Effect of Liming on the Plant Availability and Distribution of Zinc and Copper among Soil Fractions

Abstract

Information on the redistribution of applied micronutrients into different fractions as a result of lime application is important to predict plant accumulation of nutrients and to select appropriate chemical extraction procedures for evaluation of micronutrient availability. The present work was carried out to study the influence of liming on the availability and redistribution of zinc (Zn) and copper (Cu) among soil fractions. Additionally, the effect of liming was evaluated on the recovery of these micronutrients by different chemical extractants (Mehlich‐1, Mehlich‐3, and diethylenetriaminepentaacetate (DTPA), which were correlated with Zn and Cu concentrations in corn (Zea mays L.) plants and soil fractions (exchangeable, organic matter, amorphous iron oxides, and crystalline iron oxides). The results showed that Zn added to soil samples that did not receive lime was retained mainly in the exchangeable and organic matter fractions. The liming resulted in distribution of Zn into iron oxides and as a result decreased the plant accumulation of Zn. Mehlich‐3 was the most efficient extractant to predict the plant accumulation of Zn in the acid soils, whereas DTPA was the most efficient in the limed soils. The oxide crystalline fraction was the major fraction responsible for retaining Cu in the soils. However, Cu added to soil was distributed mainly into organic matter. Mehlich‐3 was the most suitable extractant for predicting the bioavailability of Cu in limed or unlimed soils.     

Availability of Cu and Zn in an acidic sludge-amended soil as affected by zeolite application and liming

Purpose  

Acidic soils exhibit high trace element availability compared to neutral pH soils, and thus, when trace metals are added (e.g. due to sewage sludge application), measures should be taken to reduce their mobility. In this experiment, we tested two such methods, liming and zeolite addition. The aim was to measure the availability, in ryegrass (Lolium perenne L.), of heavy metals (Cu and Zn) added to soil with sewage sludge in both acidic and limed soil.     

Labile pools of copper and zinc in calcareous soils as measured by DTPA and plant extraction

Abstract

Labile pools of Cu and Zn were measured on two calcareous soils from Saudi Arabia, using successive extraction with DTPA, and successive cropping followed by extraction with DTPA after cropping. The examined soils differed in their ability to supply Cu and Zn. The first DTPA extraction removed a major proportion of the labile pool, particularly in the sandy soil. The two soils showed a general decrease in extractable Cu and Zn with progressive extractions, with DTPA extractable Cu declining more rapidly than Zn. DTPA extractable Cu and Zn determined after cropping were highly correlated with DTPA extractable Cu and Zn values obtained after successive extractions. The results gave evidence on both the contribution of element dissolution from insoluble forms with progressive extraction or cropping, and the usefulness of the DTPA extractant for monitoring the availability of Cu and Zn in these calcareous soils.     

黄河三角洲不同土地利用土壤有效态微量元素提取与丰缺评价

利用EDTA、DTPA、M3和ASI 4种提取剂对黄河三角洲不同利用方式土壤中Fe、Mn、Cu、Zn 4种微量元素有效形态进行提取,探讨不同提取剂对土壤微量元素的提取效果,并以DTPA提取的结果为基础,评价Fe、Mn、Cu、Zn 4种元素在土壤中的丰缺状况。结果表明:EDTA对4种元素的提取能力最强,M3提取能力相对较弱,但各提取剂对不同利用方式土壤微量元素的提取能力并不一致;DTPA所提取的微量元素有效态含量与总量相关性最好,其相关性程度均达到显著或极显著水平,明显优于其他3种提取剂;土壤中有效态含量较为丰富的元素是Cu,其含量范围为0.62～2.31mg/kg,除未利用地土壤有效Cu为中等水平外,其他3种用地类型中土壤有效Cu均达到丰富和极丰富水平,而土壤有效Mn含量范围为2.2～7.54mg/kg,4种用地类型土壤有效Mn均处于较低和极低的水平。     

AB‐DTPA and Mehlich III soil tests unable to predict copper available to creeping bentgrass

