STUDIES ON SOIL COPPER

A method based on that used by McAuliffe et al. (1948) for phosphorus was developed for determining isotopically exchangeable copper in soils using the radioisotope ⁶⁴Cu. The authors are confident that, with a few exceptions, isotopic equilibrium in soil/solution systems is attained rapidly enough to overcome possible difficulties resulting from the short half-life of this isotope. For the twenty-four soils examined, amounts of isotopically exchangeable copper were found to be between 0.19 and 12-24 μg g^-I and represented between 2 and 21 per cent of the total soil copper. A correlation test and an experiment involving fractionation of labelled soils both demonstrated that the bulk of the isotopically exchangeable copper was located in the organic-bound fraction. Not all copper specifically adsorbed by organic matter was readily exchangeable with ⁶⁴Cu : for one sample of organic material examined only 20 per cent of the adsorbed copper was isotopically exchangeable after 24 hours equilibration. The corresponding figures for clay materials and oxide material were found to be between 75 and 60 per cent.     

Changes in aluminum pools of andisols due to soil acidification

Abstract

Aluminum concentrations in soil solutions are not only controlled by inorganic clay minerals but also by organically bound aluminum. The objective of this study was to determine which pools contribute to Al dissolution. Soil samples were taken at various distances from tree trunks and at various depths at the Rolling Land Laboratory (RLL), Hachioji, Tokyo. Selective dissolution techniques were used to analyze the changes in pools of solid-phase aluminum. Soil pH values around Hinoki cypresses were in the aluminum buffer range. Exchangeable aluminum contents in soils under Hinoki cypresses were 104 mmol_c kg-^?1 on the average. This value was similar to that of the cation exchange capacity (CEC) of Andisols at RLL at a soil pH of 4. The relationship between the soil pH and exchangeable, organically bound, and amorphous aluminum pools showed that dissolved aluminum ions in the soil solution were primarily derived from the amorphous Al pool. Dissolved aluminum ions were substituted with base cations of soils, resulting in the increase of the content of exchangeable Al and/or the formation of complexes with organic matter which increased the proportion of organically bound Al pools. Increase in the proportion of organically bound Al pools indicated the importance of complexation with soil organic matter for controlling the aluminum concentration in the soil solution.     

STUDIES ON SOIL COPPER

Adsorption isotherms were determined for the specific adsorption of copper by soils and soil constituents. Adsorption was found to conform to the Langmuir equation. The Langmuir constants, a (adsorption maximum) and b (bonding term), were calculated. Soils were found to have specific adsorption maxima at pH 5.5 of between 340 and 5780 μg g^?1, and a multiple regression analysis revealed that organic matter and free manganese oxides were the dominant constituents contributing towards specific adsorption. Adsorption maxima for soil constituents followed the order manganese oxides > organic matter > iron oxides > clay minerals, which supported the findings for whole soils. The cation exchange capacities (non-specific adsorption) of the test soils were found to be far greater than the specific adsorption maxima. However, evidence suggests that, for the relatively small amounts of copper normally present in soils, specific adsorption is the more important process in controlling the concentration of copper in the soil solution.     

THE ADSORPTION OF COPPER BY SOIL MATERIALS AT LOW EQUILIBRIUM SOLUTION CONCENTRATIONS

The adsorption of copper by individual soil components (organic matter fractions, oxides and clay minerals) was examined at equilibrium solution concentrations of copper within the range found in natural soils, the distribution of copper between solution and solid phases being measured by means of labelling with radioactive ⁶⁴Cu. At these low solution concentrations it was found that the copper adsorption isotherms were essentially linear. The oxides and organic materials adsorbed the greatest amounts of copper. The concentration of copper in natural soil solutions will be controlled by these materials to a far greater extent than by the clay minerals, the influence of which may be negligible in some soils. Solution concentrations of copper are relatively unaffected by both the background concentration of major cations and by changes in pH within the ionic strength and pH range found in normal agricultural soils. Copper adsorption studies with humic and fulvic acids showed that total solution copper concentrations could be greatly enhanced above the equilibrium levels for ionic copper by the presence of soluble organic complexes. The importance of taking into account the presence of such copper complexes in soil copper studies is emphasised.     

