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1.
This study reports the influence of a 20th century pollution signal recorded in the δ13C and δ18O of absolutely dated tree rings from Quercus robur and Pinus sylvestris from southern England. We identify a correspondence between the inter-relationship and climate sensitivity of stable isotope series that appears to be linked to recent trends in local SO2 emissions. This effect is most clearly exhibited in the broadleaved trees studied but is also observed in the δ13C values of the (less polluted) pine site at Windsor. The SO2 induced stomatal closure leads to a maximum increase of 2.5‰ in the isotope values (δ13C). The combined physiological response to high pollution levels is less in δ18O than δ13C. The SO2 signal also seems to be present as a period of reduced growth in the two ring-width chronologies. Direct, quantitative correction for the SO2 effect represents a significant challenge owing to the nature of the records and likely local plant response to environmental pollution. Whilst it appears that this signal is both limited to the late industrial period and demonstrates a recovery in line with improvements in air quality, the role of atmospheric pollution during the calibration period should not be underestimated and adequate consideration needs to be taken when calibrating biological environmental proxies in order to avoid development of biased reconstructions.  相似文献   

2.
The isotopic composition of fossil fuels is an important component of many studies of C sources and sinks based on atmospheric measurements of CO2. In C budget studies, the isotopic composition of crude petroleum and CH4 are often used as a proxy for the isotopic composition of CO2 emissions from combustion. In this study, the C isotope composition (δ13C) of exhaust from the major fossil fuel emission sources in Salt Lake City, USA, was characterized with 159 measurements of vehicle exhaust of various types and eight measurements of residential furnace exhaust. These two sources were found to be isotopically distinct, and differed from global-scale estimates based on average values for crude petroleum and CH4. Vehicle-specific factors such as engine load and operation time had no effect on δ13C of vehicle exhaust. A small difference was found between the mean δ13C of vehicle exhaust collected randomly from different vehicles and the mean δ13C of gasoline collected from multiple fueling stations representing major gasoline distributors in Salt Lake City and the surrounding area. However, a paired comparison of δ13C of exhaust and gasoline for six different vehicles did not show any consistent C isotope fractionation during vehicle combustion. The mean δ13C of crude petroleum processed for local distribution differed slightly from refined gasoline collected at multiple fueling stations, but time lags between processing and transportation cannot be ruled out as an uncontrollable contributing factor. Measured isotope ratios were then combined with fuel consumption statistics to predict the annual cycle of δ13C of fossil fuel emissions for the Salt Lake City metropolitan area. The results showed that the isotopic composition of CO2 emissions from fossil fuel combustion varied by almost 3‰ over the course of the 2002 calendar year. This study illustrates that on a regional scale, the isotopic composition of fossil fuel emissions shows a high degree of both spatial and temporal variability that may influence characterization of C sources and sinks with atmospheric measurements.  相似文献   

3.
Pollution from urban centers and fossil fuel combustion can decrease forest growth and interfere with physiological processes. To evaluate whether tree growth and the carbon isotope ratio (δ13C) and nitrogen isotope ratio (δ15N) in tree rings can serve as proxies for air pollution, this study compared these indices for poplar (Populus cathayana) growing at urban and suburban locations in Lanzhou, in northwestern China. Basal area increment values were much lower at the urban site than in the suburbs from 1985 to 2009, were negatively correlated with NO2 (r = ?0.56, p < 0.01) and SO2 (r = ?0.52, p < 0.05) emissions from 1990 to 2009, and increased abruptly after the Lanzhou urban steel factory closed. Urban tree-ring δ13C values were not significantly correlated with NO2 and SO2 concentrations, and did not differ significantly between the two sites, indicating that other environmental effects (such as precipitation) masked the pollution effects. Tree-ring δ15N values in the urban samples were much higher than the suburban values. Such differences may be attributable to uptake of 15N-enriched compounds caused by a higher urban N deposition rate. Tree growth is a promising tool for detecting ecophysiological responses of trees to both diffuse and point-source air pollution, but δ13C and δ15N in poplar were not sensitive to point-source air pollution in a heavily polluted environment.  相似文献   

