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1.
Complexation of Cu, Pb, and Cd by water soluble humic substances I. The polarographic proof of heavy metal complexation by water soluble humic substances The complexation of Cu, Pb, and Cd by water soluble humic substances in aqueous solution decreases the peak height of differential pulse polarograms. Using the law of mass action with respect to definite complex formulae, empirical stability constants can be calculated, which are roughly independent from the presence of other cations.  相似文献   

2.
Electron microprobe studies on soil samples with varying heavy metal contamination. 2. Contents of heavy metals and other elements in aggregations of humic substances, litter residues and charcoal particles EMA point analysis show that the organic matter constituents of heavy metal contaminated soils are highly enriched with heavy metals. The maximal trace element accumulation were for Cu up to 13,000 mg/kg, for Zn up to 48,000 mg/kg, for Cd up to 2,100 mg/kg and for Pb up to 193,000 mg/kg. The affinity for the accumulation of the different heavy metals in aggregations of humic substances can be described by the sequence Cu > Pb ? Cd > Zn ? Ni > Co. In very strongly acidified humic top soil horizons the Pb and Cd accumulation in the organic matter constituents is in competition with the accumulation in Fe and Mn oxides. The heavy metal contents (especially of Cu) of the organic matter are often correlated with the content of organically bound calcium. The EMA results also show that high heavy metal amounts occur in combination with Ca-accumulations in the epidermis and the outer bark parenchym of decayed roots. EMA point analysis of the interior of fungus sclerotias show that sclerotias can contain high amounts of heavy metals, in particular lead (up to 49,700 mg Pb/kg). From statistical results of EMA point analysis follows that lead and other heavy metals attached to humic substances are not only bound as metal organic complexes but also as organic metal phosphate complexes. Also charcoal particles of polluted soils contain high amounts of heay metals. The accumulation affinity is quite similar to that of humic substances.  相似文献   

3.
Aqueous extracts of terrestrial and underwater soils were prepared by Soxhlet extractions at temperatures between 100 and 37°C (under reduced pressure). From the law of mass action, stability constants were derived for the complexation of Cd, Cu, and Pb by these extracts. The activity of the heavy metals was determined polarographically, whereas the concentration of acid functional groups was used for ligand activity. Visible spectra, electrical conductivity, organic matter contents, and complexation constants depended on extraction temperature as well as on soil properties. In most cases, complex stability increased with increasing pH of the polarographic medium, but sometimes maximum stability was found around pH 7.  相似文献   

4.
Fulvic acid is a water-soluble humic material that occurs widely in soils and waters and that tends to form water-soluble and water-insoluble complexes with a variety of metal ions, some of which are toxic. This paper presents information on the conditions under which the different types of FA-metal complexes are formed. The solubility in water, separately and after mixing, of FA (2 to 30 mg/100 ml) and eleven metal ions (Fe(III), Al, Cr(III), Pb, Cu, Hg(II), Zn, Ni, Co, Cd and Mn; 1 × 10?5 moles of each metal ion) was investigated over the pH range 4 to 9. After mixing, the solubility of the components was significantly affected by pH only when less than 20 mg of FA was present. As the systems became richer in FA (22 to 30 mg), most of the metal ions remained in the aqueous phase, likely due to the formation of FA-metal complexes, inhibiting the formation of metal hydroxides. The order in which the eleven metal ions tended to form water-insoluble FA-metal complexes depended on the pH. At pH 6 it was: Fe = Cr = Al > Pb = Cu > Hg > Zn = Ni = Co = Cd = Mn. This order appeared to correlate with the valence, 1st hydrolysis constants and effective hydrated ionic diameters of the metal ions. In general, FA/metals weight ratios of > 2 favored the formation of water-soluble FA-metal complexes; at lower ratios, water-insoluble complexes, which could accumulate in soils and sediments, were formed.  相似文献   

