子等也会对吸附机制和吸附效果产生影响。最后,文章进一步探讨了生物质炭吸附有机污染相关研究未来应着重解决的问题,以及生物质炭在有机污染土壤修复中的应用前景。     

Sorption isotherms for predicting potassium requirements of some Iowa soils

Abstract

The sorption isotherm technique was used in predicting potassium requirements of some Iowa soils for growing tomatoes, potatoes, celery and beans. Based on previous comparisons, all of these soils would require additional amounts of K for optimum yields of celery, potatoes, tomatoes and beans. According to Woodruff's energy of exchange concept of K availability, all the soils used in this study are potassium deficient. Amounts of K needed to maintain a specific level of K in sorption equilibrium solution appeared to be largely a function of physicochemical characteristics of the soil. Predicted K requirements of these soils for optimum yields of these crops are reported.     

pH对土壤重金属吸附动力学的影响

The pH effect on the sorption kinetics of heavy metals in soils was studied using a constant flow leaching method. The soil samples were red soil collected from Yingtan, Jiangxi, and yellow-brown soil from Nanjing, Jiangsu. The heavy metals tested were zinc and cadmium. Assuming that the experimental data fitted to the following kinetic rate equation: 1/c·dx/dt = kx_∞-kx, the rate constant k of sorption could be determined from the slope of the straight line by plotting of 1/c·dx/dt vs. x. The results showed that the pH effect on the rate constants of heavy mental sorption in soils was very significant. The values of k decreased with increasing pH. The sorptions were more sensitive to pH in red soil than in yellow-brown soil.     

海泡石对典型水稻土镉吸附能力的影响

通过吸附解吸实验研究了添加海泡石后典型水稻土对Cd的吸附解吸特性及其对吸附溶液pH值变化的响应。结果表明,Freundlich方程可以较好地拟合红黄泥、黄泥田和红沙泥3种典型水稻土对Cd的等温吸附过程（R2〉0.962）。在溶液初始Cd浓度相同的情况下,添加海泡石可使3种水稻土对Cd的吸附量增加20%以上,增强土壤对Cd的吸附强度,有效降低吸附Cd的解吸率,其效果随海泡石添加量的增大而增强。3种水稻土吸附Cd的解吸率均高于70%,而且都随吸附量的增加而上升。溶液的pH值是影响土壤吸附Cd的一个重要因素,在低pH值的条件下（pH〈4）,随着溶液pH值的降低,土壤对Cd的吸附量迅速降低,当溶液pH值高于5时,pH值的变化对吸附量的影响较小。在溶液初始pH值2-8范围内,添加海泡石均能有效提高3种水稻土对Cd的吸附能力。     

Evaluation of relationship between dispersibility of soils and charge characteristics using a modified ion adsorption method; An example of soils from Wakayama Prefecture,Japan

The relationship between the charge characteristics and the dispersibility of soils from reclaimed land (highly dispersive) and adjacent forest area (physically stable) was investigated.

To evaluate the amount of soil charges quantitatively, the measurement based on cation and anion adsorption (ion adsorption method) was attempted in two ways, where special attention was paid to the solution concentration. In the conventional ion adsorption method, the treatments with concentrated solutions (1 mol L^-1) were included in the process. In the modified method, soils were treated with dilute solutions (5 mmol L^-1), in taking account of the soil solution concentration in humid temperate regions. The amount of charges derived from the modified method was smaller than that from the conventional one, especially in the high pH zone. In a preliminary experiment, the extraction of polyvalent cations from soils was found to be significantly affected by the salt concentration. Thus, the use of solutions with an excessively high concentration was considered to result in an error in the estimation of the active charges in soils which would contribute to the dispersion behavior in the field.

The applicability of the modified method for analyzing the dispersion behavior of soils was evaluated by relating the dispersibility of silts and clays at different pHs with the charge characteristics determined under the same ionic strength. The dispersion ratio of silts of the reclaimed land reached maximum values at pH 5.5, above which the ratio decreased, whereas the ratio of clays began to increase in the pH range above 6. The dispersion ratio of silts of the forest area increased in the pH range above 6, whereas that of clays remained constant at a low level in all the pH ranges below 7. The changes in the dispersibility of silt plus clay fractions corresponded to total charge characteristics determined by the modified method. Thus, the evaluation of soil charges by the modified ion adsorption method was considered to be effective to predict soil dispersibility under field conditions, indicating that it could replace electrokinetic analyses such as electrophoresis in studies on the dispersion/flocculation behavior of soils.     

Competitivity,selectivity, and heavy metals-induced alkaline cation displacement in soils

Abstract

The simultaneous incorporation of heavy metals into the soil is still a matter of great concern. Interaction (competitive sorption) between these metals and the soil solid phase may result in a deterioration of soil quality which relies basically on amounts of alkaline cations saturating soils sorptive complex. Results of this study indicate that Pb, Cu, C d, and Zn have induced solution pH decreases which were more intensive at highest metal loading rates. Partition parameters (Kd)-based sequences showed that Pb and Cu were more competitive than Cd and Zn and the overall selectivity sequence followed: Pb > Cu > Cd > Zn. Metal loadings and their competitive sorption have led to a strengthened displacement of alkaline cations (i.e. Ca²⁺, Mg²⁺, K⁺, Na⁺), especially of Ca²⁺ as a factor “stabilizing” soil sorptive complex. Such metals impact jointly with soils acidification are of great environmental concern since tremendous amounts of alkaline cations (especially Ca²⁺) may be potentially leached out, irrespective of the degree of soil contamination, as evidenced in the current study. High and positive ΔG values implied that the studied soils were characterized by generally low concentrations of exchangeable potassium which required high energy to get displaced (desorbed). Further studies on heavy metal uncontaminated or contaminated areas should be undertaken to provide with data which should be used for predictions on changes related to soil buffering capacity as impacted by heavy metal inputs.     

