Production and degradation of fluorescent dissolved organic matter derived from bacteria

Dynamics of fluorescent dissolved organic matter (FDOM) in ocean environments has received attention over the past few decades. Although it has appeared that in situ production of oceanic FDOM is mainly due to bacteria, the production and bio- and photodegradation processes of bacterial FDOM have not been elucidated. In this study, a culture experiment with bacteria was carried out to assess the production and biodegradation processes of bacterial FDOM. Photodegradation of bacterial FDOM and dissolved organic carbon (DOC) was also examined by exposure to a solar simulator. Bacterial FDOM consists of six components which were determined by parallel factor analysis (PARAFAC). Fluorescence intensities of protein-like FDOM increased with the bacterial biomass, but the increases of humic-like FDOM lagged behind the protein-like FDOM by 5–10 days. Exposure to simulated sunlight caused significant decreases in fluorescence intensities of all components; 52–94% of the initial intensities were lost during 24 h. While, the DOC concentration exhibited a small decrease through the experiment (1.9–11.1%). These results showed that photodegradability of bacteria derived DOC was much less than the fluorescence, indicating that the lifetime of bacteria-derived DOC is much longer than the length estimated by the fluorescence. The role of photobleached FDOM derived from bacteria may be significant in the biogeochemical cycle at the surface layer.     

Mantle hornblendites of Naein ophiolite (Central Iran): Evidence of deep high temperature hydrothermal metasomatism in an upper mantle section

The Naein ophiolite is the most complete ophiolitic exposure in Cental Iran and considered as a remnant of the Mesozoic Central East Iranian microcontinent (CEIM) confining oceanic crust. In the northeastern part of this ophiolite (Darreh Deh area) within the mantle peridotites, a few hundred meters below the top of the Moho transition zone (MTZ), the hornblendites are present as dykes (former cracks and joints) from a few millimeters to nearly 50 cm wide. They have sharp boundaries with the surrounding mantle harzburgites and dunites. These hornblendites are pale green and coarse-grained in hand specimen and composed of magnesio-hornblende (Mg# = 0.93), chlorite (penninite and clinochlore, Mg# = 0.95), Cr-spinel (chromite, Cr# = 0.67 and Mg# = 0.55), tremolite, calcite and dolomite. Tremolites were formed by retrograde metamorphism of hornblendes. Calcite and dolomite occur as late-stage veins. Very high amount of primary hydrous phases (~94 vol % hornblende and chlorite), as well as peculiar mineralogical and chemical characteristics of the Naein ophiolite mantle hornblendites, do not match a magmatic origin. They are possibly products of the reaction between mantle peridotites and seawater-originated supercritical fluids, rich in silicate components. The presence of primary hydrous phases (hornblende and chlorite) may reveal high activity of H₂O in the involved solution. The chemical composition of chromite in the hornblendites is near to the average chromite composition from the surrounding harzburgite and dunite. This suggests that the main source of Cr should be chromites of nearby peridotites, which were totally or partly dissolved by hydrothermal fluids. The positive anomaly of Eu in the chondrite-normalized REE patterns of hornblendes, high modal abundance of Ca-rich hornblende, as well as presence of calcite and dolomite, point to seawater ingression through the gabbros in to the uppermost mantle peridotites. The higher value of MgO than CaO, presence of high-Cr chromite and Cr-enrichment of hornblendes and chlorites indicate a higher contribution of peridotites rather than gabbros to the chemical characteristics of the involved fluids. This study shows that circulation of possibly seawater-derived high temperature hydrous fluids in the upper mantle can leach and provide necessary elements to form hornblendite in joints and cracks of the uppermost mantle.     

Occurrence and chemical composition of amphiboles and related minerals in corundum-bearing mafic rock from the Horoman Peridotite Complex, Japan

A corundum-bearing mafic rock in the Horoman Peridotite Complex, Japan, was derived from upper mantle conditions to lower crustal conditions with surrounding peridotites. The amphiboles found in the rock are classified into 3 types: (1) as interstitial and/or poikilitic grains (Green amphibole), (2) as a constituent mineral of symplectitic mineral aggregates with aluminous spinel at grain boundary between olivine and plagioclase (Symplectite amphibole) and (3) as film-shaped thin grains, usually less than 10 μm in width, at grain boundary between olivine and clinopyroxene (Film-shaped amphibole). The Film-shaped amphibole is rarely associated with orthopyroxene extremely low in Al₂O₃, Cr₂O₃ and CaO (Low-Al OPX). These minerals were formed by infiltration of SiO₂- and volatile-rich fluids along grain boundaries after the rock was recrystallized at olivine-plagioclase stability conditions, i.e. the late stage of the exhumation of the Horoman Complex.

