Asymmetrically substituted 5,5 `-bistriazoles - nitrogen-rich materials with various energetic functionalities

In this contribution the synthesis and full structural and spectroscopic characterization of three asymmetrically substituted bis-1,2,4-triazoles, along with different energetic moieties like amino, nitro, nitrimino and azido moieties, is presented. Additionally, selected nitrogen-rich ionic derivatives have been prepared and characterized. This comparative study on the influence of these energetic moieties on structural and energetic properties constitutes a complete characterization including IR, Raman and multinuclear NMR spectroscopy. Single crystal X-ray crystallographic measurements were performed and provide insight into structural characteristics as well as inter-and intramolecular interactions. The standard enthalpies of formation were calculated for all compounds at the CBS-4M level of theory, revealing highly positive heats of formation for all compounds. The detonation parameters were calculated using the EXPLO5 program and compared to the common secondary explosive RDX as well as recently published symmetric bistriazoles. As expected, the measured sensitivities to mechanical stimuli and decomposition temperatures strongly depend on the energetic moiety of the triazole ring. All compounds were characterized in terms of sensitivities (impact, friction, electrostatic) and thermal stabilities, the ionic derivatives were found to be thermally stable, insensitive compounds

Organic Nutrients Induced Coupled C- and P-Cycling Enzyme Activities During Microbial Growth in Forest Soils

Besides environmental and soil physical drivers, the functional properties of microbial populations, i. e., growth rate, enzyme production, and maintenance requirements are dependent on the microbes' environment. The soil nutrition status and the quantity and quality of the substrate input, both infer different growth strategies of microorganisms. It is uncertain, how enzyme systems respond during the different phases of microbial growth and retardation in soil. The objective of this study was to uncover the changes of microbial functioning and their related enzyme systems in nutrient-poor and nutrient-rich beech forest soil during the phases of microbial growth. We determined microbial growth via kinetic approach by substrate-induced respiratory response of microorganisms, enabling the estimation of total, and growing biomass of the microbial community. To induce microbial growth we used glucose, while yeast extract simulated additional input of nutrients and factors indicating microbial residues (i.e., necromass compounds). Microbial growth on glucose showed a 12–18 h delay in associated enzyme activity increase or the absence of distinct activity responses (Vmax). β-glucosidase and chitinase (NAG) demonstrated clear differences of Vmax in time and between P-rich and P-poor soils. However, during microbial growth on glucose + yeast extract, the exponential increase in enzymatic activity was clearly stimulated accompanied by a delay of 8–12 h, smoothing the differences in nutrient-acquisition dynamics between the two soils. Furthermore, cross-correlation of β-glucosidase and acid phosphatase between the two sites demonstrated harmonized time constraints, which reflected the establishment of comparable and balanced enzymatic systems within the decomposition network

Impacts of Logging-Associated Compaction on Forest Soils: A Meta-Analysis

Soil compaction associated with mechanized wood harvesting can long-lastingly disturb forest soils, ecosystem function, and productivity. Sustainable forest management requires precise and deep knowledge of logging operation impacts on forest soils, which can be attained by meta-analysis studies covering representative forest datasets. We performed a meta-analysis on the impact of logging-associated compaction on forest soils microbial biomass carbon (MBC), bulk density, total porosity, and saturated hydraulic conductivity (Ksat) affected by two management factors (machine weight and passage frequency), two soil factors (texture and depth), and the time passed since the compaction event. Compaction significantly decreased soil MBC by −29.5% only in subsoils (>30 cm). Overall, compaction increased soil bulk density by 8.9% and reduced total porosity and Ksat by −10.1 and −40.2%, respectively. The most striking finding of this meta-analysis is that the greatest disturbance to soil bulk density, total porosity, and Ksat occurs after very frequent (>20) machine passages. This contradicts the existing claims that most damage to forest soils happens after a few machine passages. Furthermore, the analyzed physical variables did not recover to the normal level within a period of 3–6 years. Thus, altering these physical properties can disturb forest ecosystem function and productivity, because they play important roles in water and air supply as well as in biogeochemical cycling in forest ecosystems. To minimize the impact, we recommend the selection of suitable logging machines and decreasing the frequency of machine passages as well as logging out of rainy seasons especially in clayey soils. It is also very important to minimize total skid trail coverage for sustainable forest management

Decreased rhizodeposition, but increased microbial carbon stabilization with soil depth down to 3.6 m

Despite the importance of subsoil carbon (C) deposition by deep-rooted crops in mitigating climate change and maintaining soil health, the quantification of root C input and its microbial utilization and stabilization below 1 m depth remains unexplored. We studied C input by three perennial deep-rooted plants (lucerne, kernza, and rosinweed) grown in a unique 4-m deep RootTower facility. 13C multiple pulse labeling was applied to trace C flows in roots, rhizodeposition, and soil as well as 13C incorporation into microbial groups by phospholipid fatty acids and the long-term stabilization of microbial residues by amino sugars. The ratio of rhizodeposited 13C in the PLFA and amino sugar pools was used to compare the relative microbial stability of rhizodeposited C across depths and plant species. Belowground C allocation between roots, rhizodeposits, and living and dead microorganisms indicated depth dependent plant investment. Rhizodeposition as a fraction of the total belowground C input declined from the topsoil (0–25 cm) to the deepest layer (360 cm), i.e., from 35%, 45%, and 36%–8.0%, 2.5%, and 2.7% for lucerne, kernza, and rosinweed, respectively, where lucerne had greater C input than the other species between 340 and 360 cm. The relative microbial stabilization of rhizodeposits in the subsoil across all species showed a dominance of recently assimilated C in microbial necromass, thus indicating a higher microbial stabilization of rhizodeposited C with depth. In conclusion, we traced photosynthates down to 3.6 m soil depth and showed that even relatively small C amounts allocated to deep soil layers will become microbially stabilized. Thus, deep-rooted crops, in particular lucerne are important for stabilization and storage of C over long time scales in deep soil

