Plant Macro- and Micronutrient Minerals

Michael A Grusak, USDA/ARS Childrens Nutrition Research Center, Texas, USA

All plants must obtain a number of inorganic mineral elements from their environment to ensure successful growth and development of both vegetative and reproductive tissues. A total of fourteen mineral nutrients are required.

Secondary article
Article Contents
. Introduction . Criteria for Essentiality . Functions and Sources of Mineral Nutrients . Nutrient Deficiencies

Introduction
All plants must obtain a number of inorganic mineral elements from their environment to ensure successful growth and development of both vegetative and reproductive tissues. These minerals serve numerous functions: as structural components in macromolecules, as cofactors in enzymatic reactions, as osmotic solutes needed to maintain proper water potential, or as ionized species to provide charge balance in cellular compartments. Minerals can be divided into two classes, based on the relative amounts needed for plant growth (see Table 1). The macronutrients include nitrogen (N), potassium (K), calcium (Ca), magnesium (Mg), phosphorus (P) and sulfur (S); these are generally found in plants at concentrations greater than 0.1% of dry tissue weight. The currently recognized micronutrients include iron (Fe), zinc (Zn), manganese (Mn), copper (Cu), boron (B), chlorine (Cl), molybdenum (Mo) and nickel (Ni); these generally are found at concentrations less than 0.01% of dry tissue weight. These

14 minerals, along with the elements carbon (C), hydrogen (H) and oxygen (O), are broadly accepted as essential for the growth of all plants. Additional minerals, such as cobalt (Co), sodium (Na), silicon (Si), selenium (Se), iodine (I) and vanadium (V), have been shown to be essential or benecial for certain plant species, but their widespread essentiality has yet to be established. Many other elements can be found in plants (over half the elements in the periodic table have been identied in some plant tissue), but these are thought to enter plants nonselectively. Most of these nonessential elements confer no known benet to the plant, and many, such as cadmium (Cd) or chromium (Cr), are actually detrimental to plant growth.

Criteria for Essentiality

Scientists have been interested in plant mineral requirements for many years. As long ago as the early 1800s, it was recognized that mineral fertilization of soils could stimu-

Table 1 Average concentrations of mineral nutrients in plant shoots (dry weight basis) considered sucient for adequate growtha Element mmol g 2 1 mg g 2 1 % Relative number of atoms 1 1 100 300 1000 2000 2000 3000 30 000 60 000 80 000 125 000 250 000 1 000 000

Molybdenum Nickelb Copper Zinc Manganese Iron Boron Chlorine Sulfur Phosphorus Magnesium Calcium Potassium Nitrogen
a

0.001 0.001 0.10 0.30 1.0 2.0 2.0 3.0 30 60 80 125 250 1000

0.1 0.1 6 20 50 100 20 100

0.1 0.2 0.2 0.5 1.0 1.5

From Epstein (1972).bBased on Brown et al. (1987).

ENCYCLOPEDIA OF LIFE SCIENCES / & 2001 Nature Publishing Group / www.els.net

Plant Macro- and Micronutrient Minerals

late growth and improve crop yields. By the early 1900s, the six macronutrients N, P, K, S, Ca and Mg, along with the micronutrient Fe, were regarded as critical for plant growth, but the status of the other micronutrients was uncertain and quite controversial. In 1939, three criteria were suggested for classication of a chemical element as an essential mineral nutrient (Arnon and Stout, 1939). These can be restated as: (1) a given plant must be unable to complete either the vegetative or reproductive stages of its life cycle in the absence of the mineral nutrient; (2) the function of the element is specic for that element and cannot be replaced by another mineral element; and (3) the element must be directly involved in a plant metabolic or structural process, rather than having an indirect eect on plant growth through the correction of some unfavourable microbiological or chemical condition of the soil. Plant nutritionists have used the technique of solution culture, or hydroponics, to assess these criteria in various plant species. Hydroponics is a method in which plants are grown in an aerated liquid medium of dened chemical composition; individual nutrients can be selectively withheld from this medium to test the inuence of their absence on plant growth and metabolism. All micronutrient minerals so far deemed essential have been determined using hydroponic culture, with experiments sometimes requiring exhaustive removal of impurities from the chemicals used to make the hydroponic solutions, absolute cleansing of containers used to grow the plants, and/or ltration of the air supply to prevent contamination from dust. Thanks to these eorts, a clearer understanding of the common essential mineral nutrients has been established.

phytosiderophores). Nitrogen is also a major structural component of chlorophyll.

