Spatial distribution of organic matter in the Bells CM2 chondrite using near‐field infrared microspectroscopy

Abstract– Distributions of organic functional groups as well as inorganic features were analyzed in the Bells (CM2) carbonaceous chondrite using near‐field infrared (NFIR) spectroscopy. NFIR spectroscopy has recently been developed to enable infrared spectral mapping beyond the optical diffraction limit of conventional Fourier transform infrared microspectroscopy. NFIR spectral mapping of the Bells 300 nm thick sections on Al plates for 7.5 × 7.5 μm² areas showed some C‐H‐rich areas which were considered to represent the organic‐rich areas. Heterogeneous distributions of organic matter as well as those of inorganic phases such as silicates (Si‐O) were observed with 1 μm spatial resolution. The NFIR mappings of aliphatic C‐H (2960 and 2930 cm^?1) and structural OH (3650 cm^?1) confirm that organic matter is associated with phyllosilicates as previously suggested. The NFIR mapping method can provide 1 μm spatial distribution of organic functional groups and their association with minerals. High local sensitivity of NFIR enables us to find organic‐rich areas and to characterize them by their aliphatic CH₂/CH₃ ratios. The aliphatic CH₂/CH₃ ratio of Bells is slightly higher than Murchison, similar to Orgueil, and lower than literature values of IDPs and cometary dust particles.     

Does heavy oil pollution induce bacterial diseases in Japanese flounder Paralichthys olivaceus?

As basic research for the effect of heavy oil on the fish immune system, in this study, the number of leukocyte was counted in Japanese flounder Paralichthys olivaceus, after exposure to heavy oil at a concentration of 30 g/8 L for 3 days. To compare the numbers of bacteria in the skin mucus between oil-exposed and control fish, viable bacteria were enumerated by counting colony forming unit (CFU). Compared with 5.79 ± 1.88 × 10⁷ leukocytes/mL in the controls, the exposed fish demonstrated higher counts, averaging 1.45 ± 0.45 × 10⁸ cells/mL. The bacterial numbers of control fish were 4.27 ± 3.68 × 10⁴ CFU/g, whereas they were 4.58 ± 1.63 × 10⁵ CFU/g in the exposed fish. The results suggest that immune suppression of the fish occurred due to heavy oil stressor, and bacteria could invade in the mucus, resulting in the increasing leukocyte number to prevent infectious disease.     

Mobility of metamorphic fluids inferred from infrared microspectroscopy on natural fluid inclusions: the example of Tinos Island,Greece

OH structure of metamorphic fluids has been studied by high temperature infrared (IR) microspectroscopy on natural fluid inclusions contained in quartz veins, over the temperature range 25–370 °C. Blueschist-facies veins from Tinos island core complex (Cyclades, Greece) display H₂O–NaCl–CaCl₂–CO₂ inclusions whereas greenschist-facies veins contain H₂O–NaCl ± CO₂ inclusions. From 25 to 370 °C, peak positions of OH stretching IR absorption bands increase quasi-linearly with slopes of 0.25 and 0.50 cm^–1 °C^–1 for inclusions trapped under blueschist and greenschist conditions, respectively. Extrapolation to 400 °C yield peak positions of 3,475 cm^–1 for blueschist inclusions and 3,585 cm^–1 for greenschist inclusions. Because the smaller wave number indicates the shorter hydrogen-bond distance between water molecules, fluids involved in the greenschist event have a loose structure compared with blueschist fluids. We suggest that these properties might correspond to a low wetting angle of fluids. This would explain the high mobility of aqueous fluids suggested by structural observation and stable isotope analysis.Editorial responsibility: J. Hoefs     

Calcium-alkalinity-nitrate relationship in the north pacific and the Japan Sea

When biogenic particles of calcium carbonate and organic matter are formed or decomposed in sea water, calcium concentration, alkalinity and nitrate concentration are changed according to the following equation: ΔCa=0.5 ΔTA+0.63 ΔNO ₃, where ΔCa, ΔTA and ΔNO ₃ are the differences in calcium, alkalinity and nitrate concentration, respectively, between two waters. This relationship was pointed out in a previous paper of ours, and it holds well for data obtained from the North Pacific and the Japan Sea. Furthermore, in sea water containing little or no nutrients, the variations in calcium concentration and alkalinity are consistent with the variations expected from the formation and dissolution of calcium carbonate alone.     

Water content in natural eclogite and implication for water transport into the deep upper mantle

Infrared spectroscopy and ion micro-probe measurements showed that the major constituent minerals of eclogites from the Kokchetav massif, which have been subducted to 180 km depths, contain significant amounts of water up to 870 ppm H₂O (by weight) in omphacite, 130 ppm H₂O in garnet and 740 ppm H₂O in rutile. Omphacite shows three hydroxyl absorption bands at 3440–3460, 3500–3530 and 3600–3625 cm^− 1, garnet has a single band at 3580–3630 cm^− 1 and rutile has a single sharp band at 3280 cm^− 1. The hydroxyl absorbance at these wavenumbers changes with the crystal orientation in polarized infrared radiation, indicating that the water is structurally incorporated in these minerals. The water contents in omphacite and garnet increase systematically with the metamorphic pressure of the host eclogites. The partitioning coefficient of the water content between coexisting garnet and omphacite is similar in different eclogites, D^Grt/Omp0.1–0.2, but decreases slightly at high pressure. Based on the mineral proportions of the eclogites, we estimate bulk-rock water content in the eclogites ranging from 3070 to 300 ppm H₂O (by weight). Although hydrous minerals are absent in the diamond-grade eclogite (60 kbar and 1000 °C), trace amounts of water are incorporated in the nominally anhydrous minerals such as omphacite and garnet. The presence of significant water in these minerals implies that the subducting oceanic crust can transport considerable amounts of water into the deep upper mantle beyond the stability of hydrous minerals. Such water may be stored in the deep upper mantle and have an important influence on dynamics in the Earth's interior.     

