Fluid–rock interaction during seprentinization of oceanic ultramafic rocks hosting the Lost City hydrothermal field, 30° N,MAR

The estimation of the fluid/rock (W/R) ratio during serpentinization on the basis of oxygen isotope characteristics is peculiar, because this process is accompanied by not only changes in the stoichiometric proportions of oxygen in fluid and rock, but also by the formation of associated minerals. These factors should be taken into account for environments when the volume of aqueous fluid is limited, for instance, for serpentinization of the deep-seated rocks of oceanic lithosphere under low spreading rates. We studied isotope characteristics of samples collected in dives of submersible MIR during Cruise 50 of the R/V Akademik Mstislav Keldysh along vertical profile on the southern slope of the Atlantis Massif, which hosts the Lost City hydrothermal field. Almost all studied serpentinites have homogenous strontium isotope composition corresponding to the composition of the modern seawater. Oxygen isotope composition of these serpentinites shows systematic variations from 2. 6 to 6.1‰ with sampling depth, which indicates the preservation of stratigraphic position of samples in the sequence of the Atlantis Massif and the global serpentinization of the entire plutonic sequence. The value of the fluid–rock ratio during serpentinization in a system closed to fluid was estimated using the dissolution–crystallization model. This model takes into account the variable stoichiometry of oxygen and the effect of the simultaneous crystallization of brucite on the oxygen isotope composition of newly formed serpentine. The results show that at moderately elevated temperatures (≈300°C) and 0.1 < W/R < 5, fluid, crystallizing serpentine, and brucite are characterized by sharp variations in oxygen isotope composition: 1.3–7.8, 2.5–8.9, and 4.5–1.9‰, respectively. The model explains the observed range of δ¹⁸O in the serpentinized harzburgites of the Atlantis Massif. According to our estimates, the rocks of the studied sequence of the Atlantis Massif were serpentinized at 270–350°C and W/R = 0.7–3. For lower temperature serpentinization, for instance, at T = 250°C, the W/R ratio can be as high as 6. The present-day serpentinization of the deepseated zones of the Atlantis Massif with the Lost City fluid participance proceeds at T > 270°C and W/R ratio <1. These conditions are similar to those of serpentinization of harzburgites from the lower parts of the studied sequence of the Atlantis Massif.     

The transfer of oxygen isotopic signals from precipitation to drip water and modern calcite on the seasonal time scale in Yongxing Cave,central China

Stable isotope data of precipitation (δ¹⁸O_p and deuterium excess), drip water (δ¹⁸O_d), and modern calcite precipitates (δ¹⁸O_c and δ¹³C_c) from Yongxing Cave, central China, are presented, with monthly sampling intervals from June 2013 to September 2016. Moderate correlations between the monthly variation of δ¹⁸O_p values (from ??11.5 to ??0.7‰) and precipitation amount (r = ??0.59, n?=?34, p?<?0.01) and deuterium excess (r?=?0.39, n?=?31, p?<?0.01) imply a combined effect of changes in precipitation amount and atmospheric circulation. At five drip sites, the δ¹⁸O_d values have a much smaller variability (from ??9.1 to ??7.5‰), without seasonal signals, probably a consequence of the mixing in the karst reservoir with a deep aquifer. The mean δ¹⁸O_d value (??8.4‰) for all drip waters is significantly more negative than the mean δ¹⁸O_p value (??6.9‰) weighted by precipitation amount, but close to the wet season (May to September) mean value (??8.3‰), suggesting that a threshold of precipitation amount must be exceeded to provide recharge. Calculation based on the equilibrium fractionation factor indicates that the δ¹⁸O_c values are not in isotopic equilibrium with their corresponding drip waters, with a range of disequilibrium effects from 0.4 to 1.4‰. The δ¹⁸O_c and δ¹³C_c values generally increase progressively away from the locus of precipitation on glass plates. The disequilibrium effects in the cave are likely caused by progressive calcite precipitation and CO₂ degassing related to a high gradient of CO₂ concentration between drip waters and cave air. Our study provides an important reference to interpret δ¹⁸O_c records from the monsoon region of China.     

