激光诱导击穿光谱技术检测土壤中的铅和镉含量

为了满足土壤重金属快速准确检测的需求,同时为土壤的重金属污染防治和农业的可持续发展提供理论指导,该研究利用激光诱导击穿光谱(laser-induced breakdown spectroscopy,LIBS)技术结合定标曲线法和化学计量学方法对土壤中重金属铅(Pb)和镉(Cd)元素进行定量分析。在获取LIBS数据之后,结合土壤LIBS发射谱线中Pb和Cd谱峰信息以及美国国家标准与技术研究院(national institute of standards and technology,NIST)的标准原子光谱数据库,选取了Pb和Cd的特征谱线分别为Pb I 405.78和Cd I 361.05 nm。首先对谱线信息进行预处理后,根据谱峰信息和元素的含量,分别建立了基于谱线峰强度、归一化后洛伦兹拟合强度、谱峰积分强度与对应元素浓度之间的关系模型和定标曲线。对于Pb元素的3种定标方法得到的线性关系的决定系数(R2)分别为0.983 85、0.970 97、0.993 21,且模型反演的结果与实际值的相对误差较小;而Cd元素的3种定标方法没有得到明显线性关系。然后运用偏最小二乘回归(partial least-squares regression,PLSR)建立了土壤Pb和Cd元素的定量分析模型,Pb元素PLSR模型的结果与定标曲线法的结果类似,其预测的相关系数(RP)为0.948 5,预测均方根误差(RMSEP)为2.044 mg/g;而Cd元素的PLSR模型的结果比起定标曲线法有较大提升,其预测的相关系数(RP)为0.994 9,预测均方根误差(RMSEP)为97.05μg/g,结果说明PLSR方法在光谱化学分析领域中比定标曲线法进行定量分析有更好的适用性。研究表明,LIBS技术能够实现对土壤重金属Pb和Cd含量的定量检测,为开发实时便携式LIBS土壤重金属检测仪提供了理论基础。     

基于内定标法的大豆油中铬含量的LIBS定量分析

为了寻求大豆油中铬(Cr)的快速检测方法,应用激光诱导击穿光谱(LIBS)技术对大豆油中Cr含量进行定量检测研究,采用松木对大豆油样品中的Cr进行富集,并利用双通道光谱仪采集其LIBS光谱信号;选择钙(Ca)422.64 nm为内标线,并以Cr的原子谱线Cr I 425.44 nm、Cr I 427.48 nm、Cr I428.94 nm及3条谱线之和为分析线,应用直接定标法和内定标法分别建立上述分析线的定标曲线。结果表明,Cr I 425.44 nm建立的定标曲线性能最佳,直接定标法和内定标法所建立的定标曲线的拟合度R2分别为0.9598和0.9894,检测限分别为14.82μg·g~(-1)和8.45μg·g~(-1);3个验证样品预测的相对误差分别为11.32%、12.78%、12.48%和7.91%、4.28%、7.64%。由此可知,LIBS技术用于大豆油中重金属Cr的检测具有一定的可行性,松木富集结合内定标法能减少定量分析误差,提高大豆油中Cr含量的预测精度。本研究结果可为食用油中重金属的快速检测提供理论依据。     

基于激光拉曼光谱的脐橙内部品质无损检测

论文初步探讨了运用激光拉曼光谱技术来检测脐橙内部品质的方法。应用激光拉曼光谱仪获取脐橙拉曼谱线,通过对拉曼谱线处理与分析得到了预测脐橙果肉糖度和硬度的谱线特征值,以四个谱线特征值为输入参数、脐橙糖度和硬度为输出建立了三层BP神经网络模型。结果表明,模型的糖度预测值与实测值之间的误差总体方差为0.0656,模型的硬度预测值与实测值之间的误差总体方差为0.0062。研究表明,采用激光拉曼光谱技术检测脐橙内部品质是可行的。     

