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,应用小波包分解的拉曼光谱对滤除有机质的磷酸盐参杂土壤中磷素浓度进行预测,回归模型精度R2达到0.94。拉曼光谱检测的样本范围取决于激发光照射在样本上的光点尺寸,而土壤样本的空间变异性为聚焦目标物质带来困难。因此,实现现场高分辨率检测的关键是获取有效拉曼信号、同时降低背景信号的干扰。移频激发技术与显微拉曼技术为农田土壤养分的原位测量提供了技术保障。建议：1）采用光谱融合方法提升回归模型的预测精度。2）降低冗余变量,提升模型的可解读性与重现性。3）充分考虑土壤对拉曼光谱的影响,为开发农田现场土壤成分快速监测技术提供参考。     

Innovative methods in soil phosphorus research: A review

Phosphorus (P) is an indispensable element for all life on Earth and, during the past decade, concerns about the future of its global supply have stimulated much research on soil P and method development. This review provides an overview of advanced state‐of‐the‐art methods currently used in soil P research. These involve bulk and spatially resolved spectroscopic and spectrometric P speciation methods (1 and 2D NMR, IR, Raman, Q‐TOF MS/MS, high resolution‐MS, NanoSIMS, XRF, XPS, (µ)XAS) as well as methods for assessing soil P reactions (sorption isotherms, quantum‐chemical modeling, microbial biomass P, enzymes activity, DGT, ³³P isotopic exchange, ¹⁸O isotope ratios). Required experimental set‐ups and the potentials and limitations of individual methods present a guide for the selection of most suitable methods or combinations.     

近红外反射高含量泥沙传感器研制

水流含沙量测量是水土流失监测体系的重要内容,开展含沙量测量传感器的研究对于实时监测具有重要意义。为了实现对水流高含沙量的测量,该文根据含沙水对不同光谱的吸收和反射特性,采用1 800 nm（强水分反射波长）和1 940 nm（强水分吸收波长）近红外光源开发了泥沙测量传感器和测量装置,并对新型传感器进行了标定试验,分别建立了取自黄河、渭河和天水的泥沙与传感器输出信号之间响应关系。结果表明,当含沙量小于300 kg/m3时,测量得到的反射光强度随含沙量的增加而增加,传感器输出信号与含沙量之间具有很好的线性相关性,并建立了线性模型,决定系数均大于0.9。为了验证模型的精度,将实际含沙量与模型计算含沙量进行比较,结果表明,二者回归系数接近于1,相对误差小于10%,可以使用模型计算值代替实际含沙量。2种波长的传感器对含沙量的测量范围均为1～300 kg/m3,当含沙量大于10 kg/m3时测量精度大于90%,同时传感器精度受到泥沙种类、吸光物质和气泡等其他因素的影响。设计的传感器可以满足对高含沙量水流的测量要求,适用于土壤侵蚀严重的地区。研究结果在水土流失自动监测中具有良好的应用前景。     

近红外反射土壤含水率测量仪设计

水资源是制约中国农业生产最重要的因素之一,土壤含水率的检测对农业生产实践具有至关重要的指导意义。该文根据土壤水分对不同光谱的吸收和反射特性,以发光二极管作为测量仪器光源,中心波长为1 940 nm的光为测量光,1 800 nm为参考光设计了专用的测量电路和相应的软件程序来测量土壤含水率。系统光源发出的光照射到土壤表面,经反射后光电转换器,再送至放大电路、模数转换器、显示和存储。试验表明:土壤含水率与相对吸收深度之间存在正比例关系,线性回归的确定系数为0.86。为了证明测量仪器的测量进度,将实际土壤含水率与仪器的测量结果进行比较修正,结果表明:烘干法与本仪器测量的土壤含水率的结果的均方根误差均为3.9%。因此,本次设计的测量仪器可满足对土壤含水率的测量要求,研究结果在指导农业生产,水资源合理利用,精细灌溉的实时监测中具有良好的应用前景。     

Near-Infrared-Spectroscopy for Determination of Carbon and Nitrogen in Indian Soils

The present study aims to evaluate the potential of near-infrared reflectance (NIR) spectroscopy to determine the carbon and nitrogen content in soils and also to assess the effectiveness of NIR spectroscopy to predict carbon and nitrogen content in freshly collected soil samples. Soil samples (n = 179) were collected from different locations in India. Soil carbon and nitrogen contents were successfully predicted (R² = 0.90 for carbon and R² = 0.85 for nitrogen) by NIR spectroscopy. The root mean square error (RMSE) and ratio performance deviation (RPD) for the validation of predicted equations for carbon and nitrogen were 0.83 and 2.83 and 0.01 and 6.98, respectively. The efficacy of NIR spectroscopy on the prediction of carbon and nitrogen content in Indian soils is highly reliable. Water content in soil samples could affect the NIR absorbance spectra and in turn affect the quantification of carbon and nitrogen.     

