Cu^2＋、Zn^2＋复合条件下Cd^2＋在陕西5种土壤中的吸附

通过平衡吸附的方法,研究了Cd2＋在单一及与Cu2＋、Zn2＋复合条件下,在陕西塿土、黄绵土、黑垆土、黄褐土、砂土5种土壤中的吸附特征,并通过多重相关分析探讨了其吸附机制。结果表明,在20、30℃条件下,Cd2＋在各供试土样中吸附等温线总体上呈H或L型等温线形式,黑垆土对Cd2＋总是吸附最强,而砂土的吸附总是最弱;Cd2＋吸附的温度效应呈现升温负效应特征,塿土土样中,Cu2＋的共存对其温度效应影响较大,而在其他4种土样中Zn2＋的共存具有较大影响;Cu2＋、Zn2＋的共存均降低了Cd2＋的吸附量,具有显著的拮抗作用;Freundlich模型是描述Cd2＋吸附等温线最佳模型。相关分析结果表明,Cd2＋在土壤中的吸附主要以电性引力吸附为主,Cu2＋的共存主要和其与土壤有机质之间的络和吸附等化学吸附作用有关,因此其对Cd2＋以化学竞争性吸附的影响相对较弱,而Zn2＋共存吸附与Cd2＋吸附机制类似,因此表现出Zn2＋共存对Cd2＋吸附影响较大的特点。     

草酸对不同土壤中Cd Zn吸附及其交互作用影响的初步研究

研究了草酸对Cd2＋、Zn2＋单一及复合条件下在陕西塿土、黄绵土、黑垆土、黄褐土、砂土5种土壤中的吸附特征,并探讨了草酸的影响机制。结果表明,除在低Zn2＋平衡浓度下,5种土壤中草酸促进了Zn2＋的吸附外,总体上在Cd2＋、Zn2＋单一处理及其复合处理中,草酸降低了土壤对Cd2＋、Zn2＋的吸附。草酸既没有改变塿土、黑垆土吸附能力最强、砂土吸附能力最弱的结果,也没有改变Cd2＋、Zn2＋之间的相互拮抗作用。草酸对Cd2＋、Zn2＋吸附的影响机制主要在于其与Cd2＋、Zn2＋形成络合物。草酸主要通过降低电性引力的方式减弱土壤对Cd2＋的吸附能力,而对于Zn2＋,在低平衡浓度下,草酸对Zn2＋吸附的促进作用来源于在土壤氧化物矿物表面形成少量的三元表面络合物的桥键合效应,在高平衡浓度下,对Zn2＋吸附的抑制作用来源于草酸对土壤有机质化学吸附点位的竞争。对Cd2＋、Zn2＋吸附起决定作用的依然是土壤本身性质。     

胶体存在时不同质地土壤对锌镉的吸附试验研究

以重金属离子Zn和Cd及胶体为对象,通过等温静态批量平衡吸附试验,分析了3种不同质地土壤对Zn、Cd单一吸附和等量竞争吸附特征,胶体对土壤吸附Zn、Cd的影响,并用Langmuir和Freundlich方程对试验结果进行了拟合。结果表明,随着平衡液中Zn2+、Cd2+浓度的增加,土壤对Zn、Cd的吸附量逐渐增大;3种质地土壤对Zn、Cd吸附量顺序为砂壤>粉壤>壤砂土;Zn2+、Cd2+共存时,土壤对这两种离子的吸附量比单一离子存在的情况下明显下降;胶体存在时抑制了土壤对Zn的吸附,促进了土壤对Cd的吸附;就本试验来说,Freundlich方程拟合效果优于Langmuir方程。     

