菲在土壤/沉积物上的吸附-解吸过程及滞后现象的研究

实验研究了菲在土壤 /沉积物上的吸附 解吸过程。CHL土壤和HFH沉积物中有机质的固相13 CCPMASNMR谱图很相似 ,表明样品中有机质的组成差异不大 ;菲在土壤 /沉积物上的吸附过程表现出明显的非线性 ;线性模型不适合拟合菲的吸附等温线 ,Freundlich模型和双区位反应模型 (DRDM)较好地拟合了菲的吸附等温线 ,其中DRDM模型还清楚地反映菲在低浓度和高浓度下不同的吸附方式 ;另外 ,研究表明菲在土壤 /沉积物上的解吸过程中存在明显的滞后现象 ,这可能和土壤 /沉积物有机质的异质性和土壤胶团微小孔隙的存在有关。     

不同条件下菲和萘在塿土上的吸附特征研究

以平衡吸附法研究了菲和萘在塿土上的吸附行为,考察了初始浓度、温度、pH、离子强度和CaCO3对塿土吸附菲和萘的影响,Henry方程、Freundlich方程和deBoer-Zwikker极化方程被用来拟和吸附等温线。结果表明,菲和萘在塿土上的吸附等温线为非线性,Freundlich方程最符合其吸附行为。菲和萘在塿土上的吸附量随温度升高而降低,其吸附是一个放热过程;吸附自由能小于零,表明吸附过程是自发的;熵变值也小于零,说明焓变是吸附过程的驱动力。随着pH增加,塿土对菲和萘的吸附量下降;而随着离子强度增加,塿土对菲和萘的吸附量增加。CaCO对菲和萘的吸附等温线也为非线性,其对塿土吸附菲和萘具有较大的贡献。     

萘在土壤上的吸附行为及温度影响的研究

采用批量平衡法研究了多环芳烃萘在塿土耕层土、塿土粘化层土、塿土古土壤、黄壤、紫色土和石灰土上的吸附行为,比较了不同吸附模型方程对实验数据的拟合情况,并探讨了温度对萘在土壤上吸附行为的影响机理及吸附热力学特征。Henry模型、Freundlich模型和deBoer-Zwikker极化模型均能较好地拟合萘的吸附等温线;45℃下的吸附等温线明显地高于25℃的吸附等温线,表现出随温度升高吸附量增大的趋势。Freundlich模型的吸附容量参数Kf和deBoer-Zwikker模型的起始吸附势ε0在两个温度下有极显著的差异;但Freundlich模型的n参数表征了土壤颗粒表面的性质,对温度变化不敏感。在25℃条件下,萘在土壤有机碳上的分配可能是吸附的主要机制,但随着温度增加,吸附机制变得复杂。土壤对萘的吸附是一吸热反应,整个吸附体系中熵增是吸附作用进行的主要驱动力。     

澳洲坚果果仁粉水分解吸-吸附等温线的测定与分析

为给澳洲坚果果仁粉的干燥和贮藏条件的确定提供技术依据,试验测定了其在室温(25℃)下的水分解吸-吸附等温线。采用非线性回归的方法,应用常见的BET、GAB、Halsey、Henderson、Oswin和Smith模型对试验所得解吸-吸附等温线进行拟合分析,以确定最佳拟合模型及其参数。结果表明,其解吸等温线属于国际理论和应用化学联合会分类的第Ⅱ种类型,其吸附等温线属于第Ⅲ种类型,解吸-吸附滞后现象属于H3型;GAB模型是其最佳的解吸等温线拟合方程,Henderson模型是最佳的吸附等温线拟合方程;GAB模型拟合解吸等温线的参数A、B、C分别为8.2439、0.4815、1.3545。Henderson模型拟合吸附等温线的参数A、B分别为0.3006、0.8682。     

