氯苯类化合物在沉积物上的非线性吸附行为

以5种自然沉积物为对象,采用批量平衡法,测定了氯苯、1,4-二氯苯、1,2,4-三氯苯和1,2,4,5-四氯苯在这5种沉积物样品上的吸附等温线,以研究沉积物自然有机质（NOM）的性质对氯苯类化合物（chlorobenzenes, CBs）吸附行为的影响.结果表明,1,2,4-三氯苯在虎门、黄沙、雅岗、三水、长洲5种沉积物中的等温吸附线性因子n都小于1,分别为0.956、 0.858、 0.872、 0.947和0.915,说明所有吸附等温线均为非线性;同时,非线性的程度n与极性指数（O+N）/C呈负相关关系,相关系数R²达0.994 7,表明NOM的聚合度（以极性指数为表征）直接影响着吸附非线性程度;5种沉积物对1,2,4-三氯苯的吸附亲和力（K_oc）随沉积物极性指数的增大而减弱,说明NOM聚合度较高的沉积物对1,2,4-三氯苯的吸附亲和力更强;氯苯、1,4-二氯苯、1,2,4-三氯苯、1,2,4,5-四氯苯在同一种沉积物（黄沙）上吸附等温线的线性因子n分别0.755、 0.788、 0.858、 0.949,非线性程度按溶质分子由小到大的顺序依次减弱,说明溶质分子本身的性质也影响着CBs在沉积物上的吸附性能.     

Contribution of black carbon to nonlinearity of sorption and desorption of acetochlor on sediment

In order to investigate the contribution of various black carbon (BC) contents to nonlinearity of sorption and desorption isotherms for acetochlor on sediment, equilibrium sorption and desorption isotherms were determined to measure sorption and desorption of acetochlor in sediment amended with various amounts of BC. In this paper, two types of BC referred to as BC400 and BC500 were prepared at 400°C and 500°C, respectively. Higher preparation temperature facilitated the formation of micropores on BC to enhance its sorption capacity. Increase of the BC content obviously increased the sorption amount and reduced the desorption amount for acetochlor. When the BC500 contents in total organic carbon (TOC) increased from 0 to 60%, Freundlich sorption coefficient (K _f) increased from 4.07 to 35.74, and desorption hysteresis became gradually obvious.When the content of BC in TOC was lower than 23%, the sorption isotherm had a significant linear correlation (p = 50.05). In case of desorption, a significant nonlinear change could be observed when the content of BC was up to 13%. Increase of BC content in the sediment would result in shifting the sorption-desorption isotherms from linearity to nonlinearity, which indicated that contribution of BC to nonlinear adsorption fraction became gradually remarkable.     

Effects of different sediment fractions on sorption of galaxolide

Sorption isotherms of galaxolide (HHCB) of different fractions from two sediments with different mineral and organic carbon contents were determined to compare HHCB sorption behavior and contribution to the total sorption. The HHCB sorption isotherms that used the batch equilibration method were studied on different sediments of different fractions. The sorption isotherms of 600°C heating fractions were detailed using the linear model, while the other fractions were nonlinear and fitted well with the Freundlich model. The dissolved organic carbon (DOC) removed, NaOH extracted, and 375°C heating fractions showed more nonlinear sorption than the original sediments, which suggested more heterogeneous sorption sites in these fractions. Compared to the original sediments, the 375°C heating fractions had higher carbonnormalized distribution coefficient (K _oc) values, indicating a higher sorption affinity for HHCB. Among the different sediment fractions, the contribution of the 600°C heating fractions to the overall sorption were the lowest (< 20%), while the 375°C heating fractions were the highest (up to 85%).     

