Use of portable X-ray fluorescence in the analysis of surficial sediments in the exploration of hydrothermal vents on the Southwest Indian Ridge

Hydrothermal plumes released from the eruption of sea floor hydrothermal fluids contain large amounts of oreforming materials. They precipitate within certain distances from the hydrothermal vent. Six surficial sediment samples from the Southwest Indian Ridge（SWIR） were analyzed by a portable X-ray fluorescence（PXRF） analyzer on board to find a favorable method fast and efficient enough for sea floor sulfide sediment geochemical exploration. These sediments were sampled near, at a moderate distance from, or far away from hydrothermal vents. The results demonstrate that the PXRF is effective in determining the enrichment characteristics of the oreforming elements in the calcareous sediments from the mid-ocean ridge. Sediment samples（〉40 mesh） have high levels of elemental copper, zinc, iron, and manganese, and levels of these elements in sediments finer than 40 mesh are lower and relatively stable. This may be due to relatively high levels of basalt debris/glass in the coarse sediments, which are consistent with the results obtained by microscopic observation. The results also show clear zoning of elements copper, zinc, arsenic, iron, and manganese in the surficial sediments around the hydrothermal vent. Sediments near the vent show relatively high content of the ore-forming elements and either high ratios of copper to iron content and zinc to iron content or high ratios of copper to manganese content and zinc to manganese content. These findings show that the content of the ore-forming elements in the sediments around hydrothermal vents are mainly influenced by the distance of sediments to the vent, rather than grain size. In this way, the PXRF analysis of surface sediment geochemistry is found to satisfy the requirements of recognition geochemical anomaly in mid-ocean ridge sediments. Sediments with diameters finer than 40 mesh should be used as analytical samples in the geochemical exploration for hydrothermal vents on mid-oceanic ridges. The results concerning copper, zinc, arsenic, iron, and manganese and their ratio features can be used as indicators in sediment geochemical exploration of seafloor sulfides.

Portable fluorescence instrument for detecting membrane integrity in membrane bioreactor (MBR)

This study proposed the design, fabrication, and assembly of membrane integrity detection instruments in membrane bioreactors (MBR) based on fluorescence spectroscopy. Based on the PARAFAC model, we found that the peak at 280/335 nm strengthened after membrane breakage. The peak at 340/430 nm reflected the sludge concentration in the MBR and reduced the influence of internal filtration effects on detection. Therefore, we determined that the dual-LED light source excitation detection system can detect tryptophan-like substances at 280 nm (T-peak) and humic acid at 340 nm (C-peak). T-peak was identified as the core index indicating membrane integrity. Moreover, the C-peak is the reference indicator factor for a sensitive response to changes in the sludge concentration. The portable fluorescence instrument exhibited high sensitivity and good feedback accuracy compared to particle counting and turbidity detection, where the log reduction value was greater than 3.5. This overcomes the disadvantage of false alarms in particle counters and is not affected by the position of the pump system. This portable instrument provides a flexible and highly sensitive method for the assessment of industrial membrane integrity.

Application of a Portable XRF Spectrometer for <i>In-Situ</i>and Nondestructive Investigation of Pigments in Two 15th Century Icons

A simple portable X-Ray Fluorescence (XRF) spectrometer was successfully used for in-situ and nondestructive identification of the painting materials in two 15th century icons from the Onufri Museum in Beart, Albania. The spectrometer is based on a low power X-ray tube, a thermoelectrically cooled Si PIN detector and the spectrum acquisition system. It was assembled and adjusted at our laboratory for the investigation of the icons. A small number of pigments were clearly identified by X-Ray Fluorescence (XRF) measurements in both icons. This includes Lead white for the white color, gold and yellow ochre for the yellow color, red lead, cinnabar and red ochre for the red color, as well as cooper based pigments for the green color. At the same time, the investigation raised some new questions that need further investigations by the use of additional analytical techniques. The results show that in both icons are used similar pigments, which are in accordance with the Byzantine icon painting tradition.

A TOTAL CONTENT X—RAY FLUORESCENCE METHOD FOR COPPER PROSPECTING

A new method is proposed to prospect copper deposits with portable XRF analyzer. The method is based on the close relation between Cu and the chalcophile elements or some other elements in the geochemical anomalies of a Cu deposit. Applications of the technique in Northeast China are presented.

