Content and composition of free and occluded particulate organic matter in a differently textured arable Cambisol as revealed by solid‐state 13C NMR spectroscopy

The composition of functional light soil organic matter pools of arable Cambisols with a gradient in clay content was investigated. Soil texture differences originate from increasing loess admixture to the parent material (coarse‐grained tertiary sediments). Using density fractionation in combination with ultrasonic dispersion, two types of particulate organic matter (POM) were obtained: (1) free POM and (2) POM occluded in soil aggregates. Both POM fractions were analyzed by elemental analysis (C, N) and CPMAS ¹³C NMR spectroscopy. With increasing clay content the amount of organic carbon stored in the occluded POM fraction increased considerably, whereas the amounts of free POM were not related to the soil clay content. With increasing soil clay contents increasing proportions of O‐alkyl C and decreasing proportions of aryl C were found for both POM fractions. The occluded POM fraction showed a higher degree of degradation as indicated by lower amounts in O‐alkyl carbon. A lower degree of POM degradation was associated with higher clay contents. Higher soil clay contents promoted the conservation of POM with a low degree of alteration. This effect of soil texture was found to be highly significant when the aryl C : O‐alkyl C ratio was used as indicator for POM decomposition rather than the alkyl C : O‐alkyl C ratio.     

Assessment of biogeochemical trends in soil organic matter sequestration in Mediterranean calcimorphic mountain soils (Almería, Southern Spain)

Total soil organic matter levels and humic acid formation processes in mountain calcimorphic soils from Sierra María-Los Vélez Natural Park (Almería, Southern Spain) were found to differ depending on soil use (pine and oak forests, and cleared areas either cultivated or affected by bush encroachment). Biogeochemical indicators such as the concentration of exchangeable cations, or the concentration of the different types of humic substances were neither influenced by the type of vegetation nor soil use. In fact, multidimensional scaling and multiple correlations suggest that soil carbon sequestration processes are controlled by small-scale topographical features and their impact on water holding capacity. From a qualitative viewpoint, there were two more or less defined sets of soils: one set consisted of soils with humic acids with marked aliphatic character, displayed intense 2920 cm⁻¹ infrared band, and had low optical density. The resolution-enhanced infrared spectra suggested typical lignin patterns and well-defined amide bands, which point to a selective preservation of comparatively young organic matter. This situation contrasts with that in other set of soils with low C levels (<20 g kg⁻¹) where humic acids with featureless infrared spectra showed high aromaticity and were associated with perylenequinonic chromophors of fungal origin: this is considered the consequence of overlapping biogeochemical mechanisms involving both microbial synthesis and condensation processes. The results from visible and infrared derivative spectroscopies suggest that the reliability of statistically assessing the biogeochemical performance of the different uses on the site studied in terms of the intensity of the prevailing humic acid formation mechanisms, i.e., accumulation of inherited macromolecular substances in the former set, vs. microbial synthesis including the condensation of precursors of low molecular weight substances in the latter.     

土壤可见光-近红外反射光谱与重金属含量之间的相关性

发展基于反射光谱技术的快速、简便、低成本的土壤重金属信息提取方法是区域土壤重金属污染治理所需要的。选择江西贵溪铜冶炼厂污染区,分析了9种重金属元素(Cu、Pb、Zn、Cd、Co、Ni、Fe、Mn及Cr)与土壤可见光-近红外反射光谱之间的相关性及其相关的原因。研究表明,研究区土壤中存在Cu(含量介于66.71~387 mg kg-1之间)和Cd(含量介于0.36~6.019 mg kg-1之间)的强烈富集。土壤重金属含量与反射光谱之间存在显著相关,污染元素Cu的最高相关系数为-0.87,Pb、Zn、Co、Ni、Fe的最高相关系数达到高度相关(|r|>0.80),Cr、Cd、Mn的最高相关系数达到显著相关(|r|>0.70)。微分光谱适于获取土壤中的重金属元素信息,利用组合波段能显著提高相关性。Cu与反射光谱之间的相关性主要受有机质的影响;Pb、Zn、Co、Ni主要受黏土矿物和铁锰氧化物的影响;Cr与反射光谱之间的相关性同时受有机质和黏土矿物的影响。     

基于差异化光谱指数的盐渍土水分含量预测——以滨海盐土为例

以滨海盐土为研究对象,通过添加不同浓度的盐溶液并模拟蒸发过程,获取不同含水、含盐量的土壤样品,并测定土壤光谱和土壤含水量,分别运用光谱指数法和偏最小二乘回归法(PLSR)对土壤含水量进行预测。结果表明：由2027 nm和1878 nm构建的土壤水分差异化光谱指数(NDMI2027,1878)是预测土壤水分的最优指数,且适用于任何等级的盐渍化土壤,其建模集和验证集的预测结果均优于PLSR方法,验证集R2达0.99,RMSE仅为21.84 g/kg,可比较准确地预测盐渍化土壤的含水量。     

pH变化条件下针铁矿表面吸附的磷酸盐联合态的转化

X-ray photoelectron spectroscopy(XPS) and automatic titrimeter were used to study the relation bewteen pH and the transformation of the coordinate forms of P on goethite surfaces.The results showed that for a given P concentration,increasing the pH of suspension could cause a fast transformation of monodentate complexes of phosphate ions on goethite surfaces to binuclear ones,When lowering the pH,additional adsorption of P occurred and the binuclear complexes reverted slowly to the monodentate ones,The dissociation and association of protons of the sorbed P caused by pH changes was considered to be a major reason leading to the transformation of the coordinate forms of P on the surfaces.The stability of binuclear surface complex of P was greater than that of monodentate omplex.The possible reactions on the interface of goethite and solutions with pH changes,and the reasons causing the different stabilities of the two coordinate P complexes are discussed in the paper.     

