Soluble organic matter represent less than 1% of total soil organic matter (SOM) - but it contributes to many terrestrial ecosystem processes, due to its high mobility and reactivity in soil. Although it has been suggested that soluble organic matter (OM) may serve as an early indicator of soil quality changes as a result of shifts in land-use and management practices, only a few studies have addressed the dynamics of soluble OM in relation to land-use and specifically soil depth. This study focuses on two aspects of soluble OM. In the first part, I hypothesized that extractable OM obtained by aqueous solutions is a continuum of substances that depending on the extraction method can be separated into two operationally different fractions. The size and properties of these fractions may consistently differ among different land uses and at different soil depths. The objective of this part of the study was then to assess dynamics (size and properties, biodegradability and seasonality) of water extractable organic matter (WEOM) and salt extractable organic matter (SEOM) in a sequence of human dominated land-uses at topsoil and subsoil. At the second part of the study, I tested the regulatory gate hypothesis –abiotic solubilization of OM- as a primary controlling factor in soluble OM production. The objective of this study was to evaluate the impact of the microbial activity on the net production of dissolved organic matter (DOM) from the native SOM in the presence of added DOM and plant residue. For the first part of the experiment, the soil samples were collected from four land-uses under bog pine (Halocarpus bidwillii) woodland, tussock grassland (Festuca novae-zelandiae and Heiracium pilosella), cropland (Medicago sativa) and plantation forest (Pinus nigra). The selected land uses were located in the Mackenzie Basin, Canterbury, New Zealand and occurring on the same soils, topography and experienced similar climates. Soil samples were obtained from topsoil (0-20 cm) and subsoil (60-80 cm) at the end of each season (November, February, May and August) during 2007-2008. The sampled soils were adjusted to the same water status prior to extraction. While WEOM was obtained during a mild extraction procedure and using 0.01M CaCl2, SEOM was extracted with 0.5M K2SO4 at high temperature (75οC for 90 min). Both extracts were filtered through a 0.45 μm filter size. In the first part of the study, I assessed the biodegradation dynamics of WEOM and SEOM (spring samples), using a double-exponential decay model. The WEOM and SEOM were inoculated and incubated at 22°C for 90d under aerobic conditions. Subsamples were removed on days 1, 3, 7, 12, 16, 30, 42, 60, 75, and 90, filtered (0.22 μm), and analyzed for organic C and N content, UV absorption, and 13C natural abundance (δ13C). The results of the biodegradation experiment indicated a similar pattern for both C and N of SEOM and WEOM as that of previously shown for soil DOM. However, C and N mineralization rate were considerably larger in the WEOM than SEOM. The parameters of the double-exponential model suggested that regardless of the land-use and soil depth, both the WEOM and SEOM can be modeled in two biological pools, with a largely similar “fast decomposable” but different “slowly decomposable” pools. However, since the extraction was not sequentially followed, a very small portion of the SEOM was comprised of the WEOM and given the greater observed biodegradability of the WEOM, the overall biodegradable portion of the SEOM would be lower than the observed. Despite a greater biodegradability of the organic N than C of both WEOM and SEOM; mainly due to a longer HL of the slowly biodegradable pool of C; the C/N ratio of the samples did not change very much during the biodegradation. This led us to conclude that the biodegradation of soluble OM may occur as a function of N availability. Parallel to C and N loss, a considerable increase in SUVA254 of SEOM, and particularly WEOM occurred during the incubation period. The greater increase in the proportion of aromatic compounds (assessed by SUVA) in the WEOM than SEOM, implied consumption of simple compounds (vs. very humified) during decomposition and further supported the observed faster biodegradation rate of the WEOM. The data indicated a relatively strong correlation (R2=0.66 and 0.74 for the WEOM and SEOM, respectively) between the amount of biodegraded C and the increase in SUVA254. This suggested that SUVA254 can be used as a simple, low-cost but reliable approach for describing the biodegradability of soluble OM, as previously suggested by others. At the end of the bioassay, the 13C natural abundance of the WEOM was significantly depleted, and showed a clear relationship with the proportion of the biodegraded C. This confirmed the previously suggested preferential biodegradation of simple organic constituents (13C enriched), resulting in the accumulation of more depleted 13C compounds (often recalcitrant compounds). Moreover, the results of the δ13C technique revealed that the relatively greater 13C enrichment of the WEOM obtained from subsoil, seems to be due to the presence of root exudates (often highly 13C enriched). In contrast, a proportionally greater 13C depletion observed in the SEOM particularly at subsoil samples, suggests that there is a close relationship between the SEOM and the typically 13C depleted humified SOM. The results of the biodegradation model (half-life of both C and N), in addition to dynamics of SUVA254 and δ13C of the WEOM and SEOM were very comparable between top and subsoil samples. This implied that the potential biodegradability of soluble OM under laboratory conditions does not necessary reflect the reported lower in situ biodegradability at soil depth, in agreement with recent evidence suggested by others. Instead, this may be largely due to the lack of optimum conditions (oxygen, nutrients, and moisture) for the decomposer community at soil depth. Although there was a tendency for a generally greater biodegradability of the samples from the soils under the crop land (both WEOC and SEOC), along with relatively greater increase in SUVA, there was not a consistent trend of the effect of land use on the biodegradation of either WEOM or SEOM. The lower C/N ratio of the soils under the crop land seemed to be related with the observed proportionally greater biodegradability of these soils. During the second part of the study, I assessed seasonal variations of the size and properties of the previously defined WEOM and SEOM, collected from top-and subsoil from the land-uses. I observed that 10-year after conversion of the degraded tussock grassland to cropland or plantation, the total C stock of topsoil (0-20 cm) when above- and below-ground plant biomass is