The chemistry of the anoxic waters in the Framvaren Fjord,Norway

In the summer of 1993, a number of chemical parameters (H₂S, O₂, pH, TA, TCO₂, NH ₄ ⁺ , PO ₄ ^3– , SiO₂, Mn²⁺ and Fe²⁺) were measured in the Framvaren Fjord, a permanently super-anoxic fjord in southern Norway. The extremely steep gradient of sulfide near the interface suggests that other than downward flux of oxygen, three other possible oxidants, particulate manganese and iron oxides, phototrophic sulfur oxidation bacteria and horizontally transported oxygen account for the oxidation of the upward flux of H₂S. Water intrusion through the sill accounts for the temperature inflection above the interface, which, together with internal waves (Stigerbrandt and Molvaer, 1988), may cause fluctuations of the depth of interface. Significant gradients of hydrographic properties and chemical species between 80–100 m suggest that there is a second interface at about 90 m that separates the deep and older bottom waters. A stoichiometric model is applied to examine the biogeochemical cycles of S, C, N and P in the Framvaren. High C:S, C:N and C:P ratios are found while the nutrients (N, P) have Redfield ratio. Based on the C:N:P ratio of 155:16:1 in organic matter, about 30% of sulfide produced by sulfate reduction is estimated to be removed by processes such as oxidation, formation of FeS₂, degassing and incorporation into organic matter. The rates of oxidation of H₂S by Mn and Fe oxides in the water near the interface were slightly faster than the observed values in the laboratory, probably due to the presence of bacteria.     

Trace metals in suspended particulate matter and in sediment trap material from a permanently anoxic fjord — Framvaren, South Norway

Geochemical studies of the trace metal concentrations in suspended particulate matter (SPM) and sediment trap material from a permanently anoxic fjord, Framvaren, South Norway in 1989 and 1993 indicate that extremely high concentrations of zinc (max = 183920 mg/kg), copper (max = 4130 mg/kg), lead (max = 2752 mg/kg), and cadmium (max= 8.1 mg/kg) sometimes (1993) occur in the SPM collected in the anoxic water layer. The highest concentrations of Zn occur just below the redoxcline at 22 m water depth (in 1993), and copper, lead and cadmium have maximum concentrations between 30 and 80 m depth, where the amount of total SPM is at a minimum (about 0.3 mg/L). On a mass per volume (g/L) basis, the maximum concentrations of Cd, Cu and Fe occur at the interface (21m) and those of Zn occur just below the redoxcline (22 m depth). The SPM and sediment trap data suggest that the metals are precipitated as sulfide minerals in the anoxic water. The presence of particulate sulfides was confirmed by SEM studies that show the occurrence of discrete metal (Cu, Fe, Pb, and Zn) sulfide particles in size from 10–20 m as well as framboidal pyrites (1–5 m in size). Higher levels of metal sulfides at intermediate depths rather than in the deep water of Framvaren (> 100 m), may be due to input of trace metals by water exchange over the sill in the upper part of the water column. In the deep water, less metal sulfide precipitation takes place due to depletion of trace metals, and the dilution of particulate metal concentrations by organic matter and by the chemogenic formation of calcite.     

Stable isotope evidence for multiple fluid regimes during carbonate cementation of the Upper Tertiary Hazeva Formation, Dead Sea Graben, southern Israel

