Multi-element Concentration Research Articles

Evaluation of the Profiles of Essential and Potentially Toxic Elements Present in Grape Must Grown and Soil from the Region Submedium São Francisco, Brazil

This work evaluated the multi-element concentration in grape must and soil samples employing inductively coupled plasma optical emission spectrometry (ICP OES), after microwave-assisted digestion. The study aimed to establish a profile of seven grape varieties produced in Petrolina, region Submedium São Francisco, Brazil. Principal component analysis (PCA) clearly showed a good separation of samples in terms of mineral constituents. Although some soil samples showed concentrations of Co, Cu and Ni higher than the prevention values (VP), no sample exceeded the values stipulated for an intervention in agricultural soils based on Resolution No. 420/2009 of the National Council for the Environment (CONAMA). So, the results obtained contribute to food mineral composition table, as it brings unprecedented information about the concentration of the elements in seven grape varieties, providing indicators of geographic location, and contributing to the preliminary construction of a geochemical base of the regional soil.

Investigation the grain size effect on multi-element concentration using statistical analysis of INAA and laser-diffraction data for estuarine sediments of Hau River, Vietnam

Investigation the grain size effect on multi-element concentration using statistical analysis of INAA and laser-diffraction data for estuarine sediments of Hau River, Vietnam

New constraints on the formation of main group pallasites derived from in situ trace element analysis and 2D mapping of olivine and phosphate

Pallasites are stony‑iron meteorites consisting mainly of olivine and Fe-Ni metal with a formation history that remains widely debated. Despite their simple mineralogy, relatively limited data are available on their geochemistry and the lateral elemental distribution in individual pallasite olivine crystals. In this work, laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS) was used for the elemental analysis of both pallasite olivine and phosphate phases, including 2D trace element mapping of olivine crystals. While the results obtained are in good agreement with literature values, important differences are observed for Al and Ni concentrations compared with bulk analytical methods. The element distribution maps reveal complex zoning in pallasite olivine, which can be explained based on i) diffusion gradients formed during olivine cooling, ii) the crystal chemistry of element substitution due to charge-balancing, and iii) inherited features of olivine before the metal-olivine mixing. Oscillatory zoning in an olivine crystal from Imilac provides strong evidence for the olivine not being a restite of partial melting, but rather having crystallized from a melt. Concentrations of Cr and Al are correlated both within single olivine crystals and between olivine crystals of different pallasites, forming a 1:1 linear trend. This likely results from a spinel-type charge-balancing substitution mechanism in pallasite olivine. Additionally, principle component analysis of laterally resolved multi-element concentration data of pallasite olivine provides an independent measure of the genetic relationships between the different main group pallasites within their parent body (−ies). Rare earth element (REE) contents of pallasite phosphate grains range from concentrations typically measured for chondritic or primitive achondrite-like phosphates to more (light) REE-depleted signatures, revealing the overall primitive nature of the melts from which the phosphate minerals crystallized. Phosphate in pallasites may thus have formed through the consumption of apatites during pro-grade metamorphism, melting, and melt extraction. Combined, the trace element signatures of olivine and phosphate in pallasites of the main group (PMG) suggest that these meteorites are common products of planetary processes on chondritic or primitive achondrite-like precursor bodies, with the different subgroups highlighting distinct formation and evolution histories.

Geochemistry of carbonate rocks of the Chilpi Group, Bastar Craton, India: Implications on ocean paleoredox conditions at the late Paleoproterozoic Era