Copper Dynamics in a Typic Hapludalf Under Rice-Wheat Cropping System After Twelve Years of Annual Lantana Camara L. Residue Incorporation

Long term effects of lantana (Lantana camera L.) residue and fertilizer application were studied on copper (Cu) fractions in a Typic Hapludalf under rice-wheat cropping at Palampur, India (32°6′N, 76°3′E). A partitioning of soil Cu revealed residual Cu and organically bound Cu as the most dominant fractions followed by Cu occluded by free oxides, specifically exchangeable Cu and soil solution and exchangeable Cu. Continuous incorporation of lantana after 12 years resulted in redistribution of Cu from non-available forms to readily and potentially available forms in soil. All the Cu fractions were positively interrelated amongst themselves and with grain yield and Cu uptake in rice and wheat crops. Specifically exchangeable Cu followed by organically bound Cu were the most important Cu fraction contributing towards grain yield and Cu uptake in rice and wheat crops.     

Factors influencing adoption of soil and water conservation measures in southern Mali

A soil and water conservation (SWC) extension programme, promoting erosion control measures and soil fertility measures, has been going on in southern Mali since 1986. Five factors that influence farmer adoption of SWC measures were analysed: land pressure, cotton‐growing area, possession of ploughing equipment, possession of a donkey cart and farmer training in SWC. Interviews were carried out with 298 farmers and two to three fields per farmer were visited, in 30 representative villages and 30 villages with high SWC adoption. Correlation, regression and factor analysis led to the following conclusions:

• (1) Farmers in the high land‐pressure area adopt more soil fertility measures.
• (2) Farmers in the cotton‐growing area adopt less SWC measures.
• (3) Farmers with more ploughing equipment adopt more SWC measures.
• (4) Farmers with a donkey cart adopt more soil fertility measures.
• (5) Trained farmers adopt more erosion control measures.

There is a strong correlation between the adoption of erosion control measures and soil fertility measures that could not be explained by these five factors only. This suggests that there are additional factors that trigger the adoption of SWC measures. Copyright © 2003 John Wiley & Sons, Ltd.     

蚓粪对黑麦草吸收污染土壤重金属铜的影响

在长江冲积物形成的高沙土中加入CuSO4.5H2O模拟土壤污染,使Cu污染浓度分别为200、400、600 mg kg-1,并设置加蚓粪(15%)和加原土(15%)处理,二处理各设种植黑麦草(Lolium multiflorum)和不种黑麦草培养试验,研究蚓粪对黑麦草生长及对Cu吸收的影响,以揭示蚓粪在Cu污染土壤植物修复中的作用。结果表明:蚓粪显著增加了黑麦草的地上部和地下部的生物量(p<0.001**)以及根系的长度、表面积、体积和根尖数(p<0.05*),在Cu浓度为200 mg kg-1时促进作用最大;蚓粪还显著提高了黑麦草地上部Cu的浓度及累积量,但显著降低了地下部的Cu浓度(p<0.05*),而对地下部的铜累积量没有影响,显示蚓粪能促进Cu从根系向地上部的运移及在地上部的富集。通过对土壤的pH和Cu的形态特征分析,发现种植黑麦草处理降低了土壤的pH并增加了可交换态铜的含量,而且这种作用在加入蚓粪后更加明显。推测蚓粪主要通过促进黑麦草根系的生长和活性而影响根系周围环境,提高重金属铜的生物有效性进而增加植物对铜的吸收。     

Effect of sewage sludge application on cotton yield and contamination of soils and plant leaves