Stable carbon- and oxygen-isotope compositions of calcite and dolomite cements have been used to understand porewater evolution in the Upper Tertiary Hazeva Formation within the Dead Sea Graben, southern Israel. Sandstone samples were obtained from four boreholes in three tectonic blocks of the graben over depths of 253–6448 m, a variation that largely reflects differential subsidence of individual fault-bounded blocks. Early carbonate cements dominate diagenesis. Calcite occurs at <1600 m, but was replaced by dolomite at greater depths. Dolomite at 1600–2700 m is Fe-poor (<0.8 mol% FeCO₃), and at 4700–6200 m, Fe-rich (0.5–7.2 mol% FeCO₃). Magnesite, anhydrite and halite are the final diagenetic phases. Calcite has positively correlated δ¹⁸O (+21‰ to +25‰) and δ¹³C (−6‰ to −2‰) values that generally decrease with depth. Dolomite has a wider variation in δ¹⁸O (+18‰ to +30‰) and δ¹³C (−8‰ to −1‰) values, which also generally are lower with increasing depth. However, the δ¹³C and δ¹⁸O values of dolomite from the uppermost 400 m of the Hazeva Formation in the Sedom Deep-1 borehole are anomalous in spanning the entire range of stable carbon and oxygen isotopic compositions over this relatively small interval.The decreasing dolomite δ¹³C values likely indicate an increased contribution of carbon from organic sources with increasing depth. Except for the uppermost 400 m, Hazeva Formation dolomite in the Sedom Deep-1 borehole has stable carbon-isotope compositions that imply initial dolomitization at much shallower levels, prior to the preferential subsidence of this tectonic block. The oxygen isotopic compositions of the calcite cement are best explained by equilibration at present burial temperatures (≤55 °C) with porewater of meteoric origin. Its δ¹⁸O values increased from −5‰ at the shallowest depths to 0‰ at 1600 m. The dolomite oxygen isotopic compositions also reflect equilibration at present burial temperatures with porewaters ranging from 0‰ at 1600 m to +7‰ at 3600 m (100 °C). In the deepest fault block (Sedom Deep-1 borehole), however, increasingly Fe-rich dolomite has (re)equilibrated with porewater whose δ¹⁸O values decreased from +9‰ at 4750 m (120 °C) to +1‰ to +2‰ by 6200 m (150 °C).Much of the dolomite likely formed at relatively shallow depths from saline brines derived from precursors to the Dead Sea. These infiltrated the Hazeva Formation, mixing with and largely displacing meteoric water, and dolomitizing calcite. Rock–water ratios tended to be high during these processes. However, the upper 400 m of the Hazeva Formation in the deepest fault block were likely deposited during its rapid tectonic subsidence, and largely escaped the initial style of dolomitization pervasive elsewhere in the study area. These sediments were also capped by evaporites. This relatively thin interval likely became a preferential conduit for brines that escaped underlying and overlying strata, including the Fe-rich, lower ¹⁸O fluids (evolved seawater?) present in the deepest part of the graben. These rocks present the most promising target for the passage and accumulation of hydrocarbons in the study area.     

Geochemical characteristics of the Zhaolanzhuang sour gas accumulation and thermochemical sulfate reduction in the Jixian Sag of Bohai Bay Basin

Natural gas from the Zhaolanzhuang field of the Jizhong Superdepression, Bohai Bay Basin contains the highest proportions of H₂S (40–92%) among the sour gases encountered in China. The gas payzones include the Eocene–Oligocene Kongdian Formation (Ek) and the Es4 member of the Shahejie Formation. The sedimentary sequence consists of halite, anhydrite, carbonate, sandstone and shale interbeds deposited in the evaporative brackish water lacustrine – salt lake setting. In the deepest part of the Jinxian sag, the total thickness of evaporites is more than 1000 m, of which halite accounts for over 40%. Various organic-rich mudstones intercalated with the evaporites are currently within the conventional hydrocarbon window (with a depth of 2500–3500 m), and likely the source for the oil and sour gas in the Zhaolanzhuang field. The temperatures of the gas reservoirs range from 75 to 100 °C, too low for significant thermochemical sulfate reduction. The co-occurrence of abundant elemental sulfur with the sour gas and the δ³⁴S values of the various sulfur-containing compounds indicate that the H₂S gases were most likely derived from much deeper source kitchens where significant thermochemical sulfate reduction has occurred.     

12,000-Year, preliminary results of the stable nitrogen and carbon isotope record from the Empakai Crater lake sediments, Northern Tanzania

The stable isotope compositions of organic carbon and nitrogen, the contents of organic carbon and nitrogen and C/N ratios for two cores recovered from the Empakai Crater at water depths of 11 and 20 m are used to document climatic changes in northern Tanzania. Eight ¹⁴C AMS dates determined on total organic matter (OM) indicate that the sedimentation rate in this lake is about 30 cm/ka for the late Pleistocene to early Holocene period. There are differences in the δ¹³C values of organic carbon between the two cores, which may be a result of differences in location from the present shoreline and of different water depths. In the deeper-water core the δ¹³C values show a general downcore decrease to the base of the core with a sharp change to lower values of about 4‰ at a depth of 100 cm (8.7 ka). The general trend of downcore decrease in ¹³C values can be attributed either to a systematic decrease in the relative proportion of C₄ type of OM, owing to an increase in precipitation and change in vegetation cover from grassland to forest, or to utilization of isotopically enriched carbon during photosynthesis. The δ¹⁵N values show a general downcore increase with again a sharp change of about 5‰ to lower values at about 8.7 ka. A sharp change of about 5‰ and 4‰ to more depleted values at a depth of 100 cm of both ¹⁵N and ¹³C, respectively, suggests either hiatus or abrupt change in climatic condition from wetter conditions to drier conditions. There is enhanced preservation of OM in the lake as depicted by high mean values of organic carbon and nitrogen at both sites.     

