镉在不同质地水稻土剖面中的分布特征及与作物吸收的关系

通过野外定点采集土壤和作物植株、籽粒样品, 利用石墨炉(novAA400)原子吸收法, 研究了成都平原稻麦轮作下水稻土剖面中镉的分布特征及其与水稻、小麦吸收镉的相关性。结果表明,土壤剖面中的镉主要集中在0～15 cm的耕层土壤,总体表现为“向根层富集”的特征,土壤全镉和有效态镉均随土层深度的增加而逐渐降低,30～45 cm土层的全镉和有效态镉含量平均值分别为表层的47.60%和39.49%。不同质地土壤中的镉向下迁移量大小顺序为砂壤>重壤>中壤,以15～30 cm土层的迁移量差异最大。土壤pH与0～15 cm土层的有效态镉含量间相关性不显著(r=-0.46),与15～30 cm和30～45 cm土层有效态镉含量间呈显著的负相关(r=-0.78*～-0.86**)。水稻、小麦秸秆和籽粒镉含量与0～15 cm和30～45 cm土层的全镉含量间相关性不大(r=-0.092～-0.383, 0.174～0.424),但与0～15 cm和15～30 cm土层的有效态镉含量呈显著正相关(r=0.766*～0.953**),与30～45 cm土层的有效态镉含量相关性不显著(r=0.526～0.584)。因此,土壤有效态镉含量比全镉含量更适合作为农作物产品安全的土壤镉污染评价指标。     

酸洗处理对生物质炭表面吸附特性及光谱特性的影响

生物质炭表面灰分的存在会严重影响生物质炭的表面结构特性及吸附能力。采用HCl-HF对400和600 ℃两种温度制备的玉米秸秆生物质炭进行酸洗处理,去除生物质炭表面的灰分。通过对比酸洗前后玉米秸秆生物质炭的元素含量、比表面积、孔径分布、红外光谱分析图和吸附平衡试验结果探究酸洗处理对生物质炭表面吸附特性和光谱特性的影响。结果表明：酸洗处理能有效去除生物质炭表面存在的无机盐、焦油等一系列副产物,显著改变生物质炭的表面结构特性,提高生物质炭的吸附性能。(1)酸洗后生物质炭的碳含量相对增加,疏水性及芳香官能团含量增加,极性降低;(2)酸洗处理显著增加了生物质炭的比表面积,处理后炭比表面积分别增加了3.46倍和6.75倍;酸洗还显著提高了生物质炭的孔容及介孔含量,从而大大增加了生物质炭的吸附能力;(3)两种生物质炭酸洗前后的红外光谱上关键官能团峰强差异显著,尤其在3 398～3 447,2 924～3 056,1 378～1 439 cm-1范围内,酸洗后生物质炭的振动峰强度显著减小,表明生物质炭在酸洗后其表面脂肪结构和羟基减少。(4)酸洗前后的吸附试验表明,酸洗处理能够去除炭表面的灰分,增加生物质炭的吸附位点,进而提高其对2,4-D的吸附量。     

运用光谱参数冠层覆盖度建立作物长势及氮营养状态模型

为了探索运用数码照片中光谱(红、绿、蓝)的像素计算得到的冠层覆盖度(canopy cover, CC)对玉米长势及氮素营养状态进行非破坏性监测的技术。通过获取玉米冠层的数码照片图像,定量化数码照片色彩参数与作物叶面积指数(leaf area index, LAI)、冠层干重(shoot dry matter weight, DM)、叶片氮素含量(leaf nitrogen content percentage, N%)之间的关系。试验于2012年和2013年在中国农业科学院试验田进行,运用基于Visual Basic Version 6.0研发的玉米冠层图像分析系统,分析了玉米品种中单909在3个氮素水平条件下分别于9叶展时期、抽雄期和灌浆期的CC、11种色彩指数与植株LAI,DM,N%及产量之间的相关性,并对相关性显著的指标进行了拟合与建模。结果表明,CC与LAI(r=0.93, p＜0.01),DM(r=0.94, p＜0.01),N%(r=0.82, p＜0.01)之间均达到了极显著水平;用CC估算LAI,DM和N%的模型均为幂函数,方程式分别是y=3.281 2x0.763 9,y=283.658 1x0.553 6,y=3.064 5x0.932 9;用与建模相独立的数据对模型验证,结果表明,CC估算LAI模型的实测值与模拟值基于1∶1直线的R2,RMSE和RE分别是0.996,0.035和1.46%;CC估算DM模型的R2,RMSE和RE分别是0.978,5.408 g和2.43%;CC估算N%模型的R2,RMSE和RE分别是0.990,0.054和2.62%。综上所述,模型能够较准确的通过CC估算不同氮肥水平条件下玉米9叶展时期、抽雄期和灌浆期的LAI,DM与N%,表明应用数码相机的光谱信息可实现对玉米生长过程中的生长状况及氮素营养状态进行实时无损快速监测与预测。     

