Polarized Energy Dispersive X-ray Fluorescence Research Articles

Elemental assay of the fumarolic microecology of the Los Azufres (México) volcanic complex using nuclear analytical techniques

The elemental composition of the mantle is a key factor for the understanding of the science of the earth’s interior. However, the direct sampling of the mantle is a difficult and involved task. Fumarolic vapours carry a certain imprint of the mantle composition but are also relatively difficult to sample directly given their high temperature and acidity. Many terrestrial fu- marolic vents are colonized by extremophilic mosses that absorb the vapours and become repositories of the mantle elements brought up by the vapours. The elemental composition of the niche ecology of the fumarole therefore may serve as a near “proxy” for the deep-earth elemental profile of the region. Our study concerns the elemental composition of fumarolic plants, their rhizospheric soil, hydrothermal sediment and volcanic substrate collected from three geothermal microecological sites of the Los Azufres volcanic complex of Mexico. This work presents the results for the heavy elements (HE) Cd, Hg, Pb, Th and U that have been determined using the nuclear analytical techniques of Polarized Energy Dispersive Xray Fluorescence (PEDXRF) spectrometry, Instrumental Neutron Activation Analysis (INAA) as well as Inductively Coupled Plasma Mass spectrometry (ICPMS). The distributions of these HE in the aforesaid biogeochemical matrices are examined and rationalized with respect to possible mechanisms of their deposition. Comparisons with literature reports of the HE composition of fumarolic sulphur deposits and fumarolic vapours of the volcanoes of the Kuril Islands and geothermal aquifers of Iceland, are made. The HE composition is found to vary considerably by the geographic location of the fumarole. However, the trend of the concentrations of these 5 HE is found to be approximately the same for the fumarolic plants of Los Azufres as with the fumarolic vapours of the Kuril volcanoes the displacement being only in the magnitudes. Consequently, the concentrations of these 5 HE in the fumarolic plants are direct qualitative analogues of the vapours of those particular fumaroles of Los Azufres and thereby of the deep-earth geochemistry of that particular geothermal zone.

Total Reflection Xray Fluorescence (TXRF) spectrometry as a powerful and broad-spectrum analytical tool in the nuclear sciences

X-ray spectroscopy is widely used in nuclear reaction and structure studies. To aid such studies the technological envelope is continually being pushed to achieve higher quality such as superior power and brilliance, higher resolution and sensitivity. We present the discussion of a relatively new form of X-ray fluorescence spectrometry - Total Reflection X-ray Fluorescence (TXRF) spectrometry that can achieve analytical sensitivities of the order of parts per billion (ppb). An overview of the TXRF technique is presented and its utility for nuclear materials analysis discussed. Polarized Energy Dispersive X-ray Fluorescence (PEDXRF) spectrometry is also an XRF technique that can complement TXRFS where it may not be applicable. That scenario is discussed with respect to our results using PEDXRF on geothermal samples that serve to corroborate the recent findings of the Borexino Geoneutrino Experiment regarding the high Th, U concentrations in the earth’s mantle.

Determination of the chemical composition and Raman characterization of barite samples from Denizli and Akdamadeni, Turkey, using Energy Dispersive X-ray fluorescence and Raman microscopy

Accurate analysis of samples is very important for scientists working in many fields. XRF device is used very frequently especially in mine analysis. However, researchers are trying to reach accurate results with many different analysis methods. In addition to the known analysis methods, alternative research methods also guide the studies. In this study, two barite ore samples, collected from two regions of different nature (Denizli and Akdağmadeni) by following specified sampling methods, were analyzed using Confocal Raman Spectroscopy (CRS) and Polarized Energy Dispersive X-Ray Fluorescence (PEDXRF) spectrometer. The first sample was from a metamorphic basement, and the second was from an alkali syenite rock unit. The main objective of this paper is to compare the optical characteristics of these two different barite samples collected from different regions under a polarized microscope, using CRS and PEDXRF. The results of polarized microscopy analysis showed that the barite taken from Denizli is associated with calcite. On the other hand, the barite taken from Akdağmadeni is associated with galena, celestite, and quartz. Two different colors were observed in the barite samples. CRS and PEDXRF results showed that the barites collected from two regions differed in mineral association, chemical composition, and physical properties. The accuracy of the chemical analysis technique was ensured by following USGS standards, GBW 7109, and GBW-7309 Sediment. Barite ores were analyzed using HR-800 (HORIBA-Jobin Yvon) CRS and a polarized microscope (Leica DMLP). Thanks to this study, it has been shown that mineral analyzes can be performed with an accuracy close to XRF with Confocal Raman spectroscopy. Confocal Raman spectroscopy will also guide researchers for mineral analysis.