Rare earth element fractionation during the precipitation and crystallisation of hydrous ferric oxides from anoxic lake water

An enrichment of light rare earth elements (LREE) is characteristic for most of the acidic, Fe- and SO₄-rich pit lakes and groundwaters in the lignite mining area of Lower Lusatia (Germany). One of these acidic lakes – the pit lake “RL 1223” – has a strong thermal and chemical stratification. The upper water layer (0–9 m) shows pH values of about 3 during all seasons. The monimolimnion (10–17 m) of the lake is anoxic and has pH values of about 7. The rare earth element (REE) patterns of the upper lake water show enriched LREE (La_N/Yb_N = 1.6) whereas the opposite patterns (depletion of LREE, La_N/Yb_N = 0.4) are found in the anoxic water of the monimolimnion. Experiments were conducted to observe the behaviour of REE during Fe oxidation in water from the monimolimnion (depth 14 m). The sampled monimolimnion water was placed in plastic bottles, and the changing water chemistry was observed for 40 weeks after sampling. Due to the initial anoxic conditions almost all Fe precipitated in the investigated water, and the pH value decreased from about 7 to 3 during the oxidation. The Fe precipitates are identified as ferrihydrite which is transformed into goethite within the oxidation process. Stable pH conditions (pH 3.0) were reached after about 10 weeks of oxidation.The original REE patterns of the investigated water are generally reflected in the Fe precipitates collected at the beginning of the experiment as well as after up to 40 weeks of oxidation. However, in the corresponding water LREE were temporally enriched with a maximum La_N/Yb_N ratio of 1.0 and a maximum La_N/Sm_N ratio of 2.3 after 6 weeks of oxidation time (pH 3.8–4.9). Although complex geochemical changes took place between the start and the end of the experiment REE patterns observed at these points in time are nearly identical. These differences of the REE pattern can be explained by the sampling procedure. The experimental findings can be transmitted to the mining dump aquifers of the study area where geochemical conditions comparable to the experimental oxidation time from 3 to 6 weeks are found and hydrous ferric oxides are precipitating. Groundwater passing through the mining dumps can preferentially desorb LREE from the Fe precipitates and display the typical LREE enrichment and carry it to the epilimnion of the acidic pit lakes in Lower Lusatia.     

Integrated hydrochemical method of water quality assessment for irrigation in arid areas: application to the Jilh aquifer, Saudi Arabia

Water samples from 72 wells tapping the Jilh aquifer were collected and analyzed for 10 different water quality parameters. Using these data, a regional irrigation water quality was assessed using three techniques: (i) United States Department of Agriculture method (USDA), (ii) Food and Agriculture Organization (FAO) guidelines for water quality assessment, and (iii) Water-Types approach. The USDA method revealed that the aquifer water salinity, as represented by electrical conductivity, EC_w, ranges from high salinity (C3: EC_w > 0.75–2.25 dS/m) to a very high salinity (C4: EC_w > 2.25 dS/m). The sodium adsorption ratio (SAR) varied from low (S1) to very high (S4) sodicity. Therefore, the water of the Jilh aquifer is dominantly of the C4–S2 class representing 56% of the total wells followed by C4–S1, C4–S3, C3–S1 and C4–S4 classes at 19%, 14%, 8%, and 3% of the wells respectively. The FAO system indicated moderate to severe restriction on the use for irrigation and slight to moderate ion toxicities for Na⁺, Cl⁻, B⁺, NO₃⁻ and HCO₃⁻. It is clear that, both USDA and FAO systems condemn the Jilh groundwater as hazardous for irrigation due to its high salt content, unless certain measures for salinity control are undertaken. The dominant salt constituents in the water are Mg–Cl₂, Na–Cl and Ca–Cl₂ as per the Water-Types method. However, due to the complexity in classifying the aquifer groundwater for irrigation, a simplified approach acknowledging three class groups (I-suitable water, II-conditionally suitable water and III-unsuitable water) adopted from the three methods, is suggested in this paper. The simplified approach combines C–S classes of the USDA method among these three groups according to the lowest ratings. The salinity of the FAO method has been split arbitrarily into slight and moderate subclasses with values of 0.7–2.25 and >2.25 dS/m, respectively; to match with the C3-class of the USDA system. The Water-Types were classified assuming that Ca–Cl₂ is the least hazardous salt, followed by Mg–Cl₂ and Na–Cl. Using this integrated hydrochemical method, the majority of the wells (92%) contain unsuitable water for irrigation (Group III) while the remaining wells (8%) are in Group II with water considered conditionally suitable for irrigation.     

