加氢和TSR反应对天然气同位素组成的影响

天然气形成过程中的加氢作用和 TSR 反应是有机-无机相互作用的重要方式。相邻水体和深部来源的氢,是天然气形成的重要氢源,塔里木盆地天然气的甲烷氢同位素组成明显表现出不同沉积水体对甲烷氢同位素的控制作用,大宛105～25井和阿克1井具有深部流体加氢的特征;TSR 反应中硫同位素在不同反应阶段和反应过程具有不同的分馏特征,这种特征在四川盆地高舍硫天然气中具有很好的表现,TSR 反应硫同位素分馏一般小于20‰,而单体硫、黄铁矿和硫酸盐矿物等其它反应过程的产物硫同位素分馏不明显。     

硫酸盐热化学还原作用的启动机制研究

硫酸盐热化学还原作用(TSR)是导致高含硫化氢天然气生成和聚集、碳酸岩盐储层酸化和溶蚀的重要因素,是地质盆地内烃-水-岩三者之间的复杂反应。本文利用黄金管热模拟实验,对TSR反应的可能启动机制及控制因素进行了研究。通过不同盐溶液与原油的热解实验,证实了硫酸盐的存在是启动TSR反应的必要因素,MgSO4比CaSO4和Na2SO4更容易启动TSR反应,体系中盐度的增加会加速H2S的生成。实验结果表明,不同水介质条件下,TSR反应的程度与溶液的离子强度呈正相关,弱酸性环境并不足以启动TSR反应;原油中不稳定含硫化合物的含量越高越有利于TSR反应的发生,饱和链烷烃比原油中其它组分更容易引发TSR反应,且大分子烷烃比小分子烷烃更容易被硫酸盐氧化。     

川东北地区酸性气体中CO2成因与TSR作用影响

通过对川东北地区52个天然气样品化学组分和稳定碳同位素分析,天然气以烃类气体为主,且甲烷占绝对高含量,重烃气体甚微,干燥系数C1/C1+为0.989～1.0。非烃气体H2S和CO2含量变化较大,当二者含量大于5.0％时,具有较好的正相关性。川东北地区天然气中CO2主要包括碳酸盐岩热分解和TSR作用,其中碳酸盐岩热分解生成的CO2含量一般小于5.0％,13CCO2值小于-2‰,且CO2含量与13CCO2值具有正相关性;而TSR作用生成的CO2含量大于5.0％,13CCO2值多大于-2‰,且CO2含量与13CCO2值具有较弱的负相关性。CH4/CO2比值和（H2S+CO2）/（H2S+CO2+∑C1-3）比值能够较好地反映TSR作用程度;当CH4/CO2比值和（H2S+CO2）/（H2S+CO2+∑C1-3）比值分别小于10和大于0.1时,随着TSR作用增强,CH4/CO2比值减少,而（H2S+CO2）/（H2S+CO2+∑C1-3）比值呈指数增加。同时,遭受TSR作用改造的天然气具有较高CO2含量和重的13CCO2,造成13CCO2值与实验结果不一致性的可能原因是在TSR反应过程中部分CO2与硫酸盐中Mg2+、Fe2+和Ca2+等金属离子以碳酸盐的形式沉淀且残余的重碳同位素组成的CO2与酸性气体腐蚀碳酸盐储层形成的CO2相混合。     

