Dynamics and transformations of micronutrients in agricultural soils as influenced by organic matter build-up: A review

Environmental and Sustainability Indicators 1-2 (2019) 100007

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Dynamics and transformations of micronutrients in agricultural soils as influenced by organic matter build-up: A review S.S. Dhaliwal a, *, R.K. Naresh b, Agniva Mandal c, Ravinder Singh a, M.K. Dhaliwal d a

Department of Soil Science, Punjab Agricultural University, Ludhiana, India Department of Agronomy, Sardar Vallabbhai Patel University of Agriculture and Technology, Meerut, India Department of Agricultural Chemistry and Soil Science, Bidhan Chandra Krishi Viswavidyalaya, Mohanpur, West Bengal, India d Department of Soil and Water Conservation, Government of Punjab, India b c

A R T I C L E I N F O

A B S T R A C T

Keywords: Soil organic matter Dynamics of micronutrients (Fe, Mn, Zn, Cu, B and Mo) micronutrient transformations soil environment

The dynamics and transformations of micronutrients (Zn, Cu, Fe, Mn, B and Mo) in soils, are governed by various factors like pH, EC, soil organic matter etc. Soil organic matter (SOM) is known to modify different physiochemical reactions that influence the available component of micronutrients. Soil organic matter favors reduced (lower redox potential) environment and enhances the accessibility of micronutrient cations in the soil. Also, SOM has direct and indirect impacts on nutrient transformations. Soil organic matter (SOM) also serves as source of soil organic carbon (SOC) comprising about 60% on a mass basis. Under reduced environment the addition of SOM increased complexed forms of micronutrients. Build-up of SOM in soil converts adsorbed fractions to more plantaccessible forms of micronutrients. Soil organic matter addition increases the water soluble and exchangeable forms of micronutrients in soil which further increase the uptake of micronutrients. High amount of SOM in soils assists the various reactions of micronutrients resulting in formation of more stable complexes of micronutrient. Soil organic matter binds more Zn, Cu, B and Mo compared to Fe and Mn because the former are less sensitive to redox changes. The accretion of organic matter near the soil surface increases transformations (towards adsorbed fractions) of Mn and Fe and possibly decreases the availability of Zn, Cu, B and Mo by causing their redistribution among other complex fractions.

Introduction Soil organic carbon (SOC) is the most important component in maintaining soil quality because of its role in improving physical, chemical and biological properties. Agricultural productivity has been improved in many regions of the world, where addition of nitrogen, phosphorus, and potassium (NPK)-containing fertilizers results in Green Revolution. Along this line, in recent days, innovative fertilization is of great need to retain the sustainability of soil (Bindraban et al., 2015). Along with NPK, calcium (Ca), magnesium (Mg), and sulphur (S) are considered as essential macronutrients. Micronutrients at a concentration less than 0.5 g per kg plant dry matter such as copper (Cu), iron (Fe), manganese (Mn) and zinc (Zn) are also considered essential for plant nutrition. These micronutrients act as a co-factor for various enzymes associated in the metabolism of various organic molecules such as carbohydrates, nucleic acids, proteins and lipids (Barker and Pilbeam, 2015). Concentrations of Cu, Fe, Mn and Zn per kg soil were reported to

be in range of 2–100 mg (Lindsay, 1979), 20,000–550,000 mg, 450–4000 mg (Noll, 2003) and 10–300 mg (Barber, 1995) respectively in agricultural soils. Several factors govern the micronutrients movement that comprises their naturally low total concentrations, practically defined chemical fractions, soil organic matter, pH, soil-plant/soil-microbe interactions, and plant genotype (Shukla et al., 2015; Rengel, 2015; Agrawal et al., 2016). The micronutrients deficiency became a restriction to productivity, stability and sustainability of soils (Bell and Dell, 2008). Fluctuation in micronutrient deficiency levels in soil, is a global phenomenon these days (Voortman and Bindraban, 2015; Monreal et al., 2016). However, in different agricultural ecosystems worldwide, one common fact is micronutrients deficiency associated with crops having low use efficiency i.e. low capability of uptaking micronutrients (Baligar et al., 2001). In arable soil in vast regions of the earth, manifold micronutrient deficiencies could be observed (Monreal et al., 2016; Voortman and Bindraban, 2015; Oliver and Gregory, 2015) and the insufficient restoration of micronutrients via fertilization which

* Corresponding author. E-mail address: [email protected] (S.S. Dhaliwal). https://doi.org/10.1016/j.indic.2019.100007 Received 22 May 2019; Received in revised form 13 September 2019; Accepted 15 September 2019 Available online 21 September 2019 2665-9727/© 2019 Published by Elsevier Inc. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

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Cu, Fe and Mn in soil as well as their concentration in different crops could be enhanced by application of N, P and K fertilizers (Zhang et al., 2004). In alkaline soils, higher uptake of Zn, Cu, Fe and Mn were generally associated with increased application of N-fertilizer. This increase can be related to the reduction of soil pH due to N fertilization which further results in increase of the availability of Zn, Cu, Fe and Mn in soil. The combined application of P with N showed a notable increase in Zn and Fe contents in soil while minimal effect was observed in case of Cu and Mn (Setia and Sharma, 2004). However, high phosphate content of soils or high fertilization with phosphate may reduce the uptake of Zn and other nutrients (Dadlich and Somani, 2007; Kizilgoz and Sakin, 2010). Thus indiscriminate use of macronutrients may affect uptake of micronutrients in soils. One of the major problems both in regional and global aspects is micronutrient deficiency which affects more than two billion people (De-Regil et al., 2013; Bailey et al., 2015; FAO, 2015). Although significant contribution of chemical fertilizers was found effective in nutrient supply for intensive cultivation but the increased use of these fertilizers in an imbalanced manner is also responsible micronutrient deficiency. Organic manures application coupled with application of inorganic fertilizers on the other hand effectively enhances the micronutrient availability in soils. For the maintenance/adjustment of soil factors to an optimum level to get better crop productivity and highest benefit from all possible sources of plant nutrients (i.e. both organic and inorganic) integrated nutrient management is the most suitable option (Aulakh and Grant, 2008). Organic manures and crop residues applied in conjunction with mineral fertilizers can improve the physical and chemical properties of soil resulting in higher fertilizer use efficiency (Lamps, 2000). Micronutrients occur in different forms and their transformations from one to another are affected by various cropping sequences. Elements like Cu and Zn present in soils were found in numerous physicochemical forms/fractions (Berti and Jacobs, 1996; Sekhon et al., 2006). The element boron (B) is distinct and only element amongst the essential mineral elements that usually present in soil solution as nonionized molecule (H3BO3). Its quantitative requirement is very small to the tune of 10–20 mg kg
1 depending on the plant species. However the difference between deficiency and toxicity limits is very narrow, hence B requires judicious fertility management. Boron (B) is vital for standard growth of plants because it promotes proper cell division, cell elongation, cell wall strength, flowering, seed set and sugar translocation (Sims and Johnson, 1968). Boron is important in cell division process at all growing ends of plants where cell division is active. Plants lacking B, continue to undergo cell division in developing tips without separation of cells which otherwise would results in the cells that becomes stems, leaves, flowers, etc. Over the years, researchers have observed a close relationship between the primary cell walls and boron nutrition. Around 90% of the cellular B is localized in the cell wall fraction (Hanson, 1991). The initial symptoms of B deficiency include cell wall abnormalities and organization of middle lamella (Hu and Brown, 1996). Molybdenum (Mo) is a one the important trace micronutrient which plays an important part in ecological cycling of N, C and other elements essential to life. Mo act as a co-factor in the nitrogenase enzyme, thus biological N2 will be effected by fixation when Mo is in short supply (Wurzburger et al., 2012; Jean et al., 2012). To evaluate their impact on agriculture, it is essential to identify the different forms found in the soil, since the mobility and bioavailability of these elements are governed by dynamic processes and not by the total content of the elements (Kuo et al., 1983). The addition of organic matter via manure (FYM), green manure and organic waste redistributes the applied micronutrients in their different fractions (Sekhon et al., 2006; Rupa et al., 2001; Dhaliwal and Walia, 2008). Micronutrient concentration in crops increased with incorporation of green manure and application of inorganic and organic sources of nutrients (Soni et al., 2000; Ram and Singh, 2005).

