Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol in supercritical water

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol (o-CP) in supercritical water (SCW) were studied in this paper under the conditions of 450 degrees C and 25 MPa. Experimental results indicated that the dechlorination of o-CP can be accelerated significantly by all alkalis investigated. The dechlorination of o-CP proceeded mainly via two pathways: hydrodechlorination and hydrolysis. Both of the two pathways can be promoted by alkalis, and the dechlorination of o-CP can be accelerated by both the cations and hydroxide ion dissociated from alkalis. The overall dechlorination of o-CP can be accelerated by cations via promoting the hydrodechlorination pathway, while, hydroxide ion via promoting the hydrolysis pathway. In addition, the hydrodechlorination can be accelerated faster by sodium alkalis than that by potassium ones, while, the hydrolysis can be promoted faster by potassium alkalis. This difference may be caused by the different charge density between potassium ion and sodium ion, and the different solubility and dissociation constant between potassium alkalis and sodium alkalis in SCW. Dechlorination of o-CP with addition of alkalis prior to supercritical water oxidation (SCWO) process not only can avoid the reactor corrosion caused by the generated hydrochloric acid in direct SCWO of o-CP, but also can reduce the formation of toxic chlorinated byproducts compared with direct SCWO process or SCWO of o-CP with addition of alkali.     

An exquisitely preserved troodontid theropod with new information on the palatal structure from the Upper Cretaceous of Mongolia

Troodontidae is a clade of small-bodied theropod dinosaurs. A new troodontid, Gobivenator mongoliensis gen. et sp. nov., is described based on the most complete skeleton of a Late Cretaceous member of this clade presently known, from the Campanian Djadokhta Formation in the central Gobi Desert. G. mongoliensis is different from other troodontids in possessing a pointed anterior end of the fused parietal and a fossa on the surangular in front of the posterior surangular foramen. The skull was superbly preserved in the specimen and provides detailed information of the entire configuration of the palate in Troodontidae. Overall morphology of the palate in Gobivenator resembles those of dromaeosaurids and Archaeopteryx, showing an apparent trend of elongation of the pterygoid process of the palatine and reduction of the pterygopalatine suture toward the basal Avialae. The palatal configuration suggests that the skull of Gobivenator would have been akinetic but had already acquired prerequisites for later evolution of cranial kinesis in birds, such as the loss of the epipterygoid and reduction in contact areas among bones.     

Diffusivity measurement of heavy ions in Wyoming montmorillonite gels by X-ray computed tomography

Medical X-ray computed tomography (CT) was applied to the measurement of the diffusion coefficients of heavy ions in an artificial barrier material for the disposal of nuclear wastes. Cs(+), Sr(2+), I(-), and Br(-) are the heavy ions measured and the barrier used is the water-rich gel of Wyoming montmorillonite (86.5-100 wt.% H(2)O). X-ray CT yields an inevitable artifact (beam-hardening) in the obtained images. Before the diffusion experiments, the polychromatic primary X-ray spectrum of the CT scanner was measured by a CdZnTe detector, and the effects of the artifact were examined for an aqueous CsCl solution sample. The results show that the beam-hardening artifact derived from the polychromatic photon energy distribution can be suppressed by applying a special image reconstruction method assuming the chemical composition of samples. The transient one-dimensional diffusion of heavy ions in a plastic container filled with the gel was imaged nondestructively by the X-ray CT scanner with an in-plane resolution of 0.31 mm and slice thickness of 2 mm. The results show that diffusivities decrease with increasing clay weight fraction. The degree of the diffusivity decrease was high for cations (Cs(+) and Sr(2+)) and low for anions (I(-) and Br(-)). The quantitative decomposition of the contribution of the geometrical tortuosity and of the sorption to the diffusivity was performed by subtracting the diffusivity of nonsorbing I(-) from the measured diffusivities. The results show that the contribution of the sorption is large for Cs(+), Sr(2+) and small for Br(-). Because X-ray CT allows nondestructive and quick measurements of diffusivities, the technique would be useful particularly for measuring the diffusive migration of harmful radioactive elements.     

