Amino Acid 15N/14N Analysis at Natural Abundances: A New Tool for Soil Organic Matter Studies in Agricultural Systems

Abstract

The effects of landuse, fertilizer history and soil type on the quantity and isotopic quality of hydrolysable soil amino acids were examined in 3 grassland and 2 arable soils. Results showed, (i) that overall concentrations of individual amino acids were highest in the grassland soils, (ii) that ‰δ¹⁵N values of the individual amino acids differed considerably between the five soils, and (iii) that the combination of amino acid ‰δ¹⁵N values and concentrations could be used to distinguish between landuse, crop type and fertilizer history. This preliminary study indicates that the pathways of transformation of soil amino acid N are influenced by long term N inputs and that associated biological processes are reflected in differences in concentrations and ‰δ¹⁵N values of individual soil amino acids.     

Simulation of EPR Spectra as a Tool for Interpreting the Degradation Pathway of Hyaluronan

Electron paramagnetic resonance (EPR) spin trapping is one of the choice techniques for identifying free radicals and is often used in the study of biological systems. However, its sensitivity can result in a typical complicated EPR spectrum. The accurate simulation of these systems is essential for correct identification of the radical species, whenever more than one species contributes to the spectrum. Programs implementing the linear combination of single simulations allow the interpretation of EPR spectra without modifying experimental conditions. In this study, this approach was used to investigate the influence of the ferrous ion and the role of oxygen, as well on the formation of transient radical species, in the whole mechanism of hyaluronan degradation. Degradation was carried out under different environmental conditions (air, O₂, Ar, N₂, N₂ + CO₂) and EPR spin trapping studies were performed. The advantages of the simulation of multiple species EPR spectra were applied to the obtained results and some aspects of hyaluronan degradation mechanism were elucidated. The depolymerization reaction pathway has been defined according to two possible subsequent steps: the first is consistent with formation of an amidyl radical that induces a series of strand scissions, which stabilize at two different levels of molecular weight. The second step occurs when the molecular weight is lower than before and two different adducts are generated.     

A Pulsed EPR and DFT Investigation of the Stabilization of Coordinated Phenoxyl Radicals in a Series of Cobalt Schiff-Base Complexes

We recently demonstrated how the aerobic addition of acetic acid to N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co^II, [Co(1)], leads to the formation of an unusual coordinated Co^III-phenoxyl radical. In this work, some of the structural aspects associated with the Schiff-base-derived ligand (1) that are crucial for the acid-mediated formation of the phenoxyl radical are investigated. For comparison with [Co(1)], we therefore studied the influence of acetic acid on two complexes: (1) the N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethane-diamino Co^II complex, [Co(2)], that lacks the cyclohexyl group of [Co(1)], and (2) the N′-disalicylidene-ethylenediamine Co^II salen complex, [Co(3)], that lacks both the tertiary butyl groups and the cyclohexyl groups. It is shown that the cyclohexyl group of [Co(1)] is not involved in the formation or stabilization of the phenoxyl radical, whereas the tertiary butyl groups of [Co(1)] play a crucial role. In addition, the characteristics of the phenoxyl radical, formed after aerobic addition of acetic acid to [Co(2)], are analyzed in detail by pulsed electron paramagnetic resonance, in combination with isotopic labeling. The experimental data are compared to density functional theory computations and to previous data on the acid-mediated phenoxyl radical of [Co(1)].     

Radicals excess in the retina: A model for light flashes in space

The risk due to cosmic radiation is a major issue in planning future missions to the Moon or Mars and would be critical if inadequately addressed. Functional risks must also be considered. The perception of light flashes reported by astronauts in space, and ascribed mostly to the action of ionizing radiation in the eye (retina), is an evidence for radiation functional interaction. No detailed model of the ion/retina interaction is yet available.Here we present the first model for a generation mechanism compatible with light flashes in space, and the results of in vitro tests supporting it. The model can be a common end point for the interactions between ionizing radiation and visual system in space. It would also support the assessment of functional radiation risks in space.     

