Chemically driven desorption of CO from icy grains in dark clouds

The chemical desorption of an adsorbed CO molecule in the vicinity of H₂-forming sites on cosmic dust grains in cold dense clouds is investigated theoretically, mainly using a model based on a classical molecular dynamics computational simulation. As a model surface for icy mantles of dust grains, an amorphous water ice slab is generated at 10 K, and the first and the second H atoms are thrown on to the model surface to reproduce the recombination process of the two H atoms, H+H→H₂. Then, the time and space dependence of the local temperature increase of icy mantles caused by the release of H₂ formation energy in the vicinity of H₂-forming sites is examined. It is found that icy mantles are heated locally up to about 30 K in the surface region at R 4 Å and about 20 K at 4 R 6 Å, where R is the distance from the H₂-forming site. The critical temperature of CO desorption is estimated to be about 20–30 K under conditions in typical dense clouds, which might be seen to be comparable to the above result. However, the lifetime of local heating of icy mantles is found to be too short, compared with the time-scale of CO desorption (10¹³ s) and that for H₂ forming in the vicinity of an adsorbed CO molecule (more than 2×10¹³ s). Thus, it is found that the efficiency of chemical desorption of CO on a large dust grain is negligible. On the other hand, chemical desorption can occur on a small dust grain with size less than 20 Å.     

Assessing the designs and effectiveness of Japan's emissions trading scheme

After years of discussions and trials, Japan's domestic emissions trading scheme remains purely voluntary. The newly elected Democratic Party of Japan (DPJ) has taken a firmer stance on climate change, initially intending to establish a nationwide mandatory cap-and-trade as early as 2011. This has promoted several questions regarding the possible designs and feasibility of such a scheme. This article describes the key features of the two trial schemes implemented, thus far, assesses the effectiveness of their implementation and discusses what will be the likely areas of contention should the Japanese government introduce a mandatory cap-and-trade in the future. The analyses indicate that the initial years of ‘Japan's Voluntary Emissions Trading Scheme’ (JVETS) implementation have shown positive performance, although its scale has remained limited. The ‘Trial Implementation of an Integrated Domestic Market for Emissions Trading’ emerged as a hybrid scheme, one that incorporated varying interests. Significant institutional developments have taken place in recent years, however the effectiveness of the present trial scheme also seems restricted.     

Isomer specific determination of hexabromocyclododecanes (HBCDs) in small cetaceans from the South China Sea--Levels and temporal variation

A diastereoisomer (alpha, beta, and gamma) specific analytical method for measuring hexabromocyclododecanes (HBCDs) was developed using liquid chromatography-tandem mass spectrometry (LC-MS-MS). The method developed was applied to analyze blubber of small cetaceans to divulge the distribution and temporal variation of HBCDs in the Asian marine environment. HBCDs were detected in all the blubber samples of finless porpoises (Neophocaena phocaenoides) and Indo-Pacific humpback dolphins (Sousa chinensis) collected from the South China Sea during 1990-2001. Concentrations of HBCDs were higher in humpback dolphins (31-380 ng/g lipid) than in finless porpoises (4.7-55 ng/g lipid), which can be attributed to habitat differences. Average concentrations of alpha-HBCD in finless porpoises increased from 9.5 ng/g lipid in 1990 to 35 ng/g lipid in 2000/01. alpha-HBCD was predominant among the three isomers with some exceptions in finless porpoises collected in 1990. This is the first report on HBCDs contamination in marine mammals from Southeast Asia.     

Placental transfer of arsenic to fetus of Dall’s porpoises (Phocoenoides dalli)

Concentrations of total arsenic and individual arsenic compounds were determined in liver, muscle, kidney and blubber of mother and fetus of Dall’s porpoises collected from off Sanriku, Japan, in the year 2000 to characterize the placental transfer of arsenic to fetus in cetaceans. Arsenic was detected in all the tissues of Dall’s porpoises. Total arsenic concentrations in liver, kidney, muscle and blubber were 0.76, 0.69, 0.35 and 0.55 μg/g wet wt, respectively, for mother and 0.28, 0.23, 0.26 and 0.07 μg/g wet wt, respectively, for fetus. In all the tissues, concentrations of total arsenic in mother Dall’s porpoise were higher than in fetus. Arsenic speciation revealed that arsenobetaine was the major arsenic compound in liver, kidney and muscle of both mother and fetus. The percentage of arsenobetaine to total arsenic ranged from 76.0 to 91.0% in the tissues. Dimethylarsinic acid, arsenocholine, methylarsonic acid and an unidentified arsenic compound were also detected in tissues of both mother and fetus as minor constituents, whereas tetramethylarsonium ion was not detected in tissues of the fetus. These results suggest that arsenobetaine, dimethylarsinic acid, arsenocholine and methylarsonic acid are transferable from mother to fetus in Dall’s porpoises. To our knowledge, this is the first report on placental transfer of arsenic compounds to fetus in marine mammals.     