Abstract

In a two‐year field experiment, dry sewage sludge was applied to fields plots at rates of 0,26,42,58, or 77 tons ha^‐1 year^‐1 on a clay loam soil (calcixerrolic xerochrept), well drained with a pH value of 8.15. Cotton was the cultivated plant (Gossypiumhirsutum variety korina). Sequential extraction was used to separate the different forms of the metals (exchangeable, organically bound, carbonates and residual) in the soil‐sludge mixtures. Cotton yield increased in the second year of experimentation compared with the control treatment (without fertilization and no application of sewage sludge). Most of the metals studied [cadmium (Cd), zinc (Zn), copper (Cu), and nickel (Ni)] were found in the organically bound, carbonate or residual forms. From the elements in the soil fractions, only Zn in the residual form was correlated with the Zn content of cotton leaves. The diethylenetriaminepentaacetic acid (DTPA) extraction of the plant‐available levels of the elements showed only for Cd a simple linear correlation, between concentration in soils and cotton leaves.     

Extractability and Transformation of Copper and Zinc Added to Tropical Savanna Soil under Long-Term Pasture

The extractability and slow reactions of copper (Cu) and zinc (Zn) in a weathered savanna soil under Brachiaria decumbens, Digitaria smutsii, and Stylosanthes guianensis pastures were determined in a laboratory incubation study using a sequential extraction to remove operationally defined fractions of the metals, consisting of exchangeable, organically bound, precipitate [occluded in aluminum (Al) and iron (Fe) oxides], and residual metal fractions. The soils from the pasture fields were spiked with 100 mg Cu kg^–1 soil and 200 mg Zn kg^–1 soil for 24 weeks. Copper and Zn extractable with 1 N potassium nitrate (KNO₃) solution decreased exponentially with time but reached a steady state after 2–3 weeks. The concentrations of Cu and Zn exchangeable with potassium (K) were greater in the Digitaria smutsii field soil than Brachiaria decumbens and Stylosanthes guianensis field soils. The exchangeability of added Cu and Zn (indexed Mⁿ⁺ _(exch)) with time was described by a simple exponential decay equation: Mⁿ⁺ _(exch) = αe^βt, where α is a constant, β is a coefficient that defines the rate of transformation of added Cu and Zn from the exchangeable to nonexchangeable pools, and t is time. The β values for Cu (0.040–0.076 mg kg^–1 d^–1) were almost 10 times greater than those of Zn (0.005–0.007 mg kg^–1 d^–1). Sequential extraction of added Cu and Zn indicated that between 26 and 30% of the total Cu and between 19 and 30% of the total Zn were associated with organic matter. Similarly, between 35 and 38% of total Cu and between 47 and 60% of total Zn were associated with Fe, Al, and manganese (Mn) oxides. The differential capacity of the pasture fields to transform added Cu and Zn from exchangeable and labile form to nonlabile and nonexchangeable form appears to be governed by organic matter (OM), pH, and active Fe ratio in the pasture field soils.     

Comparison of single and sequential soil extractions for predicting copper phytotoxicity

Abstract

Phytotoxicity of copper (Cu) and other heavy metals is related to their forms in soil. In this study, different forms of Cu in the soil solid phase, i.e. exchangeable, sorbed, organically bound, precipitate, and residual forms were measured, using a sequential fractionation procedure (SFP), in a soil amended with various rates of Cu. The relationships between different forms of Cu by SFP in soil or Cu extractable by Mehlich 1 (M1) and Mehlich 3 (M3) and accumulation of Cu by citrus roots or shoots were examined. The results showed that Cu mainly existed in the organic fraction. An increase in soil pH decreased the organic fraction and increased the precipitate fraction of Cu. Copper concentration in citrus root was found to correlate with the water soluble, organic, or precipitate fractions of Cu in the soil. Multiple regressions using different forms of Cu in soil gave the same prediction of Cu concentration in citrus root as that using Ml‐ or M3‐extractable Cu.     

