Properties of neutral phosphate buffer extractable organic matter in soils revealed using size exclusion chromatography and fractionation with polyvinylpyrrolidone

Abstract

A neutral phosphate buffer (NPB) extraction method has been used to estimate the amount of available N in soil. However, the properties of soil NPB-extractable organic N have not been fully elucidated. The purpose of the present study was to characterize the properties of organic matter in the NPB extracts of soils. The NPB extracts were obtained from three soil samples, and the organic matter in the extracts was separated into three fractions according to its solubility in acid and adsorption onto polyvinylpyrrolidone (PVP). High-performance size exclusion chromatography (HPSEC) with ultraviolet (UV) and fluorescence detections was applied to the NPB extracts and their fractions. The HPSEC analysis of the NPB extract revealed the presence of a single broad peak, irrespective of the detection methods. The broad peak was identified as humic substances using the on-flow measurements of UV absorption spectra and fluorescence emission spectra. Among the fractions, the PVP-non-adsorbed fulvic acid (FA) fraction accounted for the largest proportion of organic C or N in the NPB extract, followed by the PVP-adsorbed FA and humic acid (HA) fractions. The peak of humic substances was observed for all fractions using HPSEC with the on-flow measurement of UV absorption and fluorescence emission spectra. The molecular weight of the humic substances varied with each fraction. When the Coomassie Blue-reactive substances (CBRS) were quantified using a Bradford protein assay, they were detected in the NPB extract and almost half were distributed in the PVP-non-adsorbed FA fraction. However, humic substances were considered to be the main constituents of CBRS in the soil NPB extract because of their reactivity with Coomassie Blue and the absence of proteinaceous materials. Furthermore, an incubation experiment revealed that the organic matter available to microorganisms was included in the HA and PVP-non-adsorbed FA fractions. Based on the HPSEC analysis of the NPB extracts and their fractions, it was observed that the humic substances in the NPB extract, particularly in the HA and PVP-non-adsorbed FA fractions, were available to microorganisms.     

Using pXRF and vis-NIR spectra for predicting properties of soils developed in loess

Visible near-infrared (vis-NIR) and portable X-ray fluorescence (pXRF) spectrometers have been increasingly utilized for predicting soil properties worldwide. However, only a few studies have focused on splitting the predictive models by horizons to evaluate prediction performance and systematically compare prediction performance for A, B, and combined A+B horizons. Therefore, we investigated the performance of pXRF and vis-NIR spectra, as individual or combined, for predicting the clay, silt, sand, total carbon (TC), and pH of soils developed in loess, and compared their prediction performance for A, B, and A+B horizons. Soil samples (176 in A horizon and 172 in B horizon) were taken from Mollisols and Alfisols in 136 pedons in Wisconsin, USA and analyzed for clay, silt, sand, pH, and TC. The pXRF and vis-NIR spectrometers were used to measure the pXRF and vis-NIR soil spectra. Data were separated into calibration (n=244, 70%) and validation (n=104, 30%) datasets. The Savitzky-Golay filter was applied to preprocess the pXRF and vis-NIR spectra, and the first 10 principal components (PCs) were selected through principal component analysis (PCA). Five types of predictor, i.e., PCs from vis-NIR spectra, pXRF of beams at 0-40 and 0-10 keV (XRF40 and XRF10, respectively) spectra, combined XRF40 and XRF10 (XRF40+XRF10) spectra, and combined XRF40, XRF10, and vis-NIR (XRF40+XRF10+vis-NIR) spectra, were compared for predicting soil properties using a machine learning algorithm (Cubist model). A multiple linear regression (MLR) model was applied to predict clay, silt, sand, pH, and TC using pXRF elements. The results suggested that pXRF spectra had better prediction performance for clay, silt, and sand, whereas vis-NIR spectra produced better TC and pH predictions. The best prediction performance for sand (R²=0.97), silt (R²=0.95), and clay (R²=0.84) was achieved using vis-NIR+XRF40+XRF10 spectra in B horizon, whereas the best prediction performance for TC (R²=0.93) and pH (R²=0.79) was achieved using vis-NIR+XRF40+XRF10 spectra in A+B horizon. For all soil properties, the best MLR model had a lower prediction accuracy than the Cubist model. It was concluded that pXRF and vis-NIR spectra can be successfully applied for predicting clay, silt, sand, pH, and TC with high accuracy for soils developed in loess, and that spectral models should be developed for different horizons to achieve high prediction accuracy.     

