TS-1@MCM-48 Core-Shell Catalysts for Efficient Oxidation of p-Diethylbenzene to High Value-Added Derivatives.

To expand the market capacity of p-diethylbenzene (PDEB), core-shell zeolite (TS-1@MCM-48) is designed as a catalyst for PDEB oxidation. TS-1@MCM-48 catalyst is synthesized by in-situ crystallization method and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), N2 adsorption-desorption, in-situ electron paramagnetic resonance (EPR) and 29Si nuclear magnetic resonance (29Si MAS-NMR). Oxidation of PDEB by H2O2 was investigated systematically in liquid phase. The conversion of PDEB over TS-1@MCM-48 was 28.1 % and the total selectivity was 72.6 %, where the selectivity of EAP (p-ethylacetophenone) and EPEA (4-ethyl-α-methylbenzyl alcohol) was 28.6 % and 44.0 %, respectively. Compared with TS-1 and MCM-48 zeolite, the conversion rate of reactants and the selectivity of products have been significantly improved. The catalytic performance of TS-1@MCM-48 is derived from its well-crystallized microporous core and mesoporous shell with regular channels, which make active sites of TS-1 zeolite in the catalyst be fully utilized and mass transfer resistance be largely reduced. Further through theoretical calculation, we propose that the oxidation of PDEB is the result of the combination and mutual transformation of free radical process and carbocation process. Core-shell structure ensures the conversion rate of raw materials and improves the selectivity of products.

Twelve-year conversion of rice paddy to wetland does not alter SOC content but decreases C decomposition and N mineralization in Japan.

Land-use change worldwide has been driven by anthropogenic activities, which profoundly regulates terrestrial C and N cycles. However, it remains unclear how the dynamics and decomposition of soil organic C (SOC) and N respond to long-term conversion of rice paddy to wetland. Here, soil samples from five soil depths (0-25 cm, 5 cm/depth) were collected from a continuous rice paddy and an adjacent wetland (a rice paddy abandoned for 12 years) on Shonai Plain in northeastern Japan. A four-week anaerobic incubation experiment was conducted to investigate soil C decomposition and N mineralization. Our results showed that SOC in the wetland and rice paddy decreased with soil depth, from 31.02 to 19.66 g kg-1 and from 30.26 to 18.86 g kg-1, respectively. There was no significant difference in SOC content between wetland and rice paddy at any depth. Soil total nitrogen (TN) content in the wetland (2.61-1.49 g kg-1) and rice paddy (2.91-1.78 g kg-1) showed decreasing trend with depth; TN was significantly greater in the rice paddy than in the wetland at all depths except 20-25 cm. Paddy soil had significantly lower C/N ratios but significantly larger decomposed C (Dec-C, CO2 and CH4 production) and mineralized N (Min-N, net NH4+-N production) than wetland soil across all depths. Moreover, the Dec-C/Min-N ratio was significantly larger in wetland than in rice paddy across all depths. Rice paddy had higher exponential correlation between Dec-C and SOC, Min-N and TN than wetland. Although SOC did not change, TN decreased by 14.1% after the land-use conversion. The Dec-C and Min-N were decreased by 32.7% and 42.2%, respectively, after the12-year abandonment of rice paddy. Conclusively, long-term conversion of rice paddy to wetland did not distinctly alter SOC content but increased C/N ratio, and decreased C decomposition and N mineralization in 0-25 cm soil depth.

Phosphorus deficiency alters root length, acid phosphatase activity, organic acids, and metabolites in root exudates of soybean cultivars.

