Geochemistry of soil gas in the seismic fault zone produced by the Wenchuan Ms 8.0 earthquake, southwestern China

The spatio-temporal variations of soil gas in the seismic fault zone produced by the 12 May 2008 Wenchuan Ms 8.0 earthquake were investigated based on the field measurements of soil gas concentrations after the main shock. Concentrations of He, H₂, CO₂, CH₄, O₂, N₂, Rn, and Hg in soil gas were measured in the field at eight short profiles across the seismic rupture zone in June and December 2008 and July 2009. Soil-gas concentrations of more than 800 sampling sites were obtained. The data showed that the magnitudes of the He and H₂ anomalies of three surveys declined significantly with decreasing strength of the aftershocks with time. The maximum concentrations of He and H₂ (40 and 279.4 ppm, respectively) were found in three replicates at the south part of the rupture zone close to the epicenter. The spatio-temporal variations of CO₂, Rn, and Hg concentrations differed obviously between the north and south parts of the fault zone. The maximum He and H₂ concentrations in Jun 2008 occurred near the parts of the rupture zone where vertical displacements were larger. The anomalies of He, H₂, CO₂, Rn, and Hg concentrations could be related to the variation in the regional stress field and the aftershock activity.     

Geochemical hydrocarbon exploration — a new/old exploration tool

The search for petroleum has evolved into a highly sophisticated technology where today almost every scientific discipline known is being brought to bear upon the endeavour. Yet, the use of geochemical hydrocarbon exploration remains a peripheral exploration tool. The trend toward scientific integration has led the petroleum explorationist to the point of being a specialist. It would seem that our petroleum scientists have focussed their interests mainly on the investigation of principles and less on their ultimate purpose of discovering new and larger oil and gas reserves. So, it is not by chance, that leading geochemists have been speaking more and more freely of the necessity to integrate our tools of exploration and thereby do a better job. The theoretical basis for hydrocarbon geochemistry is complex, and, as with all exploration tools, the problems and difficulties of interpreting the data will never be completely eliminated.This article considers the importance of using the ΔC method in geochemical hydrocarbon exploration which has been employed successfully for over 40 years. The addition of carbon-isotope ratios and trace-element analysis to this method has added a new dimension to geochemical hydrocarbon exploration. The theoretical basis of the ΔC method has been presented earlier by the author and will only be touched upon briefly here.Very simply, the basis of all geochemical hydrocarbon exploration is based on the much debated premise that the lighter hydrocarbon gases and their components migrate vertically from a trap through the overlying sedimentary pile to the surface. Upon reaching the surface, through oxidation, they leave their signatures in one form or another that can be detected by physicochemical methods. These physicochemical signatures are discernable as “geochemical haloes”.From soil samples, collected from 2–3 m deep, what is measured is the result of absorption and adsorption by soil particles that are altered to CO₂ by oxidation and form a unique, stable, carbonate system with the surface and near-surface material. This is unlike other carbonate systems and when subjected to a differential thermal technique, dissociates into CO₂ surface material is cumulative and indicates where maximum hydrocarbon leakage has taken place over the life span of the material sampled. It is durable and unaffected by pressure and temperature variation or recent hydrocarbon contamination.Values are expressed in terms of millivolts which are proportional to the CO₂ given off by the dissociation of the carbonate system under standard conditions. Frequency curves are constructed for all values for the determination of significant contour levels above the normal geochemical background for mapping.After significant ΔC anomalies are located, they can be further verified by use of carbon-isotope ratios. As methane migrates to the surface from underlying hydrocarbon accumulations, there is a progressive selection or fractionation that causes enrichment of the carbon-13 isotope. The methane, thus reaching the near-surface, is isotopically lighter. When oxidized in accordance with the equation CH₄ + 2O₂ → 2H₂O + CO₂, the carbon having been converted to carbon dioxide, is taken up in the pore-filling carbonate cements that are found in the near-surface soils and sediments.High carbon dioxide values (ΔC) in the geochemical halo are related the δ ¹³C carbon-isotope ratios from underlying hydrocarbon accumulations. This is observed over fields containing hydrocarbon accumulations where δ ¹³C values in the pore-filling carbonate cements become increasingly negative (lighter) toward the crests of traps (i.e. exhibiting lower ΔC values). This indicates enrichment of ¹²C relative to the PDB standard. Whereas, positive values of δ ¹³C indicate depletion in ¹²C or enrichment in ¹³C (i.e. exhibiting higher ΔC values away from the crests of the traps).The observed ΔC anomalies and δ ¹³C anomalies leave an indelible pattern in the near-surface sediments and soils which are herein referred to as geochemical hydrocarbon haloes.Trace-element associations, that form organometallic compounds, are found “haloed” or concentrated over or around underlying hydrocarbon reservoirs. These associations seem to have occurred from vertically migrating methane that has acted as a “carrier” sweeping up the trace elements on the pathways to the surface. Vanadium, nickel, chromium, iron, cobalt, copper, manganese, strontium, barium are various trace element ratios seen to also halo and indicate subsurface hydrocarbon accumulations.An example presented from the Ocho-Juan Field, a producing reef field, located in Scurry and Fisher Counties, Texas shows that the combination of ΔC, δ ¹³C and trace-element analysis from near-surface soil sampling is a significant step forward in improving geochemical hydrocarbon exploration methods.     

