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1.
The mass of volatiles emitted during volcanic eruptions is often estimated by comparing the volatile contents of undegassed melt inclusions, trapped in crystals at an early stage of magmatic evolution, with that of the degassed matrix glass. Here we present detailed characterisation of magmatic volatiles (H2O, CO2, S, Fl and Cl) of crystal-hosted melt and fluid inclusions from the 2014–2015 Holuhraun eruption of the Bárðarbunga volcanic system, Iceland. Based on the ratios of magmatic volatiles to similarly incompatible trace elements, the undegassed primary volatile contents of the Holuhraun parental melt are estimated at 1500–1700 ppm CO2, 0.13–0.16 wt% H2O, 60–80 ppm Cl, 130–240 ppm F and 500–800 ppm S. High-density fluid inclusions indicate onset of crystallisation at pressures?≥?0.4 GPa (~?12 km depth) promoting deep degassing of CO2. Prior to the onset of degassing, the melt CO2 content may have reached 3000–4000 ppm, with the total magmatic CO2 budget estimated at  23–55 Mt. SO2 release commenced at 0.12 GPa (~?3.6 km depth), eventually leading to entrapment of SO2 vapour in low-density fluid inclusions. We calculate the syn-eruptive volatile release as 22.2 Mt of magmatic H2O, 5.9–7.7 Mt CO2, and 11.3 Mt of SO2 over the course of the eruption; F and Cl release were insignificant. Melt inclusion constraints on syn-eruptive volatile release are similar to estimates made during in situ field monitoring, with the exception of H2O, where field measurements may be heavily biased by the incorporation of meteoric water.  相似文献   

2.
The Candamo Cave contains an important group of paleolithic paintings which have been seriously deteriorated due to mass tourism. In this work, an analysis was carried out of different climatic parameters (CO2, temperature, humidity, 222Rn) during annual cycles with the cave closed to the public and during an experimental period of controlled visits. The effect of visits on the geochemical characteristics of karstic water was also analyzed together with the cave ventilation. The natural variations in the cave air CO2 were above 3000 ppm, the increase produced through visits was only 100–110 ppm and since the humidity is almost permanently at saturation point, the critical parameter which limits the visitor capacity becomes air temperature. The temperature changes during the annual cycle are of the order of 1  °C in the external part and less than 0.5  °C in the internal part of the cave and a maximum increase of 0.13  °C was observed during the period of the visits. The 222Rn and CO2 concentration minimums in the summer period (July–October) show that this is the most propitious time for visits, since the greatest ventilation is produced in the cave at this time and, therefore, the greatest capacity for recovery. The geochemistry of the water, on the other hand, indicated that this is the period of the year in which processes of wall corrosion can be most easily introduced, although this would be of limited magnitude. The visitor capacity calculated was 29 visitors/day. Received: 29 August 1996 · Accepted: 23 June 1997  相似文献   

3.
Cave dripwater hydrochemistry responds to environmental changes, both within and outside of the cave, and thereby conveys this information to any stalagmite fed by the drips. As stalagmites are important archives of climate proxy information, understanding how dripwater hydrochemistry responds to environmental forcing is critical. However, despite the large number of speleothems in SW China, the response of dripwater to regional climate variability is not yet adequately understood. A 3‐year study of three drip sites in Xueyu Cave, Chongqing Municipality, SW China, revealed the most important mechanisms controlling dripwater chemical variability. The principal chemical indices (pH, specific conductivity, Ca2+, Mg2+, Sr2+ and ) in collected dripwaters and the local climate data were analysed in this study. The principal controls on the hydrochemistry were found to be the external climate and its changes, groundwater residence time, cave ventilation and prior calcite precipitation (PCP) processes. Dripwater hydrochemistry showed strongly coherent seasonal patterns despite the fact that all sites are Ca–HCO3 type waters and supersaturated with calcite. Seasonal changes in dripwater hydrochemistry were influenced by the soil and vadose zone CO2 content as well as groundwater residence time in the upper karst zone. Cave‐air CO2 seasonal variations were consistent with changes in dripwater PCO2 and cave ventilation. Trace element ratios (Mg/Ca and Sr/Ca) of dripwater were controlled by PCP processes. Seasonal variations in dripwater Mg/Ca and Sr/Ca ratios in Xueyu Cave showed inverse changes with the Asia Monsoon Index during the monitoring period, reflecting the seasonal climate changes that may have been recorded in the speleothems. Based on a linear regression of PCO2 and the Ca2+ data in the cold–dry winter season, a 130‐ppm shift in cave‐air PCO2 results in a 1‐ppm shift in dripwater Ca2+ concentration in Xueyu Cave. This study illustrates the importance of understanding factors controlling the changes in the composition of dripwater before it reaches the speleothem.  相似文献   

