农田灰钙土中有机质和碳酸钙对Zn吸附-解吸行为的影响

采用序批平衡法,研究了Zn在去除有机质及去除碳酸钙前后灰钙土的吸附-解吸行为.结果表明,在试验土壤中吸附量均随着加入Zn浓度的增加而增加,且去碳酸钙土对Zn吸附固定能力明显低于灰钙土,即有机质对灰钙土Zn的吸附影响小于碳酸钙;去有机质及去碳酸钙前后灰钙土对Zn的吸附过程不适合用 Langmuir方程描述,而 Freundlich方程能够很好地拟合,调整后的决定系数R2￠均大于0.90,达到极显著水平(P<0.01);去除有机质和碳酸钙后灰钙土对Zn的解吸率都升高,且灰钙土去碳酸钙后解吸率略高于去有机质;去除有机质及碳酸钙前后灰钙土的解吸量均随吸附量的升高而升高,且去碳酸钙土解吸量最大,去有机质土次之,灰钙土最小;土壤有机质和碳酸钙对Zn均有较强的络合吸附效应,能有效降低Zn的迁移活性,从而促进吸附,抑制解吸.     

锌、镉在紫色土中的竞争吸附

研究了3种紫色土及2种黏土矿物对Zn、Cd的吸附特点.结果表明,中性紫色土中Zn、Cd的吸附特点相似,等温吸附符合Langmuir方程,最大吸附量分别为147.9,104.7 mg/kg其吸附动力学过程先快后慢,符合一级动力学方程与Elovich方程,快速吸附段的吸附量与易解吸量相近,且符合一级动力学方程,为交换吸附;慢速吸附段的吸附量与难解吸量相近,且满足Elovich方程,可能属于深层吸附或专性吸附,3种紫色土及2种黏土矿物对Zn、Cd的吸附量及其土壤理化性质的相关分析表明,CEC与最大吸附量显著相关,表明紫色土对Zn、Cd的吸附机理为交换吸附所控制.Zn、Cd共存时吸附速度与吸附量降低,表明二者对吸附位的竞争,竞争吸附服从质量作用定律,高浓度者占优,高浓度Zn对Cd的吸附有明显抑制,完善的土壤重金属阈限指标应包含复合污染的考虑.     

固化填埋污泥对Cu2+、Zn2+吸附特征的比较研究

比较研究了固化填埋污泥对Cu2+、Zn2+吸附特征差异.结果表明,固化填埋污泥对Cu2+、Zn2+的吸附量及吸附率均在pH 3时达最大值;当固化填埋污泥质量浓度为6.0g/L时,其对初始浓度为150mg/L 的Cu2+、Zn2+吸附率均可达90%以上.固化填埋污泥对Cu2+、Zn2+的吸附等温式与Henry、Freundlich及Langmiur方程均具有较好的拟合性,且固化填埋污泥分别对Cu2+和Zn2 +具有较高的吸附强度和吸附容量.解吸特性研究表明,盐酸仅在pH1时对固化填埋污泥中Cu2+、Zn2+的解吸率达90%以上;随EDTA浓度增加,其对固化填埋污泥中吸附态Cu2+的解吸率显著上升,0.5mmol/L EDTA即可解吸100%的吸附态Cu2+,但对固化填埋污泥中吸附态Zn2+的解吸率仅为10%左右.     

重金属镉在黑土和棕壤中的解吸行为比较

采用一次平衡法对Cd²⁺在黑土和棕壤2种土壤类型中的解吸行为进行了比较研究.结果表明,Cd²⁺在2种土壤中的解吸行为均有明显的滞后性.相对于棕壤,Cd²⁺在黑土中的解吸有更长的滞后阶段.Cd²⁺在2种土壤中的解吸过程是一个快速反应的过程,当解吸平衡时间在30min左右时,吸附态Cd²⁺的解吸量能达到总解吸量的90%以上.Cd²⁺在2种土壤中的解吸效率都比较低,相对于总吸附量而言,Cd²⁺在黑土和棕壤的解吸百分比分别低于9.0%和15.1%.解吸速率随着初始浓度的增加而升高,但随着解吸量和解吸时间增加而下降,土壤性质对解吸速率的下降并没有明显的影响.Freundlich方程是描述Cd²⁺在这2种土壤中等温解吸的最佳方程,而Elovich方程是描述其在这2种土壤中解吸动力学变化的最佳方程.     

