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Cobalt element and Cobalt Nutiriton

Author : Doctor Liu Date : 8/23/2011 5:20:28 AM

Soil pH has a major effect on the uptake of cobalt, manganese, and nickel, which become more available to plants as the pH decreases. Increase in soil pH reduces the cobalt content of ryegrass (Lolium spp.) . Reducing conditions in poorly drained soils enhance the rate of weathering of ferromagnesian minerals, releasing cobalt, nickel, and vanadium . Liming decreased cobalt mobility in soil . The presence of humus facilitates cobalt accumulation in soil, but lowers its absorption by plants. Five percent humus has been shown to decrease cobalt content by one-half or two-thirds in cultures .
 High manganese levels in soil inhibit accumulation of cobalt by plants . Manganese dioxides in soil have a high sorption capacity and accumulate a large amount of cobalt from the soil solution. Much of the cobalt in the soil is fixed in this way and is thus not available to plants . Water logging of the soil increases cobalt uptake in French bean (Phaseolus vulgaris L.) and maize (Zea mays L.) .

Cobalt may be absorbed through the leaf in coniferous forests, but the majority is through the soil, especially in wetlands. The physicochemical status of transition metals such as cobalt in the rhizosphere is entirely different from that in the bulk soil. A microenvironment is created around the root system

Handbook of Plant Nutrition
(e.g., wheat and maize), characterized by an accumulation of root-derived organic material with a gradual shift from ionic metal to higher-molecular weight forms such as cobalt, manganese, and zinc. These three metals are increasingly complexed throughout the growth period. Fallow soil has been shown to complex lower amounts (6.4%) of tracers (57Co) than cropped soil, 61% for maize and 31% for wheat . Cobalt has a stimulatory effect on the microflora of tobacco (Nicotiana tabacum L.) rhizosphere, shown by an intensification of the immobilization of nitrogen and mineralization of phosphorus . Cobalt status in moist soil from the root zone of field-grown barley shows seasonal variation, being low in late winter and higher in spring and early summer. Discrete maxima are achieved frequently between May and early July, depending on the extent of the development of the growing crop and on seasonal influences. Increased concentration may result from the mobilization of the micronutrient from insoluble forms by biologically produced chelating ligands.