4.
Volatiles contribute to magma ascent through the sub-volcanic plumbing system. Here, we investigate melt inclusion compositions in terms of major and trace elements, as well as volatiles (H2O, CO2, SO2, F, Cl, Br, S) for Quaternary Plinian and dome-forming dacite and andesite eruptions in the central and the northern part of Dominica (Lesser Antilles arc). Melt inclusions, hosted in orthopyroxene, clinopyroxene and plagioclase are consistently rhyolitic. Post-entrapment crystallisation effects are limited, and negligible in orthopyroxene-hosted inclusions. Melt inclusions are among the most water-rich yet recorded (≤?8 wt% H2O). CO2 contents are generally low (<?650 ppm), although in general the highest pressure melt inclusion contain the highest CO2. Some low-pressure (<?3 kbars) inclusions have elevated CO2 (up to 1100–1150 ppm), suggestive of fluxing of shallow magmas with CO2-rich fluids. CO2-trace element systematics indicate that melts were volatile-saturated at the time of entrapment and can be used for volatile-saturation barometry. The calculated pressure range (0.8–7.5 kbars) indicates that magmas originate from a vertically-extensive (3–27 km depth) storage zone within the crust that may extend to the sub-Dominica Moho (28 km). The vertically-extensive crustal system is consistent with mush models for sub-volcanic arc crust wherein mantle-derived mafic magmas undergo differentiation over a range of crustal depths. The other volatile range of composition for melt inclusions from the central part is F (75–557 ppm), Cl (1525–3137 ppm), Br (6.1–15.4 ppm) and SO2 (<?140 ppm), and for the northern part it’s F (92–798 ppm), Cl (1506–4428 ppm), Br (not determined) and SO2 (<?569; one value at 1015 ppm). All MIs, regardless of provenance, describe the same Cl/F correlation (8.3?±?2.7), indicating that the magma source at depth is similar. The high H2O content of Dominica magmas has implications for hazard assessment.  相似文献   

5.
Biological soil crusts (BSCs) are an important cover in arid desert landscapes, and have a profound effect on the CO2 exchange in the desert system. Although a large number of studies have focused on the CO2 flux at the soil–air interface, relatively few studies have examined the soil CO2 concentration in individual layers of the soil profile. In this study, the spatiotemporal dynamics of CO2 concentration throughout the soil profile under two typical BSCs (algae crusts and moss crusts) and its driving factors were examined in a revegetated sandy area of the Tengger Desert from Mar 2010 to Oct 2012. Our results showed that the mean values of the vertical soil CO2 concentrations under algal crusts and moss crusts were 600–1,200 μmol/mol at the 0–40 cm soil profiles and increased linearly with soil depth. Daily CO2 concentrations showed a single-peak curve and often had a 1–2 h time delay after the maximum soil temperature. During the rainy season, the mean soil CO2 concentration profile was 1,200–2,000 μmol/mol, which was 2–5 times higher as compared to the dry season (400–800 μmol/mol). Annually, soil moisture content was the key limiting factor of the soil CO2 concentration, but at the daily time scale, soil temperature was the main limiting factor. Combined with infiltration depth of crusted soils, we predicted that precipitation of 10–15 mm was the most effective driving factor in arid desert regions.  相似文献   

6.
Coastal wetlands are hotspots for biodiversity and biological productivity, yet the hydrology and carbon cycling within these systems remains poorly understood due to their complex nature. By using a novel spatiotemporal approach, this study quantified groundwater discharge and the related inputs of acidity and CO2 along a continuum of a modified coastal acid sulphate soil (CASS) wetland, a coastal lake and an estuary under highly contrasting hydrological conditions. To increase the resolution of spatiotemporal data and advance upon previous methodologies, we relied on automated observations from four simultaneous time-series stations to develop multiple radon mass balance models to estimate groundwater discharge and related groundwater inputs of acidity and dissolved inorganic carbon (DIC), along with surface water to atmosphere CO2 fluxes. Spatial surveys indicated distinct acid hotspots with minimum surface water pH of 2.91 (dry conditions) and 2.67 (flood conditions) near a non-remediated (drained) CASS area. Under flood conditions, groundwater discharge accounted for ～14.5 % of surface water entering the lake. During the same period, acid discharge from the acid sulphate soil section of the continuum produced ～4.8 kg H2SO4?ha?1 day?1, a rate much higher than previous studies in similar systems. During baseflow conditions, the low pH water was rapidly buffered within the estuarine lake, with the pH increasing from 4.22 to 6.07 over a distance of ～250 m. The CO2 evasion rates within the CASS were extremely high, averaging 2163?±?125 mmol m?2 day?1 in the dry period and 4061?±?259 mmol m?2 day?1 under flood conditions. Groundwater input of DIC could only account for 0.4 % of this evasion in the dry conditions and ～5 % during the flood conditions. We demonstrated that by utilising a spatiotemporal (multiple time-series stations) approach, the study was able to isolate distinct zones of differing hydrology and biogeochemistry, whilst providing more reasonable groundwater acid input estimates and air–water CO2 flux estimates than some traditional sampling designs. This study highlights the notion that modified CASS wetlands can release large amounts of CO2 to the atmosphere because of high groundwater acid inputs and extremely low surface water pH.  相似文献   

