The relative affinities of Cd,Ni and Zn for different soil clay fractions and goethite

Cadmium, Ni and Zn ions in aqueous solution were allowed to react with clay fractions (< 2 μm) separated from soils with a wide range of mineralogical composition and properties. Sorbed metals were separated into two components, termed specifically and non-specifically bound, by a controlled washing procedure using 10^?2M Ca(NO₃)₂.Sorption reactions were characterized by Δ pH₅₀ values, by shapes of adsorption curves, and by measuring separation factors and distribution coefficients under prescribed conditions. Three reaction types were identified, viz., (i) those associated with soil adsorbing surfaces dominated by iron oxides; these appear to be controlled by mechanisms which involve metal-ion hydrolysis and result accordingly in relative sorption affinities of Zn > Ni > Cd; (ii) those associated with organic surfaces for which metal-ion hydrolysis was of little significance and little difference in metal-ion affinity was evident; at lower pH-values, Cd and Ni were somewhat preferred over Zn, with the converse at higher pH-values; (iii) those associated with 2:1 layer lattice silicates which exhibit greater preference for Zn, i.e., Zn >> Ni, Cd and higher affinities for each metal at lower pH-values (< 5) than is shown by clays dominated by iron oxides. There was also evidence of greater relative affinity for Ni shown by clay fractions dominated by fine kaolinites when compared with other clays.This investigation has shown that a range of sorption processes are involved in reactions of heavy metals with soils. We caution against undue emphasis on any particular sorption process in developing theoretical sorption models as a basis of understanding and solving problems connected with pollution and plant nutrition; we also stress the need for studies with colloids separated from soils in conjunction with those using synthetic adsorbents as models for soil constituents.     

Retention of Ni,Zn and Cd by Si-associated goethite

Synthetic goethite used to study the effects of reaction time and temperature on the pH-dependent sorption of Ni, Zn and Cd was associated with amorphous silica. Ni interacted with dissolved Si and formed a Ni/Si precipitate on the goethite surface. Individual metals added at a concentration of 0.5 μmol g^?1 and sorbed during a reaction period of 504 hours (21 days) at 35°C were extracted by 0.7 M HNO₃ for 14 days. At the end of this period 11,28 and 40 percent of Ni, Cd and Zn, respectively, were not extracted whereas 20 percent of the total Fe content of the goethite and 39 percent of the associated Si were dissolved. During the sorption process metals became immobilized in the goethite particles. This effect can be related to a diffusion of metal ions into micropores. A total mobilization of sorbed metals can only be achieved by a complete dissolution of the goethite. The strong fixation of Ni, Zn and Cd by goethite suggests that additions of this Fe oxide could be used to ameliorate highly contaminated sludges or soils.     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

Parameters of selective sorption of Co,Cu, Zn,and Cd by a soddy-podzolic soil and a chernozem

The adsorption and ion-exchange behavior of Co, Cu, Zn, and Cd were studied in two soils of different genesis. The sorption parameters and selectivity coefficients of the Me-Ca ion exchange were determined using the Langmuir and Freundlich adsorption isotherms and two models of ion-exchange sorption based on the mass action law (a polyfunctional ion exchanger and a mixture of two ideal exchangers) for describing the relationships between the dissolved and sorbed metal forms. It was shown that simple models provided information for better understanding of the behavior of metals in sorption and ion-exchange processes, but the conclusions about the sorption of different metals in a specific soil or a specific metal in different soils based on these models can be different.     

