黄土的红外反射光谱与红外光声光谱特征及其差异研究

红外光谱法作为一种新的研究手段已经广泛应用于土壤分析,由其检测区域和手段的不同又可分为多种光谱类 型。本研究以第四纪黄土为例,系统地比较了近红外区和中红外区反射光谱和光声光谱的吸收特征及其差异。结果表明,中红外光谱比近红外光谱的信息更为丰富,且中红外光谱与样品中物质的特征吸收关系更加密切,从而更有利于土壤定性与定量分析。土壤的反射光谱和光声光谱表现出了明显不同的特征,在近红外区,反射光谱和光声光谱吸收明显不同,而在中红外区,反射光谱和光声光谱具有相对应的吸收,但相对吸收强度明显不同,且吸收峰的位置也发生改变,尤其在1 000 ~ 2 000 cm-1谱区,反射光谱相互干扰很强,而光声光谱的吸收特征更为明显。在黄土的分类鉴别上,反射光谱优于光声光谱。红外反射光谱和光声光谱在不同波段下具有不同的吸收灵敏度,在土壤定性与定量分析中各自都将具有其明显的优势。     

新书《土壤红外光声光谱原理及应用》介绍

中国科学院南京土壤研究所杜昌文著的《土壤红外光声光谱原理及应用》一书已于2012年5月由科学出版社出版。全书41.0万字,318页,每册定价88元,共分五章。土壤分析是土壤学研究中的常规性工作,现代农业对土壤信息的需求量十分巨大,传统的化学分析方法很难适应海量的土壤数据获取(土壤数字化),而仪器分析的方法则为海量土壤信息的获取提供了可能。     

中红外光谱土壤有机质含量估测研究进展

中红外光谱波段(2.5 ～ 25 μm)对土壤有机质内部分子振动高度敏感,基于中红外光谱技术的土壤有机质含量估测是土壤学科新兴的研究方向和热点。文章采用文献综述的方法,全面总结了土壤有机质含量中红外光谱估测方法的发展和应用,简述了中红外光谱响应与土壤有机质分子结构的相关性研究,对比分析了室内台式、手持式和机载中红外光谱设备估测土壤有机质含量的优势和局限性,比较分析了中红外、近红外、可见光 - 近红外光谱及其光谱组合估测土壤有机质含量的模型精度和稳定性,总结分析了基于中红外光谱技术的土壤有机质含量建模方法研究进展,以及土样制备、光谱数学变换、敏感波段选择等前处理对土壤有机质含量估测精度的影响研究,最后提出了土壤有机质含量中红外光谱估测存在的问题及发展趋势,为土壤有机质含量的测定工作提供参考。     

基于红外衰减全反射光谱的温室土壤盐分特征研究

与传统的露地耕作土壤不同,温室土壤在耕作过程中受较多的人为调控,但在调控的过程中产生了多种问题,如大量施肥导致的土壤盐渍化[1]。因此,研究如何表征温室土壤的离子特征并预测温室土壤的发展是当前设施农业发展所面临的重要问题。常规农化分析只从不同的角度分析温室土壤的特征,很难实现整体上的综合表征。红外光谱能够综合反应土壤的理化性质,在温室土壤研究中有具有明显的特点。常规的透射光谱在研究土壤时存在制样时间长和难以定量的缺点,而衰减全反射红外光谱(ATR-FTIR)则可克服这一缺点,结合化学计量学的方法,能够实现土壤的定性与定量分析[2,3]。红外光谱包含大量化学键信息,在分析时需进行合理的降维,抽取     

