Depositional history of the Miocene Lake Sinj (Dinaride Lake System,Croatia): a long-lived hard-water lake in a pull-apart tectonic setting

Early Miocene transpressional wrenching yielded a series of NW–SE-elongated pull-apart basins in the Dinarides of Croatia and Bosnia and Herzegovina. They accommodated a huge lake system that gave rise to spectacular endemic mollusk radiation. Lake Sinj, moderately sized at 342 km², flooded the south-westernmost basin of this system. Due to the karstic environment, the hard-water, alkaline, long-lived lake developed a sediment infill with an average thickness of 370 m, dominated by authigenic limestone. The studied section represents the upper third of the basinal infill and provides detailed insights into the critical period of the lake and of the basinal evolution during the final stages of its filling. It comprises two large-scale, shallowing-upward cycles, both starting with fossil-poor limestones, gradually passing into coal-bearing carbonate rocks and coal seams. The fossil-poor intervals are interpreted as phases of repetitive acidification events due to changing lake level, which induced periodic drying and flooding of the uppermost littoral zone inhabited by starfruit (Damasonium) meadows. The flooding of the aerated, limy mud plain introduced H+ ions from organic-matter decay reactions into the shallow lake. This decreased its pH level, with catastrophic consequences for its biota. The ecosystem then stabilized during the orbitally-forced, dry climate phases. Based on the mollusk record, streams still influenced the marginal lake environment and rich organic-matter production created swamps and mires. The onset of mollusk radiation in the section correlates with stabilized lake alkalinity, as indicated by the disappearance of starfruits, ongoing authigenic carbonate production and by coal seams representing textbook examples for coal formation in alkaline environments. The inferred basinal setting fits well with the pull-apart basin model, pointing to the presence of an extended shallow ramp in front of a steep, fault-induced hillside of the hinterland.     

Biomarker responses as indication of contaminant effects in blue mussel (Mytilus edulis) and female eelpout (Zoarces viviparus) from the southwestern Baltic Sea

During a field study performed in spring and autumn 2001 and 2002, blue mussels (Mytilus edulis) and female eelpout (Zoarces viviparus) were collected at three locations in the Wismar Bay (Baltic Sea), and several biomarkers of contaminant effects were analysed. Besides seasonal and inter-annual variations, biomarker signals were most pronounced at the location closest to Wismar Harbour (Wendorf) in both species. Lysosomal membrane stability (LMS) was lowest and acetylcholinesterase activity (AChE) was significantly reduced. Frequency of micronuclei (MN) was significantly higher (in blue mussels), indicating mutagenic effects. In eelpout elevated levels of DNA adducts, EROD induction and PAH-metabolites were measured. Metallothionein (MT), biomarker for trace metal exposure, showed a gradient only in spring. Organochlorine contaminant analyses (PCBs, DDTs) corresponded to the observed biomarker levels. The results obtained clearly demonstrate pollution effects in the southwestern Baltic Sea. Moreover, they show that a multibiomarker approach is also applicable in a brackish water environment.     

Miocene diagenetic and epigenetic strontium mineralization in calcareous series from Cyprus and the Arabian Gulf: Metallogenic perspective on sub- and suprasalt redox-controlled base metal deposits

