微波消解-电感耦合等离子体质谱法测定有机肥中镉、砷、汞、铅、铬含量

采用电感耦合等离子体质谱法（ICP-MS）测定,比较湿法消解30 min,湿法消解至近干和微波消解等不同前处理方法对有机肥料中镉、砷、汞、铅、铬元素的提取效果,建立了一种基于ICP-MS测定有机肥料多种重金属元素含量的方法。结果表明：湿法消解至近干和微波消解法对有机肥多元素成分分析标准物质（RMH-F001）中5项重金属含量的测试结果均满足标准要求,方法定量值、标准值偏差分别低于6.3%、5.7%;硝酸/过氧化氢体系-微波消解处理下,样品结果稳定性最佳,相对标准偏差为0.8%～6.8%,相对偏差为1.1%～9.0%,相对相差为2.2%～18.0%,加标回收率为99.4%～102.9%。硝酸/过氧化氢体系-微波消解-ICP-MS法可作为有机肥中5项重金属统一化测定的常规方法。     

微波消解—火焰光度法测定植物中全钾的研究

研究了采用HNO3—H2O2—HCl酸体系对植物样品进行微波消解,采用FP 640火焰光度计测定3种植物标准物质中全钾的含量。5个平行测定结果均在其证书标准值范围内,方法相对标准偏差为0.6%~1.6%,结果令人满意。     

微波消解塞曼火焰原子吸收法测定土壤中重金属元素的方法研究

利用光纤压力自控密闭微波消解系统和采用正交实验等方法,优选了微波消解土壤的酸用量、微波时间及压力强度等项指标。实验结果表明,在供试条件下,以HNO33ml、HClO42ml、HF3ml混合酸作消解液,采用0.5MPa3min、1 5MPa5min二段微波消解方式,可获得满意的检测结果,其准确度和精密度均符合土壤环境样品分析要求,具有操作简便、快速、经济的特点,并可在同一消解液中分别测定土壤Cu、Zn、Pb、Cd、Cr、Ni等重金属元素,是测定土壤重金属元素含量的有效方法。     

甲亚胺测定土壤有效硼的前处理方法研究

土壤有效硼测定通常采用甲亚胺-H比色法,该方法前处理(煮沸)过程分析效率低、操作步骤不易掌控,极易给测定结果带来较大误差。为此,以山西省标准土样TCB-2为检测样品,对甲亚胺-H比色法的煮沸提取步骤进行了改进,分别试验了水浴提取、微波提取时间对土壤有效硼测定的影响,确定水浴法最佳提取时间为50 min,微波提取时间为90 s。对国家土壤标准物质GBW07412a检测结果表明,水浴提取和微波提取测定结果与标准参照值符合,相对标准偏差分别为3.43%和8.91%。     

微波消解原子吸收光谱法测定土壤中铅镉铬铜

采用微波消解进行样品前处理,原子吸收光谱法测定土壤中铅、镉、铬、铜,对样品前处理、基体改进剂等一些影响因素进行了探讨。利用该方法对土壤样品进行了测定,回收率为91%～114%,相对标准偏差为2.8%～7.4%,并利用国家标准物质验证了方法的准确度。该方法快速、准确,能够满足土壤中铅、镉、铬、铜的分析要求。     

微波消解—ICP-MS法测定有机肥料中8种元素

采用电感耦合等离子体质谱法(ICP-MS)测定,来比较不同混合酸体系对有机肥料中As、Pb、Cd、Cr、Hg、Ni、Cu、Zn 8种元素的提取效果,建立了微波消解—ICP-MS测定有机肥料多元素含量的方法。研究结果表明,8种元素在0.10～1600 μg/L质量范围内线性关系良好,线性相关系数为0.99970～0.99995,检出限范围为0.003～0.400 μg/L。三水平加标回收率范围为81.8%～108.0%,相对标准偏差为0.9%～4.9%(n=6)。国家标准物质灌木枝叶GBW07603(GSV-2)除汞元素缺少相应的认定值以外,其余7种元素的测定值均在标准物质证书认定值的范围内,且相对标准偏差为0.5%～5.0%(n=6)。该方法灵敏度、准确度高,可实现有机肥料中多元素的通量检测。     

微波消解法测土壤中全磷和全钾

用微波消解法测定土壤标准样品、标准方法测定消解液P和K含量,通过实验确定最佳消解及分析条件;而且比较微波消解法和传统电热板消解法的精密度和准确度,建立微波消解技术测定土壤P和K前处理方法.结果表明:土壤样品用1∶1HNO3∶HF 10ml的混酸体系进行消解,效果最佳;对于土壤标样,微波消解法测定P和K的相对标准偏差分别为1.46%～3.20%和0.38%～0.84%,电热板消解法测定P和K的相对标准偏差分别为3.06%～4.15%和0.40%～2.08%,微波消解法的测出值均高于电热板消解法;微波消解法的准确度和重现性明显优于电热板消解法,与标准值的相对相差比较,微波消解法都低于5%;两种试验方法样品回收率测得为94%～105%,符合分析方法要求.方法快速简便并有较高准确度、精密度,值得推广和应用.     