Phosphorus (P) deficiency alters the root morphological and physiological traits of plants. This study investigates how soybean cultivars with varying low-P tolerance values respond to different P levels in hydroponic culture by assessing alterations in root length, acid phosphatase activity, organic acid exudation, and metabolites in root exudates. Three low-P-tolerant cultivars ('Maetsue,' 'Kurotome,' and 'Fukuyutaka') and three low-P-sensitive cultivars ('Ihhon,' 'Chizuka,' and 'Komuta') were grown under 0 (P0) and 258 µM P (P8) for 7 and 14 days after transplantation (DAT). Low-P-tolerant cultivars increased root length by 31% and 119%, which was lower than the 62% and 144% increases in sensitive cultivars under P0 compared to P8 at 7 and 14 DAT, respectively. Acid phosphatase activity in low-P-tolerant cultivars exceeded that in sensitive cultivars by 5.2-fold and 2.0-fold at 7 and 14 DAT. Root exudates from each cultivar revealed 177 metabolites, with higher organic acid exudation in low-P-tolerant than sensitive cultivars under P0. Low-P-tolerant cultivars increased concentrations of specific metabolites (oxalate, GABA, quinate, citrate, AMP, 4-pyridoxate, and CMP), distinguishing them from low-P-sensitive cultivars under P0. The top five metabolomic pathways (purine metabolism, arginine and proline metabolism, TCA cycle, glyoxylate and dicarboxylate metabolism, alanine, aspartate, and glutamate metabolism) were more pronounced in low-P-tolerant cultivars at 14 DAT. These findings indicate that increasing root length was not an adaptation strategy under P deficiency; instead, tolerant cultivars exhibit enhanced root physiological traits, including increased acid phosphatase activity, organic acid exudation, specific metabolite release, and accelerated metabolic pathways under P deficiency.

The effects of continuous straw returning strategies on SOC balance upon fresh straw incorporation.

Continuous straw returning is widely encouraged for augmenting soil organic carbon (SOC) in arable lands. However, the magnitude of changes in net SOC related to native SOC mineralization and new SOC development upon fresh straw incorporation remains elusive, particularly in soils after continuous straw returning with different strategies. To address this, soil that had undergone nine years of straw returning with different strategies (NS, non-straw returning; DS, direct straw returning; IS, indirect straw returning) was incubated with fresh 13C-labeled straw for 45 days. Fresh straw incorporation stimulated native SOC-derived CO2 emission in DS soil, which in turn promoted straw-derived CO2 emission in IS soil. Overall, the amounts of newly developed SOC from straw (2.41-2.59 g C/kg soil) overcompensated for the native SOC losses (0.91-1.37 g C/kg soil) by mineralization, and led to net C sequestration in all treatments. No obvious difference was found in the amounts of SOC sequestrated from straw between the DS and NS soils, while the amount of native SOC mineralization increased by 40-50% in the DS soil relative to other treatments, thus resulting in lower net C sequestration in the DS soil (1.21 g C/kg soil) than IS and NS soil (1.43 and 1.65 g C/kg for IS and NS soil, respectively). Spearman's correlation analyses indicated a significant (p < 0.01) and positive correlation between SOC contents and native soil C mineralization, while the soil microbial index played a greater role in influencing fresh straw sequestration (p < 0.01). In conclusion, the DS soil showed a weaker effect on SOC sequestration than IS after 9 years of practices, upon fresh straw incorporation. This difference may be attributed to the magnitude of native SOC mineralization in the soil. Besides the straw-C input rate, results emphasize that native soil C protection should be also considered in long-term SOC sequestration practices.

Visualization and quantification of carbon "rusty sink" by rice root iron plaque: Mechanisms, functions, and global implications.

