Molecular and bulk isotopic analyses of organic matter in marls of the Mulhouse Basin (Tertiary, Alsace, France)

Contents of 13C in kerogens and carbonates in 21 samples from a core of the MAX borehole, Mulhouse Evaporite Basin, range from -27.3 to -23.5 and -3.7 to -1.8% vs PDB, respectively. Organic nitrogen in the same samples is enriched in 15N relative to atmospheric N2 by 12.2-15.7%. Hydrogen indices and delta values for kerogens vary systematically with facies, averaging 493 mg HC/g Corg and -25.7% in the most saline facies (dominated by inputs from aquatic sources) and 267 mg HC/g Corg and -23.7% in the least saline facies (50/50 aquatic/terrigenous). Values of delta were measured for individual aliphatic hydrocarbons from three samples representing three different organic facies. For all samples, terrigenous inputs were unusually rich in 13C, the estimated delta value for bulk terrigenous debris, apparently derived partly from CAM plants, being -22.5%. In the most saline facies, isotopic evidence indicates the mixing of 13C-depleted products of photosynthetic bacteria with 13C-enriched products of halotolerant eukaryotic algae. At lower salinities, a change in the producer community is marked by a decrease in the 13C content of algal lipids. The content of 13C in algal lipids increases in the least saline facies, due either to succession of different organisms or to decreased concentrations of dissolved CO2.     

Molecular composition and organic petrographic characterization of Madbi source rocks from the Kharir Oilfield of the Masila Basin (Yemen): palaeoenvironmental and maturity interpretation

The upper part of Madbi Formation organic-rich shale is considered an important regional source rock in the Masila Basin, Yemen. Ten cutting samples from this Upper Jurassic organic-rich shale were collected from wells drilled in the Kharir Oilfield, Masila Basin in order to geochemically assess the type of organic matter, thermal maturity and depositional environment conditions. Results reveal that Upper Jurassic organic-rich shale samples contain high organic matter more than 2.0 wt.% TOC and have very good to excellent hydrocarbon potential. Marine algae organic matter is the main source input for the Upper Jurassic shale sequence studied. This has been identified from organic petrographic characteristics and from the n-alkane distributions, which dominated by n-C₁₄-n-C₂₀ alkanes. This is supported by the high value of the biomarker sterane/hopane ratio that approaches unity, as well as the relatively high C₂₇ sterane concentrations. A mainly suboxic depositional environment is inferred from pr/ph ratios (1.75–2.38). This is further supported by relatively high homohopane value, which is dominated by low carbon numbers and decrease towards the C₃₅ homohopane. The concentrations of C₃₅ homohopane are very low. The depositional environment conditions are confirmed by some petrographic characteristics (e.g. palynofacies). Detailed palynofacies analysis of Madbi shales shows that the Madbi shale formation is characterised by a mix of amorphous organic matter, dinoflagellates cysts and phytoclasts, representing a suboxic, open marine setting. The Upper Jurassic marine shale sequence in the Masila Basin is thermally mature for hydrocarbon generation as indicated by biomarker thermal maturity parameters. The 22 S/22 S + 22R C₃₂ homohopane has reached equilibrium, with values range from 0.58 to 0.62 which suggest that the Upper Jurassic shales are thermally mature and that the oil window has been reached. 20 S/(20 S + 20R) and ββ/(ββ + αα) C₂₉ sterane ratios suggest a similar interpretation, as do the moretane/hopane ratio. This is supported by vitrinite reflectance data ranging from 0.74% to 0.90%Ro and thermal alteration of pollen and spore. The thermal alteration index value is around 2.6–3.0, corresponding to a palaeotemperature range of 60–120°C. These are the optimum oil-generating strata. On the basis of this study, the Madbi source rock was deposited under suboxic conditions in an open marine environment and this source rock is still within the oil window maturity range.     

Hydrochemical,isotopic, and reservoir characterization of the Pasinler (Erzurum) geothermal field,eastern Turkey

