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.     

Soil micronutrient contents and relation to other soil properties in Ethiopia

Abstract

Alfisols, Vertisols, Inceptisols, Aridisols, Mollisols, and Entisols were sampled (0–30 cm) from 32 locations across Ethiopia. The soils were analyzed for copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe) contents using 0.005 M diethylene triamine pentaacetic acid (DTPA), 0.05 M hydrochloric acid (HC1), and 0.02 M ethylene diamine tetraacetic acid (EDTA) extractants. EDTA extracted more of each micronutrient than DTPA, which extracted greater amounts than HC1. The quantities of EDTA and DTPA‐extractable micronutrients were significantly correlated, and were in the order: Mn>Fe>Cu>Zn. The order of HCl‐extractable micronutrients was Mn>Fe>Zn>Cu. Micronutrient contents of Mollisols, Vertisols, and Alfisols were usually greater than those of the other soils, and Entisols usually had the lowest micronutrient contents. The contents were mostly positively correlated with clay and Fe₂O₃ contents, but negatively correlated with soil pH and A1₂O₃contents. While comparison of DTPA‐ and EDTA‐extractable micronutrients with critical levels showed that most soils had adequate amounts of the micronutrients for crops, the amounts extracted by HC1 were below critical levels in most soils. Since the critical levels that were used in the comparisons were not established in Ethiopia, calibration of the soil contents of these micronutrients with crops grown in Ethiopia is required to identify the most suitable extractant(s).     

Evaluation of Soil Tests for Plant‐available Mercury in a Soil–Crop Rotation System

A reliable soil test is needed for estimating mercury (Hg) availability to crop plants. In this study, four extraction procedures including 0.1 M hydrochloric acid (HCl), 1 M ammonium acetate (NH₄OAc) (pH 7.0), 0.005 M diethylenetriaminepentaacetic acid (DTPA), and 0.1 M calcium chloride (CaCl₂) (pH5.0) were compared for their adequacy in predicting soil Hg availability to crop plants of a rice–cabbage–radish rotation system. The amounts of Hg extracted by each of the four procedures increased with increasing equilibrium time. The optimal time required for extraction of soil Hg was approximately 30 min, though it varied slightly among the four extractants. The amounts of Hg extracted decreased with increasing soil/solution ratio, and a soil/solution ratio of 1:5 appeared to be adequate for soil Hg availability tests. The amounts of Hg extracted increased in the order of NH₄OAc < CaCl₂ < DTPA < HCl in silty loam soil (SLS) soil, and the order was NH₄OAc < CaCl₂ ≈ DTPA < HCl in yellowish red soil (YRS) soil. Significant positive correlations among the four extractants were obtained in SLS soil. In contrast, the correlations were poor in YRS soil, especially for HCl. There were significant correlations between concentrations of Hg in edible tissue of three plants and the amounts of soil Hg extractable to the four extractants for soil–rice system and soil–radish system, but not for soil–Chinese cabbage system. The 0.1M HCl extraction overall provided the best estimation of soil‐available Hg and could be used to predict phytoavailability of Hg in soil–crop systems.     

Prediction of Soil Cadmium Bioavailability to Cacao (Theobroma cacao L.) using Single-Step Extraction Procedures

