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.     

Sorption and desorption of cobalt by soils and soil components

The sorption of Co by individual soil components was studied at solution Co concentrations that were within the range found in natural soil solutions. Soil-derived oxide materials sorbed by far the greatest amounts of Co although substantial amounts were also sorbed by organic materials (humic and fulvic acids). Clay minerals and non-pedogenic iron and manganese oxides sorbed relatively little Co. It is considered that clay minerals are unlikely to have a significant influence on the sorption of Co by whole soils. Cobalt sorbed by soil oxide material was not readily desorbed back into solution and, in addition, rapidly became non-isotopically exchangeable with solution Co. In contrast, Co was relatively easily desorbed from humic acid and a large proportion of the Co sorbed by humic acid remained isotopically exchangeable. Cobalt sorbed by montmorillonite was more easily desorbed than that sorbed by soil oxide but less easily than that sorbed by humic acid. Cobalt sorption isotherms for whole soils at low site coverage were essentially linear and the gradients of isotherms increased with pH. A comparison of isotherm gradients for whole soils and individual soil components supported the suggestion that Co sorption in whole soils is largely controlled by soil oxide materials.     

Estimating the water retention curve from soil properties: comparison of linear, nonlinear and concomitant variable methods

The unsaturated soil hydraulic functions involving the soil–water retention curve (SWRC) and the hydraulic conductivity provide useful integrated indices of soil quality. Existing and newly devised methods were used to formulate pedotransfer functions (PTFs) that predict the SWRC from readily available soil data. The PTFs were calibrated using a large soils database from Hungary. The database contains measured soil–water retention data, the dry bulk density, sand, silt and clay percentages, and the organic matter content of 305 soil layers from some 80 soil profiles. A three-parameter van Genuchten type function was fitted to the measured retention data to obtain SWRC parameters for each soil sample in the database. Using a quasi-random procedure, the database was divided into “evaluation” (EVAL) and “test” (TEST) parts containing 225 and 80 soil samples, respectively. Linear PTFs for the SWRC parameters were calculated for the EVAL database. The PTFs used for this purpose particle-size percentages, dry bulk density, organic matter content, and the sand/silt ratio, as well as simple transforms (such as logarithms and products) of these independent variables. Of the various independent variables, the eight most significant were used to calculate the different PTFs. A nonlinear (NL) predictive method was obtained by substituting the linear PTFs directly into the SWRC equation, and subsequently adjusting the PTF parameters to all retention data of the EVAL database. The estimation error (SSQ) and efficiency (EE) were used to compare the effectiveness of the linear and nonlinearly adjusted PTFs. We found that EE of the EVAL and the TEST databases increased by 4 and 7%, respectively, using the second nonlinear optimization approach. To further increase EE, one measured retention data point was used as an additional (concomitant) variable in the PTFs. Using the 20 kPa water retention data point in the linear PTFs improved the EE by about 25% for the TEST data set. Nonlinear adjustment of the concomitant variable PTF using the 20 kPa retention data point as concomitant variable produced the best PTF. This PTF produced EE values of 93 and 88% for the EVAL and TEST soil data sets, respectively.     

Validation of water sorption‐based clay prediction models for calcareous soils

Soil particle size distribution (PSD), particularly the active clay fraction, mediates soil engineering, agronomic and environmental functions. The tedious and costly nature of traditional methods of determining PSD prompted the development of water sorption‐based models for determining the clay fraction. The applicability of such models to semi‐arid soils with significant amounts of calcium carbonate and/or gypsum is unknown. The objective of this study was to validate three water sorption‐based clay prediction models for 30 calcareous soils from Iran and identify the effect of CaCO₃ on prediction accuracy. The soils had clay content ranging from 9 to 61% and CaCO₃ from 24 to 97%. The three water sorption models considered showed a reasonably fair prediction of the clay content from water sorption at 28% relative humidity (RMSE and ME values ranging from 10.6 to 12.1 and −8.1 to −4.2, respectively). The model that considers hysteresis had better prediction accuracy than the other two that do not. Moreover, the prediction errors of all three models arose from under‐prediction of the clay content. The amount of hygroscopic water scaled by clay content decreased with increasing CaCO₃ content. The low organic carbon content of the soils and the low fraction of low‐activity clay minerals like kaolinite suggested that the clay content under‐predictions were due to large CaCO₃ contents. Thus, for such water‐sorption based models to work accurately for calcareous soils, a correction factor that considers the reduction of water content due to large CaCO₃ content should be included.     

