In this study, the effects of two different ammonium-exchange methods to improve the ammonia (NH3) gas adsorption of raw clinoptilolite (CLN) from Gördes (Türkiye) was investigated. The first method involved direct modification of CLN by 0.5 or 1.0 M NH4NO3 solutions at 80°C for 4 and 8 h followed by calcination. In the second method, CLN was converted to the Na+ form prior to modification with ammonium nitrate and calcination under the same conditions. Both methods yielded H+ forms of CLN through the removal of exchangeable cations without damaging the crystal structure. Ammonia adsorption isotherms were determined at 298 K for a total of eight different H+ forms synthetized using both methods. The Na-1.0-8h CLN sample with the highest NH3 adsorption capacity obtained using the second method was selected as the parent CLN. In addition, to determine the effects of doping different cations into the structure on the NH3 adsorption properties of the selected parent CLN sample, cation-exchange processes were carried out using 0.5 and 1.0 M NaNO3, KNO3, Ca(NO3)2 and Mg(NO3)2 solutions at 80°C for 4 h. The raw and modified CLNs were characterized using X-ray diffraction, X-ray fluorescence, scanning electron microscopy and N2 adsorption analyses. Cation-exchanged samples with a wide range of NH3 adsorption capacities (3.61–4.93 mmol g–1) were compared with other zeolites from the literature.

We studied a set of 15 reference clays from The Clay Minerals Society (CMS) Source Clays repository. Our aim was to use them as reference materials in our version of the QUAX mineral database. The QUAX software (Quantitative Phase-Analysis with X-ray Powder Diffraction) has been used successfully at the KTB site (German Continental Deep Drillling) to determine mineral assemblages quickly, in an automatic fashion, on a large number of samples (∼40,000). It was also applied to Quaternary marine sediments of the Japan Sea. Our current research focuses on marine and lacrustrine sediments from the Arctic Ocean and Siberia.

QUAX is a full-pattern method using a reference materials database. The quality of a particular quantification depends on the availability of the relevant mineral phases in the database. Our aim is to extend and improve the database continuously with new data from our current projects, particularly from clay and feldspar minerals.

A reference material in the QUAX software must be monomineralic. Before X-ray diffraction (XRD) patterns of CMS clays could be added to the database, quantification of any impurities was necessary. After measuring the bulk material by XRD, the <2 µm fraction was separated because we assumed it would contain the smallest amount of impurities. Here we present grain-size data, XRD data and X-ray fluorescence (XRF) data for this clay-sized fraction. The results of chemical and mineralogical preparation techniques and (elemental) analysis methods were combined. For XRD, random and oriented clay-aggregate samples as well as pressed pellets for QUAX analysis were prepared. Semi-quantitative clay mineral determinations were run for comparison.

The effect of FeCl3 in acetonic medium on the structure of Na-bentonite was studied using X-ray diffraction (XRD), 57Fe Mössbauer spectroscopy, X-ray fluorescence spectroscopy and infrared spectroscopy to describe the structure of the bentonite before and after treatment. In the samples treated with FeCl3, an increase in the basal spacing was found by XRD, while a new magnetically split component assigned to Fe3+ incorporated within the interlayer regions of montmorillonite showed up in the low-temperature Mössbauer spectra. The Mössbauer parameters observed were close to those of Fe oxyhydroxides, suggesting the presence of some kind of nanoparticles. These results show that the treatment with acetonic FeCl3 solution is an effective method for introducing Fe into montmorillonite in the form of Fe3+ accommodated in the interlayer region. The treated samples proved to be efficient Lewis catalysts in the acylation of aldehydes (benzaldehyde and 4-OH-benzaldehyde) by acetic acid anhydride.

