Microelemente
Microelemente
Abstract Microelements viz. zinc (Zn), iron (Fe), manganese (Mn), copper (Cu),
molybdenum (Mo), boron (B), chlorine (Cl) and nickel (Ni) have been recognized
as essential and silicon (Si), sodium (Na), cobalt (Co), and strontium (Sr) as
beneficial or quasi-essential for plants. In addition to these plant essential microel-
ements, human beings and animals require chromium (Cr), iodine (I) and selenium
(Se). Microelements are used in relatively small amounts and constitute less than
0.1% of dry plant tissue. Some of the microelements may be toxic when consumed
at high amounts. Soil is the main source of microelements for plants, except in
situations of large atmospheric deposition or from flooding by contaminated waters.
The microelements in soils undergo several transformations and their availability to
plants depends on the chemical form and distribution between soil’s solid and liquid
phases, which is influenced by soil conditions, particularly pH, texture and soil
aeration status. Microelements perform a variety of functions in plants. Besides
being component of enzymes, certain microelements are involved in activation of
enzymes and play a role in oxidation-reduction reactions of plant metabolism.
Micronutrient deficiencies in plants not only limit agricultural production but also
affect human nutrition as plant food is the main source of dietary intake. Microel-
ements in humans play several physiological functions including synthesis of
enzymes, hormones and other substances, helping to regulate growth, development
and functioning of the immune and the reproductive systems. Deficiencies of
microelements in soil and plants can be corrected by applying chemical fertilizers
either alone or in combination with organic manures. Micronutrient level in humans
can be optimized through dietary diversification, mineral supplementation, food
fortification, or increasing their concentrations and/or bioavailability in food prod-
ucts. Correction of deficiencies and optimization of micronutrient levels in humans
depends on several factors including current dietary intake, food habits and the
nutrient content of the food items consumed, metabolic pathway of a nutrient,
current body stocks, age, gender, and body weight. In this chapter, we discuss
sources of microelements, their transformations in soil, functions in plants and
humans, effects of their deficient and excessive uptake on plants and humans, and
the approaches to optimize their levels in plants and humans.
Eight microelements viz. zinc (Zn), iron (Fe), manganese (Mn), copper (Cu),
molybdenum (Mo), boron (B), chlorine (Cl), and nickel (Ni) have been recognized
as essential for plants. In addition, there are some quasi-essential or beneficial
elements including silicon (Si), sodium (Na), cobalt (Co), and strontium (Sr) that
are required by a particular group of plants for optimum growth and production.
Besides these plant essential microelements, human beings and animals require
chromium (Cr), iodine (I) and selenium (Se) in small amounts. Essentiality of
arsenic (As), fluorine (F), tin (Sn) and vanadium (V) for animals has been observed
under highly specialized conditions and these could be considered beneficial. While
plants need mineral elements, air and water and can synthesize the necessary
biomolecules such as amino acids and vitamins on their own, the animals and
humans cannot synthesize organic molecules and thus require micronutrients in the
form of vitamins (A, B, C, D, E and K) as well as minerals. In this chapter,
discussion will be primarily confined to microelements B, Cu, Co, I, Mn, Mo, Fe
and Zn, which are of most practical significance in agriculture and human health.
We have added iodine in the list even though it has not been found essential for
plants, but it is very important for humans and its deficiency has been reported
worldwide causing several illnesses or disorders. Besides being essential, some of
the microelements such as Cu, Zn, Se and Cr may be toxic when consumed at high
amounts and these are discussed in Chap. 8.
Microelements are used in relatively small amounts and constitute less than
0.1% of dry plant tissue (Table 7.1). Their uptake is usually expressed in parts per
million (ppm) or mg kg 1 but this does not mean that microelements are of lesser
importance. They have enormous impact on human health. Insufficient dietary
intakes of microelements impair several functions of the central nervous system,
reproductive system, enzyme activities and energy metabolism and thus lead to
serious illnesses. The concentrations of microelements differ greatly among soils,
plants and human body and the average concentrations shown in Table 7.1 are only
indicative of their relative abundance.
7.2 Sources of Microelements 319
Table 7.1 Mean concentrations (mg kg 1) of microelements in Earth’s crust, soil (the upper
meter), plants and human body
Element Crust Soil Plant Human body
Boron (B) 17 10 50 0.30
Chromium (Cr) 35 70 – 0.094
Cobalt (Co) 12 8 0.5 0.021
Copper (Cu) 14 20 14 1.0
Fluorine (F) 610 200 – 37
Iodine (I) 1.4 5 0.005 0.19
Iron (Fe) 31,000 40,000 140 60
Lead (Pb) 17 35 – –
Manganese (Mn) 530 800 630 0.17
Molybdenum (Mo) 1.4 3 0.05 0.08
Nickel (Ni) – – – 0.14
Selenium (Se) 0.083 0.01 0.05 0.11
Silicon (Si) – 330,000 1000 260
Sodium (Na) – 7000 1200 1400
Vanadium (V) 53 90 – 0.11
Zinc (Zn) 52 50 100 33.0
Compiled from Bohn et al. (1979), Fortescue (1980) and Lindh (2005)
Soil is the main source of microelements for plants, except in situations of heavy
atmospheric deposition or from flooding by contaminated waters. In soils, micro-
elements are generally derived from the minerals present in the parent material, and
these become plant available by weathering of soil minerals. Based on the affinity
of elements for different minerals, these may be classified as Lithophile,
Chalcophile and Siderophile elements. Lithophiles (B, Zn, Mn and Fe) show
affinity for silicate minerals, Chalcophiles (Zn, Cu and Ni) for sulphide minerals
and Siderophiles (Fe, Cu, Mo and Ni) for iron minerals. Some elements also show
secondary affinity for silicate (Fe) and sulphide (Fe and Mo) minerals. Of the
essential microelements, Co, Cu and Zn (also called heavy metals) are in lower
concentration in soils than in the material from which they are derived. All the
essential elements are derived not only from the soil minerals but some trace
elements such as boron, iodine, and selenium are supplied in significant amounts
to soils by atmospheric transport from the marine environment. The microelements
are usually taken up from soil in ionic form by the plant (Table 7.2) and their
availability to plants is controlled by a number of physical, chemical and biological
processes and transformations in soil. Boron is usually absorbed in non-ionic form
as boric acid, which has a strong ability to form complexes with diols and polyols
inside the plant (Loomis and Durst 1992). However, in certain situations, B is also
absorbed in ionic form as borate.
320 7 Microelements and Their Role in Human Health
Boron
Boron is a metalloid belonging to Group IIIA and period 2 of the Periodic Table of
Elements. It has an atomic mass of 10.81 and an atomic number 5. It ranks 51st in the
order of abundance in the Earth’s crust with an average concentration of 17 mg kg 1
(Steinnes 2009). Its concentration, in rocks, averages about 10–20 mg B kg 1. In
nature, B is always bound to oxygen as borate, less frequently as boric acid and rarely to
fluorine as in BF4 (Power and Woods 1997). Boron, in the environment, originates
mainly from marine salts, volcanic activity, and industrial pollution. Most soils have a
low B content. Soils high in B content are associated with recent volcanic activity
(Power and Woods 1997). Based on B content, soils may be divided into low (<10 mg
B kg 1) and high B containing (10–100 mg B kg 1). The sources of B include
concentrated mineral deposits that are associated with former geologic volcanic activity
and were formed because of steam volatility of boric acid. The primary B minerals
include ulexite NaCa[B5O6(OH)6]5H2O, borax (tincal) Na2[B4O5(OH)4]8H2O, natu-
ral boric acid (sassolite), colemanite Ca[B3O4(OH)2]2H2O, kernite Na2[B4O5(OH)4]
2H2O; datolite 2CaOB2O32SiO2H2O, hydroboracite CaOMgO3B2O36H2O; tour-
maline Na(FeMg)3Al6(OH)4(BO3)3Si6O8 and ascharite 2MgOB2O3H2O (Erd 1980).
Besides these natural minerals, some soluble borates are used as sources of B in
agriculture.
Cobalt
Cobalt is a lustrous silver-white, hard and brittle transition metal belonging to
Group VIII and period 4 of the Periodic Table of Elements. It has an atomic mass
of 58.93 and an atomic number 27. Cobalt is of relatively low abundance in the
Earth’s crust and most of it occurs in the Earth’s core. Its concentration averages
12 mg kg 1 in Earth’s crust and 5–45 mg kg 1 in rocks. The concentration of Co in
soils ranges between 4.5 and 12 mg kg 1 and averages 8 mg kg 1. Cobalt and iron
occur together in many geological materials and have several similar properties
such as ionic radii and charge and can replace each other. Similar to iron, cobalt can
also be magnetized. Cobalt has oxidation states varying from +1 to +5; the most
common being +2 and +3. Cobalt is stable in air and unaffected by water, but is
slowly attacked by dilute acids. Cobalt is generally found in the form of ores and the
main ores include cobaltite (CoAsS), erythrite (Co2(AsO4)2∙8 H2O), skutterudite
also called smaltite (CoAs2–3), linneite (Co3S4), and glaucodot (Co,Fe)AsS.
7.2 Sources of Microelements 321
Copper
Copper is a reddish transition metal belonging to Group IB and period 4 of the
Periodic Table of Elements. It has an atomic mass of 63.546 and an atomic number
29. It forms monovalent (cuprous) and divalent (cupric) cations. It is mined as a
primary ore product from CuS and oxide ores (Table 7.3). The mean concentration
of Cu in earth’s crust is 14 mg kg 1, which is lower than the median value of
30 mg kg 1 reported for soils. Its concentration in rocks averages between 30 and
140 mg kg 1.
Iodine
Iodine is a dark-grey/purple-black non-metal and belongs to Group VIIA and period
5 of the Periodic Table of Elements. It is the most electropositive halogen and is the
least reactive of the elements in this group. It has an atomic mass of 126.9 and an
atomic number of 53. Iodine has two radioactive isotopes, 129I (half-life 16 million
years) and 131I (8 days), which as by-products of atomic reactors are released into
the environment. Iodine forms simple anion with oxidation state 1 and exhibits
lithophilic properties. It is highly mobile in the Earth’s crust and its content in upper
continent crust is estimated to vary between 0.15 and 1.4 mg kg 1 (Kabata-Pendias
and Mukherjee 2007). Iodine content is highest in shales (~1.5 mg kg 1), interme-
diate in lime stones (~1 mg kg 1), and the lowest in acid igneous rocks (~ 0.17 mg
kg 1). Deep-sea carbonates contain high amounts (~30 mg kg 1) of iodine
(Muramatsu and Wedepohl 1998). Iodine content in soil varies over a wide range
(average 2.8 mg kg 1) from less than 1 mg kg 1 in areas far inland to about 15 mg
kg 1 in organic rich soils near the coast (Låg and Steinnes 1976). Volcanic ash soils
contain high amounts of iodine, up to 104 mg kg 1, and solonchak soils of arid and
semiarid regions contain up to 340 mg kg 1 (Kabata-Pendias and Pendias 2001).