4.
《Applied Geochemistry》2005,20(11):2116-2137
Samples of mine water from Butte, Montana were collected for paired geochemical and stable isotopic analysis. The samples included two sets of depth profiles from the acidic Berkeley pit lake, deep groundwater from several mine shafts in the adjacent flooded underground mine workings, and the acidic Horseshoe Bend Spring. Beginning in July-2000, the spring was a major surface water input into the Berkeley pit lake. Vertical trends in major ions and heavy metals in the pit lake show major changes across a chemocline at 10–20 m depth. The chemocline most likely represents the boundary between pre-2000 and post-2000 lake water, with lower salinity, modified Horseshoe Bend Spring water on top of higher salinity lake water below. Based on stable isotope results, the deep pit lake has lost approximately 12% of its initial water to evaporation, while the shallow lake is up to 25% evaporated. The stable isotopic composition of SO4 in the pit lake is similar to that of Horseshoe Bend Spring, but differs markedly from SO4 in the surrounding flooded mine shafts. The latter is heavier in both δ34S and δ18O, which may be due to dissolution of hypogene SO4 minerals (anhydrite, gypsum, barite) in the ore deposit. The isotopic and geochemical evidence suggests that much of the SO4 and dissolved heavy metals in the deep Berkeley pit lake were generated in situ, either by leaching of soluble salts from the weathered pit walls as the lake waters rose, or by subaqueous oxidation of pyrite on the submerged mine walls by dissolved Fe(III). Laboratory experiments were performed to contrast the isotopic composition of SO4 formed by aerobic leaching of weathered wallrock vs. SO4 from anaerobic pyrite oxidation. The results suggest that both processes were likely important in the evolution of the Berkeley pit lake.  相似文献   

5.
We present one millennium-long (1171-year), and three 100 year long annually resolved δ13C tree-ring chronologies from ecologically varying Juniperus stands in the Karakorum Mountains (northern Pakistan), and evaluate their response to climatic and atmospheric CO2 changes. All δ13C records show a gradual decrease since the beginning of the 19th century, which is commonly associated with a depletion of atmospheric δ13C due to fossil fuel burning. Climate calibration of high-frequency δ13C variations indicates a pronounced summer temperature signal for all sites. The low-frequency component of the same records, however, deviates from long-term temperature trends, even after correction for changes in anthropogenic CO2. We hypothesize that these high-elevation trees show a response to both climate and elevated atmospheric CO2 concentration and the latter might explain the offset with target temperature data. We applied several corrections to tree-ring δ13C records, considering a range of potential CO2 discrimination changes over the past 150 years and calculated the goodness of fit with the target via calibration/verification tests (R2, residual trend, and Durbin-Watson statistics). These tests revealed that at our sites, carbon isotope fixation on longer timescales is affected by increasing atmospheric CO2 concentrations at a discrimination rate of about 0.012‰/ppmv. Although this statistically derived value may be site related, our findings have implications for the interpretation of any long-term trends in climate reconstructions using tree-ring δ13C, as we demonstrate with our millennium-long δ13C Karakorum record. While we find indications for warmth during the Medieval Warm Period (higher than today’s mean summer temperature), we also show that the low-frequency temperature pattern critically depends on the correction applied. Patterns of long-term climate variation, including the Medieval Warm Period, the Little Ice Age, and 20th century warmth are most similar to existing evidence when a strong influence of increased atmospheric CO2 on plant physiology is assumed.  相似文献   

