Separation of H<Subscript>2</Subscript>S from CH<Subscript>4</Subscript> by polymeric membranes at different H<Subscript>2</Subscript>S concentrations

In this work, permeation of mixed gases H₂S/CH₄ through commercial polyphenylene oxide (PPO) hollow fiber and poly (ester urethane) urea (PEUU) flat membranes was studied at pressures of 345–689 kPa, at ambient temperature and at 313.15 K. Various H₂S concentrations of about 100–5000 ppm in CH₄ binary synthetic gas mixtures as well as a real natural gas sample obtained from a gas refinery containing 0.3360 mol.% H₂S (equivalent to 3360 ppm) were tested. It was observed that the permeance of components was affected by the balance between competitive sorption and plasticization effects. Separation factors of H₂S/CH₄ were in the range of 1.3–2.9, 1.8–3.1 and 2.2–4.3 at pressures of 345, 517 and 689 kPa, respectively. In the range of 101–5008 ppm of H₂S in CH₄, the effect of temperature on the separation factor was nearly negligible; however, permeances of both components of the mixtures increased with temperature. Additionally, the results obtained by PEUU membrane indicated that it was a better choice for hydrogen sulfide separation from H₂S/CH₄ mixtures than PPO. For PPO membrane, removal of hydrogen sulfide from high-concentration (up to 5008 ppm) binary mixtures of H₂S/CH₄ was compared with that of low concentration (as low as 101 ppm) through PPO. At concentrations of 101–968 ppm, plasticization was dominant compared with the competitive sorption, while for the H₂S feed concentrations of 3048 ppm, the competitive sorption effect was dominant. For H₂S concentration of 5008 ppm, the balance between these two effects played an important role for explanation of its trend.     

Modeling chromium(VI) reduction by Escherichia coli 33456 using ceramic pearl as a supporting medium

A mathematical model was developed to describe the reduction of Cr(VI) by Escherichia coli (E. coli) 33456 in a fixed biofilm reactor. A laboratory-scale column reactor was conducted to verify the model system. The batch kinetic tests were independently conducted to determine the biokinetic parameters used in the model simulation. With the assumed values of initial biofilm thickness (L _f0), the mathematical model simulated well the experimental results for Cr(VI) effluent concentration, effluent concentration of suspended E. coli cells, and Cr(III) production. The concentration of suspended E. coli cells reached up to 1.2 mg cell/L while the thickness of attached E. coli cells was estimated to be 32.6 μm at a steady-state condition. At the steady state, the removal efficiency of Cr(VI) was about 92 % and the effluent concentration of Cr(III) was approximately 1.6 mg/L. The approaches presented in this study can be employed for the design of a pilot-scale or full-scale fixed biofilm reactor to treat Cr(VI)-containing wastewater.     

A novel continuous magnetic nano-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/perlite fixed bed reactor for catalytic wet peroxide oxidation of dyes: reactor structure

In the present work, a continuous catalytic wet peroxide oxidation fixed bed reactor was employed to treat a simulated wastewater sample with malachite green dye, as a contaminant. Natural perlite particle-supported nano-Fe₃O₄ catalyst was used as a fixed bed inside a reactor, and it was immobilized by a persistent magnetic field. The range of (perlite) particle sizes was from 100 to 1000 nm. The effects of various operating parameters, including temperature of the reactor, pH, initial hydrogen peroxide concentration and initial dye concentration, were investigated on the percentage removal of malachite green dye. Load of catalyst of 2 g and volumetric flow rate of 1 L/h were selected for all the tests. Maximum malachite green degradation was 99.5 ± 0.3%. This removal percentage was attained at temperature of 80 °C, pH = 6, initial dye concentration of 6 mg/L and initial hydrogen peroxide concentration of 100 mg/L. The process was isotherm, and the catalyst showed high catalytic activity in the steady-state condition. The loss of catalyst was less than 0.3%.     