矿物对溶解性有机质及其不同组分的吸附作用

溶解性有机质(Dissolved Organic Matter,DOM)在土壤矿物表面的吸附控制着其在土壤中的迁移,会影响土壤/矿物对重金属、有机污染物等的传质过程[1～3]。已往资料揭示,土壤中黏土矿物是DOM的重要吸附质;但迄今,有关DOM在不同类型黏土矿物表面吸附的差异及机制尚很不清楚。另外,不同DOM组分在土壤矿物上的吸附各异,土壤矿物对DOM不同成分的吸附具有选择性;因此分离DOM不同组分,分别研究其在土壤矿物上的吸附有助于揭示DOM与土壤矿物的结合机理,但该研究尚待深化。此外,目前研究中DOM多以土壤中提取的为主[4],对于因污泥农用等农业管理措施而从外部引入土壤的DOM的研究还较     

Effects of Cd,Zn, or both on soil microbial biomass and activity in a clay loam soil

We investigated Cd, Zn, and Cd + Zn toxicity to soil microbial biomass and activity, and indigenous Rhizobium leguminosarum biovar trifolii, in two near neutral pH clay loam soils, under long-term arable and grassland management, in a 6-month laboratory incubation, with a view to determining the causative metal. Both soils were amended with Cd- or Zn-enriched sewage sludge, to produce soils with total Cd concentrations at four times (12 mg Cd g⁻¹ soil), and total Zn concentrations (300 mg Zn kg⁻¹ soil) at the EU upper permitted limit. The additive effects of Cd plus Zn at these soil concentrations were also investigated. There were no significant differences in microbial biomass C (B _C), biomass ninhydrin N (B _N), ATP, or microbial respiration between the different treatments. Microbial metabolic quotient (defined as qCO₂ = units of CO₂–C evolved unit⁻¹ biomass C unit⁻¹ time) also did not differ significantly between treatments. However, the microbial maintenance energy (in this study defined as qCO₂-to-μ ratio value, where μ is the growth rate) indicated that more energy was required for microbial synthesis in metal-rich sludge-treated soils (especially Zn) than in control sludge-treated soils. Indigenous R. leguminosarum bv. trifolii numbers were not significantly different between untreated and sludge-treated grassland soils after 24 weeks regardless of metal or metal concentrations. However, rhizobial numbers in the arable soils treated with metal-contaminated sludges decreased significantly (P < 0.05) compared to the untreated control and uncontaminated sludge-treated soils after 24 weeks. The order of decreasing toxicity to rhizobia in the arable soils was Zn > Cd > Cd + Zn.     

Partition of Cd,Cu, Pb and Zn among mineral particles during their sorption in soils

Journal of Soils and Sediments - Heterogeneity of soil mineral particles may lead to the misinterpretation of bulk sorption data on their role in metal sorption, which may be resolved through the...     

Role of soil constituents in fixation of soluble Zn, Cu, Ni and Cd added to soils

Slow immobilization of trace metals in soil, termed ‘fixation’, affects their natural attenuation but it is still unclear which reactions occur. Twenty‐eight soils were selected to assess the role of Fe oxides and carbonates on fixation of Cu, Cd, Zn and Ni. Soils included samples from 2 toposequences (Vietnam, Spain) and 13 European topsoils with different soil characteristics (pH 3.4–7.7). Samples were amended with 250 mg Zn kg⁻¹, 100 mg Cu kg⁻¹, 80 mg Ni kg⁻¹ and 2.5 mg Cd kg⁻¹ as metal salts and incubated for 850 days. Fixation was measured as the increase of the fraction of added metals that were not isotopically exchangeable. Fixation increased with time and was, averaged over all the soils, 43% (Cu), 41% (Zn), 41% (Ni) and 28% (Cd) after 850 days. Metal fixation within samples from each toposequence was generally positively related to total Fe oxide concentration (Fe_d) for Zn, Ni and Cd. However, the fixation of Cd, Zn and Ni was mainly explained by pH and not by Fe_d when considering all soils. Fixation of Zn and Cd in soils with pH >7.0 increased with increasing concentrations of carbonates at initial ageing times. Fixed fractions of Zn, Ni and Cd were significantly released when experimentally removing 50% of carbonates by acidification. Fixation of Cu was most poorly related to soil properties. Our data suggest that fixation of Cd, Zn and Ni is related to a pH‐dependent diffusion into oxides and that of Cd and Zn also to diffusion and/or coprecipitation in carbonates. Fixation of Ni at neutral pH may also be related to stabilization of precipitates that form readily in soil.     

