济阳拗陷第三纪玄武岩的氧同位素

研究了山东刘阳拗陷29个第三纪玄武岩样品的氧同位素组成。结果表明，这些玄武岩的全岩氧同位素组成变化明显，δ^18○值为6．3‰－12．2‰。其中，蚀变轻微的晚第三纪玄武岩的δ^18○值为6．3‰－7．9‰，与正常大陆玄武岩的值（5．0‰－7．4‰）相似；而蚀变明显的早第三纪玄武岩的δ^18○值为6．3‰－12．2‰，并且90％以上样品的δ^18○值都大于7．5‰。结合岩石学与岩石化学研究，是第三纪玄武岩δ^18○值不同程度升高是由低温雨水热液蚀变（碳酸盐化）作用造成的。     

The strontium isotopic composition and origin of burial cements in the Lincolnshire Limestone (Bajocian) of central Lincolnshire, England

Strontium isotopic composition (⁸⁷Sr/⁸⁶Sr) of two petrographically, chemically and isotopically (δ¹⁸O and δ¹³C) distinct phases of burial calcites from the Lincolnshire Limestone are indistinguishable (0.70820± 26). The mean ⁸⁷Sr/⁸⁶Sr ratio of these phases is considerably more radiogenic than ⁸⁷Sr/⁸⁶Sr ratios of Bajocian marine waters (～0.70725). Neither Bajocian marine waters nor meteoric waters buffered by host marine carbonate in the Limestone could have precipitated the burial spars. Radiogenic strontium may have been contributed from K-feldspar dissolution and/or clay recrystallization, either within clastic portions of the Limestone itself, or from major clastic units adjacent to the Limestone. Alternatively, Palaeozoic marine waters or remobilized Palaeozoic marine carbonate and/or sulphate could have supplied the necessary radiogenic strontium.     

Understanding groundwater sources and movement using water chemistry and tracers in a low matrix permeability terrain: the Cretaceous (Chalk) Ulster White Limestone Formation,Northern Ireland

The Cretaceous Chalk [Ulster White Limestone Formation (UWLF)] in Northern Ireland has been diagenetically altered to a hard, low porosity, low matrix-permeability rock. It subcrops extensive beneath thick horizontal Tertiary Basalt lavas, but has a restricted strip of outcrop (approximately 80 km²) around the periphery of the overlying igneous rock. Despite its nature and location, numerous springs issue from the Chalk and are used for public and local supply, although little is known about the origin of the groundwater or the type of flow within the Chalk. We have addressed these unknowns using hydrogeochemical data from both rock types and surface stream waters, and fluorescent dye tracing. We have demonstrated that leakage recharge from the basalt to the Chalk accounts for less than 20% of the total water issuing from the Chalk springs using geochemical mass balance of conservative species and discharge data. The majority of the discharge derives from streams coming off the basalt and entering sink holes in the Chalk aquifer. Field and water tracing evidence shows that groundwater flow in the Chalk is dominated by conduit and fissure flow near to the outcrop areas. Karstification has been widespread near outcrop but has not ocurred in the sub-basalt region. Beneath the basalts, the Chalk exhibits different hydraulic properties due to the reduced recharge and dissolution potential that has prevented extensive development of fissure permeability in the UWLF. The Chalk aquifer thus appears to be strongly zoned in terms of the source of water, flow regime and recharge rate.     

Ordovician low- to intermediate-Mg calcite marine cements from Sweden: marine alteration and implications for oxygen isotopes in Ordovician seawater