恒电荷土壤胶体对Cu2+ 、Pb2+ 的静电吸附与专性吸附特征

供试土壤胶体对Cu2 、Pb2 的吸附强度用pH50 值表示 ,其大小次序为 :土 >黄绵土、黑垆土 >黄褐土。离子强度实验和表面络合反应机制证明恒电荷土壤胶体对Cu2 、Pb2 的吸附含有专性吸附 ,n值可作为判断专性吸附与静电吸附比例的特征值 ,低pH值时 ,以水解 -络合吸附为主 ;高pH值时 ,以水解 -络合与沉淀吸附为主。静电吸附和专性吸附的比例与pH有关 ,各土壤胶体专性吸附百分数大小为 :黄褐土 >土 >黑垆土 >黄绵土。不同土壤胶体在同一介质中对Cu2 、Pb2 的固有络合常数logKintM 值及固有络合ΔG m 负值大小次序与吸附强度大小一致。在定pH定浓条件下 ,考虑离子之间的相互作用时 ,土壤胶体对重金属离子的吸附过程可用BDM等温式描述。供试土壤胶体对Cu2 、Pb2 专性吸附ΔG m 的大小与固有络合ΔG m 接近且大小次序也一致。     

长链两性修饰土对Cd2＋的吸附动力学

以两性表面修饰剂十八烷基二甲基甜菜碱（BS-18）修饰的塿土土样为研究对象,在Cd2＋单一条件和与苯酚共存的复合条件下,通过不同的速度参数研究了修饰土样对Cd2＋的吸附动力学特征,并对吸附机制进行探讨。结果显示,在20℃和40℃温度下单一、复合两种处理的条件下,不同修饰比例BS-18修饰土样的各速度参数均大于未修饰土样,且总体上均随着修饰比例的增加而增大,表明修饰可以显著加快塿土土样对Cd2＋的吸附速度;吸附反应分为快速反应和慢速反应2个阶段,总反应平均速度Vt由快速吸附反应速度Vf和慢速吸附反应速度Vs共同决定;温度升高,单一处理Cd2＋的总反应平均速度基本不变,复合处理则下降;加入苯酚可以加快Cd2＋的总反应平均速度,40℃时则表现为抑制效应。Cd2＋吸附速度的描述以双常数方程动力学模型为最佳模型,模型参数A、B值可以用来描述吸附速度的大小。     

模拟降雨条件下黄土坡地土壤溶质迁移特征试验研究

土壤质地和溶质性质对土壤溶质地表迁移过程有较大影响.通过室内模拟降雨试验,以杨凌壤土、安塞黄绵土和神木绵砂土为研究对象.研究了土壤NO3-、NH4+、PO43-、K+和Br-的迁移特征.结果表明,塿土的溶质地表流失量均高于黄绵土和绵砂土.尤其是吸附性强的NH4+和PO43-、NO3-与Br-坡面流失以随地表径流流失为主,且主要集中在产流开始的初期阶段.3种土壤处理中径流溶质最高浓度ρmax(mg/L)大小顺序为:ρmax塿土＞ρmax＞黄绵土＞max绵砂土,土壤溶质随入渗水分的迁移能力由大至小依次为:Br-＞NO3-＞K+＞NH4+＞PO43-.塿土等效径流迁移深度EDR最大,黄绵土次之,砂绵土最小,各溶质EDR与溶质垂向迁移能力无明显相关性.     

萘在土壤上的吸附行为及温度影响的研究

采用批量平衡法研究了多环芳烃萘在塿土耕层土、塿土粘化层土、塿土古土壤、黄壤、紫色土和石灰土上的吸附行为,比较了不同吸附模型方程对实验数据的拟合情况,并探讨了温度对萘在土壤上吸附行为的影响机理及吸附热力学特征。Henry模型、Freundlich模型和deBoer-Zwikker极化模型均能较好地拟合萘的吸附等温线;45℃下的吸附等温线明显地高于25℃的吸附等温线,表现出随温度升高吸附量增大的趋势。Freundlich模型的吸附容量参数Kf和deBoer-Zwikker模型的起始吸附势ε0在两个温度下有极显著的差异;但Freundlich模型的n参数表征了土壤颗粒表面的性质,对温度变化不敏感。在25℃条件下,萘在土壤有机碳上的分配可能是吸附的主要机制,但随着温度增加,吸附机制变得复杂。土壤对萘的吸附是一吸热反应,整个吸附体系中熵增是吸附作用进行的主要驱动力。     