White marble sculpture is a cornerstone of Western art history. Archaeological inquiry, however, has demonstrated that Classical sculpture and its associated architecture were once coloured. The authors examine the Parthenon Sculptures at the British Museum to identify traces of colour and carving on their surfaces. Using close examination and archaeometric techniques, the study shows that the sculptors finished surfaces with textures that reflected specific elements (e.g. skin, wool, linen) and these were then enhanced through the application of colour, including a purple colourant and Egyptian blue. The latter was used extensively to paint elaborate figurative designs on the carved textiles. Despite the complexity of the carved drapery, elaborate ornament was applied to the finish. The findings encourage a reconsideration of the appearance of the Parthenon in the fifth century BC.

During the early first millennium BC, Phoenician peoples settled the Iberian coasts instigating cultural innovations known as the orientalising; indigenous communities of the interior have long been considered as passively dependent on, or isolated from, these developments. Recent excavations at the Early Iron Age village of Cerro de San Vicente in central Spain, however, have yielded domestic contexts that prompt reconsideration of this relationship. The authors use settlement layout, architecture and locally made tablewares to identify heterarchical organisation around virilocal and bilateral kinship and hybrid practices that attest to adoption of know-how and practices from distant places. Emphasis is placed on the role of embodied craftworking skills and female mobility in transculturation processes.

Se presentan los resultados de fluorescencia de rayos-X realizados a 12 artefactos provenientes de contextos funerarios Chinchorro, Arica, norte de Chile, focalizándose la discusión en el manganeso (Mn). La muestra con mayor concentración de Mn fue analizada con espectrometría Raman, para avanzar en la identificación estructural del cromóforo negro correspondiente. Todos los artefactos dieron positivo para la presencia de Mn con un rango de 1,11%-63,66%, considerándose antrópico sobre 2% (83,33% del total) y el pigmento analizado fue identificado como criptomelano y goetita.

We present a novel approach to developing a unified radiocarbon-based chronology for multiple sediment cores from a location where radiocarbon dating is challenging. We used 36 radiocarbon ages from eight terminal Pleistocene and Holocene sediment cores with correlated stratigraphies. Stratigraphic correlation was accomplished using a combination of high-resolution photography, high-resolution X-ray fluorescence-based elemental composition data, and volcanic tephra identification. Results show that despite problems associated with potential contamination or radiocarbon reservoir effect, a useful age-depth model has been created for the correlated lacustrine sections of these eight sediment cores, providing chronological controls for future paleoenvironmental analyses of the cores.

The obsidian mirror associated with the Elizabethan polymath and magus John Dee (1527–1608/1609) has been an object of fascination for centuries. The mirror, however, has a deeper history as an Aztec artefact brought to Europe soon after the Spanish conquest. The authors present the results of new geochemical analysis, and explore its history and changing cultural context to provide insights into its meaning during a period in which entirely new world views were emerging. The biography of the mirror demonstrates how a complex cultural history underpins an iconic object. The study highlights the value of new compositional analyses of museum objects for the reinterpretation of historically significant material culture.

As a producer of certified reference materials (CRMs), NIST faces high demand for Standard Reference Materials (SRMs). The demand is exacerbated by widespread misuse of CRMs. When should one use CRMs? When should one not use CRMs? Must labs always use NIST SRMs? How can labs demonstrate analytical capabilities for their accreditation scopes? Why so many questions? Standards developers, laboratory accreditors, and laboratory staff must be able to understand these topics with respect to quality systems in compliance with ISO/IEC 17025. They must calibrate and validate test methods and document traceability to the International System of Units (SI). Many people working in laboratory accreditation and under the umbrella of a quality system do not fully understand what these things are, let alone the language of chemical metrology. On average, they have little training in analytical chemistry, elemental analysis, and reference material development. It is hoped this paper will impress upon the reader the need for understanding how CRMs can be best used in the laboratory. This paper provides a brief background on the above problems and then looks at some of the support and reference information provided by NIST to metals and mining industries labs, commercial CRM producers, and accrediting bodies. The concepts and guidance apply broadly to chemical metrology and fundamental analytical chemistry. The paper includes examples (some from X-ray fluorescence spectrometry) to illustrate concepts.

