Sulfur isotopic compositions of individual organosulfur compounds and their genetic links in the Lower Paleozoic petroleum pools of the Tarim Basin, NW China

During thermochemical sulfate reduction (TSR), H2S generated by reactions between hydrocarbons and aqueous sulfate back-reacts with remaining oil-phase compounds forming new organosulfur compounds (OSCs) that have similar δ34S values to the original sulfate. Using Compound Specific Sulfur Isotope Analysis (CSSIA) of alkylthiaadamantanes (TAs), alkyldibenzothiophenes (DBTs), alkylbenzothiophenes (BTs) and alkylthiolanes (TLs), we have here attempted to differentiate OSCs due to primary generation and those due to TSR in oils from the Tarim Basin, China. These oils were generated from Cambrian source rocks and accumulated in Cambrian and Ordovician reservoirs. Based on compound specific sulfur isotope and carbon isotope data, TAs concentrations and DBT/phenanthrene ratios, the oils fall into four groups, reflecting different extents of source rock signal, alteration by TSR, mixing events, and secondary generation of H2S. Thermally stable TAs, that were produced following TSR, rapidly dominate kerogen-derived TAs at low to moderate degrees of TSR. Less thermally stable TLs and BTs were created as soon as TSR commenced, rapidly adopted TSR-δ34S values, but they do not survive at high concentrations unless TSR is advanced and ongoing. The presence of TLs and BTs shows that TSR is still active. Secondary DBTs were produced in significant amounts, sufficient to dominate kerogen-derived DBTs, only when TSR was at an advanced extent. The difference in sulfur isotopes between (i) TLs and DBTs and (ii) BTs and DBTs and (iii) TAs and DBTs, represents the extent of TSR while the presence of TAs at greater than 20 μg/g represents the occurrence of TSR. The output of this study shows that compound specific sulfur isotopes of different organosulfur compounds, with different thermal stabilities and formation pathways, not only differentiate between oils of TSR and non-TSR origin, but can also reveal information about relative timing of secondary charge events and migration pathways

The Red Sea, Coastal Landscapes, and Hominin Dispersals

This chapter provides a critical assessment of environment, landscape and resources in the Red Sea region over the past five million years in relation to archaeological evidence of hominin settlement, and of current hypotheses about the role of the region as a pathway or obstacle to population dispersals between Africa and Asia and the possible significance of coastal colonization. The discussion assesses the impact of factors such as topography and the distribution of resources on land and on the seacoast, taking account of geographical variation and changes in geology, sea levels and palaeoclimate. The merits of northern and southern routes of movement at either end of the Red Sea are compared. All the evidence indicates that there has been no land connection at the southern end since the beginning of the Pliocene period, but that short sea crossings would have been possible at lowest sea-level stands with little or no technical aids. More important than the possibilities of crossing the southern channel is the nature of the resources available in the adjacent coastal zones. There were many climatic episodes wetter than today, and during these periods water draining from the Arabian escarpment provided productive conditions for large mammals and human populations in coastal regions and eastwards into the desert. During drier episodes the coastal region would have provided important refugia both in upland areas and on the emerged shelves exposed by lowered sea level, especially in the southern sector and on both sides of the Red Sea. Marine resources may have offered an added advantage in coastal areas, but evidence for their exploitation is very limited, and their role has been over-exaggerated in hypotheses of coastal colonization

Freshening of the Mediterranean Salt Giant: controversies and certainties around the terminal (Upper Gypsum and Lago-Mare) phases of the Messinian Salinity Crisis

The late Miocene evolution of the Mediterranean Basin is characterized by major changes in connectivity, climate and tectonic activity resulting in unprecedented environmental and ecological disruptions. During the Messinian Salinity Crisis (MSC, 5.97-5.33 Ma) this culminated in most scenarios first in the precipitation of gypsum around the Mediterranean margins (Stage 1, 5.97-5.60 Ma) and subsequently > 2 km of halite on the basin floor, which formed the so-called Mediterranean Salt Giant (Stage 2, 5.60-5.55 Ma). The final MSC Stage 3, however, was characterized by a "low-salinity crisis", when a second calcium-sulfate unit (Upper Gypsum; substage 3.1, 5.55-5.42 Ma) showing (bio)geochemical evidence of substantial brine dilution and brackish biota-bearing terrigenous sediments (substage 3.2 or Lago-Mare phase, 5.42-5.33 Ma) deposited in a Mediterranean that received relatively large amounts of riverine and Paratethys-derived low-salinity waters. The transition from hypersaline evaporitic (halite) to brackish facies implies a major change in the Mediterranean’s hydrological regime. However, even after nearly 50 years of research, causes and modalities are poorly understood and the original scientific debate between a largely isolated and (partly) desiccated Mediterranean or a fully connected and filled basin is still vibrant. Here we present a comprehensive overview that brings together (chrono)stratigraphic, sedimentological, paleontological, geochemical and seismic data from all over the Mediterranean. We summarize the paleoenvironmental, paleohydrological and paleoconnectivity scenarios that arose from this cross-disciplinary dataset and we discuss arguments in favour of and against each scenario

Mine closure of pit lakes as terminal sinks: best available practice when options are limited?

