Elemental and proximate analysis of coal by x-ray fluorescence assisted laser-induced breakdown spectroscopy

Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in thermal power plants,the measurement repeatability of LIBS needs to be further improved due to the difficulty in controlling the stability of the generated plasmas at present.In this paper,we propose a novel x-ray fluorescence(XRF) assisted LIBS method for high repeatability analysis of coal quality,which not only inherits the ability of LIBS to directly analyze organic elements such as C and H in coal,but also uses XRF to make up for the lack of stability of LIBS in determining other inorganic ash-forming elements.With the combination of elemental lines in LIBS and XRF spectra,the principal component analysis and the partial least squares are used to establish the prediction model and perform multi-elemental and proximate analysis of coal.Quantitative analysis results show that the relative standard deviation(RSD) of C is 0.15%,the RSDs of other elements are less than 4%,and the standard deviations of calorific value,ash content,sulfur content and volatile matter are 0.11 MJ kg,0.17%,0.79% and 0.41%respectively,indicating that the method has good repeatability in determination of coal quality.This work is helpful to accelerate the development of LIBS in the field of rapid measurement of coal entering the power plant and on-line monitoring of coal entering the furnace.

Apply X-Ray Fluorescence and γ-Ray Spectroscopy to Analyze Igneous and Sedimentary Environmental Samples of Al-Atawilah (Al-Baha), Saudi Arabia

Igneous and sedimentary rocks contain an amount of natural radioactivity (NORM). U-238, Th-232 and their decay products, and K-40 are important sources of gamma-radiation. Knowledge of the radionuclide content of rocks is necessary to estimate the exposure of the population to the radiation. Many types of rocks are used in building and industries, thus the radiation detection is important, it provides a baseline map of levels of the radioactivity in the study region. The purpose of this study is to evaluate the activity concentrations of the natural radionuclides (U-238 (Ra-226), Th-232 and K-40) and the fallout nuclide (Cs-137) (if found) in thirty samples of igneous and sedimentary rocks of Al-Atawilah (Al-Baha). The samples were collected and prepared during 2018/2019, and analyzed with a good experimental instrument (High energy resolution γ-ray spectroscopy with HPGe detector), also these rock samples were analyzed with X-ray fluorescence to subdivided these rocks based on the major oxides proportions contained of each sample. The mean activity concentrations of naturally radionuclides were found in the igneous rock samples varied depending on the type of the igneous rock. For sedimentary rock samples, the activity concentrations were found high for quartz sandstone sample, which may be due to its high proportion of SiO2 and K2O. The estimated mean values of absorbed dose rate are within the permissible limit value. The findings indicate high dose level values in granite (rhyolite) and most of diorite (andesite) igneous rock samples while gabbro (basalt) igneous rock samples (except for one sample) record low levels of dose rate. All sedimentary rock samples have low dose rate (except for the quartz sand-stone sample).

A method for correcting characteristic X-ray net peak count from drifted shadow peak

To correct spectral peak drift and obtain more reliable net counts,this study proposes a long short-term memory(LSTM)model fused with a convolutional neural network(CNN)to accurately estimate the relevant parameters of a nuclear pulse signal by learning of samples.A predefined mathematical model was used to train the CNN-LSTM model and generate a dataset composed of distorted pulse sequences.The trained model was validated using simulated pulses.The relative errors in the amplitude estimation of pulse sequences with different degrees of distortion were obtained using triangular shaping,CNN-LSTM,and LSTM models.As a result,for severely distorted pulses,the relative error of the CNN-LSTM model in estimating the pulse parameters was reduced by 14.35%compared with that of the triangular shaping algorithm.For slightly distorted pulses,the relative error of the CNN-LSTM model was reduced by 0.33%compared with that of the triangular shaping algorithm.The model was then evaluated considering two performance indicators,the correction ratio and the efficiency ratio,which represent the proportion of the increase in peak area of the two characteristic peak regions of interest(ROIs)to the peak area of the corrected characteristic peak ROI and the proportion of the increase in peak area of the two characteristic peak ROIs to the peak areas of the two shadow peak ROI,respectively.Ten measurement results of the iron ore samples indicate that approximately 86.27%of the decreased peak area of the shadow peak ROI was corrected to the characteristic peak ROI,and the proportion of the corrected peak area to the peak area of the characteristic peak ROI was approximately 1.72%.The proposed CNN-LSTM model can be applied to X-ray energy spectrum correction,which is of great significance for X-ray spectroscopy and elemental content analyses.

