初始浓度对六氯苯在土壤中的吸附-解吸的影响及解吸

Adsorption and desorption are important processes that influence the transport, transformation, and bioavailability of hexachlorobenzene (HCB) in soils. To examine the adsorption-desorption characteristics of HCB, equilibrium batch experiments were carried out using two soils (red soil and paddy soil) with different initial HCB concentrations (0.25, 0.50, 0.75, 1.00, 1.50, 2.50, 3.50, and 5.00 mg L^-1) by using 0.01 mol L^-1 calcium chloride as the background solution. The successive desorption experiments (48, 96, 144, 192, and 240 h) were conducted after each adsorption equilibrium experiment. The results revealed that adsorption and desorption isotherms of HCB on two soils were nonlinear, which can be best described by the Freundlich equation with the square of the correlation coefficient (r²) ranging from 0.97 to 0.99. Desorption of HCB from the two soils exhibited hysteresis at all HCB concentrations because the Freundlich desorption coefficients were always higher than the Freundlich adsorption coefficients. The hysteretic effect was enhanced with increasing initial HCB concentration, and positive hysteresis was observed at different concentrations.     

Equations to describe the amount and rate of sorption

The partition of materials that react with soil between the solid and the solution phase, and how this changes with time, can often be described by a simple equation: S = a c^b1t^b2 where S is the amount sorbed, c is the solution concentration, t the time of contact, and a, b₁ and b₂ are parameters. However, when the range of values for sorption is large, it is apparent that both b₁ and b₂ increase with decreasing sorption. At low values for sorption, b₁ approaches 1, and sorption plots are nearly linear. These observations are consistent with a mechanistic model in which it is postulated that the materials react with heterogenous sites. As the amount of sorption decreases, the heterogeneity of the occupied sites decreases. This is why b₁ increases. Because there is heterogeneity of occupied sites, there is a range of rates for the subsequent reaction. This is why the rates are proportional to a fractional index of time. It is better to describe the effects of time this way than by using several first-order equations.     

Effects of soil organic matter on pH-dependent phosphate sorption by soils

Effects of soil organic matter (80M) on P sorption of soils still remain to be clarified because contradictory results have been reported in the literature. In the present study, pH-dependent P sorption on an allophanic Andisol and an alluvial soil was compared with that on hydrogen peroxide (H₂0₂)-treated, acid-oxalate (OX)-treated, and dithionite-citrate- bicarbonate (DCB)-treated soils. Removal of 80M increased or decreased P sorption depending on the equilibrium pH values and soil types. In the H₂O₂ OX-, and DCB-treated soils, P sorption was pH-dependent, but this trend was not conspicuous in the untreated soils. It is likely that 80M affects P sorption of soils through three factors, competitive sorption, inhibition of polymerization and crystallization of metals such as AI and Fe, and flexible structure of metal-80M complexes. As a result, the number of available sites for P sorption would remain relatively constant in the wide range of equilibrium pH values in the presence of 80M. The P sorption characteristics were analyzed at constant equilibrium pH values (4.0 to 7.0) using the Langmuir equation as a local isotherm. The maximum number of available sites for P sorption (Q _max) was pH-dependent in the H₂0₂-, OX-, and DCBtreated soils, while this trend was not conspicuous in the untreated soils. Affinity constants related to binding strength (K) were less affected by the equilibrium pH values, soil types, and soil treatments, and were almost constant (log K ≈ 4.5). These findings support the hypothesis that 80M plays a role in keeping the number of available sites for P sorption relatively constant but does not affect the P sorption affinity. By estimating the Q _max and K values as a function of equilibrium pH values, pH-dependent P sorption was well simulated with four or two adjustable parameters. This empirical model could be useful and convenient for a rough estimation of the pH-dependent P sorption of soils.     

Verification of the prediction technique for the amount of adsorbed linuron on soils

The Freundlich isotherm was used to estimate the adsorption of the herbicide linuron on 39 Japanese soils to confirm the suitability of the prediction technique used in atrazine adsorption. Linuron was adsorbed on the soils according to the Freundlich isotherm. In conjunction with the log K _F prediction equation derived from the soil characteristics, it was possible to predict the linuron adsorption. Comparison of the equations for linuron with those for atrazine, indicated that the difference in the intercept of the 1 / n regression line against log K _F reflected the adsorptive characteristics of the herbicides.     

