Nature of the Ore-Forming Fluid at the Quaternary Noya Gold Deposit in Kyushu,Japan

We discuss the nature of the ore-forming hydrothermal fluid in the Noya gold-bearing calcite-quartz-adularia veins of central Kyushu, Japan on the basis of oxygen, carbon, and strontium isotope ratios, and aqueous speciation calculations for the present-day geothermal fluid. The isotopic values of the Noya ore-forming fluid were estimated to be −6.5‰ for δ¹³C and −7.5‰ for δ¹⁸O. The oxygen isotopic equilibrium temperatures for vein calcite are more than 180°C at the bottom of the Noya mineralization zone, and decrease with increasing elevation. As the temperature decreased, the dominant carbon species in the fluid changed from H₂CO₃ to HCO₃^- at about 120°C. The equilibrium temperatures for vein quartz are consistent with the calcite calculations. The carbon and oxygen isotope trends of the Noya vein calcite and the isotope ratios of strontium suggest that the fluids that precipitated the Noya veins were controlled by an andesite-dominated geology. Chondrite-normalized REE patterns for the white-colored veins from wells 51-WT-1 and 51-WT-2 displayed a light REE-rich pattern with positive Eu anomalies, suggesting the existence of a reducing environment for the fluid. The pyrite-rich gray-colored veins and a silicified rock from well 51-WT-2 showed higher REE concentrations than did the white veins. Altered host andesitic rocks have similar REE patterns to that of the silicified rock, and have higher REE contents than the others in the drill cores. Aqueous speciation calculations showed that the fluid in the hydrothermal reservoir is currently in muscovite stability. The fluid at the ore-mineralization stage may have contained more potassium or have had a higher pH, so that adularia precipitated with calcite and quartz, as well as gold. Fluid boiling at depth in the system produced the gold-bearing calcite-quartz-adularia veins.     

Long-Term Observations of Isotope Ratio Accuracy and Reproducibility Using Quadrupole ICP-MS

High precision isotope ratio and trace element determination can be achieved with modern quadrupole ICP-MS provided that short and long-term instrument performance is accurately monitored. Here we present results for the isotope ratios ⁶Li/⁷Li, ¹⁴⁷Sm/¹⁴⁹Sm, ¹⁶⁰Dy/¹⁶¹Dy, ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb and ²³⁵U/²³⁸U with which we determined long-term isotope ratio stability of relevance to both trace element and isotope determination. With respect to trace element determination, we first present long-term observations regarding oxide formation rates of Ba and Nd on light REE and heavy REE, as well as Zr on Ag. These showed good correlations and could be used to correct effectively the interference. The efficacy of this correction was demonstrated with analyses of the rock reference material BHVO-2 at both low and high oxide formation rates. Next, we studied the long-term reproducibility of a Dy isotope ratio that was measured to correct for the isobaric interference on Gd. It was found that, regardless of tuning condition, the ratio reproduced very well (0.58% RSD, 1s) and that the estimate of the Gd concentration did not suffer from the large correction (> 10%) caused by the Dy isobar. Long-term reproducibilities of Li, Sm and U isotope ratios, required for accurate mass bias correction when isotopically enriched internal standards of these elements are employed, were measured in the rock reference materials AGV-2 and JA-3 over a time period of up to 3 years. As expected, the Li isotope ratio showed the largest variability (RSD = 7%), but the other two ratios had relative external reproducibilities of only 1.01% (1s, U) and 0.67% (Sm). The mass bias-induced scatter in measurements for Sm and U was so small that the internal standard correction was effective, even for samples with high concentrations of these elements. With regard to Pb-isotope ratio determination, we also present long-term reproducibility for NIST SRM 982, run as an unknown and two accuracy tests for Pb separated from granitoids and from meteorites. It is demonstrated that the obtained ratios, including those involving ²⁰⁴Pb, are accurate relative to MC-ICP-MS determinations and of comparable precision to conventional TIMS analysis. The excellent agreement between all data sets shows the potential of modern quadrupole ICP-MS instrumentation for Pb-isotope determination, particularly for samples with very low Pb content.     