Petrography demonstrates the presence of three types of fibrous calcite cement in buildup deposits of the Kullsberg Limestone (middle Caradoc), central Sweden. Translucent fibrous calcite has intrinsic blue luminescence (CL) indicative of pure calcite. This cement has 2–5 mol% MgCO₃, low Mn and Fe (≤ 100 p.p.m.), and is considered to be slightly altered to unaltered, primary low- to intermediate-Mg calcite. Grey turbid fibrous calcite has variable but generally low MgCO₃ content (most analyses <2 mol%) and variable CL response, with Mn and Fe concentrations up to 1200 and 500 p.p.m., respectively. The heterogeneous characteristics of this variety of fibrous calcite are caused by diagenetic alteration of a translucent fibrous calcite precursor. Light-brown turbid fibrous calcite has low MgCO₃ (near 1 mol%) and variable Mn (up to 800 p.p.m.) and Fe (up to 500 p.p.m.) concentrations, with an abundance of bright luminescent patches, which formed during alteration caused by reducing diagenetic fluids. The δ¹³C and δ¹⁸O values of all fibrous calcite form a tight field (δ¹³C=1·7 to 3·1‰ PDB, δ¹⁸O= ? 2·6 to ? 4·1‰ PDB) compared with fibrous calcite isotope values from other units. Fibrous calcite δ¹⁸O values are larger than adjacent meteoric or burial cements, which have δ¹⁸O δ ? 8‰ PDB. Consequently, most diagenetic alteration of Kullsberg fibrous calcite is interpreted to have occurred in the marine diagenetic realm. First-generation equant and bladed calcite cements, which pre-date fibrous calcite, are interpreted as unaltered, low-Mg calcite marine cements based on δ¹³C and δ¹⁸O data (δ¹³C = 2·3 to 2·7‰ PDB, δ¹⁸O= ? 2·8 to ? 3·5‰ PDB). Unlike fibrous cement, which reflects global sea water chemistry, first-generation equant and bladed calcite are indicators of localized modification of seawater chemistry in restricted settings. Kullsberg abiotic marine cements have larger δ¹⁸O values than most Caradoc marine precipitates from equatorial Laurentia. Positive Kullsberg δ¹⁸O values are attributed to lower seawater temperatures and/or slightly elevated salinity on the Baltic platform relative to seawater from which other marine precipitates formed.     

Recrystallization of dolomite: evidence from the Monterey Formation (Miocene), California

Dolomites from the upper calcareous-siliceous member of the Miocene Monterey Formation exposed west of Santa Barbara, California, were analysed for geochemical, isotopic and crystallographic variation. The data clearly document the progressive recrystallization of dolomite during burial diagenesis in marine pore fluids. Recrystallization is recognized by the following compositional and crystallographic variations. Dolomites have decreasing δ¹⁸O and δ¹³C compositions, decreasing Sr contents and increasing Mg contents with increasing burial depths and temperatures from east to west in the study area. δ¹⁸O values vary from 5·3‰ in the east to − 5·5‰ PDB in the west and are interpreted to reflect the greater extent and higher temperature of dolomite recrystallization in the west. δ¹³C values correlate with δ¹⁸O and decrease from 13·6‰ in the east to − 8·7‰ PDB in the west. Sr concentrations correlate positively with δ¹⁸O values and decrease from a mean of 750 ppm in the east to a mean of 250 ppm in the west. Mol% MgCO₃ values inversely correlate with δ¹⁸O values and increase from a minimum of 41·0 in the east to a maximum of 51·4 in the west. Rietveld refinements of powder X-ray diffraction data indicate that the more recrystallized dolomites have more contracted unit cells and increased cation ordering. The fraction of the Ca sites in the dolomites that are occupied by Ca atoms increases slightly with the approach to stoichiometry. The fraction of the Mg sites occupied by Mg atoms strongly correlates with mol% MgCO₃. Even in early diagenetic, non-stoichiometric dolomites, there is little substitution of Mg in Ca sites. During recrystallization, the amount of Mg substituting for Ca in Ca sites decreases even further. Most of the disorder in the least recrystallized, non-stoichiometric dolomites is related to substitution of excess Ca on Mg sites.     

Deep‐burial alteration of early‐diagenetic carbonate concretions formed in Palaeozoic deep‐marine greywackes and mudstones (Bardo Unit,Sudetes Mountains,Poland)