Abstract

Copper (Cu) can be toxic to creeping bentgrass (Agrostis palustris ’Penncross') grown in sand‐based systems. Plant analysis is not always a reliable predictor of toxic levels of Cu in these sand‐based systems. Therefore, there is need for soil analysis to detect potentially toxic Cu concentrations in soil. The objective of this research was to determine the effectiveness of AB‐DTPA and Mehlich III soil tests to assess Cu availability to ‘Penncross’ creeping bentgrass grown in calcareous and silica sand/peat media. Samples of sand/ peat were removed from greenhouse pots, air dried, and Cu was analyzed by inductively coupled argon plasma spectrometry (ICAP/IRIS). Correlations were made between extracted Cu and Cu in the shoot and root tissue of the plant. The AB‐DTPA‐extractable Cu was 24% and 42% higher for the calcareous sand at the 400 and 600 mg kg^‐1 Cu treatments, respectively, when compared with Cu extracted from the silica sand. The Mehlich III soil test extracted 25% more Cu at the 400 mg kg^‐1 Cu treatment and 37% more Cu at the 600 mg kg^‐1 Cu treatment from the calcareous as compared to the silica medium. Shoot and root tissue Cu concentrations were higher at all Cu treatment levels for plants grown in silica sand. Although correlations were significant between Cu extracted from both sands by the AB‐DTPA and Mehlich III soil tests and Cu in the shoot and root tissue of plants, these extractants were unsuccessful in determining Cu availability from the two sand medium. This research indicates a need for a soil test which can be effectively used to extract plant‐available Cu from sand‐based systems.     

Availability and speciation of cadmium added to a calcareous soil under various managements

Potential risks for human health and adverse effects on soil quality caused by accumulation of cadmium (Cd) in soil at concentrations around or exceeding current European Union (EU) permitted limits have long been recognized. We have assessed availability and partitioning of Cd in a Mediterranean calcareous soil under four management regimes. Cadmium was added as a single pulse of CdSO₄ at the maximum Cd concentration established by the EU for sludge‐amended agricultural soils and concentrations exceeding the mandatory limits. Soils were treated with 0, 3, 10 and 50 mg Cd kg^?1 soil, incubated moist and analysed at selected times up to 600 days. Cadmium availability and distribution in soil were studied by neutral electrolyte and sequential extractions. During the incubation, the availability of Cd was not strictly dependent on the amount of metal added as the exchangeable fractions were similar shortly after the additions of Cd regardless of its initial concentration. Sequential extractions showed that for concentrations of 3 and 10 mg Cd kg^?1 soil Cd was evenly distributed among the soil phases, and its mobility was reduced mainly by adsorption on carbonates. At Cd concentrations exceeding 10 mg Cd kg^?1 soil a residual fraction appeared, perhaps from precipitation of Cd. Most of the Cd was associated with carbonates; land management and organic matter content had no major effects on the Cd distribution among different soil phases. The extraction protocols were effective for studying the fate of Cd in this calcareous soil as almost all of the Cd added was recovered. However, the introduction of a preliminary step with buffered NH₄NO₃ improved the determination of the most labile pools. Availability of Cd in calcareous soils estimated with reference methods appeared to be very small even when its total concentration far exceeded the current EU limits.     

Effect of elemental sulphur and sulphur containing waste in a calcareous soil in Turkey

The effect of elemental sulphur (S) and S containing waste applications on soil pH treated with 0–2,000 kg ha^‐l elemental S, and 0–100 tons ha‐¹ of waste was determined in the field and the pots. Sorghum (Sorghum bicolor L.) was grown in a Lithic Xerorthent soil which was taken from where the field experiment was conducted in pots receiving 5 kg soil. Plants were harvested 20 weeks after planting or 30 weeks after the applications for determination of dry matter yield and phosphorus (P), iron (Fe), zinc (Zn), manganese (Mn), and copper (Cu) uptake by shoots. EC, NaHCO₃‐extractable P, and DTPA‐extractable Fe, Zn, Mn, Cu also were measured in pot soil at the 5th, 10th, and 30th weeks. All treatments led to a decrease in soil pH though pH tended to increase again during course of time in both field and pot experiments. The both elemental S and waste applications in pot experiment caused an increase in dry matter yield and P, Fe, zinc (Zn), Mn and Cu uptake (mg pot^‐1) by shoots in sorghum plant. There was also an increase in EC of soil due to both applications of S. The concentration of available P extracted by NaHCO₃ in the pot soil, though not significantly different, was slightly higher compared with the control. Waste applications increased DTPA‐extractable Fe content of the soil, DTPA‐extractable Mn and DTPA‐extractable Cu. DTPA‐extractable Zn content, however, was reduced by the same applications.     