Competitive sorption of cadmium and lead in acid soils of Central Spain

The bioavailability and ultimate fate of heavy metals in the environment are controlled by chemical sorption. To assess competitive sorption of Pb and Cd, batch equilibrium experiments (generating sorption isotherms) and kinetics sorption studies were performed using single and binary metal solutions in surface samples of four soils from central Spain. For comparisons between soils, as well as, single and binary metal solutions, soil chemical processes were characterized using the Langmuir equation, ionic strength, and an empirical power function for kinetic sorption. In addition, soil pH and clay mineralogy were used to explain observed sorption processes. Sorption isotherms were well described by the Langmuir equation and the sorption kinetics were well described by an empirical power function within the reaction times in this study. Soils with higher pH and clay content (characterized by having smectite) had the greatest sorption capacity as estimated by the maximum sorption parameter (Q) of the Langmuir equation. All soils exhibited greater sorption capacity for Pb than Cd and the presence of both metals reduced the tendency for either to be sorbed although Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (k) was always greater for Pb than for Cd. However, these k values tended to increase as a result of the simultaneous presence of both metals that may indicate competition for sorption sites promoting the retention of both metals on more specific sorption sites. The kinetic experiments showed that Pb sorption is initially faster than Cd sorption from both single and binary solutions although the simultaneous presence of both metals affected the sorption of Cd at short times while only a minor effect was observed on Pb. The estimated exponents of the kinetic function were in all cases smaller for Pb than for Cd, likely due to diffusion processes into micropores or interlayer space of the clay minerals which occurs more readily for Cd than Pb. Finally, the overall sorption processes of Pb and Cd in the smectitic soil with the highest sorption capacity of the studied soils are slower than in the rest of the soils with a clay mineralogy dominated by kaolinite and illite, exhibiting these soils similar sorption rates. These results demonstrate a significant interaction between Pb and Cd sorption when both metals are present that depends on important soil properties such as the clay mineralogy.     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Properties of sub soils in relation to various measures of surface area and water content

Neither the specific surface area values (from N₂ sorption) nor the ethylene glycol monoethyl ether (EGME) retention values of 21 soil samples from New Zealand and Fiji could all be accounted for by the sum of the contributions from their component minerals. Much EGME is probably retained by internal surfaces of inter layered and interstratified clay minerals. EGME retention correlated well with cation exchange capacity (CEC) and a number of measures of water content of these soils. The water contents of air-dried soils (measured as ‘moisture factors’ or the ratios of air-dry and oven-dry weights) showed almost as close a relationship to CEC as EGME retention for this set of 21 subsoils. Moisture factors and CEC were closely related, within groups defined by dominant clay mineralogies, for a much wider selection of 1318 New Zealand soil horizons with low carbon contents. The relationships between surface area and a number of other soil properties including dispersibility of soils were also examined.     

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.     

Azimsulfuron sorption--desorption on soil

The sorption and desorption of the herbicide azimsulfuron, N-[[(4-dimethoxypyrimidin-2-yl)amino]carbonyl]1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfonamide, were studied using five soils. Sorption isotherms conformed to the Freundlich equation. It was found that pH is the main factor influencing the sorption and that the sorption on soils was negatively correlated with pH. The highest level of sorption was measured on soils with low pH and high organic carbon content. Moreover, inorganic soil colloids, for example, smectite clay minerals and iron oxides, contributed to the sorption of azimsulfuron. Desorption was hysteretic on soils with high organic and inorganic colloid contents.     

Effect of Long-Term Effluent Recharge on Phosphate Sorption by Soils in a Wastewater Reclamation Plant