Carbonate concretions formed in bathyal and deeper settings have been studied less frequently than those formed in shallow‐marine deposits. Similarly, concretions affected by catagenetic conditions have rarely been reported. Calcite concretions in deep‐marine mudstones and greywackes of the Bardo Unit (Sudetes Mountains, Poland) formed during early diagenesis and were buried to significant depths. Petrographic and geochemical (elemental and stable C and O isotopic) analyses document their formation close to the sediment–water interface, prior to mechanical compaction within the sulphate reduction zone and their later burial below the oil window. Although the concretions were fully formed during early diagenesis, the effects of increased temperature and interaction with late‐diagenetic interstitial fluids can be discerned. During maximum burial, the concretions underwent thorough recrystallization that caused alteration of fabric and elemental and O isotope composition. The initial finely crystalline cement was replaced by more coarsely crystalline, sheaf‐like, poikilotopic calcite in the concretions. These large calcite crystals engulf and partially replace unstable detrital constituents. The extremely low δ¹⁸O values (down to ?21·2‰ Vienna Pee Dee Belemnite) in the concretions are the result of the increased temperature in combination with alteration of volcanic glass, both causing a significant ¹⁸O‐depletion of bicarbonate dissolved in the interstitial fluids. Recrystallization led to uniform O isotope ratios in the concretions, but did not affect the C isotope signature. The δ¹³C values of the late‐diagenetic cements precipitated in the greywacke and in cracks cutting through concretions imply crystallization in the catagenetic zone and decarboxylation as a source of the bicarbonate. These late‐diagenetic processes took place in a supposedly overpressured setting, as suggested by clastic dykes and hydrofractures that cut through both concretions and host rock. All of these features show how the effects of early and late diagenesis can be distinguished in such rocks.     

Preservation of biosignatures in metaglassy volcanic rocks from the Jormua ophiolite complex,Finland

Evidence of microbially-mediated alteration of basaltic glass is preserved in originally glassy basalts (rims of pillow lavas, hyaloclastite breccias, and chilled margins of dykes) from the well-preserved 1.95 Ga Jormua ophiolite complex (JOC) of Northeastern Finland. Although textural evidence of microbial alteration is commonly observed in relic glass from recent oceanic crust and some ophiolites, these textures have been destroyed during greenschist to lower amphibolite facies regional metamorphism and deformation of the JOC. However, another robust biosignature is found in the generally depleted δ¹³C values of disseminated carbonate extracted from originally glassy basalts, relative to crystalline samples. The same distribution of δ¹³C values is well documented in samples from recent oceanic crust as well as ophiolites of Phanerozoic age. This characteristic contrast in the δ¹³C values of disseminated carbonate is interpreted to result from microbe-induced fractionation during oxidation of organic matter. X-ray mapping of initial alteration zones has identified residual carbon associated with highly-concentrated S that is unrelated to carbonate. We attribute these biosignatures to microbially-mediated alteration of originally glassy material prior to ophiolite emplacement.     

Diagenesis of a mixed siliciclastic/evaporitic sequence of the Middle Muschelkalk (Middle Triassic), the Catalan Coastal Range, NE Spain

The Middle Muschelkalk (Middle Triassic) of the Catalan Coastal Range (north-east Spain) comprises sandstone, mudstone, anhydrite and minor carbonate layers. Interbedded sandstones and mudstones which are dominant in the north-eastern parts of the basin are terminal alluvial fan deposits. South-westward in the basin, the rocks become dominated by interbedded evaporites and mudstones deposited in sabkha/mudflat environments. The diagenetic and pore water evolution patterns of the Middle Muschelkalk suggest a strong facies control. During eodiagenesis, formation of microdolomite, anhydrite, baryte, magnesite, K-feldspar and mixed-layer chlorite/smectite was favoured within and adjacent to the sabkha/mudflat facies, whereas calcite, haematite, mixed-layer illite/smectite and quartz formed mainly in the alluvial facies. Low δ¹⁸O_SMOW values for microdolomite (+23.7 to +28.4%) and K-feldspar overgrowths (+17.3 to +17.7%) suggest either low-temperature, isotopic disequilibrium or precipitation from low-¹⁸O porewaters. Low-¹⁸O waters might have developed, at least in part, during low-temperature alteration of volcanic rock fragments. During mesodiagenesis, precipitation of quartz overgrowths and coarse dolomite occurred in the alluvial sandstones, whereas recrystallization of microdolomite was dominant in the sabkha/mudflat facies. The isotopic compositions of these mesogenetic phases reflect increasing temperature during burial. Upon uplift and erosion, telogenetic calcite and trace haematite precipitated in fractures and replaced dolomite. The isotopic composition of the calcite (δ¹⁸O_SMOW=+21.5 to +25.6%o; δ¹³C= 7.7 to - 5.6%o) and presence of haematite indicate infiltration of meteoric waters.     