岷江成都段底泥中重金属的原子吸收多元素同时测定及趋势分析

在单元素原子吸收法的基础上，使用瓦里安SpectrAA220FS原子吸收光谱仪，建立了底泥中部分金属元素的原子吸收多元素同时测定方法。应用本法测定了岷江成都段底泥中的部分金属元素铜、镍、锌、铅、镉的含量，分析了污染物质的分布规律与变化趋势，为水环境研究、保护和管理提供更快捷方便的测试方法。     

红河野生马蹄香根茎及花中金属元素含量分析

采用火焰原子吸收光谱法分别测定了红河州个旧和蒙自2个地区的野生马蹄香根茎和花中金属元素Fe、Ni、Pb、Cd、Co、Cr、Cu、Zn的含量。结果表明:马蹄香根茎和花中金属元素的含量,根茎低于花。个旧地区马蹄香根茎中的金属元素含量高于蒙自地区,而花中金属元素含量个旧地区则低于蒙自地区,马蹄香根茎和花中的金属元素含量由高到低顺序均为:Fe>Zn>Cu>Pb>Ni>Co>Cd>Cr。     

微波消解-ICAP法测定土壤中总铬含量的研究

采用微波消解仪对土壤样品进行前处理,用ICAP测定土壤中总铬含量。通过硝酸-氢氟酸以及硝酸-盐酸-过氧化氢体系消解液对土壤样品消解,优化试验选择出微波最佳消解条件和ICAP的工作参数。结果表明,发现用硝酸-氢氟酸体系消解液,在谱线283.56 nm、267.72 nm处用ICAP能够准确而稳定地测得土壤中总铬含量。     

Trace Element Analysis via Open‐Vessel or Microwave‐Assisted Digestion in Calcareous Mediterranean Soils

Abstract

Different digestion methods can be applied for analyzing trace elements in soils. Selection of the most useful and convenient method is critical for the adequate determination of their concentrations in each type of soil to appropriately detect potential environmental pollution. Open‐vessel digestion using a digester block (method 1) and microwave‐assisted digestion (method 2) were compared using a certified reference material (CRM) with similar properties and characteristics to calcareous Mediterranean soils. Both methods were contrasted in terms of accuracy by calculating the recovery of cobalt (Co), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in the CRM and precision of replicate analysis through the relative standard deviation (RSD). Recoveries from the digester block method were slightly higher than recoveries from microwave digestion because the use of perchloric acid (HClO₄), whereas RSD values for microwave digestion were generally lower but with higher measured precision than values obtained by open‐vessel digestion. The digestion methods were compared for analyzing trace elements in calcareous agricultural soils devoted to vegetable crops in the Alicante province (southeast Spain), as a representative area of the European Mediterranean region. Results of the paired‐sample t‐test showed significant differences between both methods for Co, Cr, Cu, and Pb in calcareous Mediterranean soils, whereas regression analysis indicated a good correlation between both methods for Cu, Ni, Pb, and Zn. Consequently, the choice of the digestion method is more relevant for minor elements such as Co and Cr. Microwave‐assisted digestion seems to be the best option to determine most of the trace elements in calcareous Mediterranean soils, because closed‐vessel digestion exhibited lower variability according to the RSD values obtained in the study area, particularly for Co and Cr. Trace element concentrations were in agreement with background levels, except for Cu and Pb in some soils, which seem to be related to anthropic activities.     