Correlation between geological units and mineralized zones using fractal modeling in Zarshuran gold deposit (NW Iran)

In this study, the relation between ore grade and geological characteristic has been studied as a principle and also important conceptual in Zarshuran gold deposit in NW Iran. The main subject in this study was identifying a correlation among the ore grade populations and rock types which could be used in other steps of local estimation in the deposit concentration–number (C–N) fractal model and logratio matrix. The C–N log–log plot reveals six geochemical zones defined by Au?<?0.02 ppm as non-mineralized zone and Au?>?0.02 ppm as mineralized zones. According to geological logging and field geology inspection, black gauge, jasperoid, fault gauge and breccia, and carbonaceous rocks are considered as main rock types which contain major Au mineralized zones. The correlation between geological and fractal modeling by logratio matrix shows that there is a good correlation between geological assumed host rocks and C–N fractal modeling. Black gauge rock type with 93.48 % of overall accuracy shows a significant correlation with supergene zone of fractal model, and jasperoid with 92.5 % and carbonaceous rock type with 52.90 % have a decent correlation with highly and lowly mineralized zone of fractal model relatively. Black gauge, jasperoid, and fault gauge and breccia have an approximately near cooperation in this zone for mineralization.     

Ameliorating nitrite inhibition in a low-temperature nitritation–anammox MBBR using bacterial intermediate nitric oxide

The long-term sustainability of an anaerobic ammonium oxidation (anammox) process in a moving bed biofilm reactor (MBBR) treating highly concentrated (mean of 740 mg NH₄ ⁺-N L^?1) wastewater was demonstrated by 1600 days of efficient operation. A high maximum total nitrogen removal rate (TNRR) of 1.5 g N m^?2 d^?1 was achieved at the low temperature of 20 °C. For nitrogen removal recovery in cases of nitrite inhibition, anammox intermediate nitric oxide (NO) was tested in batch experiments as an N-removal accelerating agent. The effect of the addition of various NO dosages (8–72 mg NO-N L^?1) was studied under inhibitory nitrite concentrations (>100 mg NO₂ ^?-N L^?1) for anammox bacteria. Optimal maintained NO concentration was 58 mg NO-N L^?1 and brought about the highest biofilm-specific anammox activity (SAA). Compared to a blank test, the minimum concentration of added NO of 40 mg NO-N L^?1 showed a statistically significant (p < 0.05) accelerating effect on SAA. No inhibition of SAA by NO was observed, although at NO concentrations exceeding 72 mg NO-N L^?1, the acceleratory effect upon SAA was decreased by 8%. Changes in the bacterial consortia involved in nitrogen conversion were determined concurrently for the different nitrogen removal rates and operational conditions. Quantities of Planctomycetales clone P4 strains, which are the closest (99% similarity) relative to Candidatus Brocadia fulgida, increased from 1 × 10³ to 1 × 10⁶ anammox gene copies per g total suspended solids during reactor operation days 568–1600, which was determined by quantitative polymerase chain reaction. During the operation of the MBBR, the abundance of ammonium-oxidizing bacteria (AOB) increased proportionally (up to 30%). The abundance of nitrite-oxidizing bacteria (NOB) did not increase (remaining below 10%) during days 232–860. AOB became predominant over NOBs owing to the inhibition of free ammonia spiking on NOBs.     

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.     

