水稻秸秆生物碳对重金属Pb2+的吸附作用及影响因素

以农业废弃物水稻秸秆为原料,采用限氧裂解法制备了不同温度(350、500和700℃)下的秸秆生物碳(RC350、RC500和RC700),研究了生物碳对Pb2+的吸附性能、作用机制及影响因素,为准确预测生物碳还田固碳对土壤中重金属迁移行为的影响提供理论参考.结果表明,生物碳对Pb2+的吸附行为符合准一级动力学方程,Pb2+在RC350、RC500、RC700上的吸附速率分别为0.167h-1、0.154h-1、0.388h-1;其等温吸附曲线符合Langmuir方程,最大吸附量分别为65.3、85.7和76.3mg·g-1,是原秸秆生物质RC100的5～6倍、活性炭AC的2～3倍.生物碳单位面积上的有效吸附点位比AC高约10倍.经酸化去除表面矿物成分后,RC350和RC700对Pb2+的吸附能力急剧下降,其最大吸附量、吸附亲和力与AC相近;红外光谱分析表明,去灰分后生物碳上有机碳官能团并无明显减少,而无机矿物(如SiO2)含量显著降低.生物碳中的有机碳组分和无机矿物组分对其吸附Pb2+均有重要贡献,其中无机矿物组分的吸附量及亲和力均大于有机碳组分.     

生物炭对紫色土中氟苯尼考吸附与迁移的影响

氟苯尼考作为我国常用的兽用抗生素在土壤中被广泛检出,在有机质含量低(约<2%)、吸附性能差的紫色土中具有高迁移性,而具有多孔结构的生物炭对其具有较强的阻控能力. 本文采用批量平衡吸附试验与填装土柱淋溶试验,探究生物炭对氟苯尼考在紫色土中吸附与迁移的影响. 结果表明:Freundlich等温吸附模型可较好地刻画氟苯尼考在供试土壤上的吸附行为,其中,紫色土对氟苯尼考的吸附过程更接近于线性吸附(1/n=0.99±0.07),而生物炭施用使得紫色土对氟苯尼考的吸附容量常数(K_f)提高了9.69倍,且非线性增强;两点化学非平衡模型可较好地刻画供试土柱中Br?示踪剂与氟苯尼考的穿透曲线(R2≥0.964,RMSE≤0.09),生物炭施用分别提高了水动力弥散系数、瞬时吸附常数、瞬时吸附交换所占分数及一阶动力学速率系数,但因水土接触时间受限,瞬时吸附常数(K_d-c)远小于分配系数(K_d)和吸附容量常数(K_f);生物炭的施用使得紫色土中氟苯尼考的残留率增加了38%. 研究显示,紫色土中施用生物炭虽然促进了水分运动,但仍可通过提高吸附能力阻控氟苯尼考的迁移.      

Sorption of BTEX mixtures to organobenonites

Organobentonites synthesized by replacing the metal ions in bentonite with cetyltrimethylammonium (CTMA) or tetramethylammonium cation(TMA) were investigated for their behaviors to sorb benzene, toluene, pxylene from water. The results served to distinguish the sorption mechanisms (adsorption or partition) of the two types of organobentonites. Bentonites modified with short-chain alkyl functional groups(e, g., TMA) sorb organic contaminants primarily by an adsorption process, in which the sorbed amount decreases with increasing steric hindrance of the organic compound and the process exhibits a competitive effect because of steric hindrance in multisolute systems. In contrast, the sorption of contaminants to organobentonites modified with long-chain alkyl groups (e. g., CTMA) occurs by partition process without exhibiting a competitive effect, and the additional organic compounds may induce a cosorptive effect. In the latter case, the measured distribution coefficients of organic compounds between organobentonites and water( log Kd ) are positively correlated with the octanol-water partition coefficients of the compounds (logKow) and the sorption process exhibits no competitive effect in multi-solute systems.     

