Characterization and determination of linear alkylbenzenesulfonates in environmental water samples by high-performance liquid chromatography with a hydrophilic polymer column and electrospray ionization mass spectrometric detection.

A liquid chromatography-mass spectrometry (LC/MS) method was developed for the separation and determination of linear alkylbenzenesulfonates (C10-C14 LAS) in environmental water samples using a hydrophilic polymer column (Shodex Mspak GF-310 4D). This method involves a solid-phase extraction of the LAS samples with a Sep-Pak PS-2 cartridge. The LAS components were separated on the column with a mobile phase of 29% (w/v) acetonitrile-water containing 0.8 mM di-n-butylammonium acetate and 0.2 M acetic acid, and were detected by mass spectrometry with electrospray ionization. Detection limits of the developed method based on selected ion monitoring (SIM) technique for the C10-C14 LAS standards were 13-47 ng L(-1). The concentrations of the C10-C14 LAS in the environmental water samples ranged between 5-317 microg L(-1) for a river water sample and 0.4-6.4 microg L(-1) for a seawater sample. Linear relationships between the logarithms of retention factors and the alkyl chain lengths for each phenyl positional isomer of LAS could successfully be used for the identification of the isomer peaks.     

Tolerance,bioaccumulation and biotransformation of arsenic in freshwater prawn (Macrobrachium rosenbergii)

Tolerance bioaccumulation and biotransformation of arsenic compounds by a freshwater prawn (Macrobrachium rosenbergii) were investigated. M. rosenbergii was exposed to 10, 20, 30 and 35 μg As cm⁻³ of disodium arsenate [abbreviated as As(V)], 25, 50, 100 and 120 μg As cm⁻³ of methylarsonic acid (MMAA), or 100,200, 300 and 350 μg As cm⁻³ of dimethylarsinic acid (DMAA). Tolerances (50% lethal concentration: LC₅₀) of the prawn against As(V), MMAA, and DMAA were 30, 100, and 300 μg As cm⁻³, respectively. The prawn accumulated arsenic compounds directly from aqueous phase and biotransformed them in part. Both methylation and demethylation of the arsenicals were observed in vivo. Highly methylated and less toxic arsenicals were less accumulated in M. rosenbergii.     

Effect of the chemical species of arsenic on sensitivity in graphite furnace atomic absorption spectrometry.

The sensitivity of graphite furnace atomic absorption spectrometry (GFAAS) to arsenobetaine (AB) was 1.3-times higher than to inorganic As. In order to understand the mechanism underlying this observation, the atomization processes for both chemical species were investigated in terms of the enthalpy change (DeltaH) during the atomization process in GFAAS. The enthalpy change of AB was slightly lower than that of inorganic As, which suggested that AB was atomized more efficiently than was inorganic As. Moreover, it was observed that some co-existing organic materials enhanced the analytical sensitivity of inorganic As. The sensitivity difference between inorganic As and AB depended upon the mechanisms of their atomization processes.     

Preparation and certification of arsenate [As(V)] reference material, NMIJ CRM 7912-a

Arsenate [As(V)] solution reference material, National Metrology Institute of Japan (NMIJ) certified reference material (CRM) 7912-a, for speciation of arsenic species was developed and certified by NMIJ, the National Institute of Advanced Industrial Science and Technology. High-purity As₂O₃ reagent powder was dissolved in 0.8 M HNO₃ solution and As(III) was oxidized to As(V) with HNO₃ to prepare 100 mg kg^-1 of As(V) candidate CRM solution. The solution was bottled in 400 bottles (50 mL each). The concentration of As(V) was determined by four independent analytical techniques—inductively coupled plasma mass spectrometry, inductively coupled plasma optical emission spectrometry, graphite furnace atomic absorption spectrometry, and liquid chromatography inductively coupled plasma mass spectrometry—according to As(V) calibration solutions, which were prepared from the arsenic standard of the Japan Calibration Service system and whose species was guaranteed to be As(V) by NMIJ. The uncertainties of all the measurements and preparation procedures were evaluated. The certified value of As(V) in the CRM is (99.53 ± 1.67) mg kg^-1 (k = 2).     

Lagrange-type duality in DC programming

We show a Lagrange-type duality theorem for a DC programming problem, which is a generalization of previous results by J.-E. Martínez-Legaz, M. Volle [5] and Y. Fujiwara, D. Kuroiwa [1] when all constraint functions are real-valued. To the purpose, we decompose the DC programming problem into certain infinite convex programming problems.     

