Sediment certified reference materials for the determination of polychlorinated biphenyls and organochlorine pesticides from the National Metrology Institute of Japan (NMIJ)

Two marine sediment certified reference materials, NMIJ CRM 7304-a and 7305-a, have been issued by the National Metrology Institute of Japan in the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST) for the determination of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). The raw materials of the CRMs were collected from a bay near industrial activity in Japan. Characterization of these CRMs was conducted by NMIJ, where the sediments were analyzed using multiple analytical methods such as pressurized liquid extraction (PLE), microwave-assisted extraction (MAE), saponification, Soxhlet extraction, supercritical fluid extraction (SFE), and ultrasonic extraction; the target compounds were determined by one of the primary methods of measurements, isotope dilution–mass spectrometry (ID-MS). Certified values have been provided for 14 PCB congeners (PCB numbers 3, 15, 28, 31, 70, 101, 105, 138, 153, 170, 180, 194, 206, 209) and 4 OCPs (γ-HCH, 4,4′-DDT, 4,4′-DDE, 4,4′-DDD) in both CRMs. NMIJ CRM 7304-a has concentrations of the contaminants that are a factor of 2–15 greater than in CRM 7305-a. Both CRMs have information values for PCB homolog concentrations determined by collaborative analysis using a Japanese official method for determination of PCBs. The total PCB concentrations in the CRMs are approximately 920 and 86 μg kg⁻¹ dry mass respectively. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Certification of butyltins and phenyltins in marine sediment certified reference material by species-specific isotope-dilution mass spectrometric analysis using synthesized <Superscript>118</Superscript>Sn-enriched organotin compounds

A new marine sediment certified reference material, NMIJ CRM 7306-a, for butyltin and phenyltin analysis has been prepared and certified by the National Metrological Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Candidate sediment material was collected at a bay near industrial activity in Japan. After air-drying, sieving, and mixing the material was sterilized with γ-ray irradiation. The material was re-mixed and packaged into 250 glass bottles (15 g each) and these were stored in a freezer at −30 °C. Certification was performed by use of three different types of species-specific isotope-dilution mass spectrometry (SSID–MS)—SSID–GC–ICP–MS, SSID–GC–MS, and SSID–LC–ICP–MS, with ¹¹⁸Sn-enriched organotin compounds synthesized from ¹¹⁸Sn-enriched metal used as a spike. The ¹¹⁸Sn-enriched mono-butyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were synthesized as a mixture whereas the ¹¹⁸Sn-enriched di-phenyltin (DPhT) and triphenyltin (TPhT) were synthesized individually. Four different extraction methods, mechanical shaking, ultrasonic, microwave-assisted, and pressurized liquid extraction, were adopted to avoid possible analytical bias caused by non-quantitative extraction and degradation or inter-conversion of analytes in sample preparations. Tropolone was used as chelating agent in all the extraction methods. Certified values are given for TBT 44±3 μg kg⁻¹ as Sn, DBT 51 ± 2 μg kg⁻¹ as Sn, MBT 67 ± 3 μg kg⁻¹ as Sn, TPhT 6.9 ± 1.2 μg kg⁻¹ as Sn, and DPhT 3.4 ± 1.2 μg kg⁻¹ as Sn. These levels are lower than in other sediment CRMs currently available for analysis of organotin compounds.     

Precise Zn isotopic ratio measurements of human red blood cell and hair samples by multiple collector-ICP-mass spectrometry.

Precise 66Zn/64Zn and 68Zn/64Zn isotopic ratios of biochemical samples have been measured using multiple collector-ICP-mass spectrometry (MC-ICPMS). In order to eliminate the mass spectrometric interferences on Zn isotopes (e.g., 64Ni+ and 136Ba2+), we chemically purified the analyte using an ion chromatographic technique. The resulting precisions of the 66Zn/64Zn and 68Zn/64Zn ratio measurements were 0.05/1000 and 0.10/1000 (2SD), respectively, which were enough to detect the isotopic variation of Zn in nature. Red blood cell (RBC) samples were collected from five volunteers (four males and one female), including a series of 12 RBC samples from one person through monthly-based sampling over a year. These were analyzed to test possible seasonal changes and variations in 66Zn/64Zn and 68Zn/64Zn ratios among the individuals. The 66Zn/64Zn and 68Zn/64Zn ratios for a series of 12 RBC samples collected over a year were 0.43/1000 and 0.83/1000 higher than the values of highly purified Zn metal (JMC Zn), and no seasonal change could be found. The 66Zn/64Zn and 68Zn/64Zn ratios for RBC samples collected from five volunteers did not vary significantly. In order to investigate Zn isotopic heterogeneity in a human body, Zn isotopic ratios of a hair sample collected from one of the volunteers was also analyzed. The 66Zn/64Zn and 68Zn/64Zn ratios for the hair sample were 0.59/1000 and 1.14/1000 lower than the mean value of RBC samples. This result demonstrates that detectable isotopic fractionation occurs in the human body. The data obtained here suggest that the isotopic ratios of trace metals could provide new information about transportation of metal elements in vivo.     

