砖红壤及其矿物表面对重金属离子的专性吸附研究

本文对Ｃｕ＾２＋、Ｚｎ＾２＋、Ｃｏ＾２＋、Ｎｉ＾２＋和Ｃｄ＾２＋在砖红壤、针铁矿、无定形氧化铝和高岭石表面上的专性吸附进行的研究结果表明：ＰＨ是影响重金属离子吸附过程的最重要因素，而表面带电性质对吸附过程的影响不大。砖红壤表面的吸附顺序是Ｃｕ＾２＋〉Ｚｎ＾２＋〉Ｃｏ＾２＋〉Ｎｉ＾２＋≥Ｃｄ＾２＋；针铁矿表面的吸附顺序是Ｃｕ＾２＋〉Ｚｎ＾２＋〉Ｃｄ＾２＋〉Ｎｉ＾２＋〉Ｃｏ＾２＋；而无定形氧化铝和高岭     

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.     

Effect of the particle-size distribution on the adsorption of copper, lead, and zinc by Chernozemic soils of Rostov oblast

The parameters of adsorption of Cu²⁺, Pb²⁺, and Zn²⁺ cations by soils and their particle-size fractions were studied. The adsorption of metals by soils and the strength of their fixation on the surface of soil particles under both mono- and polyelement contamination decreased with the decreasing proportion of fine fractions in the soil. The adsorption capacity of the Lower Don chernozems for Cu²⁺, Pb²⁺, and Zn²⁺ depending on the particle-size distribution decreased in the following sequence: clay loamy ordinary chernozem ∼ clay loamy southern chernozem > loamy southern chernozem > loamy sandy southern chernozem. According to the parameters of the adsorption by the different particle-size fractions (C _max and k), the heavy metal cations form a sequence analogous to that obtained for the entire soils: Cu²⁺ ≥ Pb²⁺ > Zn²⁺. The parameters of the heavy metal adsorption by similar particle-size fractions separated from different soils decreased in the following order: clay loamy chernozem > loamy chernozem > loamy sandy chernozem. The analysis of the changes in the parameters of the Cu²⁺, Pb²⁺, and Zn²⁺ adsorption by soils and their particlesize fractions showed that the extensive adsorption characteristic, namely, the maximum adsorption (C _max), was a less sensitive parameter characterizing the soil than the intensive characteristic of the process—the adsorption equilibrium constant (k).     

Adsorption features of Cu(II), Pb(II), and Zn(II) by an ordinary chernozem from nitrate,chloride, acetate,and sulfate solutions

The effect of Cl^?,SO ₄ ^2? , CH₃COO^?, and NO ₃ ^? anions on the adsorption of copper, lead, and zinc by an ordinary chernozem has been studied. The effect of the anions on the adsorption of Cu²⁺, Pb²⁺, Zn²⁺ ions is significant but uncertain. It has been shown that the attendant anions affect the shape of the adsorption isotherms, which are described by the Langmuir, Freundlich, or Henri equations. The constants of the adsorption from a nitrate solution calculated from the Langmuir equation (K _L) decrease in the following order: Cu²⁺ > Pb²⁺ >> Zn²⁺. The values of the maximum adsorption (C _max) decrease in the following order: Cu²⁺ ≥ Zn²⁺ > Pb²⁺ for acetate solutions and in the series Pb²⁺ > Zn²⁺ ≥ Cu²⁺ for nitrate solutions. The values of the Henry constants (K _H) calculated for the adsorption of the same cations from chloride solutions decrease in the same order as the values of K _L. The CH₃COO^? anion has the highest effect on the constant values. The NO ₃ ^? and Cl^? anions “switch their places” depending on the attendant cation, but their effect is always lower than that of the acetate anion. The values of C _max for copper and zinc are most affected by the CH₃COO^? anion, and the adsorption of zinc is most affected by the Cl^? and NO ₃ ^? anions. The assessment of the mobility of the adsorbed cations from the extraction with ammonium acetate (pH 4.8) has shown that the content of the desorbed metals is always lower than the content of the adsorbed cations and varies from 0.025 to 83%. According to their mobility, the adsorbed metals form the following order: Zn²⁺ > Pb²⁺ > Cu²⁺. The effect of the attendant anions on the extractability of the adsorbed cations decreases in the following order: chlorides > sulfates > acetates > nitrates.     