is biologically excavated from the soil by plant roots, which had possessed negative agronomic concerns for crop productivity. For example, in India over several decades NPK fertilization contributed to higher yields in case of rice and wheat cultivation but also responsible for extraction of micronutrients from the soil by crops to such an extent that the bioavailability of micronutrients like Zn has become so limited that it indirectly hampers Zn nutrition in humans (Cakmak, 2009; Monreal et al., 2016). Positive yield responses by crops such as soybean (Glycine max), tobacco (Nicotiana sp.), wheat (Triticum aestivum L.), and cauliflower (Brassica oleracea) were observed upon micronutrients application along with application of one or all of the NPK nutrients (Rietra et al., 2015). Different organic materials (e.g. plant residues, manures and waste materials) application is known as an effective strategy for improving nutrient use efficiency and fertility of soil. Under several cropping systems application of organic sources is a management practice which is found helpful for sustaining high crop productivity. Use of organic sources affects the soil physical and chemical properties which in turn affect the micronutrient nutrition of crops by providing better environment for root growth as well as by adding some additional micronutrients to soil also (Rengel et al., 1999). Influence of soil organic matter (SOM) on soil micronutrient availability as well as their uptake by plants was observed in many findings both in direct and indirect manner (Rengel et al., 1999). Reduction in free cation concentration in soil solution may occur due to binding of metals to organic matter but dissolution of these organo-metallic complexes enhances the phyto-availability of metals at root-rhizosphere interface by increasing total dissolved ion concentration which in turn depends on mobility of metal-dissolved organic carbon (DOC) complexes and their dissociation kinetics. Chelation of Zn and Fe with organic matter is responsible to a great extent for augmentation of root accessible forms of these nutrients and also prevents formation of insoluble forms such as carbonates and oxides in soil (Schulin et al., 2009). Addition of organic resources such as crop residues, green manure, municipal bio solids, composts, livestock manure to soil exhibits several benefits coupled with micronutrient nutrition including additional supply of some other nutrients along with added organic matter, enhancement of ion exchange capacity, soil structure, water storage capacity, improved drainage, aeration and reduction of soil salinity also. Exogenous addition of organic matter stimulates the microbial exudation of organic ligands (enhance microbial biomass carbon), nutrient supply through mycorrhizae, protection against root pathogens and other activities of microbes which collectively helps in development of the root system and thus its micronutrients acquiring capacity which eventually promotes plant growth (Schulin et al., 2009). Soils with low Zn may have a low total Zn content (some leached acidic soils in tropics) or may have a comparatively high total Zn content, but a plant-accessible fraction is low due to the soil chemistry that favors the synthesis of poorly soluble Zn complexes (Rengel, 2002). If they are grown in soils with poor micronutrient availability due to chemical or biological fixation or spatial or temporal unavailability, micronutrient-efficient genotypes yields more than inefficient ones, even if they are fertilized with smaller or are less frequent (Rengel and Marschner, 2005). Due to intensive cropping of high yielding varieties of rice and wheat, Zn and Fe deficiency in rice and Mn deficiency in wheat emerged as major threats to sustaining high levels of food production. In the soils of Punjab, the magnitude of deficiency of Zn, Cu, Fe and Mn in soil during 1990s has been reported to be 48, 1, 14 and 2 percent, respectively (Singh et al., 1999). In the last decade, Zn deficiency decreased to 22 per cent, while there was an increase in deficiency of Mn and Cu to 11 and 2 percent respectively and Fe deficiency remained unchanged. The soil conditions and the cultivated crops positively govern the severity of these deficiencies. Uptake of micronutrients is affected by the presence of major nutrients due to either negative or positive interaction (Fageria, 2008). Practice of different fertilization methods and cropping sequences are responsible for variation in behavior of Fe, Mn, Zn and Cu in soil and crop. Both the availability of Zn, 2

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Review of literature

Fiore, 2013) were applied to improve both yield of crop and quality of soil. Different organic fertilizers application along with chemical N fertilizer to agricultural lands is a widespread practice in crop production. Dhaliwal et al. (2010) described that the organic carbon (OC) content increased to 0.49% in organic farming treatments over its initial value (0.39%) and chemical treatment (0.38%) (Table 1). Organic sources helped to build-up the OC 23.1% over the initial level at the end of third crop cycle, which proved the hypothesis true with consistent improvement in soil fertility. The addition of organic manures also improved the status of Zn, Cu, Fe and Mn in soil over time (Table 2).

The present manuscript describes the effect of soil organic matter, its type, its buildup in soil and different application methods on the availability of micronutrients in soil environment. Among different application methods of soil organic matter, application of manures alone or in combination with inorganic fertilizers, fulfills a marvelous job in buildup of micronutrient status of soil. Major efforts are warranted in order to increase our understanding of the agro-ecological complexities associated with micronutrients with manures application, thus, harness the full benefits of micronutrients to crops. Taking into consideration the benefit of organic matter build-up in the soil and its possible effect on the release of micronutrients, the review of the problem is discussed under the following heads;

Effect of soil organic matter (SOM) build-up on available micronutrients (Zn, Cu, Fe, Mn, B and Mo) Avaiable zinc (Zn)

Effect of soil organic matter build-up on soil organic carbon level Deficiency of Zn is a vital problem in areas particularly in developing countries mainly relying on cereals to fulfil their need for food and nearly 50 percent of global population is found affected by this problem (Cakmak, 2008; Alloway, 2008). The concern regarding this problem is growing day by day as Zn plays numerous roles in biological functions of plants as well as humans and considered as an essential micronutrient for their growth and development (Hortz and Brown, 2004; Fraga, 2005; Alloway, 2008). But Zn deficiency is found fifth among the causes of mortality and diseases in developing countries due to consumption of staple grains (e.g., rice [Oryza sativa L.], wheat [Triticum aestivum L.], and maize [Zea mays L.]) with low Zn contents (Yang et al., 2007). Thus, increasing Zn in edible plant parts is a strategic aim in agricultural systems to combat widespread Zn deficiency in human nutrition (Cakmak, 2008; Cakmak and Kutman, 2018; White and Broadley, 2011). The accessibility of soil Zn for uptake by crop plants is restricted by pH, cation exchange capacity (CEC) of soil and solubility of the mineral itself which is directed mainly by adsorption to mineral surfaces, complex formation with organic matter and formation of precipitates (Baird and Cann, 2005; Smolders and Mertens, 2013; Fan et al., 2016a,b). SOM exhibit a complex role in Zn partitioning in soils (Chami et al., 2013). Whereas solid form of organic matter decreases Zn solubility by sorbing Zn on to surface functional groups (Boguta and Sokolowska, 2016), the complexation of Zn with dissolved organic compounds increases Zn solubility and mobility (Weng et al., 2002; Houben and Sonnet, 2012). Negative correlations between SOM and Zn availability was found by Eyupoglu et al. (1994) from the analysis of 1511 soil samples of Turkey. On the contrary, an opposite result was observed by Catlett et al. (2002) in Colorado soils. Thus, understating the effect of SOM on Zn availability is of utmost

It is widely recognized that the application of organic materials is one of the most effective ways of increasing SOC levels and improving soil quality. Applying an adequate amount of fertilizer is an important cultivation practice for the yield and quality of crops, environmental protection and soil sustainability (Oenema et al., 2009; Atafar et al., 2010). As a rule, for every tonne of carbon in SOM about 100 kg of nitrogen, 15 kg of each phosphorus and sulphur becomes available to plants as organic matter is broken down (Hoyle, 2013). Soil consists of numerous minerals associated with organic matter and parent materials on which a soil is developed. They cover a broad range of micronutrients conferring to their composition. Micronutrient accessibility in soil is measured by parent materials and the effects of edaphic and biological factors in soil such as redox potential, pH, soil microbial activity, their interaction with coexisting ions, reaction with soil minerals and organic matter. Accessibility of soil micronutrient can change via agricultural practices like the application of soil water management and soil amendments. Crop residues are reported to be an important sources of many micronutrients. By assessing the total crop residue production of 105 million tons in India, and on the basis of contents of micronutrient of the residues, the micronutrient prospective related with crop residues would be about 35,400 tons (Prasad, 1999). About 50–80% of Zn, Cu, and Mn taken up by rice and wheat crops can be recycled through residue incorporation. Therefore, enhancement of soil micronutrients accessibility could be amended by crop residues recycling. Addition of crop residues into flooded soils stimulates Fe and Mn concentrations in soil solution which increases the microbial metabolism that might be accredited for greater redox potential change. Organic acids produced in calcareous soils, during crop residue decomposition may improve Zn uptake of plant by dissolving Zn from the solid-phase pool to soil solution (Prasad and Sinha, 1995a). Chelating agents produced due to decomposition of crop leftovers increases the concentration of total diffusible Zn and its diffusion coefficient (Singh et al., 2005). Rice straw application was found to escalate the Zn content of rice plants, probably due to its amelioration of soil pH and exchangeable sodium percentage (Singh et al., 2005). Significant increase in SOC under high residue input in case of legume-based cropping systems was observed by Diekow et al. (2005). Xin et al. (2016) also described that under manure application, the contents of SOC in yearly rotation of winter wheat–summer maize for 23 years were 2.4 times greater than those under inorganic fertilizer and application of compost manure on a sandy loam textured soil. Significant improvements in soil physical, chemical and biological properties have been reported in organic matter application systems (Carpenter-Boggs et al., 2003; Chang et al., 2008; Moeskops et al., 2010; Surekha et al., 2010; Subehia et al., 2013). Dissimilar types of organic amendments including municipal solid wastes (Morra et al., 2010), peat (Vestberg et al., 2009), crop residues (Diouf et al., 2010), composted FYM (Wang et al., 2013; Heinze et al., 2011), and green manure (Miller et al., 2011; Yang et al., 2012; Piotrowska and Wilczewski, 2012; Subehia et al., 2013; Montemurro and