The chemogenic sediments of the Chilpi Group (~2.0–1.8 Ga) of the Bastar Craton have been analysed for the sedimentary environment, geochemistry and redox evaluation of seawater towards the end of the Paleoproterozoic Era. Fabric-retentive fine-grained micritic and oolitic carbonates suggest preservation of primary texture and precipitation from contemporaneous seawater in a shallow water tidal environment. Reducing condition of shallow sea for the Chilpi Group is also recognized by the presence of chamosite associated with Mn-ankerite. The Post-Archean Australian Shale (PAAS) normalized positive Gd and La anomalies, Lu/La, Y/Ho molar ratios and the Y anomaly indicate the preservation of pristine marine nature of the carbonates. Evaluation of multi-element concentration indicates no significant effects of detrital contamination, diagenesis, metamorphism and contributions from hydrothermal sources. Positive Ce anomalies observed in all the samples, with maximum Ce/Ce* up to 2.83, and redox responsive trace element ratio patterns in association with enrichment of Mn and other redox responsive elements such as Zn, Fe, Mo and U indicate a reducing marine environment of deposition of the Chilpi carbonates. Display of positive europium anomalies (Eu/Eu* = 1.02 – 1.56) can be attributed to the reducing environment as contributions of hydrothermal fluids are ruled out for lack of LREE enrichment compared to HREE. We infer suboxic to anoxic conditions of shallow sea in the Chilpi basin towards the end of the Paleoproterozoic Era, with estimated atmospheric oxygen level of ~10-3 PAL. Reducing conditions in shallow sea indicate that the Great Oxidation Event did not affect seawater composition during late Paleoproterozoic.

Geographic origin determination of Brazilian Cannabis sativa L. (Marihuana) by multi-element concentration

The Marihuana Polygon production of Cannabis sativa L. supplies the northeastern region of Brazil and represents 30% of the nation’s market. The international trend of indoor cultivation is also occurring in Brazil, and the Brazilian Federal Police (BFP) has been increasing its apprehension of cannabis seeds sent by mail. The present work aims to assess the utility of the multi-element composition of different cannabis plant parts and soil samples where the plants were cultivated to determine their geographic origin. Statistical tools were applied to classification of marijuana samples from distinct geographic regions within northeastern Brazil, including indoor cultivated samples. The multi-element quantification was determined using inductively-coupled plasma – optical emission spectrometry (ICP-OES), and the data were compared by the Kruskal-Wallis H test, and subsequently, multiple discriminant analysis (MDA). The results of the multi-element concentration of cannabis plant samples were also subjected to a principal component analysis (PCA) and an orthogonal partial least squares discriminant analysis (OPLS-DA). The cannabis plant samples from the Marihuana Polygon could be clearly separated from those cultivated indoors, and the distance between them was detectable. The MDA revealed that phosphorus, calcium, magnesium, selenium, and arsenic concentrations were used as variables for this separation. Our results demonstrate that multi-element composition analysis can be used to indicate the origin or cultivation location of cannabis plants. Routine laboratory analyses consisting of multi-element composition combined with statistical analyses provide a reliable tool by which C. sativa movement, cultivation, and interdiction efforts in Brazil may be assessed.

Supergene gold in silcrete as a vector to the Scuddles volcanic massive sulfides, Western Australia

This study reports data on the first occurrence of economic supergene Au in a near-surface silcrete horizon over the Scuddles volcanic massive sulfide (VMS) deposit in the Golden Grove district, Western Australia. A deep weathering profile was developed on dacite, rhyodacite, siltstone, and breccia that host primary Cu, Zn, and Pb sulfides with Au-Ag ore. From the base, the weathering profile at Scuddles is subdivided into five main zones: (1) supergene sulfide enrichment zone; (2) supergene oxide enrichment zone; (3) ferruginous saprolite; (4) leached zone of kaolinitic saprolite and silcrete; and (5) lateritic zone of mottled clays, ferruginous duricrust, and gravels. Silcrete at Scuddles hosts supergene Au deposit that formed in two generations: the first is intimately associated with Ag halides during supergene enrichment of the primary VMS, and the second is associated with kaolinite in dissolution cavities inside Ag halides during lateritic weathering. These two Au generations imply more than one mechanism of Au remobilization and formation, multiple fluid pathways, and superimposed episodes of weathering under variable timing and climatic conditions. Gold grains are pure, nanocrystalline (up to 10 nm) and clustered together forming microcrystalline aggregates. A few Au grains are residual in silcrete with Ag-Sb-rich cores and Ag-poor rims possibly formed during dealloying of Ag and Sb. Chemically, Au in silcrete is associated with a multi-element concentration of Ag, I, Br, Cl, Sb, Sn, Bi, Hg, Mo, W, Te, and Ge. Gold and Ag in the supergene weathering profile were mobilized to silcrete as a halide complex under acidic and saline conditions generated during the oxidation of massive sulfides at depth. The precipitation of Au-Ag halides in the silcrete may have taken place in response to a rise in pH. Gold was likely remobilized with kaolinite from the surface lateritic zone, facilitated by decays of plant roots and bioturbation. The clustered spongy, cube-octahedral, platy (six-sided), dendritic-, and reniform-like morphologies of Au in cavities inside Ag halides may indicate biogenic-related processes in its precipitation. Recognizing Au-Ag-rich silcrete over the buried VMS at Scuddles highlights the significance of the silcrete in finding buried VMS, particularly if the gossan is absent.