excluded; has remained unchanged. This was attributed to the limited biomass production of the region, more likely as a result of low productivity of the soil, but also harsh climatic conditions. Not only soil depth, but land-use affected both C concentration and C/N ratio of soil organic matter (SOM), with the greatest C concentration of soils under grassland and plantation in topsoil and subsoil, respectively. Despite the WEOM, the size of SEOM was largely unaffected by land-use and soil depth; instead, the properties of SEOM was more consistent with the effect of soil depth. Given the observed large temporal and spatial variability of the WEOM, the study suggests that the SEOM more consistently reflects the influence of land use and soil depth. No consistent effect of seasonality was observed in terms of size or properties of the SOM and the WEOM and SEOM. Overall comparison of the size and properties of the WEOM and SEOM indicated that OM extraction efficiency may vary largely, depending on extraction conditions. Using more concentrated salt solutions consistently yielded greater amount of OM (N, and especially C) release from soil with properties resembling more those of total soil OM (more humified) compared to the WEOM. The SEOM was also less variable by time and space. The last part of the study was aimed to assess biotic vs. non-biotic solubilization of OM in the presence of added plant residue. Given the need to recognize the source of the solubilized OM during the experiment, I used enriched (13C) plant residue as the source of fresh OM. The above-ground part of ryegrass was added to soil either as plant residue or residue extract (extracted with CaCl2 followed by 0.45μm filtration) -termed DOM. These two forms of added OM (residue/DOM) were conceived to represent two levels of bioavailability for the decomposer community for further assessing possible biotic solubilization of OM. Two soils similar in their OM content and other properties, but different in mineralogy were selected for the experiment. Soils were incubated for 90d under sterilized vs. non-sterile conditions and leached regularly with a dilute aqueous solution (0.05M CaCl2). Plant residue was added to soil (1:100, residue: soil, w/w) prior to the start of the incubation, but DOM was frequently applied to the soils along with each leaching experiment. The greater C and N concentration in the leachates of both sterilized residue-amended and DOM-amended soils compared to that of living soils, indicated a high microbial activity, as determined by CO2 loss, in the living soils. However, the proportion of the solubilized C (determined by 13C) from sterilized soils was largely comparable to that of living soils. This supports the recently suggested “regulatory gate” hypothesis, stating that solubilisation of OM largely occurs independent of the size or community structure of microorganisms. In addition, I observed that even with the presence of adequate amount of added fresh OM (ryegrass residue), about 70% of the solubilized C consistently originated from the humified soil OM, highlighting the role of native soil OM as the source of soluble OM in soil. In addition, in the DOM-amended soils, there was strong evidence, indicating that in the sterilized soils, the added DOM was exchanged with the humified soil OM as observed by an increase in SUVA, and humification index (HI) of the leached OM. Although the results of the study did not show a considerable difference in the solubilisation rate of added OM as a function of biological activity (either in the residue- or DOM-amended soils), there was clear evidence that the presence of microbial activity has resulted in further decomposition of the solubilised OM through biological transformations. Together, the results suggested that the proposed fractionation method can be used to separate two operationally defined pools of soluble OM with consistent differences in their size (C and N), properties (δ13C, SUVA254, and C/N ratio) and biodegradability across the land-uses and soil depth. The second part of the study supported the primary role of abiotic factors on the production of soluble OM from native soil OM. Although the abiotic mechanisms involved in the solubilization remain to be addressed by future studies. Cons and pros of the methods with some suggestions for further works have been mentioned in the last chapter.

This study presents an analysis of the organic matter in meteorites, particularly carbonaceous chondrites (CCs), using advanced experimental techniques such as Two-step laser desorption laser ionization mass spectrometry (L2MS-oTOF) and Atmospheric Pressure Photoionization-Orbitrap (APPI-Orbitrap). The analysis focuses on the molecular complexity of both soluble (SOM) and insoluble (IOM) organic matter as well as the bulk rock and identifying and classifying different molecular families to understand the chemical composition of the meteorites. A new software tool, SpectraC, was developed to aid in analysing and comparing mass spectra from multiple meteorite samples simultaneously. The findings of the study reveal the complex chemical composition of meteorites, with condensed aromatics dominating most samples, and highlight the importance of using multiple techniques for a more complete understanding of the sample’s contents. This research lays the foundation for future work in astrochemistry, including the development of a state-of-the-art analytical tool and further exploration of the organic matter in meteorites. / Cette étude présente une analyse de la matière organique dans les météorites, en particulier les chondrites carbonées (CC), en utilisant des techniques expérimentales avancées telles que la spectrométrie de masse à ionisation laser par désorption en deux étapes (L2MS-oTOF) et l’ionisation photochimique à pression atmosphérique-Orbitrap  (APPI-Orbitrap). L’analyse se concentre sur la complexité moléculaire de la matière organique soluble (SOM) et insoluble (IOM) ainsi que sur la roche globale, et identifie et classe différentes familles moléculaires pour comprendre la composition chimique des météorites. Un nouvel outil logiciel, SpectraC, a été développé pour aider à analyser et comparer les spectres de masse de plusieurs échantillons de météorites simultanément. Les résultats de l’étude révèlent la composition chimique complexe des météorites, avec une domination des aromatiques condensés dans la plupart des échantillons, et mettent en évidence l’importance d’utiliser plusieurs techniques pour une compréhension plus complète du contenu des échantillons. Cette recherche pose les bases des travaux futurs en astrochimie, y compris le développement d’outils analytiques de pointe et l’exploration plus poussée de la matière organique dans les météorites.