7.
Cave air CO2 is a vital part of the cave environment. Most studies about cave air CO2 variations are performed in caves with no streams; there are few studies to date regarding the relationship of cave air CO2 variations and drip water hydrochemistry in underground stream–developed caves. To study the relationship of underground stream, drip water, and cave air CO2, monthly and daily monitoring of air CO2 and of underground stream and drip water was performed in Xueyu Cave from 2012 to 2013. The results revealed that there was marked seasonal variation of air CO2 and stream hydrochemistry in the cave. Daily variations of cave air CO2, and of stream and drip water hydrochemistry, were notable during continuous monitoring. A dilution effect was observed by analyzing hydrochemical variations in underground stream and drip water after rainfall. High cave air CO2 along with low pH and low δ13CDIC in stream and drip water indicated that air CO2 was one of the dominant factors controlling stream and drip water hydrochemistry on a daily scale. On a seasonal scale, stream flows may promote increased cave air CO2 in summer; in turn, the higher cave air CO2 could inhibit degassing of drip water and make calcite δ13C more negative. Variation of calcite δ13C (precipitated from drip water) was in reverse of monthly temperature, soil CO2, and cave air CO2. Therefore, calcite δ13C in Xueyu Cave could be used to determine monthly changes outside the cave. However, considering the different precipitation rate of sediment in different seasons, it was difficult to use stalagmites to reconstruct environmental change on a seasonal scale.  相似文献   

8.
During the formation and development of glacial meltwater runoff, hydrochemical erosion is abundant, especially the hydrolysis of K/Na feldspar and carbonates, which can consume H+ in the water, promote the formation of bicarbonate by dissolving atmospheric CO2, and affect the regional carbon cycle. From July 21, 2015, to July 18, 2017, the CO2 concentration and flux were observed by the eddy covariance (EC) method in the relatively flat and open moraine cover area of Koxkar Glacier in western Mt. Tianshan, China. We found that: (1) atmospheric CO2 fluxes ranged from ??408.95 to 81.58 mmol m?2 day?1 (average ? 58.68 mmol m?2 day?1), suggesting that the study area is a significant carbon sink, (2) the CO2 flux footprint contribution areas were primarily within 150 m of the EC station, averaging total contribution rates of 93.30%, 91.39%, and 90.17% of the CO2 flux in the snow accumulation, snow melting, and glacial melting periods, respectively. Therefore, the contribution areas with significant influences on CO2 flux observed at EC stations were concentrated, demonstrating that grassland CO2 flux around the glaciers had little effect at the EC stations, (3) in the predominant wind direction, under stable daytime atmospheric stratification, the measurement of CO2 flux, as interpreted by the Agroscope Reckenholz Tanikon footprint tool, was 79.09% ± 1.84% in the contribution area. This was slightly more than seen at night, but significantly lower than the average under unstable atmospheric stratification across the three periods of interest (89%). The average distance of the farthest point of the flux footprint under steady state atmospheric conditions was 202.61?±?69.33 m, markedly greater than that under non-steady state conditions (68.55?±?10.34 m). This also indicates that the CO2 flux observed using EC was affected primarily by hydrochemical erosion reactions in the glacier area, (4) a good negative correlation was found between net glacier exchange (NGE) of CO2 and air temperature on precipitation-free days. Strong ice and snow ablation could promote hydrochemical reactions of soluble substances in the debris area and accelerated sinking of atmospheric CO2. Precipitation events might reduce snow and ice melting, driven by reduced regional temperatures. However, a connection between NGE and precipitation, when less than 8.8 mm per day, was not obvious. When precipitation was greater than 8.8 mm per day, NGE decreased with increasing precipitation, (5) graphically, the slope of NGE, related to daily runoff, followed a trend: snow melting period?>?snow accumulation period?>?early glacial ablation period?>?late glacier ablation period?>?dramatic glacier ablation period. The slope was relatively large during snow melting, likely because of CO2 sinking caused by water–rock interactions. The chemical reaction during elution in the snow layer might also promote atmospheric CO2 drawdown. At the same time, the damping effect of snow cover and the almost-closed glacier hydrographic channel inhibited the formation of regional runoff, possibly providing sufficient time for the chemical reaction, thus promoting further CO2 drawdown.  相似文献   