During the Neogene, celestite deposits evolved in the Neo-Tethys basins, in what is today called the Mediterranean Sea and the Arabian Gulf. Two evaporite deposits, in Cyprus and in Qatar have been investigated from the sedimentological and mineralogical point of view with emphasis placed on Sr, S and Ca isotopes of carbonate, gypsum and celestite.During the early Miocene shallow marine environments occurred in the Gulf region and in Cyprus both of which are abundant in syndiagenetic sulphate minerals. The calcareous environments had a strong impact on the fluid migration leading to the Sr mineralization. In the Gulf region algal biostromes favored the lateral migration of fluids but had a sealing effect so that any epigenetic mineralization based on vertical fluid flow was hampered. In contrast, the Cypriot depocentre overlying the Troodos ophiolite is dominated by patch and knoll reefs (bioherms) which provide enough porosity and permeability to be favorable for the circulation of fluids with a strong vertical component. Owing to these changes in the calcareous host series, epigenetic sulphate mineralization evolved in Cyprus during the late Miocene. This occurred as the Mediterranean Sea gradually became isolated from the open ocean and, as a precursor to the “Messinian salinity crisis” evaporitic brines circulated deep into the Meso-Cenozoic platform sediments and the underlying Troodos ophiolite where these fluids leached some base metals and sulphur for the celestite mineralization. The Red Sea Rifting was at full swing during the Late Miocene and its northern propagation into the Mediterranean Sea is assumed to have had a structural control on the positioning of the Sr deposits in Cyprus. In the Gulf area, the final closure of the Neo-Tethys and Zagros folding terminated deposition of marine calcareous rocks and alluvial-fluvial siliciclastic rocks were deposited across an unconformity. Missing circulation of highly saline brines was responsible for the absence of an epigenetic Sr mineralization of Cyprus-type in the Gulf area. Assemblages of light (e.g. zeolites) and heavy minerals (e.g. rutile, zoisite, clinopyroxene) and Ca isotope analyses support basic igneous rocks as the source for the detrital and dissolved matter in the depositional environments in Cyprus and the Arabian Gulf. The Ca isotope data imply formation of the sulphate and carbonate minerals in a marine environment without significant contributions of more radiogenic ⁴⁰Ca coming from old continental crust, e.g., the Kyrenia Range or Mamonia Complex, both of which containing rocks as old as Permian.Cyprus-type (bioherm-type) and Gulf-type (biostrome-type) evaporites are potential progenitors of sediment-hosted mineral deposits (SHSCD) or base metal vein-type deposits. Syndiagenetic celestite-bearing evaporites of the Gulf-type are a model source and progenitor of base metal deposits of stratigraphically-controlled fixed or mobile reductants such as Kupferschiefer-type deposits. Is the Arabian Gulf a Kupferschiefer basin in the making? The epigenetic celestite-bearing mineralization of the Cyprus-type reflects an advanced stage of fluid migration relative to the celestite deposits along the Trucial coast but this brine mobilization failed to create a base metal deposit of its own mainly due to the absence of fixed or mobile reductants. These reductants were present in the western Mediterranean regions in Tunisia and Algeria, where evaporite-associated base metal deposits are going to be mined and in the Mesozoic through Cenozoic platform sediments in central Europe, where numerous suprasalt unconformity-related metal deposits were mined in the past.     

Paleoenvironmental and paleoecological reconstruction of a freshwater oasis in savannah grassland at FLK North, Olduvai Gorge, Tanzania

The records of early hominins are commonly localized both temporally and spatially even in archaeologically rich basins like Olduvai Gorge, Tanzania. The FLK North site was discovered in 1960, but the reason for the exact location of this dense concentration of fossils and stone tools on a lake-margin flat has not been explained. We present new geological and geochemical information from six excavations in upper Bed I, which revealed up to 1.4-m-thick carbonate deposits, attesting to the presence of freshwater springs in the area surrounding FLK North. The δ¹⁸O signatures of the tufa are typical for meteoric water that has evolved during evaporation. Tuff IF that caps the sequence was deposited on uneven topography with the highest area a low-relief ridge between two faults at the archaeological site and lowest areas being sites of groundwater discharge. The model proposed here is that rainfall on adjacent highlands was transported to the basin where faults acted as conduits for water. Similar hydrogeological settings at modern lakes Manyara and Eyasi, currently support lush groundwater forest and woodland despite arid climate. FLK North may have been an “oasis” offering freshwater and shelter for consuming meat by both carnivores and hominins.     

A review of volatiles in the Martian interior

Multiple observations from missions to Mars have revealed compelling evidence for a volatile‐rich Martian crust. A leading theory contends that eruption of basaltic magmas was the ultimate mechanism of transfer of volatiles from the mantle toward the surface after an initial outgassing related to the crystallization of a magma ocean. However, the concentrations of volatile species in ascending magmas and in their mantle source regions are highly uncertain. This work and this special issue of Meteoritics & Planetary Science summarize the key findings of the workshop on Volatiles in the Martian Interior (Nov. 3–4, 2014), the primary open questions related to volatiles in Martian magmas and their source regions, and the suggestions of the community at the workshop to address these open questions.     

