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1.
Modern seawater has a uniform δ37Cl value (0.0‰), with an exception in the upper current of the Bosphorus (0.4‰). Marine halite ranging in age from Cambrian to Miocene has δ37Cl values of 0.0 ± 0.9‰, with most of the data in the range 0.0 ± 0.5‰. Mean δ37Cl values differ measurably between basins, with no evident relationship to basin size or to age. Smaller evaporite bodies have the largest δ37Cl ranges. Potash facies halite has mean δ37Cl values lower than those of halite facies salt in the East Siberia and Zechstein basins. The bulk δ37Cl of bedded halite preserving sedimentary textures cannot be shifted measurably after deposition under plausible natural conditions. During the Phanerozoic, a detectable change in the δ37Cl values of the oceans is unlikely as a result of Cl fluxes to and from the mantle and evaporites. In halite, the values of δ37Cl that cannot be explained by fractionation occurring on crystallization are best explained by the addition of non-marine Cl with δ37Cl ≠ 0.0‰ to evaporite brine. 相似文献
2.
This study is a comprehensive, stable isotope survey of the marine carbonate-dominated, upper Paleo- to lower Neoproterozoic stratigraphy of Jixian County, China. Carbonate-associated sulfate (CAS) was extracted and measured for δ34SCAS using the same samples analyzed for δ13Ccarbonate. This integrated proxy approach is a step towards a more comprehensive picture of secular variation in the composition of Proterozoic seawater. We specifically sampled marine carbonate intervals from the lower section of the Chuanlinggou Formation, Changcheng Group (ca. 1700 Ma) to the top of the Jingeryu Formation, Qingbaikou Group (ca. 800 Ma). δ13Ccarbonate values are mostly negative in the upper Paleoproterozoic Changcheng Group, with an ascending trend from −3‰ to 0‰. We observed variation of approximately 0 ± 1‰ in the Mesoproterozoic Jixian Group, and positive values of +2 ± 2‰ characterize the lower Neoproterozoic Qingbaikou Group. Stratigraphic variations in δ34SCAS are more remarkable in their ranges and magnitudes, including conspicuously high values exceeding +30‰ in the three intervals at ca. 1700 Ma, 1300-1100 Ma, and 1000-900 Ma. In the Changcheng Group, δ34SCAS values are typically higher than +25‰, with only a few values of less than +15‰. In contrast, most of the data spanning from the Mesoproterozoic Tieling Formation of the Jixian Group to the lower Neoproterozoic Jingeryu Formation of the Qingbaikou Group are highly variable between +10‰ and +25‰, with some values exceeding +25‰.In the late Paleoproterozoic (1700-1600 Ma), a >10‰ decrease in δ34SCAS and ∼3‰ increase in δ13Ccarbonate are coincident with, and likely related to, the breakup of Columbia, a supercontinent that predated Rodinia. Carbon and sulfur isotope data from the Mesoproterozoic, when global tectonic activity was comparatively weaker, fall mostly in the ranges of +15 ± 10‰ and 0 ± 1‰, respectively, but fluctuations of >20‰ for δ34SCAS and >3‰ for the δ13Ccarbonate at ca. 1450-1400 Ma may reflect subduction and large-scale magmatic activity in island arcs marking the end of Columbia breakup. From the late Mesoproterozoic (ca. 1300-1100 Ma) to the early Neoproterozoic (ca. 800 Ma), the δ13C and δ34S of seawater increased gradually with increasing variability. Most impressive areδ34SCAS values that exceed +30‰ in two intervals at ca. 1300-1100 Ma and ca. 1000-900 Ma, which may reflect the assembly and early breakup of Rodinia. Although gaps in the record remain, and studies of even higher resolution are warranted, our results suggest that changes in paleoceanographic conditions linked to global tectonics strongly influenced the biogeochemical cycles of C and S. Furthermore, periods of the Proterozoic previously noted for their isotopic invariability show clear isotopic expressions of this tectonic activity. 相似文献
3.
4.
Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ13Cmean = −2.49 ± 0.99‰; δ18Omean = −9.43 ± 1.40‰). The δ13C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ18O values are typical of fresh water carbonates. Covariation between δ13C and δ18O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ13Cmean = −2.06 ± 0.84‰; δ18Omean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)molar, δ13C and δ18O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records. 相似文献
5.