Stable isotope characteristics of precipitation of Pamba River basin,Kerala, India

Stable isotope composition of precipitation from Pamba River basin, Kerala, India, is evaluated to understand the role of spatial and temporal variations on rainwater isotope characteristics. Physiographically different locations in the basin showed strong spatial and temporal variations. δ ¹⁸O varied from ?7.63 to ?1.75 ‰ in the lowlands; from ?9.32 to ?1.94 ‰ in the midlands and from ?11.6 to ?4.00 ‰ in the highlands. Local Meteoric Water Lines (LMWL) for the three regions were determined separately and an overall LMWL for the whole of the basin was found to be δ ²H = 6.6 (±0.4) δ ¹⁸ O+10.4 (±2.0). Altitude effect was evident for the basin (0.1 ‰ for δ ¹⁸O and 0.8 ‰ for δ ²H per 100 m elevation), while the amount effect was weak. The precipitation formed from the marine moisture supplied at a steady rate, without much isotopic evolution in this period may have masked the possible depletion of heavier isotopes with increasing rainfall. Consistently high d-excess values showed the influence of recycled vapour, despite the prevailing high relative humidity. The oceanic and continental vapour source origins for the south-west and north-east monsoons were clearly noted in the precipitation in the basin. Rayleigh distillation model showed about 30% rainout of the monsoon vapour mass in the basin.     

Titanium- and water-rich metamorphic olivine in high-pressure serpentinites from the Voltri Massif (Ligurian Alps,Italy): evidence for deep subduction of high-field strength and fluid-mobile elements

Titanium- and water-rich metamorphic olivine (Fo 86–88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H₂O (up to 0.7 wt%) and TiO₂ contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H₂O (x ~ 0.1 in the formula 4Mg₂SiO₄·(1?x)Mg(OH,F)₂·xTiO₂) than Ti-clinohumite in the sample matrix (x = 0.34–0.46). In addition to TiO₂ and H₂O, secondary olivine contains significant Li (2–60 ppm), B (10–20 ppm), F (10–130 ppm) and Zr (0.9–2.1 ppm). It is enriched in ¹¹B (δ¹¹B = +17 to +23 ‰). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H₂O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.     

Accuracy assessment of near-shore bathymetry information retrieved from Landsat-8 imagery

The improvement in the capabilities of Landsat-8 imagery to retrieve bathymetric information in shallow coastal waters was examined. Landsat-8 images have an additional band named coastal/aerosol, Band 1: 435–451 nm in comparison with former generation of Landsat imagery. The selected Landsat-8 operational land image (OLI) was of Chabahar Bay, located in the southern part of Iran (acquired on February 22, 2014 in calm weather and relatively low turbidity). Accurate and high resolution bathymetric data from the study area, produced by field surveys using a single beam echo-sounder, were selected for calibrating the models and validating the results. Three methods, including traditional linear and ratio transform techniques, as well as a novel proposed integrated method, were used to determine depth values. All possible combinations of the three bands [coastal/aerosol (CB), blue (B), and green (G)] have been considered (11 options) using the traditional linear and ratio transform techniques, together with five model options for the integrated method. The accuracy of each model was assessed by comparing the determined bathymetric information with field measured values. The standard error of the estimates, correlation coefficients (R ² ) for both calibration and validation points, and root mean square errors (RMSE) were calculated for all cases. When compared with the ratio transform method, the method employing linear transformation with a combination of CB, B, and G bands yielded more accurate results (standard error = 1.712 m, R ² _calibration = 0.594, R ² _validation = 0.551, and RMSE =1.80 m). Adding the CB band to the ratio transform methodology also dramatically increased the accuracy of the estimated depths, whereas this increment was not statistically significant when using the linear transform methodology. The integrated transform method in form of Depth = b ₀  + b ₁ X _CB  + b ₂ X _B  + b ₅ ln(R _CB )/ln(R _G ) + b ₆ ln(R _B )/ln(R _G ) yielded the highest accuracy (standard error = 1.634 m, R ² _calibration = 0.634, R ² _validation = 0.595, and RMSE = 1.71 m), where R _i (i = CB, B, or G) refers to atmospherically corrected reflectance values in the i ^th band [X _i  = ln(R _i -R _{deep water})].     