Experimental constraints on hydrogen diffusion in garnet

The incorporation mechanisms and diffusional loss of hydrogen in garnet have been experimentally investigated. A suite of gem-quality hydrous spessartine- and grossular-rich garnets were analysed by Fourier transform infrared spectroscopy (FTIR) and by ion microprobe (SHRIMP-SI) to determine the calibration coefficients for quantification of FTIR data. The excellent agreement between measured absorption and OH/O indicates that the same molar extinction coefficient can be used for spessartine and grossular. The coefficient of 14400 l mol^??1 cm^??2 proposed by Maldener et al. (Phys Chem Miner 30:337–344, 2003) seems the most appropriate for both minerals. A grossular with 6.4% andradite and 1.6% almandine containing 834 ppm H₂O, and an almost pure spessartine with 282 ppm H₂O, were selected for diffusion experiments. 1.5-mm cubes of garnets were heated between 12 h and 10 days at 1 atm under various temperature (750–1050 °C) and oxygen fugacity (\({f_{{{\text{O}}_2}}}\)) conditions, (ΔQFM +?15.2 to ??3.0). Diffusion profiles were acquired from sections through the cubes using FTIR, with a deconvolution algorithm developed to assess peak-specific behaviour. Different families of peaks have been identified based on their diffusive behaviour, representing hydrogen incorporated in different H-bearing defects. A dominant, fast, strongly \({f_{{{\text{O}}_2}}}\)-dependent oxidation-related diffusion mechanism is proposed \(\left( {\{ {{\text{M}}^{2+}}+{{\text{H}}^+}\} +\frac{1}{4}{{\text{O}}_2}={{\text{M}}^{3+}}+\frac{1}{2}{{\text{H}}_2}{\text{O}}} \right)\) (M=Fe, Mn) with a relatively low activation energy (158?±?19 kJ mol^??1). This diffusion mechanism is likely restricted by availability of ferrous iron in grossular. At low oxygen fugacity, this diffusion mechanism is shut off and the diffusivity decreased by more than three orders of magnitude. A second, slower hydrogen diffusion mechanism has been observed in minor bands, where charge balance might be maintained by diffusion of cation vacancies, with much higher activation energy (≈?200–270 kJ mol^??1). Spessartine shows clear differences in peak retentivity suggesting that up to four different H sites might exist. This opens exciting opportunities to use hydrogen diffusion in garnet as speedometer. However, it is essential to constrain the main diffusion mechanisms and the oxygen fugacity in the rocks investigated to obtain timescales for metamorphic or igneous processes.     

Development of a CO2 emission factor in Korea from sub-bituminous coal by the classification method

While the Intergovernmental Panel on Climate Change classifies coal as anthracite, bituminous coal, and sub-bituminous coal, Korea only distinguishes coal as anthracite and bituminous coal while sub-bituminous coal is considered bituminous coal. As a result, Korea conducted research in the CO₂ emission factors of anthracite and bituminous coal, but largely ignored sub-bituminous coal. Therefore, the purpose of this research is to develop the CO₂ emission factor of sub-bituminous coal by classifying sub-bituminous coal from resources of bituminous coal activities collected in Korea between 2007 and 2011. The 2007–2011 average carbon content of sub-bituminous coal was analyzed to be 69.63 ± 3.11 %, the average hydrogen content 4.97 ± 0.37 %, the inherent moisture 12.60 ± 4.33 %, the total moisture 21.91 ± 5.45 %, and the dry-based gross calorific value was analyzed to be 5,914 ± 391 kcal/kg; using these analyzed values, the as-received net calorific value was found to be 20.75 ± 7.59 TJ/Gg and the CO₂ emission factor was found to be 96,241 ± 4,064 kg/TJ. In addition, the 62.7 million ton amount for the 2009 greenhouse gas emission from sub-bituminous coal as estimated with the analyzed value of this study is an amount that is equivalent to 11.1 % of the 2009 total greenhouse gas emission amount of 564.7 million tons, and this amount is larger than the 9.3 % for the industrial processes sector, 3.3 % for the agricultural sector and 2.5 % for the waste sector. Therefore, it is important to reflect the realities of Korea when estimating the greenhouse gas emission from such sub-bituminous coals.     

Formation of Water-Bearing Defects in Olivine in the Presence of Water–Hydrocarbon Fluid at 6.3 GPa and 1200°C

The main trends of water dissolution in Fe-bearing olivine have been investigated in the olivine–H₂O–hydrocarbon fluid system in experiments at a pressure of 6.3 GPa, a temperature of 1200°C, and hydrogen fugacity ( fH₂) buffered by the Mo–MoO₂ equilibrium. The content and contribution of ОH defects of different types in Fe-bearing olivines depend on the composition of reduced fluids in the system. As the fraction of hydrocarbons in the fluid increases, the H₂O content in olivine crystals decreases from 900 to 160–180 ppm, while the ОН absorption peaks become lower at high frequencies and occupy a larger part of the infrared spectrum in the low-frequency region. According to the experimental results, even the deepest seated mantle olivines with OH defects were not equilibrated with a fluid rich in light alkanes or oxygenated hydrocarbons.     