Characteristics and origin of sediment-hosted disseminated gold deposits: a review

Sediment-hosted disseminated gold (SHDG) deposits comprise a major portion of the gold production and reserves in the US. Although presently known to be common only in western North America, SHDG deposits are a significant source of world gold production. These deposits are characterized by extremely fine-grained disseminated gold, hosted primarily by arsenian pyrite. Other metals show very little enrichment although in addition to As, anomalous concentrations of elements such as Sb, Hg, Tl and Ba are utilized as exploration tools. The host rocks are dominantly silty carbonates, but ore concentrations are also present in siliceous and silicified rocks as well as intrusive rocks. Alteration consists of decarbonatization, silicification (jasperoid formation) and argillization, which are arranged both spatially and temporally in that order. Argillic alteration is zoned from kaolinite-dominated cores to sericite-dominated margins. The deposits commonly exhibit significant structural (faults) and stratigraphic (composition/permeability) controls. Until the last few years, SHDG deposits were considered as near-surface, epithermal type deposits in origin. Because of their fine-grained nature and the lack of macroscopic features such as veins, it has proven quite difficult to extract geochemical data that are clearly related to their genesis. However, fluid inclusion data indicate pressures corresponding to depths of 2–4 km under lithostatic conditions. Temperatures are constrained by fluid inclusions and phase equilibria to near 225°C. Stable isotope data from alteration minerals and fluid inclusions indicate that the ore fluids were dominated by meteoric waters, some of which had clearly exchanged oxygen with wallrocks during their passage through the crust. Although the data vary, most ore fluids probably had δD values near −150‰ and δ¹⁸O values ranging from −10 to +5‰. Sulfur isotope values reported from SHDG deposits span a wide range, from −30 to +20‰ (sulfides) and 0 to >45‰ (sulfates). Ore-related sulfides (pyrite, realgar) fall at the upper end of the range reported for sulfides. The alteration and mineral assemblage indicate the ore fluids were probably near neutral and gold was likely carried as a bisulfide complex. The depositional mechanism(s) probably included mixing, cooling and oxidation. These mechanisms are consistent with the observed alteration features, i.e. quartz precipitation, calcite dissolution and sericite-kaolinite coexistence. It also explains the presence of both siliceous ores containing native Au and sulfide ores containing Au in pyrite. The extreme variations in sulfur isotopes as seen at Post and fluid inclusion data from Carlin may be indicative of some phase separation (‘boiling’), but such relations have not been documented in other deposits and the importance of phase separation to gold deposition appears minimal.     

Dominant amphipods of Posidonia oceanica seagrass meadows display considerable trophic diversity

Gut content examination and trophic markers (fatty acids, stable isotopes of C and N) were combined to delineate the diet of the dominant species of amphipods from Mediterranean Posidonia oceanica seagrass meadows and to highlight trophic diversity among this community. Our results indicate that, although all dominant species heavily relied on macroalgal epiphytes, considerable interspecific dietary differences existed. Carbon stable isotope ratios notably showed that some of the amphipod species favored grazing on epiphytes from leaves or litter fragments (Apherusa chiereghinii, Aora spinicornis, Gammarus aequicauda), while others such as Dexamine spiniventris preferred epiphytes from rhizomes. The remaining amphipods (Caprella acanthifera, Ampithoe helleri and Gammarella fucicola) readily consumed both groups. In addition, SIAR modeling suggested that most species had a mixed diet, and relied on several food items. Fatty acid analysis and gut contents revealed that contributions of microepiphytic diatoms and of benthic and suspended particulate organic matter to the diet of amphipods were anecdotal. None of the examined species seemed to graze on their seagrass host [low 18:2(n‐6) and 18:3(n‐3) fatty acids contents], but Gammarus aequicauda partly relied on seagrass leaf detritus, as demonstrated by the lesser ¹³C‐depletion of their tissues. Overall, our findings suggest that amphipods, because of their importance in the transfer of organic matter from primary producers and detritus to higher rank consumers, are key items in P. oceanica‐associated food webs.     

