有机酸对几种土壤胶体吸附解吸镉离子的影响

用平衡法研究了有机酸对土壤胶体吸附 解吸Cd2 的影响。结果表明 ,黄棕壤、红壤、砖红壤胶体Cd2 最大吸附容量 (Qm)分别为 4 3 7、16 8、1 5 8mmolkg-1。在加入Cd2 浓度相同的条件下 ,土壤胶体Cd2 吸附量随有机酸浓度的升高呈峰形曲线变化。当有机酸与Cd2 共存时 (竞争吸附 ) ,低浓度的草酸 (小于0 5～ 2mmolL-1)或柠檬酸 (小于 0 0 2 5～ 0 2mmolL-1)提高Cd2 吸附量 ,高浓度的草酸或柠檬酸能降低Cd2 吸附量。吸附有机酸后的土壤胶体 (次级吸附 )对Cd2 次级吸附量的影响与竞争吸附一致 ,但两者的Cd2 吸附量变化幅度不一样。这是由于两种吸附体系液相中有机酸残留浓度不同所致。土壤胶体吸附态Cd2 的解吸结果表明 ,草酸浓度不仅影响Cd2 的总解吸量、总解吸率 ,还影响土壤胶体表面KNO3 解吸态与DTPA解吸态Cd2 的分配比例     

羟基磷灰石对铅锌矿区土壤吸附Zn2+、Cd2+的影响

为探究羟基磷灰石(HAP)对矿区土壤重金属的固化效果,采用吸附试验,研究施加HAP的铅锌矿区土壤对Cd~(2+)、Zn~(2+)的动力学吸附和等温吸附效果。结果表明:土壤对Cd~(2+)、Zn~(2+)的吸附量随Cd~(2+)、Zn~(2+)初始浓度的增加而增加;在酸性条件下,其吸附量随pH上升而上升;准二级动力学方程能很好地描述两者的吸附过程,土壤吸附能力随HAP的添加量增大而增强;在Zn—Cd共存体系中,当初始浓度为20mg/L时,土壤对Zn~(2+)、Cd~(2+)的吸附无明显差异,2种金属离子竞争力度小,随着初始浓度上升,竞争明显,对Zn~(2+)的最大吸附量能达到单一体系中的79%～87%,而Cd~(2+)的最大吸附量只有单一体系中的57%～72%,Zn~(2+)的竞争力优于Cd~(2+),Zn~(2+)对Cd~(2+)吸附产生严重的抑制。综上可知,HAP能提高矿区土壤的吸附性能,在Zn、Cd污染土壤中,更能提升土壤对Zn~(2+)的吸附固持能力。     

KINETICS OF ION EXCHANGE IN SOIL ORGANIC MATTER. IV. ADSORPTION AND DESORPTION OF Pb2+, Cu2+, Cd2+, Zn2+ AND Ca2+ BY PEAT

The equilibria as well as the rates of adsorption and desorption of the ions Pb²⁺, Cu²⁺, Cd²⁺, Zn²⁺, and Ca²⁺ by soil organic matter were determined in batch experiments as a function of the amount of metal ions added to an aqueous suspension of HCl-washed peat. Simultaneous determination of the metal ions and hydrogen ions in the solution by atomic absorption spectrophotometry and pH-measurements showed that the adsorption of one divalent metal ion by peat was coupled with the release of two hydrogen ions. Since this equivalent ion-exchange process causes a corresponding increase of the electric conductivity of the solution, the rates of the adsorption and desorption processes were determined by an immersed conductivity electrode. The distribution coefficients show that the selective order for the metal adsorption by peat is Pb²⁺ > Cu²⁺ > Cd²⁺≌ Zn²⁺ > Ca²⁺ in the pH range of 3·5 to 4·5. The slope of -2, as observed in a double logarithmic plot of the distribution coefficients versus the total solution concentration confirms the equivalence of the ion-exchange process of divalent metal ions for monovalent H₃O⁺ -ions in peat. The absolute rates of adsorption, as well as the rates for the fractional attainment of the equilibrium, increase with increasing amounts of metal ions added. This behaviour is also observed for the subsequent desorption of the metal ions by H₃O⁺-ions. At a given amount of metal ions added, the absolute rates of adsorption decrease in the order Pb²⁺ > Cu²⁺ > Cd²⁺ > Zn²⁺ > Ca²⁺, while the rates for the fractional attainment of the equilibrium decrease in the order Ca²⁺ > Zn²⁺≌ Cd²⁺ > Pb²⁺ > Cu²⁺. The half times for adsorption and desorption were in the range of 5 to 15 sec.     