Speciation and sorption structure of diphenylarsinic acid in soil clay mineral fractions using sequential extraction and EXAFS spectroscopy

Purpose

The mobility of arsenic (As) in soils is fundamentally affected by the clay mineral fraction and its composition. Diphenylarsinic acid (DPAA) is an organoarsenic contaminant derived from chemical warfare agents. Understanding how DPAA interacts with soil clay mineral fractions will enhance understanding of the mobility and transformation of DPAA in the soil-water environment. The objective of this study was to investigate the speciation and sorption structure of DPAA in the clay mineral fractions.

Materials and methods

Twelve soils were collected from nine Chinese cities which known as chemical weapons burial sites and artificially contaminated with DPAA. A sequential extraction procedure (SEP) was employed to elucidate the speciation of DPAA in the clay mineral fractions of soils. Pearson’s correlation analysis was used to derive the relationship between DPAA sorption and the selected physicochemical properties of the clay mineral fractions. Extended X-ray absorption fine structure (EXAFS) L_III-edge As was measured using the beamline BL14W1 at Shanghai Synchrotron Radiation Facility (SSRF) to identify the coordination environment of DPAA in clay mineral fractions.

Results and discussion

The SEP results showed that DPAA predominantly existed as specifically fraction (18.3–52.8%). A considerable amount of DPAA was also released from non-specifically fraction (8.2–46.7%) and the dissolution of amorphous, poorly crystalline, and well-crystallized Fe/Al (hydr)oxides (20.1–46.2%). A combination of Pearson’s correlation analysis and SEP study demonstrated that amorphous and poorly crystalline Fe (hydr)oxides contributed most to DPAA sorption in the clay mineral fractions of soils. The EXAFS results further demonstrated that DPAA formed inner-sphere complexes on Fe (hydr)oxides, with As-Fe distances of 3.18–3.25 Å. It is likely that the steric hindrance caused by phenyl substitution and hence the instability of DPAA/Fe complexes explain why a substantial amount of DPAA presented as weakly bound forms.

Conclusions

DPAA in clay mineral fractions predominantly existed as specifically, amorphous, poorly crystalline, and crystallized Fe/Al (hydr)oxides associated fractions. Amorphous/poorly crystalline Fe rather than total Fe contributed more to DPAA sorption and DPAA formed inner-sphere complexes on Fe (hydr)oxides.

     

Effect of organic matter on the parameters of the selective sorption of cobalt and zinc by soils and their clay fractions

The sorption and ion-exchange behavior of Co(II) and Zn in the soil-equilibrium solution system was studied for different types and varieties of native soils and their clay fractions before and after mild oxidation with H₂O₂ to remove the organic carbon. The parameters of the ion-exchange adsorption and the selectivity coefficients of the (Co(II), Zn)/Ca ion exchange were determined using different models for describing the relationship between the dissolved and sorbed forms of the metals. These were the empirical Langmuir and Freundlich adsorption isotherms and the model of the ion-exchange adsorption based on the acting mass law. It was found that the soil organic matter played an important role in the selectivity of the ion-exchange adsorption of Co(II) and Zn by the soils and their clay fractions. This was confirmed by an abrupt decrease (to almost 1) of the selectivity coefficients of the Co²⁺/Ca²⁺ and Zn²⁺/Ca²⁺ exchange after the treatment of the clay fraction with hydrogen peroxide.     

The determination of Zn,Cd, Pb and Cu in soil extracts by anodic stripping voltammetry

This work describes simultaneous determination of Zn, Cd, Pb and Cu in soil extract by d. c. anodic stripping voltammetry at the hanging mercury drop electrode. Soil samples were taken from six different areas characterized by different degrees of heavy metal pollution. The metals were extracted from the soil samples using 0.5 M HCI. The base electrolyte for ASV was 0.2 M acetic buffer at pH 5.0. These results are compared with those obtained by using atomic absorption spectrophotometric method. The accuracy and precision of the presented method are satisfactory (relative standard deviation is 3.5 to 11%). Iron, Al and Ti contained in the extract in the concentration of 1120, 5400, and 480 µg g^?1, respectively, do not present measurement difficulties.[/p]     

