Automatic spectrophotometric determination of copper in plant material,soil, and fertilizer mixtures by a kinetic method

Abstract

Knowledge of metal concentration in soils, plant material, and fertilizers is important both for plant nutrition as for environment contamination studies. In this paper, an automated spectrophotometric method using Flow Injection Analysis (FIA) for copper (Cu) determination was studied. That method was based on the catalytic effect of Cu²⁺ ions in the color fading of the red‐purplish complex formed when iron (Fe³⁺) and thiosulfate (S₂O₃ ^2‐) ions react. The principal feature of the studied method is its high selectivity, which allowed the Cu determination in a complex matrix as nitrogen (N):phosphorus (P):potassium (K) fertilizer mixtures without effect of interference. Soil and plant tissue samples were also analyzed with good precision and accuracy when compared with atomic absorption spectrophotometry.     

Determination of iron in soils by flow injection atomic absorption spectrometry

Abstract

A single‐channel flow injection system was optimized for the determination of available iron (Fe) in soil extracts by atomic absorption spectrophotometry. This method of introducing the samples in the spectrophotometer worked particularly well in preventing blockage of the burner head which was observed in the conventional introduction of Fe for its determination by atomic absorption spectrophotometry. The appropriate selection of the manifold parameters, such as injection volume, tube length and flow rate, allowed introduction of any soil extract without requiring any pre‐treatment. This system allowed determinations at a detection limit of 0.36 mg L^‐1 to 5 mg L^‐1, with an output of 300 determinations per hour. The results obtained for analysis of 15 soil extracts were in good agreement with those provided by the colorimetric method, with average relative deviations of 1.6%. Relative standard deviations of 4.8, 2.5, and 2.3% were obtained for contents of 1.03, 1.85, and 3.99 mg Fe L^‐1, respectively.     

Determination of surface charge density of soils

Abstract

A simple and precise method for determination of surface charge density of soils is described. It involves saturating the negative and positive exchange sites with NH⁺ ₄ and NO^‐ ₃ ions, respectively, removing the excess solution by centrifugation, and determining the ions on the exchange sites by a steam distillation method. Results showed that the concentration and type of saturating ions and the extractant used significantly affected the surface negative charge densities. The average value of surface negative charge densities of 10 surface soils from Iowa, Chile, and Costa Rica by the proposed method agreed closely with that obtained by the original method proposed by Schofield in 1949 (14.6 vs. 13.7 cmol(‐) kg^‐1 soil). The advantages of the proposed method are no need for the laborious extraction steps and simplicity of the steam distillation method for determination of NH⁺ ₄ and NO^‐ ₃ in soil samples.     

Comparing tests for soil fertility. III. Evaluation of phosphate availability in Alfisols by Olsen,Mehlich 3, electro‐ultrafiltration,and the paper‐strip methodology procedures