几种常见矿物与硼作用的红外光谱特性研究

对几种常见矿物及其与硼反应的红外光谱比较发现 ,硼在供试矿物上解吸的图谱更接近硼在矿物上吸附的图谱 ,而与无硼矿物图谱相差较大 ,故硼在几种常见矿物上都表现出不同程度的滞后性。针铁矿吸附硼后 ,在 1 40 0～ 1 44 0cm- 1 和 1 0 0 0～ 1 2 0 0cm- 1 范围处谱峰有不同程度的增强 ;水锰矿、三羟铝石和Ca 蒙脱石吸附硼后 ,此处谱峰却减弱 ,而在30 0 0～ 360 0cm- 1 处的谱峰 ,也随硼的吸附而明显减弱 ;Ca 蒙脱、三羟铝石吸附硼后 ,其图谱在 1 40 0～ 1 44 0cm- 1 和 1 62 0～ 1 670cm- 1 处的谱峰变化相似 ;水锰矿吸附硼的图谱在 1 0 0 0cm- 1 和 1 40 0～ 1 44 0cm- 1 处与三羟铝石吸附硼的图谱也有相似之处。     

基于高分辨率反射光谱的土壤营养元素估算模型

研究了土壤中营养元素含量（N、P、K）与土壤可见光／近红外光谱之间的关系。在对原始光谱进行预处理分析后，计算出了4种光谱指标：反射率Reflectance、一阶导数FDR、倒数之对数log（1／R）和波段深度Depth。通过偏最小二乘回归分析建立了营养元素与4种光谱指标的经验模型，并且利用验证样本集对回归模型进行了验证。结果表明，可见光／近红外反射光谱具有快速估算土壤中营养元素含量的潜力。     

不同年代的埃特纳火山土壤上用甘油萃取有机质的特性

We characterized humic acids (HAs) and glycerol-extractable organic fractions (GEOFs) extracted from four Andisols, taken from comparable soil-climate conditions on the east side of Mount Etna. The soils were formed on old lava (about 9 000 years ago), old tephra (about 8 700 years ago), recent lava (about 2 600 years ago) and recent tephra (about 3 600 years ago). A part of the organic matter of the soils, deprived of HAs and fulvic acids (FAs), was isolated by glycerol extraction. The GEOF can not be extracted with alkaline solutions, probably because it is closely bound to the mineral component of the soil. The characterization of the extracted organic fraction was carried out using elementary and functional group analysis and Fourier transform infrared (FT-IR) spectroscopy. About 20 extractions were necessary to extract the HA and FA from the older soils and about 10 extractions to extract them from the younger soils. Data showed that the GEOFs had a greater ash content and a smaller N content, as well as a greater presence of aliphatic compounds and carboxylic groups as compared to the HA extracted from the same soil. The GEOFs extracted from younger soils also had a lower yield, ash and COOH-group content, and were more aliphatic than the GEOF extracted from older soils. Finally, the GEOFs were more closely bound to the amorphous component of the soil (‘short-range’ minerals) and consequently less subject to biodegradation.     

全光谱匹配算法在苹果分类识别中的应用

为进一步提高光谱匹配准确率,该研究对杰卡德相似性原理（jaccard similarity coefficient,JSC）进行改进并提出新的光谱相似度的计算方法。同时,对光谱进行一阶导数二值化,以保证改进后的算法适用于光谱的匹配。此外,对不同光谱分辨率对该算法的影响进行了研究。试验样本选用阿克苏红富士、山东红将军、陕西红富士和陕西金帅4个品种的苹果进行算法能力验证,在2～128 cm-1之间,共7个不同水平的分辨率上进行比较。试验结果表明：该研究提出的算法正确分类识别率为94.5%;研究提出算法在8或16cm-1分辨率水平下取得最佳分类识别结果。因此,基于JSC的全谱匹配算法在光谱数据库系统中的应用将有助于光谱查询精度的提高。     

