中红外光声光谱法测定土壤顶空氨气浓度

利用中红外光声光谱对土壤顶空氨气(NH3)浓度进行测定。结果表明,在动镜速率为0.16 cm/s,分辨率为4 cm–1时获得的NH3光谱噪音较少且信号强度高。利用选定的参数采集不同浓度NH3光谱,其中位于900~1 000 cm–1的特征吸收峰适于定量分析。分别选用该特征吸收的峰高、峰面积和第一主成分与NH3浓度进行回归建模,线性决定系数(R2)均达到0.9以上,表明三者都呈显著线性相关,中红外光声光谱可以用于快速测定土壤顶空中NH3浓度,这为土壤氮素循环研究提供了新手段。     

不同傅里叶变换红外光谱法研究土壤光谱特征的比较与应用

为了将傅里叶变换红外光谱技术更好地应用于土壤中官能团的定量分析,通过比较3种不同傅里叶变换技术下土壤特征吸收峰的差异,来选取最佳的光谱技术应用于土壤的相关研究。采用透射(T-FTIR)、衰减全反射(ATR-FTIR)和漫反射(DR-FTIR)3种光谱技术分别对有机物(苯甲酸、硬脂酸)和土壤(辽东栎)进行了分析。并将辽东栎和草地土壤样品按不同比例混合,使用T-FTIR和DR-FTIR对混合土样进行光谱测定,用于定量分析研究。结果表明:(1)有机物样品在3种光谱技术中均出现特征吸收峰,苯甲酸在1 600～1 400 cm^-1出现苯环C=C骨架特征峰,硬脂酸在2 900～2 800 cm^-1显现甲基的特征峰。有机物中羧酸-COOH内羰基-C=O在1 720～1 680 cm^-1出现伸缩振动吸收峰,羟基-OH分别在1 430～1 410 cm^-1,940～930 cm^-1附近出现面内和面外弯曲振动吸收峰。有机物在T-FTIR技术中需要用溴化钾(KBr)对其稀释。(2)辽东栎土壤样品在T-FTIR和DR-FTIR技术测试中发现,其土壤谱图中有较多有效特征吸收峰,土壤样品在T-FTIR技术中也需要用KBr进行稀释并使样品均匀的分布在锭片中; 而ATR-FTIR技术测试中仅出现个别有效特征吸收峰,不利于对土壤谱图鉴别与进一步分析。(3)辽东栎和草地土壤样品按不同比例混合的测试结果表明:T-FTIR和DR-FTIR技术测试中质量分数与峰面积比呈正相关,线性拟合分别为R²=0.70和R²=0.88。土壤在3种不同红外技术中,DR-FTIR光谱具有较好的土壤特征吸收峰,对土壤样品可以不用KBr稀释。测试步骤简单易操作,可用于土壤样品定量分析研究。     

高耐铝红酵母RS1的红外光谱和拉曼光谱研究

微生物菌株RS1是从江西鹰潭油茶酸性土壤中筛选获得的一株高耐铝红酵母，能够忍耐高达200 mmol/L以上的铝浓度。前期研究表明RS1可以把铝固定在细胞表面，阻挡其进入细胞内部，但是细胞表面何种基团参与铝的固定并不清楚。本文综合采用傅里叶红外光谱和拉曼光谱技术研究了铝胁迫下红酵母RS1细胞表面官能团变化，以期从光谱学角度来探索RS1的高耐铝机制。研究发现，70 mmol/L铝处理24小时后RS1红外光谱中1403 1/cm 处的吸收峰红移到1397 1/cm处，这可能是羧基峰；在1706 1/cm处出现新的吸收峰，这可能是羰基峰；多糖、β-1，3-葡聚糖、酰胺I带、脂肪酸对应的吸收峰强度均显著减弱，且甘露聚糖的吸收峰消失。拉曼光谱在779 1/cm 、856 1/cm处和1270 1/cm处出现新的吸收峰，可能分别为核糖核酸、酪氨酸和酰胺Ш带的吸收峰。综合结果表明，RS1细胞表面与铝吸附相关的物质主要是细胞壁多糖和蛋白质，主要涉及到的官能团包括羧基、羰基和酰胺基。这些细胞表面官能团对铝的固定作用可能是红酵母RS1高耐铝的一个重要机制。     