Quantification of photosynthetic inorganic carbon utilisation via a bidirectional stable carbon isotope tracer

The amount of bicarbonate utilised by plants is usually ignored because of limited measurement methods. Accordingly, this study quantified the photosynthetic assimilation of inorganic carbon (CO₂ and HCO₃ ^?) by plants. The net photosynthetic CO₂ assimilation (P _N), the photosynthetic assimilation of CO₂ and bicarbonate (P _N’), the proportion of increased leaf area (f _LA) and the stable carbon isotope composition (δ¹³C) of Orychophragmus violaceus (Ov) and Brassica juncea (Bj) under three bicarbonate levels (5, 10 and 15 mm NaHCO₃) were examined to determine the relationship among P _N, P _N’ and f _LA. P _N’, not P _N, changed synchronously with f _LA. Moreover, the proportions of exogenous bicarbonate and total bicarbonate (including exogenous bicarbonate and dissolved CO₂-generated bicarbonate) utilised by Ov were 2.27 % and 5.28 % at 5 mm bicarbonate, 7.06 % and 13.28 % at 10 mm bicarbonate, and 8.55 % and 17.31 % at 15 mm bicarbonate, respectively. Meanwhile, the proportions of exogenous bicarbonate and total bicarbonate utilised by Bj were 1.77 % and 3.28 % at 5 mm bicarbonate, 2.11 % and 3.10 % at 10 mm bicarbonate, and 2.36 % and 3.09 % at 15 mm bicarbonate, respectively. Therefore, the dissolved CO₂-generated bicarbonate and exogenous bicarbonate are important sources of inorganic carbon for plants.     

Hydrochemical and isotopic investigation of a tropical wetland system in the Indian subcontinent

The study reported here is a part of an attempt to establish a comprehensive hydrochemical and isotopic baseline for a tropical wetland system as background data for a range of applications. Surface water samples of Vembanad Lake were collected from 20 stations in three seasons during the period 2007–2009. The analytical results were subjected to different chemical classification techniques to understand processes affecting the chemical concentration of waters. The Piper diagram classified the water samples as 100% alkali group in pre-monsoon followed by 15% in monsoon and 85% in post-monsoon, and for anions 100% samples were of strong acids followed by 90% in monsoon and 100% in post-monsoon season. The plot to decipher the mechanism controlling water chemistry placed the Vembanad Lake in the region of precipitation and rock dominance in the monsoon season and in the field of saline water dominance in pre-monsoon and post-monsoon season. The positive values for the chloro-alkaline indices in pre and post-monsoon season promoted cation exchange in the system. The stable isotopes of water samples ranged from ?20.21 to +17.0‰ and ?5.6 to +3.34‰ for δ ²H and δ ¹⁸O, respectively. The most depleted δ values observed in the monsoon are due to the amount effect. The high enrichment observed in pre-monsoon is primarily due to evaporation and salinity mixing. The variation of isotopes in the whole system point toward the fact that salinity mixing can be indicated by the δ ¹⁸O variation and δ ²H indicates the evaporation effect. The plot of δ ¹⁸O with chloride concentration showed precipitation dominance in the monsoon season, mixing of saline water and evaporation in pre-monsoon season, whereas the post-monsoon samples plot in both fresh and saline region.     

Modeling and mapping of solar radiation using geostatistical analysis methods in Iran

Because of economic and technical limitations, measuring solar energy received at ground level (R _s ) isn’t possible in all parts of the country, and in only 12% of synoptic stations is this parameter measured and recorded. Thus, it should be estimated and modeled spatially based on other climatic variables using mathematical methods. In this research, many attempts have been made to introduce an air temperature-based model for Rs estimation, and then, based on the output of the mentioned models, several geostatistical methods have been tested, and finally an elegant spatial model is proposed for (Rs) zoning in Iran. In this regard, the relationships between the measured amounts of monthly solar radiation and other climatic parameters, such as a monthly average, maximum and minimum temperature, precipitation, relative humidity, and the number of sunny hours during the period 1970–2010, are examined and modeled. It was revealed that based on the linear relationship between the monthly average air temperatures and solar radiation values recorded in each of the stations, that the best-fit linear model, with R ²  = 0.822, MAE = 1.81, RMSE = 2.51%, and MAPE = 10.08, can be introduced for Rs estimation. Then, using the outputs of the proposed model, the amounts of (R _s ) are estimated in another 171 meteorological stations (a total of 192 stations), and eight geostatistical methods (IDW, GPI, RBF, LPI, OK, SK, UK, and EBK) were investigated for zoning. Comparing the resulting variograms showed that in addition to proof of spatial correlation between solar radiation data, they can be applied for modeling changes in various directions. Analyzing the ratio of the nugget effect on the roof of the variograms showed that the Gaussian model with the lowest ratio (Co/Co + C = 0.883) and (R ²  = 0.972), could model the highest correlation between the data and, therefore, it was used for data interpolation. To select the best geostatistical model, R2, MAE, and RMSE were used. On this basis, it was found that the RBF method with R ²  = 0.904, MAE = 3.02, RMSE = 0.39% is the most effective. Also, the IDW method with R ²  = 0.90, MAE = 3.08, RMSE = 0.391%, compared to other methods is the most effective. In addition, for data validation, correlations between observed and estimated values of solar radiation were studied and found R ²  = 0.86.     