Interactions between cobalt and several essential enzymes have been demonstrated in plants and animals. Two metal-bound intermediates formed by Co2 activate ribulose-1,5 bisphosphate carboxylase/oxygenase (EC Studies by electron paramagnetic resonance (EPR) spectroscopy have shown the activity to be dependent on the concentration of ribulose 1,5 bisphosphate . This finding  suggested  that  the  enzyme-metal  coordinated  ribulose 1,5  bisphosphate  and  an enzyme-metal coordinated enediolate anion of it, where bound ribulose 1,5 bisphosphate appears first, constitute the two EPR detectable intermediates, respectively.
Ganson and Jensen  showed that the prime molecular target of glyphosate (N-[phosphonomethyl]glycine), a potent herbicide and antimicrobial agent, is known to be the shikimatepathway enzyme 5-enol-pyruvylshikimate-3-phosphate synthetase. Inhibition by glyphosate of an earlier  pathway  enzyme  that  is  located  in  the  cytosol  of  higher  plants, 3-deoxy-D-arabinoheptulosonate-7 phosphate synthase (DS-Co), has raised the possibility of dual enzyme targets in vivo. Since the observation that magnesium or manganese can replace cobalt as the divalentmetal activator of DS-Co, it has now been possible to show that the sensitivity of DS-Co to inhibition  by  glyphosate  is  obligately  dependent  on  the  presence  of  cobalt.  Evidence  for  a cobalt(II):glyphosate complex with octahedral coordination was obtained through examination of the effect of glyphosate on the visible electronic spectrum of aqueous solutions of CoCl2.
Two inhibition targets of cobalt and nickel were studied on oxidation-reduction enzymes of spinach (Spinacia oleracea L.) thylakoids. Compounds of complex ions and coordination compounds of cobalt and chromium were synthesized and characterized . Their chemical structures and  the  oxidation  states  of  their  metal  centers  remained  unchanged  in  solution.  Neither chromium(III) chloride (CrC13) nor hexamminecobalt(III) chloride [Co(NH3)6C13] inhibited photosynthesis. Some other coordination compounds inhibited ATP synthesis and electron flow (basal phosphorylating, and uncoupled) behaving as Hill-reaction inhibitors, with the compounds targeting electron transport from photosystem II (P680 to plastoquinones, QA and QB, and cytochrome).
The final step in hydrocarbon biosynthesis involves the loss of cobalt from a fatty aldehyde . This decarbonylation is catalyzed by microsomes from Botyrococcus braunii. The purified enzyme releases nearly one mole of cobalt for each mole of hydrocarbon. Electron microprobe analysis revealed that the enzyme contains cobalt. Purification of the decarbonylase from B. braunii grown in 57CoCl2  showed that 57Co co-eluted with the decarbonylase. These results indicate that the enzyme contains cobalt that might be part of a Co-porphyrin, although a corrin structure (as in vitamin B12) cannot be ruled out. These results strongly suggest that biosynthesis of hydrocarbons is effected by a microsomal Co-porphyrin-containing enzyme that catalyzes decarbonylation of aldehydes and, thus, reveals a biological function for cobalt in plants .
The role of hydrogen bonding in soybean (Glycine max Merr.) leghemoglobin was studied .  Two  spectroscopically  distinct  forms  of  oxycobaltous  soybean  leghemoglobin (oxyCoLb), acid and neutral, were identified by electron spin echo envelope modulation. In the Cobalt acid form, a coupling to 2H was noted, indicating the presence of a hydrogen bond to bound oxygen. No coupled 2H occurred in the neutral form . The oxidation-reduction enzymes of spinach thylakoids are also affected by chromium and cobalt .
 The copper chaperone for the superoxide dismutase (CCS) gene encodes a protein that is believed to deliver copper to Cu-Zn superoxide dismutase (CuZnSOD). The CCS proteins from different organisms share high sequence homology and consist of three distinct domains, a CuZnSOD-like central domain flanked by two domains, which contain putative metal-binding motifs. The Co2   -binding properties of proteins from arabidopsis and tomato (Lycopersicon esculentum Mill.) were characterized by UV-visible and circular dichroism spectroscopies and were shown to bind one or two cobalt ions depending on the type of protein. The cobalt-binding site that was common in both proteins displayed spectroscopic characteristics of Co2 bound to cysteine ligands .
 The inhibition of photoreduction reactions by exogenous manganese chloride (MnCl2) in Tristreated photosystem II (PSII) membrane fragments has been used to probe for amino acids on the PSII reaction-center proteins, including the ones that provide ligands for binding manganese. Inhibition of photooxidation may involve two different types of high-affinity, manganesebinding components: (a) one that is specific for manganese, and (b) others that bind manganese, but may also bind additional divalent cations such as zinc and cobalt that are not photooxidized by PSII. Roles for cobalt or zinc in PSII have not been proposed, however.
Cobalt uptake by plants allows its access to animals. Kosla  demonstrated the effect of irrigation of meadows with the water of the river Ner in Poland on the levels of iron, manganese, and cobalt in the soil and vegetation. Experiments were also carried out on young bulls (Bos taurus L.) fed with the hay grown on these meadows. The levels of iron and cobalt were determined in the blood plasma, and manganese level in the hair of the bulls. The irrigation caused an increase of the cobalt content in the soil, but had no effect on cobalt content in the plants or in the blood plasma of the bulls. Webb et al.  stated that animals may act as bioindicators for the pollution of soil, air, and water. To monitor changes over time, a baseline status should be established for a particular species in a particular area. The concentration of minerals in soil is a poor indicator of mineral accumulation by plants and availability to animals.
 The chemical composition of the body tissue, particularly the liver, is a better reflection of the dietary status of domestic and wild animals. Normal values for copper, manganese, and cobalt in the liver have been established for cattle, but not for African buffalo. As part of the bovine-tuberculosis (BTB) monitoring program in the KNP in South Africa, 660 buffalo were culled. Livers were randomly sampled in buffered formalin for mineral analysis. The highest concentrations of copper in livers were measured in the northern and central parts of the KNP, which is downwind of mining and refining activities. Manganese, cobalt, and selenium levels in the liver samples indicated neither excess nor deficiency although there were some significant area, age, and gender differences. It was felt that these data could serve as a baseline reference for monitoring variations in the level and extent of mineral pollution on natural pastures close to mines and refineries. Cobalt is routinely added to cattle feed, and deficiency diseases are known. Of interest also are the possible effects of minor and trace elements in Indian herbal and medicinal preparations .