水稻秸秆主要组分的提取及其对芘的吸附作用

从水稻秸秆中提取主要组分--木质素、纤维素、半纤维素,利用元素分析和红外光谱对其性质进行了表征,并研究了芘在秸秆及其3种组分上的吸附行为.结果表明,各组分性质差异很大,木质素具有较高的芳香性和较低的极性,而纤维素和半纤维素具有较高的极性和脂肪性.不同组分对芘的吸附等温线均符合Freundlich方程,但吸附能力因其结构的差异而不同,木质素对芘的吸附能力最强, 吸附容量KF为5.04×104,比纤维素高100倍左右,而芘在半纤维素上的吸附能力略低于纤维素.低浓度(水相平衡浓度ce=0.01 Sw)下,秸秆对芘的吸附主要受木质素的控制,而且分配系数Kd略低于按照木质素质量分数计算的预测值,可能是由于木质素的烷基和芳香结构被周围的极性结构所覆盖.但在高浓度(ce = 0.5 Sw)时,秸秆对芘的吸附高于各组分的加和,芘向秸秆其他组分的分配作用不能忽略.芘在木质素上的吸附表现为非线性(非线性指数,n = 0.89),而其它3种吸附剂对芘的吸附更趋向于线性(n > 0.96).n值与芳香性呈负相关关系,而与极性呈正相关关系,表明芳香性导致的特殊作用力是造成吸附非线性的主要原因.有机碳标化分配系数Koc随吸附剂芳香性的增强而增大,但随极性的增强而减小.     

土壤-水体系中固/液比对溶解性石油烃吸附的影响

采用批实验的方法,研究了2种土壤在不同的固/液比（solid-to-solution ratio,SSR）条件下对溶解性石油烃（DPH）的吸附-解吸特性.结果表明,DPH在土壤中的吸附-解吸等温线符合线性方程;解吸表现出明显的滞后现象,滞后因子随SSR的升高而增加,随土壤有机碳含量（OC）的升高而减小,对于OC=1.54%的稻田土,当SSR从10.00 g·L^-1变化至75.00 g·L^-1,DPH的解吸滞后因子从1.43升高到2.21;对于OC=15.91%的黑土,当SSR从2.50 g·L^-1变化至5.00 g·L^-1,DPH的解吸滞后因子从1.18升高到1.37.说明吸附的不可逆性随SSR的升高而增强,随土壤有机碳含量的升高而减弱.另外,研究发现由吸附等温线计算得到的k_OC随SSR的升高（不可逆性的增强）而减小,在此基础上建立了固定体系中k_OC与SSR的关系模型,用于预测实际环境中DPH在土-水界面的迁移.     

环丙沙星在潮土中的吸附特性

为了探明环丙沙星在潮土中的吸附特性,采用静态吸附试验,研究了环丙沙星在潮土中的吸附动力学、等温吸附特性以及pH值对其吸附过程的影响.结果表明,环丙沙星在潮土中的吸附过程可分为快速吸附和慢速平衡2个阶段.整个吸附过程符合二级反应动力学方程,吸附常数为1.138×10-3～2.849×10-2kg.(min.mg)-1.环丙沙星的吸附等温线能够较好地符合Freundlich方程和Langmuir方程,其中Freundlich方程的拟合效果更佳,吸附容量(lgKf)为2.725.研究发现,在pH值为4～9条件下,环丙沙星的吸附参数对数值lgKd呈随pH的增加先增加后降低的趋势,当pH值为5时,潮土对环丙沙星的吸附效果最好,lgKd为3.11,强酸性和碱性条件均不利于潮土对环丙沙星的吸附.由此推断阳离子吸附可能是潮土对环丙沙星吸附的重要机制之一.     

Sorption of tetracycline to sediments and soils: assessing the roles of pH, the presence of cadmium and properties of sediments and soils

Batch sorption experiments were conducted to evaluate the sorption behavior of tetracycline (TC, H₃L) on sediments and soils in the presence and absence of cadmium (Cd), as affected by pH and properties of sediments and soils. The results indicated stronger nonlinearity and higher capacity of TC sorption on sediments than on soils. Sorption of TC also strongly depended on environmental factors and sediment/soil properties. Lower pH facilitated TC sorption through a cation exchange mechanism, which also took place at pH values above 5.5, where TC existed as a zwitterion (H₂L⁰) or anions (HL⁻ and L²⁻). When pH was above 7, however, ligand-promoted dissolution of TC might occur due to TC weakening the Al-O bond of aluminum oxide and the Fe-O bond of iron oxide. Natural organic matter (NOM) plays a more important role in TC sorption than cation exchange capacity (CEC) and clay contents. The presence of Cd (II) increased TC sorption on both sediments and soils, which resulted from the decrease of equilibrium solution pH caused by Cd²⁺ exchange with H⁺ ions of sediment/soil surfaces. The increase of TC sorption was also related to the formation of TC-Cd complexes, where Cd²⁺ acted as a bridge between the sediment/soil and TC.     

