Competitive adsorption,release and speciation of heavy metals in the Yellow River sediments,China

The competitive adsorption and the release of selected heavy metals and their speciation distribution before and after adsorption in the Yellow River sediments are discussed. The adsorption of metals onto sediments increases with increasing pH value and decreases with increasing ionic strength. The competitive coefficient K _c and the distribution coefficient K _d are obtained to analyze the competitive abilities of selected heavy metals, which are ranked as Pb > Cu >> Zn > Cd. The competition among selected heavy metals becomes more impetuous with increasing ion concentration in water. Speciation analysis was done by an improved analytical procedure involving five steps of sequential extraction. Cu, Pb and Zn were mainly transformed into the carbonate-bound form (50.8–87.7%) in adsorption. Most of (60.7–77.3%) Cd was transformed into the exchangeable form, and the percentage of carbonate-bound Cd was 19.7–30.4%. The release reaction was so quick that the release capacity of selected heavy metals from sediments to aqueous solution reached half of the maximum value only in 30 s. As opposed to adsorption, the release capacities of selected heavy metals were ranked as Cd > Zn >> Cu > Pb. In this study, Cd produces the most severe environmental hazards, because its concentration in the release solution is 85.8 times more than the human health criteria of US EPA.     

Potential hyperaccumulation of Pb, Zn, Cu and Cd in endurant plants distributed in an old smeltery, northeast China

The absorption and accumulation of Pb, Zn, Cu and Cd in some endurant weed plant species that survived in an old smeltery in Liaoning, China, were systematically investigated. Potential hyperaccumulative characteristics of these species were also discussed. The results showed that metal accumulation in plants differed with species, tissues and metals. Endurant weed plants growing in this contaminated site exhibited high metal adaptability. Both the metal exclusion and detoxification tolerance strategies were involved in the species studied. Seven species for Pb and four species for Cd were satisfied for the concentration time level standard for hyperaccumulator. Considering translocation factor (TF) values, one species for Pb, seven species for Zn, two species for Cu and five species for Cd possessed the characteristic of hyperaccumulator. Particularly, Abutilon theophrasti Medic, exhibited strong accumulative ability to four heavy metals. Although enrichment coefficients of all samples were lesser than 1 and the absolute concentrations didn’t reach the standard, species mentioned above were primarily believed to be potential hyperaccumulators.     

Interactions between Cd,Cu, Pb,and Zn and four different mine soils

The chemical associations of Cd, Cu, Pb, and Zn in four mine soil samples from the Amizour-Bejaia Pb/Zn mine (Algeria) have been investigated by a five-step sequential extraction procedure. Although Cd preferentially binds to carbonates, Cu, Pb, and Zn are mainly associated with the organic and reducible fractions. Batch adsorption experiments with either mono- or multi-metallic solutions are described with the Freundlich isotherm model. Whatever the nature of the soil sample, the sorption behavior for each given metal except Pb is very similar, indicating that the binding sites at the soil surface are progressively occupied by the metal from the solution. On each soil sample, the decreasing order of sorption can be established as Pb >> Cu > Cd > Zn. When the four metals are simultaneously applied to each soil sample, their specific behavior is strongly affected by their interactions and/or competition for the available surface sites: we generally observed isotherm curves with a slight maximum before the plateau at higher solution concentration. Although Cu is only slightly affected by the other metals, in the case of Pb, Cd, and Zn, the sorbed amounts strongly decreased.     

Distribution of Cd,Pb, Zn and Cu and their chemical speciations in soils from a peri-smelter area in northeast China

An exploratory study on soil contamination of heavy metals was carried out surrounding Huludao zinc smelter in Liaoning province, China. The distribution of total heavy metals and their chemical speciations were investigated. The correlations between heavy metal speciations and soil pH values in corresponding sites were also analyzed. In general, Cd, Zn, Pb, Cu and As presented a significant contamination in the area near the smelter, comparied with Environmental Quality Standards for Soils in China. The geoaccumulation index showed the degree of contamination: Cd > Zn > Pb > Cu > As. There was no obvious pollution of Cr and Ni in the studied area. The speciation analysis showed that the dominant fraction of Cd and Zn was the acid soluble fraction, and the second was the residual fraction. Pb was mostly associated with the residual fraction, which constituted more than 50% of total concentration in all samples. Cu in residual fraction accounted for a high percentage (40–80%) of total concentration, and the proportion of Cu in the oxidizable fraction is higher than that of other metals. The distribution pattern of Pb and Zn was obviously affected by soil pH. It seemed that Pb and Zn content in acid solution fraction increased with increasing soil pH values, while Cd content in acid soluble fraction accounted for more proportion in neutral and alkaline groups than acidic one. The fraction distribution patterns of Cu in three pH groups were very similar and independent of soil pH values. And the residual fraction of Cu took a predominant part (50%) of the total content.     