Carbon and nitrogen utilization in two species of Red Sea corals along a depth gradient: Insights from stable isotope analysis of total organic material and lipids

We examined the utilization of carbon and nitrogen in two common Red Sea coral species (Stylophora pistillata and Favia favus), differing in colony morphology and polyp size, along a depth gradient down to 60 m. We describe the changes in C/N ratios and in the stable isotope composition of carbon and nitrogen of coral’s tissue and algal symbionts. We also measured the carbon isotopic composition of the lipid fraction extracted from both coral tissue and algal symbionts in order to reveal the changes in the carbon source utilized by the host coral for lipid synthesis.The results show that for both species, δ¹³C decreases by 7–8‰ in animal tissue, algal symbionts and in the lipid fractions as depth increases. However, in contrast to previous reports, the difference between δ¹³C values of coral tissue and algal symbionts does not increase with depth. δ¹⁵N values of coral tissue and algal symbionts in both species do not correlate with depth suggesting that the heterotrophic capacity of these corals does not increase with depth. δ¹³C values of tissue lipids were depleted by an average of 3.5‰ compared to δ¹³C of the entire tissue at all depths. δ¹³C values of algal lipids were depleted by an average of 2‰ compared to δ¹³C of the entire zooxanthellae at all depths, indicating high efficiency of carbon recycling between the two symbiotic partners along the entire gradient. The depletion of lipids is attributed to the fractionation mechanism during lipid synthesis. In addition, for both species, δ¹³C values of algal lipids were enriched compared with δ¹³C of tissue lipids. In S. pistillata, the difference between δ¹³C values of tissue lipids and algal lipids increased linearly with depth, indicating a change in the sources of carbon utilized by the coral for lipid synthesis below 20 m from an autotrophic to a heterotrophic source. However, in F. favus, this average difference was 4 times larger compared to shallow S. pistillata and was constant along the entire depth gradient, suggesting that F. favus uses heterotrophically-acquired carbon for lipid synthesis regardless of depth. Overall, F. favus exhibited enriched δ¹³C and δ¹⁵N values compared to S. pistillata along the entire gradient. We attribute these differences to both morphological differences (i.e. colony morphology, tissue thickness and polyp size) between the two species and to a higher heterotrophy/autotrophy ratio in F. favus at all depths. The C/N ratio in S. pistillata tissue decreased with increasing water depth whereas in F. favus it remained constant. This reflects a higher heterotrophic capacity in the large polyped F. favus, at all depths.     

Authigenic layer silicate minerals in borehole Elmore 1, Salton Sea Geothermal Field,California, USA

A combined petrographic/X-ray/electron microprobe and energy dispersive system investigation of sandstone cuttings from borehole Elmore # 1 near the center of the Salton Sea Geothermal Field has revealed numerous regular variations in the composition, texture, mineralogy and proportions of the authigenic layer silicate minerals in the temperature interval 185° C (411.5 m depth) to 361° C (2,169 m). At temperatures near 190° C, dolomite/ankerite+calcite-bearing sandstones contain an illite/mixed layer phase with 10% expandable layers (dolomite/ankerite zone). In shale, the percentage of expandable layers in the mixed layer phase changes from 10–15% at 185° C to 5% at 210° C (494 m). In the interval 250° C (620 m) to 325° C (1,135 m), the calcite+pyrite+epidote-bearing sandstones contain a layer silicate assemblage of chlorite and illite (chlorite-calcite zone). In the shallower portions of this metamorphic zone, the illite contains 0–5% expandable layers, while at depths greater than 725 m (275° C) it is completely free of expandable layers. On increasing temperature, the white mica shows regular decreases in Si^IV, Mg and Fe, and increase in Al^IV, Al^VI, and interlayer occupancy, as it changes gradually from fine-grained illite (=textural sericite) to coarse-grained recrystallized phengitic white mica. In the same interval, chlorite shows decreases in Al^VI and octahedral vacancies and an increase in total Mg+Fe. The sandstones range from relatively unmodified detrital-textured rocks with porosities up to 20% and high contents of illite near 250° C to relatively dense hornfelsic-textured rocks with trace amounts of chlorite and phengite and porosities near 5% at 325° C. Numerous complex reactions among detrital (allogenic) biotite, chlorite, and muscovite, and authigenic illite and chlorite, occur in the chlorite-calcite zone.Biotite appears, and calcite disappears, at a temperature near 325° C and a depth of 1,135m. The biotite zone so produced persists to 360° C in sandstone, at which temperature orthoclase disappears and andradite garnet appears at a depth near 2,155 m. Throughout the biotite zone and into the garnet zone, the biotite undergoes compositional changes that are very similar to those observed in illite/phengite in the chlorite-calcite zone, including increases in interlayer occupancy, Al^IV, Al^VI, and Ti, and decreases in F^–, Si^IV, and Mg/Fe_t+Mg, on increasing temperature. Biotite thus changes from a siliceous, K-deficient biotite at the biotite isograd to a typical low-grade metamorphic biotite at temperatures near 360° C. Minor amounts of talc appear with biotite at the biotite isograd in sandstone, while actinolite appears in both sandstone and shale at temperatures near 340° C (1,325 m). Chlorite completely disappears from sandstone at temperatures of approximately 350° C (1,500 m), and diminishes abruptly in amount in the more chloritic shales at the same depth.     