SOIL APPLIED COBALT AND COPPER ALTER THE RHIZOBIUM SYMBIOSIS AND GROWTH STATUS OF LABLAB PURPUREUS (L.) SWEET

A pot experiment was performed to investigate the effect of cobalt (Co) and copper (Cu) nutrition on nodulation, nodule activity and growth of Lablab purpureus plants growing in sandy clay loam soil collected from Toshka region in south of Egypt. The pots were given nutrient solution only once with addition of increasing levels of cobalt and copper (50, 100, 150 and 200 μg) as cobalt or copper sulfate solution. The present study has provided a new insight into the effect of cobalt and copper on nodulation and nodule physiology of Lablab purpureus (L.) Sweet (kashrangeeg) that has not yet been examined. Thus, the present work suggest that Co and Cu application is essential for the enhancement of nodulation, nodule activity and growth of Lablab purpureus plants growing in sandy clay loam soil deficient for theses microelements.     

Fractionation and colorimetric determination of boron in soils

We attempted to modify and evaluate existing sequential fractionation schemes for B involving the use of chemicals, which subsequently do not interfere with the measurement of B by colorimetry. Also evaluated was the contribution of various soil B fractions to the amount of B extracted by hot CaCl₂, CaCl₂‐mannitol, salicylic acid, ammonium acetate, HCl, and tartaric acid. For this purpose, 17 soils with diverse properties were used. The extraction scheme proposed here partitioned B into five pools, (i) readily soluble, (ii) specifically adsorbed, (iii) oxide bound, (iv) organically bound, and (v) residual boron, respectively extracted with 0.01 M CaCl₂, 0.05 M KH₂PO₄, 0.175 M NH4‐oxalate (pH 3.25), 0.5 M NaOH, and HF + H₂SO₄ + HClO₄. The procedure of elimination of color from extracts of oxide bound, organically bound, and residual B fractions was also evolved. Relationships of individual B fractions with physicochemical properties of the experimental soils confirmed the general validity of the proposed fractionation scheme. The relationships of different B fractions with extractable B in soils suggest that hot CaCl₂ and salicylic acid may be better extractants for available B in soils.     

Mobilization and turnover of soil phosphorus in the rhizosphere

Recent progress in methods enables a better understanding of the turnover of P in the rhizosphere. Examples of this progress are the separation of soil layers differing in proximity to the roots, improved methods for extraction and fractionation of soil P, application of ³²P isotope dilution analysis to follow P fluxes between various fractions and direct determination of microbially bound P and of root phosphatases.

• These methods were combined to investigate the following aspects
• –labile P pools, the P fluxes between these pools and their contribution to the P supply to growing maize roots
• –the role of microbial biomass in these interactions and the partition of mobilized P between plants and microorganisms
• –modifications of sorption and transport of P in the rhizosphere
• –plant availability of native and added organic phosphates, and the relative significance of root and soil phosphatases.

There is a significant transformation of P in the rhizosphere with a corresponding redistribution among fractions of different plant availability. About 9% of the inorganic ³²P added to soil were incorporated within 2 weeks into microbial and organic fractions. The transfer of P from non-exchangeable forms exceeded the depletion of the exchangeable P by a factor of 5. About 53% of the mobilized P originated from inorganic, the remaining 47% from organic fractions. Of the mobilized P 80% was taken up by the plants and 20% was found in the microbial biomass. Up to 90% of the P in the rhizosphere soil solution was organic with a maximum just outside the root zone. Soluble inositol hexaphosphate modified the sorption of inorganic P, thus shifting its equilibrium solution concentration. The phosphatase activity of the roots is considerable. Both root phosphatase activity and the utilization of inositol hexaphosphate depend on the P supply and nutritional status of plants with regard to P. It is concluded that the rhizosphere is a key site of P transformation with a significant mobilization of P from the non-exchangeable inorganic and organic fractions. Organic P fractions not only play a significant role as a P source but also modify important soil parameters related to the sorption and transport of P in the rhizosphere.     

