Advantages of the iridium permanent modifier in fast programs applied to trace-element analysis of plant samples by electrothermal atomic absorption spectrometry

The application of a fast program combined with the advantages of the iridium permanent modifier is proposed for trace element analysis of plant samples by electrothermal atomic absorption spectrometry (ETAAS). For two volatile elements (Cd, Pb) and two mid-refractory elements (Cr, Ni) it was demonstrated that coating of the platform or of the tube atomization area with Ir is an efficient means of improving the accuracy and precision of results. A detailed study of interference from individual main matrix components and from composite plant matrices has confirmed the usefulness of the whole approach. The validity of the method has been confirmed by analysis of eight reference plant materials.     

Effect of motorway traffic emissions on roadside wild-plants in Saudi Arabia

The levels of several composite elements of two wild plants, namelyEuphorbia terracina andCalotropis procera were evaluated. These plant species are quite abundant all year round in the Makkah province of Saudi Arabia. Leaves from the above plants were collected at 5 km intervals from the sides of two stretches, 50 kilometres each, of two motorways between the cities of Makkah and Taif. One of the motorways (Aljabal motorway) is dominated by petrol fuelled passenger and light goods vehicles whereas the other motorway (Assail motorway) has a significant number of diesel fuelled heavy goods vehicles totalling up to 40% of the traffic volume. Instrumental neutron activation analysis (INAA) was employed with different irradiation and counting conditions. The suitability of the two wild plant species for botanical environmental monitors was investigated and the effects of the different vehicular emissions on the concentration levels of 15 elements is discussed. Control samples from rural environment were also collected and analysed in order to provide baseline levels of the elemental concentrations.     

Determination of As,Bi, Sb and Sn in conifer needles from various locations in Poland and Norway by hydride generation inductively coupled plasma atomic emission spectrometry

Hydride generation inductively coupled plasma atomic emission spectrometry (HG-ICP-AES) in the system with aerosolised sample introduction has been employed for the first time for analysis of conifer needles. Arsenic, bismuth, antimony and tin along with other trace elements were simultaneously determined in pine, spruce, yew and thuja foliage sampled from various locations in Poland and Norway. Quality of the measurements was assured by examination of two attested plant reference materials. The application of different analyte introduction techniques and interference effects from matrix elements, i.e. Na, K, Mg, Ca and transition metals in the analysis of needles are discussed.     

The Design of Experiment as a Tool to Model Plant Trace-Metal Bioindication Abilities

Bioindicator plants are species that have the capacity to linearly uptake some elements (metal and metalloids) from the growing substrate, thus reflecting their concentration in the soil. Many factors can influence the uptake of these elements by plants, among which is the simultaneous presence of several metals, a common situation in contaminated or natural soils. A novel approach that can be used to validate the bioindication ability of a species growing on a polymetallic substrate is the design of experiment (DoE) approach. The aim of the present study was to apply the DoE in full factorial mode to model the Cu, Cd, Pb, Zn, and Cr bioindication capacity of Polygonum aviculare, used as the model plant. The results showed that P. aviculare has the ability to bioindicate Cd and Cr with a linear uptake (from 0.35 to 6.66, and 0.1 to 3.4 mg kg⁻¹, respectively) unaffected by the presence of other metals. Conversely, the uptake of Pb, Cu, and Zn is strongly influenced by the presence of all the studied metals, making their concentration in the plant shoot not proportional to that of the soil. In conclusion, these preliminary results confirmed that the DoE can be used to predict the bioindicator abilities of a plant for several elements at the same time and to evaluate the interactions that can be established between variables in the growing medium and in the plant itself. However, more studies including other plant species are needed to confirm the effectiveness of this method.     