生物质炭及老化过程对土壤吸附吡虫啉的影响

通过批处理恒温振荡法,系统考察了土壤类型(熟化红壤、新垦红壤)、生物质炭种类(竹炭、稻草炭)、生物质炭用量(0、0.1%和0.5%,质量分数)及老化过程(恒湿30 d)对土壤吸附吡虫啉的影响.Freundlich曲线描述的研究结果表明,有机质含量高的熟化红壤对吡虫啉的吸附能力强于有机质含量低的新垦红壤.生物质炭的添加能增强土壤对吡虫啉的吸附能力,且吸附能力随生物质炭施用量的增加而显著提高.添加等量生物质炭,新垦红壤吸附吡虫啉能力的增强效果强于熟化红壤;在同种土壤中添加不同种类的等量生物质炭,新垦红壤添加稻草炭后吸附能力更强,熟化红壤添加竹炭后吸附能力更强.恒湿老化后的处理对吡虫啉的吸附能力与新鲜处理相比明显降低,且添加竹炭的处理比稻草炭处理受老化过程影响更大.     

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.     

Chemical behavior of organic compounds in the interface of water/dual-cation organobentonite

The sorption behavior of polar of ionizable organic compounds,such as p-nitrophenol,phenol and aniline,in the water/organobentonite systems is investigated.Both adsorption and partition occur to the sorption of organic compounds to dual-cation organobentonites.The separate contributions of adsorption and partition to the total sorption of organic compounds to dual-cation organobentonites are analyzed mathematically in the first time.The factors to the contributions are also discussed.The results indicated that the contribution of adsorption and partition is related to the composition and ratio of dual-cation surfactants exchanging onto the bentonite.The sorption of organic compounds to dual-cation organobentonite is dominated by adsorption at low concentrations and by partition at high concentrations,making the organobentonites powerful sorbents for organic contaminants over wide range of concentrations.     

腐殖酸对苯并三唑的吸附动力学及热力学研究

HA(腐殖酸)是土壤和沉积物中有机质的重要组成部分,能在很大程度上影响有机污染物的环境行为和毒理效应. 采用批量平衡法研究了BT(苯并三唑)在HA上的吸附动力学、等温吸附和吸附热力学等内容,结果表明:拟二级动力学能较好地描述BT在HA上的吸附行为,吸附过程分为快速吸附阶段和慢速吸附阶段,但主要以快速吸附为主;0~40min为快速吸附阶段,吸附总量占平衡吸附量的89.0%以上. 吸附等温线较好地符合Freundlich模型,R2均在0.9996以上. 初始ρ(BT)为300.0mg/L时,温度由288.15K升至308.15K,吸附量从15.70g/kg降至11.58g/kg,减少了26.24%. 此外,ΔH0(吸附焓变)为-30.19kJ/mol,说明吸附过程为放热反应;ΔG0(吉布斯自由能变)小于零,说明反应是自发的. 吸附反应的E_a(活化能)为19.35kJ/mol,表明吸附属于物理吸附.      

阴-阳离子有机膨润土协同吸附作用及其机理研究

合成并研究了一系列阴-阳离子有机膨润土对水中苯酚、苯的吸附作用及其机理.结果表明,阴-阳离子有机膨润土对水中有机物具有协同吸附作用,其作用大小与改性时所用表面活性剂的种类、组成、配比及有机物本身的性质有关;对苯酚的吸附符合Langmuir和Freundlich吸附等温式,是分配作用(partition)和表面吸附(adsorption)共同作用的结果,分配作用的贡献率随改性时阴离子表面活性剂加入量的增大而增大;对水中苯的吸附以分配作用为主,分配系数大于原土及单阳离子有机膨润土,且与有机碳含量呈正相关.     

羧酸类药用活性化合物在生物碳质上的吸附特性

为研究生物碳质吸附在处理水土环境中羧酸类PhACs（药用活性化合物）的作用,通过比表面积、红外光谱、元素分析及电镜扫描对商业水稻秸秆生物碳质的结构与性质进行了讨论,同时研究了生物碳质对不同初始pH及不同初始质量浓度的五种羧酸类PhACs[KTP（酮洛芬）、IBP（布洛芬）、NPX（萘普生）、ASP（阿司匹林）、SYA（水杨酸）]吸附特征的影响.结果表明:吸附过程包括前期快速吸附和后期缓慢吸附至平衡两个阶段;在第一阶段,外表面吸附与大孔及中孔扩散是控制吸附的机制,在第二阶段,生物碳质内表面吸附及基质在微孔中的扩散是影响吸附的主要机制.初始pH为6.0~7.0时,等温吸附数据符合Freundlich吸附等温方程,反映了非均匀性表面的吸附特性.五种羧酸类PhACs在生物碳质上的吸附能力[通过K_d,0.01（特定液相浓度下的单点分配系数）表达]表现为NPX（24.30 g/L）> IBP（15.82 g/L）> KTP（10.44 g/L）> SYA（2.64 g/L）> ASP（1.24 g/L）.溶液初始pH变化对所选PhACs的吸附量有显著影响,初始溶液pH处于pKa±1.0范围内时,所选吸附质的吸附量达到最大值,随着初始pH的升高,所选PhACs主要以阴离子形式存在,同时生物碳质表面负电性增加,增强的静电斥力减弱了氢键作用.研究显示,氢键作用在生物碳质吸附PhACs过程中起到主要促进作用,除此之外,还受到范德华力及π-π电子供受体等多种作用驱动.      