Post-collisional calc-alkaline lamprophyres from the Kadiri greenstone belt: Evidence for the Neoarchean convergence-related evolution of the Eastern Dharwar Craton and its schist belts

Lamprophyres from the greenstone belts play a crucial role in deciphering tectonic and geodynamic processes operating during the Archean. This study presents a comprehensive mineralogical and geochemical study of three lamprophyre dykes with calc-alkaline to shoshonitic affinities from the Neoarchean Kadiri schist belt, eastern Dharwar craton, southern India. These rocks display porphyritic-panidiomorphic texture, typical of the lamprophyres with amphibole (magnesio-hornblende) as phenocrysts, biotite as microphenocrysts and feldspar, epidote, titanite and apatite confined to the groundmass. Alteration of biotite to chlorite is observed along with mild deformation in the amphibole phenocrysts. Based on mineralogy and major oxide geochemistry, these rocks are classified as the calc-alkaline lamprophyres. Higher Ba/Nb and low Nb/La points to their derivation from an enriched lithospheric mantle source and higher Th/Yb ratio along with negative TNT (Ti-Nb-Ta) and Zr-Hf anomalies on the primitive mantle (PM) normalized multi-element diagram indicates dehydrated fluids from the foundering slab could be the possible metasomatic agent. Fractionated HREE ratios (GdN/YbN >1.9) and higher SmN/YbN suggests that the source region lies in the garnet stability field. Higher than PM Rb/Sr along with positive correlation between K/La and Rb/La reveals presence of metasomatic phlogopite in the source region. Strong negative initial εNd along with radiogenic 87Sr/86Sr ratios further support an enriched mantle reservoir involved in their genesis. Non-modal batch melting (1–5%) of a mixed source (phlogopite-garnet peridotite) assuming 5% mixing of subducted sediment with ambient mantle wedge (depleted mantle) satisfies the multi-element concentration pattern shown by the Kadiri lamprophyres. The source enrichment can be linked to the accretion-related growth of Dharwar craton and its schist belts during Neoarchean. Our study shows that a majority of lamprophyres associated with the Archean greenstone belts display a shoshonitic character; this highlights the role of subduction-related processes in the growth and evolution of the greenstone belts

Environmental Monitoring and Peat Assessment Using Multivariate Analysis of Regional-Scale Geochemical Data

A compositional multivariate approach was used to analyse regional-scale soil geochemical data obtained as part of the Tellus Project generated by the Geological Survey of Northern Ireland. The multi-element total concentration data presented comprise X-ray fluorescence (XRF) analyses of 6862 rural soil samples collected at 20-cm depth on a non-aligned grid at one site per 2,hbox {km}^{2}. Censored data were imputed using published detection limits. Each soil sample site was assigned to the regional geology map, resulting in spatial data for one categorical variable and 35 continuous variables comprised of individual and amalgamated elements. This paper examines the extent to which soil geochemistry reflects the underlying geology or superficial deposits. Since the soil geochemistry is compositional, log-ratios were computed to adequately evaluate the data using multivariate statistical methods. Principal component analysis (PCA) and minimum/maximum autocorrelation factors (MAF) were used to carry out linear discriminant analysis (LDA) as a means to discover and validate processes related to the geologic assemblages coded as age bracket. Peat cover was introduced as an additional category to measure the ability to predict and monitor fragile ecosystems. Overall prediction accuracies for the age bracket categories were 68.4 % using PCA and 74.7 % using MAF. With inclusion of peat, the accuracy for LDA classification decreased to 65.0 and 69.9 %, respectively. The increase in misclassification due to the presence of peat may reflect degradation of peat-covered areas since the creation of superficial deposit classification.