IAEA quality control studies on determining trace elements in bioindicators

Twenty laboratories from 17 countries around the world participated in two analytical quality control exercises, coded NAT-5 and NAT-6, on determining trace and minor elements in plant bioindicator samples. 1398 laboratory mean values for 51 elements were submitted for two lichen and two moss materials. The submitted measurement results were evaluated as interlaboratory comparison (IC) exercises and as proficiency tests (PT) following standard procedures developed by the International Atomic Energy Agency (IAEA). The evaluations confirmed good performance of the participating laboratories for many elements. Furthermore, the laboratories performance based on IC criteria improved from the first exercise to the second one. Subsequent NAT-5 evaluation revealed systematic differences between the analytical values obtained non-destructively or after the total sample dissolution and the measurements following nitric acid sample dissolution (without the use of hydrofluoric acid) for some elements. The most critical elements for this kind of discrepancies appeared to be Al, Ca, Cr, Fe, Na, Ni, and Pb. After changing analytical methodologies in the concerned laboratories, more consistent values for those elements were obtained in NAT-6. This revised version was published online in August 2006 with corrections to the Cover Date.     

A Brazilian coal fly ash as a potential source of rare earth elements

Rare earth elements (REEs) have several applications and their market demands have increased. Recently, coal fly ash (CFA) has been considered as a source of these elements. The purpose of this study was to evaluate the REEs content in a CFA from a Brazilian coal power plant by instrumental neutron analysis, to classify it according to commercial purposes and to assess the weathering impact in the REEs content, since it is held in fields nearby the power plant. The results pointed no significant REEs leachability and indicated this CFA as a promising REEs source.

     

交互模式-电感耦合等离子体质谱(ICP-MS)法测定生态地球化学植物样品中7种金属元素

植物样品中各元素的含量,是评价土壤质量及健康的重要指标。为满足测定大批量生态地球化学植物样品中多金属元素分析要求,建立了交互模式-电感耦合等离子体质谱(ICP-MS)法测定植物样品中7种痕量金属元素的定量分析方法。讨论了ICP-MS的STD、KED(He)、交互模式3种方法测定植物样品中7种金属元素结果。结果表明,利用工作曲线法配制Hg标准溶液,更改⁸²Se在线校正方程系数为1.83,在ICP-MS的交互模式下测定植物样品中⁸²Se、⁶³Cu、⁶⁰Ni、⁶⁶Zn、¹¹¹Cd、⁷⁵As、²⁰²Hg可以得到准确可靠的结果,克服了植物样品中Se和Hg元素测定的难题。基于所建方法各元素校准曲线系数>0.999,方法检出限为0.000 4～0.08 mg/kg,加标回收率在96.2%～107%,测定GBW10010a(大米)、GBW10012(玉米)、GBW10021(豆角)3种标准物质,结果均在参考值范围内,相对标...     

Determination of Calcium,Phosphorus and Potassium in Leaf Tissues by Extraction with Ethanol-Water Solvent

Abstract

A new method has been developed for the analysis of elements in plant leaves by aqueous-ethanol extraction. The method was initially tested for calcium, potassium and total phosphorus. Very good results were obtained when compared with those of other methods. Extraction is done with a 20% v/v ethanol-water mixture, refluxing the plant material during 15 to 30 minutes. After treatment with activated carbon the solution is filtered through fast quantitative filter paper (Whatman nr. 40). The elements can be analysed as usual, by atomic absorption, flame photometry, etc. The procedure is promising for routine analysis because of its low cost, simplicity of operation, rapidity, safety characteristics and quality of the results. 30 to 40 minutes are sufficient to prepare solution samples from the dried plant material.     