便携式X射线荧光光谱仪检验无碳复写纸的研究

利用便携式X射线荧光光谱仪对收集到的45个不同品牌、不同类型的无碳复写纸样品进行检验,根据显色层中各元素的含量比对无碳复写纸样品进行区分,并利用SPSS24.0软件进行聚类分析,效果良好。该方法无损检材、方便快捷、检测限低、稳定性好,可用于无碳复写纸物证的检验鉴别。

翡翠成分、结构和矿物组成的无损分析

利用便携式能量色散型X射线荧光(portable energy-dispersive X-ray fluorescence,PXRF)、外束质子激发X射线(external beam proton induced X-ray emission,PIXE)、X射线衍射(X-ray diffraction,XRD)和激光拉曼光谱(laser Raman spectroscopy,LRS)对12块样品进行了成分、结构和矿物组成分析。结果表明,PXRF和PIXE的分析结果有较好的可比性,样品主要由较纯的硬玉组成,次要元素含量较低。1块样品含少量绿辉石,一块样品主要由绿辉石组成。硬玉的Raman特征峰位于201,372,698,985,1 037cm-1,绿辉石的特征峰位于680和1 017cm-1。利用Raman光谱测试样品的裂隙处,发现3块样品含白蜡,1块样品含环氧树脂。白蜡的Raman特征峰位于2 846和2 880cm-1,环氧树脂的特征峰位于2 924和3 065cm-1。无损分析技术在翡翠中的应用拓展了样品的研究范围,为翡翠的进一步研究、鉴定和分级提供了技术支持。

鄂尔多斯盆地西缘北段乌达剖面石炭系羊虎沟组地球化学特征及其古环境意义

鄂尔多斯盆地西缘石炭系羊虎沟组的烃源岩条件好,但其沉积环境存在较大的争议,因盆地中部、南部的羊虎沟组露头的部分层位存在缺失,以北部地区乌达剖面为例开展了系统研究。采用便携式X射线荧光光谱仪对剖面进行连续精确测试,结合孢粉古生物、干酪根-δ^(13)C‰、稀土元素分析,对工区的古氧化还原环境、古气候、古水深及体系域进行分析。结果表明:通过V/(V+Ni)、Ni/Co、δEu值判别羊虎沟时期处于氧化到还原的过渡阶段;Sr/Cu介于1.3~7.8,蕨类植物孢子占绝对优势地位,处于温暖潮湿气候;羊虎沟时期从低水位体系域到海侵体系域再到高位体系域,Al元素的质量分数和Sr/Ba值由高→低→高,而Mg元素的质量分数由低→高→低。该区域主要受西北部阿拉善古陆物源控制,总体表现为滨浅海-三角洲复合沉积环境。

A New Discovery of Ag-Pb-Zn Mineralization via Modern Portable Analytical Technology and Stream Sediment Data Processing Methods in Dajiacuo Area, Western Tibet(China)

Tibet, which is rich in mineral resources, is a treasure trove for geological explorers. However, prospecting work has been slow, especially in the western part, due to the precipitous terrain, changeable climate and low access. Hence, modern advanced field analytical technology and effective data processing methods play significant roles in rapid and efficient exploration in Tibet. In this paper, spectrum-area fractal modeling and portable X-ray fluorescence analysis(pXRFA) were used to identify and verify geochemical anomalies associated with Ag-Pb-Zn mineralization based on a stream-sediment dataset of 39 elements in the Dajiacuo-Xurucuo region of western Tibet. First, staged factor analysis(SFA) was used to obtain the Ag-Pb-Zn-Cd geochemical assemblage. Second, the first-factor pattern obtained using SFA was dissociated by a spectrum-area(S-A) fractal model and a digital elevation model(DEM)-based geochemical model(DGM) was constructed. Finally, the sections of Ag, Cd, Pb, and Zn were obtained using pXRFA. The results show that Ag-Pb-Zn-Cd enrichment zones were mostly located around the contact belt of volcanic rocks and intrusions, or along SE-NW trending faults. Considering the variable terrain and catchment basin, the extension of long axes of Ag-Pb-Zn-Cd anomalies into higher elevation areas that are favorable for Ag-Pb-Zn mineralization should be investigated. Anomaly maps created with the aid of a DGM show promising potential for mineralization in the Dajiacuo-Xurucuo region, and abundant Ag-Pb-Zn mineralization was identified with the assistance of pXRFA in the source areas for the geochemical anomalies in the Dajiacuo. We conclude that SFA and the S-A fractal model constitute a valid tool to identify or verify geochemical anomalies in areas of low-density stream-sediment sampling. The pXRFA can accurately determine the source of geochemical anomalies and improve anomaly verification efficiency.