Atmospheric carbon dioxide is widely studied using records of CO2 mixing ratio, δ13C and δ18O. However, the number and variability of sources and sinks prevents these alone from uniquely defining the budget. Carbon dioxide having a mass of 47 u (principally 13C18O16O) provides an additional constraint. In particular, the mass 47 anomaly (Δ47) can distinguish between CO2 produced by high temperature combustion processes vs. low temperature respiratory processes. Δ47 is defined as the abundance of mass 47 isotopologues in excess of that expected for a random distribution of isotopes, where random distribution means that the abundance of an isotopologue is the product of abundances of the isotopes it is composed of and is calculated based on the measured 13C and 18O values. In this study, we estimate the δ13C (vs. VPDB), δ18O (vs. VSMOW), δ47, and Δ47 values of CO2 from car exhaust and from human breath, by constructing ‘Keeling plots’ using samples that are mixtures of ambient air and CO2 from these sources. δ47 is defined as , where is the R47 value for a hypothetical CO2 whose δ13CVPDB = 0, δ18OVSMOW = 0, and Δ47 = 0. Ambient air in Pasadena, CA, where this study was conducted, varied in [CO2] from 383 to 404 μmol mol−1, in δ13C and δ18O from −9.2 to −10.2‰ and from 40.6 to 41.9‰, respectively, in δ47 from 32.5 to 33.9‰, and in Δ47 from 0.73 to 0.96‰. Air sampled at varying distances from a car exhaust pipe was enriched in a combustion source having a composition, as determined by a ‘Keeling plot’ intercept, of −24.4 ± 0.2‰ for δ13C (similar to the δ13C of local gasoline), δ18O of 29.9 ± 0.4‰, δ47 of 6.6 ± 0.6‰, and Δ47 of 0.41 ± 0.03‰. Both δ18O and Δ47 values of the car exhaust end-member are consistent with that expected for thermodynamic equilibrium at∼200 °C between CO2 and water generated by combustion of gasoline-air mixtures. Samples of CO2 from human breath were found to have δ13C and δ18O values broadly similar to those of car exhaust-air mixtures, −22.3 ± 0.2 and 34.3 ± 0.3‰, respectively, and δ47 of 13.4 ± 0.4‰. Δ47 in human breath was 0.76 ± 0.03‰, similar to that of ambient Pasadena air and higher than that of the car exhaust signature. 相似文献
6.
An anomalous enrichment in marine sulfate δ34SSO4 is preserved in globally-distributed latest Ediacaran-early Cambrian strata. The proximity of this anomaly to the Ediacaran-Cambrian boundary and the associated evolutionary radiation has invited speculation that the two are causally related. Here we present a high-resolution record of paired sulfate (δ34SSO4) and pyrite (δ34Spyr) from sediments spanning ca. 547-540 million years ago (Ma) from the Ara Group of the Huqf Supergroup, Sultanate of Oman. We observe an increase in δ34SSO4 from ∼20‰ to ∼42‰, beginning at ca. 550 Ma and continuing at least through ca. 540 Ma. There is a concomitant increase in δ34Spyr over this interval from ∼ −15‰ to 10‰. This globally correlative enrichment, here termed the Ara anomaly, constitutes a major perturbation to the sulfur cycle. The absolute values of δ34Spyr reported here and in equivalent sections around the world, require the isotopic composition of material entering the ocean (δ34Sin) to be significantly more enriched than modern (∼3‰) values, likely in excess of 12‰ during the late Ediacaran-early Cambrian. Against this background of elevated δ34Sin, the Ara anomaly is explained not by increased fractionation between sulfate and pyrite (Δδ34S), but by an increase in pyrite burial (fpyr), most likely driven by enhanced primary production and sequestration of organic carbon, consistent with earlier reports of elevated organic carbon burial and widespread phosphorite deposition. 相似文献
7.
This paper presents the results of an isotopic study of spring waters in ?wi?tokrzyski (Holy Cross Mountain) National Park (?NP), south-central Poland. The δ34SV-CDT and δ18OV-SMOW of soluble sulfates (n = 40) varied from 0.5‰ to 18.1‰ and from 3.5‰ to 12.2‰, respectively. The average δ34S values are closely similar to those of rainwater, soils and rocks (comprising scattered pyrite). This suggests that soluble sulfates in the springs originated from mixing of recent and historic deposition, sulfates derived from pyrite oxidation, and CS-mineralization in soils and debris. An additional anthropogenic sulfur input (inorganic fertilizer) occurs in the water of spring S-61 located in the ?wi?tokrzyski National Park buffer zone. The δ18OV-SMOW of spring waters (n = 4) were in the range of −10.6‰ to −10.2‰ indicating that they are derived from vadose groundwater in ?NP. This was the first isotope study of spring waters in the national parks of Poland. It enabled the determination of sulfur pathways and discrimination between natural and anthropogenic sources of this element in a relatively pristine area. 相似文献
8.
