Changes in chemical forms of lead in temperate and semiarid soils in sterile and unsterile conditions

Sequential extraction has been used as a suitable method for fractionation of chemical forms of trace elements and study of their plant availability. Surface soils were sampled from Guilan and Hamadan provinces in north and northwest of Iran with temperate and semiarid climates. The chemical forms of Pb in the Pb(NO₃)₂-treated (400 μg Pb g⁻¹) soils have been studied in solid state incubation (FC) at 27°C in sterile and unsterile conditions. After 20 min and 3600 h a sequential extraction scheme was also used to fractionate Pb of incubated samples into soluble-exchangeable (Sol-Exch), carbonates associated (ACar), organic matter associated (AOM), Mn oxide associated (AMnOx), Fe oxide associated (AFeOx), and residual (Res) forms. Temperate soil samples had higher clay content, cation exchange capacity (CEC), dichromate oxidable organic carbon (OC), total Kjeldahl-nitrogen (TN), biological activity, amorphous and crystalline Fe and Al, but semiarid soil samples had higher sand content, pH, equivalent calcium carbonate (ECC), available P and K. Soil lead fractionation revealed that in both groups of soils Pb largely changed to exchangeable, carbonates associated and organic associated forms after 20 min. The chemical forms of Pb differed widely among soils after 3600-h incubation. The conversion rate of Pb from more available forms to less available forms was higher in temperate soils with higher Fe–Mn oxides and OM contents compared to semiarid soils. In temperate soils after 3600-h incubation, greater content of Pb was observed in Res (68%), AOM (14%), ACar (7%), and AMnOx (5%) fractions. However, in semiarid soils greater content of Pb was observed in Res (61%), ACar (16%), Sol-Exch (8%), and AOM (8%) fractions. The sum of AMnOx and AFeOx chemical forms for Pb in semiarid soils compared to temperate soils was lower. It was only 7% against 9% in temperate soils. Soil microorganisms in unsterile soils had significant effect on AOM, AFeOx and Res fractions of Pb. They not only increased AOM and AFeOx fractions of Pb in soils but also decreased Res fraction of Pb significantly.     

A sandy loam soil as a natural control for Pb contamination

The Pb (II) adsorption/desorption mechanism onto a natural sandy loam soil was studied by batch experiments at different pHs (3.0, 4.5, 6.0), at different ionic strength (0, 0.02 and 0.1 M) and with different electrolytes solutions of NaCl, NaAcO and NaNO₃. Pb was strongly adsorbed onto the soil due to the formation of a mix of inner-sphere and outer-sphere complexes. Experimental adsorption data fitted Freundlich and Langmuir isotherms. The desorption results with 0.1 M Mg (NO₃)₂ and 0.1 M NaAcO solutions corroborated the mechanisms proposed. The strong binding of Pb (II) to high affinity sites on soil minerals seems to be responsible for the extent of hysteresis. The sandy loam soil under study thus constitutes a natural control for Pb contamination.     

添加羟基磷灰石对土壤铅吸附与解吸特性的影响

采用羟基磷灰石对四种不同类型的土壤进行铅的吸附-解吸试验.结果表明:四种土壤对铅的吸附均可用Langmuir和Freundlich方程进行描述,土壤中加入羟基磷灰石明显增加了土壤对铅的吸附量和吸附亲和力,同时降低了土壤中铅的解吸百分数,在偏酸性的红壤上表现更为明显,其最大吸附量增加28%.羟基磷灰石对铅吸附的反应机理可能与磷灰石溶解后与铅形成磷酸盐沉淀及其对铅的表面吸附作用有关.土壤对铅的吸附量及吸附亲和力与土壤的有机质、阳离子交换量及粘粒含量有显著正相关,而与土壤砂粒的含量呈负相关.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

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.     

