A Baseline Study of Metal Ion Content of Irish Canals by ICP-MS

The first systematic study of the metal ion content of the four main Irish Canal Systems is presented. Samples were collected seasonally over a twelve month period and analysed for 16 trace elements and metals by ICP-MS. The results show that three of the four canals (Royal, Grand, Shannon-Erne) have distinctly different elemental profiles, while the fourth (Barrow) is similar to the Grand Canal, which is to be expected, as they are broadly part of the same system, with a common main feeder. Spatial plots reveal local variations in certain elements, which are related to the nature of feeders in those localities. Simple tests based solely on the 16 elements measured showed that it may be possible to broadly define 'normal' compositions for each canal system, which can be then used to identify 'abnormal' data, and hence provide indicators for environmental change.     

激光电离飞行时间质谱用于矿石表面元素成像

在自行研制的LI-TOF-MS[6]的基础上, 发展了新的LI-TOF-MS固体元素成像分析系统, 并在优化了的实验条件下, 对辉锑矿矿石样品(主要成分为Sb2S3)的表面进行了元素分析, 得到了Sb, S, Si, Al, K, Ca和Fe等元素的表面成像图. 矿石表面或截面的元素成像(或分布)对矿石乃至矿床的形成过程及分布特征等的研究具有很大的参考价值, 在地质学上具有重要意义.     

Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry

Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (−52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments.     

Laser ablation in liquids as a new technique of sampling in elemental analysis of solid materials

Laser ablation in liquid media is considered as a new sample preparation technique in the elemental composition analysis of materials using optical emission spectroscopy of inductively coupled plasma (ICP-OES). Solid samples are transformed into uniform colloidal solutions of nanosized analyte particles using laser radiation focused onto the sample surface. High homogeneity of the resulting solution allows performing the ICP-OES quantitative analysis especially for the samples, which are poorly soluble in acids. The technique is compatible with the conventional solution-based standards.     

Underwater sediment analyses by laser induced breakdown spectroscopy and calibration procedure for fluctuating plasma parameters

Laser Induced Breakdown Spectroscopy (LIBS) was applied on sediments directly under water. The aim of the research was to develop a method for measuring the sediment elemental composition, including minor elements, which could be implemented in-situ. The plasma was generated by a double-pulse, Q-Switched Nd:YAG laser operated at 1064 nm. For signal detection, both ICCD and non-gated, compact detectors were used. The major difficulties in underwater sediment analyses are related to the natural and laser induced surface roughness, and to the sample softness. The latter is responsible for the formation of particle clouds above the surface, which scatter both the laser and plasma radiation, and often results in breakdown formation above the analyzed surface. In such cases, a broad sonoluminescence emission from water, formed during the gas bubble collapse was sometimes registered. Under optimized experimental conditions, even by using a non-gated detector and single shot acquisition, it was possible to detect several minor sediment constituents, such as titanium, barium, manganese and others. A crude estimation of the Limit of Detection (LODs) for these elements was performed by underwater measurements on certified soils/sediments. Due to strong shot-to-shot fluctuations in the plasma temperature, well correlated calibration curves, aimed for quantitative analyses, could only be obtained after applying an appropriate data processing procedure. The latter selects automatically only the spectra characterized by similar plasma parameters, which are related to their continuum spectral distribution. Application of such a procedure improves the measurement accuracy also in other surroundings and on samples different from the ones analyzed here.     

Determination of trace element pathways in a petroleum distillation unit by instrumental neutron activation analysis

The concentrations of 11 trace and minor elements (Na, Al, S, Cl, Ca, V, Mn, Ni, As, Br, I) have been measured by instrumental neutron activation analysis in a sample of crude oil from Venezuela, and in 7 of its distillates and in the final residue produced in a primary distillation unit. Concentrations range from 0.5 ppb to 2.0%. The elements have been classified in 4 categories on the basis of their distributions among the fractions analyzed. The results on concentrations have also been used to establish elemental balances in the distillation unit studied operating under steady-state conditions. Only S and V have been found to give rise to losses by emission.     