Concentration levels of rare-earth elements and thorium in plants from the Morro do Ferro environment as an indicator for the biological availability of transuranium elements

Plants and soils from a natural thorium and rare-earth element occurrence (Morro do Ferro, Brazil) were analyzed by alpha spectrometry (Th) and ICP-AES (REE), after pre-concentration of the elements by solvent extraction, co-precipitation and ion exchange procedures. Leaching experiments with humic acid solutions and different soils were performed to estimate the fraction of elements biologically available. High concentrations of the light rare-earth elements (LREE) and of Th, reaching some hundreds of g/g-ash, were measured in plant leaves from the areas of the highest concentration of these elements in soil and in near-surface waters. Chondrite normalized REE plots of plant leaves and corresponding soils are very similar, suggesting that there is no significant fractionation between the REE during uptake from the soil solution and incorporation into the leaves. However, Ce-depletion was observed for some plant species, increasing forSolanum ciliatum in the sequence: leaves<fruits<seeds. Soil to plant concentration ratios (CR's) for Th and the REE, based on the total concentration of these elements in soils, are in the range of 10^–3 to 10^–2. Leaching experiments confirmed the importance of humic acid complexation for the bio-uptake of Th and REE and further showed that only a very small fraction of these elements in soil is leachable. The implications of these results on the calculated CR's will be discussed.     

The recognition of similarities in trace elements content in medicinal plants using MLP and RBF neural networks

The objective of the paper was to verify if the content of some elements provides enough information for proper classification of the medicinal plant raw materials. Such information could be helpful in standardization process of herbal products. Four elements—zinc, copper, lead and cadmium were determined using inverse voltammetry in commercially available medicinal herbal raw materials. Initially, principal component analysis (PCA) was employed to investigate the relationships among the analyzed trace elements. In the next stage of the study, two different types of feed-forward artificial neural networks (FANNs)—multilayer perceptron (MLP) and radial basis function (RBF) were applied. The concentrations of the elements were used as input variables to neural networks models, which were to recognize the taxonomy of the plant and the anatomical part it originated from. Although full recognition of the samples with use of FANNs on the basis of some trace elements content was not achieved, it was possible to identify two elements—cadmium and lead as the most important in the classification analysis of medicinal plants.     

Determination of concentrations of chromium and other elements in soil and plant samples from leather tanning area by Instrumental Neutron Activation Analysis

Chromium, one of the toxic elements, along with other elements has been determined in samples of soil and plant (leaves and seeds) from Jajmau Area, Kanpur district, India, which is irrigated with effluent waste water from leather tanning industries. Soil and plant samples were collected from these areas and analyzed by Instrumental Neutron Activation Analysis (INAA) using high flux reactor neutrons and high resolution gamma-ray spectrometry. Concentrations of fifteen elements in soil and five elements in plant samples were determined by relative method. Chromium concentrations were found to be in range of 45–3,900 mg kg^?1in soil samples and 14–83 mg kg^?1 in plant samples. This study showed that Cr is present in significant amounts, in the soil as well as in the plant samples, near to the leather tanning area. As a part of quality control work, IAEA reference material (RM) SL-3 and NIST standard reference material (SRM) 1645 were analyzed and the quality of the results has been evaluated by calculating % deviations from recommended/literature/certified values.     

A new phthalic acid ester from Ajuga bracteosa

A new phthalic acid ester 1,2-benzenedicarboxylic acid bis(2S-methyl heptyl) ester (1) was isolated from the hexane extract of the whole plant of Ajuga bracteosa. In addition, chloroform and methanol extracts yielded neo-clerodane diterpene ajugarin-I and two iridoid glycosides, reptoside and 8-O-acetyl harpagide. The structures of all the compounds were confirmed by extensive spectroscopic analysis. From the two oily fractions nine and six volatile constituents respectively were identified by GCMS. Linalyl acetate was found to be common in both the oil fractions. This plant is a new source of linalyl acetate, a valuable perfumery compound.     