Table 1 Status of soil with respect to OC, as influenced by organic integrated and chemical sources of nutrition (Source: Dhaliwal et al., 2010). Treatments

Different treatments of maize-potato-onion experiment

OC (%)

T1

50% recommended NPKþ50% N as FYM/crop residues/ composts/other organic sources–inorganic sources of micronutrient as per soil test report Different organic sources each equivalent of 1/3 of recommended N (FYM þ vermicompost þ nonedible oil cake) T2 þ intercropping or trap crop (location specific in each season) T2 þ agronomic practices fro weed and pest control (No chemical, pesticides and herbicides) 50% N as FYM/other organic sources þ biofertilizer for N þ rock phosphate to substitute the P requirement of crops þ phosphate solublizing bacterial (PSB) cultures T2 þ Biofertilizer containing N and P carriers 100% NPK þ secondary and micronutrients based on soil test repot Dummy plot (T2)

0.44

T2

T3 T4 T5

T6 T7 T8 Initial

3

0.49

0.47 0.50 0.42

0.49 0.38 0.47 0.39

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et al., 2007). The lack of stability of Cuþ makes Cu2þ as its major form in soil (Reichman, 2002). Matijevic et al. (2014) found an appreciable increase in total Cu in soil as a result of SOM application. Rise in total soil Cu with application of SOM may be attributed to adsorption of Cu2þ ions on OM as sorption and formation of complexation with OM influence the bioavailability of Cu. Cu has a tendency to form stronger inner-sphere complex with SOM (Boudesocque et al., 2007) as compared to other alkali earth metals (e.g., Ca, Mg) which usually forms weaker outer-sphere complex (Tessier et al., 1996). Roussos et al. (2017) found an increase in Cu in an experiment where organic fertilizers were applied in two newly planted olive (Olea europaea L.) cultivars which may be due to the ability of organic matter to form stable metal complexes, especially in calcareous soils. In the paddy-soils, 32.6% Cu, 12.1% Fe and 14.7% Zn was found to be higher in the RFS (rainfed system) system. Walia et al. (2010) reported that the slight increase in the Cu content (1.35–1.66 mg kg
1) was notably observed in plots treated with organic manures over the control plots. The adding of FYM, green manure (GM) and wheat cut straw (WCS) results in greater micronutrients release in available forms in the soil as compared with chemical fertilization alone. Organic manure addition lowers the soil redox-potential which eventually increases the available Cu in soil. Increment of Diethylenetriaminepentaaceticacid (DTPA)-extractable Cu might be associated with the chelating action of organic compounds that are liberated due to decomposition of FYM, GM, and WCS that helps in availability of micronutrients through the prevention of some particular processes like fixation, oxidation, precipitation and leaching. Dhaliwal et al. (2010) reported in a field experiment with rice-wheat cropping system observed an overall improvement of Zn and Cu in the soil with the addition of FYM, WCS and GM. The results showed an increased concentrations of water soluble and exchangeable (WS þ EX) amorphous iron oxide (AFeOX), crystalline iron oxide (CFeOX) and organic matter (OM) bound fractions of Zn and Cu in case of rice cultivation where GM, FYM and WCS are incorporated whereas, a reduction was noted regarding Cu fractions held on specifically adsorbed (SPAD) on inorganic and adsorbed on manganese oxides (MnOX) sites. Zn fractions reported increase whereas, Cu fractions decreased in SPAD and MnOX sites. Variation in the activation of Zn and Cu fractions were observed due to decomposition of GM, FYM and WCS which affects the dynamics of their inter conversion from one fraction to other.

Table 2 Micronutrients status as influenced by sources of nutrition in maize-potato-onion cropping system periods (Source: Dhaliwal et al., 2010). Treatments

T1

T2

T3 T4

T5

T6 T7

T8 Control

Different treatments of maizepotato-onion experiment 50% recommended NPKþ50% N as FYM/crop residues/composts/ other organic sources–inorganic sources of micronutrient as per soil test report Different organic sources each equivalent of 1/3 of recommended N (FYM þ vermi-compost þ nonedible oil cake) T2 þ intercropping or trap crop (location specific in each season) T2 þ agronomic practices for weed and pest control (No chemical, pesticides and herbicides) 50% N as FYM/other organic sources þ biofertilizer for N þ rock phosphate to substitute the P requirement of crops þ phosphate solublizing bacterial (PSB) cultures T2 þ Biofertilizer containing N and P carriers 100% NPK þ secondary and micronutrients based on soil test repot Dummy plot (T2)

Micronutrients status (μg/g) Zn

Cu

Fe

Mn

0.76

0.44

13.92

5.02

0.58

0.46

14.30

6.30

0.61

0.56

12.84

6.08

0.74

0.44

11.66

4.70

0.61

0.46

13.50

5.84

0.53

0.40

10.68

5.60

0.68

0.38

11.48

5.54

0.62 0.56

0.42 0.42

11.76 6.70

6.12 3.80

importance as it varies with types of soils and their properties across the globe (McBride et al., 1997). Turnover of SOM can positively affect the solubility of Zn as decomposition of litter releases Zn in soil solution but may be leached into the deeper layers of soil or sorbed by the organic matter of the soil surface (Scheid et al., 2009). Moreover, retention of metallic elements such as Zn that is incorporated and present in organo-mineral associations could be observed due to transformation of OM. The gradual SOC decomposition and its reaction with mineral surfaces in soil aggregates results in the formation of organic molecules having variable rates of mineralization that depends on their accessibility for enzymatic activity (Lehmann and Kleber, 2015). Maturity of added OM actively influences the soil Zn availability. Presence of mature OM restricts the Zn availability in soil solution as it forms stable complexes with humic substances (Smith, 2009) whereas addition of decomposable OM results in dissolution of insoluble Zn that enhances the bioavailability of Zn. This may be due to association of several functional groups (e.g. phenolic, carboxyl, amino etc.) with the labile organic compounds that are responsible for strong chelation (Fuente et al., 2011). Addition of organic chelating agents augments Zn diffusion rate and uptake in case of wheat under calcareous soil (Sinha and Prasad, 1977). Again, Degryse et al. (2008) found a positive effect of excreted labile carbon compounds from roots on Zn diffusion that enhances the Zn uptake. Different research studies showed that addition of organic matter helps in accumulation of Zn in its available fraction due to its decomposition in the soil. However, higher amount of organic matter favours decrease in the available form of Zn through chelation.

Available iron (Fe) Many cultivated soils are abundant in Fe, on an average, having a total concentration of 20–40 g kg
1 (Cornell and Schwertmann, 2003). Fe is frequently present in ferrous (Fe2þ) form in primary minerals and few phyllosilicates while its oxidation to the ferric form (Fe3þ) showed significant pedogenetic variations (Stucki et al., 2002; Adriano, 2001; Torrent and Cabedo, 1986) and a sequence of conjugate bases formation where Fe was found to be linked with water and hydroxyls (Stumm and Furrer, 1987; Sposito, 1989; Cornell et al., 1989). Goethite (α-FeOOH) and hematite (α-Fe2O3) are the most abundant minerals among pedogenic forms of crystalline Fe (hydro) oxides in well-drained soil. Occurrence of other Fe oxides could be seen in poorly drained soil as crystalline minerals (magnetite, lepidocrocite and maghemite) or short-range ordered crystalline minerals (ferroxite and ferrihydrite) or non-crystalline precipitates (Schwertmann, 1985; Cornell and Schwertmann, 2003). The redox potential (i.e., oxidizing or reducing conditions) and pH are the two factors that govern the behavior of Fe in soil. Precipitation of poorly ordered Fe minerals (ferrihydrite) is promoted by neutral pH, while acidic and reduced conditions facilitates the mobilization of Fe minerals. Higher stability (i.e. low solubility) is a prime characteristic of hematite and goethite in the most habitual Eh–pH soil conditions. In soil solution concentration of Fe produced by hematite (Fe oxides) and goethite (hydroxides) is generally almost similar at a specific pH while in case of ferrihydrite lower Eh helps in higher Fe supply. However, occurrence of metastable minerals such as lepidocrocite and ferrihydrite

Available copper (Cu) Cu is an important constituent of several enzymes, plant proteins, plastocyanin and actively takes part in electron transport system (Hochmuth et al., 1991). Cu is taken up by the plants after binding of Cu2þ ions to specific carriers present on the surface of the plasmalemma of root cells (Jiang et al., 2001) and its uptake is highly dependent to the soil Cu availability (Tang et al., 1999). Cu-organic complexation plays a great role in Cu availability (Mengel and Kirkby, 1979; Boudesocque 4

