Portable XRF Spectrometer Research Articles

Combined in situ XRF–LIBS analyses as a novel method to determine the provenance of central Mediterranean obsidians

This work presents a new calibration method for determining the provenance of obsidian artefacts based on the combined use of XRF and laser-induced breakdown spectroscopy (LIBS). At first, obsidian samples collected from the main Mediterranean sources were characterized using portable XRF and LIBS systems. After data treatment, elemental information was used to carry out principal component analysis (PCA) for each technique. Rb, Sr, Zr, Y and Fe elements, detected by using XRF, were found to be the key parameters enabling obsidians discrimination. Likewise, LIBS data helped differentiating the analysed patterns by the intensity of their main elemental components (Ca, Al, Mg and K). After selecting the key parameters detected by each technique, a new data matrix combining XRF and LIBS data was finally built. According to PCA results, the discrimination of Mediterranean sources based on combined XRF–LIBS data ensured a higher reliability over mono-analytical models, by increasing the Euclidean distance between sources projections over three-dimensional principal components plots. Knowing that the representativeness of elemental data could be compromised by the presence of superficial degradation products or deposition patinas, a shot-to-shot comparison of in-depth LIBS analyses is finally proposed as a method to disclose whether the spot under analysis was superficially contaminated or altered. Thus, the proposed strategy based on the combined use of portable XRF and LIBS spectrometers could be particularly useful for the in situ analysis of obsidian artefacts that underwent superficial alteration or could be covered by patina products.Graphical abstract

In situ analysis of pigments on the murals of Yanshan Temple in Fanshi County, Shanxi Province, China by portable Raman and XRF spectrometers

In situ analysis of pigments on the murals of Yanshan Temple in Fanshi County, Shanxi Province, China by portable Raman and XRF spectrometers

In situ crystallization of non-cotectic and foliated igneous rocks on a magma chamber floor

Layered mafic intrusions commonly contain non-cotectic, foliated igneous rocks that are traditionally attributed to processes involving settling, transport, and redeposition of crystals. Here we examine the chemistry of magnetitite layers of the Bushveld Complex using a portable XRF spectrometer on drill core and dissolution ICP-MS analysis on pure magnetite separates. While magnetitites contain foliated plagioclase grains in non-cotectic proportions, the magnetite is characterized by a regular upwards-depletion of Cr which is best explained by in situ crystallization. We suggest that plagioclase nucleation in thin residual compositional boundary layers atop a solidification front causes in situ growth of plagioclase in proportions much lower (<10%) than those expected from cotectic crystallization (±85%). Crystallization in such a boundary layer also favours lateral growth of the plagioclase, producing the foliation. We suggest that some non-cotectic, foliated rocks that are commonly interpreted to arise from gravity-induced sedimentary processes may instead be produced by in situ crystallization.

Podrobnosti o počátcích sedimantace a vulkanické činnosti na začátku permu (asselu); rudnický obzor v sz. části podkrkonošské pánve