Two-stage Batch Adsorber Design: A Time-Dependent Langmuir Model for Adsorption of Pb2+ and Cd2+ onto Modified Kaolinite Clay

The kinetics of the adsorption of Pb²⁺ and Cd²⁺ by sodium tetraborate (NTB)-modified kaolinite clay adsorbent was studied. A one-stage and two-stage optimization of equilibrium data were carried out using the Langmuir and time-dependent Langmuir models, respectively. Increasing temperature was found to increase the pseudo-second order kinetic rate constant and kinetic data for Pb²⁺ adsorption were found to fit well with the pseudo-second order kinetic model (PSOM) while that for Cd²⁺ were found to show very good fit to the modified pseudo-first order kinetic model (MPFOM). Binary solutions of Pb²⁺ and Cd²⁺ reduced the adsorption capacity of the modified adsorbent for either metal ion with increased initial sorption rate due to competition of metal ions for available adsorption sites. The use of NTB-modified kaolinite clay adsorbent reduces by approximately 72.2% and 96.3% the amount of kaolinite clay needed to adsorb Pb²⁺ and Cd²⁺ from wastewater solutions. From the two-stage batch adsorber design study, the minimum operating time to determine a specified amount of Pb²⁺ and Cd²⁺ removal was developed. The two-stage batch adsorption process predicted less than half the minimum contact time to reach equilibrium in the one-stage process for the adsorption of Pb²⁺ and Cd²⁺ by NTB-modified kaolinite clay adsorbent and requires 0.05 times the mass of the adsorbent for the single-stage batch adsorption at the same operating conditions.     

Stability constants of complexes of metals with humic and fulvic acids under non-acid-conditions

Stability constants of complexes of four divalent metal ions viz. Cu²⁺, Zn²⁺, Mn²⁺ and Ca²⁺ with humic (HA) and fulvic acids (FA) at pH values of 7 and 8 were determined. The log K (logarithm of the stability constant) ranged from 3.09 to 7.77 and from 2.22 to 5.98 for metal-humic and metal fulvic acid complexes, respectively. Sequentially, the order of stability constants were as follows: Cu> Ca> Mn> Zn and Cu> Ca> Zn> Mn for metal -HA and metal-FA complexes, respectively, indicating a higher degree of complexation with Cu metal ion.     

Effects of Graphene Oxide and/or Cd<Superscript>2+</Superscript> on Seed Germination,Seedling Growth,and Uptake to Cd<Superscript>2+</Superscript> in Solution Culture

With increasing graphene oxide (GO) applications in industry and biomedicine, effects of GO on microorganisms, animals, and human health have been frequently studied; however, direct and indirect effects of GO on plants are seldom concerned. In this study, effects of GO and/or Cd²⁺ on seed germination, seedling growth, and uptake to Cd²⁺ were investigated in solution culture. The results showed that GO could quickly adsorb Cd²⁺ in solution, and the higher the GO concentration was, the lower the residual Cd²⁺ concentration was in solution. Rice seed germination, seminal root length, and bud length decreased with increasing GO and Cd²⁺ concentrations respectively, while the presence of GO could alleviate the inhibitive effects of Cd²⁺ on seminal root and bud growth compared with the single Cd²⁺ treatment. In maize seedling, fresh weights of shoot and root showed similar responses to the presence of Cd²⁺ and/or GO. Compared with the single Cd²⁺ treatment, root Cd concentrations were generally increased by GO in high Cd²⁺ solution (20 mg/L), while were slightly affected by GO in low Cd²⁺ solution (5 mg/L) independent of GO concentrations except for 100 mg/L GO. Shoot Cd concentrations were decreased by low GO (100 mg/L) while were increased by high GO (>?500 mg/L) independent of Cd²⁺ concentrations in solution. Moreover, significant interactive effects of GO and Cd²⁺ on root and shoot Cd concentrations were observed. This study indicates that GO can change the effects of Cd²⁺ on seed germination, seedling growth, and uptake to Cd²⁺ in solution through its adsorption on Cd²⁺.     