Langmuir,Temkin和Freundlich方程应用于土壤吸附锌的比较

本文分别用Langmuir,Temkin和Freundlich方程拟合土壤吸附锌的等温线。结果表明,吸附数据能很好地符合Freunblich方程,而Langmuir和Temkin方程拟合程度较差。作者从吸附热角度证明了土壤表面不均匀性是造成这种差别的最主要因子。土壤吸附锌过程中吸附热与吸附量的关系满足Freundlich方程模型中关于能量的假设。所以Freundlich方程能比较真实地反映土壤吸附锌的本质,可用予锌吸附机制的探讨。     

菲在不同性质黑炭上的吸附动力学和等温线研究

在300、500和700℃3种条件下加热木屑制备得到3种黑炭,并对其结构和组成进行了表征。通过吸附动力学实验和平衡吸附实验,研究了菲在这些黑炭样品上的吸附动力学和平衡吸附,分别应用拟一阶、拟二阶和叶洛维奇3种动力学模型及Freundlich吸附等温方程对实验数据进行了拟合。结果表明,菲在黑炭样品上的吸附可以分为极快吸附、快吸附和慢吸附3个阶段,拟一阶动力学和叶洛维奇动力学方程仅能对菲在黑炭上吸附动力学的某个阶段拟合较好,而拟二阶动力学模型可较好地拟合菲的整体吸附动力学过程。说明菲在黑炭上的吸附由多个过程控制,水膜扩散、吸附剂颗粒表面扩散和吸附剂内部微孔扩散等多个过程导致了其吸附动力学的复杂性。在快吸附阶段,菲在各个黑炭上吸附动力学的差异,主要受黑炭疏水性影响。Freundlich模型对吸附等温数据的拟合结果进一步证实,多环芳烃菲在黑炭样品上的吸附受多种机制影响。     

不同磷浓度对土壤吸附锌特性的影响

通过等温吸附试验,研究了不同磷浓度条件下水、旱田两种土壤吸附锌的规律,结果表明:在本试验条件下,以Freundlich方程拟合土壤对锌的吸附等温线的效果最好;不同磷浓度条件下,同一土壤的吸附等温线方程参数k和n均没有显著的变化;不同磷浓度对土壤吸附锌的量没有显著影响。因此,磷锌拮抗的原因可能不是施磷加强了土壤对锌的吸附作用。     

诺氟沙星在胡敏酸上的吸附热力学与动力学特征研究

根据OECD Guideline106批平衡实验,研究了诺氟沙星在胡敏酸上的吸附热力学和动力学,并探讨了其可能吸附机理。结果表明,诺氟沙星在经过约12h的快速吸附阶段后,进入缓慢吸附阶段,其吸附平衡时间为48h。伪二级动力学方程能够较好地描述不同pH条件下诺氟沙星在胡敏酸上的吸附动力学特性。诺氟沙星在胡敏酸上的吸附等温线符合Freundlich方程,该方程的拟合系数1/n〈0.5,表明诺氟沙星在胡敏酸上为非线性吸附。ΔH0=-48.85kJ·mol-1和ΔG0〈0,表明诺氟沙星在胡敏酸上的吸附是自发进行的放热过程,且离子交换是其主要吸附机理,同时也可能存在着偶极间作用力、氢键力和电荷转移等吸附机理;ΔS0〈0表明吸附过程中熵在减小。吸附位点的能量随着吸附量的增大而降低,也表明胡敏酸的异质性和吸附的非线性。     

稻谷水分吸附与解吸等温线拟合模型的选择及其参数优化

评价5种最常用的数学模型对中国不同类型的稻谷(籼稻、粳稻、糯稻)吸附与解吸等温线数据的拟合效果，以确定最佳拟合模型及其参数。测定中国不同类型稻谷的吸附与解吸等温线数据，用非线性回归进行统计分析并评价数学模型的拟合效果。结果表明，美国农业工程学会(ASAE)推荐的修正Chung-Pfost模型及其参数并不能与中国稻谷的吸附与解吸等温线数据很好地拟合。Strohman-Yoerger模型最适于拟合籼稻、粳稻的吸附与解吸等温线及糯稻的吸附等温线。而修正Oswin模型最适合拟合糯稻的解吸等温线。Strohman-Yoerger模型拟合籼稻、粳稻吸附等温线的参数C₁、C₂、C₃、C₄分别为1.44871、0.20898、7.32345、0.18647；拟合解吸等温线的参数C₁、C₂、C₃、C₄分别为2.25071、0.24167、8.32543、0.19035；拟合珍糯吸附等温线的参数为1.55680，0.19179，6.19676，0.17155。修正Oswin模型拟合珍糯的解吸等温线的参数为13.63642，-0.05638，3.60042。本研究为中国的稻谷贮藏与加工提供了基础性数据。     