植物角质层的蜡质组分对甲萘酚的吸附作用

采用批量平衡法,比较研究了苹果角质结合蜡质、分离蜡质和重建蜡质对极性有机污染物甲萘酚的吸附作用,并探讨了不同负载量的重建蜡质的吸附性能,以期为准确预测有机污染物在不同状态蜡质组分上的吸附行为提供依据.结果表明,甲萘酚在苹果角质层、脱蜡角质层、分离蜡质(IW)、重建蜡质(BW)上的等温吸附线呈非线性,符合Freundlich方程.植物蜡质对甲萘酚的吸附作用与蜡质所处状态密切相关,吸附能力(Koc)大小顺序为:重建蜡质(321.2) > 分离蜡质(190.4) > 角质结合蜡质(128.4),表明植物角质层进入土壤后发生演化过程中,其中不易降解的蜡质的吸附能力逐渐增大.重建蜡质(BW)的吸附系数(Kd)与甲萘酚的浓度呈负相关,与蜡质的负载量呈正有关.在低浓度时,甲萘酚的有机碳标化吸附系数Koc值随有机碳含量(foc)增大先增大后减小,存在一些强的特殊作用;而高浓度时, Koc-基本为一常数,不随蜡质负载量而变化,主要吸附机理为分配作用.角质结合蜡质(CW)对角质层的总吸附作用的贡献较小,但随甲萘酚平衡浓度的增大而逐渐增大,并于高浓度时, CW的吸附能力与IW相当.     

Influence of organic amendments on the sorption of pentachlorophenol on soils

The influence of pH on the sorption of pentachlorophenol (PCP) onto three organic amendments, char, humic acid (HA) and peat, and the effect of organic amendments on PCP sorption to three kinds of soils were evaluated. The sorption of PCP on these sorbents fitted the Freundlich model well, suggesting that PCP sorption isotherms were nonlinear with exponential coefficient (N) value lower than 1. The PCP sorption capacity on three organic amendments and the N values increased with decreasing pH. The sorption capacities were in the order: char > HA > peat. Organic amendments resulted in an enhancement of sorption capacities of soils. The N values of PCP sorption on soils were decreased by char amendment and increased by HA and peat amendments. This study demonstrated that application of traditional organic amendments led to the enhancement of PCP sorption by soils. This information may aid both in predicting environmental fates of hydrophobic ionizable organic compounds and in developing remediation strategies for them.     

Sorption mechanism of naphthalene by diesel soot: Insight from displacement with phenanthrene/p-nitrophenol

The nonlinear sorption of hydrophobic organic contaminants (HOCs) could be changed to linear sorption by the suppression of coexisting solutes in natural system, resulting in the enhancement of mobility, bioavailability and risks of HOCs in the environment. In previous study, inspired from the competitive adsorption on activated carbon (AC), the displaceable fraction of HOCs sorption to soot by competitor was attributed to the adsorption on elemental carbon fraction of soot (EC-Soot), while the linear and nondisplaceable fraction was attributed to the partition in authigenic organic matter of soot (OM-Soot). In this study, however, we observed that the linear and nondisplaceable fraction of HOC (naphthalene) to a diesel soot (D-Soot) by competitor (phenanthrene or p-nitrophenol) should be attributed to not only the linear partition in OM-Soot, but also the residual linear adsorption on EC-Soot. We also observed that the competition on the surface of soot dominated by external surface was different from that of AC dominated by micropore surface, i.e., complete displacement of HOCs by p-nitrophenol could occur for the micropore surface of AC, but not for the external surface of soot. These observations were obtained through the separation of EC-Soot and OM-Soot from D-Soot with organic-solvent extraction and the sorption comparisons of D-Soot with an AC (ACF300) and a multiwalled carbon nanotube (MWCNT30). The obtained results would give new insights to the sorption mechanisms of HOCs by soot and help to assess their environmental risks.     