A succession of the early Permian (Asselian) Rudník member exposed at the locality Škodějov – Hrádecký potok in the northwestern part of the Krkonoše Piedmont Basin (eastern Bohemia) contains light-colored clastic rocks with macroscopically conspicuous lamination, overlying lacustrine bituminous claystones and siltstones (ʻblack shalesʻ). This work aims to constrain the origin of those laminated strata. They can be macroscopically described as heterolithic sequence formed by fine- to medium-, exceptionally coarse-grained sandstone with intraclasts of mudstone, calcified fine-grained sandstone, mudstone and claystone with interlayers of organic-rich laminae. Volcaniclastic rocks are also present. The heterolithic volcanosedimentary sequence comprises cyclic (up to 4 dm), mostly horizontally laminated rocks, in places with soft- sediment deformation structures. Diagenetic phenomena, related to calcification of volcaniclastic layers and growth of pyrite crystals and framboids, are common. Volcaniclastic rocks with a predominance of albitized volcanic glass fragments are interpreted as vitritic tuffs. Fragments of volcanic glass floating in silty to fine-grained sandy matrix contain vesicules and are locally brown- colored. They are reinterpreted as being derived from contemporary intermediate (andesitic) volcanism, most likely extrabasinal. Extensive alteration of volcanic material makes characterization of the original composition of volcaniclastic deposits difficult. Trace element analysis using a portable XRF spectrometer revelaed negligible concentrations of V, Ni and Ti, which are indicative of rather basic volcanism. Results of outcrop-scale gammaspectrometry are presented here as trends of Th/U ratio of relevant lithotypes from several localities of the Rudník member. Organic-rich laminae present within the heterolithic succession at Hrádecký potok section are commonly rich in pyrite clusters. Those are the most probably related to formation of algal mats stimulated by input of fine-grained volcaniclastic material into the Rudník Lake. However, elevated siliciclastic and volcaniclastic input, particularly during periods of intensified volcanic activity, with related seismic events (that may have triggered gravity flows), may have disturbed or punctuated growth of algae on the lake floor. Our work has shown that the volcanic activity at the onset of deposition of the Rudník member in the northwestern part of Krkonoše Piedmont Basin (Škodějov – Hrádecký potok) was probably of intermediate nature and that it influenced depositional environment. Particularly, the fluctuating input of clastic and volcanogenic material could have caused an alternation of oxic and dysoxic conditions in the lake lacustrine environment over time. The intermediate character of volcanism in this locality contrasts with confirmed acidic volcanism documented in volcaniclastic layers in another lacustrine succession at Vrchlabí – roadcut (Martínek et al. 2006) that probably represent a different eruptive phase recorded within the Rudník member.

A comparison of XRFS and ICP-OES methods for soil trace metal analyses in a mining impacted agricultural watershed.

Field portable X-ray fluorescence spectroscopy (XRFS) has become increasingly prevalent for in situ detection of trace metals, as it is both rapid and cost effective. The accuracy of in situ XRFS analyses has been questioned due to possible interferences from elevated soil moisture and organic content. In this study, three metal analysis protocols (Cd, Pb, Zn) were compared for surface soil samples collected near the Tar Creek Superfund Site in northeastern Oklahoma. The protocols included the use of a field portable XRF spectrometer for in situ analyses and on homogenized, pulverized, air-dried soil samples sieved to < 250-µm fraction in the laboratory. A subset of soil samples was also analyzed after microwave-assisted hot HNO3 digestion followed by inductively coupled plasma-optical emission spectrometry (ICP-OES) analyses. Moisture content and loss-on-ignition (as a surrogate for organic matter) were determined for each sample. Soil moisture exceeding 10% in situ caused underreporting of field XRF readings when compared to the laboratory XRF readings. Relationships between concentrations determined by laboratory XRFS and ICP-OES for Pb (r2 = 0.96) and Zn (r2 = 0.91) were not statistically different (p < 0.025 for both analytes). A strong relationship between ICP-OES analyses of Zn and Cd (r2 = 0.93) allowed prediction of Cd concentrations for additional samples not analyzed by ICP-OES. This study recommends that XRFS field readings be used for initial screening only and that samples analyzed via field portable XRFS be homogenized, air dried, sieved and re-analyzed in the laboratory to yield the most accurate results.

Evaluation of pattern recognition techniques for the attribution of cultural heritage objects based on the qualitative XRF data

