The soil solution

In this chapter, we shall introduce soil speciation concepts by consideration of inorganic trace elements in dissolved and adsorbed forms, with reference to both their molecular speciation and their operationally defined soil component speciation. We shall then consider the implications of chemical speciation in soils for agriculture and soil pollution. 

The soil solution is the medium through which dissolved species are transported to a root surface and carried to groundwaters or surface waters. In addition, it acts 

Adapted from Kabata-Pendias and Pendias (1992) and references therein. 

The general behaviour and properties of the soil solution have been reviewed (Adams, 1974 Sposito, 1981 1986), as have the reactions of trace elements in soil solutions (Lindsay, 1972 1979 Stevenson and Ardakani, 1972 Norvell, 1972 Kabata-Pendias and Pendias, 1992). The total dissolved concentrations of trace elements vary quite widely (Table 9.1), depending on several factors such as soil type and use, and proximity to potential pollution sources (Kabata-Pendias and Pendias, 1992). 

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The phenoxyalkanoic herbicides are acidic in nature and thus subject to some degree of ionization. The extent to which the herbicide ionizes is controlled by the acid dissociation constant (fQ of the herbicide in question and the soil solution pH (238). The leaching potential is significantly influenced by these reactions. 

Sorbed pesticides are not available for transport, but if water having lower pesticide concentration moves through the soil layer, pesticide is desorbed from the soil surface until a new equiUbrium is reached. Thus, the kinetics of sorption and desorption relative to the water conductivity rates determine the actual rate of pesticide transport. At high rates of water flow, chances are greater that sorption and desorption reactions may not reach equihbrium (64). NonequiUbrium models may describe sorption and desorption better under these circumstances. The prediction of herbicide concentration in the soil solution is further compHcated by hysteresis in the sorption—desorption isotherms. Both sorption and dispersion contribute to the substantial retention of herbicide found behind the initial front in typical breakthrough curves and to the depth distribution of residues. 

Agronomic Properties and Nutrient Release Mechanism. The conversion of UF reaction products to plant available nitrogen is a multistep process, involving dissolution and decomposition. Materials are slow to enter the soil solution by virtue of their low solubiUty. Longer polymer chain products are less soluble than shorter chains and take longer to become available to the plants. 

Once in the soil solution, urea—formaldehyde reaction products are converted to plant available nitrogen through either microbial decomposition or hydrolysis. Microbial decomposition is the primary mechanism. The carbon in the methylene urea polymers is the site of microbial activity. Environmental factors that affect soil microbial activity also affect the nitrogen availabiUty of UF products. These factors include soil temperature, moisture, pH, and aeration or oxygen availabiUty. 

CDU in pure form is a white powder. It is made slowly available to the soil solution by nature of its limited solubihty in water. Once in the soil solution, nitrogen from CDU is made available to the plant through a combination of hydrolysis and microbial decomposition. As with any CRE which is dependent on microbial action, the mineralization of CDU is temperature dependent. Product particle size has a significant effect on CDU nitrogen release rate. Smaller particles mineralize more rapidly because of the larger surface contact with the soil solution and the microbial environment. The rate of nitrogen release is also affected by pH because CDU degrades more rapidly in acidic soils. 

Following slow dissolution into the soil solution, oxamide undergoes stepwise hydrolysis to Hberate ammonia. Oxamic acid is formed in the first... 

Soluble salts of the soil Water in the soil should most properly be considered as the solvent for salts of the soil the result being the soil solution. In temperate climates and moderate rainfall areas, the soil solution is relatively dilute, with total dissolved salts ranging from 80 to 1 500 p.p.m. Regions of extensive rainfall show lower concentrations of soluble salts as the result of leaching action. Conversely, soils in arid regions are usually quite high in salts as these salts are carried to the surface layers of the soil by water movement due to surface evaporation. 

Generally, the most common cations in the soil solution are potassium, sodium, magnesium and calcium. Alkali soils are high in sodium and potassium, while calcareous soils contain predominantly magnesium and calcium. Salts of all four of these elements tend to accelerate metallic corrosion by the mechanisms mentioned. The alkaline earth elements, calcium and magnesium, however, tend to form insoluble oxides and carbonates in nonacid conditions. These insoluble precipitates may result in a protective layer on the metal surface and reduced corrosive activity. 

The anionic portions of the soil solution play a role of equal importance to the cations. The anions function in the manner outlined for cations in conductivity and concentration-cell action, and have an additional action if they react with the metal cation and form insoluble salts. Thus, if the metal is lead and the predominant anion is sulphate, a layer of insoluble lead sulphate may precipitate on the metal surface and form an effective barrier against further loss of metal. 

The salts content of soils may be markedly altered by man s activities. The effect of cathodic protection will be discussed later in this section. Fertiliser use, particularly the heavy doses used in lawn care, introduces many chemicals into the soil. Industrial wastes, salt brines from petroleum production, thawing salts on walks and roads, weed-killing salts at the base of metal structures, and many other situations could be cited as examples of alteration of the soil solution. In tidal areas or in soils near extensive salt deposits, depletion of fresh ground-water supplies has resulted in a flow of brackish or salty sea water into these soils, causing increased corrosion. 

The most commonly observed effect of current flow is the development of alkaline conditions at the cathode. On bare metal this alkaline zone may exist only at the metal surface and may often reach pH values of 10 to 12. When the soil solution contains appreciable calcium or magnesium these cations usually form a layer of carbonate or hydroxide at the cathodic area. On coated lines the cations usually move to holidays or breaks in the coating. On failing asphalt or asphalt mastic type coatings, masses of precipitated calcium and magnesium often form nodules or tubercles several centimetres in diameter. 