Duality Theorems for Separable Convex Programming Without Qualifications

In the research of mathematical programming, duality theorems are essential and important elements. Recently, Lagrange duality theorems for separable convex programming have been studied. Tseng proves that there is no duality gap in Lagrange duality for separable convex programming without any qualifications. In other words, although the infimum value of the primal problem equals to the supremum value of the Lagrange dual problem, Lagrange multiplier does not always exist. Jeyakumar and Li prove that Lagrange multiplier always exists without any qualifications for separable sublinear programming. Furthermore, Jeyakumar and Li introduce a necessary and sufficient constraint qualification for Lagrange duality theorem for separable convex programming. However, separable convex constraints do not always satisfy the constraint qualification, that is, Lagrange duality does not always hold for separable convex programming. In this paper, we study duality theorems for separable convex programming without any qualifications. We show that a separable convex inequality system always satisfies the closed cone constraint qualification for quasiconvex programming and investigate a Lagrange-type duality theorem for separable convex programming. In addition, we introduce a duality theorem and a necessary and sufficient optimality condition for a separable convex programming problem, whose constraints do not satisfy the Slater condition.     

Rapid and highly sensitive method for determination of methamphetamine and amphetamine in urine by electron-capture gas chromatography

A rapid and sensitive method for determination of methamphetamine and amphetamine in urine was developed by using electron-capture gas chromatography. The extraction procedure, the experimental conditions for pentafluorobenzoyl derivative formation and the percentage recovery of the drugs from urine are described. The pentafluorobenzoyl derivative of methamphetamine showed a higher electron-capture sensitivity and was detected in at least 23-fold lower concentration than the heptafluorobutyryl derivative which is commonly used as a derivatizing agent for the amine. The detection limit of pentafluorobenzoyl derivatives of methamphetamine and amphetamine was ca. 10 pg. A concentration as low as 10 ng/ml of methamphetamine and amphetamine in urine was easily detected by this method.     

Probing the oxygen activation reaction in intact whole mitochondria through analysis of molecular vibrations

The process of dioxygen reduction catalyzed by cytochrome c oxidase was investigated by examining intact porcine mitochondrial preparations using a novel time-resolved resonance Raman measurement system at experimental accuracy levels equivalent to those of the reaction system of the solubilized and purified enzyme. The resonance Raman bands assignable to the initial three intermediates were detected at frequencies identical to those observed with purified enzyme preparations. However, the lifetime of the initial intermediate (the oxygenated species) in the mitochondrial preparation was found to be significantly longer than that observed in purified preparations, suggesting that control of the stability of the oxygenated species is imposed by the mitochondrial membrane system.     

Biomethylation and biotransformation of arsenic in a freshwater food chain: Green alga (chlorella vulgaris)→shrimp (neocaridina denticulata)→killifish (oryzias iatipes)

Tolerance, bioaccumulation, biotransformation and excretion of arsenic compounds by the fresh–water shrimp (Neocaridina denticulata) and the killifish (Oryzias latipes) (collected from the natural environment) were investigated. Tolerances (LC₅₀) of the shrimp against disodium arsenate [abbreviated as As(V)], methylarsonic acid (MAA), dimethylarsinic acid (DMAA), and arsenobetaine (AB) were 1.5, 10, 40, and 150μg As ml^?1, respectively. N. denticulata accumulated arsenic from an aqueous phase containing 1 μg As ml^?1 of As(V), 10 μg As ml^?1 of MAA, 30 μg As ml^?1 of DMAA or 150 μg As ml^?1 of AB, and biotransformed and excreted part of these species. Both methylation and demethylation of the arsenicals were observed in vivo. When living N. denticulata accumulating arsenic was transferred into an arsenic–free medium, a part of the accumulated arsenic was excreted. The concentration of methylated arsenicals relative to total arsenic was higher in the excrement than in the organism. Total arsenic accumulation in each species via food in the food chain Green algae (Chlorella vulgaris) → shrimp (N. denticulata) → killifish (O. latipes) decreased by one order of magnitude or more, and the concentration of methylated arsenic relative to total arsenic accumulated increased successively with elevation in the trophic level. Only trace amounts of monomethylarsenic species were detected in the shrimp and fish tested. Dimethylarsenic species in alga and shrimp, and trimethylarsenic species in killifish, were the predominant methylated arsenic species, respectively.