水稻土中重金属元素Cd、Pb的竞争吸附——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

水稻土中重金属元素Cd、Pb的竞争吸附 ——以长株潭地区水稻土为例

对中国南方的3个水稻土样品进行了Cd、Pb单一离子和混合离子吸附特点的研究。结果表明,3个水稻土样品中Cd、Pb的吸附特点都相似,Langmuir等温方程可很好地描述Cd、Pb的吸附等温线。3个土壤样品中,有较高pH值和较低有机物、CEC浓度、粘土含量、高岭石含量的2个土壤样品对Cd、Pb有较大的吸附量,且其等温吸附拟合的最大吸附量(B)也较大。在两组分混合溶液中,尽管共存离子的存在影响了土壤对单一离子的吸附,同时土壤对Cd的吸附在一定程度上受影响的程度大,但3个土壤样品都表现出对Pb有强的吸附能力。在3个土壤样品中,Langmuir等温方程中Pb的健合能常数(K)都大于Cd的健合能常数(K),混合溶液中的K值高于单一溶液的K值,表明2种金属离子对吸附位点的竞争提高了特定吸附位点的保持力,使金属离子在土壤中特定位点的吸附更加坚固。     

北京城区土壤中Hg、Pb、Cd、Cu及Zn化学形态及环境效应

为弄清北京城区土壤中Hg、Pb、Cd、Cu及Zn五种重金属元素的化学形态分布特征,系统采集了126件城区表层土壤样品,采用连续提取法对重金属元素各化学形态含量进行了测定。结果表明:土壤中土壤中Hg、Pb、Cd、Cu、Zn含量差异显著。Hg元素以残渣态和强有机结合态为主,Cd元素离子交换态、碳酸盐结合态、残渣态、铁锰氧化物结合态含量较高,Pb、Cu、Zn元素以残渣态、铁锰氧化物结合态为主。Hg元素的有效态含量最低(不足1%),现情况下不会对环境造成污染;Cd元素的有效态含量最高(40%),生物有效性和潜在生态危害性较大,运用植物修复技术对其治理为经济有效的方法;Pb、Cu、Zn有效态含量较低(约10%),生物有效性和潜在生态危害性均有限。各元素形态与全量之间相关程度虽有差别,但基本呈正相关关系。     

Test of experimental set-ups for electrodialytic removal of Cu, Zn, Pb and Cd from different contaminated harbour sediments

Electrodialytic removal of heavy metals from different harbour sediments was investigated. Electrodialytic remediation experiments in laboratory scale were made with calcareous and non-calcareous harbour sediments. Two different experimental set-ups were used for the study, one with stirring of the sediment slurry, the other without stirring. The removal of heavy metals was highest in the non-calcareous sediment, where 94% Cd, 91% Zn and 73% Cu were removed after 24 days. The highest removal obtained for the calcareous sediment was 81% Cd, 76% Zn, 75% Pb and 53% Cu after 21 days, with stirred sediment slurry. Electrodialytic experiments without stirring of calcareous sediment gave high removals (84% Zn, 58% Pb and 48% Cu), but there were problems with precipitations in the sediment, which limited the removal. The stirred experiments gave the highest removals of heavy metals and the voltage was the most stable in these experiments, and thus, the stirred set-up is the best choice for experimental set-up. The order in which the heavy metals were removed from the harbour sediments was Cd>Zn>Pb>Cu.     