Petrology and isotopic geochemistry of dawsonite-bearing sandstones in Hailaer basin, northeastern China

The CO₂ gas reservoir sandstones in the Hailaer Basin contain abundant dawsonite and provide an ideal laboratory to study whether any genetic relationship exists between dawsonite and the modern gas phase of CO₂. The origins of dawsonite and CO₂ in these sandstones were studied by petrographic and isotopic analysis. According to the paragenetic sequence of the sandstones, dawsonite grew later than CO₂ charging at 110–85 Ma. The dawsonite δ¹⁸O value is 7.4‰ (SMOW), and the calculated δ¹⁸O values of the water present during dawsonite growth are from −11.4‰ to −9.2‰ (SMOW). This, combined with the NaHCO₃-dominated water linked to dawsonite growth, suggests meteoric water being responsible for dawsonite growth. The δ¹³C values of gas phase CO₂ and the ratios of ³He/⁴He of the associated He suggest a mantle magmatic origin of CO₂-rich natural gas in Hailaer basin. Dawsonite δ¹³C values are −5.3‰ to −1.5‰ (average −3.4‰), and the calculated δ¹³C values of CO₂ gas in isotopic equilibrium with dawsonite are −11.4‰ to −7.3‰. These C isotopic values are ambiguous for the dawsonite C source. From the geological context, the timing of events, together with formation water conditions for dawsonite growth, dawsonite possibly grew in meteoric-derived water, atmospherically-derived CO₂ maybe, or at least the dominant, C source for dawsonite. It seems that there are few relationships between dawsonite and the modern gas phase of CO₂ in the Hailaer basin.     

Carbon mass-balance modelling and carbon isotope exchange processes in dynamic caves

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 δ¹³C_DIC 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.     

Nitrogen as the carrier gas for helium emission along an active fault in NW Taiwan

Variations of He gas concentration are widely applied in studies devoted to the location of faults and to monitor seismic activities. Up to now, its migration mechanism in soil is not fully understood. A systematic soil gas survey across an active fault in NW Taiwan provides the opportunity to closely examine the mechanism of He migration in the fault zone. Significant spatial and temporal correlations observed between soil N₂ and He gas support the hypothesis that N₂ is the probable carrier gas for He emission in the studied area. Based on N₂/Ar ratios and N₂ isotopic results, the excess soil N₂ in this study is considered to be largely derived from ancient atmospheric air which was dissolved in groundwater. Furthermore, observations rule out the possibility of CO₂ being the dominant carrier gas for He in the studied area based on the C and He isotopic compositions and the relationship between concentrations of these gases. At least two soil gas sources, A and B, can be identified in the studied area. Source A is an abiogenic gas source characterized by excess N₂ and He, and very low O₂ and CO₂ content. Source B, on the other hand, is a mixture of biogenic gas and atmospheric air. The development of the fault system is an important factor affecting the degree of mixture between sources A and B. Therefore, variations of soil gas composition, in particular those derived from source A, could be a useful proxy for tracing faults in the area.     