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are noted particularly in younger soils characterizing the non-equilibrium state in the pedo-environment under cold climate and acidic conditions (Schwertmann, 1988). Little amount of Fe minerals could also be found as pyrite (FeS2) under reducing conditions in acid soils or as siderite (FeCO3) in alkaline soils. Release of Fe due to weathering of minerals is a very slow process governed mainly by pH and O2 concentration and by the dissolution–precipitation phenomena (Mengel, 1994; Lindsay, 1988). After mobilization due to weathering, the fate of Fe-II is regulated by the redox reaction and on pH conditions of the soil. Fe-II released from primary minerals is readily oxidized under aerobic conditions and pH ranging from 5 to 8. Reduction of Fe-III occurs readily either by inorganic chemical reactions or by microbial processes under anaerobic conditions. Bacteria associated with Fe cycle acquire nourishment from organic molecules, often exudates of plant roots and from the decomposed SOM (Lovley, 1991). Therefore, bacterial activity is mostly dependent on the OC availability. Thus, the interaction between bacteria and Fe minerals is largely controlled by plant actions, particularly root exudation plays an important role as bacteria use the complex organic molecules of root exudates as source of their sustenance. In fact, in studies of many plants and microorganisms it was observed that, the rate of weathering of these minerals could be accelerated by the activities of living organisms (Welch et al., 1999; Baker and Banfield, 2003; Hansel et al., 2004; Liu et al., 2006). Decomposition of OM is a vital process associated with the soil Fe cycle. In cold–temperate climate, crystalline Fe and poorly crystalline hydroxide contents largely affects the storage of carbon in Spodosols (Wiseman and Püttmann, 2005). In case of hot and humid regions, the strong microbial activity helps in complete and rapid mineralization of available Fe and OM preventing formation of poorly ordered Fe minerals. A wide range of organic compounds such as cellulose, lignocellulose, sugars, organic acids, amino acids, pectin, lignin, tannin etc. are used by bacteria and fungi for their nutrition and produce more complex molecules which are mainly the precursors of humic substances (HS). Due to the complex nature and less decomposability of HS they are not capable of stimulating microbial growth and activity as root exudates. On the contrary, by improving the Fe solubility in soil, HS could directly affect in the soil Fe chemistry (Schnitzer, 1978; Stevenson, 1994; Colombo et al., 2012). Dhaliwal et al. (2012) reported significant changes in the different fractions of Fe and Mn when FYM, WCS and GM were applied in conjunction with different combinations of chemical fertilizers. In a broader aspect, the results indicated an increase in the concentrations of WS þ EX, AFeOX, CFeOX and OM-bound fractions of Fe and Mn under the application of GM, FYM and WCS before transplantation of rice whereas, decrease in their fractions held on SPAD on inorganic sites and MnOX decreased with the incorporation of these organic manures was also noted. Walia et al. (2010) observed an appreciable increase in Fe contents of soil over its initial value of 9.6 mg kg
1 in all the treatments including control plot which is notably higher than other micronutrients (Table 3). Enhanced DTPA-Fe concentration in soil due to FYM application was also observed by Mann et al. (1978) in a maize-wheat cropping system.

Table 3 Effects of chemical fertilizers and organic manures on Zn, Fe and Mn status (mg kg
1) of soil after 23 years of rice–wheat cropping (Source: Walia et al., 2010). Treatment

Fertilizer use (% of recommended NPK)

Zn (mg kg
1)

Fe (mg kg
1)

Mn (mg kg
1)

0.76 1.53 1.69

13.65 17.51 17.79

8.41 10.53 10.82

Rice

Wheat

T1 T2 T3

Control 50 50

T4 T5

75 100 (recommended dose) 50 þ 50% N(FYM) 75 þ 25% N(FYM) 50 þ 50% N(WCS) 75 þ 25% N(WCS) 50 þ 50% N (GM) 75 þ 25% N (GM) 100 þ 50% N(FYM) N180P30K30 100

Control 50 100 (recommended dose) 75 100 (recommended dose) 100

1.82 1.94

18.00 18.05

11.18 11.32

2.29

22.98

13.74

75

2.24

20.84

13.43

100

2.19

20.67

12.71

75

2.12

19.99

12.24

100

2.53

23.01

13.32

75

2.65

22.92

13.03

100

2.59

23.19

14.41

N150P60K30 100 þ Cowpea

1.90 1.95 0.940 1.96

18.76 19.87 1.515 9.60

11.91 11.42 1.06 9.15

T6 T7 T8 T9 T10 T11 T12 T13 T14 CD (0.05) Initial status

submergence. Dhaliwal (2008) revealed that under rice cultivation, the green manure application enlarged the concentrations of DTPA-extractable-Mn, WS þ EX and SPAD Mn on inorganic sites, whereas, there was a decrease in Mn fractions held on organic sites and oxide surfaces due to the incorporation of green manure and soil applied Mn. The effect of flooding was mainly non-significant on different chemical pools of Mn. Similar trend of different forms of Mn after the harvest of wheat due to residual effect of green manure was observed. Hence, rise in the contents of DTPA-extractable, WS þ EX and inorganic Mn indicated the augmented availability of Mn with green manure application. No significant effect on different factions of Mn was noted due to application of manganese sulphate in soil. Walia et al. (2010) observed a rise in DTPA-Mn which might be attributed to the reduction of Mn4þ to Mn2þ along with its increased solubility under submerged conditions and the chelating action of organic manures. Further, comparing different organic sources, application of FYM could be considered as an effective practice as it helps to add more DTPA- Mn in soil than the recommended NPK dose.

Available manganese (Mn)

Available boron (B)

Manganese (Mn) availability in soils is determined by various factors like organic matter, pH, CaCO3, and redox conditions. The conditions of soil that favors the increase of reducing environments and its availability in soil (Zhu et al., 2002). Submergence brings various changes in soils i.e. physical, biological and chemical, which are usually advantageous for the growth and nutrition of rice. Flooded conditions causes higher valent forms of Mn like MnO2, Mn2O3 and Mn3O4 to get reduced to Mn2þ form which is accessible to plants (Ponnamperuma, 1972). Green manuring is another way to upsurge the Mn availability in soils. Organic matter, during its decomposition liberates a number of organic acids, lowers the soil pH and increases the intensity of reduction in soils. In this way the green manuring enhances the availability of Mn in soils. Reduction of oxides of Mn is more when green manuring was combined with

Organic matter is an important soil constituent affecting the availability of B. This is considered as the leading source of reserve B because it complexes with B to remove it from the soil solution when the levels are high after B fertilization (Borax, 1998). It then replenishes the soil solution with B to sustain ample levels when B is removed by crops or by leaching. Soil organic matter adsorbs more B than mineral soil constituents on a weight basis (Gu and Lowe, 1990). Boron adsorption on an organic soil (Mengel and Kirkby, 2001) and composted organic matter increased with increasing pH (Yermiyahu et al., 1995). Adsorption of B on soil humic acid increased with increasing pH up to a maximum near pH 9, and decreased with increasing pH above 9 (Gu and Lowe, 1990). Communar and Keren (2008) studied different impacts of dissolved organic matter (DOM) and treated sewage effluents on B adsorption in 5

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Fertilization and soil organic matter addition affecting micronutrients availability

soil. They revealed that concentrations of micro and macro elements with organic matter amplified in treated sewage waste-matter via their complexation at pH of 7.70. The influences of humus on adsorption of B were more than that of DOM. Moreover, DOM formed various complexes with free soil solution-B. Consequently, soil B concentration significantly reduced as the total DOM concentration increased. Many researchers conducted experiments on organic matter (OM) in relation to available B fraction and they concluded that organic matter straightforwardly bestow an imperative responsibility in controlling the soil solution B concentration and there was a significant role of OM in desorption or adsorption of B in soils with respect to solution concentration (Marzadori et al., 1991). Yermiyaho et al. (1988) conducted an experiment on B sorption on composted organic matter and results showed that at pH 8.0, the extent of sorbed B enhanced by almost 57%. They also determined the sorption isotherms of B on organic matter at three pH levels of soil 7.0, 7.90, and 8.90. The sorption improved with high pH and increasing B concentration in solution. The compost restrained 158 g kg
1 and 56 g kg
1 of humic acid and fulvic acid, respectively, adding together 21.40% of the OM. They further concluded that at pH 8, the amount of sorbed B increased by about 57%. The sorption of B enhanced with increasing concentration in solution and pH. They also studied the influence of soil OM content on B uptake by bell pepper along with soil solution B concentration. He revealed that OM significantly affected B uptake by bell pepper plants. Moreover he reported that uptake of B by plant is controlled by soil solution B levels than total soil B content. On the commencement of the trial, B concentration in the soil solution diminished with improving rates of compost and ultimately increasing levels of compost guided to smaller amount of B in the leaf tissues. This decline in B concentration was more at elevated levels of B application. Similarly, the consequences of compost levels on plant B concentration were too enormous at highest B application levels. Adjusted soil solution B concentration was positively correlated with the leaf B concentration. Mandal et al. (1993) studied the influence of organic matter and lime application on the recovery of added B by different extractants in two B deficient acid alluvial soils and concluded that the effect is well pronounced in the finer textured soils than the coarse textured soils. The available B status of the major soil groups of Madhya Pradesh showed a positive correlation with organic matter content (Saha et al., 1998). Ghosh and Sarkar (1994) showed that available B content of the soils of Sinhbhum and Debatoli soil series had significantly and positively correlated with organic matter content (0.6647) and negatively correlated with clay.

