U–Pb and fission‐track dating of a submarine pyroclastic rock from southwest Japan

The Okinoshima Formation crops out on Okinoshima Island and comprises a thick sequence (> 200 m) of pyroclastic rocks and alternating beds of sandstone and mudstone. Because Okinoshima Island is located between Honshu and Tsushima Island, the Okinoshima Formation potentially provides an important record of volcanism during the opening of the Japan Sea in northwest Kyushu, as well as a record of the formation of the present Genkai Sea region. In consideration of the lack of previous geochronological work, dating (fission‐track and U–Pb) of igneous zircons extracted from the Okinoshima Formation were undertaken and studied the clay mineral alteration in the pyroclastic material in order to reveal its thermal history. These data are used to constrain the age of the Okinoshima Formation and the present Genkai Sea region. Our results show that no thermal event has reset the fission‐track age after deposition of the pyroclastic rocks, and that the Okinoshima Formation was deposited at 16.2 Ma. The present Genkai Sea region is a deep‐sea basin, and its formation at 16.2 Ma was accompanied by submarine volcanism and rapid subsidence that marked the climactic stage of Japan Sea formation. After 16 Ma, the tectonic setting of the present Genkai Sea region changed from one of extension (related to the formation of the Japan Sea) to one of compression, with uplift occurring under the influence of the clockwise rotation of southwest Japan. Consequently, after 16 Ma the present Genkai Sea region became isolated from the forming processes of the Japan Sea.     

Grazing impact of the copepod community in the Oyashio region of the western subarctic Pacific Ocean

The role of copepod grazing on the ecosystem dynamics in the Oyashio region, western subarctic Pacific was investigated during six cruises from June 2001 to June 2002. In situ grazing rates of the copepod community (CGR) were measured by the gut fluorescence method in respect to developmental stages of dominant species. In terms of biomass, more than 80% of the copepod community was dominated by six large calanoid species (Neocalanus cristatus, Neocalanus flemingeri, Neocalanus plumchrus, Eucalanus bungii, Metridia pacifica and Metridia okhotensis) throughout the year. Resulting from the observed pattern of the interzonal migrating copepods, the CGR in the Oyashio region was divided into three phases, i.e. spring (bloom), summer (post-bloom) and autumn-winter phase. During the spring bloom, late copepodites of the interzonal migrating species, N. cristatus, N. flemingeri and E. bungii appeared in the surface layer (0-50 m) to consume the production of the bloom, resulting in a high grazing rate of the copepod community (7.9 mg Chl m⁻² d⁻¹), though its impact on phytoplankton community was low due to the high primary productivity. During the post-bloom period, although the copepod community which was dominated by N. cristatus, N. plumchrus, M. pacifica and newly recruited E. bungii still maintained a high biomass, the CGR was generally lower (1.8-2.6 mg Chl m⁻² d⁻¹ for June and August 2001), probably due to the lower availability of phytoplankton. Nevertheless, the highest CGR was also observed during this period (10.5 mg Chl m⁻² d⁻¹ in June 2002). The high CGR on autotrophic carbon accounted for 69% of the primary production, suggesting that the copepod community in the Oyashio region potentially terminates the phytoplankton bloom. Abundant occurrence of young E. bungii, which is a characteristic phenomenon in the Oyashio region, was largely responsible for the high grazing pressure in June 2002 suggesting that success of reproduction, growth, and survival in E. bungii during the spring bloom is an important factor in controlling phytoplankton abundance during the post-bloom season. During autumn and winter, CGR was the lowest in the year (0.29-0.38 mg Chl. m⁻² d⁻¹) due to the disappearance of the interzonal migrating copepods from the surface layer. Diel migrant M. pacifica was the most important grazer during this period. The annual ingestion of the copepod community is estimated as 37.7 gC m⁻² on autotrophic carbon (converted using C:Chl ratio of 30) or 137.9 gC m⁻² on suspended particles (using C:Chl ratio of in situ value, 58-191), accounting for 13% and 46% of annual primary production, respectively. This study confirms that copepod grazing is an important pathway in carbon flow in the Oyashio region and in particular their role in the phytoplankton dynamics is significant for the termination of the spring bloom.     

Fractional Determination of Gold in Twenty Six Geological Reference Materials by Sequential Extraction with Graphite Furnace Atomic Absorption Spectrometry

A method is described to estimate the chemical form of gold (Au) in a variety of geological reference samples, combining a sequential extraction scheme with graphite furnace atomic absorption spectrometry, after extraction of Au as iodide or chloride with methyl isobutyl ketone. The fractions dissolved by sequential extraction are empirically defined as the exchangeable, amorphous, metallic, aqua regia-soluble and residual fractions. The amounts of Au in the amorphous fraction have been derived mainly from oxide or amorphous phases, and the chemical forms of Au are considered to be mostly amorphous and partly metallic. The metallic fraction of Au is likely to exist as submicroscopic grains of native metal which are relatively free from the rock-forming minerals, whereas the aqua regia-soluble or residual fraction of Au may be bound more intimately perhaps as inclusions or solid solutions of either native metal or electrum in most cases. Satisfactory agreement was observed between the sum of the Au values from exchangeable to residual fractions and the reported total Au values, except for a few samples which contained a large amount of reducing materials. Analytical results of Au for twenty six geological reference materials are tabulated, and geochemical and mineralogical features are discussed.     