Potassium
Potassium is absorbed as the cation, K 1 , which is readily soluble in soil solutions. It is the most abundant cation in the cytoplasm and, because it is not metabolized, K 1 and its accompanying anions contribute signicantly to the osmotic potential of cells. Thus, potassium functions in plant water relations processes and aects cell extension and growth through the regulation of turgor, leaf gas exchange through the control of stomatal opening/closing, and long-distance nutrient ow through pressure-driven phloem translocation. The potassium ion also helps establish the electrochemical gradient across membranes, and thus contributes to the membrane transport of numerous chemical species.

Calcium
The major functions of calcium are related to its capacity to form coordinate bonds, and its ability to establish stable but reversible intra- and intermolecular linkages, especially in the cell wall and at the surface of membranes. Calcium is readily absorbed from soils as the abundant cation, Ca2 1 , but its free ion concentration in the cytoplasm is kept low by sequestration in the vacuoles, by complexing with calcium-binding proteins (e.g. calmodulin), or by chemical precipitation as calcium oxalate crystals. Calcium plays an important role in stimulusresponse coupling involving signal transduction pathways, as its release from intracellular pools activates various protein kinases, phosphatases, or phospholipases, whose target molecules subsequently regulate many cellular functions (Bush, 1995).

Functions and Sources of Mineral Nutrients

Nitrogen
As a constituent of all amino acids and proteins (and thus all enzymes), nitrogen serves a central role in cellular metabolism. Additionally, as a component of nucleotides and nucleic acids (deoxyribonucleic acid (DNA) and ribonucleic acid (RNA)), nitrogen is critical for the transcription, translation and replication of genetic information. Nitrogen is obtained from the soil environment either as the ammonium (Ne) or nitrate (N4 ) ions, with nitrate being chemically reduced within the plant to ammonium prior to incorporation into organic molecules. An alternative source of nitrogen for some species is atmospheric nitrogen (N2), obtained through the process of nitrogen xation. Other nitrogenous compounds include various secondary metabolites derived from amino acids; these include compounds of low relative molecular mass used in osmoregulation (e.g. betaine), stress responses (e.g. plant hormones), or metal chelation (e.g.
2

Magnesium
Magnesium is absorbed as the highly soluble divalent cation, Mg2 1 , and its functions in plants relate to its capacity to interact with various ligands through ionic bonding. Numerous enzymes and enzyme reactions require or are strongly promoted by magnesium, including phosphatases, adenosine triphosphatases (ATPases), and carboxylases (e.g. ribulose-bisphosphate carboxylase). Adenosine triphosphate (ATP) synthesis has an absolute requirement for magnesium and Mg2 1 plays an essential function in protein synthesis, because it serves as a bridging element for the aggregation of ribosome subunits. Additionally, magnesiums most signicant function in green tissues is its role as the central atom in the porphyrin structure of the chlorophyll molecule.

ENCYCLOPEDIA OF LIFE SCIENCES / & 2001 Nature Publishing Group / www.els.net

Plant Macro- and Micronutrient Minerals

Phosphorus
Phosphorus is a structural component of numerous macromolecules, including nucleic acids, phospholipids, certain amino acids, and several coenzymes. It has a signicant role in energy transfer via the pyrophosphate bond in ATP, and the attachment of phosphate groups to many dierent sugars provides metabolic energy in photosynthesis and respiration. Phosphorus is absorbed by plants largely as the primary or secondary orthopho2 2 and HPO2 sphate anions, H2PO4 4 .

complexed with macromolecules. The metabolic functions of zinc are based on its ability to form tetrahedral complexes with N-, O-, and S-ligands (Vallee and Auld, 1990), thereby inuencing both the tertiary structure of proteins (e.g. via the formation of zinc ngers) and enzyme catalytic activity. Important zinc-containing enzymes are alcohol dehydrogenase, carbonic anhydrase, superoxide dismutase and RNA polymerase.

Manganese
The predominant source of manganese in soils is Mn2 1 , but manganese can exist in the oxidation states ii , iii and iv, within biological systems. Because Mn(ii) can be oxidized readily to Mn(iv), manganese plays an important role in redox reactions. Of prominence are its inclusion in the manganese-containing superoxide dismutase, and in the water-splitting protein complex associated with photosystem II. Manganese also serves as a cofactor, activating numerous enzymes involved in the catalysis of oxidation reduction, decarboxylation and hydrolytic reactions.