Paddies contain 78% higher organic carbon (C) stocks than adjacent upland soils, and iron (Fe) plaque formation on rice roots is one of the mechanisms that traps C. The process sequence, extent and global relevance of this C stabilization mechanism under oxic/anoxic conditions remains unclear. We quantified and localized the contribution of Fe plaque to organic matter stabilization in a microoxic area (rice rhizosphere) and evaluated roles of this C trap for global C sequestration in paddy soils. Visualization and localization of pH by imaging with planar optodes, enzyme activities by zymography, and root exudation by 14 C imaging, as well as upscale modeling enabled linkage of three groups of rhizosphere processes that are responsible for C stabilization from the micro- (root) to the macro- (ecosystem) levels. The 14 C activity in soil (reflecting stabilization of rhizodeposits) with Fe2+ addition was 1.4-1.5 times higher than that in the control and phosphate addition soils. Perfect co-localization of the hotspots of ß-glucosidase activity (by zymography) with root exudation (14 C) showed that labile C and high enzyme activities were localized within Fe plaques. Fe2+ addition to soil and its microbial oxidation to Fe3+ by radial oxygen release from rice roots increased Fe plaque (Fe3+ ) formation by 1.7-2.5 times. The C amounts trapped by Fe plaque increased by 1.1 times after Fe2+ addition. Therefore, Fe plaque formed from amorphous and complex Fe (oxyhydr)oxides on the root surface act as a "rusty sink" for organic matter. Considering the area of coverage of paddy soils globally, upscaling by model revealed the radial oxygen loss from roots and bacterial Fe oxidation may trap up to 130 Mg C in Fe plaques per rice season. This represents an important annual surplus of new and stable C to the existing C pool under long-term rice cropping.

Stable Carbon Isotope Analysis of Hexachlorocyclohexanes by Liquid-Liquid Extraction Gas Chromatography Isotope Ratio Mass Spectrometry: Method Evaluation and Applications.

Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) are powerful tools for assessing the fate of hexachlorocyclohexanes (HCHs) in the environment. However, there is no systematic study on the CSIA and ESIA analysis test methods of the carbon isotopes of HCHs in water and soil environments, in particular the isotope fractionation in the pre-concentration process. We endeavored to test the compatibility of CSIA and ESIA with the liquid-liquid extraction method of HCHs in water. The results showed that there were negligible changes in the δ13C of HCHs after extraction, indicating that liquid-liquid extraction can be used as a pre-concentration method for the determination of δ13C of HCHs in water. The optimized method was validated and then applied to differentiate three HCHs from different manufacturers, to identify in situ degradation of HCHs of groundwater from a contaminated site and to resolve the carbon isotope fractionation occurring in the α-HCH oxidation by CaO2/Fe(II) Fenton system. The results showed that the same reagents from different manufacturers have different carbon isotope compositions, and different isomers from the same manufacturer also have different isotope compositions, showing useful evidence in identifying the source of HCHs. The more enriched δ13C in the down-gradient wells indicated that HCHs have undergone biodegradation or/and chemical reactions in the groundwater system of the site. Carbon isotopic enrichment factors (εC) of -1.90 ± 0.10‱ were obtained in the oxidation process. Hence, the method validated in this study has great potential as a method for identifying the degradation of HCHs in a water environment.

Nitrogen and phosphorus concentrations in growth media affect the relationship between root endophytic fungi and host plant.

Endophytic fungi (EPF) colonize plant roots and enhance their growth. The relationship between host plant and EPF can be affected by several factors, such as growth media, host species, and fungal species. The objective of this study was to clarify the effect of nutrient concentration in growth media on the relationship between host plant and root EPF. Brassica campestris was grown in 1/100 Murashige and Skoog (MS), 1/10 MS, 1/100 MS and 1/10 nitrogen (high N), and 1/100 MS and 1/10 phosphorus (high P) media. B. campestris was inoculated with four root EPFs isolated from forest soils in Indonesia and harvested 28 days after transplant. Shoot dry weight (SDW) and colonization in roots were measured. All the isolates colonized roots of B. campestris. Two isolates increased the SDW of B. campestris grown on 1/100 MS media. The shoot growth response of B. campestris to EPF colonization on 1/100 MS was higher than that on 1/100 high N and 1/100 high P MS media. These results suggest that concentration of nitrogen and phosphorus in growth media determine the relationship between B. campestris and root EPF.

Multiple analysis of root exudates and microbiome in rice (Oryza sativa) under low P conditions.

