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1.
The Bijgan barite deposit, which is located northeast of Delijan in Markazi Province of Iran, occurs as a small lenticular body at the uppermost part of an Eocene volcano-sedimentary rock unit. The presence of fossiliferous and carbonaceous strata suggests that the host rocks were deposited in a quiet marine sedimentary environment. Barite, calcite, iron oxides and carbonaceous clay materials are found as massive patches as well as thin layers in the deposit. Barite is marked by very low concentrations of Sr (1–2%) and total amounts of rare earth elements (REEs) (6.25–17.39?ppm). Chondrite-normalized REE patterns of barite indicate a fractionation of light REEs (LREEs) from La to Sm, similar to those for barite of different origins from elsewhere. The LaCN/LuCN ratios and chondrite-normalized REE patterns reveal that barite in the Bijgan deposit is enriched in LREE relative to heavy rare earth elements (HREEs). The similarity between the Ce/La ratios in the barite samples and those found in deep-sea barite supports a marine origin for barite. Lanthanum and Gd exhibit positive anomalies, which are common features of marine chemical sediments. Cerium shows a negative anomaly in most samples that was inherited from the negative Ce anomaly of hydrothermal fluid that mixed with seawater at the time of barite precipitation. The δ18O values of barites show a narrow range of 9.1–11.4‰, which is close to or slightly lower than that of contemporaneous seawater at the end of the Eocene. This suggests a contribution of oxygen from seawater in the barite-forming solution. The δ34S values of barites (9.5–15.3‰) are lower than that of contemporaneous seawater, which suggests a contribution of magmatic sulfur to the ore-forming solution. The oxygen and sulfur isotope ratios indicate that submarine hydrothermal vent fluids are a good analog for solutions that precipitated barite, due to similarities in the isotopic composition of the sulfates. The available data including tectonic setting, host rock characteristics, REE geochemistry, and oxygen and sulfur isotopic compositions support a submarine hydrothermal origin for the Bijgan barite deposit. At the seafloor, barite deposition occurred where ascending Ba-bearing hydrothermal fluids encountered seawater. Sulfate was derived from the sulfate-bearing marine waters, and, to a lesser extent, by oxidized H2S, which was derived from magmatic hydrothermal fluids.  相似文献   

2.
It is well known that the incorporation of isotopically light metabolic carbon (CM) significantly affects the stable carbon isotope (δ13C) signal recorded in biogenic carbonates. This can obscure the record of δ13C of seawater dissolved inorganic carbon (δ13CDIC) potentially archived in the shell carbonate. To assess the CM contribution to Mercenaria mercenaria shells collected in North Carolina, USA, we sampled seawater δ13CDIC, tissue, hemolymph and shell δ13C. All shells showed an ontogenic decrease in shell δ13C, with as much as a 4‰ decrease over the lifespan of the clam. There was no apparent ontogenic change in food source indicated by soft tissue δ13C values, therefore a change in the respired δ13C value cannot be the cause of this decrease. Hemolymph δ13C, on the other hand, did exhibit a negative relationship with shell height indicating that respired CO2 does influence the δ13C value of internal fluids and that the amount of respired CO2 is related to the size or age of the bivalve. The percent metabolic C incorporated into the shell (%CM) was significantly higher (up to 37%, with a range from 5% to 37%) than has been found in other bivalve shells, which usually contain less than 10%CM. Interestingly, the hemolymph did contain less than 10%CM, suggesting that complex fractionation might occur between hemolymph and calcifying fluids. Simple shell biometrics explained nearly 60% of the observed variability in %CM, however, this is not robust enough to predict %CM for fossil shells. Thus, the metabolic effect on shell δ13C cannot easily be accounted for to allow reliable δ13CDIC reconstructions. However, there does seem to be a common effect of size, as all sites had indistinguishable slopes between the %CM and shell height (+0.19% per mm of shell height).  相似文献   