Study of the hydro-sedimentary dynamics of lakes provides key information on hydrological changes. In this work, we investigate Lake Azigza in the Moroccan Middle Atlas, a region that suffers from a scarcity of observational hydrological data necessary for a coherent management of water resources. Sedimentary deposits of Lake Azigza (32°58′N, 5°26′W, 1,550 m above sea level) were dated and analyzed by combining geochemical and mineralogical measurements coupled with microfacies characterization for the last 134 yr. The detrital component derived from X-ray fluorescence elemental composition and microstructures analysis of the lake sediments provided proxies of runoff activity and lake-level changes, respectively. These proxies were calibrated with regional hydro-climatic and instrumental measurements available over the last 50 yr and used to reconstruct past hydrological changes on inter-annual to decadal time scales between 1879 and 2013. Since 1879, lake level and runoff proxies responded in phase to regional inter-annual precipitation variations. We also show that after the major lake-level drop observed in 2008, the response of the runoff proxy to variable precipitation regime is enhanced. Such an approach emphasizes the potential of these hydro-climate-sensitive sedimentary archives to assess the impact of climate change in the Mediterranean region.

Geochemical analysis of the first obsidian artefact discovered in Belarus reveals its source to be the Trans-Caucasus, rather than the expected Carpathian source for prehistoric obsidian in Eastern Europe.

Various physical and analytical techniques (XRD, XRF, SEM, FTIR and EPR) have been used to investigate the effects of chemical and/or physical modification of Ranong kaolin, which has been proposed as a potential bleaching clay for vegetable oils. Acid treatment after grinding resulted in major changes compared with acid treatment of the original mineral sample or mechanical treatment alone. Previous work has shown that the combined treatments produce increases in surface area and new porous structures, and the present measurements show reductions in Al:Si ratios. These are accompanied by a major reduction in O–H stretching vibrations as a result of grinding, although acid treatment produced little subsequent effect on the O–H bands in the FTIR spectra. However, acid treatment resulted in a reduction in the Al–OH–Al bending vibrations and the appearance of Si–O bands associated with newly synthesized material; these effects were much greater with samples that had been ground prior to the acid treatment. There were appreciable qualitative differences in the way in which the EPR spectra of Fe and Mn were affected; the Fe signal was sensitive to mechanical treatment, but little subsequent change was induced by acid extraction, whereas the Mn peaks were sensitive to the both the pH and the chemical nature of the acid used. These results therefore indicate that the Fe and Mn are in different types of site in the kaolin structure. Little change was observed in the main oxygen-based free radical centre associated with Si atoms, but that associated with Al was lost as a result of the treatments. Such mineral characterization is of fundamental importance to understanding the modification of kaolins and their uses as adsorbents in the food and environmental sciences.

Over the past several decades, kaolin has been used intensively in the paper industry as a coating and filler material. These applications require kaolin of a high brightness grade, which depends heavily on the level of impurities (mainly Fe-bearing minerals such as Fe oxides and hydroxides) and may be improved by beneficiation processes involving grain-size classification, magnetic separation and chemical treatments. This investigation was carried out on five Brazilian kaolin samples of different geographical and geological origins. Granulometric, mineralogical, chemical and physical characterizations were performed on all samples before and after the beneficiation process.

Chemical compositions were determined by X-ray fluorescence and the most important crystalline phases were identified using X-ray diffraction. Kaolinite is the dominant mineralogical phase with minor amounts of muscovite and quartz. The nature of Fe impurities was investigated by electron spin resonance and 57Fe Mössbauer spectroscopy. For all studied kaolin samples, Fe ions (Fe3+ and Fe2+) are present in variable amounts, in the kaolinite structure and also in Fe oxides (magnetite, hematite and goethite). The beneficiation procedure aims to remove these Fe oxides and was found to be most efficient for the Mogi das Cruzes kaolin. The Seridó kaolin had the best whiteness index observed among the analysed samples.

