Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

The persistence of lead from past gasoline emissions and mining drainage in a large riparian system: Evidence from lead isotopes in the Sacramento River, California

Lead concentrations and isotope ratios measured in river water colloids and streambed sediment samples along 426 km of the Sacramento River, California reveal that the influence of lead from the historical mining of massive sulfide deposits in the West Shasta Cu-mining district (at the headwaters of the Sacramento River) is confined to a 60 km stretch of river immediately downstream of that mining region, whereas inputs from past leaded gasoline emissions and historical hydraulic Au-mining in the Sierra Nevadan foothills are the dominant lead sources in the remaining 370 km of the river. Binary mixing calculations suggest that more than 50% of the lead in the Sacramento River outside of the region of influence of the West Shasta Cu-mining district is derived from past depositions of leaded gasoline emissions. This predominance is the first direct documentation of the geographic extent of gasoline lead persistence throughout a large riparian system (>160,000 km²) and corroborates previous observations based on samples taken at the mouth of the Sacramento River. In addition, new analyses of sediment samples from the hydraulic gold mines of the Sierra Nevada foothills confirm the present-day fluxes into the Sacramento River of contaminant metals derived from historical hydraulic Au-mining that occurred during the latter half of the 19th and early part of the 20th centuries. These fluxes occur predominantly during periods of elevated river discharge associated with heavy winter precipitation in northern California. In the broadest context, the study demonstrates the potential for altered precipitation patterns resulting from climate change to affect the mobility and transport of soil-bound contaminants in the surface environment.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

A spectrophotometric study of Nd(III), Sm(III) and Er(III) complexation in sulfate-bearing solutions at elevated temperatures

The speciation of Nd(III), Sm(III), and Er(III) in sulfate-bearing solutions has been determined spectrophotometrically at temperatures from 25 to 250 °C and a pressure of 100 bars. The data obtained earlier on the speciation of Nd in sulfate-bearing solutions (Migdisov et al., 2006) have been re-evaluated and corrected using a more appropriate activity model and are compared with the corresponding data for Sm(III) and Er(III) and new data for Nd(III). Based on this comparison, the dominant species in the solution are interpreted to be and , with the latter complex increasing in importance at higher temperature. Equilibrium constants were calculated for the following reactions:

     

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.     

Large and giant hydrocarbon accumulations in the transitional continent-ocean zone

The petroleum resource potential is considered for the Atlantic, West Pacific, and East Pacific types of deepwater continental margins. The most considerable energy resources are concentrated at the Atlantic-type passive margins in the zone transitional to the ocean. The less studied continental slope of backarc seas of the generally active margins of the West Pacific type is currently not so rich in discoveries as the Atlantic-type margin, but is not devoid of certain expectations. In some of their parameters, the margins bounded by continental slopes may be regarded as analogs of classical passive margins. At the margins of the East Pacific type, the petroleum potential is solely confined to transform segments. In the shelf-continental-slope basins of the rift and pull-apart nature, petroleum fields occur largely in the upper fan complex, and to a lesser extent in the lower graben (rift) complex. In light of world experience, the shelf-continental-slope basins of the Arctic and Pacific margins of Russia are evaluated as highly promising.     

Campanian-Maastrichtian radiolarians from the Malokuril’skaya Formation,the Shikotan Island

The results of radiolarian analysis confirm the Campanian-Maastrichtian age of the Malokuril’skaya Formation in the Shikotan Island. The Campanian-Maastrichtian age of the formation is implied simultaneously by radiolarians and inoceramids. The studied Campanian and Campanian-Maastrichtian radiolarian assemblages include abundant specimens representing genus Prunobrachium, characteristic of which was bipolar distribution in cold-water to temperate basins. The new occurrence site of prunobrachids is established at the latitude of 43°N, the Far East of Russia.     

New fusulinids of the Moscovian Stage found in Iran

The described fusulinids of the Moscovian Stage are found in the Asad-Abad section of the Sanandaj-Sirjan tectonic zone of Iran. Five successive fusulinid assemblages are distinguished. Three lower of them belong to the Kashirian Substage, the other two to the Podolskian Substage. The section studied is correlated with most complete sections of the Moscovian Stage in the western Tethys. Two new species Fusulinella (Moellerites) pygmea and Putrella primaris are identified; in addition to nominative taxon, the latter includes new subspecies P. primaris compacta.     

