不同离子桥键的有机矿质复合体对菲的吸附-解吸研究

从自然土壤中有机质与矿物的结合方式出发,研究了Ca²⁺、Fe³⁺和Al³⁺桥键的有机矿质复合体对菲的吸附-解吸行为.结果表明,不同离子饱和的蒙脱石及其相应的胡敏酸-矿物复合体对菲的吸附-解吸数据都能用Freundlich模型较好地拟合,吸附容量（K_f）大小的顺序分别为Ca-Mont（0.184）>Fe-Mont（0.028）>Al-Mont（0.015）和Fe-Mont-HA（2.341）>Ca-Mont-HA（1.557）>Al-Mont-HA（1.136）.有机矿质复合体的K_f值远远高于相应的矿物,表明了复合体中的胡敏酸对菲的吸附容量贡献较大.但不同离子桥键的复合体K_f值的大小与它们有机质的含量高低次序不一致,表明了复合体中有机质的含量以及有机质与矿物结合方式的不同,都可能会影响它们对菲的吸附.Ca²⁺和Al³⁺桥键的有机矿质复合体对菲的解吸都有滞后现象,滞后现象主要来自有机质对菲的吸附,而矿物对菲的解吸滞后现象影响不明显.     

渤海湾表层沉积物重金属在不同粒级有机-矿质复合体中的分布

采用超声分散法分离沉积物中不同粒级有机-矿质复合体,研究了渤海湾沉积物中Pb,Cd,Cr等重金属的污染及其在不同粒级有机-矿质复合体中的分布.结果表明,3种重金属含量总体上随着复合体粒径增大而减小.X射线衍射(XRD)结果显示,随着沉积物粒径的增大,主要来自原生矿物的石英和长石等岩石结构物质的含量增加,但这些物质中的重金属含量较低.渤海湾表层沉积物中重金属污染主要发生在以次生硅酸盐矿物及硅、铁、铝等氧化物或氢氧化物为主的细粒沉积物上,细粒样品由于其较大的比表面积和富含有机质的特性,通过吸附、沉淀、离子交换等,导致所含重金属含量较高.粘粒复合体中Pb含量是粗砂中的2.3倍,Cd是粗砂的3.8倍,而Cr是粗砂的2.8倍.      

有机氯农药污染场地表层土壤有机-矿质复合体中污染物的分布

采用湿法物理分级方法将北京市某农药厂遗留场地表层土壤分成4种粒径的有机-矿质复合体组分:粘粒、粉粒、细砂和粗砂(<2 ìm、2～20ìm、20～200ìm、>200 ìm),研究有机氯农药在其中的分布特征及土壤不同有机-矿质复合体组分中有机质和矿物质组成的差异对污染物赋存分布的影响.结果表明,污染物质六六六(HCHs)和滴滴涕(DDTs)在粉粒中分布较多,含量分别为463.1 mg·kg-1和1225.6 mg·kg-1,粗砂中分布最少,含量仅为157.8 mg·kg-1和384.5 mg·kg-1.1gKoc与污染物质在粘粒上的分布量存在显著的相关关系.通过对有机-矿质复合体进行x射线衍射分析发现,场地土壤粘粒和粉粒中粘土矿物含量较高.由于有机-矿质复合体中粘土矿物组成和含量存在差别,这在一定程度上影响了污染物质在其中的分布.同时,所研究的场地土壤中污染物易于富集的粒径范围与报道的北京大气颗粒物上HCHs和DDTs有较多吸附的粒径相近.因此,应当重视污染场地表层土壤对大气污染的可能贡献及其环境风险.     