小白菜的中红外光谱特征及其在氮营养诊断中的应用

采用不同中红外光谱（漫反射光谱、 衰减全反射光谱和光声光谱）对不同氮处理的小白菜进行表征。结果表明,小白菜不同的红外光谱具有明显不同的光谱特征,主要表现于峰形、 峰位以及相对峰强度;中红外漫反射光谱的主要吸收峰分别为2800~3800 cm-1、 2200~2500 cm-1、 1500~1700 cm-1和1000~1500 cm-1,衰减全反射光谱由于水的强烈干扰可用的吸收峰主要在1200~1500 cm-1,而中红外光声光谱的主要吸收峰分别为2800~3800 cm-1、 1500~1700 cm-1、 1200~1500 cm-1和1000~1200 cm-1。漫反射光谱、 衰减全反射光谱和光声光谱的主成分分析表明,不同氮处理主成分分布特征明显不同,且第一主成分（PCA1）均与施氮量显著相关,相关系数（r）分别为0.9103、 0.8527和0.9366。这三种光谱利用主成分分布均可实现小白菜氮营养快速诊断,且光声光谱由于其独特的原位逐层扫描功能而表现出更好的诊断效果,在植物营养诊断中表现出较强的应用潜力。     

蔬菜间作对土壤和蔬菜硝酸盐累积的影响

大量氮肥施用,易造成菜地土壤硝酸盐累积并引起地下水硝酸盐污染和蔬菜硝酸盐含量超标。为降低菜田氮素累积及环境污染风险,采用根深差异蔬菜间作的方法,研究其对土壤硝态氮时空变异规律和蔬菜硝酸盐含量的影响,选择根系较深的萝卜和根系较浅的芹菜进行间作种植大田试验。结果表明,无论在作物的生长前期还是收获期,此种间作增加了0～20cm土层NO3^- -N含量,同时降低了20cm以下土层NO3^- -N含量,能够减少土壤中NO3^- -N的向下移动。从土壤NO3^- -N累积剖面分布规律看,间作区0～40cm土层NO3^-—N累积量高于单作区,而40～100cm土层NO3^- -N累积量低于单作区,间作区土壤0—100cm土层NO3^- -N总累积量减少,收获期分别比萝卜和芹菜单作区降低1．4％、9．0％。间作有降低萝卜和芹菜硝酸盐的趋势,而间作区萝卜全氮含量显著高于单作区,同时间作显著提高了萝卜产量,此种间作还能够减少氮素的表观损失。总之,合理搭配的蔬菜间作既能够增强土壤对氮素的保蓄能力,减少土壤NO3^- -N淋移,对蔬菜产量和品质也有一定正效应。     

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...     

田块尺度上土壤/地下水中硝态氮动态变化特征及模拟

以青岛市大沽河下游地区冬小麦–夏玉米轮作农田为对象,通过田间试验和室内分析,研究了不同深度土壤和地下水中NO3–-N在一个轮作周期内的动态变化特征,探讨了不同氮肥施用量和灌溉量对土壤-地下水系统中NO3–-N时空分布的影响,并基于土壤水动力学和溶质运移理论对土壤中NO3–-N运移过程进行了数值模拟。模拟结果表明:小麦季施氮(N)量达到380 kg/hm2,玉米季施氮量达到290 kg/hm2时,季末剖面深度130~160 cm土壤NO3–-N含量超过10 mg/kg;由地下水NO3–-N月累计量估算模型得出,NO3–-N在6月和8月向浅部地下水的淋失量最大,分别为7.20、7.67 mg/L。     

测定土壤硝态氮的紫外分光光度法和镉柱还原法比较

使用改进的紫外分光光度法(校正因素法)和基于镉柱还原的流动注射分析法(镉柱还原法)测定了中国10种不同类型土壤的NO3–-N含量,分析了两种方法的差异性及其适用性。统计分析表明,改进紫外分光光度法与镉柱还原法测定的结果具有极显著的相关性,测定样品的准确度介于89%~104%,具有可比性。在浓度适用上略有差异,对NO3–-N含量极低的土壤样品,采用镉柱还原法可提高精确度;对于NO3–-N含量高的土样选用紫外法可提高测定精确度,测定结果变异性低于镉柱还原法,且紫外法测定值都要高于镉柱还原法。从仪器操作及校准角度来看,紫外法测定操作过程简便,影响因子较少,对NO3–-N批量快速测定更为适用。     

