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.     

Magnesium,Potassium and Phosphorus in Available Forms in Luvisols in the Vicinity of Głogów Copper Smelter

Region near G?ogów is characterized as industrial—agricultural area, intensively used. Presented study was undertaken to estimate the impact of agricultural land use and the vicinity of G?ogów copper smelter on the contents of available forms of magnesium, phosphorus and potassium in selected profiles of Luvisols. The following analysis were performed: soil particle-size distribution, pH, organic carbon contents, CaCO₃ contents. The contents of available forms of phosphorus and potassium were determined by Egner- Riehm method and that of magnesium using Schachtschabel’s method. The results of the study showed that the contents of available P is medium (III class of abundance), very low in K (V class) and for available Mg very low (V class) to medium for surface horizons and very high (I class of abundance) in other soil horizons. The soils, in spite of the elevated copper content in humus horizons, according to IUNG, were classified as uncontaminated soils, therefore, can be used in plant production for all types of crops.     

Copper availability in two soils amended with eleven annual applications of copper‐enriched hog manure

Abstract

Relatively high amounts of Cu are found in manure of hogs (Sus scrofa domesticus) maintained on diets containing growth‐stimulating levels of Cu. While disposal of Cu‐enriched hog manure through repeated long‐term application to agricultural land is commonly practiced, concern exists regarding Cu availability in these soils. Field studies were conducted on a Bertie fine sandy loam (Aquic Hapludults) and a Starr‐Dyke clay loam (Fluventic Dystochrepts‐Typic Rhodudults), located in the Coastal Plain and Piedmont regions of Virginia. The objective was to examine the effects of long‐term Cu application on corn (Zea mays L.) growth and to ascertain the Cu sorption capacity of these soils. Field plots were treated with Cu‐enriched hog manure or CUSO₄ (on an equivalent Cu basis) annually. Manure amendments totaled about 240 t ha^‐1 (dry weight) over an 11 yr period (1978 through 1989). The manure averaged 1300 mg Cu kg^‐1 (dry weight) over this time period totaling 340 kg Cu ha^‐1. Sorption isotherms were determined for sorption of Cu by the Bertie and Starr‐Dyke soils. In comparison with unamended control plots, studies conducted in 1989 showed an early season stunting effect for corn grown on the CUSO₄ treated Bertie soil. No differences in plant heights were observed for corn grown in CuSO₄ treated Starr‐Dyke soil or control plots. Plant growth rates were increased on plots amended with Cu‐enriched hog manure. Copper sorption capacity of Bertie and Starr‐Dyke soils increased following several annual applications of manure.     

Changes of Bacterial Community Structure in Copper Mine Tailings After Colonization of Reed （Phragmites communis）

Soil samples were collected from both bare and vegetated mine railings to study the changes in bacterial communities and soil chemical properties of copper mine tailings due to reed （Phragmites communis） colonization. The structures of bacterial communities were investigated using culture-independent 16S rRNA gene sequencing method. The bacterial diversity in the bare mine tailing was lower than that of the vegetated mine tailing. The former was dominated by sulfur metabolizing bacteria, whereas the latter was by nitrogen fixing bacteria. The bare mine tailing was acidic （pH = 3.78）, whereas the vegetated mine tailing was near neutral （pH ： 7.28）. The contents of organic matter, total nitrogen, and ammonium acetate-extractable potassium in vegetated mine tailings were significantly higher than those in the bare mine railings （P 〈 0.01）, whereas available phosphorus and electrical conductivity were significantly lower than those in the bare mine tailings （P 〈 0.01）. The results demonstrated that 16S rRNA gene sequencing could be successfully used to study the bacterial diversity in mine tailings. The colonization of the mine tailings by reed significantly changed the bacterial community and the chemical properties of tailings. The complex interactions between bacteria and plants deserve further investigation.     