Elemental mapping and quantitative analysis of Cu, Zn, and Fe in rat brain sections by laser ablation ICP-MS

This report details the application of laser ablation quadrupole ICP-MS for the (multi)elemental mapping of 100-μm-thick sections of rat brain. The laser spot size used was 60 μm, and the laser scan speed was 120 μm s⁻¹. The analysis was relatively rapid, allowing mapping of a whole brain thin section (≈1 cm²) in about 2 h. Furthermore, the method was amenable to multi-element data collection including the physiologically important elements P and S and afforded sub μg g⁻¹ detection limits for the important trace elements Cu and Zn. Calibrations were performed with pressed pellets of biological certified reference materials, and the elemental distributions and concentrations of Cu, Zn, and Fe were determined in whole rat brain sections. The distributions and concentration ranges for these elements were consistent with previous studies and demonstrate the utility of this technique for rapid mapping of brain thin sections.     

Neutron capture prompt gamma-ray analysis of stratospheric and groundfall ASH following the MT. ST. Helens eruption of May 18, 1980

Neutron-capture prompt γ-ray analysis (PGAA) is an exceptionally good method for the determination of the major and minor elements Na, Mg, Al, Si, K, Ca, Ti, Mn and Fe in most geological matrices. The trace elements H, B, S, Cl, Cd, Sm and Gd can often be readily measured in most geological materials. This technique was applied to volcanic ash samples collected in Washington and Montana by various groups following the May 18 eruption of the Mt. St. Helens volcano, as well as to several particulate samples collected at altitudes between 13 and 18 km by a NASA U-2 research aircraft. Groundfall ash samples show distinct elemental variations versus distance from the volcano. For example, Si/Al ratios vary from 2.85 near the volcano to about 3.70 at≽400 km to the east. Samples collected sequentially at a given location (Almira, Washington) also exhibit variations in the elemental ratios. These sequential samples were also subjected to leaching studies to determine soluble B, Cl and S. On the average, PGAA is able to account for 99.4±1.7% of the mass of each sample when the elements are considered to be in their common oxide forms. The stratospheric samples were collected May 19 on IPC cellulose filters on apparatus in a wing tank of the U-2. The PGAA results indicate that the sample from the greatest altitude resembles ashfall near the volcano, while those at lower altitudes somewhat resemble more distant ashfall.     

Distribution of trace elements in the marine sediments along the South China Sea,Malaysia

In order to complete having data base of elemental assessment of the east coast of Peninsular Malaysia marine sediments along the South China Sea coasts, trace elements are analyzed and their distribution in marine sediments is undertaken. The present study is done parallel with pervious study on elemental assessment of heavy metals, rare earth elements and actinides in the marine sediments of the east coast of Peninsular Malaysia. Thirty surface sediment samples were collected in this area, including regions of Kelantan, Terengganu, Pahang, Rompin and Johor Baharu. Multielemental analysis was carried out by instrumental neutron activation analysis and inductively coupled plasma atomic emission spectroscopy. In both cases methodology validation was performed by certified reference material analyses. For the surface elemental distributions the enrichment factor values, average I _geo and mC _d values indicate that the trace elements of the surface sediments are uncontaminated in all sampling stations that are consistent with previous studies results of heavy metals, rare earth elements and actinides.     

Elemental concentrations in sediments of the Patras Harbour, Greece, using INAA, ICP-MS and AAS

Twenty marine sediment samples, selected downcore from six sediment cores, which were retrieved from the Patras Harbour, were studied for their elemental composition using three analytical techniques: INAA, ICP-MS and AAS. Standard reference materials were used to verify the accuracy of the analysis techniques. In total, the concentrations of 30 major, minor and trace elements were measured. The vertical distribution of most elements in the examined cores could be characterized as relatively uniform. The eastern part of the harbour seems to be more polluted in respect to some elements (Ag, Br, Cd, Cr, Cu, Pb and Zn) compared to the western one. The concentrations of a number of elements (As, Cd, Cr, Cu, Ni, Pb and Zn) determined in the sediment samples of the present work are discussed regarding to those obtained from other harbours in the world and compared against sediment quality guidelines (SQGs) to assess the ecotoxicological significance of the sediment contaminants to benthic biota.     

