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 Cd, Cu, Pb and Zn by Wood Ash, Lime and Fume Dust

Heavy metals are of interest due to their deleterious impacts on both human and ecosystem health. This study investigated the effectiveness of wood ash in immobilizing the heavy metals Pb, Cd, Cu and Zn from aqueous solutions. The effects of initial metal concentrations, solution pH, ash dose and reaction time on metal sorption, as well as the metal sorption mechanisms were studied. To investigate the effect of initial metal concentrations, solutions containing Cd, Zn (25, 50, 75, 100 or 125 mg L^?1), Cu (25, 50, 75, 100, 125, 150 or 175 mg L^?1) or Pb (250, 500, 750, 1000, 1250, or 1500 mg L^?1) were reacted with 10 g L^?1 ash for two hours. For the effect of pH, solutions containing 100 mg L^?1 of Cd, Cu or Zn or 1500 mg L^?1 of Pb were reacted with 15 g L^?1 ash over a pH range of 4 to 7. The wood ash was effective in immobilizing the four metals with a sorption range of 41–100 %. The amounts of metals retained by the ash followed the order of Pb > Cu > Cd > Zn. As expected, absolute metal retention increased with increasing initial metal concentrations, solution pH and ash dose. Metal retention by the ash exhibited a two-phase step: an initial rapid uptake of the metal followed by a period of relatively slow removal of metal from solution. Metal retention by the ash could be described by the Langmuir and Freundlich isotherms, with the latter providing a better fit for the data. Dissolution of calcite /gypsum minerals and precipitation of metal carbonate/sulfate like minerals were probably responsible for metal immobilization by the ash in addition to adsorption.     

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.     

Cd/Zn 及Cd /Zn/Ni复合污染对胡萝卜生长吸收特征的影响

利用盆栽试验对胡萝卜在不同浓度Cd/Zn及Cd/Zn/Ni复合作用下的重金属吸收效应进行了研究。结果表明,在Cd/Zn/Ni和Cd/Zn复合污染条件下,胡萝卜茎叶和块茎干重与对照土壤比较均受到显著影响（P＜0.05）,尤其是含Ni组合,在Ni浓度达到250 mg·kg-1后,胡萝卜块茎和茎叶生物量都锐降（P＜0.01）。对比不同剂量下两组合富集系数（EF）和转运系数（TF）的结果发现,含Ni组合中, Cd、Zn、Ni 3种重金属在不同迁移界面以及不同浓度水平时的活性不同：在土壤-胡萝卜块茎迁移界面,当土壤中Cd、Zn、Ni浓度分别在0.35～1.8、50～300 mg·kg-1以及60～250 mg·kg-1之间时,活性大小为Cd〉Zn〉Ni;当其浓度分别达到3.5 mg·kg-1（Cd）、600 mg·kg-1（Zn）以及500 mg·kg-1（Ni）时,活性大小变为 Zn〉 Ni 〉Cd ;而在胡萝卜块茎－茎叶界面,Cd的活性在任何浓度水平下始终最大,当Zn、Ni浓度分别在50～180 mg·kg-1以及 60～170 mg·kg-1之间时,活性大小为Zn＞Ni ,但在此浓度之后Ni的作用突显,活性大小变为Ni＞Zn。非含Ni组合中,在两迁移界面和不同浓度水平下,两种重金属的迁移能力始终为Cd＞Zn。此外,在碱性较高的绿洲灌淤土中,Cd、Zn、Ni之间的交互作用表     

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.     

Cd, Ni, Pb, and Zn Concentrations in Forest Vegetation and Soils in Maine

Bioaccumulation of trace metals in plant tissues can present a health risk to wildlife, and potentially to humans. The Passamaquoddy tribe in Maine was concerned about health risks of cadmium (Cd) because of a health advisory for moose liver and kidney consumption due to high Cd levels. This study found relatively low to moderate concentrations of Cd, nickel (Ni), lead (Pb), and zinc (Zn) concentrations in four common terrestrial moose browse species, associated forest soils, and two species of aquatic vegetation on Passamaquoddy tribal land in eastern Maine. Terrestrial plant tissue concentrations ranged from 0.1 to 1.97, 0.65 to 7.08, 0.29 to 2.0, and 42 to 431 mg kg^?1 for Cd, Ni, Pb and Zn, respectively. Deciduous species, particularly aspen and birch, may be a more significant source of Cd and Zn to wildlife compared to coniferous or aquatic species. Aquatic plant tissue concentrations ranged from 0.11 to 0.14, 0.46 to 1.01, 0.8 to 0.9, and 22 to 41 mg kg^?1 for Cd, Ni, Pb and Zn, respectively. Total O horizon concentration means for coniferous and deciduous were 0.50 and 1.00, 4.27 and 4.11, 55 and 21, and 55 and 167 mg kg^?1 for Cd, Ni, Pb and Zn, respectively. The study provides baseline vegetation and soil trace metal concentrations for a remote region in Maine impacted by non-point sources.     