6.
In regions with seasonal temperate climatic regimes, tree growth is rarely controlled by any single environmental factor. As a consequence, the development of robust palaeoclimate reconstructions has proved challenging. Tree‐ring stable carbon isotope ratios (δ13C), however, are controlled primarily by photosynthetic rate, not by net growth. Therefore, at sites where climatic controls on tree‐ring growth are not strongly expressed, a robust (isotopic) palaeoclimate signal may still potentially be preserved. This hypothesis was tested using a 160‐year record of δ13C measured from the pooled latewood cellulose of six Quercus petraea L. (sessile oak) trees from Allt Lan‐las in West Wales, UK. Raw δ13C values were corrected for changes in the isotopic ratio of atmospheric carbon dioxide and for changes in the behaviour of trees due to the increasing availability of atmospheric CO2 since AD 1850. Strong correlations with local summer temperature and sunshine are reported, and also with the Central England Temperature record over the full length of the isotopic chronology (AD 1850–2010) (r = 0.69, P < 0.001). We conclude that tree‐ring stable isotopes can be used to extract strong palaeoclimate signals even from oak trees growing in a temperate maritime climate. This demonstrates the potential for extracting robust palaeoclimatic information from the very long and well‐replicated oak chronologies which have been developed in western and central Europe primarily for dating rather than palaeoclimatic research purposes. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

7.
This paper gives the stable carbon isotopic data in coals from the Late Namurian to Kazanian stages inthe Serteng Mt., Xishan and Huainan coalfields of the North China Platform. Its stratigraphic pattern shows that sev-eral isotopic shifts are apparent, and the large δ~(13)C negative shifts (approximately 2.5 to 3.0‰) occurred during theStephanian, Artinskian and Kazanian are observed in three Permo-Carboniferous coalfields. Those negative shifts areneither related to the coal rank and coal macerals, nor caused by the variety of peat-forming plants. The general de-crease in the δ~(13)C values of the Stephanian, Artinskian and Kazanian coals is consistent with an overall decrease inthe δ~(13)C values of ambient atmospheric CO_2 and/or a relative increase in atmospheric P_(CO2) during the coal-forming pe-riods. Therefore the authors postulate that the oxidation of peat, and the δ~(13)C-depleted CO_2 flux into the atmosphereduring the above stages may have contributed to coeval palaeoclimatic warming by way of the greenhouse effect.  相似文献   

8.
《Applied Geochemistry》2001,16(4):475-488
The usefulness of stable isotopes of dissolved SO4 (δ34S and δ18O) to study recharge processes and to identify areas of significant inter-aquifer mixing was evaluated in a large, semi-arid groundwater basin in south-eastern Australia (the Murray Basin). The distinct isotopic signatures in the oxidizing unconfined Murray Group Aquifer and the deeper reducing Renmark Group confined aquifer may be more sensitive than conventional chemical tracers in establishing aquifer connections. δ34S values in the unconfined Murray Group Aquifer in the south and central part of the study area decrease along the hydraulic gradient from 20.8 to 0.3‰. The concomitant increasing SO4/Cl ratios, as well as relatively low δ18OSO4 values, suggest that vertical input of biogenically derived SO4 via diffuse recharge is the predominant source of dissolved SO4 to the aquifer. Further along the hydraulic gradient towards the discharge area near the River Murray, δ34S values in the unconfined Murray Group Aquifer increase, and SO4/Cl ratios decrease, due to upward leakage of waters from the confined Renmark Group Aquifer which has a distinctly low SO4/Cl and high δ34S (14.9–56.4‰). Relatively positive δ34S and δ18OSO4 values, and low SO4/Cl in the Renmark Group Aquifer is typical of SO4 removal by bacterial reduction. The S isotope fractionation between SO4 and HS− of ∼24‰ estimated for the confined aquifer is similar to the experimentally determined chemical fractionation factor for the reduction process but much lower than the equilibrium fractionation (∼70‰) even though the confined groundwater residence time is >300 Ka years. Mapping the spatial distribution of δ34S and SO4/Cl of the unconfined Murray Group Aquifer provides an indicative tool for identifying the approximate extent of mixing, however the poorly defined end-member isotopic signatures precludes quantitative estimates of mixing fractions.  相似文献   