Various instrumental and experimental modifications of portable XRF (pXRF) spectrometers meet nearly all the requirements for safe and efficient analysis of objects of cultural heritage, allowing this technique to be the most used analytical method for that purpose. The technique was used in a joint campaign (involving scientists, curators and art historians) to examine and protect an iconostasis containing well-preserved and reliably dated icons from four different centuries. The number of acquired XRF spectra was sufficient to be treated with pattern recognition techniques. Different pattern recognition techniques were applied in the analysis of cultural heritage object, both unsupervised and supervised. The results of various analytical examinations (non-invasive or performed on samples) pretreated or not, even a fusion of different techniques, were subjected to pattern recognition analysis.The possibilities of select pattern recognition techniques to analyze data obtained by a pXRF spectrometer from the surfaces of paintings and icons are presented in this study. Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA), and Scattering Matrix Based Dimension Reduction (SMBDR) were used to process generated datasets of peak areas and spectral intensities providing dimension reduction of the initial datasets. The efficiency of this process is evaluated and discussed using the calculated index of informativeness and Bhattacharyya’s distance. Based on the results, the possibility of classification is discussed in terms of choosing proper classifiers, which were designed thereafter. The classification is evaluated by recognition ability and prediction ability parameters, and then tested by the leave-one-out procedure and using pXRF spectra collected from different color and support (cardboard paintings). An efficient procedure was developed for the attribution of artwork origin, based solely on XRF spectral data and PCA dimension reduction, followed by linear classification.

Determination of the chemical and mineral composition of rocks with the use of a portable XRF spectrometer operating in a helium atmosphere

W pracy przedstawiono możliwości prowadzenia pomiarów chemicznych z zastosowaniem przenośnego spektrometru fluorescencji rentgenowskiej z dyspersją energii EDXRF w atmosferze helu. Metodyka badawcza wraz z tworzeniem modeli i interpretacją danych powstała w oparciu o zastosowanie aparatu XRF firmy Bruker, model Tracer 5g. Prowadzenie pomiarów w atmosferze helu umożliwia obniżenie progów detekcji dla pierwiastków lekkich, w tym określanie udziałów sodu (Na) i magnezu (Mg) oraz pierwiastków wchodzących w zakres spektrometrycznego profilowania gamma: potasu (K), uranu (U) i toru (Th). Jednym z elementów nowej procedury pomiarowej jest przygotowanie preparatów w formie pastylek, przy użyciu prasy hydraulicznej o sile nacisku do 25 ton. Pomiary w atmosferze helu mogą być wykonywane jedynie na materiale skonsolidowanym (lita skała, rdzeń wiertniczy lub twarda pastylka). Materiał do badań został pobrany z rdzeni wiertniczych, następnie skwartowany i rozdzielony na poszczególne analizy. Wyniki analiz XRF uzyskane metodą, w której zastosowano przepływ helu, porównano z wynikami pomiarów wykonanych standardową aparaturą XRF, chemicznych badań laboratoryjnych, analiz składu mineralnego XRD oraz badań naturalnej promieniotwórczości gamma. Analizy XRF bez możliwości prowadzenia pomiarów w atmosferze helu wykonane zostały aparatem Titan S1 (firmy Bruker). Badania przeprowadzono na próbkach skał pochodzących z dwóch otworów wiertniczych – P4 (19 próbek) i J1 (11 próbek). W przypadku P4 dysponowano dokładnymi pomiarami laboratoryjnymi ICP-MS (ang. Inductively Coupled Plasma Mass Spectrometry), ICP-OES (ang. inductively coupled plasma mass spectrometry) oraz wynikami XRD, natomiast w J1 – wynikami badań radiometrycznych i mineralnych. W próbkach z otworu J1 występowały skalenie oraz dolomit, co umożliwiło przetestowanie budowy modeli uwzględniających te minerały w odniesieniu do wyznaczenia udziałów sodu i magnezu. W końcowej części pracy przedstawiono wykresy korelacyjne dla wybranych, najważniejszych pierwiastków budujących matrycę skalną, modele mineralno–chemiczne zbudowane na ich podstawie oraz wykresy korelacyjne dla spektrometrycznych pomiarów gamma.