5.
Heavy metal accumulations in Salic Fluvisols of the southern North Sea coast The total contents of Cd, Pb, Cu and Zn (HNO3 bomb digestion) and their EDTA extractable fractions in Salic Fluvisols were investigated. The mean total content of Cd was 0,09 mg/kg, of Pb 44,1 mg/kg, of Cu 11,4 mg/kg and of Zn 105,6 mg/kg. Mostly the highly developed soils showed higher contents than poorly developed ones. The EDTA extractable fractions were comparatively small: they were 59% (Cd), 44% (Pb), 15% (Cu) and 10% (Zn) of the total content. The heavy metal contents of the soils in Elisabeth-Außengroden were higher than of those in Jadebusen. The vertical heavy metal distribution showed a different sedimentation pattern over the last hundred years. Compared with the geological background values Cd was 2- to 3-fold enriched, Pb 7-fold, Cu 3- to 4-fold and Zn 3-fold in soils with high sedimentation rates. Even higher values are likely in soils with smaller sedimentation rates.  相似文献   

6.
The lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes were studied using diffusive gradients in thin films (DGT). A unique feature of this research was (1) the use of DGTs with diffusive layer thicknesses ranging from 0.4 to 2.0 mm to study lability and mobility of Zn(II)–, Cd(II)–, Pb(II)–, and Cu(II)–humic acid complexes, combined with (2) the application of a competing ligand exchange (CLE) method using Chelex 100, the same chelating resin that is used in DGT, to study the kinetic speciation. The CLE experiments were run immediately after the completion of the DGT experiments, thereby allowing effects of the competing ligand to be separated from the effects introduced by the use of the polyacrylamide gel that is used in DGT. The results indicate that Zn(II) and Cd(II) tend to form more labile and more mobile complexes with humic acid than Pb(II) or Cu(II). The dissociation rate constants of Zn(II), Cd(II), and Pb(II) were found to increase with the ionic potential of the metal, suggesting that the binding between some trace metals and humic acid has a significant covalent component. Furthermore, the results suggest that the Eigen mechanism may not be strictly obeyed for metals such as Cu(II) which have high rate constants of water exchange, k w. Consequently, the markedly slow kinetics of Cu(II)-HA species suggests that the usual equilibrium assumption may not be valid in freshwaters.  相似文献   

7.
The aim of this review is to describe the main physicochemical characteristics of diverse types of humic‐metal‐phosphate acid complexes. The effects of these complexes on phosphorus (P) fixation in soils with different pH values and physicochemical features and on plant phosphorus uptake are also discussed. Humic‐metal‐phosphate complexes have apparent stability constants in the same range as those of metal‐humic complexes, in solutions with diverse pH and ionic‐strength values. Likewise, the molecular‐size distribution of humic‐metal‐phosphate complexes as a function of pH is similar to that of potassium or sodium humates and metal‐humic complexes. Humic‐metal‐phosphate complexes are able to decrease phosphate fixation in soils and increase plant growth and phosphate uptake. Phosphorus fertilizers containing humic‐metal‐phosphate complexes proved to be efficient to improve plant growth and P uptake with respect to conventional fertilizers such as single superphosphate. The values of parameters related to plant phosphorus‐utilization efficiency (PUt E) suggest that the regulation of root acquisition of phosphate from these complexes could involve the interregulation of a system for the optimization of metabolic P utilization in the shoot and another system involving stress responses of roots under phosphorus deficiency.  相似文献   