Diagenesis of the Gully Oolite (Lower Carboniferous), South Wales

Deposition of the Gully Oolite was locally interrupted by emergence and a regionally extensive palaeosol is present at the top of the unit. Early diagenetic phases include isopachous, fibrous submarine cements, nonluminescent vadose cements, and mixing zone dolomite. Subsequent nonferroan phreatic cements are non- to dully luminescent and in restricted vertical intervals predate significant compaction. More usually, however, phreatic cements postdate extensive overpacking of allochems. Ooid isotopic composition (δ¹⁸O=-7·80° to -3·10° and δ¹³C = -2·38° to +3·28°) is similar to that of associated phreatic cements and the data suggest that the bulk of ooid stabilization and cementation occurred within meteoric groundwaters. The extensive allochem overpacking appears to have occurred during the first few tens of metres of burial and intergranular macroporosity was eliminated prior to deep burial. Fracturing of the Gully Oolite during the Hercynian Orogeny and subsequent post-orogenic uplift led to localized dolomitization, several generations of calcite veins, and the restricted occurrence of ¹⁸O depleted cements in inter- and intragranular microporosity. Some of the veins clearly relate to Triassic exhumation of the Carboniferous Limestone, but others may be related to post-Mesozoic uplift and erosion of South Wales. Fracture-associated dolomitization may have occurred within a large-scale post-orogenic groundwater system, with Mg²⁺ being supplied through the release of deeply buried diagenetic brines.     

Low-O18 basalts from Iceland

The volcanic rocks of Iceland are anomalous in their oxygen isotope content. Recent tholeiitic and transitional alkali basalts from Iceland range in (δO¹⁸ from 1·8 to 5δ7%. Most of the tholeiitic basalts and their phenocrysts are at least 1% lower in δO¹⁸ than unaltered basalts from other oceanic islands or oceanic ridges. The Icelandic basalts that resemble ridge basalts in δO¹⁸ also resemble them in major element chemistry. δO¹⁸ values of alkali olivine basalts are closest to those of other oceanic islands. Secondary alteration processes have lowered as well as raised the δO¹⁸ values of some Icelandic rocks, but such surface mechanisms cannot account for the distribution of oxygen isotopes in the Recent basalts of Iceland. Three mechanisms that could give rise to the low-O¹⁸ magmas are (1) exchange of oxygen between magma and low-O¹⁸ hydrothermally altered rock, (2) exchange with low-O¹⁸ meteoric water, or (3) an exceptional mantle under Iceland. None of the above models can satisfactorily account for all the observations.     

Dedolomitization and calcite cementation in the Middle Devonian Winnipegosis Formation in Central Saskatchewan,Canada

Limestone consisting of finely to medium crystalline calcite mosaics is present in the upper part of the Winnipegosis Formation on the east‐central margin of the Elk Point Basin where the overlying Prairie Evaporite deposits have been removed. This type of crystalline limestone is interpreted as dedolomite, based on petrographic observations. The δ¹⁸O and δ¹³C values of the Winnipegosis dedolomite vary from ?12·8‰ to ?11·9‰ VPDB (Vienna Pee Dee Belemnite) and from ?0·5‰ to +1·7‰ VPDB, respectively; both values are significantly lower than those for the corresponding dolomite. The ⁸⁷Sr/⁸⁶Sr ratios of the dedolomite are significantly higher, between 0·7082 and 0·7087. The spatial distribution and geochemical data of the Winnipegosis dedolomite suggest that dedolomitization was related to an influx of fresh groundwater and dissolution of the Prairie Evaporite anhydrite during the latest Mississippian to the Early Cretaceous when the basin was subjected to uplift and erosion. The Winnipegosis dedolomite displays a series of replacement fabrics showing progressive calcitization of dolomite, including the occurrence of dedolomite restricted along fractures and adjacent areas, dolomite patches ‘floating’ in the dedolomite masses and massive dedolomite with sparsely scattered dolomite relicts. However, the characteristic fabrics resulting from dedolomitization documented in the literature have not been observed in the Winnipegosis dedolomite. Coarsely to very coarsely crystalline, subhedral to euhedral calcite cement is restricted in the dedolomite. The petrographic features, isotopic compositions and homogenization temperatures, coupled with the burial history of the Winnipegosis Formation, constrain the precipitation of the calcite cement from a mixing of basinal brines and fresh groundwater during Late Cretaceous to Neogene time. The more negative C‐isotopic signatures of the calcite cement (?5·3‰ to ?2·3‰ VPDB) probably reflect a hydrocarbon‐derived carbon.     