Organic matter addition affecting micronutrients availability Zinc, a vital micronutrient, is released in duration of mineral weathering. SOM exhibit an important role in inducing partitioning of Zn and thus on biogeochemical cycling of Zn. The SOM is divided into C, which is more readily available for microbial decomposition, and the more stable C is transiently conserved by decomposition. The importance of the stable SOM fraction in the biogeochemical cycle of Zn is still not properly known. The pool of stable C is governed by its combination with mineral constituents or material that is naturally resistant to disintegration (Opfergelt et al., 2017). Potential precipitation of ZnS in buried residues and association of Zn with sinking POC could be measured as a sink for light Zn (Little et al., 2014, 2016). In partitioning of Zn in soils SOM plays a complex role. While SOM is responsible for decrease in solubility of Zn due to its sorption on to surface functional groups (Boguta and Sokolowska, 2016), the dissolved organic compounds forming complexes with Zn enhances its mobility (Weng et al., 2002; Houben and Sonnet, 2012). Turnover of SOM is an effective process that affects solubility of Zn by releasing it during litter decomposition which may undergo leaching into the soil or become sorbed by the OM of the soil surface (Scheid et al., 2009). Progressive decomposition and retention of metallic elements such as Zn into organo-mineral associations is greatly influenced by transformation of OM. The formation of organic molecules of variable rates of mineralization results from progressive decomposition and reactivity of soil OC with mineral surfaces in soil aggregates. Variations in the rate of mineralization of such organic molecules depend on their accessibility for enzymatic activity (Lehmann and Kleber, 2015). Advantages of inclusion of organic matter addition over sole application of mineral fertilization Greater availability of Zn, Cu, Fe, and Mn is common expectation in soils where application of FYM or other organic manures have been practices for several years. A significant rise in DTPA-extractable Zn, Cu, Fe, and Mn in the surface layer loamy sand soil of Fatehpur in case of FYM application under maize-wheat sequence was reported by Mann et al. (1978). When FYM was applied @ 10 tonne ha
1 yr
1, level of DTPA-Fe increased from 5.5 to 5.8 mg kg
1, Mn from 5.0 to 5.7 mg kg
1, Zn from 0.21 to 0.32 mg kg
1 and Cu from 0.22 to 0.26 mg kg
1 after the maize harvest. Shivay et al. (2010) observed that Zn concentration in T. aestivum and T. durum cultivar was more in organically grown (with farmyard manure) than in conventionally grown wheat. However, differences in the two cultivars were observed in terms of Fe content in wheat grain. Significantly higher Fe concentration in grain was found in organically grown Triticum aestivum cultivar ‘HD 2733’ as compared to those grown conventionally while a reverse case was observed in case of Triticum durum cultivar ‘PDW 215’. Dhaliwal et al. (2013) reported the significant increase in Zn in soil during 1st, 2nd and 3rd sampling when treated with manure as compared to control (Table 4). The range of total Zn concentration varied from 19.3 to 32.8 mg kg
1. Among all the manure treatments, total Zn was reported highest under CGM (39.7 mg kg
1) followed by DGM (34.8 mg kg
1) and BGS (32.8 mg kg
1), where a rise in concentration of total Fe from 1st up to 3rd sampling was also noted. Higher content of total Fe was observed in case of PM (10,017 mg kg
1) followed by CGM (9652 mg kg
1) and DGM (9303 mg kg
1). Appearance of Fe deficiency occurs during 4th week after transplantation of paddy which disappeared later and might be attributed to transformation of total Fe to DTPA-Fe fraction (52.1 mg kg
1). Increase in Zn availability is found scarcely affected by sole addition of straw in case of wheat cultivation particularly under calcareous soil having high pH (Chen et al., 2017a). Chen et al. (2017a) observed that application of water-soluble Zn alone raise the concentration of soil DTPA-Zn through the LOM (organic matter with low bonding forces) bound Zn fraction increment

Available molybdenum (Mo) Agricultural researches had highlighted the important role of Mo in the development and health of both nitrogen fixing and non-fixing crops, which contributed to understanding of Mo in soil systems (Kaiser et al., 2005; Gupta, 1997). Available molybdenum (Mo) concentrations could largely altered by the use of organic matter. Molybdenum (Mo) concentrations upsurge intensely during the decomposition of litter, even when regulated to the loss of matter through mineralization which suggests that atmospheric inputs of Mo strongly affects the levels of Mo in soil. The main factors supposed to regulate soil Mo availability were pH and sorption by oxides of Fe and Al. Lower pH causes strong adsorption of Mo on oxides of Fe, Al and Mn (Karimian and Cox, 1979; Goldberg and Forster, 1991; Goldberg et al., 2002; Xu et al., 2006). Higher soil pH increases the Mo solubility and decreases adsorption to Fe and Mn oxides, which eventually increases Mo loss as soluble molybdate (MoO2
4 ). The organic matter is a rich source of micronutrient and trace elements like Mo and on other hand organic matter causes changes in pH which can affect the concentration of Mo already present in soil. The actual relation between organic matter and molybdenum could only be understood by taking different factors into account viz. extent of pH alteration, type and composition of organic matter etc. 6

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resulted from the supply of various levels of Zn due to poultry manure amended with Zn and on Zea Mays L. However, poultry manure amended with Zn was more effective than the ZnSO4.7H2O at all levels of Zn application. Application of different type of wastes on lettuce-barley cropping sequence in calcareous soils amplified the contents and uptake of Mn. This increase, however, was significant when higher rates of MSW compost was added (Francisco et al., 2006). Bukvi
c et al. (2003) reported that foliar application of Zn resulted in increase of Zn concentration in the ear-leaf of the investigated lines in comparison to the soil application. Arbuscular mycorrhizal infected roots mine native soil-Zn and inoculation improved both Zn levels as well as uptake along with successive growth of rice (Purakayastha and Chhonkar, 2001). A positive effect of arbuscular mycorrhizal inoculation in improvement of Zn nutrition and growth was noted under wheat and maize cultivation in soils which are deficient in Zn and this may be due to enhanced access of roots to Zn present as native and added as fertilizer also (Kothari et al., 1990). It is widely reported that AM-fungi increase plant Cu and Zn uptake (Clark et al., 1999; Liu et al., 2000b; Lambert et al., 1980). More Cu and Zn were measured in mycorrhizal soybean plants than in P-supplemented non-mycorrhizal soybean plants of the same size, in soil with low levels of Cu and Zn. Veeranagappa et al. (2010) observed that the treatment receiving NPK þ Zn-E (Zn enriched) compost at 15 and 10 kg ha
1recorded significantly higher uptake of micronutrients followed by Zn enriched treatments and was superior over other treatments. The increase in uptake may be attributed to more favorable conditions either through an increase in solubility in soil solution or by possible stimulation of root absorption. Total Fe, Zn, Cu and Mn uptake was significantly more in M20-W20-RI (FYM 20 t ha
1each to maize and wheat and incorporation of residues) over recommended chemical fertilizer treatments (Walia and Kler, 2010). Total Zn uptake was enhanced by 100.3 g ha
1 in case of FYM application coupled with 100 per cent NPK fertilizers as compared sole 100 per cent NPK treatment. The control plot showed the lowest uptake of Zn followed by fertilizer treatments without Zn under wheat cultivation (Mishra et al., 2009). Lower uptake of Zn was observed in case of continuous cropping with or without fertilizers in absence of Zn over treatments with Zn. Incorporation of FYM raised Zn uptake both in grains and in straw in case of wheat crop which is due to greater amount of organically bound Zn in soil. HCl-extractable Zn was considered as major chemical fraction of soil Zn in terms of crop uptake. Kansal et al. (1981) studied the effect of different levels of nitrogen (0, 30, 60, 90 kg N ha
1) and FYM (0, 10, 20 t ha
1) on yield and nutrient uptake of spinach and reported that Fe, Zn, Cu and Mn uptake increased with the application of both inorganic nitrogen fertilizer and farmyard manure with maximum at highest level of both. As compared to control an increase in Zn, Cu and Fe content in wheat grain was observed under nitrogen application (0, 130, and 300 kg N ha
1). However, further rise in the three micronutrient densities in grain was not reported under enhancement of N application rate from 130 to 300 kg N ha
1 (Shi et al., 2010).