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.     

Comparative analysis of mono- and polyelement adsorption of copper,lead, and zinc by an ordinary chernozem from nitrate and acetate solutions

Isotherms of mono- and polyelement adsorption of Cu²⁺, Pb²⁺, and Zn²⁺ by an ordinary chernozem were described by the Langmuir equation. The values of the adsorption constant k decreased in the range Cu²⁺ > Pb²⁺ ≫ Zn²⁺ for the monoelement adsorption from nitrate and acetate salt solutions, Cu²⁺ > Pb²⁺ > Zn²⁺ for the polyelement adsorption from nitrate solutions, and Pb²⁺ > Cu²⁺ ≫ Zn²⁺ for the polyelement adsorption from acetate solutions. The maximum adsorption (C _{max, ∞}) of individual cations at the polyelement contamination was always lower than at the monoelement contamination because of the mutual competition. At the same time, the values of k for the polyelement adsorption were higher than those for the monoelement adsorption because heavy metals (HMs) interact with most of the specific adsorption centers. It was shown that the ratio between the content of exchangeable cations displaced from the soil exchangeable complex (SEC) into the solution and the content of adsorbed HMs decreased with the increasing concentration of adsorbed HMs. These values could be higher (for Cu²⁺), equal, or lower than 1 (for Pb²⁺ and Zn²⁺). In the former case, this was due to the dissolution of readily soluble salts at low HM concentrations in the SEC. In the latter case, this was related to the adsorption of associated HMs and the formation of new phases localized on the surface of soil particles at high HM concentrations in the SEC.     

Effects of Several Metals on Both Fe(III)‐ and Cu(II)‐Reduction by Roots of Fe‐Deficient Cucumber Plants

Abstract

The ferric‐chelate reductase induced by Fe deficiency is also able to reduce other ions such as Cu²⁺. This Cu(II)‐reduction has been less studied and it has been suggested that Cu²⁺ ion rather than Cu²⁺‐chelate serves as the substrate. Ferric‐chelate reductase activity is inhibited by some metals, but the mechanisms implicated are not known. In the present work we use Fe‐deficient cucumber seedlings to study the interactions of Cu²⁺, Ni²⁺, Mn⁴⁺, and Fe³⁺ on both Fe(III)‐reduction and Cu(II)‐reduction activities. The response of Cu(II)‐reduction activity to Cu concentration, in the presence or absence of citrate, was also studied. Results showed that inhibition of the ferric‐chelate reductase activity by Cu²⁺ or Ni²⁺ could be partially reversed by increasing the concentration of Fe‐EDTA. The Cu(II)‐reduction activity was even stimulated by Fe‐EDTA or Ni²⁺; it was inhibited by a high concentration of Cu²⁺ itself; and it was not affected by the absence of citrate. Mn⁴⁺ caused a moderate inhibition of both Fe(III)‐reduction and Cu(II)‐reduction activities. Results agree with the hypothesis that free Cu²⁺ ion is the substrate for Cu(II)‐reduction and suggest that the mechanisms involved in Fe(III)‐reduction and Cu(II)‐reduction could have some differences and be affected by metals in different ways. The mode of action of metals on the reductase activity are discussed, but they are still not well known.     