Sulfur
Although atmospheric sulfur dioxide SO2, can be taken up and utilized by the aerial parts of plants, most sulfur is absorbed by plant roots as the divalent sulfate anion, 2 SO2 4 . Sulfate reduction then is required for the incorporation of sulfur into organic compounds. Sulfur is a constituent of the amino acids cysteine and methionine, and thus is a component of proteins, as well as several sulfur-containing coenzymes and secondary plant products derived from these amino acids. Because sulfur groups (e.g. thioethers, R-C-S-C-R or thiols, R-S-H; with R representing various chemical groups) can be reversibly oxidized and reduced, they impart protein stability via the formation of -SS- bridges and play central roles in enzymes that regulate reductionoxidation (redox) or acidbase reactions. Important sulfur compounds are the tripeptide glutathione, involved in detoxication of oxygen radicals; phytochelatins and metallothioneins, involved in heavy metal detoxication; and the proteins thioredoxin and ferrodoxin, involved in redox chemistry.

Copper
Copper is a transition metal found in soils either as the divalent (Cu2 1 ) or monovalent (Cu 1 ) cation. It complexes readily with many organic molecules, including proteins, and its strong electron anity in the monovalent form makes it well suited for numerous redox reactions. Copper-containing proteins can be grouped into three types (Sandmann and Bo ger, 1983): blue proteins, which function in one-electron transfer, such as plastocyanin, a component of the electron transport chain in photosystem I; non-blue proteins, which catalyse peroxidation reactions, such as CuZn-superoxide dismutase; and multicopper proteins, which contain at least four copper atoms per molecule and act as oxidases, such as cytochrome oxidase in the mitochondria.

Iron
Iron is a transition metal characterized by its ability to readily change its oxidation state from Fe3 1 to Fe2 1 , and by its eectiveness in forming octahedral complexes with various ligands. When incorporated into proteins, these attributes allow for controlled reversible redox reactions. Iron is found in haem proteins (which contain iron porphyrin complexes), such as cytochromes, peroxidases and catalases; in ironsulfur proteins, such as ferrodoxin, aconitase and superoxide dismutase; and in other ironcontaining enzymes, such as lipoxygenase. Iron also is required for various reaction steps in the biosynthesis of chlorophyll. Iron is found in soils predominantly as the ferric ion, Fe3 1 , but absorption mechanisms exist in dierent species for either the trivalent or divalent forms of iron.

Boron
The chemical species of boron that is absorbed by plants has not been established, but it is clear that boric acid, B(OH)3, predominates in acidic to neutral biological and soil solutions, and at alkaline pH, the borate anion 2 ] is formed. Boric acid forms complexes with [B(OH)4 diols and polyols, such as sugar alcohols and uronic acids, and thus boron plays an important role in the bridging of cell wall polymers (Blevins and Lukaszewski, 1998). Boron also contributes to the integrity and functioning of the plasma membrane, probably by aecting physical properties of membrane proteins.
3

Zinc
Zinc is taken up predominantly as a divalent cation, Zn2 1 , and it exists only in the Zn(ii ) oxidation state when

ENCYCLOPEDIA OF LIFE SCIENCES / & 2001 Nature Publishing Group / www.els.net

Plant Macro- and Micronutrient Minerals

Chlorine
Chlorine is present in aqueous solutions as the monovalent chloride ion, Cl 2 , and it is readily absorbed by plants in this form. Although numerous chlorinated organic compounds have been found in plants, few functional roles for these compounds are known. Chloride is required for the water-splitting protein complex of photosystem II, it stimulates the activity of the vacuolar proton-pumping ATPase, and it can function in osmoregulation, especially in stomatal guard cells.

Molybdenum and nickel

The requirements of plants for molybdenum and nickel are the least of all the mineral nutrients. These minerals are transition elements capable of existing in multiple oxidation states, and thereby function in redox reactions. Only a few enzymes have been conrmed that require these minerals: these are nitrate reductase, nitrogenase and xanthine oxidase/dehydrogenase for molybdenum, and urease for nickel. Thus, both of these minerals serve important roles in nitrogen metabolism.

Nutrient Deficiencies
A plants ability to obtain adequate levels of essential minerals depends in part on the availability of these minerals in the soil environment, as well as the presence of appropriate transport proteins and related ion acquisition mechanisms in the plasma membranes of root cells (Kochian, 1991). Availability is not solely a function of how much of a mineral is in the soil matrix, but more importantly depends on the molar fraction present in soil solution, and on the speciation of that minerals ions (Lindsay, 1991). Abiotic factors such as pH, redox state, and temperature can inuence mineral speciation and solubility, as can biotic factors such as microbial release of organic acids and phenolic compounds, either generated metabolically or through degradation of soil organic matter. Plant roots also can modify the rhizosphere to aect nutrient availability, through the release of protons, chelators and/or chemical reductants. When challenged with a specic nutrient deciency, i.e. low availability, plants can induce high-anity transporters and other mechanisms in their roots, to assist in meeting their mineral nutrient requirements. Mineral deciencies aect plant growth by limiting the biosynthesis or expression of key components of energy capture and/or metabolism. For example, deciencies of N, Fe or Mg reduce chlorophyll synthesis and thus photosynthetic capacity, and result in chlorosis, or yellowing, of leaves. Deciencies of P, K or S impact metabolites or enzymes involved in photosynthesis and respiration; this
4