Table 4 Total Zn and Fe concentrations during first, second and third sampling (Source: Dhaliwal et al., 2013). Treatments

1st

2nd

3rd

Zn (mg kg
1) Control Rice straw (RS) Wheat straw (WS) Maize straw (MS) Farm yard manure (FYM) Vermicompost (VC) Rice manure (RM) Poultry manure (PM) Dhaincha green manure (BGM) Cowpeas green manure (CGM) FeSO4 (Soil) Biogas slurry (BGS) CD (0.5)

1st

2nd

3rd

Fe (mg kg
1)

19.3 26.3 27.9 25.3 22.5 27.8 26.7 24.9 34.8

27.2 65.5 66.9 57.1 59.8 66.2 46.7 46.8 81.7

30.7 72.0 73.4 70.6 83.4 89.7 73.2 80.4 95.2

3439 5279 6510 5105 6709 5924 7653 5453 5589

4165 6848 7405 7977 7677 8186 8059 8984 8271

5198 7880 8438 9010 8709 9219 9092 10,017 9303

39.7

86.4

97.0

5882

8620

9652

24.6 32.8 16.8

49.5 96.0 34.6

63.0 109.5 45.8

5840 5523 1278.6

8028 7554 1732.4

9061 8587 1956.5

irrespective of soil pH, carbonate and clay contents while addition of straw coupled with soluble Zn increases the availability of the element due to enhanced rate of Zn diffusion (Table 5). In another experiment Chen et al. (2017b) noted high mobility and availability of Zn under Maize straw amendment as humic substances forms soluble complexes with Zn that reduces its sorption to minerals. Application of exogenous organic matter addition along with soluble Zn solution was eventually found most effective over sole application of these mentioned treatments (Table 6). Ojha et al. (2018) found an augmentation in available Fe, Mn and Zn in an incubation with organic amendments. In which a continuous rise in available Zn was observed which might be attributed to the formation of chelating complex with organic material slow mineralization rate of applied OM for which Zn become slowly unavailable even after extraction of the element from insoluble compounds (Sanchez-Monedero et al., 2004; Kizilkaya, 2004). However, availability of Fe and Mn initially raises and decreases after reaching the peak while availability of Cu was decreased with time (Ojha et al., 2018). Walia et al. (2010) reported a reduction in DTPA-Zn (1.90 mg kg
1) an with the increase in dose of N beyond the 100% recommended N dose (Table 3) as compared to the 100% NPK fertilizer dose (1.94 mg kg
1). The data further showed a decreasing tendency in case of treatments with only fertilizer, including the control in terms of DTPA-Zn which may be due to the association greater Zn uptake with the additional N supply. Ram and Singh (2005) reported that with long term application of N, Zn and farmyard manure; uptake of micronutrients by rice-wheat-cowpea cropping system varied from 143 to 597, 2274 to 6169, 384 to 1234 and 119–521 g ha
1 for Zn, Fe, Mn and Cu, respectively. The maximum crop removal of Zn was noted under 100% NPK þ Zn treatment while that of Fe, Mn and Cu was under 100% NPK þ FYM treatment. Use of organic and organo-mineral fertilizer at 0, 2.5 and 10 t ha
1 rates along with NPK (300 kg ha
1) enlarged the Cu, Zn, Fe and Mn levels in maize (Ayeni et al., 2012). Singh et al. (1979) stated a significant escalation in Zn uptake and dry matter yield

Table 5 DTPA-Zn concentration (mean  SE, n ¼ 3) of soils with the addition of straw and Zn at the various incubation periods (Source: Chen et al., 2017a). Treatments

0 Zn LSD0.05 LSD0.05 a b

0 Straw 0 Straw of A or Ba of A  Bb

DTPA-Zn concentration (mg kg-1) 60

120

150

165

180

195

210

0.75  0.03 0.81  0.08 4.65  0.05 4.87  0.05 0.12 0.18

0.77  0.07 0.69  0.01 5.06  0.15 5.15  0.11 0.24 0.33

0.72  0.08 0.62  0.04 4.57  0.21 4.43  0.33 0.27 0.39

0.65  0.05 0.73  0.02 4.23  0.19 4.09  0.10 0.25 0.36

0.76  0.04 0.98  0.05 4.66  0.05 4.77  0.05 0.31 0.45

0.75  0.04 0.98  0.05 4.66  0.05 4.77  0.05 0.11 0.15

0.86  0.01 0.99  0.02 4.60  0.15 4.54  0.08 0.20 0.28

The value of LSD (least signi®cant difference) for main effects of Zn (A) or straw (B) at 5%. The values of LSD for interaction between Zn (A) and straw (B) at 5%. 7

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Table 6 Soil diethylenetriaminepentaacetic acid (DTPA)-Zn concentration of the initial soil (IS) and soil after 75% removal of organic matter (RS) (Source: Chen et al., 2017b). Treatments

Soil DTPA-Zn concentration (mg kg
1) 3

0 0.71  0.04 Zn 6.56  0.39 Zn þ St 6.18 0.37 IS 0 1.12  0.04 Zn 9.27  1.36 Zn þ St 8.75 0.14 P value (LSD0.05) in the two-way ANOVAs Soil (a) 0.002 (1.07) Amendment (b) <0.001 (1.31) ab NS RS

7

15

30

45

60

75

0.50  0.06 4.58  0.45 4.32 0.560 0.88  0.04 9.08  1.29 7.72 1.04

0.74  0.03 4.16  0.43 6.03 0.88 1.22  0.01 7.88  1.19 9.62 0.94

0.61  0.04 3.82  0.79 5.02 0.44 1.12  0.03 8.74  0.25 7.51 0.18

0.55  0.03 3.54  0.57 3.80 0.45 0.88  0.06 6.31  0.59 8.24 1.13

0.44  0.05 3.69  0.39 5.00 0.30 0.91  0.04 6.80  0.22 8.19 0.42

0.74  0.12 4.19  0.75 4.88 0.68 1.16  0.02 4.54  0.08 7.97 1.18

<0.001 (1.31) <0.001 (1.60) 0.041

<0.001 (1.30) <0.001 (1.59) 0.039

<0.001 (0.69) <0.001 (0.85) <0.001

<0.001 (1.06) <0.001 (1.30) 0.016

<0.001 (0.49) <0.001 (0.61) 0.005

<0.005 (1.28) <0.001 (1.56) 0.027

Values are mean  SE (n ¼ 3).

(2006) observed that uptake of Zn and Cu by individual crops (rice and wheat) and system was significantly greater with organic manures. Uptake of Zn and Fe in soybean was significantly raised by the combined use of P levels and biofertilizers (phosphate-solubilizing bacteria þ vesicular arbuscular mycorrhiza). The highest Zn and Fe uptake (125.77 mg kg
1 and 562.03 mg kg
1, respectively) was recorded with the combined use of 40 kg P2O5 ha
1 þ dual inoculation. Among the biofertilizers, dual inoculation with phosphate-solubilizing bacteria (PSB) þ vesicular arbuscular mycorrhiza (VAM) gave the best performance (Dadhich and Somani, 2007).

Effect of integrated nutrient management on soil micronutrient availability The pH of the soil affects the root system and its capacity to absorb other nutrients. If the pH of the soil is more than 8, the plant may be unable to absorb enough Fe, Zn, and Mn, even though the availability of phosphorus is high. The micronutrients Zn, Cu, Fe and Mn which are necessary for plant growth and development, are usually taken up by plants in soluble forms (i.e. Zn2þ, Cu2þ, Fe2þ and Mn2þ). However, uptake of micronutrients in the form of soluble organic complexes was noted in certain conditions of soils (in calcareous/alkaline soils). In many cases arbuscular mycorrhiza fungi (AMF) were found responsible for the uptake of these complexes (Alifragis, 2008). Arbuscular mycorrhiza undoubtedly can increase accumulation of many nutrients, including Zn (Rehman et al., 2012; Srinivasagam et al., 2013), but their practical importance varies in dependence on fertilization practices, soil and crop properties and management, etc. The effect of crop rotation on the available and total micronutrient contents in soils was also noted by Wei et al. (2006). Smolders et al. (2013) reported a better contribution of Zn-exudate complexes towards nutrition of Solanum lycopersicon L. plants under calcareous/alkaline soil conditions. Along with the soluble and organically bound forms of Zn, Cu, Fe and Mn the contribution of exchangeable forms to make the nutrients available plants was also found appreciable. According to Norouzi et al. (2014), significant roles of organically bound Zn and exchangeable Zn that are considered as labile pools could be found in supplying Zn for plants. Apart from plant-available forms of Fe, Mn, Zn and Cu, there are some insoluble (or partially insoluble), and not available (or not directly available for plant uptake) forms which include micronutrients that are bound to carbonates (moderate to strongly acidic condition potentially makes them available) and to Fe and Mn oxides (only flooding and anaerobic soil conditions makes them potentially available) (Alifragis, 2008), as well as the residual metal forms (entirely insoluble and non-available for plants) (Gasparatos et al., 2015). In many cases micronutrients are attached on the Fe and Mn oxides present in soils as concretions, nodules, cement between particles, or simply as a coating on particles (all these oxides are excellent scavengers for trace metals) (Gasparatos, 2013). Depending on the physico-chemical properties of soil the metals associated with oxides of Fe, Mn and Al could be considered as potentially active or strongly bound micronutrient forms (Ahumada et al., 2004; Jamali et al., 2006). Finally, the primary and secondary minerals, which may hold trace metals within their crystal structure generally comes under the residual trace elements. Pooniya et al. (2012) evaluated the effects of summer green manuring crops and Zn fertilization on soil biological properties, nutrient dynamics and productivity of basmati rice. Among the different sources, levels and methods of Zn application, application of 2.0% Zn-enriched urea (ZEU) as hydrated Zn sulphate was found to be best with respect to total uptake of Zn by rice. Singhal et al. (2012) revealed that nitrogen fortified crop residue compost increases the total uptake of micronutrient in maize over the treatment where N was applied through urea alone. Mishra et al.