pH及表面活性剂对诺氟沙星在海洋沉积物上吸附行为的影响

采用批量平衡法系统考察了pH值和4种表面活性剂对诺氟沙星在海洋沉积物上吸附行为的影响.结果表明,不同pH值下,诺氟沙星在海洋沉积物上的吸附行为均可以较好地用Freundlich等温式拟合.Freundlich常数KF与诺氟沙星的平衡吸附量均随pH值的增大而减小,且在pH值为8.10时,出现最小值;研究发现,pH值为6.01时,诺氟沙星以阳离子交换为主要机制吸附在海洋沉积物上;pH值为8.10时,诺氟沙星在海洋沉积物中的吸附以范德华力、疏水作用、静电作用为主.加入表面活性剂后,其吸附行为能较好地用吸附二级动力学方程拟合.加入表面活性剂对诺氟沙星的平衡吸附量Qe有影响,饱和吸附量Qe由小到大依次为:Qe(Tween80)相似文献   

除草剂草萘胺在土壤-水环境中的吸附行为及其机理

采用高效液相色谱法(HPLC)测定了土壤、胡敏酸及粘土矿物对除草剂草萘胺的吸附效应,并用FTIR图谱分析对其吸附机理进行了研究.结果表明,草萘胺在5种土壤上的吸附均很好地符合Freundlich方程,吸附常数Kf值在3.98～12.82之间.5种土壤对草萘胺吸附容量大小的次序为:黄泥土＞黑土＞黄棕壤＞红壤＞潮土.将吸附常数Kf与土壤的理化性质进行多元逐步回归分析表明,土壤有机碳含量与草萘胺吸附容量呈线性关系(R2=0.997,p＜0.05 n=5).红外光谱分析结果表明,草萘胺可能通过脂肪族分配及疏水吸附等形式与HA发生了结合.     

老化对黑碳中吸附态苯酚的脱附及微生物降解的影响

采用松木基黑碳为吸附剂,考察了老化作用对吸附态苯酚的脱附及微生物降解作用的影响.苯酚吸附等温线数据采用非线性Freundlich方程拟合,脱附数据采用三位点脱附模型拟合,微生物降解试验分别在恶臭假单胞菌ATCC 11172的两种菌密度下进行.结果表明,平衡位点、非平衡位点以及不可脱附位点这三种位点在不同老化时间内都存在,其中不可脱附位点上的比例(fnd60.4%)都占绝大部分,并且随着老化时间增加,易脱附位点上的苯酚逐渐往不易脱附的位点转移;通过对连续稀释脱附数据的分析表明,脱附体系中脱附产物的不定期移除(非生物移除)能够极大地促进脱附的进行;老化时间越长,吸附态苯酚的生物可利用性越小,但同一老化时间内两组不同菌密度之间的生物可利用性并无明显的统计学差异;同时发现黑碳中不可脱附位点上的部分苯酚亦能被降解.     

Removal of fluoride from water using titanium-based adsorbents

Three adsorbents including TiO₂, Ti-Ce, and Ti-La hybrid oxides were prepared to remove fluoride from aqueous solution. The Ti-Ce and Ti-La hybrid adsorbents obtained by the hydrolysis-precipitation method had much higher sorption capacity for fluoride than the TiO₂ adsorbent prepared through hydrolysis. Rare earth (Ce and La) oxides and TiO₂ exhibited a synergistic effect in the hybrid adsorbents for fluoride sorption. The sorption equilibrium of fluoride on the three adsorbents was achieved within 4 h, and the pseudo-second-order model described the sorption kinetics well. The sorption isotherms fitted the Langmuir model well, and the adsorption capacities of fluoride on the Ti-Ce and Ti-La adsorbents were about 9.6 and 15.1 mg·g⁻¹, respectively, at the equilibrium fluoride concentration of 1.0 mg·L⁻¹, much higher than the 1.7 mg·g⁻¹ on the TiO₂. The sorption capacities of fluoride on the three adsorbents decreased significantly when the solution pH increased from 3 to 9.5. The electrostatic interaction played an important role in fluoride removal by the three adsorbents, and Fourier transform infrared (FTIR) analysis indicated that the hydroxyl groups on the adsorbent surface were involved in fluoride adsorption.     