Thermal equation of state of natural tourmaline at high pressure and temperature

Synchrotron-based in situ angle-dispersive X-ray diffraction experiments were conducted on a natural uvite-dominated tourmaline sample by using an external-heating diamond anvil cell at simultaneously high pressures and temperatures up to 18 GPa and 723 K, respectively. The angle-dispersive X-ray diffraction data reveal no indication of a structural phase transition over the P–T range of the current experiment in this study. The pressure–volume–temperature data were fitted by the high-temperature Birch–Murnaghan equation of state. Isothermal bulk modulus of K ₀ = 96.6 (9) GPa, pressure derivative of the bulk modulus of \(K_{0}^{\prime } = 12.5 \;(4)\), thermal expansion coefficient of α ₀ = 4.39 (27) × 10^?5 K^?1 and temperature derivative of the bulk modulus (?K/?T) _P  = ?0.009 (6) GPa K^?1 were obtained. The axial thermoelastic properties were also obtained with K _a0 = 139 (2) GPa, \(K_{a0}^{\prime }\) = 11.5 (7) and α _a0 = 1.00 (11) × 10^?5 K^?1 for the a-axis, and K _c0 = 59 (1) GPa, \(K_{c0}^{\prime }\) = 11.4 (5) and α _c0 = 2.41 (24) × 10^?5 K^?1 for the c-axis. Both of axial compression and thermal expansion exhibit large anisotropic behavior. Thermoelastic parameters of tourmaline in this study were also compared with that of the other two ring silicates of beryl and cordierite.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Using Stable Isotopes to Assess the Contribution of Terrestrial and Riverine Organic Matter to Diets of Nearshore Marine Consumers in a Glacially Influenced Estuary

Terrestrial and marine ecosystems in Southeast Alaska are linked by the flow of freshwater from precipitation and glacial runoff, which transports nutrients and organic matter (OM) downstream to estuaries. We examined the contribution of terrestrial-riverine and marine OM to diets of fishes (N = 257, four species) and invertebrates (N = 90, six species) collected from glacially influenced estuaries in Southeast Alaska using multiple stable isotopes (δ¹³C, δ¹⁵N, and δ³⁴S). Multivariate analysis of similarity (ANOSIM) was used to quantify variation in stable isotope composition of consumers across 6 months and three sites with watersheds that differed in their glacier and forest composition. Fishes showed weak differences (ANOSIM R = 0.141) in stable isotope composition among sampling months, moderate differences (ANOSIM R = 0.375) among sites, and strong differences (ANOSIM R = 0.583) among species. Invertebrates showed moderate differences (ANOSIM R = 0.352) in stable isotope composition among sampling months and strong differences among sites (ANOSIM R = 0.710) and species (ANOSIM R = 0.858). We found the greatest differences in stable isotope composition between the two estuary sites with watersheds containing the highest and lowest glacial coverage, indicating that the contribution of allochthonous OM to consumer diets varies across watershed types. Invertebrates collected from the site with the lowest glacial coverage in the watershed were more depleted in δ¹³C and δ³⁴S, indicating higher use of terrestrial-riverine OM, than those at sites with higher watershed glacial coverage. High variation in stable isotope composition among species, months, and sites underscores the complexity of estuary food web responses to future glacier loss.     

