Composition and stability of organic matter fractions in soils under different land use regimes

Soil organic matter (SOM) vitally impacts all soil functions and plays a key role in the global carbon (C) cycle. More than 70% of the terrestric C stocks that participate in the active C cycle are stored in the soil. Therefore, quantitative knowledge of the rates of C incorporation into SOM fractions of different residence time is crucial to understand and predict the sequestration and stabilization of soil organic carbon (SOC). Consequently, there is a need of fractionation procedures that are capable of isolating functionally SOM fractions, i.e. fractions that are defined by their stability. The literature generally refers to three main mechanisms of SOM stabilization: protection of SOM from decomposition by (i) its structural composition, i.e. recalcitrance, (ii) spatial inaccessibility and/or (iii) interaction with soil minerals and metal ions. One of the difficulties in developing fractionation procedures for the isolation of functional SOM fractions is the marked heterogeneity of the soil environment with its various stabilization mechanisms – often several mechanisms operating simultaneously – in soils and soil horizons of different texture and mineralogy. The overall objective of the present thesis was to evaluate present fractionation techniques and to get a better understanding of the factors of SOM sequestration and stabilization. The first part of this study is attended to the structural composition of SOM. Using 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, (i) the effect of land use on SOM composition was investigated and (ii) examined whether SOM composition contributes to the different stability of SOM in density and aggregate fractions. The second part of the present work deals with the mineral-associated SOM fraction. The aim was (iii) to evaluate the suitability of chemical fractionation procedures used in the literature for the isolation of stable SOM pools (stepwise hydrolysis, treatments using oxidizing agents like Na2S2O8, H2O2, and NaOCl as well as demineralization of the residue obtained by the NaOCl treatment using HF (NaOCl+HF)) by pool sizes, 13C and 14C data. Further, (iv) the isolated SOM fractions were compared to the inert organic matter (IOM) pool obtained for the investigated soils using the Rothamsted Carbon Model and isotope data in order to see whether the tested chemical fractionation methods produce SOM fractions capable to represent this pool. Besides chemical fractionation, (v) the suitability of thermal oxidation at different temperatures for obtaining stable SOC pools was evaluated. Finally, (vi) the short-term aggregate dynamics and the factors that impact macroaggregate formation and C stabilization were investigated by means of an incubation study using treatments with and without application of 15N labeled maize straw of different degradability (leaves and coarse roots). All treatments were conducted with and without the addition of fungicide. Two study sites with different soil properties and land managements were chosen for these investigations. The first one, located at Rotthalmünster, is a Stagnic Luvisol (silty loam) under different land use regimes. The Ah horizons of a spruce forest and continuous grassland and the Ap and E horizons of two plots with arable crops (continuous maize and wheat cropping) were examined. The soil of the second study site, located at Halle, is a Haplic Phaeozem (loamy sand) where the Ap horizons of two plots with arable crops (continuous maize and rye cropping) were investigated. Both study sites had a C3-/C4-vegetational change on the maize plot for the purpose of tracing the incorporation of the younger, maize-derived C into different SOM fractions and the calculation of apparent C turnover times of these. The Halle site is located near a train station and industrial areas, which caused a contamination with high amounts of fossil C. The investigation of aggregate and density fractions by 13C CPMAS NMR spectroscopy revealed that density fractionation isolated SOM fractions of different composition. The consumption of a considerable part (10–20%) of the easily available O-alkyl-C and the selective preservation of the more recalcitrant alkyl-C when passing from litter to the different particulate organic matter (POM) fractions suggest that density fractionation was able to isolate SOM fractions with different degrees of decomposition. The spectra of the aggregate fractions resembled those of the mineral-associated SOM fraction obtained by density fractionation and no considerable differences were observed between aggregate size classes. Comparison of plant litter, density and aggregate size fractions from soil under different land use showed that the type of land use markedly influenced the composition of SOM. While SOM of the acid forest soil was characterized by a large content (> 50%) of POM, which contained high amounts of spruce-litter derived alkyl-C, the organic matter in the biologically more active grassland and arable soils was dominated by mineral-associated SOM (> 95%). This SOM fraction comprised greater proportions of aryl- and carbonyl-C and is considered to contain a higher amount of microbially-derived organic substances. Land use can alter both, structure and stability of SOM fractions. All applied chemical treatments induced considerable SOC losses (> 70–95% of mineral-associated SOM) in the investigated soils. The proportion of residual C after chemical fractionation was largest in the arable Ap and E horizons and increased with decreasing C content in the initial SOC after stepwise hydrolysis as well as after the oxidative treatments with H2O2 and Na2S2O8. This can be expected for a functional stable pool of SOM, because it is assumed that the more easily available part of SOC is consumed first if C inputs decrease. All chemical treatments led to a preferential loss of the younger, maize-derived SOC, but this was most pronounced after the treatments with Na2S2O8 and H2O2. After all chemical fractionations, the mean 14C ages of SOC were higher than in the mineral-associated SOM fraction for both study sites and increased in the order: NaOCl < NaOCl+HF ≤ stepwise hydrolysis << H2O2 ≈ Na2S2O8. The results suggest that all treatments were capable of isolating a more stable SOM fraction, but the treatments with H2O2 and Na2S2O8 were the most efficient ones. However, none of the chemical fractionation methods was able to fit the IOM pool calculated using the Rothamsted Carbon Model and isotope data. In the evaluation of thermal oxidation for obtaining stable C fractions, SOC losses increased with temperature from 24–48% (200°C) to 100% (500°C). In the Halle maize Ap horizon, losses of the young, maize-derived C were considerably higher than losses of the older C3-derived C, leading to an increase in the apparent C turnover time from 220 years in mineral-associated SOC to 1158 years after thermal oxidation at 300°C. Most likely, the preferential loss of maize-derived C in the Halle soil was caused by the presence of the high amounts of fossil C mentioned above, which make up a relatively large thermally stable C3-C pool in this soil. This agrees with lower overall SOC losses for the Halle Ap horizon compared to the Rotthalmünster Ap horizon. In the Rotthalmünster soil only slightly more maize-derived than C3-derived SOC was removed by thermal oxidation. Apparent C turnover times increased slightly from 58 years in mineral-associated SOC to 77 years after thermal oxidation at 300°C in the Rotthalmünster Ap and from 151 to 247 years in the Rotthalmünster E horizon. This led to the conclusion that thermal oxidation of SOM was not capable of isolating SOM fractions of considerably higher stability. The incubation experiment showed that macroaggregates develop rapidly after the addition of easily available plant residues. Within the first four weeks of incubation, the maximum aggregation was reached in all treatments without addition of fungicide. The formation of water-stable macroaggregates was related to the size of the microbial biomass pool and its activity. Furthermore, fungi were found to be crucial for the development of soil macroaggregates as the formation of water-stable macroaggregates was significantly delayed in the fungicide treated soils. The C concentration in the obtained aggregate fractions decreased with decreasing aggregate size class, which is in line with the aggregate hierarchy postulated by several authors for soils with SOM as the major binding agent. Macroaggregation involved incorporation of large amounts maize-derived organic matter, but macroaggregates did not play the most important role in the stabilization of maize-derived SOM, because of their relatively low amount (less than 10% of the soil mass). Furthermore, the maize-derived organic matter was quickly incorporated into all aggregate size classes. The microaggregate fraction stored the largest quantities of maize-derived C and N – up to 70% of the residual maize-C and -N were stored in this fraction.