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).     

Effect of pH on Removal of Cu,Cd, Zn,and Ni by Cement Kiln Dust in Aqueous Solution

A batch experiment was conducted to study the effect of pH on the sorption of copper (Cu), cadmium (Cd), zinc (Zn), and nickel (Ni) by cement kiln dust (CKD). The experiment was carried out by adding 25 mL of solutions containing concentrations of 200, 400, 600, 800, and 1000 mg/L of each of these heavy metal cations to 1.00 g of CKD. The pH of these suspensions was adjusted to 2, 5, and 7 as well as non-adjusted. The sorbed amount (Cs) and the sorption percentage of Cu, Cd, Zn, and Ni by CKD increased with increasing the suspension pH. The adsorption data of Cu, Cd, Zn, and Ni were generally well correlated with Langmuir model when the suspension pH was adjusted to 5, 7, non-adjusted and 7, respectively. However, they could be well described by Freundlich model when the suspension pH was adjusted to 5, 2, non-adjusted and 5, respectively.     

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).     

磷肥和有机肥对不同磷水平土壤磷吸附-解吸的影响

采用培养试验结合Langmuir吸附等温方程进行拟合求出吸附、解吸的相关参数的方法,研究了磷肥和有机肥对不同磷水平土壤磷吸附和解吸特性的影响。结果表明,随土壤磷水平和磷肥和有机肥用量的增加,土壤最大吸磷量、土壤磷最大缓冲能力显著降低;土壤易解吸磷和土壤磷的解吸率显著增加。土壤易解吸磷和土壤磷的解吸率与土壤Olsen-P呈显著正相关;土壤最大吸磷量、土壤磷最大缓冲容量与土壤Olsen-P呈显著负相关。单位量磷肥所增加的土壤易解吸磷随着磷肥用量和土壤磷水平的增加而增大;土壤磷水平和磷用量是影响土壤磷最大吸磷量和土壤磷最大缓冲能力的重要因素。     

甲硫嘧磺隆在土壤中的吸附和解吸特性研究

Methiopyrsulfuron is a new low-rate sulfonylurea herbicide for weed control in wheat; however, there is a lack of published information on its behavior in soils. In this study, methiopyrsulfuron adsorption and desorption were measured in seven soils sampled from Heilongjiang, Shandong, Jiangxi, Sichuan, Anhui, and Chongqing provinces of China using a batch equilibrium method. The Freundlich equation was used to described its adsorption and desorption. Adsorption isotherms were nonlinear with the values of Kf-ads, the Freundlich empirical constant indicative of the adsorption capacity, ranging from 0.75 to 2.46, suggesting that little of this herbicide was adsorbed by any of the seven soils. Soil pH and organic matter content (OM) were the main factors influencing adsorption; adsorption was negatively correlated with pH and positively correlated with OM. Methiopyrsulfuron desorption was hysteretic on the soils with high OM content and low pH.     

Modelling the effects of pH on phosphate sorption by soils

Samples of six soils were incubated at 60°C for 24 h with several levels of either calcium carbonate or hydrochloric acid. Phosphate sorption was then measured on sub-samples of the treated soils over 24 h at 25°C. In one set of measurements on all soils, 0.01 M calcium chloride was used as the background electrolyte. In another set, on two soils, 0.01 M sodium chloride was used. An interpolation method was used to give points on the three-dimensional surface relating the final pH of the suspensions to sorption of phosphate at specified solution concentrations of phosphate. The effects of pH on phosphate sorption differed between soils. For unfertilized soils, increases in pH up to about pH 5.5 decreased sorption. Further increases in pH decreased sorption further in one soil and increased it in three others. For fertilized soils, measured sorption increased with pH. When sodium chloride was used instead of calcium chloride, there was a more marked trend for sorption to decrease as pH increased. Differences between the soils were ascribed to differences in two soil properties. One was the rate at which the electrostatic potential in the plane of adsorption decreased as pH increased. Only small differences in the rate of change of potential were needed to reproduce the observed differences between soils. The electrostatic potential would decrease more quickly in solutions of a sodium salt than in solutions of a calcium salt and this explains the observed differences between these media. The other soil property that affected observed sorption was the release of phosphate from the soil. The amount released was largest at low pH. Consequently, for fertilized soils, measured sorption increased with pH.     

