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。     

施用猪粪对棕壤胡敏酸和富里酸热力学参数的影响

应用Vodyanitsky提出的方法，根据元素组成数据，计算了施用猪粪对棕壤胡敏酸(HA)、富里酸(FA)热力学参数的影响。结果表明，HA、FA的形成都是自发进行的放热反应；与HA相比，FA的能态较低，分子结构有序度和热稳定性较高；FA在土壤中比HA更容易形成。施用猪粪后，HA、FA的能态降低，分子结构有序度和热稳定性也降低，形成的自发性减弱且放热量减少，这些与它们元素组成的变化有关。     

考虑焦油的生物质气化过程热力学模型

在生物质气化过程中焦油是不利产物,由于焦油成分的复杂性,传统生物质气化热力学模型均未考虑焦油。为了研究操作运行条件对燃气成分、焦油等影响,本文引入焦油模型化合物,考虑系统散热和碳不完全转化等因素影响,基于物质平衡、能量平衡和化学反应平衡建立了考虑焦油的生物质气化过程热力学模型。使用Newton-Raphson方法对模型进行了求解。利用文献数据验证了模型的有效性。最后,利用所建模型计算了空气预热温度、空气当量比、水蒸汽添加率等操作条件对燃气成分、焦油含量等指标的影响。结果表明,空气预热温度提高,焦油含量下降,气体热值提高;空气当量比从0.2提高到0.3,焦油含量降低,燃气中有效成分减少;水蒸汽添加率从0增加到10%,焦油含量下降,气化效率提高。研究结果可为生物质能低焦清洁利用提供参考。     

基于集中参数热模型法的自卸车油气悬架系统热分析

针对目前非公路自卸车油气悬架系统温度变化的研究中未考虑缸筒和活塞杆热容的问题,该文引入集中参数热模型法对非公路自卸车油气悬架系统温度变化进行研究.运用热学理论、气体状态方程,建立包含缸筒、活塞杆热容的非公路自卸车油气悬架系统的集中参数热力学模型.通过求解热力学模型方程组,分析非公路自卸车油气悬架系统中油液温度的变化趋势,并将结果与试验结果进行了对比.对比的结果表明集中参数热力学模型能较准确的描述非公路自卸车油气悬架的热力学状态,而且考虑缸筒、活塞杆热容量会增加系统的温度变化的迟滞效应.该研究将有利于精确描述非公路自卸车油气悬架的动力学特性,同时也为其他工程或农用车辆上油气悬架热力学研究提供了有益的参考.     

基于二叉树结构的参数化L系统的计算模型研究

在虚拟植物生长模型的设计与研究中,L系统一直是主要的研究热点。基于二叉树结构的三维植物模型,深入研究了参数化L系统,提出了基于二叉树的参数化L系统模型,并设计了相关的算法。此模型能够清晰地表明三维植物图形的生成以及植物器官间的遗传关系,为虚拟植物生长模型建立提供了新的方法。     

Green-Ampt模型参数简化及与土壤物理参数的关系

简化模型表达形式从而减少参数个数,对于Green-Ampt入渗模型的实际应用具有重要的现实意义。该文通过推导湿润锋处平均基质吸力与Philip模型中土壤吸湿率关系基础上提出了简化的Green-Ampt入渗模型,基于新疆222兵团两块壤质土壤田块上土壤水分入渗试验资料,分析了Green-Ampt简化入渗模型参数与土壤物理参数之间的关系,建立了模型参数与土壤物理参数之间的定量经验转换函数。结果表明,入渗参数A(组合参数)与土壤初始含水率呈对数负相关,相关系数为0.77,A与土壤紧实度和黏粒含量均呈指数负相关,相关系数分别为0.70和0.74。饱和导水率Ks与土壤紧实度和黏粒呈指数负相关,相关系数分别为0.74和0.73。A和Ks与土壤初始含水率、土壤紧实度和黏粒含量呈高度和中度多元线性相关,相关系数分别为0.9和0.79。研究表明Green-Ampt简化入渗模型能够在一定精度下分析土壤入渗过程。     

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。     

PID优化算法在分布式水文模型参数优化计算中的应用研究

采用PID优化算法对分布式水文模型VIC模型进行参数自动优化计算,并对比分析参数优化前后对分布式水文模型模拟精度的影响。结果表明:参数优化后,分布式水文模型VIC模型在年尺度和小时尺度的水文模拟精度均有所改善,误差减少13.8%和13.2%,拟合度提高0.28和0.14。研究成果对于分布式水文模型参数优化方法提供参考价值。     