Portable XRF spectrometer with helium flow as a tool for lithological interpretation

Portable EDXRF (Energy Dispersive X-Ray Fluorescence) spectrometer with the ability to perform rock tests in a helium atmosphere was applied to prepare unique calibration coefficients and mineralogical models. These data could be used for the chemical profiling, chemostratigraphy, gamma-ray, TOC and lithological interpretation of borehole geological profile. The measurements were conducted on 19 samples of sandstones and compared to the XRF data without helium flow. The acquired dataset was calibrated to the chemical laboratory tests (ICP-MS), gamma-ray spectrometry measurements (RT-50) and combined with the mineralogical data (XRD). The new methodology enables the measurement of sodium and enhances the possibility of detecting magnesium, thorium and uranium, compared to standard handheld XRF spectrometers. The applied method is dedicated to whole cores (without sample preparation) or cuttings which must be cleaned, dried, milled and pressed.

XRF ANALYSIS OF ARSENIC AND SELECTED METALS IN CONTAMINATED SAND FROM THE DISMANTLING OF INDUSTRIAL DISTILLATION PLANTS

This paper refers to the application of XRF method for the simultaneous determination of arsenic and selected metals from waste samples resulted from the dismanlting of distilleries in the perimeter of Azomures S.A., Mures County, Romania. The dismantling operation was carried out by a specialized Romanian company, and from this operation resulted several refractory construction wastes, such as sands with a very high content of arsenic and its chemical compounds. In order to determine the arsenic and other metals concentration, the energy-dispersive X-ray fluorescence (ED-XRF) spectrometric technique was employed. Application of the ED-XRF method was performed in an accredited laboratory for the determination of toxic substances from various samples, using a Genius portable XRF (p-XRF) spectrometer manufactured by Skyray Instruments Inc.

Downhole Lithological Profile Reconstruction Based on Chemical Composition of Core Samples and Drill Cuttings Measured with Portable X-ray Fluorescence Spectrometer

The reconstruction of a lithological profile based on geophysical logs of chemical composition provided by geochemical gamma-gamma well logging probes has been increasingly used for geophysical interpretation. A chemical profile, analogous to the measurements mentioned above, can be determined based on measurements made with a portable X-ray fluorescence spectrometer (pXRF). This paper presents a methodology for determining the mineral composition of drilled, clastic, as well as clay-rich rocks on the basis of both inexpensive and timesaving pXRF measurements as well as models combining the results of chemical composition analysis with results of mineral composition analysis (XRD). The results of chemical composition analysis obtained with a portable XRF spectrometer were calibrated based on a detailed analysis produced with ICP-OES and ICP-MS methods. A significant advantage of the proposed method is the possibility to apply it with regard to drill cuttings as well as archival cores. However, considerable discrepancies in the results obtained were identified while comparing the results of chemical composition analysed directly on the core and milled material. The analysed material comprised Carboniferous rocks derived from three boreholes located in Poland: Kobylin-1 as well as Biesiekierz-1 and -2. It was possible to directly compare the lithological profile obtained based on measurements taken on drill cuttings with the results of the lithological interpretation of a geochemical probe log.

Development of a Portable XRF Spectrometer and Its Application

We have developed 2 kinds of portable XRF spectrometers for on-site analysis. The first is equipped with a monochromator, making it possible to sensitively analyze under a low background. This equipment is used widely in the archaeology field and an industrial field. Recently, we also developed equipment that improved the analysis sensitivity of the light element.Another equipment is a portable total reflection X-ray fluorescence (TXRF) spectrometer. We developed this equipment using polychromatic X-rays from an X-ray source of single-digit Watt. It has an analysis sensitivity of pg order. This equipment is used in the environment field, biological samples and in the analysis of uranium from nuclear power plants. This report, introduces an outline and application examples about 2 kinds of portable XRF spectrometers.