基于光谱分析的土壤游离铁预测研究

土壤游离铁含量的高低可作为土壤系统分类中判断土壤类型的诊断指标,同时也对土壤风化程度具有指示作用,并在一定程度上反映了土壤的成土环境。本研究调查了安徽宣城的91个土壤剖面,共398个土壤样品,采集了样品在350~2500 nm波段的漫反射光谱数据,并对游离铁含量进行化学分析。光谱数据包括反射率(R)、反射率一阶导数(FDR)和吸收度(Log(1/R))3种形式。本文采用偏最小二乘回归算法(PLSR)和反向神经网络(BPNN)建模预测游离铁含量,并分析不同形式光谱数据的建模预测效果。结果表明:当存在游离铁20 g/kg的样本时,传统建模方法不能准确预测游离铁含量(R20.6,RPD1.5),相对R和Log(1/R)两种光谱数据,以FDR作为自变量建模预测游离铁含量的效果最差。     

硼酸共沉淀法合成含硼氧化铁的结构状况解析

在水合法制备针铁矿过程中添加HBO3,对合成的样品作红外光谱和比表面积分析.结果表明,共沉淀法合成的样品在1343 cm处有特征吸收峰,说明在针铁矿形成过程中,如果有H3BO3参与,则形成的氧化铁中存在Fe-O-B键结构,可能在氧化铁内部有一种新硼铁化合物生成.比表面积测定表明,含B氧化铁比表面积增加4倍以上,反映了氧化铁与H3BO3并非机械混合物,其表面性质因为Fe与B反应而发生改变,B阻止氧化铁向高聚合态转变.     

土壤腐殖酸对毒死蜱水解的影响

土壤腐殖酸的VIS-UV光谱特征和E465/E665的测定结果表明,各种土壤腐殖酸的VIS-UV吸收曲线相似,但吸收峰强度和E465/E665差异较大,进而推得它们的腐殖化程度排序为:紫色潮土腐殖酸>中性紫色土腐殖酸>酸性紫色土腐殖酸>腐殖土腐殖酸,说明它们在组成上有共同的本性,但结构和性质差异较大。在此基础上,研究它们对毒死蜱水解的影响。结果表明,不同来源土壤腐殖酸均促进了毒死蜱的水解,但它们的影响程度有明显的差异。对于腐殖化程度最低的腐殖土腐殖酸,浓度为120mg L-1时,对毒死蜱水解的促进作用最大,而随着腐殖酸浓度的增大,促进作用却越来越弱;而对于其它三种样品,腐殖酸溶液对毒死蜱水解的促进作用随着腐殖酸浓度增大而加强,其中以腐殖化程度较低的酸性紫色土的促进作用较为明显。可见,毒死蜱的水解速率与土壤腐殖酸的浓度和腐殖化程度有关。其中,腐殖酸腐殖化程度的影响机理主要与腐殖酸的酸性和腐殖酸的吸附—催化作用有关,其具体作用机理有待于进一步从定性和定量方面去研究,以更好地指导毒死蜱农药的合理施用和污染土壤的修复。     

翅碱蓬野外光谱对土壤化学性质的响应

翅碱蓬(Suaeda salsa)是土壤盐渍化较为严重的地区常见的植被类型,研究翅碱蓬群落特征可以间接反映下方土壤的化学性质。通过野外采集的17个翅碱蓬野外光谱数据和相应土壤样品的理化分析数据,探讨了土壤化学性质和翅碱蓬野外光谱之间的关系。结果表明,翅碱蓬二阶导数光谱1 121nm波段可用来反映土壤有机质和全氮的含量变化,二阶导数光谱1 208nm波段可以很好地反映土壤全磷的含量变化,一阶导数光谱353nm波段可以很好地反映土壤速效钾的含量变化最好,二阶导数光谱724nm波段可以很好地反映土壤pH值的变化,而反映土壤盐分含量变化最好的为一阶导数光谱950nm,这为翅碱蓬覆盖的区域利用遥感技术进行土壤化学性质监测奠定了基础。     

Comparison of the plant-damaging spectral solar ultraviolet radiation between three locations in Eastern USA in the year 2000