沙土不同粒径微团聚体对磷的富集特征

流失的水土是污染物的重要载体,为估算沙土吸附态磷流失量,采用平衡吸附法研究了沙土不同粒径微团聚体对磷的富集特征.结果表明,不同粒径微团聚体对磷的富集系数为:黏粒(3.79)＞粉粒(2.98),沙土中微团聚体对磷的富集作用比较强,其原因有三:细粒级微团聚体中腐殖质含量显著高于粗粒级;细粒级微团聚体中有机质是通过可溶有机质与黏土矿物相互结合形成复合体而富集,在复合体结构中存在孔隙填充方式磷吸附;粘粒和粉粒中的铁铝键有机矿质复合体所占比例显著高于其它粒级,在对磷吸附中发挥重要作用,其吸附机制除孔隙填充方式外,还存在铁铝氧化物及水化氧化物对磷的配位吸附.不同粒径团聚体对磷的吸附分配系数和富集系数均与腐殖质总量呈显著正相关(p＜ 0.01,r分别为0.854和0.954);西辽河流域沙土在暴雨径流中黏粒级和粉粒级冲泻质泥沙所携载的吸附态磷质量分数可分别按1269.15 mg·kg-1和997.53 mg·kg-1估算,黏粒和粉粒级微团聚体对磷的富集系数(Er)可分别按3.79和2.98计算.     

模拟有机-矿质体中不同吸附域对TCE的吸附影响

为研究无机矿物与有机质相互作用形成复合体对有机污染物的吸附行为影响,制备了蒙脱土-腐植酸复合体以及混合体模拟土样,分别代表蒙脱土与腐植酸之间有相互作用和无相互作用,并运用批实验的方法,针对不同有机质与无机矿物质量比(C/M)的有机-矿质复合体及混合体开展了三氯乙烯(TCE)吸附实验研究.结果表明,TCE在不同C/M的有机-矿质复合体和混合体中的吸附符合Freundlich等温吸附模型.采用纯蒙脱土及腐植酸的吸附方程叠加计算获取无相互作用模拟土样的固相吸附量计算值,计算值均小于复合体和混合体的实际固相吸附量,表明复合体中蒙脱土与腐植酸吸附域之间存在相互作用,导致腐植酸性质改变,使复合体的吸附能力增强,而混合体由于等温吸附实验过程中有水的参与,也可能在一定程度上形成了复合体.随着C/M的增大,有机-矿质复合体和混合体对TCE的吸附能力增强.当 C/M小于0.08时,复合体中蒙脱土与腐植酸发生较为充分的相互作用,导致腐植酸性质改变,增强了复合体对TCE的吸附能力,因而复合体对TCE的吸附能力明显强于混合体;当C/M大于0.08时,复合体中后续叠加在补丁上的有机质保留了源腐植酸的特性,这部分有机质将掩盖变性有机质的吸附影响,因而复合体与混合体对TCE的吸附能力基本相当.TCE初始浓度影响分析表明,当C/M固定时,随着TCE初始浓度(C0)的增大,非线性叠加模型的固相吸附量计算值与实测值的差值(?Qe)呈增大趋势,分析认为复合体中的变性有机质较其他组分对TCE具有更强的亲和力,随着C0的增加,变性有机质的吸附贡献率增大,因此导致?Qe的增大.     

黑土不同粒径有机-矿质复合体对镉的吸附特性

采用振荡平衡法研究了黑土不同粒级有机-矿质复合体对Cd2+的吸附等温过程和吸附动力学过程,并采用常见数值模型进行了拟合. 结果表明,原土及各粒级复合体对Cd2+的吸附量随平衡液中ρ(Cd2+)的增加而增加. 各粒级组分对Cd2+的吸附量表现为黏粒＞粉粒＞原土＞粗砂＞细砂. Langmuir和Freundlich方程对Cd2+的等温吸附过程均有较好的拟合效果,线性方程拟合效果较差. 最大吸附量与吸附作用强度均呈随粒径增大而减小的趋势. 对影响最大吸附量和吸附作用强度的因子进行回归分析表明,w(有机质)、CEC(阳离子交换量)和比表面积的影响较大,其中w(有机质)是最主要因素,CEC和比表面积的影响次之. 各粒级复合体对土壤吸附Cd2+的贡献率为粉粒＞细砂＞黏粒＞粗砂,99%的Cd2+吸附在＜200 μm的组分上. 不同粒级组分对Cd2+的吸附动力学过程可分为0~20 min的快速反应阶段（吸附量均达到饱和吸附量的90%以上）和慢速反应阶段. 各组分对Cd2+的吸附符合二级动力学过程,表明吸附过程以化学吸附为主,并且吸附速率随颗粒粒径的增大而减小.      

