Effect of ionic strength on adsorption of As（Ⅲ） and As（Ⅴ） on variable charge soils

The study was to investigate the adsorption behavior of arsenite (As(Ⅲ)) and arsenate (As(Ⅴ)) on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at different ionic strengths and pH with batch methods. Results indicated that the amount of As(Ⅲ) adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As(Ⅲ) was mainly adsorbed on soil positive charge sites through electrostatic attraction under the acidic condition. Moreover, intersects of As(Ⅴ) adsorption-pH curves at different ionic strengths (a characteristic pH) are obtained for both soils. It was noted that above this pH, the adsorption of As(Ⅴ) was increased with increasing ionic strength, whereas below it the reverse trend was true. Precisely the intersect pH was 3.6 for Haplic Acrisol and 4.5 for Rhodic Ferralsol, which was near the values of PZSE (soil point of zero salt effect) of these soils. The effects of ionic strength and pH on arsenate adsorption by these soils were interpreted by the adsorption model. The results of zeta potential suggested that the potential in adsorption plane becomes less negative with increasing ionic strength above soil PZSE and decreases with increasing ionic strength below soil PZSE. These results further supported the hypothesis of the adsorption model that the potential in the adsorption plane changes with ionic strength with an opposite trend to surface charge of the soils. Therefore, the change of the potential in the adsorption plane was mainly responsible for the change of arsenate adsorption induced by ionic strength on variable charge soils.     

Degradation of 14C-glyphosate and aminomethylphosphonic acid (AMPA) in three agricultural soils

Glyphosate (N-phosphonomethyl glycine) is the most used herbicide worldwide. The degradation of 14C-labeled glyphosate was studied under controlled laboratory conditions in three di erent agricultural soils: a silt clay loam, a clay loam and a sandy loam soil. The kinetic and intensity of glyphosate degradation varied considerably over time within the same soil and among di erent types of soil. Our results demonstrated that the mineralization rate of glyphosate was high at the beginning of incubation and then decreased with time until the end of the experiment. The same kinetic was observed for the water extractable residues. The degradation of glyphosate was rapid in the soil with low adsorption capacity (clay loam soil) with a short half-life of 4 days. However, the persistence of glyphosate in high adsorption capacity soils increased, with half-live of 19 days for silt clay loam soil and 14.5 days for sandy loam soil. HPLC analyses showed that the main metabolite of glyphosate, aminomethylphosphonic acid (AMPA) was detected after three days of incubation in the extracts of all three soils. Our results suggested that the possibility of contamination of groundwater by glyphosate was high on a long-term period in soils with high adsorption capacity and low degrading activities and/or acid similar to sandy loam soil. This risk might be faster but less sustainable in soil with low adsorption capacity and high degrading activity like the clay loam soil. However, the release of non-extractable residues may increase the risk of contamination of groundwater regardless of the type of soil.     

Adsorption and desorption characteristics of diphenylarsenicals in two contrasting soils

Diphenylarsinic acid(DPAA) is formed during the leakage of aromatic arsenic chemical weapons in soils,is persistent in nature,and results in arsenic contamination in the field.The adsorption and desorption characteristics of DPAA were investigated in two typical Chinese soils,an Acrisol(a variable-charge soil) and a Phaeozem(a constant-charge soil).Their thermodynamics and some of the factors influencing them(i.e.,initial pH value,ionic strength and phosphate) were also evaluated using the batch method in order to understand the environmental fate of DPAA in soils.The results indicate that Acrisol had a stronger adsorption capacity for DPAA than Phaeozem.Soil DPAA adsorption was a spontaneous and endothermic process and the amount of DPAA adsorbed was affected significantly by variation in soil pH and phosphate.In contrast,soil organic matter and ionic strength had no significant effect on adsorption.This suggests that DPAA adsorption may be due to specific adsorption on soil mineral surfaces.Therefore,monitoring the fate of DPAA in soils is recommended in areas contaminated by leakage from chemical weapons.     

土壤粉碎粒径对土霉素在土壤中吸附的影响

为了探明土壤粉碎粒径对土霉素在土壤上吸附的影响,以2个性质差异较大的潮土和紫色土为供试土壤,采用批量平衡法,研究了土霉素在不同粉碎粒径的2种土壤上的吸附行为.结果表明,①潮土和紫色土对土霉素的吸附量均随时间逐渐增大,最后在24 h时趋于平衡.一级动力学方程模型、抛物线模型、Elovich模型、双常数模型可以较好地拟合土...     