3.
The bioaccumulation of trace metals in the carbonate shells of mussel and clams was investigated at seven hydrothermal vent fields of the Mid-Atlantic Ridge (Menez Gwen, Snake Pit, Rainbow, and Broken Spur) and the Eastern Pacific (9°N and 21°N at the East Pacific Rise and the southern trough of Guaymas Basin). Mineralogical analysis showed that the carbonate skeletons of the mytilid mussel Bathymodiolus sp. and the vesicomyid clam Calyptogena m. are composed mainly of calcite and aragonite, respectively. The first data were obtained for the content of a variety of elements in the bivalve carbonate shells from various hydrothermal vent sites. The analysis of the chemical compositions (including Fe, Mn, Zn, Cu, Cd, Pb, Ag, Ni, Cr, Co, As, Se, Sb, and Hg) of 35 shell samples and 14 water samples from the mollusk biotopes revealed the influences of environmental conditions and some biological parameters on the bioaccumulation of metals. Bivalve shells from hydrothermal fields with black smokers are enriched in Fe and Mn by a factor of 20–30 relative to the same species from the Menez Gwen low-temperature vent site. It was shown that the essential elements Fe, Mn, Ni, and Cu were more actively accumulated during the early ontogeny of the shells. The high concentration factors of most metals (n × 102−n × 104) indicate an efficient accumulation function of bivalve carbonate shells. Passive metal accumulation owing to adsorption on the shell surface was estimated to be no higher than 50% of the total amount, varying from 14% for Fe to 46% for Mn.  相似文献   

4.
Submarine metalliferous sedimentary rocks are chemical precipitates resulted from hydrothermal exhalation near mid‐ocean ridge or faults. They record the submarine hydrothermal activity between lithosphere and hydrosphere and are critical for understanding Fe cycling in marine environment. Fe was expelled from the hydrothermal vent systems and was oxidized and precipitated in the ambient seawater, where the precipitation of hydrothermal Fe is largely controlled by oxidation state of seawater and is potentially revealed by its Fe isotope compositions. This hydrothermal process in modern hydrothermal vent systems have been well observed, but that for the ancient ones are still not well known. Umbers, or ferromanganoan sediments, overlying Troodos ophiolite in Cyprus of Mid‐Cretaceous age thus provides an excellent example for understanding the Fe cycles in ancient submarine hydrothermal process. Samples were collected from Margi village in Troodos and are mostly amorphous Fe‐Mn oxy‐hydroxides with very minor quartz, goethite, smectite and silicates such as clinopyroxene derived from the volcanic rocks. There is no terrestrial, detrital component. Samples were analyzed for their whole‐rock element and Fe isotope compositions. The results show that samples are composed mainly of SiO2 (13～80 wt%), Fe2O3 (9～54 wt%) and MnO (1.5～10.4 wt%), with minor Al2O3 (0.7～4.3 wt%). PAAS‐normalized REE patterns are near flat with significantly negative Ce anomalies (Ce/Ce* is from 0.2 to 0.5) and slightly positive Eu anomalies (Eu/Eu* is around 1.1), indicating a source from the oxidized seawater and the high‐temperature hydrothermal fluids. δ56FeIRMM‐014 values of samples are ‐0.32‰ to ‐0.15‰, with an average of ‐0.20‰, which are consistent with those of the hydrothermal fluids previously reported. The narrow Fe isotope compositions of Cyprus umbers that are close to those of submarine hydrothermal fluids indicates near complete oxidation of hydrothermal Fe2+ during its expulsion from the hydrothermal vent.  相似文献   

5.
Mussel shells have been used in a number of paleoecological and environmental studies. The interpretation of stable carbon isotopic composition of shell material is still controversial. The carbon for shell carbonate precipitation can either be derived from ambient dissolved inorganic carbon (DIC), with shells recording environmental signals, or from metabolic CO2, with the potential to disguise environmental signals. To gain insight into this question, we investigated four nearly 100-yr long-term records of aragonite shells from an extant freshwater bivalve species, the endangered freshwater pearl mussel (Margaritifera margaritifera L.). Single growth increments of the outer prismatic and the inner nacreous zones were successfully and easily separated with a simple heat treatment for chronological analyses of δ13C in single layers of each zone. Autocorrelation and semivariance statistical methods reveal that mussels show distinct individual signal patterns, which extend up to 25 yr. Signal patterns are reliably reproduced with replicate samples from defined layers within one shell and show similar patterns with a slight offset for inner nacreous and outer prismatic layers for individual animals. Mussels exposed to the same environmental conditions exhibit distinct and contradictory signature patterns, which do not match between individuals. This observation can only be explained by strong metabolic influences on shell precipitation. Environmental changes in pH, temperature, electric conductivity and atmospheric carbon signature had no or little (<5%) influence, whereas body tissue protein and body tissue δ13C signatures negatively correlated with the youngest produced shell δ13C signatures, indicating that respiration causes a preferential loss of light isotopes from body mass and an inverse enrichment in shell aragonite. Hence, the shells of the freshwater pearl mussel yield a long-term record of metabolic activity, whereas the use of δ13C in these shells as recorder for environmental signals is questionable. This may also be true for shells from other species, for which metabolic carbon incorporation has been acknowledged.  相似文献   