Distribution coefficients of Cd, Co, Ni, and Zn in soils

Batch adsorption experiments were conducted with a mixture of solutes at low equilibrium concentrations of Cd (0.7-12.6 μg1⁻¹), Co (18-118μg1⁻¹, Ni (22-330 μg 1⁻¹), and Zn (40-1480 μg1⁻¹) in 38 different soils. Statistical correlations indicated that metal sorption onto the soils was influenced by the presence of clays and hydrous oxides of Fe and Mn. Based on calculated distribution coefficients for these metals, Co will generally exhibit the highest mobility in soils, but the mobility of Zn will increase faster with decreasing pH. Two types of empirical relationships are developed from these data to estimate values for the distribution coefficients.     

不同Zn浓度对黑麦草根分泌物、根际Zn形态及植物Zn蓄集的影响

A glasshouse experiment was conducted using a root-bag technique to study the root exudates, rhizosphere Zn fractions, and Zn concentrations and accumulations of two ryegrass cultivars (Lolium perenne L. cvs. Airs and Tede) at different soil Zn levels (0, 2, 4, 8, and 16 mmol kg-1 soil). Results indicated that plant growth of the two cultivars was not adversely affected at soil Zn level≤8 mmol kg-1. Plants accumulated more Zn as soil Zn levels increased, and Zn concentrations of shoots were about 540 /μg g-1 in Aris and 583.9μg g-1 in Tede in response to 16 mmol Zn kg-1 soil. Zn ratios of shoots to roots across the soil Zn levels were higher in Tede than in Airs, corresponding with higher rhizosphere available Zn fractions (exchangeable, bound to manganese oxides, and bound to organic matter) in Airs than in Tede. Low-molecular-weight (LMW) organic acids (oxalic, tartaric, malic, and succinic acids) and amino acids (proline, threonine, glutamic acid, and aspartic acid, etc.) were detected in root exudates, and the concentrations of LMW organic acids and amino acids increased with addition of 4 mmol Zn kg-1 soil compared with zero Zn addition. Higher rhizosphere concentrations of oxalic acid, glutamic acid, alanine, phenylalanine, leucine, and proline in Tede than in Airs likely resulted in increased Zn uptake from the soil by Tede than by Airs. The results suggested that genotypic differences in Zn accumulations were mainly because of different root exudates and rhizosphere Zn fractions.     

Concentration Changes of Cd, Ni and Zn in Sugarcane Cultivated Soils

In the southwest of Iran over 130,000 ha of land are under sugarcane (Saccarum officinarum). In these sugarcane fields, about 400 kg ha^?1 diamonium phosphate (DAP) and 400 kg ha^?1 urea are applied annually. Four sugarcane growing sites were selected for this study: Haft-tapeh, Karoon, Shoeibieh and Ghazali with cultivation histories of 36, 20, 2 and 1 years, respectively. For each area, soil samples (0–30 cm) were taken from a transect of uncultivated, and both furrows and ridges of cultivated land. Electrical conductivity (EC), pH, clay, and calcium carbonate and organic carbon (OC) contents, Cl, Cd, Ni and Zn of 101 soil samples were measured. Cadmium profile distribution to a soil depth of 300 cm was determined, and the heavy metal concentrations in sugarcane and the associated soil samples of the three sugarcane sites were measured. The Cd and Ni contents among the sugarcane sites differed where Cd was related to clay content and Ni was related to OC content of soils. Cadmium content in sugarcane cultivated soil was lower compared to uncultivated soil even after years of application of P fertilizers. Nickel and Cd contents of sugarcane were much higher than levels in top soils but there was no significant relationship between Cd or Ni contents of sugarcane and soil chemical properties. The Zn content of soils decreased as either EC or Cl concentration of soils increased. There were no significant differences in Zn contents between different sugarcane sites and also between cultivated and uncultivated soils. Results also indicated that Cd was accumulated in bagasse and Ni was primarily accumulated in bagasse and molasses, but these heavy metals of white sugar were lower than the detectable values.     