棉花冠层水分含量估算的高光谱指数研究

适宜的光谱指数对于地表参数高光谱诊断模型的估算精度具有决定性作用。通过不同棉花冠层水分含量表征参数冠层等效水厚度EWT_canopy, 植株含水量VWC及其对应的光谱数据分析,构建350～2 500 nm范围内所有波段两两组合的比值指数RVI和归一化指数NDVI,分析水分含量表征参数与所有指数之间的相关关系,筛选最大相关系数对应的指数作为最佳水分指数,利用新指数构建水分含量表征参数的估算模型,并与已知的各种水分指数估算精度进行比较。结果表明：新建比值指数R_{1 475}/R_{1 424}及其归一化指数(R_{1 475}-R_{1 424})/(R_{1 475}+R_{1 424})对EWT_canopy的估算效果最佳,由其得到的估算值与实测值之间的相关系数r值达到0.849;已知指数(R₈₃₅-R_{1 650})/(R₈₃₅+R_{1 650})对VWC的估算效果最佳,由其得到估算值与实测值之间的相关系数r值为0.805。     

四种姜黄素类似物核磁共振谱的理论研究

在B3LYP/6-31G(d, p)水平下优化了四种姜黄素类似物的几何构型,并通过振动分析验证了其构型稳定性。在B3LYP/6-311G(d, p)水平下计算了该类化合物的核磁共振谱,研究结果表明：四种化合物主体结构共平面性较好,为一较大共轭体系。由于羟基及甲氧基的引入,使Compound-B/C/D中C₃,C₄以及Compound-A/D中C₅均具有较大δ值,Compound-A中C₄和C₆的δ值相对较小,C₃的δ值相对较大。而在羰基与碳碳双键所形成的共轭羰基化合物中,羰基C₁₃的δ值(183 ppm)相对于乙醛中的δ值(201ppm)有所减小,C_{11, 15}(α碳)的δ值(122 ppm)相对减小,而C_{9, 17}(β碳)的δ值(145 ppm)相对增大。最后,通过线性回归方法,利用相关系数值r研究了1H NMR δ值的实验和理论计算值的相关性,结果表明相关性较好,实验值和理论值基本吻合。     

应用近红外光谱法建立伤疖膏制备过程中黄芩苷含量模型

建立一种伤疖膏制备过程提取液中黄芩苷动态含量快速测定的近红外光谱分析方法,近红外透射光谱法扫描得到65组伤疖膏制备过程中提取液的近红外光谱图,以提取液中黄芩苷的HPLC测量值作为对照值,采用偏最小二乘回归算法(PLSR)建立NIR光谱与对照值的校正模型。校正模型主成分数为8,交叉验证均方根差(RMSECV)为0.006 8,相关系数(r)为0.999 1。应用校正模型对预测集的30组样品进行黄芩苷含量预测,所得预测均方根差(RMSEP)为0.009 2,r为0.998 7。结果表明,该方法快速、准确,为复方膏剂制备过程中化学成分快速定量和质量控制提供了方法和依据。     

辽东湾海冰反射特性

海冰反照率是研究海冰表面特性、海冰分布、海冰厚度和极地气候的重要光学量之一。将卫星于不同位置所测量到的海冰双向反射率准确地转化为相应的反照率的值,对于获得大规模海冰的时空特性是非常重要的。研究了辽东湾海冰反照率与海冰双向反射分布函数之间的相关关系。结果表明：(1)反照率与海冰组分密切相关,海冰表层颗粒物浓度越高,反照率α(λ)的值越小,气泡的含量越高,α(λ)越大;(2)当仪器探头天顶角θ为0°时,所测量的双向反射因子R_f与反照率α(λ)的值是相似的;随着θ的增大,R_f的值逐渐增大,且与探头方位角的相关性逐渐增强;当θ的值等于太阳天顶角63°时,R_f的值最大,且与探头方位角的相关性最强;(3)不同类型的冰具有不同的各向异性反射因子。     