6.
We describe a new method for the calculation of river flow that uses the oxygen isotope composition of bivalve mollusk shells that grew in the river-water/seawater mixing zone of the Colorado River estuary. Sclerochronological techniques are used to identify tidally-induced, fortnight-scale bundles of daily growth increments within shell cross-sections. These fortnightly markers are used to establish a chronology for samples taken for δ18O analysis. A composite seasonal δ18O profile derived from five shells that grew in the absence of river-water flow is used as a baseline against which profiles of river-influenced shells are compared. Because this comparison is between matched fortnights within a year, the temperature of shell growth is likely to be very similar. The difference in δ18O between the river-influenced shell and the “no-flow” composite shell therefore represents the change in the δ18O of the water due to the presence of river water in the mixing zone. The river water end-member is also determined within a fortnightly context so that the change in the δ18O of mixing-zone water can be used to calculate the relative proportions of seawater and fresh-water. The fresh-water end-member is calculated from the δ18O of bivalves alive prior to the emplacement of dams and water diversions on the Colorado River. The marine end-member is based on direct measurements of the δ18O of northern Gulf of California water during times of no Colorado River flow. The system has been calibrated to absolute flow amounts using recent releases of known volume and rate.  相似文献   

7.
《Geochimica et cosmochimica acta》1999,63(11-12):1787-1804
Rift-related lavas of the North Shore Volcanic Group (NSVG) are intruded by plutonic rocks of the Duluth Complex along the unconformity between the NSVG and the underlying Proterozoic metasedimentary rocks (Animikie Group) and Archean volcano-sedimentary and plutonic rocks. Heat associated with the emplacement of the mafic intrusions generated fluid flow in the overlying plateau lavas. δ18O values for whole rocks from the NSVG and hypabyssal sills range from 5.5 to 17.7‰ and 5.3 to 11.5‰, respectively, and most values are higher than those considered “normal” for basaltic rocks (5.4 to 6.0‰). In general, there is a positive correlation between whole rock δ18O and water content, which suggests that elevated δ18O values are related primarily to secondary mineral growth and isotopic exchange during hydrothermal alteration and metamorphism. δ18OH2O values computed from amygdule-filling minerals such as smectite, chlorite, and epidote found in low- to high-temperature metamorphic zones range from ∼−1 to 6‰ with an average value of ∼3‰. Smectite in the lower-grade zones gives computed δDH2O values between −26 and −83‰, whereas epidote in the higher-grade zones gives δDH2O values of −15 to 6‰. Fluid isotopic compositions computed from epidote and smectite values are suggestive of the involvement of at least two fluids during the early stages of amygdule filling. Fluid δD and δ18O values determined from epidote at the higher metamorphic grades indicate that seawater dominated the deeper portions of the system where greenschist facies assemblages and elevated δ18O values were produced in flow interiors, as well as margins. Smectite isotopic compositions suggest that meteoric water was predominant in the shallower portions of the system. The increase in δ18O values of massive flow interiors with depth is interpreted as a result of rock interaction with a fluid of constant oxygen isotopic composition with increasing temperature. The stable isotopic data are supportive of previous suggestions that seawater was involved in the hydrothermal system associated with the Midcontinent Rift. Although the origin of the seawater remains problematic, it appears that marine incursions may have occurred during the late stages of Portage Lake volcanism, and periodically thereafter.  相似文献   