Iodine content is usually higher in fine-textured soils rich in humus compared to
light soils of humid climates. But there could be large variations in soil iodine
content because of difference in atmospheric deposition depending on the distance
from the coast. Soils close to the coast are rich in iodine, whereas those derived
from recent glacial deposits are generally poor in this element (Kabata-Pendias and
Mukherjee 2007). The major source of iodine appears to be volatile methyl iodide
released by marine organisms (Yoshida and Muramatsu 1995) and transferred from
ocean to land through volatilization of seawater into the atmosphere (Fuge 2005).
322 7 Microelements and Their Role in Human Health
Iron
Iron is a lustrous, ductile, malleable, silver-grey transition metal belonging to
Group VIII and period 4 of the Periodic Table of Elements. It has an atomic mass
of 55.85 and an atomic number 26. It is known to exist in four distinct crystalline
forms. Iron is the tenth most abundant element in the universe and is the most
abundant (by mass 34.6%) element making up the Earth. The concentration of iron
in the various layers of the Earth ranges from high at the inner core to about 5% in
the outer crust. Most of this iron is found in various oxides and hydroxides and
occurs in the crystal lattices of a number of primary and secondary minerals
(Table 7.4). Iron dissolves readily in dilute acids. It is chemically active and
forms the divalent iron (II), or ferrous compounds and the trivalent iron (III), or
ferric compounds.
Manganese
Manganese is a pinkish-grey, hard and very brittle transition metal belonging to
Group VIIB and period 4 of the Periodic Table of Elements. It has an atomic mass
of 54.94 and an atomic number 25. It is easily oxidized but is difficult to melt.
Manganese is reactive when pure, and as a powder it burns in oxygen. Similar to
iron, it reacts with water and rusts and dissolves in dilute acids. The average content
of Mn in lithosphere is 1000 mg kg 1. Its total quantity in soils vary from less than
100 to several thousand mg kg 1, where it occurs in the form of oxides, carbonates
and silicates such as pyrolusite (MnO2), rhodochrosite (MnCO3), hausmannite
(Mn3O4), manganite (MnOOH) and rhodonite (MnSiO3). It cycles through various
oxidation states Mn(II), Mn (III) and Mn (IB). Besides these, Mn also forms
hydrated oxides with mixed valence states.
Molybdenum
Molybdenum is silvery white, very hard transition metal belonging to Group VIB
and period 5 of the Periodic Table of Elements. It has an atomic weight of 95.94 and
an atomic number 42. The mean crustal concentration of Mo is 2.3 mg kg 1 and
averages 1.4–2.0 mg kg 1 in rocks. In soils, Mo content averages 1.4 mg kg 1 and
ranges between 0.1 and 7.4 mg kg 1 in different soils. Molybdenum is attacked
slowly by acids. Mineral form of molybdenum in rocks include molybdenite
7.3 Microelement Transformations in Soil 323
The microelements occur in soils in several forms and their transformations and
availability to plants depends on their distribution between solid and liquid phases
of soil. Based on exchange, complexation and chelation reactions between soil’s
liquid and solid phases, Viets (1962) proposed the existence of five distinct pools
viz. (i) soil solution or water soluble, (ii) exchangeable, (iii) adsorbed, complexed
and chelated, (iv) associated with secondary minerals and as insoluble metal
oxides and hydroxides, and (v) associated with primary minerals (Fig. 7.1). The
water-soluble pool is almost negligible for Cu and Zn and very small for Fe and
Mn in well aerated neutral soils. However, poor aeration, low redox potential and
low pH can increase the amount of Mn and Fe in this pool, but may not affect Cu
and Zn. The exchangeable pool, which also includes water soluble pool, is
324 7 Microelements and Their Role in Human Health
relatively large in size except for Cu and Mn. The third pool comprises cations
that can be replaced by mass action of cations with similar affinities or by
extraction with chelating agents such as ethylenediamine tetraacetic acid
(EDTA). The first three pools exist in dynamic equilibrium and constitute the
labile pool from which the plants draw micronutrients. The chemical composition
of liquid phase keeps on changing because of contact with highly diverse soil
solid phase and the uptake of water and microelement ions by plants (Kabata-
Pendias 2004).
The available forms of micronutrient cations (Fe, Zn, Mn, Cu and Co) are
usually present in their divalent form and are either adsorbed on the soil colloids
or become part of the secondary silicate minerals through isomorphic substitution.
The micronutrient anions (Mo and B) combine with soil constituents and form new
reaction products and may also precipitate in some soils. The micronutrients, held
strongly in organic and inorganic forms, become slowly available by weathering
and microbial decomposition. The availability of micronutrients is greatly
influenced by soil conditions, particularly pH and soil aeration status. The solubility
of divalent and trivalent cations changes 100 and 1000-fold with a unit change in
pH (Lindsay 1979). Generally, in well-aerated acid soils, several essential trace
elements, including Fe, Al, Mn, and Zn are mobile and readily available to plants.
In the poorly aerated neutral or alkaline soils, metals are considerably less avail-
able. On the contrary, elements such as Mo and Se are strongly bound in the pH
range 5.5–7.5 and are readily available in alkaline soils. In addition to soil condi-
tions, competition between different metals may inhibit uptake of a particular
7.3 Microelement Transformations in Soil 325
nutrient, such as high concentrations of Cu, Fe and Ca may depress the availability
of Zn (Kiekens 1995).
Boron
Boron in soil exists in organic and inorganic forms, both of which are in equilibrium
with each other. In acid soils, much of the B is in inorganic form and is lost by
leaching rendering these soils low in B. In arid and semi-arid regions, inorganic B
may occur as Na and Ca salts. Usually less than 10% of the total B in soil is
available to plants. Soil factors affecting availability of B to plants include pH,
texture, moisture, temperature, organic matter and clay mineralogy. Boron
adsorbing surfaces in soils are: aluminium and iron oxides, magnesium hydroxide,
clay minerals, calcium carbonate, and organic matter (Goldberg 1997). With
increase in soil pH, B availability to plants decreases. Therefore, liming of acid
soils can result in reduced B availability and its deficiency in plants. Native B is
positively correlated with soil clay content (Elrashidi and O’Connor 1982) and
coarse-textured soils contain less available B than fine textured soils. Therefore, B
deficiency often occurs in plants growing in sandy soils (Fleming 1980; Gupta
1968). Total and plant available B content is reported to be significantly related to
soil organic matter (Berger and Truog 1945; Elrashidi and O’Connor 1982;
Miljkovic et al. 1966). Boron availability generally decreases as soils become
dry. Soils may also have high concentrations of B that could cause B toxicity and
decrease crop yields. The highest naturally occurring concentrations of B are in
soils derived from marine evaporites and marine argillaceous sediment (Nable et al.
1997). In addition, anthropogenic sources of B including irrigation water, waste
from surface mining, fly ash and industrial chemicals may increase soil B to toxic
levels for plants.
Cobalt
A number of factors influence Co distribution in soils, the most important ones
being hydrous oxides of Fe and Mn. Oxides of Fe possess strong affinity for the
selective adsorption of Co. The oxidation of Co2+ to Co3+, particularly by Mn
oxides, commonly occurs in soils. Interchange reactions are involved in the sorp-
tion of Co by Mn oxides, resulting in the formation of hydroxyl species, Co(OH)2
that precipitate at the oxide surface (Kabata-Pendias and Mukherjee 2007). In most
soils, Co is slowly mobilized and its concentration in soil solution ranges between
0.3 and 87 μg L 1 (Kabata-Pendias and Pendias 2001). Common ionic species in
soil solution include Co2+, Co3+, CoOH+, and Co(OH)3 . Soil redox potential
(Eh) and pH influence speciation and availability of Co to plants. The Co avail-
ability is higher at low pH than at high pH values. Liming decreases Co availability.
Soil texture and organic matter also influence behaviour of cobalt in soils. Gener-
ally, soils high in organic matter have low total and plant available Co. Cobalt
occurs in both inorganic and organic forms. The inorganic form is essential for
human body and the organic form is present in green parts of plants, fish, cereals,
and water.
326 7 Microelements and Their Role in Human Health
Copper
The total amount of Cu in soil depends on the parent material, the degree of
weathering, soil texture, extent of leaching and soil acidity. Solution and soil
chemistry have a strong influence on the speciation of Cu. In alkaline aerobic
systems, CuCO3 is the dominant Cu species. The cupric ion, Cu2+, and Cu hydrox-
ides, CuOH+ and Cu(OH)2, are also commonly present. The factors affecting Cu
availability to plants include organic matter content, soil pH, CaCO3 and clay
content. Copper in soil is strongly bound to soil organic matter and clay minerals.
As a result, it is not leached to the groundwater (Cynthia and David 1997). The
affinity of Cu to SOM increases as pH increases. If sulfur is present in anaerobic
environments, CuS is formed.
Iodine
In soil, iodine is oxidized to iodate and the most common species in aqueous phase
include I , I3 , IO3 , and H4IO6 (Kabata-Pendias and Sadurski 2004). Majority of
iodine in soil occurs either sorbed with organic matter and clay or fixed in minerals
and only a small fraction (<1–25%) is available to plants; the species I being
absorbed at a higher rate than iodate (IO3–) (Yuita 1983). Iodate (IO3 ) adsorption
is negatively related to soil organic matter and positively to free Fe oxides (Dai
et al. 2004). Volatile iodine compounds are commonly exchanged between soils
and the atmosphere.
Iron
Iron occurs in soils in various forms including water soluble and exchangeable,
insoluble Fe2+ compounds and Fe-organic complexes and active iron oxides. Iron is
absorbed by plants as Fe2+ and the low solubility of Fe3+ containing compounds
limits its availability for plant uptake. Compared to total Fe content in soil, the
amount of soluble Fe is very low and in well-aerated soils iron solubility is mainly
controlled by the solubility of Fe3+ hydroxides. The reaction is pH dependent and
the activity of Fe3+ decreases with increasing pH and the solubility is minimum at
pH 7.4–8.5 (Lindsay and Schwab 1982). Therefore, iron availability is higher in
acid soils compared to calcareous and alkali soils. Under anaerobic/waterlogged
conditions, Fe3+ is reduced to Fe2+ by anaerobic bacteria which use iron oxides as
electron acceptors during respiration. The extent of reduction depends on period of
submergence, soil organic matter content and active Fe, Mn and NO3-N contents.