土壤不同有机质组分对菲的吸附特征研究

采用批次实验,研究了三种不同类型土壤黄红壤、水稻土和草甸土的全土、重组、去松结态和紧结态4个组分对菲的吸附,结果表明,菲在不同土壤及其组分上的吸附等温线都能用Freundlich方程进行拟合,所有等温线都具有一定程度的非线性,指数N值的大小顺序基本都为全土>重组>去松结态>紧结态.除了黄红壤的紧结态比去松结态对菲的吸附容量KF值略小外,不同土壤及其组分对菲吸附的KF值以及有机碳归一化的KFoc值大小顺序都为紧结态>去松结态>重组>全土.不同类型土壤之间的KF值大小顺序为草甸土>水稻土>黄红壤,而KFoc值大小顺为水稻土>草甸土>黄红壤.KF值与有机碳含量之间呈显著性正相关(P<0.05),KFoc与N之间呈极显著负相关(P<0.001).土壤及其组分对菲的吸附强度与有机质的结构特征和聚合程度有关.     

农药西维因及敌草隆在草木灰上的吸附行为研究

测定分析了草木灰的孔隙结构、表面性质及化学组成,选择理化参数接近,空间构型不同的2种农药西维因和敌草隆作为吸附质,研究其在草木灰上吸附行为,结果表明两者在草木灰上吸附模式理截然不同,线性吸附方程及准一级动力学方程能够拟合平面型分子西维因的吸附等温线及动力学曲线,Freundlich吸附等温式及二级动力学方程吸附对非平面型分子敌草隆的等温线及动力学曲线拟合程度最高,说明平面型分子的吸附可能以简单的线性分配为主,而非平面型分子可能以多过程非线性吸附为主;等温线及动力学拟合参数显示,草木灰对平面型分子西维因的吸附量远大于非平面型分子敌草隆,说明吸附质分子的空间位阻效应是影响吸附的重要因素.     

粉煤灰吸附铀的影响因素探讨

为探讨粉煤灰对铀的吸附特性,考察pH、吸附时间、铀溶液浓度对吸附能力的影响,测定了吸附等温线和吸附动力学。结果表明:其吸附等温线符合Freundlich和Langmuir吸附模型,pH值是影响铀去除率的主要因素,吸附铀的最佳pH=5,铀初始浓度越高,粉煤灰的吸附量越高。实验可为地下水复原特别是采用粉煤灰渗透反应墙修复受放射性污染的地下水提供设计依据。     

紫外辐照引入含氧官能团对生物炭吸附气体和水中苯的影响

以椰壳为原料制备生物炭,采用365 nm紫外光辐照增加吸附剂表面含氧官能团,探究其对生物炭吸附气体和水中苯的影响.理化表征和吸附实验结果表明,生物炭表面含氧官能团增加后,对气体中苯的吸附量提高9.25倍,而对水中苯的吸附量却降低14.64%.生物炭对气体中苯的吸附过程符合Elovich动力学模型,而对水中苯的吸附过程符合准二级动力学模型.含氧官能团的引入使生物炭对气体和水中苯的等温吸附过程从符合Freundlich模型变为符合Langmuir模型.Weber-Morris模型分析认为,增加含氧官能团,可增强生物炭对气体中苯的表面吸附速率,却阻碍了苯从水中向吸附剂颗粒内扩散的过程,水分子与苯竞争吸附是导致生物炭对水中苯吸附量降低的主要原因.     