Soil cadmium stabilization using an Iranian natural zeolite

In recent years, natural substances such as zeolite have been used to absorb heavy metals in soil in an attempt to decrease their availability to plants. Compared to other techniques, the use of zeolite is fast, clean, and inexpensive. This research was carried out to investigate the effects of an Iranian natural zeolite (clinoptilolite) on stabilizing Cd-contaminated soil treated with 0.01 M CaCl₂ leaching solution. Zeolite from Firoozkouh (Tehran Province) was added to four soils from Gilan province, northern Iran. The stabilization of Cd in soils mixed with zeolite was measured in both column and batch experiments. The results from the batch experiment showed that application of zeolite to soil reduced Cd leaching in all the contaminated soils. When more zeolite was added to soil, lower Cd concentrations were detected in the leaching solution. When 15% zeolite was applied, Cd concentration in the leachate decreased to below 0.1 mg l^− 1. Cadmium depth analysis showed little migration of Cd in sand and clay textures with no zeolite addition and after adding 15 and 75 pore volumes of leaching solution, the remaining Cd levels were 12% and 35% of the original Cd concentration, respectively. However, these values for 9% zeolite treatments were 97% and 99%, respectively. The higher cation exchange capacity of the zeolite/soil mixture and the higher pH levels were responsible for stabilizing Cd in these soils. The effect of preventing heavy metals from leaching was found to be more pronounced when zeolite was applied to clay soils.     

Kinetics of Copper Desorption from Highly Calcareous Soils

Abstract

Desorption of copper (Cu) is an important factor in determining Cu availability in calcareous soils. Kinetics of native and added Cu desorption by DTPA (diethylene‐triaminepentaacetic‐acid) from 15 highly calcareous soils of southern Iran were studied in a laboratory experiment. Our results showed that two constant‐rate, Elovich, simple Elovich, and parabolic‐diffusion equations were the best‐fitted equations among eight kinetic models used. The copper desorption pattern based on the parabolic‐diffusion equation revealed that the rate of native Cu desorption was higher in the first 2 h followed by a slower release rate, which suggests that two different mechanisms are involved. The trend may describe why the DTPA soil test has been considerably successful in predicting Cu availability in calcareous soils. Stepwise multiple regression equations indicated that CCE (calcium carbonate equivalent), CEC (cation exchange capacity), and clay content are the most important soil characteristics that predict the rate constants of the kinetic models. Mean extractant recovery percentage (ERP) of the soils was only 20%, which indicated that after 20 days, DTPA extracted only one‐fifth of added Cu. Regression equations indicated that as soil OM (organic matter) content increased, the value of ERP decreased. From results reported herein it seems that CCE, CEC, and clay are the most important factors controlling Cu release from highly calcareous soils of southern Iran. However, the initial soil Cu desorption rate is probably controlled by CEC.     

Optimization of DTPA and calcium chloride extractants for assessing extractable metal fraction in polluted soils

Abstract

Metal availability in soils is often assessed by means of extraction with chemical solutions, among others the chelating agent DTPA (diethylenetriaminepentaacetic acid) and the non‐buffered salt calcium chloride (CaCl₂). The same procedures are used for polluted soils that were originally created to assess the nutrient status of arable soils. We studied the influence of various parameters (type of shaker, shaking time, soil to solution ratio, and concentration of chemical extractant) and modify the DTPA and CaCl₂ extraction procedures to make them suitable for the study of polluted soils. The chosen extraction ratio and extractant concentration were the followings: 8 g/20 mL of 0.1 MCaCl₂ and 2 g/20 mL of 0.005 M DTPA. The optimized procedures were applied to nine soil samples affected by different sources of pollution (mine works, vehicle emissions, and various industries). Cadmium (Cd) showed the highest extractability with both extractants. Depending on the soil, copper (Cu) and zinc (Zn) (using DPTA) and Cu and manganese (Mn) (using CaCl₂) were the followings in the extractable amounts. Cadmium, Cu, and Zn were highly correlated in both extractions and with total contents.     

Chemical and organic immobilization treatments for reducing phytoavailability of heavy metals in copper‐mine tailings