去除氧化铁对Al在土壤中吸附-解吸的影响

用连二亚硫酸钠-柠檬酸钠-碳酸氢钠(DCB)法研究了去除土壤中的氧化铁后Al的吸附-解吸特征的变化情况.结果表明,在pH值<4.5条件下,去除氧化铁可使土壤对Al的吸附量有所增加,这种变化在赤红壤中尤为明显;而此后随pH值的升高,原土和去铁土对Al的吸附量基本相等.造成该现象的原因可归纳为去除氧化铁能降低土壤的电荷零点(ZPC)和增加土壤表面负电荷的数量,从而增强了土壤表面与离子之间的静电引力.另一方面,去除氧化铁后Al的解吸量也增加.其原因是与原土相比,去铁土吸附Al的机理中包含有部分静电吸附,这从离子强度对去铁土吸附Al的影响实验能得到较好的验证,因为在pH值<4.5时,提高离子强度将降低Al的吸附量,用高岭石做参考材料时也发现了类似的现象.     

低分子量有机酸对几种可变电荷土壤吸附氟的影响

用一次平衡法研究了四种低分子量有机酸对几种可变电荷土壤吸附氟的影响，结果表明，低分子量有机酸可以通过竞争吸附作用抑制土壤对氟的吸附，化学结构相对简单的草酸和丙二酸对氟吸附的抑制作用大于柠檬酸和苹果酸。有机酸对氟吸附的抑制作用随土壤氧化铁含量的增加而增加，并随体系pH的增加而增强。在低pH和氟加入量较高的情况下，有机酸通过与氟竞争可溶性铝而增加土壤对氟的吸附量，这在对铝溶解度较高的酸性土壤中尤为明显。     

Effect of ionic strength on adsorption of As(Ⅲ) and As(V) on variable charge soils

The study was to investigate the adsorption behavior of arsenite (As(III)) and arsenate (As(V)) on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at dierent ionic strengths and pH with batch methods. Results indicated that the amount of As(III) adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As(III) was mainly adsorbed on soil positive charge sites through electrostati...     

氟污染对土壤胶体稳定性影响的研究

 通过对土壤黏粒悬浮液中加入氟,研究了氟污染对1种水稻土和2种红壤胶体稳定性的影响.结果表明,氟污染使土壤黏粒的稳定性增强,土壤胶体的临界聚沉浓度增大;土壤中增加氟,对土壤胶体临界聚沉浓度增大的影响程度因土壤类型不同而不同,表现为红壤大于水稻土;氟污染使土壤胶体的临界聚沉浓度增大的机理是土壤胶体对氟的配位吸附放出羟基而使溶液的pH值升高,增大了胶体负电荷间的静电排斥力,土壤胶体趋向稳定.表明氟污染不利于土粒聚沉,且使其他污染物质易从土壤进入水体,进而污染水源.     

环丙沙星在亚高山草甸土和沼泽土中的吸附特性

为了研究环丙沙星（Ciprfloxacin,CIP）在土壤中的吸附过程及主要影响因素,以川西北高原亚高山草甸土和沼泽土为研究对象,采用OECD guideline 106批平衡方法,分析了亚高山草甸土和沼泽土对CIP的吸附动力学特征、吸附热力学特征以及pH、温度、CIP初始浓度等对其吸附过程的影响.结果表明:①不同初始浓度CIP在两种土壤中的吸附过程均符合准二级吸附动力学模型,R2为0.920 2~0.988 6.②Freundlich等温吸附模型能够较好地拟合两种土壤对CIP的吸附热力学过程,吸附等温线符合“L”型.③在15~35℃范围内,吸附热力学参数ΔHθ（吉布斯自由能）和ΔGθ（焓变）均小于0,ΔSθ（熵变）大于0,表明两种土壤对CIP的吸附过程以物理吸附为主,属于吸附体系混乱度增加的自发进行的放热反应.④吸附容量lg K_f满足沼泽土大于亚高山草甸土,说明沼泽土对CIP的吸附能力强于亚高山草甸土,且两种土壤的吸附能力与CIP的初始浓度呈正相关.⑤在pH为3~9条件下,吸附量均随pH的增加呈现先增后减的趋势,当pH为5时,两种土壤对CIP的吸附效果均最好,表明强酸和碱性环境均不利于土壤对CIP的吸附.研究显示,CIP在两种土壤中的吸附容量、吸附强度以及吸附速率均存在较大差异,温度、CIP的初始浓度和pH对两种土壤吸附CIP存在一定影响.      

