Application of sorbents in different soil types from small arms shooting ranges for immobilization of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb)

Journal of Soils and Sediments - Soil contamination of ammunition residues at shooting ranges for small arms may be followed by leaching of lead (Pb), copper (Cu), zinc (Zn), and antimony (Sb)....     

Phytostabilisation of a copper contaminated topsoil aided by basic slags: assessment of Cu mobility and phytoavailability

Purpose

Basic slags are alkaline by-products of the steel industry with potential properties to ameliorate nutrient supply and metal stabilisation in contaminated soils. This study aimed at investigating the potential of a P-spiked Link Donawitz slag and a conventional basic slag called Carmeuse for the aided phytostabilisation of a Cu-contaminated soil at a wood treatment site. The effects of basic slag addition on Cu fractionation, mobility and (phyto) availability were assessed.

Materials and methods

Both slags were incorporated at 1 % w/w into the Cu-contaminated soil phytostabilised with Cu-tolerant plants, using either outdoor lysimeters or a field plot. Untreated soil (UNT), amended soils with the P-spiked Link Donawitz slag (PLDS) and the conventional slag (CARM) respectively, and a control soil (CTRL) were sampled, potted and cultivated with dwarf bean. Physico-chemical analysis, determination of total soil elements and a Cu-sequential extraction scheme were carried out for all soils. Physico-chemical characteristics of soil pore water and Cu speciation (rhizon, ion selective electrode and diffusive gradient in thin film (DGT)) were determined. Shoot dry weight yield and leaf ionome (i.e. all inorganic ions present in the primary leaves) of dwarf beans were investigated.

Results and discussion

The slag incorporation at only 1 % w/w increased the soil pH from 1.5 to 2 U and electrical conductivity in soil pore water by three times. The residual Cu fraction increased for both slag amended soils compared to the UNT soil by six times in parallel to the decrease of the Cu oxidisable fraction (1.5 times) and to a less extent the reducible fraction. The incorporation of both slags did not reduce the total dissolved Cu concentration in the soil pore water but significantly reduced the real dissolved Cu concentration ca five times, the Cu labile pool as measured by DGT (at least two times) and the Cu phytoavailability. The dwarf bean total biomass was also improved with the slag addition especially for the P-spiked Linz–Donawitz slag.

Conclusions

The addition of both slags in the contaminated soil increased Cu concentration in the residual fraction and thus reduced its potential mobility. Though the total dissolved Cu soil pore water concentration remained identical, its speciation changed as the real dissolved fraction diminished and lowered the Cu bioavailability. The addition of small amount of P-spiked Linz–Donawitz and Carmeuse slags was beneficial for this Cu-contaminated soil in the context of aided phytostabilisation.

     

Forms of Cu (II), Zn (II), and Pb (II) compounds in technogenically transformed soils adjacent to the Karabashmed copper smelter

Purpose

The aim was to study Cu (II), Zn (II), and Pb (II) forms in technogenically transformed soils adjacent to the Karabashmed copper smelter.

Materials and methods

Studies were performed in the plume zone of the Karabash smelter and in the floodplains of Ryzhii Brook and Sak-Egla River. Geomorphological and geochemical migration processes prevail in technogenic landscapes. The differentiation of landscape-geochemical conditions plays the dominant role, which determines the localization of metals. The total Mn, Cr, Ni, Cu, Zn, Pb, Cd, and As contents and the macroelement compositions of soils were determined by X-ray fluorescence. The composition of Cu, Pb, and Zn compounds in soils was determined by the Tessier sequential fractionation. The determination of the geochemical fractions of heavy metals in soils is a key issue in the study of their mobility. The metals were fractionated into the following five fractions: exchangeable, bound to carbonates, bound to Fe and Mn oxides, bound to organic matter, and residual fractions.

Results and discussion

It is shown that the total Zn and As contents in the 0- to 5-cm layer of soils on monitoring plots exceed their lithosphere clarks in hundreds of times, and the total Cu, Pb, and Cr contents exceed their lithosphere clarks in tens of times. Factors and processes controlling the distribution and transport of Cu, Pb, and Zn forms in soils were determined. According to landscape-geochemical differentiation, the eluvial (automorphic) catena (plot T4) takes the main technogenic load of dust fallouts from the Karabash copper smelter. The accumulation of material brought from above and the geochemical precipitation of discharges from tailings dumps occur in superaqual catenas (plots T1, T2, and T3). In the technogenically transformed soils, the basic stabilizers of the mobility of Cu is organic matter, for Pb it is Fe-Mn (hydro) oxides, and for Zn - it is clay minerals.