Archaeometric Studies on the Characterization and Deteriorations of Glass Artifacts of Su Terazisi and Kral Kızı Regions in Enez (Ainos) Excavation

Archaeometric investigations were carried out to determine and correlate the chemical contents with the layers of deterioration of the 19 glass finds dating to the Roman Period uncovered from Su Terazisi and Kral Kızı Regions of Enez (Ainos) ancient city. The physical condition of glass finds was firstly examined, the layers of deterioration on the glass surface were documented with photographs, their thickness was measured with a digital thickness meter, their colors were identified by a chromameter, and images of the bubbles and deterioration products were taken under an optical microscope. When the deterioration layers of the samples belonging to the Roman Period were examined visually and with an optical microscope, the types of deterioration resulting from the chemical composition of the glass, such as iridescence, dulling, black discoloration and pitting were identified. A table was created of the existing degree of deterioration. Micro-XRF and Polarized Energy Dispersive-X-Ray Fluorescence (PED-XRF), Scanning Electron MicroscopeEnergy Dispersive Spectrometry (SEM-EDS), and Raman (Confocal) Spectroscopy methods were used to determine the element and mineralogical contents, and the deterioration layer of the glass samples. When all the archaeometric results were evaluated, it was revealed that there was a difference between the bulk glass and the deterioration layers.

Construction and application of a micro-area polarized energy dispersive X-ray fluorescence spectrometer with polycapillary X-ray lens in a conventional laboratory

The polarized energy dispersive X-ray fluorescence analysis method can effectively reduce detection limits by improving the signal-to-noise ratio. However, the lack of high-power density and small analysis area of the polarized X-ray beam has hindered more accurate analysis of samples in conventional laboratory. A polycapillary X-ray lens can be applied to micro-area analysis. Therefore, a micro-area polarized energy dispersive X-ray fluorescence spectrometer based on a bent highly oriented pyrolytic graphite and a polycapillary X-ray lens is proposed. The polarization degree of the polarized X-ray beam is 99.76% and its focal spot size is 338.8 μm × 404.5 μm. The new spectrometer feasibility was proved by effective production of high-resolution element distribution maps of a holly (Ilex chinensis Sims) leaf sample.

Elemental monitoring of street dusts in Konya in Turkey

In this study, we tried to obtain information about the level of pollution in the region by analyzing the solid residues collected from the roadsides of Konya, which is an industrialized city of Turkey. In the study, solid powder samples were collected from Konya city in September 2014, at 4 different times by the municipal vehicles. The samples, collected from a total of 21 different regions were analyzed. Collected samples were first sifted through 250 μm sieves, then pelletized into 32 mm pellets with a wax binder. The elements in the prepared samples were determined by polarized energy-dispersive X-ray fluorescence (PEDXRF) spectrometry. Elements such as Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Rb, Sr, Zr, Ba, La, Ce and Pb were determined by PEDXRF. The reliability of the method was also tested with CRM 2126–81 standard substance. The amount of elements such as As, Cr, Ni, Co and Fe were particularly discussed in the regions close to industrial establishments, whereas the amount of Pb was discussed for the routes on the main road.

Lead uptake by the symbiotic Daucus carota L.-Glomus intraradices system and its effect on the morphology of extra- and intraradical fungal microstructures.