Loading of VO2+ and Cu2+ to partially oxidized charcoal fines rejected from Brazilian metallurgical industry

Purpose

Charcoal is utilized in Brazil for the metallurgical industry. Small size pieces, called charcoal fines, are rejected and sometimes are used to produce energy by burning. This charcoal can be used as soil conditioner to improve retention of metal ions in soil. However, changing the charcoal's surface chemistry via oxidation may increase retention of metal ions.

Materials and methods

Two kinds of oxidants were employed, nitric acid and selenium dioxide/hydrogen peroxide. Vanadyl ion (VO²⁺) and copper ion (Cu²⁺) were utilized as probe to study the metal ion complexation by the partially oxidized charcoal obtained. FTIR and EPR spectroscopy were used to characterize the materials.

Results and discussion

Oxidation with nitric acid increased nitrogen content, while oxidation with SeO₂/H₂O₂ elevated carbon content of treated charcoals. Organic free radicals (OFRs) with the unpaired electron in p orbitals of aromatic structures were confirmed by the EPR g-factors that ranged from 2.0038 to 2.0031. The oxidation with selenium dioxide/hydrogen peroxide formed charcoal with largest quantity of OFR. Loading charcoal with VO²⁺ and Cu²⁺ resulted in formation of complexes were oxygen acted as coordination atom. The formed complexes were of axial symmetry. The configurations around the Cu²⁺ ions were: CUNCu²⁺ complex (more stable square planar symmetry) and CFNCu²⁺ complex (less stable distorted tetrahedral configuration). Both complexes had oxygen as coordinating atoms. CFNVO²⁺ and CFSeVO²⁺ complexes presented complexation sites of axial symmetry, C_4v, with oxygen as coordinating atoms.

Conclusions

The oxidative treatment of charcoal with SeO₂/H₂O₂ is more appropriate to produce soil organic conditioner for complexation of metal ions.     

Sorption of cadmium on suspended matter under estuarine conditions; competition and complexation with major sea-water ions

Sorption of Cd at low concentrations onto river Rhine suspended matter was examined in terms of sorption rate, reversibility and factors such as competition and complexation with major inorganic sea-water ions. More than 90% of the final amount of Cd is sorbed within the first few hours. Desorption experiments show that the process is virtually reversible. In experiments with diluted sea water the sorption of Cd strongly decreases even at low salinity. Sorption isotherms show that the sorption of Cd in NaNO₃ solutions is regulated by the free Cd²⁺ activity. In a Ca(NO₃)₂ environment the Cd sorption decreases with increasing Ca²⁺ concentrations, which implies competition between Ca²⁺ and Cd²⁺ for the different sorption sites. In different electrolyte solutions of similar ionic strength the sorption of Cd decreases in the solution order NaNO₃ > NaCl > NaCl+MgCl₂+CaCl₂ > diluted sea water. Although inorganic speciation calculations show that even at low salinities dissolved Cd is dominated by Cd-chloro complexes, chloride accounts for only about one third of the increased mobility of Cd. As a result of addition of Ca²⁺ and Mg²⁺ the sorption capacity of suspended matter for Cd is further reduced by a factor three.     

Combined Removal of Zinc (II) and Cadmium (II) from Aqueous Solutions by Adsorption onto High-Calcium Turkish Fly Ash

The aim of this work is the investigation of possible use of flyash in the removal of zinc (Zn²⁺) and cadmium (Cd²⁺) contained in aqueous solutions. Batch adsorption experiments wereperformed in order to evaluate the removal efficiency oflignite-based fly ash. The parameters studied include contact time, pH,temperature, initial concentration of the adsorbate and fly ashdosage. The contact time necessary to attain equilibrium was found to be two hours. Maximum adsorption occurred in the pH range of 7.0 to 7.5. The percent adsorption of Zn²⁺ and Cd²⁺ increased with an increase in concentration of Zn²⁺ and Cd²⁺, dosage of fly ash and temperature. Theapplicability of Langmuir isotherm suggests the formation ofmonolayer coverage Zn²⁺ and Cd²⁺ ions at the outer surface of the adsorbent. Thermodynamic parameters suggested the endothermic nature of the adsorption process. The fly ashwas found to be an metal adsorbent as effective as activated carbon.     

Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Infrared spectra of Cu2+ Pb2+ and Ca2+ complexes of soil humic substances

An infrared spectroscopic investigation of the complexes of Cu²⁺, Pb²⁺, and Ca²⁺ with humic and fulvic acids demonstrated the participation of OH and CO groups in addition to COOH in the binding of heavy-metal cations. The degree to which metal-carboxylate linkages are ionic or covalent cannot be accurately determined from the positions of antisymmetric and symmetric carboxylate stretching vibrations due to interference from covalent bonding with other groups. The apparent order of the reaction of three divalent cations with humic and fulvic acids was Cu²⁺ > Pb²⁺ > Ca²⁺.     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.     

The Adsorption Behavior of Pb<Superscript>2+</Superscript> and Cd<Superscript>2+</Superscript> in the Treated Black Soils with Different Freeze-Thaw Frequencies

Batch experiments were conducted to study the effect of freeze-thaw frequency on the adsorption behavior of Pb²⁺ and Cd²⁺ and its related mechanisms. The results indicated that the adsorption capacities of Pb²⁺ and Cd²⁺ to the freeze-thaw treated soil were lower than those to the unfrozen soil, and with increasing freeze-thaw frequency, the adsorption capacities of them decreased. These were attributed to the fact that freeze-thaw cycles reduced pH value, CEC, organic matter content, and free iron oxide content of soil, and these soil properties presented negative correlations with freeze-thaw frequency. Freeze-thaw cycles reduced specific adsorption capacities of Pb²⁺ and Cd²⁺ and enhanced nonspecific adsorption ratios of Pb²⁺ and Cd²⁺ compared with the unfrozen soil. The higher freeze-thaw frequency, the higher nonspecific adsorption ratio was. However, the relationship between specific adsorption capacities of Pb²⁺ and Cd²⁺ and freeze-thaw frequency was opposite. Furthermore, the adsorption processes to the unfrozen and freeze-thaw treated soils were spontaneous, for Pb²⁺, its adsorption to soil was endothermal process, for Cd²⁺, on the contrary.     

几种铵盐对土壤吸附Cd2+和Zn2+的影响

采用平衡吸附法,研究了不同铵盐对潮褐土、红壤吸附Cd2+、Zn2+的影响。结果表明,土壤对Cd2+、Zn2+的吸附量随平衡溶液中Cd2+、Zn2+浓度的增加而增加;潮褐土和红壤对Cd2+、Zn2+的最大吸附量为:Zn2+ Cd2+,且潮褐土红壤;随NH4HCO3浓度的增加,两种土壤对Cd2+、Zn2+的吸附率显著提高,NH4Cl、NH4NO3和(NH4)2SO4抑制红壤对Cd2+、Zn2+的吸附及潮褐土对Cd2+的吸附,对潮褐土Zn2+的吸附率影响不显著;铵盐浓度相同时,红壤对Cd2+吸附率为:NH4HCO3NH4ClNH4NO3≈ (NH4)2SO4,红壤对Zn2+吸附率为:NH4HCO3NH4Cl NH4NO3(NH4)2SO4。     

Efficacy of N2O2 donor schiff bases and their Zn2+ complexes on various morphological and biochemical parameters of Cicer arietinum L.

Schiff-base polydentate ligands types of salen and salophen can form stable complexes with Zn²⁺ and these metal complexes can act as a source of zinc (Zn) to plant's body if they are used as micronutrient supplements. Inspired by these facts, four different Schiff-base ligands and their Zn²⁺ complexes were first synthesized and then characterized by different analytical and spectroscopic techniques. To investigate their effects local chickpea seeds were treated with each ligands and complexes and different morphological and biochemical parameters were monitored. Among all the complexes and ligands it was found that the C4 complex, that is, [N,N'-(o-phenylene)bis-(3-methoxysalicylidenediamine)] monohydrate showed the maximum efficacy when treated as a micronutrient supplement for Cicer arietinum L. So that these complexes especially the C4 can act as an potential source of Zn.     