The ICDD has developed a microanalysis tool to help scientists identify minerals from their elemental analyses, most typically micro-XRF or a microprobe analysis. Many minerals have characteristic elemental profiles that can often distinguish the mineral from others by their composition differences. In Release 2016 ICDD® PDF-4 databases 20 670 unique compositions have been identified out of 45 497 mineral and mineral-related entries. The application utilizes several common features of PDF® databases to enhance correct identification, most notably those formulas are expressed in weight and atomic percent, data sets are classified by mineral nomenclature and structural classifications, and most minerals have associated atomic and molecular structures. These crystal structures are very useful in determining compositional variants and solid solutions. The ICDD has developed algorithms that are analogous to the search/match processes used for powder diffraction identification. Data can be input as either the element or common oxide. To test the algorithm and graphics interfaces we compared results from the microanalysis module to published data from the Smithsonian Microbeam reference mineral collection. The software correctly identified 24/28 minerals by the highest merit score in the algorithm. In two cases, an isoelemental mineral was identified and in two other cases, the specimens had more elements than the reference standards hindering positive phase identification.

Roman bronze coins from the 3rd and 4th century AD exhibit a wide variety of chemistries on their surfaces. This variation has been attributed to the variable methods used to produce the coins, a large number of mints producing bronze currency, and the periods of currency devaluation within the Roman Empire. Besides the base bronze metallurgy (Cu,Sn), Ag, Pb, and Zn were frequently used as coinage metals. Silver coatings were often applied to increase the apparent value of the coins. Over the centuries these surfaces corroded producing a range of patinas. Non-destructive X-ray diffraction and X-ray fluorescence methods were used to evaluate ancient bronze coins. These methods are limited by their half depth of penetration into the coins, so the focus was on the chemistry of the patina's and how they related to the current appearance. Several 3rd-century bronze coins exhibited a very dark patina that was often composed of CuCl, Cu2O (cuprite) and several forms of copper hydroxyl chloride, resulting from surface deterioration caused by corrosion and is often referred to as bronze disease. Coins of the latter 3rd century and 4th century often exhibit patinas that are corrosion products of lead, silver, and tin, as lead and tin preferentially oxidize relative to the bronze alloys.

In precision agriculture, the selection and use of appropriate sensors determine the type and quality of information that will feed decision-support models. A wide variety of sensors, spectral ranges, data collection and processing approaches are used, sometimes leading to confusion. Whether in transmission or reflectance mode, multispectral or hyperspectral, laboratory or field-based or even satellite-borne, in order to achieve meaningful and accurate measurements it is essential to have a clear understanding of which part of the electromagnetic spectrum the sensors relate to and how the corresponding radiation interacts with the substrate (e.g. soils, crops, livestock products). Sensors in the visible range (390-700 nm) use colour to identify certain properties of the substrate (e.g. chlorophyll and pigments in crops, organic matter contents in soil) and can be used to detect and quantify colour changes that could, in turn, be correlated with changes in those properties. Alternatively, radiation in the near (NIR, 750-2500 nm) and mid infrared (MIR, 2500-25 000 nm) interacts with the molecular bonds that constitute organic and inorganic matter and, therefore, sensors with detectors in these ranges provide different but interrelated information on the chemical composition of the substrate. Shorter wavelength radiation in the form of X-Rays (0.1-10 nm) induces fluorescence in the substrate and XRF sensors provide elemental atomic information that is highly applicable to the study of soils, sediments and fluids. At the James Hutton Institute, we have expertise in the use of all these types of sensors and are developing practical applications based on a thorough understanding of the processes involved. In this paper we provide an overview of the capabilities and applications of the different sensors used in precision agriculture, not only with a theoretical understanding, but also with an awareness of the practicalities involved.

A new methodology for very high-speed, energy-dispersive detection of X-ray fluorescence is being developed. The underlying reasoning behind it, as well as early results from the evaluation of the first prototype, is presented.