Higher the organic matter content, greater is the reduction of Fe. Iron availability in
soils, besides depending on pH, is influenced by presence of CO32 and HCO3
ions, organic matter content, soil aeration status, soil moisture regime, soil texture
and nutrient interactions. Plant genotypes also differ in their ability to absorb iron
from soil. Some crop varieties are genetically more efficient in taking up iron from
the soil than the other varieties.
Manganese
Manganese exists in soil as water soluble, organically bound, clay minerals bound
crystalline and amorphous oxides. Different forms of Mn are in dynamic equilib-
rium with each other and the form in which Mn occurs in soil is influenced by pH
7.3 Microelement Transformations in Soil 327
and the oxidation reduction conditions. The tetravalent form is likely to be more
prevalent in alkaline soils, the divalent form in acid soils and the trivalent form
mainly occurs in neutral or near neutral soils. Available or active Mn in soils
comprises water soluble, exchangeable and reducible forms. The water soluble
and exchangeable forms usually exist in divalent form and are considered readily
available to plants. Reducible Mn represents higher oxides that can be reduced by
easily oxidizable organic substances such as quinol or hydroquinol. Factors affect-
ing Mn availability in soil include pH, organic matter content, presence of CaCO3,
soil texture, and soil submergence. In soils with pH less than 5.5, large amount of
Mn may be present as water soluble and exchangeable forms and their amount
decreases with increase in pH. High organic matter content in neutral and alkaline
soils decreases the availability of Mn by forming insoluble complexes with Mn3+.
The organic matter can influence Mn transformations in soil through (i) the pro-
duction of complexing agents that effectively reduce the activity of free ions in
solution, (ii) decrease in the oxidation potential of the soil, and (iii) the stimulation
of microbial activity that results in the incorporation of Mn in biological tissue
(Hodgson 1963). Presence of CaCO3 reduces the availability of Mn by surface
adsorption. Soil submergence, as in paddy fields, leads to reduction of Mn oxides
and thus increases their availability to plants.
Molybdenum
Compared to other microelements, Mo behaves differently in soils. Unlike other
microelements, it is highly mobile in alkaline soils (pH >6.5) and only slightly
mobile in acid soils (pH <4–5). The MoO42 anion dominates in the neutral and
moderate alkaline pH range, whereas HMoO4 occurs at lower pH values. Both
anions occur in soil solution (Kabata-Pendias and Sadurski 2004). However, solu-
ble Mo anions are readily precipitated by organic matter, CaCO3, and a number of
other cations (Fe, Mn, Cu, Zn and Pb). Under reducing conditions, Mo can form
soluble thiomolybdates (e.g. MoS42 , MoO2S22 ). All these reactions being soil Eh
and pH dependent may vary considerably. Every unit increase in pH above 3.0,
increases MoO42 solubility 100-fold mainly because of decreased adsorption of
metal oxides (Lindsay 1979).
Zinc
Zinc in the solid phase exists as adsorbed to organic and inorganic particles and as
Zn precipitates. Clay and soil organic matter are capable of holding Zn quite
strongly, especially at neutral and alkaline pH regimes (Kabata-Pendias and
Pendias 2001). Two different mechanisms of Zn sorption exist, one in acid soils
related to cation exchange sites, and the other in alkaline soils (chemisorptions) that
is greatly influenced by organic ligands. Hydroxides of Al, Fe, and Mn may also be
involved in binding Zn in some soils. In the soil solution, Zn occurs in the form
of free hydrated [Zn(6H2O)2+] and complexed species as cations (Zn2+, ZnCl+,
ZnOH+, ZnHCO3+) and anions (ZnO22 , Zn(OH)3 , and ZnCl3 ) (Kabata-Pendias
and Sadurski 2004). The concentration of Zn in soil solution is very low, and may
range between 4 10 10 and 4 10 6 M (Barber 1995). Zinc concentration in soil
solution is negatively correlated to soil pH because of its strong sorption on the
328 7 Microelements and Their Role in Human Health
solid phase at high pH values (Jeffery and Uren 1983). Availability of Zn to plants
from soil and fertilizers depends on soil pH, organic matter and CaCO3 contents,
soil P status and adsorption by clay. Generally, Zn availability is higher in acid soils
than in alkaline soils. In alkaline soils having pH greater than 7.85, Zn forms
negatively charged zincate ions, Zn(OH)42 . Because of interaction between zinc
and calcium, the availability of zinc decreases in alkaline soils. Organic matter
increases the availability of Zn by complexing with other substances that may
fix Zn.
Microelements perform a number of functions in plants and humans; the major ones
are summarized in Table 7.6. Besides being component of enzymes, certain micro-
elements are involved in cellular functions, activation of enzymes and function in
oxidation-reduction reactions of plant metabolism.
7.4.1 Plants
Boron
The essentiality of B for higher plants was established in 1923 (Warington 1923).
The possible roles of B in plants include sugar transport, protein synthesis, cell wall
synthesis, lignifications, cell wall structure integrity, carbohydrate metabolism,
ribose nucleic acid (RNA) metabolism, respiration, indole acetic acid (IAA) metab-
olism, phenol metabolism, and as part of the cell membranes (Parr and Loughman
1983; Welch 1995; Ahmad et al. 2009). Boron increases the transport of chlorine
and phosphorus becuase of plasmalemma ATPase induction.
Cobalt
Cobalt is involved in N2-fixation in legumes. Three cobalamin dependent enzyme
systems in Rhizobium may account for the influence of cobalt on nodulation and
N2-fixation in legumes. Cobalt increases the weight and cobalt content of nodules,
number of bacteroides per nodule, cobalamin and leghemoglobin concentration.
Copper
Presence of Cu in chloroplasts is related to binding of solar energy during photo-
synthesis. The Cu-Zn- superoxide dismutase (SOD) enzyme in green leaves is
involved in the detoxification of O2 produced in photorespiration. Cytochrome
oxidase, an enzyme involved in respiration, contains Cu. Both phenolase and
laccase contain Cu and are involved in lignin synthesis. Cell wall loosening
involving Cu plays a role in cell expansion and fruit softening. Copper is an
essential element of various enzymes, such as polyphenol oxidases, plastocyanin
of the photosynthetic transport chain, and cytochrome-c oxidase, the terminal
7.4 Beneficial Effects of Microelements 329
7.4.2 Humans
Boron
Well defined biochemical function for B in humans has not been identified; it
probably affects the metabolism of macrominerals, energy, nitrogen, and reactive
oxygen. Data from animal studies indicate a functional role for B. Boron forms
complexes with some biologically important substances such as diadenosine
polyphosphates, S-adenosylmethionine, pyridoxine, riboflavin, dehydroascorbic
acid and pyridine nucleotides which may regulate certain functions (Nielsen
2006). A number of organoboron compounds (boroesters) including antibiotics
produced by microorganism, plant cell wall component (rhamnogalacturonan-II)
and a bacterial extracellular signaling molecule have been identified (Sato et al.
1978; Schummer et al. 1994; O’Neill et al. 1996; Matoh 1997; Chen et al. 2002).
Cobalt
Cobalt is essential for humans as a component of cobalamin, the functional unit of
Vitamin B12, which is the only vitamin containing a metal ion (Carmel 2007).
Vitamin B12 is synthesized by microorganisms such as algae and yeast which are
abundantly present in soil. Two forms of vitamin B12 viz. methylcobalamin and
5-deoxyadenosyl cobalamin are utilized in the human body. Cobalamin acts as a
cofactor for two enzymes L-methylmalonyl-CoA mutase involved in the synthesis
of haemoglobin, and methionine synthase important in cancer prevention. Cobalt
binds to Fe-transport proteins and is thus involved in the synthesis of haemoglobin.
It seems that some organic Co compounds are involved in processes of stabilizing
the DNA structure, which has a role in cancer prevention (Munno De et al. 1996).
Vitamin B12 is also required for the development of nerve cells, growth and repair
of cells and for the movement of carbohydrates and fats in the body (Seatharam and
Alpers 1982). Cobalt is important for forming amino acids and some proteins to
create myelin sheath in nerve cells (Ortega et al. 2009). The salts of cobalt stimulate
the synthesis of erythropoietin, which is involved in the formation of erythrocytes
in bone marrow (Simonsen et al. 2012). Cobalt may be bound by some proteins to
replace other divalent cations such as Zn and Mn in different enzymes.
Copper
The essentiality of copper for humans was established during the 1960s in mal-
nourished children from Peru (Cordano et al. 1964). Copper is essential for the
development of connective tissue, nerve coverings, and bone; participates in both
Fe and energy metabolism; acts as a reductant in several oxidases that reduce
molecular oxygen; and is involved in enzyme catalysis. Copper-containing
332 7 Microelements and Their Role in Human Health
Molybdenum
Molybdenum is a component of several metalloenzymes including xanthine oxi-
dase, aldehyde oxidase, nitrate reductase, and hydrogenase (Soetan et al. 2010).
Xanthine oxidase and aldehyde oxidase play a role in iron utilization as well as in
cellular metabolism in electron transport. Mo is a co-factor for enzymes necessary
for the metabolism of S-containing amino acids and nitrogen-containing com-
pounds present in DNA and RNA, the production of uric acid, and the oxidation
and detoxification of various other compounds.
Zinc
The essentiality of Zn was established in 1869 for plants, in 1934 for animals and in
1961 for humans (King and Cousins 2006). Zinc occurs in all living cells and is an
important constituent of plasma (Murray et al. 2000). It is involved in the function-
ing of a number of enzymes and serves as a structural, catalytic, and regulatory ion.
Zinc is the only metal involved in all six classes of enzymes viz. oxido-reductases,
transferases, hydrolases, lyases, isomerases and ligases (Barak and Helmke 1993).