This study was conducted to evaluate the efficiency of diammonium phosphate (DAP), agricultural limestone (lime), and green‐waste compost mixed with 30% treated sewage sludge (GCS) applied alone or in combination as chemical immobilization treatment using tomato as a test crop. Mine waste was collected from an abandoned copper‐mine tailing site at Mynydd Parys, Anglesey (UK). Lime was applied at the rate of CaCO₃ equivalent (CCE, pH = 7), DAP at the rate of 23 g P per kg substrate, and 10% by weight, GCS as sole application. Half rate of each amendment was also tested as a combined treatment and an untreated substrate (control). Plant‐available metals (Cd, Cu, Fe, Pb, and Zn) were measured in substrate with conventional diethylenetriaminepentaacetic acid (DTPA) and sequential Ca(NO₃)₂ extraction. Plant–dry biomass yield was significantly (p < 0.001) increased by the combined application of all the three amendments while sole application of DAP reduced yield by 4‐fold compared to unamended soil probably due to P toxicity. Addition of lime reduced the DTPA‐extractable Cu, Fe, and Zn by 75%, 81%, and 85%, respectively, while Pb availability was reduced by 88% in combined DAP + lime + GCS treatment compared to control. The extraction capacity of DTPA was higher than that of Ca(NO₃)₂ by 3‐fold for Cu and Fe, 8‐fold for Pb, and 2‐fold for Zn. The leaf‐tissue concentrations of Cu and Fe were reduced by 77% and 83% in the lime + GCS amendment, respectively, while both Pb and Zn were reduced by 89% and 33%, respectively, in substrate treated with the combined application of all three amendments. These results suggest that alkaline amendments (both lime and GCS) were effective in reducing the phytoavailability of Cu, Fe, and Zn while DAP mixed with either GCS or lime was effective in reducing Pb availability.     

Boron behavior in apple plants in acidic and limed soil

In dry Mediterranean‐type climates boron (B) levels may naturally be high and even toxic to plants. Although liming of an acidic soil is expected to decrease B levels, it is not known what the effects would be in such areas of high‐B soils, especially in B‐sensitive crops such as apple trees. Thus, our aim was to study the behavior of added B in newly planted apple rootstocks in an acidic soil which was limed to pH 6.5 in an outdoor pot experiment. Added B increased significantly B extractability from soil, and B levels were lower in the limed compared to the acidic soils. Plant B concentrations also increased with added B but differences between limed and unlimed soils were not evident, because plant B did not seem to reflect changes in B behavior in soil. However, B uptake was significantly increased with added B, and was further increased with liming, contrary to what the soil extractions indicated, due to improved growth conditions. Our results show that although liming decreased soil B levels, at the same time it did not affect plant B concentration and accelerated the uptake of added B, indicating a possibility for increased soil‐to‐plant mobility of B.     

Immobilization of Zinc Fertilizer in Flooded Soils Monitored by Adapted DTPA Soil Test

Zinc (Zn) deficiency is a persistent problem in flooded rice (Oryza sativa L.). Severe Zn deficiency causes loss of grain yield, and rice grains with low Zn content contribute to human nutritional Zn deficiencies. The objectives of this study were to evaluate the diethylenetriaminepentaacetic acid (DTPA) extraction method for use with reduced soils and to assess differences in plant availability of native and fertilizer Zn from oxidized and reduced soils. The DTPA‐extractable Zn decreased by 60% through time after flooding when the extraction was done on field‐moist soil but remained at original levels when air‐dried prior to extraction. In a pot experiment with one calcareous and one noncalcareous soil, moist‐soil DTPA‐extractable Zn and plant Zn uptake both decreased after flooding compared with the oxidized soil treatment for both soils. In the flooded treatment of the calcareous soil, both plant and soil Zn concentrations were equal to or less than critical deficiency levels even after fertilization with 50 kg Zn ha^?1. We concluded that Zn availability measurements for rice at low redox potentials should be made on reduced soil rather than air‐dry soil and that applied Zn fertilizer may become unavailable to plants after flooding.     

Effects of long‐term applications of various nitrogen sources on chemical soil properties and composition of bromegrass hay

Effects of 15 annual applications (from 1979 to 1993) of ammonium nitrate (AN), urea, ammonium sulfate (AS), and calcium nitrate (CN) applied at 168 and 336 kg N ha^‐1 to bromegrass (Bromus inermis Leyss.) on soil acidification, and concentration of aluminum (Al), iron (Fe), manganese (Mn), zinc (Zn), and copper (Cu) in soil and in hay were investigated in a field experiment on a thin Black Chemozemic (Typic Boroll) soil in Alberta, Canada. Soil was acidified and the concentration of extractable Al, Fe, and Mn was increased by nitrogen (N) application, but the magnitude varied with N source. Soil acidification was greatest with AS, followed by AN and urea, with no effect of CN. At 336 kg N ha^‐1 rate, soil was acidified to a depth of 10, 15 and 30 cm with urea, AN AS, respectively. Soil acidification was also greater at 336 kg than 168 kg N ha^‐1. The CaCl₂‐extractable Al and Fe in the 0–15 cm layer increased with N application, which closely followed the decrease in soil pH from various N sources. Extractable Al and Fe concentration in the 15–30 cm layer increased in response to reduction in soil pH by AS only, and there was no change in the extractable Al and Fe below the 30‐cm depth by any form of N. The DTPA‐extractable Mn in soil generally changed in response to N application. There was no effect of N source on the DTPA‐extractable Zn and Cu in soil. When soil pH had been lowered from N application, the concentration of Al in hay decreased while Zn concentration increased. The Mn concentration in forage increased markedly in response to reduced soil pH from application of AN, urea and AS. There was no effect of N fertilization on the Cu and Fe concentration in hay. In conclusion, the magnitude of soil acidification, changes in the Al, Fe, and Mn concentrations in soil and changes in the Al, Zn, and Mn concentrations in bromegrass hay varied with N source. The results suggest the need for periodic monitoring of soil pH and consideration of liming costs in the economics of various N fertilizers.     