秸秆深还对土壤团聚体中胡敏酸结构特征的影响

秸秆深还(Deep application of straw,DAS)是指将玉米秸秆施入土壤亚表层(20~40cm),可以解决秸秆焚烧的问题,同时提高土壤肥力、蓄水能力和作物产量。本文采集了吉林农业大学试验站玉米连作耕地试验田中的秸秆深还土壤和未秸秆深还土壤,采用湿筛法将其分为2 mm、2~0.25 mm、0.25~0.053 mm和0.053 mm 4个粒级,定性分析提取胡敏酸(HA),通过元素组成、红外光谱和差热分析研究了秸秆深还对黑土各粒级团聚体中HA结构特征的影响。结果表明:黑土团聚体中的优势粒级为2~0.25 mm粒级,优势粒级的团聚体含量和有机碳含量均是表层较亚表层低,DAS有利于优势粒级团聚体的形成,促使优势粒级团聚体中有机碳增多;与亚表层相比,表层各粒级团聚体HA的缩合度、氧化度和热稳定性普遍较低,脂族碳/羧基碳和脂族碳/芳香碳较高;DAS促使土壤表层和亚表层各粒级团聚体中HA的缩合度、氧化度和热稳定性下降,其中表层HA的缩合度降低更明显;而亚表层氧化度和热稳定性的降低幅度较大。表层中HA的分子结构较亚表层的简单、年轻,秸秆深还促使土壤中有机碳含量增加,HA的结构简单化、年轻化。     

近红外光谱分析技术在畜禽粪便堆肥研究中的应用

针对近红外光谱分析技术在畜禽粪便堆肥组分含量测定及其品质评价中的应用问题,结合近红外光谱分析技术原理,对国内外相关研究进展进行综述,就其存在的问题进行了分析。研究结果表明:应用近红外光谱分析技术可对畜禽粪便堆肥产品的含水率、粗灰分、碳素、氮素、钾、纤维素等组分进行定量分析,但在具体应用过程中尚存在诸如相关研究多局限于科研院所、缺乏广泛的在线应用、非专业人员适用性较差等问题,有待于在全国范围内建立良好的协作关系,对该技术的深入应用进行系统研究与完善,并制定统一的测定标准,以指导和规范我国正在兴起的生物有机肥行业的生产过程监控及该行业的良性发展。     

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.     

可见-近红外光谱联合随机蛙跳算法检测生物柴油含水量

生物柴油是一种优质清洁柴油,可从各种生物质中提炼,其特有的优势受到越来越广泛的关注。该文应用可见-近红外光谱技术原理对生物柴油的含水率进行了检测。配置含水率分别为0、2.5%、5.0%、7.5%和10.0%的试验样品并获取可见-近红外光谱,进行主成分分析,观察不同含水率生物柴油的聚类性,并采用Random Frog算法进行特征波段的提取,最后采用随机蛙跳算法(Random Frog)挑选出的特征波段作为偏最小二乘回归(partial least squares regression,PLSR)和最小二乘支持向量机(least squares-support vector machine,LS-SVM)模型的输入量,建立生物柴油含水量的预测模型。结果发现:采用Random Frog提取出的8条特征波段(563、560、642、565、562、493、559和779 nm)所建立非线性模型LS-SVM所得到的结果较好,其中Random Frog-LS-SVM的结果中R均大于0.95,校正集均方根误差RMSEC=0.722,预测集均方根误差RMSEP=0.520。结果表明采用Random Frog-LS-SVM模型可以准确的预测生物柴油的含水量,为实际应用提供参考。     

拉曼光谱法无损检测蜂蜜中的果糖和葡萄糖含量

应用拉曼光谱结合化学计量学方法对蜂蜜果糖和葡萄糖含量进行了定量分析。用自适应迭代重加权惩罚最小二乘(adaptive iteratively reweighted penalized least squares,airPLS)算法进行基线校正,用竞争性自适应重加权采样(competitive adaptive reweighted sampling,CARS)算法筛选变量,分别用线性的偏最小二乘(partial least squares,PLS)回归算法和非线性的支持向量机(support vector machines,SVM)回归算法建立定量校正模型,并进行预测。2种模型都有较好的预测结果。对果糖,SVM模型预测值与高效液相色谱法(high performance liquid chromatography,HPLC)测定值的相关系数(R)和预测均方根误差(root mean square error of prediction,RMSEP)分别为0.902和1.401,略优于PLS模型(R为0.892,RMSEP为1.604);对葡萄糖,PLS模型的R和RMSEP分别为0.968和0.669,优于SVM模型(R为0.933,RMSEP为1.410)。结果表明拉曼光谱结合化学计量学方法可快速无损测定蜂蜜果糖和葡萄糖含量。