Use of Fe/Al drinking water treatment residuals as amendments for enhancing the retention capacity of glyphosate in agricultural soils

Fe/Al drinking water treatment residuals (WTRs), ubiquitous and non-hazardous by-products of drinking water purification, are cost-effective adsorbents for glyphosate. Given that repeated glyphosate applications could significantly decrease glyphosate retention by soils and that the adsorbed glyphosate is potentially mobile, high sorption capacity and stability of glyphosate in agricultural soils are needed to prevent pollution of water by glyphosate. Therefore, we investigated the feasibility of reusing Fe/Al WTR as a soil amendment to enhance the retention capacity of glyphosate in two agricultural soils. The results of batch experiments showed that the Fe/Al WTR amendment significantly enhanced the glyphosate sorption capacity of both soils (p < 0.001). Up to 30% of the previously adsorbed glyphosate desorbed from the non-amended soils, and the Fe/Al WTR amendment effectively decreased the proportion of glyphosate desorbed. Fractionation analyses further demonstrated that glyphosate adsorbed to non-amended soils was primarily retained in the readily labile fraction (NaHCO₃-glyphosate). The WTR amendment significantly increased the relative proportion of the moderately labile fraction (HCl-glyphosate) and concomitantly reduced that of the NaHCO₃-glyphosate, hence reducing the potential for the release of soil-adsorbed glyphosate into the aqueous phase. Furthermore, Fe/Al WTR amendment minimized the inhibitory effect of increasing solution pH on glyphosate sorption by soils and mitigated the effects of increasing solution ionic strength. The present results indicate that Fe/Al WTR is suitable for use as a soil amendment to prevent glyphosate pollution of aquatic ecosystems by enhancing the glyphosate retention capacity in soils.     

不同类型土壤中As(Ⅴ)解吸行为的研究

为了解As(Ⅴ)在土壤中的解吸行为及不同类型试剂(NaOH、NaCl、NaHCO3、柠檬酸、草酸及磷酸盐缓冲液)对所吸附砷的解吸效果,对As(Ⅴ)在不同类型土壤中的解吸热力学和动力学效果进行了研究.结果表明,NaOH和磷酸盐缓冲液对几种土壤吸附砷的解吸效果较好,解吸率分别在47.3%～73.0%和35.4%～66.6%...     

滇池泥炭土对两种抗生素和双酚A的吸附

用不同浓度NaOH溶液处理采集自云南滇池的泥炭土,研究处理前后的泥炭土对两种抗生素磺胺甲恶唑（SMX）、卡马西平（CBZ）及双酚A（BPA）的吸附机理,并深入探讨3种污染物及泥炭土性质对吸附特性的影响.吸附等温线拟合结果表明,Freundlich模型对3种物质在泥炭土上的吸附等温线有较好的拟合优度.3种物质中,BPA的非线性指数n值最低,这可能是由于其不对称的结构特征导致.随着处理泥炭土的NaOH浓度增加,3种吸附质在泥炭土上的吸附顺序为BPA > CBZ > SMX,BPA的吸附最高可能是由于其含有两个酚羟基,与泥炭土有较强的极性作用导致,而CBZ的吸附比SMX的吸附高是由憎水性作用引起.NaOH处理后并没有增加泥炭土对这3种吸附质的吸附,说明对于离子型化合物,吸附过程和机理复杂,BPA蝴蝶状结构及苯环上含有两个羟基可能导致其在泥炭土上出现特异性吸附,这导致其吸附系数最高;NaOH处理后泥炭土的有机碳含量增加但比表面积可能降低,从而使3种污染物的吸附降低.因此,本研究3种离子型化合物在泥炭土上的吸附受到吸附质的官能团及溶解度、泥炭土的有机碳含量及官能团等多种因素的影响.     

可变电荷土壤和恒电荷土壤与氢离子的反应动力学

在研究可变电荷土壤和恒电荷土壤与H+的反应动力学中,重点考察了H⁺、表面正电荷和可溶性铝随时间变化的特征及影响因素.结果表明,1类土壤中H⁺消耗都可分快速反应和慢速反应2个阶段,但其具体表现和影响因素不同;因氧化铁含量不同,H⁺加入后2类土壤表面正电荷变化存在明显差异;可溶性铝随时间的变化主要受土壤粘土矿物组成、溶解度及溶解动力学控制;2类土壤的可溶性铝的变化可同时用修正的Elovich方程和双常数速率方程描述.     