9.
Spherulitic textures in the Rocche Rosse obsidian flow (Lipari, Aeolian Islands, Italy) have been characterized through petrographic, crystal size distribution (CSD) and in situ major and volatile elemental analyses to assess the mode, temperature and timescales of spherulite formation. Bulk glass chemistry and spherulite chemistry analyzed along transects across the spherulite growth front/glass boundary reveal major-oxide and volatile (H2O, CO2, F, Cl and S) chemical variations and heterogeneities at a ≤5 μm scale. Numerous bulk volatile data in non-vesicular glass (spatially removed from spherulitic textures) reveal homogenous distributions of volatile concentrations: H2O (0.089 ± 0.012 wt%), F (950 ± 40 ppm) and Cl (4,100 ± 330 ppm), with CO2 and S consistently below detection limits suggesting either complete degassing of these volatiles or an originally volatile-poor melt. Volatile concentrations across the spherulite boundary and within the spherulitic textures are highly variable. These observations are consistent with diffusive expulsion of volatiles into melt, leaving a volatile-poor rim advancing ahead of anhydrous crystallite growth, which is envisaged to have had a pronounced effect on spherulite crystallization dynamics. Argon concentrations dissolved in the glass and spherulites differ by a factor of ~20, with Ar sequestered preferentially in the glass phase. Petrographic observation, CSD analysis, volatile and Ar data as well as diffusion modeling support continuous spherulite nucleation and growth starting at magmatic (emplacement) temperatures of ~790–825 °C and progressing through the glass transition temperature range (T g ~ 750–620 °C), being further modified in the solid state. We propose that nucleation and growth rate are isothermally constant, but vary between differing stages of spherulite growth with continued cooling from magmatic temperatures, such that there is an evolution from a high to a low rate of crystallization and low to high crystal nucleation. Based on the diffusion of H2O across these temperature ranges (~800–300 °C), timescales of spherulite crystallization occur on a timescale of ~4 days with further modification up to ~400 years (growth is prohibitively slow <400 °C and would become diffusion reliant). Selective deformation of spherulites supports a down-temperature continuum of spherulite formation in the Rocche Rosse obsidian; indeed, petrographic evidence suggests that high-strain zones may have catalyzed progressive nucleation and growth of further generations of spherulites during syn- and post-emplacement cooling.  相似文献   

10.
Diverse interpretations have been made of carbon isotope time series in speleothems, reflecting multiple potential controls. Here we study the dynamics of 13C and 12C cycling in a particularly well-constrained site to improve our understanding of processes affecting speleothem δ13C values. The small, tubular Grotta di Ernesto cave (NE Italy) hosts annually-laminated speleothem archives of climatic and environmental changes. Temperature, air pressure, pCO2, dissolved inorganic carbon (DIC) and their C isotopic compositions were monitored for up to five years in soil water and gas, cave dripwater and cave air. Mass-balance models were constructed for CO2 concentrations and tested against the carbon isotope data. Air advection forces winter pCO2 to drop in the cave air to ca. 500 ppm from a summer peak of ca. 1500 ppm, with a rate of air exchange between cave and free atmosphere of approximately 0.4 days. The process of cave ventilation forces degassing of CO2 from the dripwater, prior to any calcite precipitation onto the stalagmites. This phase of degassing causes kinetic isotope fractionation, i.e. 13C-enrichment of dripwater whose δ13CDIC values are already higher (by about 1‰) than those of soil water due to dissolution of the carbonate rock. A subsequent systematic shift to even higher δ13C values, from −11.5‰ in the cave drips to about −8‰ calculated for the solution film on top of stalagmites, is related to degassing on the stalagmite top and equilibration with the cave air. Mass-balance modelling of C fluxes reveals that a very small percentage of isotopically depleted cave air CO2 evolves from the first phase of dripwater degassing, and shifts the winter cave air composition toward slightly more depleted values than those calculated for equilibrium. The systematic 13C-enrichment from the soil to the stalagmites at Grotta di Ernesto is independent of drip rate, and forced by the difference in pCO2 between cave water and cave air. This implies that speleothem δ13C values may not be simply interpreted either in terms of hydrology or soil processes.  相似文献   

11.
Generation of CO2-rich melts during basalt magma ascent and degassing   总被引：1，自引：0，他引：1  
To test mechanisms of basaltic magma degassing, continuous decompressions of volatile-bearing (2.7–3.8 wt% H2O, 600–1,300 ppm CO2) Stromboli melts were performed from 250–200 to 50–25 MPa at 1,180–1,140 °C. Ascent rates were varied from 0.25 to ~1.5 m/s. Glasses after decompression show a wide range of textures, from totally bubble-free to bubble-rich, the latter with bubble number densities from 104 to 106 cm?3, similar to Stromboli pumices. Vesicularities range from 0 to ~20 vol%. Final melt H2O concentrations are homogeneous and always close to solubilities. In contrast, the rate of vesiculation controls the final melt CO2 concentration. High vesicularity charges have glass CO2 concentrations that follow theoretical equilibrium degassing paths, whereas glasses from low vesicularity charges show marked deviations from equilibrium, with CO2 concentrations up to one order of magnitude higher than solubilities. FTIR profiles and maps reveal glass CO2 concentration gradients near the gas–melt interface. Our results stress the importance of bubble nucleation and growth, and of volatile diffusivities, for basaltic melt degassing. Two characteristic distances, the gas interface distance (distance either between bubbles or to gas–melt interfaces) and the volatile diffusion distance, control the degassing process. Melts containing numerous and large bubbles have gas interface distances shorter than volatile diffusion distances, and degassing proceeds by equilibrium partitioning of CO2 and H2O between melt and gas bubbles. For melts where either bubble nucleation is inhibited or bubble growth is limited, gas interface distances are longer than volatile diffusion distances. Degassing proceeds by diffusive volatile transfer at the gas–melt interface and is kinetically limited by the diffusivities of volatiles in the melt. Our experiments show that CO2-oversaturated melts can be generated as a result of magma decompression. They provide a new explanation for the occurrence of CO2-rich natural basaltic glasses and open new perspectives for understanding explosive basaltic volcanism.  相似文献   