Distribution and Accumulation of Copper and Cadmium in Soil–Rice System as Affected by Soil Amendments

The effects of seven amendments on the distribution and accumulation of copper and cadmium in a soil–rice system were investigated using a pot experiment. Results showed that application of limestone, calcium magnesium phosphate (Ca–Mg–P fertilizer), calcium silicate (silicon fertilizer), Chinese milk vetch, pig manure, and peat significantly decreased the concentrations of Cu and Cd in rice roots by 24.8–75.3% and 9.7–49.9%, respectively. However, no significant difference was observed between zinc sulfate (zinc fertilizer) and the control treatment. The concentrations of Cu and Cd in different parts of rice followed the order: root > straw > grain, and all amendments restrained the transfer of Cu and Cd from rice root to stem. Copper and Cd concentrations in rice stems at the tillering stage were the highest, and then decreased from the tillering stage to the heading stage. However, they increased again at the ripening stage. The results also showed that application of amendments changed Cu and Cd solubility in soil and decreased their bioavailability, which resulted in the reduction of Cu and Cd uptake by rice. Significant correlations between the concentrations of Cu and Cd in soil solutions and in rice stems were found. The result demonstrated that limestone has the best efficiency among all the amendments used in reducing Cu and Cd contamination to rice production.     

Study on “Blind—Ear”——Copper Deficiency Symptom in Wheat on Subtropic Hill Soils

The “blind-ear” as a Cu deficiency symptom in wheat on upland soils in the hilly area of Zhejiang Province was discussed in this paper.Through 3 years of field experiments,it was elucidated that “blind-ear” in wheat plant appeared due to the low level of available Cu in the soils,and the critical value 3 mg/kg for total Cu in the plant at grain filling stage and 1 mg/kg for available Cu(0.1 M HCl)in the soils.A basal dressing of 30 kg/ha of Cu sulfate to the soils could completely eliminate Cu deficiency symptoms,obtain normal grain yield and have residual effect for at least 3 years.     

Copper in soils,plants, and ruminant animal nutrition with special reference to sub‐Saharan Africa

Copper (Cu) is not only essential as a component of a number of different plant enzymes and necessary for the activity of several specific enzymes, it is also an important constituent of blood proteins necessary for the normal physiological functioning of the animal body. The role of Cu in agricultural production has been documented by several authors and these reviews mainly relate to work in the temperate regions.

This review has attempted to extract all available information in sub‐Saharan Africa (SSA) on the role of Cu on the soil, plant and animal systems. It discusses the content of Cu in the soil and plant, its role and biochemistry and methods of analysis with special reference to research in SSA. The need to maintain adequate levels of Cu levels in the soil and forage crops for ruminant animal consumption is emphasised. Factors such as age, physiological state, breed, dry matter intake and source of Cu which influence dietary Cu requirements of ruminant animals were reviewed. Deficiency and toxicity cases of Cu in animals have been diagnosed in many SSA countries. Although there are several ways of correcting Cu deficiency and toxicity problems, success depends on the ability to identify the underlying causes. The interaction of Cu with other minerals, in particular molybdenum (Mo) and sulfur (S), is an important factor determining whether a deficiency or toxicity is “simple”; or “conditioned”;.     

Determination of Uranium and Thorium in Soil and Plant Parts around Abandoned Lead–Zinc–Copper Mining Area

This study reports distribution of uranium (U) and thorium (Th) in soil samples and the roots and shoots of some plants grown around an abandoned lead (Pb)–zinc (Zn)–copper (Cu) mining area. The plants Euphorbia macroclada, Verbascum cheiranthifolium Boiss, and Astragalus gummifer were examined. The determinations of U and Th were carried out by inductively coupled plasma‐mass spectrometry (ICP‐MS). Uranium and Th levels of the studied soil samples were found to be in the range of 1.1–70.3 mg kg^?1 and 2.1–62.1 mg kg^?1, respectively. Some results obtained from this study were higher than the mean U and Th concentrations of soils reported around the world. Uranium and thorium concentrations in studied plant roots were in the range of 0.04–16 and 0.08–14.57 mg kg^?1, whereas in plant shoots they were 0.02–2.76 and 0.07–12.3 mg kg^?1, respectively. It was concluded that the shoots of Astragalus and roots of Euphorbia and Verbascum can be used as both a biomonitor for environmental pollution and biogeochemical indicator because of their higher U and Th concentrations.     