8.
Estuarine systems adjacent to urban areas are at risk of contamination by contaminants from anthropogenic sources, such as heavy metals. We anticipated that the sediments of the Swan River estuary, which runs through metropolitan Perth in Western Australia, would show metal contamination related to industrialization and inputs of stormwater. Total Cu, Pb and Cd concentrations, and Cu, Pb, Cr and Zn inoperationally-defined fractions, were determined inseparate sampling exercises in near-shore sediments ofthe upper Swan River estuary.Total metal concentrations in sediments were not high (maximum values of 297 mg kg-1 for Cu, 184 mg kg-1 for Pb and 0.9 mg kg-1 for Cd) when compared with Australian environmental assessmentguidelines for soils. On the basis of linear regressions between sediment metal concentrations andphysicochemical properties of the sediments (pH, organic carbon, particle size distribution), no single parameter could explain the variation in metal concentrations for all metals. Sediment organic carbon content was positively correlated with Cu concentration; Cu concentrations also increased significantly with increasing clay content anddecreasing sand content. Pb concentrations showed a significant increase with increasing sediment pH, and were approximately three-fold higher in sediments adjacent to stormwater drain outfalls than in sediments remote from drains; no such effect was observed for Cu or Cd. No effect of distance downstream was observed. Sequential extraction of sediments showed that most of the metals were in relatively immobile forms, for example bound to Feoxides, or only extractable by aqua regia. The enhanced concentrations of Pb near stormwater outfalls suggest that vehicle-derived Pb may be an important contributor of Pb to the estuary.  相似文献   

9.
Abstract

Levels of cadmium (Cd) in New Zealand pastoral soils have increased due to Cd impurities in applied fertilisers. As there is little information on the interaction of Cd with soil mineral‐organic matter complexes, the sorption of Cd by complexes of kaolinite with humic acid has been investigated. Sorption was measured at pH and ionic strength values typically found for solutions of pastoral soils in New Zealand. Sorption increased with the content of humic acid in the complex, and as the pH of the medium was raised from 4.2 to 6.3. Sorption was also influenced by the ionic strength of the ambient solution, notably by the nature of the cation in the added electrolyte. The experimental data were interpreted in terms of the effect of solution pH and ionic composition on the charge characteristics of kaolinite and humic acid. These factors, in turn, influence clay particle association as well as the clay‐humic and metal‐humic interaction.  相似文献   

10.
The extent to which heavy metal ions (Cu, Pb, Zn, Cd) are removed from aqueous solution by humic acid suspensions has been found to vary with solution pH, concentration of competing cations, nature of the organic material, and the complexing power of any ligands present. The amount adsorbed in acid media increased with pH until the threshold value required for partial dissolution of the solid, and formation of soluble metal humates, was exceeded The adsorption maximum pH, and the apparent capacity at lower values, varied with the substrate used and cation being sorbed. The affinity order sequence, as derived from adsorption isotherm studies, was Pb > Cu > Cd > Zn ? Ca > Mg. The retention of metal ion by the solid was reduced in the presence of ligands, with zero uptake occurring when the soluble complexes formed had a greater effective stability than those resulting from humic acid-metal ion interactions. With environmental systems having a high organic content, the humic acid component can play a dominant role in determining the final distribution of metal ions, and for predictive purposes, investigation of the effect of pH on uptake is more informative than measurement of adsorption isotherm parameters, since the observed trends reflect differences in functional group properties, relative affinities and solubility effects. The curves have minima which fall within the pH spreads encountered in natural systems, and small pH changes can cause significant variations in solution levels.  相似文献   

11.
The leaching of heavy metals from plant growth medium, admixed with different amounts of compost (prepared from sewage sludge and yard waste) at pH 5, 6 and 7 was determined over a six-month period. Twelve-week old rhododendron cuttings were planted in 2-L containers and rainfall was supplemented with irrigation to supply two centimeters of water per day. Leachates collected over each two to four week period were analyzed for Cd, Cr, Cu, Ni, Pb and Zn using atomic spectrometry. The concentrations of Cd, Cu, Ni and Zn in the leachates increased with increasing proportions of compost in the medium and decreased with increasing time of leaching. Decreasing media pH dramatically increased the concentrations of Cd, Ni and Zn in the leachates, but had no effect on the Cu concentrations. For example, as the proportion of the compost in the pH 5 medium increased from 0 to 100 percent, the concentrations of metals (μg L?1) in the leachates collected during the first two weeks increased from 1 to 33 (Cd), 10 to 123 (Cu), 8 to 113 (Ni) and 300 to 24,000 (Zn). Corresponding increases at pH 7 were 0.4 to 0.8 (Cd), 14 to 141 (Cu), 8 to 28 (Ni) and 100 to 400 (Zn) μg L?1. The concentrations of Cr and Pb in the leachates remained below the detection limits regardless of media pH and amounts of compost.  相似文献   