柠檬酸对茶园紫色土微团聚体竞争吸附Zn、Cd影响

采用批量培养和平衡吸附法,选取原土及微团聚体颗粒组为对象,研究Zn(II)、Cd(II)单一存在、二元竞争及竞争体系中加入柠檬酸(0.1,1,10mmol/L)等3种处理的等温吸附特性及影响。结果表明:(1)以专性吸附方式为主的多层吸附随Zn~(2+)、Cd~(2+)强度增加逐渐饱和,吸附能力以0.002mm最优、0.05~0.002mm和原土次之,0.25~0.05mm和2~0.25mm结合能力稍差,不同条件下Cd较Zn更易积累。吸附过程为自发吸热反应,热力学Freundlich方程(Zn:R2=0.960~0.997;Cd:R2=0.957~0.995)拟合结果优于Langmiur方程(Zn:R2=0.952~0.995;Cd:R2=0.913~0.991)。最大吸附量与有机质含量具有显著相关性。(2)单一处理Zn、Cd的固持效果明显、共存处理时Zn、Cd竞争行为表现为彼此削弱,Zn对Cd的吸附具有更强抑制作用。(3)添加不同浓度柠檬酸后Zn、Cd吸附水平介于单一及共存处理之间呈动态变化(Zn、Cd接近),0.1~1mmol/L利于Zn、Cd固持,增至10mmol/L后加速淋洗,仅0.002mm粒径富集量持续提升。表明柠檬酸作为一种调节剂,能适度保持土壤Zn供给并弱化Cd迁移活性,缓解茶园土壤复合污染。     

CTMAB对塿土表面的修饰机制

以平衡吸附法研究了十六烷基三甲基溴化铵(CTMAB)对塿土耕层·粘化层表面的修饰机制,结果表明,CTMAB在两层次土样上吸附等温线20℃时均呈直线型,40℃时均转变为H型等温线形式·在修饰比例0%～100%CEC区间,土壤表面对CTMAB的亲和力随温度的升高均增加,其吸附具有熵增控制自发性反应的热力学特征,两个温度下,土层吸附CTMAB亲和力之比与土层CEC之比相近;在修饰比例100%～200%CEC区间,土壤表面对CTMAB的亲和力随温度的升高均呈现下降的趋势,呈现放热熵减反应特征,20℃时土层吸附CTMAB亲和力之比与土层CEC之比相近,而40℃时则与土层性质无关。CTMAB在两层次土样上解吸等温线均呈直线型。CTMAB对塿土表面的修饰在100%CEC修饰比例前以离子交换为主,100%后以疏水键结合为主,CTMAB在塿土表面易于吸附但难于解吸,解吸的CTMAB主要是以疏水键形式结合在土壤表面上。     

BS-Tween20复配修饰膨润土对Cd~(2+)吸附的研究

采用不同比例十二烷基二甲基甜菜碱(BS-12)+Tween20复配修饰膨润土,以批处理法研究了不同修饰比例、温度、p H、离子强度下,修饰膨润土对Cd2+吸附的效果,并从吸附等温线、温度效应和热力学角度探讨了吸附机制。结果表明,供试土样对Cd2+的平衡吸附量呈现BS+0.25TBS+0.5TBSBS+1TBS+1.5TCK的趋势,复配修饰土样对Cd2+的吸附随Tween20修饰比例的增加而降低。Tween20复配修饰比例小于0.5时有利于复配修饰土对Cd2+的吸附,而大于0.5时复配修饰土对Cd2+的吸附量则降低。修饰膨润土对Cd2+的吸附等温线均符合Langmuir模型。温度升高、p H增加、复配修饰土对Cd2+的吸附量增加、离子强度的增大减弱了土样对Cd2+的吸附。热力学参数结果表明,修饰土样对Cd2+的吸附是熵增控制的自发性过程;各土样对Cd2+吸附均为吸热过程。     