leads to inadequacies in the transfer of light energy to chemical bonds, or in the export of sugars from chloroplasts, and can result in the development of necrotic lesions on leaves. Similarly, deciencies of Zn, Cu or Mn can impair enzyme activity or the function of structural proteins, such that overall metabolism is reduced; these deciencies also lead to chlorotic or necrotic symptoms. Interestingly, the occurrence of deciency symptoms throughout the plant can dier from older to younger leaves, depending on whether the mineral can be mobilized in the phloem pathway from older senescing tissues to young growing regions of the plant. For instance, Ca has poor phloem mobility, and Ca deciency leads to necrosis of new leaves and apical meristems, whereas a deciency of K, which is highly phloem mobile, appears initially on older, more mature leaves at the base of the plant. Because mineral deciencies impair plant growth and metabolism, their most signicant outcome in the case of agronomically important crop plants is a reduction in harvest yields, or in some cases, total loss of the crop. However, even moderate nutrient deciencies can reduce the general health of the plant, inhibiting its ability to withstand environmental or biotic stresses. Additionally, as all the essential minerals required by plants are essential for the health of humans and other animals, plant mineral deciencies can reduce the nutritional content and quality of our harvested food supply (Grusak and DellaPenna, 1999).

References
Arnon DI and Stout PR (1939) The essentiality of certain elements in minute quantity for plants with special reference to copper. Plant Physiology 14: 371375. Blevins DG and Lukaszewski KM (1998) Boron in plant structure and function. Annual Review of Plant Physiology and Plant Molecular Biology 49: 481500. Brown PH, Welch RM and Cary EE (1987) Nickel: a micronutrient essential for higher plants. Plant Physiology 85: 801803. Bush DS (1995) Calcium regulation in plant cells and its role in signaling. Annual Review of Plant Physiology and Plant Molecular Biology 46: 95122. Epstein E (1972) Mineral Nutrition of Plants: Principles and Perspectives. New York: Wiley. Grusak MA and DellaPenna D (1999) Improving the nutrient composition of plants to enhance human nutrition and health. Annual Review of Plant Physiology and Plant Molecular Biology 50: 131161. Kochian LV (1991) Mechanisms of micronutrient uptake and translocation in plants. In: Mortvedt JJ, Cox FR, Shuman LM and Welch RM (eds) Micronutrients in Agriculture, pp. 229296. Madison, WI: Soil Science Society of America. Lindsay WL (1991) Inorganic equilibria aecting micronutrients in soils. In: Mortvedt JJ, Cox FR, Shuman LM and Welch RM (eds) Micronutrients in Agriculture, pp. 89112. Madison, WI: Soil Science Society of America. Sandmann G and Bo ger P (1983) The enzymatological function of heavy metals and their role in electron transfer processes of plants. In: La uchli A and Bieleski RL (eds) Encyclopedia of Plant Physiology, New Series, vol. 15A, pp. 563596. Berlin: Springer-Verlag.

ENCYCLOPEDIA OF LIFE SCIENCES / & 2001 Nature Publishing Group / www.els.net

Plant Macro- and Micronutrient Minerals

Vallee BL and Auld DS (1990) Zinc coordination, function, and structure of zinc enzymes and other proteins. Biochemistry 29: 5647 5659.

Further Reading
da Silva JJRF and Williams RJP (1991) The Biological Chemistry of the Elements: The Inorganic Chemistry of Life. Oxford: Oxford University Press.

Fox TC and Guerinot ML (1998) Molecular biology of cation transport in plants. Annual Review of Plant Physiology and Plant Molecular Biology 49: 669696. Grusak MA, Pearson JN and Marentes E (1999) The physiology of micronutrient homeostasis in eld crops. Field Crops Research 60: 4156. Loneragan JF (1997) Plant nutrition in the 20th and perspectives for the 21st century. Plant and Soil 196: 163174. Marschner H (1995) Mineral Nutrition of Higher Plants. San Diego, CA: Academic Press.

ENCYCLOPEDIA OF LIFE SCIENCES / & 2001 Nature Publishing Group / www.els.net