The degassing behavior of Au, Tl, As, Pb, Re, Cd and Bi from silicate liquids: Experiments and applications

We investigate the degassing of volatile heavy metals from natural basalt and dacite and synthetic rhyolite melts doped with Bi, Pb, Tl, Au, Re, Sb, Sn, Cd, Mo, As, Cu in Pt capsules over a range of temperatures (1200-1430 °C) exposed to air at 0.1 MPa. We also investigated the effects of ligands on degassing by adding known concentrations of Cl and S. During the experiments concentration gradients normal to the melt/gas interface arose for the trace metals Au, Tl, As, Cd, Re, Bi and Pb, as shown by measurements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the quenched glasses. In contrast, erratic concentration gradients occurred for Cu, Mo, Sn, Sb due to the development of compositional cords in the glass for those elements. The diffusivities for Au, Tl, As, Cd, Re, Bi and Pb (in decreasing order of volatility) followed an Arrhenius relationship with log D at 1260 °C varying from −12 to −17. The addition of Cl and S were shown to increase by two-to five-fold the volatilities of all metals, with S having a more profound effect. Diffusivities from the experiments were applied in a bubble growth model to examine the behavior of Tl and Pb in volcanic gases. The Tl/Pb ratio in gases shows much greater variation than can be explained by partitioning and magma composition alone, with diffusion serving to drastically enrich or deplete the Tl/Pb of gases to values significantly different from that of the melt.     

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.     

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.     

Effect of Microbial Siderophore DFOB on Pb, Zn, and Cd Sorption Onto Zeolite

Recent studies suggest that siderophores form stable complexes with divalent metals and affect their mobility. In this work, effects of trihydroxamate microbial siderophores and desferrioxamine-B (DFOB) on Pb(II), Zn(II), and Cd(II) sorption by two kinds of synthesized zeolites (13X and Na?CY) as a function of pH were investigated. Results showed that 13X zeolite has a higher sorption affinity for studied metals than Na?CY. DFOB strongly affected metal sorption on both zeolites. Under slightly acidic to neutral condition, DFOB increased the metal sorption on zeolites due to the sorption of positively charged heavy metal?CDFOB complexes. Whereas by increasing pH (>7), the mobilizing effect of DFOB was observed for Pb, Zn, and Cd. DFOB drastically decreased (80?%) Zn sorption in alkaline condition. As a result, siderophores can weaken the treatment efficiency of zeolites and increase the bioavailability of metals in soils. Surface complexation modeling revealed that the effects of DFOB on metal sorption by 13X and Na?CY zeolites can be explained by the differences in their surface charge. In general, the result shows the influence of DFOB on metal sorption by zeolites over the pH range 4?C9 and decreasing in the sequence Zn?>?Pb?>?Cd.     

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.     

Biogeochemistry of trace metals (Mn, Sr, Rb, Ba, Cu, Zn, Pb and Cd) in a river-wetland-lake system (Balaton Region, Hungary)

Mn, Sr, Ba, Rb, Cu, Zn, Pb and Cd concentrations have been measured seasonally in the water and deposited sediments of the system comprising: Zala river (main input) — Lakes Kis-Balaton 1 and 2 (small artificial lakes created in a former bay of Lake Balaton) — Keszthely bay (hypertrophic part of Lake Balaton). The concentrations of the trace elements together with pH, alkalinity, dissolved cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺), dissolved inorganic ligands (Cl^–, SO₄ ^2–), particulate Al, Ca, inorganic and organic carbon are used to assess the contamination of the study area and biogeochemical processes controlling trace element concentrations. Thermodynamic speciation calculations have also been utilized to enhance our understanding of the system. In the sediments Rb, Ba, Cu and Zn concentrations were mainly controlled by the abundance of the aluminosilicate fraction. Strontium was mainly associated with the calcium carbonate fraction. The aluminosilicate fraction constitutes a major sink for Mn and Cd but the concentration of these elements are also strongly related to calcite precipitation. The main processes that control the dissolved distribution of trace elements in the Balaton system were: solid phase formation (carbonate) for Mn; coprecipitation with calcite for Sr, Ba, Rb and possibly Mn and Cd; adsorption/desorption processes (pH dependent) for Zn and Pb; solubilization of Mn and precipitation of Cd and Cu in reed covered wetland areas where anoxic conditions were probably existing during the warm season. A preliminary budget of atmospheric and river input to Lake Balaton has also been outlined. Although Lake Balaton, is subjected to anthropogenic inputs mainly from agricultural and domestic activities, their impact on trace element concentrations in the Balaton system is very limited due to the efficiency of removal processes (i.e. adsorption and co-precipitation) and to high sedimentation rates and strong sediment re-suspension. Anthropogenic inputs are only detected for Pb.     