An Isotope and Trace Element Study of the East Greenland Tertiary Dyke Swarm: Constraints on Temporal and Spatial Evolution during Continental Rifting

Dykes of the East Greenland Tertiary dyke swarm can be dividedinto pre- and syn-break-up tholeiitic dykes, and post-break-uptransitional dykes. Of the pre- and syn-break-up dykes, themost abundant group (Tholeiitic Series; TS) has major elementcompositions similar to the main part of the East Greenlandflood basalts. A group of high-MgO tholeiitic dykes (Picrite–AnkaramiteSeries; PAS) are much less common, and are equivalent to someof the oldest lavas of the East Greenland flood basalts. Isotopiccompositions of the TS and PAS dykes partly overlap with thosefor Iceland, but Pb isotopic compositions extend to less radiogenicvalues than those seen in either Iceland or North Atlantic mid-oceanridge basalt (MORB). The isotopically depleted source requiredto account for this isotopic variation is interpreted as subcontinentallithospheric mantle with low ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb and high     

The oxygen isotope composition, petrology and geochemistry of mare basalts: Evidence for large-scale compositional variation in the lunar mantle

To investigate the formation and early evolution of the lunar mantle and crust we have analysed the oxygen isotopic composition, titanium content and modal mineralogy of a suite of lunar basalts. Our sample set included eight low-Ti basalts from the Apollo 12 and 15 collections, and 12 high-Ti basalts from Apollo 11 and 17 collections. In addition, we have determined the oxygen isotopic composition of an Apollo 15 KREEP (K - potassium, REE - Rare Earth Element, and P - phosphorus) basalt (sample 15386) and an Apollo 14 feldspathic mare basalt (sample 14053). Our data display a continuum in bulk-rock δ¹⁸O values, from relatively low values in the most Ti-rich samples to higher values in the Ti-poor samples, with the Apollo 11 sample suite partially bridging the gap. Calculation of bulk-rock δ¹⁸O values, using a combination of previously published oxygen isotope data on mineral separates from lunar basalts, and modal mineralogy (determined in this study), match with the measured bulk-rock δ¹⁸O values. This demonstrates that differences in mineral modal assemblage produce differences in mare basalt δ¹⁸O bulk-rock values. Differences between the low- and high-Ti mare basalts appear to be largely a reflection of mantle-source heterogeneities, and in particular, the highly variable distribution of ilmenite within the lunar mantle. Bulk δ¹⁸O variation in mare basalts is also controlled by fractional crystallisation of a few key mineral phases. Thus, ilmenite fractionation is important in the case of high-Ti Apollo 17 samples, whereas olivine plays a more dominant role for the low-Ti Apollo 12 samples.Consistent with the results of previous studies, our data reveal no detectable difference between the Δ¹⁷O of the Earth and Moon. The fact that oxygen three-isotope studies have been unable to detect a measurable difference at such high precisions reinforces doubts about the giant impact hypothesis as presently formulated.     

Dolomitization of the Waulsortian Limestone (Lower Carboniferous) in the Irish Midlands

The Waulsortian Limestone (Lower Carboniferous) of the southern Irish Midlands is dolomitized pervasively over a much larger region than previous studies have documented. This study indicates a complex, multistage, multiple fluid history for regional dolomitization. Partially and completely dolomitized sections of Waulsortian Limestones are characterized by finely crystalline (0·01–0·3 mm) planar dolomite. Planar replacive dolomite is commonly followed by coarse (≥0·5 mm) nonplanar replacive dolomite, and pervasive void‐filling saddle dolomite cement is frequently associated with Zn–Pb mineralization. Planar dolomite has average δ¹⁸O and δ¹³C values (‰ PDB) of –4·8 and 3·9 respectively. These are lower oxygen and slightly higher carbon isotope values than averages for marine limestones in the Waulsortian (δ¹⁸O=–2·2, δ¹³C=3·7). Mean C and O isotope values of planar replacive dolomite are also distinct from those of nonplanar and saddle dolomite cement (–7·0 and 3·3; –7·4 and 2·4 respectively). Fluid inclusions indicate a complex history involving at least three chemically and thermally distinct fluids during dolomite cementation. The petrography and geochemistry of planar dolomites are consistent with an early diagenetic origin, possibly in equilibrium with modified Carboniferous sea water. Where the Waulsortian was exposed to hydrothermal fluids (70–280 °C), planar dolomite underwent a neomorphic recrystallization to a coarser crystalline, planar and nonplanar dolomite characterized by lower δ¹⁸O values. Void‐filling dolomite cement is isotopically similar to nonplanar, replacive dolomite and reflects a similar origin from hydrothermal fluids. This history of multiple stages of dolomitization is significantly more complex than earlier models proposed for the Irish Midlands and provides a framework upon which to test competing models of regional vs. localized fluid flow.     