重金属和pH值对类芦种子萌发的影响

类芦(Neyraudia reynaudiana)是一种具有极强耐干旱、贫瘠、高温等逆境的多年生禾草植物,是南方水蚀荒漠化地区、采矿采石厂及各类边坡植被自然恢复中的先锋植物。为探索在各类矿区及受重金属污染的地区采用类芦进行生态修复的可行性,通过室内发芽试验,对类芦种子在Hg2+,Cr6+,Cd2+,Pb2+,Zn2+,Cu2+等6种重金属离子胁迫及不同pH值条件下的萌发能力进行了研究。结果表明,类芦种子在pH值为5.0~9.0的范围内具有良好的萌发能力;6种重金属离子随着处理浓度的升高,对类芦种子的抑制作用逐渐加强,且出现显著抑制作用的最低浓度顺序为:Cd2+Cu2+Hg2+,Zn2+,Cr6+Pb2+;6种重金属对类芦种子活力指数出现显著影响的浓度均较显著影响发芽率、发芽势和发芽指数3个指标的浓度低,说明类芦幼苗生长比种子萌发对6种重金属更加敏感。     

Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

Standard potentials (Eo) of iron(III) oxides under reducing conditions

Partial reduction of iron(III) oxides with hydrogen in the presence of a platinum catalyst leads to an equilibrium state after 4–20 h. From the measured Eh, pH, and Fe²⁺ concentration conditional standard potentials can be calculated using the formula E_o (volt) = Eh + 0.059 lg(Fe²⁺) + 0.18 pH which indicate the stability of Fe oxides against reduction. The reduceability decreases following the order ferrihydrite > lepidocrocite > hematite > goethite. The difference between hematite and goethite was more pronounced than that predicted from thermodynamic data.     

Heavy Metal Uptake by Rape

Abstract

In pot experiments, the effect of single and combined pollution of soil by lead (Pb), cadmium (Cd), and zinc (Zn) and uptake of heavy metals in Brassica napus L. were investigated. There were two main factors that affected the assimilation of Pb, Cd, and Zn by rape: (i) level of soil pollution by the particular element and (ii) the combined influence of Pb, Cd, and Zn. In general, with the increase of the concentrations of Pb, Cd, and Zn in the soil, there were increases in the concentrations of those elements in the roots, stems, and seeds. The main part of the Pb and Zn amounts taken up by the roots from the soil are fixed and accumulated in the roots, and small amounts of them move through the conductive system to the seeds. Cadmium moves relatively easily from root to stem and is accumulated in higher concentrations in the top of the plant.

There is a well‐expressed synergistic interaction between Pb²⁺ and Cd²⁺, as well as of Cd²⁺ and Zn²⁺. Zinc has a highly depressing effect on the assimilation of Cd²⁺, as does Pb²⁺ on the assimilation of Zn²⁺. The combined pollution by Pb, Cd, and Zn stimulated the assimilation of these elements by the roots and foliage and eliminated the effect of Zn²⁺ on Cd²⁺ and of Pb²⁺ on Zn²⁺.     

Sorption of Heavy Metals by Canola Meal

The results from this research indicate that canola meal (CM) can be used for adsorption of Zn²⁺, Cd²⁺, Cu²⁺, Pb²⁺and Ni²⁺from aqueous solutions. The order of sorption for these metals in single metal systems was as follows (molar basis): Zn²⁺> Cu²⁺> Cd²⁺> Ni²⁺> Pb²⁺. It was noted that a decrease in the concentration of CM caused a higher metal loading on the meal. Increases in the metal concentration, temperature or pH resulted in increased sorption of the metals by the meal. The systems with identical ratios of CM to Zn²⁺concentrations, regardless of their levels, resulted in the same amount of metal adsorbed per unit weight of meal. The Freundlich isotherm type model was used in this study and was found to fit the experimental equilibrium concentration data of Zn²⁺and Cd²⁺; however, the Langmuir isotherm model fit only the equilibrium data of Zn²⁺. Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray (EDX) microanalyses revealed that the metal ions were sorbed mainly at the cell wall and only small amounts of ions diffused into the cytoplasm of the CM cells. The Electron Spin Resonance (ESR) tests were inconclusive regarding the direct participation of free radicals in copper sorption.     