基于叶绿素荧光光谱的生菜硝酸盐含量检测

为了寻求生菜叶片硝酸盐含量的快速无损检测方法,该文利用叶绿素荧光光谱分析技术对生菜(Lactuca sativa L.)叶片硝酸盐含量进行检测研究。对比及分析500~550、650~715和715~800 nm 3个波段的叶绿素荧光光谱特征参数与生菜叶片硝酸盐含量的关系,得出650~715 nm波段的叶绿素荧光光谱特征参数与生菜叶片硝酸盐含量之间线性关系显著,决定系数R2为0.816,标准误差为0.147,以此建立的回归模型能够很好地反映生菜叶片硝酸盐含量与叶绿素荧光光谱特征参数的关系;将同批进行试验的30个样本作为回归方程的校验集,进行模型验证,预测值与实测值之间决定系数R2为0.752,表明回归模型对生菜叶片硝酸盐含量有良好的预测效果。研究结果为生菜叶片硝酸盐含量的快速无损检测提供参考。     

红壤区土壤有机质光谱特征与定量估算——以江西省吉安县为例

通过对江西省吉安县不同有机质含量土壤的光谱曲线吸收特征进行分析,得到不同有机质含量土壤的光谱曲线特征响应波段,建立了县级尺度基于有机质响应波段的定量估算模型。结果表明,红壤和水稻土土壤光谱曲线特征具有明显差异,560~710 nm为吉安县土壤有机质含量的特征吸收波段;基于特征吸收波段范围的吸收面积(s)的对数和有机质含量的相关性为0.86,拟合方程为y=-20.91 ln(s)-27.26,决定系数为0.74,经不同类型土壤的有机质数据检验,预测的决定系数(R2)、均方根误差(RMSE)和预测相对分析误差(RPD)分别为0.75、0.61和1.88;包络线去除和反射率的倒数的对数处理建立的偏最小二乘回归(PLSR)模型预测效果最佳,预测决定系数均达0.83以上,相对偏差均为2.4以上,基于特征吸收波段560~710 nm建立的模型能定量估算红壤地区有机质含量,为土壤有机质估测提供参考。     

Potential Use of Raman Spectroscopy for Determination of Amylose Content in Maize Starch

An analytical method using Raman spectroscopy was developed for the determination of amylose concentration in maize starches. FT-Raman spectra of four maize starches with amylose content varying from 3.3 to 66% were obtained. A Raman band at ≈1657 cm^-1 correlated linearly with amylose concentration in the four maize starches, and a calibration curve for Raman band intensity versus amylose content was developed. The linear correlation of the I₁₆₅₇/I₉₀₀ integrated areas with amylose content was r = 0.997. The Raman-based calibration curve allows fast and nondestructive determination of the amylose content in maize starches with minimal sample preparation.     

An Alternate Method for Fourier Transform Infrared (FTIR) Spectroscopic Determination of Soil Nitrate Using Derivative Analysis and Sample Treatments

This study aimed at examining effective sample treatments and spectral processing for an alternate method of soil nitrate determination using the attenuated total reflectance (ATR) of Fourier transform infrared (FTIR) spectroscopy. Prior to FTIR measurements, soil samples were prepared as paste to enhance adhesion between the ATR crystal and sample. The similar nitrate peak heights of soil pastes and their supernatants indicated that the nitrate in the liquid portion of the soil paste mainly responded to the FTIR signal. Using a 0.01-M CaSO₄ solution for the soil paste, which has no interference bands in the characteristic spectra of the analyte, increased the concentration of the nitrates to be measured. Second-order derivatives were used in the prediction model to minimize the interference effects and enhance the performance. The second-order derivative spectra contained a unique nitrate peak in a range of 1,400–1,200 cm^?1 without interference of carbonate. A partial least square regression model using second-order derivative spectra performed well (R ²?=?0.995, root mean square error (RMSE)?=?23.5, ratio of prediction to deviation (RPD)?=?13.8) on laboratory samples. Prediction results were also good for a test set of agricultural field soils with a CaCO₃ concentration of 6% to 8% (R ²?=?0.97, RMSE?=?18.6, RPD?=?3.5). Application of the prediction model based on soil paste samples to nitrate stock solution resulted in an increased RMSE (62.3); however, validation measures were still satisfactory (R ²?=?0.99, RPD?=?3.0).     