蒙脱石/DOM复合体对菲的吸附

以垃圾渗滤液为水溶性有机质(DOM)提取原料,通过与吸附载体蒙脱石的有机-无机复合制得蒙脱石/DOM复合体,研究其对菲的吸附作用以及温度、pH值、固液比等不同因素对吸附过程的影响.结果表明,相比蒙脱石原土,蒙脱石/DOM复合体对菲的吸附能力得到显著提高;随着温度升高吸附量呈下降趋势;介质pH值对吸附影响不大;随着固液比的增大,平均吸附量逐渐减小,吸附率逐渐增大.动力学研究表明,菲在蒙脱石/DOM复合体上的吸附等温线与Henry线性方程和Freundlich经验方程的线性拟合较好.另外,对菲在蒙脱石/DOM复合体上的解吸实验表明,菲在蒙脱石/DOM复合体上的吸附有较好的稳定性.     

土壤有机质对土霉素在土壤中吸附-解吸的影响

采用批量平衡方法,研究了土霉素在原土及去除有机质土壤中的吸附和解吸.结果表明,土霉素在原土和去除有机质土壤中的吸附和解吸等温线均不同程度地偏离线性模型,其中Freundlich模型可以对吸附和解吸数据进行良好的非线性拟合,在不同土壤以及不同土壤处理中的拟合相关系数(r)均达到极显著水平.去除有机质能够降低土霉素在土壤中的吸附容量(lgKf),但增加了吸附强度(1/n).土霉素在土壤上的解吸过程存在明显的滞后现象,在所设土霉素浓度范围内,土霉素在褐土和红壤中的平均滞后系数(HIa)分别为0.039和0.015;去除有机质后的褐土和红壤对土霉素的解吸滞后现象显著增强(P<0.01),其HIa分别增加到0.068和0.028.     

黄泥土不同粒径微团聚体对Cd2+的吸附与解吸研究

对采自太湖地区黄泥土进行了低能量超声波分离,采用平衡吸附法研究了不同粒径微团聚体颗粒对重金属Cd²⁺的吸附和解吸特点.结果表明,不同粒径微团聚体对Cd²⁺的吸附特性均符合Freundlich方程,模拟方程得到的K值介于152～503之间,以粘粒级和粗砂级为最大.微团聚体对Cd²⁺的吸附容量与其中游离氧化铁含量、CEC呈显著正相关.不同微团聚体Cd的解吸特点不同,粘粒级的解吸率仅为8.4%,远远低于其它粒径的微团聚体,这些结果有助于了解田间条件下土壤重金属化学行为和微观尺度的化学过程.     

芘在土壤中的长期吸附和解吸行为

研究了芘在6种不同性质土壤中长期吸附解吸及不可逆吸附行为.实验结果表明:长期实验中芘在土壤中的吸附和解吸都存在快过程和慢过程2个阶段.不同吸附平衡时间下,有机质含量高于1%时,不同土壤的吸附平衡常数随有机质含量的增加而增加;有机质含量低于1%时,黏粒含量对土壤的吸附能力有着重要影响;平衡时间由2d增加到180d后,6种土壤的Kd值增加了35.1%～557.9%,其中土壤有机质对Kd值有不同程度的影响,而黏粒对Ka值影响最大,平衡时间对部分土壤Kd值影响不容忽视.长期解吸过程中,6种土壤慢解吸部分占总解吸量的12.05%～41.00%,有机质含量越高,慢解吸对解吸过程的贡献越大.不考虑老化的影响,有机质含量对不可逆吸附容量的贡献明显高于黏粒的贡献,与有机质对慢解吸过程的影响有一致性.     

土壤中多环芳烃的SPMD辅助解吸行为研究

为了开发一种表征土壤中憎水性有机污染物解吸及生物有效性的新方法,建立了半透膜被动采样装置（SPMD）研究土壤中有机污染物解吸行为的方法,利用SPMD分析了多环芳烃菲、芘和苯并［a］芘在3种不同性质土壤中的辅助解吸行为.结果表明,SPMD是一种很好地表征土壤中憎水性有机污染物解吸及生物有效性的手段. SPMD辅助解吸多环芳烃的效率与土壤有机质及多环芳烃性质有关.随着土壤有机质含量的降低,土壤中菲和芘的SPMD解吸率逐渐升高,对于10 mg/kg染毒水平,当土壤有机质含量由18.68%降低到0.3%时,2种化合物的解吸率分别由56.45%和48.28%上升到接近100%;但是对于苯并［a］芘,粘土表现出明显的滞留能力,在有机质含量（0.3%）很低、粘土含量（39.05%）较高的3号土壤中,苯并［a］芘的解吸率仅有66.97%.不同多环芳烃SPMD辅助解吸率差别很大,随着土壤有机质含量的降低,以及污染物浓度的提高,菲和芘的解吸差异逐渐缩小,而苯并［a］芘与上述2种多环芳烃的差异很大,主要是由于苯并［a］芘具有高度亲脂性,并且分子较大,造成其容易滞留在粘土的微孔及有机质的致密结构中.     