土壤矿物和胡敏酸对阿特拉津的吸附-解吸作用研究

选取了6种土壤矿物(蒙脱石、高岭石、钙饱和处理蒙脱石、钙饱和处理高岭石、无定型氧化铁和无定型氧化铝),以及从土壤中提取纯化的3种胡敏酸为材料,采用批量吸附平衡法,研究土壤矿物和胡敏酸对阿特拉津的吸附特性。结果表明,各吸附剂对阿特拉津的吸附均能采用Frundlich方程进行较好地拟合(r≥0.982,p0.01)。胡敏酸对阿特拉津具有最大的吸附性能,其固-液分配系数(Kd值)随平衡浓度(Ce值)的变化基本恒定,吸附等温线呈线性(Frundlich方程常数N≈1),吸附以分配溶解作用为主,吸附可逆性较高。黏土矿物(特别是蒙脱石)对阿特拉津也具有较强的吸附能力,Kd值随Ce值增加而增加,吸附等温线呈S型(N1),吸附主要是通过表面亲水作用。无定型氧化铁铝的Kd值随Ce值增加而降低,当Ce达到一定水平后,Kd趋于恒定,吸附等温线呈L形(N1),吸附主要是通过无定型氧化物表面的羟基与阿特拉津分子间的化学键合作用,吸附可逆性最差。     

Sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Minerals contribute crucially to the retention of polycyclic aromatic hydrocarbons (PAHs) in subsurface environments. To investigate the sorption behaviour to mineral surfaces batch sorption experiments were conducted using three PAHs (phenanthrene, pyrene, benzo(a)pyrene) and three mineral sorbents that were representative of subsurface materials (quartz, goethite‐coated quartz, quartz‐montmorillonite mixture). Sorption kinetics showed an instantaneous, considerable PAH sorption to all minerals, except for phenanthrene sorption to quartz at small aqueous‐phase concentrations. Apparent sorption equilibrium was achieved after 4 hours of contact time. The sorption characteristics were fitted to six isotherm models by applying Monte Carlo simulation and nonlinear regression. Best‐fit models were obtained by a model discrimination approach. Phenanthrene and pyrene sorption were best described by the Freundlich isotherm model, with the exception of phenanthrene sorption to quartz (linear isotherm). Good fit results for quartz were also obtained for the combined linear‐Freundlich isotherm. Benzo(a)pyrene sorption to all minerals followed linear high‐affinity isotherms. In the case of phenanthrene and pyrene, the Monte Carlo simulations resulted in mean values with small standard deviations for the isotherm parameters, indicating a negligible influence of the experimental uncertainties on the accuracy of the fitted parameters. For phenanthrene, (i) linear isotherms to quartz and goethite‐coated quartz and (ii) a nonlinear concave‐shaped isotherm to quartz–montmorillonite, assuming a pore‐filling process to micropores formed by clay aggregates, were confirmed. For pyrene, nonlinear convex‐shaped isotherms to the mineral surfaces were assessed. A specific sorption affinity of pyrene to the goethite surface indicated a non‐covalent cation‐π interaction. Small sorption affinities to quartz–montmorillonite support an unfavourable partitioning into the adjacent water.     