The Soreq recharge basins, used for wastewater reclamation employing the Soil-Aquifer Treatment (SAT) system, have been recharged, on average, by about 1,800 m depth of secondary effluent during their operation period of ～25 years. An estimated amount of ～6 kg P m^?2 was added to the soil/sediment column during this period. The objective of this study was to compare phosphorous sorption characteristics of representative pristine soils in the Soreq recharge site to those of the basin soils sampled after a long period of effluent recharge. Batch isotherm experiments were conducted: samples of one g of soil were equilibrated with 25 mL of 0.02 M NaCl solution containing 0–3.2 mM of phosphate for 7 days at 25± 1^°C and P sorption was measured. Long-term effluent recharge significantly decreased the maximum P sorption capacity of the top sandy soil (0.15–0.3 m) and only very slightly decreased maximum P isotherm capacity of the deep clayey-sand soil (10–10.5 m). The retention of P in the basin sandy soil primarily involved sorption and surface precipitation reactions on soil carbonates. In the basin clayey-sand soil, P was retained by its sorption on surfaces of Fe, Al, Mn oxide/hydroxides and clay minerals. Long-term effluent recharge increased EPC₀, (the equilibrium P concentration in solution at which there is no sorption or desorption to or from the soil under the given conditions), of the basin soils compared to the pristine soils. Due to loading of the top horizons with P by prolonged recharge and reduced P concentration in the effluent, EPC₀ of the basin sandy soil is now equal to the average P concentration of the recharged effluents. If effluent P concentration will decrease further, the top sandy soil will become a source of P to the reclaimed water, rather than a sink. The clayey-sand layers and lenses in the vadose zone of the SAT system of the Soreq site offer a large capacity for P adsorption. With gradual leaching of carbonate minerals and synthesis of secondary clay minerals, driven by long-term effluent recharge, P retention mechanisms in the basin soil may be changed, but this process would be extremely slow.     

水溶性有机碳在各种粘土底土中的吸附：土壤性质的影响

Clay-rich subsoils are added to sandy soils to improve crop yield and increase organic carbon (C) sequestration; however, little is known about the influence of clay subsoil properties on organic C sorption and desorption. Batch sorption experiments were conducted with nine clay subsoils with a range of properties. The clay subsoils were shaken for 16 h at 4 ^oC with water-extractable organic C (WEOC, 1 224 g C L^-1) from mature wheat residue at a soil to extract ratio of 1:10. After removal of the supernatant, the residual pellet was shaken with deionised water to determine organic C desorption. The WEOC sorption was positively correlated with smectite and illite contents, cation exchange capacity (CEC) and total organic C, but negatively correlated with kaolinite content. Desorption of WEOC expressed as a percentage of WEOC sorbed was negatively correlated with smectite and illite contents, CEC, total and exchangeable calcium (Ca) concentrations and clay content, but positively correlated with kaolinite content. The relative importance of these properties varied among soil types. The soils with a high WEOC sorption capacity had medium CEC and their dominant clay minerals were smectite and illite. In contrast, kaolinite was the dominant clay mineral in the soils with a low WEOC sorption capacity and low-to-medium CEC. However, most soils had properties which could increase WEOC sorption as well as those that could decrease WEOC sorption. The relative importance of properties increasing or decreasing WEOC sorption varied with soils. The soils with high desorption had a low total Ca concentration, low-to-medium CEC and low clay content, whereas the soils with low desorption were characterised by medium-to-high CEC and smectite and illite were the dominant clay minerals. We conclude that WEOC sorption and desorption depend not on a single property but rather a combination of several properties of the subsoils in this study.     

Correlation of solution and extractable phosphorus with vegetative growth of teff

Abstract

Three soils, Hiwassee loam (clayey, kaolinitic, thermic, Typic Rhodudults), Vaiden clay (very fine, montmorillonitic, thermic, Vertic Hapludalfs) and Marvyn sand (fine, loamy, siliceous, thermic, Typic Hapludults), were used in this study. Phosphorus sorption and desorption isotherms of the soils were determined in the laboratory. Average P sorption maximum (b) was calculated using the Langmuir isotherm equation. Based on the P sorption capacity, each soil was fertilized with different P rates and teff [Eragrostis tef (Zucc)] was grown in the greenhouse. The amount of P sorbed and desorbed increased as the concentration of equilibrating solution P increased. Phosphorus sorption maximum from sorption and desorption isotherms was 278, 251, and 37 mg P/kg for Hiwassee, Vaiden, and Marvyn soils, respectively, and for maximum dry matter yield of teff the soils needed a minimum of 0.029, 0.048, and 0.065 mg/L soil solution P, respectively, which were all below the soil solution P at P adsorption maximum.

Soil P was extracted by the Mehlich I, Mehlich III, modified Mississippi, Bray P‐l and Olsen methods. Plant‐available P extracted by each of the five methods was significantly correlated with teff dry matter yield, and statistically any of the five methods can be used as the basis for predicting teff yield responses.     

