Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: synthesis of a dithiane triterpenoid

In order to confirm the tentative structure of a dithiane sulfide with a bicyclic squalene hydrocarbon skeleton representing the predominant alkyl sulfide in Shell Beach samples from the Monterey Formation (Miocene, CA) and also occurring in various immature sulphur-rich sediments [Schouten, S., Sinninghe Damsté, J.S., de Leeuw, J.W., 1995. A novel triterpenoid carbon skeleton in immature sulphur-rich sediments. Geochimica et Cosmochimica Acta 59, 953–958], synthesis of a reference compound bearing two thiochromane moieties has been carried out. The product was obtained as a diastereomeric mixture appearing in the form of five peaks (partly) resolved in gas chromatography (GC). This is in sharp contrast with the geochemical compound, which appears as a single broad peak in GC. Co-elution experiments showed that none of the peaks from the synthetic mixture coelute in GC with that of the geochemical sulfide. Furthermore, the different synthetic isomers have identical mass spectra, which are clearly distinct from that of the naturally-occurring compound. The results unambiguously indicate that the natural compound is not the dithiane triterpenoid originally envisaged. Instead, we propose that the compound has a structure of a bicyclic squalene derivative bearing two “S-spiro”-type moieties as is the case for other sulfides related to regular polycyclic polyprenoids and hopanoids in Monterey sediments.     

Simulation analysis of domestic water demand and its future uncertainty in water scarce areas

This paper demonstrates a practical simulation approach to analyze domestic water demand and its future uncertainty in water scarce areas through a case study of Beijing, China. Analytic models and a forecasting model were constructed using statistic and econometric regression approaches. The analytic models were used to analyze the interrelationships between domestic water demand and some socio-economic factors of Beijing. The forecasting model was applied to predict domestic water demand from 2009 to 2015, and this model was validated by comparing the prediction values with the observations. Scenario analysis was applied to simulate uncertainty and risks in domestic water demand in the future. The simulation results proved that domestic water demand will increase from 13.9×10⁸ m³ to 16.7×10⁸ m³ from 2009 to 2015. Three more sustainable strategies were also found through scenario analysis. The simulation and modeling approaches and results would be very supportive for water decision makers in allocating water efficiently and making sustainable water strategies.     

Groundwater flow dynamics in the complex aquifer system of Gidabo River Basin (Ethiopian Rift): a multi-proxy approach

Hydrochemical and isotope data in conjunction with hydraulic head and spring discharge observations were used to characterize the regional groundwater flow dynamics and the role of the tectonic setting in the Gidabo River Basin, Ethiopian Rift. Both groundwater levels and hydrochemical and isotopic data indicate groundwater flow from the major recharge area in the highland and escarpment into deep rift floor aquifers, suggesting a deep regional flow system can be distinguished from the shallow local aquifers. The δ¹⁸O and δ²H values of deep thermal (≥30 °C) groundwater are depleted relative to the shallow (<60 m below ground level) groundwater in the rift floor. Based on the δ¹⁸O values, the thermal groundwater is found to be recharged in the highland around 2,600 m a.s.l. and on average mixed with a proportion of 30 % shallow groundwater. While most groundwater samples display diluted solutions, δ¹³C data of dissolved inorganic carbon reveal that locally the thermal groundwater near fault zones is loaded with mantle CO₂, which enhances silicate weathering and leads to anomalously high total dissolved solids (2,000–2,320 mg/l) and fluoride concentrations (6–15 mg/l) exceeding the recommended guideline value. The faults are generally found to act as complex conduit leaky barrier systems favoring vertical mixing processes. Normal faults dipping to the west appear to facilitate movement of groundwater into deeper aquifers and towards the rift floor, whereas those dipping to the east tend to act as leaky barriers perpendicular to the fault but enable preferential flow parallel to the fault plane.     