Distribution of Total and DTPA‐Extractable Zinc,Copper, Manganese,and Iron in Vertisols of India

Abstract

Vertisols of India are developed over isohyets of 600 to 1500 mm, and their chemical cycles are set by drainage, landforms, and particle size, which results in variable pedogenic development within the otherwise homogeneous soils. The purpose of this study was to identify pedogenic processes in the distribution of total and DTPA‐extractable zinc (Zn), copper (Cu), manganese (Mn), and iron (Fe). The soils are developed over basaltic parent material of Cretaceous age. Soil samples were drawn from genetic horizons of the 13 benchmark profiles and analyzed by using HF–HClO₄ acid for total and DTPA extraction. Correlation coefficients were calculated taking all samples together. The total concentration varied from 24 to 102 mg kg^?1 for Zn, 21 to 148 mg kg^?1 for Cu, 387 to 1396 mg kg^?1 for Mn, and 2.36 to 9.50% for Fe. Their variability was proisotropic and haplodized, and their concentrations increased with advancing isohyets. Within the isohyets, hindrance in drainage caused retention of Zn and Cu but loss of Fe. The piedmont soils had more Fe than alluvium soils. The spatial distribution of total contents of Zn, Cu, and Fe was influenced by the pedogenic processes associated with Haplusterts but not with provenance materials. Surface concentrations of the elements by biotic lifting and/or harvest removal were negated by the pedoturbation that further contributed to the irregular distribution of the elements in the profiles. Total Zn and total Cu had positive coefficients of correlations with coarse clay, whereas total Mn and total Fe were positively correlated with fine clay. The DTPA‐extractable forms were functions of isohyets and drainage and showed association with organic carbon content and coarse clay.     

Distribution and Transport of Residual Lead and Copper Along Soil Pro?les in a Mining Region of North China

Residual heavy metals are commonly considered to be immobile in soils,leading to an underestimation of their environmental risk.This study investigated the distribution and transport of residual heavy metals along soil pro?les,using the Xiaoqinling gold mining region in North China as a case study.Soil samples were collected at three depths from three locations near the tailing heap.The speciation of copper(Cu) and lead(Pb)(exchangeable,carbonate-bound,Fe-Mn oxide-bound,organic matter-bound,and residual fractions) was determined using a sequential extraction procedure.The residual fraction's morphology was observed using scanning electron microscopy(SEM).Results showed that metal fraction distributions along the soil pro?les were in?uenced by each fraction's mobility.Residual fraction with high chemical stability can not be transformed from or into other fractions.This led to the conclusion that the high concentration of residual metals in soils mainly resulted from residual fraction transport.The SEM analysis showed that ?ne particles(submicrons) were mainly attached to large particles and were likely released and transported by water?ow.The more sorptive fractions(non-residual fractions) were mainly retained in the top soil,and the more mobile fractions(residual fraction) were mainly leached to the deep soil.Cu and Pb concentrations in the residual fraction decreased slightly and those in the non-residual fractions decreased signi?cantly with soil depth.These suggest a relatively higher residual metal mobility along the soil pro?les.Therefore,residual metals can be transported in soils and their environmental risk can not be ignored in assessing soil contamination.     

Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

Effect of Selenium on Magnesium,Iron, Manganese,Copper, and Zinc Accumulation in Corn Treated by Indole‐3‐acetic Acid

In this work, the relationship among accumulation of selenium, auxin, and some nutrient elements [magnesium (Mg²⁺), iron (Fe³⁺), manganese (Mn²⁺), copper (Cu²⁺), zinc (Zn²⁺)] in tissues of roots, mesocotyls, and leaves of Zea mays L. plants was studied. Seeds of maize were cultivated for 4 days in the darkness at 27 °C on moist filter paper, then the individual seedlings were transferred into an aerated solution containing the macro‐ and microelements and were cultivated in a greenhouse for 12 h in the light and 12 h (12‐h photoperiod) in the dark at 25 °C. The seedlings were exposed to the solution containing sodium hydrogen selenite (NaHSeO₃), indole‐3 acetic acid (IAA), or IAA+NaHSeO₃ for approximately 96 h before chemical analysis. The concentration of IAA in the external medium was 10^?4 mol dm^?3, concentration of selenite (NaHSeO₃) was 10^?6 mol dm^?3, and the pH of the medium was 6.5.