This work examines the strategies adopted by an arbuscular mycorrhizal symbiotic system to ameliorate environmental Pb stress by examining the concentrations of P, Fe, and Pb in the fungal microstructures and the host's root. In vitro cultures of Ri-T DNA-transformed carrot (Daucus carota L.) roots were inoculated with Glomus intraradices and treated with Pb(NO3)2 solution and the extraradical spores and mycelia (S/M) and the root with the vesicles, mycelia, and root cells were subsequently analyzed by polarized energy dispersive x-ray fluorescence (PEDXRF) spectrometry. Upon Pb treatment, within the root, the percentages of mycorrhizal colonization, the vesicles, and mycelia increased as well as the areas of the vesicles and the (extraradical) spores, although the number of spores and arbuscules decreased. The S/M and the mycorrhizal root showed enhanced concentrations of Pb, Fe, and P. These were particularly marked for Fe in the Pb-treated cultures. This indicates a synergistic relationship between the arbuscular mycorrhizal fungus and the host that confers a higher Pb tolerance to the latter by the induction of higher Fe absorption in the host. The intraradical vesicle, mycelia, and arbuscule numbers are interpreted as a "tactic to divert" the intraradical Pb traffic away from the root cells to the higher affinity cell walls of the arbuscular mycorrhizal fungi (AMF) microstructures in the apoplast. The results of this work show that the symbiosis between the AMF G. intraradices and the host plant D. carota distinctly improves the latter's Pb tolerance, and imply that the appropriate metal tolerant host-AMF combinations could be employed in process designs for the phytoremediation of Pb.

Use of tourmaline as a potential petrogenetic indicator in the determination of host magma: CRS, XRD and PED-XRF methods

Tourmaline defines a group of complex borosilicate forms as accessory mineral in igneous and metamorphic rocks and they act an important role in the interpretation of the chemical composition changes of the composition of the host fluid of the magma.The variety of tourmaline can be identified by using optical microscopy, X-Ray Diffraction (XRD) and by determining its chemical composition through Polarized Energy Dispersive X-Ray Fluorescence (PED-XRF) methods. However, microscopic investigations and XRD analyses are not quite adequate for detailed determination of tourmaline sub-groups. In addition, the use of chemical composition of tourmaline as a strict indicator of geochemical processes might be a misleading method. In this study, variable tourmaline crystals were collected from three different pegmatitic occurrences in Behrekdag, Yozgat and Karakaya granitic bodies of Central Anatolia to identify their chemical properties through Confocal Raman Spectroscopy (CRS), PED-XRF and XRD analyses.The confocal Raman spectrometry of collected tourmalines from the Behrekdag, Yozgat and Karakaya granites are in the compositions of schorl, schorl and elbaite respectively. The dominant compositional groups of these tourmalines are in the form of schorl. Raman shift values of tourmalines revealed four bands centered at almost 1050, 750, 400 and 300cm−1. The first group of the band arises from SiO stretching, the second from BO stretching and the other two belong to bending modes of OBO and BOAl with symmetrical deformation of SiOSi. The strongest spectra near 360cm−1 should belong to the bonding of AlO. As a result, the confocal Raman studies are more sensitive for identification of tourmaline subgroup compositions and have a quite important in the explaining source of the magma.

A Rapid Determination Method of <sup>40</sup>K Concentration in the Soil

The pressed powder sample was determined by Epsilon 5 high-energy polarized energy dispersive X-ray fluorescence (EDXRF) spectrometer. The correlation coefficient of the standard curve method is 0.991 0. The precision is 2.98% and the relative deviation of the measurement standard samples is up to 6.40%, which showed that the precision and accuracy of the method were also good. Simultaneous measurement of seven soil samples with this method and γ-spectrometer were carried, the results of two analytical methods was compared using a paired t-test by SPSS program, which showed that there was no significant difference in the two sets of data. The results predicated that EDXRF could be a potential simple method for analyzing 40K in soil samples.