The reservoir temperature and conceptual model of the Pasinler geothermal area, which is one of the most important geothermal areas in Eastern Anatolia, are determined by considering its hydrogeochemical and isotope properties. The geothermal waters have a temperature of 51 °C in the geothermal wells and are of Na–Cl–HCO₃ type. The isotope contents of geothermal waters indicate that they are of meteoric origin and that they recharge on higher elevations than cold waters. The geothermal waters are of immature water class and their reservoir temperatures are calculated as 122–155 °C, and their cold water mixture rate is calculated as 32%. According to the δ¹³C_VPDB values, the carbon in the geothermal waters originated from the dissolved carbon in the groundwaters and mantle-based CO₂ gases. According to the δ³⁴S_CDT values, the sources of sulfur in the geothermal waters are volcanic sulfur, oil and coal, and limestones. The sources of the major ions (Na⁺, Ca²⁺, Mg²⁺, Cl^?, and HCO₃ ^?) in the geothermal waters are ion exchange and plagioclase and silicate weathering. It is determined that the volcanic rocks in the area have effects on the water chemistry and elements like Zn, Rb, Sr, and Ba originated from the rhyolite, rhyolitic tuff, and basalts. The rare earth element (REE) content of the geothermal waters is low, and according to the normalized REE diagrams, the light REE are getting depleted and heavy REE are getting enriched. The positive Eu and negative Ce anomalies of waters indicate oxygen-rich environments.     

Speciation and stable isotopic compositions of humic sulfur in mud sediment of the East China Sea: Constraints on origins and pathways of organic sulfur formation

Humic sulfur is commonly the most important pool of organic sulfur (OS) in marine sediments and also important for the budget of total sedimentary sulfur. In this study, contents and stable sulfur isotopic compositions of hydrolyzable organic sulfur (HYOS), humic acid sulfur (HA-S) and fulvic acid sulfur (FA-S) in one core collected from the East China Sea (ECS) inner shelf were determined to investigate the sources and pathways of OS formation and to compare diagenetic geochemistry of HA-S and FA-S. HYOS in the core is essentially biological in origin and diagenetically refractory, with a fairly low fraction of labile sulfur bearing biomolecules. HA-S in the core is largely terrigenous residual bio-OS, while FA-S is a mixture of marine bio- and diagenetic OS (diag-OS), with the diag-OS fractions between 44% and 71%. Both HA-S and FA-S contents in the core are at the lower ends of the corresponding values reported in the literature. The HA in the sediments is diagenetically inert, subject to neither significant diagenetic sulfurization nor bio-OS mineralization loss, while the FA is reactive, prone to both sulfurization and decomposition loss of diagenetically bound OS. Low contents of humic S [i.e., ∑(HA-S + FA-S)] in the core may suggest that OS burial has only minor contribution to the burial of total sulfur in the sediments due to generally low OM sulfurization.     

The sulfur and strontium isotopic compositions of Permian evaporites from the Zechstein basin, northern Germany

The sulfur isotopic composition of stratigraphically well constrained samples from five evaporitic cycles of the German Zechstein (upper Permian) displays no systematic lateral variation and no significant temporal trend. With an average δ³⁴S value close to 11‰, results confirm the previously determined sulfur isotope minimum for Phanerozoic seawater. Least radiogenic ⁸⁷Sr/⁸⁶Sr ratios for these sulfates define a clear temporal variation with a minimum value at 0.707008. A conclusive assessment of this temporal trend in comparison with other data sets for upper Permian seawater is not possible due to substantial differences in (bio)stratigraphic assignments.     

大西洋洋中脊TAG热液区硫化物铅和硫同位素研究

位于大西洋洋中脊26.08°N的TAG热液区是目前已知的赋存在无沉积物覆盖的洋中脊区的一个最大的海底热液硫化物矿床.新测得来自ODP-158航次钻孔的9件热液硫化物的铅、硫同位素组成;2件铁锰氧化物和1件底盘玄武岩的铅同位素组成.结果表明,矿石硫化物的铅同位素组成206Pb/204Pb为18.2343～18.3181,207Pb/204Pb为15.4717～15.5061,208Pb/204Pb为37.7372～37.8417;它们位于该区底盘玄武岩(206Pb/204Pb=18.1454,207Pb/204Pb=15.4572,208Pb/204Pb=37.6534)和近洋底铁锰氧化物(206Pb/204Pb,207Pb/204Pb,208Pb/204Pb分别为18.6907～18.9264,15.5615～15.6279,38.1164～38.3687)的铅同位素组成之间.三者呈线性相关关系,说明硫化物中铅来源于地幔(玄武岩)与海水(铁锰氧化物)的两端元混合.硫化物的硫同位素组成δ34S为6.2‰～9.5‰,它明显高于地幔玄武岩的硫同位素组成(δ34S=±0‰),也高于东太平洋海隆EPR21°N(δ34S=0.9‰～4.0‰)和大西洋洋中脊MAR23°N(δ34S=1.2‰～2.8‰)等热液活动区硫化物的硫同位素组成,这一特征反映了TAG热液体系中硫来源于地幔玄武岩硫与海水硫酸盐无机还原作用产生的硫的两端元混合.因此,铅硫同位素研究为现代大洋底热液硫化物矿床形成过程中矿质来源及流体混合作用提供了十分有益的信息.     

