The role of the acquisition methods in the analysis of natural and synthetic steroids and cholic acids by gas chromatography-mass spectrometry

An exhaustive GC-MS acquisition study was performed, for the simultaneous analysis of natural and synthetic steroids and cholic acids (in order to insert them into the last tierce of our multiresidue analysis system), such as androsterone, β-estradiol, transdehydroandro-sterone, transdehyroandrosterone, mestranol, dihydrotestosterone, ethinylestradiol, testosterone, norethisterone, estriol, 4-androstene-3,17-dione, gestodene, levonorgestrel, etonogestrel, coprostanol, progesterone, cholesterol, medroxyprogesterone-acetate, lithocholic acid, stigmasterol, cholic acid, chenodeoxycholic acid, β-sitosterol, ursodeoxycholic acid, 3-hydroxy-7-ketocholic acid and dehydrocholic acid, in total 26 compounds. As novelties to the field, for the trimethylsilyl (TMS) oxime ether/ester derivatives of steroids and cholic acids, at first, a tandem mass spectrometric (MS/MS), multiple reaction monitoring (MRM) type acquisition method has been developed in a single run; also for the first time, the three acquisition techniques, the full scan (FS), the selective ion monitoring (SIM), in our case the multiple ion monitoring (MIM) and the currently optimized MRM methods, have been compared; all three, in parallel, under strictly the same derivatization/instrumental conditions, both in matrix free solutions and municipal wastewater from two Hungarian wastewater treatment plants (WWTPs). Critical evaluation of the three acquisition protocols was collated on their analytical performances and validated under the same conditions. The data of six point calibration curves for FS, MIM and MRM methods, showed that both R2 (0.9995, 0.9858, 0.9975) and RSD (5.3, 5.8, 5.0), for two parallel derivatizations, each injected three times, proved to be independent of the acquisition processes. Whereas, for the method limit of quantification (LOQ) and the instrument limit of quantification (ILQ) values showed considerable differences. LOQ data, were decreasing in the FS, MIM, MRM line (expressed in ng/L), for all steroids and cholic acids. The same trend was determined in terms of the ILQ values. The practical utility of the optimized acquisition techniques was confirmed by the quantitation of the steroids and cholic acids contents of wastewater samples. Results confirmed the importance of the MRM acquisition method, even in comparison to the MIM one: with particular interest in selected cases: avoiding the extreme overestimation of the β-estradiol (156-1325%) and that of the ethinylestradiol (582-831%) concentrations in the wastewater samples.     

Hydrothermal interactions of basalts with Cs and Sr of spent fuel elements: Implications to basalt as a nuclear waste repository

The immobilization reactions of Cs, Sr, U and Mo from spent fuel elements (SFE) in the presence of basalts and basalt phases were investigated under hydrothermal, closed-system conditions. The exact Cs and Sr phases in SFE are not known with certainty, but Cs₂MoO₄, CsI, Cs₂O, β-Cs₂U₂O₇ and SrZrO₃ are some of the predicted possibilities. These phases were mixed with basalts and basalt phases along with water, sealed in gold capsules and reacted at 100, 200 and 300°C under a confining pressure of 300 bars. The Cs and Sr concentrations of the product solutions were measured to determine the partitioning of these elements between the liquid and solid phases. Results varied substantially, depending on the particular basalt or basalt phase or Cs phase, the temperature and the duration of run. For example, a Deep Drill Hole (DDH-3) basalt-Cs₂MoO₄ reactions resulted in 15, 78 and 99% fixation of added Cs at 100, 200 and 300°C respectively. Fixation of up to 99.7 and 99.8% of the added Cs and Sr respectively were observed in some cases. X-Ray diffraction (XRD) analysis of the solid products revealed that Cs was immobilized by the formation of pollucite, (Cs, Na)AlSi₂O₆ in most cases and the formation of CsAlSiO₄ in some cases. The interactions of basalts and basalt phases with Cs₂MoO₄ also resulted in the immobilization of Mo by the formation of powellite, CaMoO₄ because Ca is available in the reaction mixtures. The U⁶⁺ in β-Cs₂U₂O₇ was reduced to form uraninite, UO₂ by the divalent iron component of basalts. The exact nature of Sr reaction with basalts is not clear because no new Sr phases could be detected by XRD. The reaction products, pollucite, CsAlSiO₄, powellite and uraninite from SFE-basalt interactions serve to immobilize Cs, Mo and U because Cs in pollucite and CsAlSiO₄ is difficult to exchange and Mo and U in powellite and uraninite are quite insoluble.     