The National Ultraviolet Monitoring Center (NUVMC) maintains a network of Brewer Spectrophotometers that collect spectrally resolved, full sky ultraviolet (UV) irradiance values throughout the day. Using these data, an investigation into the spectral UV irradiances at several Brewer locations has been carried out by employing plant action spectra that represent a generalized response of plants to UV exposure. Analysis was performed for the year 2000 on the Chicago, Virgin Islands, and Shenandoah Brewer sites of the Eastern USA, which are of varying latitude, elevation, and atmospheric composition. The weighted and unweighted UV data grouped in SZA ranges of 10° increments is analyzed seasonally, highlighting the seasonal atmospheric differences between the sites. Results obtained in this paper suggest that UV data, when weighted with certain plant action spectra, show the potential sensitivity of plants to small changes in UV irradiances.     

冬小麦冠层光谱红边特征分析

通过对不同N素营养水平冬小麦冠层光谱特性的田间试验研究,发现红边位移现象:在孕穗期前,红边随施N量增加向长波方向"红移";孕穗期后"红移"现象基本消失,继而发生"蓝移"。红边参数中红边斜率(dλred)与叶片N累积量(TN.D)、叶绿素含量(CHL.T)、叶绿素密度(CHL.D)的相关关系通过显著性检验,红边面积(∑dλ680~760)和叶片全N含量(N%)的相关关系通过显著性检验,红边位置(λred)、红边斜率、红边面积与叶面积指数有着密切关系,均通过极显著性检验,一些红边参数可作为小麦农学参数估测的简便方法。     

镁(Ⅱ): 水溶态镁在中国粘土上的吸附及复合物形成的稳定常数

Techniques for measurement of the N status of rice can be an aid to making manaement decisions with economic and environmental implications.A field experiment was conuced to identify spectral variables most sensitive to N deficiency detection in rice canopy with the possibiliy for their use as a management tool. Spectral and agronomic measurements were collected in the evaluation experiment of N status from rice canopy under vive N treatments in a silt loam soil ,Nitroen fertilization effects were seen across the entire wavelength measured .Red refectance decreased and near infrared reflectance increased with increasing N fertilizer application.Spectral differences between treatments were seen throughout the test period.The naer infrared refectnce/red reflectance ration (RVI) differed mored between treatment than between single bands.Variations in canopy reflectances due to other environmental factors were reduced by the use of RVI.In the spectral variables examined ,the RVI separated the treatments most effectively,and three or four treatments can be separated.Differences in spetral responses betwenn the treatments were attributable to leaf area index ,leaf chlorophyll concentration and phtomass,wich all changed with N fertilization.     

稀土农膜转光材料合成与性质研究

采用乙醇 水溶液析出法合成了 1 1种以稀土三价铕离子为中心离子 ,以 β二酮 (α 噻吩甲酰三氟丙酮、二苯甲酰甲烷、苯甲酰丙酮 )和芳香羧酸 (肉桂酸、烟酸 )为主配体 ,有机胺类 (邻菲咯啉、三辛胺、三乙胺 )为协同配体的二元及三元配合物 ,通过荧光光谱和TG DTA谱线分析配合物荧光性能及热力学稳定性结果表明 ,所合成的配合物中仅三 (α 噻吩甲酰三氟丙酮根 ) (邻菲咯啉 )·合铕 (Ⅲ )和三 (二苯甲酰甲烷根 ) (邻菲咯啉 )·合铕 (Ⅲ )荧光强度高于对照 ,且依次为三 (α 噻吩甲酰三氟丙酮根 ) (邻菲咯啉 )·合铕 (Ⅲ ) >三 (二苯甲酰甲烷根 ) (邻菲咯啉 )·合铕 (Ⅲ ) >对照。三 (α 噻吩甲酰三氟丙酮根 ) (邻菲咯啉 )·合铕 (Ⅲ )和三 (二苯甲酰甲烷根 ) (邻菲咯啉 )·合铕 (Ⅲ )起始分解温度分别为 2 2 0℃和 2 5 0℃ ,高于膜的加工温度 ,可满足生产需要。而三 (二苯甲酰甲烷根 ) (邻菲咯啉 )·合铕 (Ⅲ )生产成本低于对照和三 (α 噻吩甲酰三氟丙酮根 ) (邻菲咯啉 )·合铕 (Ⅲ ) ,因而更具竞争优势     