Genesis of sediment-hosted stratiform copper–cobalt mineralization at Luiswishi and Kamoto, Katanga Copperbelt (Democratic Republic of Congo)

The sediment-hosted stratiform Cu–Co mineralization of the Luiswishi and Kamoto deposits in the Katangan Copperbelt is hosted by the Neoproterozoic Mines Subgroup. Two main hypogene Cu–Co sulfide mineralization stages and associated gangue minerals (dolomite and quartz) are distinguished. The first is an early diagenetic, typical stratiform mineralization with fine-grained minerals, whereas the second is a multistage syn-orogenic stratiform to stratabound mineralization with coarse-grained minerals. For both stages, the main hypogene Cu–Co sulfide minerals are chalcopyrite, bornite, carrollite, and chalcocite. These minerals are in many places replaced by supergene sulfides (e.g., digenite and covellite), especially near the surface, and are completely oxidized in the weathered superficial zone and in surface outcrops, with malachite, heterogenite, chrysocolla, and azurite as the main oxidation products. The hypogene sulfides of the first Cu–Co stage display δ³⁴S values (−10.3‰ to +3.1‰ Vienna Canyon Diablo Troilite (V-CDT)), which partly overlap with the δ³⁴S signature of framboidal pyrites (−28.7‰ to 4.2‰ V-CDT) and have ∆³⁴S_SO4-Sulfides in the range of 14.4‰ to 27.8‰. This fractionation is consistent with bacterial sulfate reduction (BSR). The hypogene sulfides of the second Cu–Co stage display δ³⁴S signatures that are either similar (−13.1‰ to +5.2‰ V-CDT) to the δ³⁴S values of the sulfides of the first Cu–Co stage or comparable (+18.6‰ to +21.0‰ V-CDT) to the δ³⁴S of Neoproterozoic seawater. This indicates that the sulfides of the second stage obtained their sulfur by both remobilization from early diagenetic sulfides and from thermochemical sulfate reduction (TSR). The carbon (−9.9‰ to −1.4‰ Vienna Pee Dee Belemnite (V-PDB)) and oxygen (−14.3‰ to −7.7‰ V-PDB) isotope signatures of dolomites associated with the first Cu–Co stage are in agreement with the interpretation that these dolomites are by-products of BSR. The carbon (−8.6‰ to +0.3‰ V-PDB) and oxygen (−24.0‰ to −10.3‰ V-PDB) isotope signatures of dolomites associated with the second Cu–Co stage are mostly similar to the δ¹³C (−7.1‰ to +1.3‰ V-PDB) and δ¹⁸O (−14.5‰ to −7.2‰ V-PDB) of the host rock and of the dolomites of the first Cu–Co stage. This indicates that the dolomites of the second Cu–Co stage precipitated from a high-temperature, host rock-buffered fluid, possibly under the influence of TSR. The dolomites associated with the first Cu–Co stage are characterized by significantly radiogenic Sr isotope signatures (0.70987 to 0.73576) that show a good correspondence with the Sr isotope signatures of the granitic basement rocks at an age of ca. 816 Ma. This indicates that the mineralizing fluid of the first Cu–Co stage has most likely leached radiogenic Sr and Cu–Co metals by interaction with the underlying basement rocks and/or with arenitic sedimentary rocks derived from such a basement. In contrast, the Sr isotope signatures (0.70883 to 0.71215) of the dolomites associated with the second stage show a good correspondence with the ⁸⁷Sr/⁸⁶Sr ratios (0.70723 to 0.70927) of poorly mineralized/barren host rocks at ca. 590 Ma. This indicates that the fluid of the second Cu–Co stage was likely a remobilizing fluid that significantly interacted with the country rocks and possibly did not mobilize additional metals from the basement rocks.     