Effect of zeolite application and soil pH on cadmium sorption in soils

Abstract

In this study the influence of zeolite application and soil liming on cadmium (Cd) sorption by soils in Greece was investigated. The zeolite was natural and consisted mainly of clinoptilolite. The soil samples were strongly acid surface horizons of an Alfisol limed from a pH of 4.0 to 8.5, and a neutral Bt horizon. The result showed that liming and zeolite application substantially increased sorption of Cd in the soils. Cadmium sorption was described adequately by the Freundlich equation whereas the Langmuir model failed to describe Cd sorption in the soils. The Freundlich constant K increased in value by zeolite application as well as by soil liming. A strong relationship was observed between this parameter and soil pH. A high percentage of cadmium sorbed was released in the desorption procedure. The amount of Cd released was reduced by zeolite application as well as by soil liming. It is concluded that zeolite application as well as soil liming increased Cd sorption by the soils.     

Zinc Release Characteristics from Calcareous Soils using Diethylenetriaminepentaacetic Acid and Other Organic Acids

Adsorption and desorption reactions of zinc (Zn) in soils control its availability to plants. In the present investigation, time-dependent Zn release was evaluated using three organic acids [diethylenetriaminepentaacetic acid (DTPA), citric acid, and maleic acid] to depict the Zn fraction controlling Zn release rate from slightly calcareous to calcareous soils. Eight surface and two subsoil samples of selected soil series varied in their physicochemical properties, amount of Zn held in different chemical pools, and Zn-retention capacities (21–61%). Each soil was extracted for a total period of 24 h at 1:10 soil/extractant suspension ratio using 0.005 M DTPA. The time-dependent parabolic diffusion model best described the Zn release in six consecutive extractions. Soils differed in cumulative Zn extracted (1.09–3.81 mg kg^?1 soil) and Zn release rate. Under similar conditions, three soils differing in Zn-retention capacities were also extracted with five different concentrations (0.01–0.0001 M) of citric and maleic acids. Although both maleic and citric acids released soil Zn at greater rates and in greater amounts than DTPA, maleic acid was more efficient. Soil Zn bound to amorphous iron (Fe) + manganese (Mn) oxides was the main Zn pool that controlled Zn release characteristics.     

Surface Liming and Zinc Availability in a Long‐Term Experiment under No‐Till System