渔塘坝富硒硅质岩成因及沉积环境探讨：硅、氧、碳和硫同位素证据

鄂西渔塘坝含碳硅质岩段(P³₁m)为硒矿床的主要赋硒层位,其硅、氧同位素组成δ³⁰Si变化范围为0.5‰~1.8‰（平均1.25‰）;δ¹⁸O为22.7‰~27.1‰ （平均25.3‰）;硅质岩中黄铁矿 δ³⁴S的值变化范围为-27.7‰~-5.65‰,幅度大于20‰;硅质岩层位中方解石样品的δ¹³C值范围为4.19‰~0.52‰。综合研究表明,渔塘坝硅质岩在成因上主要表现为热水沉积特征,成岩温度为45℃,形成于半封闭的浅海至滨浅海（滞留的盆地）缺氧沉积环境。     

Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield,Anhui, China

Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re–Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The γ_Os values of the two pyrite samples are + 17 and + 18, respectively. Such high γ_Os values are reported for the first time for recycles crustal materials from a sedimentary basin.     

兰坪白秧坪铜银多金属矿床成矿物质来源的铅和硫同位素示踪

白秧坪铜银多金属矿床主要产于白垩系下统景星组石英砂岩、粉砂岩中,矿石铅同位素组成特征与景星组砂岩的铅同位素组成比较接近,表明壳源物质参与了成矿作用。作ZartMan图解和Δγ-Δβ图解表明,矿石铅属于壳幔混合来源。矿石铅μ值介于9.43~9.65之间,Th/U比值介于3.72~3.87之间,表明矿石铅为壳幔混合铅。该矿床硫同位素组成表明,硫来源于深部地幔硫遭受地壳硫的混入。该矿床的成矿作用发生于开放体系之中,成矿物质来源为深部幔源物质混合了壳源物质。     

藏南柯月铅锌矿床成矿物质来源:来自硫、铅同位素的证据

藏南柯月铅锌矿床位于特提斯喜马拉雅构造域Sb-Au-Pb-Zn成矿带东段,矿体主要呈透镜状或脉状,严格受北东向断裂构造所控制,赋矿地层为下侏罗统日当组含碳钙质板岩。矿石硫化物硫同位素δ³⁴S介于9.2 ‰~11.2 ‰之间,平均值为9.85‰,与区内日当组地层的δ³⁴S值变化范围相似,表明成矿流体中的硫主要来源于容矿地层。矿石硫化物铅同位素组成为:²⁰⁶Pb/²⁰⁴Pb为19.669~19.813,平均值19.740;²⁰⁷Pb/²⁰⁴Pb为15.823~15.979,平均值15.902;²⁰⁸Pb/²⁰⁴Pb为40.104~40.687,平均值40.410。其结果显示,矿石中的铅具有高放射性成因铅的特征,与喜马拉雅结晶基底的铅同位素组成具有相似的比值,表明矿石铅主要来源于喜马拉雅结晶基底。     

The sulfur isotopic composition of sulfides from ores and host rocks of the Upper Kolyma region,Magadan Oblast

More than 200 analyses of the sulfur isotopic composition of sulfides from various terrigenous and intrusive host rocks, metasomatically altered wall rocks, and gold lodes of the Upper Kolyma region are presented. In accessory pyrite of the metaterrigenous rocks, δ³⁴S varies from ?23.1 to +5.7‰ δ³⁴S of pyrite and arsenopyrite from gold-quartz mineralization is within the range ?10.6 to ?0.4‰ and is close to the average δ³⁴S of pyrite from the metaterrigenous rocks (?4.4‰). In the intrusive rocks, δ³⁴S of pyrite varies from ?3.8 to +2.6‰ (+0.7‰, on average) and drastically differs from δ³⁴S of arsenopyrite from postmagmatic gold-rare-metal mineralization (?7.9 to ?2.7‰; ?5.2‰, on average). The comparison of the δ³⁴S of accessory sulfides from the host rocks with δ³⁴S of sulfides from the gold deposits suggests that sulfur mobilized from the terrigenous sequences participated in the hydrothermal process. The results obtained are consistent with the metamorphic model of the formation of gold-quartz deposits in the Upper Kolyma region.     