Multielemental fast analysis of vegetation samples by wavelength dispersive X-ray fluorescence spectrometry: Possibilities and drawbacks

X-ray fluorescence spectroscopy (XRF) is universally recognized as a non-destructive method for rapid and sequential, or simultaneous analysis of elemental composition of a material. The use of this technique for the direct determination of chemical elements in plant matrices has increased over the last few years.In the present study, a wavelength dispersive X-ray fluorescence (WDXRF) method for the quantitative analysis of some major elements (Na, Mg, Al, P, S, K, Ca), trace elements (Mn, Fe, Co, Zn, As) and non-essential elements (Sr, Pb) in vegetation specimens has been developed. The method uses a quick and easy sample preparation procedure since only drying, pulverizing and pressing of the samples are necessary. The calibration procedure was established by employing four plant reference materials and several synthetic cellulose calibrators spiked with appropriate amounts of analytes. Matrix effects were corrected employing the method of the influence coefficients on the basis of the computerized routine program linked to the equipment.Trueness of the experimental procedure was checked by using the standard reference material GBW07602 “Bush branches and leaves”. In general, good agreement was achieved between certified values and the measured ones with recoveries ranging from 94% to 107%. Moreover, quality parameters, including repeatability and reproducibility of the developed method, were also evaluated.On the whole, from results obtained, WDXRF method proposed prove to be good and effective tool for environmental investigation and quality control processes in vegetation specimens.     

Terpenoids from Loxocalyx urticifolius

Two new diterpenoids, loxocalyxin A ( 1 ) and 13‐epiloxocalyxin A ( 2 ), and two new sesquiterpenoids, loxocalyxins B and C ( 3 and 4 , resp.), together with three known compounds, were isolated from the MeOH extract of the whole plant of Loxocalyx urticifolius Hemsl . The structures of the new compounds were established by means of spectroscopic analysis including one‐ and two‐dimensional NMR spectroscopy. All new structures were confirmed by X‐ray crystallographic analysis. Their absolute configurations were established.     

Synthesis and properties of novel cationic gemini surfactants with adamantane spacer

Novel quaternary ammonium cationic gemini surfactants, with two hydrocarbon chains and an adamantane core, were designed and synthesized by three-step reactions from adamantane. The structure of obtained surfactants were confirmed by 1H NMR, FTIR and elements analysis and the surface properties of these surfactants were also studied by surface tension measurements. These target surfactants exhibit much lower critical micelle concentrations （CMC） and higher efficiency in lowering the surface tension of water than typical surfactants.     

Revisitation of mineralization modes for arsenic and selenium determinations in environmental samples

Mineralization procedures for arsenic and selenium analysis are usually limited to wet digestion methods owing to high volatility of these analytes. On the other hand, variable amounts of silicon in some types of samples imply elaborated mineralization procedures to liberate analytes which may be retained in an insoluble residue. Consequently, methods for such material generally include an hydrofluoric step followed by an evaporation to dryness. This type of mineralization is most easily accomplished using a dry ashing procedure. For plant analysis, a well validated and readily applicable dry ashing method is used for a long time in several laboratories but up today one could suppose that As and Se determinations cannot be performed after such a type of mineralization. Surprisingly, it has been observed that for plant samples these analytes are detected even after a calcination at 450 degrees C. The general usefulness of a dry ashing method for analysis of all other analytes (main, minor and trace elements) incitates us to also verify As and Se recoveries. Results obtained in this work indicate clearly that plants of terrestrial origin may be mineralized using dry ashing procedure without As and Se losses. This statement was confirmed by analyses of several reference terrestrial plant samples (RMs) and laboratory control samples. Another confirmation was given by the direct graphite furnace analysis of the same plant samples but in slurried form (SS-ETAAS). As a direct consequence, As and Se analysis in terrestrial plants no more necessitates a separate preparation methodology. On the other hand, significant losses of As and Se were observed for aquatic plants, e.g. algaes. For the analysis of this type of samples, a separate wet digestion procedure remains unavoidable if the determination of As and Se has to be considered. Also some preparation procedures were tested for As and Se-analysis of soil and sediment reference samples. In these cases the wet digestion with a mixture of nitric, perchloric and hydrofluoric acids seems to remain the best alternative.     