Carbon dioxide in Postojna Cave (Slovenia): spatial distribution,seasonal dynamics and evaluation of plausible sources and sinks

The CO₂ concentration of the air in Postojna Cave (400–7900 ppm) is found to be induced by CO₂ sources (human respiration contributing?~?20,000–58,000 ppm per breath, outgassing of dripwater and water seeping from the vadose zone/epikarst with a pCO₂ values of 5000–29,000 ppm, and underground Pivka River having pCO₂ at 2344–4266 ppm) and CO₂ dilution (inflow of outside air with a CO₂ concentration of?~?400 ppm). Measurements show that sinking Pivka River has the lowest CO₂ concentration among plausible CO₂ sources but still continuously exceeds the surrounding cave air CO₂ concentration. During the winter months, intensive ventilation reduces the cave air CO₂ concentration to outside levels (~?400 ppm), even in the centre of the cave system. CO₂ dilution is less pronounced in summer (CO_2(min)?≈?800 ppm), since the ventilation rate is not as strong as in winter and the outside air that enters the cave through breathing holes and fractures is enriched with soil CO₂. During spring and autumn, the daily alternation of the ventilation regime with a smaller rate of air exchange results in yearly cave air CO₂ peaks of up to?~?2400 ppm. Some dead-end passages can be much less affected by ventilation, resulting in a cave air CO₂ concentration of up to 7900 ppm. The strongest diurnal CO₂ peaks due to human respiration were recorded during the spring holidays (increase of up to 1300 ppm day^?1), compared to considerably smaller summer peaks despite peak visits (increase of?~?600 ppm day^?1).     

Estimation of Cd,Pb and flame retardants in electric mosquito bat using EDXRF,ICP-OES,AAS and GC–MS

In the present study, investigated the concentrations of hazardous substances such as Pb, Cd and polybrominated flame retardants present in an electric mosquito bats, which are used for trapping the mosquitoes in the domestic areas. China has captured a big share of mosquito bat market in India and penetrated deep into rural areas also. The presence of hazardous substances is fatal to environment and human beings. Hence, the concentrations of hazardous substances present in the bats need to be estimated accurately. The dismantled homogeneous samples were subjected to estimate the toxic metals like cadmium and lead by using energy-dispersive X-ray fluorescence spectroscopy, inductively coupled plasma optical emission spectroscopy and atomic absorption spectroscopy for comparison. The flame brominated retardants were tested using gas chromatography–mass spectrometer. The analytical data obtained from the power supply wires of the bat suggest that the concentration levels of cadmium found to be below the detection limits. Whereas the lead content has higher in the range of 3574–7575 ppm than the permissible limits set by the e-waste rule, i.e. 1000 ppm. Moreover, the high amount of lead (>80,000 ppm) was obtained in the printed circuit board apart from power supply wires of mosquito bat. The content of brominated flame retardants in mosquito bat was estimated to be within the limits of e-waste rule. Considering their significant high hazardous metals content, coupled with their large quantities of mosquito bats used in the country, there is a need to control the hazardous waste of mosquito bats.     

