Analysis of phosphorus herbicides by ion-pairing reversed-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry with octapole reaction cell

A reversed phase ion-pairing high performance liquid chromatographic (RPIP-HPLC) method is developed for the separation of two phosphorus herbicides, Glufosinate and Glyphosate as well as Aminomethylphosphonic acid (AMPA), the major metabolite of Glyphosate. Tetrabutylammonium hydroxide is used as the ion-pairing reagent in conjunction with an ammonium acetate/acetic acid buffering system at pH 4.7. An inductively coupled plasma mass spectrometer (ICP-MS) is coupled to the chromatographic system to detect the herbicides at m/z = 31P. Historically, phosphorus has been recognized as one of the elements difficult to analyze in argon plasma. This is due to its relatively high ionization potential (10.5 eV) as well as the inherent presence of the polyatomic interferences 14N16O1H+ and 15N16O+ overlapping its only isotope at m/z = 31. An octapole reaction cell is utilized to minimize the isobaric polyatomic interferences and to obtain the highest signal-to-background ratio. Detection limits were found to be in the low ppt range (25-32 ng/l). The developed method is successfully applied to the analysis of water samples collected from the Ohio River and spiked with a standard compounds at a level of 20 microg/l.     

Application of magnetic nanoparticles for the extraction of radium-226 from water samples

Bare (unmodified) and crown ether (CE)-modified Fe₃O₄ magnetic nanoparticles (MNPs) were investigated for the rapid extraction of ²²⁶Ra from water samples. It involved synthesizing the MNPs, introducing them into the sample solutions, ultrasonicating and agitating the suspension, magnetically separating the nanoparticles from solution, and measuring the ²²⁶Ra content in the supernatant. Experimental parameters such as salt choice, salt concentration and pH were optimized to achieve maximum extraction of ²²⁶Ra onto the MNPs. ²²⁶Ra content was determined using a Hidex 300SL liquid scintillation counter with α/β separation capability, or a gamma spectrometric detection system. The bare Fe₃O₄ nanoparticles showed significant pH dependence for the extraction of ²²⁶Ra from an aqueous solution over a pH range of 2–10. They gave an extraction of 95 ± 1 and 98 ± 1 % at pH 9 in 0.1 M NaCl and 0.1 M NaClO₄, respectively, whereas an extraction of 8–24 % was obtained, over the pH ranges from 2 to 5. The CE-modified MNPs yielded extraction efficiencies as high as 99 ± 1 % in the presence of 0.01 M picric acid at pH 4. This study demonstrates that the surface functionalization of Fe₃O₄ MNPs with suitable ligand modification can offer a selective mode of extraction for ²²⁶Ra in the presence of its daughter progenies.     

Photodegradation of poly(3-hydroxybutyrate)

The effect of ultraviolet radiation on the properties of poly(3-hydroxybutyrate) (PHB) was studied. The PHB investigated is produced from microbial fermentation using saccharose from sugarcane as the carbon source to the bacteria. The material was exposed to artificial UV-A radiation for 3, 6, 9 and 12 weeks. The photodegradation effect was followed by changes of molecular weight, of chemical and crystalline structures, of thermal, morphological, optical and mechanical properties, as well as of biodegradability. The experimental results showed that PHB undergoes both chain scission and crosslinking reactions, but the continuous decrease in its mechanical properties and the low amount of gel content upon UV exposure indicated that the scission reactions were predominant. Molar mass, melting temperature and crystallinity measurements for two layers of PHB samples with different depth suggested that the material has a strong degradation profile, which was attributed to its dark colour that restricted the transmission of light. Previous photodegradation initially delayed PHB biodegradability, due to the superficial increase in crystallinity seen with UV exposure. The possible reactions taking place during PHB photodegradation were presented and discussed in terms of the infrared and nuclear magnetic resonance spectra. A reference peak (internal standard) in the infrared spectra was proposed for PHB photodegradation.     

Phase transformations and phase diagram at equilibrium in the Cu-Ni-Sn system

The Cu-Ni-Sn ternary phase diagram in the Cu rich side has not been experimentally determined or calculated at low temperatures. Two Cu9NixSn alloys with x=2 and 6 mass% Sn were studied. The precipitation sequence during the ageing and phases responsible for the strengthening were determined.     