Characterizing fundamental parameter-based analysis for soil–ceramic matrices in polarized energy-dispersive X-ray fluorescence (PEDXRF) spectrometry

Analytical polarized energy-dispersive X-ray fluorescence (PEDXRF) spectrometry (PEDXRFS) represents a substantial advancement over conventional XRF. The higher signal-to-noise commensurate with background lowering and better energy resolution, permits trace analysis for elements with Z ≥ 11. Concomitantly, improvements in analytical software based on the fundamental parameters (FP) approach have improved accuracies and precisions for standard-less analysis (SLA). Two ceramic and soil standard reference materials (SRMs), 98a-Plastic Clay and GSS-1 powders, differed in their intrinsic matrix properties of grain size, bulk, and surface monolayer densities as well as the elemental concentrations. The SRMs were analyzed as powder and as pellets compacted under the same pressure conditions to double the bulk density. Different geometries represented by the sample cup (10, 15, and 24 mm) and pellet (10, 15, and 25 mm) diameters with the same sample thickness (with differing masses and aspect ratios), as well as (for powder samples only) identical low masses (0.5 g) but with varying thicknesses, were analyzed. PEDXRFS combined with TURBOQUANT® (TQ) as SLA-FP enables good quantitative analysis for powders (Z ≥ 13) even for masses significantly lower than recommended, for soil–ceramic samples. Pellets (Z ≥ 12) yielded the best accuracy factor (AF) at high aspect ratio and thicknesses of the matrix analytical depth. Binder in pellets depreciates the AF. TQ needs to adequately quantitate matrix interferences effects, to improve accuracy in the analysis of low atomic numbers, e.g. Na and Mg.

ELEMENTAL COMPOSITION OF PEPPER PLANTS FERTILIZED WITH PELLETIZED POULTRY MANURE

Poultry manure (PM) has been traditionally applied to crops for decades as an organic fertilizer, because it is a good and balanced source of plant nutrients. Its effect on plant growth and yield has been widely investigated and is well known. However, there has been little effort to relate elemental compositions of the manure applied to their concentrations in the plants. The objective of this study was to examine the effects of PM on the growth, and essential and non-essential element composition of pepper (Capsicum annuum) leaves and also fruits. Pepper plants were grown in soil with 0, 10, 20, and 40 g kg−1 PM under greenhouse conditions. Concentrations of nitrogen (N), phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), silicon (Si), aluminum (Al), iron (Fe), zinc (Zn), copper (Cu), manganese (Mn), molybdenum (Mo), chloride (Cl), nickel (Ni), bromine (Br), rubidium (Rb), strontium (Sr), barium (Ba), lanthanum (La), and cerium (Ce) in leaves at the flowering stage and in fruits were determined by polarized energy dispersive X-ray fluorescence (PEDXRF). Poultry manure fertilization significantly improved pepper shoot growth and also fruit yield, and increased leaf and fruit P concentrations but not N, K, Mg, Si, Al, Ni, and Fe. Leaf Ca was significantly reduced by increased rate of PM application. Applied PM increased the concentrations of leaf and fruit Zn and Cl. Poultry manure applications had a positive effect on the concentrations of leaf Cu, and fruit Mn. The concentrations of Rb and Ce in fruits and Br in fruit and leaves were increased by PM treatments. Applied PM levels had no clear effect on the concentrations of Ba and La in pepper leaves. The leaf Ba was the highest with 10 g kg−1 PM, and leaf La was higher in 20 and 40 g kg−1 PM treatments than in the control.