Carbon dioxide in Postojna Cave (Slovenia): spatial distribution,seasonal dynamics and evaluation of plausible sources and sinks

The CO₂ concentration of the air in Postojna Cave (400–7900 ppm) is found to be induced by CO₂ sources (human respiration contributing?~?20,000–58,000 ppm per breath, outgassing of dripwater and water seeping from the vadose zone/epikarst with a pCO₂ values of 5000–29,000 ppm, and underground Pivka River having pCO₂ at 2344–4266 ppm) and CO₂ dilution (inflow of outside air with a CO₂ concentration of?~?400 ppm). Measurements show that sinking Pivka River has the lowest CO₂ concentration among plausible CO₂ sources but still continuously exceeds the surrounding cave air CO₂ concentration. During the winter months, intensive ventilation reduces the cave air CO₂ concentration to outside levels (~?400 ppm), even in the centre of the cave system. CO₂ dilution is less pronounced in summer (CO_2(min)?≈?800 ppm), since the ventilation rate is not as strong as in winter and the outside air that enters the cave through breathing holes and fractures is enriched with soil CO₂. During spring and autumn, the daily alternation of the ventilation regime with a smaller rate of air exchange results in yearly cave air CO₂ peaks of up to?~?2400 ppm. Some dead-end passages can be much less affected by ventilation, resulting in a cave air CO₂ concentration of up to 7900 ppm. The strongest diurnal CO₂ peaks due to human respiration were recorded during the spring holidays (increase of up to 1300 ppm day^?1), compared to considerably smaller summer peaks despite peak visits (increase of?~?600 ppm day^?1).     

Statistical approach for the geochemical signature of two active normal faults in the western Corinth Gulf Rift (Greece)

Soil–gas measurements of different gas species were performed in two distinct areas of the Corinth Gulf Rift (Greece): the Aigion-Neos Erineos-Lambiri (ANEL) fault zone and the Rion-Patras fault zone. Both zones lie in one of the most seismically active areas of the Euro-Mediterranean region, where a fast-opening continental rift is located. In particular, the geochemical investigations were focused on fault segments and fracture systems previously inferred by geomorphological, lithological and structural studies.In this work the applicability of soil–gas geochemistry surveys for the exploration of buried/hidden faults was tested by using various statistical methods. Moreover, a comprehensive geostatistical treatment of the collected data provided new insights into the control exerted by active structures on deep-seated gas migration towards the surface. In both investigated areas, the highest ²²²Rn and CO₂ concentration peaks correspond with zones where the interaction among fracture and fault segments was inferred by structural and morphological methods. This indicates a clear correlation between the shape and orientation of the anomalies and the different attitude and kinematic behavior of the faults recognized in the two areas. Furthermore, obtained results show that gases migrate preferentially through zones of brittle deformation by advective processes, as suggested by the relatively high rate of migration needed to obtain anomalies of short-lived ²²²Rn in the soil pores.     

Possible errors in helium analyses of soil gases by mass spectrometers having constant-pressure inlet systems

Published data suggest that soil gas helium concentrations of 5.28–5.34 ppm v/v over uranium and hydrocarbon deposits are significantly anomalous compared to the ambient atmospheric background of 5.24 ppm. However, analyses for helium by mass spectrometers having constant-pressure inlet systems, from which most of these data are derived, are subject to errors of equivalent magnitude. These errors arise when the major component composition of unknown and standard gases differ, for the different gases have different flow rates through the inlet system — relative rates being O₂ < dry air < water-saturated air < N₂ < CO₂ CH₄. Soil gas compositions can vary greatly and, compared to a dry air standard, the flow-rate of a water-saturated gas containing 10% biogenic CO₂ will increase, enhancing the apparent He content to 5.33 ppm. Accurate helium analyses can be achieved by using a constant-volume inlet and integrating the detector response over the period of the samples' passage through the detector.     