Diffusion and solubility of hydrogen and water in periclase

Cylinders of synthetic periclase single crystals were annealed at 0.15–0.5 GPa and 900–1200 °C under water-saturated conditions for 45 min to 72 h. Infrared spectra measured on the quenched products show bands at 3,297 and 3,312 cm^?1 indicating V _OH ^? centers (OH-defect stretching vibrations in a half-compensated cation vacancy) in the MgO structure as a result of proton diffusion into the crystal. For completely equilibrated specimens, the OH-defect concentration, expressed as H₂O equivalent, was calculated to 3.5 wt ppm H₂O at 1,200 °C and 0.5 GPa based on the calibration method of Libowitzky and Rossmann (Am Min 82:1111–1115, 1997). This value was confirmed via Raman spectroscopy, which shows OH-defect-related bands at identical wavenumbers and yields an H₂O equivalent concentration of about 9 wt ppm using the quantification scheme of Thomas et al. (Am Min 93:1550–1557, 2008), revised by Mrosko et al. (Am Mineral 96:1748–1759, 2011). Results of both independent methods give an overall OH-defect concentration range of 3.5–9 (+4.5/?2.6) ppm H₂O. Proton diffusion follows an Arrhenius law with an activation energy E _a = 280 ± 64 kJ mol^?1 and the logarithm of the pre-exponential factor logD_o (m² s^?1) = ?2.4 ± 1.9. IR spectra taken close to the rims of MgO crystals that were exposed to water-saturated conditions at 1,200 °C and 0.5 GPa for 24 h show an additional band at 3,697 cm^?1, which is related to brucite precipitates. This may be explained by diffusion of molecular water into the periclase, and its reaction with the host crystal during quenching. Diffusion of molecular water may be described by logD_H2O (m² s^?1) = ?14.1 ± 0.4 (2σ) at 1,200 °C and 0.5 GPa, which is ~ 2 orders of magnitude slower than proton diffusion at identical P-T conditions.     

Galena Non-oxidative Dissolution Kinetics in Seawater

The rate of non-oxidative galena dissolution in seawater compositions over the pH range of 2–4.5 was determined from batch reactor experiments. The derivative at zero time of a polynomial fit of the Pb concentration versus time data for the first 30 min was used to determine the rate. A plot of R_Gn (rate of galena dissolution) versus pH for data from six experiments is linear (R²?=?0.96), with a slope of 0.5. The rate equation describing the rate of galena dissolution as a function of hydrogen ion activity is

$$R_{\text{Gn}} = - \,10^{ - 10.72} \left( {a_{{{\text{H}}^{ + } }} } \right)^{0.50}$$

Varying the concentration of dissolved oxygen produced no significant effect on the measured rates. The activation energy, based on four experiments carried out over the temperature range of 7–30 °C, is 61.1 kJ/mol.

     

Spectrophotometric determination of hydrogen sulfide in environmental samples using sodium 1,2-naphthoquinone-4-sulfonate and response surface methodology

A simple spectrophotometric method for determination of hydrogen sulfide in wastewater and hot spring samples was developed. The method is based on the reaction between hydrogen sulfide and sodium 1,2-naphthoquinone-4-sulfonate (NQS). The effect of various experimental factors on the reaction between hydrogen sulfide and NQS was investigated and optimized using central composite design. The optimal values of the factors were 5.00 × 10^?4 mol L^?1 for concentration of NQS and 1.00 × 10^?2 mol L^?1 for concentration of hydrochloric acid. The wavelength of the maximum absorption of the reaction product was 320 nm. Constructed calibration curve for hydrogen sulfide determination was linear in the range of 0.5–20.0 mg L^?1 with the detection limit of 0.16 mg L^?1. The method was free from interferences. Percent relative errors below 2 % were obtained for determination of hydrogen sulfide in environmental samples.     

Simultaneous electrokinetic removal of polycyclic aromatic hydrocarbons and metals from a sediment using mixed enhancing agents

The maintenance of harbor waterways generates large amounts of dredged sediments which are often rich in coexisting organic and inorganic contaminants. Electrokinetic remediation treatments have recently been developed for the simultaneous removal of heavy metals and polycyclic aromatic hydrocarbons (PAHs), using various enhancing agents generally tested sequentially. In this study, different processing fluids were tested, alone or mixed, to improve the decontamination of aged model sediment contaminated with cadmium, lead, chromium, copper, zinc, and five PAHs. Nitric acid (NA) and citric acid (CA) were tested to avoid the formation of an alkaline front into the sediment and favor the metals removal, while an anionic surfactant [sodium dodecyl sulfate (SDS)] and a nonionic surfactant (Tween 20) were tested to solubilize and mobilize PAHs. Processing fluids were circulated under a constant voltage gradient of 1 V cm^?1 for 10–14 days. NA showed an excellent potential to remove metals (76.8–99.9 % removal) and PAHs (70.3–89.7 % removal) in a single run. Besides, the mixture of Tween 20 and CA, more environmental friendly, could be considered as a relatively good processing fluid for the simultaneous removal of metals (10.3–90.8 % removal) and PAHs (53.6–61.6 % removal) from the fine-grained sediment, while SDS mixed to CA was not a good candidate for this purpose (0.1–65 % removal for metals and 34.1–41.0 % removal for PAHs).     