Seasonal variation in the biogeochemical cycling of seston in Grand Traverse Bay, Lake Michigan

This study describes the biogeochemical cycling of seston in Grand Traverse Bay, Lake Michigan. Seston was characterized by carbon and nitrogen elemental and isotopic abundances. Fluorescence, temperature, light transmittance, and concentrations of dissolved inorganic nitrogen were also determined. PCBs were analyzed from surface (10 m) seston and ΣPCB was calculated by summing all of the congeners quantified in each sample. The vertical and seasonal trends in the δ¹³C values of seston exhibited a broad range from −30.7 to −23.9‰. Low δ¹³C values that occur concurrently with a peak in fluorescence below the thermocline reflect uptake of ¹³C depleted respiratory CO₂ and/or the accumulation of ¹³C depleted lipids by phytoplankton. High δ¹³C values late in the season likely result from a reduction in photosynthetic fractionation associated with a decrease in the CO₂ pool. Seasonal δ¹⁵N values of seston were high in the spring and declined through August. The δ¹⁵N values of seston reflect a balance between fractionation during assimilation of NH₄⁺ or NO₃⁻ and degradative processes. The seston ΣPCB and fluorescence were both high in the spring and subsequently declined, suggesting that the concentrations of PCBs in seston were associated with labile material derived from primary productivity. The strong seasonal trends in the organic geochemical characteristics of seston and concentrations of PCBs emphasize the complex nature of particle cycling in aquatic environments.     

Solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions

An experimental study of the solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions was conducted at temperatures from 200° to 350 °C and at saturated vapor pressure. A 500-mL Bridgemantype pressure vessel constructed of titanium, and equipped with a motor-driven magnetic stirrer was employed. The pH and the oxidation state were buffered by the coexistence of H₂S/HS^–/SO _inf4 ^sup2– . The pH at temperature was calculated to be in the range 5.91–9.43, and S was 0.3–2.2 m. Under the experimental conditions, the measured solubility of gold is about two to three orders of magnitude greater than that of either platinum and palladium, and the measured solubility of platinum is, in general, approximately equal to that of palladium, in molal units. The solubilities are found to be in the range: platinum 4–800 ppb, palladium 1–400 ppb, and gold 2–300 ppm. The solubility data can be modeled adequately using the following reactions: Au+H₂S+HH^–=Au(HS) ₂ ^– +1/2H₂ (K₁₄); PtS+HS^–+H⁺=Pt (HS) ₂ ⁰ (K₁₅); PdS+HS^–+H⁺=Pd (HS) ₂ ⁰ (K₁₆); PtS₂+H₂=Pt (HS) ₂ ⁰ (K₂₁).With equilibrium constants determined as follows (errors represent two standard deviations): Preliminary measurements of the solubilities of metallic Pt, Pd and Au as hydroxide complexes were also conducted using a second titanium pressure vessel, at temperatures of 200° to 350 °C and vapor saturation pressure, with pH and the oxidation state controlled or buffered by adding known amounts of NaOH and H₂ gas. The concentration of NaOH was in the range 0.01–1.3 m, and the partial pressure of H₂ at 200 °C was 62–275 bars, initially. Under the temperature and pressure conditions of these experiments, the solubility of platinum in 1 m NaOH solution is less than 100 ppb, that of palladium is less than 10 ppb and that of gold is less than 0.2 ppm; and in 0.01 m NaOH solutions, both Pt and Pd solubilities are less than 1 ppb. These data indicate that the contributions of hydroxide complexes to the total solubilities in the bisulfide runs, where the pH was in the range of 5.9–9.4, are negligible. The concentrations of both Pt and Pd as bisulfide complexes in the Salton Sea geothermal system predicted using the stability constants determined in this work agree very well with those values measured by McKibben et al. (1990). This calculation strongly suggests that the PGE are transported in moderately reducing, near neutral hydrothermal fluids as bisulfide complexes, as is gold. However, the much lower maximum solubility of the PGE relative to gold severely constrains models of re genesis, and may explain the relative rarity of hydrothermal PGE deposits compared to the relative abundance of hydrothermal Au deposits.     