In this study, complexation extractants ammonium bicarbonate diethylene triamine pentaacetic acid (AB-DTPA), diethylene triamine pentaacetic acid (DTPA), and ethylene diamine tetraacetic acid (EDTA) and mild cation-exchange extractants calcium chloride (CaCl₂) and ammonium nitrate (NH₄NO₃) were used to evaluate the bioavailability of soil cadmium (Cd) to cacao in the field. Among the five extractants, the extractable Cd generally followed the order EDTA > DTPA > AB-DTPA > CaCl₂ > NH₄NO₃. Correlation analysis was done between the extractable Cd in soil and total Cd content of cacao tissues (nibs, shells, leaves, and pods). The Cd extracted by CaCl₂ and NH₄NO₃ was significantly (P < 0.05) correlated with some of the tissues but their Pearson correlation coefficients were weak. In contrast, extractants AB-DTPA, DTPA, and EDTA showed stronger, significant correlations to the Cd concentration in all four tissues. Overall, regression analysis demonstrated that AB-DTPA, DTPA, or EDTA can be used to predict bioavailable Cd in soils for cacao. Of these, AB-DTPA and DTPA both showed the strongest correlations compared to EDTA. However, the ease of preparation and the superior shelf-life of DTPA over AB-DPTA make it the preferred reagent for Cd bioavailability extractions from cacao soils and is currently being used to develop cost-effective soil treatments to reduce bioavailable Cd to cacao plants.     

Influence of residual phosphate fertilizer on labile and extractable zinc in hawaii soils

Abstract

Zinc availability was studied using five soils from Hawaii which had histories of massive phosphorus applications. Heavy phosphate fertilization usually increased extractable Zn, irrespective of the extractant used. The extra extractable Zn associated with the added P probably came from Zn as an accessory element in the fertilizer. Treble superphosphate commonly used in Hawaii contains about 1400 ppm Zn. The Zn content of phosphate fertilizers must be considered before making statements about the effect of fertilizer P on Zn solubility and availability in soils.

Two solutions (0.1N HCl and 0.005M DTPA) were compared as Zn extractants for Hawaii soils. DTPA extracted less Zn than 0.1N HCl. Zinc extracted by repeated HCl treatment was more closely related to the labile Zn pool (E‐values and L‐values) than was DTPA‐extractable Zn. The results suggest that 0.1N HCl extractable Zn, Zn E‐value and Zn L‐value measured the quantity of a single fraction of soil Zn.

Repeated extraction of soil with 0.1N HCl seems to be a suitable procedure for evaluating the Zn status of acid, highly weathered soils of Hawaii.     

Appraisal of Some Soil Tests for Zinc Availability to Late‐Sown Wheat Grown in Mollisols

Abstract

Five soil extractants, namely, 0.005 M diethylene triamine pentaacetic acid (DTPA) (pH 7.3), 0.005 M DTPA+1 M ammonium bicarbonate (pH 7.6), Mehlich 3, 0.01 M ethylene diamine tetraacetic acid (EDTA)+0.05 M ammonium carbonate (pH 8.6), and 1 M magnesium chloride (MgCl₂) (pH 6.0), were evaluated to predict the response of wheat to zinc (Zn) application in Mollisols. These extractants could be arranged in the following decreasing order of their Zn extracting power: Mehlich 3>0.005 M DTPA+1 M ammonium bicarbonate>0.01 M EDTA+0.05 M ammonium carbonate>0.005 M DTPA>1 M MgCl₂. The critical limits of Zn in soil, below which the yield response to late sown wheat (var. UP‐2338) to Zn application could be expected, were 0.57 mg 0.005 M DTPA (pH 7.3) extractable and 1.72 mg Mehlich 3–extractable Zn kg^?1 soil. The critical limit of Zn in whole shoot at 60 days after emergence was found to be 26.1 mg Zn kg^?1 plant tissue. The DTPA and Mehlich 3–extractable soil Zn also correlated significantly and positively with Zn concentration in whole shoot at 60 days after emergence and total Zn uptake by wheat at harvest.     