Coal combustion is an important atmospheric pollution source in most Chinese cities, so systematic studies on sulfur and nitrogen in Chinese coals are needed. The sulfur contents in Chinese coals average 0.9 ± 1.0%, indicating that most Chinese coals are low in sulfur. A nearly constant mean δ34S value is observed in low sulfur (TS < 1) Chinese coals of different ages (D, P1, T3 and J3). High sulfur Chinese coals (OS > 0.8%), often found at late Carboniferous (C3) and late Permian (P2) in southern China, had two main sulfur sources (original plant sulfur and secondary sulfur). The wide variety of δ34S values of Chinese coals (−15‰ to +50‰) is a result of a complex sulfur origin. The δ15N values of Chinese coals ranged from −6‰ to +4‰, showing a lack of correlation with coal ages, whereas nitrogen contents are higher in Paleozoic coals than in Mesozoic coals. This may be related to their original precursor plant species: high nitrogen pteridophytes for the Paleozoic coals and low nitrogen gymnosperms for the Mesozoic coals. Different to δ34S values, Chinese coals showed higher δ15N values in marine environments than in freshwater environments. 相似文献
9.
Br/Cl ratios and O, H, C, and B isotopic constraints on the origin of saline waters from eastern Canada 总被引：1，自引：0，他引：1
Saline groundwaters were recovered from undisturbed (Restigouche deposit) and active (Brunswick #12 mine) Zn-Pb volcanogenic massive sulfide deposits in the Bathurst Mining Camp (BMC), northern New Brunswick, Canada. These groundwaters, along with fresh to brackish meteoric ground and surface waters from the BMC, have been analyzed to determine their major, trace element and stable isotopic (O, H, C, and B) compositions. Saline groundwaters (total dissolved solids = 22-45 g/L) are characterized by relatively high Na/Ca ratios compared to brines from the Canadian Shield and low Na/Clmolar and δ11B isotopic compositions (−2.5‰ to 11.1‰) compared to seawater. Although saline waters from the Canadian Shield commonly have oxygen and hydrogen isotopic compositions that plot to the left of the global meteoric water line, those from the BMC fall close to the water line. Fracture and vein carbonate minerals at the Restigouche deposit have restricted carbon isotopic compositions of around −5‰ to −6‰. The carbon isotopic compositions of the saline waters at the Restigouche deposit (+12‰ δ13CDIC) are the result of fractionation of dissolved inorganic carbon by methanogenesis. We suggest that, unlike previous models for shield brines, the composition of saline waters in the BMC is best explained by prolonged water-rock reaction, with no requirement of precursor seawater. We suggest that elevated Br/Cl ratios of saline waters compared to seawater may be explained by differential uptake of Br and Cl during groundwater evolution through water-rock reaction. 相似文献
10.
Chemical and mineralogical changes due to pyrite weathering are of interest with respect to understanding long-term physical stability of mine rock piles at the Questa mine, New Mexico. The ability to discriminate between ancient and modern processes is important for establishing the extent of modern weathering within the piles. Initial inventories of sulfur minerals and representative isotope compositions in rocks from orebodies, the hydrothermal alteration zones associated with orebodies, hydrothermal alteration scars, and mine rock piles were determined. Ore body sulfides have δ34SCDT of 0 ± 4‰, typical for sulfides formed by magmatic processes in stockwork Mo systems. Pyrite from alteration scars has a wide range of δ34S values from 0.0‰ to −13.6‰. Sulfate from the ore body has markedly positive δ34S (5–10‰) accompanied by positive δ18OSO4 values (6–15‰) reflecting equilibrium formation from magmatic fluids. Sulfates from alteration scars have δ34S values over a broad range, similar to alteration scar pyrites, from −10.6‰ to 0‰ and δ18OSO4 of 0 ± 3‰. Sulfates with fine grained, delicate, and euhedral mineral habits suggesting recent formation within the mine rock piles, have δ34S values similar to orebody pyrite and alteration scars but more negative δ18OSO4 values (−3‰ to −10‰). Sulfates from all three sources occur in these piles, and their stable isotope values have proven useful in differentiating them and their environments of formation (i.e., hypogene, ancient supergene, and recent weathering). Correlating the isotopic compositions with textures allows petrographic assessment for the origins of sulfate minerals in the rock piles, but this must be applied with caution because some sulfate mineral recycling has occurred. 相似文献
11.