Hypersaline fluids generated by high-grade metamorphism of evaporites: fluid inclusion study of uranium occurrences in the Western Zambian Copperbelt

In the Pan-African Lufilian belt (Western Zambian Copperbelt), uranium mineralizations, preferentially scattered in kyanite ± talc micaschists (metamorphosed evaporitic sediments) or concentrated along transposed quartz veins provide an opportunity to (1) understand the time/space relationship between the ore minerals and the deformation of the host rocks, (2) identify the different fluid events associated with specific stages of quartz deformation and (3) characterize the ore fluid geochemistry in terms of fluid origin and fluid/rock interactions. In the U occurrences studied in Lolwa and Mitukuluku (Domes region, Western Zambian Copperbelt), two mineralizing stages are described. The first generation of ore fluids (53–59 wt% CaCl₂, 13–15 wt% NaCl; N₂–H₂ in the gas phase of fluid inclusions) circulated during the high-temperature quartz recrystallization, at 500–700 °C. This temperature is in agreement with the P–T conditions recorded during the crustal thickening related to continental collision at ca. 530 Ma. LA-ICPMS analyses show the presence of uranium within this fluid, with a concentration mode around 20 ppm. The second generation of ore fluid (21–32 wt% NaCl, 19–21 wt% CaCl₂; CO₂–CO in the gas phase of fluid inclusions) percolated at lower temperature conditions, at the brittle–ductile transition, between 200 and 300 °C. This temperature could be related to the exhumation of the high-grade metamorphic rocks at ca. 500 Ma. The formation of H₂ and CO is interpreted as the result of radiolysis in the presence of dissolved uranium in the aqueous phase of these fluid inclusions. Finally, a late fluid (14–16 wt% NaCl_equiv) circulated in the brittle domain but seems unrelated to U (re-)mobilization event.     

Gasification of sugarcane bagasse in supercritical water media for combined hydrogen and power production: a novel approach

A novel process based on supercritical water gasification has been used in this study for co-production of hydrogen and power from sugarcane bagasse as one of the main agricultural wastes of Iran. The cycle of the process was designed first, and then, the thermodynamic equilibrium model of the gasification process was simulated using ASPEN PLUS. The effects of temperature and feed concentration on molar fraction of main components of produced gas were investigated. The temperature was directly correlated with hydrogen production in which hydrogen and carbon monoxide production was favored at higher temperatures. The maximum hydrogen production occurred in the sugarcane bagasse concentrations about 20–30 wt%. Palladium membrane as a metallic dense membrane was used for separation of high-purity hydrogen. Hydrogen production of 8.55 kg/h and electrical power generation of 56 kW were obtained for the 20 wt% mixture of bagasse with a mass flow rate of 1000 kg/h, reactor pressure of 300 bars and temperature of 700 °C.     

Experimental reactions between olivine and orthopyroxene with phonolite melt: implications for the origins of hydrous amphibole + phlogopite + diopside bearing metasomatic veins