Some of the Zn-dependent enzymes include lactate dehydrogenase, alcohol dehy-
drogenase, glutamic dehydrogenase, alkaline phosphatase, carbonic anhydrase,
carboxypeptidase, superoxide dismutase, retinene reductase, DNA and RNA poly-
merase (Soetan et al. 2010). As a structural component, Zn allows the binding of
amino acids (cysteine and histidine residues) in the protein chain to form finger like
structure (Knez and Graham 2013). Zinc is involved in a number of biochemical,
immunological and clinical functions and is considered the most important meta-
bolic promoter (Hotz and Brown 2004). It is involved in the metabolism of nucleic
acids, amino acids, vitamin A, vitamin E and glucose. Zinc is needed for cellular
differentiation and replication, gene expression, protein synthesis, testicular devel-
opment, and functioning of taste buds (Merck 1986; Vallee and Falchuk 1993;
Szabo et al. 1999). Zinc is required for regulating immune functions including
tissue repair and wound healing. It plays a role in preventing free radical formation
and protecting biological structures from damage, and promotes the synthesis of
metallothionein, a protein present in intestinal mucosa, liver and kidneys that is
essential for heavy metal metabolism (Hotz and Brown 2004). Zinc, being an
integral constituent of insulin, is essential for its optimum activity. Zinc is essential
for thymic functions as it influences thymic hormone, thymulin, needed for T-cell
maturation and differentiation (Mocchegiani et al. 2000).
7.5.1 Plants
Under similar soil conditions, different plant species may take up widely different
amount of the same microelement from the soil (Alloway 2005). There exists a
certain concentration range representing a safe and adequate intake of a
334 7 Microelements and Their Role in Human Health
toxicity in plants is rarely seen, but the effect of excessive Mo uptake in forages and
pasture grasses is manifested in animals. Ruminants that consume plant tissue high
in Mo can develop molybdenosis, a disorder that induces Cu deficiency (Scott
1972). High concentration of Mo in tomato and cauliflower plants can lead to
accumulation of anthocyanins in leaves turning them purple. Molybdenum toxicity
commonly occurs in calcareous soils and peaty soils or as a result of over liming or
excessive application of Mo fertilizers.
Zn toxicity rarely occurs in plants under field conditions. However, continued
application of Zn fertilizers to alkaline sandy soils low in organic matter content
may lead to Zn toxicity in plants. The general symptoms of Zn toxicity in plants
include stunting of shoot, curling and rolling of young leaves, chlorosis and death of
leaf tips (Rout and Das 2003). Excessive uptake of Zn may cause growth inhibition
and oxidative damage in plants (Vaillant et al. 2005; Panda et al. 2003). Excessive
Zn can affect cell mitotic activity, membrane integrity and permeability and can
even lead to death of cell (Stoyanova and Doncheva 2002; Chang et al. 2005). Zinc
toxicity affects metabolic processes through competition for uptake, inactivation of
enzymes, displacement of essential elements from functional sites (Rout and Das
2003).
7.5.2 Humans
Studies on animals have shown that excessive consumption of B can have adverse
reproductive and developmental effects. The excessive intake of Co may cause
polycythemia (increased red blood cells), cardiomyopathy, hypothyroidism, failure
of pancreas, bone marrow hyperplasia, and some types of cancer (Plumlee and
Ziegler 2003). In occupational settings, inhalation of dust containing Co could
affect respiratory system leading to asthma, fibrosing alveolitis and lung cancer in
humans. Cobalt inhalation could also affect the hematopoietic system, the myocar-
dium, the thyroid gland, and the nervous system (Yamada 2013). The
recommended safety threshold for cobalt in workplace air ranges between 0.05
and 0.1 mg m 3 for an 8–10-h work day, 40-h work week.
Excessive ingestion of Cu can cause gastrointestinal distress and liver damage
characterized by diarrhea, vomiting, abdominal pain and nausea. Chronic high Cu
intake can lead to the hepatic accumulation of Cu, which has been suspected in
juvenile cases of hepatic cirrhosis in India. Individuals with Wilson’s disease may
be at increased risk of adverse effects of excessive Cu intake.
High intake of iodine may occur through consumption of iodine-rich diet such as
seafood or iodine containing supplements. Excessive intake of iodine causes a
decrease of thyroid hormone production resulting in formation of high iodine
goiter. Individuals with autoimmune thyroid disease or with history of iodine
deficiency are particularly susceptible to adverse effects of excessive iodine intake.
Iron toxicity is mostly associated with undue oral intake, usually in combination
with high consumption of alcohol and vitamin C. Other causes could be multiple
336 7 Microelements and Their Role in Human Health
7.6.1 Plants
root and shoot tips. In root crops, B deficiency has been associated with internal
tissue breakdown. Soils showing Co deficiency include highly leached acid soils
low in total Co, soils derived from granite, highly calcareous soils, coastal sandy
soils and peaty soils, and soils derived from rocks rich in Mg.
Iron
Despite being present in abundant amount in Earth’s crust and soil, the iron
deficiency is generally prevalent because of the insoluble nature of iron in an
oxidizing environment. Plants have their own mechanism to acquire iron from
soil. Higher plants, except cereals, depend on root-cell membrane bound ferric
reductases to take-up iron in ferrous form from soil solution (Frossard et al. 2000).
In cereals the chelates excreted by their roots are absorbed intact by root cells via a
specific ferric-phytometallophore transport system in the cell plasma membrane.
Deficient uptake of iron leads to chloroplast disorders; the synthesis of thylakoid
membranes is disturbed and the photochemical activity affected (Spiller and Terry
1980).
Manganese
Manganese deficiency is more prevalent in near neutral to alkaline (pH 6.5–8.0)
soils. Frequent fluctuation in water table or alternate submergence and drying may
lead increased incidence of Mn deficiency. This has commonly been observed in
wheat grown after lowland rice in northern India. Deficiency of Mn2+ leads to the
breakdown of chloroplasts.
Molybdenum
Growing of plants under Mo deficient conditions leads to the development of
several different phenotypes that are associated with reduced molybdoenzymes
and their presence hampers plant growth. Deficient uptake of Mo impacts plant
metabolism and the magnitude of effect depends on the requirement for various
types of molybdoenzymes present in plants. It is not simple to assign a well-defined
plant response to Mo deficiency because of its involvement in a number of
enzymatic processes. However, Mo deficiencies are primarily associated with
impaired nitrogen metabolism particularly when nitrate is the major form available
for plant growth. Moco decreases the activity of nitrogen reducing and assimilatory
enzymes including nitrate reductase and xanthine deyhydrogenase/oxidase (Kaiser
et al. 2005). In most plant species, the loss of nitrate reductase activity is usually
associated with increased tissue nitrate concentration and decreased plant growth
and yield (Spencer and Wood 1954).
Zinc
Zinc deficiency occurs worldwide in soils and crops. Soils with high pH, high
CaCO3 and low organic matter contents are more prone to Zn deficiency. About
30% of the agricultural soils in the world are estimated to be deficient in Zn
(Sillanpää 1982). Countries with large Zn-deficient areas include China, India,
Iran, Pakistan, and Turkey where 50–70% of the cultivated soils are Zn deficient
(Alloway 2009). Zinc deficiency in soils has also been observed in Australia and
Brazil. Besides low concentration of total Zn in soil, the soil properties that lead to
338 7 Microelements and Their Role in Human Health
Zn deficiency in crops include high CaCO3 content, alkaline pH, high salt concen-
tration, high levels of available P, and high concentration of Mg. Other conditions
that may induce Zn deficiency include prolonged flooding such as in paddy soils or
waterlogging and high concentration of bicarbonate in irrigation water (Alloway
2008). Zinc deficiency in agricultural soils results in poor yields and nutritional
quality. Cereals are particularly prone to Zn deficiency because of their inherently
low concentrations. It is estimated that 50% of world soils growing cereals are Zn
deficient.
7.6.2 Humans
It is estimated that more than 60% of the world population is Fe deficient, over 30%
Zn deficient, 30% I deficient and 15% are selenium (Se) deficient (White and
Broadley 2009). This situation is attributed to shift in cultivation towards cereals,
crop production in areas with low nutrient availability and consumption of food
crops with inherently low nutrient concentrations. Cereals are inherently low in
micronutrients, compared to many other food crops and their consumption as staple
food leads to micronutrient deficiencies. Because of increasing population the
dependence on cereals is increasing as cereals are often the most productive and
remunerative food crops. This is causing decline in diet diversity, particularly in the
developing countries leading to micronutrient deficiencies. The deficiencies are
exacerbated by a lack of animal products or fish in the diet (Gibson 2006). The
deficiency of a nutrient can cause impairment of some specific biochemical func-
tion and illnesses in human beings.
Boron
Though no specific biochemical function has been associated with B in humans but
it appears to have beneficial effects on bone. Therefore, B deficiency without
modification by other nutrients affects bone strength. Its deficiency together with
low dietary intake of Cu and Mg can aggravate the increase in serum calcitonin
(Nielsen 1996).
Cobalt
Endemic problems of Co deficiency in humans are not known but the deficiency
symptoms are evident as vitamin B12 deficiency. Cobalt deficiency can cause
anaemia, structural alteration of buccal cavity tissue, hypofunction of thyroid,
degeneration of the peripheral nervous system, dermal hypersensitivity and
increased risk of developmental abnormalities in infants. Its deficiency has been
observed in ruminant mammals including sheep, goat and cattle. Cobalt deficiency
is widespread in New Zealand, Australia, Great Britain, and parts of Scandinavia
(Frøslie 1990). The deficiency symptoms include emaciation, loss of appetite and
thriftiness. This condition is often called pining, salt sickness, bush sickness or
coast disease.
7.6 Effects of Deficient Micronutrient Uptake 339
Copper
Copper deficiency in humans is associated with malnutrition in children. Copper
deficiency can result in the expression of a genetic defect such as Menkes syndrome
that results in growth retardation, hypothermia, skin and hair depigmentation and
abnormal spiral twisting of the hair, lax skin and articulations, tortuosity and
dilatation of major arteries, varicosities of veins, osteoporosis, flaring of
metaphyses, bone fractures, retinal dystrophy, and damage to central nervous
system (Danks 1995). The syndrome appears before 3 months of age and usually
causes death of the child before 5 or 6 years of age. Acquired Cu deficiency results
in hypochromic, normocytic or macrocytic anaemia, neutropenia, bone abnormal-
ities, hypopigmentation of the hair, hypotonia, poor growth, increased susceptibility
to infections, abnormalities of cholesterol and glucose metabolism, and cardiovas-
cular alterations.