Conclusions

The distributions of Cu, Zn, and Pb forms in the studied technogenically transformed soils are due to a number of factors: First, these are the composition of technogenic pollutants contaminating ecosystems and the time during which the contamination occurred, and second, this is the combination of physicochemical properties controlling the buffer properties of the polydisperse system of soils and parent materials.

     

Use of Gisenyi Volcanic Rock for Adsorptive Removal of Cd(II), Cu(II), Pb(II), and Zn(II) from Wastewater

Volcanic rock is a potential adsorbent for metallic ions from wastewater. This study determined the capacity of Gisenyi volcanic rock found in Northern Rwanda to adsorb Cd, Cu, Pb and Zn using laboratory scale batch experiments under a variety of experimental conditions (initial metal concentration varied from 1 to 50 mg/L, adsorbent dosage 4 g/L, solid/liquid ratio of 1:250, contact time 120 h, particle size 250–900 μm). The adsorbent had a surface area of 3 m²/g. The adsorption process was optimal at near-neutral pH 6. The maximal adsorption capacity was 6.23, 10.87, 9.52 and 4.46 mg/g for Cd, Cu, Pb and Zn, respectively. The adsorption process proceeded via a fast initial metal uptake during the first 6 h, followed by slow uptake and equilibrium after 24 h. Data fitted well the pseudo second-order kinetic model. Equilibrium experiments showed that the adsorbent has a high affinity for Cu and Pb followed by Cd and Zn. Furthermore, the rock is a stable sorbent that can be reused in multiple sorption–desorption–regeneration cycles. Therefore, the Gisenyi volcanic rock was found to be a promising adsorbent for heavy metal removal from industrial wastewater contaminated with heavy metals.     

Solubility control of Cu, Zn, Cd and Pb in contaminated soils

We developed a semiempirical equation from metal complextion theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form: where pM is the negative logarithm (to base 10) of the metal activity, and a, b and c are constants. The equation successfully predicted free Cu²⁺ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.     

Simultaneous determination of Cd(II), Cu(II), Pb(II), and Zn(II) in citrus essential oils by derivative potentiometric stripping analysis

Citrus essential oils are widely used in the food, cosmetics, and pharmaceutical industries, so the determination of heavy metals content is of great importance to guarantee their quality. The present work deals with the quantification of Cd(II), Cu(II), Pb(II), and Zn(II) in different varieties of citrus essential oils, using derivative potentiometric stripping analysis. Two different metals extraction procedures, involving concentrated hydrochloric acid treatment and acid-alcoholic dissolution, are tested on lemon, mandarin, sweet orange, and bergamot essential oils, and they give very similar results. Cd(II), Cu(II), Pb(II), and Zn(II) recovery tests spanned from 95 to 100.50%, providing evidence that metals quantification remained unaffected by the cleanup steps of the two procedures. The repeatability of the hydrochloric acid extraction method, applied on different varieties of essential oils, is >95.00% for Cd(II), Cu(II), Pb(II), and Zn(II), whereas the repeatability of the acid-alcoholic dissolution method is >93.00% for Cu and Cd only in lemon oil. Detection limits obtained for the four analytes, using both procedures, ranged from 0.10 to 0.98 ng g(-)(1) in lemon, mandarin, sweet orange, and bergamot essential oils.     

Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在红壤胶体和非胶体颗粒上吸附的比较

研究了湖南长沙和海南昆仑的2种红壤胶体和非胶体的矿物组成、阳离子交换量(CEC)及Cu(Ⅱ)、Pb(Ⅱ)和Cd(Ⅱ)在土壤胶体和非胶体颗粒表面的吸附行为,以明确红壤胶体对土壤表面化学性质的贡献。X射线衍射分析结果表明,两种红壤胶体的矿物组成均以次生矿物为主,次生矿物又以1∶1型高岭石所占比例最高。土壤非胶体颗粒中石英等原生矿物含量较高。土壤铁铝氧化物主要富集在土壤胶体部分,土壤胶体颗粒中游离氧化铁和游离氧化铝含量明显高于非胶体颗粒,如湖南长沙红壤胶体颗粒游离氧化铁的含量为78.03 g kg~(-1),而非胶体颗粒中仅为9.93 g kg~(-1)。土壤胶体颗粒的CEC显著高于非胶体颗粒部分,2种红壤胶体的CEC约为非胶体的12倍。等温吸附实验结果表明,土壤胶体颗粒对Cu(Ⅱ)、Pb(Ⅱ)与Cd(Ⅱ)的最大吸附量和吸附亲和力均显著大于非胶体颗粒,湖南红壤胶体对3种重金属的吸附量大于海南红壤胶体,与土壤胶体的矿物组成和CEC大小一致。Cd(Ⅱ)在红壤胶体和非胶体颗粒表面主要发生静电吸附,而静电吸附和非静电吸附两种机制均对Cu(Ⅱ)和Pb(Ⅱ)的吸附有重要贡献。     