12.
Carbon dioxide gas is a key component in dissolution and precipitation of carbonates in karst and cave systems. Therefore, characterizing the internal aerology of a cave is essential to obtain the spatiotemporal distribution of temperature and CO2 level. In this research, Lascaux Cave (France), an important adorned cavity, was studied. First, the spatiotemporal distribution of CO2 and temperatures were examined using continuous monitoring at a per minute basis. High-resolution spatial measurements (14 PCO2 locations and 27 locations for temperature) were carried out for a year in the epikarst and the cave (February 2015 to February 2016). The spatiotemporal analysis presents that air and rock temperatures vary for less than a degree Celsius (12.4–12.9 °C). These are controlled by the conduction of the external thermal waves through the overlying calcarenite massif. As a consequence, two seasonal internal aerologic regimes were identified: stratification and convection. These regimes govern the spatiotemporal distribution of the CO2 levels (1.1–3.7%), showing that this parameter is a good natural marker of the internal air movements. Second, a method was proposed to estimate the calcite mass potentially affected by condensation water (dissolution process) and exfiltration water (precipitation process). This method, based on numerical simulations, relies on CO2 and air and rock temperature spatiotemporal distributions in the cave. Third, the method was applied using the case of the left wall of the Hall of the Bulls (one of the most adorned part of the cave). Results showed that the calcite mass, possibly dissolved, varies from 0.0002 to 0.006 g when the mass potentially precipitated is higher (from 0.013 to 0.067 g) depending on the aerologic conditions. This method allows determining which alteration process (e.g., precipitation or dissolution) could eventually lead to the largest variation of calcite on the wall. The results can serve as useful data to the cave experts of the French Ministry of Culture and Communication in terms of Lascaux Cave management policies.  相似文献   

13.
The present study examines the temporal variability of air–water CO2 fluxes (FCO2) and seawater carbonate chemistry in a Baja California coastal lagoon during an exceptionally warm anomaly that was developed in Northeast Pacific coasts during 2014. This oceanographic condition led to a summer-like season (weak upwelling condition) during the study period, which reached a maximum surface temperature anomaly of 2 °C in September 2014. San Quintín Bay acts as a source of CO2 to the atmosphere in 2014 (3.3 ± 4.8 mmol C m?2 day?1) with the higher positive fluxes mainly observed in summer months (9.0 ± 5.3 mmol C m?2 day?1). Net ecosystem production (NEP) switched seasonally between net heterotrophy and net autotrophy during the study period, with an annual average of 2.2 ± 7.1 mmol C m?2 day?1, which indicates that San Quintín Bay was a net autotrophic system during the atypical warm oceanographic condition in 2014. This pattern of seasonal variations in the carbon balance at San Quintín Bay appears to be linked to the life cycle of benthic communities, which play an important role in the whole-ecosystem metabolism. Under the limited input from external sources coupled with an increase in seawater temperatures, the recycled benthic carbon and nutrient fluxes play a major role to sustain water-column processes within the bay. Since the upwelling condition may influence the magnitude of the air–water CO2 fluxes, our results clearly indicated that San Quintín Bay is a net source of carbon to the atmosphere regardless of the adjacent oceanic conditions. Our study sheds light on the carbon dynamics and its metabolic implications in a shallow coastal ecosystem under a regional warm anomaly and contributes potentially relevant information in view of the likely future scenario of global climate change.  相似文献   