Evaluation of universal extractants for determining plant available potassium in intensively cultivated soils

Abstract

Eighteen soils from northwestern Switzerland were used to study the value of seven universal extractants (CaCl₂; DB‐DTPA; Mehlich 1, 2, and 3; Morgan‐Wolf; and NH₄OAc‐EDTA) for predicting plant available potassium (K) as compared to a bioassay (a modified Neubauer test with winter rye). These extractants were evaluated on the basis of K uptake by the bioassay test and the soil K status. In order to create the sufficiency level of exchangeable K for plant growth, soils were treated with 0, 20, 40, 80, and 160 mg K/kg of soil. The range of K uptake by the bioassay tests was between 89.2 and 403.0 mg/kg of soil for the control pots, and 136.6 to 495.8 for the K treatments with optimal conditions for plant growth. The average amounts of K extracted by the seven universal extractants, in ascending order, were: CaCl₂ < Morgan‐Wolf < Mehlich 1 < Mehlich 2 < NH₄OAc‐EDTA < Mehlich 3 < DB‐DTPA. The highest simple correlation with K uptake versus the bioassay test was obtained with the DB‐DTPA (r = 0.89) extractant and the lowest with the Mehlich 1 (r = 0.53) extractant. The DP‐DTPA, NH₄OAc‐EDTA and Mehlich 3‐K procedures showed an advantage over K procedures based on water soluble and exchangeable K pools in the investigated soils in order to predict the amount of plant‐available K. A simple regression and the Cate‐Nelson graphic method offer the possibility of assessing the soil‐K status using K values obtained by these universal extractants and to calibrate them against K forms as follows: exchangeable, water soluble, and non‐exchangeable.     

Measuring reactive metal in soil: a comparison of multi‐element isotopic dilution and chemical extraction

The isotopically exchangeable metal pool (E‐value) of zinc (Zn), cadmium (Cd) and lead (Pb) were simultaneously measured, using stable isotope dilution, in soils contaminated by Pb/Zn mining activities and varying in properties likely to affect metal reactivity, including pH, organic matter content, metal concentration and land use. E‐values were compared with single and sequential extraction schemes. Results showed a wide range of metal reactivity (approximately 1–100% of total) depending on the extent of contamination and on the prevailing soil conditions. Across the range of soils, the E‐values showed no consistent correspondence to any single chemical extraction procedure (EDTA, DTPA and HNO₃) although there was reasonable agreement with the extractants 0.05 m EDTA and 0.43 m HNO₃ in acidic organic soils. Extraction with 0.005 m DTPA substantially under‐estimated the isotopically exchangeable metal content. E‐values corresponded reasonably well with the exchangeable metal (fraction 1 (F1) of the sequential extraction procedure) in calcareous soils but relatively poorly and inconsistently with F1–F2, F1–F3 or F1–F4 in acidic‐neutral soils. Operational aspects associated with determination of multi‐element E‐values are discussed.     

Chemical Fractions of Mn in Acidic Soils and Selection of Suitable Soil Extractants for Assessing Mn Availability to Maize (Zea Mays L.)

Twenty surface (0–15 cm) samples of acidic soils were analyzed for water soluble (WS), exchangeable (EX), lead displaceable (Pb-disp.), acid soluble (AS), manganese (Mn) oxide occluded (MnOX), organically bound (OB), amorphous Fe oxide occluded (AFeOX), crystalline iron (Fe) oxide occluded (CFeOX) and residual (RES) fractions of Mn, and also for extractable Mn in some common soil extractants: (diethylenetriaminepentaacetic acid (DTPA) (pH 7.3), DTPA (pH 5.3), AB-DTPA (pH 7.6), Mehlich-3 (pH 2.0), Modified Olsen, 0.005 M calcium chloride (CaCl₂), 1 M magnesium chloride (MgCl₂) and ion exchange resins. The WS-Mn fraction showed a significant and positive correlation with Mn extractable in DTPA (pH 5.3) and AB-DTPA (pH 7.6), while both WS-Mn and EX-Mn fractions correlated significantly and positively with Mn concentration and uptake by maize plants grown in these soils. The AB-DTPA (pH 7.6) and DTPA (pH 5.3) appeared suitable to assess the availability of Mn in acidic soils.     