Study of Ni(II), Cu(II), Pb(II), and Zn(II) Removal Using Sludge and Minerals Followed by MF/UF

This work examined the removal of heavy metals in a system consisting of ultrafiltration (UF) or microfiltration (MF) membranes combined with sludge and minerals. The metals under examination were Ni(II), Cu(II), Pb(II), and Zn(II), while the system performance was investigated with respect to several operating parameters. Metal removal was achieved through various processes including chemical precipitation, biosorption, adsorption, ion exchange, and finally retention of the metals by the membranes. The pH had a profound effect on metal removal, as the alkaline environment favored the metal removal process. The use of sludge resulted in increased levels of metal uptake which was further enhanced with the addition of minerals. The metal removal mechanisms depended on the pH, the metal, and mineral type. The combined sludge?Cmineral?CUF system could effectively remove metal ions at an alkaline environment (pH?=?8), meeting the US EPA recommended long-term reuse limits of lead and copper and the short-term reuse limits of nickel and zinc for irrigation purposes, provided that specific mineral dosages were added.     

Speciation of cadmium,copper, lead,and zinc in contaminated soils

Abstract

To investigate the activity of free cadmium (Cd²⁺), copper (Cu²⁺), lead (Pb²⁺), and zinc (Zn²⁺) ions and analyze their dependence on pH and other soil properties, ten contaminated soils were sampled and analyzed for total contents of Cd, Cu, Pb, and Zn (Cd_T, Cu_T, Pb_T, and Zn_T, respectively), 0.43 MHNO₃‐extractable Cd, Cu, Pb, and Zn (Cd_N, Cu_N, Pb_N, and Zn_N, respectively), pH, dissolved organic matter (DOC), cation exchange capacity (CEC), ammonium oxalate extractable aluminum (Al) and iron (Fe), and dissolved calcium [Ca²⁺]. The activity of free Pb²⁺, Cd²⁺, Cu²⁺, and Zn²⁺ ions in soil solutions was determined using Donnan equilibrium/graphite furnace atomic absorption (DE/GFAA). The solubility of Cd in soils varied from 0.16 to 0.94 μg L^‐1, Cu from 3.43 to 7.42 μg L^‐1, Pb from 1.23 to 5.8 μg L^‐1, and Zn from 24.5 to 34.3 μg L^‐. In saturation soil extracts, the activity of free Cd²⁺ ions constituted 42 to 82% of the dissolved fraction, for Cu²⁺the range was 0.1 to 7.8%, for Pb²⁺ 0.1 to 5.1% and for Zn²⁺2 to 72%. The principal species of Cd, Cu, Pb, and Zn in the soil solution is free metal ions and hydrolyzed ions. Soil pH displayed a pronounced effect on the activity of free Cd²⁺, Cu^2t, Pb²⁺, and Zn²⁺ ions.     

Competition from Cu(II), Zn(II) and Cd(II) in Pb(II) Binding to Suwannee River Fulvic Acid

This is a study of trace metal competition in the complexation of Pb(II) by well-characterized humic substances, namely Suwannee River Fulvic Acid (SRFA) in model solutions. It was found that Cu(II) seems to compete with Pb(II) for strong binding sites of SRFA when present at the same concentration as Pb(II). However, Cd(II) and Zn(II) did not seem to compete with Pb(II) for strong binding sites of SRFA. These two metals did compete with Pb(II) for the weaker binding sites of SRFA. Heterogeneity of SRFA was found to play a crucial role in metal–SRFA interactions. The environmental significance of this research for freshwater is that even at relatively low Pb(II) loadings, the metals associated with lead in minerals, e.g. Cu(II), may successfully compete with Pb(II) for the same binding sites of the naturally occurring organic complexants, with the result that some of the Pb(II) may exist as free Pb²⁺ ions, which has been reported to be one of the toxic forms of Pb in aquatic environment.     