14.
We present new equilibrium mixed-volatile (H2O–CO2) solubility data for a phonotephrite from Erebus volcano, Antarctica. H2O–CO2-saturated experiments were conducted at 400–700 MPa, 1,190 °C, and ~NNO + 1 in non-end-loaded piston cylinders. Equilibrium H2O–CO2 fluid compositions were determined using low-temperature vacuum manometry, and the volatile and major element compositions of the glassy run products were determined by Fourier transform infrared spectroscopy and electron microprobe. Results show that the phonotephrite used in this study will dissolve ~0.8 wt% CO2 at 700 MPa and a fluid composition of $ X_{{{\text{H}}_{ 2} {\text{O}}}} $ ~0.4, in agreement with previous experimental studies on mafic alkaline rocks. Furthermore, the dissolution of CO2 at moderate to high $ X_{{{\text{H}}_{ 2} {\text{O}}}}^{\text{fluid}} $ in our experiments exceeds that predicted using lower-pressure experiments on similar melts from the literature, suggesting a departure from Henrian behavior of volatiles in the melt at pressures above 400 MPa. With these data, we place new constraints on the modeling of Erebus melt inclusion and gas emission data and thus the interpretation of its magma plumbing system and the contributions of primitive magmas to passive and explosive degassing from the Erebus phonolite lava lake.  相似文献   

15.
Hourly resolved cave air PCO2 and cave drip water hydrochemical data illustrate that calcite deposition on stalagmites can be modulated by prior calcite precipitation (PCP) on extremely short timescales. A very clear second-order covariation between cave air PCO2 and drip water Ca2+ concentrations during the winter months demonstrates the effects of degassing-induced PCP on drip water chemistry. Estimating the strength of the cave air PCO2 control on PCP is possible because the PCP signal is so clear; at our drip site a one ppm shift in Ca2+ concentrations requires a PCO2 shift of between 333 and 667 ppm. This value will undoubtedly vary from site to site, depending on drip water flow rate, residence time, drip water-cave air PCO2 differential, and availability of low PCO2 void spaces in the vadose zone above the cave. High-resolution cave environmental measurements were used to model calcite deposition on one stalagmite in Crag Cave, SW Ireland, and modelled growth over the study period (222 μm over 171 days) is extremely similar to the amount of actual calcite growth (240 μm) over the same time interval, strongly suggesting that equations used to estimate stalagmite growth rates are valid. Although cave air PCO2 appears to control drip water hydrochemistry in the winter, drip water dilution caused by rain events may have played a larger role during the summer, as evidenced by a series of sudden drops in Ca2+ concentrations (dilution) followed by much more gradual increases in drip water Ca2+ concentrations (slow addition of diffuse water). This research demonstrates that PCP on stalactites, cave ceilings, and void spaces within the karst above the cave partially controls drip water chemistry, and that thorough characterisation of this process at individual caves is necessary to most accurately interpret climate records from those sites.  相似文献   

16.
The origin and environmental dependencies of lamination in stalagmites from Katerloch, common in speleothems from other cave sites, are examined in detail. Petrographic observations and chemical analyses (including isotopes) of stalagmites and modern calcite were combined with multi‐annual cave monitoring. All investigated stalagmites are composed of low‐Mg calcite and show white, porous laminae and typically thinner, translucent dense laminae. The binary lamination pattern results from changes in the calcite fabric: white, porous laminae are characterized by a high porosity and abundant fluid inclusions and also by enhanced vertical growth and thinning towards the flanks. Translucent, dense laminae exhibit a compact fabric and constant thickness of individual growth layers. U‐Th dating supports an annual origin of the lamination and the seasonally changing intensity of cave ventilation provides a robust explanation for the observed relationships between lamination, stable C isotopic compositions and trace elements (Mg, Sr and Ba). The seasonally variable air exchange, driven by temperature contrasts between the cave interior and outside atmosphere, modulates the rate and amount of CO2 degassing from the drip water and affects the hydrochemistry and consequently the fabric of the precipitating calcite. Although cave air composition and drip rate are both major variables in controlling CO2 degassing from the drip water, the seasonally changing ventilation in Katerloch exerts the primary control and the results suggest a secondary (amplifying/attenuating) influence of the drip rate. Drip rate, however, might be the controlling parameter for lamina development at cave sites experiencing only small seasonal cave air exchange. Importantly, the seasonally variable composition of drip water does not reflect the seasonal cycle of processes in the soil zone, but results from exchange with the cave atmosphere. The alternating porous and dense calcite fabric is the expression of a variable degree of lateral coalescence of smaller crystallites forming large columnar crystals. The white, porous laminae represent partial coalescence and form during the warm season: low calcite δ13C values are linked to low δ13C values of cave air and drip water during that time. This observation corresponds to times of reduced cave ventilation, high pCO2 of cave air, low drip water pH, lower calcite supersaturation and typically high drip rates. In contrast, the translucent, dense laminae represent more or less complete lateral coalescence (inclusion‐free) during the cold season (high calcite, drip water and cave air δ13C values), i.e. times of enhanced cave ventilation, low cave air pCO2, increased drip water pH, relatively high calcite supersaturation and typically low drip rates. In essence, the relative development of the two lamina types reflects changes in the seasonality of external air temperature and precipitation, with a strong control of the winter air temperature on the intensity of cave‐air exchange. Thick translucent, dense laminae are favoured by long, cold and wet winters and such conditions may be related closely to the North Atlantic Oscillation mode (weak westerlies) and enhanced Mediterranean cyclone activity during the cold season. Studies of speleothem lamination can thus help to better understand (and quantify) the role of seasonality changes, for example, during rapid climate events.  相似文献   