Making continental crust through slab melting: Constraints from niobium-tantalum fractionation in UHP metamorphic rutile

The formation of the continental crust (CC) is one of the most important processes in the evolution of the silicate Earth. Exactly how the CC formed is the subject of ongoing debate that focuses on its subchondritic Nb/Ta ratio. Nb and Ta are “geochemical identical twins,” so they usually do not fractionate from each other. Here, we show that rutile grains from hydrous rutile-bearing eclogitic layers recovered from drillcores in the Dabie-Sulu ultrahigh pressure terrain have highly variable Nb/Ta values (ranging from 5.4 to 29.1, with an average of 9.8 ± 0.6), indicating major fractionation of Nb and Ta most likely occurred during blueschist to amphibole-eclogite transformation in the absence of rutile. It is suggested that the released fluids with subchondritic Nb/Ta were transported to, and retained by, hydrous rutile-bearing eclogite in colder regions, resulting in suprachondritic Nb/Ta ratios for drier eclogite in hotter regions. Further dehydration of hydrous rutile-bearing eclogites cannot transfer the fractionated Nb/Ta values to the CC due to the low solubility of Nb and Ta in fluids in the presence of rutile, while dehydration-melting results in a major component of the CC, the tonalite-trondhjemite-granodiorite (TTG) component, which is responsible for the low Nb/Ta of the CC. Consequently, residual eclogites have variable but overall suprachondritic Nb/Ta.     

Book Reviews

Books reviewed:
MARSHA ALIBRANDI, GIS in the Classroom: Using Geographic Information Systems in Social Studies and Environmental Science
JO WOOD, Java Programming for Spatial Sciences     

2: Hydrothermal ore deposits related to post-orogenic extensional magmatism and core complex formation: The Rhodope Massif of Bulgaria and Greece

The Rhodope Massif in southern Bulgaria and northern Greece hosts a range of Pb–Zn–Ag, Cu–Mo and Au–Ag deposits in high-grade metamorphic, continental sedimentary and igneous rocks. Following a protracted thrusting history as part of the Alpine–Himalayan collision, major late orogenic extension led to the formation of metamorphic core complexes, block faulting, sedimentary basin formation, acid to basic magmatism and hydrothermal activity within a relatively short period of time during the Early Tertiary. Large vein and carbonate replacement Pb–Zn deposits hosted by high-grade metamorphic rocks in the Central Rhodopean Dome (e.g., the Madan ore field) are spatially associated with low-angle detachment faults as well as local silicic dyke swarms and/or ignimbrites. Ore formation is essentially synchronous with post-extensional dome uplift and magmatism, which has a dominant crustal magma component according to Pb and Sr isotope data. Intermediate- and high-sulphidation Pb–Zn–Ag–Au deposits and minor porphyry Cu–Mo mineralization in the Eastern Rhodopes are predominantly hosted by veins in shoshonitic to high-K calc-alkaline volcanic rocks of closely similar age. Base-metal-poor, high-grade gold deposits of low sulphidation character occurring in continental sedimentary rocks of synextensional basins (e.g., Ada Tepe) show a close spatial and temporal relation to detachment faulting prior and during metamorphic core complex formation. Their formation predates local magmatism but may involve fluids from deep mantle magmas.The change in geochemical signatures of Palaeogene magmatic rocks, from predominantly silicic types in the Central Rhodopes to strongly fractionated shoshonitic (Bulgaria) to calc-alkaline and high-K calc-alkaline (Greece) magmas in the Eastern Rhodopes, coincides with the enrichment in Cu and Au relative to Pb and Zn of the associated ore deposits. This trend also correlates with a decrease in the radiogenic Pb and Sr isotope components of the magmatic rocks from west to east, reflecting a reduced crustal contamination of mantle magmas, which in turn correlates with a decreasing crustal thickness that can be observed today. Hydrogen and oxygen isotopic compositions of the related hydrothermal systems show a concomitant increase of magmatic relative to meteoric fluids, from the Pb–Zn–Ag deposits of the Central Rhodopes to the magmatic rock-hosted polymetallic gold deposits of the Eastern Rhodopes.