Catalytic properties of Fe-HMS materials in the phenol oxidation

Iron-incorporated mesoporous silica material Fe-HMS-50 (the Si/Fe molar ratio in the precursor gel is 50) was synthesized at ambient temperature by using hexadecylamine as a template and characterized by chemical analysis and N₂ adsorption measurements. The catalytic performance of Fe-HMS was studied in the phenol hydroxylation and wet phenol oxidation with H₂O₂ at 313 K. The effect of pH, H₂O₂: PhOH molar ratio and stability of the catalyst on the oxidation process was investigated. In the phenol oxidation, the activity of the catalyst increases by increasing the acidity of the reaction mixture to pH 3.4 and the amount of leached iron species was 1.95 ppm. A recycling test indicates that the catalyst recovered by drying in air at 423 K suffered, after the first run, a 12.4% drop in the catalytic activity. Fe-HMS has high catalytic activity and selectivity to dihydroxybenzene in the phenol hydroxylation. Hydroquinone was found as the predominant product under these experimental conditions with small amounts of benzoquinone appearing at the end of the reaction.     

Rapid determination of 226Ra in drinking water samples using dispersive liquid-liquid microextraction coupled with liquid scintillation counting

A new radioanalytical method was developed for rapid determination of ²²⁶Ra in drinking water samples. The method is based on extraction and preconcentration of ²²⁶Ra from a water sample to an organic solvent using a dispersive liquid-liquid microextraction (DLLME) technique followed by radiometric measurement using liquid scintillation counting. In DLLME for ²²⁶Ra, a mixture of an organic extractant (toluene doped with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone) and a disperser solvent (acetonitrile) is rapidly injected into the water sample resulting in the formation of an emulsion. Within the emulsion, ²²⁶Ra reacts with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone and partitions into the fine droplets of toluene. The water/toluene phases were separated by addition of acetonitrile as a de-emulsifier solvent. The toluene phase containing ²²⁶Ra was then measured by liquid scintillation counting. Several parameters were studied to optimize the extraction efficiency of ²²⁶Ra, including water immiscible organic solvent, disperser and de-emulsifier solvent type and their volume, chelating ligands for ²²⁶Ra and their concentrations, inorganic salt additive and its concentration, and equilibrium pH. With the optimized DLLME conditions, the accuracy (expressed as relative bias, B _r ) and method repeatability (expressed as relative precision, S _B ) were determined by spiking ²²⁶Ra at the maximum acceptable concentration level (0.5 Bq L⁻¹) according to the Guidelines for Canadian Drinking Water Quality. Accuracy and repeatability were found to be less than −5% (B _r ) and less than 6% (S _B ), respectively, for both tap water and bottled natural spring water samples. The minimum detectable activity and sample turnaround time for determination of ²²⁶Ra was 33 mBq L⁻¹ and less than 3 h, respectively. The DLLME technique is selective for extraction of ²²⁶Ra from its decay progenies.     

On stability of index of Fredholm complexes on the C* -algebra

This article deals with the index of Fredholm complexes of Λ-operators of the Hilbert Λ-modulus on C*-algebra. For this class of operators necessary and sufficient conditions in order to be a Fredholm, are obtained. Based on these results, a notion of Fredholm complex and its index is introduced. For this index, a stability theorem related to various perturbations is proved. In the second part of the article, a completation of a semigroup Fredholm complexes is analysed. It is proved that the group K _G (X, Λ) is the completation of G ? Λ-fibration of the above group on the compact space X.     

Invariant Computation in a Poset

Kong and Ribemboim (1994) define for every poset P a sequence P = D⁰(P), D(P), D²(P), D³(P)… of posets, where Dⁱ(P) = D(D^i??1(P)) consists of all maximal antichains of D^i??1(P). They prove that for a finite poset P, there exists an integer i ≥?0 such that Dⁱ(P) is a chain. In this paper, for every finite poset P, we show how to calculate the smallest integer i for which Dⁱ(P) is a chain.