Influence of phosphate sorption on dispersion of a Ferralsol

Abstract

Soil dispersion induces soil erosion and colloidal leaching. Nutrients are lost at the same time and this causes water contamination. Phosphate is an essential element for living organisms. Because phosphate influences soil dispersion and it is an important limited resource, this influence must be evaluated well in order to diminish negative effects on soil structure. In this paper, we firstly evaluated the influence of phosphate sorption on soil dispersion by calculating repulsive potential energy between soil particles. Ferralsol, which is a typical soil in rainy tropical regions, was used as the material. The dispersion-flocculation phenomena were investigated with absorbance of soil suspension under different pH, phosphate adsorption and electrolyte concentration in an Na-NO₃-PO₄ system. The repulsive potential energy was calculated based on the diffuse double layer theory and the measured zeta potential. We indicated that the measured absorbance increased with the increase of the repulsive potential energy. The repulsive potential energy increased with increasing phosphate sorption up to about 5 to 20 mmol kg^?1 at all pH, and it induced the soil dispersion, because phosphate sorption increased the negative charge of the soil. After its peak, it decreased with increasing phosphate sorption because the electrolyte concentration increased and the electrolyte screened the electric field near the soil surface. The repulsive potential energy also increased with increasing pH because of the increase of the negative charge of the soil. Even at low pH, after a certain amount of phosphate sorption, the soil dispersed due to the increase of repulsive potential energy, although the soil flocculated before phosphate application. Because the soil dispersion causes soil and phosphorus loss, the influence of soil pH and phosphate sorption on the soil dispersion should be considered for good soil management.     

发育程度对海南玄武岩发育土壤吸附铬酸根和磷酸根的影响

选择海南岛北部3个不同年代喷发的玄武岩发育的土壤研究了其对铬酸根(CrO42-)和磷酸根(PO43-)的吸附特征,结果表明随着母岩年龄的增加,土壤发育程度提高,土壤游离氧化铁和表面正电荷数量增加,对2种阴离子的吸附量增加。土壤CrO42-的解吸率在19.8%~39.6%之间,表明土壤对CrO42-的吸附涉及静电吸附和专性吸附2种机制,且随着土壤发育程度增加,CrO42-静电吸附所占比例增加。土壤对PO43-的吸附以非静电吸附为主,吸附的PO43-的解吸量非常低,其解吸率不超过6%。吸附PO43-在去离子水中的解吸量高于在0.1 mol/L NaNO3和KNO3中的解析量,KNO3体系中的解吸量低于NaNO3体系中的,电解质主要通过改变胶体表面离子吸附面上的静电电位影响PO43-的解吸。     

耕作土壤释钾速率及其与钾有效性的关系研究

对 1 0个不同母质土壤进行生物吸钾试验和化学测定 .结果表明 ,二级动力学方程dkt/dt=k(k0 -kt) 2 可以很好地描述连续提取条件下土壤释钾特性。初始释钾速率与有效钾含量呈极显著正相关 ,与黑麦草生物总量及吸钾总量均呈极显著正相关 .2mol/LHNO3提取的释钾速率相关显著性明显高于氢质树脂法 ,其中 0～ 2h的土壤释钾速率能较好地描述土壤钾的有效性     

Effect of pH on the electrical potential of barley roots

Abstract

Barley roots were interposed as membranes in electrochemical concentration cells. The electric potential which developed across the calomel electrodes, known commonly as the root potential, was measured as a function of pH. The root potential increased with pH reaching a maximum at pH 5.5, beyond which the values remained constant. This is explained in terms of the dissociation of the acid and basic groups that form part of the structures of the root surface and membranes.

The point of zero charge of the roots was determined by a method based on adding increasing amounts of roots to KC1 solutions of different pH and concentration. The results were somewhat higher than those obtained earlier from root potential measurements 1 2 i.e. 4 ‐ 5, compared to about 3^1,2. This difference was attributed to secondary reactions, related to the buffer capacity of the roots.     