Mud volcanic natural phenomena in the South Caspian Basin: geology,fluid dynamics and environmental impact

The South Caspian sedimentary basin is a unique area with thick Mesozoic-Cenozoic sediments (up to 30–32 km) characterized by an extremely high fluid generation potential. The large amount of active mud volcanoes and the volumes of their gas emissions prove the vast scale of fluid generation. Onshore and offshore mud volcanoes annually erupt more than 10⁹ cubic meters of gases consisting of CH₄ (79–98%), and a small admixture of C₂H₆, C₃H₈, C₄H₁₀, C₅H₁₂, CO₂, N, H₂S, Ar, He. Mud volcanism is closely connected to the processes occurring in the South Caspian depression, its seismicity, fluctuations of the Caspian Sea level, solar activity and hydrocarbon generation.The large accumulations of gas hydrates are confined to the bottom sediments of the Caspian Sea, mud volcanoes crater fields (interval 0–0.4 m, sea depth 480 m) and to the volcanoes body at the depth of 480–800 from the sea bottom. Resources of HC gases in hydrates saturated sediments up to a depth of 100 m and are estimated at 0.2×10¹⁵–8×10¹⁵ m³. The amount of HC gases concentrated in them is 10¹¹–10¹² m³.The Caspian Sea, being an inland closed basin is very sensitive to climatic and tectonic events expressed in sea level fluctuations. During regressive stages as a result of sea level fall and the reducing of hydrostatic pressure the decomposition of gas hydrates and the releasing of a great volume of HC gases consisting mainly of methane are observed.From the data of deep drilling, seismoacoustics, and deep seismic mud volcanic activity in the South Caspian Basin started in the Lower Miocene. Activity reached its highest intensity at the boundary between the Miocene and Pliocene and was associated with dramatic Caspian Sea level fall in the Lower Pliocene of up to 600 m, which led to the isolation of the PaleoCaspian from the Eastern ParaTethys. Catastrophic reduction of PaleoCaspian size combined with the increasing scale of mud volcanic activity caused the oversaturation and intoxication of water by methane and led to the mass extinction of mollusks, fishes and other groups of sea inhabitants. In the Upper Pliocene and Quaternary mud volcanism occurred under the conditions of a semi-closed sea periodically connected with the Pontian and Mediterranean Basins. Those stages of Caspian Sea history are characterized by the revival of the Caspian organic world.Monitoring of mud volcanoes onshore of the South Caspian demonstrated that any eruption is predicted by seismic activation in the region (South-Eastern Caucasus) and intensive fluid dynamics on the volcanoes.     

Distribution,abundance and carbon isotopic composition of gaseous hydrocarbons in Big Soda Lake,Nevada: An alkaline,meromictic lake

Distribution and isotopic composition (δ¹³C) of low molecular weight hydrocarbon gases were studied in Big Soda Lake (depth = 64 m), an alkaline, meromictic lake with permanently anoxic bottom waters. Methane increased with depth in the anoxic mixolimnion (depth = 20–35 m), reached uniform concentrations (55 μM/l) in the monimolimnion (35–64 m) and again increased with depth in monimolimnion bottom sediments (>400 μM/kg below 1 m sub-bottom depth). The μ¹³C[CH₄] values in bottom sediment below 1 m sub-bottom depth (<?70 per mil) increased with vertical distance up the core (δ¹³C[CH₄] = ?55 per mil at sediment surface). Monimolimnion δ¹³C[CH₄] values (?55 to ?61 per mil) were greater than most δ¹³C[CH₄] values found in the anoxic mixolimnion (92% of samples had δ¹³C[CH₄] values between ?20 and ?48 per mil). No significant concentrations of ethylene or propylene were found in the lake. However ethane, propane, isobutane and n-butane concentrations all increased with water column depth, with respective maximum concentrations of 260, 80, 23 and 22 nM/l encountered between 50–60 m depth. Concentrations of ethane, propane and butanes decreased with depth in the bottom sediments. Ratios of $\text{CH}{}_4\text{[C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{]}$ were high (250–620) in the anoxic mixolimnion, decreased to ~161 in the monimolimnion and increased with depth in the sediment to values as high as 1736. We concluded that methane has a biogenic origin in both the sediments and the anoxic water column and that C₂-C₄ alkanes have biogenic origins in the monimolimnion water and shallow sediments. The changes observed in δ¹³C[CH₄] and $\text{CH}{}_4\text{(C}{}_2\text{H}{}_6\text{+ C}{}_3\text{H}{}_8\text{)}$ with depth in the water column and sediments are probably caused by bacteria] processes. These might include anaerobic methane oxidation and different rates of methanogenesis and C₂ to C₄ alkane production by microorganisms.     