Fossils of megaherbivores from eight late Pleistocene 14C- and OSL-dated doline infillings of Ajoie (NW Switzerland) were discovered along the Transjurane highway in the Swiss Jura. Carbon and oxygen analyses of enamel were performed on forty-six teeth of large mammals (Equus germanicus, Mammuthus primigenius, Coelodonta antiquitatis, and Bison priscus), coming from one doline in Boncourt (~ 80 ka, marine oxygen isotope stage MIS5a) and seven in Courtedoux (51–27 ka, late MIS3), in order to reconstruct the paleoclimatic and paleoenvironmental conditions of the region. Similar enamel δ13C values for both periods, ranging from − 14.5 to − 9.2‰, indicate that the megaherbivores lived in a C3 plant-dominated environment. Enamel δ18OPO4 values range from 10.9 to 16.3‰ with a mean of 13.5 ± 1.0‰ (n = 46). Mean air temperatures (MATs) were inferred using species-specific δ18OPO4–δ18OH2O-calibrations for modern mammals and a present-day precipitation δ18OH2O-MAT relation for Switzerland. Similar average MATs of 6.6 ± 3.6°C for the deposits dated to ~ 80 ka and 6.5 ± 3.3°C for those dated to the interval 51–27 ka were estimated. This suggests that these mammals in the Ajoie area lived in mild periods of the late Pleistocene with MATs only about 2.5°C lower than modern-day temperatures. 相似文献
12.
Louise Björkvald Reiner Giesler Christoph Humborg 《Geochimica et cosmochimica acta》2009,73(16):4648-2683
Despite reduced anthropogenic deposition during the last decades, deposition sulphate may still play an important role in the biogeochemical cycles of S and many catchments may act as net sources of S that may remain for several decades. The aim of this study is to elucidate the temporal and spatial dynamics of both SO42− and δ34SSO4 in stream water from catchments with varying percentage of wetland and forest coverage and to determine their relative importance for catchment losses of S. Stream water samples were collected from 15 subcatchments ranging in size from 3 to 6780 ha, in a boreal stream network, northern Sweden. In forested catchments (<2% wetland cover) S-SO42− concentrations in stream water averaged 1.7 mg L−1 whereas in wetland dominated catchments (>30% wetland cover) the concentrations averaged 0.3 mg L−1. A significant negative relationship was observed between S-SO42− and percentage wetland coverage (r2 = 0.77, p < 0.001) and the annual export of stream water SO42− and wetland coverage (r2 = 0.76, p < 0.001). The percentage forest coverage was on the other hand positively related to stream water SO42− concentrations and the annual export of stream water SO42− (r2 = 0.77 and r2 = 0.79, respectively). The annual average δ34SSO4 value in wetland dominated streams was +7.6‰ and in streams of forested catchments +6.7‰. At spring flood the δ34SSO4 values decreased in all streams by 1‰ to 5‰. The δ34SSO4 values in all streams were higher than the δ34SSO4 value of +4.7‰ in precipitation (snow). The export of S ranged from 0.5 kg S ha−1 yr−1 (wetland headwater stream) to 3.8 kg S ha−1 yr−1 (forested headwater stream). With an average S deposition in open field of 1.3 kg S ha−1 yr−1 (2002-2006) the mass balance results in a net export of S from all catchments, except in catchments with >30% wetland. The high temporal and spatial resolution of this study demonstrates that the reducing environments of wetlands play a key role for the biogeochemistry of S in boreal landscapes and are net sinks of S. Forested areas, on the other hand were net sources of S. 相似文献
13.
Copper isotope fractionation in acid mine drainage 总被引：4，自引：0，他引：4
B.E. Kimball R. Mathur A.J. Wall S.L. Brantley 《Geochimica et cosmochimica acta》2009,73(5):1247-1263
We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ65Cu values (based on 65Cu/63Cu) of enargite (δ65Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ65Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ65Cu < 1‰). These mineral samples show lower δ65Cu values than stream waters (1.38‰ ? δ65Cu ? 1.69‰). The average isotopic fractionation (Δaq-min = δ65Cuaq − δ65Cumin, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in 65Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δaq-mino=-0.57±0.14‰, where mino refers to the starting mineral) and no apparent fractionation for enargite (Δaq-mino=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of 65Cu+ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of 65Cuaq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ65Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes. 相似文献
14.