The role of labile sulfur compounds in thermochemical sulfate reduction

The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n-octane and CaSO₄ in the presence of reduced sulfur (e.g. H₂S, S°, organic S) at temperatures of 330 and 356 °C under a constant confining pressure. The in-situ pH was buffered to 3.5 (∼6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H₂S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n-octane, which is comparable to the concentration of organic S that is common in many oils (∼0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H₂S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H₂S. Second, we considered the generation of olefines in association with the elimination of H₂S during thermal degradation of thiols because olefines are much more reactive than n-alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of organic LSC creates free-radicals that in turn might initiate a radical chain-reaction that creates more reactive species. Experiments involving radical initiators, such as diethyldisulfide and benzyldisulfide, did not show an increase in reactivity compared to 1-pentanethiol. Therefore, we conclude that none of these can sufficiently explain our observations of the initial stages of TSR; they may, however, be important in the later stages. In order to gain greater insight into the potential mechanism for the observed reactivity of these organic sulfur compounds during TSR, we applied density functional theory-based molecular modeling techniques to our system. The results of these calculations indicate that 1-pentanethiol or its thermal degradation products may directly react with sulfate and reduce the activation energy required to rupture the first S-O bond through the formation of a sulfate ester. This study demonstrates the importance of labile sulfur compounds in reducing the onset timing and temperature of TSR. It is therefore essential that labile sulfur concentrations are taken into consideration when trying to make accurate predictions of TSR kinetics and the potential for H₂S accumulation in petroleum reservoirs.     

Experimental study of the effects of thermochemical sulfate reduction on low molecular weight hydrocarbons in confined systems and its geochemical implications

Experimental studies of the effects of thermochemical sulfate reduction (TSR) on light hydrocarbons were conducted in sealed gold tubes for 72 h at 400 °C and 50 MPa. A variety of pyrolysis experiments were carried out, including anhydrous, hydrous without MgSO₄ (hydrous experiments) and hydrous with MgSO₄ (TSR experiments). Common reservoir minerals including montmorillonite, illite, calcite and quartz were added to various experiments. Measurements of the quantities of n-C₉₊ normal alkanes (high molecular weight, HMW), n-C_6-8 normal alkanes (low molecular weight, LMW), C_7-8 isoalkanes, C_6-7 cycloalkanes and C_6-9 monoaromatics and compound specific carbon isotope analyses were made. The results indicate that TSR decreases hydrocarbon thermal stability significantly as indicated by chemically lower concentrations and isotopically heavier LMW saturated hydrocarbons in the TSR experiments compared to the hydrous and anhydrous experiments. In the LMW saturated hydrocarbon fraction, cycloalkanes tend to be more resistant to TSR than n-alkanes and isoalkanes. TSR promotes aromatization reactions and favors the generation of monoaromatics, resulting in higher chemical concentrations and isotopically equivalent compositions of monoaromatics in the anhydrous, hydrous and TSR experiments. This indicates that LMW monoaromatics are thermally stable during the pyrolysis experiments. Acid rather than basic catalyzed ionic reactions probably play a major role in TSR. This is suggested by the promotion effects of acid-clay minerals including illite and particularly montmorillonite. The basic mineral calcite retards the destruction of n-C₉₊ normal alkanes within the TSR experiments. Furthermore, clay minerals have a minor influence on the generation of LMW monoaromatics and play a negative role in regulating the concentrations of LMW saturated hydrocarbons; calcite does not favor the generation of LMW monoaromatics and plays a positive role in controlling the concentrations of LMW saturates relative to clay minerals. Quartz has a negligible role in the TSR experiments.Due to their differential responses to TSR, LMW hydrocarbon parameters, such as Schaefer [Schaefer, R.G., Littke, R., 1988. Maturity-related compositional changes in the low-molecular-weight hydrocarbon fraction of Toarcian Shale. Organic Geochemistry 13, 887-892], Thompson [Thompson, K.F.M., 1988. Gas-condensate migration and oil fractionation in deltaic systems. Marine and Petroleum Geology 5, 237-246], Halpern [Halpern, H., 1995. Development and application of light-hydrocarbon-based star diagrams. American Association of Petroleum Geologists Bulletin 79, 801-815] and Mango [Mango, F.D., 1997. The light hydrocarbons in petroleum: a critical review. Organic Geochemistry 26, 417-440] parameters and stable carbon isotopic compositions of individual LMW saturated hydrocarbons in TSR affected oils should be used with caution. In addition, water promotes thermal cracking of n-C₉₊ normal alkanes and favors the generation of LMW cycloalkanes and monoaromatics. The result is lower concentrations of n-C₉₊ HMW normal alkanes and higher concentrations of LMW cycloalkanes and monoaromatics in hydrous experiments relative to anhydrous experiments with or without minerals.This investigation provides a better understanding of the effects of TSR on LMW hydrocarbons and the influence of reservoir minerals on TSR in natural systems. The paper shows how LMW hydrocarbon indicators in TSR altered oils improve understanding of the processes of hydrocarbon generation, migration and secondary alteration in subsurface petroleum reservoirs.     