土法炼锌区大气沉降Pb、Zn、Cd及其对土壤质量的影响

Dust emissions from smelters, as a major contributor to heavy metal contamination in soils, could severely influence soil quality. Downwind surface soils within 1.5 km of a zinc smelter, which was active for 10 years but ceased in 2000, in Magu Town, Guizhou Province, China were selected to examine Pb, Zn, and Cd concentrations and their fractionation along a distance gradient from a zinc smelter, and to study the possible effects of Pb, Zn, and Cd accumulation on soil microorganisms by comparing with a reference soil located at a downwind distance of 10 km from the zinc smelter. Soils within 1.5 km of the zinc smelter accumulated high levels of heavy metals Zn (508 mg kg-1), Pb (95.6 mg kg-1), and Cd (5.98 mg kg-1) with low ratios of Zn/Cd (59.1--115) and Pb/Cd (12.4--23.4). Composite pollution indices (CPIs) of surface soils (2.52--15.2) were 3 to 13 times higher than the reference soils. In metal accumulated soils, exchangeable plus carbonate-bound fractions accounted for more than 10% of the total Zn, Pb, and Cd. The saturation degree of metals (SDM) in soils within 1.5 km of the smelter (averaging 1.25) was six times higher than that of the reference soils (0.209). A smaller soil microbial biomass was found more frequently in metal accumulated soils (85.1--438 μg C g-1) than in reference soils (497 μg C g-1), and a negative correlation (P < 0.01) of soil microbial biomass carbon to organic carbon ratio (Cmic/Corg) with SDM was observed. Microbial consumption of carbon sources was more rapid in contaminated soils than in reference soils, and a shift in the substrate utilization pattern was apparent and was negatively correlated with SDM (R = -0.773, P < 0.01). Consequently, dust deposited Pb, Zn, and Cd in soils from zinc smelting were readily mobilized, and weredetrimental to soil quality mainly in respect of microbial biomass.     

Forms of Cd,Cu, Pb,and Zn in soil and their uptake by cereal crops when applied jointly as carbonates

The cereal crops (barley -Hordeum vulgare L., maize -Zea mays L., wheat -Triticum vulgare L.) were grown in a greenhouse using a sandy soil type treated with various doses of cadmium carbonate (salt), copper carbonate (malachite), lead carbonate (cerussite), and zinc carbonate (smithsonite), added jointly. The following levels of these metals were used: Cd ? 5, 10, 50μg g^?1 soil; Cu and Pb - 50,100, 500 μg g^?1 soil; Zn-150, 300, 1500 μg g-1 soil. Sequential extraction was adopted to partition the metals into five operationally-defined fractions: exchangeable, carbonate, Fe-Mn oxides, organic, and residual. The residual was the most abundant fraction in the untreated (control) soil for all the metals studied (50 to 60% of the total metal content). The concentrations of exchangeable Cd, Cu, Pb, and Zn were relatively low in untreated soil but increased (over the three year period) in treated soils for Cd, Zn, and Cu, whereas only small changes were observed for Ph. This experiment showed a significant increase in Cd, Zn, and Cu in tissue of plants grown on the treated soil, but a non-significant change in plant tissue with respect to Pb concentration.     

The sorption of Cd and Zn by different soils in the presence of dissolved organic matter from sludge

Dissolved organic matter (DOM) is one of the important factors affecting metal mobility and phytotoxicity in the soils receiving sewage sludge. The aim of this study was to investigate the effects of DOM from anaerobically digested dewatered sludge on Cd and Zn sorption by three different soil types (calcareous clay loam, calcareous sandy loam and acidic sandy loam) of different physico-chemical properties through batch studies. The addition of DOM significantly reduced the Cd and Zn sorption capacity by a factor of 2.1–5.7 for Cd and 2.3–13.7 for Zn for these three soils as seen by their K values in the Freundlich equation compared to the control receiving no DOM, suggesting that DOM had a stronger inhibitory effect on Zn sorption than that of Cd. The reduction in metal sorption caused by DOM was very apparent in the pH range of 5 to 8, with a maximum inhibition on metal sorption occurring at pH 7–7.5 especially for Zn but the effect was minimal at lower pH. At a DOM concentration of < 200 mg C l^− 1, Cd and Zn sorption by all the three soils decreased with an increase in DOM concentration. At each given DOM concentration, the inhibition of metal sorption of the different soil types increased in the following order: acidic sandy loam < calcareous sandy loam < calcareous clay loam. DOM derived from sludge would significantly reduce metal sorption and increase its mobility through the formation of soluble DOM–metal complexes and poses risk of metal leaching and phytotoxicty in near-neutral and alkaline soils.     