自动双环入渗仪设计与试验

为克服传统双环入渗仪的供水不稳定、读取和记录数据工作量大的问题,该文基于定水头法测量导水率的原理,设计了一种高效的自动双环入渗仪。该入渗仪采用非接触式电容感应液位传感器来监测内环和外环内的水位（精度<1.5 mm）;将激光测距传感器（精度<1 mm）安装在圆柱形蓄水器的顶部,以连续自动监测供水量;高精度液位控制系统与电磁阀组合以保持恒定水头。通过理论分析,增大蓄水器中的液面与双环中的液面之间的压力差,可使自动双环入渗仪的初始供水速率远高于马氏瓶的初始供水速率。自动双环入渗仪的精度和可靠性试验于2019年7月至2019年10月在中国农业大学绿苑试验场进行,并进行了该自动双环入渗仪和传统双环入渗仪之间的比较。试验结果显示,在选定土壤的稳定入渗阶段,用马氏瓶测量的稳定入渗速率为0.068 5 cm/min,该自动双环入渗仪的稳定入渗速率为0.068 7 cm/min,自动双环入渗仪实测数据与Philip的理论入渗模型计算结果吻合（R2>0.99）。结果表明,该自动双环入渗仪的自动化测量结果可靠,对今后土壤水分入渗过程研究提供了更加高效的手段。     

解磷菌剂对作物生长和土壤磷素的影响

利用课题组自行分离筛选的B2和B67解磷菌株研制的菌剂,在盆栽和大田试验过程中,菌剂在增加作物产量的同时,有提高土壤速效磷含量、培肥土壤的作用,而且是菌剂和化肥配合施用效果显著。施用了解磷菌剂或菌剂和化肥配合施用后,盆栽玉米的株高、鲜重和干重,较CK增加15．2％～89．2％,玉米单株吸养量较CK增加20％～146％;青菜的鲜重、干重和生物量较CK增加15．8％～41．6％,和CK比较差异显著;小麦的株高、有效小穗数、穗粒数、粒重以及生物量也较CK差异显著,大田试验的几种作物也有不同程度的增产。另外B2和B67接种到山西省典型土壤中,土壤速效磷含量较CK增加1．35～3．04倍,且发现其溶磷效果和土壤磷酸酶活性与有效活菌数相关,解磷菌剂在提高土壤速效磷含量的同时,也有提高土壤速效钾含量的作用。     

In Situ Soil Phosphorus Monitoring Probe Compared with Conventional Extraction Procedures

In this work, selective chemical sensors of phosphorus (PO₄ ^3?) installed in PVC probes and their associated instrumentation were evaluated in soil solution phosphorous monitoring. The evaluation was carried out with the addition of a 0.1 mol L^?1 P‐PO₄ ^3? solution in the soil, followed by data acquisition supplied by the probes; by collecting soil samples in the region where the probes were installed; and by phosphorus determination through conventional laboratory techniques. The phosphorus amounts were determined by spectrophotometry after the following extraction methodologies: Mehlich 1, Mehlich 3, and ionic exchange resin. The results, compared with the potentials registered by the probes, express the best correlation with the results obtained with the resin method. The results indicate good response of the sensors and the potential applicability of these probes to assist in the monitoring of soil nutrients, helping to establish rational processes in the use of fertilizers in crops.     