Indoor radon correlated with soil and subsoil radon potential—a case study

High indoor radon concentrations in a uranium-radium low-level area in the Eifel region, Germany, near the village of Döttingen are caused by ascending radon migration following the convection of groundwater and soil gas along pathways (fractures and faults) in the bedrock sediments of Lower Devonian age. Positive radon anomalies in the soil gas are found to coincide with the locations of houses showing the highest concentrations. These houses are older buildings without concrete foundation slabs. Normally radon concentrations in soil gas are highly correlated with the values of emanated radon calculated on the basis of radium content in the surrounding soils and rocks (diffusive radon potential). However, close to zones of tectonic fractures and faults around the maar-type volcano of Döttingen abnormally high radon concentrations, which were transported by circulating groundwater and postvolcanic exhalation of CO₂ (convective radon potential) were detected.     

Soil air carbon dioxide and oxygen measurements as a guide to concealed mineralization in semi-arid and arid regions

The differences between the CO₂ and O₂ concentrations in soil air and atmospheric air have been measured where sulfide mineralization occurs beneath transported exotic overburden in semi-arid and arid areas of the USA, South West Africa (Namibia) and Saudi Arabia. These mineralizations are reflected near surface by anomalous levels of CO₂ and O₂ in soil air, whereas in most cases heavy-metal anomalies are absent. The normal background variability of CO₂ and O₂ in soil air falls with increasing aridity, and anomaly definition improves with increasing aridity. Thus soil air CO₂ and O₂ data are potentially useful in exploring for concealed mineralization, especially in regions with an arid climate or conspicuous dry season.     

车载小型气体质谱仪现场地气分析应用

OmniStar小型气体质谱仪用于车载实验室,可根据野外情况采取灵活的采样方式,实现对H2、He、CH4、N2、O2、Ar、CO2以及C3H8、C4H10的现场分析。对浓度为100×10-6的H2、He、CH4、N2、O2、Ar、CO2混合标气进行100次连续测定,得到的各组分的精密度(RSD)均优于1%,H2、He、Ar、CO2准确度(RE)分别为3.74、0.94、1.83、10.5;对室内空气进行连续3 500次测定,得到的H2、He、CO2的精密度分别为2.25%、5.55%、4.06%,N2、O2、Ar的精密度优于1%;对CH4、C2H6、C3H8、C4H10混合标准气体进行连续13次测量,得到的C3H8、C4H10的精密度(RSD)优于1%,测量的平均值与标准值完全吻合,能够满足野外现场分析需求。在内蒙古西乌旗及新疆金窝子地区应用该仪器,采用采样袋取气、螺旋钻及井孔原位在线测定等方式得到样品数据,并发现两区域内部分采样点的CO2、H2及He异常。     

Numerical analysis of the effect of natural microcracks on the supercritical CO2 fracturing crack network of shale rock based on bonded particle models

The problem of predicting the geometric structure of induced fractures is highly complex and significant in the fracturing stimulation of rock reservoirs. In the traditional continuous fracturing models, the mechanical properties of reservoir rock are input as macroscopic quantities. These models neglect the microcracks and discontinuous characteristics of rock, which are important factors influencing the geometric structure of the induced fractures. In this paper, we simulate supercritical CO₂ fracturing based on the bonded particle model to investigate the effect of original natural microcracks on the induced‐fracture network distribution. The microcracks are simulated explicitly as broken bonds that form and coalesce into macroscopic fractures in the supercritical CO₂ fracturing process. A calculation method for the distribution uniformity index (DUI) is proposed. The influence of the total number and DUI of initial microcracks on the mechanical properties of the rock sample is studied. The DUI of the induced fractures of supercritical CO₂ fracturing and hydraulic fracturing for different DUIs of initial microcracks are compared, holding other conditions constant. The sensitivity of the DUI of the induced fractures to that of initial natural microcracks under different horizontal stress ratios is also probed. The numerical results indicate that the distribution of induced fractures of supercritical CO₂ fracturing is more uniform than that of common hydraulic fracturing when the horizontal stress ratio is small.     

Soil CO2 flux measurements in volcanic and geothermal areas

The accumulation chamber methodology allows one to obtain reliable values of the soil CO₂ flux, ϕ_{soil CO2}, in the range 0.2 to over 10 000 g m⁻² d⁻¹, as proven by both laboratory tests and field surveys in geothermal and volcanic areas. A strong negative correlation is observed between Δϕ_{soil CO2}/Δt and ΔP_atm/Δt. Maps of classes of log ϕ_{soil CO2} for the northern sector of Vulcano Island, Solfatara of Pozzuoli, Nea Kameni Islet and Yanbajain geothermal field evidence that active faults and fractures act as uprising channels of deep, CO₂-rich geothermal or magmatic gases. The total diffuse CO₂ output was evaluated for each surveyed area.     