Predicting phosphorus sorption isotherm parameters in soil using data of routine laboratory tests

Knowledge of phosphorus(P) sorption dynamics across different soil types could direct agronomic and environmental management of P. The objective of this study was to predict P isotherm parameters for a national soil population using data of routine laboratory tests. Langmuir and Freundlich sorption parameters were calculated from two different ranges(0–25 and 0–50 mg P L~(-1)) using an archive of representative agricultural soil types from Ireland.Multiple linear regression(MLR) identified labile forms of aluminium(Al) and iron(Fe), organic matter(OM), cation exchange capacity(CEC), and clay as significant drivers. Langmuir and Freundlich sorption capacities, Freundlich affinity constant, and Langmuir buffer capacity were predicted reliably, with R~2 of independent validation 0.9. Sorption isotherm parameters were predicted from P sorbed at a single concentration of 50 mg P L~(-1)(S_(50)). An MLR prediction of P sorption maximum in the 0–50 mg P L~(-1) range was achieved, to an accurate standard, using S_(50), OM, and Mehlich-3 Fe(R~2 of independent calibration and validation being 0.91 and 0.95, respectively). Using Giles' four shapes of isotherms(C, L, H, and S), L non-strict-and C-shaped isotherm curves accounted for 64% and 27% of the soils, respectively. Hierarchical clustering identified a separation of isotherm curves influenced by two ranges of Mehlich-3 Al. Soils with a low range of Mehlich-3 Al(2.5–698 mg kg~(-1)) had no incidence of rapid sorption(C shape). Single point indices, Al, or available soil data make the regression approach a feasible way of predicting Langmuir parameters that could be included with standard agronomic soil P testing.     

Desorption kinetics of arsenate adsorbed on Al (oxy)hydroxides formed under the influence of tannic acid

Although, much research has been done on arsenate adsorption by Al (oxy)hydroxides, relatively little is known about the kinetics of arsenate desorption from these (oxy)hydroxides, especially those formed in the presence of organic acids. The desorption kinetics of arsenate adsorbed on Al (oxy)hydroxides, formed under the influence of tannic acid, was investigated using 0.1 and 0.5 mM phosphate at pH 5.5 and an ionic strength of 0.01 M at 298 and 318 K. The kinetic data expressed as the mole fraction of the arsenate remaining adsorbed on the Al (oxy)hydroxides after different desorption periods indicated multiple rate characteristics; a fast reaction period from 0.083 to 3 h and a slow reaction period from 3 to 24 h. The second-order rate equation of the six kinetic models tested was chosen to compare the desorption rate of arsenate. The rate constants of arsenate desorption from the Al (oxy)hydroxides formed at different tannate/Al molar ratios (MRs) followed the order: tannate/Al MR of 0 > tannate/Al MR of 0.1 > tannate/Al MR of 0.01 > tannate/Al MR of 0.001 in the fast reaction period, and tannate/Al MR of 0.1 > tannate/Al MR of 0 > tannate/Al MR of 0.01 > tannate/Al MR of 0.001 in the slow reaction period both in 0.1 and 0.5 mM phosphate systems. The data indicate that the Al (oxy)hydroxides formed in the presence of small amounts of tannic acid (tannate/Al MR = 0.001 and 0.01) had a higher adsorption affinity for arsenate and resulted in slower desorption rates of the adsorbed arsenate compared with the Al (oxy)hydroxides formed in the absence of tannic acid. This is ascribed to the tannate-induced structural perturbation, development of microporosity, enhanced specific surface area, and reactivity of the Al precipitates. As the tannate/Al MR increased from 0.001 to 0.1, the rate constants of arsenate desorption steadily increased. This was attributed to the decrease in the point of zero salt effect (PZSE) of the Al precipitates with the increase of the tannate/Al MR and the resultant electrostatic repulsion from coprecipitated tannate which would weaken the binding of arsenate on the Al precipitates. The effect of temperature on the desorption rate of arsenate, which was governed by the activation energy and the pre-exponential factor (collision frequency), varied with the nature of the Al precipitates. The findings obtained in the present study indicate that the relative effects of tannate-induced structural perturbation, enhanced specific surface area, decreased PZSE, and development of micropore structure in the Al (oxy)hydroxides determine the overall impact of tannate on the kinetics of arsenate desorption from these Al (oxy)hydroxides.     

