I. Queralt

Use of coal fly ash for ceramics : a case study for a large Spanish power station

Abstract Ceramic products with up to 50 wt% of mullite and 16 wt% of feldspars were obtained from binary mixtures of fly ash from the Teruel power station (NE Spain) and plastic clays from the Teruel coal mining district. The firing behaviour of fly ash and the ceramic mixtures was investigated by determining their changes in mineralogy and basic ceramic properties such as colour, bulk density, water absorption and firing shrinkage. To determine the changes on heating suffered by both the fly ash and the ceramic bodies, firing tests were carried out at temperatures between 900 and 1200°C in short firing cycles. The resulting ceramic bodies exhibit features that suggest possibilities for use in paving stoneware manufacture, for tiling and for conventional brickmaking.

Green Approach for Ultratrace Determination of Divalent Metal Ions and Arsenic Species Using Total-Reflection X-ray Fluorescence Spectrometry and Mercapto-Modified Graphene Oxide Nanosheets as a Novel Adsorbent

A new method based on dispersive microsolid phase extraction (DMSPE) and total-reflection X-ray fluorescence spectrometry (TXRF) is proposed for multielemental ultratrace determination of heavy metal ions and arsenic species. In the developed methodology, the crucial issue is a novel adsorbent synthesized by grafting 3-mercaptopropyl trimethoxysilane on a graphene oxide (GO) surface. Mercapto-modified graphene oxide (GO-SH) can be applied in quantitative adsorption of cobalt, nickel, copper, cadmium, and lead ions. Moreover, GO-SH demonstrates selectivity toward arsenite in the presence of arsenate. Due to such features of GO-SH nanosheets as wrinkled structure and excellent dispersibility in water, GO-SH seems to be ideal for fast and simple preconcentration and determination of heavy metal ions using methodology based on DMSPE and TXRF measurement. The suspension of GO-SH was injected into an analyzed water sample; after filtration, the GO-SH nanosheets with adsorbed metal ions were redispersed in a small volume of internal standard solution and deposited onto a quartz reflector. The high enrichment factor of 150 allows obtaining detection limits of 0.11, 0.078, 0.079, 0.064, 0.054, and 0.083 ng mL(-1) for Co(II), Ni(II), Cu(II), As(III), Cd(II), and Pb(II), respectively. Such low detection limits can be obtained using a benchtop TXRF system without cooling media and gas consumption. The method is suitable for the analysis of water, including high salinity samples difficult to analyze using other spectroscopy techniques. Moreover, GO-SH can be applied to the arsenic speciation due to its selectivity toward arsenite.

Dispersive micro solid-phase extraction using multiwalled carbon nanotubes combined with portable total-reflection X-ray fluorescence spectrometry for the determination of trace amounts of Pb and Cd in water samples

In this paper the combination of dispersive micro solid-phase extraction (DMSPE), using multiwalled carbon nanotubes (MWCNTs) as solid sorbents, with total-reflection X-ray fluorescence spectrometry (TXRF) is proposed for preconcentration and determination of lead and cadmium ions in water samples. The proposed sample preparation is quite simple and economic. After the sorption processes of the metals on the MWCNTs, the aqueous sample is separated by centrifugation and the metal loaded MWCNTs are suspended using a small volume of an internal standard solution and analyzed directly by TXRF. Parameters affecting the extraction process (complexing agent, pH of the aqueous sample, amount of MWCNTs) and TXRF analysis (volume of the deposited suspension on the reflector, drying mode, and instrumental parameters) have been carefully evaluated to test the real capability of the developed methodology for the determination of Cd and Pb at trace levels. For both elements the linear range is observed up to 50 ng mL−1. Under optimized conditions detection limits are 1.0 ng mL−1 and 2.1 ng mL−1 for Cd(II) and Pb(II) ions, respectively. Both of the examined elements can be determined with quantitative recoveries (ca. 100%) and with an adequate precision (RSD = 6.0% and 10.5% for Cd(II) and Pb(II), respectively). Our results give insight into the possibilities of the combination of DMSPE and TXRF for trace metal determination in different types of environmental waters (sea, river and waste water).