Effect of pH on Removal of Cu,Cd, Zn,and Ni by Cement Kiln Dust in Aqueous Solution

A batch experiment was conducted to study the effect of pH on the sorption of copper (Cu), cadmium (Cd), zinc (Zn), and nickel (Ni) by cement kiln dust (CKD). The experiment was carried out by adding 25 mL of solutions containing concentrations of 200, 400, 600, 800, and 1000 mg/L of each of these heavy metal cations to 1.00 g of CKD. The pH of these suspensions was adjusted to 2, 5, and 7 as well as non-adjusted. The sorbed amount (Cs) and the sorption percentage of Cu, Cd, Zn, and Ni by CKD increased with increasing the suspension pH. The adsorption data of Cu, Cd, Zn, and Ni were generally well correlated with Langmuir model when the suspension pH was adjusted to 5, 7, non-adjusted and 7, respectively. However, they could be well described by Freundlich model when the suspension pH was adjusted to 5, 2, non-adjusted and 5, respectively.     

Fluxes of Cu,Zn, Pb,Cd, Cr,and Ni in temperate forest ecosystems

The literature on the fluxes of six heavy metals in temperate forest ecosystems is reviewed. Special attention is given to wet and dry deposition and internal flux, to metal budgets for ecosystems and soils, to concentrations in aqueous compartments of the ecosystem and to speciation in soil solutions. Metal fluxes are discussed in relation to pollution load, soil type, tree species and land use. The mobility of Cu and Pb is strongly dependent on the solubility of organic matter. These metals are commonly accumulated in forest soils. Zinc, Cd and Ni are greatly influenced by soil acidity and are often lost in considerable amounts from acidified soils. Chromium is often at balance in forest ecosystems. Implications for metal solubility and budgets in forest soils are discussed in connection with an increase in soil acidification.     

Effect of Cd,Ni, Pb and Zn on growth and chemical composition of onion and fenugreek

Abstract

Onion (Allium cepa) and fenugreek (Trigonella poenum‐graceum) growth was measured in glasshouse on a slightly alkaline clay‐loam soil from Northern India. Cadmium, Ni, Pb and Zn were applied at the rate of 0, 50, 100, 200 and 400 mg/kg of soil. The fresh and dry weights of onion and fenugreek were drastically reduced even at the 50 mg/kg soil addition of Cd and decreased further at higher applied levels. There was a slight decrease in the yield of both of the vegetables at 50 mg Ni/kg soil but at 100 mg Ni/kg soil and above yield decrease was significant. No growth was observed at 400 mg Ni/kg soil. The application of 50 mg Zn/kg soil slightly increased the yield of both of the vegetables, but the yield decreased at higher levels of applied Zn and more so for fenugreek. The threshold concentration, toxicity index and loading rate to produce ten percent yield reduction were also calculated. These values suggested that the toxicity of heavy metals varied with crop species. The concentrations of the elements in onion bulb and fenugreek root and leaves increased linearally with increasing levels of applied elements. The uptake of Zn was highest, followed by Cd, Ni and then Pb. The roots accumulated higher amounts of these elements than the leaves. Tissue concentrations of Cd, Ni, Pb and Zn associated with ten percent yield reduction for onion were 6, 3.2, 8 and 75 ppm, respectively, and for fenugreek, the concentrations were 1.5, 7.8, 11.5 and 54.5 ppm, respectively. In general, phytotoxicities were found to be in the order: Cd > Ni > Pb > Zn. The DTPA extractable elements in soil, after the harvest of crops, increased with increasing levels of applied elements in soil.     