The sources and petrogenetic processes that generated some of the Earth’s oldest continental crust have been more tightly constrained via an integrated, in situ (U-Pb, O and Hf) isotopic approach. The minerals analysed were representative zircon from four Eoarchaean TTG tonalites and two felsic volcanic rocks, and olivine from one harzburgite/dunite of the Itsaq Gneiss Complex (IGC), southern West Greenland. The samples were carefully chosen from localities with least migmatisation, metasomatism and strain. Zircon was thoroughly characterized prior to analysis using cathodoluminescence, scanning electron, reflected and transmitted light imaging. The zircon from all but one sample showed only minor post-magmatic recrystallisation. 207Pb/206Pb dating of oscillatory-zoned zircon using SHRIMP RG (n = 142) indicates derivation of the felsic igneous rocks from different batches of magma at 3.88, 3.85, 3.81, 3.80 and 3.69 Ga.Analyses of 18O/16O compositions of olivine from a harzburgite/dunite (n = 8) using SHRIMP II in multi-collector mode, indicate that the oxygen isotopic composition of this sample of Eoarchaean mantle (δ18OOl = 6.0 ± 0.4‰) was slightly enriched in 18O, but not significantly different from that of the modern mantle. Zircon δ18O measurements from the six felsic rocks (n = 93) record mean or weighted mean compositions ranging from 4.9 ± 0.7‰ to 5.1 ± 0.4‰, with recrystallised domains showing no indication of oxygen isotopic exchange during younger tectonothermal events. δ18OZr compositions indicate that the primary magmas were largely in equilibrium with the mantle or mantle-derived melts generated at similar high temperatures, while calculated tonalite δ18OWR compositions (6.7-6.9‰) resemble those of modern adakites.LA-MC-ICPMS zircon 176Hf/177Hf analyses were obtained from six samples (n = 122). Five samples record weighted mean initial εHf compositions ranging from to 0.5 ± 0.6 to −0.1 ± 0.7 (calculated using λ176Lu = 1.867 × 10−11 yr−1), while one sample records a composition of 1.3 ± 0.7, indicating the magmas were generated from a reservoir with a time averaged, near chondritic Lu/Hf. The derivation of TTG magmas from a chondritic Lu/Hf source implies either that there was not voluminous continental crustal growth nor major mantle differentiation leading to Lu/Hf fractionation during the Hadean or Eoarchaean, or alternatively that rapid recycling of an early formed crust allowed the early mantle to maintain a chondritic Lu/Hf.Previous studies have demonstrated that ancient TTG rocks were mostly produced by dehydration melting of mafic rocks within the stability field of garnet, probably in flatly-subducted or buried oceanic crust. The oxygen isotopic signatures measured here at high spatial resolution allow the source materials to be better defined. Melting of a mixed mafic source consisting of ∼80% unaltered gabbro (δ18OWR = 5.5‰) with ∼20% hydrothermally altered gabbro/basalt (δ18OWR = 4.0‰) would produce tonalite magmas within the average compositional range observed. 18O-enriched components such as altered shallow basaltic oceanic crust and pelagic or continental sediments were not present in the sources of these TTG melts. The absence of high 18O signatures may indicate either the rarity of low temperature altered sediments, or their effective removal from the down-going slab. 相似文献
15.