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.     

硫酸盐热化学还原作用对原油裂解成气和碳酸盐岩储层改造的影响及作用机制

硫酸盐热化学还原作用(Thermochemical sulfate reduction, TSR)是发生在油气藏中复杂的有机-无机相互作用,它不仅会引起含H₂S天然气的富集,其产生的酸性气体对碳酸盐岩储层还具有明显的溶蚀改造作用。本文基于黄金管热模拟实验,研究了TSR反应对原油裂解气的生成的影响,发现这种氧化还原反应的存在能明显降低原油的稳定性,促进具高干燥系数的含H₂S天然气的生成。结合原位激光拉曼实验结果,证实了实际油藏中启动TSR反应的最可行的氧化剂应该是硫酸盐接触离子对(CIP)。全面探讨了影响TSR反应的地质和地球化学因素,提出除了初始原油的组分特征、不稳定含硫化合物(LSC)的含量外,地层水的含盐类型及盐度同样是控制TSR反应的关键因素。同时,基于大量地质分析,发现TSR对碳酸盐岩储层具有明显的溶蚀改造作用。结合溶蚀模拟实验,提出了酸性流体对碳酸盐储层溶蚀改造的机制,且深层碳酸盐岩层存在一个由TSR作用形成的次生孔隙发育带。研究认为,烃类与硫酸盐矿物的氧化还原反应与其产物对碳酸盐岩储层的改造是TSR作用的两个不可分割的部分,它们相互依存和制约。     

The genesis of calcite in carbonate rocks of the sedimentary basins: Evidence from the stable carbon and oxygen isotopes composition

The distributions of stable carbon and oxygen isotopes in modern and ancient limestones of various types were studied. Carbonate samples from modern sediments were collected in the Black and Barents Seas. Ancient carbonates were represented by Upper Jurassic (Kimmeridgian-Tithonian) limestones from the central part of the West Siberian basin. Carbonate samples include remains of modern and Upper Jurassic fauna, carbonate crust from sediments of the Black Sea, carbonate tube from sediments of the Barents Sea, and Upper Jurassic limestone from the carbonate layer found at top of Abalak, bottom of Bazhenov deposits in the central part of the West Siberian basin. According to the results of the isotope analysis and comparison with modern carbonates, Upper Jurassic limestones of the West Siberian basin belong to the group of methane-derived carbonates and precipitated as a result of anaerobic oxidation of methane (AOM). Fractures in limestones are filled with secondary calcite.     

Oil-source correlation of the pre-Tertiary in the Huanghua Depression： Insights from stable carbon isotopes and molecular markers

Stable carbon isotopes were used together with molecular markers to constrain genetic relationships between sandstone extracts and potential source rocks in the pre-Tertiary in the Huanghua Depression, North China. Comparison of the extracts from Permo-Carboniferous terrigenous mudstones and Ordovician marine carbonates indicated that their prominent differences are in stable carbon isotopes, molecular markers and thermal maturity. Although the extracts of the Mesozoic and Lower Permian Xiashihezi Formation sandstones have some similar iso-topic characteristics, molecular markers data provide a good correlation between the Upper Jurassic-Lower Cretaceous oils and the Upper Carboniferous Taiyuan Formation mudstones, and between the Lower Permian Xiashihezi Formation oils and the Lower Permian mudstones. The results showed that the Upper Jurassic-Lower Cretaceous sandstone oils were derived chiefly from the Upper Carboniferous Taiyuan Formation terrigenous mudstones and that the Lower Permian Xiashihezi Formation oils were sourced from the Lower Permian Shanxi Formation and Xiashihezi Formation terrigenous mudstones.     