9.
Soils overlying two porphyry Cu deposits (Spence, Gaby Sur) and the Pampa del Tamarugal, Atacama Desert, Northern Chile were collected in order to investigate the extent to which saline groundwaters influence “soil” chemistry in regions with thick Miocene and younger sediment cover. Soil carbonate (calcite) was analyzed for C and O isotopes and pedogenic gypsum for S isotopes. Soil calcite is present in all soils at the Spence deposit, but increases volumetrically above two fracture zones that cut the Miocene gravels, including gravels that overlie the deposit. The C isotope composition of carbonate from the soils overlying fracture zones is indistinguishable from pedogenic carbonate elsewhere at the Spence deposit; all δ13CVPDB values fall within a narrow range (1.40–4.23‰), consistent with the carbonate having formed in equilibrium with atmospheric CO2. However, δ18OVPDB for carbonate over both fracture zones is statistically different from carbonate elsewhere (average δ18OVPDB = 0.82‰ vs. −2.23‰, respectively), suggesting involvement of groundwater in their formation. The composition of soils at the Tamarugal anomaly has been most strongly affected by earthquake-related surface flooding and evaporation of groundwater; δ13CVPDB values (−4.28‰ to −2.04‰) are interpreted to be a mixture of dissolved inorganic C (DIC) from groundwater and atmospheric CO2. At the Spence deposit, soils only rarely contain sufficient SO4 for S isotope analysis; the SO4-bearing soils occur only above the fracture zones in the gravel. Results are uniform (3.7–4.9‰ δ34SCDT), which is near the middle of the range for SO4 in groundwater (0.9–7.3‰). Sulfur in soils at the Gaby Sur deposit (3.8–6.1‰ δ34SCDT) is dominated by gypsum, which primarily occurs on the flanks and tops of hills, suggesting deposition from SO4-rich fogs. Sulfate in Gaby Sur deposit gypsum is possibly derived by condensation of airborne SO4 from volcanic SO2 from the nearby Andes. At the Gaby Sur deposit and Tamarugal anomaly, pedogenic stable isotopes cannot distinguish between S from porphyry or redeposited SO4 from interior salars.The three sites studied have had different histories of salt accumulation and display variable influence of groundwater, which is interpreted to have been forced to the surface during earthquakes. The clear accumulation of salts associated with fractures at the Spence deposit, and shifts in the isotopic composition of carbonate and sulfate in the fractures despite clear evidence of relatively recent removal of salts indicates that transfer from groundwater is an ongoing process. The interpretation that groundwaters can influence the isotopic composition of pedogenic calcrete and gypsum has important implications for previous studies that have not considered this mechanism.  相似文献   

10.
High-resolution natural abundance stable carbon isotope analyses across annual growth rings in evergreen trees reveal a cyclic increase and decrease in the measured carbon isotopic composition (δ13C), but the causes of this pattern are poorly understood. We compiled new and published high-resolution δ13C data from across annual growth rings of 33 modern evergreen trees from 10 genera and 15 globally distributed sites to quantify the parameters that affect the observed δ13C pattern. Across a broad range of latitude, temperature, and precipitation regimes, we found that the average, measured seasonal change in δ13C (Δδ13Cmeas, ‰) within tree rings of evergreen species reflects changes in the carbon isotopic composition of atmospheric carbon dioxide (Δδ13CCO2) and changes in seasonal precipitation (ΔP) according to the following equation: Δδ13Cmeas = Δδ13CCO2 - 0.82(ΔP) + 0.73; R2 = 0.96. Seasonal changes in temperature, pCO2, and light levels were not found to significantly affect Δδ13Cmeas. We propose that this relationship can be used to quantify seasonal patterns in paleoprecipitation from intra-ring profiles of δ13C measured from non-permineralized, fossil wood.  相似文献   

