Iron release in aqueous environment by fresh volcanic ash from Mount Etna (Italy) and Popocatépetl (Mexico) volcanoes

In this study, we performed leaching experiments for timescales of hours-to-months in deionized water on fresh volcanic ash from Mt. Etna (Italy) and Popocatépetl (Mexico) volcanos to monitor Fe release as a function of ash mineral chemistry and size, with the aim of clarifying Fe release mechanisms and eventually evaluating the impact of volcanic ash on marine and lacustrine environments. To define sample mineralogy and Fe speciation, inclusive characterization was obtained by means of XRF, SEM, XRPD, EELS and Mössbauer spectroscopies. For Etna and Popocatépetl samples, glass proportions were quantified at 73 and 40%, Fe₂O₃ total contents at 11.6–13.2 and 5.8 wt%, and Fe³⁺/Fe_Tot ratios at 0.33 and 0.23, respectively. Leaching experiments showed that significant amounts of iron, ~?30 to 150 and ~?750 nmol g^?1 l^?1 for pristine Etna and Popocatépetl samples, respectively, are released within the first 30 min as a function of decreasing particle size (from 1 to 0.125 mm). The Popocatépetl sample showed a very sustained Fe release (up to 10 times Etna samples) all along the first week, with lowest values never below 400 nmol g^?1 l^?1 and a maximum of 1672 nmol g^?1 l^?1 recorded after 5 days. This sample, being composed of very small particles (average particle size 0.125 mm) with large surface area, likely accumulated large quantities of Fe-bearing sublimates that quickly dissolved during leaching tests, determining high Fe release and local pH decrease (that contributed to release more Fe from the glass) at short timescale (hours-to-days). The fractional Fe solubility (Fe_S) was 0.004–0.011 and 0.23% for Etna and Popocatépetl samples, respectively, but no correlation was found between Fe released in solution and either ash Fe content, glass/mineral ratio or mineral assemblage. Results obtained suggest that volcanic ash chemistry, mineralogy and particle size assume a relevant role on Fe release mostly in the medium-to-long timescale, while Fe release in the short timescale is dominated by dissolution of surface sublimates (formed by physicochemical processes occurring within the eruption plume and volcanic cloud) and the effects of such a dissolution on the local pH conditions. For all samples, a moderate to sustained Fe release occurred for leaching times comparable with their residence time within the euphotic zone of marine and lacustrine environments (variable from few minutes to few hours), revealing their possible contribution to increase Fe bioavailability.     

Geochemical Features of Vein Anhydrite from the Kakkonda Geothermal System, Northeast Japan

Abstract. Cathodoluminescence (CL) color, rare earth element (REE) content, sulfur and oxygen isotopes and fluid inclusions of anhydrite, which frequently filled in hydrothermal veins in the Kakkonda geothermal system, were investigated to elucidate the spatial, temporal and genetical evolution of fluids in the deep reservoir. The anhydrite samples studied are classified into four types based on CL colors and REE contents: type-N (no color), type-G (green color), type-T (tan color) and type-S (tan color with a high REE content). In the shallow reservoir, only type-N anhydrite is observed. In the deep reservoir, type-G anhydrite occurs in vertical veins whereas type-T and -N in lateral veins. Type-S anhydrite occurs in the heat-source Kakkonda Granite. The CL textures revealed that type-G anhydrite deposited earlier than type-T in the deep reservoir, implying that fracture system was changed from predominantly vertical to lateral.
Studies of fluid inclusions and δ³⁴S and δ¹⁸O values of the samples indicate that type-N anhydrite deposited from diluted fluids derived from meteoric water, whereas type-G, -T and -S anhydrites deposited from magmatic brines derived from the Kakkonda Granite with the exception of some of type-G with recrystallization texture and no primary fluid inclusion, which deposited from fossil seawater preserved in the sedimentary rocks. Type-G, -T and -S anhydrites exhibit remarkably different chondrite-normalized REE patterns with a positive Eu anomaly, with a convex shape (peak at Sm or Eu) and with a negative Eu anomaly, respectively. The difference in the patterns might result from the different extent of hydrothermal alteration of the reservoir rocks and contribution of the magmatic fluids.     

Nitrogen isotope ratios of nitrate as a clue to the origin of nitrogen on the Pacific coast of Japan

To clarify the sources and transformation of NO₃⁻ on the Pacific coast of Japan, observations over the continental shelf were conducted during the summer in 2005 and 2006 when the Kuroshio flowed close to and away from the coastal area, respectively. Below the halocline, there are two prominent salinity peaks that originated in two different waters. In the subsurface layer, the salinity maximum (S_max) was indicative of the Kuroshio Water (KW), while the salinity minimum (S_min) in the middle layer at ∼400 m depth was indicative of the North Pacific Intermediate Water (NPIW). δ¹⁵N_NO3 ranged from 4.1‰ to 5.1‰ with a mean of 4.8±0.4‰ in the deeper water around S_min. Below 50 m depth over the shelf break, δ¹⁵N_NO3 values (3.1±0.8‰ in 2005 and 4.6±0.3‰ in 2006) clearly increased as contribution of NPIW increased in 2006. On the contrary, subsurface δ¹⁵N of NO₃⁻ values (−1.1±0.1‰) remained unchanged in both years, although the contribution of the KW to the subsurface water changed significantly. This suggests that the source of NO₃⁻ has little effect on the δ¹⁵N of NO₃⁻ in this layer. The negative δ¹⁵N values also coincided with the base of the chlorophyll maximum layer suggesting that these isotopic signals must be evidence of active nitrification in the upper layer.     

Fluid inclusion from drill hole DW-5, Hohi geothermal area, Japan: Evidence of boiling and procedure for estimating CO2 content

Fluid inclusion studies have been used to derive a model for fluid evolution in the Hohi geothermal area, Japan. Six types of fluid inclusions are found in quartz obtained from the drill core of DW-5 hole. They are: (I) primary liquid-rich with evidence of boiling; (II) primary liquid-rich without evidence of boiling; (III) primary vapor-rich (assumed to have been formed by boiling); (IV) secondary liquid-rich with evidence of boiling; (V) secondary liquid-rich without evidence of boiling; (VI) secondary vapor-rich (assumed to have been formed by boiling). Homogenization temperatures (T_h) range between 196 and 347°C and the final melting point of ice (T_m) between −0.2 and −4.3°C. The CO₂ content was estimated semiquantitatively to be between 0 and 0.39 wt. % based on the bubble behavior on crushing. NaCl equivalent solid solute salinity of fluid inclusions was determined as being between 0 and 6.8 wt. % after minor correction for CO₂ content.Fluid inclusions in quartz provide a record of geothermal activity of early boiling and later cooling. The CO₂ contents and homogenization temperatures of fluid inclusions with evidence of boiling generally increase with depth; these changes, and NaCl equivalent solid solute salinity of the fluid can be explained by an adiabatic boiling model for a CO₂-bearing low-salinity fluid. Some high-salinity inclusions without CO₂ are presumed to have formed by a local boiling process due to a temperature increase or a pressure decrease. The liquid-rich primary and secondary inclusions without evidence of boiling formed during the cooling process. The salinity and CO₂ content of these inclusions are lower than those in the boiling fluid at the early stage, probably as a result of admixture with groundwater.