8.
Silicon (Si) isotope variability in Precambrian chert deposits is significant, but proposed explanations for the observed heterogeneity are incomplete in terms of silica provenance and fractionation mechanisms involved. To address these issues we investigated Si isotope systematics, in conjunction with geochemical and mineralogical data, in three well-characterised and approximately contemporaneous, ∼3.5 Ga chert units from the Pilbara greenstone terrane (Western Australia).We show that Si isotope variation in these cherts is large (−2.4‰ to +1.3‰) and was induced by near-surface processes that were controlled by ambient conditions. Cherts that formed by chemical precipitation of silica show the largest spread in δ30Si (−2.4‰ to +0.6‰) and are characterised by positive Eu, La and Y anomalies and overall depletions in lithophile trace elements. Silicon isotope systematics in these orthochemical deposits are explained by (1) mixing between hydrothermal fluids and seawater, and/or (2) fractionation of hydrothermal fluids by subsurface losses of silica due to conductive cooling. Rayleigh-type fractionation of hydrothermal fluids was largely controlled by temperature differences between these fluids and seawater. Lamina-scale Si isotope heterogeneity within individual chemical chert samples up to 2.2‰ is considered to reflect the dynamic nature of hydrothermal activity. Silicified volcanogenic sediments lack diagnostic REE+Y anomalies, are enriched in lithophile elements, and exhibit a much more restricted range of positive δ30Si (+0.1‰ to +1.1‰), which points to seawater as the dominant source of silica.The proposed model for Si isotope variability in the Early Archaean implies that chemical cherts with the most negative δ30Si formed from pristine hydrothermal fluids, whereas silicified or chemical sediments with positive δ30Si are closest to pure seawater deposits. Taking the most positive value found in this study (+1.3‰), and assuming that the Si isotope composition of seawater is governed by input of fractionated hydrothermal fluids, we infer that the temperature of ∼3.5 Ga seawater was below ∼55 °C.  相似文献   

9.
Oxygen isotope studies of the Suzhou granite have been made based on drill-hole samples. In the inner part, the δ18O values are less variable either in the whole-rock, quartz or in feldspar. Oxygen isotopic compositions are in equilibrium between coexisting quartz and feldspar. Data points from the inner part are plotted in a small area in the δ18OQ-δ18Of diagram, indicating that this part has not been affected by meteoric hydrothermal fluids. But the whole-rock δ18O values of the marginal part vary greatly. Oxygen isotopic compositions are in extreme disequilibrium between quartz and feldspar. Data points from the marginal part are displayed with a nearly vertical slope in the δ18OQ-δ18Of diagram, implying that rocks of this part are affected by the meteoric hydrothermal fluids. Extreme water-rock interactions lead to mineralizations of rare-elements (Nb, Ta, as well as Zr, Hf, Th) in the marginal part. Source materials of the Suzhou granite are also discussed in this paper.  相似文献   

10.
Farsesh barite in the central part of Iranian Sanandaj-Sirjan zone is a sample of epigenetic hydrothermal mineralization in dolomitized limestone, which provides appropriate chemicophysical conditions making the passage of mineral-bearing fluids possible. Barite veins may range from a few centimeters to 2 m in thickness that increases downward. The microthermometry measurements obtained from more than 30 fluid inclusions show relative homogenization temperatures ranging from 125 to 200 °C with an average of 110 °C for Farsesh barite deposits. The mean salinity measured proves 16 times as much as weight percentage of NaCl for barite. Coexistence of liquid- and vapor-rich fluid inclusions in barite minerals may provide an evidence of boiling in ore veins. Moreover, occurrence of bladed calcite, high-grade ore zones, and presence of hydrothermal breccia are all consistent with boiling. Thermometric studies indicate that homogenization temperatures (Th) for primary and pseudosecondary fluid inclusions in barite range from 125 to 200 °C with an average of 1,100 °C. The δ34S values of barite also lie between 8.88 and 16.6 %. The relatively narrow spread in δ34S values may suggest uniform environmental conditions throughout the mineralization field. Thus, δ34S values are lower than those of contemporaneous seawater, which indicates a contribution of magmatic sulfur to the ore-forming solution. Barite is marked by total amounts of rare Earth elements (REEs) (6.25–17.39 ppm). Moreover, chondrite-normalized REE patterns of barite indicate a fractionation of light REEs (i.e., LREEs) from La to Sm, similar to those for barite from different origins. The LaCN/LuCN ratios and chondrite-normalized REE patterns reveal that barite in Farsesh deposit is enriched in LREEs compared with heavy rare Earth elements (HREEs). Similarity between Ce/La ratios in barite samples and those found in deep-sea barite supports its marine origin. Lanthanum and Gd exhibit positive anomalies, which are common features of chemical marine sediments. Cerium shows a negative anomaly in most samples inherited from the negative Ce anomaly of hydrothermal fluid that is mixed with seawater at barite precipitation. The available data including tectonic setting, host rock characteristics, REE geochemistry, and sulfur isotopic compositions may support a hydrothermal submarine origin for Farsesh barite deposit.  相似文献   

