Gamma versus alpha sensors for Rn-222 long-term monitoring in geological environments

The behavior of alpha silicon diodes, gamma crystal scintillators and ionization chamber detectors employed for long-term radon monitoring in geological media was studied and a comparison of the efficiency and sensitivity, the capability to resolve signal to noise, background, stability, and reliability of their long-term measurements is presented. An understanding of the qualities of monitoring techniques is necessary for determining suitability to the characteristics of the individual monitoring site and what exactly they will measure: radon in an air cavity, in porous media or in water.The experimental layout was located inside the Amram Mountain research tunnel near Elat (Gulf of Aqaba), within a closed room in the tunnel core. This enabled monitoring natural temporal radon variations under fairly stable internal conditions, at a high-resolution sampling rate of once every several minutes. In an interval of several days, all the sensors responded simultaneously to the same eventual radon variations.An ionization chamber device, the AlphaGUARD designed with a long-time stable calibration factor and an inherent QA-System, was used as reference calibration of the different radon detectors.The results indicate that the higher sensitivity of 2–4 orders of magnitude exhibited by gamma sensors even with narrow dimensions (1" × 3" BGO detector) are preferred for long-term radon monitoring in comparison to the solid-state alpha detectors and ionization chambers.     

Lead determination in slurries of biological materials by ETAAS using a W-Rh permanent modifier

A tungsten-rhodium coating on the integrated platform of a transversely heated graphite atomiser (THGA) was used as a permanent chemical modifier for the determination of lead in biological materials by slurry sampling in electrothermal atomic absorption spectrometry (ETAAS). Slurries were sonicated during 20 s before being delivered to the previously W-Rh treated platform. The number of particles of biological materials introduced into the atomiser for delivering 20 μL slurry aliquot ranged from 5,100 to 39,000. The permanent W-Rh modifier remained stable during approximately 300 analytical measurements when 20 μL of slurries containing up to 1.5% m/v were delivered into the atomiser. In addition, the permanent modifier increases the tube lifetime by approximately 100% when compared to untreated integrated platforms. Also, there is less decrease of sensitivity during the atomiser lifetime when compared with the conventional modifiers, resulting in a decreased need of re-calibration during routine analysis and consequently increasing the sample throughput. The atomiser lifetime was limited to the THGA wall durability, because the W-Rh treated platform was intact after more than 650 analytical firings in a medium containing up to 1.5% m/v slurry of biological material. The detection limit based on integrated absorbance was 20 ng g^–1 Pb for 1.50% m/v slurries. Results from the determination of lead in slurries of biological materials using the W-Rh permanent modifier were in agreement with those obtained with digested solutions using Pd + Mg(NO₃)₂. Received: 11 August 2000 / Revised: 13 November 2000 / Accepted: 16 November 2000     

Analysis of recombinant human erythropoietin and novel erythropoiesis stimulating protein digests by immunoaffinity capillary electrophoresis–mass spectrometry

In this work, we demonstrate that detection of a specific peptide marker by immunoaffinity capillary electrophoresis–mass spectrometry (IA-CE–MS) could be used to confirm the presence of recombinant human erythropoietin (rhEPO) in solution. Besides the carbohydrate content, the amino acid sequence of novel erythropoiesis stimulating protein (NESP) differs from human erythropoietin (hEPO) at five positions (Ala30Asn, His32Thr, Pro87Val, Trp88Asn, and Pro90Thr). After digesting both glycoproteins in solution by trypsin and PNGase F, two specific proteotypic peptides, EPO (77–97) and NESP (77–97) which differ in three amino acids, were selected as rhEPO and NESP markers, respectively. Both digests and their mixtures were analyzed by IA-CE–MS. The IA stationary phase was prepared from a custom made polyclonal anti-EPO (81–95) antibody immobilized on a solid support of CNBr-Sepharose 4B and was packed in a microcartridge near the inlet of the separation capillary. As the antibody was directed to a synthetic peptide EPO (81–95), only the proteotypic peptide EPO (77–97) was retained. The retained peptide was eluted, separated by electrophoresis and detected by MS. The method was specific to confirm the presence of rhEPO in solution. Although the limits of detection for the peptide marker were similar to those obtained with CE–MS (a few mg/L), these results show the potential of this novel approach to detect in the future rhEPO and its analogues selectively and unambiguously at the levels expected in biological fluids.     