Thomas Rigaudier Véronique Gardien François Martineau 《Geochimica et cosmochimica acta》2011,75(16):4637-4652
Deuterium and oxygen isotope fractionations between liquid and vapor water were experimentally-determined during evaporation of a NaCl solution (35 g L−1) as a function of water temperature and wind velocity. In the case of a null wind velocity, slopes of δD-δ18O trajectories of residual waters hyperbolically decrease with increasing water temperatures in the range 23-47 °C. For wind velocities ranging from 0.8 to 2.2 m s−1, slopes of the δD-δ18O trajectories linearly increase with increasing wind velocity at a given water temperature. These experimental results can be modeled by using Rayleigh distillation equations taking into account wind-related kinetics effects. Deuterium and oxygen isotope compositions of water inclusions trapped by the precipitated halite crystals were determined by micro-equilibration techniques.These isotopic compositions accurately reflect those of the surrounding residual waters during halite growth. Isotopic compositions of water inclusions in twenty natural halites from the Messinian Realmonte mine in Sicily suggest precipitation temperatures of that match the homogenization temperatures obtained by microthermometry (median = 34 ± 5 °C). The similarity between the measured and experimental slopes of the δD-δ18O evaporation trajectories suggests that the effect of wind was negligible during the genesis of these halite deposits. Hydrogen and oxygen isotope compositions of water inclusions from Realmonte halite also define a linear trend whose extrapolation until intersection with the Mediterranean Meteoric Water Line allows the characterization of the water source with δD and δ18O values of −70 ± 10‰ and −11.5 ± 1.5‰, respectively. These results reveal that the huge amounts of salts deposited in Sicily result from the evaporation of seawater mixed with a dominant fraction (?50%) of meteoric waters most likely deriving from alpine fluvial discharge. 相似文献
16.
Tissue N contents and δ15N signatures in 175 epilithic mosses were investigated from urban to rural sites in Guiyang (SW China) to determine atmospheric N deposition. Moss N contents (0.85–2.97%) showed a significant decrease from the urban area (mean = 2.24 ± 0.32%, 0–5 km) to the rural area (mean = 1.27 ± 0.13%, 20–25 km), indicating that the level of N deposition decreased away from the urban environment, while slightly higher N contents re-occurred at sites beyond 30 km, suggesting higher N deposition in more remote rural areas. Moss δ15N ranged from −12.50‰ to −1.39‰ and showed a clear bimodal distribution (−12‰ to −6‰ and −5‰ to −2‰), suggesting that there are two main sources for N deposition in the Guiyang area. More negative δ15N (mean = −8.87 ± 1.65‰) of urban mosses mainly indicated NH3 released from excretory wastes and sewage, while the less negative δ15N (from −3.83 ± 0.82‰ to −2.48 ± 0.95‰) of rural mosses were mainly influenced by agricultural NH3. With more negative values in the urban area than in the rural area, the pattern of moss δ15N variation in Guiyang was found to be opposite to cities where N deposition is dominated by NOx–N. Therefore, NHx–N is the dominant N form deposited in the Guiyang area, which is supported by higher NHx–N than NOx–N in local atmospheric deposition. From the data showing that moss is responding to NHx–N/NOx–N in deposition it can be further demonstrated that the variation of moss δ15N from the Guiyang urban to rural area was more likely controlled by the ratio of urban-NHx/agriculture-NHx than the ratio of NHx–N/NOx–N. The results of this study have extended knowledge of atmospheric N sources in city areas, showing that urban sewage discharge could be important in cities co-generic to Guiyang. 相似文献
17.
Multiple sulfur isotope system is a powerful new tracer for atmospheric, volcanic, and biological influences on sulfur cycles in the anoxic early Earth. Here, we report high-precision quadruple sulfur isotope analyses (32S/33S/34S/36S) of barite, pyrite in barite, and sulfides in related hydrothermal and igneous rocks occurring in the ca. 3.5 Ga Dresser Formation, Western Australia. Our results indicate that observed isotopic variations are mainly controlled by mixing of mass-dependently (MD) and non-mass-dependently fractionated (non-MD) sulfur reservoirs. Based on the quadruple sulfur isotope systematics (δ34S-Δ33S-Δ36S) for these minerals, four end-member sulfur reservoirs have been recognized: (1) non-MD sulfate (δ34S = −5 ± 2‰; Δ33S = −3 ± 1‰); (2) MD sulfate (δ34S = +10 ± 3‰); (3) non-MD sulfur (δ34S > +6‰; Δ33S > +4‰); and (4) igneous MD sulfur (δ34S = Δ33S = 0‰). The first and third components show a clear non-MD signatures, thus probably represent sulfate and sulfur aerosol inputs. The MD sulfate component (2) is enriched in 34S (+10 ± 3‰) and may have originated from microbial and/or abiotic disproportionation of volcanic S or SO2. Our results reconfirm that the Dresser barites contain small amounts of pyrite depleted in 34S by 15-22‰ relative to the host barite. These barite-pyrite pairs exhibit a mass-dependent relationship of δ33S/δ34S with slope less than 0.512, which is consistent with that expected for microbial sulfate reduction and is significantly different from that of equilibrium fractionation (0.515). The barite-pyrite pairs also show up to 1‰ difference in Δ36S values and steep Δ36S/Δ33S slopes, which deviate from the main Archean array (Δ36S/Δ33S = −0.9) and are comparable to isotope effects exhibited by sulfate reducing microbes (Δ36S/Δ33S = −5 to −11). These new lines of evidence support the existence of sulfate reducers at ca. 3.5 Ga, whereas microbial sulfur disproportionation may have been more limited than recently suggested. 相似文献
18.