TSR(H2S)对石油天然气工业的积极性研究--H2S的形成过程促进储层次生孔隙的发育

TSR(硫酸盐热化学还原反应)是高含硫化氢天然气形成的重要途径,是指烃类在高温条件下将硫酸盐还原生成H2S、CO2等酸性气体的过程。由于硫化氢的剧毒和强腐蚀性,在石油天然气行业的钻井、完井、修井、净化加工以及运输等各个方面的危害一直备受人们的关注,对硫化氢和TSR的评价一直是负面的,在油气勘探中更多是在回避。最近研究发现,TSR作用对石油天然气工业具有重要的积极作用。TSR的发生,首先需要硫酸盐类溶解提供SO42-,储集空间得到初步改善;其次TSR反应形成的硫化氢,溶于水后显示出较强的酸性溶蚀作用,对白云岩储层具有最佳的溶蚀效果。在高温条件和储层中地层水的作用下,硫化氢与白云岩发生较强烈的酸性流体-岩石相互作用(水岩反应),促进了白云岩次生孔洞的发育和高孔高渗优质储集层的形成,使油气储层保存下限增大和深部天然气聚集成藏成为可能。而目前飞仙关组高含硫化氢气藏普遍压力系数小、充满度低,这与TSR及硫化氢对储层溶蚀导致储集空间增容有关。四川盆地油气勘探结果证实,所有高含硫化氢天然气藏均对应了次生孔隙十分发育的优质储层,岩性主要以白云岩为主,储层埋藏深度超过8 000 m时依然发育优质储层。     

张家口南部地区温泉形成的氢氧稳定同位素及气体组成证据

本文研究了张家口南部地区温泉(井)水的氢氧稳定同位素组成及溶解气体组分特征。结果表明,大气降水是该区温泉(井)水的补给来源。大气降水在深循环过程中,受地热增温,岩浆残余热的影响,使水温增高并在适当的构造部位涌出地表形成温泉     

The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

The yields and stable C and H isotopic composition of gaseous products from the reactions of pure n-C₂₄ with (1) MgSO₄; and (2) elemental S in sealed Au-tubes at a series of temperatures over the range 220–600 °C were monitored to better resolve the reaction mechanisms. Hydrogen sulfide formation from thermochemical sulfate reduction (TSR) of n-C₂₄ with MgSO₄ was initiated at 431 °C, coincident with the evolution of C₂–C₅ hydrocarbons. Whereas the yields of H₂S increased progressively with pyrolysis temperature, the hydrocarbon yields decreased sharply above 490 °C due to subsequent S consumption. Ethane and propane were initially very ¹³C depleted, but became progressively heavier with pyrolysis temperature and were more ¹³C enriched than the values of a control treatment conducted on just n-C₂₄ above 475 °C. TSR of MgSO₄ also led to progressively higher concentrations of CO₂ showing relatively low δ¹³C values, possibly due to input of isotopically light CO₂ derived from gaseous hydrocarbon oxidation (e.g., more depleted CH₄).     

Determining the origin of carbon dioxide and methane in the gaseous emissions of the San Vittorino plain (Central Italy) by means of stable isotopes and noble gas analysis