Petrogenesis of peralkaline granite dykes of the Straumsvola complex,western Dronning Maud Land,Antarctica

Peralkaline syenite and granite dykes cut the Straumsvola nepheline syenite pluton in Western Dronning Maud Land, Antarctica. The average peralkalinity index (PI?=?molecular Al/[Na?+?K]) of the dykes is 1.20 (n?=?29) and manifests itself in the presence of the Zr silicates eudialyte, dalyite and vlasovite, and the Na–Ti silicate, narsarsukite. The dykes appear to have intruded during slow cooling of the nepheline syenite pluton, and the petrogenetic relationship of the dykes and the pluton cannot be related to closed-system processes at low pressure, given the thermal divide that exists between silica-undersaturated and oversaturated magmas. Major and trace element variations in the dykes are consistent with a combination of fractional crystallization of parental peralkaline magma of quartz trachyte composition, and internal mineral segregation prior to final solidification. The distribution of accessory minerals is consistent with late-stage crystallization of isolated melt pockets. The dykes give an Rb–Sr isochron age of 171?±?4.4 Ma, with variable initial ⁸⁷Sr/⁸⁶Sr ratio (0.7075?±?0.0032), and have an average ε _Nd of ? 12.0. Quartz phenocrysts have δ¹⁸O values of 8.4–9.2‰, which are generally in O-isotope equilibrium with bulk rock. Differences in the δ¹⁸O values of quartz and aegirine (average Δ_{quartz?aegirine} = 3.5‰) suggest aegirine formation temperatures around 500 °C, lower than expected for a felsic magma, but consistent with poikilitic aegirine that indicates subsolidus growth. The negative ε _Nd (< ? 10) and magma δ¹⁸O values averaging 8.6‰ (assuming Δ_quartz?magma = 0.6‰) are inconsistent with a magma produced by closed-system fractional crystallization of a mantle-derived magma. By contrast, the nepheline syenite magma had mantle-like δ¹⁸O values and much less negative ε _Nd (average ??3.1, n?=?3). The country rock has similar δ¹⁸O values to the granite dykes (average 8.0‰, n?=?108); this means that models for the petrogenesis of the granites by assimilation are unfeasible, unless an unexposed high-δ¹⁸O contaminant is invoked. Instead, it is proposed that the peralkaline syenite and granite dykes formed by partial melting of alkali-metasomatised gneiss that surrounds the nepheline syenite, followed by fractional crystallization.     

On the crystal chemistry and elastic behavior of a phlogopite 3<Emphasis Type="Italic">T</Emphasis>

The crystal chemistry and the elastic behavior under isothermal conditions up to 9 GPa of a natural, and extremely rare, 3T-phlogopite from Traversella (Valchiusella, Turin, Western Alps) [(K_0.99Na_0.05Ba_0.01)(Mg_2.60Al_0.20Fe _0.21 ²⁺ )[Si_2.71Al_1.29O₁₀](OH)₂, space group P3₁12, with a = 5.3167(4), c = 30.440(2) Å, and V = 745.16(9) ų] have been investigated by electron microprobe analysis in wavelength dispersion mode, single-crystal X-ray diffraction at 100 K, and in situ high-pressure synchrotron radiation powder diffraction (at room temperature) with a diamond anvil cell. The single-crystal refinement confirms the general structure features expected for trioctahedral micas, with the inter-layer site partially occupied by potassium and sodium, iron almost homogeneously distributed over the three independent octahedral sites, and the average bond distances of the two unique tetrahedra suggesting a disordered Si/Al-distribution (i.e., 〈T1-O〉 ~ 1.658 and 〈T2-O〉 ~ 1.656 Å). The location of the H-site confirms the orientation of the O–H vector nearly perpendicular to (0001). The refinement converged with R ₁(F) = 0.0382, 846 unique reflections with F _O > 4σ(F _O) and 61 refined parameters, and not significant residuals in the final difference-Fourier map of the electron density (+0.77/?0.37 e ^?/ų). The high-pressure experiments showed no phase transition within the pressure range investigated. The P–V data were fitted with a Murnaghan (M-EoS) and a third-order Birch-Murnaghan equation of state (BM-EoS), yielding: (1) M-EoS, V ₀ = 747.0(3) ų, K _T0 = 44.5(24) GPa, and K′ = 8.0(9); (2) BM-EoS, V ₀ = 747.0(3) ų, K _T0 = 42.8(29) GPa, and K′ = 9.9(17). A comparison between the elastic behavior in response to pressure observed in 1M- and 3T-phlogopite is made.     