桑沟湾表层沉积物性质及对磷的吸附特征

通过研究桑沟湾表层沉积物对磷的吸附动力学曲线和吸附等温线,并结合沉积物的表面电荷性质及磷的形态分析,考察了沉积物对磷的吸附性能和吸附机制.结果表明,桑沟湾表层沉积物对磷的吸附过程包括快吸附过程和慢吸附过程,可用快慢二段一级动力学方程描述,等温线符合Langmuir交叉式模型.夏季沉积物样品的最大吸附量高于春季样品,粒级较小的沉积物吸附能力较强.沉积物样品对磷的最大吸附量Qm在0.047 1~0.123 0 mg·g-1之间,吸附/解吸平衡磷浓度(EPC0)范围在0.059 6~0.192 7 mg·L-1,沉积物充当"磷源"的作用.不同站位表层沉积物中无机磷(IP)是磷在沉积物中的主要赋存形态,吸附后的沉积物样品中弱吸附态磷(Ex-P)、铁结合态磷(Fe-P)明显增加.吸附过程包括物理吸附和化学吸附,以物理吸附为主.     

莠去津降解菌HB-5的最佳产酶培养基及发酵条件

从农药厂废水中分离到一株降解莠去滓的节杆菌(Arthrobacter sp.)HB-5,以从该菌中提取到的降解酶对莠去津的降解率为指标,进行最佳产酶培养基及发酵条件的优化研究,对其产酶量进行了评价.通过正交试验和均匀试验,对细菌HB-5的发酵培养基进行了优化研究.运用SAS软件进行结果分析,所获优化培养基配方为:蔗糖3.0g·L-1,莠去津0.38g·L-1,K2HPO40.5g·L-1,KH2PO41.2 g·L-1,MgSO4·7H2O 1.2g·L-1,NaCl 0.1g·L-1,微量元素溶液3.8mL·L-1.得到菌株培养的最佳优化条件为:菌株发酵液培养时间为48h.接种量为2%,发酵液初始pH值为9,250mL三角瓶中装液量为80mL经优化后,降解酶对莠去津的降解率(91.64%)比原培养基(40.67%)提高了125%.     

生态沟渠底泥属性与磷吸附特性研究

对种植水生植物铜钱草、黑三棱的生态沟渠和有杂草生长的自然沟渠中0～5 cm和5～15 cm底泥属性及磷吸附特性进行比较研究.结果表明,铜钱草0～5 cm底泥中草酸提取态铁、铝和磷含量均高于自然杂草和黑三棱段底泥.Freudlich和Langmiur方程拟合吸附数据得出:试验底泥的吸附、解吸平衡时磷浓度(EPC0)在0.009～0.031 mg·L-1范围;铜钱草0～5 cm底泥的Kf和Smax值最大,分别为352.2 L.kg-1、562.7 mg·kg-1,表明该底泥样对磷的吸附能力最强.回归分析得出磷吸附参数与底泥属性有显著的相关性(P<0.05),主要受草酸提取态铁、黏粒含量、磷饱和度的影响.可见,水生植物对底泥属性及磷吸附能力都有影响,在生态沟渠中优选植物种植能降低面源污染中磷流失风险.     

Effect of biosurfactant on the sorption of phenanthrene onto original and H2O2-treated soils

The objective of this study was to examine the effect of biosurfactant on the sorption of phenanthrene (PHE) onto the original or H2O2-treated black loamy soil (typic isohumisols) and red sandy soil (typic ferralisols). The sorption isotherms were performed with the original and “soft” carbon-removed soils in the presence and absence of biosurfactant (200 mg/L). The sorption and degradation of biosurfactant were investigated. The result showed that organic matter played an important role in PHE sorption onto the black loamy and red sandy soils, and the PHE sorption isotherms on the “soft” carbon-removed soils exhibited more nonlinearity than those on the original soils. The values of partition coe cient (Kd) on the original black loamy soil with or without 200 mg/L biosurfactant were 181.6 and 494.5 mL/g, respectively. Correspondingly, in the red sandy soil, Kd was 246.4 and 212.8 mL/g in the presence or absence of biosurfactant, respectively. The changes of Kd suggested that biosurfactant inhibited PHE sorption onto the black loamy soil, but facilitated PHE sorption onto the red sandy soil. The nonlinearity of PHE sorption isotherm was decreased in the presence of biosurfactant. Site specific sorption might occur during PHE sorption onto both the original and the “soft” carbon-removed soils in the presence of biosurfactant. It was noted that biosurfactant could also be sorbed onto soils. The maximal sorption capacity of the red sandy soil for biosurfactant was (76.9 0.007) g/g, which was 1.31 times that of black loamy soil. Biosurfactant was degraded quickly in the two selected soils, and 92% of biosurfactant were mineralized throughout the incubation experiment for 7 d. It implied that biosurfactant should be added frequently when the remediation of polycyclic aromatic hydrocarbon (PAH)-contaminated soils was conducted through PAH desorption approach facilitated by biosurfactant.     

