Comparison of reductive accumulation of Re and Os in seawater-sediment systems

In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO₂, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high ¹⁸⁷Re/¹⁸⁸Os ratio can occur only in reducing sediments, such as black shales. The high¹⁸⁷Re/¹⁸⁸Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower ¹⁸⁷Re/¹⁸⁸Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the ¹⁸⁷Os/¹⁸⁸Os ratio cannot grow significantly due to its extremely low ¹⁸⁷Re/¹⁸⁸Os ratio.     

Distribution and alteration of amino acids in bulk DOM along a transect from bay to oceanic waters

A systematic survey of the concentrations and composition of total hydrolyzable amino acids (THAA) in bulk dissolved organic matter (DOM) was conducted at 11 stations along the 137°E transect from bay to oceanic areas in the northwestern Pacific. Concentrations of THAA and their contributions to dissolved organic carbon were high in the bay and coastal areas, declined toward the oceanic area and decreased with depth in the water columns. From the distribution patterns of the relative abundances of amino acids along the transect, individual amino acids were divided into four groups. One group included tyrosine, valine, isoleucine, phenylalanine, leucine and tryptophan, and was considered to represent easily degradable THAA, while glycine and alanine belonged to a more biorefractory group of THAA. Principal components analysis (PCA) was conducted to quantitatively differentiate patterns of amino acid composition. Amino acid groups based on PCA agreed with the groups classified by distribution patterns, indicating that first principal component scores reflected the degree of degradation of THAA in DOM, and were defined as a degradation index (DI). Two amino acids, glycine and alanine, increased in relative abundance with increasing DI, while valine, isoleucine, phenylalanine and leucine decreased with decreasing DI. The agreement indicated that the degradation process was the key factor controlling the quantity and quality of THAA in bulk DOM.     

Application of excitation emission matrix fluorescence monitoring in the assessment of spatial and seasonal drivers of dissolved organic matter composition: Sources and physical disturbance controls

The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.     

Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

Stream response to subsidence from underground coal mining in central Utah

 Short-term geomorphic and hydrologic effects of subsidence induced by longwall mining under Burnout Creek, Utah were evaluated. During the year after longwall mining, 0.3–1.5 m of subsidence was measured near impacted reaches of the mountain stream channel. The major channel changes that occurred in a 700-m reach of Burnout Creek that was subsided from 1992 to 1993 were: (1) increase in lengths of cascades and to a lesser extent glides; (2) increases in pool length, numbers and volumes; (3) increase in median particle diameter of bed sediment in pools; and (4) some constriction in channel geometry. Most of the changes appeared short-lived, with channel recovery approaching pre-mining conditions by 1994. In a 300-m reach of the South Fork that was subsided from 1993 to 1994, only channel constriction was observed, although any impacts on pool morphology may have been confounded by heavy grazing in the riparian reaches during the dry summer of 1994. Similar near-channel sedimentation and loss of pool volume between 1993 and 1994 were noted throughout Burnout Creek and in adjacent, unmined James Creek. Subsidence during the 3-year period had no effect on baseflows or near-channel landslides. Received: 10 April 1998 · Accepted: 21 September 1998     

Eoarchean–Paleoproterozoic zircon inheritance in Japanese Permo-Triassic granites (Unazuki area,Hida Metamorphic Complex): Unearthing more old crust and identifying source terrranes

U–Pb zircon geochronology of two Permo-Triassic granites (samples OT-52 and OT-272 with ages of 229 ± 8 Ma and 256 ± 2 Ma, respectively) in the Unazuki area, Hida Metamorphic Belt, southwest Japan, revealed the presence of Eoarchean to Paleoproterozoic inheritance. Inheritance is consistent with both samples showing low zircon saturation temperatures for their bulk compositions. In OT-52, dark in CL, low Th/U zircon domains have a mean ²⁰⁷Pb/²⁰⁶Pb age of 1940 ± 17 Ma, which is consistent with an age of 1937 ± 6 Ma for anatexis in the Precambrian Busan gneiss complex in Korea. Eoarchaean inherited zircons with ²⁰⁷Pb/²⁰⁶Pb ages from ca. 3750 to 3550 Ma are common in OT-272 but are few in OT-52, suggesting a source from rocks with affinities to those in the Anshan area in the northeast China part of the North China Craton. On the other hand, a Hida Metamorphic Belt metasedimentary gneiss into which the granites were intruded contains ca. 1840, 1130, 580, 360, 285 and 250 Ma zircons (Sano et al., 2000). These ages suggest that the Unazuki Mesozoic granites did not originate from proximal Hida Metamorphic Complex rocks, but instead from unrelated rocks obscured at depth. The predominance of Eoarchean to Paleoproterozoic age components, and the marked lack of 900–700 Ma components suggest that the source was the (extended?) fringe of the North China Craton, rather than from Yangtze Craton crust. The Mesozoic evolution of Japan and its linkages to northeast Asia are discussed in the context of these results.     

Measurements of carbon dioxide in the Seto Inland Sea of Japan

The carbon dioxide in seawater (pCO₂) was measured in the Seto Inland Sea of Japan using newly developed equilibrator instrument designed to be free from the correction for addition or extraction of the carbon dioxide from carrier gas. The temperature dependence of pCO₂ was about 4.5%pCO₂/°C for a single seawater sample which was processed as free from biological activity and change in total carbon dioxide content during an experiment. The decrease in pCO₂ during daylight hours due to the photosynthetic fixation was about 30% of the daily mean of pCO₂ during warm months and about 15% during cold months. The effect of carbon dioxide exchange between air and seawater on pCO₂ was about 0.6 ppm in August and about 0.1 ppm in March. This is negligible small compared with the daily oscillation of carbon dioxide in seawater.     

Determination of the freshwater origin of Coastal Oyashio Water using humic-like fluorescence in dissolved organic matter

Coastal Oyashio Water (COW), defined as a water mass with a temperature lower than 2 °C and a salinity lower than 33.0, is distributed in the North Pacific Ocean off southeastern Hokkaido, Japan, from winter to spring. COW is rich in macronutrients and dissolved iron and is thus considered to affect the spring phytoplankton blooms in the Oyashio region. Although river water and sea-ice melt water have been considered freshwater end-members of COW, the contributions of these freshwater sources to COW have not been well described. In this study, the humic-like components in dissolved organic matter were first applied as a parameter to evaluate the freshwater end-members of COW in March 2015. Linear regressions with negative slopes were determined between the humic-like components and the salinity of COW. The intercepts of the regressions against the humic-like components were within the ranges of those observed for the local rivers of Hokkaido but were very different from those of sea ice. These findings suggest that river water contributed to the COW observed here as a freshwater end-member, although the contribution of sea-ice melt water to COW could not be evaluated. This novel approach also highlighted two different less-saline water masses in COW. The first was characterized by a lower temperature and relatively high levels of humic-like components, while the second was higher in temperature and had higher levels of humic-like components. It is suggested that these different characteristics are due to the contributions of water from different rivers and/or different effects of sea-ice melt water.