Analysis of nickel distribution by synchrotron radiation X-ray fluorescence in nickel-induced early- and late-phase allergic contact dermatitis in Hartley guinea pigs

Background: Nickel-induced allergic contact dermatitis (Ni-ACD) is a global health problem. More detailed knowledge on the skin uptake of haptens is required. This study aimed to investigate the penetration process and distribution of nickel in skin tissues with late phase and early phase of Ni-ACD to understand the mechanisms of metal allergy. Methods: Forty Hartley guinea pigs were divided into four groups according to the NiSO4 sensitizing concentration and the NiSO4 challenged concentration: the 5% NiSO4-group, 5% to 10%(sensitization-challenge;late phase group);10% NiSO4-group, 10% to 10%(sensitization-challenge;early-phase group);and the positive and negative controls. Pathological biopsies were performed on each group. The depth profile of nickel element concentration in the skin of guinea pigs was detected by synchrotron radiation micro X-ray fluorescence spectroscopy (SR-μ-XRF) and micro X-ray absorption near-edge spectroscopy (μ-XANES). Results: In each section, the nickel element concentration in both the 5% NiSO4-group and 10% NiSO4-group was significantly higher than that in the negative control group. In the upper 300-μm section of skin for the early phase group, the nickel element concentration was significantly higher than that in the lower section of skin. In deeper sections (>200 μm) of skin, the concentration of nickel in the early phase group was approximately equal to that in the late phase group. The curve of the late phase group was flat, which means that the nickel element concentration was distributed uniformly by SR-μ-XRF. According to the XANES data for the 10% NiSO4 metal salt solution, structural changes occurred in the skin model sample, indicating that nickel was not present in the Ni^2+ aqueous ionic state but in the nickel-binding protein. Conclusions: This study showed that the distribution of the nickel element concentration in ACD skin tissue was different between the early phase and late phase groups. The nickel element was not present in the Ni^2+ aqueous ionic state but bound with certain proteins to form a complex in the stratum corneum in ACD model tissue.

Application and Development Trends of Spectral Analysis in Draft of Non-Ferrous Metal Standards in China

Spectral analysis was a method of identifying substances, determining their chemical composition and calculating their content based on their spectral characteristics. This paper mainly discussed the application of various spectroscopic techniques, mainly including atomic absorption spectrometry (AAS) inductively coupled plasma emission spectrometry (ICP-AES) X-ray fluorescence spectroscopy (XRF) atomic fluorescence spectroscopy (AFS) direct reading spectroscopy (OES) glow discharge emission spectroscopy (GD-OSE) laser-induced breakdown spectroscopy (LIBS), in the formulation of non-ferrous metal standards in China. The AAS method was the most widely used single-element microanalysis method among the non-ferrous metal standards. The ICP-AES method was good at significant advantages in the simultaneous detection of multiple elements. The XRF method was increasingly used in the determination of primary and secondary trace elements due to its simple sample preparation and high efficiency. The AFS was mostly detected by single-element trace analysis. OES GD-OES and LIBS were playing an increasingly important role in the new demand area for non-ferrous metals. This paper discussed matrix elimination, sample digestion, sample preparation, instrument categories and other aspects of some standards, and summarized the advantages of spectral analysis and traditional chemical analysis methods. The new methods of future spectroscopic technology had been illustrated in the process of developing non-ferrous metal standards.