Abstract

The suitability of the “iron‐impregnated paper‐strip”; (Pi) methodology for the assessment of phosphate (P) availability in soils has been tested on the basis of a comparison with the classical Olsen method as well as with the new‐generation electro‐ultrafiltration (EUF) and Mehlich No. 3 (M3) extraction procedure. The EUF extractions were performed by a first 30 min run at low (L) energy conditions (20°C, max 15 mA, and 200V), followed by a 10 min run at high (H) energy conditions (80°C, max 150 mA, and 400V). The total EUF‐P extracted (T‐EUF‐P), given by the sum L‐EUF‐P + H‐EUF‐P, was also considered. The investigation was carried out on twenty samples of representative Alfisols ("Terra Rossa") from the pedoclimatic environments of the Mediterranean area. The soil samples were characterized by a large variability of their available‐P values, whose ranges were, as mg‐kg^‐1 soil, 0.1–34.0 for L‐EUF‐P, 0.2–39.3 for HEUF‐P, 0.3–73.3 for T‐EUF‐P, 0.8–113.6 for Olsen‐P, 1.0–122.4 for Pi‐P, 1.1–224.6 for M3‐P. The respective mean values were 4.6, 5.1, 9.6, 17.2, 20.1, and 29.7 mg P/kg soil, with ratios L‐EUF‐P:H‐EUF‐P:T‐EUF‐P:Olsen‐P:Pi‐P:M3‐P increasing as 0.27:0.29:0.56: 1.00:1.17:1.73. A good compliance among all methods was verified; the most significant correlations were determined for Pi‐P versus M3‐P (R²=0.993***) and for Pi‐P versus Olsen‐P (R²=0.988***), clearly indicating the liability of the Pi procedure for the assessment of the P fertility in Alfisols. A multiple linear regression analysis revealed that all the available P values, afar from the individual procedure, were significantly (P<0.01) dependent on M3 exchangeable iron (Fe) (positively) and aluminum (Al) (negatively). This could lead one to argue that the prevailing available soil P source in the investigated Alfisol samples was that connected with the labile Fe‐P pool. Withal, one could infer that the A1‐M3 and Fe‐M3 parameters should also be considered for the making of P fertilizer recommendations. From this standpoint, the M3 is a well‐proved multielement extractant suitable for the simultaneous determination of available P and exchangeable Fe and Al as well.     

Spectrophotometric determination of silicon in soil solutions by flow injection analysis: Reduction of phosphate interference

Abstract

A flow injection analysis (FIA) procedure for the determination of dissolved silica (0.04–20 mg/L Si) in aqueous solution has been optimized to reduce phosphate interference. Determinations are based on measurement of absorbance at 790 nm of heteropoly molybdenum blue formed by reduction with ascorbic acid at room temperature. Phosphate did not interfere in a 15‐fold excess. The optimized procedure was tested on soil solutions isolated by centrifugation of various horizons from a Typic Haplohumod. Si concentrations of 1.3–4.8 mg/L Si were found with a variation coefficient of about 2. Results obtained compared well with those obtained by a manual reference method and a proprietary FIA method except in solutions high in dissolved humic material where slightly higher values were obtained by the optimized method. In a standard addition mode the optimized method yielded 5–15% lower values than in the ordinary mode. This difference was reduced by persulfate oxidation of organic matter. Soil solutions investigated were very low in phosphate but phosphate spiking experiments demonstrated that phosphate interference was less than in model solutions matched in metal ion concentrations and insignificant in solutions low in humic material and with less than 10 mg/L P. Dissolved silica was unstable in a solution isolated from an organic horizon of high biological activity.     

Molybdenum Determination in Mehlich‐1 and Mehlich‐3 Soil Test Extracts and Molybdenum Adsorption in Brazilian Soils

Abstract

The extractant Mehlich‐1 is routinely used in Brazil for determination of soil nutrients, whereas Mehlich‐3 has been suggested as a promising extractor for soil fertility evaluation. Both were used for extraction of molybdenum (Mo) in Brazilian soils with Mo dosage by the KI+H₂O₂ method. The Langmuir and Freundlich isotherms were used to study soil Mo adsorption. Mehlich‐1 extracted more Mo than Mehlich‐3 in soils with high contents of organic matter, clay, and iron (Fe) oxides. Mehlich‐3 and Mehlich‐1 extractions correlated positively and significantly with amorphous Fe oxides, crystalline Fe oxides, and organic matter. Molybdenum recovering rates correlated to crystalline Fe oxides and clay contents but not to organic matter, pH, and Mo adsorption capacity. Amorphous and crystalline Fe oxides, clay, and organic matter were responsible for most of the Mo adsorption. The Langmuir isotherm described better the Mo adsorption to soil amorphous Fe oxides and organic matter than the Freundlich isotherm.     