Mackenzie Inuit Lithic Raw Material Procurement in the Lower Mackenzie Valley: The Importance of Social Factors

Oral and written historical records indicate that the Mackenzie Inuit traveled up the Mackenzie River from the Arctic Coast to procure lithic raw material in the interior from a quarry at the mouth of the Thunder River, which is known locally by the Gwich’in of the lower Mackenzie Valley as Vihtr’ii Tshik. We evaluate this proposition using non-destructive polarized energy dispersive X-ray fluorescence to compare the geochemical signatures of the lithic raw material from Vihtr’ii Tshik (MiTi-1) and flakes and tools from the Mackenzie Inuit village of Kuukpak (NiTs-1), which is located more than 400 km downriver of the quarry source. The concentrations of nine selected elements—three major elements expressed as oxides (SiO2, Fe2O3T, and K2O) and six trace elements expressed as metals (Rb, Sr, Y, Zr, Ba, and Ce)—are compared using descriptive statistics, spider diagrams, and principal components analysis. The geochemical effects of chemical weathering on the surfaces of artifacts are evaluated by measuring element concentrations before and after removal of the weathering rind from select artifacts. The results of our analyses demonstrate that the lithic raw material available at Vihtr’ii Tshik is best characterized as chert, and that 86% of the flakes and tools from Kuukpak analyzed in this study are chemically similar to the raw material from Vihtr’ii Tshik. Historical records and archaeological data indicate that the people of Kuukpak traversed a complex social landscape to obtain stone from Vihtr’ii Tshik through direct procurement.

Localization and distribution of nickel and other elements in in-vitro grown Alyssum corsicum exhibiting morphological changes in trichomes: initial insights into molecular mechanisms of nickel hyperaccumulation

Alyssum corsicum Duby is a candidate plant used for phytomining and phytoremediation studies with its high Ni-accumulating ability of the aboveground tissues. Metal localization and concentration by hyperaccumulator plants and the physiological basis of these phenomena have been of great interest in recent years. A. corsicum seeds were grown at different concentrations of Ni in Murashige and Skoog medium. Multielement concentrations of the plant roots and shoots were determined by polarized energy dispersive X-ray fluorescence. Ni, Ca, Mg, and Fe localization and concentration at the upper and lower leaf surfaces were determined by scanning electron microscopy coupled with the energy-dispersive X-ray analysis technique (SEM-EDX). Results showed that Ni is accumulated more by the shoots than the roots of the plant and that Ni is concentrated mainly in the trichome and the stoma guard cells of the leaves. Trichome density on the leaves was reduced, and some morphological changes of the trichome structure were also observed with increasing Ni levels. Analysis of antioxidant enzyme activities in roots and shoots was performed. The total leaf proteins of the plant were examined by sodium dodecyl sulfate polyacrylamide gel electrophoresis, and differentially expressed genes were detected by specifically designed primers.

The effects of surface weathering on the geochemical analysis of archaeological lithic samples using non‐destructive polarized energy dispersive XRF

AbstractThe purpose of this paper is to show the effects of lithic artifact surface weathering on whole rock non‐destructive polarized energy dispersive X‐ray fluorescence (P‐ED‐XRF) major and trace element determinations. Chemical results for a weathered and subsequently mechanically ground subset of New Hampshire Ossipee archaeological flakes, cataloged as hornfels, show that both groups of elements are variably affected by weathering. A graphic approach is developed and proposed to highlight the role and importance of immobile elements. A case is made and an analytical method is proposed for the routine use of P‐ED‐XRF spectrometers to determine the chemical makeup of lithic artifacts and therefore provide a data set compatible with existing geochemical databases and literature. The use of specific variation diagrams is adopted to portray the weathering trend. Internationally approved geochemical rock type diagrams are used to correct the rock type previously assigned to Ossipee artifacts and in turn narrow down potential quarry sources. © 2011 Wiley Periodicals, Inc.