Synthesis of SiC/graphene nanosheet composites by helicon wave plasma

We report an approach to the rapid, one-step, preparation of a variety of wide-bandgap silicon carbide/graphene nanosheet(Si C/GNSs) composites by using a high-density helicon wave plasma(HWP) source. The microstructure and morphology of the Si C/GNSs are characterized by using scanning electron microscopy(SEM), Raman spectroscopy, x-ray diffraction(XRD), x-ray photoelectron spectroscopy(XPS), and fluorescence(PL). The nucleation mechanism and the growth model are discussed. The existence of Si C and graphene structure are confirmed by XRD and Raman spectra.The electron excitation temperature is calculated by the intensity ratio method of optical emission spectroscopy. The main peak in the PL test is observed at 420 nm, with a corresponding bandgap of 2.95 e V that indicates the potential for broad application in blue light emission and ultraviolet light emission, field electron emission, and display devices.

Palaeodiet of Miocene Producers and Depositional Environments:Inferences from the First Evidence of Microcoprolites from India

This paper reviews research on coprolites from India,providing the first evidence of microcoprolites from the early Miocene(Aquitanian)Khari Nadi Formation sedimentary succession,exposed about 1.5 km northeast of the village of Kotada,Kachchh(Kutch)District,Gujarat State,western India.Morphometric and size comparisons(in a statistical framework)with known coprolites from the Mesozoic-Cenozoic successions of India(including those recorded herein)and globally suggest that fishes were the likely producers of the Kotada coprolites.Scanning electron microscopy confirms the presence of fish dental remains within the coprolites,while both Scanning Electron Microscopy(SEM)and Energy Dispersive X-ray Spectroscopy(EDS)reveal the phosphatic nature of the microscopic coprolite specimens(recorded herein)hinting that the producer(s)were predominantly carnivorous(ichthyophagous)in their diet.Furthermore,X-Ray Fluorescence(XRF)analysis of the host and associated lithologies allows us to deduce that the Kotada coprolites were deposited in a shallow marine environment,with possible aerial exposure of the host lithology occurring at some point after deposition.To the best of our knowledge,the present report is the first record of microscopic fish coprolites from India,as well as being the first from the Aquitanian of India and the oldest Neogene record from India.

Soil Clay Mineralogical Phase Analysis of Ganges Floodplain Soils by XRD and XRF

Soil minerals study is vital in terms of investigating the major soil forming compounds and to find out the fate of minor and trace elements in soils. It is also essential for the soil-plant interaction purpose. To identify soil mineral phases especially clay minerals, X-ray diffraction (XRD) has been a popular technique. The clay mineralogical information of soils in Bangladesh is limited, especially in Ganges flood plain region (Agro Ecological Zone (AEZ) 12 and 13). Therefore, to overcome this limitation, in this study, we performed XRD analysis of <2 mm fractions soil samples of AEX 12 and 13. However, identifying mineralogical phases by XRD in <2 mm fractions soils is not so straight-forward due to many practical problems. We fully matched only two mineralogical phases in all the soil samples which is quartz and potassium-Aluminum-Silicate. However, the full XRD peaks indicate that more minerals are also present, but due to heterogeneity of soils samples, it is difficult to find other minerals phases by only XRD peak of <2 mm fractions. Therefore, to find more information about mineralogical phases, we performed XRF analysis that provides the elemental composition of minerals phase as oxide. XRF analysis indicated the presence of secondary minerals like illite and chlorite. The presence of high percentage Fe oxide not only indicated the iron mineral phase (goethite and ferrihydrite) but also indicated iron rich high charge smectite minerals (beidellite). The presence of iron rich smectite minerals in the Ganges sediments reported in several previous studies. Thus, we concluded that only XRD in <2 mm fractions of soils is not adequate to identify the mineralogical phases of soil samples. Others analyses like XRF, XRD in <2 μm fractions will be necessary to locate an entire image of soil mineralogical phases.