The accumulation of the probed elements in seedlings of maize was measured by inductively coupled plasma optical emission spectroscopy (ICP‐OES). It was determined that the selenite and IAA, present in the external medium of growing plants, changed the uptake and accumulation of some cations in tissues of leaves, mesocotyls, and roots. The change of transport conditions of these nutrient elements is probably one of the first observed symptoms of selenium effects on plants.     

Lead, Zinc, Arsenic and Copper Pollution in the Alluvial Plain of a Mining Wadi: The Beal Case (Cartagena–La Union Mining District, SE Spain)

The distribution and mobility of heavy metals in the non-saturated zone of the alluvial plain of a wadi in the Cartagena–La Union mining district was investigated. The elemental chemistry of soils, in-depth sediments and different plant species (namely Hirsfeldia incana, Ditrichia viscosa and Piptatherum miliaceum) was carried out by using X-ray fluorescence and X-ray diffraction techniques. Potential mobility of metals was assessed by using lixiviation test runs (DIN 38414-S4). Concentrations detected in soils and sediments were higher than the acceptable limits reported in official regulations. Regarding metals mobility, values obtained for Pb, Zn and As exceed the limits established by European Union for DIN 38414-S4 leachates. Whilst the obtained leaching percentages for Pb, Cu and As were not especially high (<2%), Zn exhibit a very high leaching potential (up to 60% of the total metal content), involving potential risk of pollution events.     

Molybdenum and Copper Uptake by Forage Grasses and Legumes Grown on a Metal‐Contaminated Sludge Site

Abstract

Wastes applied to agricultural land can contain significant concentrations of bioavailable molybdenum (Mo). Because Mo uptake by forage crops could lead to hypocuprosis in ruminants, more knowledge is needed about which crops are most efficient in accumulating Mo. At an old sewage sludge‐amended site, the concentrations of Mo, copper (Cu), and several other trace metals were measured in various grass species. Generally, the grasses grown on the sludge site contained higher Mo concentrations than the same species grown on a nearby control site. However, because Cu concentrations were also higher in the sludge‐grown grasses, Cu:Mo ratios in the grasses were frequently higher on the sludge site. In contrast, all legumes tested (alfalfa, birdsfoot trefoil, red clover, pea), as well as canola and beets, had lower Cu:Mo ratios when grown on the sludge site. Sulfur concentrations in the two crops analyzed for this element (canola and pea) were higher on the sludge site than the control. It is concluded that Mo, Cu, and sulfur (S) bioavailability remains elevated in the soil several decades after sewage sludge application.     

Water-soluble organic matter in incipient podzols: accumulation in B horizons or in fibres?

To elucidate the mechanism of podzolization in its first stages we studied the fate of the water-soluble organic matter (WSOM) in incipient podzols in sandy soils by comparing the composition of the WSOM from L, F and H horizons with that in the bulk of the Bh horizons and fibres of three profiles. The WSOM appeared to consist significantly of ligno-cellulose and proteins, but these biopolymers were hardly present in the Bh horizons. The material of the fibres, however, greatly resembled the WSOM composition, thereby suggesting that in these soils most of the WSOM is transported through the B horizon and accumulates hardly changed in thin bands where the water stops moving. This implies that in the early steps of podzolization, accumulation of organic matter in the B horizon is not likely to be caused by water-soluble material.     

Bioavailability of β-cryptoxanthin in the presence of phytosterols: in vitro and in vivo studies

Bioactive compounds are used in the design and development of new food products with potential health benefits, although little is known regarding their bioavailability and interactions. This study assessed the stability, in vitro bioaccessibility, and human bioavailability of β-cryptoxanthin from β-cryptoxanthin-rich drinks with and without added phytosterols developed for this purpose. The developed drinks showed no difference in the content of β-cryptoxanthin, and they were stable over 6 months. In vitro, hydrolysis of β-cryptoxanthin esters and the amount of free β-cryptoxanthin at duodenal and micellar phases were similar regardless of the presence of phytosterols. In the human study, the daily intake provoked significant increments of β-cryptoxanthin in serum regardless of the type of the drink. In conclusion, in vitro and in vivo human studies have shown that the bioavailability of β-cryptoxanthin is not significantly affected by the presence of phytosterols when they are simultaneously supplied in a drink.     