海水环境因子对聚乙烯微塑料吸附锌离子行为的影响研究

聚乙烯（PE）微塑料是一种新型海洋污染物,易与海水中的锌离子（Zn2+）吸附产生复合生态毒性,危害海洋生态系统。不同海水环境因子对PE微塑料吸附Zn2+行为的影响不同,本文探究了Zn2+浓度、微塑料的投加量、盐度和pH等对3种不同目数的PE微塑料吸附Zn2+行为的影响,并对其吸附动力学和热力学进行了讨论。结果表明,3种不同目数的PE微塑料对Zn2+的最佳吸附时间均为4 h;吸附能力为30目<100目<500目,最大平衡吸附量分别为1.428 mg/g、1.454 mg/g和1.498 mg/g;盐度（0～10）对吸附量的抑制率为7%;吸附量随pH的增加而增加,3种目数PE微塑料的最佳投加量均为0.1 g。Freundlich模型为最佳等温吸附方程,3种目数PE微塑料的拟合相关系数R2均大于0.982（p < 0.01）,说明存在多层化学吸附。准二级动力学方程为最佳吸附动力学方程,3种目数PE微塑料拟合相关系数 R2均大于0.991（p < 0.01）,表明该吸附过程主要为化学吸附。吸附热力学 ?G < 0, ?H > 0,说明PE微塑料对Zn 2+的吸附为自发吸热过程。     

Cd2+、Pb2+在根际和非根际土壤中的吸附-解吸行为

采用1次平衡法对Cd²⁺、Pb²⁺在小麦根际和非根际土壤中的吸附-解吸行为进行比较研究.结果表明,根际土对Cd²⁺和Pb²⁺的吸附能力高于非根际土,2类土壤对Cd²⁺的吸附等温线与Freundlich方程有较好的拟合性,Pb²⁺的等温吸附过程可由Langmuir方程与Freundlich方程来描述.双常数方程是描述根际、非根际土Cd²⁺和Pb²⁺吸附动力学行为的最优模型,其次为Elovich方程,最差模型是一级动力学方程.Cd²⁺、Pb²⁺ 的解吸存在滞后现象,相比于非根际土,根际土吸附态Cd²⁺、Pb²⁺ 的解吸率更低,Cd²⁺、Pb²⁺的解吸量与其初始吸附量之间的关系符合2次幂方程.2类土壤Cd²⁺、Pb²⁺的解吸速率随重金属初始浓度的增加而增加,随解吸时间的延长而不断降低.描述根际和非根际土Cd²⁺、Pb²⁺的解吸动力学过程的最优模型均为双常数方程,其次为Elovich方程,一级动力学方程拟合效果不佳.     

金鱼藻对Cu2+的生物吸附特征

研究了沉水植物金鱼藻对Cu2 的吸附动力学及热力学特征.结果表明,金鱼藻对Cu2 的吸附在20min内达到平衡,吸附动力学的实验结果符合伪二级动力学方程,其相关系数达到0.9937,表明该吸附为多种反应同时作用的复杂过程.用Langmuir和Freundlich2种吸附等温式拟合吸附热力学的实验结果表明,以Langmuir模型拟合效果更好,相关系数为0.9977,其最大吸附量为7.79mg/g.在解吸实验中,各浓度组的解吸率均在1%以下,表明金鱼藻对Cu2 的吸持作用较强.     