A new protease assay system using gelatin thin film for monitoring indoor air quality

Airborne particulates have a major influence on the quality of indoor environments, which in turn affects human health. Both allergens and proteases are major etiological factors in allergic disease. Thus, the monitoring of environmental protease particulates is very important for the management of allergic disease. Protease-monitoring systems have been introduced in industry, but have not been applied to domestic settings, probably because of the high cost and many complex steps involved in these systems. In this study, we developed an indoor protease-monitoring system which can easily detect protease particulates without need for pre-treatment of dust samples or complex measuring instruments such as fluorescent plate reader. As a protease substrate, gelatin thin film (GTF) was adopted to evaluate small amounts of house dust particulates. The principle of this assay is based on the hydrolysis of GTF. Protease molecules spread from a particulate to GTF can hydrolyze the gelatin, thereby producing a spot on the GTF. This hydrolyzed spot visualized by staining was much larger than the particulate size, making visible to naked eye. The GTF method facilitated the observation of a subtle increase in protease particulates fallen on the GTF after the turnover of a used bed-quilt. The newly developed GTF method seems to be a suitable tool for protease monitoring at home.     

Three-dimensional diffusion of non-sorbing species in porous sandstone: computer simulation based on X-ray microtomography using synchrotron radiation

The diffusion pathways of porous sandstone were examined by a three-dimensional (3-D) imaging technique based on X-ray computed tomography (CT) using the SPring-8 (Super Photon ring-8 GeV, Hyogo, Japan) synchrotron radiation facility. The analysis was undertaken to develop better understanding of the diffusion pathways in natural rock as a key factor in clarifying the detailed mechanism of the diffusion of radionuclides and water molecules through the pore spaces of natural barriers in underground nuclear waste disposal facilities. A cylindrical sample (diameter 4 mm, length 6 mm) of sandstone (porosity 0.14) was imaged to obtain a 3-D image set of 450(3) voxels=2.62(3) mm(3). Through cluster-labeling analysis of the 3-D image set, it was revealed that 89% of the pore space forms a single large pore-cluster responsible for macroscopic diffusive transport, while only 11% of the pore space is made up of isolated pores that are not involved in long-range diffusive transport. Computer simulations of the 3-D diffusion of non-sorbing random walkers in the largest pore cluster were performed to calculate the surface-to-volume ratio of the pore, tortuosity (diffusion coefficient in free space divided by that in porous rock). The results showed that (i) the simulated surface-to-volume ratio is about 60% of the results obtained by conventional pulsed-field-gradient proton nuclear magnetic resonance (NMR) laboratory experiments and (ii) the simulated tortuosity is five to seven times larger than the results of laboratory diffusion experiments using non-sorbing I(-) and Br(-). These discrepancies are probably attributed to the intrinsic sample heterogeneity and limited spatial resolution of the CT system. The permeability was also estimated based on the NMR diffusometry theory using the results of the random walk simulations via the Kozeny-Carman equation. The estimated permeability involved an error of about 20% compared with the permeability measured by the conventional method, suggesting that the diffusometry-based NMR well logging with gradient coils is applicable to the in-situ permeability measurement of strata. The present study demonstrated that X-ray CT using synchrotron radiation is a powerful tool for obtaining 3-D pore structure images without the beam-hardening artifacts inevitable in conventional CT using X-ray tubes.     

Concentrations of dioxins and related compounds in the blood of Fukuoka residents