Sliding-spark spectrometry of sediment samples

Direct analysis of non-conducting solids and dielectric surface layers for elements at trace levels has been shown to be feasible by the new so-called sliding-spark spectroscopy, in which a discharge plasma is bound by, and propagates on, the surface of a dielectric sample matrix. By using a river sediment as a model matrix, bound in PVC to improve elemental atomization and excitation efficiency, as a result of the formation of volatile chlorides, the potential of the technique for environmental applications has been investigated by studying the characteristic UV-visible radiation emitted in the wavelength range 210-510 nm for the elements Fe, Cr, Ni, Cu, Pb, Cd, Zn, Co, V, Ti, and Mn. The radiation was detected by means of a CCD spectrometer and analysed for spectral line identification, selection, and the linearity of the spectral response, to determine whether this was suitable for establishing a calibration strategy for quantitative analysis using the sliding-spark source.     

Elemental analysis of selected Indian monazite ores by energy dispersive X-ray fluorescence /EDXRF/ spectroscopy

Analysis by Energy Dispersive X-ray Fluorescence spectroscopy of monazite ores from Kerala /Chavara and Manavalakurichi/, Orissa /Chattrapur/ and Tamil Nadu /Tirunelveli/ has been carried out for the determination of their elemental composition using¹⁰⁹Cd /annular/ and²⁴¹Am /disc/ radioisotope sources. The elements Y, Zr, Mo, Pb, Th and U were analyzed using a¹⁰⁹Cd source, and the elements La, Ce, Pr, Nd, Sm, Gd and Dy were analyzed using the²⁴¹Am source in side source geometry. Quntitative results on these 13 elements present in these ores were obtained by the EDXRF technique. It was seen that despite the diverse geological settings, there is remarkable similarity in the elemental composition of these ores, although some trace elements do show certain variations from sample to sample. These results are presented and discussed in this paper.     

Infrared laser ablation study of pressed soil pellets with inductively coupled plasma atomic emission spectrometry

Potential of infrared laser ablation (LA) coupled with ICP-AES as a technique suitable for the determination of trace elements (Zn, Cu, Ni, Cr, and V) in agricultural soils was studied. Operating parameters such as laser beam energy, laser beam focusing with respect to the sample surface, and velocity of the sample translation in the plane perpendicular to the laser beam were optimized. Soil samples were mixed with powdered Ag as a binder, and an internal standard (GeO(2)), and pressed into pellets. Calibration samples were prepared by adding known amounts of oxides of elements of interest into soils of known elemental composition and then processed in the same way as the analyzed samples. Calibration curves were found to be linear at least up to several hundreds of mg kg(-1) for the elements of interest. The elemental contents obtained by using LA-ICP-AES were compared with those obtained by analysis using wet chemistry followed by ICP-AES with pneumatic nebulization (PN). The results were in good agreement. Accuracy was also tested using certified reference soils with a bias not exceeding 10% relative.     

Total-Reflection X-ray fluorescence analysis of elements in size-fractionated particulate matter sampled on polycarbonate filters — Composition and sources of aerosol particles in Göteborg,Sweden

This is the first study applying the technique of cold plasma ashing on polycarbonate filters as a preparative step for subsequent elemental analysis of aerosol particles by Total-Reflection X-ray fluorescence. The procedure has been validated by analyzing blanks of the filter material, chemicals used as additives as well as certified standard reference material. The results showed that cold plasma ashing is superior to conventional digestion methods with regard to the ease of sample preparation and contamination. A PIXE cascade impactor was used to collect size-fractionated aerosol particles in 9 size classes ranging from 16 to 0.06 µm aerodynamic diameter at an urban and a suburban site in Göteborg, Sweden. Filter segments loaded with the aerosol particles were cut out and fixed on Quartz carriers. After adding 10 ng of Ga as internal standard the samples were dried, digested by cold plasma ashing and analyzed by Total-Reflection X-ray fluorescence. The analysis of aerosol particles showed that elemental concentrations at both the urban and the suburban site in Göteborg were low compared to central Europe. More and concurrent sampling of size-fractionated particles is required to identify local sources of trace elements in the urban area of Göteborg.     