12.
为了研究珠三角滩涂围垦农田土壤和农作物重金属污染状况,采集了广州南沙、中山一带围垦农田农作物及其根际土壤样品,测定重金属的质量分数。结果表明,围垦农田土壤样品中Cu、Ph、Cd、Ni、Cr和Zn含量均大于广东省相应土壤环境背景值,其中Cu（56．06mg·kg^-1）、Pb（48．30mg·kg^-1）、Cd（0．72mg·kg^-1）、Ni（41．15mg·kg^-1）、Cr（115．1mg·kg^-1）和Zn（200．1mg·kg^-1）分别为背景值的3．30、1．34、12．82、2．26、2．28和4．23倍。与《土壤环境质量标准》（GB15618-1995）中Ⅱ级标准（pH〈6．5）比较,土壤样品中Cu、Cd、Ni和Zn的超标率分别为73．7％、88．6％、59．6％和28．9％。以GB15618-1995中Ⅱ级标准为评价标准,采用Nemerow指数法进行评价,土壤重金属平均综合污染指数为1．86,属3级轻污染。与《食品中污染物限量》（GB2762-2005）等相关标准比较,农作物中Cu、Pb、Cd、Ni、Cr和Zn含量的样品超标率分别为0、28．9％、2．6％、48．3％、12．3％和6．1％。由此可见,珠三角滩涂围垦农田土壤和农作物重金属污染问题已经比较突出,土壤污染以Cd为主,而农作物污染则以Ni、Ph、Cr为主。  相似文献   

13.
石灰石和海泡石组配对水稻糙米重金属积累的影响   总被引：14，自引：0，他引：14  
周歆  周航  曾敏  胡淼  杨文弢  刘丽  廖柏寒 《土壤学报》2014,51(3):555-563
为了研究组配改良剂(石灰石+海泡石,LS)对于重金属Pb、Cd、Cu和Zn复合污染稻田的修复效果,在湘南某矿区附近稻田中进行了组配改良剂的田间试验。结果表明:施用0~1.8 kg m-2的组配改良剂LS使土壤pH和CEC显著增加,使土壤中Pb、Cd、Cu和Zn交换态含量显著降低。土壤Pb、Cd、Cu和Zn交换态含量的降低是pH升高,土壤胶体的CEC增加及土壤吸附能力增强的共同作用。施用组配改良剂LS显著降低了3个水稻品种(黄华占、丰优9号、Ⅱ优93)糙米中Pb、Cd和Cu的累积量,最大降幅分别为55.8%、66.9%、37.4%,而对糙米中Zn的含量没有明显影响。当LS施用量为1.8 kg m-2时,能使丰优9号糙米中Cd含量(0.195 mg kg-1)达到国家食品中污染物限量标准(0.20 mg kg-1)以下。土壤中交换态Pb、Cd和Cu含量的降低是糙米中重金属累积量减少的原因。土壤交换态Pb、Cd和Cu含量的对数值(lnC交换态)与其糙米中含量(lnC糙米)的对数值之间存在显著的线性相关关系。  相似文献   