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。     

Sorption of trace quantities of cadmium by soils with different chemical and mineralogical composition

Cadmium sorption experiments were performed using four soil separates of different chemical and mineralogical composition, adding Cd solutions with initial concentrations ranging from 15 to 150 μg l^?1. At the soils pHs, the sorption isotherms were a mixture of a constant partition isotherm with a high affinity one. Also, more than 90% of the initially added Cd was sorbed by all four soils. These results indicate a high affinity of these soils for trace amounts of Cd. The effect of pH was, in general, to decrease the amount of sorbed Cd as the pH decreased. The sorption isotherms were linear at all pH's. Also, the data fitted the Freundlich's sorption isotherm in all cases, but not Langmuir's. Freundlich's k values were found to be a good index of the relative Cd sorption affinities of the four soils at all the pH's used. It was found that the structural and chemical nature of the soils sorbent complex was a more important parameter than the CEC when studying the sorption of these trace amounts of Cd by soils.     

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。     

Effect of liming on hexazinone sorption and desorption behavior in various soils

Liming is a practice commonly used to modify soil acidity, neutralize aluminum, and increase calcium and magnesium in the soil. Liming can change herbicide retention processes and consequently weed control and potential environmental contamination. The effects of liming on the sorption and desorption of hexazinone in different soils were evaluated. Samples from seven Brazilian soils were collected and separated into two subsamples, with and without limestone incubation. Hexazinone was quantified using ultra high-performance liquid chromatography. The sorption and desorption coefficients were determined in soils using Freundlich isotherms. Increasing the pH did not alter the sorption kinetics of hexazinone in the same soil class. The shortest sorption time of hexazinone occurred in soils with higher organic matter (OM) and clay content. Liming reduced the sorption and increased the desorption of hexazinone in the soils, which was caused by the increase in pH and reduction of OM content. Although the application of limestone increased desorption, the rate at which this process occurred was less than the sorption rate of hexazinone in most cases. In alkaline soils, the recommended dose of hexazinone for pre-emergence application should be low to avoid leaching and reduce the contamination of groundwater resources.     

Role of Different Soil Fractions in Copper Sorption by Soils

Abstract

To evaluate contributions of organic matter, oxides, and clay fraction to copper (Cu) adsorption in six characterized soils, adsorption isotherms and distribution coefficients were obtained by a batch experimental method. Copper adsorption isotherms from untreated soil, organic matter removed from samples, and organic‐matter‐ and oxide‐removed samples were compared with curve patterns and correlated to Langmuir and Freundlich models. Copper sorption data on untreated soils described L or H‐curves, whereas in soils deprived of any component, their curves were S‐type. Distribution coefficients allowed knowing Cu adsorption capacity of untreated soil and of organic matter, oxides, and clay fraction. Soil organic matter is the main component that affects Cu adsorption as long as soil pH is near neutrality. At acid pH, oxides are the main component that affects Cu adsorption, although to a much smaller extent than organic matter near neutral conditions. Soil pH is the main soil factor that determines Cu adsorption.     

铬在土壤中的吸附解吸研究进展

对铬在土壤中的吸附解吸研究进行了综述,土壤中铬的吸附解吸机理包括非专性吸附(离子交换吸附)、专性吸附以及物理表面吸附,分别对pH、氧化还原电位、土壤组分(土壤矿物和有机质)、竞争离子以及离子强度等因素对铬吸附解吸的影响作了论述。文章进一步描述了土壤中铬吸附解吸的数学模型Freundlich方程、Langmuir方程、一级动力学模型、金属-腐殖酸模型(one-sitemodel)和表面络合模型-扩散层模型(DLM)等的研究情况,并对今后的研究方向进行了探讨。     

含岩屑紫色土水力特性及饱和导水率传递函数研究

紫色土中存在的岩石碎屑会对土壤的水力性质如饱和导水率、水分特征曲线产生显著影响.以两种不同母质发育的土壤(紫色页岩和紫色泥岩)为研究对象,设置0.25～2、2～5、5～10 mm三个岩屑粒径水平,0、30％、50％、70％、100％五个岩屑含量水平,采用压力膜仪法和定水头法分别测定水分特征曲线和土壤饱和导水率.利用BP...