含氧有机物对碱金属原子吸收光谱吸光度影响规律的研究

原子吸收光谱法是目前对碱金属族各元素进行分析检测的主要方法之一,在检测的过程中若试样中存在水中溶解度较大的含氧有机物时,碱金属元素的吸光度将受到影响。实验结果表明,不同浓度的含氧有机物对碱金属族各元素的吸光度影响幅度是不同的,其影响规律也有所不同。有机物官能团上的差异也将对碱金属元素的吸光度产生不同的影响。     

施加有机肥对农田有机质和氮素演化影响的光谱学分析

施用有机肥是改善土壤物理结构、提升土壤肥力、调控养分平衡的的有效手段之一,但目前有机肥施用对农田有机质和氮素演化的影响尚不清楚。研究了施入有机肥后土壤总有机碳(TOC)、可溶性有机碳(DOC)、无机氮含量的变化特征,并利用三维荧光光谱分析了施加有机肥后土壤DOM光谱学特性的变化规律,结合PARAFAC分析法分析了施加有机肥后不同时期土壤水溶性有机物(DOM)各组分相对含量的变化,利用2D-COS技术分析各荧光组分随时间的变化顺序,此外采用典型相关度分析法研究了DOM各组分相对含量与土壤氮素的响应关系,以探究施入有机肥对土壤有机质和氮素演变的影响。结果表明：(1)施加有机肥提高了土壤总有机碳、水溶性有机碳和硝态氮含量,降低了铵态氮含量;(2)土壤DOM三维荧光光谱图出现了A峰(UV类腐殖酸)、 M峰(UVA类腐殖酸)、 T峰(类色氨酸), PARAFAC分析结果显示试验土壤DOM主要由陆地源类腐殖酸(C1)、典型类腐殖酸(C2)、类色氨酸(C3)组成。结果还显示,施加有机肥能提高土壤C1, C2和C3组分的相对含量,试验期间,施加有机肥处理后土壤C1, C2和C3组分的相对含量均呈现先上...     

Pulse EPR, ENDOR, and ELDOR Study of Anionic Flavin Radicals in Na+-Translocating NADH:Quinone Oxidoreductase

The Na⁺-translocating nicotinamide adenine dinucleotide (NADH):quinine oxidoreductase (Na⁺–NQR) is a component of respiratory chain of various bacteria and it generates a redox-driven transmembrane electrochemical Na⁺ potential. It contains four different flavin prosthetic groups, including two flavin mononucleotide (FMN) residues covalently bound to the subunits NqrB and NqrC. Na⁺–NQR from Vibrio harveyi was poised at different redox potentials to prepare two samples, containing either both FMN_NqrB and FMN_NqrC or only FMN_NqrB in a paramagnetic state. These two samples were comparatively studied using pulse electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR), and electron-electron double resonance (ELDOR) spectroscopy. The echo-detected EPR spectra and electron spin relaxation properties were very similar for flavin radicals in both samples. The splitting of the outer peaks in the proton ENDOR spectra, assigned to the C(8α) methyl protons, allows to identify both radicals as anionic flavosemiquinones. The mean interspin distance of 20.7 Å between these radicals was determined by pulse ELDOR experiment, which allows to estimate the edge-to-edge distance (r _e) between these flavin centers as: 11.7 Å < r _e < 20.7 Å. The direct electron transfer between FMN_NqrB and FMN_NqrC during the physiological turnover of the Na⁺–NQR complex is suggested.     

制革废水处理过程溶解性有机物的光谱特性研究

制革工业是我国国民经济的传统产业,制革废水已成为工业废水的重要组成部分。现阶段对于制革废水的研究多关注于进水和出水的水质状况,对于废水处理过程溶解性有机物(DOM)的转化规律和净化行为涉及很少。通过紫外光谱和三维荧光光谱跟踪识别制革废水不同处理工段水体DOM的生成特性,尝试建立总荧光强度与水质参数的线性关系。结果表明：废水DOM的吸光度随着紫外波长的增加先上升后下降,最大吸收峰位于230 nm附近。A₂₅₃/A₂₀₃比值和SUVA₂₅₄的参数值先增大后减小,暗示了废水游离取代基和芳环取代基种类和数量的变化。废水原水荧光峰主要出现在λ_ex/em=320～350/440～460和λ_ex/em=270～300/390～420区域,分别归属为可见光区类腐殖酸荧光峰和可见光区类富里酸荧光峰。随着废水处理过程的进行,相继检测到类腐殖酸荧光峰蓝移(水解酸化池)、类色氨酸荧光峰(λ_ex/em=290/340,二级生化池)、弱荧光峰(λ_ex/em=350/520,四级生化池)以及荧光特性趋于稳定(二沉池和出水口)等现象,证实了废水有机物的降解特性和生成规律对荧光图谱的影响。制革废水总荧光强度去除率与总有机碳去除率的线性关系更好,相关系数r为0.835 5。紫外光谱和荧光光谱能在一定程度上揭示制革废水的净化规律和机制。     