拉曼光谱在精细农业土壤成分快速检测中的研究进展

拉曼光谱分析技术利用分子运动对入射光产生非弹性散射的原理对分子成分进行检测,具有受水分干扰小、样本预处理小、与红外光谱信息互补等特点,在土壤成分快速分析方面展现了很大的优势。但是拉曼光谱信号弱,受荧光干扰强,为土壤拉曼信号的有效获取带来困难。为了分析拉曼光谱在土壤成分检测中的应用潜力,该研究综述了移频激发差分拉曼光谱技术、共焦显微拉曼技术以及表面增强技术等基于拉曼光谱的土壤成分检测技术,分析了土壤成分拉曼光谱检测的研究进展,并提出进一步研究建议。结果表明：1)脂肪族化合物以及芳香族化合物都具有拉曼活性,为基于拉曼光谱的土壤有机质含量的定性、定量分析提供了理论依据。为了弥补拉曼光谱对有机质整体定量预测精度的不足,采用红外-拉曼光谱融合方式补偿单独拉曼光谱数据中缺失的土壤有机质信息,可显著改善预测精度。2)利用表面增强技术可以增强土壤溶液中可溶性氮与土壤有效氮拉曼特征波峰的强度,获得了良好的定量预测效果,回归模型决定系数R²达到0.91～0.99。3)土壤中很多含磷的化合物都具有拉曼活性,拉曼光谱是识别土壤中不同磷酸盐形态的极其有效的工具,在土壤磷素含量的分析中,应用...     

激光诱导击穿原子光谱在土壤分析中的应用

土壤分析是土壤学研究及应用的前提和基础,传统化学土壤分析方法逐渐不能适应现代土壤学海量信息数据快速获取的需求。激光诱导击穿光谱作为一种全新的、反映土壤组成元素原子信息的光谱技术,其无需对样品进行复杂前处理,可实现原位、快速、多元素连续在线检测,每条光谱记录土壤样本独一无二的特征,可以视为土壤“指纹”,成为现代土壤分析的有效技术之一。首先介绍和分析了激光诱导击穿原子光谱的原理、光谱获取的主要影响因素、光谱数据处理的化学计量学方法等;然后阐述和梳理了基于激光诱导击穿光谱技术在土壤分析方面的应用成果和进展,包括土壤鉴定、土壤养分评估、土壤重金属测定、微观/介观尺度土壤原位表征等;最后讨论和总结了激光诱导击穿光谱技术在土壤分析中所面临的挑战及其应用展望。     

基于红外光声光谱的蒙脱石-黄原糖复合体界面层特征研究

粘土矿物-有机物复合体在土壤中具有重要的作用,而土壤粘土矿物-多糖复合体是粘土矿物-有机物复合体形成的前体,多糖是它形成过程中的表面催化剂,但其具体的作用机制尚不清楚。本研究制备了蒙脱石-黄原糖模型复合体,采用X-衍射分析了复合体的结构信息,并利用傅里叶转换红外光声光谱原位逐层扫描功能,探测了蒙脱石-黄原糖复合体表面下不同深度的光谱信息。结果表明,蒙脱石与黄原糖的相互作用主要发生在蒙脱石的表面,并形成表面反应层;该表面层具有明显的红外光声光谱特征,所形成的复合体有更强的持水能力,且表层与亚表层的光谱信息明显不同;红外光声光谱逐层分析表明蒙脱石-黄原糖复合体界面反应层厚度大约在2.05㎛~6.47㎛之间。本结果为揭示复杂的矿物-有机物复合体形成过程及其影响因素提供了定量依据。     

基于红外光声光谱的蒙脱石-黄原糖复合体界面层特征研究

黏土矿物-有机物复合体在土壤中具有重要的作用,而土壤黏土矿物-多糖复合体是黏土矿物-有机物复合体形成的前体,有利于复合体的形成和转化,但其具体的作用机制尚不清楚。本研究制备了蒙脱石-黄原糖模型复合体,采用X-衍射分析了复合体的结构信息,并利用傅里叶转换红外光声光谱原位逐层扫描功能,探测了蒙脱石-黄原糖复合体表面下不同深度的光谱信息。结果表明,蒙脱石与黄原糖的相互作用主要发生在蒙脱石的表面,并形成表面界面层;该界面层具有明显的红外光声光谱特征,所形成的复合体有更强的持水能力,且表层与亚表层的光谱信息明显不同;红外光声光谱逐层分析表明,蒙脱石-黄原糖复合体界面层厚度大约在2.05～6.47μm之间。本结果为揭示复杂的矿物-有机物复合体形成过程及其影响因素提供了定量依据。     