Rapid Growth of Pentaerythritol Crystal

Pentaerythritol（PET） crystal has been grown rapidly from the solution with sulfuric acid as the additive. The growth rate of PET crystal in prismatic shape exceeds 1.5 mm/day and crystallization size is 55×55×50 mm^3. X-ray diffraction analysis was used to confirm the structure integrity. The diffraction efficiency of rapid-grown crystal was characterized as effective as that of normal growth.

Metal Accumulation Capability by <i>Platanus acerifolia</i>(Aiton) Willd., <i>Ailantus altissima</i>(Mill.) Swingle, <i>Robinia pseudoacacia</i>L. and <i>Quercus ilex</i>L., Largely Distributed in the City of Rome

The main of the research was to analyze the leaf metal accumulation capability of Platanus acerifolia (Aiton) Willd., Ailantus altissima (Mill.) Swingle, Robinia pseudoacacia L. and Quercus ilex L., largely distributed in Rome. In addition, metal concentration was analyzed in the soil, sampling sites were chosen in historical parks (A sites) and high traffic level sites (B sites). The results highlight significant higher leaf and soil metal concentrations in B than in A sites. The ratio between metal concentration in leaves and soils (Biological Absorption Coefficient, BAC) for all the considered sites was significantly different among the species. Morphological and anatomical leaf traits of the considered species show significant differences in A and B sites in response to traffic level. Overall, the results highlight the importance of the selection of tree species in urban areas for their ability to lower pollution levels.

便携式X射线荧光光谱技术在泥河铁矿岩心矿化蚀变信息识别中的应用

便携式X射线荧光光谱(PXRF)是针对野外原位快速分析而发展起来的一项新技术,常被用于岩石露头地球化学研究和土壤重金属污染评价等方面.本研究以安徽省泥河铁矿钻孔为例,在野外对5个钻孔的岩心系统划分岩性段,利用便携式X射线荧光光谱仪原位测量每个岩性段的Fe、Mn、Cr、Co、Ni、Ti、V、Cu、Zn、Pb、Ag、Mo、K、Ca、As、Sb、Bi、Cs、Zr、Nb等元素含量,绘制钻孔各元素含量分布图.研究发现,(1)利用PXRF技术获得的岩心Fe元素高含量部位与根据化学分析得到的铁矿石品位数据而圈定的磁铁矿体范围吻合较好;(2)Fe元素和Fe-V-Mn-Cr-Ni-Ti-Bi组合异常、Zn元素和Zn-Cu-Cd组合异常分别对铁矿化和铜、锌矿化具有较好的指示作用;(3)K、Ca异常分别对钾长石化、硬石膏化等蚀变具有较好的指示作用.由此可见,PXRF技术在野外岩心矿化和蚀变信息识别中具有方便、快捷、实用、可靠、无损、成本低廉等优点.

天然玻璃化学成分、结构和物相的无损分析

通过便携式能量色散型X射线荧光、X射线衍射和激光Raman光谱等无损分析技术研究了11块天然玻璃样品的化学成分、结构和物相。结果表明:除两件样品(B1和H3)外,其它样品均为玻璃态,主要化学成分为SiO2与Al2O3。通过化学成分分析可以区分玻陨石和黑曜石样品,玻陨石中铁与碱土金属含量比黑曜石高,而碱金属含量比黑曜石低。激光Raman光谱测试表明:样品在470 cm–1附近有玻璃态特征的弥散包络峰,应为含有6个[SiO4]组成的变形环状结构单元。

Using pXRF and vis-NIR spectra for predicting properties of soils developed in loess