基于可见-近红外反射光谱的土壤碳酸钙含量与反演效果关系研究

土壤可见-近红外反射光谱中包含了大量的土壤属性信息,研究人员根据土壤属性信息在光谱上的特征,对土壤属性进行定量反演。是否属性值越高,反演精度越高?目前对于属性含量与反演效果的定量关系尚不清楚。采集了我国西北地区黑河流域69个代表性干旱土剖面(292个发生层土样),以气量法测定其碳酸钙含量,使用Cary 5000分光光度计测定其可见-近红外光谱反射率,以样本量和离散度(变异系数)作为数据集划分标准,分别建立了11个相同样本量子集(A)和5个相近离散度子集(B),应用偏最小二乘回归(PLSR)算法对各子集进行土壤碳酸钙含量反演,以此探究碳酸钙含量与反演效果的定量关系。结果表明,碳酸钙可增加可见-近红外波段的光谱反射率,但利用可见近红外光谱反演土壤碳酸钙含量,其反演效果与碳酸钙含量关系不显著。     

干燥后稻米食味值的预测与分析

为了采用神经网络方法预测干燥后稻米食味值，依据稻米的食味值与其主要成分(水分、蛋白质、直链淀粉和脂肪酸)和干燥温度有关这一研究结论，用近红外光谱谷物成分分析仪测定了稻米的主要成分值，用专家模糊评判方法确定稻米的食味值，建立了稻米食味值与其主要成分之间的网络结构模型，误差分析结果表明：该方法可以较好预测稻米的食味值，并分析了干燥条件对稻米理化指标的影响规律，影响程度为干燥温度：-0.7；水分：0.68、脂肪酸：-0.56、直链淀粉：0.48和蛋白质含量：-0.33。     

不同氮营养冬小麦冠层光谱红边特征分析

利用FieldSpec FR2500光谱仪测定了不同氮素处理冬小麦冠层光谱,分析其红边特征变化规律及与农学成分的相关关系。结果表明,波长550 nm、680 nm、980 nm、1100 nm与350～680 nm和750～1100 nm可作为氮素营养诊断的敏感特征点与波段范围。随着施氮量的提高,拔节期、抽穗期以及灌浆期的红边位置（REP）、红谷位置（Lo）与光谱反射率一阶微分极大值（FD_Max）均增大,红边宽度（Lwidth）则有减小的趋势。总体上看,施氮与无氮处理在整个生育期均存在较大差异,施氮处理之间差异较小。冠层反射光谱的红边位置、红谷位置、随生育期向长波方向移动,呈现红移现象;从抽穗期开始逐渐减小,呈现蓝移现象。冬小麦红边参数中红边位置与农学组分之间的相关性优于其他参数,除与地上部生物量正相关显著外,与叶面积指数、叶含水率、叶绿素含量、叶可溶性蛋白含量、叶鲜重、叶含氮量均呈正相关且达到极显著水平。红谷位置则与叶面积指数、叶含水率、叶绿素含量、叶鲜重以及SPAD值呈极显著正相关;与可溶性蛋白呈显著正相关。红边宽度与叶面积指数、叶含水率、叶氮含量、叶绿素含量以及叶鲜重均呈极显著正相关;与可溶性蛋白含量呈显著正相关。反射率一阶导数极大值与叶面积指数、叶含水率、叶鲜重呈极显著正相关,与叶含氮量极显著负相关。通过红边参数与农学组分稳定良好的数学关系,可以对农学组分进行预测估算。     

基于NIR-SVM对鸭梨褐变病果的识别

本文针对水果内部品质评定分类存在主观性强和一致性差的特点,提出了一种新的鸭梨褐变识别分类方法,该方法是利用近红外光谱仪获取正常鸭梨和褐变鸭梨近红外光谱并对其进行分析的基础上,应用支持向量机(SVM)算法的识别原理建立正常鸭梨和褐变鸭梨的分类识别模型。在多项式核函数下对试验样品的识别准确率为95%。研究结果表明NIR-SVM用于对于鸭梨褐变病果的无损检测识别是可行的。