Olaf Nehlich Benjamin T. Fuller Mandy Jay Alice Mora Colin I. Smith Michael P. Richards 《Geochimica et cosmochimica acta》2011,75(17):4963-4977
This study investigates the application of sulphur isotope ratios (δ34S) in combination with carbon (δ13C) and nitrogen (δ15N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans (n = 83), terrestrial animals (n = 11), and freshwater fish (n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ34S values were found. The δ34S values from the terrestrial animals were highly variable (−13.6‰ to +0.5‰), but the δ34S values of the fish were clustered and 34S-depleted (−20.9‰ to −17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly 34S-depleted sulphur influenced the soil. The humans show the largest range of δ34S values (−18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ34S values were found between the males (−7.8 ± 6.0‰) and females (−5.3 ± 6.8‰), but the females had a linear correlation (R2 = 0.71; p < 0.0001) between their δ15N and δ34S compositions. These δ34S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ34S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period. 相似文献
19.
Water samples from the Fraser, Skeena and Nass River basins of the Canadian Cordillera were analyzed for dissolved major element concentrations (HCO3−, SO42−, Cl−, Ca2+, Mg2+, K+, Na+), δ13C of dissolved inorganic carbon (δ13CDIC), and δ34S of dissolved sulfate (δ34SSO4) to quantify chemical weathering rates and exchanges of CO2 between the atmosphere, hydrosphere, and lithosphere. Weathering rates of silicates and carbonates were determined from major element mass balance. Combining the major element mass balance with δ34SSO4 (−8.9 to 14.1‰CDT) indicates sulfide oxidation (sulfuric acid production) and subsequent weathering of carbonate and to a lesser degree silicate minerals are important processes in the study area. We determine that on average, 81% of the riverine sulfate can be attributed to sulfide oxidation in the Cordilleran rivers, and that 25% of the total weathering cation flux can be attributed to carbonate and silicate dissolution by sulfuric acid. This result is validated by δ13CDIC values (−9.8 to −3.7‰ VPDB) which represents a mixture of DIC produced by the following weathering pathways: (i) carbonate dissolution by carbonic acid (−8.25‰) > (ii) silicate dissolution by carbonic acid (−17‰) ≈ (iii) carbonate dissolution by sulfuric acid derived from the oxidation of sulfides (coupled sulfide-carbonate weathering) (+0.5‰).δ34SSO4 is negatively correlated with δ13CDIC in the Cordilleran rivers, which further supports the hypothesis that sulfuric acid produced by sulfide oxidation is primarily neutralized by carbonates, and that sulfide-carbonate weathering impacts the δ13CDIC of rivers. The negative correlation between δ34SSO4 and δ13CDIC is not observed in the Ottawa and St. Lawrence River basins. This suggests other factors such as landscape age (governed by tectonic uplift) and bedrock geology are important controls on regional sulfide oxidation rates, and therefore also on the magnitude of sulfide-carbonate weathering—i.e., it is more significant in tectonically active areas.Calculated DIC fluxes due to Ca and Mg silicate weathering by carbonic acid (38.3 × 103 mol C · km−2 · yr−1) are similar in magnitude to DIC fluxes due to sulfide-carbonate weathering (18.5 × 103 mol C · km−2 · yr−1). While Ca and Mg silicate weathering facilitates a transfer of atmospheric CO2 to carbonate rocks, sulfide-carbonate weathering can liberate CO2 from carbonate rocks to the atmosphere when sulfide oxidation exceeds sulfide deposition. This implies that in the Canadian Cordillera, sulfide-carbonate weathering can offset up to 48% of the current CO2 drawdown by silicate weathering in the region. 相似文献
20.
Eight DSDP/ODP cores were analyzed for major ion concentrations and δ37Cl values of water-soluble chloride (δ37ClWSC) and structurally bound chloride (δ37ClSBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (XWSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (XSBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl− site and the water-soluble Cl− site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ37Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ37Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ37Cl values also have variable Cl− / SO42 ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization. 相似文献