Characterization of iron in alkaline EDTA and NH4OH extracts of podzols

Mössbauer and ESR spectroscopy have shown that the iron extracted from the Bh horizons of an iron humus podzol and an iron podzol by EDTA at pH 9.1 is predominantly in the form of complexes * 1 The use of the word ‘complex’ in this paper in the context of polymeric iron species and organic matter is not intended to imply any single specific type of complex, such as exists in Fe(II1) EDTA, for example, but to embrace many possible modes of association including salt formation, direct coordination, Van der Waal's adsorption, and electrostatic attraction.
of polymeric Fe(III) hydroxide and oxide with organic matter (O.M.). Small amounts of monomeric Fe(III)-O.M. and Fe(III)-EDTA complexes also occur. In contrast EDTA at pH 7 extracts iron from these podzols predominantly in the form of iron-EDTA complexes. Some monomeric Fe(III)-O.M. complex also occurs in a pH 9.1 NH₄ OH extract of these horizons and in a pH 9.1 EDTA extract of the B₃ horizon of a peaty podzol. Dialysis experiments show that the particle dimensions of the polymeric hydroxy Fe(III)-O.M. complex, which accounts for about 66% of the Fe extracted from the iron humus podzol and about 36% of that from the iron podzol, are greater than 2.4 nm. The thermal behaviour of the Mössbauer peaks indicated that the size of the iron cores was of the order of 5 nm, thus suggesting that the complex probably consists of hydroxyiron cores surrounded by large organic molecules. Results from XRD and IR suggest that these hydroxyiron cores may have structural organizations similar to those of goethite and ferrihydrite. The relationship between these forms of iron in the extracts and those in the soil is briefly discussed.     

Influence of electrolytes on EDTA extraction of Pb from polluted soil

Because the economics of soil extraction processes depend on conservation and reuse of costly chelating agents, the ability of various electrolytes to modify EDTA extraction of Pb from a grossly-contaminated soil (Pb_T=21%) was investigated using batch equilibration experiments. In the absence of added electrolyte, a single 5-hr. extraction with 0.04 M EDTA (corresponding to 1∶1 Pb_T to EDTA ratio) released 65% of Pb_T over the pH 5 to 9 range. Under these conditions, Na⁺-, Li⁺-, and NH₄ClO₄ salts at 0.5 M increased Pb desorption to nearly 80%, probably from exchange displacement of soilbound Pb²⁺ and increased solubility of Pb-containing phases at higher ionic strength. Because Cl^? and ClO₄ ^? salts were equally effective, chlorocomplex formation was insignificant. Under slightly acidic conditions, Ca(ClO₄)₂ and Mg(ClO₄)₂ at 0.167 M caused roughly the same elevation in Pb recovery as 0.5M of the monovalent electrolytes. However, with progressively higher pH, Ca, and to a lesser extent Mg, suppressed Pb solubilization by competitive chelation of EDTA. Pb recovery by EDTA soil washing could be enhanced by addition of Ca salts at pH 4 to 6. Subsequent pH elevation in the presence of Ca would promote decomposition of Pb-EDTA complexes and separation of Pb as a hydroxide precipitate.     

Comparison of various methods for the determination of inorganic species in airborne atmospheric particulates

