pH dependence of copper adsorption in vineyard soils of Geneva

Copper adsorption by vineyard soils of the Geneva canton was evaluated by batch equilibration experiments in a pH range from 4 to 6. The adsorption curves fit significantly to Freundlich function log q = n log C + log K_f, where q is adsorbed Cu concentration on the solid phase and C is solution Cu concentration at the end of the equilibration time. Moreover, we found that Freundlich parameters n and log K_f are moderately correlated to pH, yielding the following equations: log K_f = 0.23 pH + 0.51 (R ² 0.59) and n = –0.12 pH + 1.06 (R ² 0.59). Such equations may be useful to predict Cu mobility for risk assessment studies.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Adsorption and movement of carbaryl in soils: A verification of cosolvent theory and comparison of batch equilibrium and soil thin layer chromatography results

Batch equilibrium and soil thin layer chromatography (TLC) techniques were used to investigate the influence of different volume fractions of organic cosolvents (acetone and methanol) on the adsorption and movement of carbaryl in four different types of Indian soils. L-shaped isotherms were obtained for both the cosolvent–water mixtures at all f _s values and were in close agreement with the Freundlich equation. Higher adsorption was observed on F.R.I. soil (FSL) followed by Alampur soil (ASL), Kalai soil (KL), and Bhoran soil (BSL) at all f _s values for both the cosolvent systems as was anticipated from the K and K _D values. The K and K _D values also confirmed that carbaryl adsorption was higher in methanol–water mixture than acetone–water mixture and decreased with increasing f _s values. The frontal R _f values obtained from soil TLC studies were inversely proportional to the K and K _D values for both the cosolvent systems. The higher K and K _D values and lower R _f values in methanol–water mixtures relative to acetone–water mixtures for all the soils indicated that acetone had a greater potential for ground water contamination compared to methanol. The adsorption data were used to evaluate the cosolvent theory for describing adsorption of carbaryl in acetone–water and methanol–water mixtures. The aqueous phase partition coefficients, K _DW (mol g^?1), normalized with respect to f _oc for carbaryl was evaluated by extrapolating f _s → 0.     

雄烯二酮在我国典型土壤中的吸附特性

采用批吸附室内模拟实验研究了雄烯二酮在我国红壤、潮土、黑土3种典型土壤中的吸附特征,以及牛粪溶解态有机质(DOM)对土壤吸附雄烯二酮的影响。结果表明,雄烯二酮在土壤中吸附动力学符合Elovch方程(R20.89),热力学特征可通过Freundlich等温吸附方程(R20.83)描述,土壤对雄烯二酮的吸附呈非线性吸附特征,其中潮土吸附等温线的非线性最强(n=0.37);吸附系数K f介于6.0~20.2,并与有机质含量呈显著正相关(p0.05)。雄烯二酮浓度较低时,共存牛粪DOM抑制其在土壤表面的吸附作用。研究认为,有机质是土壤吸附雄烯二酮的主要组分,共存牛粪DOM可促进雄烯二酮向地表水和地下水的迁移。     

Adsorption of pesticides by salorthids and camborthids of Punjab,Pakistan

This study was conducted to examine adsorption of pesticides bifenthrin, carbosulfan, λ-cyhalothrin, cypermethrin, endosulfan, parathion methyl, monocrotophos and 4-nitrophenol by sandy clay loam (S.C.L) and sandy loam (S.L) soils (with varying organic content). There was no significant difference between the observed soil water partitioning coefficient values (K _d) derived from linear and nonlinear Freundlich isotherms. Adsorption of pesticides on S.C.L soils was higher than those on S.L soils. K _d values showed significant correlations (r ²?=?0.8???0.99 and 0.65???0.97) with soil organic carbon content (OC) and weak correlations (r ²?=?0.2???0.29 and 0.1???0.18) with clay contents of S.C.L and S.L soil at p?≤?0.05, respectively for all pesticides (except monocrotophos). Observed K _oc values (soil-water partitioning constants based on the organic C fraction of the soil) were in accordance with the literature values of Wauchope and Tomlin with a maximum deviation of less than 0.5 log units. Ten Quantitative Property-Property Relationships (QPPR) among water solubility, n-octanol water coefficient (K _ow) and K _oc were proposed for studied pesticides except monocrotophos. The models were considered acceptable when predicted-observed difference for log?K _ow and log?K _oc were ≤?0.3 and ≤?0.5?log units, respectively, during the validation procedure. This work indicates that the log?K _oc derived from the log K_ow, from some of existing relationships, may be a fair predictor where observed values (i.e., K _d and K _oc) are not available. Furthermore, predicted leaching potential by groundwater ubiquity scores (GUS) equation was solved by using observed K _oc values and literature reported half lives of pesticides. GUS ranked the mobility of nonvolatile compounds i.e., bifenthrin, λ-cyhalothrin, cypermethrin and endosulfan extremely low; methyl parathion very low; 4-nitrophenol low; carbofuran and monocrotophos very high in S.C.L and S.L soils, respectively. Results discussed in this paper provide background to prioritize pesticides or chemical groups that should be evaluated under field conditions with regard to their leaching potential to groundwater in arid climates.     