盐碱土壤Philip入渗模型参数的神经网络预报模型

以改良盐碱土壤、提供入渗参数为研究目的,在山西省北部的4种盐碱荒地进行了系列入渗试验和基本理化参数测定试验。基于误差反向传播算法(Back Propagation算法),建立了盐碱地土壤基本理化参数与Philip入渗模型参数之间的神经网络预报模型。预测所得Philip入渗模型参数的平均相对误差如下:稳渗率A为4.30%、吸渗率S为0.31%,预测值与实测值吻合程度高。研究结果表明,基于盐碱地土壤条件,选择土壤体积含水率、容重、质地、有机质含量、全盐量以及p H作为预报模型输入变量,Philip入渗模型参数为输出变量的BP神经网络的预报模型是可行的。     

Parameterization and regionalization of Cd sorption characteristics of sandy soils. I. Freundlich type parameters

Cd sorption isotherms (n = 24) were established for arable, sandy soils of the ‘Fuhrberger Feld’ catchment area northeast of Hannover (Germany) using 0.01 M_c Ca(NO₃)₂ solution with Cd additions ranging from 0 to 44 μM_c Cd. Alternative fractions of initially (prior to analysis) sorbed Cd (S₀) were added to the amount sorbed during the experiments. The Freundlich equation was fitted to the resulting isotherms. The obtained retention parameters k and M varied with respect to the different S₀ fractions. Isotherms corrected with Cd_EDTA as S₀ fraction were nonlinear in their log-form. The highest degree of log-linearity is obtained if S₀ is characterized by 40% of the agua regia extractable Cd. The corresponding k values ranged from 36 to 1275 g^1-M L^M kg^?1 (mean 338 g^1-M L^M kg^?1, cv = 92%). The Freundlich exponent M showed less variation (0.7 to 1.1, cv = 12%) with a mean of 0.88. Functions based on these parameters predicted Cd concentrations in Ca(NO₃)₂?soil suspensions well (r² = 0.96) but were hardly related to Cd concentrations of ‘fresh’ soil solutions (r² = 0.20).     

Relationship between Freundlich isotherm Coefficients,log K F and 1 / n for atrazine desorption from soils in Japan

Desorption experiments were conducted on 21 soils at 3 atrazine concentrations. The Freundlich isotherm was used to estimate atrazine desorption. For the relationship between Freundlich isotherm coefficients, log K _F and 1 / n, 1 / n was also represented by a linear regression of log K _F as in the case of atrazine adsorption. All the linear regression lines of desorption exhibited larger slopes and intercepts than those of adsorption. When the atrazine concentration was high, the slope and intercept values were smaller than those for the desorption regression lines. The results showed that the larger the capacity of a soil to adsorb atrazine, the lesser the amount of atrazine desorbed. For the cultivated soils except for Andisols, the percentages of atrazine taken from solutions using the sequential exchange method after the first adsorption experiments, were the same as those desorbed from soils in relation to the initial amount adsorbed. Thus, reversible adsorption occurred in the soils due to weak physical adsorption.     

Freundlich动力学方程与二级方程的异同

A mathematical expression of Freundlich kinetic equation,lnS=A‘ B‘lnt,is presented,and the physical meanings of its parameters are indicated.Although the Freundlich kinetic equation and the two-constant equation are the same in the form,the derivation of the Freundlich kinetic equation is precise,while the derivation of the two-constant equation has some contradictions and is unreasonable,And it is suggested that the Freundlich kinetic equation should have prority over the two-constant equation to be used.     

一个新的土壤重金属竞争吸附等温模型

A new competitive adsorption isothermal model (CAIM) was developed for the coexistent and competitive binding of heavy metals to the soil surface. This model extended the earlier adsorption isothermal models by considering more than one kind of ion adsorption on the soil surface. It was compared with the Langmuir model using different conditions, and it was found that CAIM, which was suitable for competitive ion adsorption at the soil solid-liquid surface, had more advantages than the Langmuir model. The new competitive adsorption isothermal model was used to fit the data of heavy metal (Zn and Cd) competitive adsorption by a yellow soil at two temperatures. The results showed that CAIM was appropriate for the competitive adsorption of heavy metals on the soil surface at different temperatures. The fitted parameters of CAIM had explicit physical meaning. The model allowed for the calculation of the standard molar Gibbs free energy change, the standard molar enthalpy change, and the standard molar entropy change of the competitive adsorption of the heavy metals, Zn and Cd, by the yellow soil at two temperatures using the thermodynamic equilibrium constants.     