The performance of various filters used for determining inorganic species (heavy metals, light metals, anions and ammonium ion) in airborne particulates was comparatively assessed. Filters used in the determination of Ca²⁺, Mg²⁺, Na⁺, K⁺, Fe³⁺, Zn²⁺, Pb²⁺, Cr³⁺, Ni²⁺, V (V), Mn²⁺ and Cd²⁺ were attacked by acid extraction (glass microfibre filters, GF/A), acid extraction and microwave oven digestion (quartz filters, QM-A), and muffle furnace calcination and microwave oven digestion (Whatman-41 cellulose filters, W-41). The behaviour of the different filters tested towards aqueous extraction for the determination of anions (Cl^?, NO ₃ ^? , SO ₄ ^? , ammonium ion and light metals (Ca²⁺, Mg²⁺, Na⁺ and K⁺) was also studied and the results obtained for the light metals were compared with those provided by acid attack. All metals except vanadium were determined by ICP-AES; cadmium, lead and vanadium were analysed for by GFAAS; anions were quantified by ion chromatography (SO ₄ ^? was also measured by ICP-AES); and ammonium ion was determined by the Indophenol Blue method.     

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.     

Bioremediation of heavy metals from municipal sewage by cyanobacteria and its effects on growth and some metabolites of Beta vulgaris

The present research was done to study the ability of cyanobacterial species for removing heavy metals from sewage. As well, to estimate the growth and some metabolites of Beta vulgaris irrigated with sewage treated by cyanobacterial species. The best removal results were obtained by Anabaena oryzae compared to the other studied cyanobacteria. Whereas A. oryzae showed high removal efficiency for cadmium (Cd²⁺) followed by lead (Pb²⁺), zinc (Zn²⁺), iron (Fe²⁺), copper (Cu²⁺) and manganese (Mn²⁺) (88.5, 83.1, 68.8, 62.0, 55.2 and 42.4%, respectively). Irrigation of plants by untreated or treated sewage generally caused stimulation in the total proteins, proline, carbohydrates and ascorbic acid. B. vulgaris grown in soil irrigated with untreated sewage showed maximum catalase, peroxidase activity, hydrogen peroxide (H₂O₂) and lipid peroxidation compared to the other treatments. The heavy metals availability was relatively low in the plant irrigated with treated sewage by cyanobacterial species, so the antioxidants requirement was low and hence the induction of antioxidants was lower compared to the plant irrigated with untreated sewage.     

磷和柠檬酸共存对高岭石和针铁矿吸附铅的影响

通过平衡吸附试验及矿物电动电位(Zeta电位)的变化分析,研究了磷(P)和柠檬酸(CA)共存对针铁矿和高岭石吸附铅的影响。结果表明:(1)针铁矿和高岭石对铅的吸附量随柠檬酸浓度的升高呈现"峰形"曲线变化,铅吸附量达到峰值的柠檬酸浓度均为0.5 mmol L~(-1),不同浓度磷存在下柠檬酸对矿物吸附Pb2+量有不同程度增加。(2)随着磷添加浓度的增加,两种矿物对铅吸附量均呈增加趋势,磷添加浓度分别为1 mmol L~(-1)和0.6 mmol L~(-1)时,针铁矿和高岭石吸附铅量达到平衡;当处理中添加不同浓度柠檬酸,两种矿物均表现为对铅的吸附量增加,且随着柠檬酸浓度增加促进铅吸附的作用增强,说明在磷及试验浓度柠檬酸存在下促进了矿物对铅的吸附。(3)高岭石体系中,加入磷或(和)柠檬酸后,Zeta电位-pH曲线向负值方向位移,降低程度大小顺序为1.0 mmol L~(-1) P+0.5mmol L~(-1) CA0.5 mmol L~(-1) CA1.0 mmol L~(-1) P,说明高岭石表面增加的负电荷也部分增加了其对铅的电性吸附;添加磷和柠檬酸处理针铁矿的Zeta电位显著降低,且随着体系pH的升高其Zeta电位没有明显变化,表明磷和柠檬酸均主要是通过吸附到针铁矿表面而增加对铅的专性吸附。     

Uptake of Iron (59Fe) Complexed to Water‐Extractable Humic Substances by Sunflower Leaves