Difference in selenium accumulation in shoots of two rice cultivars

Two japonica rice （Oryza sativa L.） cultivars, Xiushui 48 and S. Andrea, differing in their ability to accumulate Se in the grain （as high as a three-fold difference）, were compared for selenium （Se） accumulation in their shoots when their growth media was supplied with different forms of Se. Results indicated that when treated with 0.25μmol L^-1 Na2SeO3, Xiushui 48 accumulation of Se in the shoots was significantly more rapid （P〈0.05） than S. Andrea, probably because of greater Se uptake and transport in Xiushui 48. Xiushui 48 rice seedlings had a higher shoot-Se accumulation rate and absorbed selenocysteine （Se-Cys） more rapidly than S. Andrea seedlings. However, when treated with Se as 0.25μmol L^-1 selenomethionine （Se-Met）, the S. Andrea seedlings＇ accumulation rate was significantly greater （P〈0.05） than that of Xiushui 48. Possibly, the high Se accumulation rate of Xiushui 48 seedling shoots compared to S. Andrea shoots was the result of a higher capacity of Xiushui 48 to transform selenite to organic Se compounds and a higher selenite uptake rate.     

Metal Contamination in Nullah Dek Water and Accumulation in Rice

A research study was carried out to determine the electrical conductivity （EC）, residual sodium carbonate （RSC）, sodium adsorption ratio （SAR）, pH and metals in metal-polluted irrigation water from a nullah and those in soils over a period of time, and the effect of metals on rice yield and metal concentrations in rice grain and straw. Two sites （I and If） were selected on the bank of Nullah Dek at Thatta Wasiran in Sheikhupura District （Pakistan）, with two rice varieties, Super Basmati and Basmati 385, at both sites. Water samples were collected during rice crop growth at 15-day intervals from August 3 to November 1, 2002. The results showed that Nullah Dek water had an EC 〉1.0 dS m^-1 and RSC of 2.78-4.11 mmolc L^-1, which was hazardous for crops, but the SAR was within the safe limit. Cu, Mn Cd and Sr were also within safe limits. The soil analysis showed that Site Ⅱ was free from salinity/sodicity, whereas Site Ⅰ was saline sodic. Among metals, Zn was sometimes deficient, Cu, Mn and Fe were adequate, and St, Ni and Cd were within safe limits in the soil at both the sites. After the rice crop harvest, concentrations of all metals tested were usually slightly increased, being higher in the upper soil layer than the lower. In addition, Basmati 385 produced higher rice grain and straw yield than Super Basmati. Chemical analysis of rice grain indicated the presence of Zn, Cu, Fe, Mn, Pb and Sr, whereas rice straw contained Zn, Cu, Fe, Mn and Sr, with Cd and Ni both being found in minute quantities.     

Metal contamination in Nullah Dek water and accumulation in rice

Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KCl were applied at rates of 187.5, 33.3, and 125 kg ha^-1, respectively, on soils derived from Quaternary red clay were conducted in the hilly red soil region of Zhejiang Province, China. Plant grains and stalks were collected for determination of K content. Seven equations were used to describe the kinetics of K release from surface soil samples taken before the corn experiments under electric field strengths of 44.4 and 88.8 V cm^-1 by means of electro-ultrafiltration （EUF） and to determine if their parameters had a practical application. The second-order and Elovich equations excellently described K release; the first-order, power function, and parabolic diffusion equations also described K release well; but the zero-order and exponential equations were not so good at reflecting K release. Five reference standards from the field experiments, including relative grain yield （yield of the NP treatment/yield of the NPK treatment）, relative dry matter yield （dry matter of the NP treatment/dry matter of the NPK treatment）, quantity of K uptake in the NP treatment （no K application）, soil exchangeable K, and soil HNO3-soluble K, were used to test the effectiveness of equation parameters obtained from the slope or intercept of these equations. Correlations of the ymax （the maximum desorbable quantity of K） in the second-order equation and the constant b in the first-order and Elovich equations to all five reference standards were highly significant （P ≤ 0.01）. The constant a in the power function equation was highly significant （P 〈 0.01） for four of the five reference standards with the fifth being significant （P ≤ 0.05）. The constant b in the parabolic equation was also significantly correlated （P ≤ 0.05） to the relative grain yield and soil HNO3-soluble K. These suggested that all of these parameters could be used to estimate the soil K supplying capacity and the crop response to K fertilizer.