Pb, Sr and Nd isotope study of two co-existing magmas in the Nízke Tatry Mountains, Western Carpathians (Slovakia)

Summary Two co-existing plutonic rocks (diorite and granodiorite) were studied from an intrusion of Variscan age in the Raztocna Valley – Nízke Tatry Mountains, Western Carpathians. Geochemical analyses of major and trace elements constrain a volcanic arc as emplacement environment and give the first hints of a mixture of two magmatic end-members: the so-called Prasivá granodiorite and the Raztocna diorite. The ⁸⁷Sr/⁸⁶Sr₍₀₎ ratios vary between 0.7075 and 0.7118, the ε Nd₍₀₎ values range from −1.4 to −5.0. Common Pb isotopes reveal a dominant crustal source with minor influences from a mantle and a lower crustal source. Modelling based on Sr and Nd isotope data and using three component mixing calculations indicates that mixing of 2/3 of upper mantle material with 1/3 upper crustal material can produce the isotopic composition of the Raztocna diorite. Very minor amounts of lower crust were incorporated in the diorite. For the Prasivá granodiorite, the mixing ratio of upper mantle and upper crust is similar, but a lower crustal reservoir contributed about 5–10% of the source material.     

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O₂), hypoxic (2% O₂, 98% N₂), and anoxic (5% H₂, 95% N₂) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.     

Total amount of oceanic excess CO2 taken from the North Pacific subpolar region

Concentrations of total carbonate, alkalinity and dissolved oxygen were obtained near the 1973 GEOSECS stations in the North Pacific subpolar region north of 40°N along 175°E between 1993 and 1994. A difference of excess CO₂ content between the GEOSECS and our expeditions was estimated. The maximum difference in water column inventory of excess CO₂ has increased by about 280 gC m^–2 above 2000 m depth which apparently means an uptake of excess CO₂ taken from air to sea during the last two decades. An averaged value of the annual flux of excess CO₂ at 75–1000 m depth was 8.63±2.01 gC m^–2yr^–1 in the North Pacific subpolar region. By introducing the annual flux of excess CO₂ into a two-box model for the North Pacific subpolar region, a penetration factor of excess CO₂ from air to sea was obtained to be 1.08×10^–2 gC m^–3ppm^–1 in the North Pacific subpolar region. Based on this factor, the surface concentration of excess CO₂ in the North Pacific subpolar region was estimated to be 68 mole I^–1, suggesting that the North Pacific subpolar region absorbed atmospheric excess CO₂ more than the saturated concentration of excess CO₂. Total amount of excess CO₂ taken from the North Pacific subpolar region by 1993 was estimated to be 36.2×10¹⁵ gC, which was equal to about one tenth of that released by human activities after the preindustrial era.     

A Preliminary Study of Oceanic Bomb Radiocarbon Inventory in the North Pacific during the Last Two Decades

Radiocarbon and total carbonate data were obtained near the 1973 GEOSECS stations in the North Pacific along 30°N and along 175°E between 1993 and 1994. In these stations, we estimated radiocarbon originating from atomic bomb tests using tritium, trichlorofluoromethane and silicate contents. The average penetration depth of bomb radiocarbon during the two decades has deepened from 900 m to 1300 m. Bomb radiocarbon inventories above the average value for the whole North Pacific were found widely in the western subtropical region around 30°N both in the 1970s and 1990s, and its area in the 1990s was broader than that in the 1970s. In most of the North Pacific, while the bomb radiocarbon has decreased above 25.4, the bomb radiocarbon flux below 25.4 was over 1 × 10¹² atom m^-2yr^-1 in the subtropical region around 30°N. In the tropical area south of 20°N, the bomb radiocarbon inventory below 25.4 increased from zero to over 10 × 10¹² atom m^-2 during the last three decades. These distributions suggest that the bomb radiocarbon removed from the surface is currently accumulated with bomb ¹⁴C flux of over 1 × 10¹² atom m^-2yr^-1 below 25.4 in the subtropical region, mainly by advection from the higher latitude, and that part of the accumulated bomb ¹⁴C gradually spread southward with about 30 years.     

Air-Sea Gas Transfer Velocity in Stormy Winter Estimated from Radon Deficiency

Thirteen vertical profiles of ²²⁶Ra and ²²²Rn in the near-surface water were obtained in the western North Pacific in winter, and the gas transfer velocities across the air-sea interface were estimated. The transfer velocities found by applying a steady state model varied widely from 2.1 to 30.2 m day⁻¹ with a mean of 9.4 m day⁻¹. The mean value is almost 5 times higher than that in summer in other oceans, and the maximum value is a record high for world oceans. This is partly due to the inadequacy of the steady state model, which overestimates when stronger winds blow in more recent days than the ²²²Rn half-life of about 4 days. In fact, a strong low pressure zone passed through the station about 2 days earlier, which was one of the low pressure zones that with a period of develop once a week or so in the northwestern North Pacific in winter. Instead of steady-state removal, if half of the radon removal occurred sporadically every 7 days, and the last removal took place two days before the observation, the transfer velocity would be 26 m day⁻¹. Our mean transfer velocity, which is less than 20% different from the steady state value including both overestimated and underestimated values, 9.4 ± 4.8 m day⁻¹, seems to represent the mean state of this region in winter. This suggests that the gas exchange fluxes under extremely rough conditions in the open ocean are larger than those estimated by using a transfer velocity equation with a linear or quadratic relationship with wind speed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Interviewing in 'place': the socio-spatial construction of interview data

The intersubjective dialogic exercise through which identities and knowledge are constructed exists in a dialectic relation with the 'place' of the interview. The in situ nature of interviewing should not be overlooked. Two case studies of interviews conducted with older people in Britain about their social network and support are used to illuminate two aspects of the socio-spatial construction of interview data. First, interview sites can yield important information about the way participants construct their individual and social identities. Second, such identities can influence interviewer–interviewee dynamics.     