Insight into modified biochars and their immobilizing effects on heavy metal(loid)s in contaminated soils: Mechanisms and influencing factors

Soil contamination by heavy metal(loid)s is a considerable environmental concern, and immobilization is a promising way to reduce toxicity. In recent years, modified/engineered biochars have gained enormous attention for their use in soil remediation, and various studies have reported notable results from their application and their ability to immobilize heavy metal(loid)s. In this review, a summary of publications on the utilization of modified biochars is presented to address the heavy metal(l...     

Immobilization of heavy metals in soils amended by nanoparticulate zeolitic tuff: Sorption‐desorption of cadmium

Immobilization of Cd in contaminated soil is a technique to improve soil quality. Zeolites are potentially useful additives to bind heavy metals. This study examines the influence of decreasing the grain size of raw zeolitic tuff to the nano‐range on Cd sorption‐desorption isotherms in a sandy soil. The aim was to evaluate the feasibility of using nanoparticulate zeolitic tuff as a sequestering agent for Cd in soil. Sorption and desorption of Cd on zeolitic nanotuff was investigated in batch experiments. The sandy soil was amended with zeolitic nanotuff, synthetic Al oxide nanoparticles, or raw zeolitic tuff. After a 48 h sorption step, three desorption steps were induced using the sequential dilution method. The measured sorption‐desorption data were adequately described by the Freundlich equation. A nonlinear two‐stage one‐rate model matched well with measured Cd sorption‐desorption isotherms of zeolitic nanotuff, raw zeolitic tuff, Al oxide nanoparticle, and control soil. The batch experiments demonstrated the strong influence of pH on Cd sorption. Zeta‐potential measurements of zeolitic nanotuff indicated that electrostatic interaction was important for sorption. Soil amended with zeolitic nanotuff showed the lowest hysteresis index based on the differences obtained from sorption‐desorption isotherms regarding the amount of Cd sorbed. The index decreased with increasing metal concentration. For soil amended with nanoparticulate zeolitic tuff, the estimated Freundlich coefficient was 4 orders of magnitude higher than in the control soil and 2 orders of magnitude higher than the soil amended with raw zeolitic tuff. In addition, this sorbent decreased the amount of Cd released after three desorption steps by up to 12 and 7 times compared to the control soil and the soil amended with raw zeolitic tuff, respectively. The effect on Cd sorption of grinding the raw zeolitic tuff to the nanorange was considerably more pronounced than the effect of raw zeolitic tuff.     

复合污染土壤上几种叶类蔬菜对Cd和As的富集效应

[目的]不同蔬菜镉、砷富集系数各异,对镉和砷污染土壤的响应也不同。研究复合污染土壤上不同叶类蔬菜对Cd和As的积累效应,为轻度中度Cd和As污染土壤的合理与安全利用提供适宜的蔬菜种类。[方法]采集了西安市12个污染程度不同的菜地耕层土壤,于2015年3月6日5月26日在西北农林科技大学资源环境学院遮雨大棚内进行了盆栽试验。供试7种叶菜,包括菠菜、油菜、生菜、油麦菜、苋菜、空心菜和茼蒿。蔬菜收获后,测量了蔬菜产量、Cd和As含量与吸收累积量,计算了蔬菜对Cd和As的富集系数等,并用线性回归模型研究了不同蔬菜栽培的土壤Cd和As安全临界值。[结果]镉污染土壤(0.6~2.4 mg/kg)对大多数蔬菜生物量有抑制效应,中、低浓度镉砷复合污染(Cd 1.0~2.4 mg/kg,As 24.9~26.8 mg/kg)对供试蔬菜生长没有叠加效应。镉污染土壤上,菠菜、油菜、苋菜叶、生菜可食部Cd含量均超出食品安全限量标准(0.2 mg/kg),其中菠菜和油菜Cd最高超标4倍以上;而茼蒿和空心菜茎秆Cd未超标。虽然供试蔬菜砷含量随着土壤砷含量增加有升高趋势,但叶菜As含量没有超标。7种蔬菜Cd富集系数为0.083~0.491,高低顺序为油菜、菠菜、生菜和苋菜叶>油麦菜、苋菜茎和空心菜叶>空心菜茎和茼蒿。菠菜、油菜、生菜、油麦菜、苋菜、空心菜和茼蒿土壤Cd安全临界值分别为0.33、0.38、0.46、1.15、0.59~1.79、1.49~8.16和8.98~17.11 mg/kg,其中菠菜、油菜和生菜阈值与现行标准(0.3~0.6 mg/kg)相当,而油麦菜、苋菜、空心菜和茼蒿均大于土壤重金属污染限量值。As富集系数为0.002~0.006,空心菜叶和茼蒿叶片As富集系数显著高于其他蔬菜。7种蔬菜的土壤As临界阈值分别为62.31、70.35、70.21、67.41、67.86~90.43、57.21~75.70和72.43~105.06 mg/kg,均高于现行标准(25 mg/kg)。[结论]中等程度的Cd和As复合污染土壤上,Cd对蔬菜的生长有显著的抑制,As与Cd没有叠加作用。不同蔬菜的产量、污染程度和安全阈值等有显著差异,因此选择低富集、抗污染蔬菜品种是利用中低重金属污染土壤的一条可行途径。空心菜和茼蒿对Cd富集系数低,可推荐在中、低污染土壤上种植。     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.