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.     

Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectroscopy

This research investigates the adsorption mechanisms of fluoride (F) on four clay minerals (kaolinite, montmorillonite, chlorite, and illite) under different F⁻ concentrations and reaction times by probing their fluoride superficial layer binding energies and element compositions using X-ray photoelectron spectroscopy (XPS). At high F⁻ concentrations (C ₀ = 5–1000 mg·L⁻¹), the amount of F⁻ adsorbed (Q _F), amount of hydroxide released by clay minerals, solution F⁻ concentration, and the pH increase with increasing C ₀. The increases are remarkable at C ₀>50 mg·L⁻¹. The QF increases significantly by continuously modifying the pH level. At C ₀<5–100 mg·L⁻¹, clay minerals adsorb H⁺ to protonate aluminum-bound surface-active hydroxyl sites in the superficial layers and induce F⁻ binding. As the C ₀ increases, F⁻, along with other cations, is adsorbed to form a quasi-cryolite structure. At C ₀>100 mg·L⁻¹, new minerals precipitate and the product depends on the critical Al³⁺ concentration. At [Al³⁺]>10^−11.94 mol·L⁻¹, cryolite forms, while at [Al³⁺]<10^−11.94 mol·L⁻¹, AlF₃ is formed. At low C ₀ (0.3–1.5 mg·L⁻¹), proton transfer occurs, and the F⁻ adsorption capabilities of the clay minerals increase with time.     

Brown marine algae turbinaria conoides as biosorbent for Malachite green removal: Equilibrium and kinetic modeling

In this study, the biosorption of Malachite green (MG) onto Turbinaria conoides, brown marine algae, was studied with respect to initial pH, temperature, initial dye concentration, and sorbent dosage. The optimum initial pH and temperature values for MG removal were found to be 8.0 and 30°C, respectively. Sorbent dosage was found to strongly influence the removal of MG. Equilibrium studies were carried out to test the validity of the Langmuir (q _max = 66.6 mg/g and b = 0.526 mL mol/L) and the Freundlich (n = 1.826 and K = 3.751 mg/g) isotherms. The kinetic studies indicated the validity of the pseudo first-order and second-order equation.     

水环境中典型纳米颗粒对菲的吸附特征

以典型三环多环芳烃菲为代表,选取11种典型纳米颗粒对水中不同浓度的菲进行吸附实验,探究水体中的纳米颗粒对菲的吸附特征.结果表明,Freundlich模型对所有样品的拟合结果最好.logKFr值显示,有机膨润土及3种炭黑对菲的吸附作用最强,且远远大于其他纳米颗粒.有机膨润土对菲的吸附表现为线性吸附(n=1.08),而3种炭黑均表现出显著的非线性特征(n＜0.5),且非线性特征随吸附能力的增强而增强,其他几种纳米颗粒均表现出非线性吸附特征(n＜0.9).水中所有的纳米颗粒在与菲作用的过程中,吸附的强弱与颗粒表面电位、粒径及比表面积均无显著相关性,即对于所有纳米颗粒来说,这几种性质并不是决定吸附作用的最主要因素,而吸附剂的化学组成及结构特性可能是引起吸附作用差异的主要原因.     

深圳湾生态系统多环芳烃(PAHs)特征及其生态危害

2004年在深圳湾海域采集海水、悬浮物、表层沉积物和柱状沉积物样品,并分析其中15种多环芳烃的含量及其相关参数,同时采用210Pb法测定柱状沉积物的年龄.结果表明,海水、悬浮物、表层沉积物和柱状沉积物中总的PAHs含量分别为(69.4±24.7)ng·L-1、(429.1±231.8)ng·g-1、(353.8±128.1)ng·g-1和(321.1±134.6)ng·g-1,各介质优势组分均为菲、荧蒽和芘;1948～2004年期间,深圳湾柱状沉积物中PAH各单体的浓度总体上一直在增加,PAHs的平均沉积通量为89.9ng/(cm2·a);PAH各单体在沉积物/海水中的分配系数(Koc)与其相应的辛醇/水比(Kow)存在明显的正相关性,即可用PAH的Kow值来预测深圳湾海域PAH的Koc.目前,水体与沉积物中PAH含量对该海域的水生生物尚未构成威胁.