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.     

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.     

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。     

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.     

Competitive adsorption of Cd,Cu, Pb and Zn by different soils of Eastern China

Simultaneous competitive adsorption behavior of Cd, Cu, Pb and Zn onto nine soils with a wide physical–chemical characteristics from Eastern China was measured in batch experiments to assess the mobility and retention of these metals in soils. In the competitive adsorption system, adsorption isotherms for these metals on the soils exhibited significant differences in shape and in the amount adsorbed. As the applied concentration increased, Cu and Pb adsorption increased, while Cd and Zn adsorption decreased. Competition among heavy metals is very strong in acid soils with lower capacity to adsorb metal cations. Distribution coefficients (K _dmedium) for each metal and soil were calculated. The highest K _dmedium value was found for Pb and followed by Cu. However, low K _dmedium values were shown for Zn and Cd. On the basis of the K _dmedium values, the selectivity sequence of the metal adsorption is Pb > Cu > Zn > Cd and Pb > Cu > Cd > Zn. The adsorption sequence of nine soils was deduced from the joint distribution coefficients (K _dΣmedium). This indicated that acid soils with low pH value had lower adsorption capacity for heavy metals, resulting in much higher risk of heavy metal pollution. The sum of adsorbed heavy metals on the soils could well described using the Langmuir equation. The maximum adsorption capacity (Q _m) of soils ranged from 32.57 to 90.09 mmol kg⁻¹. Highly significant positive correlations were found between the K _dΣmedium and Q _m of the metals and pH value and cation exchange capacity (CEC) of soil, suggesting that soil pH and CEC were key factors controlling the solubility and mobility of the metals in soils.     

Contamination of the biological compartment in the Seine estuary by Cd, Cu, Pb, and Zn

A study of contamination of the biological compartment of the Seine estuary was carried out by measuring the concentrations of cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn) in 29 estuarine and marine species belonging to 6 phyla. Species came from three main biological zones of the estuary: the Seine channel (copepods, mysids, shrimps, and fish), the intertidal mudflats (Macoma balthica community), and the subtidal mudflats (Abra alba community). Two fish species, the bass (Dicentrarchus labrax) and the flounder (Platichthys flesus), were also selected for analyses. A comparison of metal concentrations in estuarine species of the Seine with those found in the same species collected on contaminated and non-contaminated sites showed a contamination of the estuary by Cu, Zn, and Pb. For Cd, the contamination is mainly observed in bivalves, although the concentrations observed were low and less than 2 μg g^?1 d.w. High concentrations of Cu were found in copepods, shrimps, and fish. Pb contamination was mainly found in species living in the Seine channel where the copepodEurytemora affinis shows an average concentration of 22 μg g^?1 d.w. High concentrations of Pb (>10 μg g^?1 d.w.) were found in deposit-feeders benthic invertebrates. Elevated levels of Zn were seen in all species collected in the Seine estuary, including fish and in particular small flounder. The concentrations of Cd, Cu, Pb, and Zn found in edible estuarine species (shrimp and fish) were in the same order of magnitude than those found in fish and shrimps fished along the French coast.     

The accumulation of Cu, Zn, Cd, and Pb in the aquatic biomass of sulphide tailing ponds

Flooding mine tailings to limit the oxidation of sulfides provides a habitat for aquatic organisms, such as plants, plankton, insects, and fish, which can uptake metals and, thus, threats for local ecosystems and influence the cycling of elements in biogeocenosis. An aquatic ecosystem developed naturally in sulphide tailing ponds containing cyanidation wastes of the Salair ore-refining plant (SORP), Russia, was studied. The objectives of this research were to: (i) reveal the level of contamination of living organisms in the tailing ponds compared to a natural control site and (ii) calculate the weight of metals in aquatic biomass to estimate the amount of metals transferring from the tailing ponds into the biogechemical cycle. The concentration of Cu, Zn, Cd, and Pb in the sediments of the tailing ponds is significantly higher than from the control site. Concentrations of Cu, Zn, Cd, and Pb in plant shoots were significantly higher than in the control and accumulated mainly in cell envelopes and membranes. The concentration of Pb in fish liver and eggs were 41 and 7.5 times higher, respectively, than maximum allowable concentrations. The biomass distribution between producers and consumers of the tailing pond ecosystem is similar to those of natural pond ecosystems. However, the weights of Cu, Zn, Cd, and Pb in all trophic levels per hectare of the tailing pond are orders of magnitude higher than those for Lake Baikal. The largest portion of metal circulates within the ecosystem of the Dyukov Ravine Pond with a maximum of 5 to 13% of this amount transferred into the surrounding environment through the food chains.     

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.     

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.     

Uptake of Zn,Cu, Pb,and Cd by water hyacinth in the initial stage of water system remediation

The removal efficiency of water hyacinth for Zn, Cu, Pb and Cd after their entry into an undisturbed fresh water body was studied using minicosms placed within a reservoir. Variable parameters were water pH (6 or 8), single or multi-metal additions, and the plant biomass. The initial concentrations of Zn, Cu, Pb and Cd in water (500, 250, 250 and 50 μg/L, respectively) quickly decreased in the order Pb ≈ Cu ? Cd ≈ Zn in the first days. Metal removal was more efficient at pH 8 than at pH 6, and it was only slightly higher for single metals compared to multi-metal additions. After 8 days the remaining amounts of metals relative to their initial concentrations for multi-metal pollution treatments were 8% and 24% (Cu), 11% and 26% (Pb), 24% and 50% (Cd), and 18% and 57% (Zn) at pH 8 and pH 6, respectively. Increasing plant biomass promoted faster metal removal. The bioconcentration factor (the ratio of the metal concentration in whole plants to the initial metal concentration in water) exceeds 2000 for all metals (with the exception of Zn and Cd at pH 6). It was concluded that the water hyacinth can be successfully used for fast removal of metals in the initial stage of water body remediation.     