应用红外光声光谱技术及支持向量机模型测定土壤有机质含量

快速测定土壤有机质含量对作物生产和土壤肥力评价具有重要意义,红外光声光谱技术的应用为土壤有机质快速测定提供了可能。本研究以江苏省南京市溧水区水稻土土样为材料,探究了红外光声光谱技术在有机质测定中的应用。采用主成分分析、偏最小二乘和独立成分分析,分别提取了土壤光谱的主成分、偏最小二乘潜变量和独立成分,并以提取的信息输入支持向量机,从而构建了三种支持向量机校正模型。同时,偏最小二乘也被用于建立校正模型,作为支持向量机模型的对照。预测结果表明,基于独立成分的支持向量机模型效果最好,预测相关系数R2、均方根误差RMSEP和实际测量值的标准差与光谱模型预测值标准差的比值即RPD值分别为0.808、0.575和2.28。F检验表明,该模型显著优于基于主成分的支持向量机模型,但与基于偏最小二乘潜变量的支持向量机模型,以及经典偏最小二乘模型没有显著差异。t检验表明,各校正模型对有机质的预测结果与化学测定结果没有显著差异。因此,红外光声光谱技术为土壤有机质的快速测定提供了新的技术手段。     

现代分析技术在土壤腐殖质研究中的应用

土壤腐殖质的研究已成为土壤学、环境化学和地球化学等领域的热点方向之一。应用核磁共振光谱 (NMR)、红外光谱 (IR)、荧光光谱 (FS)、电子自旋共振谱 (ESR)等现代分析技术 ,对在土壤腐殖质组成和结构研究中取得的主要成果进行了综述。     

苏北滨海土壤碳酸钙含量反射光谱估算研究

土壤属性的快速、精确测定是实现现代精细农业的基础。本研究分析了江苏省北部滨海土壤的属性特征以及碳酸钙的可见-近红外反射光谱特征,探讨利用可见-近红外光谱估算滨海土壤碳酸钙含量的可行性,比较不同光谱反射率数据集、不同预处理方法以及不同建模方法定量反演的优劣。结果表明:(1)苏北滨海土壤有机质含量较低、碳酸钙含量较高,其光谱曲线在2 340 nm处有较明显的碳酸钙吸收特征;(2)滨海土壤碳酸钙含量与土壤的可见-近红外波段反射率呈正相关,且碳酸钙含量高低对于土壤的近红外波段反射率的影响高于可见光波段;(3)可见-近红外反射光谱可用于估算滨海土壤碳酸钙含量。就建模结果而言,381~2 459 nm波段反射光谱数据集、log(1/R)预处理、偏最小二乘回归三者结合的效果比较理想。     

Continuum removal versus PLSR method for clay and calcium carbonate content estimation from laboratory and airborne hyperspectral measurements

Reflectance spectroscopy provides an alternate method to classical physical and chemical laboratory soil analysis for estimation of a large range of key soil properties. Techniques including classical chemometrics approaches and specific absorption features studies have been developed for deriving estimates of soil characteristics from visible and near-infrared (VNIR, 400-1200 nm) and shortwave infrared (SWIR, 1200-2500 nm) reflectance measurements. This paper examines the performances of two distinct methods for clay and calcium carbonate (CaCO₃) content estimation (two key soil properties for erosion prediction) by VNIR/SWIR spectroscopy: i) the Continuum Removal (CR) has been used to correlate spectral absorption bands centred at 2206 and 2341 nm with clay and CaCO₃ concentrations and ii) the partial least-squares regression (PLSR) method with leave-one-out cross-validation, which is a classical chemometrics technique, has been used to predict clay and CaCO₃ concentrations from VNIR/SWIR full spectra. We tried to respond to the question “should we use all bands in the 400-2500 nm range or should we focus our analysis on selected spectral absorption bands to determine soil properties from reflectance data?” In this paper, the CR and PLSR methods were applied to VNIR/SWIR laboratory and airborne HYMAP reflectance measurements collected over the La Peyne Valley area in southern France.This study shows that the performance of both techniques is dependent on the spectral feature for the soil property of interest and on the level data acquisition (lab or airborne) face to the instrument specifications. When airborne HYMAP reflectance measurements are used, the PLSR technique performs better than the CR approach. As well, when the soil property of interest has no well-identified spectral feature, which is the case of clay, the PLSR technique performs better than the CR approach. In this last situation, PLSR is able to find surrogate spectral features that retain satisfactory estimations of the studied soil properties. However, parts of these spectral features remain difficult to explain or relate to area-specific correlations between soil properties, which means that extrapolation to larger pedological contexts must be envisaged with care. In the near future, VNIR/SWIR airborne hyperspectral data processed by the PLSR technique will allow for accurate mapping of clay and CaCO₃ contents, which will contribute significantly to the digital mapping of soil properties.     