Thermal analysis (TG–DTA) and isotopic characterization (13C–15N) of humic acids from different origins

Thermal analyses (TG–DTA), elemental composition and isotope analyses (¹³C and ¹⁵N) were performed on humic acids (HA) from peats, leonardites and lignites, in order to investigate their structure and the changes taking place during the humification process. Thermal analyses showed structural differences between HA samples in relation to their coalification rank. In particular the lignite HA were characterized by a more stable chemical composition at high temperatures.The δ¹³C and δ¹⁵N values can provide information on the biogeochemical processes involved in HA formation. In particular, peat HA were linked to anoxic environments that enable plant residues to persist in their structure. In contrast, leonardite and lignite HA formation seems to be governed by different biogeochemical processes from those responsible for peat diagenesis. However, the isotopic analyses did not provide any distinction between leonardite and lignite HA. On the basis of the data presented in this study, it may be concluded that TG–DTA and isotope ratio measurements are powerful tools for investigating the formation pathway of humic substances from coals.     

High-precision Pb isotopic measurements of teeth and environmental samples from Sofia (Bulgaria): insights for regional lead sources and possible pathways to the human body

High-precision Pb isotopic measurements on teeth and possible sources in a given area can provide important insights for the lead (Pb) sources and pathways in the human body. Pb isotopic analyses on soils from the area of Sofia, Bulgaria show that Pb is contributed by three end-members represented by two natural sources and leaded gasoline. Sequential leaching experiments reveal that the alumosilicate fraction of the soils is mainly controlled by natural Pb derived from two mountain massifs bordering the city. Around 1/3 to a half of the Pb in the soil leachates, however, can be explained by contamination from leaded gasoline. Contemporary teeth from Sofia residents show very similar Pb isotopic compositions to the soil leachates, also indicating that around 1/3 to a half of the Pb can be explained by derivation from leaded gasoline. The remarkable isotopic similarities between the teeth and the most labile fractions of the local soils suggest that the lead can be derived from the latter. Pb incorporation in the human body via soil-plant–human or soil–plant–animal–human chains is unlikely due to the fact that no significant farming occurs in the city area. The isotopic compositions of the local soil labile fractions can be used as approximation of the bioaccessible lead for humans. Considering all possible scenarios it appears that soil and/or soil-born dust inhalation and/or ingestion is the most probable pathway for incorporation of local soil lead in the local population. The high-precision Pb isotope data presented in this work indicate that apparently the local soil is what plays major role in the human Pb exposure.     

Trace metals and organic compounds in sediment samples from the River Danube in Russe and Lake Srebarna (Bulgaria)

 In 1995 the contamination status of accumulated fine surface sediments and effluent material from the River Danube in Russe (Bulgaria) was analysed for trace metals (Hg, Cd, Pb, Cu, Zn, Cr, Ni, As), polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), hexachlorobenzene (HCB), 1,1,1-trichloro-2,2-bis [chlorophenyl] ethane (DDT), 1,1-dichloro-2,2-bis [chlorophenyl] ethylene (DDE), 1,1-dichloro-2,2-bis [chlorophenyl] ethane (DDD), and hexachlorocyclohexanes (α-, β-, γ- and δ-HCH) to achieve basic information about the River Danube in Bulgaria. The range of trace-metal levels came close to or below the intended quality criteria for the River Elbe in Germany. The only exceptions were Pb in a shipyard, exceeding the final criteria by a factor of 17, and Cr downflow from a metal factory. In one sample from a shipyard (D8) the highest trace metal concentrations were analysed in the fraction 125–2000 μm. The maximum measured PAH contents exhibited a contamination on the lower μg g^–1 d.w.-level (dry weight base), traces of PCBs, HCB and DDD/DDE were analysed in the ng g^–1 d.w.-range. DDT and HCHs were not detected in any sample. The trace-metal and organic-compounds level in sediments from Lake Srebarna (UNESCO-Biosphere Reserve) displayed completely background character. Received: 18 March 1997 · Accepted: 21 July 1998     

Geochemical and isotopic characterization of groundwater from shallow and deep limestone aquifers system of Aleppo basin (north Syria)

Stable isotopes (δ¹⁸O, δ²H and ¹³C) and radioactivity (³H, ¹⁴C) have been used in conjunction with chemical data to evaluate the processes generating the chemical composition, reconstruct the origin of the water and groundwater residence time. The Aleppo basin is comprised of two main limestone aquifers: the first one is unconfined of Paleogene age and the second is confined of Upper Cretaceous age. The chemical data indicate that the dissolution of minerals and evaporation are the main processes controlling groundwater mineralization. The groundwater from the two aquifers is characterized by distinctive stable isotope signatures. This difference in water isotopes is interpreted in terms of difference origin and recharge period. Fresh and brackish shallow groundwater were mostly recharged during the Holocene period. The presence of ³H in several groundwater samples of this aquifer gives evidence that groundwater recharge is going on. Brackish water of the deep confined aquifer has depleted stable isotope composition and very low ¹⁴C activity that indicates recharge during the late Pleistocene cold period.     