用于暗物质探测实验的CsI(Tl)晶体探测器性能的实验研究

在直接测量暗物质的实验中,反冲核能量的Quenching Factor是一个重要参数.用低能X射线源对一套测量入射中子引起的反冲核能量Quenching Factor的系统进行了能量刻度,得到了这套系统的能量响应关系.PMT单光电子的发射对应于晶体中的能量沉积约为0.32keV.同时研究了不同能量的X射线引起的PMT输出电流信号的积分时间宽度与积分电荷的关系,得到最佳的PMT输出电荷收集条件.     

Determination of Radicals Energy Levels in the Bandgap of Nanocrystalline Oxides of Titanium,Molybdenum, and Vanadium Using EPR Spectroscopy

Doklady Physics - A new method for constructing energy band diagrams based on EPR spectroscopy data is proposed and applied to study nitrogen-doped nanocrystalline oxides of titanium, molybdenum,...     

基于FTIR分析猪场废水有机物分解过程中组成结构变化

猪场废水排放的环境污染问题日益受到重视,研究废水中有机物的组成结构变化将可为制订合理的污染防治措施提供科学依据。本研究通过设置不同规模化猪场废水的室内培养试验,在培养过程中定期采样,采用抽滤、冷冻干燥等方法获得可溶性有机物(DOM)固体样品;运用FTIR光谱仪采集样品的红外谱图,研究废水中DOM组成结构在有机分解过程中的变化。结果表明,不同猪场来源的废水中DOM具有类似的组成结构,且主要由蛋白质、脂质类、腐殖酸、多糖类和酚类等有机物组成。随着培养天数的增加,与脂质类、蛋白质和酚类等相关的官能团含量逐渐降低并趋于稳定,而与腐殖酸和多糖类相关的官能团显著增加直至平稳。与初始样品相比,培养20天后样品中DOM组成结构以腐殖酸和多糖类为主,表明DOM的腐殖化程度有所提高。此外,与纤维素分子内氢键缔合的羟基(OH)相比,纤维素分子间氢键缔合的羟基降解速率相对更快,而以前者对微生物的降解更为敏感。废水中DOM以酚羟基C—O的降解速率更快,随后是芳香族COOH、糖类C—O和酰胺羰基CO,而糖类C—O倾向于优先被微生物所利用。综上所述,废水中不同的DOM组成结构在有机降解过程中的变化存在一定差异。     

A method for enhancing the resolution of overlapping EPR lines

A simple and fast method for enhancing the resolution of overlapping EPR lines based on the convolution theorem of Fourier analysis is presented. The method provides two analytic expressions in real space by means of which the user can remove, by deconvolution, either a Lorentzian or a Gaussian function from a given experimental spectrum. This method is applied to deconvolve the line-overlapping EPR spectrum of molybdenumphthalocyanine (MoPc) in solution in fuming sulfuric acid. The deconvolved spectrum is then compared with the EPR spectrum of MoPc incorporated in concentrated sulfuric acid where the lines do not extensively overlap. Comparison shows that the method is able to enhance the resolution of the originally masked hyperfine pattern of MoPc in the fuming sulfuric acid spectrum. This method can be easily applied to other spectroscopies.     

介质pH对渗滤液中水溶性有机物荧光光谱特性的影响

采用荧光分析方法,对不同pH条件下3个填埋年限渗滤液中水溶性有机物(DOM)的荧光特性进行了研究。同步荧光光谱表明,填埋1年及10年渗滤液DOM的同步荧光图中各峰的荧光强度pH 4时最强;填埋5年渗滤液DOM在pH 12时荧光强度最强,而pH 4时的荧光强度次之。渗滤液DOM三维荧光光谱表明,填埋1及5年类蛋白峰强度在pH 10达到最大,而填埋10年在pH 8荧光强度最强;可见区类富里酸峰强度在pH=10达到最大值,而紫外区类富里酸峰较强的荧光强度则分别在pH 4和10时;与类富里酸物质相比,类蛋白物质更容易受pH的影响。紫外区类富里酸荧光强度与可见区类富里酸荧光强度比值[r_{(A, C)}]受pH的变化影响较大,因此,当比较不同来源DOM的r_{(A, C)}值时,应使其pH处于同一水平。     