Effects of free iron oxyhydrates and soil organic matter on copper sorption-desorption behavior by size fractions of aggregates from two paddy soils

Effects of free iron oxyhydrates (Fed) and soil organic matter (SOM) on copper (Cu2+) sorption-desorption behavior by size fractions of aggregates from two typical paddy soils (Ferric-Accumulic Stagnic Anthrosol (Soil H) and Gleyic Stagnic Anthrosol (Soil W)) were investigated with and without treatment of dithionite-citrate-bicarbonate and of H2O2. The size fractions of aggregates were obtained from the undisturbed bulk topsoil using a low energy ultrasonic dispersion procedure. Experiments of equilibrium sorption and subsequent desorption were conducted at soil water ratio of 1:20, 25℃. For Soil H, Cu2+ sorption capacity of the DCB-treated size fractions was decreased by 5.9% for fine sand fraction, by 40.4% for coarse sand fraction, in comparison to 2.9% for the bulk sample. However, Cu2+ sorption capacities of the H2O2-treated fractions were decreased by over 80% for the coarse sand fraction and by 15% for the clay-sized fraction in comparison to 88% for bulk soil. For Soil W, Cu2+ sorption capacity of the DCB-treated size fraction was decreased by 30% for the coarse sand fraction and by over 75% for silt sand fraction in comparison to 44.5% for the bulk sample. Cu2+ sorption capacities of the H2O2-treated fractions were decreased by only 2.0% for the coarse sand fraction and by 15% for the fine sand fraction in comparison to by 3.4% for bulk soil. However, Cu2+ desorption rates were increased much in H2O2-treated samples by over 80% except the clay-sized fraction (only 9.5%) for Soil H. While removal of SOM with H2O2 tendend to increase desorption rate, DCB- and H2O2-treatments caused decrease in Cu2+ retention capacity of size fractions. Particularly, there hardly remained Cu2+ retention capacity by size fractions from Soil H after H2O2 treatment except for clay-sized fraction. These findings supported again the dominance of the coarse sand fraction in sorption of metals and the preference of absorbed metals bound to SOM in differently stabilized status among the size fractions. Thus, enrichment and turnover of SOM in paddy soils may have great effects on metal retention and chemical mobility in paddy soils.     

有机粘土矿物对水中菲蒽混合物的吸附

选用长碳链季铵盐阳离子型表面活性剂十六烷三甲基溴化铵(HDTMA-Br)作为改性剂对天然粘土矿物进行改性。利用改性后的粘土矿物对混合污染物进行吸附/解吸实验,结果显示:HDTMA改性粘土矿物对混合溶液中菲、蒽及混合物的吸附等温线均呈线性,是分配作用结果;随着改性土用量的增加,其吸附量逐渐减小,对污染物的去除率逐渐增大,最后趋于平衡;有机粘土矿物吸附混合污染物后解吸率均在5%以下;将改性土对混合污染物的吸附与对单体污染物的吸附进行对照,改性土总的吸附量大大增加,基本是对单体污染物的吸附量之和。     

Adsorption and desorption of Cu~(2+) 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 Cu~(2+) of soil aggregates,free iron oxyhydrates-removed soil aggregates,goethite,and kaolinite with batch adsorption method.The results showed that Cu~(2+) 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 Cu~(2+) was reduced when P application rates were lower than 260,220,130 and110 mg/kg for coarse,clay,silt and fine sand fractions,respectively.On the contrary,the adsorption capacity of Cu~(2+) 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 Cu~(2+) was enhanced at low levels of P,but suppressed at high levels of P,displaying an inverted V-shaped change over P adsorption.The Cu~(2+) 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 Cu~(2+)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 Cu~(2+) adsorption.     