14.
粉煤灰对污染土壤中铜镉的稳定化   总被引：2，自引：0，他引：2  
采用批衡量吸附和室内培养实验,考察了粉煤灰对Cu和Cd的吸附等温线及0.2%、0.5%、1%和2%用量的粉煤灰对土壤pH、有效态Cu和Cd、以及5种化学形态Cu和Cd分布的影响。结果表明:粉煤灰对Cu和Cd的吸附等温线均可以用Langmuir和Freundlich方程进行拟合,其对Cu的最大吸附量(9.90 mg/g)高于对Cd的最大吸附量(9.43 mg/g)。随着粉煤灰用量的增加,土壤pH显著增加,有效态Cu和Cd显著降低。同时,粉煤灰处理显著降低了离子交换态Cu和Cd含量,增加了铁锰氧化物结合态Cu和Cd含量,降低了Cu和Cd活性,使活性态Cu和Cd逐渐向潜在活性态和非活性态转化。其中培养60天后,2%处理的粉煤灰处理较对照pH提高了0.44个单位,离子交换态Cu和Cd分别降低了35.7%和35.9%。因此,粉煤灰能够有效吸附Cu和Cd,显著降低土壤有效态和离子交换态Cu和Cd的含量,在重金属稳定化修复应用中具有较好的应用前景。  相似文献   

15.
Depositions originating from a central Slovak Al smelter may increase metal solubility in adjacent soils because they contain F (mainly HF). The reason for fluoro‐mobilization of metals may be the formation of soluble fluoro‐metal complexes or the mobilization of organic matter and subsequent formation of organo‐metal complexes. The objectives of our work were (1) to assess the extent of metal mobilization by fluoride in a Slovak Lithic Eutrochrept affected by the emissions of an Al smelter and (2) to model the dissolved metal species with the help of a chemical equilibrium model (MINEQL+). The O (Moder), A, and B horizons were equilibrated with solutions at F concentrations of 0, 0.9, 2.7, and 9.0 mmol l—1. In the extracts, the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Zn, dissolved organic carbon (DOC), free and complexed F, and the pH and electrical conductivity (EC) were determined. The heavy metal concentrations in the O horizon (Cd: 0.99, Cr: 18.0, Cu: 44, Ni: 26, Pb: 110, and Zn: 84 mg kg—1) were 2.5 to 9 times larger than those in the A and B horizons. The concentrations of H2O‐soluble F decreased from the O (261 mg kg—1) to the A (103 mg kg—1) and B horizon (92 mg kg—1). In batch experiments increasing addition of F increased the equilibrium concentrations of Al, Cr, Cu, Fe, Ni, Pb, and DOC in all samples, of Cd in the A, and of K in the B horizon. At the same time the concentrations of complexed F and pH increased whereas EC decreased. Chemical equilibrium modelling indicated that the mobilizing effect of F resulted from the formation of fluoro‐Al complexes and organo‐complexes of all other metals.  相似文献   

16.
The adsorption of ionic Cd has been investigated on three humic acids isolated from podzol, rendzina and brown Mediterranean soils of Tuscany. The adsorption isotherms have been determined at 5 and 25°C. Cadmium adsorption was described by the Langmuir adsorption equation. Langmuir parameters were related to the functional groups content of humic acids and decreased in the following order: rendzina>brown Mediterranean soil>podzol. Adsorption was independent on temperature and increased with pH. Desorption experiments with 0.1 N NH4OAc and 0.25 M Cu (OAc)2 proved that Cd is adsorbed on humic acid about 50% in an exchangeable form and 50% in coordination complexes.  相似文献   

17.
The influence of different agricultural treatments on the contents of Cd, Zn, and Co in the organic matter and humic acids of soddy-podzolic and dark gray forest soils was studied in long-term field experiments. The use of gel chromatography proved the complicated molecular-weight composition of the humic acids in all the studied soils. The contents of heavy metals and their distribution by the molecular-weight fractions of humic acids were determined in the experimental soils and in the virgin podzolic soils. The complex nature of organomineral compounds of Cd and Zn with humic acids was shown by means of gel filtration. The thermodynamic stability of the organomineral complexes increased with the increasing weight of the initial molecular-weight fractions of humic acids.  相似文献   