No‐till (NT) system with crop rotation is one of the most effective strategies to improve agricultural sustainability in tropical and subtropical regions. To control soil acidity in NT, lime is broadcast on the surface without incorporation. The increase in soil pH due to surface liming may decrease zinc (Zn) availability and its uptake by crops. A field experiment was performed in Paraná State, Brazil, on a loamy, kaolinitic, thermic Typic Hapludox to evaluate Zn bioavailability in a NT system after surface liming and re‐liming. Dolomitic lime was surface applied on the main plots in July 1993 at the rates of 0, 2, 4, and 6 Mg ha^?1. In June 2000, the main plots were divided in two subplots to study of the effect of surface re‐liming at the rates of 0 and 3 Mg ha^?1. The cropping sequence was soybean [Glycine max (L.) Merrill] (2001–2 and 2002–3), wheat (Triticum aestivum L.) (2003), soybean (2003–4), corn (Zea mays L.) (2004–5), and soybean (2005–6). Soil samples were collected at the following depths: 0–0.05, 0.05–0.10, and 0.10–0.20 m, 10 years after surface liming and 3 years after surface re‐liming. Soil Zn levels were extracted by four extractants: (i) 0.005 mol L^?1 diethylenetriaminepentaacetic acid (DTPA) + 0.1 mol L^?1 triethanolamine (TEA) + 0.01 mol L^?1 calcium chloride (CaCl₂) solution at pH 7.3 (DTPA–TEA), (ii) 0.1 mol L^?1 hydrochloric acid (HCl) solution, (iii) Mehlich 1 solution, and (iv) Mehlich 3 solution. Zinc concentrations in leaves and grains of soybean, wheat, and corn were also determined. Soil pH (0.01 mol L^?1 CaCl₂ suspension) varied from 4.4 to 6.1, at the 0‐ to 0.05‐m depth, from 4.2 to 5.3 at the 0.05‐ to 0.10‐m depth, and from 4.2 to 4.8 at the 0.10‐ to 0.20‐m depth, after liming and re‐liming. Zinc concentrations evaluated by DTPA–TEA, 0.1 mol L^?1 HCl, Mehlich 1, and Mehlich 3 solutions were not changed as a result of lime rate application. Re‐liming increased Zn concentrations extracted by 0.1 mol L^?1 HCl at 0–0.05 m deep and by DTPA–TEA at 0.05–0.10 m deep. Surface‐applied lime promoted a decrease in Zn concentrations of the crops, mainly in grains, because of increased soil pH at the surface layers. Regardless of the liming treatments, levels of Zn were sufficient to soybean, wheat, and corn nutrition under NT.     

Fractions of Copper in Soil under a Long-Term Experiment and Their Contribution to Copper Availability and Uptake by Maize—Wheat Cropping Sequence

ABSTRACT

Soil and plant samples were collected from on-going long-term experiment at Indian Agricultural Research Institute, New Delhi farm to study the distribution of various forms of copper (Cu) and their contribution to availability and plant uptake in maize (Zea mays L.)—wheat (Triticum aestivum L.) sequence. The optimum dose-based treatments selected for the study were nitrogen-phosphorus-potassium (NPK), NPK + Farmyard manure (FYM), NPK+ zinc (Zn) and control (no fertilizer or manure). Uptake of Cu by maize and wheat varied from 17.0 to 37.5 and 60.8 to 149.3 g ha^?1, respectively, under different treatments. Copper uptake by wheat was significantly higher under 100% NPK + FYM than that with 100% NPK. There was no significant difference among the treatments with respect to diethylenetriaminepentaacetic acid (DTPA)-extractable Cu in 0–15, 15–30, 30–45, and 45–60 cm soil layers. However, with increasing depth of soil, it showed declining trend under all the treatments. Mean value of total Cu was 28, 32, 25, and 21 mg kg^?1 in 0–15, 15–30, 30–45, and 45–60 cm depths, respectively. Major part of the total Cu was present as residual form. Sorbed copper (SORB–Cu) contributed directly towards its availability both in pre-sowing maize and post-harvest wheat soil samples. SORB–Cu and organic matter bound Cu (OM–Cu) contributed directly towards the uptake by the component crops. Copper associated with easily reducible manganese, carbonate, and iron and aluminum oxides were most recalcitrant forms present in soil and their effects on availability and crop uptake were adverse.     

Changes in copper content and distribution in young,old and abandoned vineyard acid soils due to land use changes

We studied total Cu content and its distribution in 33 surface soil samples cultivated with vines for variable lengths of time in the Monterrei designation of origin (DO), located in Galicia (NW Spain). The study was focused on the influence of land use changes on soil degradation by effect of Cu accumulation and availability. Total copper concentration in soils ranged from 25 to 272 mg kg⁻¹. The time during which each soil was cultivated with vines was found to affect both the total concentration of copper and its distribution. The average concentration of copper in young vineyards was 64 mg kg⁻¹, whereas those in old and abandoned vineyards were 100 and 132 mg kg⁻¹, respectively. Copper bound to organic matter and to amorphous inorganic colloids were greater in old and abandoned vineyards, where they accounted for 51 and 52 per cent, respectively, of total copper, than in young vineyards (39 per cent). Copper bound to crystalline Al and Fe colloids accounted for 21, 22 and 12 per cent of total Cu in old, abandoned and young vineyards respectively. The prevalence of Cu bound to the organic fraction reduces the adverse environmental effects of this metal on soil organisms and plants. However, some management practices such as organic matter addition or liming should be implemented in order to delay or avoid soil degradation in young vineyards. For abandoned vineyards, the influence of new land uses on potential Cu mobilisation necessitates careful examination. Copyright © 2007 John Wiley & Sons, Ltd.     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.