Characterizing ablation and aerosol generation during elemental fractionation on absorption modified lithium tetraborate glasses using LA-ICP-MS

The influence of sample matrix composition, absorption behavior and laser aerosol particle size distribution on elemental fractionation in laser ablation inductively coupled plasma mass spectrometry was studied for nanosecond laser ablation at a wavelength of 266 nm. To this end, lithium tetraborate glass samples with different iron oxide contents and trace amounts of a group of 11 elements were prepared synthetically. The samples were characterized in terms of optical absorbance, melting points, trace element concentrations and homogeneity. UV/VIS spectra showed that sample absorption rises with increasing Fe₂O₃ content. Crater depths and time-dependent particle size distributions were measured, and ablated and transported sample volumes were estimated. Furthermore, the laser aerosol was filtered using a particle separation device and transient ICP-MS signals were acquired with and without filtering the aerosol. The results demonstrate that the amount of ablated sample is related to the absorption coefficient of the sample and therefore to the optical penetration depth of the laser beam into the sample. The higher energy densities resulting from the shorter penetration depths result in smaller average particle sizes for highly absorbing samples, which allows more efficient transport to and atomization and excitation of the ablated material within the ICP. The particle size distribution changes continuously with ablation time, and larger particle fractions occur mainly at the beginning of the ablation, which leads to particle-related fractionation processes at the beginning of the transient signal. Exceeding a critical depth to diameter ratio, laser-related elemental fractionation processes occur. Changes in the volatile to non-volatile element intensity ratio after the aerosol is filtered indicate that particle size-related enrichment processes contribute to elemental fractionation.     

Determination of elemental concentrations in environmental plant samples by instrumental neutron activation analysis

The intake of leafy vegetables in daily diet is very important to meet our nutritional needs. Vegetables provide the essential elements which are necessary and recommended for human growth. However, due to rapid industrialization and urbanization our environment becomes polluted and this affects the normal growth of agricultural products and composition of environmental species. The elemental concentrations present in the environmental samples are good indicators to assess the toxicological levels due to pollution affects. In the present work we have analysed several vegetable plant samples by instrumental neutron activation analysis to determine the elemental concentrations at major, minor and trace levels. The leafy vegetables like spinach, red leafy veagetable, pui, gourd leaf, lettuce and katoua were chosen as these are extensively consumed by local peple in eastern part of India. We have determined 15 elements in the above mentioned vegetable samples and some of these are essential elements and some are toxic elements. It was found that Na and K were present as major elements, Fe and Zn as minor elements and As, Ce, Cr, Co, La, Mo, Rb, Sc, Sm, Sr as trace elements. The concentration level of Cr was found to be higher than that of recommended value certified by WHO and National environment quality control for human consumption. The validation of our analytical results have been performed by the Z-score tests through the determination of concentrations of the elements of interest in certified reference materials.     

Sample Preparation Techniques—An Important Part in Trace Element Analysis for Environmental Research and Monitoring

Abstract

For the determination of minute amounts of elements in environmental samples combined analytical procedures are frequently employed. The combination of suitable sample preparation techniques with adequate detection methods lead to powerful analytical procedures. Decomposition methods are an important part of combined procedures for the determination of trace elements in solid samples. After a short summary of the potential sources for systematic errors two new decomposition methods are described that are suitable for the ashing of organic environmental samples. In one method the organic sample is ashed in a high-frequency excited oxygen plasma. The second method is a high pressure decomposition that permits mineralization of the sample in sealed quartz vessels with nitric acid at temperatures up to 320°C.

For both methods the ratio of sample weight to decomposition reagents is comparatively high. This makes these methods in combination with adequate detection methods suitable for the determination of elements at very low concentrations.

X-ray fluorescence spectrometry combined with adequate preconcentration methods is very well suited for the simultaneous determination of trace elements. Following a critical evaluation of various preconcentration techniques the analytical characteristics of filter paper with immobilized complexing agents are described. Particular emphasis is given to filter papers with dithiocarbamates as chelating group.     