11.
Fault-controlled hydrothermal dolomitization in tectonically complex basins can occur at any depth and from different fluid compositions, including ‘deep-seated’, ‘crustal’ or ‘basinal’ brines. Nevertheless, many studies have failed to identify the actual source of these fluids, resulting in a gap in our knowledge on the likely source of magnesium of hydrothermal dolomitization. With development of new concepts in hydrothermal dolomitization, the study aims in particular to test the hypothesis that dolomitizing fluids were sourced from either seawater, ultramafic carbonation or a mixture between the two by utilizing the Cambrian Mount Whyte Formation as an example. Here, the large-scale dolostone bodies are fabric-destructive with a range of crystal fabrics, including euhedral replacement (RD1) and anhedral replacement (RD2). Since dolomite is cross-cut by low amplitude stylolites, dolomitization is interpreted to have occurred shortly after deposition, at a very shallow depth (<1 km). At this time, there would have been sufficient porosity in the mudstones for extensive dolomitization to occur, and the necessary high heat flows and faulting associated with Cambrian rifting to transfer hot brines into the near surface. While the δ18Owater and 87Sr/86Sr ratios values of RD1 are comparable with Cambrian seawater, RD2 shows higher values in both parameters. Therefore, although aspects of the fluid geochemistry are consistent with dolomitization from seawater, very high fluid temperature and salinity could be suggestive of mixing with another, hydrothermal fluid. The very hot temperature, positive Eu anomaly, enriched metal concentrations, and cogenetic relation with quartz could indicate that hot brines were at least partially sourced from ultramafic rocks, potentially as a result of interaction between the underlying Proterozoic serpentinites and CO2-rich fluids. This study highlights that large-scale hydrothermal dolostone bodies can form at shallow burial depths via mixing during fluid pulses, providing a potential explanation for the mass balance problem often associated with their genesis.  相似文献   

12.
The oxygen isotopic composition of land-snail shells may provide insight into the source region and trajectory of precipitation. Last glacial maximum (LGM) gastropod shells were sampled from loess from Belgium to Serbia and modern land-snail shells both record δ18O values between 0‰ and − 5‰. There are significant differences in mean fossil shell δ18O between sites but not among genera at a single location. Therefore, we group δ18O values from different genera together to map the spatial distribution of δ18O in shell carbonate. Shell δ18O values reflect the spatial variation in the isotopic composition of precipitation and incorporate the snails' preferential sampling of precipitation during the warm season. Modern shell δ18O decreases in Europe along a N-S gradient from the North Sea inland toward the Alps. Modern observed data of isotopes in precipitation (GNIP) demonstrate a similar trend for low-altitude sites. LGM shell δ18O data show a different gradient with δ18O declining toward the ENE, implying a mid-Atlantic source due to increased sea ice and a possible southern displacement of the westerly jet stream. Balkan LGM samples show the influence of a Mediterranean source, with δ18O values decreasing northward.  相似文献   

13.
13C/12C and 18O/16O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ18O values (PDB scale) ranged from −4.1‰ to 1.2‰, while δ13C values ranged from −13.2‰ to 0.0‰. δ18O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ18O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ18O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ13C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ13C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C3, C4) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the “neighborhood” scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.  相似文献   

14.
Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of 24Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of 26Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ26Mgsw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ26Mgsw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ26Mg: (1) micrite samples ranged from ?2.86‰ to ?2.97‰; (2) pure marine cements varied from ?3.40‰ to ?3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (?3.27‰ to ?3.75‰); (3) values for the mixture component were ?3.17‰ and ?3.49‰; and (4) brachiopod shells ranged from ?2.20‰ to ?3.07‰, with the thickened hinge area enriched in 24Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ26Mgsw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ26Mgsw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ26Mg of the Huangjin limestone makes it difficult to reconstruct δ26Mgsw using bulk carbonate/calcareous sediments. Finally, δ26Mgsw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.  相似文献   