Efficacy of ultraviolet radiation and hydrogen peroxide oxidation to eliminate large number of pharmaceutical compounds in mixed solution

Ultraviolet photolysis and ultraviolet and hydrogen peroxide oxidation of fourteen commonly used pharmaceutical compounds and two personal care products in mixed solution using low pressure ultraviolet lamp was investigated in laboratory batch experiments. Removal of the compounds followed the first-order reaction kinetic. Three distinct impacts of hydrogen peroxide on ultraviolet and hydrogen peroxide oxidation of the compounds (positive, negative and no significant effect) were observed. Removal behavior of the several tested compounds in mixed solution varied significantly than their respective behavior in absence of coexisting compounds. Clofibric acid, diclofenac, fenoprofen, isopropylantipyrine, ketoprofen, phenytoin and triclosan were removed very efficiently (> 96 %) by ultraviolet photolysis alone. Residual hydrogen peroxide during ultraviolet and hydrogen peroxide oxidation was quantitated for the first time. Hydrogen peroxide addition to ultraviolet photolysis was not worthy for majority of the tested compounds as their removal did not increase significantly and very big fractions (> 85 %) of the added hydrogen peroxide (0.29 ～ 1.47 mM) remained unused presumably due to small fluence of the lamp, very small molar absorption for hydrogen peroxide at 254 nm (27.06 /M.cm) and acidic pH of reaction solution (< 5.7). Further exploration on ultraviolet and hydrogen peroxide oxidation with higher fluence lamp and alkaline solution pH will clarify usefulness of the method to treat pharmaceutical contaminated waters.     

Mineralogical Associations of Arsenic and Antimony in Thirty Five Geochemical Reference Materials by Sequential Extraction with Hydride Generation and Atomic Absorption Spectrometry

A method is described to estimate the chemical forms of arsenic (As) and antimony (Sb) in a variety of geochemical reference materials, combining a sequential extraction scheme with hydride generation and atomic absorption spectrometry (HG-AAS). The fractions dissolved by sequential extraction are empirically defined as the exchangeable, EDTA soluble, oxide, sulfide and residual fractions. The amount of As and Sb in the EDTA soluble fraction have been derived mainly from oxide phases, and partly from carbonate minerals. Most sulfide minerals in common geological samples were considered to be dissolved with the digestion of 0.7 mol l⁻¹ NaOCl, but only small fraction of arsenopyrite and loellingite in ores could be dissolved in this way. Satisfactory agreement was observed between the sum of the As or Sb values from exchangeable to residual fractions and the reported total As or Sb values, with a few exceptions. Analytical results of As and Sb for thirty five geochemical reference materials are tabulated, and geochemical and mineralogical features are discussed.     

Nitrate pollution of groundwater in the Yellow River delta,China

Nitrate pollution of groundwater in the Yellow River delta, China is an important issue related not only to nitrate dispersion and health concerns but also to mass transport and interactions of groundwater, sea, and river waters in the coastal area. The spatial distribution of nitrate, nitrate sources, and nitrogen transformation processes were investigated by field surveys and geochemical methods. Nitrate occurred mainly in shallow layers and had a spatial distribution coinciding with geomorphology and land/water use. Irrigation water from the Yellow River and anthropogenic waste are two main nitrogen sources of nitrate in the delta, and both denitrification and mixing processes could take place according to characteristics identified by ionic and isotopic data.     

Degradation of common pharmaceuticals and personal care products in mixed solutions by advanced oxidation techniques

Widespread detection of pharmaceutical compounds in water environment has been a serious concern recently, while conventional sewage treatments are ineffective for their elimination. But, advanced oxidation techniques are very promising to remove varieties of organic contaminants in water. This research aims to elucidate oxidation potentials of sixteen commonly used pharmaceutical compounds in mixed solutions by seven advanced oxidation techniques in laboratory batch experiments. The removal profiles exhibited four distinct patterns: a) easily degradable by all seven techniques, b) not easily degradable by all seven techniques, c) easily degradable by ozone-based techniques, but not by ultraviolet radiation-based techniques and d) easily degradable by ultraviolet radiation-based techniques, but not by ozone-based techniques. Ozone-based techniques rather than ultraviolet radiation-based techniques were very powerful for simultaneous removal of the compounds efficiently. Moreover, ozonation combined with ultraviolet radiation was the most appropriate technique for simultaneous removal of the tested compounds efficiently. Increased ozone dissolution and decomposition with ozone-based techniques did not always enhance the compounds’ removal. Physicochemical properties of the compounds and solution pH also presumably played an important role on the removal which merits further attention.     

Effect of the variation in the lower tropospheric temperature on the wind onset of the Indian summer monsoon

There is a large thermal contrast between the Arabian Peninsula and India (Δθ _AI) at the mature stage of the Indian summer monsoon (ISM). The forming process of Δθ _AI is investigated analyzing various datasets. It forms earlier in the lower troposphere than in the middle and upper layers. The potential temperature in the lower troposphere over the west coast of India (θ _IW) abruptly decreases in advance of the rapid enhancement of the westerly wind over the Arabian Sea corresponding to the ISM onset. Such a process was observed for all the target years and the rapid decrease in θ _IW could trigger the ISM onset. The decrease in θ _IW had two patterns. In one case, cooler air is brought by the strong winds around a cyclone over the Arabian Sea. In another case, θ _IW decreases gradually by a synergy of a southwesterly wind over the Arabian Sea and the enlargement of Δθ _AI.