Essential and non-essential element composition of tomato plants fertilized with poultry manure

Poultry manure (PM) must be disposed of from poultry farms, but is a potentially valuable source of macro- and micronutrients for plant growth. The objective of this study was to examine the effects of poultry manure on the growth of tomato ( Lycopersicon esculentum) plants. Yields of fruits and vegetative material of plants grown in soil with 0, 10, 20 and 40 g kg −1 PM added were measured. Concentrations of N, P, K, Ca, Mg, S, Fe, Zn, Cu, Mn, Mo, Cl, Si, Br, Rb, Sr and Ba in leaves at flowering and at final harvest and in fruits were determined by polarized energy dispersive X-ray fluorescence (PEDXRF). Poultry manure fertilization improved tomato shoot growth and also fruit yield and increased leaf N concentrations at the harvest stage. In addition, P concentrations of the leaves and fruits were increased as the application rate of PM was increased. Fruit Ca and Mg were significantly reduced by increased rate of PM application, but not to the extent to cause the calcium deficiency disorder blossom end rot. Applied high levels of PM slightly increased the concentrations of leaf Mo and Br at the harvest stage. Poultry manure applications had a positive effect on the concentrations of leaf Zn, Cu, Cl and Rb at both sampling stages, but leaf Si concentration was reduced by PM treatments. The concentrations of Zn and Rb were increased in the fruits by PM treatments, but the concentrations of Br were decreased. Applied PM levels had no significant effects on the concentrations of K, S, Fe, Sr or Ba in tomato plants. It is concluded that the increased fruit yield, and the increased concentration of Zn (an element required in the human diet) and the lowered concentration of potentially harmful Br in the fruit make poultry manure a valuable growing medium for tomato production.

Sources of Environmental Pollution in Ankara (Turkey): Geochemistry and Traffic Effects—PEDXRF Applications

ABSTRACT Road dusts were collected from the main streets in the vicinity of Ankara, the capital city of Turkey, including exhaust dust samples from the different fuel-based motor vehicles and sample pieces of brake pads to characterize their metal compositions by polarized energy-dispersive X-ray fluorescence (PEDXRF) spectrometry. Road dust samples were gathered by a vacuum dust sweeper from nine different densely populated residential settlement regions of Ankara, far from large industrial plants. Heavy metal contents of the road dusts were analyzed during the summertime to determine the metal pollution due to the motor vehicle exhaust, abrasion of brake pads, and lithology, ignoring the industrial and heating sources of pollution. The results of the analysis showed that the elements of Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sn, Pb, and Th in road dust samples were not derived from the lithology and industrial plants but from the motor fuel exhausts and brake pad abrasion. Generally, urban environmental pollution due to the toxic trace metals from traffic is harmful for the human health as well as the ecosystems near Ankara.

Combined Effect of Arsenic and Phosphorus on Mineral Element Concentrations of Sunflower

This study was undertaken to examine the combined effect of soil‐applied phosphorus (P) and arsenic (As) on P, As, potassium (K), calcium (Ca), magnesium (Mg), silicon (Si), iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), titanium (Ti), rubidium (Rb), strontium (Sr), barium (Ba), lantanium (La), and cerium (Ce) concentrations of sunflower plants under glasshouse conditions determined by polarized‐energy‐dispersive x‐ray fluorescence (PEDXRF). Three levels of As (0, 30, and 60 mg kg−1) and four levels of P (50, 100, 200, and 400 mg kg−1) were applied to soil‐grown plants. Increasing levels of both As and P significantly increased As concentrations in the plants. Plant growth was significantly reduced with increased As supply regardless of applied P levels. Arsenic toxicity caused significant increases in the concentrations of Mn, La and Ce, but it decreased K, Ca, Mg, Si, Fe, Zn, Cu, Rb, and Sr concentrations. Applied P increased the concentrations of Ti, Sr, and Ba and decreased Zn and Cu. In conclusion, the use of P fertilizers in As‐contaminated soils should be carefully considered in respect to increased As, Ti, Sr, and Ba availability and reduced Zn and Cu availability.