丹参等11种中药金属元素含量测定及聚类分析研究

采用原子吸收分光光度法检测了丹参、枸杞子、党参、绞股蓝、冬虫夏草、黄芪、肉桂、细辛、龙胆草、山茱萸、杜仲共11种中药中钾、钙、镁、铁、锰、铜、锌和铬元素的含量, 运用模糊分类方法研究药物金属元素与药物疗效的相关性。结果显示,相关系数r=0.50时,有7种药物聚类相似;相关系数r=0.65时,有3种药物聚类相似;r=0.75时,有2种药物聚类相似。药物中金属元素含量丰富,相关系数较大的药物,其药物疗效相似性较大,揭示中药中微量元素与药物疗效密切相关。该研究为中药的质量评价提供一种新的方法,为研制新型的药物提供了有用的科学数据。     

稻壳热解的动力学模拟

生物质热解过程的动力学行为研究对于热化学转化过程机理的掌握和热化学转化技术的开发具有重要意义.本文采用Miller模型对稻壳在低升温速率下的热解进行了动力学模拟,并利用热重分析实验结果对模拟过程的有效性进行了对比验证.模拟计算结果显示气体百分含量在650～780K范围内随温度升高迅速增加,炭含量在500～680K之间随温度升高迅速下降,焦油含量随着温度升高在650K左右达到最高值.同时升温速率的提高可以抑制炭的生成,增加气体和焦油最大产量,在100K/min的升温速率下,气体产量在780K达到最大56.3%,焦油产量在678K左右达到最大26.8%.     

基于模糊识别的苹果花期冠层钾素含量高光谱估测

依据2008年和2009年2年在栖霞试验区利用地物光谱仪ASD FieldSpec3测定的苹果花期冠层高光谱和实验室内测定的钾素含量数据,以冠层高光谱反射率及其11变换形式与钾素含量分别进行相关分析,以相关系数最大者为自变量,采用模糊识别算法,建立钾素含量估测模型;以2008年的检验样本对模型进行检验,并利用2009的独立试验数据对模型进行验证。结果表明,原始光谱反射率(R)及其倒数(1/R)、对数(lgR)、平方根(R1/2)与钾素含量的相关性较差,但它们的一阶微分和二阶微分与钾素含量之间的相关性明显增强;建立的钾素含量估测模型=11.344 5h+1.309 7的相关系数r为0.985 1,总均方根差RMSE为0.355 7,F统计量为3 085.6;24个检验样本实测值与估测值的平均相对误差为9.8%,估测精度为90.2%;2009年试验验证精度达到了83.3%。表明模型用于苹果花期冠层钾素含量的估测具有较高的稳定性,模型精度能满足生产上对苹果钾素含量估测的要求。     

The Characterization of Pyrolytic Carbon Black Prepared from Used Tires and Its Application in Styrene–Butadiene Rubber (SBR)

The pyrolytic carbon black (PCB) made from used tires was used in styrene‐butadiene rubber (SBR). The basic properties of PCB were characterized. The effects of PCB on the processing properties of SBR compounds and the mechanical properties of vulcanizates were investigated and compared with other traditional fillers. The results showed that the chemical composition of PCB was mainly C, O, S, Zn and Si. The content of ash wa as much as 13.3%. The SEM photos showed that the primary particle size of PCB was smaller than that of N774, but the aggregate size was larger than that of N774. The effect of PCB on the processing properties of SBR compounds was similar to that of other fillers. The reinforcing effect of PCB was similar to that of N774, but inferior to that of N330.     

The phase and morphological inhomogeneity of the Ti-C system deposits formed at the plasma-titanium substrate interface

We have studied the mechanism of structure formation and the local chemical composition of the Ti-C system deposits formed at the interface between a carbon-argon-titanium plasma and a titanium substrate under conditions of the titanium content in the plasma decreasing with time. The deposits were studied in a scanning electron microscope (SEM) equipped with an energy-dispersive X-ray (EDX) analyzer. The spatially distributed growth of various structural modifications of carbon in the deposit is related to the mass transfer redistribution at the substrate surface and to the selective deposition of adatoms forming sufficiently stable chemical bonds to the growth surface in the thermal accommodation stage.     