Finding the Most Significant Elements for the Classification of Organic Orange Leaves: A Data Mining Approach

Brazil is the world’s largest producer of oranges. The Brazilian conventional citrus crop requires repeated application of agrochemicals to achieve satisfactory levels of productivity. The organic citriculture is an alternative production system, which is environmentally friendly and offers a safe food to consumers. However, it is difficult to determine if a food or plant was cultivated in organic or conventional system by just common observation, which makes the customers of organic food market vulnerable against fraudulent entrepreneurs. In this study, we present a data mining approach for the study of Brazilian organic citrus leaves which can aid in the certification of authenticity of the citrus leaves. The elemental composition is determined by inductively coupled plasma-mass spectrometry (ICP-MS). We developed classification models based on support vector machines and artificial neural networks capable of predicting whether a citrus leaf is organic or conventional through analysis of the concentration levels of the 14 chemical elements (Al, Ba, Co, Cr, Cs, Cu, Fe, Mg, Mn, Ni, Rb, Si, Sr, and V) found in both types of leaves. Feature selection filter methods are used to determine the most relevant elements for the classification process. Our best model obtained was a support vector machine with approximately 88% prediction accuracy. The elements Mn, Mg, and Rb were evaluated as the most significant for the classification decision. This is the first paper which addresses the problem of classification of organic orange leaves based on chemical composition. The presented methodology is useful for attesting authenticity of organic citrus leaves and can be adapted for other organic food or substances.     

Low-frequency optical phonons in silica

Measurements of low_frequency Raman spectra of silica fibers under longitudinal tensions as a function of temperature have been correlated with the measurements of FIR spectra of bulk silica in reflection and transmission. The results indicate existence of an LO-TO pair of a low-frequency optical phonon branch in amorphous silica.     

Minimal Whitney stratification and Euler obstruction of discriminants

In this work we show how to obtain the minimal Whitney stratification of the discriminant of finitely determined map germs from \((\mathbb {C}^m,0)\) to \((\mathbb {C}^p,0)\), of corank one if \(n<p\), and only with \(A_k\) singularities, when \(m = n+p\) with \( n \ge 0\). We apply the theory developed by Gaffney which shows how to compute a Whitney stratification of discriminants of any finitely determined holomorphic map germ in the nice dimensions of Mather, or in its boundary. For the pairs cited above we show that both stratifications coincide. We also compute the local Euler obstruction at 0 in a class of discriminants of finitely determined map germs from \(\mathbb {C}^{n+p}\) to \(\mathbb {C}^p\) with \(n\ge 0\) and only with \(A_k\) singularities.     

Autoprotolysis constants and standardization of the glass electrode in acetonitrile-water mixtures. Effect of solvent composition

Standard e.m.f.s for the cell GE/HCl/AgCl/Ag/Pt (GE=glass electrode) in acetonitrile-water mixtures containing 0–70% (w/w) of acetonitrile were obtained. Values of the autoprotolysis constant, K_ap, of these mixed solvents were also determined from e.m.f. measurements of the cell GE/KCl + KS/AgCl/Ag/Pt. The influence of variations in the solvent composition on pK_ap values was evaluated. Over the whole of the composition range studied the pK_ap values were linearly correlated with the mole fraction of acetonitrile and with the reciprocal of the relative permittivity of solvent mixtures. Linear relationships were also obtained for pK_ap values vs. the Kamlet-Taft π^★ polarizability/dipolarity parameter in the range 0–50% (w/w).     

Raman scattering investigations of KY3F10

Single crystals of the fluoride compound KY₃F₁₀ (O_h⁵) were studied by Raman scattering from 40 to 950 K. Group theory analysis predicts 3A_1g + 4E_g + 6F_2g Raman-active modes, but the experimental spectra show two F_2g modes missing. Over the whole temperature range the frequency shifts are negligible whereas the line widths show a strong increase with temperature. Both reversible and irreversible line width behaviour are exhibited for different temperature runs, indicating a complex microscopic phenomenon underlying the creation of defects responsible for these line widths and their interaction with the different phonon modes. An approximate activation energy for defect creation of ΔE ≈︁ 0.3 eV can be obtained from the temperature behaviour of the line widths. This activation energy may be connected with the high-temperature ionic conduction mentioned previously for this crystal.