Cation exchange capacities of soil organic matter fractions in a Ferric Lixisol with different organic matter inputs

Soil organic matter (SOM) has an important effect on the physicochemical status of highly weathered soils in the tropics. This work was conducted to determine the contribution of different SOM fractions to the cation exchange capacity (CEC) of a tropical soil and to study the effect of organic matter inputs of different biochemical composition on the CEC of SOM. Soil samples were collected from a 20-year-old arboretum established on a Ferric Lixisol, under seven multipurpose tree species: Afzelia africana, Dactyladenia barteri, Gliricidia sepium, Gmelina arborea, Leucaena leucocephala, Pterocarpus santalinoides, and Treculia africana. Fractions were obtained by wet sieving and sedimentation after ultrasonic dispersion. Relationships between CEC and pH were determined using the silver thiourea-method and were described by linear regression. The CEC of the fractions smaller than 0.053 mm was inversely related to their particle size: clay (<0.002 mm)>fine silt (0.002–0.02 mm)>coarse silt (0.02–0.053 mm), except for the soils under T. africana, D. barteri, and L. leucocephala, where the CEC of the fine silt fraction was highest or comparable to the CEC of the clay fraction. The clay and fine silt fractions were responsible for 76–90% of the soil CEC at pH 5.8. The contribution of the fine silt fraction to the CEC at pH 5.8 ranged from 35 to 50%, which stressed the importance of the fine silt fraction for the physicochemical properties of the soil. Differences in CEC between treatments for the whole soil and the fractions could be explained by the differences in carbon content. Except for the intercept for the clay fraction, SOM had a significant (P<0.001) contribution to both the intercepts (=estimated CEC at pH 0) and slopes (=pH-dependent charge) of the CEC–pH relationships for the whole soil and the fractions. The CEC of SOM at pH 5.8 varied between 283 cmol_c kg⁻¹ C for particulate organic matter, and 563 cmol_c kg⁻¹ C for the fine silt fraction. The biochemical composition of the organic inputs did not have an important effect on the CEC of SOM. In total, SOM was responsible for 75–85% of the CEC of these soils.     

Sorption of pyrene on two paddy soils and their particle-size fractions

In the present study, the sorption of pyrene on two kinds of bulk paddy soils, Gleyic Stagnic Anthrosols, and Ferric accumulic Stagnic Anthrosols as well as their particle-size fractions was investigated. The sorption isotherms fitted well with Freundlich equation. For both soils, the clay fraction（ 〈 2μm） and coarse sand fraction（2000-250μm） had higher sorption capacity than fine sand fraction（250-20 μm） and silt fraction（20-2 μm）. The IogKoc values obtained of each soil and its particle-size fractions were similar, proving that SOM content was a key factor affecting pyrene sorption. The Kd values showed a significant correlation with contents of dithionite-extractable Fe in both paddy soils and a good relationship with CEC in Gleyic Stagnic Anthrosols, indicating possible effects of surface properties of particle-size fractions on the sorption of pyrene.     

溶解性有机质对菲在沉积物上吸附与解吸性能的影响

采集了北京通州凉水河(标记为L)以及广东东江流域(标记为D)的沉积物,并进行菲(Phe)的连续吸附-解吸实验,研究了不同含量及组成的溶解性有机质(DOMs)对其吸附与解吸性能的影响.结果表明,DOMs能明显抑制菲在沉积物上的吸附,在实验浓度范围内(0~110mg/L),菲在沉积物上的吸附量与DOC浓度呈显著的负线性相关,并且DOC浓度越高,对吸附作用的抑制越显著.在溶解性有机质存在条件下,菲在2种沉积物上的吸附均呈线性吸附特征,kd值随加入沉积物浸出液DOC浓度的减小呈增大的趋势.菲在2种沉积物上的解吸过程均呈现一定的迟滞性,其解吸迟滞性可用热力学指数TII来描述.随着菲初始浓度的增加,TII值先减小后增加,其变化可以用吸附在高低位点上的菲分子比例以及菲分子是否能够被禁锢在吸附剂微孔内部来加以解释;溶解性有机质的存在,能促进菲从沉积物上的解吸,从而使菲的解吸滞后性减弱, 增强其在水环境介质中的迁移与传输能力.