Mehlich‐1‐ and DTPA‐extractable lead in soils in relation to soil properties

Abstract

Mehlich‐1 and DTPA extractants are frequently used to predict metal availability in soils. Metal extractability by the acid or chelate extractant reflects the metal characteristics and metal‐soil interactions. In this study, samples of eight topsoils from the southeastern United States were incubated with added lead (Pb) at the rate of 40 mg#lbkg^‐1. After five months in the greenhouse, Mehlich‐1 and DTPA extractants were employed to extract Pb in both metal‐amended and natural soils. For the natural soils, Pb concentration in the DTPA extractant was always higher than that in the Mehlich‐1 extractant. This indicates that the DTPA chelate extractant is able to dissolve some Pb in soils which is not solubilized by protons. The negative correlation found between Mehlich‐1‐extractable Pb and soil clay content might result from two mechanisms: i) strong association between Pb and soil surfaces, or ii) readsorption of Pb during extraction. None of the correlations between DTPA‐extractable Pb and soil properties was significant, suggesting that the DTPA‐extractable Pb is not heavily dependent on soil properties. The DTPA extractant showed a high ability to solubilize Pb in the natural soils possibly due to a high affinity of Pb for soil organic matter.     

Comparative evaluation of Ca chloride and Ca phosphate for extractable sulfur in soils with a wide range in pH

Deficiency of sulfur (S) is becoming widespread in the rainfed systems of India, and there is increasing need for diagnosing the deficiency. Calcium chloride and Ca phosphate are commonly used for extracting available S in soils. Because of cost and the ease of availability locally, we prefer using Ca chloride as an extractant over Ca phosphate, for extracting available S. However, there is paucity of data on the comparative evaluation of the two extractants to extract available S, especially in soils having a wide range in natural pH (from acidic to alkaline range). It is recognized that soil pH plays a dominant role in the adsorption–desorption and extractability of sulfate‐S in soils. We compared the extraction of S by Ca chloride and Ca phosphate in 86 Indian soils having a wide range in pH (4.5 to 10.6). Sulfur in the extracts was determined by ICP‐AES. Considering all the 86 soil samples tested, there was an excellent agreement between the values of extractable S determined by using the two extractants (r = 0.96, p < 0.001). However, the correlation coefficient (r) between the values of extractable S by the two reagents, although highly significant, varied among the groups of soil samples according to the range in soil pH. The highest correlation coefficient (r = 0.99, p < 0.0001, n = 17) was found for soils with pH in the alkaline range (8.5–10.6), and the lowest correlation coefficient (r = 0.71, p < 0.0001, n = 58) was obtained with a set of soil samples with pH in the acidic range (4.5–6.5). For soil samples having pH in the near‐neutral range (6.7–7.3), an excellent agreement was observed (r = 0.93, p < 0.0001, n =11) between the extractable‐S values obtained by the two extractants. While Ca phosphate extracted higher amount of S compared to Ca chloride in soil samples with pH in the acidic range, the two extractants were equally effective for soil samples with pH in the neutral or alkaline range. Our results suggest that for most of the soils in the semiarid tropical regions, which have pH in the neutral to alkaline range, Ca chloride can replace Ca phosphate as an extractant for removing available S in such soils.     

Evaluation of soil extractants to estimate available micronutrients under wheat‐field conditions

Abstract

Three extracting reagents were evaluated by correlation analyses to provide the best index of Zn, Cu, Mn and Fe availability to wheat (Triticum aestivum L.) plants growing under open field conditions. Twenty one soils were selected to obtain the widest range in properties of soils of the land wheat cultivated. The magnitude of the extractive power varied in the following order: 6NHCl ? EDTA + NH₄OA_C, pH4.65 > DTPA‐TEA, pH 7.3. The mild extractants, EDTA and DTPA, gave the same order of removal of micronutrients being Zn < Cu < Fe < Mn. The acid extractant was on the contrast more effective on Cu and Fe with respect to Zn and Mn, respectively. Wheat concentrations of Zn, Mn and Fe were significantly correlated to soil micronutrients. Highly significant relationships were found for Zn extracted by DTPA solution (r = 0.737***) and for Mn and Fe extracted by EDTA solution (r = 0.710*** and r = 0.564**). Plant Zn and Mn were also well predicted by the acid extraction. The absence of correlation for plant Cu vs. soil Cu occurred probably because of wheat concentrations almost constant, ranging from 5.0 to 8.0 mg/kg.     