Use of time series analysis for the identification of tidal effect on groundwater in the coastal area of Kimje, Korea

The purpose of this study is to apply time series analysis to investigate whether the groundwater quality in the coastal area is affected by the tide. Continuous and regular in situ monitoring data of electrical conductivity (EC) and groundwater level, and tidal level data measured by the National Oceanographic Research Institute were used for the time series analysis. Through the time series analysis, it is known that EC and groundwater level conspicuously fluctuate with two periodicities (15.4 and 0.52-day), which is very similar to those of the tide. Also the behaviors of their fluctuations vary in accordance with the tidal period. These indicate that the groundwater quality has been mainly controlled by the tidal level, and the strength of tidal effect on the groundwater quality is different according to the tidal period.     

A high-resolution TEM-AEM, pH titration, and modeling study of Zn coprecipitation with ferrihydrite

Experiments of Zn²⁺ and Fe³⁺ coprecipitation as a function of pH were conducted in the laboratory at ambient temperature and pressure. X-ray diffraction patterns of the coprecipitates show two broad peaks at 0.149 and 0.258 nm, which is consistent with published patterns for pure 2-line ferrihydrite. Zn²⁺ uptake occurred at pH ≥5 while Fe³⁺ precipitation occurred between pH 3 and 4, although both Zn²⁺ and Fe³⁺ were present in the same solution during the entire range of pH titration. High-resolution transmission electron microscopy shows that the coprecipitates are 2 to 6 nm sized single crystalline particles but aggregated to 50 to 400 nm sized clusters. Analytical electron microscopy indicated that the 5% atomic Zn with respect to Fe was homogeneously distributed. No segregated phases were found in the clusters or at single crystal edges, which is consistent with published extended X-ray absorption fine structure (EXAFS) results at similar Zn/(Zn + Fe) ratios. Hence, occlusion and surface precipitation may be excluded as possible coprecipitation mechanisms. The bulk solution Zn²⁺ sorption edge was fitted to both solid solution and generalized diffuse layer surface complexation models. However, a solid solution model is inconsistent with published EXAFS results that show tetrahedral polydentate Zn²⁺ complexes sharing apices with Fe³⁺octahedra.     

Quantitative estimation of submarine groundwater discharge using airborne thermal infrared data acquired at two different tidal heights

Submarine groundwater discharge (SGD) plays an important role in coastal biogeochemical processes and hydrological cycles, particularly off volcanic islands in oligotrophic oceans. However, the spatial and temporal variations of SGD are still poorly understood owing to difficulty in taking rapid SGD measurements over a large scale. In this study, we used four airborne thermal infrared surveys (twice each during high and low tides) to quantify the spatiotemporal variations of SGD over the entire coast of Jeju Island, Korea. On the basis of an analytical model, we found a linear positive correlation between the thermal anomaly and squares of the groundwater discharge velocity and a negative exponential correlation between the anomaly and water depth (including tide height and bathymetry). We then derived a new equation for quantitatively estimating the SGD flow rates from thermal anomalies acquired at two different tide heights. The proposed method was validated with the measured SGD flow rates using a current meter at Gongcheonpo Beach. We believe that the method can be effectively applied for rapid estimation of SGD over coastal areas, where fresh groundwater discharge is significant, using airborne thermal infrared surveys.     

Submarine groundwater discharge revealed by aerial thermal infrared imagery: a case study on Jeju Island,Korea

Submarine groundwater discharge (SGD) is a global phenomenon that carries large volumes of groundwater and dissolved chemical species such as nutrient, metals, and organic compounds to coastal zones. We report the influence of SGD on the coastal waters of Jeju Island, Korea, using high‐resolution aerial thermal infrared (TIR) mapping techniques and field investigations. An aircraft‐based system was implemented using a cost‐effective TIR camera for aerial TIR mapping. Ground‐based calibrations and system integration with GPS/IMU (global positioning system/inertial measurement unit) were performed for the aerial systems. The aerial surveys showed distinct low‐temperature signatures of SGD along the coasts of Jeju Island, revealing large groundwater inputs from the coastal aquifers to the ocean. Multiple aerial surveys over a range of seasons and tidal stages revealed that SGD rates dynamically affect the sea surface temperature (SST) of the coastal zone. The in‐situ measurements supported that SGD has a substantial influence on the coastal water chemistry as well as SST. Our observations highlight the extent to which aerial‐based TIR mapping can serve as a powerful tool for studying SGD and other coastal processes. Copyright © 2016 John Wiley & Sons, Ltd.