Exchangeability of phosphate extracted by four chemical methods

Isotopically exchangeable phosphate (P) is a major source of P for plants. In practice, however, plant‐available P is assessed by chemical extractions solubilizing a mixture of P forms the availability of which is ill defined. We undertook an isotopic approach to assess the exchangeability of P extracted by (1) CO₂‐saturated water (P‐CO₂), (2) ammonium acetate EDTA (P‐AAEDTA), and (3) sodium bicarbonate (P‐NaHCO₃) compared to the exchangeability of P extracted by water. Five topsoils with similar P‐fertilization histories but different soil properties were studied. Phosphorus was extracted from soils labeled with carrier‐free ³³P after 1 week of incubation, and the specific activity (SA = ³³P / ³¹P) of the extracts was compared with the SA of P extracted by water to calculate the amount of P isotopically exchangeable that had been solubilized during the extraction. P‐CO₂ extracted between 20 and 100 times less P than P‐AAEDTA and P‐NaHCO₃. The SA of P‐CO₂ was not different from the SA of water‐extractable P, showing that P‐CO₂ solubilized similar forms of P as water and that these forms can be considered as available. The SA of P extracted by the two other methods ranged between 25% and 63% for P‐AAEDTA and 66% and 92% for P‐NaHCO₃ of the SA of water‐extractable P. The fraction of exchangeable P extracted by AAEDTA decreased linearly with increasing soil pH, suggesting that this method dissolves slowly or non‐exchangeable P from calcium phosphates.     

磷处理土壤中磷的释放动力学研究

Phosphate release from three selected soils after treatments of 1.6 and 2.4 mmol L^-1 P was investigated using sequential extractions and fitted using six kinetic models, including zero order （Z）, first order （F）, second order （S）,parabolic diffusion （PD）, two constant rate （TC）, and Elovich type （ET） equations. The results showed that the rate of P release was initially rapid and then gradually declined with time. Also, P release increased with added P. Total P release followed the order： paddy soil with 2.4 mmol L^-1 P 〉 red soil with 2.4 mmol L^-1 P 〉 paddy soil with 1.6 mmol L^-1 P〉 fluvo-aquic soil with 2.4 mmol L^-1 P 〉 fluvo-aquic with 1.6 mmol L^-1 P 〉 red soil with 1.6 mmol L^-1 P. For the two P treatments P release from the paddy soils in the first extraction was 44.3% and 45.6% of total released P, respectively,which were higher than those from red and fluvo-aquic soils. The ratio of P release at the end of release time was 14.0%and 13.1% in the paddy soil treated with 1.6 and 2.4 mmol L^-1 P, respectively, but only 5.1% and 9.2% in the red soil and 7.0% and 5.2% in the fluvo-aquic soil, respectively. Comparison of the coefficients of determination （R^2） indicated that ET, TC, and PD equations could describe the P release data better than Z, F, and S equations.     

不同磷酸盐对污染土壤中镉生物有效性的影响

采用盆栽试验,在镉二级和三级污染的红壤和褐土上添加不同磷酸盐（磷酸二氢铵、磷酸二氢钾、磷酸二氢钙）后种植小油菜40d,测定植株生物量、镉吸收量、土壤有效态镉含量、pH值,分析不同磷酸盐对污染土壤中镉生物有效性的影响。结果表明,3种磷酸盐使污染红壤和褐土上小油菜生物量分别提高了18.7%～291.1%和31.5%～991.2%,在红壤上提高顺序为磷酸二氢钙〉磷酸二氢钾〉磷酸二氢铵,而在褐土上则表现为磷酸二氢钙≈磷酸二氢钾〉磷酸二氢铵。3种磷酸盐影响下小油菜吸收镉量,在镉二级污染水平的红壤上表现为显著提高8.3%～60.6%,而在镉三级污染水平的红壤上则表现为显著降低了4.6%～58.4%。污染红壤有效态镉含量在加入3种磷酸盐后提高了17.0%～122.7%,提高顺序为磷酸二氢钙〉磷酸二氢钾〉磷酸二氢铵;而磷酸二氢铵使污染褐土有效态镉含量降低了2.4%～13.4%。3种磷酸盐使红壤pH值提高了0.24～0.99。可见,不同土壤类型、不同镉污染水平下,3种磷酸盐对土壤镉的生物有效性的影响存在差异,其机制有待进一步研究。     