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.     

An Apatite II permeable reactive barrier to remediate groundwater containing Zn,Pb and Cd

Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca_10−xNa_x(PO₄)_6−x(CO₃)_x(OH)₂], where x < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO₄ and NO₃. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d’Alene River, Idaho. Microbially mediated SO₄ reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb₁₀(PO₄)₆(OH,Cl)₂] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L⁻¹), has reduced Zn to near background in this region (about 100 μg L⁻¹), and has reduced SO₄ by between 100 and 200 mg L⁻¹ and NO₃ to below detection (50 μg L⁻¹). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).     

An Apatite II permeable reactive barrier to remediate groundwater containing Zn,Pb and Cd

Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca_10−xNa_x(PO₄)_6−x(CO₃)_x(OH)₂], where x < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO₄ and NO₃. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d’Alene River, Idaho. Microbially mediated SO₄ reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb₁₀(PO₄)₆(OH,Cl)₂] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L⁻¹), has reduced Zn to near background in this region (about 100 μg L⁻¹), and has reduced SO₄ by between 100 and 200 mg L⁻¹ and NO₃ to below detection (50 μg L⁻¹). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).     

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.     

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.     

成都盆地平原区浅层土壤Cd、Pb、Zn分布特征及其成因初探

通过多目标地球化学调查在成都盆地平原区浅层土壤内发现呈面状分布的Cd、pb、Zn等元素高值区.为了研究它们的成因,应用多元统计方法分析了这些元素在不同景观区及不同环境介质中的分布特征及相关关系,利用参考元素对Cd、Pb、Zn的富集含量进行了定量估算.结果表明,平原区浅层土壤内Cd、Pb、Zn元素的分布明显不同于物源区及平原区深层土壤,在元素之间的典型相关关系及元素富集的分布特征上,均表现出明显的人为源特征.Cd、Pb、Zn元素的富集主要出现在平原区中部的城镇及农田区,与成都盆地浅层样地球化学图上的高值区一致.Cd、Pb、Zn元素的富集,是在自然背景的基础叠加了人为源含量,但尚未达到危害程度.     

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.     

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.     

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.     

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。     

Kinetics of DTPA extraction of Zn,Pb, and Cd from contaminated calcareous soils amended with sewage sludge

The aim of this study was to determine the influence of sewage sludge (SLU) amendment on the desorption characteristics of zinc (Zn), lead (Pb), and cadmium (Cd) in contaminated calcareous soils. Three levels of SLU (0, 1, and 3% w/w) were added to the two calcareous contaminated soils. Samples were incubated for 30 days and equilibrated with 0.005 M DTPA for 0.25 to 240 h. The addition of SLU significantly increased the amount of DTPA-extractable Zn in soils. While the amounts of Cd, Pb, dissolved organic carbon (DOC), and pH showed a significant increase only in 3% w/w of SLU, with the exception of Cd desorption in 1% w/w of SLU, kinetics of Zn, Pb, and Cd extraction increased together with an increase in the level of applied SLU. The best models for describing desorption data were explicitly power function and Elovich. The rate constants of Zn and Pb had significant correlations with DTPA-extractable Zn and Pb, DOC and pH, which affect Zn and Pb desorption. Also, the rate constants of Cd had significant correlations with CEC that can be deemed as equivalent to the fact that Cd desorption is controlled by surface adsorption, particularly in the lower sludge application amount. These results can be used for management of sewage sludge application in contaminated calcareous soils.     

Pb、Zn、Cd和Cr等元素的生物有效性研究——以胶州湾水生系统为例

本文首先利用同站位多介质同采的资料分析研究了各环境介质中的不同痕量金属对生物富集的贡献,提出孔隙水中Pb、Zn、Cd、Cr对生物体中同名组分富集的贡献较大;进而采用PHREEQC软件模拟了孔隙水中Pb、Zn、Cd、Cr四种元素的组分存在形态,结果表明:PbCO3、Zn2 、CdCl2、Cr(OH)3分别为孔隙水中Pb、Zn、Cd、Cr的优势态,但其生物有效形态依次为PbSO4、ZnOHCl、CdCl 、Cr(OH)2 。最后作者提出生物对其所处环境介质中痕量金属的富集并不取决于痕量金属的总量或其相应的优势态浓度的多寡,而是取决于痕量金属的生物有效态的浓度大小。     

XRF Determination of Zr, Nb, Y, Sr, Rb, Zn, Pb in Fifteen International Geochemical Reference Samples

Fifteen geochemical reference samples were analysed for Zr, Nb, Y, Sr, Rb, Pb and Zn, using a X-ray fluorescence spectrometric method. In general, the results are in good agreement with those proposed or recommended.