The chemistry and isotope ratios of He, C (δ¹³C) and H (δD) of free gases collected in the San Vittorino plain, an intramontane depression of tectonic origin, were determined to shed light on mantle degassing in central Italy. The C isotopic composition of CO₂ (δ¹³C–CO₂ −2.0‰ to −3.8‰) and He isotope ratios (R/R_A 0.12–0.27) were used to calculate the fraction of CO₂ originating from mantle degassing vs. sedimentary sources. The results show that CO₂ predominantly (average of 75%) derives from the thermo-metamorphic reaction of limestone. Between 6% and 22% of the CO₂ in the samples derives from organic-rich sedimentary sources. The mantle source accounts for 0–6% of the total CO₂; however, in two samples, located in proximity to the most important faults of the plain, the mantle accounts for 24% and 42%. The presence of faults and fractures allows upward gas migration from a deep source to the Earth’s surface, not only in the peri-Tyrrhenian sector, as generally reported by studies on natural gas emissions in central Italy, but also in the pre-Apennine and Apennine belts. Isotope ratios of CH₄ (δ¹³C–CH₄ −6.1‰ to −22.7‰; δD–CH₄ −9‰ to −129‰) show that CH₄ does not appear to be related to mantle or magma degassing, but it is the product of thermal degradation of organic matter (i.e. thermogenic origin) and/or the reduction of CO₂ (i.e. geothermal origin). Most of the samples appear to be affected by secondary microbial oxidation processes.     

Using stable and radioactive isotopes for the investigation of contaminant metal mobilization in a metal mining district

Naturally occurring stable and radioactive isotopes were used as environmental tracers to investigate contaminant metal mobilization processes in a metal smelter dump mainly consisting of slag. Water emerging from the dump at a spring is heavily contaminated by metals. The smelter dump contains minor amounts of flue dust, a material which shows a high potential for metal mobilization. Nearby dumps mainly consist of low-grade ore. Concentration patterns of ²³⁸U, ²²⁶Ra and ²¹⁰Pb determined in sediment deposited close to the contaminated spring reveal the flue dust to be the major local metal source rather than the slag or the low-grade ore. Contamination pathways inside the dump were investigated using hydrological, chemical and isotopic data. Strong negative correlation between water discharge and metal concentration in the spring water suggests, besides short-term dilution of the metal concentration by direct rainwater runoff, distinct long-term dilution of the spring water by groundwater being discharged at a significantly increased rate as a result of heavy rains. δ¹⁸O and δD signatures of rain, local groundwater and spring water confirm the importance of groundwater derived from the local aquifer. Another hydrological component with importance for metal mobilization was found to be water that is recharged in the dump itself. Tritium analysis allowed an assessment of the probable residence time of that water component in the smelter dump. Since that water component seems to represent a major local contamination pathway the findings of the study are of substantial importance for site remediation planning. As a primary result it could be stated that covering the dump would not result in any noteworthy short-term improvement of the spring water quality. First significant effects would only be visible after 2–3 decades at the earliest.     

Oxygen and carbon stable isotopes in otoliths record spatial isolation of Patagonian toothfish (Dissostichus eleginoides)

Strong contrasts in ambient isotope ratios and in diet suggest stable isotopes in the otoliths of oceanic fish can resolve water masses and geographic areas, promising a powerful multivariate approach for examining population structure and provenance. To test this, whole otoliths were taken from Patagonian toothfish (Dissostichus eleginoides) sampled off the Patagonian Shelf and South Georgia, on either side of a population boundary, and otolith δ¹⁸O and δ¹³C values were measured to see if they could distinguish South American-caught fish from those taken in the Antarctic. Values of otolith δ¹⁸O and δ¹³C predicted capture area with 100% success, validating their use for distinguishing provenance and corroborating the prior evidence of population isolation. Values of δ¹⁸O in the otoliths reflected ambient values as well as seawater temperature: low values in Patagonian Shelf fish were consistent with exposure to Antarctic Intermediate Water (AAIW), and high values in South Georgia fish were consistent with exposure to Circumpolar Deep Water (CDW). In contrast, differences in otolith δ¹³C appeared to reflect diet: relative depletion of otolith δ¹³C at South Georgia compared to the Patagonian Shelf were most likely linked to differences in sources of metabolic carbon, as well as δ¹³C in dissolved inorganic carbon (DIC) of seawater. These contrasting properties strongly suggest that stable isotopes can resolve the provenance of toothfish from Antarctic sampling areas that hitherto have been difficult to separate. These results show that, by using the chemistry recorded in otoliths, researchers can exploit biogeochemical variation in fully marine environments to examine the spatial ecology of oceanic fish.     