Iodine
Iodine deficiency in humans may cause a number of illnesses or disorders
including thyroid hypertrophy or goitre and mental retardation. Under iodine
deficiency condition, the thyroid may not be able to synthesize sufficient amounts
of thyroid hormone. The resulting low level of thyroid hormones in the blood
(hypothyroidism) is mainly responsible for damage to the developing brain and
other harmful effects known collectively as “iodine deficiency disorders”
(Table 7.8; Hetzel 1983). Iodine deficiency during pre-natal development and
the first year of life can result in endemic creatinism, a disease which causes
stunted growth and general development along with brain damage. This mental
deficiency has an immediate effect on child’s learning capacity and women’s
health. An estimated two billion people worldwide have insufficient iodine
intake, which is the single most important preventable cause of brain damage
(WHO 2007; Zimmermann et al. 2008). The regions of the world mostly affected
by iodine deficiency include developing countries of Africa, Asia, and Latin
America particularly located far from the ocean (Fuge 2005). Even in some
developed countries of Western Europe it has been suggested that 50–100 million
people may be at risk of iodine deficiency (Delange 1994). Population mainly
dependent on vegetarian diet have low iodine intake, which could lead to iodine
deficiency (Davidsson 1999; Remer et al. 1999).
Iron
Iron deficiency mainly occurs in infants, children, pregnant women that are depen-
dent on plant foods as their main source of iron. This deficiency is caused by
malnutrition and is associated with inadequate intake, poor absorption from diets
high in phytate or phenolic compounds or excessive losses such as through
menstruation, gastrointestinal haemorrhage, etc. Iron deficiency results in
decreased blood haemoglobin and the appearance of microcytic hypochromic
anemia. Red blood cells (RBC) have a life span of about 4 months and a
continuous supply of iron from the diet (together with folate and proteins) is
required to make haemoglobin and replace dead RBCs. Iron deficiency is the most
significant cause of anaemia worldwide so that iron deficiency anaemia (IDA) and
anaemia are often used synonymously. Approximately, 50% of the cases of
anaemia are assumed to be due to iron deficiency (WHO 2001). However, the
proportion may vary among population groups and in different regions depending
on the local conditions (Fig. 7.2). According to a recent family health survey
(WHO 2015) more than half of the children (58%) below the age of 5 in India are
anaemic because of insufficient intake of iron. Other causes of anaemia include
parasite infections (such as hookworms, ascaris, and schistosomiasis); acute and
chronic infections (malaria, cancer, tuberculosis, and HIV) and the occurrence of
other micronutrient deficiencies such as vitamins A and B12, folate, riboflavin,
and copper (WHO 2008).
Besides anaemia, the other effects of iron deficiency include muscle dysfunction
due to decrease in the concentration of α-glycerol-phosphate oxidase in muscle and
increased intracellular formation of lactic acid (Ohira et al. 1979); decreased
Fig. 7.2 Global distribution of anaemia in preschool-age children (Source: WHO 2008, p. 9;
reprinted with kind permission from WHO)
7.6 Effects of Deficient Micronutrient Uptake 341
Fig. 7.3 Global distribution of Zn deficiency in (a) soils (Alloway 2008, p. 109; with kind
permission from International Zinc Association) and (b) humans (Wessells and Brown 2012,
p. 2; unrestricted reproduction permitted by PLOS ONE)
7.7.1 Plants
Boron
Boron deficiency first appears on young leaves which are thickened and may curl
and become brittle. The deficiency symptoms of B differ in different crop plants.
Boron deficiency results in hollow hearts in peanuts, black hearts in beets, distorted
and lumpy fruit in papaya, and pith in hollow stem in cabbage and cauliflower.
Boron deficiency commonly occurs in soil which are highly leached or developed
from calcareous, alluvial and loess deposits.
Copper
Copper deficiency mostly occurs in soils with high organic matter content. Copper
deficiency symptoms appear as interveinal chlorosis of new leaves followed by
chlorosis of the veins and rapid and extensive necrosis of leaf blades. Copper
deficiency leads to reduced and stunted growth of plants and give a bushy appear-
ance. Ears may or may not form depending upon the severity of the deficiency.
Iron
Iron deficiency in plants appears as interveinal chlorosis of the young or new leaves
(Fig. 7.4). Soon after the veins also loose green colour and the whole leaf turns
yellow. Under acute deficiency, there is bleaching of the affected leaves and the
newly emerging leaves also look bleached. In sugarcane, red pigmentation/lesions
may also develop along the bleached area. With time the affected leaves turn
papery, necrotic and ultimately die. The symptoms of Fe deficiency are similar in
most of the crops. Iron deficiency in plants growing on calcareous soils is not due to
insufficient Fe uptake from the soil but due to a physiological disorder in leaves,
affecting the Fe distribution in the leaf tissue (Mengel and Geurtzen 1986).
Fig. 7.4 Symptoms of iron deficiency in rice, chickpea (Cicer aeriertinum L.), groundnut
(Arachis hypogaea L.), sugarcane (Sachharum officinarum) and kinnow (Citrus reticulate x
C. deliciosa) (Source: Nayyar and Chhibba 2000; with kind permission)
344 7 Microelements and Their Role in Human Health
Fig. 7.5 Manganese deficiency symptoms in wheat (Source: Nayyar and Chhibba 2000; with kind
permission)
Manganese
Manganese deficient plants are stunted with restricted foliage and root system. The
symptoms of Mn deficiency first appear on the lower and middle leaves as small
chlorotic spots in the interveinal area and extend from base of the leaf towards the
tip (Fig. 7.5). Under acute deficiency the spots join together to form streaks of
pinkish brown colour in the interveinal areas. At ear formation, these symptoms are
conspicuous on the flag leaf of wheat. In Mn deficient plants, ears emerge with great
difficulty and are deformed/sickle shaped. Similar symptoms of Mn deficiency are
observed in most of the crops.
Molybdenum
Molybdenum deficiency usually appears in legumes and the symptoms resemble N
deficiency because Mo is involved in nitrogen assimilation in plants. Mo deficiency
appears on old and middle leaves, which become chlorotic with inward rolling of
leaf margins. The most well-known Mo deficiency is the “whiptail” of cauliflower.
The characteristic symptoms include twisted and elongated leaves with cupped
lamina showing various degrees of narrowness and irregularities. Citrus plants
suffering from Mo deficiency develop yellow spots.
Zinc
The general symptoms of Zn deficiency in plants include stunted growth, leaf
chlorosis, small leaves, spikelet sterility, poor quality of crop products, and sus-
ceptibility to biotic and abiotic stresses. However, specific symptoms of Zn defi-
ciency are different in different crops (Fig. 7.6). In rice, Zn deficiency first appears
on old leaves as light yellow spots in the interveinal area about 15–20 days after
transplanting. These spots later turn yellowish-brown and join together giving
reddish brown or rusty look. With intensification of pigmentation, the midrib and
the leaf sheaths also look like the rest of the leaf. Under acute deficiency, the plants
give rusty look. The affected leaves wither with time and further growth of plant is
restricted giving bushy appearance. Most of the tillers fail to develop panicles
resulting in very poor grain yield. In maize, Zn deficiency first appears on
3 weeks old plants as a white patch between the mid-rib and the margin at the
basal part of the lamina of the second or third leaf from top. The white patch extends
along the mid-rib towards tip and the colour changes to reddish/bluish red. The
7.7 Symptoms of Micronutrient Deficiencies 345
Fig. 7.6 Symptoms of zinc deficiency in rice, maize, chickpea (Cicer aeriertinum L.), black gram
(Phaseolus mungo L.) and kinnow (Citrus reticulate x C. deliciosa) (Source: Nayyar and Chhibba
2000; with kind permission)
mid-rib and the margins, however, remain green for a longer time. Sometimes even
the leaf sheaths and the internodes also develop reddish color. The internodal length
decreases and the leaves appear to arise from points close to each other. Under
moderate Zn deficiency, tasselling and silking are delayed and in severe deficiency
tasselling may not take place and the crop virtually fails. In wheat, the symptoms of
Zn deficiency appear first on the second or third leaf from top of the plant at tillering
stage. They show up as light yellow white tissue between the mid-rib and margins
in the middle or lower half of the affected leaf. The effects of Zn deficiency in plant
include short internodal length, less number of productive tillers, poor foliage
expansion, bushy growth, small ears, poor grain formation and delayed maturity.
In Zn-deficient plants, protein synthesis is hampered and free amino acids
accumulate.
7.7.2 Humans
has been reported to increase serum glucose and decrease serum triglyceride
concentration (Nielsen 1996). Cobalt deficiency leads to perinicious anemia and
methylmalonic academia. The deficiency symptoms of copper include anemia,
leucopenia, neutropenia, disturbed maturation of myeloleukocytes. The deficiency
of copper also leads to bone changes in children i.e. reduced osseous age, irregular/
spurring metaphysic, bone radiolucency and bone cortex thinning. Associated
changes due to Cu deficiency may include subperiosteal hemorrhages, hair and
skin depigmentation and defective elastin formation (Lonnerdal and Uauy 1998).
Iodine deficiency causes goiter (enlarged thyroid gland) and hypothyroidism. Iron
deficiency leads to development of anemia when iron supply is inadequate to
synthesize normal level of hemoglobin. Common symptoms of Fe deficiency
include tiredness, lethargy, breathlessness (dyspnoea) and palpitation. The defi-
ciency of manganese leads to reduced serum cholesterol, reduced coagulation, hair
reddening, dermatitis, growth retardation and increased radiolucency at the epiph-
yses of long bones. Molybdenum deficiency symptoms are tachycardia, polypnea,
night blindness, scotoma, irritability, somnolence, disorientation and coma. Several
physiological signs of Zn deficiency, depending on its severity and age of the
individual, are discernible. Signs of severe Zn deficiency were identified in persons
suffering from acrodermatitis enteropathica, a genetic disorder that affects Zn
absorption (Van Wouwe 1989). The major symptoms of zinc deficiency appear as
gradually worsening eruptions (acne), which first affect the face and perineum. The
associated symptoms of zinc deficiency include stomatitis, glossitis, alopecia, white
spots on nails, diarrhea, vomiting, fever, delayed wound healing, dwarfism, growth
retardation, negative nitrogen balance, immune-suppression, depression, taste dis-
order and anorexia. Adverse effects of Zn deficiency generally vary with age. While
diarrhea, anorexia, low weight gain and neurobehavioral changes are more frequent
during infancy, the skin changes, blepharoconjuctivities and growth retardation are
common among school children (Hambidge 1997). The other symptoms are more
frequent in elderly people.
application of a nutrient have been standardized for different soils, crops and
environmental conditions.