Thirty years of continuum solvation chemistry: a review,and prospects for the near future

With the recent occurrence of the 30^th anniversary of the first quantum mechanical continuum solvent code (Rinaldi D, Rivail J-L (1973) Theor Chim Acta 32:57), it seems like an appropriate moment to briefly review the variety of continuum QM models now available. This paper begins with such an overview, before shifting the discussion to a critical examination of some aspects of the basic theory, taking as the definition and evaluation of the solvation energy as an example. Advantages and disadvantages of using continuum-discrete models are examined, with particular attention paid to the evaluation of the solutes response properties. Some guidelines, and an operative definition of specific solute-solvent interactions, are presented. Then the paper moves on to examine problems regarding solutes of very large size, as well as complex systems. An example of the latter is the surface enhancing properties of large metal cluster aggregates with respect to the optical properties of a chromophore in a liquid medium. The paper ends with some extrapolations to the near future, mostly based on the material presented in the preceding sections.Proceedings of the 11th International Congress of Quantum chemistry satellite meeting in honour of Jean-Louis Rivail     

The role of the acquisition methods in the analysis of the non-steroidal anti-inflammatory drugs in Danube River by gas chromatography - mass spectrometry

In this paper authors describe a GC-MS acquisition study, relating to the most common, non-steroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen, naproxen, ketoprofen and diclofenac. As novelties to the field, for the trimethylsilyl (TMS) oxime ester derivatives of NSAIDs, at first, a tandem mass spectrometric (MS/MS) acquisition method has been developed, and, also for the first time, the three acquisition techniques, the full scan (FS), the selective ion monitoring (SIM) and the currently optimized MS/MS ones, have been compared: all three in parallel, under strictly the same derivatization/instrumental conditions, both from model solutions and from the Danube River samples. Critical evaluation of the three acquisition protocols was collated on their analytical performances and validated with the same characteristics like the six point calibration curve, the relative standard deviation percentages (RSD%) of parallel tests, the limit of quantitation (LOQ) and the instrumental limit of quantitation (ILQ) values. Data of six point calibration (r² ≥ 0.997) and RSD% (average: 5.8 RSD%) values proved to be independent on the acquisition methods, while, LOQ and ILQ values furnished considerable differences. Decreasing LOQ data, (expressed in ng/L concentrations) were obtained in the FS, SIM, MS/MS line for ibuprofen (1.0, 0.43, 0.41), naproxen (1.1, 1.0, 0.42), ketoprofen (2.6, 1.0, 0.49) and diclofenac (1.4, 0.41, 0.21), respectively. The same trend was determined in terms of the ILQ values. The practical utility of the optimized MS/MS technique was confirmed by the quantitation of the NSAID contents of the Danube River samples, determined by all three acquisition techniques. Results obtained confirmed the primary importance of the MS/MS acquisition method, even in comparison to the SIM one: avoiding the extreme overestimation of the ibuprofen (≈100%) and ketoprofen (≈400%) concentrations in the Danube River samples.     

Mass transfer in porous systems, flooded in part with water, of gas diffusion and catalytic layers of the cathode of a fuel cell with a solid polymer electrolyte

Mass transfer in porous gas diffusion and catalytic layers of the cathode of a hydrogen-air fuel cell with a solid polymer electrolyte is considered. The transport processes are considered with allowance made for the partial flooding of porous systems of these layers with water, which forms during the fuel cell operation. The consideration also allows for the influence of the diluent gas present when air oxygen is used as the oxidant. The fraction of water-flooded pores is calculated within percolation theory as a function of structural parameters of the porous system. Conditions leading to the beginning of the gas diffusion layer flooding are presented.     