Radiofrequency plasma beam deposition of various forms of carbon based thin films and their characterization

The characteristics of carbonic materials obtained by downstream deposition in a low pressure argon plasma beam injected with acetylene are reported. The influence of substrate temperature, presence of Ni catalyst and hydrogen in gas composition on the material properties is described. By increasing the substrate temperature, an enhanced order in the material is revealed by Raman spectroscopy, while FTIR measurements show a decreasing of the hydrogen content and the disappearing of sp¹ hybridized carbon in the deposit. The SEM and Raman investigation show a clear tendency of crystalline phases formation when hydrogen is assisting the deposition.     

以醇溶剂为碳源制备碳点的荧光性能

以乙二醇和丙三醇为碳源,用一元醇（异丙醇和乙醇）为对比,通过溶剂热法制备得到碳点。通过傅里叶红外光谱、紫外-可见吸收光谱和激发光谱对所制得的碳点进行表征和分析,探讨了不同碳源对碳点的表面官能团、荧光性能等的影响,从而分析其荧光的发光机理。结果表明：乙二醇与丙三醇制备的碳点含有C=C键和C=O键,均在365 nm光激发后在450 nm处有荧光峰;而一元醇是由C-OH基团中的孤对电子产生荧光,碳源分子中羟基含量对碳点的荧光性能有很大影响,羟基含量越高,越容易形成双键结构。     

水稻秸秆田间焚烧残留物的结构特征初探

秸秆焚烧残留物(生物质炭,biochar)因其特殊的结构特征,对土壤的碳固定及其污染物的迁移转化行为产生重要的影响。本文利用扫描电镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)等一系列定性定量分析方法研究了田间不同焚烧强度下产生的稻杆残留物的基本理化性质及结构特征。结果表明: 田间秸秆焚烧残留物的基本理化特征与焚烧强度密切相关。焚烧强度越高,TOC含量越低,但所产生残留物中碳原子的有序度增加,其中的脂肪性成分逐渐减少而芳香性则逐渐增加。此外,有机组分对田间秸秆焚烧残留物比表面积的贡献较为显著。     

Synthesis of anatase titania-carbon nanotubes nanocomposites with enhanced photocatalytic activity through a nanocoating-hydrothermal process

Anatase TiO₂ nanoparticles were covalently anchored onto acid-treated multi-walled carbon nanotubes (MWNTs) through a nanocoating-hydrothermal process to obtain TiO₂-MWNTs nanocomposites. The composition and structural properties of the nanocomposites were characterized by XRD, BET, TG, TEM, HRTEM, EDX, XPS, and FTIR, and the formation of ester-bond linkage between TiO₂ nanoparticles and MWNTs was demonstrated. The enhanced photocatalytic activity of TiO₂-MWNTs nanocomposites was probed by photodegradation reaction of methylene blue under visible-light irradiation.     

Improving the thermal properties of fluoroelastomer (Viton GF-600S) using carbon nanotube

Nanocomposites were prepared using carbon nanotubes (CNTs) in the formulations of fluoroelastomer (FE). Thermogravimetric analysis (TGA) results revealed that CNT improved the thermal properties of FE, resulting in higher amount of FE and char remaining within the temperature range of 520–900 °C, relative to unfilled FE and carbon black (CB)-filled FE. The same results also revealed that more percentage of FE was undegraded or less degraded especially near CNT. Energy dispersive X-ray (EDX) results indicated that the percentage of carbon and fluorine in the residue of TGA scans up to 560 °C of CNT-filled FE (CNT/FE) were higher compared to the CB-filled FE (CB/FE), and CB/FE was higher than FE. EDX results of TGA residue (run up to 900 °C) showed that most of the undegraded FE which was not degraded at temperatures below 560 °C was degraded from 560 °C to 900 °C in both CNT/FE and CB/FE, with the char in CNT/FE being more than that in CB/FE. Residue of samples after TGA scans up to 900 °C indicated that, Zn did not undergo any reaction with CNT in the CNT/FE. In CB/FE, some percentage of ZnO reacted with carbon. EDX analysis of thermal aged specimens under air showed that with increasing aging time, more percentage of C, O, and F were lost from the surface of filler/FE and FE. The order of element loss is: CNT/FE < FE < CB/FE.     