Thermodynamics of phenanthrene partition into solid organic matter from water

IntroductionSorptionofanorganicpollutanttosoilhasamajorinfluenceonitstransport,bioavailabilityandfateinnaturalenvironmentsanddevelopingsoilpollutionremediationtechnologies .Extensiveresearch(Chiou ,1979;1983;1985 ;1998a ;Karickhoff,1979;Kile ,1995 ;Rutherford ,1992 )suggestedthatsorptionofnonionicorganiccompounds(NOCs)fromwatertosoilisdueprimarilytothepartitioningintosoilorganicmatter(SOM ) .AdsorptionofNOCsfromwaterbyrelativelypolarsoilmineralsissuppressedbythestrongcompetitiveadsorption…     

低分子量腐殖酸改性蒙脱土对黄曲霉素的吸附作用

采用振荡平衡法研究了相对分子质量<3 500的低分子量腐殖酸改性蒙脱土对黄曲霉素(AFB1)的吸附作用及机制.吸附动力学实验结果表明,0～24 h内,蒙脱土原土快速吸附AFB1,在2 h处吸附量即至最大值,而后吸附量持续降低,12 h后趋于稳定、吸附量为1.01μg.g-1;0～24 h内,改性蒙脱土对AFB1的吸附量则持续增加,12 h时吸附量达最大值(1.60μg.g-1),其后吸附达平衡.用腐殖酸改性后,蒙脱土对AFB1的等温吸附曲线由Langmuir型转变为Freundlich型,平衡浓度较高条件下,AFB1在改性蒙脱土上的吸附量明显高于蒙脱土原土.蒙脱土改性后晶层坍塌,出现不规则和絮状松散结构,与其表面聚集的腐殖酸形成较为稳定的"矿物-腐殖酸"复合体,增强了其对疏水性AFB1的吸附能力.随溶液pH值的增大,原土和改性蒙脱土对AFB1的吸附量均增大,但AFB1在改性蒙脱土上吸附量的增加幅度较大,这可能主要与溶液碱性的提高促进了AFB1与蒙脱土矿物的氢键及电性结合有关.研究结果可为进一步阐明AFB1在土壤中的界面过程和环境归趋提供依据.     

垃圾防渗粘性土对多环芳烃菲(PHEs)的吸附作用研究

研究了持久性有机污染物多环芳烃菲(PHEs)在垃圾防渗粘性土中的吸附机理规律及其吸附模型,探讨了pH值及土样颗粒等影响因素对吸附效果的作用机制,提出了垃圾填埋场防渗粘性土的优化设计。结果表明:菲在粘性土中的吸附过程包括4个阶段,达到吸附平衡的时间为9h;吸附等温线符合Freundlich模型,相关系数为0.98,属于非线性等温吸附;菲的水-土分配系数Kd为0.01,有机碳和水之间的分配系数为14.29;当pH值7.42时,土样对菲的吸附量随pH值的增大而迅速增大;pH值7.42的酸性环境中,对菲的吸附量也变大,但是随着酸性的加强,当pH值6.74之后,吸附能力不再有明显变化;菲的最大吸附量与土体的粘粒含量、比表面积呈正比,由大到小顺序为粘性土粉质粘土细砂。     

Phosphorus recovery from biogas fermentation liquid by Ca-Mg loaded biochar

Shortage in phosphorus (P) resources and P wastewater pollution is considered as a serious problem worldwide. The application of modified biochar for P recovery from wastewater and reuse of recovered P as agricultural fertilizer is a preferred process. This work aims to develop a calcium and magnesium loaded biochar (Ca-Mg/biochar) application for P recovery from biogas fermentation liquid. The physico-chemical characterization, adsorption efficiency, adsorption selectivity, and postsorption availability of Ca-Mg/biochar were investigated. The synthesized Ca-Mg/biochar was rich in organic functional groups and in CaO and MgO nanoparticles. With the increase in synthesis temperature, the yield decreased, C content increased, H content decreased, N content remained the same basically, and BET surface area increased. The P adsorption of Ca-Mg/biochar could be accelerated by nano-CaO and nano-MgO particles and reached equilibrium after 360 min. The process was endothermic, spontaneous, and showed an increase in the disorder of the solid-liquid interface. Moreover, it could be fitted by the Freundlich model. The maximum P adsorption amounts were 294.22, 315.33, and 326.63 mg/g. The P adsorption selectivity of Ca-Mg/biochar could not be significantly influenced by the typical pH level of biogas fermentation liquid. The nano-CaO and nano-MgO particles of Ca-Mg/biochar could reduce the negative interaction effects of coexisting ions. The P releasing amounts of postsorption Ca-Mg/biochar were in the order of Ca-Mg/B600 > Ca-Mg/B450 > Ca-Mg/B300. Results revealed that postsorption Ca-Mg/biochar can continually release P and is more suitable for an acid environment.