疏解棉秆的微波干燥动力学及能耗分析

为了研究疏解棉秆微波干燥过程中装载量对干燥时间、干燥速率、干燥效率以及单位能耗的影响,该试验采用微波频率为2 450 MHz,输出功率为1 k W的微波干燥设备,装载量范围在34~200 g的疏解棉秆进行干燥。结果显示:干燥过程经过一个短暂的升速后较长时间处于降速阶段;采用7种常见薄层干燥模型对干燥数据进行非线性拟合,通过比较决定系数、均方根误差、离差平方和,发现Midilli模型是表述疏解棉秆微波干燥的最优模型,干燥系数随着装载量的增加而减小;装载量从34 g增加到200 g时,干燥时间也随之从10 min增加到20 min;疏解棉秆的水分有效扩散系数随着装载量的增加而减小,其平均值介于1.8078×10-8~4.1997×10-8 m2/s,同时基于Arrhenius方程,求得平均活化能为4.82 W/g;装载量在34~200 g时,通过提高装载量能够提高微波干燥效率(7.52%~19.78%),同时降低微波干燥的单位能耗(12.49~35.90 MJ/kg)。研究结果为棉秆的干燥和工业化生产提供参考。     

Comparison of microwave digestion with conventional wet ashing and dry ashing digestion for analysis of lead, cadmium, chromium, copper, and zinc in shellfish by flame atomic absorption spectroscopy

A closed vessel microwave digestion procedure was developed for shellfish samples. This procedure was compared with wet and dry ash procedures for levels of lead, cadmium, chromium, copper, and zinc. Results obtained for microwave and conventional wet ash digestion were comparable. The dry ashing procedure produced results consistently lower than either of the other methods. Recoveries ranged from 80-92% for microwave and wet ashing procedures and 54-72% for the dry ashing procedure. Accuracy was also determined by analyzing lobster hepatopancreas marine reference material. Values for Pb, Cd, and Cr fell within the range specified for the reference material for all 3 digestion procedures; however, values were lower for Cu and Zn. Results of this study show that microwave digestion is comparable to wet ashing.     

土壤总砷测定前处理方法探讨

采用加标回收方法比较研究了5种土壤总砷测定的前处理方法(分别为浓HNO3-浓H2SO4-HC1O4法、王水法、浓HNO3-浓H2SO4-V2O5法、浓HNO3-浓H2SO4-V2O5Ⅰ法和浓HNO3-浓H2SO4-V2O5Ⅱ法),结果表明,5种前处理方法的加标回收率在89.9%～102%之间,变异系数在0.56%～5.27%之间。其中,浓HNO3-浓H2SO4-V2O5Ⅰ法处理,土壤所用消解时间40min左右,其回收率较高,在98.5%～99.1%之间,变异系数较小,在0.56%～0.85%之间;该前处理方法具有消解时间最短、加标回收率和精密度高及重现性最好的特点,优于其他4种前处理方法,可作为推荐方法应用。     

化学与生物预处理对玉米秸生物气产量影响的初步比较研究

为实现玉米秸的高效能源化转化，提出通过生物与化学预处理提高厌氧消化效率和生物气产量的新方法。研究了经白腐真菌Pleurotus florida生物处理和经氢氧化钠、氨水与尿素化学处理后，玉米秸主要成份木质素、纤维素、半纤维素、总氮和干物质等的变化规律，及其对生物气产量的影响。对经不同处理后的玉米秸进行了相应厌氧消化试验。结果显示，除尿素处理外，所有其它处理都可不同程度地提高玉米秸的产气量；其中，经氢氧化钠处理的获得了最高的产气量，与未处理和经生物处理的玉米秸相比，其产气量分别提高了78.3%和13.2%。由于化学处理方法简单、管理容易、处理时间短，并可获得较高的产气量，因此，在大规模应用时，推荐使用氢氧化钠作预处理（添加量为干物质质量的8%）。该研究结果为大幅提高玉米秸的产气量提供了一个新的有效的方法。     

Elemental analysis of solid samples by low temperature plasma ashing and microwave acid digestion

Sixteen elements (Mn, Zn, Cu, Fe, B, Sr, Ba, Cr, Pb, As, Cd, Ni, Co, Se, Sb, Hg) were determined in oils, sediments, plants and marine organisms by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) or by Graphite Furnace Atomic Absorption Spectroscopy (GF-AAS) after plasma ashing followed by microwave acid digestion with HNO₃/HCl/H₂O₂. Soil and sediment samples were treated directly in the microwave oven without ashing, but the complete procedure must be applied in case of high organic content. The method was tested on a variety of standard reference materials. Good recoveries were obtained for most of the considered trace elements with less time and reagents consumption than conventional open vessels acid digestion procedures. Hg was determined with good recovery in soil samples by the same method and in organic materials by a modified procedure involving digestion of fresh material with nitric acid in a reflux quartz system.     

A comparison between the H2SO4‐H2O2‐Li2SO4‐Se oxidation method and alternative digestion procedures for plant nutrient analysis.