冻融作用对土壤镉动力学吸附解吸的影响

为了研究冻融作用对土壤镉吸附解吸过程的影响,采用人工控温、室内培养方法对土壤进行冻融处理,并通过土壤镉动力学吸附解吸试验,分析了土壤对镉的吸附解吸量、吸附解吸率及吸附解吸速率.结果表明,冻融作用能够促进土壤对外源镉的吸附,镉的吸附量、吸附率和吸附速率均随着冻融次数的增加而增加.同时,冻融作用能减缓土壤对镉的解吸,随着冻融次数的增加,土壤对镉的解吸速率和解吸率降低,土壤镉解吸速率的下降率随冻融次数的增加而增大.     

Hg在玲珑金矿区典型农田土壤中的吸附特征研究

采集烟台玲珑金矿区不同性质的土壤,通过吸附解析实验研究了矿区2种典型农田土壤对重金属汞的吸附特征.等温吸附-解吸实验结果表明,酸性土壤对Hg（Ⅱ）的平均吸附率高于中性土壤,中性土对Hg（Ⅱ）的最大吸附量为156.9μg/g,酸性土达到201.38μg/g.2种土壤结合Hg（Ⅱ）的解吸量和解吸率都较低,且酸性土的解吸率（...     

Cd2+、Pb2+在根际和非根际土壤中的吸附-解吸行为

采用1次平衡法对Cd2 、Pb2 在小麦根际和非根际土壤中的吸附-解吸行为进行比较研究.结果表明,根际土对Cd2 和Pb2 的吸附能力高于非根际土,2类土壤对Cd2 的吸附等温线与Freundlich方程有较好的拟合性,Pb2 的等温吸附过程可由Langmuir方程与Freundlich方程来描述.双常数方程是描述根际、非根际土Cd2 和Pb2 吸附动力学行为的最优模型,其次为Elovich方程,最差模型是一级动力学方程.Cd2 、Pb2 的解吸存在滞后现象,相比于非根际土,根际土吸附态Cd2 、Pb2 的解吸率更低,Cd2 、Pb2 的解吸量与其初始吸附量之间的关系符合2次幂方程.2类土壤Cd2 、Pb2 的解吸速率随重金属初始浓度的增加而增加,随解吸时间的延长而不断降低.描述根际和非根际土Cd2 、Pb2 的解吸动力学过程的最优模型均为双常数方程,其次为Elovich方程,一级动力学方程拟合效果不佳.     

Chemical composition and Zn bioavailability of the soil solution extracted from Zn amended variable charge soils

A study on variable charge soils (volcanic Italian and podzolic Scottish soils) was performed to investigate the influence of soil properties on the chemical composition of soil solution. Zinc speciation, bioavailability and toxicity in the soil solution were examined. The soils were spiked with increasing amounts of Zn (0, 100, 200, 400 and 1000 mg/kg) and the soil solutions were extracted using rhizon soil moisture samplers. The pH, total organic carbon (TOC), base cations, anions, total Zn and free Zn2+ in soil solution were analysed. A rapid bioassay with the luminescent bacterium Escherichia coli HB101 pUCD607 was performed to assess Zn toxicity. The influence of soil type and Zn treatments on the chemical composition of soil solution and on Zn toxicity was considered and discussed. Di erent trends of total and free Zn concentrations, base cations desorption and luminescence of E. coli HB101 pUCD607 were observed. The soil solution extracted from the volcanic soils had very low total and free Zn concentrations and showed specific Zn2+/Ca2+ exchange. The soil solution from the podzolic soil had much higher total and free Zn concentrations and showed no evidence of specific Zn2+/Ca2+ exchange. In comparison with the subalkaline volcanic soils, the acidic podzol showed enhanced levels of toxic free Zn2+ and consequently stronger effects on E. coli viability.     