基于可见-近红外光谱的滨海盐土土壤盐分预测方法

我国目前尚存盐渍土0.35亿hm2,潜在盐渍化土壤0.17亿hm2,15 m等深线以内的浅海和滩涂有0.14亿hm2,黄河河口及长江口以南诸省的滨海盐土都有逐年递增的趋势[1]。因此,对盐渍化土壤盐渍化程度的连续、实时监测尤为重要。然而,我国在区域盐渍土制图、分区及全国性的监测预报体     

近红外光谱法在土壤有机质研究中的应用

近红外光谱技术(Near Infrared Reflectance Spectroscopy,NIRS)具有快速、低成本、无损等优点。目前利用NIRS获取土壤信息已成为国内外学者研究的重点,但是在我国利用NIRS对土壤成分进行定量分析才刚刚起步。本文简要介绍了近红外光谱分析的基本原理、模型的建立及评价,详细论述了该技术在预测土壤有机质及其组分方面的应用,并对NIRS在我国土壤有机质定量研究方面的应用前景进行了展望。     

基于相似光谱匹配预测土壤有机质和阳离子交换量

土壤可见光-近红外波段光谱(350~2 500 nm)包含了大量的土壤属性信息,相同类型的土壤具有相似的光谱曲线特征,但相似光谱曲线是否具有相似的属性含量?探讨此问题可为土壤光谱库的应用提供依据,从而最终服务于快速获取土壤信息技术体系的构建。该研究以安徽宣城为研究区,根据母质、地形特征和土地利用等信息,采集91个典型土壤剖面,共含400个土壤发生层样品,测定了有机质(soil organic matter,SOM)和阳离子交换量(cation exchange capacity,CEC)含量,同时采用VARIAN公司的Cary 5000分光光度计测定了土壤光谱,并将光谱数据变换为反射率(R)、反射率一阶导数(FDR)和吸收度(Log(1/R))3种形式。该文采用光谱角(spectral angle mapper,SAM)、偏最小二乘回归(partial least square regression,PLSR)和SAM-PLSR(spectral angle mapper-partial least square regression,SAM-PLSR)3种方法预测土壤SOM和CEC。SAM方法是通过对测试集104个光谱曲线与参考集的296个光谱曲线进行相似性计算,并以此实现土壤SOM和CEC含量的预测。SAM-PLSR方法以SAM算法下的匹配结果作为建模样本建立PLSR模型和进行预测分析。结果表明,具有相似光谱曲线的土壤具有相似的SOM和CEC含量,SAM算法下相似光谱匹配可直接预测SOM(R2=0.78,RPD=2.17)和CEC(R2=0.82,RPD=2.41)。PLSR方法可很好地预测SOM(R2=0.87,RPD=2.77)和CEC(R2=0.87,RPD=2.59);相较之下,SAM-PLSR方法不仅可以更加准确预测SOM(R2=0.89,RPD=3.00)和CEC(R2=0.91,RPD=3.06),而且大大减少了建模样本的数量。该研究使可见光-近红外光谱可更加高效地用于土壤属性分析,并为土壤光谱数据库的建设及应用提供技术参考。     