Alkalinization and acidification of stream water with changes in atmospheric deposition in a tropical dry evergreen forest of northeastern Thailand

Field surveys on atmospheric deposition and stream water chemistry were conducted in an evergreen forest in northeastern Thailand characterized by a tropical savanna climate with distinct dry and wet seasons. Atmospheric deposition of ion constituents by throughfall and stemflow was shown to increase in the beginning and end of the wet season, reflecting the precipitation pattern. The pH and electrical conductivity of stream water increased with alkalinity and base cation concentrations due to mineralization of organic matter by the first rain and retention of anions in soil during the start of the wet season. After initial alkalinization, the pH and alkalinity declined rapidly with the highest SO₄^2? concentration displayed in the middle towards the end of the wet season. The magnitude of peaks in SO₄^2? concentration (13.5–60.6 μmol_c/L) reflects deposition during the first 2 months of the wet season (March and April) in respective years (60.8–170 mol_c/ha). Release of SO₄^2? with H⁺, which is retained in soil during the early wet season, may cause acidification later in the season. The deposition and concentration of SO₄^2? declined over 6 years. However, the pH of stream water declined with increasing concentrations of SO₄^2? and other major ions. The release of materials accumulated in the ecosystem was facilitated by the decrease in SO₄^2? concentration/deposition and increased precipitation in the middle–late wet season. The retention‐release cycle of SO₄^2? largely contributed to both seasonal and interannual variations in stream water chemistry in the tropical savanna climate studied.     

Hydrothermal Alteration and Cu-Au Mineralization at Nena High Sulfidation-type Deposit, Frieda River, Papua New Guinea

Abstract. The Nena Cu‐Au deposit, located in the Frieda River mineral district of northwestern mainland Papua New Guinea, is a composite structurally‐lithologically controlled high sulfidation (HS) system. Its hydrothermal alteration and Cu‐Au mineralization are presented in this paper. Initially propylitized andesitic volcanics veined by epithermal quartz were pervasively superimposed by zoned HS alteration. The zonation grades from vuggy silica core to sulfur‐rich, pyritic silica‐alunite halo followed by pyrophyllite‐dickite‐kaolinite interval and finally to thin illite‐smectite margin, suggesting progressive decrease in temperature and increase in pH. This zonation is enveloped by chlorite‐epidote‐calcite‐gypsum alteration. The acid altered rocks were then invaded by multiple phases of pyrite, subsequently crosscut by quartz, vein alunite and barite. Then sequential deposition of bladed covellite, enargite, luzonite and stibioluzonite occurred from the NW to the SE portions of the deposit, forming a zonation suggestive of progressive decrease in temperature, sulfur fugacity and sulfidation stage. Most ore mineralization occurs in the vuggy silica core. Gold mineralization commenced from the transition of enargite to luzonite and continued throughout the stibioluzonite stage. Associated with gold deposition are Au‐rich pyrite, tennantite‐tetrahedrite, chalcopyrite‐bornite, native tellurium, electrum, calaverite, bismuthinite and galena. Native sulfur occupied the remaining cavities and represents the waning stage of the hydrothermal system. Fluid inclusions studies distinguished magmatic (>300–350d?C, 9–15 wt% NaCl equiv.) and meteoric (<150–200d?C, 1–2 wt% NaCl equiv.) fluids (Holzberger et al., 1996). Temperatures and salinities of fluid inclusions from barite associated with Cu sulfides show a general decrease from NW (330d?C, 9–15 wt% NaCl equiv.) to SE (172d?C, 10 wt% NaCl equiv.) parts of the deposit, indicating gradual entrainment of ground water (Hitchman and Espi, 1997). Interaction of magmatic fluids with meteoric water accompanied by changes in temperature, salinity, acidity and oxidation state of the resultant fluids is interpreted to have been the main cause of metal precipitation. Finally, supergene processes generated Au zone with an underlying chalcocite‐covellite‐digenite blanket over the primary sulfides at depth. Gold occurs as lattice constituent in scorodite, limonite‐goethite and jarosite. Chalcocite is more abundant and widespread than other Cu sulfides. Acidic fluids deposited powdery alunite and kaolinite, vein alunite and amorphous silica. Weakly secondary biotite‐quartz altered porphyry located below the known HS Cu‐Au deposit contains chalcopyrite‐bornite and is overprinted by quartz‐alunite‐pyro‐phyllite‐pyrite assemblage. This feature indicates close temporal, spatial and genetic relation between the two deposit types.     