15.
Eight pectinid shells were collected and subjected to quantitative study using δ18O and δ13C isotopic analysis in order to study the paleoenvironment which prevailed during their calcification. The scalerochronological variations in δ18O and δ13C values, among these shells are also discussed. The Early Miocene pectinid shells display highly depleted δ18O and δ13C signature as a result of paleo-meteoric water with heavy rainfall that was produced by Tropical Cyclones when the Mediterranean Sea was open. The Early Pliocene pectinid shells reveal depleted δ18O values, related to the influx of fresh water influenced by monsoonal activity following the formation of the Tibetan Plateau. Their enrichment in the δ13C isotopic excursion is referred to high productivity of the Indian Ocean, which was the main source of the Red Sea water. The Pleistocene pectinid shell shows highly depleted δ18O and δ13C signature with obvious diagenetic shell structure, indicating that a wetter humid climate prevailed during the Early–Middle Pleistocene and long sub-arial exposure of the shell. The Recent Mediterranean pectinid shell displays slight enrichment in δ18O and δ13C values referring to deeper inhabitation of this species with a low temperature and high salinity environment. The scalerochronological variations in both δ18O and δ13C values, along these shells is referred to seasonal variations or kinetic effects.  相似文献   

16.
Banded iron formations (BIFs) are Precambrian chemical marine sedimentary formations that record major transitions of chemical composition, and oxidation–reduction state of oceans at the time of their deposition. In this paper, we report silicon and oxygen isotope compositions of a variety of BIFs from the North China Craton (NCC) in order to deduce the mechanism of their formation. Quartz in the various types of BIFs from the NCC are generally depleted in 30Si, where δ30SiNBS-28 values range from − 2.0‰ to − 0.3‰ (average, − 0.8‰), similar to δ30SiNBS-28 values measured from modern submarine black chimneys and sinters. The δ18OV-SMOW values of quartz in the BIFs are relatively high (8.1‰–21.5‰; average, 13.1‰), similar to those of siliceous rock formed by hydrothermal activities. The δ30SiNBS-28 values of quartz in magnetite bands are commonly lower than those of quartz in adjacent siliceous bands within the same sample, whereas δ18OV-SMOW values are higher in the magnetite bands. A negative correlation is observed between δ30SiNBS-28 and δ18OV-SMOW values of quartz from siliceous and magnetite bands in BIF from Fuping, Hebei Province. The isotopic compositions of silicon and oxygen of quartz in BIFs provide insights for the formation mechanisms of silicon–iron cyclothems in BIFs. After the silicon- and iron-rich hydrothermal solution was injected onto the seabed, the abrupt temperature drop caused oversaturation of silicic acid, resulting in rapid precipitation of SiO2 and deposition of siliceous layers. Ferric hydroxide was precipitated later than SiO2 because of low free-oxygen concentration in the ocean bottom. Progressive mixing of hydrothermal solution with seawater caused a continuous drop in temperature and an increase in Eh values, resulting in gradual oxidation of hydrothermal Fe2 + and deposition of iron-rich layers. In summary, each silicon–iron cyclothem marks a large-scale submarine hydrothermal exhalation. The periodic nature of these exhalations resulted in the formation of regular silicon–iron cyclothems. The widespread distribution of BIFs indicates that volcanism and submarine hydrothermal exhalation were extensive; the low δ30SiNBS-28 and high δ18O V-SMOW values of the BIFs indicate that the temperature of seawater was relatively high at the time of BIF formation, and that concentrations of Fe2 + and H4SiO4 in seawater were saturated.  相似文献   

17.
Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REEN patterns measured in anhydrite from mid-ocean ridge deposits. The REEN patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. 87Sr/86Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate δ34S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate δ34S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO2 degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.  相似文献   

18.
Well-preserved aragonitic land snail shells (Vallonia) from late Pleistocene Eolian sediment in the Folsom archaeological site in New Mexico exhibit an overall decrease of δ18OPDB from maximum values of +2.7‰ (more positive than modern) to younger samples with lower average values of about −3.6‰ (within the modern range). The age of the samples (approximately 10,500 14C yr B.P.) suggests that the decrease in δ18O may manifest climatic changes associated with the Younger Dryas. Some combination of increased relative humidity and cooler temperatures with decreased δ18O of precipitation during the times of snail activity can explain the decrease in shell δ18O. A well-known Paleoindian bison kill occurred at the Folsom site during this inferred environmental transition.Average δ13C values of the aragonite shells of the fossil Vallonia range from −7.3 to −6.0‰ among different archaeological levels and are not as negative as modern values. This suggests that the proportion of C4 vegetation at the Folsom site approximately 10,500 14C yr B.P. was greater than at present; a result which is consistent with other evidence for higher proportions of C4 plants in the region at that time.  相似文献   