The role of natural and man-made ice-forming nuclei in the atmosphere

Water-soluble and insoluble, organic and inorganic, natural and man-made aerosol particles participate in vapor-liquid, vapor-solid (ice), and liquid-solid phase transitions in the atmosphere. Hydrosol particles (aerosol particles that have been transferred into water droplets) nucleate ice through freezing. A small without scavenging or being scavenged by another aerosol particle. It is also difficult to imagine that pure mineral particles can be lifted from soil surfaces. In view of this, an ice-nucleating site may be a much smaller particle attached to a larger clay particle. To this category belong, e.g., silver iodide-clay mixed particles. Limited studies indicate that decaying leaves and forest litter under the surface of soils are a potential source of biogenic ice-forming nuclei but that their contribution to the atmosphere is very limited. Research should be directed to study possible relations between cloud condensation nuclei and ice-forming nuclei derived from natural organic compounds (terpenes, leaf-derived nuclei, bacteria, etc.).

A balance must be maintained between large cloud chambers, in which duplication of in-cloud processes is possible, and the special instrumentation which provides information about the modes of ice nucleation on aerosol particles. The two modes of instrumentation should supplement each other.

The greatest difficulty in attempting to make a comparison between the number of ice-forming nuclei estimated in the laboratory and the number in a cloud is the lack of knowledge of the time-temperature-humidity history of the aerosol particles. In nature, the ability of an aerosol particle to nucleate ice may be destroyed or“poisoned“ in the presence of pollutants. An aerosol particle may, on the other hand, become an activated or warmer ice-forming nucleus, e.g.,after the sublimation of ice once formed on it. The temperature of ice nucleation is not a singular property of a particle; the warmest temperatures of ice nucleation of, e.g., particles of a certain soil 10cm in diameter are-15°C,-10°C, and-8°C for nucleation through freezing, condensation followed by freezing and contact, respectively (ref.26). The progress made in instrumentation permits studies of the modes of ice nucleation. Understanding the physical and chemical processes taking place in clouds makes estimates of the rates of ice particle formation more realistic (Young [ref.157]).

The reader should examine two previous reviews written by Mossop (1963) and Montefinale . (1971) for a more complete list of references.     

Biogas as a fuel for solid oxide fuel cells and synthesis gas production: effects of ceria-doping and hydrogen sulfide on the performance of nickel-based anode materials

Numerous investigations have been carried out into the conversion of biogas into synthesis gas (a mixture of H(2) + CO) over Ni/YSZ anode cermet catalysts. Biogas is a variable mixture of gases consisting predominantly of methane and carbon dioxide (usually in a 2 : 1 ratio, but variable with source), with other constituents including sulfur-containing gases such as hydrogen sulfide, which can cause sulfur poisoning of nickel catalysts. The effect of temperature on carbon deposition and sulfur poisoning of 90 : 10 mol% Ni/YSZ under biogas conversion conditions has been investigated by carrying out a series of catalytic reactions of methane-rich (2 : 1) CH(4)/CO(2) mixtures in the absence and presence of H(2)S over the temperature range 750-1000 °C. The effect of ceria-doping on carbon dioxide reforming, carbon deposition and sulfur tolerance has also been investigated by carrying out a similar series of reactions over ceria-doped Ni/YSZ. Ceria was doped at 5 mol% of the nickel content to give an anode catalyst composition of 85.5 : 4.5 : 10 mol% Ni/CeO(2)/YSZ. Reactions were followed using quadrupolar mass spectrometry (QMS) and the amount of carbon deposition was analysed by subjecting the reacted catalyst samples to a post-reaction temperature programmed oxidation (TPO). On undoped Ni/YSZ, carbon deposition occurred predominantly through thermal decomposition of methane. Ceria-doping significantly suppressed methane decomposition and at high temperatures simultaneously promoted the reverse Boudouard reaction, significantly lowering carbon deposition. Sulfur poisoning of Ni/YSZ occurred in two phases, the first of which caused the most activity loss and was accelerated on increasing the reaction temperature, while the second phase had greater stability and became more favourable with increasing reaction temperature. Adding H(2)S significantly inhibited methane decomposition, resulting in much less carbon deposition. Ceria-doping significantly increased the sulfur tolerance of Ni/YSZ, however, in the presence of H(2)S ceria did not promote the reverse Boudouard reaction and at high temperatures carbon deposition was greater over ceria-doped Ni/YSZ. In order to further study the effects of ceria-doping, a solid oxide fuel cell (SOFC) was constructed with a ceria-doped anode cermet and its electrical performance on simulated biogas compared to hydrogen was tested. This fuel cell was subsequently ran for 1000 h on simulated biogas with no degradation in its overall electrical performance.     