17.
The 19th Common Wealth Games was organized at Delhi, India, during October 3 to 14, 2010, where more than 8,000 athletes from 71 Commonwealth Nations have participated. In order to give them better environment information for proper preparedness, mass concentrations of particulate matters below 10 microns (PM10) and 2.5 microns (PM2.5), black carbon (BC) particles and gaseous pollutants such as carbon monoxide (CO) and nitrogen oxide (NO) were monitored and displayed online for ten different locations around Delhi, including inside and outside the stadiums. This extensive information system for air quality has been set up for the period from September 24 to October 21, 2010, and data have been archived at 5-min interval for further research. During the study period, average concentration of PM10 and PM2.5 was observed to be 229.7 ± 85.5 and 112.1 ± 56.0 μg m?3, respectively, which is far in excess of the corresponding annual averages, stipulated by the national ambient air quality standards. Significant large and positive correlation (r = 0.93) between PM10 and PM2.5 implies that variations in PM10 mass are governed by the variations in PM2.5 mass. The mass concentrations of PM2.5 inside the stadium were found to be ~18 % lower than those outside; however, no large variations were observed in PM10. Mean concentrations of BC, CO and NO for the observation period were 10.9 μg m?3 (Min, 02 μg m?3; Max, 31 μg m?3), 1.83 ± 0.89 ppm (Min, 0.48 ppm; Max, 4.55 ppm) and 37.82 ppb (Min, 2.4 ppb; Max, 206.05 ppb), respectively. BC showed positive correlation (r = 0.73) with CO suggests unified source for both of them, mainly from combustion emissions. All the measured parameters, however, show a significant diurnal variation with enhanced peaks in the morning and late night hours and lower values during daytime.  相似文献   

18.
The well-documented eruptive history of Mount Mazama, Oregon, provides an excellent opportunity to use pre-eruptive volatile concentrations to study the growth of an explosive silicic magmatic system. Melt inclusions (MI) hosted in pyroxene and plagioclase crystals from eight dacitic–rhyodacitic eruptive deposits (71–7.7?ka) were analyzed to determine variations in volatile-element concentrations and changes in magma storage conditions leading up to and including the climactic eruption of Crater Lake caldera. Temperatures (Fe–Ti oxides) increased through the series of dacites, then decreased, and increased again through the rhyodacites (918–968 to ~950 to 845–895?°C). Oxygen fugacity began at nickel–nickel-oxide buffer (NNO) +0.8 (71?ka), dropped slightly to NNO +0.3, and then climbed to its highest value with the climactic eruption (7.7?ka) at NNO +1.1 log units. In parallel with oxidation state, maximum MI sulfur concentrations were high early in the eruptive sequence (~500?ppm), decreased (to ~200?ppm), and then increased again with the climactic eruption (~500?ppm). Maximum MI sulfur correlates with the Sr content (as a proxy for LREE, Ba, Rb, P2O5) of recharge magmas, represented by basaltic andesitic to andesitic enclaves and similar-aged lavas. These results suggest that oxidized Sr-rich recharge magmas dominated early and late in the development of the pre-climactic dacite–rhyodacite system. Dissolved H2O concentrations in MI do not, however, correlate with these changes in dominant recharge magma, instead recording vapor solubility relations in the developing shallow magma storage and conduit region. Dissolved H2O concentrations form two populations through time: the first at 3–4.6 wt% (with a few extreme values up to 6.1 wt%) and the second at ≤2.4 wt%. CO2 concentrations measured in a subset of these inclusions reach up to 240?ppm in early-erupted deposits (71?ka) and are below detection in climactic deposits (7.7?ka). Combined H2O and CO2 concentrations and solubility models indicate a dominant storage region at 4–7?km (up to 12?km), with drier inclusions that diffusively re-equilibrated and/or were trapped at shallower depths. Boron and Cl (except in the climactic deposit) largely remained in the melt, suggesting vapor–melt partition coefficients and gas fractions were low. Modeled Li, F, and S vapor–melt partition coefficients are higher than those of B and Cl. The decrease in maximum MI CO2 concentration following the earliest dacitic eruptions is interpreted to result from a broadening of the shallow storage region to greater than the diameter of subjacent feeders, so that greater proportions of reservoir magma were to the side of CO2-bearing vapor bubbles ascending vertically from the locus of recharge magma injection, thereby escaping recarbonation by streaming vapor bubbles. The Mazama melt inclusions provide a picture of a growing magma storage region, where chemical variations in melt and magma occur due to changes in the nature and supply rate of magma recharge, the timing of degassing, and the possible degree of equilibration with gases from below.  相似文献   