外源Cl-添加对不同母质土壤溶液Cd2+浓度的影响

土壤镉(Cd)的环境行为与其在土壤溶液中的存在形态以及陪伴离子有关,然而外源Cl~-与土壤溶液中Cd~(2+)的关系以及不同母质土壤对Cd~(2+)的环境行为的影响并没有明确的结论.选取2种水稻土(第四纪红色黏土母质发育的红黄泥、紫色砂页岩母质发育的紫泥田)为研究对象,添加离子态外源Cd~(2+)(0、1、2.5、5 mg·kg~(-1)),平衡老化后添加外源Cl~-(0、0.6、1.2 mg·kg~(-1)),在保持水分恒定的情况下进行模拟培养试验,研究外源Cl~-添加对土壤溶液Cd~(2+)浓度的影响.结果表明,随着外源Cd~(2+)的增加,土壤溶液Cd~(2+)的浓度提高,红黄泥土壤溶液Cd~(2+)的浓度显著高于紫泥田;添加Cl~-会使土壤溶液中Cd~(2+)浓度升高,且Cd~(2+)浓度与外源Cl~-呈显著正相关,红黄泥和紫泥田土壤溶液中Cd~(2+)的平均浓度比不添加Cl~-时Cd~(2+)的平均浓度分别增加了12.74%、51.49%;土壤对Cd~(2+)的吸附关系符合Freundlich等温吸附方程,紫泥田对Cd~(2+)的吸附量显著高于红黄泥,添加Cl~-对红黄泥Cd~(2+)的吸附影响很小,而对紫泥田的影响显著.Cl~-存在下,红黄泥和紫泥田的解吸率分别为12.50%～19.25%、14.76%～24.99%,外源Cl~-添加对Cd~(2+)解吸影响小.综合分析认为,Cl~-对不同土壤Cd~(2+)的吸附解吸行为影响有较大的差异.     

4种金属离子对高岭土胶体上蒽分布的影响

在水/土比10、180r/min振荡和室温28℃条件下,研究Fe3+、Cu2+、Zn2+、Ca2+对高岭土上蒽分布的影响.结果表明,高岭土对Fe3+、Cu2+、Zn2+、Ca2+的吸附平衡时间和平衡浓度分别为24h和(20 ± 3)mg/g.当金属离子负荷330mg/g时,上清液中高岭土胶体最低浓度为(40 ± 3)mg/L.添加Fe3+时,总胶体浓度从52mg/L增加到133mg/L;添加Cu2+或Zn2+时,总胶体浓度从52mg/L增加到110mg/L;添加Ca2+时,总胶体浓度从52mg/L增加到73mg/L.上清液中蒽浓度增加趋势与上清液中总胶体浓度的变化趋势一致,添加Fe3+时,蒽浓度从30ng/L增加到73ng/L;添加Cu2+或Zn2+时,蒽浓度从28,35ng/L增加到65,66ng/L;添加Ca2+时,蒽浓度从40ng/L增加到50ng/L.上清液中蒽浓度的增加趋势与所添加的金属电荷密度高低顺序一致(Fe3+ > Cu2+、Zn2+).在pH值为6.5时,Ca2+对增加上清液中蒽浓度能力最弱.     

黄壤表面电场作用下Cu~(2+)与Zn~(2+)的吸附/解吸动力学研究

利用静态恒流法研究了黄壤表面电场作用下Cu2+与Zn2+的吸附/解吸动力学.结果发现:考虑黄壤表面电场作用下,Cu2+和Zn2+的吸附实验呈现初期强吸附作用下的零级动力学过程和一定时间之后弱吸附作用下的一级动力学过程,与理论预期一致;在Cu2+和Zn2+的解吸实验中,只有前期出现了弱吸附作用下的一级动力学过程,实验结果与理论预期存在差别,原因在于专性吸附的Cu2+、Zn2+很难被解吸下来;在交换/吸附实验中,Cu2+的吸附速率值和平衡吸附量均大于Zn2+,且Cu2+-K+体系的表面电化学参数φ0、σ0、E0均大于Zn2+-K+体系中的对应值,证明了黄壤颗粒表面对Cu2+的吸附作用强于Zn2+;在交换/解吸实验中,Zn2+的解吸速率值和平衡解吸量均大于Cu2+,Zn2+-K+体系的表面电化学参数φ0、σ0、E0均大于Cu2+-K+体系中的对应值,证明Zn2+-K+体系中Zn2+的解吸作用比Cu2+-K+体系中的Cu2+解吸作用强.     