Influence of soil organic matter build-up on micronutrient dynamics and transformations Dhaliwal et al. (2013) reported different significant effects of different manures on Zn and Fe transformation under rice cultivation in light textured soils. Manures of ten different types viz. rice straw (RS), wheat straw (WS), maize straw (MW), cowpeas green manure (CGM), Dhaincha green manure (DGM), farm yard manure (FYM), poultry manure (PM), rice straw manure (RSM), vermi-compost (VC) and biogas slurry (BGS), were applied for ameliorating deficiency of Zn and Fe. Incorporation of these manures before transplantation of rice helped in the transformation of Zn and Fe in the soil. Although the concentration was above the critical level of Zn, a notable reduction in DTPA-Zn during third sampling was observed under VC treatment. No Zn deficiency was exhibited by rice crop as in all treatments the results showed concentrations above the critical limit (0.6 mg kg
1) in terms of DTPA-Zn. Poultry manure (PM) treated plot showed higher DTPA-Fe content (52.1 mg kg
1) which was further followed by DGM (41.0 mg kg
1) and VC (38.0 mg kg
1). Occurrence of Fe deficiency was observed during fourth week of transplantation of paddy at maximum tillering stage. Comparing total Zn, highest content was recorded in case of CGM (39.7 mg kg
1) followed by DGM (34.8 mg kg
1) and BGS (32.8 mg kg
1) while total Fe content was found maximum under PM treatment (10, 017 mg kg
1) followed by CGM (9652 mg kg
1) and DGM (9303 mg kg
1) (Table 4). The decomposition of results in more supply of DTPA-Fe in soil and was transformed to unavailable forms under oxidized environment. This F buildup was about double as compared to its 1st sampling with gradual decomposition of manures. Fe chlorosis in the rice plants could not be cured by application of FeSO4. They eventually found that manures application prior to transplantation of rice is an effective practice for mitigating Fe-chlorosis in rice. Dhaliwal and Singh (2013) reported significantly higher levels of macro-, micro-nutrients under forest land use system. Microbial parameters were also reported to be higher in comparison to cultivated, undisturbed and pasture land use systems (LS). Moreover, forest and cultivated LS were more fertile and productive amongst all the studied LS. The greater contents of nutrients and microbial parameters in cultivated LS were the results of fertilizers and FYM addition while the greater contents of microbial parameters in forest LS were due to the regular addition of 8

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Dhaliwal et al. (2012) in different fractions of Fe and Mn when farmyard FYM, GM and WCS were applied under rice-wheat system along with inorganic fertilizers. The concentration of WS þ EX, AFeOX, CFeOX and OM-bound fractions of Fe and Mn were increased by the application of GM, FYM and WCS while there was a decrement in fractions specifically adsorbed on inorganic sites and Mn surfaces. Boron (B) deficit is usually detected in light-textured acidic soils that contains either high levels of CaCO3 or oxides and hydroxides of Fe and Al or had lower organic matter content (Keren and Bingham, 1985; Mandal et al., 2004). Sarkar et al. (2014) reported that removal of soil organic matter resulted in an increase in B adsorption. The level of increase in B values were 34 and 204% in two tested lands. Similar results were reported by Diana et al. (2010) and Marzadori et al. (1991). But majority of researcher reported contrast results (Sharma et al., 2006; Yermiyaho et al., 1995), i.e. a strong adsorptive capacity of organic matter for B. The intensification in B adsorption by soil after removal of organic matter might be attributed to adsorption sites activation such as Fe- and Al-oxides and hydroxides that were earlier covered by the organic matter or by freshly formed sites on the mineral surfaces (Marzadori et al., 1991). Different forms of Fe and Al with strong B affinities showed intensifying tendency of B adsorption in soils (Mandal et al., 1993). The organic matter plays a noticeable role in B distribution. Deficiency of Boron were observed in soils with high organic matter contents (Liu et al., 1989; Valk et al., 1989) and the deficiency were assumed to be attributed to the high affinity of organic matter for B (Yermiyahu et al., 1988, 1995; Liu et al., 1989). The positive correlations reported amongst soil organic matter content and B adsorption (Elrashidi and O’connor, 1982; Hue et al., 1988) supported above supposition. Boron adsorption was perceived to be very small in acidic to neutral pH thus not of great significance, but was of greater importance in high pH soil containing organic matter (Gu and Lowe, 1990) Garate and Meyer (1983) established that the chief factors affecting B holding by organic matter were pH, Ca, content of fulvic acid and the humic:fulvic acid ratio. In contrast, Marzadori et al. (1991) reported that the amount of B adsorbed by soil is significantly larger afterwards the organic matter was removed and that hysteresis is observed. Addition of organic matter to soil was also reported to upsurge B content and its availability to plants (Blagojevic and Zarkovic, 1990; Pakrashi and Haldar, 1992). Boron adsorption by organic matter and soils was explained by a competitive adsorption model (Mezuman and Keren, 1981; Yermiyahu et al., 1988). This model permits the fact that two aqueous species of B i.e. B(OH)3 and B(OH)-4 with different affinities for adsorbent, were involved and that their quantities in the equilibrium solution vary with pH. With this adsorption model, the B adsorption capacity of the soil-organic matter mixture was seen to increase with organic matter content (Yermiyahu et al., 1995). Understanding the comparative significance of organic matter in adjusting soil Mo behavior is important for measuring the bioavailability of soil Mo for N-fixing organisms, and eventually the potential N-supply capacity of an ecosystem. If soil organic matter had a foremost control over soil Mo then the long-term Mo availability will be related to pH, dynamics organic matter decay and the specific binding mechanisms of Mo with organic matter. Freund et al. (2016) studied the effect of organic matter on the adsorption of Mo to pyrite via equilibration experiments with MoO2
4 , MoS2
4 and 2-mercaptopropionic acid (2MPA). 2MPA exhibited more affinity than MoO2
4 for surface sites of pyrite, which indicates the comparatively weaker interactions between MoO2
4 -pyrite. It was also found that presence of 2MPA on the surface of pyrite inhibited MoO2
4 access to catalytic mineral sites on the surface of pyrite for the transformation to MoS2
4 . Tribovillard et al. (2004) stated that levels of Mo are positively related with the quantity of sulfurized organic matter but not with abundance of pyrite. These results revealed the importance of sulfurized OM in geologic-scale of Mo detention and holding, and also highlighted

organic matter in the form of leaf litter. Pasture and undisturbed LS showed small magnitude of SF parameters and eventually lesser productive. Soil samples taken from cultivated and forest LS profiles in the watershed showed greater levels of SF parameters in comparison to the other LS. The greater levels of these parameters were related with greater level of clay and organic matter. The amount of SF parameters generally declined with depth in profile. Dhaliwal et al. (2010) stated that the inclusion of organic nutrition in maize, potato and onion improved the micronutrient status of soil. With the integrated nutrient management approach the micronutrient content in the soil improved substantially. Nayyar and Takkar (1989) reported the similar results in their research under rice-wheat cropping system practiced on coarse textured soils. Rupa et al. (2001) reported that the amount of Cu present in water-soluble plus exchangeable fraction was very small. The water-soluble plus exchangeable Cu, inorganically-bound Cu, organically-bound Cu, and oxide-bound Cu fractions increased and residual Cu was not significantly affected by Cu application. No significant variation was observed between Cu application with and without FYM on the distribution of different fractions of soil Cu except organically-bound Cu. In surface soil declination of DTPA–Fe and Mn (but not Zn and Cu) was may be due to intensive cropping for more than 30 years in all the treatments (Control, NP, NPK, NPK þ FYM, NPK þ Zn) in maize-wheat cropping sequence (Behera et al., 2009). Dhaliwal et al. (2012) reported higher productivity in rice-wheat systems when 50% NPK was applied through chemical fertilizers integrated with 50% N through FYM or GM to obtained grain yield of 11.0 t ha
1 in rice-wheat system over time. The inclusion of FYM, WCS and GM in the soil not only supplies the macro-nutrients but also exhibited valuable effect on soil health by enhancing the physico-chemical parameters and improving the availability of the micronutrients in the soil. Highest content of DTPA-extractable Zn in soil (2.70 mg kg
1) was observed under FYM treatment followed by GM (2.50 mg kg
1) and WCS (1.48 mg kg
1) whereas, significant upsurge in Cu content in the organic manured plots (0.82–0.98 mg kg
1 soil) was also observed. The greatest Fe content was observed when 50% of recommended N was applied using FYM. Maximum uptake of Fe, Mn, Zn and Cu was recorded both in case of rice and wheat under treatments where 50 per cent additional dose of N was applied in the form of FYM. The maximum counts of bacteria (54.8  106 cfu g
1), fungi (26.8  103 cfu g
1) and actinomycetes (4.26  104 cfu g
1) were observed in the treatment with 50% NPK fertilization of inorganic sources in combination of 50% N through FYM. Saha et al. (1999) reported that in tea garden soil, metals were mobilized into organic complexation (in case of Zn and Mn) and amorphous Fe oxides bound (in case of Zn, Cu, and Fe); whereas in field cropped soil these were mobilized into ‘gel’ hydrous oxides and amorphous oxides fractions (except Cu) due to lime application. In both the soils a decrease in readily available WS þ EX forms of metals was observed due to lime application. No significant changes were exhibited by tea garden soils as a result of exogenous supply of OC source in terms of micronutrient fractions. Cheng et al. (2014) examined the effect of the nano-scale carbon black (MCB) on Cu and Zn fractionations in soil. DTPA extractable Cu and Zn in soil significantly decreased with the increasing amount of MCB addition. The metal contents of exchangeable and bound to carbonates (EC-Cu or EC-Zn) in the treatments with MCB were generally lower than those without MCB. Behera and Singh (2010) concluded that the overall mean total Fe content varied from 2.36 to 2.61 percent under different treatments (Control, NP, NPK, NPK þ FYM, NPK þ Zn) with maximum under NPK þ FYM treatment. The Fe associated with easily reducible Mn and organic matter bound contributed directly to DTPA-extractable Fe both in pre-maize and post-wheat soil in maize-wheat sequence. Regmi et al. (2010) reported that among all fractions water soluble and exchangeable fraction of Zn was higher in biological (combination of organic and conventional farming practices) than conventional soils. Plant available and total Zn pools was enhanced significantly in which management systems, particularly biological practices played a pivotal role. Significant changes were observed by 9