Monitoring of heavy metals in topsoils, atmospheric particles and plant leaves to identify possible contamination sources

The research reveals results of metal pollution on urban topsoil in relation to the metal content in leaves of two plant species and atmospheric particles. The content of pollutants (Ba, Cd, Cu, Fe, Mn, Ni, Pb, V and Ti) was determined by ICP-OES. Twenty-two samples of soil were collected over a six-month period from two different urban sites and one from a rural zone. Regarding the pollution level, the studied soils were found to be low. Results for enrichment (EF) and concentration (CF) factors showed that soils were enriched in Pb, Ba, Cu and Ni. However, both species of plants showed a common behavior for all elements acting as excluders. ANOVA and different multivariate statistical analyses confirmed that the main pollution source of soil was traffic and fertilizers. Cd, Fe, Mn, Ti and V elements were attributed to natural sources. Also, it was suggested that N. oleander leaf is useful as a bio-monitors of soil pollution by Cu. Similarly, a direct relationship was found between the content of Cu in soils with the Cu level in PM₁₀ atmospheric particles. The origin was attributed to dry and wet atmospheric deposition processes.     

Analysis of non-organic elements in plant foliage using polarised X-ray fluorescence spectrometry

An X-ray fluorescence (XRF) method for the rapid and non-destructive analysis of 30 non-organic elements in plant leaves over five orders of magnitude concentration from several percentage of dry weight to sub-milligram per kilogram, is described. There is a growing need for a simple method of monitoring non-organic trace elements in plant material, especially those which accumulate in soils with application of fertilisers, both inorganic and biosolids. Earlier attempts to use XRF for the analysis of plant material suffered from sensitivity loss due to the high background of organic matrices caused by scattering of the X-ray source. We overcome this by using polarised X-ray sources in a Cartesian geometrical arrangement with sample and energy dispersive detector (EDPXRF), a configuration which can achieve an order of magnitude reduction in background compared with unpolarised sources. Further sensitivity gains are made using a high power tube as a source of primary X-rays and for some analytes employing secondary targets for near-monochromatic excitation. Sample preparation is simple involving only pulverising and briquetting of dried samples. Accuracy is evaluated by comparing data obtained for the suite of NIST plant leaf samples (NIST 1515 apple leaves, NIST 1547 peach leaves, NIST 1570a spinach leaves, NIST 1573a tomato leaves and NIST 1575a pine needles) and tobacco leaf standards CTA-OTL-1 and CTA-VTL-2. The data compare well over the whole concentration range and the method provides a rapid analytical tool for monitoring potentially toxic trace elements in all types of foliage with adequate sensitivity for many purposes.     

Neutron activation analysis study of distribution of certain elements between plant and soil

Some elements are recognized as essential for the optimal growth of plants but their number and their role is not clearly asserted up to now. Instrumental neutron activation analysis has been employed to determine the elements arsenic, barium, bromide, cerium, europium, gold, hafnium, lanthanum, lutecium, samarium, scandium, tantalum, thorium and ytterbium in different parts of Helleborus cyclophyllus BOISS. and in the soil in which the plant had grown. It has been found that bromine is selectively accumulated in plant from soil, where the value in petioles is four times higher than the value in soil while the value in leaves is about twice as high. The other elements determined show a certain distribution in plant organs but no selective accumulation.     

固相微萃取-气相色谱/质谱测定植物叶片中的挥发性物质

采用固相微萃取（SPME)方法吸附植物叶片中的挥发性物质,然后采用气相色谱/质谱法（GC/MS）分析了挥发性物 质的成分。在45 ℃水浴温度下,采用Polyacrylate(85 μm)固相微萃取头,在广口瓶中植物叶片的上方顶空吸附60 min,然后进行GC/MS分析。结果表明,植物叶片中的挥发性物质得到了很好的分离,受山楂叶螨(Tetraychus vienneis) 危害严重的植物的完好叶片中的挥发性物质均含有顺-3-己烯-1-醇乙酸酯、顺-3-己烯-1-醇丁酸酯和α-法呢烯,且含量 较大。初步确定这些物质是对山楂叶螨具有引诱作用的主要物质,从而为利用天然生物活性物质防治山楂叶螨提供了理论 依据。