The evolution of marine evaporitic brines in inland basins: The Jordan-Dead Sea Rift valley

Marine-evaporitic brines frequently display Na, Cl and Br concentrations that significantly deviate from seawater evaporation paths, yielding markedly conflicting degrees of evaporation calculated for a specific brine. Here we present 493 new and 33 previously reported analyses of Ca-chloridic waters of Neogene age from the Dead Sea Rift (DSR) valley to explain such offsets. The DSR brines plot along an almost perfect mixing line (R² = 0.990) on a Br/Cl-Na/Cl diagram, extending between two end members A and B. Points A and B are located at Na/Cl = 0.804 and Br/Cl = 0.00193, and at Na/Cl = 0.00773 and Br/Cl = 0.0155, respectively, within the halite and bischofite stability fields.Brines A and B originated in a dual-mode evaporation basin. Brine A formed under the classic lagoon scenario (mode A), with seawater inflow and brine outflow at steady state. Occasional drops in water level, imposed by climatic or tectonic causes, resulted in outflow cutoff and in rapid concentration buildup. The second mode (B) initiated upon equilibration of the activity of water in the brine with the overlying relative humidity, resulting in composition and salinity approaching that of brine B, sustaining it until the next reversal to mode A.Thick evaporite deposits inhibited infiltration of brines A and B into the subsurface terrain, a process that was enabled only when the brine reached the permeable carbonate rock rim and border faults of the basin. Hence, brines that formed during the relatively short shifts from mode A to mode B could not penetrate into the deep subsurface, and bittern minerals that were formed during the frequent mode shifts were dissolved and flushed out into the sea upon the next resumption of outflow.The proposed model accounts for the deviations of brines from the marine evaporitic evolution curve by brine mixing, rather than due to a change in ocean chemistry. It also explains the absence of bittern minerals in the thick halite and gypsum/anhydrite succession, and the compositional gap between the widely different end member hypersaline fluids. This model applies directly to the studied DSR brines and evaporites, but it may be relevant to other inland evaporitic basins.     

Mixing of shallow and deep groundwater as indicated by the chemistry and age of karstic springs

Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO₃ (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO₃ spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (³H), helium-3 (³He_trit), sulfur hexafluoride (SF₆)—for four Ca–HCO₃ spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.An erratum to this article can be found at     

The behavior of lithium and its isotopes in oilfield brines: evidence from the Heletz-Kokhav field, Israel

Twenty-four brine samples from the Heletz-Kokhav oilfield, Israel, have been analyzed for chemical composition and Li isotope ratios. The chemical composition of the brines, together with geological evidence, suggests derivation from (Messinian) seawater by evaporation that proceeded well into the gypsum stability field but failed to reach the stage of halite crystallization. The present salinity of the samples (18-47 g Cl/L) was achieved by dilution of the original evaporitic brine by local fresh waters. Like brines from other sedimentary basins, the Li/Cl ratios in the Heletz-Kokhav samples show a prominent Li enrichment (five-fold to eight-fold) relative to modern seawater. The isotopic ratios of Li, expressed in the δ ⁶Li notation, vary from −26.3 to −17.9‰, all values being significantly higher than that of modern seawater (−32‰) irrespective of their corresponding Li concentration (1.0-2.3 mg/L). The isotopic composition of Li and the Li/Cl ratio in the oilfield brines were acquired in two stages: (a) The original evaporated seawater gained isotopically light Li during the diagenetic interaction between the interstitial Messinian brine and the basin sediments. A parent brine with an elevated Li/Cl ratio was formed. The brine was later diluted in the oilfields. (b) The δ ⁶Li values of the final brines were determined during epigenetic interaction with the Heletz-Kokhav aquifer rocks. At the same time, the Li/Cl ratio inherited from stage (a) remained largely unchanged. This work represents the first use of lithium isotopic composition to elucidate the origin and evolution of formation waters in sedimentary basins.     

Heavy metals behavior in coastal sediments of southern California: a critical review and synthesis

The present paper reviews and discusses the studies on heavy metals behavior in coastal sediments of southern California which have been published since 1970.The available data allow for the estimation of pollution-free ‘base-line’ concentrations of some heavy metals in southern California sediments (Ag, 0.4 ppm; Cd, 0.4 ppm; Cr, 25 ppm; Cu, 9 ppm; Ni, 15 ppm; Pb, 10 ppm; and Zn, 44 ppm) which may be used as references for monitoring future metal pollution.The transport of most, if not all, heavy metals through the near-shore and shelf environments is controlled by their association with particles, a significant fraction of which is sewage-derived and rich in organic carbon. Changes in the relative abundances of the heavy metals are brought about mainly by settling differentiation of their host particles, and much less so by diagenetic solubilization. The bulk of the heavy metals are transported, within fine-grained particles, out from the shelf into deep ocean regions.Simple linear mixing of polluted outfall materials with clean natural sediments cannot explain the distribution of heavy metals in near-shore and basinal sediments in southern California, unless significant protective effects of organic coatings (near outfalls) and of grain-size distributions are taken into account. Heavy metal pollution from oil seepages are significant for only a very limited number of metals (Ni, Ba, etc.) and only on a local scale.The urgent need for standardization of heavy metal leaching techniques is demonstrated and emphasized.     

Fundamental studies on kinetic isotope effect (KIE) of hydrogen isotope fractionation in natural gas systems

Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ¹³C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane.     

Rock fall hazard along the railway corridor to Jerusalem,Israel, in the Soreq and Refaim valleys

We evaluate rock fall hazard along the railway corridor to Jerusalem, Israel, in the Soreq and Refaim valleys. For the purpose, we use a combination of historical information on past rock fall events, field surveys aided by the interpretation of aerial photographs, and numerical rock fall modeling. Historical information indicates that on July 11, 1927 an m _L 6.2 Dead-Sea transform earthquake caused rock falls in the studied area. The seismically induced rock falls damaged the railway tracks. Field observations revealed that the source area for the 1927 failures was located in the Aminadav formation, at the contact with the Moza formation. At the stratigraphic contact, rock blocks 10⁰–10¹ m³ in size are formed as a result of tensile stresses and associated fracturing in the dolomite of the Aminadav formation, combined with continuous creep of the blocks on the marl of the underlying Moza formation. We use topographical, geological, and geomorphological information to calibrate a three-dimensional numerical simulation of rock falls in the studied area. We use the results of the numerical modeling, and additional independent information, to assess rock fall hazard and the associated risk in the Soreq and Refaim valleys. Results indicate that in the studied area, rock fall risk to the railway line to Jerusalem is due primarily to Dead-Sea transform earthquakes, with m _L  > 6. We identify nine sections of the railway line where rock fall risk exists, for a total length of 2.5 km. We further note that seismically induced rock falls can produce damage to the road network in the studied area, make it difficult or impossible for earthquake casualties to reach hospitals in Jerusalem. We conclude offering recommendations on how to mitigate the risk posed by earthquake-induced rock falls in the studied area.