Toxic effect of Pb, Cd, Ni and Zn on Azolla filiculoides in the International Anzali Wetland

The limitation of plant growth in the polluted mediums can be used as a factor to determine of plant tolerance and the toxic effect of these mediums. In this work, the effect of Pb²⁺, Cd²⁺, Ni²⁺and Znsu2+ (individually) on Azolla filiculoides growth in the aqueous solution and using this method to water post treatment were studied. During 15 days the biomass the fresh Azolla with initial mass of 20 g was grown on the nutrient solution containing these metal ions, each in a concentration 4 mg/l. The presence of these ions, caused about 25%, 42%, 31% and 17% inhibition of biomass growth, respectively, in comparison to Azolla control weight which had not heavy metals. The water salinity of 1, 2 and 4 g. NaCl/l decreased the removal of these heavy metals about 4–7%, 20–24% and 40–55%, respectively. The addition of total dissolved solids (TDS) from 50 to 300 ppm. (as CaCO₃) into the samples of containing heavy metals increased Azolla growth, but decreased the control Azolla growth.     

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.     

Bioaccumulation of Cu, Zn and Ni from the wastewater by treated Nasturtium officinale

Aquatic plants are well known in accumulating and in concentrating heavy metals. In this study, several physiological responses of aquatic vascular plant, Nasturtium officinale (watercress), which were elevated concentrations of copper, zinc and nickel have been investigated. It was found that Nasturtium officinale were able to accumulate both copper and zinc at upper levels, but was able to accumulate to nickel at low levels. The final goal of this work was to examine the copper, zinc and nickel uptake using this aquatic plant from their solutions.     

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.     

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.     

Biosorption characteristics of heavy metals (Ni2+, Zn2+, Cd2+, Pb2+) from aqueous solution by Hizikia fusiformis

Heavy metal ions (Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺) were biosorbed by brown seaweed (Hizikia fusiformis), which was collected from Jeju Island of South Korea. The metal adsorption capacity of H. fusiformis improved significantly by washing with water or by base or acid treatments. The maximum sorption by NaOH-pretreated biomass was observed near a slightly acidic pH (pH 4?6) for Pb²⁺, Cd²⁺, Ni²⁺, and Zn²⁺. This result suggests that the treatment of H. fusiformis biomass with NaOH helped increase the functional forms of carboxylate ester units. Kinetic data showed that the biosorption occurred rapidly during the first 60 min, and most of the heavy metals were bound to the seaweed within 180 min. The maximum metal adsorption capacities assumed by a Langmuir model were on the order of Pb²⁺ > Cd²⁺ > Ni²⁺ > Zn²⁺. Equilibrium adsorption data for the heavy metal ions could fit well in the Langmuir model with regression coefficients R ² > 0.97.     

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.     

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.     

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。     

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.     

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.     

Application of artificial neural networks for estimating Cd,Zn, Pb removal efficiency from wastewater using complexation-microfiltration process

Complexation-microfiltration process for removal of heavy metal ions such as lead, cadmium and zinc from water had been investigated. Two soluble derivates of cellulose was selected as complexing agents. The dependence of the removal efficiency from the operating parameters (pH value, pressure, concentration of metal ion, concentration of complexing agent and type of counter ion) was established. Two approaches of preparation of input data and two different artificial neural network architectures, general regression neural network and back-propagation neural network have been used for modeling of experimental data. The extrapolation ability of selected architectures, i.e., the prediction of rejection coefficient with inputs beyond the calibration range of original model, was also determined. The predictions were successful, and after evaluation of performances, the models that were developed gave relatively good results of mean absolute percentage error from 4 to 14% and R-squared from 0.717 to 0.852 for general regression neural network and from 0.897 to 0.955 for back-propagation neural network.     

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 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.     

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.     

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.     

Chemical speciation of Cd,Cu, Pb,and Zn in mixed freshwater,seawater, and brine solutions

A theoretical model was developed to study the chemical speciation of the trace elements Zn, Cd, Cu and Pb aqueous solutions and their responses to variations in ionic strength and complexation. Two mixing solutions were investigated, a freshwater-seawater system and a freshwater-brine system. The brine was a calcium, sodium-chloride solution with a molal ionic strength of two. Trace element associations with the ligands OH^?, Cl^?, CO^2?₃, SO^2?₄, and HCO^?₃ were considered at pHs from 3.5 to 11.0 at 25°C. In general, the relative importance of the various ligand-trace element complexes can be predicted from a comparison of their stability constants. However, the effect of pH on the importance of a given complex is not readily apparent from the stability constants. Freshwater-seawater mixtures, as might be found in a totally mixed estuary, show that seawater composition is the dominant control on chemical complexing. Chloride complexing is similar for lead and zinc in the freshwater-brine mixtures. This similarity may account in part for the association of lead and zinc in strata-bound ore deposits.     

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.     

The transfer and fate of Cd, Cu, Pb and Zn from two historic metalliferous mine sites in the U.K.

Monitoring of heavy metal transfers, aerial deposition and fluvial transport to soil, stream sediment and vegetation compartments surrounding two former PbZn mines are reported. Results show that 80–100 a after the closure of the mines relatively large amounts of Cd, Pb, Zn and, in once case, Cu are entering the soil and fluvial systems.Aerial deposition of heavy metals within a 300 m radius of the centre of the tailings heaps is shown to be contributing up to 3.3 kg Cd, 71 kg Cu, 373 kg Pb and 1041 kg Zn annually to the surrounding soil and vegetation compartments. It is shown that more than 4.2 kg Cd/a and 1387 kg Zn/a are being transferred from the tailings heaps via the streams in the form of dissolved load. However, the greatest quantities of Cu (38 kg/a) and Pb (74 kg/a) are transported from the heaps as wash load. Transfers calculated as percentages of the total metal quantities in the tailings heaps highlight the greater relative mobility within the fluvial system of Cd and Zn compared to Cu and Pb. Outside of the tailings heaps, the greatest accumulation of metals is in the surrounding soil, while the smallest was observed to occur in the surrounding mixed grassland vegetation.The most important implications of these findings are in the long-term release and partitioning of pollutant metal species from historic metalliferous mine tailings within the terrestrial and fluvial environments. This information is of major ecotoxicological and agronomic importance and is necessary for the effective reclamation and remediation of such contaminated sites.