Mineralogical and Geochemical Characteristics of Caprock Formations Used for Storage and Sequestration of Carbon Dioxide

The main objective of the present study is to characterize cap rock formation used for geological storage of carbon dioxide (CO2). The petrophysical properties of several rocks were studied before CO2 injection. This step is necessary for an understanding of CO2-brine-rock interactions. The mineralogical composition of several clay samples collected from real storage sites located in the south of Tunisia was determined by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) coupled to a probe EDS, infrared spectroscopy, thermal analysis and fluorescence spectra. The obtained experimental results reveal that illite, calcite and quartz are the dominant clay minerals. Dolomite and albite are also present. Besides, SEM analysis shows laminated structure for these samples which suggests low crystallinity. This sample contains a higher content of Fe, Cl, Ca and O. The clay cover may also be useful in storage process by immobilizing the migration of CO2 outer of the geological site and activating the process of mineral sequestration.

A statistic comparison of multi-element analysis of low atmospheric fine particles(PM_(2.5)) using different spectroscopy techniques

Over the past few decades,the metal elements(MEs)in atmospheric particles have aroused great attention.Some well-established techniques have been used to measure particlebound MEs.However,each method has its own advantages and disadvantages in terms of complexity,accuracy,and specific elements of interest.In this study,the performances of inductively coupled plasma-optical emission spectrometry(ICP-OES)and total reflection X-ray fluorescence spectroscopy(TXRF)were evaluated for quality control to analyze data accuracy and precision.The statistic methods(Deming regression and significance testing)were applied for intercomparison between ICP-OES and TXRF measurements for same lowloading PM_(2.5)samples in Weizhou Island.The results from the replicate analysis of standard filters(SRM 2783)and field filters samples indicated that 10 MEs(K,Ca,V,Cr,Mn,Fe,Ni,Cu,Zn,and Pb)showed good accuracies and precision for both techniques.The higher accuracy tended to the higher precision in the MEs analysis process.In addition,the interlab comparisons illustrated that V and Mn all had good agreements between ICP-OES and TXRF.The measurements of K,Cu and Zn were more reliable by TXRF analysis for low-loading PM_(2.5).ICP-OES was more accurate for the determinations for Ca,Cr,Ni and Pb,owing to the overlapping spectral lines and low sensitivity during TXRF analysis.The measurements of Fe,influenced by low-loading PM_(2.5),were not able to determine which instrument could obtain more reliable results.These conclusions could provide reference information to choose suitable instrument for the determination of MEs in low-loading PM_(2.5)samples.

Foliar application of rare earth elements on soybean(Glycine max(L)):Effects on biometrics and characterization of phytotoxicity

This study aims at investigating the effects of foliar application of aqueous solutions of La3+and Ce3+nitrates on soybean plants(Glycine max).First,we observe that Triton HW 1000 surfactant at 0.01 vol%reduces droplets contact angle and increases their drying time.Under greenhouse conditions,the foliar treatments do not affect chlorophyll content,plant height,number of leaves,number of pods,number of seeds per pod,and average seed weight.However,the treatments induce phytotoxicity since foliar injuries appear after the spraying.Microprobe X-ray fluorescence spectroscopy combined to scanning electron microscopy shows that the leaf lesions are positively correlated to accumulation of Ce and La on the leaf surface and also promote structural alteration to the epidermal cells.X-ray absorption near edge structure shows that the La and Ce nitrates are partially bio transformed into oxides by the leaves which might explain the harmful effects.

Total electron yield mode for XANES measurements in the energy region of 2.1-6.0 keV

The total electron yield （TEY） mode has been developed successfully for XANES measurements at Beamline 4BTA of BSRF （Beijing Synchrotron Radiation Facility）. Its performance was studied by measuring sulphur K-edge XANES of three CdS samples （mixed with graphite powder as an electric conductor） with different concentration： 75%, 50~ and 25%. The data are collected in TEY mode and fluorescence yield （FY） mode respectively for comparison. The results demonstrate that the TEY spectra of three samples agree well with each other after the background is subtracted and normalized. The measured XANES spectra by TEY mode without bias and with 100V bias are almost identical to one another, but the signal-to-noise ratio of spectra measured without bias is better than that with 100V bias. The consistency of the self-absorption corrected FY spectra and TEY spectra are within 10% for the three samples.