Changes in distribution of inorganic soil phosphorus forms with phosphate desorption by iron oxide‐impregnated paper strips

Abstract

The release of soil phosphorus (P) to solution has been described by extraction of soil with iron (Fe)‐oxide coated paper strips. Little information is available, however, on where this P is coming from. The effect of removal of reversibly adsorbed soil P on the distribution of inorganic P forms was investigated for 12 Italian soils. Phosphate was removed from these soils by Fe‐oxide strips after incubation with P (0 and 100 mg P kg^‐1) for 90 days. With no applied P, 3 to 17% of the total soil active P [saloid‐P, aluminum‐phosphate (Al‐P), iron‐phosphate (Fe‐P), and calcium‐phosphate (Ca‐P) was removed by the Fe‐oxide strips. The change in strip‐P following P addition (100 mg kg^‐1 soil), ranged from 12.9 to 53.5 mg P kg^‐1, with P coming almost entirely from the active P fractions. A close relationship between the changes in desorbed strip‐P after P equilibration and soil P sorption index (SI) was found for the studied soils (r²=0.96). Thus, the release of soil P for plant uptake or transport in runoff was a function of the amount of “actively”; sorbed P and an estimate of P sorption.     

Determination of total boron in soils by inductively coupled plasma atomic emission spectrometry using microwave‐assisted digestion

Abstract

A method is described in which total soil boron (B) was determined by inductively coupled plasma atomic emission spectrometry (ICP‐AES). The method is based on microwave‐assisted digestion of soil samples with nitric acid (HNO₃), hydrofluoric acid (HF) and hydrogen peroxide (H₂O₂). Excess HF was eliminated by adding silicon (IV) oxide (SiO₂). The B 208.959 nm line was chosen as the analytical line to avoid the spectral interferences of iron (Fe). A detection limit of 0.0045 mg L^‐1 was obtained with the selected analytical line under the optimized operating conditions. Four National Institute of Standards and Technology (NIST) standard reference materials (three soils and one river sediment) and four different type of practical soils were analyzed to test the reliability of the method. The total B concentration in selected samples ranged from 19 to 76 mg kg^‐1. The excellent recoveries of the spike (98.5–101%) indicate that the proposed procedure is effective and feasible for the determination of total B in soils.     

Cadmium copperization assays for the preparation of nitrate‐reducing columns

Abstract

An electrolytic method for the copperization of cadmium as a reducing agent for nitrate‐nitrogen (NO₃ ^‐‐N) determination is described. The conditions, medium, and time of copperization as well as the length of the cadmium reducing column has been studied in detail. This column was placed in a flow injection analyzer for the online determination of NO₃ ^‐‐N in soil extracts. The results obtained show that 1% copper sulfate (CuSO₄), 30 min and 55 mm are the optimal medium, time, and column length, respectively. With this reducing column, the method is linear between 0 and 12 ppm NO₃ ^‐‐N with a precision of 0.29% and a sampling frequency of 80 determinations per hour. The proposed method has been applied to the determination of NO₃ ^‐‐N in soil extracts and the results agree with those obtained by the reference method (r = 0.9998). The optimized electrolytic procedure for the copperization of cadmium permits more than 3000 determinations without any significant loss of sensitivity.     

A simple non‐atomic absorption procedure for determining the effective cation exchange capacity of tropical soils

Abstract

A simple non‐atomic absorption procedure for determining the effective cation exchange capacity of tropical soils has been developed. The method involves the shaking of soil samples (10g) with ammonium chloride (3 x 25 cm³, 1 mol/L) to displace the exchangeable cations. The soil is then equilibrated with dilute ammonium chloride (3 x 25 cm³, 0.01 mol/L). After the final equilibration the ammonium ions retained by the soil are determined to facilitate the calculation of the ECEC. Data obtained for 22 tropical soils ranging in ECEC values from 1–50 cmol(+)/kg show a highly significant correlation with values derived using the compulsive exchange or summation procedures. The silver thiourea procedure data gave significantly poorer correlations with that obtained using all three of the above methods.     