土壤中铜、铅离子的竞争吸附动力学

研究了Cu²⁺、Pb²⁺在2种土壤上的竞争吸附动力学过程.结果表明,Cu²⁺、Pb²⁺在乌栅土上的吸附量均高于在红壤上的吸附量,Pb²⁺又较Cu²⁺在土壤上的吸附量大.分别用一级、二级动力学方程、抛物线方程、Elovich方程和幂函数方程对该吸附动力学过程进行了拟合,其中幂函数方程拟合结果最好.Cu²⁺、Pb²⁺在乌栅土上的吸附主要是通过与土壤中的Ca²⁺、Mg²⁺进行交换,其累积吸附量与Ca²⁺、Mg²⁺的累积解吸量线性关系显著(R2为0.990～1);在红壤上是通过与土壤中的H+进行离子交换而吸附.Pb²⁺对Ca²⁺和Mg²⁺的交换能力比Cu²⁺强,其存在显著降低了Cu²⁺在2种土壤上的吸附量;Cu²⁺的存在略降低Pb²⁺在土壤上的吸附量.     

Adsorption and desorption of Cu on paddy soil aggregates pretreated with different levels of phosphate

Interactions between anions and cations are important for understanding the behaviors of chemical pollutants and their potential risks in the environment. Here we prepared soil aggregates of a yellow paddy soil from the Taihu Lake region, and investigated the effects of phosphate (P) pretreatment on adsorption-desorption of Cu²⁺ of soil aggregates, free iron oxyhydrates-removed soil aggregates, goethite, and kaolinite with batch adsorption method. The results showed that Cu²⁺ adsorption was reduced on the aggregates pretreated with low concentrations of P, and promoted with high concentrations of P, showing a V-shaped change. Compared with the untreated aggregates, the adsorption capacity of Cu²⁺ was reduced when P application rates were lower than 260, 220, 130 and 110 mg/kg for coarse, clay, silt and fine sand fractions, respectively. On the contrary, the adsorption capacity of Cu²⁺ was higher on P-pretreated soil aggregates than on the control ones when P application rates were greater than those values. However, the desorption of Cu²⁺ was enhanced at low levels of P, but suppressed at high levels of P, displaying an inverted V-shaped change over P adsorption. The Cu²⁺ adsorption by the aggregate particles with and without P pretreatments was well described by the Freundlich equation. Similar results were obtained on P-pretreated goethite. However, such P effects on Cu²⁺ adsorption-desorption were not observed on kaolinite and free iron oxyhydrates-removed soil aggregates. The present results indicate that goethite is one of the main soil substances responsible for the P-induced promotion and inhibition of Cu²⁺ adsorption.     

Effects of metal cations on sorption-desorption of p-nitrophenol onto wheat ash

The mutual e ects of metal cations (Cu2+, Pb2+, Zn2+, and Cd2+) and p-nitrophenol (NP) on their adsorption desorption behavior onto wheat ash were studied. Results suggested that Cu2+, Pb2+, and Zn2+ diminished the adsorption and increased the desorption of NP remarkably, while Cd2+ had no such e ect. In contrast, NP diminished the adsorption of Cu2+, Pb2+, and Zn2+ onto ash, however, this suppression e ect depended on the initial concentrations of metal cations. NP had no e ect on Cd2+ adsorption on ash. Fourier transform infrared (FT-IR) and X-ray absorption spectroscopic (XAS) studies suggested the following mechanisms responsible for the metal suppression e ect on NP adsorption: (1) large hydrated Cu2+, Pb2+, and Zn2+ shells occupied the surface of ash and prevent nonspecific adsorption of NP onto ash surface; (2) Cu2+, Pb2+, and Zn2+ may block the micropores of ash, resulting in decreased adsorption of NP; (3) complexation of Cu2+, Pb2+, and Zn2+ was likely via carboxyl, hydroxylic and phenolic groups of wheat ash and these same groups may also react with NP during adsorption. As a “soft acid”, Cd2+ is less e cient in the complexation of oxygencontaining acid groups than Cu2+, Pb2+, and Zn2+. Thus, Cd2+ had no e ect on the adsorption of NP on wheat ash.     