A Study of Diffusive Gradients in Thin Films for the Chemical Speciation of Zn(II), Cd(II), Pb(II), and Cu(II): The Role of Kinetics

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

Element (Ag, Cd, Cu, Pb, Sb, Tl and Zn), element ratio and lead isotope profiles in a sediment affected by a mining operation episode during the late 19th century

Mining operations at Mårsätter in 1877–81 resulted in increased metal loading to a small lake, notably as sulphidic tailings. The event is taken as an opportunity to study the present environmental impact of a historical single major metal release. Lake water and four sediment cores were sampled and analysed for principal and trace elements in solid and aqueous phases as well as general hydrochemical conditions. Chronologies were determined from ²⁰⁶Pb/²⁰⁷Pb ratios and historical records. Ordinary sedimentation after the event has lead to that the tailings are found as a distinct layer at a depth of 18–22 cm in the sediment. The layer is characterized by elevated metal concentrations in the solid and pore water phases, respectively, circum neutral pH and sulphate concentrations below detection. Geochemical modelling indicated a preference for carbonate equilibrium in the waste while sulphides prevailed above it. It is concluded that the growth of the ordinary sediment on top of the waste has lead to a physicochemical barrier that seals of the waste from the overlying sediment. Chemical or physical rupture of the barrier will release the metals to downstream regions. According to the chronologies at least three sources have contributed to the present elevated levels of metals, in additions to the release of tailings. Copper from a historical blast furnace prior to the event at Mårsätter, transport from mineralized parts of the watershed and release of contaminated water from present mining operations maintain elevated levels of notably zinc, silver, cadmium and lead. At present less than 10% of the lead content at the sediment/water interface comes from atmospheric deposition. Increased levels of antimony and thallium were not observed prior to ca 1950.     

Retention and mobility of cations in a small peatland: trends and mechanisms

Inputs and net storage or release of cations can have a large impact on the acid-base balance of any ecosystem. Because of the absence of mineral soils, ion exchange and accretion in biomass are the major internal processes governing cation accumulation in peatlands. It is widely believed that peatlands have a large capacity to store cations, and thus to affect the acidity of surface waters. A long-term record of hydrologic and chemical inputs and outputs to the S-2 peatland in the Marcell Experimental Forest was used to construct annual and monthly mass balances for the four major cations. Bulk deposition and throughfall measurements suggest that deposition of Na, Ca and Mg has increased over the period 1971–1984; wet-only and dry bucket measurements do not show such a change. Seasonal and annual variations in cation inputs are not visible in the cation export from the peatland because the large cation reservoir on exchange sites in peat buffers the surface waters and prevents them from responding rapidly to changing inputs. Nevertheless, ion exchange represents a relatively minor source of acidity to this peatland, and accumulation of cations in woody biomass accounts for the majority of the cation retention. The major mechanism of retention in the peatland is different for each cation; accumulation in woody biomass is most important for Ca, storage on ion exchange sites in peat is most important for Mg, green plant tissues are the dominant site of K storage, and Na is bound by unknown mechanisms in the peat. Retention efficiencies show large annual variations but average 50% for Ca, 22% for Mg, 29–44% for Na, and 21% for K.     

Preparation of Titanate Whiskers Starting from Metatitanic Acid and Their Adsorption Performances for Cu(II), Pb(II), and Cr(III) Ions

The accumulation of metals and nutrients in biosolid-amended soils and the risk of their excess uptake by plants is a topic of great concern. This study examines the elemental uptake and accumulation in five vegetable plants grown on biosolid-applied soils and the use of spectral reflectance to monitor the resulting plant stress. Soil, shoot, root, and fruit samples were collected and analyzed for several elemental concentrations. The chemical concentrations in soils and all the plant parts increased with increase in applied biosolid concentrations. The Cu and Zn concentrations in the plant shoots increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The Cu and Zn concentrations accumulated significantly in the fruits of the tomato plants compared to other plants. Among all the plants, the shoot concentration factor (SCF) of Zn was significantly higher for pepper plants, indicating increase in uptake of Zn. The shoot relative uptake index (SRUI) of Cu and Zn increased in the order of collard?<?radish?<?lettuce?<?tomato?<?pepper. The shoot dry weight and spectral reflectance of the radish plants in the near-infrared (NIR) region (800–1,300 nm) decreased significantly with increase in biosolid concentration compared to other plants. Increase in plant stress with increase in biosolid dose was evident in radish plants through significant reduction in Normalized Difference Vegetative Index (NDVI). This study indicates the potential use of spectral reflectance as a tool for the screening and monitoring of stress-sensitive plant species and their physiology and as a result, indirectly assesses the chemical concentrations in soils and plants.     