U-Pb age and lead isotopic characterization of Au-bearing skarn related to the Andorra granite (central Pyrenees,Spain)

Auriferous skarns are associated with post- and late-kinematic Hercynian granites that intruded into Cambro-Ordovician to Devonian sediments of the central Pyrenees. We determined the age of the Andorra granite and the associated skarn at 305 ± 3 Ma by U-Pb dating titanite from the endo-skarn. The sulfur isotopic composition from sulfides in the skarn (Cardellach et al. 1992) shows a significant variation with isotopically light sulfur (³⁴S +3) in the barren skarns and heavy sulfur (³⁴S +11) in the gold-bearing skarns. Outwards, it increasingly resembles sulfur from arsenopyrite disseminations in the Cambro-Ordovician sediments. The lead isotopic composition from sulfides of the skarns is very homogeneous (²⁰⁶Pb/²⁰⁴Pb = 18.410, ²⁰⁷Pb/²⁰⁴Pb = 15.699, ²⁰⁸Pb/²⁰⁴Pb = 38.574) in contrast to the one in gold-bearing arsenopyrite veins and in arsenopyrite disseminations in the sediments (e.g. ²⁰⁶Pb/²⁰⁴Pb varies from 18.54 to 30.36). Combined, sulfur and lead isotope data indicate that the lead in the skarn is dominantly derived from the granite, whereas the sulfur is derived at variable portions from both the granite and the sediments.     

The palaeoenvironmental and palaeohydrological evolution of Padul Peat Bog (Granada, Spain) over one million years, from elemental, isotopic and molecular organic geochemical proxies

The elemental (concentration of organic carbon, atomic H/C and C/N ratios), isotopic (δ¹³C values of organic matter) and molecular (predominant n-alkane chain length and carbon preference index (CPI)) organic components were measured for 600 samples taken from a 107-m long core from the Padul Basin (Andalusia, Spain). The record runs from the Lower Pleistocene (ca. 1 Ma B.P.) to the mid-Holocene (ca. 4.5 ka B.P.) with, in general, little diagenesis (removal of components). Two markedly different hydrogeological scenarios were interpreted: (1) From ca. 1 Ma to ca. 400 ka B.P. run-off recharge was significant and water depths were greater (lacustrine scenario). From ca. 400 to 4.5 ka B.P., the Padul Basin became a peat bog s.s. with the major water input coming from groundwater inflow. From ca. 400 to ca. 180 ka B.P. alternating episodes with either predominant grasses, trees or aquatic macrophytes which were linked to wet/dry phases, took place. An important deglaciation episode has been interpreted to occur between ca. 180 and 170 ka B.P. The global climatic changes occurring from ca. 170 to 25 ka B.P. were not recorded in the proxies, though they do show important variations linked to the Last Glacial Maximum and the beginning of the Holocene (ca. 25–10 ka B.P.): (2) Cold phases coexisting with dry periods produced the recession of forests and the development of grasses. After these periods, as both temperature and precipitation increased, forests expanded and the water level, linked to thaw, rose, especially at ca. 20 ka B.P. Few changes occurred during the Holocene, although there were short alternations between wet and dry episodes. Overall, the techniques applied proved to be excellent palaeoenvironmental proxies for studying the basin’s palaeoclimatological and palaeohydrological evolution.     

Geochemical and isotopic characterization of groundwater from the Paleogene limestone aquifer of the Upper Jezireh,Syria

This research aims to evaluate the groundwater resources of Paleogene aquifer in the Upper Jazireh area (Syria), in terms of chemical water type, recharge zones and water ages. The results show that the main recharge zones for the Paleogene aquifer range between 650 and 900 m a.s.l., which coincide with the outcrop of the karstified limestone in the Mardin uplift. The chemical and isotopic behaviors of groundwater, together with radiometric ¹⁴C reflect the existence of three different groundwater groups: (1) the fresh and cold water, percolating in short and shallow flow paths, for which the main replenishment processes are recent; (2) the brackish and thermal water containing certain amounts of H₂S gas, that percolate in longer and deeper flow paths, for which the main replenishment processes occurred during the palaeoclimatic humid conditions of Pleistocene time, placed at 10–18 Ka BP; (3) the brackish and admixed thermal groundwater with intermediate ¹⁴C age, which seems to be formed as a result of mixing between the previous two groups.