天然有机质对土霉素在西北灰钙土上吸附行为的影响

抗生素被广泛应用于日常生活中,大量含有抗生素的废弃物通过多种途径进入土壤给人类健康和土壤环境带来了严重危害,因此,探索抗生素类有机污染物在土壤中的吸附机理对土壤污染防治具有重要意义.以西北灰钙土为研究对象、以OTC（oxytetracycline,土霉素）为目标污染物,采用批量法分析灰钙土在添加有机质前、后对OTC的吸附动力学、热力学特征及其影响因素.结果表明:OTC的动力学吸附过程分快吸附阶段（0~2 h）和慢吸附阶段（2~10 h）,10 h之后吸附基本达到平衡,吸附过程拟合均符合准二级动力学模型.对不同温度下OTC在灰钙土上的吸附过程进行拟合显示,Langmuir和Freundlich热力学模型拟合的R2分别在0.930~0.985和0.967~0.973之间;对于不同初始ρ（OTC）在添加有机质灰钙土上的等温吸附过程,Langmuir和Freundlich热力学模型拟合的R2分别在0.952~0.988和0.936~0.971之间,表明这两种模型均可较好地解释此吸附过程;热力学参数ΔGθ（吉布斯自由能变）小于0,ΔHθ（焓变）和ΔSθ（熵变）均大于0,表明吸附为自发进行的混乱程度增大的吸热反应.添加外源性有机质HA（humic acid,胡敏酸）和FA（fulvic acid,富里酸）能增加OTC的吸附量,且自制有机质的促进作用大于市售有机质,HA的促进作用大于FA.随着初始ρ（OTC）的增大,吸附量呈增加趋势;Ca2+和Na+的加入均使OTC的吸附量减小,且离子浓度越高、价态越高,抑制效果越明显;不同pH对OTC吸附的影响均较小.研究显示,不同来源、种类的有机质均可促进OTC吸附,但不会改变吸附平衡时间;HA的疏水性较FA强,对OTC的吸附量较高;溶液pH对OTC吸附影响不显著,但不同价态、浓度的金属阳离子对OTC的吸附有较大影响.      

新疆不同质地土壤对石油类污染物的吸附作用

石油类污染物的迁移转化研究对环境保护及人体健康均有重要意义。由于石油类污染物在不同质地土壤中的吸附行为不同,采用静态吸附实验方法,研究了新疆甘泉堡工业区3种质地土壤(粉土、粉砂、粉质黏土)对石油烃的吸附动力学及吸附热力学行为,进行了吸附动力学和等温吸附拟合,并分析了土壤粒径、有机质含量、pH值及以含盐量对石油烃吸附量的影响。结果表明:粉土、粉砂、粉质黏土对石油烃的吸附均能在240 min达到吸附平衡,平衡吸附量分别为0.7765,0.6763,0.7173 mg/g;吸附能力顺序为粉土>粉质黏土>粉砂,准二级动力学模型(R2=0.9967~0.9989)能够更加准确地描述石油烃在土壤中的吸附过程;等温线为Langmuir型,其吸附平衡常数(K_a)分别为0.6126(粉土)、3.1310(粉砂)和0.1180(粉质黏土),表明石油烃在不同质地土壤中的吸附为单分子层吸附;土壤对石油烃的吸附量随土壤粒径和pH值的减小、有机质含量和含盐量的增加而逐渐增大。     

土壤组分对磷形态和磷吸附-解吸的影响——基于三峡库区消落带落干期土壤

通过选择性去除土壤组分的方法,探讨了三峡库区消落带落干期3种典型土壤中有机质、铁氧化物组分对磷形态和磷吸附-解吸的影响.结果发现,三峡库区消落带落干期3种典型土壤去除的有机质以易氧化组分为主,去除有机质后,土壤中各种磷形态的含量变化较小.然而,去除游离铁氧化物后,土壤中各种磷形态的含量均发生明显降低.同时,去除有机质、游离铁氧化物组分后并未改变土壤中各种磷形态的相对大小顺序,均为：钙结合磷（Ca-P） > 有机磷（OP） > 铁/铝结合磷（Fe/Al-P）.此外,黄壤（FJ）、紫色潮土（KX）和灰棕紫泥（FL）去除有机质后对磷的吸附能力较原始土壤仅分别降低0.5%、2.3%、6.5%（P=0.017<0.05,显著性差异）,表明3种土壤中有机质组分对磷吸附的影响较小;而去除游离铁氧化物后对磷的吸附能力分别降低45.6%、51.7%、43.9%（P=0.004<0.05,显著性差异）,表明土壤中游离铁氧化物组分是决定磷吸附大小的重要因素.另外,3种土壤去除游离铁氧化物后较原始土壤吸附磷的解吸能力明显增加,表明游离铁氧化物组分是控制3种土壤吸附磷的解吸的重要因素.FL土壤去除有机质组分后较原始土壤吸附磷的解吸能力略有降低,而KX和FJ土壤去除有机质组分后较原始土壤吸附磷的解吸能力无明显差异,表明有机质组分对土壤吸附磷的解吸的影响与土壤类型有关.     