菜园土壤铜吸附--解吸特性的研究

研究了菜园土壤铜的吸附—解吸特性。结果表明 ,3种菜园土壤吸附 Cu2 的量均随平衡液中Cu2 浓度的增加而增大 ,可用 L angmuir方程和 Freundlich方程来描述。由 Langmuir方程求得的菜园土壤对 Cu2 的最大吸附量和最大缓冲容量的大小顺序为 :黄松土 >江涂土 >粉泥土 ,菜园土壤对 Cu2 的解吸量和解吸率均随其吸附量的增加而增加 ,吸附量与解吸量之间呈显著或极显著线性正相关。     

己唑醇在土壤中的吸附-解吸特性

采用批量平衡法和气相色谱法研究了己唑醇在3种土壤中的吸附-解吸特性.结果表明,己唑醇在3种供试土壤中的等温吸附-解吸曲线能较好地符合Freundlich模型,其吸附常数(Kf)分别为0.791、2.274和43.800,显示3种土壤吸附行为存在较大差异.吸附率与土壤有机质含量(OM)、土壤阳离子交换量(CEC)和粘粒含量呈良好相关性.己唑醇在粘土和壤土中的等温吸附线属于L型等温吸附线,砂土中属S型.己唑醇在土壤中的吸附自由能为-5.186—-8.164 kJ.mol-1,表示吸附机理主要为物理吸附.     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

Phytoavailability and potential transfer of Pb from a salt-affected soil to Atriplex verucifera,Salicornia europaea and Chenopodium album

The phytoavailability and potential transfer of Pb to Atriplex verucifera, Salicornia europaea and Chenopodium album in two calcareous soils with different salinity/sodicity were compared. The soils were spiked with 0, 250, 500 and 1000 mg Pb kg^?1 soil. Plant shoots were harvested and analysed for total Pb after they had been grown in the contaminated soils. Visual MINTEQ 3.0 was used to calculate the speciation of soluble Pb in the experimental soils. Results showed that although the concentrations of 1 M NH₄NO₃-extractable Pb were relatively similar, speciation of Pb in the soils were not the same. Salicornia europea was found to be the most salinity/sodicity-tolerant plant. When the plants were grown in non-saline soil, the Pb tolerance of the three plants was as follows: A. verucifera > C. album >S. europea, whereas in saline (sodic) soil, Pb tolerance was in the order S. europea > C. album > A. verucifera. Lead phytotoxicity to A. verucifera and C. album was higher in the saline soil, whereas for S. europea, Pb toxicity was higher in the non-saline soil. It could be concluded that the phytoavailability of Pb and its interactions with plants are widely dependent on soil salinity level and type of plant.     

Adsorption‐desorption hysteresis of α‐endosulfan in tropical soils using isotopic techniques

This study was designed to evaluate the adsorption‐desorption hysteresis of endosulfan (1,2,3,4, 7,7‐hexachlorobicyclo[2,2,1]‐2‐heptene‐5,6‐bisoxymethylene sulfite) in selected tropical soils. Two major tropical soils from Thailand were selected, Rangsit lowland soils (Rangsit series) and Phrabat upland soils (Pakchong series). The soil types were sub‐divided into plow soils, 0–20cm depth from the surface, and subsoils, 20–40cm depth. Adsorption was determined in 24h batch equilibrium, with five different concentrations of ¹⁴C endosulfan ranging from 1.04 to 16.64 ng/mg soils. Four successive desorption studies were performed continuously after three adsorption concentrations, 24h for each successive. Adsorption coefficient values (K _ads) as determined by Freundlich model ranged from 0.02 to 0.14 and found to be higher in Rangsit soils as expected when compared with Phrabat soils. Desorption was hysteresis in every desorption study. Desorption coefficient values (K _des) were higher than adsorption (K _des).     

多氯联苯在土壤中的吸附规律及其影响因素研究

为了建立定量描述土壤中多氯联苯（PCBs）迁移规律的数学模型,以采自现代黄河三角洲地区的土壤为研究对象,针对类二噁英类多氯联苯PCB81及阻转类多氯联苯PCB95在土壤中的吸附行为进行了研究,获得了其吸附等温方程并分析了土壤有机质含量、颗粒组成、pH、矿物质含量等特性参数对吸附量的影响。结果表明,PCBs在土壤中的吸附行为符合Langmuir吸附等温方程;PCBs的吸附量与土壤中有机质含量和土壤粘粒含量呈正相关关系,与土壤pH值及土壤矿物质含量无明显相关关系。     

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.     