Chondrite-normalized rare earth element patterns and primitive mantle-normalized trace-element patterns of the Green amphibole and clinopyroxene are characterized by LREE-depleted patterns with Eu positive and negative anomalies of Zr and Hf. These geochemical characteristics of the constituent minerals were inherited from original whole-rock compositions through a reaction involving both pre-existing clinopyroxene and plagioclase. We propose that the fluids were originally rich in a SiO₂ component but depleted in trace-elements. Dehydration of the surrounding metamorphic rocks in the Hidaka metamorphic belt, probably related to intrusion of hot peridotite body into the Hidaka crust, is a plausible origin for the fluids.     

Formation and compositional variation of phlogopites in the Horoman peridotite complex,Hokkaido, northern Japan: implications for origin and fractionation of metasomatic fluids in the upper mantle

Harzburgite and lherzolite tectonites from the Horoman peridotite complex, Hokkaido, northern Japan, contain variable amounts of secondary phlogopite and amphibole. Phlogopite-rich veinlets parallel to the foliation planes usually cut olivine-rich parts of the rocks; single-grained interstitial phlogopites are usually associated with orthopyroxene grains. Amphiboles are disseminated in rocks or sometimes occur in the phlogopite-rich veinlets. Within individual veinlets, phlogopites show extensive inter-grain variations in K/(K + Na) ratio (0.96–0.75), generally decreasing from the central (usually the thickest) part towards the marginal parts of veinlets. In contrast, Ti contents are nearly constant in Ti-poor veins or decrease slightly with decreasing K/(K + Na) in T-rich veins. Variation of Ti in phlogopites is very large (0.1–6.8 wt%) and is inversely correlated with Mg/(Mg + Fe^*) (Fe^*, total iron) atomic ratios, which vary from 0.96 to 0.88. Intra-vein variation of phlogopite chemistry (especially K/(K + Na) ratio) could be achieved by in situ fractional crystallization of trapped fluids; variation of Ti, however, cannot be explained by in situ fractionation of the fluids, indicating various Ti contents of the parent fluids. It is suggested that fluids responsible for the formation of the Horoman phlogopites and amphiboles were magmatic volatiles successively released from evolving alkali basaltic magmas. Individual fluids trapped within peridotites were fractionated, precipitating phlogopites successively poorer in K. When the fluids became rich enough in Na, amphiboles co-precipitated with phlogopites. Similar fractional crystallization of phlogopites and amphiboles is expected in the upper mantle on a larger scale if fluids move upwards. This process may control, at least partly, a lateral K/Na distribution in the upper mantle; K and Na may be concentrated in deeper and shallower parts, respectively.     

Size distribution of condensed aromatic rings in various soil humic acids

Condensed aromatic rings are important skeletal components with regard to the recalcitrant nature of humic acids (HAs) in the environment. However, they have not been extensively studied. The relative content and composition (size distribution) of condensed aromatic rings in HAs were obtained from various soils subjected to transmission electron microscopy (TEM) and X-ray diffraction (XRD) profile analysis. In the XRD profiles of all the HAs, the 11 band that was derived from the carbon layer planes was clearly observed. Analysis of the 11 band indicated that the size of the carbon layer planes in HAs ranged from 0.48-1.68 nm, corresponding to 4- to 37-ring condensed aromatic structures. The contents of the total and larger carbon layer planes were larger in HAs with darker color and larger aromatic carbon content. At the same time, the carbon layer planes in HAs were smaller than those in a carbon black reference (from 0.24 to >3.66 nm). In the TEM analysis, fringes observed in HAs were less distinct and less ordered than those in carbon black, which was in agreement with the XRD result.     

Did boninite originate from the heterogeneous mantle with recycled ancient slab?

Boninites are widely distributed along the western margin of the Pacific Plate extruded during the incipient stage of the subduction zone development in the early Paleogene period. This paper discusses the genetic relationships of boninite and antecedent protoarc basalt magmas and demonstrates their recycled ancient slab origin based on the T–P conditions and Pb–Hf–Nd–Os isotopic modeling. Primitive melt inclusions in chrome spinel from Ogasawara and Guam islands show severely depleted high‐SiO₂, MgO (high‐silica) and less depleted low‐SiO₂, MgO (low‐silica and ultralow‐silica) boninitic compositions. The genetic conditions of 1 346 °C at 0.58 GPa and 1 292 °C at 0.69 GPa for the low‐ and ultralow‐silica boninite magmas lie on adiabatic melting paths of depleted mid‐ocean ridge basalt mantle with a potential temperature of 1 430 °C in Ogasawara and of 1 370 °C in Guam, respectively. This is consistent with the model that the low‐ and ultralow‐silica boninites were produced by remelting of the residue of the protoarc basalt during the forearc spreading immediately following the subduction initiation. In contrast, the genetic conditions of 1 428 °C and 0.96 GPa for the high‐silica boninite magma is reconciled with the ascent of more depleted harzburgitic source which pre‐existed below the Izu–Ogasawara–Mariana forearc region before the subduction started. Mixing calculations based on the Pb–Nd–Hf isotopic data for the Mariana protoarc basalt and boninites support the above remelting model for the (ultra)low‐silica boninite and the discrete harzburgite source for the high‐silica boninite. Yb–Os isotopic modeling of the high‐Si boninite source indicates 18–30 wt% melting of the primitive upper mantle at 1.5–1.7 Ga, whereas the source mantle of the protoarc basalt, the residue of which became the source of the (ultra)low‐Si boninite, experienced only 3.5–4.0 wt% melt depletion at 3.6–3.1 Ga, much earlier than the average depleted mid‐ocean ridge basalt mantle with similar degrees of melt depletion at 2.6–2.2 Ga.     