Phenanthrene sorption by compost humic acids

Nonlinear isotherms were observed for sorption of polycyclic aromatic hydrocarbons (PAHs) to humic materials, but the exact sorption mechanism is not clearly understood. This study aimed to investigate the sorption of PAHs by compost humic materials. Humic acids (HAs) were progressively extracted from two compost samples by a 0.1-M sodium pyrophosphate solution. Sorption of phenanthrene by the extracted HAs was studied with a batch equilibration technique. Competitive sorption between pyrene and phenanthrene in the HAs was also examined. Elemental analysis and solid-state ¹³C NMR were used to characterize HAs. All sorption isotherms were nonlinear although these samples contained little black carbons if any. Isotherm linearity increased with increasing number of extractions. Isotherm nonlinearity was negatively related to HA aliphaticity. Addition of pyrene to the phenanthrene-HA system increased isotherm linearity. Competition between phenanthrene and pyrene sorption was more pronounced in the first fraction of HAs with a higher content of aromatic moieties. This study showed that humic materials alone could lead to nonideal sorption for PAHs.     

Sorption behavior of prochloraz in different soils.

The sorption behavior of the imidazole fungicide prochloraz [PCZ; N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide] was studied in batch experiments with different soils. The soil organic matter content was found to control the amount sorbed by different soils. K(d) values ranged from 56 +/- 0 to 552 +/- 10 (mean = 221 +/- 5) and K(OC) values from 7273 +/- 0 to 16250 +/- 1300 (mean = 11829 +/- 303). As calculated from a linear regression of K(d) versus %OC, K(OC) was 12900 +/- 1300. Additionally, the pH value of the soil had considerable influence on the sorption of the weakly basic PCZ (pK(a) = 3.8), giving rise to stronger sorption at lower pH. K(d) values determined on pH-modified soils confirmed the pH dependency. Sorption isotherms on two soils were recorded, initial concentrations ranging from 0.09 to 5.71 mg L(-)(1). The Freundlich isotherm was fitted to the values measured. The Freundlich exponents calculated were significantly smaller than unity, indicating nonlinear sorption. Sorption experiments with two metabolites of PCZ (PCZ-formylurea and PCZ-urea) revealed K(d) values one-fourth to one-third those for PCZ on two soils.     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

对硝基氯苯在土壤和腐殖酸上的长期吸附与多步解吸的研究

采用批量平衡实验法研究了对硝基氯苯（p-NCB）在土壤和腐殖酸上的长期吸附和多步解吸,比较了连续的多步解吸与一步解吸的差异。结果表明,随着吸附时间的增加吸附量均会有所增加,随吸附时间增加吸附等温线的非线性增强。p-NCB在液相和固相上的初始浓度对吸附速率有一定影响,低浓度比高浓度时达到平衡的速率要低。对于两种受试土壤,两次解吸得到的等温线均无法与吸附等温线重合,表现出很强的吸附不可逆性。而尽管p-NCB在腐殖酸上表现出明显的非线性吸附（n = 0.794）,但4次解吸后所得到的平衡位点与吸附所得的平衡位点基本落在同一条直线上,对数坐标下进行线性拟合的相关系数（R2）可达0.988,说明吸附过程是完全可逆的。     

Preferential sorption of phenolic phytotoxins to soil: implications for altering the availability of allelochemicals