Photochemical ion receptor based on a structurally distorted ruthenium(II) complex having a crown-ether moiety at the 3,3'-positions on the 2,2'-bipyridine ligand.

Ru(bpy)2(CE-bpy)2+ was prepared where bpy and CE-bpy were 2,2'-bipyridine and bpy having a crown-ether moiety at the 3,3'-positions, respectively. Although Ru(bpy)2(CE-bpy)2+ showed only very weak emission in acetonitrile, recognition of Na+, Li+, or K+ by the crown-ether moiety in CE-bpy resulted in increases in both the emission intensity and the lifetime of the complex, demonstrating that it acted as a photoreceptor. The results were discussed in terms of a steric hindrance between the 3,3'-substituents on CE-bpy and structural changes in both CE-bpy and the complex upon ion recognition, as studied by variable-temperature 1H-NMR and steady-state/dynamic emission spectroscopy of the complex.     

Partitionings and kinetic behaviors of major-to-ultratrace elements between industrial waste incineration fly and bottom ashes as studied by ICP-AES and ICP-MS.

The partitionings of major-to-ultratrace elements between industrial waste incineration fly ash (IWIFA) and industrial waste incineration bottom ash (IWIBA) in industrial waste incinerators were investigated by measuring their concentration distributions, where the incineration ash samples were collected from three different types of industrial waste incinerators. The concentrations of the elements in the incineration ash samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from mg g(-1) to sub-microg g(-1) could be determined in both IWIFA and IWIBA samples. The concentration ratios of CF/CB (CF, concentration in fly ash; CB, concentration in bottom ash) for analyte elements were used to evaluate the partitionings of the elements between fly and bottom ashes. Then, the correlations between the CF/CB values of the elements and the dissociation energies of their monoxides were examined to evaluate the kinetic behaviors of the elements during the incineration processes. It was found that lithophile and siderophile elements, which have a large affinity with oxygen, were almost equally distributed between fly and bottom ashes, regardless of the dissociation energies of their monoxides. On the other hand, chalcophile elements with rather large volatility provided different behaviors; the elements with the smaller dissociation energies of monoxides were more partitioned in fly ashes than those with the larger ones.     

Stochastic thermoelastic problem of a functionally graded plate under random temperature load

This study attempts to derive the statistics of temperature and thermal stress in functionally graded material (FGM) plates exposed to random external temperatures. The thermomechanical properties of the FGM plates are assumed to vary arbitrarily only in the plate thickness direction. The external temperatures are expressed as random functions with respect to time. The transient temperature field in the FGM plate is determined by solving a nonhomogeneous heat conduction problem for a multilayered plate with linear nonhomogeneous thermal conductivity and different homogeneous heat capacity in each layer. The autocorrelations and power spectrum densities (PSDs) of temperature and thermal stress are derived analytically. These statistics for FGM plates composed of partially stabilised zirconia (PSZ) and austenitic stainless steel (SUS304) are computed under the condition that the fluctuation in the external temperature can be considered as white noise or a stationary Markov process.     

Numerical simulation of flow kinematics for suspensions containing continuously dispersed aspect ratio fibers

Fiber suspension flow and fiber orientation through a parallel-plate channel were numerically simulated for fiber suspensions including continuously dispersed aspect ratios from 10 to 50. In the simulations, both the fiber–fiber and fiber–wall interactions were not taken into account. A statistical scheme that proceeds by evaluating the orientation evolution of a large number of fibers from the solution of the Jeffery equation along the streamlines was confirmed to be a very useful and feasible method to accurately analyze the orientation distribution of fibers with continuously dispersed aspect ratios. For monodisperse suspensions with small-aspect-ratio fibers, flip-over or oscillation phenomenon of the orientation ellipsoid caused the wavy patterns of the velocity profile and the streamlines as well as the abrupt and complex variation of the shear stress and the normal stress difference near the channel wall as proven in one of our former works. On the other hand, continuous dispersions containing from small- to large-aspect-ratio fibers were able to induce smoother evolutions of the fiber orientation and the flow kinematics. In the processing of fiber composites, the length of suspended fibers is always continuously distributed because of fiber breakage during processing; thus, the smooth evolutions of the flow kinematics and the stress distribution can be attained.This paper was presented at the Annual Meeting of the European Society of Rheology, Grenoble, April 2005.     

An attrition game on an acyclic network

This paper deals with noncooperative games in which two players conflict on a network through an attrition phenomenon. The associated problem has a variety of applications, but we model the problem as a military conflict between an attacker and a defender on an acyclic network. The attacker marches from a starting node to a destination node, expecting to keep his initial members untouched during the march. The defender deploys his forces on arcs to intercept the attacker. If the attacker goes through an arc with deployed defenders, the attacker incurs casualties according to Lanchester’s linear law. In this paper, we discuss two games having the number of remaining attackers as the payoff and propose systems of linear programming formulations to derive their equilibrium points. One game is a two-person zero-sum (TPZS) one-shot game with no information and the other is a TPZS game with two stages separated by information acquisition about players’ opponents.