The role of swelling methods in surfactant phase science: past,present, and future

The foundation for surfactant phase science was established largely using isoplethal phase study methods, but some use has been made of qualitative isothermal penetration experiments. In 1987 a quantitative swelling method (the Diffusive Interfacial Transport method) was reported in which the analysis of phase compositions is based on refractive index data. Experience obtained to date during use of this DIT-NDX method is reviewed.These investigations have demonstrated the considerable value of swelling studies, but revealed serious flaws in the DIT-NDX method. Swelling studies are exceptionally efficient, reliable, and provide considerable information regarding the physical science of the system in addition to the phase diagram. Unfortunately, this method is incapable of accurately defining the compositions of many birefringent phases. A DIT-IR method, presently under development, should resolve this problem. Analysis of composition using the DIT-IR method will be based on infrared data obtained using a near-infrared microscope. In addition to providing better composition data, infrared studies are expected to provide information on conformational structure, crystal hydration, and hydration thermodynamics. The future of swelling methods is discussed.     

The natural zeolite,laumontite, as a potential material for the treatment of aqueous nuclear wastes

A natural laumontite from the Isle of Skye, Scotland has been examined as a candidate material for aqueous nuclear waste treatment, and its fully Ca exchanged form has been shown to be Sr selective. Laumontite has a good pH stability in acid and alkaline media. The materials used have been characterized by wet chemical analysis, XRD and thermal analysis. The studies include both ion exchange kinetics and equilibrium isotherm studies which tend to confirm simple K_d tests.     

Ignition of coal powders in the presence of natural gas,oxygen, and reactive admixtures

At elevated temperatures (650–750°C), coating the inner surface of the reactor with coal dust exerts a significant effect on the ignition of hybrid coal-gas mixtures because coal evolves an effective inhibitor of methane combustion upon heating. The hybrid mixtures consisting of a coal powder and a stoichiometric natural gas-oxygen mixture do not ignite in the reactor lined with coal dust.     

On-line monitoring of nitrite in fertilizer process streams, natural and waste water effluents with sequential injection analysis

A sequential injection system for the online monitoring of nitrite in fertilizer process streams, natural and waste water effluents is proposed. Nitrite is diazotised in the SIA system with N-(1-naphthyl) ethylenediammonium dichloride to form a highly coloured azo dye which is measured at 525 nm. The proposed system is fully computerised and is able to monitor nitrite at a frequency of 49 samples per hour with a relative standard deviation of < 2.7%. The calibration curve is linear up to 5 mg/l. The detection limit is 0.053 mg/l.     

Reporting gamma-ray spectrometric measurement results near the natural limit: primary measurement results,best estimates calculated with the Bayesian posterior and best estimates calculated with the probability density distribution resembling shifting

When reporting best estimates as measurement results, systematic influences near the natural limit are introduced that originate not only in the possible inconsistency of the analytical procedure but also in the conversion of the primary measurement results to best estimates. It has been shown that the probability density distribution resembling shifting of values observed in the unfeasible region to the limit of the feasible range (the natural limit) introduces a smaller systematic influence than the Bayesian posterior, resembling censoring with repetition of the measurements that result in observed values in the unfeasible region. The drawback that the uncertainty intervals calculated with the Bayesian posterior do not encompass the natural limit and may not encompass the observed value, although it lies within the feasible region, is avoided by using the probability density distribution resembling shifting. Therefore, such best estimates introduce a smaller systematic influence into the measurement results and are better suited as inputs for subsequent analyses.     

Verification of a method for microcoulometric determination of adsorbable organic halide pollutants in natural, drinking, waste, and treated waters

A microcoulometric method is described for the determination of organic-halide pollutants at 2-2000 microg/L in natural, drinking, waste, and treated waters. The conditions for the adsorption of organic halides, using a microcolumn with activated charcoal-and for the desorption of inorganic halides-as well as for the pyrolysis process, were optimized for the successful determination of priority organic halide pollutants. An appropriate criterion was proposed to stop the desorption step. The mean recovery was 100.3%, and the mean relative standard deviation was 9.9%. The detection limit based on 3 times the standard deviation of the blank sample was 2 microg/L.     