Determination of the provenance of medieval silver coins: potential and limitations of x‐ray analysis using photons,electrons or protons

One hundred and fifty seven ‘Tiroler Kreuzer’, a medieval currency from the county of Tyrol/Austria, were analysed in order to determine their place of mintage. The silver coins were produced during the 15th century in the mints of Merano (South Tyrol) and Hall (North Tyrol) but they have no marks or punches which would allow a clear distinction. Energy‐dispersive x‐ray fluorescence analysis (EDXRF) was applied without sampling in order to determine the silver contents and also minor (Cu, Pb, Bi) and trace elements (Fe, Au, Hg, Ni). Owing to corrosion processes, which changed the chemical composition of the surfaces of the coins, investigations of cross‐sections were necessary using energy‐dispersive x‐ray microanalysis in a scanning electron microscope (SEM/EDX) to determine the stage of corrosion and the Ag concentration of the core of the coins. The results showed differences of up to 50% between the composition of the core and the surface. Finally, proton‐induced x‐ray emission (PIXE) at an external proton beam was applied, in order to detect also Ni, an element which could not be measured by either EDXRF or SEM/EDX in the ppm range. The data show a clear difference in the Ni content between the coins from Merano (～0.1% Ni) and Hall (～0.01% Ni). Copyright © 2003 John Wiley & Sons, Ltd.     

生物炭施用对土壤磷及磷酸酶活性影响的可见和荧光光谱法研究

含碳丰富的秸秆在无氧或限氧的条件下低温热解后得到生物炭可施入土壤,有利于缓解秸秆处理压力、减少污染、减少温室气体排放,并改良土壤。在重要的农粮基地辽宁潮棕壤上布置了生物炭还田试验。玉米田施用不同量的生物炭(0,360,1 800和3 600 kg·ha-1)一个生长季后,研究土壤有效磷(P)、有机P和全P含量的变化,并采用荧光共轭物质作为测定底物,通过酶解产生荧光物质研究土壤磷酸酶活性的响应。结果表明,生物炭添加到土壤后,土壤有效P含量随生物炭施用量增加而显著升高、有机P和全P的含量没有显著的变化。其原因是生物炭携带有效P而引起的。碱性磷酸单酯酶和磷酸二酯酶活性随生物炭添加量的增加而增大,适量生物炭处理(1 800 kg·ha-1)可显著增加酸性磷酸酶,而高量生物炭处理(3 600 kg·ha-1)对酸性磷酸酶略有抑制,可能是生物炭自身的偏碱性使土壤pH值增大所致。生物炭的添加对土壤磷素和磷酸酶活性的影响是土壤物理性质、化学性质及土壤微生物群落结构和代谢能力的综合体现,需要进一步深入研究。     

Microwave-assisted digestion for trace elements analysis of tree nut oil: evaluation of residual carbon content

Abstract

An inductively coupled plasma mass spectrometer method for estimating trace elements in tree nut oils has been developed which employs microwave digestion equipped with high pressure subassembly. Residual carbon content and residual acidity were determined to evaluate the efficiency of digestion. The best digestion efficiency was obtained using Easyprep? system with 0.5?g of oil, 4?mL concentrated nitric acid, and 2?mL hydrogen peroxide, and a final temperature of 235?°C. Residual carbon content and residual acidity were estimated as 1.7% (corresponding to 852?mg L^?1 of carbon in sample solution) and 7.5%, respectively, and recovery values ranged from 90.7% to 107.7%. Whereas, only 0.2?g of oil could be digested through conventional microwave system with 5?mL concentrated nitric acid and 2?mL hydrogen peroxide at 205?°C (residual carbon content?=?3.2%). The developed method has been applied to determine nine trace elements (Cr, Mn, Fe, Ni, Cu, As, Zn, Cd, and Pb) in different categories of tree nut oils, and high content of Fe, Mn, and Zn were found in some of those oils. To the best of our knowledge, the present investigation is the first attempt to analyze trace elements in different categories of tree nut oils consumed in China.