Studying soil organic matter using 13C CP-MAS NMR: the effect of soil chemical pre-treatments on spectra quality and representativity

¹³C CP-MAS NMR spectroscopy is a technique that has proved to be useful in studying soil organic matter (SOM). Nevertheless, NMR spectra exhibit a weak signal and have very low resolution due to: the low natural abundance of ¹³C (1.1 % of C) in SOM, the generally low SOM content of soils, and the presence of paramagnetic impurities. This paper studies the effects of soil chemical pre-treatments on ¹³CP-MAS NMR spectra quality and spectra representativity i.e. soil C mass balance.

After chemical pre-treatment to increase total organic carbon (TOC) content and C/Fe ratio, eight soils characterized by different levels of organic carbon content and C/Fe ratios were studied using ¹³CP-MAS NMR. Moreover, where chemical treatments were not applicable due to high carbon losses, the number of ¹³CP-MAS NMR scans was increased in order to obtain satisfactory spectra.

Results show that chemical pre-treatment of soils with C/Fe > 1 caused high C losses. Bulk soils were therefore studied by increasing the number of ¹³CP-MAS NMR scans. Acceptable spectra were obtained from 8K scans (1K = 1024 transient). On the other hand, even when a large number of scan (32K) are used, soil with C/Fe < 1 cannot be studied. As these soils are characterized by low C losses after HCl treatments (range of 2.9–25.4%), a pre-treatment of at least 1.39 mol l⁻¹ HCl removes excess Fe and at the same time increases C/Fe ratio resulting in 32K scans providing good spectra.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.     

硅铝比对Cu/SSZ-13SCR活性位的影响

采用固态离子交换法制备了不同硅铝比（Si/Al=5,10,25）的Cu/SSZ-13分子筛催化剂,探究硅铝比对其NH₃选择性催化还原（NH₃-SCR）活性位的影响规律,并通过X射线衍射（XRD）,H₂程序升温还原（H₂-TPR）,NO_x程序升温脱附（NO_x-TPD）,NH₃程序升温脱附（NH₃-TPD）,原位红外实验（in situ DRIFTS）等手段进行物化性质表征.活性测试结果表明,当Cu负载量为4wt%时,不同硅铝比的Cu/SSZ-13具有显著差异的SCR活性;其中,Cu/SSZ-13（10）的SCR活性最佳,200~450℃温度范围内NO转化率均大于80%.XRD和H₂-TPR结果表明,硅铝比会影响Cu/SSZ-13的Cu物种的分布和氧化还原性.NO_x-TPD和NH₃-TPD结果表明,3种催化剂中Cu/SSZ-13（10）具有最多Cu²⁺离子,Cu²⁺离子可以为Cu/SSZ-13（10）提供更多的NO_x吸附位点和Lewis酸性位点,而Lewis酸性位是Cu/SSZ-13主要的低温SCR活性位点,因此有利于NH_3-SCR反应的进行.当硅铝比增加到25时,Cu/SSZ-13（25）的Lewis酸性位大量损失,导致其SCR活性明显下降.     

高Al13纳米聚合氯化铝的结构表征及混凝效果

采用AlCl36H2O和Na2CO3制备了聚合氯化铝(PAC),并采用SO42-/Ba2+沉淀-置换法分离提纯了其中的纳米Al13形态,应用27Al-NMR和XRD等现代实验技术对其中的Al13形态进行了分析表征,27Al-NMR结果表明,分离提纯后样品中的Al13含量明显高于PAC,XRD结果表明,Al13的衍射峰出现在2q角为5~25之间;混凝烧杯实验表明,纳米级PAC较传统的混凝剂AlCl3、Al2(SO4)3和PAC具有更好的除浊、脱色效果.     

硫酸参与喀斯特流域(北盘江)风化过程的碳同位素证据

在碳酸盐岩地区,流域侵蚀过程中硫酸是否参与,对于我们正确理解流域化学风化速率,以及流域侵蚀对大气CO2的消耗和全球碳循环等都有重要的意义。本工作在前期工作(乌江)的基础上,对贵州喀斯特地区的河流(北盘江)和支流的水化学特征以及水体溶解无机碳同位素组成进行了初步研究,研究结果证实硫酸参与了该喀斯特流域岩石/土壤化学风化过程。     

喀斯特高原区5种常见灌木叶片δ~(13)C值的季节变化及其对石漠化程度的响应

测定了贵州高原喀斯特石漠化小流域内5种灌木叶片δ13C值的季节变化,旨在探讨季节及石漠化等级对植物叶片δ13C值的影响。结果表明:不同季节间植物叶片δ13C值呈显著差异,生长初期(4月)叶片的δ13C值显著高于生长中后期(7月、9月及12月);5种灌木种种间差异显著,火棘的叶片δ13C值最负,荚蒾的叶片δ13C值最正,粉枝莓,鼠李和竹叶椒的叶片δ13C值居中;7月不同石漠化等级间植物叶片δ13C值存在显著差异,而在其余月份(即4月、9月及12月)不同石漠化等级间植物叶片δ13C值不存在显著差异,但基本呈现无、轻度石漠化植物叶片小于中度石漠化植物叶片δ13C值的格局;整个生长季中,叶片δ13C值与土壤含水量的相关关系研究表明大多数种在大多数时间随土壤水分的减少其δ13C值增高。     

两种HP13Cr110钢腐蚀性能对比研究

针对2种不同厂家的HP13Cr110钢,通过模拟高温高压腐蚀试验和标准耐点蚀试验,借助表面形貌的观察分析,评价对比了2种材质HP13Cr110钢的高温高压下CO2腐蚀性能和耐点蚀性能,为油田井下油套管选材提供技术支持。结果表明,在高温高压腐蚀环境条件下2种材质的腐蚀类型均以均匀腐蚀为主,腐蚀程度处于较轻的中度腐蚀,使用时基本上是安全的。     

Synthesis of polyaluminum chloride with a membrane reactor: Process characteristics and membrane fouling

Polyaluminum chloride was synthesized with a membrane reactor, and the process characteristics, membrane fouling and cleaning were investigated.     

Hydrolyzed Al(Ⅲ) clusters: Speciation stability of nano-Al13

Pure nano-Al13 and aggregates at various concentrations were prepared to examine the particle size effect of coagulation with inorganic polymer fiocculant. The property and stability of various species formed were characterized using Infrared, 27Al-NMR,photo correlation spectroscopy (PCS), and Ferron assay. Results showed that concentration and temperature exhibited different roles on the stability of Al13. The quantity of Alb species analyzed by ferron assay in the initial aging period corresponded well with that of Al13, which has been confirmed in a dimension range of 1-2 nm by PCS. Al13 solutions at high concentrations (0.5-2.11 mol/L)were observed to undergo further aggregation with aging. The aggregates with a wide particle size distribution would contribute to the disappeared/decreased Al13 basis on the 27Al-NMR spectrum, whereas a part of Al13 would still remain as Alb. At low concentrations,Al13 solution was quite stable at normal temperature, but lost its stability quickly when heating to 90°C.