Boron
Plant species differ greatly in their B requirement and the differences are reflected in
optimum concentration of B in leaf tissue (Marschner 1995). Boron concentration in
plants generally ranges between 3 and 100 μg g 1 dry matter. Based on B require-
ment and optimum leaf concentration, the plants could be grouped (Goldbach 1997)
into (i) very low B requiring, which rarely show B deficiency (e.g. Graminaceous
species) and have optimum leaf concentrations between 2 and 5 μg g 1 dry matter,
(ii) severely affected by high B concentration in soil (e.g. non-grass monocotyledons
and dicotyledons) and have optimum leaf concentrations between 20 and 80 μg g 1
dry matter and (iii) high B requiring (e.g. latex containing plants) with optimum leaf
concentration greater than 80 μg g 1 dry matter. Boron deficiency can be overcome
by adding soluble borates to soils or as foliar application (Table 7.9). Boron to soils
can also be added in the form of crushed ores but these are mostly insoluble and have
variable B content. Reclaiming high-B soils is really difficult because of narrow
range between deficiency and toxicity of B in plants (Marschner 1995). Commonly
used method of reclaiming high B soils include extensive leaching with low B water,
the use of soil amendments such as lime and gypsum and the planting of B-tolerant
plant genotypes (Nable et al. 1997).
Cobalt
Cobalt availability to plants increases with increasing acidity and waterlogging.
Cobalt deficiency in soil can be corrected by adding CoCl2, CoSO4, cobaltized
superphosphate, and pulverized serpentine rock. The Co containing fertilizers can
be applied as soil, foliar and seed treatment.
Copper
Copper deficiency has rarely been encountered in soils, which are sandy or have
high organic matter content. The deficiency of Cu is generally corrected by
application of copper sulphate (CuSO45H2O) either to soil or foliage depending
on the plant species. In wheat, soil application of Cu has been found to be more
beneficial. In vegetables and food crops, the Cu deficiency is controlled by foliar
application of boardeux mixture, which is generally used for control of diseases.
Copper being immobile in plant, multiple sprays are required to ameliorate its
deficiency and maximise productivity. Other carriers of Cu include Cuprous/Cupric
oxide, Cupric chloride and synthetic chelates (Table 7.10).
Iron
Out of a number of available Fe containing fertilizers (Table 7.11), ferrous sulphate
(FeSO47H2O) has been rated as the most efficient source and is commonly used for
correcting its deficiency in different crops. Use of organic manures alone or in
combination with FeSO47H2O has also been found to be effective in correcting Fe
deficiency. Since inorganic Fe-carriers are less effective when applied to soil
because of their quick reversion, the amelioration of Fe deficiency can be best
accomplished by its foliar application. Ineffectiveness of the soil applied Fe is
because of inadequate degree of reduction of Fe3+ to Fe 2+ under aerobic conditions.
However, in lowland rice prevalence of reduced conditions due to standing water
help reduce Fe deficiency to some extent.
Manganese
Soil management practices, which transform insoluble form of manganese to
mobile form (Mn2+) increase the availability of Mn to plants. Manganese deficiency
generally occurs in highly permeable coarse textured soils. Ameliorative measures
include soil or foliar application of MnSO4, but foliar application is generally
superior. The results of the studies relating to the time of foliar application of Mn
have revealed that an equal number of sprays of a particular concentration of
MnSO4 initiated prior to the first irrigation to wheat crop helped increase the
yield significantly over that obtained when the sprays were initiated after the first
irrigation. Besides MnSO4, the other sources include oxide, carbonate, chloride and
phosphate of manganese (Table 7.12).
7.8 Optimizing Microelement Status 349
Molybdenum
Molybdenum deficiency can be corrected by soil application of sodium molybdate
along with superphosphate or by foliar application of molybdate. A number of other
sources can be used as Mo fertilizers (Table 7.13). Frequently, phosphate, sulphate
and Mo deficiencies occur together, which can be corrected by applying
350 7 Microelements and Their Role in Human Health
7.8.2 Humans
Average Requirement (EAR), Adequate intake (AI) and Tolerable upper limit
(TUL) for different life stage groups and gender are advocated for optimizing
level of nutrients in humans. Recommended Dietary Allowance (RDA) is the
average daily dietary intake sufficient to meet the nutrient requirements of nearly
all (97–98%) healthy individuals in a life stage and gender group (Table 7.15). It is
calculated from EAR, which represents average daily nutrient intake level esti-
mated to meet the requirement of half of the healthy individuals in an age group
(Table 7.16). If information on EAR is not available, then AI for different life stage
groups and gender is established, which is considered to cover the needs of all
healthy individuals in the group. In order to avoid excessive consumption, a TUL is
fixed, which represents the maximum level of daily nutrient intake that is unlikely
to pose any risk of adverse effects to almost all individual in the population
(Table 7.17). It represents total intake from all sources including food, water, and
supplements.
Boron
In the human body, B is distributed throughout soft tissue and fluids at concentra-
tions between 0.015 and 0.6 μg g 1 fresh tissue (Bai and Hunt 1996; Ward 1993;
Shuler et al. 1990). Bone, fingernails, hair, teeth and spleen usually contain high
amounts of B. World Health Organization (1996) suggested an acceptable safe
intake level of 1–13 mg day 1 for adults. In the US, the TUL of B is 20 mg day 1
for adults above 18 years of age and 11–17 mg day 1 for 9–18 years of age
(Table 7.17; IOM 2001). Diet is the main source of B and typical daily intake of
352 7 Microelements and Their Role in Human Health
Table 7.15 Recommended Dietary Allowances (RDA) of microelements for different life stage
groups
Copper Iodine Iron Molybdenum Zinc
Life stage group (μg day 1) (μg day 1) (mg day 1) (μg day 1) (mg day 1)
Children
1–3 year 340 90 7 17 3
4–8 year 440 90 10 22 5
Males
9–13 year 700 120 8 34 8
14–18 year 890 150 11 43 11
19–50 year 900 150 8 45 11
>51 year 900 150 8 45 11
Females
9–13 year 700 120 8 34 8
14–18 year 890 150 15 43 9
19–50 year 900 150 18 45 8
>51 year 900 150 8 45 8
Pregnancy 1000 220 27 50 12
Lactation 1300 290 9–10 50 13
Sources: Dietary reference intakes for vitamin A, vitamin K, arsenic, boron, chromium, copper,
iodine, iron, manganese, molybdenum, nickel, silicon, vanadium, and zinc (2001); Available at
[Link]
Compiled from Food and Nutrition Board, Institute of Medicine, National Academies
B ranges between 0.75 and 1.35 mg depending on the food products consumed
(Nielsen 2006). Fruits, vegetables, pulses, legumes, nuts and chocolates are rich
sources of B compared to dairy products, fish, meat and grains (Table 7.18). Wine,
cider and beer also have high B content.
Cobalt
The adult human body (70 kg) contains about 1.1 mg Co mainly in the heart, liver,
kidney, and spleen, with relatively small amounts in the pancreas, brain, and serum.
The daily requirement of cobalt is 0.1 μg day 1. The requirement for Co is not for
the element but for a preformed compound, Cobalamin (Vitamin B12) produced by
microorganisms, including bacteria and fungi. Higher plants and animals are unable
to produce cobalamin. The cobalamin synthesized in microorganisms enters the
human food chain through incorporation into food of animal origin. In many
animals, gastrointestinal fermentation supports the growth of vitamin B12 synthe-
sizing microorganisms, and subsequently the vitamin is absorbed and incorporated
into the animal tissues. The RDA for cobalamin for adults is 2.4 μg day 1, the
lowest for all essential nutrients (Yamada 2013). In humans, most of the dietary
intake of Co is inorganic with vitamin B12 representing only a small fraction. The
bioavailability of inorganic Co compounds varies between 5 and 45% depending on
their water solubility. Dietary sources of Co are the same as for vitamin B12. The
vitamin B12 content of food is very low and it is generally absent in fruits and
7.8 Optimizing Microelement Status 353
Table 7.16 Estimated Average Requirements (EAR) of microelements for different life stage
groups
Copper Iodine Iron Molybdenum Zinc
Life stage group (μg day 1) (μg day 1) (mg day 1) (μg day 1) (mg day 1)
Children
1–3 year 260 65 3.0 13 2.5
4–8 year 340 65 4.1 17 4.0
Males
9–13 year 540 73 5.9 26 7.0
14–18 year 685 95 7.7 33 8.5
19–50 year 700 95 6 34 9.4
>51 year 700 95 6 34 9.4
Females
9–13 year 540 73 5.7 26 7.0
14–18 year 685 95 7.9 33 7.3
19–50 year 700 95 8.1 34 6.8
>51 year 700 95 5 34 6.8
Pregnancy
14–18 year 785 160 23 40 10.5
19–50 year 800 160 22 40 9.5
Lactation
14–18 year 985 209 7 35 10.9
19–50 year 1000 209 6.5 36 10.4
Source: Dietary reference intakes for vitamin A, vitamin K, arsenic, boron, chromium, copper,
iodine, iron, manganese, molybdenum, nickel, silicon, vanadium, and zinc (2001); Available at
[Link]
Compiled from Food and Nutrition Board, Institute of Medicine, National Academies
vegetables. Organ meats (liver, kidney, heart and pancreas), clams, oysters, fish,
seafood, chicken, eggs, milk products and an edible green and purple seaweed- nori
contain significant amounts of vitamin B12. Apparently, humans get dietary vitamin
B12 almost exclusively from animal tissues or products such as milk, butter, cheese,
eggs, meat, poultry. Dietary Co absorption is reduced in the presence of high dietary
intakes of iodine. Ionic forms of iinorganic cobalt are toxic for the humans.
Copper
The human body weighing 70 kg contains about 120 mg Cu, which is widely
distributed in tissues and fluids bound to proteins or to organic compounds.
About two-thirds of body copper is found in the skeleton and muscles. Copper
homeostasis is accomplished at enteric absorption level. It is excreted in the bile
and only a small amount is lost through urine. Copper absorption in the body is
inversely related to its intake and about 50–60% of Cu intake is retained. The
recommended dietary allowance (RDA) of Cu ranges between 340 and 440 μg day
1
for children up to 8 years of age; 700–890 μg day 1 for ages 14 through 18, and
900 μg day 1 for adults (IOM 2001). The RDA of Cu is higher during pregnancy
and lactation. The average daily Cu requirements are 12.5 μg kg 1 of body weight
354 7 Microelements and Their Role in Human Health
Table 7.17 Tolerable Upper Intake Levels (TUL) of microelements for different life stage groups
for adults and about 50 μg kg 1 of body weight for infants (WHO 1996). The
recommended tolerable upper intake level from foods and supplements varies with
age group and ranges between 1–3 mg day 1 for children below 8 years of age and
10 mg day 1 for adults (Table 7.17; IOM 2001). Generally, dietary Cu intakes for
adults range between 1 and 3 mg day 1 (IPCS 1998; IOM 2001) and together with
uptake from water it ranges between 1 and 5 mg day 1. Food is the main source of
Cu for humans and about 40% of dietary copper is derived from yeast breads,
potatoes, tomatoes, cereals, beef and dried beans and lentils (Subar et al. 1998).