11.
Natural gases and associated condensate oils from the Zhongba gas field in the western Sichuan Basin, China were investigated for gas genetic types and origin of H2S by integrating gaseous and light hydrocarbon geochemistry, formation water compositions, S isotopes (δ34S) and geological data. There are two types of natural gas accumulations in the studied area. Gases from the third member of the Middle Triassic Leikoupo Formation (T2l3) are reservoired in a marine carbonate sequence and are characterized by high gas dryness, high H2S and CO2 contents, slightly heavy C isotopic values of CH4 and widely variable C isotopic values of wet gases. They are highly mature thermogenic gases mainly derived from the Permian type II kerogens mixed with a small proportion of the Triassic coal-type gases. Gases from the second member of the Upper Triassic Xujiahe Formation (T3x2) are reservoired in continental sandstones and characterized by low gas dryness, free of H2S, slightly light C isotopic values of CH4, and heavy and less variable C isotopic values of wet gases. They are coal-type gases derived from coal in the Triassic Xujiahe Formation.The H2S from the Leikoupo Formation is most likely formed by thermochemical SO4 reduction (TSR) even though other possibilities cannot be fully ruled out. The proposed TSR origin of H2S is supported by geochemical compositions and geological interpretations. The reservoir in the Leikoupo Formation is dolomite dominated carbonate that contains gypsum and anhydrite. Petroleum compounds dissolved in water react with aqueous SO4 species, which are derived from the dissolution of anhydrite. Burial history analysis reveals that from the temperature at which TSR occurred it was in the Late Jurassic to Early Cretaceous and TSR ceased due to uplift and cooling thereafter. TSR alteration is incomplete and mainly occurs in wet gas components as indicated by near constant CH4 δ13C values, wide range variations of ethane, propane and butane δ13C values, and moderately high gas dryness. The δ34S values in SO4, elemental S and H2S fall within the fractionation scope of TSR-derived H2S. High organo-S compound concentrations together with the occurrence of 2-thiaadamantanes in the T2l reservoir provide supplementary evidence for TSR related alteration.  相似文献   

12.
Elemental and isotopic composition of leaves of the seagrassThalassia testudinum was highly variable across the 10,000 km2 and 8 years of this study. The data reported herein expand the reported range in carbon:nitrogen (C:N) and carbon:phosphorus (C:P) ratios and δ13C and δ15N values reported for this species worldwide; 13.2–38.6 for C:N and 411–2,041 for C:P. The 981 determinations in this study generated a range of ?13.5‰ to ?5.2‰ for δ13C and ?4.3‰ to 9.4‰ for δ15N. The elemental and isotope ratios displayed marked seasonality, and the seasonal patterns could be described with a simple sine wave model. C:N, C:P, δ13C, and δ15N values all had maxima in the summer and minima in the winter. Spatial patterns in the summer maxima of these quantities suggest there are large differences in the relative availability of N and P across the study area and that there are differences in the processing and the isotopic composition of C and N. This work calls into question the interpretation of studies about nutrient cycling and food webs in estuaries based on few samples collected at one time, since we document natural variability greater than the signal often used to imply changes in the structure or function of ecosystems. The data and patterns presented in this paper make it clear that there is no threshold δ15N value for marine plants that can be used as an unambiguous indicator of human sewage pollution without a thorough understanding of local temporal and spatial variability.  相似文献   

13.
Laboratory experiments on reagent-grade calcium carbonate and carbonate rich glacial sediments demonstrate previously unreported kinetic fractionation of carbon isotopes during the initial hydrolysis and early stages of carbonate dissolution driven by atmospheric CO2. There is preferential dissolution of Ca12CO3 during hydrolysis, resulting in δ13C-DIC values that are significantly lighter isotopically than the bulk carbonate. The fractionation factor for this kinetic isotopic effect is defined as εcarb. εcarb is greater on average for glacial sediments (−17.4‰) than for calcium carbonate (−7.8‰) for the < 63 μm size fraction, a sediment concentration of 5 g L−1 and closed system conditions at 5°C. This difference is most likely due to the preferential dissolution of highly reactive ultra-fine particles with damaged surfaces that are common in subglacial sediments. The kinetic isotopic fractionation has a greater impact on δ13C-DIC at higher CaCO3:water ratios and is significant during at least the first 6 h of carbonate dissolution driven by atmospheric CO2 at sediment concentrations of 5 g L−1. Atmospheric CO2 dissolving into solution following carbonate hydrolysis does not exhibit any significant equilibrium isotopic fractionation for at least ∼ 6 h after the start of the experiment at 5°C. This is considerably longer than previously reported in the literature. Thus, kinetic fractionation processes will likely dominate the δ13C-DIC signal in natural environments where rock:water contact times are short <6-24 h (e.g., glacial systems, headwaters in fluvial catchments) and there is an excess of carbonate in the sediments. It will be difficult apply conventional isotope mass balance techniques in these types of environment to identify microbial CO2 signatures in DIC from δ13C-DIC data.  相似文献   