Multielement concentration analysis of Swiss mice brains on experimental model of Alzheimer's disease induced by β‐amyloid oligomers

Alzheimer's disease (AD) is an insidious, progressive, and irreversible brain disorder that leads to memory loss and severe cognitive decline. However, the discovery that soluble β‐amyloid oligomers are potent central nervous system neurotoxins has led to a new view of AD pathogenesis. Metals, such as zinc, iron, and copper, are all increased in the aged brain, and the contents of those metals in the brain of AD patients are higher than non‐AD people. So, altered homeostasis of metal may result in the development of AD. Total reflection X‐ray fluorescence analysis (TXRF) is a multielement analytical technique, which can be used for elemental trace analysis. In this work, TXRF was used to evaluate the elemental concentration and distribution on mice brain regions. Three groups were studied: control, AD10, and AD100, being the two latter were given a single intracerebroventricular injection of 10 pmol and 100 pmol (β‐amyloid oligomers), respectively, to induce experimental AD. All samples were submitted to acid digestion. The TXRF measurements were performed at the X‐Ray Fluorescence Beamline at Brazilian National Synchrotron Light Laboratory, using a monochromatic beam (11.5 keV) for the excitation. It was possible to determine the concentrations of the following elements: P, S, K, Fe, Cu, and Zn. Results showed differences in the elemental concentration in some brain regions between the AD groups and the control group. Furthermore, the difference in the hypothalamus in AD10 groups, both female and male, suggests an association between AD and changes in these elements. Copyright © 2017 John Wiley & Sons, Ltd.

Liquid Electrode Plasma Atomic Emission Spectrometry Combined with Multi-Element Concentration Using Liquid Organic Ion Associate Extraction for Simultaneous Determination of Trace Metals in Water

液体電極プラズマ発光分析法（LEP-AES）は小型化可能な元素分析法であり，ガス供給や大型電源が不要なため，現場分析に適する．本研究では，LEP-AESと微小体積に短時間で高濃縮できる有機イオン会合体抽出法による濃縮を組み合わせ，微量金属（Cu，Mn，Pd，Zn，Cd，Pb）の一括濃縮/同時定量法を開発した．試料水40 mLにキレート試薬を加え，重金属を錯体とし，水相から生成させた有機イオン会合体中に抽出した．この会合体の体積はμLレベルである．これをメタノールに溶解し，硝酸溶液を加え400 μLとした．40 μLを分取してLEP-AESで測定した．濃縮倍率は100倍である．以上の濃縮/定量法より，短時間で高感度な現場元素分析が可能となり，検出限界は数μg L－1～数百μg L－1となった．いくつかの元素は濃縮倍率以上に感度が上昇した．また，廃液の認証標準物質に適用したところ，測定値は認証値の許容範囲内であった．

Three-dimensional (3D) visualisation: the application of terrestrial laser scanning in the investigation of historical Scottish farming townships

Recent developments in digital technologies are heralding significant changes in the way we acquire, visualise and analyse archaeological data. Terrestrial laser scanners can be used to create photo-realistic virtual copies of landscapes, and archaeological features, and offer the potential to improve our understanding of three-dimensional (3D) spatial relationships at study sites. Here we present a methodology for the integration of a high-resolution 3D site model with soil chemical data obtained from an abandoned settlement site located in the Central Highlands of Scotland. At this site, the multi-element concentration in soil, co-visualised within a topographic setting, has an important role to play in elucidating settlement layout and activity. The methods described here are also of significance in archiving sites of archaeological/historical importance where development activities and/or environmental processes may destroy remains, or where access to field sites is restricted.