Characterization of accumulated precipitates during subsurface iron removal

The principle of subsurface iron removal for drinking water supply is that aerated water is periodically injected into the aquifer through a tube well. On its way into the aquifer, the injected O₂-rich water oxidizes adsorbed Fe²⁺, creating a subsurface oxidation zone. When groundwater abstraction is resumed, the soluble Fe²⁺ is adsorbed and water with reduced Fe concentrations is abstracted for multiple volumes of the injection water. In this article, Fe accumulation deposits in the aquifer near subsurface treatment wells were identified and characterized to assess the sustainability of subsurface iron removal regarding clogging of the aquifer and the potential co-accumulation of other groundwater constituents, such as As. Chemical extraction of soil samples, with Acid-Oxalate and HNO₃, showed that Fe had accumulated at specific depths near subsurface iron removal wells after 12 years of operation. Whether it was due to preferred flow paths or geochemical mineralogy conditions; subsurface iron removal clearly favoured certain soil layers. The total Fe content increased between 11.5 and 390.8 mmol/kg ds in the affected soil layers, and the accumulated Fe was found to be 56-100% crystalline. These results suggest that precipitated amorphous Fe hydroxides have transformed to Fe hydroxides of higher crystallinity. These crystalline, compact Fe hydroxides have not noticeably clogged the investigated well and/or aquifer between 1996 and 2008. The subsurface iron removal wells even need less frequent rehabilitation, as drawdown increases more slowly than in normal production wells. Other groundwater constituents, such as Mn, As and Sr were found to co-accumulate with Fe. Acid extraction and ESEM-EDX showed that Ca occurred together with Fe and by X-ray Powder Diffraction it was identified as calcite.     

Decadal variation of surface solar radiation in the Tibetan Plateau from observations, reanalysis and model simulations

In this study, the annual and seasonal variations of all-sky and clear-sky surface solar radiation (SSR) in the eastern and central Tibetan Plateau (TP) during the period 1960–2009 are investigated, based on surface observational data, reanalyses and ensemble simulations with the global climate model ECHAM5-HAM. The mean annual all-sky SSR series shows a decreasing trend with a rate of ?1.00 Wm^?2 decade^?1, which is mainly seen in autumn and secondly in summer and winter. A stronger decrease of ?2.80 Wm^?2 decade^?1 is found in the mean annual clear-sky SSR series, especially during winter and autumn. Overall, these results confirm a tendency towards a decrease of SSR in the TP during the last five decades. The comparisons with reanalysis show that both NCEP/NCAR and ERA-40 reanalyses do not capture the decadal variations of the all-sky and clear-sky SSR. This is probably due to a missing consideration of aerosols in the reanalysis assimilation model. The SSR simulated with the ECHAM5-HAM global climate model under both all-sky and clear-sky conditions reproduce the decrease seen in the surface observations, especially after 1980. The steadily increasing aerosol optical depth (AOD) at 550 nm over the TP in the ECHAM5-HAM results suggests transient aerosol emissions as a plausible cause.     

Viscosity of the Martian mantle and its initial temperature: Constraints from crust formation history and the evolution of the magnetic field