生物质炭对不同pH值土壤矿质氮含量的影响

为了揭示生物质炭作为土壤调理剂添加后对土壤矿质氮形态、含量等土壤性质的影响,该研究利用芒草分别在350和700℃裂解制得生物质炭,发现2个温度尤其是700℃制得的生物质炭,对NH4+有很强的吸附能力,但对NO3-的吸附能力很弱。将生物质炭分别加入到酸性(pH值为3.8)和碱性(pH值为7.6)土壤中,25℃下室内培养180d。结果表明,生物质炭提高了土壤全氮含量,酸性和碱性土壤分别平均提高了22%和17%;但使土壤铵态氮含量大幅降低至接近仪器检测限水平;生物质炭对土壤硝态氮含量的影响因生物质炭和土壤类型而异。生物质炭对土壤矿质氮形态和含量的影响,显然与生物质炭对铵的吸附作用、提高土壤pH值、增强氨挥发损失,以及形成微生物量氮等密切相关。该研究可为开展生物质炭基氮素新型肥料及制剂等方面的科学研究提供参考。     

连续种植蔬菜对潮土磷素水平的影响

Soil P status, inorganic P fractions, and P sorption properties were studied using sandy fluvo-aquic horticultural soils, which are high in organic matter content for vegetable production in comparison with a soil used for grain crop production in Zhengzhou, Henan Province, China. P fractions, Olsen-P, and OM were determined at different depths in the soil profile and sorption isotherm experiments were performed. Most P in excess of plant requirements accumulated in the topsoil and decreased with soil depth. Total P, inorganic P, and OM concentrations increased with continued horticultural use. Olsen-P concentrations in the 0-20 cm depth of horticultural soils were 9 to 25 times higher than those of the grain crop soil. A linear transformation of the Langmuir equation showed that the P adsorption maximum (491.3 mg P kg^-1) and the maximum phosphate buffering capacity (162.1 L kg^-1) for 80-100 cm were greater in the grain crop soil than the horticultural soils. Thus, the most immediate concern with excess P were in areas where heavy P fertilizer was used for vegetable crops and where soil P sorption capacities were low due to sandy soils and high organic matter content.     

Effects of temperature on phosphate sorption isotherms and phosphate desorption

Abstract

Phosphorus sorption isotherms were constructed for two Idaho soils with widely different chemical properties. The soils were equilibrated with various amounts of Ca(H₂PO₄)₂ in 0.01 M CaCl₂ for 1, 3, 7, and 11 days at temperatures of 5°C and 20°C. The two soils which had been equilibrated previously for 11 days at 20°C with various amounts of Ca(H₂PO₄)₂ in 0.01 M CaCl₂ were desorbed at 5°C and 20°C.

The rates of sorption and desorption were decreased as the equilibration temperatures were lowered. The effect of temperature on these processes was detected during the first day of equilibration. Less P was found in the equilibrating solution at the lower temperature. The two soils varied widely in sorption and desorption properties.     

可溶性有机物对土壤中绿麦隆吸附与解吸的影响

A batch equilibrium techniques was used to examine the effect of dissolved organic matter （DOM） extracted from both non-treated sludge （NTS） and heat-expanded sludge （HES） on the sorption and desorption of chlorotoluron （3-（3-chloro-p-tolyl）-1,1-dimethylurea） in two types of soils, a yellow fluvo-aquic and a red soil from China. Without DOM,sorption of chlorotoluron was significantly greater （P 〈 0.05） in the red soil than in the yellow fluvo-aquic soil. However,with DOM the effect was dependent on the soil type and nature of DOM. Chlorotoluron sorption was lower in the yellow fluvo-aquic soil than in the red soil, suggesting that with the same DOM levels the yellow fluvo-aquic soil had a lower sorption capacity for this herbicide. Application of DOM from both NTS and HES led to a general decrease in sorption to the soils and an increase in desorption from the soils. Desorption of chlorotoluron also significantly increased （P 〈 0.05） with an increase in the DOM concentration. Additionally, for sorption and desorption, at each DOM treatment level the NTS treatments were significantly lower （P 〈 0.05） than the HES treatments. This implied that non-treated sludge had a greater effect on the sorption and desorption of chlorotoluron than heat-expanded sludge.