Removal of congo red and basic violet 1 by chir pine (Pinus roxburghii) sawdust,a saw mill waste: batch and column studies

The efficiency of chir pine sawdust (CPS) for adsorptive removal of the dyes, congo red (CR) and basic violet 1 (BV), from aqueous solution was evaluated using batch and column studies. The equilibrium was attained in 60 min for CR and 45 min for BV. The adsorption of BV obeyed the Langmuir isotherm model while the Freundlich isotherm fitted the equilibrium data of CR adsorption. The Langmuir monolayer adsorption capacities (Q_o) of CPS for BV and CR were 11.3 and 5.8 g kg^?1, respectively. The kinetic data for CR were best fitted to the Lagergren pseudo-first-order model and for BV to the pseudo-second-order model. The intra-particle diffusion was found to be the rate-controlling step for CR adsorption, while the adsorption kinetics of BV were controlled by both intra-particle and liquid-film diffusion. The thermodynamic parameters indicated that the adsorption process was spontaneous and endothermic in nature. The adsorption activation energy (E_a) for CR (124 kJ mol^?1) implied chemical adsorption while that for BV (5.4 kJ mol^?1) indicated physical adsorption. An increase in the Thomas model constant (K_Th) with increasing flow indicated that for both dyes the mass transport resistance decreased during adsorption. Thus, CPS may be an efficient low-cost adsorbent for decolorization of dye-containing wastewaters.     

Selenium content of rice,mixed plant foods and fish from Bangladesh

Static and dynamic adsorption studies of Co (II) ions have been undertaken at fixed pH and ionic strength taking binary biopolymeric beads of cross-linked calcium alginate and carboxy methylcellulose as biosorbents. The adsorption data were applied to Langmuir and Freundlich isotherm equations and various static parameters were calculated. The dynamic nature of adsorption process was quantified in terms of several kinetic constants such as rate constants for adsorption (K) and Lagergreen rate constant (K _ad). The influence of various experimental parameters such as solid-to-liquid ratio, pH, and temperature, the presence of salts and chemical composition of biopolymeric beads were investigated on the adsorption of cobalt ions.     

Copper (II) adsorption studies using models of synthetic humic acids

A polymer with characteristics similar to those of humic acids was obtained by synthesis reactions from oxidative polymerization in an alkaline medium using para-benzoquinone, hydroquinone and 4-aminobenzoic acid as precursors. Samples of natural and synthetic humic acid were used to examine the adsorption behavior of Cu²⁺ ions on these substrates. The mathematical models described by Langmuir and Freundlich equations were applied, yielding the maximum adsorption intensity values K′ (Langmuir), maximum adsorption capacity, b (Langmuir) and the adsorbent adsorption capacity, m (Freundlich). Based on solubility studies, pH 3 was selected for the development of the adsorption experiment. The Cu²⁺ ion presented a favorable adsorption, with RL (equilibrium parameter) responses in Langmuir isotherms falling within the desirable ranges.     

Adsorption of cationic and anionic surfactants onto organic polymer resin Lewatit VPOC 1064 MD PH

The adsorption of a cationic (CTAB, cetyl trimethylammonium bromide) and an anionic surfactant (SLES, sodium dodecylethersulfate) from aqueous solution onto organic polymer resin (Lewatit VPOC 1064 MD PH) was studied. A series of batch experiments were performed to determine the sorption isotherms of surfactants to organic polymer resin. The experimental studies were analyzed by Langmuir and Freundlich isotherms. Furthermore, the isotherm parameters, average percentage errors (ε) of model data, and separation factor (R _L) were calculated. Other factors influencing the adsorption capacity (contact time, adsorbent amount, and initial surfactant concentration) were also discussed. The experimental data fitted very well to the Langmuir equilibrium model in the studied concentration range. The calculated R _L values showed that the adsorption of both surfactants were favorable. Among the surfactants, CTAB showed higher adsorption capacity onto organic polymer resin compared to SLES (Q ⁰ = 250 and 34.36 mg g⁻¹, respectively).     