The adsorption of Cu,Pb, Zn,and Cd on goethite from major ion seawater

The adsorption of Cu, Pb, Zn, and Cd on goethite (αFeOOH) from NaNO₃ solutions and from major ion seawater was compared to assess the effect of the major ions of seawater (Na, Mg, Ca, K, Cl, and SO₄) on the adsorption behavior of the metals. Magnesium and sulphate are the principal seawater ions which enhance or inhibit adsorption relative to the inert system. Their effect, as determined from the site-binding model of Davis et al. (1978), was a combination of changing the electrostatic conditions at the interface and decreasing the available binding sites.The basic differences between the experimental system of major ion seawater and natural seawater were examined. It was concluded that: 1) although the experimental metal concentrations in major ion seawater were higher than those found in natural seawater, estimates of the binding energy of Cu, Zn, and Cd with αFeOOH for natural seawater concentrations could be made from the data, 2) Cu, Pb, Zn, and Cd showed little or no competition for surface sites on goethite, and 3) the presence of carbonate, phosphate, and silicate had little or no effect on the adsorption of Zn and Cd on goethite.     

Influence of operating conditions on the removal of Cu, Zn, Cd and Pb ions from wastewater by adsorption

Nile Rose Plant was used to study adsorption of several cations (Cu²+, Zn²+, Cd²+ and Pb²+) from wastewater within various experimental conditions. The dried leaves of Nile Rose Plant were used at different adsorbent/ metal ion ratios. The influence of pH, contact time, metal concentration, and adsorbent loading weight on the removal process was investigated. Batch adsorption studies were carried out at room temperature. The adsorption efficiencies were found to be pH dependent, increasing by increasing the pH in the range from 2.5 to 8.5 exept for Pb. The equilibrium time was attained within 60 to 90 min. and the maximum removal percentage was achieved at an adsorbent loading weight of 1.5 g/50 mL mixed ions solution. Isothermal studies showed that the data were best fitted to the Temkin isotherm model. The removal order was found to be Pb²⁺> Zn²⁺> Cu²⁺> Cd²⁺. The surface IR-characterization of Nile rose plant showed the presence of many functional groups capable of binding to the metal cations.     

Environmental contamination of Zn,Cd, Ni,Cu, and Pb from industrial areas in Hamadan Province,western Iran

Eleven surface soil samples from calcareous soils of industrial areas in Hamadan Province, western Iran were analyzed for total concentrations of Zn, Cd, Ni, Cu and Pb and were sequentially extracted into six fractions to determine the bioavailability of various heavy metal forms. Total Zn, Cd, Ni, Cu and Pb concentrations of the contaminated soils were 658 (57–5,803), 125.8 (1.18–1,361), 45.6 (30.7–64.4), 29.7 (11.7–83.5) and 2,419 (66–24,850) mg kg⁻¹, respectively. The soils were polluted with Zn, Pb, and Cu to some extent and heavily polluted with Cd. Nickel values were not above regulatory limits. Copper existed in soil mainly in residual (RES) and organic (OM) fractions (about 42 and 33%, respectively), whereas Zn occurred essentially as RES fraction (about 69%). The considerable presence of Cd (30.8%) and Pb (39%) in the CARB fraction suggests these elements have high potential biavailability and leachability in soils from contaminated soils. The mobile and bioavailable (EXCH and CARB) fractions of Zn, Cd, Ni, Cu, and Pb in contaminated soils averaged (7.3, 40.4, 16, 12.9 and 40.8%), respectively, which suggests that the mobility and bioavailability of the five metals probably decline in the following order: Cd = Pb > Ni > Cu > Zn.     

Comparison of extractability of Cd, Cu, Pb and Zn with sequential extraction in contaminated and non-contaminated soils

Various extraction procedures were employed for measuring extractable concentrations of potential toxic elements in soil. The extractability of Cd, Cu, Pb and Zn in four contaminated and four non-contaminated soils of Japan, was compared by single extraction (CaCl₂, DTPA, NH₄Cl, 0.1 M HCl and 1 M HCl ) and sequential extraction procedures [(six operationally defined chemical phases, viz. water soluble (Fl), exchangeable (F2), carbonate (F3), oxide (F4), organic (F5) and residual (F6) fractions)]. Extractability of metals from soils samples varied depending on metals and/or extradants used. Among the extradants, 1 M HCl extracted the largest proportion of Cd (79 to 96% of total), Cu (61 to 83%), Pb (51 to 99%) and Zn (23 to 52%) from soils followed by 0.1 M HCl, NH₄Cl, DTPA and CaCl₂. In all the extradants, the proportion of extractability of metals was higher in the contaminated soils than the non-contaminated soils. Regardless of soils and extradants, relative extractability was higher for Cd as compared to other three metals. The use of 1 M HCl may be recommended for first-level screening of soil contamination with heavy metals. The other four weak extradants are believed to provide a better assessment of bioavailable/mobile metals content in soils than 1 M HCl extradant. However, 0.1 M HCl mobilized all four metals irrespective of soil types, therefore, might be the best choice if only one extradant is to be used. The sequential extraction procedures showed 22 to 64% of total Cd was in the mobile fraction (sum of Fl to F3), while the corresponding values for Cu, Pb and Zn in this fractions were 2 to 23% suggesting higher mobility of Cd than other three metals. The single extraction procedures are simple and easy to perform and obtained results are comparable with sequential extraction procedure.     