14.
We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ13C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ13C values of odd carbon numbered C23-C33n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ13C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C25-C31n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.  相似文献   

15.
Hydrochemistry and isotope geochemistry of the upper Danube River   总被引：7，自引：0，他引：7  
The upper Danube River and 19 of its major tributaries were monitored for 1046 km downriver and seasonally for Ca, Mg, Sr, Na, K, HCO3, CO2, Cl, PO4, SiO2, NO3, NO2, NH4, SO4, δ13CDIC, δ18OH2O, δDH2O, δ34SSO4, δ18OSO4, and 87Sr/86Sr. Hydrological considerations and δ18O/δD data show that the water balance in the river, particularly after its confluence with the Inn, is controlled by the southern tributaries draining the Mesozoic carbonate complexes of the Alps. As a result, chemical balance at Bratislava is mostly a conservative product of its tributaries. The concentrations of Ca, Mg, and Sr in the Danube are 6 to 9 times higher than in “pristine” rivers. Although all these cations are derived from dissolution of Mesozoic carbonates, the ultimate cause is likely the enhanced generation of soil CO2 due to agricultural and forestry practices. Dissolution of Triassic sulfates is an additional factor for Ca enrichment in the headwater section of the river. Dissolved sulfate, with a comparable enrichment factor to that of alkaline earths, appears to be derived mostly from atmospheric deposition, a proposition based on consideration of its sulfur and oxygen isotopic compositions. Na, K, and Cl are enriched by a factor of 2.5 to 4 times, mostly as a result of industrial and municipal pollution sources.In contrast to the above components, which behave mostly conservatively during the downriver flow of the Danube, biogenic elements such as nutrients and Si are influenced by in-river processes. The photosynthesis/respiration balance that impacts the carbon cycle and the oxygen balance has been discussed elsewhere (Pawellek and Veizer, 1994). NO3, NO2, and NH4 are enriched by a factor of 10 to 16 times from point and diffuse sources along the watercourses, generating at times downflow nitrification plumes from NH4 to NO3. PO4 varies seasonally, chiefly as a result of biologic demand during the warm periods. For SiO2, the biological uptake (mostly for secretion of diatom frustules), combined with the deficiency of this compound that results from the predominantly carbonate lithology of the catchment, results in concentrations that are below those of pristine rivers. Overall, the present-day “salted” characteristics of the river are chiefly a consequence of the long habitation history of the upper Danube watershed.  相似文献   

16.
Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ13CDIC) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in 13C due to enhanced carbonate dissolution associated with the release of H2SO4 from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ34SSO4 and δ18OSO4 isotopic signatures of the mine drainage and the presence of presumptive SO4-reducing bacteria suggest that SO4 reduction activity also contributes C depleted in 13C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H2SO4 dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO2 outgassing.  相似文献   