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.     

载铁活性炭对水中草甘膦吸附性能研究

通过浸渍-焙烧法制备载铁活性炭,并用SEM电镜分析了载铁活性炭表面形态,研究了载铁活性炭(Fe-AC)对草甘膦溶液的吸附等温线和吸附动力学,并分析了各种影响因素对载铁活性炭吸附性能的影响.实验表明,Freundlich方程可以对Fe-AC草甘膦吸附等温线进行很好拟合,最大吸附量约为5.8mmol/g;其吸附动力学过程用Lagergren方程拟合,吸附速率常数在0.088min-1左右,且随着温度的升高逐渐减小.根据Kannan & Sundaram颗粒内扩散模型拟合,颗粒内扩散速率常数kp大于10mg·min-1/2/g,并随着起始温度的升高而减小.由于草甘膦的存在形态和Fe-AC材料表面性质的变化,AC-Fe对草甘膦的吸附能力随水溶液的pH升高而降低.NaCl的存在产生拮抗效应使得Fe-AC对草甘膦的吸附容量大大下降,随着NaCl浓度增加至4g/L后,盐析效应开始占主导地位,使得Fe-AC的吸附容量略有增加;由于草甘膦分子的空间位阻效应和亚磷酸根与载铁活性炭表面形成较强的络合物,使得随亚磷酸根浓度的升高Fe-AC对草甘膦的吸附量持续下降.     

Adsorption of chloroacetanilide herbicides on soil (I). Structural influence of chloroacetanilide herbicide for their adsorption on soils and its components

Adsorption of chloroacetanilide herbicide acetochlor,alachlor, metolachlor and propachlor on soils and soil components was determined, and the structural differences of these herbicides were used to explain the order of sorptivity. Adsorption isotherms for all herbicide-soil combinations conformed to the Freundlich equation, and Kf increased with increasing soil organic carbon content. Kd on soil humic acid was greater than that on clay, but association of humic acid with clay reduced the overall adsorption. On all soils and soil humic acids, herbicide adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca²⁺-montmorrilonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR spectra of herbicide-clay or herbicide-humic acid-clay mixtures showed that H-bonding and charge transfer were the primary interaction pathways between these compounds and the surface of clay or humic acids. The different moieties attached to 2-chloro-acetanilide and their unique arrangement may have influenced the binding mechanisms and thus the sorptivity of these herbicides. This study indicates that the structural difference of pesticides in the same classes may be used as a molecular probe to obtain a better understanding of sorption mechanisms of pesticides on soil.     

亚热带可变电荷土壤磷素淋失临界点及其与土壤特性的关系

选取我国亚热带地区16种典型可变电荷土壤,通过室内模拟试验测定其磷素(P)淋失临界点的Olsen-P含量,以及可能对其构成有影响的8个化学性质指标(pH、CEC、粘粒、有机质、交换性钙、镁和铁铝氧化物含量),以探讨可变电荷土壤P淋失临界点的特点及其与土壤相关性质的关系,并评价当前的P淋失潜在风险.结果表明:可变电荷土壤P淋失临界点的Olsen-P含量(56 ～ 123 mg·kg-1)差异很大,旱地土壤临界点Olsen-P含量主要集中在低值区间(＜60 mg·kg-1),而水稻土临界点Olsen-P含量集中在高值区间(＞80 mg·kg-1);旱地土壤P淋失风险高于水稻土.主成分分析显示,可变电荷土壤的pH、粘粒、CEC、有机质、交换性钙镁、氧化铁铝等化学性质同时对其临界点Olsen-P含量构成正的或负的影响.因此,临界点Olsen-P含量与单一因素的回归分析不仅不能够确切地反映临界点Olsen-P含量与这些化学性质的关系(与pH、CEC、粘粒、交换性钙镁含量无显著相关),甚至与理论上的关联相违(与氧化铁铝含量呈负相关).与以往研究结果比较,可变电荷土壤在旱作和稻作下的P淋失临界点的Olsen-P含量都普遍高于永久电荷土壤,研究的16种可变电荷土壤的实际Olsen-P含量也远低于临界点Olsen-P含量,由此推断南方地区耕作土壤的P淋失风险仍较小.