几类有机污染物的微塑料/水分配系数的线性溶解能关系模型

水体中的微塑料会吸附其中的有机污染物,影响有机污染物和微塑料的环境归趋和生态毒性。研究微塑料对有机污染物的吸附行为,对于评价有机污染物和微塑料的环境赋存、迁移及生物有效性有重要意义。污染物在微塑料与水之间的平衡分配系数(Kd),是表征微塑料对有机污染物吸附能力的重要参数。实验方法难以逐个测定众多有机污染物的Kd值,有必要发展其预测模型。本研究搜集了有机污染物的线性溶解能关系(LSER)参数及Kd值,构建了可预测有机污染物在聚丙烯微塑料与海水、聚乙烯微塑料与海水、聚乙烯微塑料与淡水之间Kd值的LSER模型。模型具有良好的拟合优度(R2adj介于0.794~0.903)、稳健性(Q2LOO和Q2BOOT分别介于0.763~0.863和0.720~0.804)和预测能力(R2ext和Q2ext分别介于0.886~0.971和0.825~0.954),能够用于预测多氯联苯、多环芳烃、六氯环已烷和氯苯类有机污染物的Kd值。     

Polyoxometalates for photocatalytic degradation of aqueous dyestuff solutions and quantitative structure–property relationship study on photolysis rate constants

Polyoxometalate, K₆TiW₁₁O₃₉Sn·7H₂O (TiW₁₁Sn), was synthesized and characterized. TiW₁₁Sn and K₆ZrW₁₁O₃₉Sn·12H₂O (ZrW₁₁Sn) were evaluated for their photocatalytic degradation of triarylmethane (brilliant green and acid blue 9), bisazo (C.I. reactive black 5), and monoazo dyestuffs (C.I. reactive red 24, C.I. reactive red 194, and C.I. reactive orange 5) with natural sunlight in homogeneous aqueous solutions. TiW₁₁Sn and ZrW₁₁Sn effectively and photocatalytically decolorized the dyestuffs. The TiW₁₁Sn- and ZrW₁₁Sn-mediated photocatalytic degradation of the dyestuffs involved a pseudo-first-order reaction and was modeled by Langmuir–Hinshelwood-type kinetics. The observed pseudo-first-order rate constants (K^/) of triarylmethane dyestuffs were generally bigger than that of the azo dyestuffs. Quantitative structure–property relationship models of the K^/ of the dyestuffs were developed using partial least-square regression. The cumulative variance of the dependent variable explained by the partial least-square components was > 0.753 for each optimal model. This value indicated that the model had good predictive ability and robustness. The K^/ values of the dyestuffs were related to the energy of the lowest unoccupied molecular orbital, and the most positive net atomic charges on a sulfur atom of dyestuffs. The linear correlation coefficients between the predicted and experimental values were all > 0.9950.     

Determination and QSPR analysis of log Kow and log Koc for fluorine containing benzene derivatives

Octanol‐water partition coefficients (Kow) and soil organic carbon sorption coefficients (Koc) were determined for 14 fluorinated benzene derivatives. Quantitative structure‐property relationships were developed using molecular connectivity indices and quantum chemical parameters to analyze the most significant factors influencing these physico‐chemical properties of the compounds. The substitution by F in benzene derivatives has greater influence on Koc than on Kow.     