Sulfate Reduction and Sulfur Cycles at Two Seagrass Beds Inhabited by Cold Affinity <Emphasis Type="Italic">Zostera marina</Emphasis> and Warm Affinity <Emphasis Type="Italic">Halophila nipponica</Emphasis> in Temperate Coastal Waters

To evaluate the impact of invading seagrass on biogeochemical processes associated with sulfur cycles, we investigated the geochemical properties and sulfate reduction rates (SRRs) in sediments inhabited by invasive warm affinity Halophila nipponica and indigenous cold affinity Zostera marina. A more positive relationship between SRR and below-ground biomass (BGB) was observed at the H. nipponica bed (SRR = 0.6809 × BGB ? 4.3162, r ² = 0.9878, p = 0.0006) than at the Z. marina bed (SRR = 0.3470 × BGB ? 4.0341, r ² = 0.7082, p = 0.0357). These results suggested that SR was more stimulated by the dissolved organic carbon (DOC) exuded from the roots of H. nipponica than by the DOC released from the roots of Z. marina. Despite the enhanced SR in spring-summer, the relatively lower proportion (average, 20%) of acid-volatile sulfur (AVS) in total reduced sulfur and the strong correlation between total oxalate-extractable Fe (Fe_(oxal)) and chromium-reducible sulfur (CRS = 0.2321 × total Fe_(oxal) + 1.8180, r ² = 0.3344, p = 0.0076) in the sediments suggested the rapid re-oxidation of sulfide and precipitation of sulfide with Fe. The turnover rate of the AVS at the H. nipponica bed (0.13 day^?1) was 2.5 times lower than that at the Z. marina bed (0.33 day^?1). Together with lower AVS turnover, the stronger correlation of SRR to BGB in the H. nipponica bed suggests that the extension of H. nipponica resulting from the warming of seawater might provoke more sulfide accumulation in coastal sediments.     

High-pressure displacive phase transition of a natural Mg-rich pigeonite

A high-pressure single-crystal X-ray diffraction study has been carried out on a P2₁/c natural Mg-rich pigeonite sample with composition ca. Wo₆En₇₆Fs₁₈ using a diamond anvil-cell. The unit-cell parameters were determined at 14 different pressures to 7.14 GPa. The sudden disappearance of the b-type reflections (h + k = odd) and a strong discontinuity (about 2.8%) in the unit-cell volume indicated a first-order P2₁/c–C2/c phase transition between 4.66 and 4.88 GPa. The P(V) data of the P2₁/c phase were fitted to 4.66 GPa by a third-order Birch–Murnaghan equation of state (BM3 EoS), whereas the limited number of experimental data collected within the C2/c phase between 4.88 and 7.14 GPa were fitted using the same equation of state but with K′ constrained to the value obtained for the P2₁/c fitting. The equation of state coefficients are V ₀ = 424.66(6) ų, K _T0 = 104(2) GPa and K′ = 8(1) for the P2₁/c phase, and V ₀ = 423.6(1) ų, K _T0 = 112.4(8) GPa, and K′ fixed to 8(1) for the C2/c phase. The axial moduli for a, b, and c for the P2₁/c phase were obtained using also a BM3-EoS, while for the C2/c phase only a linear calculation could be performed, and therefore the same approach was applied for comparison also to the P2₁/c phase. In general the C2/c phase exhibits axial compressibilities (β _c > β _a >> β _b) lower than those of the P2₁/c phase (β _b > β _c ≈ β _a; similar to those found in previous studies in clinopyroxenes and orthopyroxenes). The lower compressibility of the C2/c phase compared with that of the P2₁/c could be ascribed to the greater stiffness along the b direction. A previously published relationship between P _c and M2 average cation radius (i.r.) has been updated using all the literature data on P2₁/c clinopyroxene containing large cations at M2 site and our new data. The following weighted regression was obtained: P _c (GPa) = 26(4) ? 28(5) ×  i.r (Å), R ² = 0.97. This improved equation can be used to predict the critical pressure of natural P2₁/c clinopyroxene samples just knowing the composition at M2 site.     