Prevention of Iron‐Deficiency Induced Chlorosis in Kiwifruit (Actinidia deliciosa) Through Soil Application of Synthetic Vivianite in a Calcareous Soil

Abstract

In this study we have tested the hypothesis that lime‐induced Fe deficiency chlorosis of kiwifruit may be prevented by the application of a synthetic iron(II)‐phosphate analogous to the mineral vivianite [(Fe₃(PO₄)₂·8H₂O)]. Two experiments, under greenhouse and field conditions, were performed. In the greenhouse, 1‐year old micropropagated plants (Actinidia deliciosa, cv. Hayward), grown in 3‐L pots on a calcareous soil, were treated in early autumn with soil‐applied: (1) synthetic vivianite (1.35 g plant^?1) and (2) Fe‐EDDHA (24 mg Fe plant^?1). The synthetic vivianite suspension, prepared by dissolving ferrous sulfate and mono‐ammonium phosphate, was injected into the soil as a sole application whereas the Fe‐EDDHA solution was applied four times at weekly intervals. The field experiment was conducted in a mature drip‐irrigated kiwifruit orchard located on a calcareous soil in the Eastern Po Valley (Italy). Treatments were performed in early autumn by injecting synthetic vivianite (1.8 kg tree^?1) and Fe‐EDDHA (600 mg Fe tree^?1) into four holes in the soil around each tree, at a depth of 25–30 cm. The Fe‐chelate application was repeated at the same rate in the following spring. Untreated (control) plants were used in both experiments. Autumn‐applied Fe fertilisers significantly prevented development of Fe chlorosis under greenhouse conditions whereas in the field only vivianite was effective. In conclusion, these 1‐year results show that vivianite represents an effective alternative to soil‐applied Fe chelates for preventing Fe chlorosis in kiwifruit orchards.     

Efficiency of diethylaminoethyl cellulose in the isolation of dissolved organic matter from forest soil solutions

Abstract

Diethylaminoethyl cellulose (DEAE cellulose), a weak anion exchange resin, has been used to isolate dissolved organic matter (DOM) from soil solutions collected from three different soil types, to investigate the amount of DOM isolated from soil solutions of various origin, and the extent to which inorganic ions are isolated together with DOM. The concentration of DOM in the various soil solutions ranged from 2.5 to 32.8 mg#lbL^‐1 DOC. More than 80% of dissolved organic carbon (DOC) was usually isolated with DEAE cellulose. High concentrations of aluminum (Al) and sulfate (SO₄ ^2‐) in the soil solutions have reduced DOC recovery. More than 90% of potassium (K⁺), calcium (Ca²⁺), and magnesium (Mg²⁺), were removed during the isolation procedure, but 10 to 20% of Al and 30 to 40% of iron (Fe) were isolated together with the DOC, probably due to strong complexation to DOM. The advantages of using DEAE cellulose were that the use of strong acids and bases was limited and that pH adjustments of the sample, leading to chemical modification of DOM, was not required.     

Soil Properties Influencing Iron Chlorosis in Grapevines Grown in the Montilla‐Moriles Area,Southern Spain

Abstract

Iron (Fe) chlorosis, an Fe deficiency commonly observed in grapevines cultivated on calcareous soils, generally inhibits plant growth and decreases yield. The objective of this research was to relate the incidence of Fe chlorosis in vines of the Montilla‐Moriles area, southern Spain, to indigenous soil properties. Thirty‐five grapevines (V. vinífera L. cv. Pedro Ximenez grafted on V. berlandieri×V. rupestris 110 Ritcher) showing different degree of Fe chlorosis were selected from 13 vineyards. The leaf chlorophyll concentration (estimated by the SPAD value measured with a Minolta meter) was positively correlated with the contents in different soil Fe forms but not with alkalinity‐related soil properties (pH, calcium carbonate equivalent, and active lime). The acid NH₄ oxalate‐extractable Fe (Fe_o) was the most useful simple variable to predict the occurrence of Fe chlorosis. A Fe_o/active lime ratio of 25×10^–4 was found to be useful to class soils into two groups according to the probability of inducing Fe chlorosis.     