外源铜对土壤果树系统中酶活性影响的研究

利用褐土和红富士苹果嫁接苗为供试材料 ,研究外源铜对土壤—苹果树系统中酶活性的影响。结果表明 ,低量的外源铜能使果树叶片的过氧化氢酶、多酚氧化酶、抗坏血酸氧化酶及根系过氧化氢酶的活性加强 ,而高量铜使活性大幅度降低 ,加入钙铁后在一定程度上使抑制缓解。土壤过氧化氢酶的活性与外源铜量具显着的曲线相关性 ,(y =x ( - 1 1 .2 6 0 .75x) ,r=0 .995 5 ) ,蔗糖酶活性与土壤施铜量呈Logistic函数关系 (y =2 .95 ( 1 0 .5 7exp( - 5 .0 2× 1 0 - 5x) ,r=- 0 .982 0 )。脲酶对铜过量非常敏感 ,大于 1 0 0mgkg- 1的各处理均未测出其活性     

Variability and relationships between Pb,Cu, and Zn concentrations in soil solutions and forest floor leachates at heavily polluted sites

Seasonal variability of Cu, Pb, and Zn concentrations in litter leachates and soil solutions was examined in an afforested zone surrounding a copper smelter in SW Poland. Litter leachates (with zero‐tension lysimeters) and soil solutions (with MacroRhizon suction‐cup samplers, installed at a depth of 25–30 cm) were collected monthly at three sites differing in contamination levels in the years 2009 and 2010 (total Cu: 2380, 439, and 200 mg kg^–1, respectively). Concentrations of Cu in the litter leachate were correlated with dissolved organic C (DOC), whereas Zn and Pb were mainly related to leachate pH. Metal concentrations in the soil solution were weakly influenced by their total content in soils and the monthly fluctuations reached 300, 600, and 700% for Cu, Pb, and Zn, respectively. Metal concentrations in soil solutions (Cu 110–460 μg L^–1; Zn 20–1190 μg L^–1; Pb 0.5–36 μg L^–1) were correlated with their contents in the litter leachates. Chemical speciation, using Visual Minteq 3.0, proved organically‐complexed forms even though the correlations between metal concentrations and soil solution pH and DOC were statistically insignificant. The flux of organically‐complexed metals from contaminated forest floors is believed to be a direct and crucial factor affecting the actual heavy metal concentrations and their forms in the soil solutions of the upper mineral soil horizons.     

SOIL WATER: QUANTITIES, UNITS AND SYMBOLS

Soil water studies involve physical quantities, units and symbols, and these are discussed in terms of the International System of Units (SI) and the soil physics terminology (1976) of the International Society of Soil Science. The author particularly examines

• (i) the relation of SI units to the familiar but superseded cgs units;
• (ii) the effect of the frame of reference on the expression of water potential and hydraulic conductivity;
• (iii) the different interpretation of hydraulic conductivity in soil physics and in biophysics; and
• (iv) methods of avoiding ambiguity in presenting data.

     

Fractions of Copper in Soil and Their Contribution to Copper Availability in Rice–Wheat Cropping System under Long-Term Integrated Nutrient Management in an Acid Alfisol

Long-term effects of integrated application of organics and chemical fertilizers on transformation of copper (Cu) into various chemical pools and their availability under rice (Oryza sativa L.)–wheat (Triticum aestivum L.) cropping system were investigated in the ongoing long-term fertilizer experiment initiated in 1991 kharif season (May–October) at the research farm of Chaudhary Sarwan Kumar Himachal Pradesh Agricultural University on an acidic soil in the Western Himalayas of India. The continuous use of chemical fertilizers alone for 20 years brought about marked depletion in all forms of copper except organically bound Cu (Cu-PYR) compared to buffer plots. Integrated use of organics and chemical fertilizers gave higher content of Cu forms over chemically treated plots except Cu occluded by free oxides (Cu-OX). Residual Cu was the most dominant form of copper contributing about 67% of the total Cu. Soil solution and exchangeable Cu (Cu-CA) was the most important fraction of copper contributing toward DTPA (diethylene triamine pentaacetic acid) extractable Cu. Content of DTPA extractable Cu increased over control when chemical fertilizers were applied in conjunction with different organics, whereas DTPA Cu content declined over control with application of chemical fertilizers alone for the last 20 years.     