Major sources of dietary Cu include liver and other organ meats, seafood, nuts, dark
chocolate and whole grains (Table 7.19). In most foods, Cu is bound to macromol-
ecules and does not exist as a free ion (IOM 2001).
Iodine
The human body contains approximately 5 mg of iodine, which functions only in
the iodine containing thyroid hormones. Iodine is absorbed through the gut as
iodide, the chemically bound form of iodine. Iodine homeostasis is realized by
the kidney through urinary excretion comprising 90% of iodine absorbed by iodine-
adequate individuals (Combs 2005). Therefore, analysis of urinary iodine concen-
tration is the most commonly used biochemical indicator of I status of an individ-
ual. Median urinary iodine concentration is used to assess iodine status of a
population. Other assessment methods include goitre, measurement of thyroid-
stimulating hormone (TSH) levels in neonates and blood thyroglobulin in school-
age children (WHO 2007; Zimmermann et al. 2008). The daily recommended
7.8 Optimizing Microelement Status 355
dietary intake of I is 110–130 μg day 1 for children under the age of 1, 90–120 μg
day 1 for children aged 1–10, and 150 μg day 1 for adults and adolescents, with
higher concentrations (250 μg day 1) required during pregnancy and lactation
(WHO 1996). The humans can obtain iodine through direct inhalation, drinking
water and beverages’ and food consumption. Inhalation cannot be a significant
pathway of iodine intake, except in near-coastal environments, where humans may
obtain some iodine by inhalation. Similarly, drinking water is unlikely to supply
more than 10% of the daily adult iodine requirement. Apparently, food is the main
source of dietary iodine. Among the food items, the major sources of dietary iodine
include iodized salt, sea fish, and kelp. The food sources having high concentrations
of iodine include marine fish, egg, milk and dairy products (Table 7.20; Haldimann
et al. 2005). Dairy products are rich sources due to the addition of iodine to cattle
feed, the use of iodine containing disinfectants in the dairy industry, and the
inadvertent ingestion of soil by the animals that could add iodine. Baked products
have high iodine concentration mainly because of addition of iodized salt during
manufacturing process. Plant foods, with the exception of leafy vegetables, are low
in iodine and the content varies considerably from species to species (Table 7.20).
356 7 Microelements and Their Role in Human Health
Even the same food product has widely different iodine content depending on the
location where it is produced as the iodine uptake is in proportion to the iodine
present in the environment. Plants grown in iodine-rich soil contain substantial
amounts of iodine. Iodine in soil is often leached and carried to the sea by repeated
flooding and glacial activity, thereby making seawater, seaweed and marine fish
rich sources of iodine. The most practical and cost-effective strategy to control
iodine deficiency is iodisation of salt. Salt is iodized by adding potassium iodate
(KIO3) or potassium iodide (KI), either in powder form or as aqueous solution.
Iodate is recommended as fortificant in preference to iodide because it is more
stable, particularly in warm, damp, or tropical climates (WHO 1991; Mannar and
Dunn 1995).
Iron
Iron is the most abundant trace element in the human body that contains ~3–4 g of
elemental iron, with almost 50% present in haemoglobin and the rest in the
myoglobin of muscle, in ferritin, and in hemosiderin (a breakdown product of
ferritin). Serum Fe is about 1.3 mg L 1, mostly bound to transferrin. The average
7.8 Optimizing Microelement Status 357
dairy products. Heme sources of iron are haemoglobin and myoglobin from meat
and poultry. The average diet in the United States contains-15 g of elemental iron,
most of which is chelated to various phytates, phosphates, and other molecules such
as oxalate and tannin and is thus unavailable for absorption. Only 1.5–2.0 g of
dietary iron is absorbed in the gastrointestinal tract. Therefore, low bioavailability
of dietary iron is one of the reasons for low iron level in the human body,
particularly for individual dependent on vegetarian plant-based foods. To compen-
sate for lower iron bioavailability, about 10%, from vegetarian diets compared with
18% from a mixed Western diet, vegetarians need to increase dietary iron by 80%
(FNB 2001). In vegetarian diets, iron intake can be augmented by increased
consumption of dried beans and legumes, fruits and vegetables, and whole-grain
rather than refined-grain products. Such food choices can considerably alter the
dietary components that enhance or inhibit the bioavailbility and absorption of
nonheme iron. Iron intake can also be optimized through supplementation and food
fortification. Iron compounds recommended for food fortification include ferrous
sulphate, ferrous fumarate, ferric pyrophosphate and electrolytic iron powder
(WHO 2006). Low cost elemental iron powders, which are sometimes used to
fortify cereal foods, are not recommended. Analysis of the previously published
(1995–2011) estimates on anaemia showed that iron supplementation could
increase the mean blood haemoglobin concentration by 8.0 g L 1 in children,
10.2 g L 1 in pregnant women and 8.6 g L 1 in non-pregnant women indicating
that about 42% of anaemia in children and about 50% in women could be elimi-
nated by iron supplementation (WHO 2015).
Manganese
The human body contains approximately 20 mg of Mn distributed mainly in the
liver, bones and kidneys. Because of lack of information on Mn deficiency induced
illnesses, not many studies have characterized the effect of Mn supplementation in
humans. Adequate intakes of Mn (mg day 1) are 1.2–1.5 for children below 9 years
of age, 1.6–2.2 for age group between 14 and 18 years. Adequate intakes for adults
above 18 years of age are 2.3 and 1.8 mg day 1 for men and women, respectively
(FNB 2001). The recommended intakes for pregnant and lactating women are 2 and
2.6 mg day 1, respectively. The UL for different life stage groups ranges between
2 mg day 1 for ages 1–3 years and 11 mg day 1 for ages above 19 years
(Table 7.17). Mean daily intakes of Mn range between 0.52 and 10.8 mg
(Freeland-Graves and Lianis 1994). Food sources of Mn include nuts, legumes,
leafy vegetables, tea and whole grains. Meats, refined grains and dairy products are
low in Mn.
Molybdenum
Food is the major source of Mo intake in humans. Plant foods such as legumes,
grain products and nuts and milk and milk products and organ meats (especially
liver and kidney) are rich sources of Mo in the diet. Non-leguminous vegetables,
fruits, oils, fats and fish are poor sources of Mo (Nielsen 1996). Dietary Mo and
supplements in the form of soluble complexes such as ammonium molybdate are
easily absorbed. The RDA for Mo is 17–22 μg day 1 for 1–8 years of ages, 34 μg
7.8 Optimizing Microelement Status 359
day 1 for 4–8 years, 43–45 μg day 1 for ages 14 years or more (Table 7.15). For
pregnant and lactating women the RDA is set at 50 μg day 1. The estimated intake
(EAR) for different life stage groups ranges between 13 μg day 1 for age 1–3 years
and 34 μg day 1 for age over 18 years (Table 7.16). Though Mo has low toxicity in
humans, yet the ULs are set because of its harmful effects on reproduction and fetal
development in animals. The ULs for different life stage groups range between
300 μg day 1 for age 1–3 years and 2000 μg day 1 for age over 18 years
(Table 7.17).
Zinc
The amount of Zn in the adult human body ranges between 1.4 and 2.3 g Zn
(Calesnick and Dinam 1988). Zinc is present in all body tissues and fluids in
relatively high concentrations, with 85% of the total Zn in muscle and bone, 11%
in the skin and the liver and the remaining in all the other tissues (Kawashima et al.
2001). Less than 0.1% of the total body Zn is in the plasma and it has a rapid
turnovers rate and thus cannot be used as an indicator of overall Zn status except
under conditions of apparent deficiency. Blood Zinc concentration does not
decrease in proportion to the magnitude of deficiency rather the physical growth
is slowed down and excretion is reduced. Therefore, Zn homeostasis is primarily
maintained by adjustments in total Zn absorption and endogenous intestinal excre-
tion (Hambidge and Krebs 2001). The RDA of Zn is 3–5 mg day 1 for children
below 9 years of age and 8 mg day 1 for children up to 13 years of age. For adults,
the dietary allowance is 11 mg day 1 for men, 8 mg day 1 for women and
12–13 mg day 1 for pregnant and breast feeding women (Table 7.15). The esti-
mated intake for different life stage groups varies between 7–9.4 mg day 1 for men
and 6.8–10.9 mg day 1 for women (Table 7.16). About one-third of the world
population is estimated to be suffering from Zn deficiency and there is a close
relationship between Zn deficiency in soils and crops and in humans (Fig. 7.3).
Generally, regions such as south and middle-east Asia, Africa and Latin American
countries having high incidence of Zn deficiency in humans are also deficient in
plant available Zn in soils. Food is the main source of Zn for humans and is present
in a number of foods including red meat and poultry, beans, nuts, legumes, seafood
(oysters), whole grains, fortified breakfast cereals, and dairy products. Zinc from
animal foods is more bioavailable than that from plant foods which contain certain
antinutrients such as fiber and phytate that inhibit Zn uptake by the intestine. Zinc is
generally associated with the protein fraction and nucleic fraction of food. Strate-
gies to manage Zn deficiency in humans include dietary diversification/modifica-
tion, supplementation (giving zinc tablets to certain target groups), food
fortification and bio-fortification. The choice of a strategy depends on the available
resources and technical feasibility.