Opacitization conditions of hornblende in Bezymyannyi volcano andesites (March 30, 1956 eruption)

The paper is devoted to the conditions under which opacite rims developed around hornblende grains in andesite of the catastrophic eruption (March 30, 1956) of Bezymyannyi volcano, Kamchatka. The opacite rims were produced by a bimetasomatic reaction between hornblende and melt with the development of the following zoning: hornblende → Px + Pl + Ti-Mag → Px + Pl → Px → melt. Biometasomatic reaction was accompanied by the active removal of CaO from the rim, addition of SiO₂, and more complicated behavior of other components. The hornblende also shows reactions of its volumetric decomposition under near-isochemical conditions. The opacite rims developed under isobaric conditions, at a pressure of approximately 6 kbar. The main reason for the instability of the hornblende was the heating of the magma chamber from 890 to 1005°C due to new hot magma portion injection. The time interval between the injection and the start of eruption was estimated from the thickness of the opacite rims and did not exceed 37 days. Hence, the March 30, 1956, eruption was not related to the volcanic activity in November of 1955 but to the injection of a fresh magma portion in February–March of 1956.     

Chemical composition,volatile components,and trace elements in melts of the Karymskii volcanic center,Kamchatka, and Golovnina volcano,Kunashir Island: Evidence from inclusions in minerals

Melt inclusions were examined in phenocrysts in basalt, andesite, dacite, and rhyodacite from the Karymskii volcanic center in Kamchatka and dacite form Golovnina volcano in Kunashir Island, Kuriles. The inclusions were examined by homogenization and by analyzing glasses in more than 80 inclusions on an electron microscope and ion microprobe. The SiO₂ concentrations in the melt inclusions in plagioclase phenocrysts from basalts from the Karymskii volcanic center vary from 47.4 to 57.1 wt %, these values for inclusions in plagioclase phenocrysts from andesites are 55.7–67.1 wt %, in plagioclase phenocrysts from the dacites and rhyodacites are 65.9–73.1 wt %, and those in quartz in the rhyodacites are 72.2–75.7 wt %. The SiO₂ concentrations in melt inclusions in quartz from dacites from Golovnina volcano range from 70.2 to 77.0 wt %. The basaltic melts are characterized by usual concentrations of major components (wt %): TiO₂ = 0.7–1.3, FeO = 6.8–11.4, MgO = 2.3–6.1, CaO = 6.7–10.8, and K₂O = 0.4–1.7; but these rocks are notably enriched in Na₂O (2.9–7.4 wt % at an average of 5.1 wt %, with the highest Na₂O concentration detected in the most basic melts: SiO₂ = 47.4–52.0 wt %. The concentrations of volatiles in the basic melts are 1.6 wt % for H₂O, 0.14 wt % for S, 0.09 wt % for Cl, and 50 ppm for F. The andesite melts are characterized by high concentrations (wt %) of FeO (6.5 on average), CaO (5.2), and Cl (0.26) at usual concentrations of Na₂O (4.5), K₂O (2.1), and S (0.07). High water concentrations were determined in the dacite and rhyodacite melts: from 0.9 to 7.3 wt % (average of 15 analyses equals 4.5 wt %). The Cl concentration in these melts is 0.15 wt %, and those of F and S are 0.06 and 0.01 wt %, respectively. Melt inclusions in quartz from the dacites of Golovnina volcano are also rich in water: they contain from 5.0 to 6.7 wt % (average 5.6 wt %). The comparison of melt compositions from the Karymskii volcanic center and previously studied melts from Bezymyannyi and Shiveluch volcanoes revealed their significant differences. The former are more basic, are enriched in Ti, Fe, Mg, Ca, Na, and P but significantly depleted in K. The melts of the Karymskii volcanic center are most probably less differentiated than the melts of Bezymyannyi and Shiveluch volcanoes. The concentrations of water and 20 trace elements were measured in the glasses of 22 melt inclusions in plagioclase and quartz from our samples. Unusually high values were obtained for Li concentrations (along with high Na concentrations) in the basaltic melts from the Karymskii volcanic center: from 118 to 1750 ppm, whereas the dacite and rhyolite melts contain 25 ppm Li on average. The rhyolite melts of Golovnina volcano are much poorer in Li: 1.4 ppm on average. The melts of the Karymskii volcanic center are characterized by relative minima at Nb and Ti and maxima at B and K, as is typical of arc magmas.