The rheology of the Martian mantle and the planet's initial temperature is constrained with thermal evolution models that include crust growth and test the conditions for magnetic field generation in the core. As observations we use the present-day average crustal thickness of 50-120 km as estimated from the Mars Global Surveyor gravity and topography data, the evidence for the crust being produced mostly early, with a rate declining from the Noachian to the Hesperian, and the evidence for an early magnetic field that likely existed for less than a billion years. We use the fact that the rate of crust growth is a function of temperature, which must be above the solidus in the sub-lithosphere mantle, and the mantle convection speed because the latter determines the rate at which melt can be replenished. The convection speed is a strong function of viscosity which, in turn, is a strong function of temperature and also of the water content of the mantle. We use a viscosity parameterization with a reference viscosity evaluated at 1600 K the value of which can be characteristic of either a dry or a wet mantle. We further consider the Fe-FeS phase diagram for the core and compare the core liquidus estimated for a sulphur content of 14% as suggested by the SNC meteorite compositions with the core temperatures calculated for our cooling models. Two data sets of the Fe-FeS eutectic temperature have been used that differ by about 200 K [Böhler, R., 1996. Fe-FeS eutectic temperatures at 620 kbar. Phys. Earth Planet. Inter. 96, 181-186; Fei, Y., Bertka, C.M., Finger, L.W., 1997. High-pressure iron-sulphur compound, Fe₃S₂, and melting relations in the Fe-FeS system. Science 275, 1621-1623] at Martian core-mantle boundary pressure and in the eutectic composition by 5 wt%. The differences in eutectic temperature and composition translate into a difference of about 400 K in liquidus temperature for 14 wt% sulphur.We find it premature to rule out specific mantle rheologies on the basis of the presently available crustal thickness and crust growth evidence. Rather a trade-off exists between the initial mantle temperature and the reference viscosity. Both a wet mantle rheology with a reference viscosity less than 10²⁰ Pas and a dry mantle rheology with a reference viscosity of 10²¹ Pas or more can be acceptable if initial mantle temperatures between roughly 1700 and 2000 K are allowed. To explain the magnetic field history, the differences in liquidus temperatures matter. For a liquidus temperature of about 1900 K at the Martian core-mantle boundary as calculated from the Böhler et al. eutectic, a dry mantle rheology can best explain the lack of a present-day dynamo. For a liquidus temperature of about 1500 K at the core-mantle boundary as calculated from the Fei et al. eutectic all models are consistent with the observed lack of dynamo action. The reason lies with the fact that at 14 wt% S the Martian core would be close to the eutectic composition if the Fei et al. data are correct. As inner core growth is unlikely for an almost eutectic core, the early field would have been generated by a thermally driven dynamo. Together with the measured strength of the Martian crustal magnetization this would prove the feasibility of a strong thermally driven dynamo.     

Variation of hydrogeochemical characteristics of water in surface flows,shallow wells,and boreholes in the coastal city of Douala (Cameroon)

ABSTRACT

Groundwater is used by 3?million inhabitants in the coastal urban city of Douala, Cameroon, but comprehensive data are too sparse for it to be managed in a sustainable manner. Hence this study aimed to (1) assess the potability of the groundwater; (2) evaluate the spatial variation of groundwater composition; and (3) assess the interaction and recharge mechanisms of different water bodies. Hydrogeochemical tools and methods revealed the following results in the Wouri and Nkappa formations of the Douala basin, which is beneath Douala city: 30% of water samples from hand-dug wells in the shallow Pleistocene alluvium aquifer were saline and highly mineralized. However, water from boreholes in the deeper (49–92 m depth) Palaeocene aquifer was saline-free, less mineralized and potable. Water in the shallow aquifer (0.5–22 m depth) was of Na⁺-K⁺-Cl^?-NO₃^? type and not potable due to point source pollution, whereas Ca⁺-HCO₃^? unpolluted water dominates in the deeper aquifer. Water in the deep and shallow aquifers indicates the results of preferential flow pass and evaporative recharge, respectively. Possible hydrogeochemical processes include point source pollution, reverse ion exchange, remote recharge areas and mixing of waters with different chemical signatures.

EDITOR D. Koutsoyiannis ASSOCIATE EDITOR M.D. Fidelibus     

Mobility of arsenic in West Bengal aquifers conducting low and high groundwater arsenic. Part II: Comparative geochemical profile and leaching study

Aquifer sediments from areas of low- and high-As groundwater were characterized mineralogically and geochemically at a field site in the Nadia district of West Bengal, India. Leaching experiments and selective extraction of the sediments were also carried out to understand the release mechanism of As in the sub-surface. The correlation between measured elements (major, minor and trace) from low- and high-As groundwater areas are only significant for As, Fe and Mn. The borehole lithology and percentage of silt and clay fraction demonstrates the dominance of finer sediments in the high-As aquifer. Multivariate analysis of the geochemical parameters showed the presence of four different mineral phases (heavy-mineral fraction, phyllosilicates/biotite/Fe-oxyhydroxides, carbonates and sulphides) in the sediments. Selective extraction of sediment reveals that amorphous Fe-oxyhydroxide acts as a potential sink for As in the sub-surface. The result is consistent with microbially mediated redox reactions, which are controlled in part by the presence of natural organic matter within the aquifer sediments. The occurrences of As-bearing redox traps, primarily formed of Fe- and Mn-oxides/hydroxides, are also important factors that control the release of As into groundwater at the study site.