19.
Land snails provide a unique opportunity to study terrestrial paleoenvironments because their shells, which are generally highly abundant and well-preserved in the fossil record, contain a temporal record of environmental change in the form of isotope codes. To evaluate the utility of this approach for a low-latitude oceanic setting, 207 modern shells of 18 species of land snail were analyzed for their oxygen and carbon isotope composition along a north and south facing altitudinal gradient (10-2160 m a.s.l.) in Tenerife Island (∼28°N) of the Canary Archipelago.Shells collected at each locality showed a relatively large range in isotope composition which was greater along the south facing transect (drier and hotter), suggesting that the variance in shell isotope values may be related to water-stress. Although pooled isotope values did not generally show strong relationships with environmental variables (i.e., altitude, temperature and precipitation), mean isotope values were strongly associated with some climatic factors when grouped by site. The mean δ18O value of the shell (δ18Oshell) by site displayed a negative correlation with elevation, which is consistent with the positive relationship observed between temperature and the δ18O value of rain (δ18Orain). Calculated δ18O values of the snail body water (δ18Obody) derived from observed temperatures and δ18Oshell values (using the equation of Grossman and Ku [Grossman E. L. and Ku T. L. (1986) Oxygen and carbon isotope fractionation in biogenic aragonite. Chem. Geol. (Isotope Geosci. Sec.)59, 59-74]) displayed a trend with respect to altitude that was similar to measured and hypothetical δ18O values for local rain water. The calculated δ18Obody values from the shell declined 0.17‰ (VSMOW) per 100 m, which is consistent with the “altitude effect” observed for tropical rains in Western Africa, and it correlated negatively with rainfall amount. Accordingly, lower δ18Oshell values indicate lower temperatures, lower δ18Orain values and possibly, higher rainfall totals. A positive correlation between the mean δ13C values of shells (δ13Cshell) and plants by site suggests that shells potentially record information about the surrounding vegetation. The δ13Cshell values varied between −15.7 and −0.6‰ (VPDB), indicating that snails consumed C3 and C4/CAM plants, where more negative δ13Cshell values probably reflects the preferential consumption of C3 plants which are favored under wetter conditions. Individuals with more positive δ13Cshell values consumed a larger percentage of C4 plants (other potential factors such as carbonate ingestion or atmospheric CO2 contribution were unlikely) that were more common at lower elevations of the hotter and drier south facing transect. The relatively wide range of shell isotope values within a single site requires the analysis of numerous shells for meaningful paleoclimatic studies. Although small differences were observed in isotope composition among snail species collected at a single sampling site, they were not significant, suggesting that isotope signatures extracted from multi-taxa snail data sets may be used to infer environmental conditions over a broad range of habitats.  相似文献   

20.
A simple flux balance model with a diffusive, evaporative boundary layer indicates that the time constant (characteristic time) for approach to oxygen isotope steady state in the body fluid of land snails is ∼19 min or less. These comparatively short times support an assumption that the snail’s aragonitic shell is commonly precipitated from a body fluid that is at, or near, isotopic steady state. The model indicates that the steady-state δ18O value of snail shell carbonate depends upon the temperature, relative humidity, δ18O of the input liquid water, and δ18O of ambient water vapor. Model shell δ18O values were calculated for the warm, wet months corresponding to times of snail activity at some European sites. Linear regression of these predicted values against published, measured values yielded the expression: δ18Ocalc = 0.93(±0.13) δ18Omeas −0.9(±0.2), with r2 = 0.65. As indicated by the value of r2, there is scatter in the relationship, but the slope and intercept are close to one and zero, respectively, which lends credence to the model. Therefore, temporal or spatial changes recorded in the δ18O values of land snail shells appear to be selectively seasonal—commonly the warm, wet months—and include the effects of relative humidity.For carbon, the time constant for approach to isotopic steady state in the bicarbonate dissolved in the body fluid of land snails is predicted to be ∼16 min or less. New and published δ13C measurements of aragonite shell and associated organic matter exhibit an overall correlation, but with considerable scatter. As noted by previous workers, 13C-rich dietary “limestone” may account for some of the scatter. Additional scatter, according to the model presented herein, could arise from changes in the proportion of total oxidized carbon that is expelled by the snail as bicarbonate dissolved in body fluid (i.e., effects of relative changes in metabolic rates). These results affirm the need for caution in the interpretation of δ13C values of land snail aragonite shells solely in terms of dietary proportions of C3 and C4 plants.  相似文献   

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