Blood samples of 152 residents (male 75 and female 77) aged 20-60 years in Fukuoka, Japan, were analyzed for dioxin toxic compounds of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs) and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) as well as 35 PCB congeners and 12 chlorinated pesticides by high-resolution gas chromatography/high-resolution mass spectrometry. Average concentrations of dioxin toxic equivalents (TEQ) from PCDDs, PCDFs, non-ortho PCBs, mono-ortho PCBs and their total in the blood of 152 residents were 10.28, 5.56, 7.75, 4.57 and 28.15 ppt in lipid, respectively. These total TEQ levels were comparable to the blood TEQ levels of normal Japanese (n=735). Lipid basis total TEQ levels progressively increased in the males from 17.1 ppt at age 20s to 47.5 ppt at age 50s and in the females from 19.5 ppt at age 20s to 54.5 ppt at age 50s. Dioxin toxic contribution of PCBs to total TEQ was increased from 31% at age 20s to 55% at age 50s. Average concentrations of total 35 PCBs and total 12 pesticides in the blood of 151 residents were 386 and 1079 ppb in lipid, respectively. Average concentrations (ppb in lipid) of total PCBs and total pesticides also progressively increased in the males from 213 and 444 at age 20s to 868 and 2140 at age 50s, respectively, and in the females from 199 and 588 at age 20s to 550 and 1977 at age 50s, respectively. The levels of TEQ, PCBs, hexachlorobenzene, beta-hexachlorocyclohexane, dieldrin, p,p'-dichlorodiphenyldichloroethylene, p,p'-dichlorodiphenyltrichloroethane, trans-nonachlor and cis-nonachlor were positively correlated with each other in most of the combinations, and the highest correlations (r>0.8) were observed between total TEQ and PCBs in both sexes.     

A preliminary estimate of the trophic position of the deep-water ram’s horn squid Spirula spirula based on the nitrogen isotopic composition of amino acids

The ram’s horn squid, Spirula spirula (Spirulida, Coleoidea), inhabits subsurface waters of the tropical and subtropical oceans. Because of the presence of an internal chambered shell in this species, it has frequently been used as a model species to investigate the paleobiology of fossil coleoids. However, the feeding and dietary habits of S. spirula in the nature are poorly known. In this study, we applied a new method (amino acid nitrogen isotopic analysis) to estimate the trophic position of S. spirula specimens captured off Suriname, as well as three cuttlefish Sepia species (Sepia officinalis, S. latimanus, and S. esculenta), with a calcified chambered shell from the shallower water. The trophic position of S. spirula was estimated to be 2.5–2.8, which was significantly lower than that for the three Sepia species (3.4–3.6). The results and available data on the gastric contents of S. spirula suggest that it feeds mainly on detritus and zooplankton, including crustaceans, from the overlying water column. The method used in this study can potentially be applied to the estimation of the trophic position of the fossil cephalopods having calcified chambered shells.     

Pathways and products of the degradation of PCBs by the sodium dispersion method

Nine polychlorinated biphenyl (PCB) congeners (2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,3,4-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,3',4,4',5-pentachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl, 2,2',4,4',5,5'-hexachlorobiphenyl, and decachlorobiphenyl) were dechlorinated by the sodium dispersion method (SD) at low temperature (60 degrees C). The dechlorination of 4-chlorobiphenyl was the fastest among the three monochlorobiphenyls. As for the other six congeners, we investigated the major dechlorination pathways. Although reaction selectivity was not very sensitive to the position of the chlorine substituent, the chlorines at the para position were slightly easier to dechlorinate than those at the ortho or meta positions. The decomposition rate increased with the total numbers of chlorine substituents. A chlorine situated between two other chlorines showed a high reactivity. When the numbers of chlorines on each of the phenyl rings were different, the reactions occurred on the more substituted ring. In the degradation of 4-chlorobiphenyl at elevated temperature (160 degrees C), we investigated the structures of the polymerized products and whether all the organic chlorinated compounds degraded finally or not. As for the dimers, p-quarterphenyl (QP) and m,p-QP were detected but not o-QP, m-QP, o,p-QP, o,m-QP, or the mono- to tetra-chlorinated QPs. Compounds with a molecular weight of 534.4183 or 758.6713 were detected. They were considered to have C40H54 or C56H86 as their molecular formula. The compounds were most probably the polymerized products resulting from coupling of hexadecane or two hexadecanes and two phenylcyclohexadienes. It was thought the dechlorination and the polymerization were the main reactions. All of many detected compounds were hydrocarbons without chlorines, and no peaks originating from organic chlorinated compounds were observed by mass spectroscopic (MS) methods.