几种市售新鲜水果重金属含量及评价

对梧州市售的几种新鲜水果样品中的铅（Pb）、镉（Cd）、砷（As）、汞（Hg）含量进行检测,对被测水果中的重金属含量进行安全评价,结果表明,梧州市售的水果的重金属含量总体上是安全的,但有个别样品出现铅和汞含量超过国家标准。     

电感耦合等离子体质谱法测定饲料标准物质中总砷、铅、镉及其不确定度评定

通过比较不同前处理方式对饲料标准物质中总砷(As)、铅(Pb)、镉(Cd)的提取效果,建立了微波消解-ICP-MS测定饲料中重金属元素的方法。研究结果表明,饲料标准物质中总砷、铅、镉的回收率为89.4%～111%, RSD为1.8%～2.7%,准确度、精密度均满足检测需求。同时通过元素含量计算公式,对试验过程中引入的不确定度进行分析,并对影响试验结果的不确定度分量进行计算评定。评定结果显示,饲料标准物质中总砷、铅、镉的测量结果分别表示为As(2.94±0.43) mg/kg, Pb (4.04±0.48) mg/kg, Cd (0.379±0.063) mg/kg,包含因子k=2。     

基于光谱分析的土壤重金属含量估算研究——以三江源区玉树县和玛多县为例

以三江源区玉树县和玛多县为研究区,利用实验室测定的As、Cu、Pb、Zn、Cr、Cd、Hg元素含量和室内采集的土壤原始光谱及其4种转换形式,建立了光谱指标与重金属含量的多元回归模型,利用决定系数(R2)、相对分析误差(RPD)及均方根误差(RMSE)评价模型的精度。研究结果表明,土壤As、Cu、Pb、Zn、Cr、Cd含量与SOM、Fe、Mn、Al、Mg等元素具有显著相关关系,Hg元素则未达到显著性水平。As、Cu、Pb、Zn、Cr和Cd元素估算模型回归方程R2达到了0.5以上,均通过了显著性检验,其中Pb、Zn和Cr元素验证样本RPD均达到了1.4以上,模型具备粗略估算能力;As、Cu和Cd元素验证样本RPD均低于1.4,模型不具备粗略估算能力。Hg元素估算模型回归方程的R2为0.28,未能通过显著性检验,无法用于对Hg含量的估算。     

黔产薏苡仁及其产地土壤重金属污染的特征

[目的]探明黔产薏苡仁及其产地土壤重金属污染特征,为黔产薏苡仁产业可持续发展及其产地土壤重金属防控提供科学依据。[方法]以黔西南薏苡仁及其产地土壤为供试样品,分析测定土壤pH值、有机质、阳离子交换量(CEC)和5种重金属元素镉(Cd)、铅(Pb)、锌(Zn)、铜(Cu)、镍(Ni)的含量,运用GIS和单因子污染风险评价等方法,探讨土壤重金属空间分布和土壤重金属污染对薏苡仁品质安全的影响。[结果]①土壤中5种重金属Cd,Pb,Zn,Cu和Ni含量范围分别为0.01~1.35,10.09~34.70,80.39~236.36,22.54~131.42,26.75~137.76 mg/kg,其中,Cd,Cu和Ni的最大值均高于国家现行标准(GB15618-2018),表明研究区土壤中主要存在一定范围的Cd,Cu和Ni污染风险;综合污染指数为1.94,污染等级为轻度污染。②薏苡仁中Cd,Pb,Zn,Cu和Ni含量范围分别为未检测到~0.027,0.179~1.348,42.615~58.961,10.028~16.244,0.552~5.045 mg/kg,Cd未超标,而Pb,Zn,Cu和Ni均有不同程度的超标,超标率依次为90%,25%,75%和30%;薏苡仁对Pb具有很强的累积效应。[结论]通过同步采集土壤样品和对应的薏苡仁样品,分析结果能更好地评估土壤重金属污染对薏苡仁品质安全的影响。     