Weathering of a gypsum-calcareous mudstone under semi-arid environment at Tabernas, SE Spain: laboratory and field-based experimental approaches

The weathering of a Late Miocene gypsum-calcareous mudstone outcropping in large badland areas of SE Spain, under a semi-arid Mediterranean climate, was studied by means of two experimental approaches. Field and laboratory experiments were carried out to reproduce, though in accelerated form, some of the weathering conditions of the consolidated mudstone. In the laboratory, three sequences of 5, 10 and 20 wetting–drying cycles were produced on undisturbed blocks of fresh mudstone samples. At the end of the three sequences, samples were analysed for their micromorphology, elemental and soluble salt chemistry, and total mineralogy. Unweathered dry samples, as blanks, and permanently wet samples were also analysed. In the field, two small plots of freshly exposed mudstone were monitored over 3 years for their response to natural weathering in terms of morphological changes and sediment output. The porosity was increased by a few wetting–drying cycles, as assessed by significant increases in water absorption capacity of the mudstone. A combination of three factors is responsible for mudstone weathering: repeated cycles of wetting–drying, the presence of geologically-induced cracks and fissures, and dissolution–crystallisation of relatively soluble minerals, gypsum being the most abundant within this category. A few wetting–drying cycles were sufficient to reveal ion migration (specially Na+, Ca++, Mg++, SO4−, HCO− and Cl−) within the mudstone, explaining mineral dissolution. In the field, surface weathering rates from 0.7 to 8 mm year−1 were measured. Weathering rates were found to be proportional to the number of rainfall events during the sampling periods, confirming what was found in laboratory conditions, namely, that the number of wetting–drying cycles has the greatest influence on weathering. These weathering rates might be considered as the probable range of incision rates under present semi-arid conditions.

Analytical possibilities of total reflection X-ray spectrometry (TXRF) for trace selenium determination in soils.

Selenium content of soils is an important issue due to the narrow range between the nutritious requirement and toxic effects upon Se exposure. However, its determination is challenging due to low concentrations within complex matrices that hamper the analysis in most spectroscopic techniques. In this study, we explored the possibilities of several analytical approaches combined with total reflection X-ray (TXRF) spectrometry for soil Se determinations. The direct analysis of a solid suspension using 20 mg of fine ground material (<50 μm) has a relatively high Se limit of detection (LOD) of 1 mg/kg (worldwide Se average in soils = 0.4 mg/kg) and is therefore only suitable for seleniferous soils. Several fast and simple analytical strategies were developed to decrease matrix effects and improve the LOD for Se determination in soil digests. On one hand, the application of a liquid-liquid extraction procedure using ethyl ether and the introduction of a Cr absorbent in the instrument configuration were carried out to avoid the associated problems on TXRF analysis of soil extracts due to the high Fe concentrations (∼700 mg/L). On the other hand, a dispersive liquid-liquid microextraction procedure (DLLME) before the TXRF analysis of the soil digest was also developed. The effects of various experimental parameters such as sample volume, effect of major elements present in the soil matrix (Fe), and Se concentration in the sample were investigated. The LOD using this analytical methodology (0.05 mg/kg of Se) was comparable to or lower than those obtained in previous works using other popular spectrometric techniques such as GFAAS, ICPMS, and AFS. The calculated Se concentration for JSAC-0411 ([Se] = 1.32 ± 0.27 mg/kg) using the combination of DLLME and TXRF ([Se] = 1.40 ± 0.23 mg/kg) was in agreement with the certified value.

Preconcentration Methods for the Analysis of Liquid Samples by X-Ray Fluorescence Techniques

Abstract This article gives an overview of the state-of-the-art of multi-element and single-element preconcentration procedures prior to X-ray fluorescence (XRF) analysis of liquid samples. Many of these preconcentration methods were developed long ago and the purpose of this review is to present some new efficient variations of these methods and new techniques extending the possibilities of XRF for liquid solutions analysis. In addition, trends and future perspectives in this domain are also commented on and discussed in the last section of the review.

Analysis of inlet and outlet industrial wastewater effluents by means of benchtop total reflection X-ray fluorescence spectrometry

The monitoring of heavy metals in industrial waste water effluents is an important activity in many laboratories. Of special interest is the screening of elemental composition of inlet effluents and quantitative analysis of outlet effluents to study the efficiency of chemical treatment process to eliminate metals and to comply with current established concentration limits, respectively. In this sense, fast analytical methodologies which entail simple sample preparation are desired. In the present work, the possibilities and drawbacks of a benchtop total reflection X-ray fluorescence spectrometer (TXRF) for the rapid and simple determination of some inorganic impurities (As, Ba, Cd, Cu, Cr, Sn, Fe, Mn, Ni, Pb, Se and Zn) in inlet and outlet industrial waste water effluents from metallurgical and tanning leather factories have been tested. An evaluation of different simple sample treatments is presented and it is followed by a discussion of spectral and chemical matrix effects when dealing with this type of samples. Analytical figures of merit such as accuracy, precision and limits of detection have also been carefully studied. Finally, the data obtained by direct TXRF analysis has been compared to that obtained by ICP-OES/ICP-MS after a microwave digestion.