17.
Sulfur isotope compositions of pumice and adsorbed volatiles on ash from the first historical eruption of Anatahan volcano (Mariana arc) are presented in order to constrain the sources of sulfur erupted during the period 10-21 May, 2003. The isotopic composition of S extracted from erupted pumice has a narrow range, from δ34SV-CDT +2.6‰ to +3.2‰, while the composition of sulfur adsorbed onto ash has a larger range (+2.8‰ to +5.3‰). Fractionation modeling for closed and open system scenarios suggests that degassing of SO2 raised the δ34SV-CDT value of S dissolved in the melt from an initial composition of between +1.6‰ and +2.6‰ for closed-system degassing, or between −0.5‰ and +1.5‰ for open-system degassing, however closed-system degassing is the preferred model. The calculated values for the initial composition of the magma represent a MORB-like (δ34SV-CDT ∼ 0‰) mantle source with limited contamination by subducted seawater sulfate (δ34SV-CDT +21‰). Modeling also suggests that the δ34SV-CDT value of SO2 gas in closed-system equilibrium with the degassed magma was between +0.9‰ and +2.5‰. The δ34SV-CDT value of sulfate adsorbed onto ash in the eruption plume (+2.8‰ to +5.1‰) is consistent with sulfate formation by oxidation of magmatic SO2 in the eruption column. The sulfur isotope composition of sulfate adsorbed to ash changes from lower δ34S values for ash erupted early in the eruption to higher δ34S values for ash erupted later in the eruption. We interpret the temporal/stratigraphic change in sulfate isotopic composition to primarily reflect a change in the isotopic composition of magmatic SO2 released from the progressively degassing magma and is attributed to the expulsion of an accumulated gas phase at the beginning of the eruption. More efficient oxidation of magmatic SO2 gas to sulfate in the early water-rich eruption plume probably contributed to the change in S isotope compositions observed in the ash leachates.  相似文献   

18.
The Deer Lake Complex, located in north-central Minnesota, consists of a series of layered peridotite-pyroxenite-gabbro sills. Sulfide minerals occur as fine disseminations throughout pyroxenite and gabbro units, and occur more sporadically in peridotite and basal chilled margin units. Sulfide volume percentage rarely exceeds 0.5. A distinct zonation in sulfide mineralogy and sulfur isotopic composition characterizes the sills. Cobaltian pentlandite is the dominant sulfide mineral in peridotite (pd) units, with Ni-enrichment most likely linked to the serpentinization process. δ34Spd values are variable, ranging from ?3.5 to +2.8‰. Sulfide assemblages in pyroxenite (px) and lower gabbro units consist of chalcopyrite, pyrrhotite, and minor pentlandite. δ34Spx values range from ?1 to +1 ‰. Pyrite is the principal sulfide mineral in upper gabbro (μg) units. Its origin may be related to increased f02 conditions of the remaining melt and to reaction between a S-bearing volatile phase and mafic silicates. δ34Sug values range from 1 to 3.5 ‰. Sulfur isotopic values of chilled margin (2–9 ‰) and peridotite units, together with the erratic spatial distribution of sulfide minerals in these zones, suggests that the parent magma was not initially saturated with sulfur, and that local sulfide concentrations are the result of incorporation of sulfur derived from metasedimentary country rocks. Sulfide saturation was more uniformly reached during pyroxenite formation, with contained sulfur being of magmatic origin. Enrichment in 34S of pyrite from upper gabbro may be explained by buildup of isotopically heavy sulfur following a Rayleigh process, coupled with possible involvement of a SO2-rich fluid phase during hydrothermal alteration.  相似文献   