Elucidation of phosphorous sorption by calcareous soils using principal component analysis

This study was conducted to understand the mechanisms governing P-sorption and desorption by calcareous soils (up to 48% CaCO ₃). Batch experiments with KCl as background were carried out by adding varying amount of P up to 100 mgP.L^?1. The desorption percentage (%DES) results show that little P was released from the adsorbed phase. Principal component analysis was applied to evaluate the combined influence of soil components on P sorption. The complex P sorption process can be related to specific soil components by the following equation: P? sorption=?2.20 (CaCO ₃% )?0.04 (Fe? oxide)+0.04 (pHe)+11.02 (sand % )+3.35 (silt)?10.73 (clay)?1.24 (EC)?0.22 (OM)?0.81 (CEC)?1.93 (P? Olsen) (R²=0.9941, SSE=380). Sand% and clay% are the most significant variables for modelling P sorption data. The derived equation could be applied to predict P sorption in other soils that have similar compositions to those investigated herein. The degree of P saturation (DPS) threshold level for all soils was less than 3% except in the soil with the lowest iron oxide. All of the studied soils have exceeded the environmentally unacceptable P concentration except the soil with the lowest iron oxide content.     

Regression models for some solute distribution equilibria in the terrestrial environment

Sorption coefficients (K_p) of several organochlorine insecticides (OCs) in volcanic ash silt from Central Java are presented.

Selected experimental and estimated octanol‐water partition coefficient (P) values are used to study log‐log regressions with K_p data collected from the literature (PAHs, chlorophenols, phenylureas, chloro‐s‐triazines, carbamates and organophosphorus insecticides) and those of the OCs determined in the present study. Leaching distances and bioactivities in soil are correlated with the K_p values of the pesticides, and with the organic matter and the water content of the soil.     

基于TLSER和QSPR关系预测PAHs和PCBs的LDPE膜-空气分配系数

有机污染物在被动采样材料与环境介质之间的平衡分配系数(K_P),是测定环境中有机污染物浓度的重要参数,但K_P值大部分都需要经过繁琐的实验测定获取,无法逐个测定数量繁多的污染物,因此需开发一种预测K_P值的方法。为此,搜集整理了一些多环芳香烃(PAHs)和多氯联苯(PCBs)的低密度聚乙烯(LDPE)-空气分配系数(K_PA)的实测值,基于理论线性溶解能(TLSER)和定量结构性质关系(QSPR),利用逐步多元线性回归(MLR)分别构建了预测K_PA值的模型。模型的决定系数R2adj分别为0.927和0.956,交叉验证系数Q2LOO分别为0.915和0.946,外部系数Q2ext分别为0.913和0.960。结果表明,2种模型具有良好的拟合优度、稳健性和预测能力,并解释了模型的机理。所构建的2种模型均可用来预测应用域内有机污染物的LDPE膜-空气分配系数。     

Toxicity of substituted benzaldehydes to photobacterium phosphoreum and quantitative structure‐activity relationship

Acute toxicities (15min‐EC₅₀) of 21 substituted benzaldehydes to Photobacterium phosphoreum were determined. A quantitative structure‐activity relationship (QSAR) was developed using molecular connectivity indices and quantum chemical parameters, which show that the toxicity is influenced mainly by the difference of the simple and valence‐corrected fourth path molecular connectivity, polarizability, dipole moment, and the most negative net atomic charge on an atom. This study further shows that benzaldehydes are reactive chemicals, which exhibit bioreactive toxicity.     

Optimisation of bisphenol A removal from water using chemically modified pine bark and almond shell

The ability of pine bark and almond shells to remove bisphenol A (BPA) from aqueous solutions was evaluated. Samples of these traditional agro-forestry by-products were milled, sieved into different particle size fractions (0.10–0.15 and 1.5–2.0 mm) and submitted to two different types of treatment. Sorption experiments were conducted in a batch system at room temperature and natural pH. Sorption equilibrium was attained after 48 h for all systems under study. Bisphenol A was adsorbed more effectively on the smaller particles of the sorbents. Pine bark and almond shell pretreated with formaldehyde presented higher sorption efficiency (95%), followed by almond shell (87%) and pine bark (82%) washed with hot water. All the sorption isotherms were found to fit a Freundlich equation, with correlation coefficients (R ²) between 0.823 and 0.989. The sorption coefficient (K _F) ranged from 0.06 to 0.74 (mg^1?1/n ·L ^1/n ·g ^?1). These results indicate that utilisation of both materials as an alternative sorbent for the removal of bisphenol A from contaminated waters is promising because they are available in large amounts and have an acceptable cost–efficiency ratio when compared with traditional adsorbents.     