Thermoelastic properties of chromium oxide Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> (eskolaite) at high pressures and temperatures

A new synchrotron X-ray diffraction study of chromium oxide Cr₂O₃ (eskolaite) with the corundum-type structure has been carried out in a Kawai-type multi-anvil apparatus to pressure of 15 GPa and temperatures of 1873 K. Fitting the Birch–Murnaghan equation of state (EoS) with the present data up to 15 GPa yielded: bulk modulus (K _0,T0), 206 ± 4 GPa; its pressure derivative K′_0,T , 4.4 ± 0.8; (?K _0,T /?T) = ?0.037 ± 0.006 GPa K^?1; a = 2.98 ± 0.14 × 10^?5 K^?1 and b = 0.47 ± 0.28 × 10^?8 K^?2, where α _0,T  = a + bT is the volumetric thermal expansion coefficient. The thermal expansion of Cr₂O₃ was additionally measured at the high-temperature powder diffraction experiment at ambient pressure and α _0,T0 was determined to be 2.95 × 10^?5 K^?1. The results indicate that coefficient of the thermal expansion calculated from the EoS appeared to be high-precision because it is consistent with the data obtained at 1 atm. However, our results contradict α ₀ value suggested by Rigby et al. (Brit Ceram Trans J 45:137–148, 1946) widely used in many physical and geological databases. Fitting the Mie–Grüneisen–Debye EoS with the present ambient and high-pressure data yielded the following parameters: K _0,T0 = 205 ± 3 GPa, K′_0,T  = 4.0, Grüneisen parameter (γ ₀) = 1.42 ± 0.80, q = 1.82 ± 0.56. The thermoelastic parameters indicate that Cr₂O₃ undergoes near isotropic compression at room and high temperatures up to 15 GPa. Cr₂O₃ is shown to be stable in this pressure range and adopts the corundum-type structure. Using obtained thermoelastic parameters, we calculated the reaction boundary of knorringite formation from enstatite and eskolaite. The Clapeyron slope (with \({\text{d}}P/{\text{d}}T = - 0.014\) GPa/K) was found to be consistent with experimental data.     

H-bonding scheme and cation partitioning in axinite: a single-crystal neutron diffraction and Mössbauer spectroscopic study

The crystal chemistry of a ferroaxinite from Colebrook Hill, Rosebery district, Tasmania, Australia, was investigated by electron microprobe analysis in wavelength-dispersive mode, inductively coupled plasma–atomic emission spectroscopy (ICP–AES), ⁵⁷Fe Mössbauer spectroscopy and single-crystal neutron diffraction at 293 K. The chemical formula obtained on the basis of the ICP–AES data is the following: \( ^{X1,X2} {\text{Ca}}_{4.03} \,^{Y} \left( {{\text{Mn}}_{0.42} {\text{Mg}}_{0.23} {\text{Fe}}^{2 + }_{1.39} } \right)_{\varSigma 2.04} \,^{Z1,Z2} \left( {{\text{Fe}}^{3 + }_{0.15} {\text{Al}}_{3.55} {\text{Ti}}_{0.12} } \right)_{\varSigma 3.82} \,^{T1,T2,T3,T4} \left( {{\text{Ti}}_{0.03} {\text{Si}}_{7.97} } \right)_{\varSigma 8} \,^{T5} {\text{B}}_{1.96} {\text{O}}_{30} \left( {\text{OH}} \right)_{2.18} \). The ⁵⁷Fe Mössbauer spectrum shows unambiguously the occurrence of Fe²⁺ and Fe³⁺ in octahedral coordination only, with Fe²⁺/Fe³⁺ = 9:1. The neutron structure refinement provides a structure model in general agreement with the previous experimental findings: the tetrahedral T1, T2, T3 and T4 sites are fully occupied by Si, whereas the T5 site is fully occupied by B, with no evidence of Si at the T5, or Al or Fe³⁺ at the T1–T5 sites. The structural and chemical data of this study suggest that the amount of B in ferroaxinite is that expected from the ideal stoichiometry: 2 a.p.f.u. (for 32 O). The atomic distribution among the X1, X2, Y, Z1 and Z2 sites obtained by neutron structure refinement is in good agreement with that based on the ICP–AES data. For the first time, an unambiguous localization of the H site is obtained, which forms a hydroxyl group with the oxygen atom at the O16 site as donor. The H-bonding scheme in axinite structure is now fully described: the O16–H distance (corrected for riding motion effect) is 0.991(1) Å and an asymmetric bifurcated bonding configuration occurs, with O5 and O13 as acceptors [i.e. with O16···O5 = 3.096(1) Å, H···O5 = 2.450(1) Å and O16–H···O5 = 123.9(1)°; O16···O13 = 2.777(1) Å, H···O13 = 1.914(1) Å and O16–H···O13 = 146.9(1)°].     