Authigenic carbonates from the eastern Black Sea as an archive for shallow gas hydrate dynamics – Results from the combination of CT imaging with mineralogical and stable isotope analyses

Authigenic carbonates associated with cold seeps provide valuable archives of changes in the long-term seepage activity. To investigate the role of shallow-buried hydrates on the seepage strength and fluid composition we analysed methane-derived carbonate precipitates from a high-flux hydrocarbon seepage area (“Batumi seep area”) located on the south-eastern Black Sea slope in ca. 850 m. In a novel approach, we combined computerized X-ray tomography (CT) with mineralogical and isotope geochemical methods to get additional insights into the three-dimensional internal structure of the carbonate build-ups.     

Sea,freshwater or saltpans? Foraging ecology of terns to assess mercury inputs in a wetland landscape: The Ebro Delta

The Ebro catchment, the largest river basin in Spain, includes various heavily industrialized areas. Among these is the Flix site, where a chemical plant has been operating since the beginning of the 20th century. This extended operational period, together with the construction of a dam next to the factory around 1960, resulted in the accumulation of large amounts of heavily polluted sediments in the adjacent riverbed, many of which are contaminated by mercury. Pollutants from Flix are carried downstream by the Ebro River to its delta. In order to assess the transfer of mercury to the complex river estuary ecosystem, we studied the ecology of the tern community living there as these birds segregate into a range of habitats. For this purpose, first we used stable isotope analysis (SIA) (δ³⁴S, δ¹³C, δ¹⁵N) of eggs to determine the trophic ecology and habitat partitioning of several tern species (Common, Sandwich, Little, Gull-Billed and Whiskered Tern) breeding sympatrically, in order to link their foraging ecology with habitat types. Next we measured mercury concentrations in eggs to monitor the input of this metal into the diverse habitats. With the exception of the Little Tern, the other terns used a restricted habitat range in the Ebro Delta, as shown by C and S isotopes; the Gull-Billed and Whiskered Tern foraged in freshwater habitats, while the Common and Sandwich Tern used marine habitats. This restricted feeding behavior of the Gull-Billed and Common Tern contrasts with previous reports in other breeding sites. The Little Tern, which showed a wide range of isotopic values, was found to be an opportunistic forager but fed mainly in saltpans, a feeding habitat not reported previously for this species in this area. We found that mercury concentrations are related to foraging habitat and diet, and are unexpectedly higher in species feeding on demersal prey in marine habitats and also higher in birds feeding in saltpans than in those feeding in freshwater habitats. The mercury concentrations found in the Little and Common Tern eggs sampled in “Punta de la Banya” may be sufficiently high to endanger breeding success.     

Chemosynthetic trophic support for the benthic community at an intertidal cold seep site at Mocha Island off central Chile

We analyzed C and N stable isotope ratios of benthic fauna and their potential food sources at an intertidal methane seep site and a control site without emanation at Mocha Island (central Chile). The objective was to trace the origin of the main food sources used by the local heterotrophic fauna, based on the hypothesis that chemosynthetic production could be partially fueling the local food web at the seep site. Food sources sampled at both sites included macroalgae, particulate organic matter and bacteria-like filaments found growing over the red algae Gelidium lingulatum within the areas of active methane release.     

Past 100 ky surface salinity-gradient response in the Eastern Arabian Sea to the summer monsoon variation recorded by δO of G. sacculifer

Northward flowing coastal currents along the western margin of India during winter–spring advect low-salinity Bay of Bengal water in to the Eastern Arabian Sea producing a distinct low-salinity tongue, the strength of which is largely governed by the freshwater flux to the bay during summer monsoons. Utilizing the sedimentary records of δ¹⁸O_{G. sacculifer}, we reconstructed the past salinity-gradient within that low-salinity tongue, which serves as a proxy for the variation in freshwater flux to the Bay of Bengal and hence summer monsoon intensity.The north–south contrast in the sea level corrected (residual)-δ¹⁸O_{G. sacculifer} can be interpreted as a measure of surface salinity-contrast between those two locations because the modern sea surface temperature and its past variation in the study region is nearly uniform. The core-top residual-δ¹⁸O_{G. sacculifer} contrast of 0.45‰ between the two cores is assumed to reflect the modern surface salinity difference of 1 psu and serves as a calibration for past variations.The residual-δ¹⁸O_{G. sacculifer} contrast varies between 0.2‰ at 75 ky B.P. (i.e., late-Marine Isotope Stage 5) and 0.7‰ at 20 ky B.P. (i.e., Last Glacial Maximum), suggesting that the overall salinity difference between the northern- and southern-end of the low-salinity tongue has varied between 0.6 and 1.6 psu. Considerably reduced difference during the former period than the modern suggests substantially intensified and northward-extended low-salinity tongue due to intense summer monsoons than today. On the other hand, larger difference (1.6 psu) during the latter period indicates that the low-salinity tongue was significantly weakened or withdrawn due to weaker summer monsoons. Thus, the salinity-gradient in the eastern Arabian Sea low-salinity tongue can be used to understand the past variations in the Indian summer monsoons.     