Soil Zinc Transformations as Affected by Applied Zinc and Organic Materials

Information on soil zinc (Zn) distribution is essential for understanding its chemical reactions and bioavailability. An experiment was conducted to evaluate the effect of wheat straw, cow manure, and vermicompost applied with Zn rates on Zn distribution in a calcareous soil. A sequential extraction scheme was used to fractionate Zn into soluble and exchangeable, bound to carbonate, organically bound, bound to manganese (Mn) oxide, bound to amorphous iron (Fe) oxide, bound to crystalline Fe oxide, and residual forms. In untreated soil, Zn was mainly in the residual fraction. Increasing rates of applied Zn increased all forms of Zn. Carbonate and residual forms showed the greatest increase. Organic materials application increased all fractions, except Mn-oxide form, and this increase was more pronounced for the organically bound form. Concentration of soluble, exchangeable, and organically bound forms was greatest in cow manure–amended samples as compared to other organic materials, suggesting that cow manure contained more bioavailable Zn than other organic materials.     

Zinc Transformation in a Calcareous Soil as Affected by Applied Zinc Sulfate,Vermicompost, and Incubation Time

An experiment was conducted to evaluate the effect of zinc (Zn) rates and vermicompost levels on distribution of Zn forms of a calcareous soil. After incubation periods, soil samples were air dried, and a sequential extraction scheme was used to fractionate Zn into soluble and exchangeable, bound to carbonate, organically bound, bound to manganese (Mn) oxide, bound to amorphous iron (Fe) oxide, bound to crystalline Fe oxide, and residual forms. In untreated soil, Zn was mainly in the residual fraction. Increasing rates of applied Zn significantly increased all forms of Zn. Carbonate and residual forms showed the greatest increase. Application of vermicompost significantly increased all fractions except Mn-oxide form. This increase was more pronounced for organically bound, soluble, and exchangeable forms, indicating an increase in bioavailability of soil Zn. Incubation time significantly decreased soluble, exchangeable, and organically bound forms but increased other forms of Zn, meaning a significant reduction in Zn phytoavailability in soil with time.     

Assessment of zinc availability to rice in mollisols of North India

Abstract

The objectives of this study were to (1) characterize zinc (Zn) fractions and their relation to Zn extracted with mixed‐bed ion exchange resin capsules and (2) assess the relationships between the latter and Zn uptake by rice in 12 Mollisols from North India. The Resin Adsorption Quantity (RAQ) of Zn was measured after 1 and 14 days of anaerobic incubation. Six organic and inorganic Zn fractions were determined on anaerobic soil. Zinc uptake by rice was studied in a greenhouse experiment. Soil Zn fractions under reduced conditions followed the order residual Zn (80%)>carbonates and amorphous oxides bound Zn (12%)>weakly organically bound Zn (3%)>crystalline oxides bound Zn (2%)>strongly organically bound Zn (2%)>water soluble + exchangeable Zn (1%). RAQ‐Zn was best correlated with Zn bound to carbonates and amorphous oxides. Due to negative interactions between bicarbonate and Zn uptake, correlations between relative dry matter yield or total Zn uptake and the different Zn fractions, DTPA‐Zn measured on dry soil, or RAQ Zn were not significant. Adjusting soil test values according to soil pH improved the prediction of relative dry matter yield, but further studies are required to determine whether the resin capsule can be used as a soil test for Zn in calcareous soils.