Sorption of the natural endocrine disruptors,oestrone and 17 beta-oestradiol in the aquatic environment

Adsorption of hydrophobic contaminants at the particle/water interface is one of the key processes controlling their fate in the aquatic environment. The sorption of the natural female hormones oestrone and 17-oestradiol has been studied under simulated riverine conditions. Both the kinetics and the effects of varying fundamental environmental parameters (e.g. sediment properties) on the thermodynamic equilibrium partition coefficient (K _p) have been studied in continuous and batch sorption experiments, respectively. Results showed that the sorption of oestrone and 17-oestradiol by sediment was relatively slow, reaching equilibrium in 50 days. In addition, relatively small adsorption of both oestrone and 17-oestradiol onto the sediment was observed, with K _p values between 200 and 250 mL g^–1. The comparable K _p values of the two compounds reflect their structural similarity. It can be concluded that the two endocrine disruptors, oestrone and 17-oestradiol remain primarily in association with the aqueous phase.     

The impacts of Robinia pseudoacacia litter cover and roots on soil erosion in the Loess Plateau,China

The impacts of vegetation on soil erosion are closely associated with the combined effects of above- and below-ground components. In this study, we explore the effects and contributions of Robinia pseudoacacia litter cover and roots on soil erosion. Experiment sites under natural conditions with vegetation cover, plant roots and bare ground plots were investigated for overland flow discharges of 0.5, 1.0 and 2.0?L?s^?1 and slope gradients of 8.7%, 17.6%, 26.8%, 36.4% and 46.6%. Results indicate that litter cover and roots have a significant impact on sediment reduction; soil loss was reduced by about 57% and plant roots had a greater impact on the reduction of soil erosion than litter cover. The combination of litter cover and plant roots had a significant effect on decreasing K_r, increasing τ_c and consequently strengthening soil resistance capacity to erosion. When plants and roots existed on the slopes, K_r decreased by 81% and 66%, and τ_c increased by 319% and 246%, respectively, in comparison with bare slopes. These results illustrate the importance of high-forest in controlling soil erosion by quantifying the specific contributions of litter cover and plant roots in erosion reduction in the Loess Plateau.     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^?1) on ¹³⁷Cs adsorption–desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26–99.97%) of added ¹³⁷Cs (3.7?×?10³?7.03?×?10⁵ Bq l^?1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K _ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄ ⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K _ads and soil pH was observed. The ¹³⁷Cs adsorption–desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09–0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Kinetic and mechanism studies of the adsorption of lead onto waste cow bone powder (WCBP) surfaces

This study examines the adsorption isotherms, kinetics and mechanisms of Pb²⁺ sorption onto waste cow bone powder (WCBP) surfaces. The concentrations of Pb²⁺ in the study range from 10 to 90 mg/L. Although the sorption data follow the Langmuir and Freundlich isotherm, a detailed examination reveals that surface sorption or complexation and co-precipitation are the most important mechanisms, along with possibly ion exchange and solid diffusion also contributing to the overall sorption process. The co-precipitation of Pb²⁺ with the calcium hydroxyapatite (Ca-HAP) is implied by significant changes in Ca²⁺ and PO₄ ^3? concentrations during the metal sorption processes. The Pb²⁺ sorption onto the WCBP surface by metal complexation with surface functional groups such as ≡ POH. The major metal surface species are likely to be ≡ POPb⁺. The sorption isotherm results indicated that Pb²⁺ sorption onto the Langmuir and Freundlich constant q _max and K _F is 9.52 and 8.18 mg g^?1, respectively. Sorption kinetics results indicated that Pb²⁺ sorption onto WCBP was pseudo-second-order rate constants K ₂ was 1.12 g mg^?1 h^?1. The main mechanism is adsorption or surface complexation (≡POPb⁺: 61.6%), co-precipitation or ion exchange [Ca_3.93 Pb_1.07 (PO₄)₃ (OH): 21.4%] and other precipitation [Pb 50 mg L^?1 and natural pH: 17%). Sorption isotherms showed that WCBP has a much higher Pb²⁺ removal rate in an aqueous solution; the greater capability of WCBP to remove aqueous Pb²⁺ indicates its potential as another promising way to remediate Pb²⁺-contaminated media.     

Struktur-Aktivitätsbeziehungen (QSAR)

The correlation between the bioconcentration (BCF) of 20 pesticides and 3 PCB-congeners from two test soils in earthworms (Lumbricus terrestris) and the corresponding log K_ow was investigated. The relationship, expressed by the equation log BCF=a· log K_ow+b, did not show strong statistical correlation, especially for the soil with higher organic matter content. However, strong statistical correlation could be demonstrated between log BCF and log K_ow for both soils when the bioconcentration in earthworms was calculated on the basis of interstitial water instead of soil. The resulting equations represent a useful tool for assessing the bioaccumulation potential of organic chemical in soil.