表面增强拉曼光谱检测脐橙果皮混合农药残留

为了研究果皮农药残留快速检测方法。该文以脐橙为例,混合农药(亚胺硫磷和乐果)为研究对象,选用银纳米线作为增强基底,利用共焦显微拉曼光谱仪对农药残留进行检测。通过表面增强拉曼光谱(surface enhanced Raman scattering,SERS)技术,采集脐橙表皮混合农药残留的SERS光谱。对混合农药定性分析,银纳米线对2种农药都有较好的增强效果。对采集的光谱进行预处理后,建立模型,进行定量分析,研究结果表明,经过二阶微分预处理后光谱数据结合偏最小二乘法(partial least squares,PLS)得到的模型预测效果最好,预测相关系数(R_p)为0.954,其预测均方根误差(root-mean-square prediction error,RMSEP)为4.822 mg/L。挑选两种农药特征峰的特征波段,混合农药中亚胺硫磷的特征波段经多元散射校正(multiplicative scatter correction,MSC)处理后,建模效果较好,其中R_p为0.898,RMSEP为6.621 mg/L;混合农药中乐果的特征波段经基线校正处理后,建模效果较好,其中R_p为0.911,RMSEP为7.369 mg/L。研究结果表明SERS技术是一种快速、可靠的检测混合农药残留的方法。     

农药残留的表面增强拉曼光谱快速检测技术研究现状与展望

果蔬农药残留危害人类健康,施药后,农药分布于其表皮和内部组织,果蔬表面农药绝对残留量低、不均匀,直接光谱检测表征难,而表面增强拉曼散射(surface-enhanced Raman scattering,SERS)技术具有分子级检测精度,可以有效扩增信号,在实现微量物质检测方面优势明显。为此,论文综述了国内外表面增强拉曼散射技术的研究现状,特别是详细介绍了通过设计合理的表面增强拉曼基底结构,实现农药残留信号增强的主要技术手段和表面增强拉曼光谱信号分析方法。在此基础上,指出农药残留的表面增强拉曼检测技术研究中的前沿热点问题,探讨并展望了表面增强拉曼技术在农药残留快速检测方面的发展趋势。基于表面增强拉曼的农药高灵敏度、快速检测表征技术,将在农药违禁使用和农药残留超标监管中有广阔应用前景。     

基于近红外光谱土壤水分检测模型的适应性

由于土壤水分的近红外光谱定量分析模型精度依赖于样品状态,故土壤水分定量分析模型的适应性极其重要。以湖北地区的3种土壤为研究对象,利用偏最小二乘法交叉验证建立了处理后样品下的土壤水分分析模型,模型预测值与标准值的决定系数R2为0.9946,交叉验证预测均方差为0.801%,模型预测决定系数R2为0.9919,预测均方差为0.912%;利用主成分分析了未处理土壤样品与处理土壤样品得分图的差异,结果表明定量分析模型对未处理样品的预测精度降低;采用斜率/截距的方法修正了12个未处理样品的模型预测值,预测平均绝对值误差从0.78%降低到0.38%,结果表明斜率/截距校正法能较好的提高近红外光谱土壤水分定量分析模型的适应性。     

应用拉曼和中红外衰减全反射光谱测定溶液和土壤中的硝酸盐

为比较拉曼光谱和红外光谱在溶液和土壤中硝酸盐含量定量分析的适用性,采用两种光谱对溶液和土壤中的NO3–-N含量(0~200 mg/L)进行快速测定。结果表明,溶液中硝酸盐的拉曼特征峰在1 047 cm–1处,该特征峰强度与NO3–-N浓度成正比,对1 035~1 060 cm-1波段拉曼光谱峰面积和NO3–-N含量进行线性回归,决定系数R2为0.995 4;溶液中硝酸盐的中红外衰减全反射光谱特征吸收峰在1 350 cm–1,吸收峰与NO3–-N含量成正比,特征吸收区1 200~1 500 cm–1峰面积与NO3–-N含量的决定系数R2为0.991 1,表明两种光谱都可用于溶液中硝酸盐的测定。对于土壤样品,红外光谱在1 250~1 500 cm–1处有硝酸盐吸收峰,且吸收峰与NO3–-N含量成正比,峰面积与NO3–-N含量之间的决定系数R2为0.968 4;而对于拉曼光谱,硝酸盐的拉曼峰因受较强干扰导致吸收峰不明显,峰面积与NO3–-N含量之间的决定系数R2仅为0.000 9,表明中红外衰减全反射光谱可用于土壤中硝酸盐的测定,而拉曼光谱则很困难。因此,拉曼光谱和中红外衰减全反射光谱都可用于溶液中硝酸盐的测定,且前者灵敏度要高于后者;中红外衰减全反射光谱可用于土壤中硝酸盐的测定,而拉曼光谱难以用于土壤中硝酸盐定量分析,这为硝酸盐的快速测定提供理论依据和技术支持。