18.
The β-thiol group containing amino acids L-cysteineand L-penicillamine were tested for their ability to releaseheavy metals (Cd, Cr, Cu, Hg, Ni, Pb, Zn) from bondings ontotypical soil components (peat, bentonite, illite) at neutral pHformed by batch adsorption procedure. Following equilibrationthe metal loaded sorbents were extracted by aqueous amino acidsolutions under various physico-chemical conditions.The extractability of metals from peat (metal contents between62.0 and 6170 mg kg-1) increased in thepresence of L-penicillamine following the order Cr < Hg < Pb <Ni ≈ Zn ≈ Cd, ranging from 9% (Cr) to 97% (Cd).The extractability by L-cysteine was slightly lower, followingthe sequence Cr < Pb < Cd < Ni < Zn. In both cases the sequencesdid not correlate with the order of the stability constants ofthe corresponding amino acid complexes. The recovery of metalsfrom bentonite was higher generally. The extent of removal increased with increasing molar excess of the amino acids and,to a lower extent, with increasing extraction volume.Presumably initiated by oxidation of amino acids or by theformation of sparingly soluble polymeric metal complexes, theconcentrations of dissolved metals dropped after an agitationperiod of 2 to 24 hr in most of the extracts. Aspects of thisprocess were discussed in detail.  相似文献   

19.
不同pH值混合螯合剂对土壤重金属淋洗及植物提取的影响   总被引：6，自引：1，他引：5  
为了得出混合螯合剂（MC）淋洗去除重金属的最佳pH值以及对后续植物提取重金属的影响,用Ca(OH)2将pH值为2.75的MC提高至pH值5、7和9,对重金属污染土壤进行了盆栽淋洗试验,而后种植东南景天（Sedum Alfredii）,测定淋出液及植物重金属含量。另外,通过浸提试验研究了含有不同阳离子的MC对重金属淋洗效果的影响。结果表明,pH值为5和7的MC显著提高了Cd、Pb和Cu的淋出率。与Na+、K+离子相比,Ca2+的存在能够提高MC对重金属的淋洗去除。pH值7和9的MC淋洗土壤后提高了东南景天的生物量,但是降低东南景天中Cd和Zn的浓度,导致其植物提取率低于无淋洗剂对照。在化学淋洗+植物提取联合技术中,Cd和Zn主要靠植物提取去除,植物提取率分别可达土壤Cd的30%～40%和土壤Zn的6.5%～6.9%;而Pb和Cu主要靠混合螯合剂淋洗去除,去除率分别为2.3%～2.6%和1.6%～2.0%。综合来说,如果需要同时去除Cd、Zn、Pb和Cu,降低土壤重金属有效态含量,用pH值9的MC淋洗土壤联合植物提取较为合适。  相似文献   

20.
Heavy metal pollution was assessed in soils collected from 0–15, 15–30 and 30–45-cm depths of three industrial (FMC, PMC and CMC), and two municipal (BSD and MLF) waste disposal sites around Chittagong city in 2008. Soils were analysed for pH, organic carbon, total nitrogen, available P, exchangeable Ca, Mg, K and Na, and total Cd, Pb, Cu, Mn and Zn. The pH, organic C, total N, available P, total Cd, Pb, Cu and Mn, and contamination indices for Cd and Pb varied significantly among sites. Mean Cd, Pb, Cu, Mn and Zn were in the range 0.5–1.9, 54–86, 25–50, 261–624 and 204–330 mg kg?1, respectively. Contamination indinces for Cd, Pb, Zn and Cu were estimated by comparison with respective threshold values. Contamination indices showed that the sites MLF and FMC had low Cu contamination. Other sites were not contaminated with thisheavy metal. All sites except PMC were highly contaminated with Cd, FMC was moderately contaminated and the others had low Pb contamination. FMC was highly contaminated, but the others were moderately contaminated with Zn. The integrated contamination index revealed that PMC had low contamination and the other sites were highly contaminated with heavy metals.  相似文献   

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