Possibilities of Determination of Risk Elements in Alluvial Agriculture Soils in the Mže and Otava River Basins by X-Ray Fluorescence Spectrometry

Abstract The undesirable, hazardous, and risk elements are introduced into all environmental parts through human activities. They enter the soil and aquatic environment by atmospheric deposition, or by application of sewage sludge, pesticides, mineral and organic fertilisers, and by organic manures. Heavy metals (HMs) and risk elements can be determined in the soil by a wide range of analytical methods that differ in terms of time and financial costs, and the demands on service. One of the methods is the use of a portable XRF spectrometer under lab conditions, offering relatively fast determination of the concentration of chemical elements in the soil. In the presented study we evaluated the accuracy and the precision of the XRF device for analysis of the concentration of heavy metals (Pb, Zn, As, Mn, Cu, and Ni) in alluvial soils from the Mže and Otava river basins (Czech Republic), and validated and compared obtained results with the conventional lab method (ICP-OES). The soil samples (n = 502) were taken at 43 sampling sites at depths of 0 – 30, 30 – 60, and 60 – 90 cm, mainly in floodplains with Fluvisol soil type (N-year flow rates = Q100 m3/s). The multiple correlation coefficients R values ranged from 0.81 to 0.99. The R2 determination coefficients for individual HMs, measured by XRF, were determined as follows: Pb – 0.98, Zn – 0.97, Cu – 0.80, Mn – 0.79, As – 0.78, Ni – 0.66. According to our results, 66 – 98% points fit the designed models. The Pb and Zn have the best dependency (relationship tightness), and regression models are excellent. Cu, Mn, and As have a slightly worse dependency (tightness of the relationship), but the regression model is still very well suitable for agriculture practice, or for the purposes of environmental monitoring.

Soil spatial patterns analysis at the ancient city of Ibida (Dobrogea, SE Romania), via portable X-ray fluorescence spectrometry and multivariate statistical methods

In this study we investigated the potential usefulness of multi-elemental soil analysis, obtained by a portable XRF spectrometer, to recognize ancient anthropogenic features, compared to the natural context on the territory of Roman-Byzantine Ibida city (Dobrogea, SE Romania). Soil samples were collected from 16 soil profiles and 2 archaeological excavations, from each soil horizon and cultural layer. Pearson correlation matrix of topsoil elements showed significant correlations among the various geogenic elements such as Ti, Fe, Mn, Zr, Ba and Cr. In the case of P, a strong correlation was found with Ca, a lower correlation with K, and no significant correlation with the other elements. Also, Cu and Zn behave differently, showing no significant correlation with any of the elements. Principal components analysis (PCA) and agglomerative hierarchical clustering (AHC) were carried out in order to identify groups of inter-correlated variables and assess the degree of association among soil profiles. The correlation between soil elements and the principal components suggest the presence of three groups which were defined as the geogenic, archaeo-anthropogenic and agro-anthropogenic component. Spatial distribution of topsoil elements was mapped by geostatistical methods in order to see if their spatial patterns reveal the influence of human activities. Although the results show that certain elements such as Ca, P and K present higher concentrations in the Ibida fortress area, we found that the interpretation of multi-elemental composition of the topsoil only is not sufficient for an accurate identification of the ancient characteristics which can be linked to the Roman-Byzantine period. Hence, we wanted to know if the presence of archaeological sites could be revealed by higher variation degree of soil elemental data along the profile depth. Therefore, we tested the utility of a synthetic statistical index, namely the variation coefficient, which was computed for each soil profile using all the available data. The results showed that if the index was standardized according to profile depth, then it became a useful indicator for the presence of ancient human activities.