Phytoremediation: novel approaches to cleaning up polluted soils

Environmental pollution with metals and xenobiotics is a global problem, and the development of phytoremediation technologies for the plant-based clean-up of contaminated soils is therefore of significant interest. Phytoremediation technologies are currently available for only a small subset of pollution problems, such as arsenic. Arsenic removal employs naturally selected hyperaccumulator ferns, which accumulate very high concentrations of arsenic specifically in above-ground tissues. Elegant two-gene transgenic approaches have been designed for the development of mercury or arsenic phytoremediation technologies. In a plant that naturally hyperaccumulates zinc in leaves, approximately ten key metal homeostasis genes are expressed at very high levels. This outlines the extent of change in gene activities needed in the engineering of transgenic plants for soil clean-up. Further analysis and discovery of genes for phytoremediation will benefit from the recent development of segregating populations for a genetic analysis of naturally selected metal hyperaccumulation in plants, and from comprehensive ionomics data--multi-element concentration profiles from a large number of Arabidopsis mutants.

Characterization of Plasma Immersion Deposited Multilayer Coatings by Ion Beam Techniques Combined with Energy Filtered Transmission Electron Microscopy

AbstractMultilayered and nanostructured coatings of amorphous carbon (DLC), silicon composite multilayers and nanocluster containing films today have great potential for applications as hard coatings, wear reduction layers and as diffusion barriers in biomaterials. Plasma immersion ion implantation and deposition (PIII&D) is a powerful technique to synthesize such films. The quantitative nanoscale analysis of the elemental distribution in such multielemental films and thin film stacks however is demanding.In this paper it is shown how the high spatial resolution capabilities of energy filtered trans-mission electron microscopy (EFTEM) chemical analysis can be combined with accurate and standard-less concentration determination of ion beam analysis (IBA) techniques like Rutherford Backscattering Spectroscopy (RBS) and Elastic Recoil Detection Analysis (ERDA) to achieve absolute and accurate multielement concentration profiles in complicated nanomaterials.

Apportionment of non-PIXE species by means of PIXE analysis

Source apportionment for air pollution by means of receptor models are often used in connection with PIXE analysis. The origin of “non-PIXE” species is assessed mainly by using PIXE based models. Three case studies are discussed. 1) Soot is often used as general indicator for anthropogenic air pollution. The trend in the source contributions are evaluated by including the measurements of soot on equal terms with multielement measurements in a factor model. Long range transport seems to be the main reason for the increasing concentrations of soot in the beginning of the 1980s. 2) A regression analysis is performed between campaign measurements of the mutagenic activity of the aerosol in the center of Copenhagen and the factor scores in a factor model based on more than one year of daily measurements of multielement concentration together with SO 2, NO, NO 2 and total particulates. It is shown that traffic is the main source at street level, but that other local anthropogenic sources as well as long range transport contribute with comparable amounts. 3) A multipoint receptor model is used to show that local sources as well as long range transport supplies the NO 3 − + HNO 3 at two sites in the southern part of Scandinavia, while no reasonable assessment of NO 2 could be achieved.

Trace-element patterns obtained by INAA as a basis for source identification

The element concentration patterns as obtained by multielement analysis techniques such as INAA, provide not only information on a number of individual elements simultaneously, but in addition information present in correlations between elements. With Target Transformation Factor Analysis, such information can be extracted from multielement concentration datasets. Application of TTFA to the element concentration patterns observed in environmental samples yields the compositions of polluting components, which may facilitate identification of the associated sources.

The use of multi-element concentration datasets obtained by INAA in the identification of sources of environmental pollutants

Trace element concentration patterns can be used for the identification of objects or materials. Early applications were related to the elucidation of identity or origin of objects. Recently, a number of applications have been reported of the use of trace element concentration patterns to recognize and identify components of mixtures of materials, mainly of environmental interest. In the present paper two examples are discussed of application of Target Transformation Factor Analysis to trace element concentration patterns, to identify sources of heavy metal air pollution. The materials studied are air particulate matter and epiphytic lichens used as biological accumulator.

Examination of Paints by Trace Element Analysis

Trace element analysis using neutron activation analysis is effective and valuable, particularly in the examination of white household paint. Although physical appearance and resin composition are generally similar in these paint samples, trace element composition provides an effective way of distinguishing among them. In the case of automobile paint samples, NAA serves as an important additional technique for discrimination. The technique is important when sample sizes are very small. The technique developed takes a few minutes for sample preparation, a few hours of irradiation time (during which the examiner's presence is not required), and then a few minutes for counting and obtaining quantitative multielement concentration patterns. A technician can easily handle 30 to 50 samples per day.