The Geochemical Characteristics and Minerogenic Model for the Amo Hypothermal Tin Deposit in Ximeng County, Yunnan Province

Through studies on the element geochemistry, alteration of country rocks, ore-forming fluids and isotopegeochemistry of the Arno tin deposit in the metamorphic rocks of the Upper Proterozoic Ximeng Group, theauthors consider that the concentration of the B-F-Li-Rb-Cs-Sn association is related to acidic magmatism inthe study area. The Fe-Mg-Li tourmaline in the ore is the replaced product of the country rocks byhypothermal fluid. The δ~(18)O values of mineral separates are +2.01- +13.16‰ and their δ~(34)S values, +2.6-+7.2‰. The ore-forming materials were derived from hydrothermal fluid of granitic magma. For themineralization, the temperature is 450°-350℃, the pressure, 450-1000×10~5 Pa, and the age, Himalayan(21.5 Ma). According to the geochemical characteristics, a minerogenic model is established: the deposit is ahypothermal cassiterite-quartz vein type tin deposit controlled by the hidden Himalayan granites.     

新疆喀喇昆仑阿然保泰二叠纪OIB型玄武岩地球化学特征及其地质意义

位于喀喇昆仑山喀喇昆仑断裂(塔什库尔干断裂)西侧的阿然保泰一带发育一套中二叠统灰岩-凝灰岩-枕状玄武岩地层。枕状玄武岩分布在北西向长约12km,宽约4.5km范围内。该套玄武岩枕状构造十分典型,岩石具气孔、杏仁状构造。玄武岩SiO2含量为44.14%～48.81%、TiO2为1.11%～1.83%,在Si2O-(Na2O+K2O)图中落入苦橄玄武岩、玄武岩和碱玄岩交界区,属于碱性岩石。稀土元素含量较高(54.40×10-6～139.9×10-6),Eu、Ce无异常,(La/Yb)N比值为2.87～6.29,配分模式为右倾型。大离子亲石元素富集(K、Rb、Ba等),但含量变化较大,高场强元素(Nb、Ta、Zr、Hf和P)相对亏损,Ti出现弱的负异常。玄武岩的地球化学特征显示阿然保泰玄武岩具洋岛玄武岩特征,源区为尖晶石二辉橄榄岩,其形成构造环境为板内拉张环境。阿然保泰OIB型玄武岩的发现证实了喀喇昆仑阿然保泰地区属于古特提斯主洋盆一部分。     

白云鄂博碳酸岩墙碳氧同位素地球化学

对内蒙古白云鄂博 REE- Fe- Nb矿床周围碳酸岩墙中共存的方解石和白云石进行了 C和 O同位素分析。结果表明，方解石和白云石的δ 13C值变化范围一致，均为－ 3.5‰～－ 7.3‰，落在正常地幔δ 13C值范围 (－ 5‰± 2‰ )内；而它们的δ 18O值可分为两组，第Ⅰ 组为 9.5‰～ 18.0‰，第Ⅱ 组为 20.6‰～ 22.6‰，均远大于正常地幔δ 18O值范围 (5.7‰± 1.0‰ )。第Ⅰ 组低δ 18O值样品中共存白云石与方解石之间的 C和 O同位素分馏均为负值，因此处于热力学不平衡状态，指示它们自形成后受到过后期热液蚀变，与先前的岩石学观察一致。相反，第Ⅱ 组高δ 18O值样品中白云石与方解石之间的 C和 O同位素分馏均为正值，处于热力学平衡状态，指示它们自形成后未受到后期热液蚀变，因此可能沉淀于晚期低温高δ 18O值流体。第Ⅰ 组碳酸岩墙中白云石的 C和 O同位素组成不呈线性分布，指示碳酸岩浆并非由幔源碳酸盐与沉积碳酸盐混合形成。应用水-岩交换模型计算得到，第Ⅰ 组碳酸岩在侵位后经历了碳酸岩浆期后热液的不均一蚀变，蚀变温度约在 220～ 800℃之间，蚀变流体的 CO2/H2O比值较小 (1/500)，但水 /岩比值变化较大 (10～ 400)。由于低温下方解石与热液之间的碳氧同位素交换速率大于白云石，导致这部分碳酸     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