The effect of grain size on the Cu, Pb, Ni, Cd speciation and distribution in sediments: a case study of Dongping Lake, China

This paper examines the surface sediments collected from Dongping Lake in China for speciation and distribution of toxic heavy metals (Cu, Pb, Ni, Cd) in different grain size fractions, and for the factors that need to be considered in potential hazard of metals to the environment. Four grain size fractions (<63, 63–78, 78–163 and 163–280 μm), divided in wet condition, and bulk samples less than 280 μm in diameter were analyzed for their distribution, density and appearance. A three-stage extraction procedure following the BCR protocol was used to chemically fractionate metals into “acid soluble”, “reducible”, “oxidizable” and “residual” fractions. Correlation analysis was used to analyze the datasets. The results showed that <63 μm grain size part constitutes the major proportion of the sediments, but its density is the smallest among the four grain size fractions. In general, the metal content curve against grain size presents “S” distribution, and the highest concentrations do not exist in <63 μm grain size. Appearance observation indicates that the adsorbed substance increases gradually along with the decreasing grain size. The dominant speciation of elements and the extent of pollution are responsible for the metal distribution in different grain size sediments. While studying bioavailability and mobilization of metals, it is advisable to take metal speciation, grain size distribution and density into consideration.     

影响向海湿地草根层土壤吸附铅、镉能力的因素

利用向海湿地采集的草根层土壤进行吸附铅、镉的热力学实验,结果表明草根层土壤吸附铅、镉的过程符合Langmuir和Freundlich等温吸附曲线(n=8,p=0.01).吸附铅、镉存在干扰吸附现象,吸附铅的能力约是吸附镉的能力的3倍.而且草根层土壤吸附铅、镉的最大吸附量与土壤中的有机质和铁、锰氧化物含量存在着正相关性.土壤的理化性质是影响土壤吸附铅、镉能力的内在主要因素;pH等是影响草根层土壤吸附铅、镉能力的外部主要因素.     

Heavy metal concentrations (Cd,Cu and Pb) in five aquatic plant species in Tasik Chini,Malaysia

The purpose of this study was to determine the levels of heavy metals namely cadmium (Cd), copper (Cu) and lead (Pb) in the five aquatic plants. For this purpose, the concentration of heavy metals were measured in water and in the five aquatic plant species, Lepironia articulata, Pandanus helicopus, Scirpus grossus, Cabomba furcata and Nelumbo nucifera, in 15 sites from Tasik Chini. The concentrations were different among the plant species as well as among the parts of plants. The highest concentration of heavy metals among the aquatic plants and plant parts was found in the roots of S. grossus. The concentrations of Cd in the leaves and stems of submerged aquatic plant, C. furcata, were higher than concentration of Cd in the leaves and stems of emergent aquatic plant and floating leaf plant. The concentration of Cu in the stem of C. furcata was greater than that in the leaf, while the concentration of Cd was more in the leaf than in the stem. The heavy metal contents of the aquatic plants were in descending order of Pb > Cu > Cd. The metal concentration quotient of leaves/roots and stems/roots (ML/MR and MS/MR) were calculated. The highest internal translocation was found in P. helicopus, while the lowest internal translocation was found in S. grossus.     