Availability of Cd,Ni and Zn to Ryegrass in Sewage Sludge-Treated Soils at Different Temperatures

A pot experiment to compare the availability of Cd, Ni and Znto ryegrass (Lolium perenne L.) was conducted at 15 and 25 °C. For this purpose, three ratesof sewage sludge (0, 10 and 50 t ha^-1) were applied in aloamy sand (LS) and a clay loam (CL). Heavy metal availabilityassessed by soil extractions with 0.05 M CaCl₂ and the organic matter content were monitored during a period of twoyears, while uptake by ryegrass was monitored over one year after addition of the sludge. The concentrations of Cd and Ni in both the ryegrass and the soil extracts increased significantly, during the first year, especially at 50 t ha^-1. However, in the second year metal availability reached a plateau. During the first year, in the ryegrass Znconcentrations did not show an increase, but in the soil CaCl₂-extracted Zn increased. During the same period,the organic matter content decreased rapidly, especially at25 °C, in the first year and much more slowly in thesecond, giving a total decrease of 16%. Temperature had a marked effect on metal availability; both soil extracts andplant samples from the 25 °C treatment had greater concentrations of Cd, Ni and Zn than those at 15 °C. This may be attributed to the organic matter, which decomposedmore rapidly at 25 °C. Moreover, soil-plant transfercoefficients (Tc) of the metals were significantly higher at 25 °C than at 15 °C, with Cd showing the greatest difference, followed in decreasing order by Zn and Ni.     

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.     

Modelling of Cd, Cu, Ni, Pb and Zn uptake, by winter wheat and forage maize, from a sewage disposal farm

Abstract. A predictive model of metal concentrations in crops was developed to optimize soil liming and sludge application strategies at a dedicated sewage sludge disposal site. Predictions of metal concentrations in plant tissue were derived from measured values of soil metal concentration, humus content and soil pH. The plant and soil data used to parameterize the model were collected on site using quadrat sampling of mature crop and underlying topsoil. The uptake model was used to map predicted metal concentrations in wheat grain and forage maize based upon a database of soil characteristics (metal content, % humus and pH) measured as part of a routine geochemical survey of the site. The effect of a management strategy to modify uptake of Cd by wheat by changing soil pH was investigated. The effect of soil dust adhering to maize plants at harvest was also simulated to investigate the importance of this pathway for Cd transfer to animal feed such as silage.
The model gave satisfactory predictions for uptake of Cd and Zn but less useful simulations for Pb, Cu and Ni. The results for Cd uptake showed a greater dependence on soil pH in the case of wheat in comparison to maize. It is suggested that, for the study site, liming to pH 7.0 will reduce Cd concentrations in wheat grain to within EC legal standards. However the Cd content of maize may still exceed these guidelines, with a relatively minor contribution from contamination with soil dust.     

重金属复合处理对小麦锌铜镍镉积累和分布的影响

为增加粮食可食用部分有益元素的浓度,同时减少有毒重金属元素的含量,需要更好地了解元素在植株和籽粒内的运输和分布。在温室盆栽条件下,以春小麦为供试材料,设置对照（不添加重金属）和重金属复合处理（同时添加铜、锌、镍、镉,以不影响小麦生长为前提）,研究锌（Zn）、铜（Cu）、镍（Ni）、镉（Cd）在成熟植株和籽粒不同部位的分布特点。结果表明,重金属复合处理对小麦成熟期籽粒和秸秆产量、收获指数以及粒重均无显著影响,但使小麦各器官重金属浓度均显著增加,增幅因不同器官和不同元素而异,籽粒中Zn、Cu、Ni和Cd浓度分别增加1.8、0.5、48.1倍和45.3倍。重金属复合处理还显著改变了Zn和Ni在地上部各器官中的分配模式：对照小麦吸收的Zn更易向生殖器官中转运,处理植株则更多地滞留在营养器官中,而Ni呈相反的趋势。激光剥蚀电感耦合等离子体质谱仪（LA-ICP-MS）对籽粒糊粉层和胚乳的定量分析表明,重金属复合处理使糊粉层Zn和Cu浓度仅增加了78%和86%,而糊粉层Ni和Cd浓度分别增加了30倍和121倍。重金属复合处理使胚乳Zn和Cu浓度分别增加了49%和48%,使Ni和Cd浓度均超出小麦标准中Ni和Cd的最大允许浓度（对照籽粒胚乳中没有检验到Ni和Cd）。以上结果表明,在小麦生物强化实践中,在增加有益营养元素（如Cu和Zn）的同时亦存在有毒重金属（如Ni和Cd）超标的巨大风险。     

The sorption of Cd,Zn and Ni by soil clay fractions: Procedures for partition of bound forms and their interpretation