Comparison of Multi-element to Single‐Element Extractants for Macro‐ and Micronutrients in Acid Soils from Spain

Abstract

Different chemical reagents are used to assess plant‐available nutrients from soils with similar properties. The use of different extractants is a serious limitation when comparing results between different soil‐testing laboratories, often leading to large differences in fertilizer recommendations for similar crops.

In this study, 80 samples from acid soils from Galicia (Spain) were used to compare several soil nutrient extractants. Traditional and tested extractants for acid soil such as Bray 2 and ammonium acetate were used to evaluate multielement extractants such as ethylenediaminetetraacetic acid–ammonium acetate (EDTA‐aa), ammonium bicarbonate–diethylenetriaminepentaacetic acid (AB‐DTPA), and Mehlich 3.

Linear regression analyses were performed to relate the amount of each nutrient obtained by traditional soil extractants to the amount obtained by multielement extractants. Strong correlation was found between extractable Bray 2 P and Mehlich 3 P (r²=0.97, slope=0.87, and intercept=?0.48). The slope of the regression line between EDTA‐aa‐extractable calcium (Ca) and that from ammonium acetate (Aa) approached 1∶1 (r²=0.86). Similar results were obtained for magnesium (Mg) (r²=0.99). Soil zinc (Zn) concentrations extracted by Mehlich 3 and EDTA‐aa were similar; slope of the regression line was 0.95 (r²=0.88). With regard to copper (Cu), Mehlich 3 extracted approximately 20% more Cu than EDTA‐aa.

The results showed that Mehlich 3 and EDTA‐aa are suitable for assessment of plant available phosphorus (P), potassium (K), Ca, Mg, Cu, Zn, and iron (Fe) in acid soils.     

Evaluation of Mehlich 3 for Extraction of Copper and Zinc from Irish Grassland Soils and for Prediction of Herbage Content

Abstract: The objective of this study was to determine how the extractant Mehlich 3 (M3) compared with other methods currently used in Ireland for determination of copper (Cu) and zinc (Zn) in soils. Samples from eight different mineral soil types, four of sandstone/shale and four of limestone origin, were analyzed for copper and zinc using M3 and conventional extractants. Herbage samples were taken from the soils and analyzed for Cu and Zn. Mehlich 3 results showed good correlation with ethylenediamine‐tetraacetic acid (EDTA)– and diethylenetriamine‐pentaacetic acid (DTPA)–extractable Cu and Zn. Inclusion of soil properties in multiple regression models improved the coefficients of determination. All extractants were equal in their ability to predict Cu and Zn herbage content. Differences between sandstone/shale and limestone soils in relation to herbage content were also found, with the better relationship found in sandstone/shale soils.     

Evaluation of efficient soil test methods for Zn and their critical vales in salt‐affects soils for rice

Abstract

Soil pot culture experiment was conducted on 22 soils of Balewal‐Phaguwala‐Narike (BPN) and 24 soils of Isri‐Langrian‐Narike (ILN) associations using rice (PR 106) as test crop at 0 and 7.5 ppm Zn levels. Chelating extractants 0.005M DTPA, 0.01M EDTA‐(NH₄)₂CO₃ and 0.05M EDTA, extracted more soil Zn than double‐acid and were significantly correlated with each other as well as with soil pH and clay in BPN and only with clay in ILN soil association. Soil CaCO₃ governed the double‐acid extractable Zn in these soils. Dry matter yield and Zn uptake by rice significantly increased with 7.5 ppm Zn application. The response was higher in ILN than BPN soil association, The DTPA method gave the highest correlation with Bray's yield and Zn uptake (r =0.72 and 0.55) followed by 0.05M EDTA (r ‐ 0.75 and 0.61) or EDTA‐(NH₄)₂CO₃ (r =0.70 and 0.61). The predictability of rice yield improved from 18–27 to 27–35, 32–43, 34–44 and 51–55 percent as a result of stepwise inclusion of pH, CaCO₃, organic carbon (OC) and clay respectively in the regression equation alongwith Zn extracted by chelating agents.