Availability of soil boron fractions to M.26 apple rootstock

The availability of various boron (B) fractions in soil to M.26 apple (Malus spp.) rootstock was examined. The study was carried out in a greenhouse on soils with diverse chemical and physical properties. The following B fractions were determined: (i) B in soil solution, (ii) B non‐specifically adsorbed on soil surface, (iii) B specifically adsorbed on soil colloid surfaces, (iv) B occluded in Mn oxyhydroxides, (v) B occluded in noncrystalline aluminum (Al) and iron (Fe) oxides, (vi) B occluded in crystalline Al and Fe oxides, (vii) B fixed with soil silicates, and (viii) total soil B. In the studied soils there were: 0.07–0.17 mg kg^‐1 B in soil solution, 0.01–0.03 mg kg^‐1 B non‐specifically adsorbed on soil surface, 0.04–0.08 mg kg^‐1 B specifically adsorbed on soil colloid surfaces, 0.28–0.67 mg kg^‐1 B occluded in manganese (Mn) oxides, 4.03–17.22 mg kg^‐1 B occluded in noncrystalline Al and Fe oxides, 8.93–50.62 mg kg^‐1 B occluded in crystalline Al and Fe oxides, 12.2–42.5 mg kg^‐1 B fixed with soil silicate, and 52.9–82.2 mg kg^‐1 total B. Simple correlation analysis showed positive correlation between B contents in M.26 apple rootstocks and amounts of B in soil solution (r=0.77), B non‐specifically adsorbed on soil colloid surfaces (r=0.65), B specifically adsorbed on soil surface (r=0.76) and B occluded in Mn oxyhydroxides (r=0.77). No relation was found between plant B contents and amounts of B occluded in non‐crystalline and crystalline Al and Fe oxides, B fixed with soil silicates and total B. The results indicated that extraction of B by 0.1 M NH₂OH HCl solution adequately represented amounts of B in soil solution, B non‐specifically and specifically adsorbed on soil compound surfaces and B occluded in Mn oxyhydroxides to assess availability of B to apple trees.     

Evaluation of an aluminum digestion block for routine total soil phosphorus determination by alkaline hypobromite oxidation

Abstract

Total soil P was determined in six soils differing in pH, and in organic matter, total Fe, clay and sand contents. This study was undertaken to determine whether replacement of a sand bath.digestion procedure by an Al‐block digestion procedure affected the efficacy of an alkaline NaOBr method for determining total soil P. An Al digestion block was used for soil oxidation with NaOBr‐NaOH and the results were compared with a sand bath NaOBr method and a HC1O4 method. Temperature variability was very low in the digestion block (S.D.= ±1.4°C) when compared with the sand bath (S.D.= +20.1°C). The digestion block resulted in a greater precision in total P determination when compared to the sand bath (S.D.= ±3.7 vs. ±5.6, respectively). Linear relationships were obtained with the sand bath digestion technique (R² = 0.981) and with the HC1O₄ method (R² = 0.982). Using an Al digestion block for NaOBr‐NaOH oxidation of soils for total P determination allows for a simple, precise alternative to sand bath digestion and to potentially hazardous HClO₄ procedures.     

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.     

Effects of Several Metals on Both Fe(III)‐ and Cu(II)‐Reduction by Roots of Fe‐Deficient Cucumber Plants