Femolite from the exogenic-epigenetic Khokhlovskoe uranium deposit (Transural Region) and hetero-organic products of its thermochemical transformation

While studying the uranium ores from the exogenic-epigenetic (infiltration) Khokhlovskoe deposit using high-resolution electron microscopy, the original mineralogical and geochemical data were obtained on Fe-bearing molybdenite—femolite (Mo,Fe)S₂ and its transformation products of a similar composition, which were formed during traditional sample preparation. Femolite is transformed into hetero-organic compounds with Mo-Fe-S polymers as inorganic constituent. Among polymer products of femolite transformation, we identified high-Fe molybdenum monosulfide (Mo,Fe)S, as well as compounds of the (Mo,Fe)S-(Mo,Fe)S₂ series termed here as metafemolites. The morphology and internal structure of femolite micropockets and phytomorphs containing hetero-organic Mo-Fe-S polymers are shown together with results of EDS analyses. The possible role of organics in the transfer of molybdenum and the geochemical transformation of Mo(Fe)-sulfides under reducing conditions are discussed.     

Moisture source in the Hyblean Mountains region (south-eastern Sicily, Italy): Evidence from stable isotopes signature

Here the authors present results of an isotope study on precipitation collected during a 2-a period from a rain-gauge network consisting of 6 stations located at different elevations in the Hyblean Mountains (HM) region, in south-eastern Sicily. The slope of the local meteoric water line (δD = 6.50 δ¹⁸O + 9.87) obtained for the region suggests that precipitation is affected by evaporation during rainfall events. The main variations in rainwater isotope composition are due to seasonal effects and elevation. An average ²H excess value of +21.2‰ was found for precipitation events less affected by evaporation (i.e. when the rainfall was >65 mm/month). The spatial distribution of O isotope composition of precipitation shows a negative gradient from east and south to the inner areas. The depositional rate of Cl, used as a tracer of the origin of air masses, is highest at the coastal rain-gauges (SR and MRG stations) and lowest on the northern flank of the HM region (SC station). Based on these findings, a model is proposed for the origin of precipitation in the HM region, which assumes that a Mediterranean-derived component is the main source of moisture in the studied area. D/H and ¹⁸O/¹⁶O ratios of inferred meteoric recharge waters were also compared with the isotope composition of waters collected from the main local springs and wells. The best linear fit of the δ¹⁸O vs δD relationship for Hyblean groundwater is δD = 4.85 δ¹⁸O–2.01. The enrichment of heavy isotopes in Hyblean groundwater is probably due to evaporation occurring after precipitation events or to a recharging contribution from surface waters (lakes or rivers) enriched in heavy isotopes.     

The Silurian of Gotland (Sweden): facies interpretation based on stable isotopes in brachiopod shells

The Silurian of Gotland, Sweden, consists of 440 m of carbonate deposits. Repeatedly, uniform sequences of micritic limestones and marls are interrupted by complex-structured reefs and by adjacent platform sediments. Generally, the alteration of facies is interpreted as the result of sea-level fluctuations caused by a gradual regression with superimposed minor transgressive pulses. The purpose of this study is a facies interpretation based on both field observations and stable isotope measurements of brachiopod shells. Approximately 700 samples from stratigraphically arranged localities in different facies areas have been investigated. The carbon and oxygen isotopes show principally parallel curves and a close relationship to the stratigraphic sequence. Lower values occur in periods dominated by deposition of marly sequences. Higher values are observed in periods dominated by reefs and extended carbonate platforms. The oxygen isotope ratios are interpreted to reflect paleosalinity changes due to varying freshwater input, rather than to paleotemperature. Carbon isotope ratios are believed to have been connected to global changes in the burial of organic carbon in black shales during periods of euxinic deep water conditions. Consequently, the facies succession on Gotland results from global paleoclimatic conditions. Changes in terrigenous input due to different rates of weathering and freshwater runoff, rather than sea-level fluctuations, control the carbonate formation of the Silurian on Gotland.