Exploring Cd,Cu, Pb,and Zn dynamic speciation in mining and smelting-contaminated soils with stable isotopic exchange kinetics

The exchange kinetics of Cd, Cu, Pb, and Zn in seven mining and smelting-contaminated soils and the other two anthropogenically contaminated soils was investigated by using multi-elementary stable isotopic exchange kinetic (SIEK) method, and the experimental results were successfully interpreted by modelling using a sum of pseudo first order kinetics equations. SIEK results show that in the studied soils the isotopic exchange of Cd is a relatively fast process, and the exchange almost reaches an apparent plateau after 3-d equilibration; whereas for Cu, Pb, and Zn, the exchange is more sluggish, suggesting that it is important to understand the time-dependent metal mobility for risk assessment and management of contaminated soils. In most of the soils, the total isotopically exchangeable pool is divided, for all the metals, into two distinct pools: a fast exchangeable pool (E₁) with a kinetic rate constant k₁ having values around 1 min⁻¹ and a much slower exchangeable pool (E₂) with k₂ ranging from 0.0001 min⁻¹ to 0.001 min⁻¹. The distribution of the two exchangeable pools varies significantly among metals. The amount of isotopically exchangeable Cd related to the fast pool is dominant, accounting for on average 60% of total isotopically exchangeable pool in the soils; whereas this pool is smaller for Cu, Zn, and Pb. The sequence of average k₁ values is Cd > Pb ≈ Zn > Cu, consistent with the reported sequence of stability constants of metal-humic substances (HS) complexes while the average k₂ values follow the order: Cd > Pb > Cu > Zn, probably controlled by the slow desorption of metal ions associated with soil organic matter (SOM) fraction. Our results imply that further study on the exchange kinetics of metals on each individual sorption surface in soils, especially SOM, is critical to help understanding the overall exchange kinetics of heavy metals in whole soils.     

无高氯酸常压酸溶-ICP-MS法同时测定土壤中的As、Cd、Pb、Cr、Zn、Cu、Ni

采用无高氯酸常压酸溶分解土壤样品,利用等离子体质谱法可以1次溶矿测定As、Cd、Pb、Cr、Zn、Cu、Ni 7个重金属元素,具有较高的分析效率、较好的分析质量、较低的分析成本。实验表明,试样溶液中氯的含量对分析元素信号有较大影响。采用硝酸-氢氟酸-硫酸-过氧化氢分解样品以避免引入氯离子,从而能有效避免Cr、As元素在样品分解过程中的损失和氯离子产生的质谱干扰。Cd的测定需采用干扰校正公式扣除Sn的干扰。对于As元素,若试样溶液中不含或仅含微量的氯离子,采用标准模式测定即可得到理想的分析结果,否则必须采用CCT模式进行测定。除As以外的其他元素不论在标准模式或CCT模式下均能得到理想的分析结果。     

海南土壤中Zn、Pb、Cu、Cd四种重金属含量及其生物有效性的研究

对海南0个土壤样品中的nl、Pb、Cu、0四种重金属的总量和生物有效态含量以及45个植物样(根、茎、叶)中的重金属含量分别进行了测定，采样点基本上覆盖了海南全省，测定结果表明，土壤中nl总量低于全国平均值，而Pb、Cu、Cd高于全国平均值，土壤中重金属生物有效态含量一般低于其总量的10％，其中Pb最高为7．71％，而Cu仅为1．13％，具有较大的变异性；植物中重金属含量与土壤中重金属总量呈现负相关性，但与土壤中有效态重金属含量一般呈现正相关性，叶中的重金属含量与土壤中有效态重金属含量之间的相关性更为显着，叶中的重金属含量与土壤中有效态重金属含量之间的相关系数分别为：Zn(0．726)，Cu(0．626)，Pb(0．n4)，Cd(0．512)。这说明土壤中重金属总量并不能全面的评价土壤的环境效应和重金属的生物有效性，应该把重金属总量和生物有效态含量结合起来加以研究，并应将土壤中重金属的含量与植物中该元素含量之间作相关分析，根据其相关系数的大小来判断其生物有效性的程度。     

微波消解—电感耦合等离子体质谱法同时测定样品中Cr、As、Se、Cd、Cu、Zn、Pb元素

建立微波消解、恒温赶酸、ICP-MS法在碰撞池（CCT）模式下同时测定生物样品中Cr、As、Se、Cd、Cu、Zn、Pb金属元素的分析方法。通过对国家一级标准物质及实际样品进行方法验证,准确度、精密度均小于10%,加标回收率90%～110%。测试结果准确可靠,能满足生物样品的分析需要。