Effects of natural zeolites on ryegrass growth and bioavailability of Cd,Ni, Pb,and Zn in an Albanian contaminated soil

Purpose

The use of eco-friendly and cost-effective adsorbent materials in the remediation of soils contaminated by potentially toxic elements (PTE) is a sustainable way of reducing the transfer of these elements into the food chain. However, an evaluation of the potential of natural zeolites to immobilize toxic elements in contaminated soils was required to enable their efficient use.

Materials and methods

The effect of natural zeolite (Stilbite-Stellerite) from the Munella area (Northern Albania), added at rates ranging from 1.25 to 10 % w/w on a contaminated soil was investigated in a greenhouse pot experiment with ryegrass (Lolium multiflorum L.) and by selective extractions. PTE availability for plants was assessed either as their accumulation in plant tissue or by DTPA-extraction. Oral bio-accessibility was estimated by the in vitro PBET method and the mobility and consequent potential risk of leaching by the USEPA TLCP method. The effect of zeolites on soil properties (pH, electrical conductivity-EC, organic C, and total N) was also investigated. A five steps sequential extraction procedure (SEP) was applied to investigate the immobilization mechanism.

Results and discussion

The addition of 2.5% w/w of natural zeolites caused a significant decrease of PTE mobility, but to observe a significant reduction of DTPA-extractable metals, it was necessary to reach 10% addition rate. In contrast, plant growth showed a gradual increase with addition rate and a corresponding decrease of concentration of PTE in plant tissue. Correlation between DTPA-extractable PTE and their concentration in both root and shoot plant tissue was rather poor. Human hazard due to soil ingestion (PBET method) changed only for Cu and Zn in the gastric phase with 1.25 and 5% addition rate respectively, whereas decreased for Cu and Zn at 5% rate in the Intestinal phase. The results of SEP support the hypothesis that the main mechanism involved in metals fixation are as follows: (1) insolubilization by pH rise, (2) adsorption on Fe/Mn oxides (3) increase of cation exchange retention, (4) organic complexation.

Conclusions

The results of this work suggest that the addition of natural zeolites from the Munella area (AL) is a sustainable practice to reduce the environmental impact of PTE contaminated soils, but an assessment on the longevity of their immobilization need to be evaluated in the long-term perspectives.

     

Characterization of clay and fine silt fractions of forest soils by standardized K/Ca sorption isotherms

For better comparison of selectivity characteristics of clay and fine silt fractions sorption isotherms standardized on the cation exchange capacity (CEC) are useful. Due to the effect of the CEC on the sorption isotherms, it is necessary to characterize the exchanging substance with regard to different ion selectivities with standardized potassium/calcium‐(K/Ca) sorption isotherms. This procedure helps to complete the knowledge about the mineralogical composition, which is obtained by X‐ray powder diffractometry. A Haplic Luvisol from boulder marl shows distinct differences in its K selectivity both between different particle size fractions and different horizons. This is partly due to the presence of smectites and vermiculites which are differently distributed within the particle size fractions. The increase of K selectivity with increasing particle diameter in the calcareous C horizon can be attributed to the marginal expansion of mica/illite by Ca²⁺ ions. The K selectivity of individual particle size fractions in different horizons of a Gleyic Cambisol from glacial sand shows major similarities. If pedogenic chlorite is formed, no changes in selectivity characteristics can be observed.