MINERAL ELEMENT DISTRIBUTION AND ACCUMULATION PATTERNS WITHIN TWO BARLEY CULTIVARS

Growth stage effects on distribution of mineral nutrients or beneficial elements phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), sulfur (S), chloride (Cl), iron (Fe), zinc (Zn), manganese (Mn), copper (Cu), molybdenum (Mo), sodium (Na), silicon (Si) and nickel (Ni), and the elements bromine (Br), rubidium (Rb), strontium (Sr), barium (Ba), lanthanum (La), cerium (Ce), and uranium (U) in two barley (Hordeum vulgare L.) cultivars and how the distribution of these elements changed were determined during the 2006–2007 growing season in a field experiment. Barley plants were sampled from the field at shooting, heading, soft dough, hard dough and harvest stages, and mineral nutrients and other elements concentrations of spike, flag leaf, old leaf, and stem samples were determined by polarized energy dispersive X-ray fluorescence (PEDXRF). Distribution patterns varied considerably from element to element. At the end of the season much of the Ca, Mg, S, Si, Fe, Mn, Cu, Ni, Sr, Ba, La, Ce, and U were located in the spikes. However, much of the P, K, Zn, Cl, Na, Br, and Rb remained in the old leaves or stem.

XRF and Raman Characterization of Antimonite

Two type Antimonite (stibnite) ore samples were analyzed by polarized energy dispersive X-ray fluorescence (PEDXRF) spectrometry and by confocal Raman spectrometry (CRS) in this study. The samples were collected from two different localities (İzmir-Ödemiş and Bursa-Uludağ zones from Turkey) according to the sampling methods. The first locality hosted within the metamorphic basement and the second locality hosted within the felsic intrusive rock units. The goal of this paper is to compare two different stibnite samples from various regions through PEDXRF and CRS with the optical characteristic features under the ore microscope. Ore microscopy studies reveal that the İzmir-Ödemiş stibnite is associated mainly with calcite and the Bursa-Uludağ stibnite is associated with celestite and quartz as gangue minerals. Two different colored species were observed in the stibnite of the studied samples. Ore microscopy results, CRS with the PEDXRF results show that the stibnites from the two different localities have different mineral associations, different chemical compositions, and different physical properties.

Effect of Sulfur on the Yield and Essential and Nonessential Element Composition of Alfalfa Determined by Polarized Energy Dispersive X‐ray Fluorescence

Alfalfa crops were grown in the field at the University of Ankara (473939 E, 4385149 N), over two seasons between 2001 and 2003 with sulfur (S) supplied at two different rates. The experimental design was a randomized complete block with five replicates and three cutting dates in each season. Sulfur was applied at rates of 0 (control), 160 (S1), and 240 (S2) kg ha−1 as gypsum. Alfalfa hay was harvested three times each year, and the concentrations of elements in the hay were measured by polarized energy dispersive x‐ray fluorescence (PEDXRF). Sulfur fertilization increased S concentrations and improved alfalfa hay yield for both years. Applied S slightly reduced phosphorus (P) and magnesium (Mg) concentrations in the first year and had no significant effect on the potassium (K) and calcium (Ca) concentrations of alfalfa hay for either year. The highest S (240 kg ha−1 S) level increased sodium (Na) concentrations in the first year but decreased them in the second year. Sulfur application also decreased chloride (Cl) concentration in the first year. Molybdenum (Mo) concentration of the alfalfa was significantly reduced by S1 treatment in year 1. Iron (Fe) concentration was increased by S2 treatment in the second year, and zinc (Zn) concentration was increased by S1 treatment in the first year. However, applied S had no effect on manganese (Mn), copper (Cu), titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), barium (Ba), uranium (U), and lead (Pb) concentrations for either year. Applied S decreased aluminum (Al) and silicon (Si) and increased bromine (Br) and rubidium (Rb) concentrations of alfalfa in the first year. In addition, strontium (Sr) concentration was increased by S2 treatment in the first year but was decreased in the second year. The stage of cutting greatly affected mineral concentrations. Compared with the first cutting, S concentrations were higher in the second and third harvest for both years. In general, the concentrations of P, Mg, Na, Cl, Mo, Ti, V, Br, Co, Ba, Sr, Rb, U, and Pb were increased, whereas the concentrations of Fe, Zn, Mn, Cu, and Ni were decreased with later cutting. The concentrations of K and Ca did not vary between cuts.