超声场中活性炭上Zn2+的吸附/脱附

采用静态条件,考察了超声波对活性炭上Zn2+吸附/脱附性能的影响.结果表明,有/无超声作用下,活性炭对Zn2+的吸附率均随Zn2+初始浓度的增加而减少,该吸附过程属于优惠吸附, Langmuir模型能更好描述该过程,超声的引入对活性炭吸附Zn2+有一定抑制作用.脱附研究发现,在蒸馏水介质中,Zn2+脱附率仅为2.11%,加入超声后Zn2+的脱附率提高至20.8%,添加NaOH后脱附率明显增加,有/无超声作用下的脱附率分别为40.1%和33.1%.动力学分析表明,Zn2+在活性炭上的吸附/脱附均符合2级反应动力学.     

磺胺嘧啶在作物根际土壤中的吸附/解吸特性研究

采用根际袋盆栽实验,研究了在小麦和玉米根际效应作用下,土壤对磺胺嘧啶(Sulfadiazine,SD)吸附/解吸热力学与动力学特性.结果表明,小麦和玉米根际与非根际对SD的吸附/解吸均较快,描述2种作物根际与非根际对SD吸附过程最优动力学方程皆为Elovich方程,其次是双常数方程和抛物线方程.在实验所采用的SD浓度范围内,不同处理小麦和玉米根际与非根际对SD的吸附量均随着SD浓度的增加而增加,但根际对SD的吸附能明显高于非根际.用Freundlich方程描述小麦和玉米根际与非根际对SD等温吸附行为最为适宜.SD在小麦和玉米根际与非根际的解吸过程都是非线性的,且在根际的解吸能力明显低于非根际.此外,将小麦和玉米根际与非根际的平均吸附常数(Kf-ads)及平均解吸常数(Kf-des)与土壤有机质、pH、黏粒3种理化性质关系进行逐步回归分析发现,有机质是影响根际SD吸附/解吸行为的关键因素.     

Experimental and density functional theory study of the adsorption of N2O on ion-exchanged ZSM-5: Part II. The adsorption of N2O on main-group ion-exchanged ZSM-5

The adsorption and desorption of N2O on main-group ion-exchanged ZSM-5 was studied using temperature-programmed desorption (TPD) and density functional theory (DFT) calculations. TPD experiments were carried out to determine the desorbed temperature Tmax corresponding to the maximum mass intensity of N2O desorption peak and adsorption capacity of N2O on metal-ion-exchanged ZSM- 5s. The results indicated that Tmax followed a sequence of Ba2+ > Ca2+ > Cs+ > K+ > Na+ > Mg2+and the amount of adsorbed N2O on main-group metal cation followed a sequence of Ba2+ > Mg2+ > Ca2+ > Na+ > K+ > Cs+. The DFT calculations were performed to obtain the adsorption energy (Eads), which represents the strength of the interaction between metal cations and the N-end or O-end of N2O. The calculation results showed that the N-end of the N2O molecule was favorably adsorbed on ion-exchanged ZSM-5, except for Cs-ZSM-5. For alkali metal cations, the Eads of N2O on cations followed the order which was the same to that of Tmax: Cs+ > K+ > Na+. The calculated and experimental results consistently showed that the adsorption performances of alkaline-earth metal cations were better than those of alkali metal cations.