Sulfur Isotope Study on Hg and Sb Deposits in Japan

Abstract. Sulfur isotope ratios of cinnabar from Hg deposits and stibnite, jamesonite and berthierite from Sb deposits in Japan are examined in order to understand metallogeneses of Hg and Sb deposits in Japanese island arcs. The studied Hg and Sb deposits include the Hg deposit at Yamato‐suigin (Honshu) and the Sb deposit at Ichinokawa (Shikoku) in the Southwest Japan arc. In addition, Hg deposits including Itomuka and Ryushoden in central Hokkaido and Hg and Sb mineralizations in Northeast Japan arc are examined. The δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, including the Itomuka and Ryushoden deposits range widely, from ‐10 to +16 %o, the highest values encountered at the Samani deposit. The δ³⁴S values of cinnabar from other areas in Japan range from ‐12 to +5 %o, having δ³⁴S values higher than +2 %o from southwestern Hokkaido (Meiji deposit), Shikoku (Suii deposit) and Kyushu (Hasami and Yamagano deposits). On the other hand, the δ³⁴S values of stibnite from all areas in Japan range from ‐14 to +5 %o, having positive δ³⁴S values higher than +2 %o up to +5 %o from southwestern Hokkaido (Yakumo, Toyotomi and Teine deposits) and eastern‐central Honshu (Hachiman and Daikoku deposits). The variation in δ³⁴S values of Hg and Sb deposits may reflect the variation in δ³⁴S values of country rocks or variation in mixing ratio of sulfur extracted from the country rocks, sulfur derived from seawater sulfate, and sulfur derived from magmatic emanations. The relatively high δ³⁴S values of cinnabar and stibnite higher than +2 %o from southwestern Hokkaido, eastern‐central Honshu and Kyushu are probably caused by contribution of volcanic emanation from arc magmas having positive σδ³⁴S values, whereas the positive δ³⁴S values of cinnabar higher than +2 %o from Suii deposit in Shikoku may be attributed to structurally substituted sulfate in limestone country rocks and/or sulfur derived from seawater sulfate. However, the wide range of the δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, is difficult to explain at this moment. Other relatively low, negative δ³⁴S values of cinnabar and stibnite, berthierite from other areas in Japan may be attributed to 1) incorporation of isotopically light sedimentary sulfur or sulfur derived from ilmenite‐series silicic magma, or 2) less contribution of volcanic emanation from arc magmas having positive σδ³⁴S values.     

Early diagenetic siderite as an indicator of depositional environment in the Triassic Rewan Group, southern Bowen Basin, eastern Australia

Early concretionary and non-concretionary siderites are common in subsurface Triassic sandstones and mudrocks of the Rewan Group, southern Bowen Basin. A detailed petrological and stable isotopic study was carried out on these siderites in order to provide information on the depositional environment of the host rocks. The siderites are extremely pure, containing 85–97 mol% FeCO₃, and are commonly enriched in manganese. δ¹³C (PDB) values are highly variable, ranging from - 18·4 to +2·9‰, whereas δ¹⁸O (PDB) values are very consistent, ranging from - 14·0 to - 10·2‰ (mean= - 11·9 ± 1·0‰). The elemental and oxygen isotopic composition of the siderites indicates that only meteoric porewaters were involved in siderite formation, implying that host rocks accumulated in totally non-marine environments. The carbon isotopic composition of the siderites is interpreted to reflect mixing of bicarbonate/carbon dioxide generated by methane oxidation and methanogenesis. Very low δ¹³C values demonstrate that, contrary to current views, highly ¹³C-depleted siderite can be produced at shallow burial depths in anoxic non-marine sediments.