Organohalogen and organotin compounds in killer whales mass-stranded in the Shiretoko Peninsula, Hokkaido, Japan

Blubber and liver samples were obtained for analysis of wide ranges of contaminants from killer whales (Orcinus orca) which were locked away in drifting sea ice on the coast of Rausu, the Shiretoko Peninsula in Eastern Hokkaido, Japan in February 2005. Among the organohalogen compounds analyzed, DDTs were the predominant contaminants with concentrations ranging from 28 to 220 microg/g on a lipid-weight basis followed by PCBs and other organochlorine pesticides. PBDEs levels were two or three orders of magnitude lower than those of PCBs and DDTs. 2,3,7,8-Tetrachlorodibenzo-p-dioxin toxic equivalents (TEQs) derived by WHO mammal-TEF in killer whales were in the range of 110-440 pgTEQ/g. Mono-ortho coplanar PCBs contributed to 75-98% of total TEQs, indicating coplanar PCBs are significant contaminants for risk assessment in this species. The fact that hepatic residue levels of butyltins (from 13 to 770 ng/g wet weight) were much higher than those of phenyltins may be reflecting extensive use of tributyltin as antifouling paint.     

Interpretation of landslide distribution triggered by the 2005 Northern Pakistan earthquake using SPOT 5 imagery

The 2005 northern Pakistan earthquake (magnitude 7.6) of 8 October 2005 occurred in the northwestern part of the Himalayas. We interpreted landslides triggered by the earthquake using black-and-white 2.5-m-resolution System Pour l’Observation de la Terre 5 (SPOT 5) stereo images. As a result, the counts of 2,424 landslides were identified in the study area of 55 by 51 km. About 79% or 1,925 of the landslides were small (less than 0.5 ha in area), whereas 207 of the landslides (about 9%) were large (1 ha and more in area). Judging from our field survey, most of the small landslides are shallow rock falls and slides. However, the resolution and whitish image in the photos prevented interpreting the movement type and geomorphologic features of the landslide sites in detail. It is known that this earthquake took place along preexisting active reverse faults. The landslide distribution was mapped and superimposed on the crustal deformation detected by the environmental satellite/synthetic aperture radar (SAR) data, active faults map, geological map, and shuttle radar topography mission data. The landslide distribution showed the following characteristics: (1) Most of the landslides occurred on the hanging-wall side of the Balakot–Garhi fault; (2) greater than one third of the landslides occurred within 1 km from the active fault; (3) the greatest number of landslides (1,147 counts), landslide density (3.2 counts/km²), and landslide area ratio (2.3 ha/km²) was found within Miocene sandstone and siltstone, Precambrian schist and quartzite, and Eocene and Paleocene limestone and shale, respectively; (4) there was a slight trend that large landslides occurred on vertically convex slopes rather than on concave slopes; furthermore, large landslides occurred on steeper (30° and more) slopes than on gentler slopes; (5) many large landslides occurred on slopes facing S and SW directions, which is consistent with SAR-detected horizontal dominant direction of crustal deformation on the hanging wall.     

Comparison between the two triggered landslides in Mid-Niigata, Japan by July 13 heavy rainfall and October 23 intensive earthquakes in 2004

On July 13, 2004, heavy rainfalls because of the intensive activities of the rain front occurred in the Mid-Niigata Region, Japan. They were as much as 400 mm in 24 h, bringing about serious flooding by breaking the river banks. The heavy rainfalls also triggered more than 3,500 landslides. Three months later, the southern region of Mid-Niigata was attacked by an earthquake of magnitude 6.8 on the Richter scale on October 23, 2004. The main earthquakes were followed by intensive aftershocks, which continued until December 2004. By these earthquakes, variable landslides of more than 4,400 also occurred in the hilly and mountainous areas. Namely, different triggers brought about the variable landslides in the hilly mountains whose features are very similar in geological and geomorphological points of view. Therefore, these two events are very useful for clearing the difference in features of the landslides between the two. We have been researching on both landslides in the field just after both occurred and later analyzing air photographs using the geographic information system (GIS). In this paper, we describe the comparison in the distribution features using GIS analytical data between the heavy rainfall-induced and the intensive earthquake-induced landslides.