Binding of Sb(III) by Sb-tolerant Bacillus cereus cell and cell-goethite composite: implications for Sb mobility and fate in soils and sediments

Journal of Soils and Sediments - Adsorption onto mineral and bacterial surfaces can profoundly affect the mobility and fate of dissolved ions in soils; however, currently, there is a poor...     

Communities of microscopic fungi in contaminated and reference Al-Fe-humus podzols and their influence on copper mobility

The transformation of microscopic fungi communities under the impact of contamination, the influence of environmental conditions (soil temperature and moisture) on the development of fungal communities in the course of model successions and on the copper mobility in soil, and the most favorable conditions for copper mobilization were studied in Al-Fe-humus podzols of the Kola peninsula contaminated with heavy metals (Cu and Ni). The long-term aerotechnogenic contamination affects the structure of the microbial communities; the species diversity of the communities can somewhat increase at the expense of the increasing diversity of rare, atypical, and “weed” species and decreasing numbers of dominants. The dynamics of fungal communities are less expressed in the contaminated soils as compared with the reference soils. The conditions of rather low temperature (5°C) and an increased moisture content (120% of the field water capacity) are the most favorable for mycelium growth and copper mobilization. Such conditions are typical of the soils in the studied region. Hence, there is a possibility for the soil self-purification due to gradual mobilization of the copper and its subsequent leaching.     

土层性质对铜和铅在土壤中保持和迁移的影响

The mobility and bioavailability of heavy metals in soils is largely governed by sorption and desorption phenomena.Cu2+ and Pb2+ are among the most potentially toxic heavy metals and they are present,often concomitantly,in many polluting spills and in agrochemicals.The objective was to assess and compare the competitive sorption and desorption capacities and sorption hysteresis of Cu2+ and Pb2+,as well as their migration through the profiles of four natural soils:a Humic Umbrisol,an Umbric Cambisol,an Endoleptic Luvisol and a Humic Cambisol.In all horizons Pb2+ was invariably sorbed and retained to a greater extent than Cu2+.The sorption and retention of Cu2+ were most in?uenced by pH,e?ective cation exchange capacity(CECe) and Mn oxide content.On the other hand,the fixation capacity of Pb2+ was most in?uenced by pH,CECe,and Mn oxide and organic matter contents.pH and CECe were the individual soil properties most markedly in?uencing Cu2+ and Pb2+ sorption and retention.In all the horizons Pb2+ exhibited greater hysteresis than Cu2+.In each soil the hysteresis in the A horizon was greater than that in the B horizon,except in the Bt horizon of the Endoleptic Luvisol,due to its high pH and vermiculite content.Based on migration indices,Pb2+ was less mobile than Cu2+ in the studied soils.     

Adsorption features of Cu(II), Pb(II), and Zn(II) by an ordinary chernozem from nitrate,chloride, acetate,and sulfate solutions

The effect of Cl^?,SO ₄ ^2? , CH₃COO^?, and NO ₃ ^? anions on the adsorption of copper, lead, and zinc by an ordinary chernozem has been studied. The effect of the anions on the adsorption of Cu²⁺, Pb²⁺, Zn²⁺ ions is significant but uncertain. It has been shown that the attendant anions affect the shape of the adsorption isotherms, which are described by the Langmuir, Freundlich, or Henri equations. The constants of the adsorption from a nitrate solution calculated from the Langmuir equation (K _L) decrease in the following order: Cu²⁺ > Pb²⁺ >> Zn²⁺. The values of the maximum adsorption (C _max) decrease in the following order: Cu²⁺ ≥ Zn²⁺ > Pb²⁺ for acetate solutions and in the series Pb²⁺ > Zn²⁺ ≥ Cu²⁺ for nitrate solutions. The values of the Henry constants (K _H) calculated for the adsorption of the same cations from chloride solutions decrease in the same order as the values of K _L. The CH₃COO^? anion has the highest effect on the constant values. The NO ₃ ^? and Cl^? anions “switch their places” depending on the attendant cation, but their effect is always lower than that of the acetate anion. The values of C _max for copper and zinc are most affected by the CH₃COO^? anion, and the adsorption of zinc is most affected by the Cl^? and NO ₃ ^? anions. The assessment of the mobility of the adsorbed cations from the extraction with ammonium acetate (pH 4.8) has shown that the content of the desorbed metals is always lower than the content of the adsorbed cations and varies from 0.025 to 83%. According to their mobility, the adsorbed metals form the following order: Zn²⁺ > Pb²⁺ > Cu²⁺. The effect of the attendant anions on the extractability of the adsorbed cations decreases in the following order: chlorides > sulfates > acetates > nitrates.