[Effects of 24 Years Different Straw Return on Soil Carbon, Nitrogen, Phosphorus, and Extracellular Enzymatic Stoichiometry in Dryland of the Loess Plateau, China].

Exploring the biogeochemical cycle characteristics of soil carbon, nitrogen, and phosphorus in farmland in the dryland of the loess plateau can provide scientific basis and technical support for efficient crop production and sustainable land use. Here, based on a long-term (24 year) straw return field experiment in Shouyang, Shanxi province, the effects of different straw return regimes, i.e., straw mulching (SM), direct straw return (DS), animal-digested straw return (AS), and non-straw return (CK), on the stoichiometric ratio of soil elements and extracellular enzyme activities were studied. The vector angle and length were calculated to indicate the resource constraints faced by microorganisms. The vector angle was greater than 45° and less than 45°, indicating that microorganisms were limited by phosphorus and nitrogen, respectively. The greater the deviation from 45°, the greater the degree of limitation, and the longer the vector length, the more severely limited by carbon. The results showed that ① the soil C/N and C/P of long-term straw returning ranged from 9.81 to 14.28 and from 14.58 to 21.92, with the mean values of 12.36 and 17.51, respectively, which were 6.0% and 4.2% lower than that at the initial stage of the experiment. The soil N/P was distributed between 1.27 and 1.57, with an average of 1.42, which was 2.2% higher than that in the initial stage. The soil C/N and C/P ratios showed a trend of first decreasing and then increasing, the soil N/P ratio basically showed a flat trend, and there was no significant difference in soil element metering ratios between different straw returning treatments. ② Compared with the 24-year long-term non-straw return treatment, the activities of ß-1,4-glucosidase (BG) and ß-1,4-N-acetylglucosaminidase (NAG) in the soil of the long-term straw mulching treatment increased by 134.4% and 107.5% (P<0.05), the activities of BG and alkaline phosphatase (AP) in the soil of the long-term straw mulching treatment decreased by 59.3% and 59.5% (P<0.05), respectively, and the activities of NAG in the soil of the long-term straw mulching treatment increased by 102.8% (P<0.05). Under the long-term straw returning treatment, soil microorganisms were faced with carbon and phosphorus limitation as a whole. Long-term straw mulching aggravated microbial carbon limitation, and animal-digested straw return could alleviate the degree of carbon limitation. Compared with that in the 24-year long-term non-straw return treatment, soil EEAC/N could be significantly reduced by the animal-digested straw return treatment, and soil EEAC/P could be increased by the direct straw return treatment. The three straw returning methods had no significant indigenous effect on soil EEAN/P. The overall vector angle was greater than 45°, and the vector length increased by 3.8%-20.1% compared with that in the initial stage. ③ Correlation analysis showed that C and N inputs were significantly negatively correlated with BG activity; available nitrogen was significantly correlated with NAG activity, AP activity, and EEAC/N; C/P was significantly positively correlated with EEAC/N; there were significant correlations between N/P and NAG activity, AP activity, EEAC/N, and EEAC/P; and there was no significant correlation between EEAN/P and any environmental factors. In conclusion, the availability of soil nitrogen and phosphorus elements and N/P ratio had significant effects on soil extracellular enzyme activity and stoichiometric characteristics under different long-term straw returning treatments. In the future, more attention should be paid to the improvement of organic carbon and the promotion of nitrogen and phosphorus availability in farmland soil in soil-efficient cultivation and agricultural production activities.

In Situ Probe of the Hydrogen Oxidation Reaction Intermediates on PtRu a Bimetallic Catalyst Surface by Core-Shell Nanoparticle-Enhanced Raman Spectroscopy.

In situ monitoring of the evolution of intermediates and catalysts during hydrogen oxidation reaction (HOR) processes and elucidating the reaction mechanism are crucial in catalysis and energy science. However, spectroscopic information on trace intermediates on catalyst surfaces is challenging to obtain due to the complexity of interfacial environments and lack of in situ techniques. Herein, core-shell nanoparticle-enhanced Raman spectroscopy was employed to probe alkaline HOR processes on representative PtRu surfaces. Direct spectroscopic evidence of an OHad intermediate and RuOx (Ru(+3)/Ru(+4)) surface oxides is simultaneously obtained, verifying that Ru doping onto Pt promotes OHad adsorption on the RuOx surface to react with Had adsorption on the Pt surface to form H2O. In situ Raman, XPS, and DFT results reveal that RuOx coverage tunes the electronic structure of PtRuOx to optimize the adsorption energy of OHad on catalyst surfaces, leading to an improvement in HOR activity. Our findings provide mechanistic guidelines for the rational design of HOR catalysts with high activity.