Adsorption kinetic investigations of phthalocyanine derivatives self assembled monolayers (SAMs) on gold: Temperature influence on the SAM formation process and quality

The ordered nano-structured surfaces, like self-assembled monolayers (SAMs) are of a great scientific interest, due to the low cost, simplicity, and versatility of this method. SAMs found numerous of applications in molecular electronics, biochemistry and optical devices. Phthalocyanine (Pc) complexes are of particular interest for the SAM preparation. These molecules exhibit fascinating physical properties and are chemically and thermally stable. Moreover their complex structure is advantageous for the fabrication of switchable surfaces. In this work the adsorption process of Pcs derivatives, namely, subphthalocyanines (SubPcB) and terbium (2TbPc) sandwich complexes on gold has been investigated. The influence of the molecular concentration, chain length of peripheral groups, and temperature on the film formation process has been examined using a number of techniques. The SAMs formation process has been followed in situ and in real time by means of second harmonic generation (SHG) and surface plasmon resonance (SPR) spectroscopy. To investigate the quality of the SAMs prepared at different temperatures atomic force microscopy (AFM) and X-Ray photoelectron spectroscopy (XPS)measurements were performed. Valuable information about SubPcB and 2TbPc adsorbtion process has been obtained in the frame of this work. The kinetic data, obtained with SHG and SPR, shows the best conformance with the first order Langmuir kinetic model. Comparing SHG and SPR results, it has been found, that the film formation occurs faster than the formation of chemical bonds. Such, the maximum amount of molecules on the surface is reached after 6 min for SubPcB and 30 min for 2TbPc. However, at this time the amount of formed chemicals bonds is only 10% and 40% for SubPcB and 2TbPc, respectively. The most intriguing result, among others, was obtained at T = 2 °C, where the formation of the less dense SAMs have been detected with SHG.However, analyzing XPS and AFM data, it has been revealed, that there is the same amount of molecules on the surface at both temperature T = 2 °C, and T = 21 °C, but the amount of formed chemicals bond is different. At T = 2 °C molecules form aggregates, therefore many of available anchor groups stay unattached.