Abstract

A research was carried out to evaluate the leaves' ability to utilize Fe supplied as a complex with water‐extractable humic substances (WEHS) and the long‐distance transport of ⁵⁹Fe applied to sections of fully expanded leaves of intact sunflower (Helianthus annuus L.) plants. Plants were grown in a nutrient solution containing 10 µM Fe(III)‐EDDHA (Fe‐sufficient plants), with the addition of 10 mM NaHCO₃ to induce iron chlorosis (Fe‐deficient plants). Fe(III)‐WEHS could be reduced by sunflower leaf discs at levels comparable to those observed using Fe(III)‐EDTA, regardless of the Fe status. On the other hand, ⁵⁹Fe uptake rate by leaf discs of green and chlorotic plants was significantly lower in Fe‐WEHS‐treated plants, possibly suggesting the effect of light on photochemical reduction of Fe‐EDTA. In the experiments with intact plants, ⁵⁹Fe‐labeled Fe‐WEHS or Fe‐EDTA were applied onto a section of fully expanded leaves. Irrespective of Fe nutritional status, ⁵⁹Fe uptake was significantly higher when the treatment was carried out with Fe‐EDTA. A significant difference was found in the amount of ⁵⁹Fe translocated from treated leaf area between green and chlorotic plants. However, irrespective of the Fe nutritional status, no significant difference was observed in the absolute amount of ⁵⁹Fe translocated to other plant parts when the micronutrient was supplied either as Fe‐EDTA or Fe‐WEHS. Results show that the utilization of Fe complexed to WEHS by sunflower leaves involves an Fe(III) reduction step in the apoplast prior to its uptake by the symplast of leaf cells and that Fe taken up from the Fe‐WEHS complexes can be translocated from fully expanded leaves towards the roots and other parts of the shoot.     

Adsorption of Heavy Metals on Mixed Fe-Al Oxides in the Absence or Presence of Organic Ligands

A study was carried out on the adsorption of Co²⁺, Cu²⁺, Pb²⁺, and Zn²⁺ ions on mixed Fe-Al oxides inthe absence or presence of increasing concentrations of oxalate or tartrate. Mixed Fe-Al oxides were prepared by precipitating at pH 5.5 mixtures of Fe and Al ions at initial Fe/Al molar ratios (R) of 0, 1, 2, 4, 10 and ∞ (R0, R1, R2, R4, R10 and R∞).The oxides aged 7 days at 20 °C or 30 days at 50 °C showed different chemical composition and physico-chemical and mineralogical properties. All the mixed Fe-Al oxides showed presence of poorly crystalline materials (ferrihydrite) even after prolonged aging. The heavy metals wereselectively adsorbed on the oxides. For all the precipitates aged7 days at 20 °C, the selectivity sequence wasPb²⁺> Cu²⁺ > Zn²⁺ > Co²⁺, but the pH at which 50% ofeach cation was adsorbed (pH₅₀) was different from sample tosample. It was found that usually the greater the amounts of Fe in Fe-Al gels the lower the pH₅₀ for each metal, but the adsorption of a heavy metal was not linearly related to Fe content. The pH₅₀ usually did not change significantly when the oxides were aged 30 days at 50 °C. Competitive adsorption of Cu and Zn on ferrihydrite (R∞) showed thatCu strongly prevented Zn adsorption even at an initial Zn/Cu molar ratio of 8, whereas Cu sorption was not inhibited. In thepresence of oxalate (OX) or tartrate (TR) (organic ligand/Pb molar ratio (r_L) from 0 to 7) the quantities of Pb adsorbedon the Fe-Al oxides usually increased with increasing r_L. The adsorption increase of Pb was particularly high on the oxidesricher in Fe (R4-R∞), but a significant increase was also observed on R0-R2 samples. The adsorption of Pb on the oxides hasbeen influenced not only by the presence and concentration of organic ligands but also by the sequence of addition of Pb and tartrate on the sorbents. It has been ascertained that on each oxide the greater amounts of Pb were adsorbed when tartrate wasadded before Pb and usually according to the following sequence: Tr before Pb > Pb before Tr > Pb + Tr > Pb.