Chemometric analysis of Mesoamerican obsidian sources

We propose a combination of portable X-ray fluorescence (pXRF) and chemometrics to discriminate between Mesoamerican obsidian sources and to assign archaeological artifacts of unknown origin to their respective deposits using a procedure that does not require any type of calibration or reference standards. A set of 109 samples of known origin and a total of 257 samples of unknown origin were analyzed with a portable XRF spectrometer. The resultant spectra were used as spectral signatures for the chemometric data analysis. First, we applied spectral pre-treatment techniques, such as CluPA algorithm for peak alignment and the Savitzky-Golay and Extended Multiplicative Signal Correction for data smoothing and noise removal, combined with methods for the selection of a spectral range containing the variables with the most relevant information (iPLS and). The full spectrum of the obsidian samples was divided into 20 subintervals, fitting a local regression model (PLS) to each subinterval. The performance was evaluated by the Root Mean Square Error of Cross-Validation, the Root Mean Square Error of Prediction and the correlation coefficient. The selected spectral regions were then analyzed with ROBPCA algorithm for the discrimination of outliers and the projection of the observations in the PCA space. For the classification, we propose a robust procedure (RSIMCA) which is based on a ROBPCA method for high-dimensional data. The classification rules were obtained by using the orthogonal and the score distances, from which it is possible to distinguish samples that belong to a given group. Using the proposed methodology, we were able to provide evidence about which variables were meaningful for the classification and provided information about group membership or provenance. This approach proves to be a valid technique for the quantitative analysis of XRF spectra.

Composition of Crystal Glass Made in the Middle of the 19th Century at the Gus-Khrustalnyi Factory

This is the first study of a crystal glass composition, as well as its thermal and spectral (Raman spectra and fluorescence) characteristics, produced at the Gus-Khrustalnyi factory in the middle of the 19th century. The sample studied is a potassium-calcium glass with a low lead content. The formula for such a composition was first developed in Central Europe in the second half of the 17th century and then improved at the beginning of the 18th century. The possibility to use a portable XRF spectrometer to analyze historical glass is demonstrated.

Multi-element mapping of anthropogenically modified soils and sediments at the Bronze to Iron Ages site of Tel Burna in the southern Levant

Human settlement activities have caused changes in soil chemical properties that might remain preserved in the soil archive for a very long time. These traces might be close to irreversible on the timescale of known civilizations. Our study explores the potential of an extensive mapping of the multi-elemental composition of soil and buried sediments by a portable XRF spectrometer, using the Tel Burna site in the southern Levant as a case study. The tell, dating from the 3rd to the 1st millennium BCE, is known as a Bronze Age Canaanite settlement, and later in the Iron Age as a stronghold on the historic border between the Kingdom of Judah and Philistia. We compared the results of our geochemical survey conducted on the surface layer of contemporary soil with the data acquired by the same method from the archaeological stratigraphy exposed during excavations of the site. We found that handheld XRF spectrometry can reveal archaeologically meaningful patterns of the multi-elemental composition of soils and sediments in the horizontal plane, as well as in vertical profiles. Such patterns correspond to areas and loci of ancient settlement activities, dated to millennia ago. This methodology, if used critically, provides a rapid and cost-effective analysis of soil chemical composition that can significantly enhance our understanding of archaeological sites in arid environments.

Determination of iron content in whole blood in different mouse strains using a portable XRFS spectrometer

Iron has an important role in blood as an indicator of a great number of anomalies. Anemia due to iron-deficiency in the world is a public health problem in all ages and socioeconomic levels. Nowadays, Brazil’s pharmaceutical companies are testing iron compounds to reduce the costs of those new drugs. In this study, Energy Dispersive X-Ray Fluorescence Technique was applied to determine Fe concentrations in blood samples of different mice strains using a Portable XRF Spectrometer. These data may help researchers choose the convenient mice strain that best meets its medical investigation, reducing costs and optimizing their researches.

Influence of Soil Pore Length upon Portable X-ray Fluorescence Spectrometer Measurements of Elements in Soils

To approximate the measurement accuracy of laborious lab approaches, soil inventories using field portable XRF (pXRF) spectrometers should take distorting parameters into account. Besides soil moisture, the length of water-filled soil pores may also affect X-ray intensity. Following the Arya-Paris approach of soil pore bundles, soil pore lengths were calculated for 20 riparian soil samples based on effective pore diameters obtained at specified pressure heads of the water retention curve. When contrasted against pXRF signals of lead, zirconium, and potassium, soil pore length information showed an explanation comparable to soil moisture values. Presumably, the bases and walls of soil pores are successively exposed to the excitation source during dewatering. Though its laborious determination, soil pore length calculation is based on comparatively static parameters, which may circumvent adverse effects occurring at moisture determination at steel-ring samples, such as artificial macropores in the course of sampling and transport or shrinkage of porosity due to pressure application.