基于光谱吸收特征的土壤含水量预测模型研究

为了定量分析土壤含水量与反射光谱特征之间关系,并为土壤含水量速测提供理论依据。以黑土作为研究对象,测定实验室光谱反射率,利用去包络线方法提取反射光谱特征指标,建立土壤水分含量高光谱预测模型。结果表明:黑土含水量与1 420 nm、1 920 nm附近吸收谷的主要光谱特征(吸收谷深度、宽度、面积)呈显著正相关;1 920 nm附近吸收谷可作为黑土土壤水分的特征吸收谷,由其光谱特征参数预测黑土含水量;以1 920 nm附近吸收谷面积为自变量建立的一元线性回归模型预测精度高,输入量少,可以作为土壤含水量速测仪器研制的理论依据。     

Quantification and depth distribution analysis of carbon to nitrogen ratio in forest soils using reflectance spectroscopy

Forest soils have large contents of carbon (C) and total nitrogen (TN), which have significant spatial variability laterally across landscapes and vertically with depth due to decomposition, erosion and leaching. Therefore, the ratio of C to TN contents (C:N), a crucial indicator of soil quality and health, is also different depending on soil horizon. These attributes can cost-effectively and rapidly be estimated using visible–near infrared–shortwave infrared (VNIR–SWIR) spectroscopy. Nevertheless, the effect of different soil layers, particularly over large scales of highly heterogeneous forest soils, on the performance of the technique has rarely been attempted. This study evaluated the potential of VNIR–SWIR spectroscopy in quantification and variability analysis of C:N in soils from different organic and mineral layers of forested sites of the Czech Republic. At each site, we collected samples from the litter (L), fragmented (F) and humus (H) organic layers, and from the A₁ (depth of 2–10 cm) and A₂ (depth of 10–40 cm) mineral layers providing a total of 2505 samples. Support vector machine regression (SVMR) was used to train the prediction models of the selected attributes at each individual soil layer and the merged layer (profile). We further produced the spatial distribution maps of C:N as the target attribute at each soil layer. Results showed that the prediction accuracy based on the profile spectral data was adequate for all attributes. Moreover, F was the most accurately predicted layer, regardless of the soil attribute. C:N models and maps in the organic layers performed well although in mineral layers, models were poor and maps were reliable only in areas with low and moderate C:N. On the other hand, the study indicated that reflectance spectra could efficiently predict and map organic layers of the forested sites. Although, in mineral layers, high values of C:N (≥ 50) were not detectable in the map created based on the reflectance spectra. In general, the study suggests that VNIR–SWIR spectroscopy has the feasibility of modelling and mapping C:N in soil organic horizons based on national spectral data in the forests of the Czech Republic.     

Soil texture prediction through stratification of a regional soil spectral library

Knowing the spatial distribution of soil texture,which is a physical property,is essential to support agricultural and environmental decision making.Soil texture can be estimated using visible,near infrared,and shortwave infrared(Vis-NIR-SWIR)spectroscopy.However,the performance of spectroscopic models is variable because of soil heterogeneity.Currently,few studies address the effects of soil sample variability on the performance of the models,especially for larger spectral libraries that include soils that are more heterogeneous.Therefore,the objectives of this study were to:i)apply Vis-based color parameters on the stratification of a regional soil spectral library;ii)evaluate the performance of the predictive models generated from the spectral library stratification;iii)compare the performance of stratified models(SMs)and the model without stratification(WSM),and iv)explain possible changes in prediction accuracy based on the SMs.Thus,a regional soil spectral library with 1535 samples from the State of Santa Catarina,Brazil was used.Soil reflectance data were obtained by Vis-NIR-SWIR spectroscopy in the laboratory using a spectroradiometer covering the 350–2500 nm spectral range.Sand,silt,and clay fractions were determined using the pipette method.Twenty-two components of color parameters were derived from the Vis spectrum using the colorimetric models.A cubist regression algorithm was used to assess the accuracy of the applicability of the initial models(SMs and WSM)and of the validation between the clusters.Fractional order derivatives(FODs)at 0.5,1.5,and 2 intervals were used to explain possible changes in the performance of the SMs.The SMs with higher contents of clay and iron oxides obtained the highest accuracy,and the most important spectral bands were identified,mainly in the 480–550 and 850–900 nm ranges and the 1400,1900,and 2200 nm bands.Therefore,stratification of soil spectral libraries is a good strategy to improve regional assessments of soil resources,reducing prediction errors in the qualitative determination of soil properties.