Variation in organotin accumulation in relation to the life history in the Japanese eel Anguilla japonica

In order to examine the ecological risks caused by organotin compounds (OTs) in diadromous fish migrating between sea and freshwaters, tributyltin (TBT) and triphenyltin (TPT) compounds and their breakdown products were determined in the catadromous eel Anguilla japonica, which has sea, estuarine and river life histories, collected in Japanese sea, brackish and freshwaters within the same region. Ontogenic changes in otolith strontium (Sr) and calcium (Ca) concentrations were examined along the life history transect to discriminate the migration type. There were generally three different patterns, which were categorized as ‘sea eels’, ‘estuarine eels’ and ‘river eels’ according to the otolith Sr:Ca ratio. The concentrations of TBT in silver eels (mature eels) were significantly higher than that in yellow eels (immature eels), and the percentages of TBT were also higher in silver eels than in yellow eels. A positive correlation was found between TBT concentration and the gonad-somatic index (GSI). It is thus considered that silver eels have a higher risk of contamination by TBT than yellow eels. TBT and TPT concentrations in sea eels were significantly higher than those in river eels, while no significant differences were observed in TBT and TPT concentrations in estuarine eels compared to sea and river eels. These results suggest that sea eels have a higher ecological risk of OT contamination than river eels during their life history, and the risk of OTs in estuarine eels is considered to be intermediate between that of sea and river eels. Positive linear relationships were found between Sr:Ca ratios and the concentrations of TBT and TPT. Therefore, these results suggest that the ecological risk of OTs increase as the sea residence period in the eel becomes longer. TBT and TPT concentrations in sea eels were significantly higher than those in river eels even at the same growth stage. Thus, it is clear that migratory type is the most important factor for OT accumulation during the life history.     

Crustal anorthosite formation by deep-seated hydrothermal circulation beneath fast-spreading axis: Constraints from chronological approach,Sr isotope,and fluid–chromite inclusion investigation

Hydrothermal circulation beneath the spreading axis plays a significant role in the exchange of energy and mass between the solid Earth and the oceans. Deep-seated hydrothermal circulation down to the crust/mantle boundary in the fast-spreading axis has been introduced by a number of studies regarding geological investigations and numerical models. In order to assess a reaction between hydrothermal fluid and host rock around the crust/mantle boundary, we conducted bulk trace element and Sr isotope analyses with a series of in situ investigations for crustal anorthosite, a reaction product between hydrothermal fluid and gabbro in the lowermost crustal section along Wadi Fizh, northern Oman ophiolite. In addition, we conducted titanite U–Pb isotope analyses to evaluate timing of the crustal anorthosite formation in the framework of the evolutional process of the Oman ophiolite. We estimated the formation age of the crustal anorthosite at 97.5 Ma ± 5.0 Ma, overlapping with the timing of the crust formation in the paleo spreading axis. The crustal anorthosite shows high-Th/U ratio (~2.5) and high-initial ⁸⁷Sr/⁸⁶Sr ratio (0.7050) due to seawater-derived hydrothermal fluid ingress into the precursor gabbro. With using analytical technique of micro-excavation at cryo-temperature, we detected Cl from a few micrometer-sized inclusion of aqueous fluid and chromite grains. The solubility of Cr was enhanced by complexation reactions with Cl in the hydrothermal fluid. Regarding reconstructed three-dimensional mass distribution of the inclusion and chromite composition, maximum Cr content of parental fluid was estimated at ~69 000 μg/g. The exceptionally high-Cr content was achieved locally by leaking of fluid and synchronous chromite crystallization during fluid entrapment. Presence of the deep-seated hydrothermal circulation could be assigned to the segment end, where cold seawater penetrates into the lowermost crust and extract heat along widely spaced network-like fluid channel.