Heat capacity anomalies at incommensurate-normal transition of åkermanite solid solution (Ca,Sr)2(Mg,Co, Zn,Fe)Si2O7

The heat capacity of åkermanite solid solutions was measured by a small scale adiabatic calorimeter near the incommensurate-normal (I-N) transition. The heat capacity anomalies caused by the I-N transition show the type characteristic behavior implying the presence of dynamical fluctuations. The heat capacity anomalies were observed over the whole range of the åkermanite solid solutions Ca₂Mg_1-xCo_xSi₂O₇ and Ca₂Mg_1-x-Zn_xSi₂O₂. With increase of Co or Zn atoms, the transition temperature, T_i, rises linearly from ca. 83° C to 220° C and to 130° C, respectively. In the system Ca₂CoSi₂O₇-Ca₂FeSi₂O₇ and Ca₂MgSi₂O₇-Ca₂-FeSi₂O₇ electronic microscopy revealed that the temperature of the heat capacity anomaly decreases with increasing Fe content, whereas the T_i rises. This unusual behavior is ascribed to the microdomains observed in high resolution lattice images.     

Stable isotope characterization of fluids from the Lake Chany complex,western Siberia,Russian Federation

The Lake Chany complex and nearby lakes in western Siberia (Russian Federation) were studied to constrain the S cycle in these terrestrial lake environments. Surface water chemistry was characterized by Na–SO₄–Cl composition, comparable to other inland basins in semi-arid climatic zones associated with marine evaporite-bearing formations at depth. Dissolved sulfates showed elevated δ³⁴S (up to +32.3‰). These values are quite distinct from those in similar saline lakes in northern Kazakhstan, the Aral Sea, Lake Barhashi, and a gypsum deposit in the Altai Mountains. The localized distribution of such a unique S isotopic signature in dissolved SO₄ negates both aeolian and catastrophic flooding hypotheses previously suggested for the genesis of the dissolved salts. The probable source of the dissolved SO₄ in Lake Chany basin is inherited from hidden saline groundwaters (whose location and origins remain unclear) from eastern Paleozoic ranges with Upper Devonian formations with heavy S isotope values. Post-depositional enrichment of heavy S in the dissolved SO₄ from saline sediments may be caused by local activity of SO₄-reducing bacteria under the ambient supply of electron donors (dissolved river load organic matter and decaying bacterial mats) in the lake complex. Such microbial processes can remove up to ca. 60% of SO₄ from the system. Extensive and intensive evaporation of lake fluids, ca. 40%, was indicated by the progressive enrichment of δ¹⁸O values in meteoric water samples collected along the river and lake system. This evaporation process compensates the microbial loss of SO₄ dissolved in the incoming river water.     

Temporal variations in the concentration and isotopic signature of ammonium- and nitrate–nitrogen in soils under a breeding colony of Black-tailed Gulls (Larus crassirostris) on Kabushima Island,northeastern Japan

Temporal variations in the concentration and N isotopic ratios of inorganic N (NH₄– and NO₃–N) as affected by the soil temperature regime together with the input of bird excreta were analyzed in a sedentary soil under a dense colony (1.6 nests/m²) of breeding Black-tailed Gulls (Laruscrassirostris: a ground-nesting seabird). Surface soil samples were taken monthly from mid-March to late July 2005 from Kabushima Island, Hachinohe, northeastern Japan. The spatial concentration of inorganic N in the soils varied considerably on all sampling dates. There may be a statistically significant trend, showing increased NH₄–N content from settlement up to early June when the input of fecal N attains its maximum, and then decreases towards the end of breeding activity (early August). Abundant NO₃–N was observed in all soils, particularly in the later stage of breeding (up to 3800 mg-N/kg dry soil), refuting earlier claims that nitrification is unimportant in the soils. δ¹⁵N values of NH₄ in the soils showed unusually high values up to +51‰, reflecting N isotope fractionation due to volatilization of NH₃ during the mineralization. Mean δ¹⁵N values of the monthly collected totals of NH₄ and NO₃ were not significantly different at the 5% level based on ANOVA and significant differences were observed only among the three means of NO₃–N collected in mid-March (settlement of colony: δ¹⁵N = −0.2 ± 3.5‰) and late July (later stages of breeding: δ¹⁵N = +22.1 ± 7.0‰, +23.3 ± 7.8‰) at the 1% and 5% levels by t-test, respectively. Such an observation of significantly increased δ¹⁵N values for NO₃–N in soils from the fledgling stage indicates the integration of denitrification coupled with nitrification under a limited supply of fecal N.     

Single-crystal X-ray diffraction study of cation distribution in MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>–MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> spinel solid solution

Synthesis experiments in the system MgAl₂O₄–MgFe₂O₄ [MgAl_2–xFe_xO₄ (0 x 2)] were carried out using a PbF₂ flux. The crystalline products synthesized in the compositional range of 0.6 <x 1.2 consisted of two spinel phases, whereas those synthesized in the compositional ranges of 0.0 x 0.6 and 1.2 < x 2.0 crystallized as single spinel phases. Structure refinements of the spinel single crystals, which grew in the ranges of 0.0 x 0.6 and 1.2 < x 2.0, show that the degree of randomness of cation distribution between A and B sites increases as x approaches the two-phase region. This means that the degree of the size mismatch among Mg²⁺, Fe³⁺ and Al³⁺occupying each equivalent mixing site increases as x approaches the two-phase region. Consequently, if the coexistence of two spinels observed in the intermediate compositions reveals the existence of a miscibility gap at low temperatures, this increase in the degree of the size mismatch among the three cations is suggested as a factor of energetic destabilization to form the miscibility gap.     

Nitrogen isotopic patterns of vegetation as affected by breeding activity of Black-tailed Gull (Larus crassiostris): A coupled analysis of feces, inorganic soil nitrogen and flora

Two currently breeding colonies (Matsushima Bay and Rishiri island; northern Japan) of predominant Black-tailed Gull (Larus crassiostris) were studied for N isotopic patterns of flora, which is affected by increased supply of inorganic soil N derived from the microbial transformation of feces. Coupled samples of feces, topsoil and flora were collected in early to mid July (2008), when input of fecal N onto soils was at its maximum. As bird migration and breeding continued, native Japanese red-pine (Pinus densiflora), junipers (Juniperus chinensis and Juniperus rigita; Matsushima Bay colony) and Sasa senanensis (Rishiri colony) declined, while ornithocoprophilus exotic plants succeeded. Among tree species on the islands, P. densiflora with ectomycorrizal colonization appears highly susceptible to elevated concentrations of NH₄–N in the topsoil. A mechanism for best explaining the plant succession associated with the breeding activity of Black-tailed Gull was evidenced by two parameters: first, concomitant elevation of N content in the flora and second, inorganic soil N content, along with changes in N isotopic composition (δ¹⁵N). Earlier isotopic data on the foliar N affected by breeding activity were compiled and reviewed. Emphasis was put on isotopic information for inorganic N in soils that controls plant succession.