This work is the first of several projects concerned with the study of higher-affinity reactions of Cd, Zn and Ni ions with soil clay fractions. Procedures for the separation of sorbed metals into fractions of lower and higher affinity for soil surfaces are described and evaluated.Various concentrations of Cd, Zn and Ni were allowed to react in the presence of 0.01 M Ca(NO₃)₂ with soil clays for 1 week after stabilization of suspension pH. The adsorbed metals were partitioned by a brief extraction with 0.01 M Ca(NO₃)₂ and the resultant fractions, called specifically and non-specifically sorbed metals, were measured by radioisotopic procedures.Measured separation factors showed that the fraction of sorbed metals that was desorbed by a rapid Ca(NO₃)₂ extraction still had a preference, sometimes marked, over Ca on the soil clay fraction. Separation of fractions of sorbed metals on the basis of affinity was reproducible, but the boundary conditions defined by separation factors vary appreciably between adsorbents, with values in the range 3–20 for amounts sorbed equivalent to ≦ 0.05% of cation exchange capacity and for pH values < 7.The proportions of Cd, Zn and Ni bound at high-affinity sites were strongly dependent on experimental conditions of pH, equilibrium time and surface saturation in relation to each soil clay. Hence, comparisons of affinities of trace metals for soils by reliance on measures of total sorption only, without assessing the contribution of lower-affinity forms, may prejudice conclusions and predictions arising from studies of the possible retention of metal pollutants in soils and fixation of micronutrients from fertilizers.     

Simultaneous Sorption of Cd,Cu, Ni,Zn, Pb,and Cr on Soils Treated with Sewage Sludge Supernatant

Disposal of sewage sludge creates the potential for heavy metal accumulation in theenvironment. This study assessed nine soils currently used as Dedicated Land Disposal units(DLDs) for treatment and disposal of municipal sewage sludge in the vicinity of Sacramento,California. Adsorption characteristics of these soils for Cd, Cu, Ni, Zn, Pb, and Cr were studiedby simultaneously mixing these elements in the range of 0-50 µmol L-1 with sludgesupernatant and reacting with the soil using a soil:supernatant ratio of 1:30, pH = 4.5 or 6.5, andconstant ionic strength (0.01 M Na-acetate). The concentration of metals in the supernatant wasdetermined after a 24 hr equilibration period. Adsorption isotherms showed that metal sorptionwas linearly related to its concentration in the supernatant solution. The distribution coefficientKd (Kd = concentration on solid phase/concentration in solution phase) was computed as theslope of the sorption isotherm. The distribution coefficients were significantly correlated to soilorganic matter content for Ni, Cu, Cd, and Pb at pH 4.5 and for Ni, Cu, Zn, and Cd at pH 6.5.There was also a correlation between Kd and soil specific surface area but no relationship to othersoil properties such as CEC, clay content, and noncrystalline Fe and Al materials. Therefore, soilorganic carbon and surface area appear to be the most important soil properties influencing metaladsorption through formation of organo-metal complexes. The Kd values for all elements werehigher at pH 6.5 than at 4.5. Selectivity between metals resulted in the following metal affinitiesbased on their Kd values: Pb>Cu>Zn>Ni>Cd≈Cr at pH 4.5 andPb>Cu≈Zn>Cd>Ni>Cr at pH 6.5.     

Modelling the effects of ageing on Cd,Zn, Ni and Cu solubility in soils using an assemblage model

Ageing reactions can reduce trace metal solubility and can explain natural attenuation of contaminated soils. We modelled ageing reactions in soil with an assemblage model that considers slow reactions in Fe‐oxyhydroxides and reversible sorption on organic matter and clay minerals. Metal adsorption kinetics on Fe‐oxyhydroxides was obtained from data with synthetic oxyhydroxides. Metal solubility and isotopic exchangeability data were obtained from 28 soils amended with Ni, Zn, Cu and Cd metal salts and monitored for 850 days. The assemblage model was constructed in WHAM 6.0 and used soil properties and dissolved organic matter as input data. The model was first validated to predict dissolved metal concentrations, based on the concentration of isotopic exchangeable metals. The model overestimated metal solubility without parameter adjustment by mean factors of 4–7, and successful fits were obtained by increasing the specific surface area of Fe‐oxyhydroxides from measured values of synthetic systems to a value of 600 m² g^?1 recommended by other authors. The effect of ageing on the isotopic exchangeable metal fraction was subsequently modelled starting from the predicted fraction of metals present on Fe‐oxyhydroxides immediately after soil spiking. The observed isotopic exchangeable metal fractions of Ni, Zn and Cd agreed reasonably well with predicted values. The model predicts that ageing reactions are more pronounced at higher pH because metal sorption is increasingly directed to oxyhydroxide surfaces with increasing soil pH. Modelling fixation of Cu requires more information on fixation of that metal in organic matter.     