The interaction of cobalt with other metals depends to a major extent on the concentration of the metals used. The cytotoxic and phytotoxic responses of a single metal or combinations are considered in terms of common periodic relations and physicochemical properties, including electronic structure,

Handbook of Plant Nutrition
ion parameters (charge-size relations), and coordination. But, the relationships among toxicity, positions, and properties of these elements are very specific and complex . The mineral elements in plants as ions or as constituents or organic molecules are of importance in plant metabolism. Iron, copper, and zinc are prosthetic groups in certain plant enzymes. Magnesium, manganese, and cobalt may act as inhibitors or as activators. Cobalt may compete with ions in the biochemical reactions of several plants .

Many trace elements in high doses induce iron deficiency in plants . Combinations of increased cobalt and zinc in bush beans have led to iron deficiency . Excess metals accumulated in shoots, and especially in roots, reduce ion absorption and distribution in these organs, followed by the induction of chlorosis, decrease in catalase activity, and increase in nonreducing sugar concentration in barley . Supplying chelated iron ethylenediamine di(o-hydroxyphenyl) acetic acid [Fe-(EDDHA),] could not overcome these toxic effects in Phaseolus spp. L. . Simultaneous addition of cobalt and zinc to iron-stressed sugar beet (Beta vulgaris L.) resulted in preferential transport of cobalt into leaves followed by ready transport of both metals into the leaf symplasts within 48 h . A binuclear binding site for iron, zinc, and cobalt has been observed .

Competitive absorption and mutual activation between zinc and cobalt during transport of one or the other element toward the part above the ground were recorded in pea (Pisum sativum L.) and wheat seedlings . Enrichment of fodder beet (Beta vulgaris L.) seeds before sowing with one of these cations lowers the content of the other in certain organs and tissues. It is apparently not the result of a simple antagonism of the given cations in the process of redistribution in certain organs and tissue, but is explained by a similar effect of cobalt and zinc as seen when the aldolase and carbonic anhydrase activities and intensity of the assimilators’ transport are determined .
 Cobalt tends to interact with zinc, especially in high doses, to affect nutrient accumulation . The antagonism is sometimes related to induced nutrient deficiency (69). In bush beans, however, cobalt suppressed to some extent the ability of high concentration of zinc to depress accumulation of potassium, calcium, and magnesium. The protective effect was stated to be the result of zinc depressing the leaf concentration of cobalt rather than the other nutrients . Substitution of Zn2 by Co2 reduces specificity of Zn2 metalloenzyme acylamino-acid-amido hydrolase in Aspergillus oryzae Cohn .

Combinations of elements may be toxic in plants when the individual ones are not . Trace elements usually give protective effects at low concentrations because some trace elements antagonize the uptake of others at relatively low levels. For example, trace elements in various combinations (Cu-Ni-Zn, Ni-Co-Zn-Cd, Cu-Ni-Co-Cd, Cu-Co-Zn-Cd, Cu-Ni-Zn-Cd, and Cu-Ni-Co-Zn-Cd) on growth of bush beans protected against the toxicity of cadmium. It was suggested that part of the protection could be due to cobalt suppressing the uptake of cadmium by roots. Other trace elements in turn suppressed the uptake of cobalt by roots . These five trace elements illustrated differential partitioning between roots and shoots . The binding of toxic concentration of cobalt in the cell wall of the filamentous fungus (Cunninghamella blackesleeana Lender) was totally inhibited and suppressed by trace elements .


The biphasic mechanism involved in the uptake of copper by barley roots after 2 h was increased with 16 μM Co2   , but after 24 h, a monophasic pattern developed with lower values of copper on the uptake site .

Cobalt and zinc increased the accumulation of manganese in the shoots of bush beans grown for 3 weeks in a stimulated calcareous soil containing Yolo loam and 2% CaCO3 
The inhibitory effects of chromium and tin on growth, uptake of NO3  and NH4 , nitrate reductase, and glutamine synthetase activity of the cyanobacterium (Anabaena doliolum Bharadwaja) was enhanced when nickel, cobalt, and zinc were used in combination with test metals in the growth medium in the following degree: Ni  Co  Zn .

The  activating  effect  of  cobalt  on  Mg2 -dependent  activity  of  glutamine  synthetase  by  the blue-green alga Spirulina platensis Geitler may be considered as an important effect. Its effect in maintaining the activity of the enzyme in vivo is independent of ATP .

The mold Cunninghamella blackesleeana Lendner, grown in the presence of toxic concentration of cobalt, showed elevated content of sulfur in the mycelia. Its cell wall contained higher concentrations of phosphate and chitosan, citrulline, and cystothionine as the main cell wall proteins .

