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.     

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.     

洞庭湖区典型蔬菜土壤镉、铜、锌、铅含量状况及评价

采用单项污染指数和综合污染指数法对湖南洞庭湖区典型蔬菜土壤Cd,Cu,Zn,Pb含量状况进行了评价。结果表明,与湖南省潮土土壤背景值相比,土壤Cd,Cu和Zn含量明显富集,Pb含量总体不高。与国家土壤质量二级标准(GB15618-1995)相比,洞庭湖区蔬菜土壤以Cd污染为主,其次是Zn和Cu。Pb含量没有超标,其中湘阴县、沅江市、资阳区和赫山区蔬菜土壤环境质量为轻度污染,华容县处于警戒水平,需要修复治理或者改变土地利用方式。君山区和南县蔬菜土壤为清洁水平,适宜发展无公害蔬菜。污染风险高的区域土壤Cd,Cu和Zn之间存在极显著或显著正相关关系,但相关性弱。     

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.     

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.     

Cd,Cu, Pb and Zn Concentrations in Atmospheric Wet Deposition at a Coastal Station in Western Europe

Water, Air, &; Soil Pollution - Bulk rainfalls were sampled during ten months in the Eastern Channel (Northern France). Chloride and sodium are the heavily loaded major ions in wet deposition,...     

绿化植物废弃物对土壤中Cu Zn Pb和Cd形态的影响

利用自制的Cu、Zn、Pb和Cd污染的灰潮土和黄泥土,通过室内培养实验研究了不同绿化植物废弃物添加量和不同培养时间对这两种污染土壤中这4种重金属形态的影响。结果表明,绿化植物废弃物的加入抑制了Cu的活化,且添加60%绿化植物废弃物时有机结合态Cu的含量最高;绿化植物废弃物与污染土培养2～3个月时,残余态Zn的含量最高,对植物的毒害最小;绿化植物废弃物添加量为60%时灰潮土中有效态Pb含量较低,而添加量为30%时黄泥土中有效态Pb含量最低;绿化植物废弃物添加量的多少对灰潮土Cd形态的影响较小,但黄泥土中的Cd则随绿化植物废弃物量的增加活性逐渐减弱,且两种土壤均在培养2～3个月时可交换态Cd的含量最低。     

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.     

Distribution of Cd, Ni, Cr, and Pb in Amended Soils from Alicante Province (SE, Spain)

Heavy metals can be transferred from soils to other ecosystem parts and affect ecosystems and human health through the food chain. Today the use of biosolids to improve the nutrient contents of a soil is a common practice. Contamination of soils by potentially toxic elements (e.g., Cd, Ni, Cr, Pb) from amendments of biosolids is subject to strict controls within the European Community in relation to total permissible metal concentrations, soil properties and intended use. In this context, heavy metal concentrations were studied in agricultural soils devoted to vegetable crops in the province of Alicante (SE Spain), where an intensive agriculture takes place. This study is aimed at ascertaining the chemical partitioning of Cd, Ni, Cr, and Pb in agricultural soils repeatedly amended with sludge. Selected soil properties relevant to control the mobility and bioavaibility of heavy metals were analyzed for the general characterisation of these agricultural soils. The distribution of chemical forms of Cd, Ni, Cr, and Pb in five biosolids-amended soils was studied using a sequential extraction procedure that fractionates the metal into soluble-exchangeable, specifically sorbed-carbonate bound, oxidizable, reducible, and residual forms. The biosolids incorporation has modified the soil composition, leading to the increment of heavy metals. The residual, reducible, and carbonate-sorbed forms were dominant. Detailed knowledge of the soil at the application site, especially pH, CEC, buffering capacity, organic matter, clay minerals, and clay content, is essential.     

Changes in Concentrations of Cd,Zn, Mn,Cu and Pb in Spruce (Picea abies) Needle Litter During Decomposition

Spruce (Picea abies (L.) Karst) needle litter was placedin litterbags and incubated (≥6 yr) at five spruce standsin southern Sweden. The litterbags were collected twice a yearduring year 1–2 and thereafter once a year, for total analyses(conc. HNO₃) of Cd, Zn, Mn, Cu and Pb. The main objectiveswere to document changes in concentrations and amounts of theseelements during litter decomposition and to investigate factorscontrolling the changes.Concentrations of Cd, Zn, Cu and Pb increased to at least 0.5, 1.5, 3 and 13 times the initial concentration. During the latterpart of the incubations, concentrations became more stable ordecreased. Concentrations at which the metals are considered to be toxic to micro-organisms in the mor layer were not reached during the experiment. Generally, concentrations of Mn decreased.Total amounts of Cd, Zn and Mn had decreased by at least15, 24 and 43%, from the initial amount at the end of theexperiment. The total amount of Cu increased (>40%) before itstarted to decrease. The total amount of Pb increased by over230%. Thereafter it became more constant or decreased.According to a PCA, the dynamics of total amounts of Cd,Zn and Mn in the litter were similar, as were those of Pb and Cu.Furthermore, in most cases the heavy metal amounts on anysampling occasion differed more between than within sites. Thedynamics of total amounts of elements were more similar betweenadjacent sites than between more distant sites.     

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.     