Oxidation and Origin of Organic Matter in Surficial Eastern Mediterranean Hemipelagic Sediments

Aerobic mineralisation of C_org in surface sedimentsof the deep (>2000 m water depth) eastern Mediterranean Sea has been quantified by analysis of detailedbox core C_org concentration versus depth profiles and the modelling environment for early diageneticproblems MEDIA. The reactive fraction comprises 60–80% of the total C_org reachingthe sediments and is largely oxidised within the surficial 10 cm. A non-reactive C _orgfraction (G_NR) dominates at depths >10 cm, and makes up20–40% of the total C _org flux to the sediments. First-order rateconstants for decomposition of the reactive fraction calculated from theC _org profiles range from 5.4 × 10^-3 to8.0 × 10^-3 y^-1 to 8.0 × 10^-3 y^-1. Total mineralization rates in thesurface sediment are between 1.7 and 2.6 mol C cm^-2 y^-1 and thus are typical for oligotrophic, deep-seaenvironments. The low fluxes and rapid remineralisation of C _org are accompanied by²¹⁰Pb_excess surface mixed layers which are only 2 cm deep, among the thinnest reported for oxygenated marine sediments.Model results indicate a mismatch between the C _org profiles and O₂ microprofileswhich were measured onboard ship. This can be attributed to a combination of decompression artefactsaffecting onboard measurement of the O₂ profiles or the leakage ofoxygen into the core during handling on deck. Furthermore, the used D_b values, based on ²¹⁰Pb, may not befully appropriate; calculations with higher D_b values improve the O₂ fits. The surficial sediment¹³C _org values of -22 become less negative with increasing depth and decreasing C _orgconcentrations. The major ¹³C change occurs in the top 3 to 4 cm and coincides with the interval weremost of the organic carbon oxidation takes place. This indicates that the reactive fractionof organic matter, commonly assumed to be marine, has a more negative ¹³C _orgthan the refractory fraction, usually held to be terrestrial. Palaeoproductivity estimates calculated from thesediment data by means of literature algorithms yield low surface productivities(12–88 gC m^-2 y^-1), which are in good agreement with field measurements of primary productivity in otherstudies. Such values are, however, significantly lower than those indicated by recent productivitymaps of the area derived from satellite imagery (>100 gC m^-2 y^-1).     

The effects of surface area, grain size and mineralogy on organic matter sedimentation and preservation across the modern Squamish Delta, British Columbia: the potential role of sediment surface area in the formation of petroleum source rocks

Surface sediment samples were collected from the Squamish River Delta, British Columbia, in order to determine the role of sediment surface area in the preservation of organic matter (OM) in a paralic sedimentary environment. The Squamish Delta is an actively prograding delta, located at the head of Howe Sound.Bulk total organic carbon (TOC) values across the Squamish Delta are low, ranging from 0.1 to 1.0 wt.%. The carbon/total nitrogen ratio (C_org/N) ranges from 6 to 17, which is attributed to changes in OM type and facies variations. The <25-μm fraction has TOC concentrations up to 2.0 wt.%, and a C_org/N ratio that ranges from 14 to 16. The 53–106-μm fraction has higher TOC concentrations and C_org/N ratios relative to the 25–53-μm fraction. The C_org/N ratio ranges from 9 to 18 in the 53–106-μm fraction and 5.5–10.5 in the 25–53-μm fraction. Surface area values for bulk sediments are low (0.5–3.0 m²/g) due to the large proportion of silt size material. Good correlation between surface area and TOC in bulk samples suggests that OM is adsorbed to mineral surfaces. Similar relationships between surface area and TOC were observed in size-fractionated samples. Mineralogy and elemental composition did not correlate with TOC concentration.The relationships between surface area, TOC and total nitrogen (TN) can be linked to the hydrodynamic and sedimentological conditions of the Squamish Delta. As a result, the Squamish Delta is a useful modern analogue for the formation of petroleum source rocks in ancient deltaic environments, where TOC concentrations are often significantly lower than those in source rocks formed in other geological settings.     