能量色散X 射线荧光光谱法快速检测含海藻酸 水溶肥中5 种重金属

建立含海藻酸水溶肥中重金属砷(As)、铅(Pb)、镉(Cd)、铬(Cr)和汞(Hg)的能量色散X 射线荧光光谱(EDXRF)快速检测方法。样品经称重、加酸涡旋,装入样品杯,直接进行EDXRF 扫描,通过识别待测元素特征能量谱峰进行定性,标准加入法进行定量。结果显示:方法选择性好,含海藻酸水溶肥基质元素对5 种重金属能量光谱无干扰;标准加入法能有效克服含海藻酸水溶肥的基质效应,实现对5 种待测重金属的准确定量;方法线性良好,R2>0.9950;检出限为0.21 ～ 6.70 mg/kg,定量限为0.70 ～ 22.40 mg/kg;加标回收率为96.83% ～ 110.63%,日内相对标准偏差为0.58% ～ 6.36%,日间相对标准偏差为0.64% ～ 6.61%。该方法操作简单、快速,有较高的准确性和可靠性,能够满足含海藻酸水溶肥产品中As、Pb、Cd、Cr 和Hg 元素快速质量监测的需要,为推动EDXRF 技术在农业领域的应用提供了有效借鉴。     

安徽省某市农田土壤与农产品重金属污染评价

为评价安徽省某市农田土壤与农产品重金属污染水平,在研究区内共布设1933个点位,采集土壤样品并在污染农田中采集43个农产品样品,对其与土壤进行一对一检测,分析研究Cr、Pb、Cd、As和Hg 5种重金属含量,对研究区农田土壤重金属含量水平、空间分布特征以及农产品重金属含量与土壤性质的关系进行分析。结果表明:研究区农田土壤中Cr、Pb、Cd、As和Hg的平均含量分别为62.5、32.6、0.209、8.85、0.080 mg·kg~(-1),点位超标率分别为0.05%、0、14.59%、0.67%和1.97%。根据单因子污染指数法评价研究区农田土壤污染情况,5种元素污染程度CdHgAsPbCr,从内梅罗综合污染指数来看,所有点位中清洁的占78.58%,综合生态风险指数法评价结果显示研究区基本处于轻微生态危害水平。农产品中Cr、Pb、Cd和As 4种重金属元素都是在偏酸性的土壤上富集系数较大,而Hg在偏碱性土壤上富集能力较强。     

福建省部分菜园土壤及蔬菜重金属含量的测量及污染评价

采集了福建省10个典型地区50份菜园土壤样品及32份小白菜样品,测定了土壤及蔬菜(小白菜)样品中的重金属含量,并采用单项及综合污染指数法对土壤及蔬菜的重金属污染进行评价分析,通过改进的BCR连续提取法测定了土壤中铅和镉的形态含量和分布,并对蔬菜中铅和镉的污染进行相关性分析。结果表明:菜园土壤和蔬菜大多存在不同程度的重金属污染,主要表现为以重金属Cd和Pb的污染。其中,德化浔中所采集的菜园土壤及蔬菜样品分别受Pb和Cd的污染特别严重;只有厦门同安、龙岩新罗地区的土壤及蔬菜则均未受重金属污染。此外,蔬菜对土壤中的Cd表现出极强的富集能力。土壤中Cd的酸可提取态比例平均为36.6%,而土壤中Pb的酸可提取态比例(除德化浔中达到13%外)则不足2%,但酸可提取态Pb的含量与蔬菜中的Pb含量具有极显著的相关性(r=0.952,P0.01),而Cd相应的相关系数只有0.66(P0.01)。     

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。     

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...     

红外光谱在土壤学中的应用

红外光谱技术在土壤学中已得到较广泛的应用,它能够综合地反映土壤体系的物质组成及其相互作用,为研究土壤中物质循环及其作用过程提供了新的手段。本文回顾了近年来红外光谱技术在土壤学中的应用,包括透射光谱在土壤定性分析中的应用,并重点介绍红外反射光谱与化学计量学相结合的光谱建模技术发展情况及其在土壤定量分析中的应用。同时本文探讨了基于光声效应的红外光声光谱技术,红外光声光谱非常适合用于土壤这种复杂、非透明体系的研究,能够克服传统透射和反射光谱中存在的缺陷,测定快速方便,并具有较高的灵敏度和测量精确度,具有很大的应用潜力。     