In moss (Timmiella anomala Limpricht), nickel overcomes the inhibitory effect of cobalt on protonemal growth whereas cobalt reduces the same effect of nickel on bud number .

Cyanide in soil was toxic to bush beans and also resulted in the increased uptake of the toxic elements such as copper, cobalt, nickel, aluminum, titanium, and, to a slight extent, iron. The phytotoxicity from cyanide or the metals led to increased transfer of sodium to the leaves and roots .


Senescence in lettuce leaf in the dark is retarded by cobalt, which acts by arresting the decline of chlorophyll, protein, RNA and, to a lesser extent, DNA. The activities of RNAase and protease, and tissue permeability were decreased, while the activity of catalase increased . Cobalt delays ageing and is used for keeping leaves fresh in vetch (Vicia spp.) . It is also used in keeping fruits such as apple fresh .
Presowing treatment of seeds with cobalt nitrate increased drought resistance of horse chestnut (Aesculus hippocastanum L.) from the Donets Basin in southeastern Europe .

Alkaloid accumulation in medicinal plants such as downy thorn apple Datura innoxia Mill. , Atropa caucasica , belladonna A. belladonna L. , and horned poppy Glaucium flavum Crantz  is regulated by cobalt. It also increased rutin (11.6%) and cyanide (67%) levels in different species of buckwheat (Fagopyrum sagittatum Gilib., F. tataricum Gaertn., and F. emargitatum) .

Handbook of Plant Nutrition

Shelf and vase life of marigold (Tagetes patula L.), chrysanthemum (Chrysanthemum spp.), rose (Rosa spp.), and maidenhair fern (Adiantum spp.) is increased by cobalt. Cobalt also has a longlasting effect in preserving apple (Malus domestica Borkh.). The fruits are kept fresh by cobalt application after picking
Cobalt acts as a chelator of salicylidine-o-aminothiophenol (SATP) and salicylidine-o-aminopyridine (SAP) and exerts biocidal activity against the molds Aspergillus nidulans Winter and A. niger Tiegh and the yeast Candida albicans . Antifungal activities of Co2 with acetone salicyloyl hydrazone (ASH) and ethyl methyl ketone salicyloyl hydrazone (ESH) against A. niger and A. flavus have been established by Johari et al. .

Cobalt inhibits IAA-induced ethylene production in gametophores of the ferns Pteridium aquilinum Kuhn and sporophytes of ferns Matteneuccia struthiopteris Tod. and Polystichum munitum K. Presl ; in pollen embryo culture of horse nettle (Solanum carolinense L.) ; in discs of apple peel ; in winter wheat and beans ; in kiwifruit (Actinidia chinensis Planch) ; and in wheat seedlings under water stress . Cobalt also inhibits ethylene production and increases the apparent rate of synthesis of peroxides and prevents the peroxidative destruction of IAA. Other effects include counteraction of the uncoupling of oxidative phosphorylation by dinitrophenol . Cobalt acts mainly through arresting the conversion of methionine to ethylene  and thus inhibits ethylene-induced physiological processes. It also causes prevention of cotyledonary prickling-induced inhibition of hypocotyls in beggar tick (Bidens pilosa L.) , promotion of hypocotyl elongation  opening of the hypocotyl hook (bean seedlings) either in darkness or in red light, and the petiolar hook (Dentaria diphylla Michx.) . Cobalt has also been noted to cause reduction of RNAase activity in the storage tissues of potato , repression of developmental distortion such as leaf malformation and accumulation of low-molecular-weight polypeptides in velvet plant (Gynura aurantiaca DC) , delayed gravitropic response in cocklebur (Xanthium spp.), tomato and castor bean stems , and prevention of 3,6-dichloro-o-anisic acid-induced chlorophyll degradation in tobacco leaves . Prevention of auxin-induced stomatal opening in detached leaf epidermis has been observed . The effects of ethylene on the kinetics of curvature and auxin redistribution in the gravistimulated roots of maize are known . 60Co γ-rays and EMS influence antioxidase activity and ODAP content of grass pea (Lathyrus sativus L.) .

Cobalt is essential for nitrogen-fixing microorganisms, including the cyanobacteria. Its importance in nitrogen fixation by symbiosis in Leguminosae (Fabaceae) has been established . For example, soybeans grown with only atmospheric nitrogen and no mineral nitrogen have rapid nitrogen fixation and growth with 1.0 or 0.1 μg Co ml  1, but have minimal growth without cobalt additions .