Characterization of humic substances by advanced solid state NMR spectroscopy: Demonstration of a systematic approach

Characterization of humic substances is challenging due to their structural complexity and heterogeneity. Solid state nuclear magnetic resonance (NMR) is regarded as one of the best tools for elucidating structures of humic substances. The primary solid state NMR technique that has been used so far is the routine ¹³C cross polarization-magic angle spinning (CP-MAS) technique. Although this technique has markedly advanced our understanding of humic substances, the full potential of NMR for characterizing humic substances has yet to be realized. Recent technical developments and applications of advanced solid state NMR have revealed the promise to provide deeper insights into structures of humic substances. In this paper, we summarized and demonstrated the systematic solid state NMR protocol for characterization of humic substances using a humic acid as an example. This protocol included (1) identification of specific functional groups using spectral editing techniques, occasionally assisted by ¹H¹³C two-dimensional heteronuclear correlation (2D HETCOR) NMR, (2) quantification of specific functional groups based on direct polarization-magic angle spinning (DP-MAS) and DP-MAS with recoupled dipolar dephasing, combined with spectral editing techniques, (3) determination of connectivities and proximities of specific functional groups by ¹H¹³C 2D HETCOR or 2D HETCOR combined with spectral editing techniques, and (4) examination of domains and heterogeneities by ¹H¹³C 2D HETCOR with ¹H spin diffusion. We used a soil humic acid as an example to demonstrate how this protocol was applied to the characterization of humic substances step by step. Afterwards, based on typical ¹³C NMR spectra of humic substances we described how we could combine different NMR techniques to identify specific functional groups band by band from downfield to upfield. Finally, we briefly mentioned the potential new NMR techniques that could be developed to enrich the current systematic protocol. This systematic protocol is not only applicable to humic substances but also to other natural organic matter samples.     

重庆南山老龙洞地下河流域岩溶地下水DIC和δ13CDIC及其流域碳汇变化特征

以重庆南山老龙洞岩溶地下河流域为例,通过分析地下河水DIC变化特征与来源,估算了流域岩溶碳汇通量,并探讨了自然条件和人类活动对岩溶碳汇的影响。研究结果表明,老龙洞地下河的水化学类型为Ca-HCO3-SO4型,显示其形成过程中受碳酸盐岩碳酸溶蚀和硫酸溶蚀共同控制。地下河水DIC浓度为3.1~6.3mmol/L,其中夏季因受降雨稀释作用影响DIC较冬季的低;地下河水δ13CDIC值介于-3.8‰~-13.1‰之间,且夏季比冬季偏高约2‰。根据地下河水DIC浓度和流域径流量计算出流域岩溶净碳汇通量均值约为167.31×103mol/(km2?a)。降雨条件下,流域岩溶碳汇通量随流域径流量的迅速增加而增加。另外,流域碳酸盐岩溶蚀还受到人类活动产生的硫酸型酸雨影响,使得地下水δ13CDIC值相对偏高,它在一定程度上减少了流域碳汇通量。      

中国北方13省市区生态安全动态变化分析

为了寻求我国北方生态安全条件的土地利用/覆盖优化格局,加强区域生态安全研究,在GIS技术的支持下,利用景观分析和空间变异分析方法对北方13省(市、区)生态安全动态变化及其空间变异特征进行了分析。结果表明研究区生态安全指数具有较强的空间相关性。人类活动等随机因素对生态安全的作用强度在增大,但是结构性因素引起的空间相关仍然是该区生态安全空间分异的决定性因素。10年间研究区生态环境质量整体表现出下降趋势;空间上,中西部地区生态安全程度低于东部地区;13个省(市、区)的生态安全指数的变化表现为三种类型:先升后降型、先降后升型和持续下降型。