Compositional and functional features of humic acids from organic amendments and amended soils in Minnesota, USA

The use of organic amendments requires an adequate control of the chemical quality of their humic acid (HA)-like fractions and of the effects that these materials may have on the status, quality, chemistry and functions of native soil HAs. In this work, the compositional, functional and structural properties of the HA-like fractions isolated from a liquid swine manure (LSM), a municipal sewage sludge (SS), and two municipal solid waste composts (MSWCs) were evaluated in comparison to those of HAs isolated from three unamended soils and from the corresponding soils amended with LSW, SS, and MSWC at various rates in three field plot experiments conducted in Minnesota, USA. With respect to the unamended soil HAs, the HA-like fractions of the three amendments featured a greater aliphatic character, a marked presence of proteinaceous, S-containing and polysaccharides-like structures, an extended molecular heterogeneity, small organic free radical contents and a small degree of humification. The MSWC-HAs featured a larger degree of humification than LSM-HA and SS-HA. The three amendments affected in different ways and by various extents the compositional, structural and functional properties of soil HAs depending upon the nature, origin and application rate of the amendment. In general, the data obtained suggested that proteinaceous, S-containing and aliphatic structures contained in HA-like fractions of organic amendments were partially incorporated into native soil HAs.     

污泥堆肥和热干燥对土壤和土壤腐殖酸性质的影响

The effect of annual additions of composted sewage sludge (CS) and thermally dried sewage sludge (TS) at 80 t ha^-1 on soil chemical properties was investigated for three years in a field experiment under semiarid conditions. Humic acids (HAs) isolated by conventional procedures from CS, TS, and unamended (SO) and sludge amended soils were analysed for elemental (C, H, N, S and O) and acidic functional groups (carboxylic and phenolic) and by ultraviolet-visible, Fourier transform infrared and fluorescence spectroscopies. With respect to CS, TS had similar pH and total P and K contents, larger dry matter, total organic C, total N and C/N ratio and smaller ash content and electrical conductivity. Amendment with both CS and TS induced a number of modifications in soil properties, including an increase of pH, electrical conductivity, total organic C, total N, and available P. The CS-HA had greater O, total acidity, carboxyl, and phenolic OH group contents and smaller C and H contents than TS-HA. The CS-HA and TS-HA had larger N and S contents, smaller C, O and acidic functional group contents, and lower aromatic polycondensation and humification degrees than SO-HA. Amended soil-HAs showed C, H, N and S contents larger than SO-HA, suggesting that sludge HAs were partially incorporated into soil HAs. These effects were more evident with increasing number of sludge applications.     

Use of near‐ and mid‐infrared spectroscopy to distinguish carbon and nitrogen originating from char and forest‐floor material in soils

The presence of relatively inert organic materials such as char has to be considered in calibrations of soil C models or when calculating C‐turnover times in soils. Rapid and cheap spectroscopic techniques such as near‐infrared (NIRS) or mid‐infrared spectroscopy (MIRS) may be useful for the determination of the contents of char‐derived C in soils. To test the suitability of both spectroscopic techniques for this purpose, artificial mixtures of C‐free soil, char (lignite, anthracite, charcoal, or a mixture of the three coals) and forest‐floor Oa material were produced. The total C content of these mixtures (432 samples) ranged from 0.5% to 6% with a proportion of char‐derived C amounting to 0%, 20%, 40%, 50%, 60%, or 80%. All samples were scanned in the visible and near‐IR region (400–2500 nm). Cross‐validation equations for total C and N, C and N derived from char (C_char, N_char) and Oa material were developed using the whole spectrum (first and second derivative) and a modified partial least‐square regression method. Thirty‐six samples were additionally scanned in the middle‐IR and parts of the near‐IR region (7000–400 cm^–1 which is 1430–25,000 nm) in the diffuse‐reflectance mode. All properties investigated were successfully predicted by NIRS as reflected by RSC values (ratio of standard deviation of the laboratory results to standard error of cross‐validation) > 4.3 and modeling efficiencies (EF) ≥ 0.98. Near‐infrared spectroscopy was also able to differentiate between the different coals. This was probably due to structural differences as suggested by wavelength assignment. Mid‐IR spectroscopy in the diffuse‐reflectance mode was also capable to successfully predict the parameters investigated. The EF values were > 0.9 for all constituents. Our results indicated that both spectroscopic techniques applied, NIRS and MIRS, are able to predict C and N derived from different sources in soil, if closed populations are considered.     