Abstract

The ferric‐chelate reductase induced by Fe deficiency is also able to reduce other ions such as Cu²⁺. This Cu(II)‐reduction has been less studied and it has been suggested that Cu²⁺ ion rather than Cu²⁺‐chelate serves as the substrate. Ferric‐chelate reductase activity is inhibited by some metals, but the mechanisms implicated are not known. In the present work we use Fe‐deficient cucumber seedlings to study the interactions of Cu²⁺, Ni²⁺, Mn⁴⁺, and Fe³⁺ on both Fe(III)‐reduction and Cu(II)‐reduction activities. The response of Cu(II)‐reduction activity to Cu concentration, in the presence or absence of citrate, was also studied. Results showed that inhibition of the ferric‐chelate reductase activity by Cu²⁺ or Ni²⁺ could be partially reversed by increasing the concentration of Fe‐EDTA. The Cu(II)‐reduction activity was even stimulated by Fe‐EDTA or Ni²⁺; it was inhibited by a high concentration of Cu²⁺ itself; and it was not affected by the absence of citrate. Mn⁴⁺ caused a moderate inhibition of both Fe(III)‐reduction and Cu(II)‐reduction activities. Results agree with the hypothesis that free Cu²⁺ ion is the substrate for Cu(II)‐reduction and suggest that the mechanisms involved in Fe(III)‐reduction and Cu(II)‐reduction could have some differences and be affected by metals in different ways. The mode of action of metals on the reductase activity are discussed, but they are still not well known.     

Nutrient‐solution techniques for evaluation of iron efficiency of soybean 1

Abstract

The iron (Fe) efficiency of soybean [Glycine max (L.) Merr.] genotypes generally has been evaluated in the field on calcareous soil. A nutrient‐solution system has been developed to permit evaluation of Fe efficiency throughout the year. The objectives of this study were to assess the effectiveness of nutrient‐solution tests for evaluating the Fe efficiency of soybean genotypes and to evaluate alternative nutrient‐solution techniques that could minimize the cost of labor and chemicals. Five bicarbonate (HCO₃ ^‐) concentrations and three solution‐change schedules were evaluated in a factorial arrangement. Eight soybean genotypes with a wide range of Fe efficiency were evaluated in each treatment and in replicated field tests on calcereous soil during 3 years. Rank correlation coefficients between mean chlorosis scores of genotypes in nutrient solution and field tests ranged from 0.81 to 0.91 for the three solution‐change schedules and from 0.85 to 0.89 for the five HCO₃ ^‐ concentrations. Replacing the solution every 4 d was not superior to replacing it only at each stage of plant development or not changing the solution throughout the test. A stepwise increase in HCO₃ ^‐ level at each stage of plant development was not superior to utilizing a constant level of HCO₃ ^‐ throughout the test. The most economical evaluation of the Fe efficiency of soybean genotypes in nutrient solution can be achieved with no change in the solution and one or more HCO₃ ^‐ levels that are held constant throughout the test.     

Automated Modification of the Molybdenum Blue Colorimetric Method for Phosphorus Determination in Soil Extracts

A flow injection analysis (FIA) method capable of automation for molybdate reactive phosphorus (P) determination in soil extracts is described. Results obtained using this method in three soil extracts [calcium chloride (CaCl₂), Olsen, and Mehlich I] were the same as those provided by the manual molybdate blue colorimetric method. Linear range extending to 2 mg P L^?1, detection limits ranging from 6 to 26 µg L^?1 depending on the soil extract, and accurate recoveries from P‐spiked samples were achieved. The sensitivity of the system was around 0.3 absorbance units per mg P L^?1, and the sampling frequency was 72 samples h^?1, higher than those described for most of the flow injection methods.     

Methane and water soluble iron production under controlled soil pH and redox conditions

Abstract

When a soil is flooded, iron (Fe) reduction and methane (CH₄) production occurred in sequence as predicted by thermodynamics. The dissolution and precipitation of Fe reflected both soil pH and soil redox potential (Eh). The objective of our experiment was to determine both CH₄ production and Fe reduction as measured by Fe in solution in a flooded paddy soil over a wide range of closely controlled pH and Eh conditions. The greatest release of CH₄ gas occurred at neutral soil pH in combination with low soil redox potential (‐250 mV). Production of CH₄ decreased when soil pH was lowered in combination with an increase in the soil redox potential above ‐250 mV. Highest concentration of ferrous‐iron (Fe²⁺) under reducing conditions occurred when soil pH was lowered. Thus Fe reduction influenced CH4 formation in the flooded paddy soil. Results indicated that CH₄ production was inhibited by the process of ferric‐iron (Fe³⁺) reduction.