填埋垃圾渗滤液中水溶性有机物去除规律研究

采集垃圾渗滤液四个不同处理阶段水样,提取制备水溶性有机物(DOM),采用荧光光谱、紫外光谱及红外光谱,研究了不同阶段渗滤液DOM含量与结构特征.结果显示,整个处理过程渗滤液DOM浓度降低了377.6 mg·L-1,总去除率为78.34％,厌氧处理氧化沟和MBR过程分别去除了不同处理阶段出水中的水溶性有机物碳(DOC);厌氧处理增加了渗滤液DOM中不饱和化合物和多糖类物质含量,提高了渗滤液的可生化性;氧化沟处理有效降解了不饱和化合物和糖类.调节池和和厌氧处理过程DOM出现了类蛋白荧光峰和类腐殖质荧光峰,而氧化沟和MBR出水只有类腐殖质荧光峰,类蛋白物质和类富里酸物质主要在厌氧区和氧化沟中去除,而类胡敏酸物质主要在MBR过程中去除.     

EPR Line Shifts and Line Shape Changes Due to Spin Exchange Between Nitroxide Free Radicals in Liquids 10. Spin-Exchange Frequencies of the Order of the Nitrogen Hyperfine Interaction: A Hypothesis

The behavior of electron paramagnetic resonance spectra due to ¹⁵N and ¹⁴N nitroxide free radicals undergoing spin exchange in liquids at frequencies \(\omega_{\text{ex}}\) that are high, of the same order of magnitude as the nitrogen hyperfine coupling constant \(A_{0}\), is investigated. The well-known features are reconfirmed: (1) at low values of \(\omega_{\text{ex}}\) where the lines broaden, shift toward the center of the spectrum, and change shape due to the introduction of a resonance of the form of a dispersion component; (2) at values of \(\omega_{\text{ex}}\) comparable to \(A_{0}\), where the lines merge into one; and (3) at values much larger than \(A_{0}\), where the merged line narrows. It is found that each line of a spectrum may be decomposed into an admixture of a single absorption and a single dispersion component of Lorentzian shape. These two- or three-line absorption–dispersion admixtures, for ¹⁵N and ¹⁴N, respectively, retain their individual identities even after the spectrum has merged and has begun to narrow. For both isotopes, the average broadening and integrated intensities are equal to the predictions of perturbation theory although, in the case of ¹⁴N, the outer lines broaden faster than the central line and intensity moves from the outer lines to the central line. In fact, the outer line intensity becomes zero and then negative at higher values of \(\omega_{\text{ex}}\) which is compensated by the central line becoming more intense than the overall integrated intensity. For both isotopes, the dispersion components and the line shifts depart from the perturbation predictions. The results are presented in terms of measurable quantities normalized to \(A_{0}\) so that they may be applied to any two- or three-line spectrum.     

EPR in the Characterization of the Shade Effect on Translucence, Remaining Free Radicals, and Polymerization Depth of Commercially Available Resin Composites

The aim of this study was to assess the relation between the number of free radicals generated and the polymerization depth in two different commercial brands of resin composites with different colors and translucence. Electron paramagnetic resonance quantified the radical populations through relative intensity (I _r) of free radicals generated, and radical decay was monitored. Sample translucence and the classical polymerization depth were measured. The analysis indicated that resin with more color pigments (MA4, I _r = 0.73 a.u) or more opacity components (ODA2, I _r = 0.84 a.u) generated smaller populations of free radicals and have the lower polymerization depth than clearer (M, I _r = 1.20 a.u and MA2, I _r = 1.02) or more translucent (OEA2, I _r = 1.00 a.u) composites for the same light-curing time. It seems that irradiation doses have to be adequate to more colored and less translucent resins.     

Search for higher oxides of Pu: A photoemission study

After decades of believing in a very stable PuO₂, suitable for final storage of nuclear waste, the existence of a higher oxide, PuO_2+x, was recently claimed. This would have far reaching consequences on the strategies of storage of Pu-based waste. Its formation therefore has been discussed controversially for several years.In this work, existence and stability of the higher oxide, PuO_2+x, has been probed by photoelectron spectroscopy study of PuO₂ exposed to atomic oxygen. The validity of this approach is first tested on UO₂, which oxidizes readily to UO₃. Under the same reaction conditions, PuO₂ is only covered by a chemisorbed layer of oxygen, which desorbs at elevated temperature. The study excludes the stability of any higher binary Pu oxide as a bulk species.     