Toxinogenicity and cytotoxicity of <Emphasis Type="Italic">Alternaria,Aspergillus</Emphasis> and <Emphasis Type="Italic">Penicillium</Emphasis> moulds isolated from working environments

There is currently limited research available on the secondary metabolites of moulds in workplaces. The aim of this study was to determine the mould contamination in museums (N = 4), composting plants (N = 4) and tanneries (N = 4) and the secondary metabolite profiles of Alternaria, Aspergillus and Penicillium isolates from these workplaces. Alternaria, Aspergillus and Penicillium species were identified using the ITS1/2 sequence of the rDNA region. Mould metabolites were quantitatively analysed on standard laboratory medium and mineral medium containing materials specific to each workplace using liquid chromatography-mass spectrometry. We also examined the cytotoxicity of the moulds using MTT (3-(4,5-dimethylthiazolyl-2)-2,5-diphenyltetrazolium bromide) assays. Air microbiological contamination analyses showed a number of microorganisms, ranging from 2.4 × 10³ CFU m^?3 (composting plants) to 6.8 × 10⁴ CFU m^?3 (tanneries). We identified high percentages of Alternaria, Aspergillus and Penicillium moulds (air 57–59%, surfaces 10–65%) in all workplaces. The following moulds were the most cytotoxic (>90%): Alternaria alternata, A. limoniasperae, Aspergillus flavus, Penicillium biourgeianum, P. commune and P. spinulosum. The same mould species isolated from different working environments exhibited varying toxigenic and cytotoxic properties. Modifying the culture medium to simulate environmental conditions most often resulted in the inhibition of secondary metabolite production. Moulds isolated from the working environments produced the following mycotoxins (ng g^?1): chanoclavines (0.28–204), cyclopiazonic acid (27.1–1045), fumigaclavines (0.33–10,640,000), meleagrin (0.57–13,393), roquefortins (0.01–16,660), rugulovasines (112–220), viridicatin (0.12–957), viridicatol (4.23–2753) and quinocitrinines (0.07–1104), which may have a negative impact on human health.     

Coral reefs as a tool for monitoring environmental and radiation hazards

Analysis of coral reef species enables characterization of the coral reefs and the degree to which human activities influence the reef composition. Geochemical characteristics, X-ray diffraction, and natural radionuclides analyses of four common coral reef species representing the branching and massive forms were conducted at the three areas under threat (Quseir Harbor, Safaga Harbor, and El-Esh area) along the Red Sea coast. Branching recorded higher carbonates and lower organic matter than the massive forms. Stylophora pistillata at Safaga Harbor and El-Esh area and Acropora humilis at Qusier Harbor recorded the highest carbonate percentages (96.88, 96.24, and 96.89%, respectively) meanwhile Platygyra daedalea at Safaga Harbor recorded the highest organic matter contents (5.07 and 4.91%). The highest Ca contents were observed in S. pistillata and Porites solida (65.87 and 64.87%), the highest Mg was in Acropora humilis and P. daedalea (1.06 and 0.88%) at Qusier Harbor, whilst the highest Sr was in S. pistillata and P. daedalea at Safaga Harbor. Then highest value of ²²⁶Ra recorded in A. humilis and P. solida (71 ± 3.5 Bq/kg and 63 ± 3.1 Bq/k) and ²³²Th in S. pistillata at El-Esh area may attribute to petroleum exploration activities. A. humilis and P. daedalea at Safaga Harbor recorded significant high ⁴⁰K values (505 ± 30 and 472 ± 13 Bq/kg, respectively) relative to the other localities. The low Ca and High Sr as well as the highest averages of ²³²Th and ⁴⁰K at Safaga Harbor indicated that the coral reef communities were highly affected by the terrestrial inputs from phosphate shipments.