Micro-FTIR spectroscopic signatures of Bacterial lipids in Proterozoic microfossils

Precambrian microbial fossils show carbonaceous cellular structure, which often resemble in shape and size cyanobacteria and other prokaryotes. Morphological taxonomy of these minute, simple, and more or less degraded fossils is, however, often not enough to determine their precise phylogenetic positions. Here we report the results of micro-FTIR spectroscopic analyses of well-preserved microfossils in 850 Ma and 1900 Ma stromatolites, together with those of 8 species of extant prokaryotes and 5 of eukaryotes for comparison. These Proterozoic fossils have low CH₃/CH₂ absorbance ratios (R_3/2 < 0.5) of aliphatic CH moieties, suggesting selective preservation of long, straight, aliphatic carbon chains probably derived from bacterial membrane lipids. All the observed R_3/2 values of coccoids, filaments and amorphous organic matter resemble lipid fractions of extant Bacteria including cyanobacteria, but not Archaea. The results indicate that Proterozoic microfossils belong to Bacteria, which is consistent with the cyanobacterial origin inferred from morphology. Moreover, the R_3/2 value of fossilized cell would reflect chemical composition of its precursor membrane lipid, thus could be a useful new tracer for distinguishing Archaea, Bacteria and possibly Eucarya for fossilized and extant microorganisms.     

Analysis of summertime atmospheric transport of fine particulate matter in Northeast Asia

In Northeast Asia, the effect of long-range transport of air pollutants is generally pronounced in spring and winter, but can be important even in summer. This study analyzed summer-time atmospheric transport of elemental carbon (EC) and sulfate (SO₄ ^2?) with the Community Multiscale Air Quality (CMAQ) model driven by the Weather Research and Forecasting (WRF) model. The WRF/CMAQ modeling system was applied to regions ranging from Northeast Asia to the Greater Tokyo Area in Japan in summer 2007. In terms of EC, while the model simulated well the effect of long-range transport, the simulation results indicated that domestic emissions in Japan dominantly contributed (85%) to EC concentrations in the Greater Tokyo. In terms of SO₄ ^2?, the simulation results indicated that both domestic emissions (62%) and long-range transport from the other countries (38%) substantially contributed to SO₄ ^2? concentrations in the Greater Tokyo. Distinctive transport processes of SO₄ ^2? were associated with typical summer-time meteorological conditions in the study region. When a Pacific high-pressure system covered the main island of Japan, domestic emissions, including volcanic emission, dominantly contributed to SO₄ ^2? concentrations in the Greater Tokyo. When a high-pressure system prevailed over the East China Sea and low-pressure systems passed north of Japan, synoptic westerly winds associated with this pressure pattern transported a large amount of SO₄ ^2? from the continent to Japan. In addition, although heavy precipitation and strong wind decreased SO₄ ^2? concentrations near the center of a typhoon, peripheral typhoon winds occasionally played an important role in long-range transport of SO₄ ^2?.     

The determination of Mn,Fe, Ni,Cu and Zn in seawater by atomic absorption spectrometry after coprecipitation with lanthanum hydroxide

A simple and rapid coprecipitation method for the determination of several trace metals in seawater is presented. These metals are coprecipitated with lanthanum hydroxide, the precipitate is dissolved, and then the metals are determined by atomic absorption spectrometry. Lanthanum hydroxide was chosen as a coprecipitant for the following reasons, (a) lanthanum hydroxide has a sufficiently low solubility and forms an easily filterable flocculate at about 80C, and (b) lanthanum has an absorption wavelength that is sufficiently separated from those of the other elements to be analysed, i.e., Mn, Fe, Ni, Cu and Zn. Experimental results show that these metals are coprecipitated by the present method with excellent recoveries.     

Carbonate Minerals in the Warrawoona Group, Pilbara Craton: Implications for Continental Crust, Life, and Global Carbon Cycle in the Early Archean

Abstract: The occurrences of the Early Archean carbonate minerals are compiled and their precipitation processes are investigated for the Warrawoona Group, Pilbara Craton. Sedimentary carbonate rocks such as limestone and dolostone are very rare, and only a small amount of sedimentary carbonate minerals are sometimes contained in the hydrothermal bedded chert, implying that a sink of CO₂ was minor in the Early Archean sediments. Moreover, it is very likely that the activity of cyanobacteria forming stromatolites was considerably low in the Early Archean. Microfossils and carbonaceous matter in the hydrothermal cherts are probably derived from a non-photosynthetic microorganisms related to the seafloor hydrothermal activity. Their preservation in sediments may play a very minor role in carbon sink of the Earth's surface.
On the other hand, carbonatized volcanic rocks subjected to seafloor hydrothermal alteration occur ubiquitously in the Early Archean greenstone belts such as the Warrawoona Group, suggesting that the hydrothermally altered oceanic crust had large amounts of CO₂ as carbonate minerals. Global carbon cycle in the Early Archean is considered to have been controlled by the intense seafloor hydrothermal alteration. Large amounts of CO₂ were sunk into the oceanic crust by the alteration. The carbonatized oceanic crust was partly accreted to the continents and/or island–arcs, and partly subducted into the mantle without decomposition. Significant amounts of carbonate minerals in the carbonatized oceanic crust were very likely to store in the accretionary prisms and mantle, consequently giving rise to a decrease of atmospheric and oceanic CO₂.