Steam activation,characterisation and adsorption studies of activated carbon from maize tassels

In this paper, steam-produced activated carbon (STAC) from maize tassel (MT) was evaluated for its ability to remove basic dye (methylene blue MB) from aqueous solution in a batch adsorption process. The equilibrium experiments were conducted in the range of 50–300 mg/L initial MB concentrations at 30°C, for effect of pH, adsorbent dosage and contact time. The experimental data were analysed by Langmuir, Freundlich and Temkin isotherm models of adsorption. Freundlich adsorption isotherm was found to have highest value of R²(R²=0.97) compared to other models of Langmuir and Temkin having (0.96 and 0.95 respectively). STAC has a high adsorptive capacity for MB dye (200 mg/g) and also showed favourable adsorption for the dye with the separation factor (R_L<1) for the dye-activated carbon system. The kinetic data obtained were analysed using pseudo first-order kinetic equation and pseudo second-order kinetic equation. The experimental data fitted well into pseudo second-order kinetic equation, as demonstrated by the high value of R².     

First determination of Cu adsorption on soil humin

Humic substances are heterogeneous mixtures of organic compounds occurring in huge amounts mainly in waters, soils, sediments and organic wastes. They are formed during the decay of living organisms. They play a very important role in many environmental processes including carbon sequestration, water cleaning and retention, soil erosion, fertility and pollutant retention. However, due to their complex nature, humic substances are still poorly characterized and much less known than living matter. Humin is the most insoluble and, in turn, the least understood fraction of humic substances. To our knowledge, no information is currently available on the adsorption and desorption behaviors of metal ions on soil humin. Here, we report the adsorption and desorption properties of Cu(II) on humin and humic acids isolated from a forest soil in northeast China using the batch equilibration method. Solid-state ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (¹³C CPMAS NMR) spectroscopy was used to characterize and compare the chemical structures of humin and humic acid. The batch experiments’ results show that humin has a lower adsorption capacity and higher adsorption reversibility for Cu(II) than humic acid. The adsorption isotherms well fitted both the Langmuir and Freundlich equations. Humin, therefore, plays an important role in controlling the fate, transport and bioavailability of Cu(II) in the environment. The ¹³C CPMAS NMR spectra showed that compared with humic acid, humin was higher in alkyl C, carbohydrate C and phenolic C and was lower in methoxyl C, aryl C and carbonyl C. These findings mean that humin was less alkylated, more aliphatic and more hydrophobic.     

Heavy metals uptake from aqueous solutions using marine algae (Colpomenia sinuosa): kinetics and isotherms

The adsorption of copper, zinc, cobalt, lead and cadmium ions onto Colpomenia sinuosa was studied as a function of contact time, initial metal ion concentration and initial pH. In addition, desorption studies were performed. Characterisation of this adsorbent was also confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) analysis. Batch adsorption experimental data were analysed using Langmuir, Freundlich and Dubinin–Raduschkevich (D–R) adsorption isotherms. The results indicated that the biosorption equilibrium was well described by both the Freudlich and D–R isotherms. Moreover, sorption kinetics was performed and it was observed that equilibrium was reached in<60 min, which could be described by the pseudo-second-order kinetic model for all heavy metals. The sorption of heavy metals onto the biomass was largely dependent on the initial solution pH. The elution efficiency for heavy metal ions desorption from C. sinuosa was determined for 0.1 M HCl, 1.0 M HCl and 1.0 M HNO₃. Desorption efficiency and also adsorption capacity were highest for Pb(II). The results indicate that C. sinuosa has great potential for the removal of heavy metals in an ecofriendly process.     

黄泥土微团聚体颗粒组对Cu2+的吸附与解吸研究

采用低能量超声波分散和冷冻机干燥法提取太湖地区黄泥土不同粒径微团聚体颗粒组样品,用平衡液吸附法和CaCl2与HCl溶液的连续解吸法研究原土和不同粒径微团聚体颗粒组对重金属Cu2 的吸附和解吸特征。结果表明,对于Cu2 的吸附,原土用Langmuir方程拟合最佳,而不同粒径微团聚体颗粒组用Freundlich方程拟合最佳。原土和不同粒径微团聚体颗粒组吸附量大小顺序为粘粒级>砂粒级>原土>粉砂级>粗粉砂级,这与其游离氧化铁和有机质含量呈显著正相关。原土和不同粒径微团聚体颗粒组对Cu2 的专性吸附质量分数随吸附量增加而减少,而非专性吸附质量分数则相反。不同粒径微团聚体颗粒组吸附总量小于原土,所以传统风干磨细的研究方法可能高估了土壤对铜固持能力。