Nitrogen Gain and Loss Along an Ecosystem Sequence: From Semi-desert to Rainforest

Plants and microorganisms, besides the climate, drive nitrogen (N) cycling in ecosystems. Our objective was to investigate N losses and N acquisition strategies along a unique ecosystem-sequence (ecosequence) ranging from arid shrubland through Mediterranean woodland to temperate rainforest. These ecosystems differ in mean annual precipitation, mean annual temperate, and vegetation cover, but developed on similar granitoid soil parent material, were addressed using a combination of molecular biology and soil biogeochemical tools. Soil N and carbon (C) contents, δ15N signatures, activities of N acquiring extracellular enzymes as well as the abundance of soil bacteria and fungi, and diazotrophs in bulk topsoil and rhizosphere were determined. Relative fungal abundance in the rhizosphere was higher under woodland and forest than under shrubland. This indicates toward plants' higher C investment into fungi in the Mediterranean and temperate rainforest sites than in the arid site. Fungi are likely to decompose lignified forest litter for efficient recycling of litter-derived N and further nutrients. Rhizosphere—a hotspot for the N fixation—was enriched in diazotrophs (factor 8 to 16 in comparison to bulk topsoil) emphasizing the general importance of root/microbe association in N cycle. These results show that the temperate rainforest is an N acquiring ecosystem, whereas N in the arid shrubland is strongly recycled. Simultaneously, the strongest 15N enrichment with decreasing N content with depth was detected in the Mediterranean woodland, indicating that N mineralization and loss is highest (and likely the fastest) in the woodland across the continental transect. Higher relative aminopeptidase activities in the woodland than in the forest enabled a fast N mineralization. Relative aminopeptidase activities were highest in the arid shrubland. The highest absolute chitinase activities were observed in the forest. This likely demonstrates that (a) plants and microorganisms in the arid shrubland invest largely into mobilization and reutilization of organically bound N by exoenzymes, and (b) that the ecosystem N nutrition shifts from a peptide-based N in the arid shrubland to a peptide- and chitin-based N nutrition in the temperate rainforest, where the high N demand is complemented by intensive N fixation in the rhizosphere

Keeping thinning-derived deadwood logs on forest floor improves soil organic carbon, microbial biomass, and enzyme activity in a temperate spruce forest

Deadwood is a key component of forest ecosystems, but there is limited information on how it influences forest soils. Moreover, studies on the effect of thinning-derived deadwood logs on forest soil properties are lacking. This study aimed to investigate the impact of thinning-derived deadwood logs on the soil chemical and microbial properties of a managed spruce forest on a loamy sand Podzol in Bavaria, Germany, after about 15 years. Deadwood increased the soil organic carbon contents by 59% and 56% at 0–4 cm and 8–12 cm depths, respectively. Under deadwood, the soil dissolved organic carbon and carbon to nitrogen ratio increased by 66% and 15% at 0–4 cm depth and by 55% and 28% at 8–12 cm depth, respectively. Deadwood also induced 71% and 92% higher microbial biomass carbon, 106% and 125% higher microbial biomass nitrogen, and 136% and 44% higher β-glucosidase activity in the soil at 0–4 cm and 8–12 cm depths, respectively. Many of the measured variables significantly correlated with soil organic carbon suggesting that deadwood modified the soil biochemical processes by altering soil carbon storage. Our results indicate the potential of thinned spruce deadwood logs to sequester carbon and improve the fertility of Podzol soils. This could be associated with the slow decay rate of spruce deadwood logs and low biological activity of Podzols that promote the accumulation of soil carbon. We propose that leaving thinning-derived deadwood on the forest floor can support soil and forest sustainability as well as carbon sequestration

Microbial Metabolism in Soil at Subzero Temperatures: Adaptation Mechanisms Revealed by Position-Specific 13C Labeling

Although biogeochemical models designed to simulate carbon (C) and nitrogen (N) dynamics in high-latitude ecosystems incorporate extracellular parameters, molecular and biochemical adaptations of microorganisms to freezing remain unclear. This knowledge gap hampers estimations of the C balance and ecosystem feedback in high-latitude regions. To analyze microbial metabolism at subzero temperatures, soils were incubated with isotopomers of position-specifically 13C-labeled glucose at three temperatures: +5 (control), -5, and -20°C. 13C was quantified in CO2, bulk soil, microbial biomass, and dissolved organic carbon (DOC) after 1, 3, and 10 days and also after 30 days for samples at -20°C. Compared to +5°C, CO2 decreased 3- and 10-fold at -5 and -20°C, respectively. High 13C recovery in CO2 from the C-1 position indicates dominance of the pentose phosphate pathway at +5°C. In contrast, increased oxidation of the C-4 position at subzero temperatures implies a switch to glycolysis. A threefold higher 13C recovery in microbial biomass at -5 than +5°C points to synthesis of intracellular compounds such as glycerol and ethanol in response to freezing. Less than 0.4% of 13C was recovered in DOC after 1 day, demonstrating complete glucose uptake by microorganisms even at -20°C. Consequently, we attribute the fivefold higher extracellular 13C in soil than in microbial biomass to secreted antifreeze compounds. This suggests that with decreasing temperature, intracellular antifreeze protection is complemented by extracellular mechanisms to avoid cellular damage by crystallizing water. The knowledge of sustained metabolism at subzero temperatures will not only be useful for modeling global C dynamics in ecosystems with periodically or permanently frozen soils, but will also be important in understanding and controlling the adaptive mechanisms of food spoilage organisms