19.
《Applied Geochemistry》2003,18(5):765-779
Stable isotope systematics of C, N and S were studied in soils of 5 European forest ecosystems. The sites were located along a North–South transect from Sweden to Italy (mean annual temperatures from +1.0 to +8.5 °C, atmospheric deposition from 2 to 19 kg N ha−1 a−1, and from 6 to 42 kg S ha−1 a−1). In Picea stands, the behavior of C, N and S isotopes was similar in 3 aspects: (1) assimilation favored the lighter isotopes 12C, 14N and 32S; (2) mineralization in the soil profile left in situ residues enriched in the heavier isotopes 13C, 15N and 34S; and (3) NO3–N as well as SO4–S in soil solution was isotopically lighter compared to the same species in the atmospheric input. In this study, emphasis was placed on S isotope profiles which so far have been investigated to a much lesser extent than those of C and N. Sulfate in monthly samples of atmospheric input had systematically higher δ34S ratios than total soil S at the 0–5 cm depth, on average by 4.0‰. Sulfate in the atmospheric input had higher δ34S ratios than in deep (>50 cm) lysimeter water, on average by 3.2‰. Organic S constituted more than 50% of total soil S throughout most of the profiles (0–20 cm below surface). There was a tendency to isotopically heavier organic S and lighter inorganic SO4–S, with ester SO4–S heavier than C-bonded S at 3 of the 5 sites. With an increasing depth (0 to 20 cm below surface), δ13C, δ15N and δ34S ratios of bulk soil increased on average by 0.9, 4.2 and 1.6‰, respectively, reflecting an increasing degree of mineralization of organic matter. The isotope effects of C, N and S mineralization were robust enough to exist at a variety of climate conditions and pollution levels. In the case of S, the difference between isotope composition of the upper organic-rich soil horizon (lower δ34S) and the deeper sesquioxide-rich soil horizons (higher δ34S) can be used to determine the source of SO4 in streams draining forests. This application of δ34S as a tracer of S origin was developed in the Jezeřı́ catchment, Czech Republic, a highly polluted site suffering from spruce die-back. In 1996–1997, the magnitude and δ34S of atmospheric input (20 kg S ha−1 a−1, 5.8‰) and stream discharge (56 kg S ha−1 a−1, 3.5‰) was monitored. Export of S from the catchment was 3 times higher than contemporary atmospheric input. More than 50% of S in the discharge was represented by release of previously stored pollutant S from the soil. Stable isotope systematics of Jezeřı́ soil S (mean of 2.5‰ in the O+A horizon, 4.8‰ in the B horizon, and 5.8‰ in the bedrock) suggests that most of the soil-derived S in discharge must come from the isotopically light organic S present in the upper soil horizon, and that mineralized organically-cycled S is mainly flushed out during the spring snowmelt. The fact that a considerable proportion of incoming S is organically cycled should be considered when predicting the time-scale of acidification reversal in spruce die-back affected areas.  相似文献   

20.
Zinc isotope ratios were measured in the top sections of dated ombrotrophic peat cores in Finland to investigate their potential as proxies for atmospheric sources and to constrain post depositional processes affecting the geochemical record. The peat deposits were located in Hietajärvi, a background site well away from any point pollution source and representing ‘background’ conditions, in Outokumpu, next to a mining site, and in Harjavalta, next to a smelter. Measured total concentrations, calculated excess concentrations and mass balance considerations suggest that zinc is subjected to important biogeochemical cycling within the peat. Significant isotopic variability was found in all three peat bogs, with heavier zinc in the deeper and lighter zinc in the upper sections. Isotope ratios and concentrations correlated in the two peats located next to dominant point sources, i.e. the smelting and mining site, suggesting that zinc isotopes trace pollution sources. Concentration and isotope peaks were offset from the period of mining and smelting activity, supporting migration of zinc down the profile. The δ66ZnJMC (where δ66Zn = [(66Zn/64Zn)sample/(66Zn/64Zn)JMC-standard − 1] × 103) of the top section sample at the remote Hietajärvi site was 0.9‰ and we suggest this represents the regional background isotope signature of atmospheric zinc. The deeper sections of the peat cores show isotopically heavier zinc than any potential atmospheric source, indicating that post depositional processes affected the isotopic records. The large variations encountered (up to 1.05‰ for δ66Zn) and Rayleigh modelling imply that multiple fractionation of zinc during diagenetic alterations occurs and nutrient recycling alone cannot explain the fractionation pattern.We propose that zinc isotopes are amenable to identify different atmospheric zinc sources, including zinc derived from anthropogenic activities such as mining and smelting, but multiple biogeochemical processes seriously affect the record and they need to be evaluated and assessed carefully if zinc isotopes are used in terrestrial paleorecords.  相似文献   

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