Coefficients of association and activity of cadmium and lead ions in soil solutions

The thermodynamic calculations were made for the contents of Pb and Cd compounds in soil solutions and water extracts of the meadow-steppe and meadow solonetzes (Rostov oblast) based on their prescribed analytic concentrations of 3 and 5 μg/l, respectively. The solonetzes studied are characterized by their high carbonate content and high alkalinity. The activity of Pb²⁺ and Cd²⁺ was shown to be many times lower than their total concentration in the solution due to the association of these metals with carbonate and other anions and the formation of hydroxocomplexes CdOH⁺ and PbOH⁺. This fact is one of the reasons for the low input of Pb²⁺ and Cd²⁺ to plants growing on calcareous soils.     

ADSORPTION ON HYDROUS OXIDES. IV. MECHANISMS OF ADSORPTION OF VARIOUS IONS ON GOETHITE

Infrared spectroscopy has been used to investigate the complexes that are formed when acids are evaporated onto goethite. It is probable that, like HPO^2?₄, the anions SO^2?₄, SeO^2?₃, and oxalate are adsorbed by ligand exchange and form binuclear bridging complexes where two singly coordinated A-type OH groups are replaced by two oxygen atoms of one ligand. There is evidence that HPO^2?₄ and oxalate are likely to be present in this form in wet environments, and this is probably also true for SO^2?₄ and SeO^2?₃. Fluoride ions can completely replace the singly coordinated A-type OH groups but do not replace C- or B-type OH groups that are coordinated, respectively, to two and three Fe³⁺ ions. The other halides, nitrate, and benzoate partially replace the A-type OH groups, benzoate being adsorbed as a monodentate ligand. Copper ions do not appear to react with A-type OH but zinc ions are probably adsorbed on the goethite (100) face in conjunction with carbonate or bicarbonate.     

TiO2 photocatalytic degradation of tetracycline as affected by a series of environmental factors

Purpose

TiO₂ photocatalytic degradation of tetracycline (TC) in aqueous solution under UV irradiation was investigated as affected by different environmental factors, including cations, anions, organic acids, and surfactants.

Materials and methods

The solution of TC with TiO₂ was irradiated by medium mercury lamp. The concentrations of TC and metal ions were analyzed by HPLC and AAS, respectively. The degradation efficiency of TC was calculated based on TC disappearance.

Results and discussion

Photocatalysis was very effective for TC removal. The degradation efficiency of TC was significantly enhanced in the presence of Cu²⁺/Pb²⁺, SO₄ ^2?/Cl^?, and humic acid (HA) in the examined range, but did no change with Ni²⁺, Cd²⁺, or Zn²⁺. In addition, the results also showed that solution Cu²⁺ and Pb²⁺ ions could be reduced during the process, while Ni²⁺, Cd²⁺, and Zn²⁺ were still kept in the solution. However, tannic acid (TA), gallic acid (GA), citric acid (CA), salicylic acid (SA), hydroxypropyl-β-cyclodextrin (HPCD), polyoxyethylene lauryl ether (Brij35), or polyoxyethylenesorbitan monooleate (Tween80) significantly decreased the degradation efficiency of TC.

Conclusions

The photocatalytic approach could be successfully applied to remove TC, and environmental factors significantly influenced its degradation efficiency. It would be useful to understand the environmental behaviors of TC and for the implementation of remediation strategies of TC.     

Formation constants of cu2+ complexes with humic and fulvic acids

Formation constants for Cu²⁺ complexes with humic and fulvic acids were determined by a modification of the well-known Bjerrum potentiometric titration method. Highly stable complexes were formed with formation constants of the order of those observed for synthetic polycarboxylic acids. Overall formation constants for a two-step process (B₂) ranged from 2.5 · 10^?4 to 7.9 · 10^?3.