Impact of Bran Addition on Water Properties and Gluten Secondary Structure in Wheat Flour Doughs Studied by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy

The aim of this work was to elucidate the underlying physical mechanism(s) by which bran influences whole grain dough properties by monitoring the state of water and gluten secondary structure in wheat flour and bran doughs containing 35–50% moisture and 0–10% added bran. The system was studied with attenuated total reflectance (ATR) FTIR spectroscopy. Comparison of the OH stretch band of water in flour dough with that in H₂O‐D₂O mixtures having the same water content revealed the formation of two distinct water populations in flour dough corresponding to IR absorption frequencies at 3,600 and 3,200 cm^–1. The band intensity at 3,200 cm^–1, which is related to water bound to the dough matrix, decreased and shifted to lower frequencies with increasing moisture content of the dough. Addition of bran to the dough caused redistribution of water in the flour and bran dough system, as evidenced by shifts in OH stretch frequency in the 3,200 cm^–1 region to higher frequencies and a reduction in monomeric water (free water). This water redistribution affected the secondary structure of gluten in the dough, as evidenced by changes in the second‐derivative ATR‐FTIR difference spectra in the amide I region. Bran addition caused an increase in β‐sheet content and a decrease in β‐turn (β‐spiral) content. However, this bran‐induced transconformational change in gluten was more significant in the 2137 flour dough than in Overley flour dough. This study revealed that when bran is added to flour dough, water redistribution among dough components promotes partial dehydration of gluten and collapse of β‐spirals into β‐sheet structures. This transconformational change may be the physical basis for the poor quality of bread containing added bran.     

小麦玉米轮作条件下不同生物质炭对土壤腐殖物质的影响

生物质炭是有效的土壤固碳材料.通过1年的田间试验探究了小麦玉米轮作施用花生壳生物质炭和木材生物质炭后盐化潮土腐殖物质(HS)含量及化学结构的变化.试验设置不施肥(CK)、常规单施化肥(T1)、花生壳生物质炭(T2)、木材生物质炭(T3)4个处理.结果表明,与CK和T1处理相比,小麦季和玉米季生物质炭处理的土壤有机碳(s...     

可见-近红外与中红外光谱预测土壤养分的比较研究

对土壤养分的快速和准确测定有助于适时指导施肥。为进一步研究可见-近红外（350～2500 nm）与中红外光谱（4000～650 cm-1）对土壤养分的预测能力,以贵州省500个土样为例,对光谱进行Savitzky-Golay（SG）平滑去噪处理,再用标准正态化（SNV）方法进行基线校正,然后分别应用偏最小二乘回归（PLSR）和支持向量机（SVM）两种方法进行建模,探讨了可见-近红外和中红外光谱对土壤全氮（TN）、全磷（TP）、全钾（TK）和碱解氮（AN）、有效磷（AP）、速效钾（AK）共六种土壤养分的预测效果。结果表明：（1）无论基于可见-近红外光谱还是中红外光谱,PLSR模型的预测精度整体均优于SVM模型。（2）中红外光谱对TN、TK和AN的预测精度均显著高于可见-近红外光谱,可见-近红外和中红外光谱均可以可靠地预测TN和TK（性能与四分位间隔距离的比率（RPIQ）大于2.10）,中红外光谱可相对较可靠地预测AN（RPIQ=1.87）;但两类光谱对TP、AP和AK的预测效果均较差（RPIQ<1.34）。（3）当变量投影重要性得分（VIP）大于1.5时,PLSR模型在中红外光谱区域预测TN和TK的重要波段多于可见-近红外光谱区域,TN的重要波段主要集中于可见-近红外光谱区域的1910和2207 nm附近,中红外光谱区域的1 120、1 000、960、910、770和668 cm-1附近;TK的重要波段主要集中于可见-近红外光谱区域的540、2176、2225和2268 nm附近,中红外光谱区域的1 040、960、910、776、720和668 cm-1附近。因此,中红外光谱技术结合PLSR模型对土壤养分预测效果较好,可快速准确预测土壤TN和TK,可为指导适时施肥提供技术支撑。     

Nitratgehalte tieferer Bodenschichten bei unterschiedlichen Fruchtfolgen auf intensiv genutzten Ackerbaustandorten

Influence of rotation upon nitrate content of deep soil layers in intensiv cropping systems Soil samples were taken down to a depth of 10 m during winter 1985/86 in some fields in Lower Bavaria with and without vegetable production. Each core was cut into 50 cm increments and soil nitrate-N and exchangeable ammonium-N determined. The results can be summarised as follows:

• 1 The content of exchangeable ammonium in 0–10 m soil depth was much less than the amount of nitrate nitrogen. Effects of different supply of inorganic fertilizer upon the NH₄-content have not been observed.
• 2 In rotations without vegetables with high supply of mineral nitrogen much nitrate-N was concentrated in the root zone. However in a depth of 4–6 m the nitrate concentration was less than 50 mg/l.
• 3 In one field only the nitrate concentration in 2,8–3,8 m was 2 to 3 times higher than in comparable cases. This seems to be the result of much nitrogen mineralized but not used, because of fallow effects (winter killing without fertilization) in 1982.
• 4 The nitrate concentration in soil cores of arable land decreased generally with sampling depth. In fields with vegetable production soil layers of high nitrate content alterated with soil layers of low nitrate content.
• 5 Because of the strong correlation between the number of soil layers with high nitrate content and the frequency of vegetables in the rotation, it can be assumed that the soil layers with much nitrate are caused by unused inorganic fertilizer applied to vegetables. This hypothesis is also supported by the fact of high nitrogen efficiency (> 70%) of agricultural plants and low nitrogen efficiency (48–13%) of vegetables, caused by high amounts of fertilizer and only low nutrient requirement of vegetables.
• 6 The total amount of nitrate-N found in 0–10 m soil depth was in vegetable rotations 2 to 4 times higher than in fields without vegetable production. The nitrate concentration of the nitrate peaks found in fields with vegetable production decreased with sampling depth, but strongly differing gradients of nitrate decrease with soil depth were observed between the fields.

     

近红外光谱分析法测定菜籽油中芥酸的含量

采用多通道PDA型近红外光谱仪,应用偏最小二乘法建立了菜籽油中芥酸含量与近红外透射光谱的校正模型,讨论多项式求导及平滑的窗口宽度和相关系数法筛选有效波长对校正模型的影响,并对10个预测集样品利用预测相关系数R_p和预测均方根误差RMSEP指标进行了预测精度分析,结果发现：在使用全谱数据进行偏最小二乘回归建模时,一阶7点求导及平滑的预处理方法结果最佳,此时建模效果为：R_p=0.739,RMSEP=1.659;在此基础上通过相关系数法筛选波长后的建模效果为：R_p=0.958,RMSEP=0.963。后者R_p提高29%,RMSEP减少42%。由此可得出多项式求导及平滑法和相关系数法相结合对校正模型稳健性,预测精度都有较大提高的结论。研究证明：多通道近红外光谱仪快速测测菜籽油中芥酸含量的方法是可行的。     

Diffuse-Reflectance Mid-infrared Spectral Properties of Soils under Alternative Crop Rotations in a Semi-arid Climate

We carried out mid-infrared (mid-IR) spectral interpretation of soils 0–5 and 5–15 cm deep in selected alternative crop rotations (ACR) treatments and an adjacent native prairie soil. Ashing and spectral subtraction shows that absorbance at 3700–2850 and 1700–1550 cm^?1 indicates organic absorbance. Prairie soils, with their greater carbon (C) content, have different spectral properties from the cropped soils. Prairie soils have greater absorbance at the 2950–2870 cm^?1 and the 1230 cm^?1 CH bands. The soils from the different depths had different spectral properties, with the soils 0–5 cm deep having stronger absorbance at the 1055 cm^?1 carbohydrate band, at 1270–1460 cm^?1, and at the 1730 cm^?1 ester band. The soils 5–15 cm deep are characterized by greater absorbance at the clay band. Soil C and nitrogen (N) correlated negatively with the 3700 cm^?1 clay band and the 1830 cm^?1 quartz band and correlated positively with the 2920 cm^?1 because of aliphatic CH absorbance.     

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。     

Comparison of nuclear and capacitance‐based soil water measuring techniques in salt‐affected soils

A field calibration experiment was carried out on salt‐affected clayey soil in Syria, to compare the sensitivity to soil electrical conductivity (ECe), and bulk density (ρ_b) of two instruments for estimating soil moisture: the neutron probe (NP) and the Diviner 2000 capacitance probe (CP). The results showed that the values of the correlation coefficient of the calibration were decreased when the ECe and ρ_b values increased; this decrease was more pronounced for the Diviner 2000, indicating that it was more sensitive to ρ_b and ECe than the NP. When only scaled frequency was used in the fitted equation, the Diviner 2000 in wet soil underestimated soil water content significantly at all depths, but especially in the top layer, by up to 0.09 cm³/cm³ compared with gravimetric determinations. However, in dry soil, the Diviner 2000 overestimated the volumetric water content by up to 0.05 cm³/cm³ in the top 15 cm, and by 0.03 cm³/cm³ at 30‐45 cm depth. The performance of the neutron probe was better overall; using a factory calibration curve no significant differences were observed between NP estimates and the gravimetric values. Including both ρ_b and ECe in the calibration equations improved the fits, although the regression coefficient (R²) for the Diviner 2000 remained low.