旱地长期培肥土壤脲酶和碱性磷酸酶动力学及热力学特征研究

研究了连续25年长期培肥试验条件下土壤脲酶和碱性磷酸酶酶促反应的动力学和热力学特征,从酶学角度揭示长期培肥的效应。结果表明,长期培肥增加了脲酶和碱性磷酸酶酶促反应的Vmax、Vmax/Km和k值;降低了Ea、△G、△H和△S值,说明培肥能提高酶促反应速度、减小活化自由能、加快土壤中物质的生物循环过程。酶促反应动力学参数和热力学参数与土壤性质相关分析表明,酶促反应动力学参数大多依赖于土壤化学性状,基于动力学参数的土壤肥力指标体系可评价土壤肥力水平,且U-Vmax、P-Km、P-Vmax可作为土壤肥力的重要指标。     

Parameterization of Freundlich adsorption isotherms for heavy metals in soils from an area with intensive livestock production

Adsorption coefficients are valuable tools used to estimate the environmental relevance of heavy metal contamination. However, their determination with batch experiments is laborious. Thus, attempts have been made to deduce these coefficients from soil parameters. However, the application of the resulting parameterized equations to different sets of samples has often yielded poor results. Hence, the objectives of the present study were (1) to deduce basic soil properties governing the coefficients of Freundlich adsorption isotherms for Cd, Cu, Ni, Pb, and Zn, and (2) to derive parameterized isotherms and examine their accuracy. For this purpose, 30 topsoil and nine subsoil samples were investigated which represented one Podzol‐Cambisol‐Gleysol soilscape in an area with intensive livestock production in Lower Saxony, Germany. Total background concentrations (aqua regia digestion) of heavy metals in topsoils ranged from 0.290 (Cd) to 19.2 mg kg^—1 (Zn) and exhibited elevated mobilizable proportions (NH₄EDTA pH 4.6 extract) of 17 (Ni) — 66 % (Zn) from the total concentration. Background concentrations were higher in topsoils than in subsoils by factors of 1.7 (Ni) — 28 (Zn). These differences were assigned to the special situation of heavy metal input mostly originating from animal excrements. The isotherms obtained by batch experiments showed larger coefficients K_F for partition among soil solid phase and soil solution in topsoils than in subsoils by a factor of 3.5. The coefficients of the isotherms were significantly correlated with routinely determined soil properties such as cation exchange capacity and pH (R = 0.36—0.89). Parameterized isotherms were calculated for each metal by inserting the relevant parameters in multiple linear regression equations. Among these parameters were the soil pH, cation exchange capacity, total metal concentration, and the concentrations of organic carbon, clay, fine silt, and various pedogenic oxides. The K_F values, separately calculated for topsoils and subsoils, agreed well with those determined by batch experiments (R = 0.63—0.97). Therefore, parameterized isotherms are valuable tools for the prediction of heavy metal partition in soils from one soilscape and for a risk assessment in the investigated, densely stocked area and similar areas.     

Parameterization and regionalization of Cd sorption characteristics of sandy soils. II. Regionalization: Freundlich k estimates by pedotransfer functions

The aim was to describe Cd sorption in spatially variable sandy soils of the ‘Fuhrberger Feld’ catchment area as a prerequisite for prognosis of Cd transport in soil and of the threat of groundwater pollution. Thus, the possibility is evaluated to derive a generalized Freundlich equation based on multiple regressions relating the retention parameters k and M (from isotherm data of part 1 of this study) to basic soil properties (pedotransfer functions). For the parameter M (exponent), the correlation ‘measured vs estimated’ was weak (r² < 0.5) whereas k was well predictable by pedotransfer functions. The best regression was obtained if organic carbon (OC). clay content and H⁺ activity were combined as independent variables (r² up to 0.96). The obtained k values were much higher than those from comparable literature models, probably due to lower ionic strength and different composition of our background solutions used for the isotherms. As a critical evaluation, the estimates for k were used to derive solute Cd concentrations (C_est) which then were compared to measured data (range 0.1–3 μg L^?1). The best but still unsatisfactory r² was 0.77, obtained if G_est was compared to Cd in 0.01 M_c Ca(NO₃)₂ equilibria (Cd₀). Cd in fresh soil solution (Cd_z) showed no significant correlation with C_est, except for one relationship where OC had been excluded from the preceding multiple regression of k. Generally, the role of the variable OC remained unclear. Direct multiple regressions of measured solute Cd vs soil properties (bypassing k, no sorbed fraction) yielded much closer correlations, with r² = 0.9 for Cd₀ vs OC, H⁺ activity, clay (log data, OC decreases C) and r² = 0.7 for Cd₂ vs OC, H⁺ activity, clay (log data, OC enhances C).     