Liquid phase microextraction strategies combined with total reflection X-ray spectrometry for the determination of low amounts of inorganic antimony species in waters

In the present study, and taking into account the microanalytical capability of total reflection X-ray spectrometry (TXRF), we explored the possibilities of hollow fibre liquid-phase microextraction (HF-LPME) and dispersive liquid-liquid microextraction (DLLME) combined with TXRF for the determination of low amounts of inorganic Sb species in waters. For each of the LPME configurations aforementioned, experimental parameters affecting Sb extraction but specially the proper sample preparation process (deposition volume on the reflective carrier and drying mode) and measurement conditions for subsequent TXRF analysis have been carefully evaluated. The best analytical strategy for the determination of Sb(III) and Sb(V) in the low μg L(-1) range was found to be the application of the DLLME mode before TXRF analysis. The developed methodology was successfully applied to the determination of inorganic Sb speciation in different types of spiked water samples.

Determination of selenium by X-ray fluorescence spectrometry using dispersive solid-phase microextraction with multiwalled carbon nanotubes as solid sorbent

A dispersive solid-phase microextraction (DSPME) with multiwalled carbon nanotubes (MWCNTs) as solid sorbent and ammonium pyrrolidinedithiocarbamate (APDC) as chelating agent was developed for determination of selenium. In the proposed procedure, the Se(IV)–APDC complex is adsorbed on MWCNTs dispersed in aqueous samples. After the adsorption process, the aqueous samples are filtered and MWCNTs with selenium chelate are collected onto a filter. The loaded filters are directly measured using X-ray fluorescence (XRF) spectrometry. In order to obtain high recovery of the Se ions on MWCNTs, the proposed procedure was optimized for various analytical parameters such as pH, amounts of MWCNTs and APDC, sample volume and time of the sorption process. Under optimized conditions Se ions can be determined with very good recovery (97 ± 3%), precision (RSD = 3.2%) and detection limits (from 0.06 to 0.2 ng mL−1, depending on counting time and XRF equipment). The effect of common coexisting ions was also investigated. Se(IV) can be determined in the presence of heavy metal ions and alkali metals. The chemical interferences observed for high concentrations of Cu(II), Fe(III), and Zn(II) can be completely eliminated using precipitation with NaOH. The proposed method was applied for the determination of Se in mineral water and biological samples (Lobster Hepatopancreas). The proposed method can also be applied for selenium speciation. The concentration of selenate can be obtained as the difference between the concentration of selenite after and before prereduction of selenate to selenite.

Analytical approaches for Hg determination in wastewater samples by means of total reflection X-ray fluorescence spectrometry

At present, there is a considerable interest in Hg monitoring in wastewater samples due to its widespread occurrence and the high toxicity of most of its compounds. Hg determination in water samples by means of total reflection X-ray fluorescence spectrometry (TXRF) entails some difficulties due to the high vapor pressure and low boiling point of this element that produce evaporation and loss of Hg from the surface of the reflector during the drying process, commonly used for sample preparation in TXRF analysis. The main goal of the present research was to develop a fast and simple chemical strategy to avoid Hg volatilization during the analysis of wastewater samples by TXRF spectrometry. Three different analytical procedures were tested for this purpose: (i) increasing the viscosity of the wastewater sample by adding a non-ionic surfactant (Triton X-114), (ii) Hg immobilization on the quartz reflectors using the extractant tri-isobutylphosphine (Cyanex 471X) and (iii) formation of a stable and non-volatile Hg complex into the wastewater sample. The best analytical strategy was found to be the formation of a Hg complex with thiourea (pH=10) before the deposition of 10 microL of sample on the reflector for following TXRF analysis. Analytical figures of merit such as linearity, limits of detection, accuracy and precision were carefully evaluated. Finally, the developed methodology was applied for the determination of Hg in different types of wastewater samples (industrial effluents, municipal effluents from conventional systems and municipal effluents from constructed wetlands).