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。     

Properties of dissolved organic matter related to soil organic matter quality and nitrogen additions in Norway spruce forest floors

The quality of dissolved organic matter (DOM) is highly variable and little information is available on the relation of DOM quality to the structure and composition of its parent soil organic matter (SOM). The effect of increasing N inputs to forest soils on the structure and composition of both SOM and DOM also remains largely unclear. Here we studied the release of DOM, its specific UV absorption and two humification indices (HIX) derived from fluorescence spectra from Oa material of 15 North- and Central-European Norway spruce (Picea abies (L.) Karst.) stands. The Oa material was incubated aerobically at 15 °C and water holding capacity over a period of 10 months and extracted monthly with an artificial throughfall solution. Soil respiration was determined weekly. The influence of mineral N inputs on composition of DOM and on respiration rates was investigated on periodically NH₄NO₃-treated Oa samples of eight selected sites. Release of dissolved organic carbon (DOC) from untreated Oa material samples ranged from 0.0 to 58.6 μg C day⁻¹ g C⁻¹ and increased with increasing C-to-N ratio. One HIX and UV absorption of DOM were negatively correlated to the degree of oxidation of lignin-derived compounds and positively to the C-to-N ratio and – HIX only – to the aromatic C content of SOM. Mineral N addition had no distinct effect on respiration rates. In six of eight samples the N-treatment caused an increase in specific UV absorption or one HIX of DOM. However, these effects were not statistically significant. Addition of mineral N did not affect the rates of DOM release. Our results show that properties of SOM largely determine the amount and quality of DOM in forest floors. Changes of DOM quality due to mineral N additions are likely, but we cannot confirm significant changes of DOM release.     

基于光子传输模拟的苹果品质高光谱检测源探位置研究

光谱无损的检测方法是质检测最常用的方法之一。传统的光谱仪光源探头位置和源探距离相对固定,导致品质检测精度受限。为解决这个问题,提出基于蒙特卡洛的苹果多层组织的光子传输模拟,分析了光子入射最佳位置和源探距离,并用点光源高光谱仪实际拍摄红富士苹果进行验证。分析表明,光子在苹果赤道位置入射,具有73.12%概率到达更深的深度。源探距离与苹果的光学参数有关,形状为圆环,源探距离内外半径为1.5～10.15 mm。点光源高光谱仪采集红富士苹果的光谱信息,光子入射位置为赤道,源探距离为距离光源点半径2.7～11.7mm的圆环,与模拟数据分析结果基本一致。蒙特卡洛光子传输模拟方法为研究高光谱苹果品质无损检测开辟了新思路,分析结果可以为研究高光谱品质检测试验设计和苹果便携式品质检测光学仪器设计提供理论基础。     

Near-Infrared Reflectance Spectroscopy as a Method for Determining Organic Carbon Concentrations in Soil

Near-infrared reflectance spectroscopy (NIRS) has the potential to be a reliable method for accurately quantifying soil organic carbon (SOC). The objective of this study was to evaluate NIRS as a method for predicting SOC. Partial least squares (PLS) regression was used to predict SOC from soil reflectance values or the first derivative of the reflectance values. Two model validation techniques were evaluated: One was a full cross-validation and in the other 30 percent of the samples were removed from the calibration data set and then tested using the calibrated model. Significant relationships were observed for predicted SOC when compared to laboratory-measured SOC for all models evaluated, regardless of validation technique. The prediction models using the first derivative of the reflectance values outperformed prediction models using the reflectance values alone. In conclusion, NIRS can be used as a quick and accurate method for measuring SOC.