Assessment of Phosphorus Requirements of Wheat on Different Textured Alluvial Soils through Freundlich Type Equations

Once soil solution phosphorus (P) level optimum for plant growth is identified, P adsorption isotherms or their equations can further be used to estimate fertilizer P rates required to adjust this desired soil solution P level to obtain maximum yield. Surface soil samples were collected from a farmer's field area and research area. An adsorption study was conducted on Ustic Endoaquerts (S₁ soil), Typic Calciargids (S₂ soil), and Typic Torripsamments (S₃ soil) to develop the Freundlich-type equations. Phosphorus adsorption data were obtained by equilibrating 10-g soil samples in 100 mL of 0.01 M calcium chloride (CaCl₂) containing various amounts of monopotassium phosphate (KH₂PO₄). Values of 1/n (slope) ranged from 0.4827 to 0.6452 L kg^?1. Based on 1/n values, it was inferred that each of the two S₁ and S₃ soils was homogeneous and S₂ was not. The K_F (mg P kg^?1) values of S₁, S₂, and S₃ soils were 92.45, 55.81, and 23.38, respectively. The highest amount of P (92.45 mg kg^?1) was adsorbed at unit EPC in S₁ soil, whereas the lowest amount (23.38 mg P kg^?1) was adsorbed in S₃ soil. Thereafter, 11 P fertilizer doses were calculated by these Freundlich-type equations to adjust different estimated soil solution P levels that were designated as treatments (0.05 to 0.90 mg L^?1). Then field experiments on wheat (cv. Inqalab-91) were conducted according to a randomized complete block design (RCBD) on these soils to determine internal (plant tissue), external (soil solution), and fertilizer P requirements. Maximum wheat gain yield (Mg ha^?1) was 6.82 with T₅ (0.25 mg P L^?1) on S₁ soil, 5.96 with T₅ (0.25 mg P L^?1) on S₂ soil, and 4.97 with T₇ (0.40 mg P L^?1) on S₃ soil that was obtained by application of 196 kg P₂O₅ ha^?1 on S₁ soil, 142 kg P₂O₅ ha^?1 on S₂ soil, and 78 kg P₂O₅ ha^?1 on S₃ soil. Internal P concentration (%) associated with 95% of maximum wheat yield at booting stage was 0.32 in S₁, 0.21 in S₂, and 0.33 in S₃ soil. In straw, it was 0.123% in S₁, 0.080% in S₂, and 0.108% in S₃ soil. The internal P requirement of wheat grain was 0.39% in S₁, 0.40% in S₂, and 0.37% in S₃ soil. External soil solution P requirement (ESPR) for 95% of maximum yield of wheat was 0.45 mg L^?1 in S₁ soil, 0.34 mg L^?1 in S₂ soil, and 0.44 mg L^?1 in S₃ soil. Quantity of P₂O₅ corresponding to ESPR values were 217 kg ha^?1 on S₁, 123 kg ha^?1 on S₂, and 60 kg ha^?1 on S₃ soil. Putting ESPR values in the respective Freundlich-type equation, P fertilizer rates (kg P₂O₅ ha^?1) were estimated that were 282 on S₁, 167 on S₂, and 83 on S₃ soil; Practically, 262, 156, and 78 kg P₂O₅ ha^?1 was applied in the field to adjust soil solution P level (mg L^?1) at 0.40 (T₇), 0.30 (T₆), and 0.40 (T₇) in S₁, S₂, and S₃ soil, respectively, that are somewhat less than determined ESPR values. Phosphorous doses applied to achieve a desired EPAS value or estimated from graphs against predicted ESPR values, or calculated from corresponding Freundlich-type equations using desired ESPR values are in close proximity to one another. Therefore, any of the techniques can be used interchangeably to estimate the P fertilizer requirement for optimum wheat yield.     

Diversity of soil cellulase isoenzymes is associated with soil cellulase kinetic and thermodynamic parameters

This study was conducted to determine how land management in three ecosystems including forest, rangeland, and saline desert soils affects the activity and diversity of isoenzymes, and the kinetic and thermodynamic parameters of soil cellulase. Cellulase was chosen because it hydrolyzes cellulose, a major plant substance entering the soils. Soil samples were collected in October 2009 from a native forest, a native rangeland, and a native saline desert as well as adjacent cultivated fields in central Iran. Land use changes of the native forest, rangeland, and saline desert soils resulted in 79%, 47%, and 73% reductions in cellulase activity, respectively. The Michaelis constant (K_m) increased but the maximum catalytic velocity (V_max) decreased for soil cellulase as a result of cultivation in the study areas. The thermodynamic parameters (E_a and Q₁₀) of soil cellulase were also affected by cultivation. Higher E_a and Q₁₀ values were obtained for the native soils, but the lower values belonged to the cultivated soils. The cellulase zymographic pattern revealed different cellulase isoenzymes in the soils. The prevailing cellulase isoenzymes in the soils were found to have molecular weights of 62 and 74 kDa in the native forest, 86 kDa in the cultivated forest, 55 and 65 kDa in the native rangeland, and 72 kDa in the reclaimed saline areas. Evidence reveals that the sensitivity of soil cellulase kinetic and thermodynamic parameters to land management seems to be due to differences in the cellulase isoenzymes present in soils.