The critical levels of DTPA, EDTA‐(NH₄)₂CO₃ and EDTA extractable Zn significantly differed in the two associations and were 0.69, 0.82 and 1.24 ppm in BPN and O.BC, 1.09 and 1.42 ppm in ILN soil association. Soil properties further affected the critical levels. This for DTPA available Zn was 0.80 and 1.03 ppm in soil containing less and greater than 2% CaCO₃, 1.03 and 0.80 ppm in soils containing less and greater than 0.25% OC. These values for EDTA‐(NH₄)₂CO₃ available Zn were 1.09 and 0.91 ppm Zn in soils containing less and greater than 15% clay suggesting that critical levels of Zn for each category of soil properties should be considered while making recommendations of Zn fertilization of crops.,     

Comparison of routine soil tests and EPA method 3050 as extractants for heavy metals in Delaware soils

Abstract

Agricultural use of sewage sludges can be limited by heavy metal accumulations in soils and crops. Information on background levels of total heavy metals in soils and changes in soil metal content due to sludge application are; therefore, critical aspects of long‐term sludge monitoring programs. As soil testing laboratories routinely, and rapidly, determine, in a wide variety of agricultural soils, the levels of some heavy metals and soil properties related to plant availability of these metals (e.g. Cu, Fe, Mn, Zn, pH, organic matter, texture), these labs could participate actively in the development and monitoring of environmentally sound sludge application programs. Consequently, the objective of this study was to compare three soil tests (Mehlich 1, Mehlich 3, and DTP A) and an USEPA approved method for measuring heavy metals in soils (EPA Method 3050), as extractants for Cd, Cu, Ni, Pb and Zn in representative agricultural soils of Delaware and in soils from five sites involved in a state‐monitored sludge application program.

Soil tests extracted less than 30% of total (EPA 3050) metals from most soils, with average percentages of total metal extracted (across all soils and metals) of 15%, 32%, and 11% for the Mehlich 1, Mehlich 3, and DTPA, respectively. Statistically significant correlations between total and soil test extractable metal content were obtained with all extractants for Cu, Pb, and Zn, but not Cd and Ni. The Mehlich 1 soil test was best correlated with total Cu and Zn (r=0.78***, 0.60***, respectively), while the chelate‐based extractants (DTPA and Mehlich 3) were better correlated with total Pb (r=0.85***, 0.63***). Multiple regression equations for the prediction of total Cu, Ni, Pb, and Zn, from soil test extractable metal in combination with easily measured soil properties (pH, organic matter by loss on ignition, soil volume weight) had R² values ranging from 0.41*** to 0.85***, suggesting that it may be possible to monitor, with reasonable success, heavy metal accumulations in soils using the results of a routine soil test.     

Soil test for available zinc in acid soils of Venezuela

Abstract

Zinc (Zn) deficiencies have been identified in Venezuela with increasing frequency in recent years. However, there are no established critical values for available Zn in the acid soils of this country. Greenhouse studies were initiated to evaluate five extractants, DTPA, DTPA‐HCl, Na‐EDTA, 0.1N hydrochloric acid (HCl), and Mehlich 1 to predict Zn availability in 14 acid soils with corn as the test crop. Significant and positive correlations were found between Zn extracted among the five extractants. Zinc extracted was not related with soil pH and organic matter content, but with the cation exchange capacity and clay content. The Na‐EDTA extractant was found to be the most suitable as an indicator of Zn‐deficient acid soils, the critical Zn value being 2.4 mg#lbkg^‐1.     