Evidence for the rapid incorporation of hopanoids into kerogen

Hopanoids bound into the insoluble organic matter (kerogen) of Recent sediments from a freshwater lake (Priest Pot) and an anoxic sulphidic fjord (Framvaren) were released by hydropyrolysis and examined by gas chromatography-mass spectrometry. Bound hopanoids are present in high concentration (190-1400 μg/g TOC) and represent 22 to 86% of the total analysable hopanoids (i.e., bound and solvent-soluble), this proportion increasing with depth in Framvaren Fjord. The hopanes generated by hydropyrolysis contain higher amounts of the C₃₅, C₃₂, and C₃₀ homologues, reflecting the carbon number distribution of the bound hopanoids and indicating that both biohopanoids (C₃₀ and C₃₅) and their diagenetic products (dominated by C₃₂) are incorporated into the kerogen on a timescale of only 0 to 350 years. Sequential (multiple temperature) hydropyrolysis experiments gave an indication of the relative strengths of bonds being cleaved in association with hopane generation: The hopanoids of a sediment from Priest Pot are almost entirely bound by strong covalent bonds, interpreted to be mainly ether linkages, whilst a Framvaren sediment contains hopanoids that are bound by a mixture of weak di-/polysulphide linkages and stronger ether bonds. Labelling with deuterium indicated that the strong covalent linkages dominate, even for the Framvaren sediment.     

Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.     

Microbial remains in some earliest Earth rocks: Comparison with a potential modern analogue

Carbonaceous matter (CM) from ca. 3.5 Ga hydrothermal black cherts of the Pilbara Craton of Western Australia and the Barberton Greenstone Belt of South Africa yielded transmission electron microscopy (TEM) images that are suggestive of microbial remains and possible remnants of microbial cell walls. These are compared to a potential modern analogue, the hyperthermophilic Methanocaldococcus jannaschii, derived from an active seafloor hydrothermal environment and cultured under similar conditions. A striking resemblance to the early Archaean forms was evident in wall structure and thermal degradation mode. Cell disintegration of the cultures occurred at 100 °C marking the limits of life. Complete disintegration, deformation and shrinkage occurred at 132 °C. A multidisciplinary approach to the characterisation of the CM was undertaken using organic petrology, TEM coupled with electron dispersive spectral analysis (EDS), high resolution TEM (HRTEM) to determine molecular ordering, and elemental and carbon isotope geochemistry. Reflectance measurements of the CM to determine thermal stress yielded a range of values corresponding to several populations, and pointing to different sources and processes. The δ¹³C values of Dresser Formation CM (−36.5 to −32.1‰) are negatively correlated with TOC (0.13–0.75%) and positively correlated with C/N ratio (134–569), which is interpreted to reflect the relative abundance of high R_o/oxidised/recycled CM and preferential loss of ¹²C and N during thermal maturation. TEM observations, inferred carbon isotopic heterogeneity and isotope fractionations of −27 to −32‰ are consistent with the activity of chemosynthetic microbes in a seafloor hydrothermal system where rapid silicification at relatively low temperature preserved the CM.     

Lithological and Hydrogeochemical Implications of Ion Exchange in Sedimentary Basins: Evidence from the Volga–Ural Basin

Implications of ion exchange processes for the formation of lithological and hydrogeochemical systems under various thermobaric conditions of the subsurface hydrosphere are discussed on the basis of on-location, experimental, and thermodynamic studies. It is shown for the case of the Volga–Ural sedimentary basin that ion exchange interaction in the water–rock system bears a zonal character and is differentiated with depth. Exchange and adsorption processes are most efficient in the upper 500-m-thick supergene zone composed of terrigenous clayey rocks, where the HCO₃–Na- and SO₄–Na-waters with a mineralization reaching 20 g/dm³ are formed. In cata- and metagenetic zones at a depth of more than 1000–1500 m, these processes do not strongly affect the brine composition. Metasomatic dolomitization of limestones as an exchange adsorption process plays the crucial role in the formation of Cl–Ca-brines at that depth.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.