Allelopathy, secondary metabolite-mediated plant-to-plant interaction, is gaining application in current agricultural science as well as in invasion ecology. However, the role of sorption to soil in modifying the bioavailability of components in complex allelochemical mixtures is still obscure. Hence, the role of preferential sorption to soil in altering the chemical composition of plant exudates was studied in a silt loam soil using representative mixtures of plant phenolic acids, namely, hydroxybenzoic acid, vanillic acid, coumaric acid, and ferulic acid. The experiment was conducted using a batch equilibration technique, and data were fitted to a Freundlich isotherm. The concentration-dependent sorption coefficient (K(d)) at 10 microg mL(-)(1) was used to assess the sorption affinity of phenolic acids across different systems. Along with solid phase dissolution, all of the phenolic acids exhibited strong site-specific sorption, as evident from their nonlinear isotherms. Removal of organic matter substantially decreased the sorption affinity of all phenolic acids. Direct competition for sorption sites was observed even at low concentrations of phenolic acids. The K(d) of hydroxybenzoic acid was decreased more than 90% in the presence of coumaric acid. About 95% of sorbed vanillic acid was displaced into the soil solution in the presence of ferulic acid. Hydroxybenzoic acid did not affect the sorption affinity of other phenolic acids significantly, whereas ferulic acid showed low displacement by other phenolic acids. The displacement pattern indicated directional sorption of phenolic acids with -OH and -COOH groups. Soil organic matter was associated with preferential sorption. This is the first study to elucidate competitive sorption characteristics of plant secondary metabolites in soil matrix. The results demonstrate that preferential sorption to soil can alter the availability of plant exudates in mixtures and thus may mediate their phytotoxic effects.     

美国不同轻质集料的磷吸附特性比较

In this study, phosphorus(P) sorption of thirteen light-weight aggregates(LWAs) from USA was compared during batch equilibrium experiments in order to identify those materials which had the highest P sorption capacity for further study. Seven different levels of sorption activity were observed, which were broadly grouped into three categories—high performing, middle performing, and low performing aggregates. Chemical analysis of Ca, Al, Fe, and Mg was used to describe the differences between LWAs. There was a significant correlation between cation(especially Al, Ca, Fe, and Mg) content and P sorbed. Langmuir isotherms were used to describe P sorption maximum and binding affinity for four of the top five performing LWAs, Universal, Stalite "D", Stalite "Mix", and TXI.The fifth aggregate, Lehigh, exhibited more complex sorption, and was better described by the Freundlich isotherm. Universal had a mean P sorption at the highest concentration of 824 mg kg-1, well above its calculated sorption maximum(702 mg kg-1), and also had the highest binding affinity(1.1 L mg-1). This experiment suggests that the top performing LWA(Universal) may perform poorly in column and field studies due to observed precipitates, which could degrade constructed wetland performance. Other LWAs may exhibit superior field performance due to their high calculated sorption maxima. In general, these results highlight the importance of batch experiments as a first step in identifying materials suitable for column and field experiments.     

Role of root exudates on the sorption of arsenate by ferrihydrite

Iron oxy‐hydroxides in soil are known to have a large affinity for arsenate (As(V)) inorganic species. At the soil–root interface such mineral components are embedded by mucilaginous material that is secreted from continuously growing root cap cells. In order to determine the role of plant mucilages in As(V) sorption by iron oxy‐hydroxides, we layered a calcium (Ca)‐polygalacturonate network (CaPGA) on to amorphous iron (Fe) (III) hydroxide (ferrihydrite, Fh) particles. The scanning electron micrographs of the CaPGA network coating the ferrihydrite (Fh–CaPGA) show a regular structure with a honeycomb‐like pattern where interlacing fibrils form a porous system. The FT‐IR spectra of Fh–CaPGA suggest that CaPGA fibrils are retained by the surface Fe(III) nuclei of Fh through electrostatic interactions. The sorption experiments carried out at pH 4.3 and 5.8 indicated a smaller amount of As(V) sorbed by Fh–CaPGA than by Fh alone, being less after 3 and 24 hours of reaction by about 70 and 30%, respectively. The sorption of As(V) by Fh was also studied in the presence of caffeic acid (CAF), an important root exudate. Simultaneous sorption kinetics show that As(V) sorption by Fh is almost independent of CAF concentration, indicating a greater affinity of arsenate ions towards the Fh surfaces. However, the amount of As(V) sorbed by the Fh coated by CaPGA, in the presence of 0.25, 0.5 and 1.0 mm CAF, is markedly smaller by about 20, 27 and 40%, respectively, than that found in the As(V)–CAF‐Fh ternary systems. This is caused mainly by redox reactions involving CAF and the surface Fe(III) nuclei of Fh leading to the formation of CAF oxidation products which prevent As(V) sorption.