Soil Test to Predict the Copper Availability in Pasture Soils

Abstract

The proportion of copper (Cu) that can be extracted by soil test extractants varied with the soil matrix. The plant‐available forms of Cu and the efficiency of various soil test extractants [(0.01 M Ca(NO₃)₂, 0.1 M NaNO₃, 0.01 M CaCl₂, 1.0 M NH₄NO₃, 0.1 M HCl, 0.02 M SrCl₂, Mehlich‐1 (M1), Mehlich‐3 (M3), and TEA‐DTPA.)] to predict the availability of Cu for two contrasting pasture soils were treated with two sources of Cu fertilizers (CuSO₄ and CuO). The efficiency of various chemical reagents in extracting the Cu from the soil followed this order: TEA‐DTPA>Mehlich‐3>Mehlich‐1>0.02 M SrCl₂>0.1 M HCl>1.0 M NH₄NO₃>0.01 M CaCl₂>0.1 M NaNO₃>0.01 M Ca(NO₃)₂. The ratios of exchangeable: organic: oxide bound: residual forms of Cu in M1, M3, and TEA‐DTPA for the Manawatu soil are 1:20:25:4, 1:14:8:2, and 1:56:35:8, respectively, and for the Ngamoka soil are 1:14:6:4, 1:9:5:2, and 1:55:26:17, respectively. The ratios of different forms of Cu suggest that the Cu is residing mainly in the organic form, and it decreases in the order: organic>oxide>residual>exchangeable. There was a highly significant relationship between the concentrations of Cu extracted by the three soil test extractants. The determination of the coefficients obtained from the regression relationship between the amounts of Cu extracted by M1, M3, and TEA‐DTPA reagents suggests that the behavior of extractants was similar. But M3 demonstrated a greater increase of Cu from the exchangeable form and organic complexes due to the dual activity of EDTA and acids for the different fractions and is best suited for predicting the available Cu in pasture soils.     

Comparison of Three Micronutrient Soil-Test Extractants in Three Greek Soil Types

The purpose of the present study was to compare the ability of three micronutrient soil-test extractants [diethylenetriaminepentaacetic acid (DTPA), Mehlich 3, and Soltanpour and Schwab] to determine plant-available concentrations of manganese (Mn), iron (Fe), and zinc (Zn) in three soils (from parent material Marl, Gneiss schist, and Peridotite) from central Macedonia, northern Greece. In black plastic bags containing 3 kg of air-dried soil, self-rooted olive plants (cv. Chondrolia Chalkidikis) were grown for about 5 months and irrigated with distilled water during the experimental period. At the end of the experimental period, the three extractants were evaluated, based on correlation analysis among leaf micronutrient concentrations, total plant micronutrient content of olive plants, and soil micronutrient concentrations determined by each extractant. The largest extractable concentrations of Mn, Fe, and Zn were determined by Mehlich 3, compared to the other two soil-test extractants. However, for the correlation analysis, the greatest correlation coefficient between leaf Mn (and total plant Mn content) and soil extractable Mn was achieved when DTPA was used (varying from 0.76 to 0.88, depending on soil type). Therefore, it is concluded that DTPA was a better extractant to determine plant-available Mn than the other extractants for the three soils studied. For correlations between leaf Fe and Zn concentrations and also for total plant Fe and Zn content, and soil extractable concentrations, the type of extractant and soil type play a very important role in determining the best correlation. This means that in each soil type the greatest correlation was achieved with the use of other extractant. For example, for Fe in the Marl and Peridotite soils the best correlation was found for Mehlich 3, whereas in the Gneiss schist the best correlation was achieved for DTPA (R = 0.72–0.94). For Zn, in the Gneiss schist soil the best extractant in determining plant available concentration was Soltanpour and Schwab (R = 0.49–0.60), whereas in the other two soil types DTPA was found to be the most reliable extractant (R = 0.51–0.78). Therefore, soil type should be carefully and thoroughly studied by the researchers in similar future experiments.     

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.