巯基棉分离富集ICP-OES测定岩盐矿中的水溶性铜铅锌镉

盐岩矿的水溶法开采是获得人类生活必需品和重要工业原料——盐的重要途径之一。在水溶法开采中,岩盐矿中的水溶性重金属会随着母液到达地表环境和后续的岩盐产品中,可能对地表环境造成污染和危害人体健康,故对岩盐矿中水溶性重金属的检测非常重要。岩盐矿中的水溶性铜铅锌镉含量较低,而盐分含量过高,过高的盐分含量会影响ICP-OES的雾化效率,故很难用ICP-OES直接测量重金属含量。本文以巯基棉为吸附材料,从溶液pH、洗脱液浓度、洗脱液体积等方面研究了分离富集岩盐矿中水溶性铜铅锌镉的实验条件。结果表明,在pH=7的介质中,巯基棉对铜铅锌镉有良好的吸附性能,被吸附的铜铅锌镉可用7 m L盐酸(15%)定量洗脱,溶液中的钠对吸附无明显影响。对解吸后的溶液,铜铅锌镉的回收率均≥92.2%,钠回收率仅0.04%,基本实现了铜铅锌镉与钠的分离,达到了ICP-OES检测要求。     

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.     

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.     

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.     

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.     

Immobilization of Cd,Zn and Pb in sewage sludge using red mud

Sewage sludge is an inevitable end by-product of sewage treatment. Land application provides a cost-effective alternative for sewage sludge disposal. However, sewage sludge contains heavy metals that may limit its application. In this work, red mud was employed for the immobilization of heavy metals in sewage sludge. The effect of red mud amendment on heavy metal immobilization was evaluated using Toxicity Characteristic Leaching Procedure (TCLP) method. The TCLP results showed that the immobilization efficiency of Cd, Zn and Pb was 100, 92, and 82%, respectively, when sewage sludge was mixed with 10% red mud. Tests carried out in leaching columns demonstrated that heavy metal concentrations in the leachate of 10% red mud amended sludge were lower than those of the unamended sludge. Moreover, red mud decreased plant available heavy metal (Cd, Zn and Pb) content from 18.1, 17.2 and 14.6% to 6.9, 11.4 and 7.6%, respectively. Sequential chemical extraction experiments showed that after sludge was amended with 10% red mud, exchangeable fraction was reduced and iron and manganese oxides fraction was increased. Red mud amendment can effectively immobilize Cd, Zn and Pb in sewage sludge before land application.     

Terrestrial geochemistry of Cd,Bi, Tl,Pb, Zn and Rb

About 2000 common magmatic, metamorphic and sedimentary rocks and rockforming minerals contained in 465 individual samples have been analyzed for 6 trace metals and potassium with high precision, mainly by combined distillation and AAS methods. Estimates of average abundances in the continental crust are: 98 ppb Cd. 82 ppb Bi. 490 ppb Tl, 14.8 ppm Pb, 77 ppm Zn and 98 ppm Rb (K/Rb: 223). These averages are close to the mean concentrations of the 6 elements in sedimentary and in low to medium grade metamorphic rocks. In relation to the upper mantle the earth's crust has very effectively accumulated Rb, Pb, Tl (and Bi). Cd and Zn are equally distributed between the upper and lower crust. Bi, Tl, Rb, Pb and K are accumulated in the upper relative to the lower continental crust by factors between 3.5 and 1.4. This is mainly due to higher concentrations in granites and lower abundances in granulites relative to gneisses and schists. The five metals form large ions with bulk coefficients less than one for the partition between metamorphic rocks and anatectic granitic melts. The major hosts of Rb, Tl, Pb and Bi in rocks are minerals with 8- to 12-coordinated sites such as mica, K-feldspar, plagioclase etc. (except for some preference of Bi for sphene and apatite). As examples of significant correlations those of Pb with Tl, K, Bi and Rb in mafic rocks and of Bi with K, Rb, Tl and Pb in sedimentary rocks can be reported. In granites and gneisses hydroxyl containing Fe²⁺-Mg-silicates are major host minerals for Zn and Cd. Except in some carbonate rocks Cd has no preference for Ca minerals.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案（1999/30/EC）,对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10 μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提出了具体测定要求。     

Preparation and solubility of northupite from brine and its adsorption properties for Cu(II) and Cd(II) in seawater

The mineral northupite Na₃Mg(CO₃)₂Cl was synthesized from a solar Adriatic seawater brine pond to which Na₂CO₃ was added at 373°K. The precipitated northupite had a surface area (P) of 6.0 ± 0.4 m²g⁻¹, and the thermodynamic solubility product was estimated to be log K Na₃Mg(CO₃)₂Cl = −4.8 ± 0.3 at 25°C. This value was used to calculate the interfacial energy (σ = 50 erg cm⁻²) for the homogeneous nucleation of northupite. The solubility constant determined in this study has been used to examine the saturation state of Mahega Lake and Lake Katwe (Uganda). The waters from Lake Katwe were found to be supersaturated with respect to northupite.The adsorption of Cu and Cd onto northupite particles was studied in seawater. Both metals are strongly adsorbed. Adsorption constants and the specific area of northupite occupied by Cd and Cu using Langmuir adsorption isotherms and equilibrium constants for surface complex formation have been determined.