绿化植物废弃物对土壤中Cu Zn Pb和Cd形态的影响

利用自制的Cu、Zn、Pb和Cd污染的灰潮土和黄泥土,通过室内培养实验研究了不同绿化植物废弃物添加量和不同培养时间对这两种污染土壤中这4种重金属形态的影响。结果表明,绿化植物废弃物的加入抑制了Cu的活化,且添加60%绿化植物废弃物时有机结合态Cu的含量最高;绿化植物废弃物与污染土培养2～3个月时,残余态Zn的含量最高,对植物的毒害最小;绿化植物废弃物添加量为60%时灰潮土中有效态Pb含量较低,而添加量为30%时黄泥土中有效态Pb含量最低;绿化植物废弃物添加量的多少对灰潮土Cd形态的影响较小,但黄泥土中的Cd则随绿化植物废弃物量的增加活性逐渐减弱,且两种土壤均在培养2～3个月时可交换态Cd的含量最低。     

磷的吸附对老成土和淋溶土中Cu、Zn离子吸附-解吸及其有效性的影响

Surface charge,secondary adsorption-desorption and form distribution of Cu^2 and Zn^2 in Ultisols and Alfisols having adsorbed phosphate were studied by potentiometric titration,adsorption equilibrium and sequential extraction method,respectively,The soil surface negative charges increased whereas the amount sequential extraction method,respectively.The soil surface ngative charges increased whereas the amount of positive charges decreased with increase of P adsorbed,The soil secondary adsorption capacity for Cu^2 and Zn^2 was positively significantly correlated with the amount of P adsorbed by the soils,which could be described by the Langmuir equation.The amounts of Cu^2 and Zn^2 desorption from soils were decreased after P adsorption by the soils and the relationship between them was linear,After the soils adsorbed P,form distribution of Cu^2 and Zn^2 in soils changed remarkably.     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

金属污染土壤中锌铜交互作用对锌吸附和植物有效性的影响

In a previous greenhouse experiment,we showed that there was an interaction between cu and Zn,which affected growth and metal uptake by young barley plants grown on soil to which Cd,Cu,Pb,and Zn had been added.We suggested that the underlying mechanism was the control of the amount of plant-available Zn by competitive adsorption between Cu and Zn,In order to test this hypothesis,the adsorption of Zn alone,and in the presence of added Cd,Cu and Pb,has been measured using the same soil.Following adsorption,the extractability of the Zn in CaCl2 solution was measured .The adsorption isotherms showed that of the added metals only Cu had a large effect on Zn adsorption.The effect of Cu was to reduce Zn adsoption and to increase the amount of CaCl2-extractable(i.e.plant-available) Zn,in agreement with the conclusions from the greenhouse experiment.The magnitude of the effect of Cu on plant-avalilable Zn was similar in both experiments.     

Pb和Cd在塿土不同剖面土壤中的竞争吸附作用

多种金属离子的共存影响土壤对重金属离子的吸附作用,从而影响其生物有效性和迁移特征。利用等温吸附方法研究了塿土不同发育层次土壤对Pb~(2+)、Cd~(2+)单一离子和两种离子共存的吸附特征。对于单一的离子吸附,Pb~(2+)在塿娄土耕层、黏化层和钙积层的分配系数为8.0、8.1和6.1,Langmuir方程最大吸附量为6.1、5.8和6.0 mmol kg~(-1);而Cd~(2+)的分配系数为4.2、7.1和4.7,最大吸附量为5.5、4.8和2.9 mmol kg~(-1);三种土壤对Pb~(2+)的吸附性能均强于对Cd~(2+)的吸附。当Pb~(2+)、Cd~(2+)共存时,两种离子间存在竞争吸附作用,致使Pb~(2+)、Cd~(2+)的吸附量均降低,Pb~(2+)、Cd~(2+)互为竞争性吸附离子的亲和力效应在0.8~0.9之间,竞争性的Langmuir吸附方程可用于描述Pb~(2+)、Cd~(2+)的竞争吸附。     

Immobilization and species of heavy metals in soils in the absence and presence of rhizobia

