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.     

Contamination by organochlorine compounds in sturgeons from Caspian Sea during 2001 and 2002

Organochlorine compounds (OCs) were determined in the five species of sturgeons collected from coastal waters of Caspian Sea in Kazakhstan, Azerbaijan, Turkmenistan and Iran during 2001 and 2002 to understand their status of contamination and accumulation features. Among OCs examined, concentrations of DDTs (DDT and its metabolites) were predominant in all the sturgeon samples with concentrations ranging from 73 to 31,000 ng/g on lipid weight basis, followed by PCBs, CHLs, HCHs, HCB, dieldrin, TCPMOH, and heptachlor epoxide in order. The concentrations of OCs in beluga (Huso huso) were the highest among all the five species. When comparing residue levels among same species, OC residues were highest in sturgeons from Azerbaijan and Kazakhstan and lowest in Turkmenistan. However, the concentrations of HCHs, dieldrin, and heptachlor epoxide in sturgeons showed less geographical variability.     

Germanium-bearing Colusite in Siliceous Black Ore from the Ezuri Kuroko Deposit, Hokuroku District, Japan

Abstract. Germanium‐bearing colusite occurs with sphalerite, galena, tetrahedrite‐tennantite, chalcopyrite and pyrite in microdruses and veinlets in the siliceous black ore from the Ezuri Kuroko deposit in the Hokuroku district of Japan. X‐ray microdiffractometry of this mineral gives strongest lines at 1.60, 1.32 and 1.09 Å, which are consistent with the known powder diffraction data of colusite. On the basis of 32 S atoms per formula unit, electron microprobe analyses yield empirical chemical formulae of (Cu_{24 0}Fe_0.3Zn_1.0)_σ25.3V_1.9(A_s4.8Sb_0.2)_σ5.0Ge _1.3S₃₂ for Ge‐bearing colusite in close association with sphalerite, and (Cu_24.6Fe_0.9)_σ25.4V_1.8(A_s4.1 Sb_0.2)_σ4.3Ge_1.7S₃₂ for that coexisting with chalcopyrite, consistent with the ideal formula of Cu_24+xV₂(As, Sb)_6‐x(Sn, Ge)_xS₃₂ (x = 0 to 2) proposed by Spry et al. (1994) for this mineral species. The Ge‐bearing colusite mineralization is suggested to have occurred concurrently with consolidation of the siliceous black ore, possibly during hydrothermal modification in association with the igneous activity of the Ohtaki quartz diorite of the later Onnagawa stage. It is likely that biogenic siliceous ooze, a possible precursor of the siliceous black ore, may have served as an in situ source of Ge as well as other essential rare elements, leading to the formation of Ge‐bearing colusite during transformation or recrystallization of biogenic opal into a‐quartz.     

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.     

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.     

Benthic Foraminifera in Siliceous Black Ore from the Ezuri Kuroko Deposit, Hokuroku District, Japan

Abstract: Abundant benthic foraminifera have been identified in thin sections of the siliceous black ore in the Ezuri Kuroko deposit, Hokuroku, Japan. By treating samples with conventional hydrofluoric acid digestion techniques, sponge spicules and radiolaria have also been recognized in the residue. Under microscopic observations, 94 individual foraminiferal specimens have been detected. However, as it is difficult to identify species or genera by means of microscope observations alone, only a small number of genera have been identified based on morphology. The foraminiferal assemblage is composed predominantly of agglutinated species (83%) with subordinate calcareous species (17%), and is assigned to the Cyclammina Assemblage based on the preponderance of Cyclammina (57%). The foraminifera are generally well preserved within micro‐crystalline to cryptocrystalline quartz, and exhibit no obvious features related to compaction or secondary deformation. Textural observations suggest that the siliceous component of this rock was not derived from an allochthonous block but instead constitutes autochthonous proto‐Kuroko sediment. The Cyclammina Assemblage in the ore is different from recently described foraminiferal assemblages in the vicinity of present deep‐sea hydrothermal vents, but is identical to those found in black shales of the Onnagawa to Funakawa stages in the Green Tuff region. The proto‐Kuroko sediment is assumed to have been deposited in an oxygen‐deficient environment within a closed, deep‐seated basin. The existence of siliceous microfossils suggests that the silica in the siliceous ore did not originate from silica sinter deposits produced by submarine hydrothermal activities, but from a biogenic siliceous ooze, probably composed of diatoms. Sulfide mineralization in the interstices of some of the microfossils is inferred to relate primarily to bacterial sulfate reduction associated with the decomposition of organic matter. The later sulfide mineralization associated with larger crystals (which contain fluid inclusions with homogenization temperatures of approximately 250C) cuts across the siliceous masses and foraminiferal septa, and may have been formed after consolidation of the siliceous ooze, accompanying the formation of acidic intrusive rocks during the late Onnagawa stage.