360 7 Microelements and Their Role in Human Health
Table 7.21 Zinc and phytate contents of selected foods (Compiled from IZiNCG 2004)
Zinc content Phytate content Phytate: zinc
Food mg 100 g 1 mg 100 g 1 Molar ratio
Liver, kidney (beef poultry) 4.2–6.1 0 0
Meat (beef, pork) 2.9–4.7 0 0
Poultry 1.8–3.0 0 0
Sea food 0.5–5.2 0 0
Eggs (chicken, duck) 1.1–1.4 0 0
Dairy (milk, cheese) 0.4–3.1 0 0
Seeds, nuts 2.9–7.8 1760–4710 22–88
Beans, lentils 1.0–2.0 110–617 19–56
Whole-grain cereals 0.5–3.2 211–618 22–53
Refined cereal grains 0.4–0.8 40–349 16–54
Bread (white flour, yeast) 0.9 30 3
Fermented cassava root 0.7 70 10
Tubers 0.3–0.5 93–131 26–31
Vegetables 0.1–0.8 0–116 0–42
Fruits 0–0.2 0–63 0–31
7.8 Optimizing Microelement Status 361
[Link] Biofortification
Table 7.22 Strengths and weaknesses of different biofortification strategies to increase nutrient
density of plant based foods (Adapted from Carvalho and Vasconcelos 2013)
Biofortification
strategy Strengths Weaknesses
Agronomic Simple method with immediate Short-term strategy, needs regular
results; can be complementary to application, successful only for
other strategies minerals, difficult distribution, suc-
cess dependent on several factors,
expensive, could have adverse envi-
ronmental effects
Conventional Successful for minerals and vitamins, Long development time, success
plant breeding one-off cost, easier distribution, long- limited to minerals available in the
term strategy, wide public acceptance soil, requires genetic variation
Genetic Successful for minerals and vitamins, Long development time, success
engineering one-off cost, easier distribution, long- limited to minerals available in the
term strategy, speeds up process of soil, interaction among transgenes
conventional breeding may limit the process, low public
acceptance, complex regulatory
approval, environmental impact
[Link] Iron
The total Fe content of a diet does not provide much information about its
bioavailability, which can vary by an order of a magnitude for different diets with
similar iron content (Hallberg and Hulthen 2000). The differences in bioavailability
of iron among different foods are attributed to the chemical form of Fe present in a
food. Dietary iron is of two types: nonheme iron present in both plant foods and
animal tissue, and heme iron present only in animal foods and is derived from
hemoglobin and myoglobin. The heme iron is better absorbed (15–35%) than the
nonheme iron. Heme iron is estimated to contribute 10–15% of total iron intake in
meat-eating population but because of higher absorption it constitutes more than
40% of the total iron absorbed (Carpenter and Mahoney 1992; Hunt 2002). Based
on intake data, iron bioavailability has been estimated between 14–18% for mixed
diets and 5–12% for vegetarian diets (Hurell and Egli 2010). In addition to the
chemical form, the amount of iron absorbed from a food by an individual is
determined by the body iron store and the presence of dietary inhibitors or
antinutrients and enhancers or promoters (Table 7.23). Both heme and non-heme
forms of iron are absorbed in inverse logarithmic proportion to body iron stores
(Hunt 2003). The main dietary antinutrients that inhibit absorption of nonheme iron
include phytic acid or phytate (inositol phosphate) present in whole grains,
legumes, lentils, and nuts; polyphenols and tannins found in tea, coffee, red
wines, a variety of cereals, vegetables, and spices; oxalates found in certain
vegetables and herbs, nuts, chocolate; and other microelements, e.g., zinc and
copper (Hallberg and Hulthen 2000; Table 7.23). The extent of inhibitory effect
364 7 Microelements and Their Role in Human Health
Table 7.23 Dietary components that can inhibit (antinutrients) and enhance (promoters) the
bioavailability of Zn and Fe in humans, if consumed concurrently (Compiled from Graham
et al. 2001; Gibson 2007 and several other sources)
Dietary component Major dietary sources Main technical influence
Inhibitors/antinutrients
Phytic acid or phytin Unrefined cereals, legumes, nuts, Binds positively charged Fe and
(myo-inositol and oil seeds Zn ions to form insoluble com-
hexaphosphate) plexes in gut
Dietary fibre Whole cereal grain products Effect compounded by the
(e.g. cellulose, hemicel- (e.g. wheat, rice, maize, oat, quantity of minerals and pro-
luloses, lignin, cutin, barley, rye), nuts, oilseeds, fruits tein, presence of phytate or
suberin etc.) and vegetables oxalic acid and type of fibre in
the diet
Polyphenols and tannins Certain cereals (red sorghum), Form insoluble complexes with
legumes (red kidney beans, black iron (e.g. iron-tanin);
beans, black gram, lentils), spin-
ach, betel leaves, oregano, bev-
erages (tea, coffee, cocoa, red
wine)
Oxalic acid/oxalates Amaranth, spinach, rhubarb, Probably oxalate forms insolu-
yam, beets, sweet potato, kale, ble complexes with Fe
sesame seeds, nuts, chocolate,
tea, wheat bran, strawberries and
herbs such as oregano, basil,
parsley, taro, sorrel
Egg factor Eggs Phosvitin, a Phosphoprotein
binds iron and decreases its
bioavailability
Soy protein Tofu, soybeans, tempeh, bean Presence of phytic acid and a
curd, soy milk functional group that makes up
part of the protein conglycinin.
Hemagglutinins Most legumes and wheat grain Lectins bind to glycoprotein
(e.g. lectins) receptors on the epithelial cells
lining the intestinal mucosa and
inhibit the absorption of
nutrients
Enhancers/promoters
Organic acids (citric, Fermented milk products (e.g., May form soluble ligands with
lactic, acetic, butyric, yogurt), vegetables (e.g., sauer- some trace minerals in the gut
propionic, formic acids) kraut), soy sauce, fresh fruits
Ascorbic acid Citrus fruits and juices, other Reduces ferric iron to more
fruits (e.g., guava, mango, soluble ferrous iron; forms iron-
papaya kiwi, strawberry), vege- ascorbate chelate; may counter-
tables (e.g., tomato, asparagus, act inhibitory effect of phytate
Brussels sprouts) and dietary fibre
Amino acids Animal meats (Beef, pork, Possibly peptides form soluble
(e.g. methionine, cyste- chicken, fish, etc) ligands; reduce or chelate iron;
ine, histidine and lysine);
meat factors
(continued)
7.8 Optimizing Microelement Status 365
of phytate on iron absorption depends on phytate to iron molar ratio. For cereals or
legume based diets that do not contain any enhancers, the molar ratio should
preferably be less than 0.4:1 so as to significantly improve iron absorption. For
composite diets comprising vegetables containing ascorbic acid and meat as
enhancers the phytate to iron molar ratio should be less than 6:1 for better iron
absorption (Hurrell 2004; Tuntawiroon et al. 1990). In cereals and legumes, poly-
phenols add to the inhibitory effect of phytate. The inhibitory effect of polyphenols
depends not only on its quantity but also the type. For example, while polyphenols
in chilli are inhibitory to iron absorption that in turmeric are not (Tuntipopipat et al.
2006). Dietary fibre per se does not clearly inhibit iron absorption and the effect is
compounded by the type of fibre, the presence of phytate or oxalic acid, and the
quantity of minerals and protein in the diet (Anderson 1990; Freeland-Graves
1988).
Food processing and preparation methods including milling, thermal processing,
soaking, malting, germination, and fermentation can be used to remove or degrade
phytate (Table 7.24; Egli et al. 2002). Food processing methods involving soaking,
malting, and fermentation hydrolyse the phytate through the activation of plant and
microbial phytases. Exogenous addition of phytase has also been shown to improve
iron absorption (Sandberg and Andersson 1988). Besides these food processing
methods, iron absorption from vegetarian diets can probably be improved by
modifying food preparation method, food selection, and food combination (Hunt
2003). Such modifications can include the use of iron cookware particularly for
cooking acidic foods that solubilise iron from the pan; the concurrent consumption
of iron and ascorbic acid containing foods while limiting inhibitory foods such as
coffee and tea in between meals; and the selection of low phytate foods (Martinez
and Vannucchi 1986; Gibson et al. 1997).
The main dietary components that enhance iron absorption include organic
acids, vitamin C or ascorbic acid, amino acids and meat, poultry, and fish
(Table 7.23). Ascorbic acid reduces ferric iron to more soluble ferrous iron and
also forms iron-ascorbate chelate. Ascorbic acid is considered to counter the
366 7 Microelements and Their Role in Human Health
Table 7.24 Categorization of diets according to their potential bioavailability of zinc (Source:
FAO/WHO 2002)
Zinc Phytate: Zn
absorption molar ratio Diet types
High <5 Highly refined low in cereal fibre and animal foods; includes
(50%) semi-purified formula diets
Moderate 5–15 Mixed diets with animal or fish protein and lacto-ovo-vegetar-
(30%) ian diets not based on unrefined cereals grains or high extrac-
tion rate (>90%) flours
Low >15 Cereal based diets with >50% energy intake from unrefined
(15%) cereal grains or legumes and negligible animal protein intake
inhibitory effects of phytate and polyphenols and enhance the absorption of iron in
vegetarian and vegan diets. However, cooking, processing and storage of food
degrade ascorbic acid nullifying its promontory effect on iron absorption. Moderate
consumption of alcohol can enhance the absorption of iron, but heavy or excessive
drinking has adverse health effects. Iron absorption from cereals and legumes can
be improved by degrading inositol phosphates to less phosphorylated inositol
phosphates because the phytates with less than three phosphate groups do not
inhibit nonheme iron absorption (Sandberg et al. 1999). Presence of β-carotene
along with phytates or tannic acid usually counters the inhibitory effect depending
on their concentrations.
[Link] Zinc
Similar to iron, the bioavailability of dietary Zn can be reduced by the phytic acid
and some other constituents of plant food. Phytic acid binds minerals, including Zn,
in the human gastrointestinal tract, forming insoluble complexes that prevent Zn
absorption (Cheryan 1980). Usually, phytic acid to zinc molar ratio of a meal is
used to estimate the fractional absorption of the ingested zinc. Based on the Zn
concentration and contents of promoters and inhibitors of Zn absorption, three
categories of diet viz. high, moderate and low in bioavailable Zn with respective
fractional absorption rates of 50%, 30% and 15% were identified (Table 7.24;
FAO/WHO 2002). Molar ratios greater than 15:1 according to World Health
Organization (2006) or 18:1 according to International Zinc Nutrition Consultative
Group (2004) severely inhibit Zn absorption and have been associated with low Zn
status in humans. Phytate with less than five phosphate groups do not inhibit Zn
absorption (Lonnerdal et al. 1989). The inhibitory effect of phytate can be coun-
tered by the addition of ascorbic acid (Siegenberg et al. 1991). However, it has been
suggested that the chelation properties of phytic acid may have some potential
beneficial effect such as lowering serum cholesterol and triglycerides, and
preventing heart disease, renal stone formation, and certain types of cancer, such
as colon cancer (Zhou and Erdman 1995).
References 367
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