Abstract

Ca, Mg, Na, K and P contents of 3 plant tissues obtained by H₂SO₄‐H₂O₂‐Li₂SO₄‐Se peroxidation digestion were compared with those determined by mixed acid (HNO₃‐H₂S0₄‐HC10₄) and dry ashing procedures. Differences between methods were not consistent between elements or tissue types but the mixed acid digestion generally yielded higher Ca, Mg and P values than did dry ashing and peroxidation. Tissue K contents estimated by both wet digestion techniques were not significantly (P ≤0.05) different. Differences in Na values between digestion methods were highly inconsistent between tissue types and the precision of the Ma data was poor. N contents determined by peroxidation digestion and a conventional Kjeldahl method agreed closely.     

Determination of Major and Trace Elements in Plant Samples by Inductively Coupled Plasma–Mass Spectrometry

The determination of several trace elements [arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), molybdenum (Mo), nickel (Ni), and lead (Pb)] in plant samples using inductively coupled plasma–mass spectrometry (ICP‐MS) was evaluated. It was established experimentally that moderate amounts (0.2–2%) of dissolved solids decreased the analyte signals significantly. Internal standardization with Rh was efficiently used to compensate for these matrix effects. The accuracy of the method was verified using reference materials digested according to two different procedures: dry ashing and microwave digestion. No significant differences were observed between measured concentrations and certified values. The investigation was next extended for the determination of major elements [aluminum (Al), boron (B), calcium (Ca), iron (Fe), potassium (K), magnesium (Mg), manganese (Mn), sodium (Na), phosphorus (P), and zinc (Zn)] on the same reference materials. The ICP‐MS values agree well with the values supplied. However, it appeared that Sc was the most useful internal standard for major elements.     

基于Kjeldahl与Dumas方法的农作物秸秆总氮含量分析

凯氏定氮法(Kjeldahl)与杜马斯燃烧法(Dumas)是测定农业生物质总氮含量的主要检测手段,但二者的测定结果数值存在差异。该研究获取农作物秸秆样本(水稻、小麦、玉米、油菜和棉花)共计1 179个,分别采用Kjeldahl和Dumas方法测定总氮(TKN和TCN,total Kjeldahl nitrogen and total combustion nitroyen)含量,通过多种统计与分析方法,系统分析比较了不同农作物秸秆总氮含量及其分布的异同和相关关系。结果表明:不同农作物秸秆氮含量分布均呈非正态分布,建议采用中位数统计;5种秸秆总体的TKN质量分数为(7.12±1.87) g/kg,TCN质量分数为(8.00±2.13) g/kg,TKN含量显著小于TCN含量;小麦和棉花秸秆的TKN含量和TCN含量与其他秸秆间均存在显著差异(P <0.05);不同生物质TKN含量与TCN含量关系不同,建议采用最小中位数二乘法进行拟合分析。研究结果可为农作物秸秆科学利用提供数据及方法互通性支撑。     

Comparison of Five Digestion Procedures for Recovery of Nutrients and Trace Elements in Plant Tissue

Comparison of five digestion procedures for recovery of nutrients and trace elements in plant tissue were examined. The objectives of this study were to compare five digestion procedures: AOAC (dry ashing), two nitric acid, (NA1, commonly used and NA2, our modification), and two aqua regia (AR1, commonly used and AR2, our modification) procedures for recovery of 15 plant nutrients and trace elements in corn, swiss chard, thorn apple, and barley flour (certified material). Generally, the recovery of various elements depended on the digestion procedure used and the plant species. In most instances, NA2 recovered more phosphorus (P), potassium (K), sulfur (S), and manganese (Mn) than the AOAC or the two AR procedures. Also, overall NA2 recovered more K and magnesium (Mg) than NA1. Extractants AR1 and AR2 recovered more iron (Fe) than the two NA procedures, and the same as the AOAC. The AR2 recovered very similar concentrations of nutrients as the AOAC; and in corn tissue, AR2 recovered more zinc (Zn), chromium (Cr), nickel (Ni), copper (Cu), and boron (B) than the AOAC. The AOAC recovered less S and B than the other procedures tested. For instance, in barley flour, AOAC recovered eight to nine times less S, while in corn tissue AOAC recovered around three times less S than the NA procedures. Overall, there are three important findings: (1) NA procedures may be used for recovery of most elements in plant tissue; (2) AR2 procedure is comparable to the official AOAC method for recovery of nutrients and trace elements in plant tissue, and (3) the official AOAC method used in Canadian plant testing laboratories may underestimate the concentration of S and B in plant tissue.