19.
Constraining the pressure of crystallization of magmas is an important but elusive task. In this work, we present a method to derive crystallization pressures for rocks that preserve glass compositions (either glass inclusions or matrix glass) representative of equilibration between melt, quartz, and 1 or 2 feldspars. The method relies on the well-known shift of the quartz–feldspar saturation surface toward higher normative quartz melt compositions with decreasing pressure. The critical realization for development of the method is the fact that melt, quartz and feldspars need to be in equilibrium at the liquidus for the melt composition. The method thus consists of calculating the saturation surfaces for quartz and feldspars using rhyolite-MELTS over a range of pressures, and searching for the pressure at which the expected assemblage (quartz+1 feldspar or quartz+2 feldspars) is found at the liquidus. We evaluate errors resulting from uncertainties in glass composition using a series of Monte Carlo simulations for a quartz-hosted glass inclusion composition from the Bishop Tuff, which reveal errors on the order of 20–45 MPa for the quartz+2 feldspars constraint and on the order of 25–100 MPa for the quartz+1 feldspar constraint; we suggest actual errors are closer to the lower bounds of these ranges. We investigate the effect of fluid saturation in two ways: (1) By applying our procedure over a range of water contents for three glass compositions; we show that the effect of fluid saturation is more important at higher pressures (~300 MPa) than at lower pressures (~100 MPa), but reasonable pressure estimates can be derived irrespective of fluid saturation for geologically relevant H2O concentrations >3 wt% and (2) by performing the same type of pressure determinations with a preliminary version of rhyolite-MELTS that includes a H2O–CO2 mixed fluid phase; we use a range of H2O and CO2 concentrations for two compositions characteristic of early-erupted and late-erupted Bishop Tuff glass inclusions and demonstrate that calculated pressures are largely independent of CO2 concentration (for CO2 <1,000 ppm), at least for relatively high H2O contents, as expected in most natural magmas, such that CO2 concentration can be effectively neglected for application of our method. Finally, we demonstrate that pressures calculated using the rhyolite-MELTS geobarometer compare well with those resulting from H2O–CO2 glass inclusion barometry and Al-in-hornblende barometry for an array of natural systems for which data have been compiled from the literature; the agreement is best for quartz-hosted glass inclusions, while matrix glass yields systematically lower rhyolite-MELTS pressures, suggestive of melt evolution during eruptive decompression.  相似文献   

20.
Using coupled terrestrial and coastal zone models, we investigated the impacts of deglaciation and anthropogenic inputs on the CO2–H2O–CaCO3 system in global coastal ocean waters from the Last Glacial Maximum (LGM: 18,000 year BP) to the year 2100. With rising sea level and atmospheric CO2, the carbonate system of coastal ocean water changed significantly. We find that 6 × 1012 metric tons of carbon were emitted from the coastal ocean, growing due to the sea level rise, from the LGM to late preindustrial time (1700 AD) because of net heterotrophy and calcification processes. This carbon came to reside in the atmosphere and in the growing vegetation on land and in uptake of atmospheric CO2 through the weathering of rocks on land. It appears that carbonate accumulation, mainly, but not exclusively, in coral reefs from the LGM to late preindustrial time could account for about 24 ppmv of the 100 ppmv rise in atmospheric CO2, lending some support to the “coral reef hypothesis”. In addition, the global coastal ocean is now, or soon will be, a sink of atmospheric CO2. The temperature rise of 4–5°C since the LGM led to increased weathering rates of inorganic and organic materials on land and enhanced riverine fluxes of total C, N, and P to the coastal ocean of 68%, 108%, and 97%, respectively, from the LGM to late preindustrial time. During the Anthropocene, these trends have been exacerbated owing to rising atmospheric CO2, due to fossil fuel combustion and land-use practices, other human activities, and rising global temperatures. River fluxes of total reactive C, N, and P are projected to increase from late preindustrial time to the year 2100 by 150%, 380%, and 257%, respectively, modifying significantly the behavior of these element cycles in the coastal ocean, particularly in proximal environments. Despite the fact that the global shoal water carbonate mass has grown extensively since the LGM, the pHT (pH values on the total proton scale) of global coastal waters has decreased from ~8.35 to ~8.18 and the carbonate ion concentration declined by ~19% from the LGM to late preindustrial time. The latter represents a rate of decline of about 0.028 μmol CO3 2? per decade. In comparison, the decrease in coastal water pHT from the year 1900 to 2000 was about 8.18–8.08 and is projected to decrease further from about 8.08 to 7.85 between 2000 and 2100, according to the IS92a business-as-usual scenario of CO2 emissions. Over these 200 years, the carbonate ion concentration will fall by ~120 μmol kg?1 or 6 μmol kg?1 per decade. This decadal rate of decline of the carbonate ion concentration in the Anthropocene is 214 times the average rate of decline for the entire Holocene. Hence, when viewed against the millennial to several millennial timescale of geologic change in the coastal ocean marine carbon system, one can easily appreciate why ocean acidification is the “other CO2 problem”.  相似文献   

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