Application of scanning electron microscopy and X-ray microanalysis: FE-SEM, ESEM-EDS, and EDS mapping for studying the characteristics of topographical microstructure and elemental mapping of human cardiac calcified deposition

To explore the pathogenic mineral formation in a huge cardiolith isolated from the left heart atrium of an 80-year-old male patient, field emission scanning electron microscopy (FE-SEM) was used to analyze the topographic microstructure and perform elemental mapping in a cross-section of the cardiac calcified deposit after dissection. Environmental SEM equipped with an energy dispersive X-ray spectrometer (EDS) was also used to investigate the composition and spatial distribution of elements in the cross-section, and fiberoptic Raman spectroscopy was used to reidentify the chemical composition of designated positions. The results indicated that calcium hydroxyapatite and cholesterol were the main components of the cardiac calculus. The plate-like structures of calcium hydroxyapatite were unevenly spread over the cholesterol of the cardiac calculus. The calcium hydroxyapatite-rich area exhibited higher amounts of C, O, P, and Ca elements as well as trace amounts of N, Na, Mg, and Al, whereas the major concentration of C, minor concentrations of N and O, and trace amounts of P and Ca were observed in the cholesterol-rich area. Hypercholesterolemia associated with calcification of this cardiac calculus was proposed. Both FE-SEM and ESEM energy dispersive X-ray microanalyses were performed directly, for the first time, to provide useful information on the microstructural characteristics and spatial distribution of elements on the surface of human cardiac calculi.

Geochemistry study of soil affected catastrophically by tsunami disaster triggered by 2004 Indian Ocean earthquake using a fourth harmonics (λ = 266 nm) Nd:YAG laser induced breakdown spectroscopy

In this work, laser induced breakdown spectroscopy (LIBS) analysis of the soil samples collected from Aceh, a place in Indonesia worst affected by 2004 Indian Ocean tsunami, was conducted. In the LIBS experimental system, a high energy pulsed laser beam was focused on the tsunami affected soil samples and the atomic emission lines, originating from the laser induced plasma were recorded using locally developed laser induced breakdown spectrometer. Our results show that the concentrations of many elements especially terrestrial markers, namely titanium, iron, and carbonate marker such as magnesium, are higher in the tsunami-affected samples than that in the unaffected samples collected from the same neighborhood. The quantification of Ti, Fe and Mg were carried out using Ti II 334.94, Fe I 438.35, and Mg I 277.98 nm atomic transition lines respectively by drawing the calibration curve by preparing the samples of known concentrations in unaffected soil matrix. In order to ensure accurate quantification, the local thermal equilibrium of the laser-induced plasma was verified using Mc Writher criterion, for which the plasma temperature was estimated using linearized Boltzmann plot for six iron atomic transition lines and the electron number density in the plasma was estimated using Stark broadened Fe I 540.4 nm atomic lines. The estimated temperature and electron number density of the laser induced plasma are 9642 K and 3.5 × 10¹⁶ cm^?3 respectively. The concentrations of Ti, Fe and Mg in tsunami unaffected soil are 0.09, 3.2 and 0.02 w/w% and in tsunami affected soil are 0.14, 7.9 and 0.048 w/w% respectively. These values are in good agreement with XRF data. The elemental ratios extracted from LIBS signal intensity revealed that LIBS emission intensity ratios of several elements, such as Si/Ti, Al/Ti and Sr/Ba are potential candidates as the distinctive geochemical signature for identification the soil impacted and unimpacted by the 2004 Indian Ocean giant tsunami. The advantage of using LIBS for the elemental analysis is that the sample can be analyzed in its pristine form without any need cumbersome sample preparation method, which has the risk of bringing in external additives through chemicals used for the sample preparation. Other advantages of LIBS technique are that the analysis can be in situ and can be carried out remotely.     

PIXE analysis of the hydrothermal leaching of trace elements in coal

The minor and trace element content in coal is of great interest due to the potential impact on the environment from the release of these elements during combustion. Reducing the concentrations of potentially hazardous elements in coal prior to combustion is one way of dealing with this issue. In this research particle induced X-ray emission (PIXE) was used to investigate a hydrothermal leaching process for the removal of trace elements from a bituminous coal. The leaching agents HNO₃ and NaOH were evaluated along with the effects of process parameters (temperature, pressure, and time) on the method's effectiveness. The variable with the greatest influence was the leaching agent itself. HNO₃ was determined to be more effective than NaOH in reducing elemental concentrations for nearly all the elements determined. Increasing the temperature did result in greater reductions for some elements (Cl, Br, Zn) whereas increasing the pressure and duration of the leaching process had minimal impact on reductions, in elemental concentrations.