In an arid climate, pit lake evaporation rates can exceed influx rates, causing the lake to function as a hydraulic terminal sink, with water levels in the pit remaining below surrounding groundwater levels. We present case studies from Western Australia for two mines nearing closure. At the first site, modelling indicates that waste dump covers for the potentially acid forming (PAF) material would not be successful over the long term (1,000 years or more). The second site is a case study where PAF management is limited by the current waste rock dump location and suitable cover materials. Pit lake water balance modelling using Goldsim software indicated that both pit lakes would function as hydraulic terminal sinks if not backfilled above long-term equilibrium water levels. Poor water quality will likely develop as evapoconcentration increases contaminant concentrations, providing a potential threat to local wildlife. Even so, the best current opportunity to limit the risk of contaminant migration and protect regional groundwater environments may be to limit backfill and intentionally produce a terminal sink pit lake

Microbial and Chemical Characterization of Underwater Fresh Water Springs in the Dead Sea

Due to its extreme salinity and high Mg concentration the Dead Sea is characterized by a very low density of cells most of which are Archaea. We discovered several underwater fresh to brackish water springs in the Dead Sea harboring dense microbial communities. We provide the first characterization of these communities, discuss their possible origin, hydrochemical environment, energetic resources and the putative biogeochemical pathways they are mediating. Pyrosequencing of the 16S rRNA gene and community fingerprinting methods showed that the spring community originates from the Dead Sea sediments and not from the aquifer. Furthermore, it suggested that there is a dense Archaeal community in the shoreline pore water of the lake. Sequences of bacterial sulfate reducers, nitrifiers iron oxidizers and iron reducers were identified as well. Analysis of white and green biofilms suggested that sulfide oxidation through chemolitotrophy and phototrophy is highly significant. Hyperspectral analysis showed a tight association between abundant green sulfur bacteria and cyanobacteria in the green biofilms. Together, our findings show that the Dead Sea floor harbors diverse microbial communities, part of which is not known from other hypersaline environments. Analysis of the water’s chemistry shows evidence of microbial activity along the path and suggests that the springs supply nitrogen, phosphorus and organic matter to the microbial communities in the Dead Sea. The underwater springs are a newly recognized water source for the Dead Sea. Their input of microorganisms and nutrients needs to be considered in the assessment of possible impact of dilution events of the lake surface waters, such as those that will occur in the future due to the intended establishment of the Red Sea−Dead Sea water conduit

Deep confined karst detection, analysis and paleo-hydrology reconstruction at a basin-wide scale using new geophysical interpretation of borehole logs

Deep karst voids can be identified by a new method of geophysical interpretation of comm used borehole logs in deeply confined carbonate aquifers. We show that deep, buried karst voids can be characterized by combining this geophysical interpretation together with geological and hydrological data, and with known speleological constraints. We demonstrate how this characterization can reveal past hydrological regimes and allow mapping of karst distribution on a basin-wide scale. A combined analysis of geophysical, geological, hydrological, and speleological data in the confined Yarkon–Taninim aquifer, Israel, led us to reconstruct past groundwater levels at different relief and sea levels, with the karst voids as a marker for long-term flow close to the water table. Paleo-canyons along the Mediterranean Sea shoreline strongly affected the region’s paleo-hydrology, by serving as major outlets of the aquifer during most of the Cenozoic. We conclude that intensive karstification was promoted by flow periods of longer duration and/or higher flux and flow velocities close to the aquifer’s past and present outlets. In addition, we suggest that karst voids found under shallow confinement were developed by renewed aggressivity due to hypogene water rising in cross-formational flow becoming mixed with fresh lateral water flow from the east

Hydrometeorological daily recharge assessment model (DREAM) for the Western Mountain Aquifer, Israel: Model application and effects of temporal patterns

[1] Recharge is a critical issue for water management. Recharge assessment and the factors affecting recharge are of scientific and practical importance. The purpose of this study was to develop a daily recharge assessment model (DREAM) on the basis of a water balance principle with input from conventional and generally available precipitation and evaporation data and demonstrate the application of this model to recharge estimation in the Western Mountain Aquifer (WMA) in Israel. The WMA (area 13,000 km2) is a karst aquifer that supplies 360–400 Mm3 yr−1 of freshwater, which constitutes 20% of Israel\u27s freshwater and is highly vulnerable to climate variability and change. DREAM was linked to a groundwater flow model (FEFLOW) to simulate monthly hydraulic heads and spring flows. The models were calibrated for 1987–2002 and validated for 2003–2007, yielding high agreement between calculated and measured values (R2 = 0.95; relative root‐mean‐square error = 4.8%; relative bias = 1.04). DREAM allows insights into the effect of intra‐annual precipitation distribution factors on recharge. Although annual precipitation amount explains ∼70% of the variability in simulated recharge, analyses with DREAM indicate that the rainy season length is an important factor controlling recharge. Years with similar annual precipitation produce different recharge values as a result of temporal distribution throughout the rainy season. An experiment with a synthetic data set exhibits similar results, explaining ∼90% of the recharge variability. DREAM represents significant improvement over previous recharge estimation techniques in this region by providing near‐real‐time recharge estimates that can be used to predict the impact of climate variability on groundwater resources at high temporal and spatial resolution