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soil is vital. Build-up of OM in soil influences its physico-chemical properties which in turn governs the soil micronutrient dynamics. Soil organic matter acts as a factor in the distribution of micronutrients between soil colloids and solution by controlling sorption of micronutrients through the active functional groups, high specific surface area, cation exchange capacity and capability to form soluble complexes. Few cases revealed a decrease in availability of soil micronutrients due to their adsorption on soil solids particularly where proportion of POM is more in soil. Again, fractions of micronutrients associated with oxides and organic matter play an important role in plant nutrients as compared to mineral associated fractions. Use of organics in the form of compost, FYM, green manures and even incorporation of plant residues in soil were noted beneficial as they contain some amount of micronutrient as well as for their ability to form soluble complexes. Thus, inclusion of organic amendments in integrated nutrient management (INM) should be highly encouraged to mitigate the world-wide phenomenon of micronutrient deficiencies in food grains. While many findings reported the exogenous supply of OM as advantageous strategy over addition of conventional application of water soluble forms of micronutrients, some researchers claimed that coupled application of these two is the most effective over their sole application. Hence, to acquire more knowledge and improve the management strategies there is an urgent need to conduct more researches on some key issues like quantification of soil micronutrient status by performing large scale field trials and simulation models for better understanding the complex relations between soil OM and micronutrients. Thus, organic matter build-up should be highly encouraged not only to improve the plant nutrition value by enhancing the micronutrient availability but also for a sustainable future ahead.

the role of reactive Fe. Substantial OM sulfurization is only possible if the quantity of reactive iron is limited. Molybdenum can also bind to soil organic matter via ligand exchange and specific adsorption, which inhibits Mo leaching (Wichard et al., 2009). Other studies also reported the potential importance of associations amongst organic matter-Mo (Bibak and Borggard, 1994; Wurzburger et al., 2012). Although associations of natural organic matter
Mo were rarely computed. Instead of the identification of retention mechanisms of Mo in soil, there are some studies that assess their relative significance for overall Mo retention in soils. Specifically, it is not known how these mechanisms vary amongst soils, or the level up to which they impacted net Mo retention or loss relative to bedrock, which was required to deduce limitations on whole-ecosystem Mo balances and bioavailability. To investigate bioavailability, selective chemical extractions of micronutrients are usually equated to their concentrations in plant tissues (Kabata-Pendias and Pendias, 2001). Similarly, labile Mo abundance is not essentially correlated to Mo nutrient limitation of heterotrophic soil N2 fixation (Jean et al., 2012). These results suggest that the utility of extractable-Mo estimation might stay quite limited due to many other soil factors that affect Mo bioavailability (Kubota and Cary, 1982). Effect of soil organic matter build-up on micronutrient sorption on soil SOM plays a pivotal role in controlling the distribution of metal ions between soil solids and solution (Shi et al., 2012). High specific surface area (approximately 800–900 m2 g
1), CEC (150–300 cmol kg
1) and presence of functional groups like carboxylic acids and phenolics, are responsible for their complex formation with metal ions which govern the retention and mobility of the metal ions in soil (Sparks, 2003; Kleber et al., 2015). Many findings support the phenomenon of alteration of binding energies and mean Gibbs free energies for adsorption of metals with the change in SOM content in soil (Wang et al., 2010, 2013; Fan et al., 2015). He et al. (2017) and Refaey et al. (2017) also found effect of OM sorption of heavy metals like Cu and Zn. Dissolved organic matter (DOM) augments the solubility of metals (Weng et al., 2002) and Sauve et al. (1998) found that DOM is capable to form organo-Pb complexes which enhances its solubility. This could be related to partial reduction of metals adsorbed on soil solid phase (Refaey et al., 2014). Again, DOM was also found capable to reduce the Cu and Zn adsorption to soil particles (Mesquita and Carranca, 2005). Fan et al. (2016a,b) observed a significant effect of SOM on reduction of non-specific adsorption of Zn on black soil particles. Organic acids having low molecular weights like oxalic, succinic, malic, citric and acetic acids were observed significantly effective in reduction of Cu adsorption on hydroxyapatite (HAP) of clay sized fractions (Weng et al., 2002; Wang et al., 2009). Alteration of SOM present as a thin layer on mineral surfaces was found responsible for changes in heavy metal sorption (Han et al., 2007). Reduction of Zn sorption capacity and binding energy of soil solids in case of SOM removal using sodium hypochlorite (Shuman et al., 1975). Two to four fold increase in Zn retention due to removal of OM was observed by Hinz and Selim (1999) which corroborates with the findings of Trehan and Sekhon (1977) also. Conversely, redistribution and decrease in availability of Pb, Cd and Cu with increase in SOM was also reported (Diagboya et al., 2015; Shi et al., 2017). Particulate organic matter (POM) is a labile fraction of SOM which is associated with soil particles sized > 53 μm diameter (Zeller and Dambrine, 2011). POM are mainly porous and due to having a high capacity adsorption than soil, more sorption of Cu and Zn was found in soils having higher amount of POM (Shi et al., 2018).

Funding Information No funding was associated with this study. Conflict of interest The authors declare that they have no conflict of interest. References Adriano, A.D., 2001. Trace Elements in Terrestrial Environments: Biogeochemistry, Bioavailability, and Risks of Metals, vol. 99. Springer, New York, pp. 183–225. Advances in Agronomy. Agrawal, R., Kumar, B., Priyanka, K., Narayan, C., Shukla, K., Sarkar, J., Anshumali, 2016. Micronutrient fractionation in coal mine-affected agricultural soils, India. Bull. Environ. Contam. Toxicol. 96 (4), 449–457. Ahumada, I., Escudero, P., Castillo, G., Carrasco, A., Ascar, L., Fuentes, E., 2004. Use of sequential extraction to assess the influence of sewage sludge amendment on metal mobility in Chilean soils. J. Environ. Monit. 6, 327–334. Alifragis, D., 2008. Soil: Genesis, Properties and Classification. In: Greek, vol. I. Aivazi Publications, Thessaloniki, Greece. Alloway, B.J., 2008. Zinc in Soils and Crop Nutrition, second ed. International Zinc Association, Brussels, Belgium. Atafar, Z., Mesdaghinia, A.R., Nouri, J., Homaee, M., Yunesian, M., Ahmadimoghaddam, M., Mahvi, A.H., 2010. Effect of fertilizer application on soil heavy metal concentration. Environ. Monit. Assess. 160 (1–4), 83–89. Aulakh, M.S., Grant, C.A., 2008. Integrated Nutrient Management for Sustainable Crop Production. Haworth Press, Taylor and Francis Group, New York. Ayeni, L.S., Adeleye, E.O., Adejumo, J.O., 2012. Comparative effect of organic, organomineral and mineral fertilizers on soil properties, nutrient uptake, growth and yield of maize (Zea Mays). International Research Journal of Agricultural Science and Soil Science 2, 493–497. Bailey, R.L., West Jr., K.P., Black, R.E., 2015. The epidemiology of global micronutrient deficiencies. Ann. Nutr. Metabol. 66 (2), 22–33. Baird, C., Cann, M., 2005. Environmental Chemistry. W.H. Freeman and Company, New York. Baker, B.J., Banfield, J.F., 2003. Microbial communities in acid mine drainage. FEMS (Fed. Eur. Microbiol. Soc.) Microbiol. Ecol. 44, 139–152. Baligar, V.C., Fageria, N.K., He, Z.L., 2001. Nutrient use efficiency in plants. Commun. Soil Sci. Plant Anal. 32, 921–950. Barber, S.A., 1995. Soil Nutrient Bioavailability: A Mechanistic Approach. John Wiley & Sons. Barker, A.V., Pilbeam, D.J., 2015. Handbook of Plant Nutrition. CRC press.

Summary and conclusions After reviewing the literature, it could be concluded that the role of OM in availability and transformation of Zn, Cu, Fe, Mn, B and Mo in the 10

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