Late glacial and Holocene environmental change in the Lake Baikal region documented by oxygen isotopes from diatom silica

We investigate late glacial and Holocene climate change recorded in Lake Baikal using the oxygen isotope composition of diatom silica (δ¹⁸O_DIAT). Evaporation from the lake is minor, and the temperature fractionations of δ¹⁸O are unable to explain variations in the δ¹⁸O_DIAT record alone. Isotopically, low meltwater input from glaciers may have some influence on δ¹⁸O_DIAT, but the assumed periods of climatic warming and wastage do not coincide with large shifts in δ¹⁸O_DIAT. There is a gradual oxygen isotope lowering from 27.0‰ to 20.6‰ over the late glacial, while, during the Holocene, δ¹⁸O_DIAT values return to relatively high values. Previous studies of the modern oxygen and hydrogen isotope composition of Lake Baikal's inputs reveal that fluvial input to the lake's North Basin are isotopically lower than fluvial input from South Basin rivers. This north–south gradient of river δ¹⁸O and δD is mainly due to the greater input from isotopically low winter precipitation in the north and isotopically higher summer precipitation in the south. As a result, the δ¹⁸O_DIAT record from Lake Baikal can at least in part be explained by varying input from these sources related to seasonal changes in precipitation. Changes in atmospheric conditions may have a role in altering seasonality and the distribution of precipitation over Lake Baikal's catchment. A feedback mechanism is well known linking higher Eurasian spring snow cover extent (ESSC) to the development of anticyclonic conditions and low precipitation the following summer in the areas south of Lake Baikal. A simultaneous increase in the importance of depleted water (snowmelt) input from the north and decreased enriched summer precipitation in the south is needed to explain depletions in δ¹⁸O of lake water and subsequently δ¹⁸O_DIAT during colder periods. The opposite of this situation is required to enrich lake water during warmer periods. The analysis of δ¹⁸O from diatom silica is a useful proxy for environmental change, especially in lakes, like Lake Baikal, where carbonates are absent or diluted. However, analysis must be based on near pure diatom samples as even trace amounts of silt can have a dominating effect on δ¹⁸O_DIAT values.     

Evidence for discrete subpopulations of sea perch (Helicolenus ercoides) across four fjords in Fiordland,New Zealand

In coastal populations of invertebrates and fishes, the distribution of discrete subpopulations is influenced by adult and larval dispersal, as well as by the effects of habitat heterogeneity on site fidelity or connectivity. Here, we examine evidence for spatial structure of sea perch, Helicolenus percoides, populations among four fjords in the Fiordland region of southwestern New Zealand. We examine patterns in adult morphology, length-at-age, δ¹³C and δ¹⁵N of muscle tissue, and trace elemental composition of whole otoliths as proxies for population isolation among the four inner fjord regions. A multivariate analysis of morphometrics reveals significant differences among populations from each of the four sites, suggesting existence of four distinct subpopulations. These patterns are consistent with observed differences in δ¹³C and δ¹⁵N, and length-at-age estimates among the four subpopulations. Differences in whole otolith concentrations of Sr, Ba, Mg and Li, and high classification scores based on the whole otolith elemental fingerprint are also consistent with significant subdivision among areas. Patterns across all four markers are consistent with discrete subpopulation structure of adult sea perch among the four study sites. These data indicate that the newly implemented network of marine protected areas in Fiordland is likely to contain discrete populations of sea perch.