Visible near-infrared (vis-NIR) and portable X-ray fluorescence (pXRF) spectrometers have been increasingly utilized for predicting soil properties worldwide. However, only a few studies have focused on splitting the predictive models by horizons to evaluate prediction performance and systematically compare prediction performance for A, B, and combined A+B horizons. Therefore, we investigated the performance of pXRF and vis-NIR spectra, as individual or combined, for predicting the clay, silt, sand, total carbon (TC), and pH of soils developed in loess, and compared their prediction performance for A, B, and A+B horizons. Soil samples (176 in A horizon and 172 in B horizon) were taken from Mollisols and Alfisols in 136 pedons in Wisconsin, USA and analyzed for clay, silt, sand, pH, and TC. The pXRF and vis-NIR spectrometers were used to measure the pXRF and vis-NIR soil spectra. Data were separated into calibration (n = 244, 70%) and validation (n = 104, 30%) datasets. The Savitzky-Golay filter was applied to preprocess the pXRF and vis-NIR spectra, and the first 10 principal components (PCs) were selected through principal component analysis (PCA). Five types of predictor, i.e., PCs from vis-NIR spectra, pXRF of beams at 0–40 and 0–10 keV (XRF40 and XRF10, respectively) spectra, combined XRF40 and XRF10 (XRF40+XRF10) spectra, and combined XRF40, XRF10, and vis-NIR (XRF40+XRF10+vis-NIR) spectra, were compared for predicting soil properties using a machine learning algorithm (Cubist model). A multiple linear regression (MLR) model was applied to predict clay, silt, sand, pH, and TC using pXRF elements. The results suggested that pXRF spectra had better prediction performance for clay, silt, and sand, whereas vis-NIR spectra produced better TC and pH predictions. The best prediction performance for sand (R2= 0.97), silt (R2= 0.95), and clay (R2= 0.84) was achieved using vis-NIR+XRF40+XRF10 spectra in B horizon, whereas the best prediction performance for TC (R2= 0.93) and pH (R2= 0.79) was achieved using vis-NIR+XRF40+XRF10 spectra in A+B horizon. For all soil properties, the best MLR model had a lower prediction accuracy than the Cubist model. It was concluded that pXRF and vis-NIR spectra can be successfully applied for predicting clay, silt, sand, pH, and TC with high accuracy for soils developed in loess, and that spectral models should be developed for different horizons to achieve high prediction accuracy.

Proximal sensor-enhanced soil mapping in complex soil-landscape areas of Brazil

Portable X-ray fluorescence(pXRF) spectrometry and magnetic susceptibility(MS) via magnetometer have been increasingly used with terrain variables for digital soil mapping. However, this methodology is still emerging in many countries with tropical soils. The objective of this study was to use proximal soil sensor data associated with terrain variables at varying spatial resolutions to predict soil classes using the Random Forest(RF) algorithm. The study was conducted on a 316-ha area featuring highly variable soil classes and complex soil-landscape relationships in Minas Gerais State, Brazil. The overall accuracy and Kappa index were evaluated using soils that were classified at 118 sites, with 90 being used for modeling and 28 for validation. Digital elevation models(DEMs) were created at 5-, 10-, 20-, and 30-m resolutions using contour lines from two sources. The resulting DEMs were processed to generate 12 terrain variables. Total Fe, Ti, and SiO_(2) contents were obtained using pXRF, with MS determined via a magnetometer. Soil class prediction was performed using the RF algorithm. The quality of the soil maps improved when using only the five most important covariates and combining proximal sensor data with terrain variables at different spatial resolutions. The finest spatial resolution did not always provide the most accurate maps. The high soil complexity in the area prevented highly accurate predictions. The most important variables influencing the soil mapping were MS, Fe, and Ti. Proximal sensor data associated with terrain information were successfully used to map Brazilian soils at variable spatial resolutions.

Field-scale spatial variability of soil calcium in a semi-arid region:Implications for soil erosion and site-specific management

Excess calcium(Ca)in soils of semi-arid and arid regions has negative effects on soil structure and chemical properties,which limits the crop root growth as well as the availability of soil water and nutrients.Quantifying the spatial variability of soil Ca contents may reveal factors influencing soil erosion and provide a basis for site-specific soil and crop management in semi-arid regions.This study sought to assess the spatial variability of soil Ca in relation to topography,hydraulic attributes,and soil types for precision soil and crop management in a 194-ha production field in the Southern High Plains of Texas,USA.Soils at four depth increments(0-2,0-15,15-30,and 30-60 cm)were sampled at 232 points in the spring of 2017.The Ca content of each sample was determined with a DP-6000 Delta Premium portable X-ray fluorescence(PXRF)spectrometer.Elevation data was obtained using a real-time kinematic GPS receiver with centimeter-level accuracy.A digital elevation model(DEM)was derived from the elevation data,and topographic and hydraulic attributes were generated from this DEM.A generalized least-squares model was then developed to assess the relationship between soil Ca contents of the four layers and the topographic and hydraulic attributes.Results showed that topographic attributes,especially slope and elevation,had a significant effect on soil Ca content at different depths(P<0.01).In addition,hydraulic attributes,especially flow length and sediment transport index(STI),had a significant effect on the spatial distribution of soil Ca.Spatial variability of soil Ca and its relationships with topographic and hydraulic attributes and soil types indicated that surface soil loss may occur due to water or wind erosion,especially on susceptible soils with high slopes.Therefore,this study suggests that the application of PXRF in assessing soil Ca content can potentially facilitate a new method for soil erosion evaluation in semi-arid lands.The results of this study provide valuable information for site-specific soil conservation and crop management.