Abstract

The effect of bacterial inoculation of Rhizobium fredii HN01 on the immobilization and speciation of Cu, Zn, and Cd was studied in Red and Cinnamon soil which are typical Chinese soils. The soil was mixed with bacterial suspension for one week followed by an immobilization of each heavy metal for another week. The total binding and fractionation of heavy metals in soils were analyzed. As compared with the control, the retention of total Cu, Zn, and Cd in Red soil increased by 28, 16, and 28%, respectively, in the presence of rhizobia. The amount of exchangeable, NH₄OAc-extractable, Mn oxides-bound and organic matter-bound Cu increased by 23–123%. There were significant decrease of exchangeable Cu and marked increases of NH₄OAc-extractable and Mn oxide-bound Cu in Cinnamon soil with the presence of rhizobial cells, although no changes for the total retention of Cu were observed. The amount of exchangeable Zn in Red soil-rhizobia composite was 20% greater than that of the no-rhizobia soil. Addition of rhizobia also increased exchangeable Cd and specifically-adsorbed Cd by 25 and 93%, respectively, in Red soil. No considerable differences were found for the total immobilization of Zn and Cd as well as their distribution in various solid fractions of Cinnamon soil in the absence and presence of rhizobial cells. In terms of soil components, it is assumed that bacterial biomass had a relatively less impact on the species of heavy metals bound with Fe oxides. Results suggested that the retention and speciation of heavy metals in soil are governed largely by the interactions of bacteria with various inorganic and organic soil constituents. The data are useful in understanding the impact of microorganisms on the behavior, mobility and transformation of heavy metals in soil environments.     

有机修饰改性土对镉离子的吸附及温度效应

主要研究了以不同比例十六烷基三甲基溴化铵(CTMAB)单一修饰和十六烷基三甲基溴化铵 十二烷基磺酸钠(CTMAB SDS)混合修饰的土耕层、黏化层土样对重金属镉离子的吸附。结果表明:吸附量顺序分别为耕层原土(GCK) >CTMAB5 0 %修饰改性土(5 0GCB) >CTMAB10 0 % SDS2 0 %修饰改性土(12 0GCS) >CTMAB10 0 %修饰改性土(10 0GCB)和粘化层原土(NCK) >CTMAB5 0 %修饰改性土(5 0NCB) >CTMAB10 0 %修饰改性土(10 0NCB) >CTMAB10 0 % SDS2 0 %修饰改性土(12 0NCS)的顺序,表明以表面修饰剂修饰土表面,确实存在着使得镉离子吸附能力减弱的趋势,但并未使修饰改性土完全丧失对于镉离子的吸附能力;吸附等温线可以用Langmuir方程描述;热力学参数的研究表明Cd2 吸附反应是熵增控制的自发性过程,但在探讨吸附自发性和最大吸附量关系时应考虑土壤本身的容量性质。机理研究认为,表面修饰剂对土壤表面的修饰改性是不均匀的,阳离子交换吸附和疏水键键合两种机制的竞争性吸附是修饰改性土壤依然具有对镉离子吸附作用的原因。土耕层各改性土样对Cd2 吸附的温度效应明显高于粘化层土样,证实了耕层对镉离子的化学吸附作用强于粘化层的结果     

不同磷浓度处理暗棕壤对Zn2+吸附解吸行为的研究

通过等温吸附试验,研究不同磷含量处理暗棕壤对Zn2+的吸附解吸行为,结果表明:(1)随平衡液中Zn2+浓度的增加,3种处理暗棕壤对Zn2+的吸附作用均表现为:低浓度下(0～100 mg/L),吸附量增加迅速,随着浓度升高(100～150 mg/L),吸附量变缓并渐趋平衡,含磷量高的土壤吸附Zn2+的量较高。(2)Freundlich、Langmuir和Temkin方程均能很好描述Zn2+在3种不同磷含量暗棕壤上的吸附等温线,拟合效果依次为Freundlich>Langmuir>Temkin。经参数计算,较高磷含量有利于提高暗棕壤的最大吸附量和土壤对Zn2+的缓冲容量,而磷含量不同对Zn2+在暗棕壤上的吸附力没有太大影响。(3)3种不同磷含量处理暗棕壤吸附量与解吸量关系图形状相似,呈高度线性相关,均表现为暗棕壤对Zn2+的解吸量随吸附量的增加而增加,磷含量较高土壤有利于Zn2+的固定且不易解吸。