Amphibole + phlogopite + diopside bearing veins are observed in a large number of upper mantle xenoliths, but the composition of the melt that forms them is poorly constrained. Recent data from the Heldburg Phonolite, Central Germany, has shown that phonolite melt will react with olivine and orthopyroxene xenocrysts to form reaction rims of amphibole + phlogopite + diopside at mid-lower crustal pressures. This is the first example of where a melt has reacted with peridotite to form the mineralogy of the metasomatic veins. It is therefore necessary to explore whether a phonolite melt could be the parent melt that forms amphibole + phlogopite + diopside metasomatic veins. Experimental reactions between single crystals of olivine and orthopyroxene with phonolite melt were conducted at upper mantle conditions of 1.0–1.5 GPa and 900–1,000 °C. Melt water contents were varied from anhydrous to >12 wt. H₂O. Olivine reacts to form phlogopite reaction rims with overgrowths of diopside <1,000 °C or rims of secondary olivine >1,000 °C. Orthopyroxene reacts to form amphibole with epitaxial diopside overgrowths <1,000 °C. No reaction rims form when the bulk melt H₂O is lower than ~3.8 wt%. Pressure has little effect over the small range tested. These experiments reproduce reaction rims on olivine and orthopyroxene observed in the Heldburg Phonolite, Central Germany, and suggest that a relatively narrow range of temperatures and melt water contents is required for rim formation. The compositions of rim amphibole, phlogopite and diopside from the experiments have very similar compositions to those from Heldburg but do not match those from metasomatic veins. Phenocrysts from Heldburg are similar to the metasomatic veins, suggesting that a phonolite could potentially form the veins if vein formation is dominated by crystallization rather than reaction and replacement of wall rock phases.     

TBM Tunnelling in Hydrogen Sulfide Gas Bearing Ground and its Solutions

In the late December of 2006 while Zagros tunnel project in western Iran was advancing according to the schedule, a sudden rush of groundwater accompanied by a nauseating odor similar to that of rotten egg intruded the tunnel. Some workers complained from eye and respiratory tract irritation. The presence of hydrogen sulfide (H₂S) gas as high as 200 ppm was soon tested positive by gas detectors and subsequently the ventilation fans (2*110 kW) speed were boosted to 1,450 rpm in order to dilute the gas concentration to safe levels (10 ppm). Nonetheless, the work continued at a rather moderate pace for another 11 days and 134 more meters excavated in the gas infested grounds before 4 men died during a damage assessment survey of the TBM after a power failure that had forced the tunnel ventilation system to temporarily shut down. This paper is to discuss hazards and geological sources of H₂S gas in of Zagros Water Conveyance Tunnel and to recommend practical solutions to prevent or mitigate the gas destructive effects on human and machinery, as well.     

Hydrogen content in clinopyroxene phenocrysts from Salina mafic lavas (Aeolian arc,Italy)

Clinopyroxene phenocrysts from the mafic calc-alkaline lavas of Salina (Aeolian arc, southern Tyrrhenian Sea, Italy) have been analysed to determine the hydrogen content and iron oxidation state of this early crystallized phase. The volcanic activity of Salina, starting at 168 ka and developed in several centres up to 24 ka, was dominated by calc-alkaline and high-K calc-alkaline basalts and andesites, with minor dacites and rhyolites. The presence of OH vibrational bands was detected in the IR spectra of clinopyroxenes phenocrysts from Corvo, Rivi-Capo (168–87 ka), Fossa delle Felci (108–59 ka) and Monte dei Porri (57 ka) eruptions. Corvo-Rivi-Capo basalts have clinopyroxenes with the lowest water contents 75–97 ppm H₂O by weight, whereas an increase in the hydrogen contents of clinopyroxenes from Fossa delle Felci centre, with 171–286 ppm H₂O by weight, and Monte dei Porri with 343–390 ppm H₂O by weight, was observed. Mössbauer spectroscopy showed only a limited variation on the Fe³⁺/Fe_tot ratio of the studied samples, and a very similar atomic Fe³⁺ content (0.042–0.047 a.p.f.u.) suggesting that only minor variation on fO₂ occurred during the crystallization of these clinopyroxenes. The water content of parental melts, calculated by applying an ^IVAl-dependent partition coefficient to the measured hydrogen contents of clinopyroxenes, is 0.4–0.8 wt% of water in melt for the Rivi-Capo-Corvo basalts, 0.5–3.7 wt% water in melt for Fossa delle Felci lavas and 1.6–2.6 wt% of water in melt for Monte dei Porri lavas. An increase in the maximum hydrogen contents of clinopyroxenes can be recognized during the evolution of the Salina volcano, with the highest hydrogen content measured in clinopyroxenes from Monte dei Porri where the eruptions were characterized by a high degree of explosivity, suggesting a key role of volatiles.