Long-term reactions of Ni, Zn and Cd with iron oxyhydroxides depend on crystallinity and structure and on metal concentrations

Iron oxyhydroxides are long-term sinks for toxic trace metals and are suggested as factors to explain long-term metal immobilization in soil. It is unknown how crystallinity and crystal structure of iron (Fe) oxyhydroxides affect the long-term kinetics of trace metal adsorption. Adsorption kinetics of nickel (Ni), zinc (Zn) and cadmium (Cd) on to four synthetic Fe oxyhydroxides (hydrous ferric oxide (HFO), ferrihydrite (FH), goethite (GT), haematite (HT)) were characterized in suspensions during 70 days at different initial metal concentrations and various pH values (3.8–7.0) maintained within 0.2 units. The slow reactions, defined as those occurring beyond day 1 were most pronounced in GT and least in HT. The extent of the slow reaction was surprisingly unrelated to crystallinity or microporosity as determined by N₂ adsorption. Freundlich adsorption isotherms fitted to the data show that ageing between 1 and 70 days decreases metal concentrations in solution by factors of 2–30 (Ni), 1–20 (Zn) and 1–4 (Cd) depending on the type of oxyhydroxide. These factors become significantly larger at smaller concentrations for Ni and Zn in some oxyhydroxides and this concentration dependency suggests that slow reactions are not only related to diffusion. The short-term adsorption strength of carrier-free metal radio-isotopes was similar at 1 or 70 days after reaction with these iron oxyhydroxides and excludes the possibility that long-term reactions are related to solid-phase transformations or changes in solution properties. The extent of slow reactions in GT decreased with decreasing pH and was less than a factor 2 within 70 days at pH 3.7. The results confirm that slow reactions in Fe oxyhydroxides can explain lessened metal availability by ageing in pH neutral soils. The uncertainty of their actual structure and crystallinity in soils does not allow quantitative predictions based on the behaviour of synthetic oxyhydroxides.     

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.

     

Temporal Patterns of the Wet Deposition of Zn,Cu, Ni,Cd and Pb: The Arcachon Lagoon (France)

We report here the first data set on wet deposition of heavy metals in the southwestern French coastal zone. In this region, there are two major sensitive coastal ecosystems: the Gironde Estuary and the Arcachon Lagoon. Chemical analyses of heavy metals were carried out by ICP-MS. Annual mean concentrations of the dissolved fraction in precipitation were 0.2, 3.4, 4.3, 8.1 and 30 μg L^-1for Cd, Ni, Cu, Pb and Zn, respectively. In terms of annual fluxes, these numbers are of the same order of magnitude as the fluxes measured in southeastern France, but are higher than those measured in western Brittany. When extrapolated to the entire Bay of Biscay, the annual wet dissolved fluxes of Cd, Ni, Cu, Pb and Zn are respectively 7, 110, 140 340 and 1440 t yr^-1. According to available data in the literature, the regional Cd, Cu, Pb and Zn atmospheric fluxes for the Bay of Biscay are of the same order of magnitude as riverine inputs (Loire and Gironde). On a daily or weekly time scale, we observed a strong variability of elemental fluxes: up to 20% of the annual dissolved flux may occur in a rain event shorter than 3.5 days. Although elements display generally parallel variations with time, they sometimes follow independent behaviours (e.g. Pb and Cd), suggesting that they may derive from different geographical and/or pollution sources.     

难溶态锌、镉对香根草抗氧化酶活性及锌、镉吸收的影响

采用土培根袋试验,研究了难溶态锌、镉对香根草生长、抗氧化酶活性、MDA含量及锌、镉吸收累积的影响.结果表明,锌、镉均不同程度抑制了香根草的生长,抑制作用均以锌镉交互＞镉＞锌,以锌、镉复合污染更加剧了对植物的胁迫,不同生长期(75 d和90 d)锌锅处理的香根草地上部和根系的SOD、POD、CAT活性及MDA含量均显著增加,且随重金属毒性增强,酶活性和MDA含量亦增加,香根草根系膜脂过氧化的程度大于地上部,香根草体内锌镉含量以地上部＜根系,但吸收的锌主要富集在地上部,吸收的镉则主要富集在根系,且随着生长期的延长,各锌镉处理的锌镉积累量明显增加.