Plants release various metabolites from roots and root exudates contribute to differences in stress tolerance among plant species. Plant and soil microbes have complex interactions that are affected by biotic and abiotic factors. The purpose of this study was to examine the differences in metabolites in root exudates of rice (Oryza sativa) cultivars and their correlation with bacterial populations in the rhizosphere. Two rice cultivars (O. sativa cv. Akamai and O. sativa cv. Koshihikari) were grown in soils fertilized with 0 g P kg-1 (- P) or 4.8 g P kg-1 (+ P). Root exudates and root-attached soil were collected at 13 and 20 days after transplanting (DAT) and their metabolites and bacterial community structure were determined. The exudation of proline, serine, threonine, valine and 4-coumarate were increased under low P conditions in both cultivars. There was a positive correlation between the concentration of pantothenate in root exudates and the representation of members of the genera Clostridium and Sporosarcina, which were negatively correlated with root dry weight. Gracilibacter, Opitutus, Pelotomaculum, Phenylobacterium and Oxobacter were positively correlated with root dry weight and presence of allantoin, 2-aminobtyrate and GlcNac. This study provides new information about the response of plants and rhizosphere soil bacteria to low P conditions.

Hydrogen bond donor functionalized poly(ionic liquid)s for efficient synergistic conversion of CO2 to cyclic carbonates.

The development of metal-free, high effective and recyclable catalysts plays a pivotal role in transforming CO2 into high value-added products such as cyclic carbonates. In this paper, we introduced the hydrogen bond donor (HBD) groups into poly(ionic liquid)s via free radical polymerization, which successfully combined the HBD and ionic liquids (ILs) into one heterogeneous catalyst. The HBD could synergistically activate epoxides with hydroxyl functionalized ionic liquids and efficiently catalyze the cycloaddition of CO2 into cyclic carbonates. The yield of propylene carbonate (PC) reached 94% (at 105 °C, 2 MPa CO2, 3 h), which far exceeded poly(ionic liquid)s without HBDs functionalization (PC yield 72%), and even approached bulk ionic liquids (PC yield 95%). Moreover, HBD-functionalized poly(ionic liquid)s (HPILs) exhibited excellent recyclability after five runs and afforded wide substrate scope. According to the experimental results, 1H NMR spectra and density functional theory (DFT) calculations showed 2-hydroxyethyl methacrylate (HEMA) and the hydroxyl of ILs would form strong H-bonds with epoxides contributing to the ring-opening process of epoxides, and a possible HBD and nucleophilic anion synergistically catalytic mechanism was proposed. The method herein paved a brand new way for green technology and utilization of poly(ionic liquid)s.

Animal abundance and soil properties affected by long-term organic farming in rice paddies in a typical Japanese yatsuda landscape.

Organic farming was developed to reduce agriculture's negative impacts on the environment and enhance biodiversity for sustainable productivity in agricultural ecosystems, but the long-term effectiveness of its application in Japanese rice paddies is unclear. We sought to understand how long-term organic farming affects the abundance of animals in both the rice growth and fallow seasons, and how soil properties change. We investigated the abundance of fishes, frogs, beetles, and shellfish in the floodwater in summer, and the abundance of earthworms (mainly Enchytraeidae), arthropods (spiders and springtails), and soil properties in aerobic soils in autumn. We examined fields which had been farmed organically for 10 and 18 years in Tochigi, Japan. Fields farmed with conventional management, located close to the selected organic fields, were used as a control. All selected fields were located in a valley, which is the typical landscape of a traditional Japanese farming village, called a yatsuda in Japanese. The results showed an increase in soil organic carbon, total nitrogen, and available phosphorus in plowed soils that had been converted from conventional to organic farming both 10 and 18 years earlier. However, the abundance of various animals were not affected significantly by long-term organic rice farming, other than arthropods in the aerobic soils that had been farmed organically for 18 years. The quantity of most animals in floodwater and fallow season soil was unaffected by long-term organic rice farming in the yatsuda paddy fields, probably due to the circumstances and similar irrigation systems for both conventional and organic rice farming, as well as lighter doses of agrochemical application for conventional rice cultivation.