Abstract
Many regulating functions of soils (Sect. 1.2) are based on biogeochemical processes, and are therefore affected by soil chemical properties. Examples are the storage and supply of nutrients, the sorption and degradation of contaminants, as well as the buffering of acid deposition. The chemical processes taking place at biogeochemical interfaces are of outstanding importance. About 40–60 % of the soil volume consists of pores, which can be filled with water (soil solution) or gases (soil air), depending on the actual soil moisture. The soil solids mainly consist of minerals and smaller fractions of organic matter. This porous system of mineral and organic soil particles, gases, aqueous solutions and organisms leads to the formation of very large and chemically reactive interfaces. These interfaces can adsorb, complex, precipitate or chemically transform various ions and molecules. This chapter provides an introduction to the chemical properties and processes regulating the behavior of nutrients and contaminants in soils.
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- 1.
Colloidal particles are defined as solid particles with a diameter between 1 and 1000 nm in at least one dimension. Colloidal particles do not settle rapidly unless they coagulate, have a very large specific surface area, and can be transported with seepage water through medium and coarse pores if they are dispersed in the pore water.
- 2.
Other abbreviations commonly used in the literature include TOC (=total organic carbon), POM (=particulate organic matter), POC (=particulate organic carbon), DON (=dissolved organic nitrogen), and DOP (=dissolved organic phosphorus).
- 3.
The molality m i is the concentration of an ion i in mol kg−1. In dilute aqueous solutions, the molality can be approximated with the molarity M i, the concentration of the ion i in mol L−1 (or M).
- 4.
Activities are represented here with curly brackets {…} and concentrations with square brackets […].
- 5.
One of the most important spectroscopic methods in this context is extended X-ray absorption fine structure spectroscopy (EXAFS), which requires the use of synchrotron X-ray radiation (extremely brilliant, monochromatic radiation).
- 6.
The specific surface area is usually determined using the N2-BET method. This is accomplished by measuring an adsorption isotherm for N2-gas at -196 °C, and using the data to calculate the specific surface area. However, the N2-BET method does not detect internal surface area of swelling clays and humic substances. These can be estimated from the adsorption of polar molecules (e.g. EGME, ethylene glycol methyl ether).
- 7.
The cations Ca2+, Mg2+, K+ and Na+ are called base cations in soil science, although they are not bases in a chemical sense. The term refers to the fact that the hydroxides of these cations (e.g. NaOH, KOH) are strong bases. The cations H+ (or H3O+) and Al3+ are called acid cations. Al3+ ions in an aqueous solution act as acid, because they can release protons through hydrolysis reactions.
- 8.
Despite their low charge density, vermiculites and smectites always have a higher cation exchange capacity (CEC) than illites, because in addition to the external surfaces, the interlayers are also accessible to cation exchange. With illites, the majority of the structural negative charge is compensated by non-exchangeable K+ ions in the interlayers, so that the CEC is lower. Kaolinite and halloysite have no (or very little) permanent negative charge.
- 9.
The pH value of an aqueous solution is defined as the negative logarithm of the H+ activity, pH = −log{H+}. The soil pH is the pH value that is established in an aqueous solution in equilibrium with the soil. In practice, 10 g of dry soil are mixed with 25 ml of 0.01 M CaCl2 solution (or water), the suspension is agitated for at least 30 min, and then the pH of the solution is measured using an electrode.
- 10.
Because the dissolved carbonic acid (H2CO3) cannot be analytically differentiated from dissolved CO2 (CO2·H2O), H2CO3* is defined as the sum of H2CO3 and CO2·H2O.
- 11.
Because using a standard hydrogen electrode is inconvenient, a calomel (Hg/Hg2Cl2) electrode or a silver/silver chloride electrode is generally preferred as a reference electrode. The measured potential can then be converted to the Eh value by adding +0.248 V (calomel) or +0.204 V (silver/silver chloride).
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Blume, HP. et al. (2016). Chemical Properties and Processes. In: Scheffer/SchachtschabelSoil Science. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-30942-7_5
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