The liquid in which the SAH swelling takes place in real soil (the soil solution) always contains a more-or-less wide set of dissolved salts. Their nature and amount depend on the soil composition, the degree of its salinity, the nature of water entering the soil (rainfall, irrigation, river, or groundwater), the fertilizers used. As a rule, alkali cations, Ca2 +, Mg2+, Fe3+, Al3+, and anions CP, CO, SO4, etc. are the main components of the soil solution there exist various models of soil solution and nutrient mixtures employed in research, including SAH testing. 

In this case the two ions, Ca" and COs , are released into the soil solution and are able to react with water (to form bicarbonate or carbonic acid) or other solution components, or be removed from the soil by leaching. The... 

The liquid phase of the soil system is the soil water, or the soil solution as it is more appro-... 

The release of ions through weathering is also considered an input to soils. Elements that were bound in mineral crystals are released into the soil solution. These ions can be involved in soil processes and the formation of new organic or inorganic materials, or leached from the soil into the groundwater. 

Secondary minerals. As weathering of primary minerals proceeds, ions are released into solution, and new minerals are formed. These new minerals, called secondary minerals, include layer silicate clay minerals, carbonates, phosphates, sulfates and sulfides, different hydroxides and oxyhydroxides of Al, Fe, Mn, Ti, and Si, and non-crystalline minerals such as allophane and imogolite. Secondary minerals, such as the clay minerals, may have a specific surface area in the range of 20-800 m /g and up to 1000 m /g in the case of imogolite (Wada, 1985). Surface area is very important because most chemical reactions in soil are surface reactions occurring at the interface of solids and the soil solution. Layer-silicate clays, oxides, and carbonates are the most widespread secondary minerals. 

Once a layer-silicate clay forms, it does not necessarily remain in the soil forever. As conditions change it too may weather and a new mineral may form that is more in equilibrium with the new conditions. For example, it is common in young soils for the concentrations of cations such as K, Ca, or Mg in the soil solution to be high, but as primary minerals are weathered and disappear, cation concentrations will decrease. With a decrease in solution cations, a layer-silicate such as vermiculite will no longer be stable and can weather. In its place. 

Oxides, non-crystalline minerals, and humified organic matter can also develop charges at their surfaces by reactions with the soil solution. In this case, the surface can have positive (CEC)... 

Biological and volcanic activities also have roles in the natural mobilization of elements. Plants can play multiple roles in this process. Root growth breaks down rocks mechanically to expose new surfaces to chenaical weathering, while chemical interactions between plants and the soil solution affect solution pFF and the concentration of salts, in turn affecting the solution-mineral interactions. Plants also aid in decreasing the rate of mechanical erosion by increasing land stability. These factors are discussed more fully in Chapters 6 and 7. 

Soillroot interactions. High external concentrations make the acquisition of water and nutrients difficult because of the low water potential of the soil solution, and of chemical competition between saline and nutrient ions. 

In soil, the chances that any enzyme will retain its activity are very slim indeed, because inactivation can occur by denaturation, microbial degradation, and sorption (61,62), although it is possible that sorption may protect an enzyme from microbial degradation or chemical hydrolysis and retain its activity. The nature of most enzymes, particularly size and charge characteristics, is such that they would have very low mobility in soils, so that if a secreted enzyme is to have any effect, it must operate close to the point of secretion and its substrate must be able to diffuse to the enzyme. Secretory acid phosphatase was found to be produced in response to P-deficiency stress by epidermal cells of the main tap roots of white lupin and in the cell walls and intercellular spaces of lateral roots (63). Such apoplastic phosphatase is safe from soil but can be effective only when presented with soluble organophosphates, which are often present in the soil. solution (64). However, because the phosphatase activity in the rhizo-sphere originates from a number of sources (65), mostly microbial, and is much higher in the rhizosphere than in bulk soil (66), it seems curious that plants would have a need to secrete phosphatase at all. 

Although in many. soils with tow P availability, significant desorption of sparingly soluble Pi forms requires at least millimolar concentration levels of specific carboxylates (e.g., citrate, oxalate) in the soil solution, much lower concentrations (0.1 mM) were necessary to reduce. soil adsorption of Pi, which was applied simultaneously with carboxylates (100). Thus, competition of carboxylates with Pi for P sorption sites in the soil matrix may be a mechanism that can. 

J. Gerke, Phosphate, aluminium, and iron in the soil solution of three different soils in relation to varying concentrations of citric acid. Z. Pfianzenernaehr. Bodenk. 755 3.39 (1992). 

Both pH and the availability of nutrient ions in soil play important roles in rhizo-sphere dynamics and are often dependent on one another. Nutrient ions move in soil toward plant roots either by mass flow with the soil water or by diffusion. Mass flow is the result of bulk convective movements of the soil solution toward roots, whereas diffusion occurs in response to a concentration gradient for a particular ion, which results from its absorption by the root and depletion from the... 

J. Gerke, Orthophosphate and organic phosphate in the soil solution of four sandy soils—evidence for humic-Fe(Al) phosphate complexes. Commim. Soil Sci. Plant Anal. 25 601 (1992). 

J. Gerke, Aluminium and iron (III) species in the soil solution including organic complexes with citrate and humic substances. Z. Pflanzenemarhr. Bodenk. 160 421 (1997). 

Depending on the ability of specific transport systems to utilize the predominant metal chelates present in the soil solution, competition may occur between plants and microorganisms and between different types of microorganisms for available iron. This has been particularly well studied for Pseudomonas sp., which produce highly unique iron chelators that are utilized in a strain specific manner but which also retain the ability to use more generic siderophores pro-... 

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