移动床生物膜技术处理校园污水过程中DOM的光谱特征

研究了厌氧-缺氧-好氧移动床生物膜(MBBR)工艺对校园污水的处理效果,采用三维荧光光谱和紫外光谱分析了污水处理过程中溶解性有机物(DOM)的降解特性及其组成特征。结果表明,MBBR对校园污水具有较好的去除效果,COD,NH₃-N,TN,TP和DOC的去除率分别达到83.0%,70.9%,52.4%,59.2%和62.2%。三维荧光光谱显示有3个明显的特征荧光峰,其中心位置分别在E_x/E_m=230 nm/325 nm(T峰)、E_x/E_m=280 nm/350 nm(S峰)、E_x/E_m=350 nm/440 nm(R峰)附近,污水中荧光类溶解性有机物主要包括类色氨酸(Trp)、类溶解性微生物代谢产物(SMP)和类腐殖酸(HA)。DOM特征荧光峰的中心位置及荧光强度随处理流程而变,说明污水中DOM的组成和相对含量经MBBR处理后发生变化。其中,类色氨酸、类溶解性微生物代谢产物荧光特征峰近乎消失,表明MBBR对这两类有机物质去除效果显著;溶解性微生物代谢产物荧光强度在厌氧池、缺氧池、好氧池分别为进水的37.1%,20.3%,13.1%,表明MBBR的各生化阶段,微生物均能很好的降解SMP;但类腐殖酸(R峰)荧光强度降低较小,微生物对类腐殖酸总的去除效果不明显。在MBBR工艺流程中,DOM腐殖化指数HIX、荧光指数FI、生物源指数BIX均逐渐增大,微生物对有机污染物降解起到了关键作用。其中,HIX值在缺氧池、好氧池、出水中增大到4以上,经MBBR处理后,DOM腐殖化程度和成熟度逐渐增加;缺氧池、好氧池及出水的荧光FI值接近1.9(分别为1.899,1.881,1.887),说明其中类腐殖质有机物主要源于微生物代谢活动;缺氧池、好氧池及出水中DOM的 BIX值约为1.0(依次为0.985,1.018,0.979),说明缺氧池、好氧池及出水中DOM也主要源于微生物代谢或死亡。污水的紫外特征值E₂₅₀/E₃₆₅随工艺流程逐渐减小、SUVA₂₅₄不断增大,表明经MBBR处理后,污水中DOM类型和含量均发生了较大变化,有机物的共轭不饱和双键或芳香性基团增多,聚合度、腐殖化程度、分子质量增大。     

去除土壤水分对高光谱估算土壤有机质含量的影响

土壤高光谱技术具有方便快捷、无破坏、成本低等优点,已被广泛应用于估算土壤有机质含量(SOMC)。然而,野外测量的土壤高光谱数据因受外部环境因素(土壤湿度、温度、表面粗糙度等)干扰,导致SOMC估算模型适用性有待提升。土壤含水率(SMC)是影响野外测量高光谱的最主要的障碍因素之一,它的变化严重影响可见-近红外(Vis-NIR)光谱反射率的观测结果。因此,消除SMC对高光谱数据的干扰是提高土壤高光谱估算SOMC模型预测精度的关键环节。以江汉平原潜江市潮土样本为研究对象,在室内人工加湿土样,分别获取6个SMC水平的土壤高光谱数据,采用标准正态变换(SNV)对光谱数据进行预处理,基于外部参数正交化法(EPO)去除土壤水分对高光谱的影响,利用偏最小二乘方法(PLSR)建立并对比EPO处理前、后不同SMC水平SOMC反演模型。结果表明,土壤水分对Vis-NIR光谱反射率有显著的影响,掩盖了SOMC的光谱吸收特征;EPO处理前不同SMC水平的光谱曲线之间的差异较为明显,而EPO处理后的各SMC水平的光谱曲线形态基本相似;采用EPO处理后的土壤高光谱数据建立SOMC估算模型,预测集的R2_p,RPD分别为0.84和2.50,其精度与EPO处理前所建模型相比有较大提升,表明EPO算法可以有效去除土壤水分的影响,从而提升SOMC的估算精度。对定向去除外部环境参数对土壤高光谱影响进行了实证,为完善野外原位获取SOMC信息技术提供理论基础。