Reduction of Pb,Zn and Cd Availability from Tailings and Contaminated Soils by the Application of Lignite Fly Ash

The effectiveness of lignite fly ash for stabilization of Pb,Zn and Cd in tailings and contaminated soils was examined. Flyash was mixed with the contaminated soil or oxidic tailingssamples at various doses and pot experiments were performed.The effectiveness of stabilization was mainly evaluated by thestandard US EPA TCLP toxicity test. The 5-stage sequentialextraction procedure was also applied to determine the form ofcontaminants in the fly ash amended soil or tailings samples.Complementary EDTA extraction tests were also carried out. Thefly ash treatment resulted in the reduction of TCLP solubilityof Pb, Zn and Cd to below the respective regulatory limits at5 and 10% w/w fly ash addition rates in tailings and soil,respectively. Speciation of lead, in the treated soil andtailings samples indicated that there was a significanttransition of the heavy metals form from the exchangeable andcarbonate fractions to reducible and residual, suggesting thatthe potential mechanisms of heavy metals retention are, apartfrom increase of pH, sorption on the oxides and hydroxidessurfaces and binding with the hydrated fly ash compounds.     

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.     

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.     

湖南4个典型工矿区大豆种植土壤Pb Cd Zn污染调查与评价

通过对湖南4个典型工矿区（郴州柿竹园矿区、郴州宝山矿区、衡阳水口山矿区、株洲清水塘工业区）大豆以及其种植土壤的采样调查,综合评价了4个工矿区大豆及其种植土壤重金属污染程度。结果显示：（1）4个工矿区21个采样点的大豆及其种植土壤已经受到了重金属污染。土壤中Pb、Cd、Zn的浓度范围分别为269.02～6450.35、3.04～23.93、104.22～381.91mg·kg-1,大豆籽粒中这3种重金属的浓度范围分别为4.69～20.05、0.81～5.48、24.87～190.48mg·kg-1,均已超过相应的标准。（2）21个采样点中大豆植株对Pb、Cd和Zn的生物富集系数大小依次为Cd〉Zn〉Pb,表明大豆植株对Cd富集能力大于Zn和Pb。（3）21个土壤样品中交换态Pb、Cd、Zn含量与大豆植株样品各部位中这3种重金属元素含量基本上存在着显著或极显著的正的线性关系。     

Changes in Cd,Cu, Ni,Pb and Zn Fractionation and Liberation Due to Mussel Shell Amendment on a Mine Soil

Mining activities are related to relevant environmental pollution issues that should be controlled. We used sequential extractions to fractionate Cd, Cu, Ni, Pb and Zn retained on unamended or mussel shell‐amended mine soil samples, all of them treated with a mixture of the five heavy metals (total metal concentration of 1·57 mmol L⁻¹), after 1, 7 and 30 days of incubation. In addition, we used the stirred flow chamber technique to study the release of each of the five heavy metals from these different unamended and shell‐amended soil samples. The results indicate that the shell amendment caused a decrease in the most soluble fraction, while increasing the most recalcitrant (least mobile) fraction. With equivalent implications, the stirred flow chamber experiments showed that mussel shell amendment was associated to a decrease in heavy metal release and increased retention. The highest mussel shell dose and incubation time caused the most relevant changes in pH values and thus in metal retention, also indicating the importance of pH modifications in the mechanism of retention acting in the amended samples. In view of these results, the use of mussel shell amendment can be encouraged to increase heavy metal retention in acid mine soils, in order to minimise risks of environmental pollution. Copyright © 2016 John Wiley & Sons, Ltd.     

Pb and Cd Concentrations in a Southern Bavarian Bog Profile and the History of Vegetation as Recorded by Pollen Analysis

In the lower part of a raised bog profile from Langegger Filz, southern Bavaria, the Pb and Cd concentrations were comparatively low while considerably higher concentrations of both elements were observed in the upper section of the profile. The peat layers with the highest concentrations of Pb and Cd were found to date from the Iron Age, the Roman Age, and the Middle Ages. The Fagus pollen curve reflects the beginning of a beech decline exactly in those peat layers in which the start of the Pb increase is visible. Therefore it appears that metal smelting caused a local release of heavy metals which were subsequently deposited in the raised bog. Metals could only be smelted when wood was cut and burned, and beech charcoal was preferred as it produces relatively high temperatures. The good agreement between the Pb concentration profile and the pollen analyses suggests that the bog provides an accurate record of atmospheric Pb deposition.     

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.

     

温州城市土壤Cu,Zn,Pb含量及其形态研究

分别采集了温州市区风景区、交通干线、住宅区、文教区、工业区土壤样品21个,郊区农田保护区土壤样品2个,测定了各土壤样品的基本理化性质和Cu,Zn,Pb,Cd含量。结果表明:各土样Cu,Zn,Pb的平均含量分别为(34.59±18.29)mg/kg,(169.40±52.97)mg/kg,(65.22±26.86)mg/kg,均超出温州土壤背景值。Cd仅在个别土样中检出,且浓度极低。各形态含量的分析结果表明,Cu,Zn,Pb均以残余态为主,分别为60.17%,50.95%,47.33%。Cu和Pb的酸提取态含量最低,Zn则是有机态含量最低。各形态含量与土壤基本理化性质的相关分析结果表明,Cu,Zn各形态与有机质含量的相关性最大,而Pb则与土壤基本理化性质之间无明显相关关系。     

The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.