Możliwości identyfikacji pierwiastków ziem rzadkich za pomocą podręcznego spektrometru XRF w rdzeniach wiertniczych z syenitowego masywu Ełku (otwór Ełk IG 3, NE Polska)

POSSIBILITIES OF IDENTIFICATION OF RARE EARTH ELEMENTS BY PORTABLE XRF SPECTROMETERS IN DRILL CORES FROM THE EŁK SYENITE MASSIF (EŁK IG 3 BOREHOLE, NE POLAND) Abstract. The main aim of this study is to determine the contents of rare earth metals, using p-XRF, in the Carboniferous Elk syenite massif that cuts the Precambrian basement of the East European Platform. The paper presents the results of drill core study in the Elk IG 3 borehole. In situ chemical analyses of borehole materials were performed using the portable XRF Olympus Delta 50 Premium spectrometer (4 W Ta anode X-ray tube, 50 kV). Prior to analyses of natural rock samples the spectrometer parameters were optimized for selected rare earth elements, such as Y, La and Ce, as well as other elements ,such as Zr, Hf, U and Th. Handheld XRF non-destructive analyses have allowed the identification of anomalies of rare earth elements and places for further detailed petrographic and mineralogical analyses.

PILOTAŻOWE BADANIA PIERWIASTKÓW ZIEM RZADKICH W STREFIE KONTAKTU BLOKU MAŁOPOLSKIEGO Z BLOKIEM GÓRNOŚLĄSKIM

PILOT STUDIES OF RARE EARTHS IN THE CONTACT ZONE OF THE MAŁOPOLSKA BLOCK WITH THE UPPER SILESIA BLOCK Abstract. The paper presents the results of a pilot prospecting study on archived drill cores from boreholes in the contact zone of the Malopolska Block with the Upper Silesia Block, with a use of a Portable XRF spectrometer Delta 50 Premium (Olympus). A few hundred measurements of concentrations of La, Ce and other trace elements were made in selected boreholes from the prospective zones for the occurrence of Mo Cu–W ore mineralization. The maximum content for La (400 ppm) and Ce (600 ppm) measured by the Portable spectrometer has been found in the Ko-4 borehole (depth interval 450–550 m). In the depth interval of ca. 400–1300 in the other boreholes (Pz-36, RK-2 and Cianowice-2), the maximum La and Ce contents were approximately twice lower than in the Ko-4. The study also shows an interdependence of the occurrence of LREE with Sr, Y or Th. The most interesting samples were additionally analyzed by ICP-MS and electron microprobe (CAMECA SX-100). The sum of REE (ICP-MS) in four samples that reveal the highest contents of these elements varied from ca. 0.02 to 0.1%. Total REE contents for samples normalized to the upper continental crust are low (1–10). The highest REE concentrations in samples of hydrothermal breccia were found in the Ko-4 borehole (depth ca. 500 m). They reach for the Ce (305.1 ppm), Nd (266.9 ppm), La (258 ppm) and Sm (31.3 ppm). Other REE occur at low concentrations. This is clearly visible on the standard logarithmic charts of REE concentration in relation to their content in chondrite and in the upper part of the continental crust. Characteristic is the lack of negative Eu anomaly on both charts. In the microprobe study, calcioancylite-(Ce), synchysite-(Ce) as well as bastnasite and zircon were also detected in addition to the unidentified minerals from the anhydrous phosphate group enriched with REE (mainly Ce, La, and Nd) and monazite. The form and composition of the REE mineralization indicate clearly that it is of hydrothermal nature. During hydrothermal processes, REE underwent redeposition and concentrated within breccia and tectonic zones in the metasomatic changed rocks. The data on REE concentrations, presented in this paper, are only of indicative significance. The REE contents are much lower than the most interesting results obtained within the framework of research projects carried out in other geological units in Poland and published in separate papers.