The reactivity, as electrogenerated bases, of chiral and achiral phenazine radical-anions, including application in asymmetric deprotonation

Radical-anions, electrochemically generated in aprotic solvent from C(2) symmetric homochiral phenazine derivatives, act as chiral electrogenerated bases (EGBs) in the desymmetrisation by selective deprotonation of a prochiral epoxide (3,4-epoxy-2,3,4,5-tetrahydrothiophene-1,1-dioxide); the anion produced is trapped by mesitoic anhydride. The phenazines may be recovered in high yield by air oxidation. Enantiomeric excesses are modest (8-34%) but this is to our knowledge the first demonstration of such stereoselective electrochemically-initiated deprotonation. The reactivity of phenazine radical-anions as EGBs has also been explored by measurements of the rates of proton transfer; the prochiral epoxide was found to have a kinetic acidity similar to that of the methyltriphenylphosphonium cation.     

Application of nanoperlite as a new natural sorbent in the preconcentration of three organophosphorus pesticides by microextraction in packed syringe coupled with gas chromatography and mass spectrometry

A rapid, low‐cost, and simple method is proposed based on a miniaturized solid‐phase extraction named microextraction in packed syringe coupled with gas chromatography and mass spectrometry for the preconcentration and determination of some organophosphorous pesticides including diazinon, ethion, and malathion. For the first time, natural nanoperlite is used as a safe sorbent. Based on this technique, the analytes are adsorbed on the solid phase and then eluted by a desorbing solvent. The influence of some important parameters such as the solution pH, type, and volume of the organic desorption solvent on the microextraction efficiency of the selected pesticide technique is investigated. The proposed method showed a good linearity in the range of 1.0–35.0 μg/L for ethion and 0.4–30.0 μg/L for both diazinon and malathion. The limits of detection in the range of 0.1–0.38 μg/L were obtained using the selected ion‐monitoring mode of the mass spectrometer. The reproducibility of the method was found to be in the range of 2.8–8.9% for the studied pesticides. To evaluate the matrix effect, the developed method is also applied to the preconcentration and determination of the selected pesticides in real water samples.     

Influence of the primary ion incidence angle on secondary ion emission in SIMS with nitric oxide as reactant gas

Summary Secondary ion emission has been investigated for Ti, V, Cr and for Co, Ni and Cu under 9 mPa of NO as reactant gas with dynamic SIMS conditions. Using pivoted targets the relative intensities of various positive secondary ions were measured for varied incidence angles of the primary Ar⁺ ions (2 keV; 32 A·cm^–2). The axis of the PI beam and the axis of the SI detector were fixed rectangular to each other. The targets could be rotated about an axis perpendicular to both the PI and the detector axis. From the directional change of the emission of the metal ions Me⁺ a geometric shift parameter P_s could be deduced which proved to be related to the relative secondary ion yield and may therefore be used for surface characterization.     

The active site structure of nitrided and oxynitrided graphite as a cathode catalyst in a fuel cell

The first-principles studies were performed for the modified graphites with various edge conformations, which revealed that the NH edge facilitates easy transfer of an electron into the adsorbed O(2).     

Dapsone a new diazotizing reagent for the spectrophotometric determination of nitrite in waste and natural water samples

A new diazotizing reagent for the spectrophotometric determination of nitrite is described. The method is based on diazotization-coupling reaction between dapsone and phloroglucinol in hydrochloric acid medium. The reactions were conducted at room temperature, the molor absorptivity at 425 nm is 4.28 x 10(4) l mol-1cm-1 and was stable for 50 h. Beer's law was obeyed in the nitrite range of 0.008-1.0 microgram ml-1. Tolerance limits were tested for 33 species. The method has been found to be applicable for the determination of nitrite in natural and wastewater.     

Production of a highly dispersed carbon material and hydrogen from natural gas in a microwave reactor with metallic catalysts

Effect of a microwave field on metallic catalysts was studied in the reaction of decomposition of methane into hydrogen and highly dispersed carbon. The dependence of the conversion of methane, yield of carbon, and its composition on the chemical nature of a catalysts and reaction conditions was examined.