蔡家营铅锌银矿区CO2异常分布特征及其成因的讨论

本文介绍了蔡家营矿区壤中气CO₂和岩矿石中热释CO₂异常的分布特征。通过CO₂异常分布与矿体赋存关系的研究,对异常形成机理做了初步探讨,阐明了厚覆盖区CO₂异常的分布规律,以及在寻找隐伏矿、查明区域控矿构造中的作用。     

Integrated geophysics and soil gas profiles as a tool to characterize active faults: the Amer fault example (Pyrenees, NE Spain)

The combined use of geophysical and soil gas composition exploration methods allows to rapidly obtain at relative low cost information that might be related to seismic activity conditions. In this study, we carried out geochemical soil gas sampling (²²²Rn, ²²⁰Rn and CO₂), electrical resistivity tomography and seismic refraction profiles in two selected zones near the town of Amer in the Spanish Pyrenees, where the presence of recent fractures is evident in the field. Data analysis clearly reveals anomalous values for each gas at specific positions along the electrical imaging transects. Geomorphologic and hydrogeologic data and the integration of geophysical data and soil gas measurements indicate that: (1) endogene gases radon (²²²Rn) and carbon dioxide (CO₂) are released from the meta-sedimentary basement rocks across the main fractured zones with higher permeability values, while lower Cenozoic detrital sedimentary formations act as an impervious boundary; (2) sites with highest radon concentrations (52?kBq?m^?3) coincide with the zones in the Amer fault showing more recent geomorphic evidence of activity, and more specifically with those areas covered by thinner surficial formations; (3) the lowest ²²²Rn values (0.2?C0.4?kBq?m^?3) were recorded just on the master active fault plane. This pattern could be explained by a dilution effect resulting from high rates of soil CO₂ efflux (267?g?m^?2?day^?1); (4) soil thoron (²²⁰Rn) activity is maximum (143?kBq?m^?3) in areas with high surficial fracturing; (5) groundwater pumping may cause important distortions in the natural flow dynamics and in the measured concentrations of gases. The agreement between the different data (geochemical, geophysical, and hydrogeological) and field observations (geology and geomorphology) leads us to propose a preliminary tectonic-gravitational model for the study area.     

Analysis of long- and short-term temporal variations of the diffuse CO2 emission from Timanfaya volcano,Lanzarote, Canary Islands

Reported herein are the results of eight soil CO₂ efflux surveys performed from 2006 to 2011 at Timanfaya Volcanic Field (TVF), Lanzarote Island with the aim of evaluating the long- and short-term temporal variations of the diffuse CO₂ emission. Soil CO₂ efflux values ranged from non-detectable up to 34.2 g m⁻² d⁻¹, with the highest values measured in September 2008. Conditional sequential Gaussian simulations (sGs) were applied to construct soil CO₂ efflux distribution maps and to estimate the total CO₂ output from the studied area at the TVF. Soil CO₂ efflux maps showed a high spatial and temporal variability. Total CO₂ emission rates ranged between 41 and 518 t d⁻¹, February 2011 (winter) being the season when maximum diffuse CO₂ emission rates were observed. To investigate the influence of external variables on the soil CO₂ efflux, a geochemical station (LZT01) was installed at TVF to measure continuously the soil CO₂ efflux between July 2010 and March 2012 Since external factors such as barometric pressure, rainfall, soil water content, soil and air temperatures, and wind speed influence strongly the observed soil CO₂ effluxes, multiple regression analysis was applied to the time series recorded by the automatic geochemical station LZT01 to remove the contribution of these external factors. The influence of meteorological variables on soil CO₂ efflux oscillations accounts for 13% of total variance, with barometric pressure, rainfall and/or soil water content having the most influence in the control of the soil CO₂ efflux. These observations along with the results from the eight soil gas surveys performed at TVF indicate that the short and long-term trends in the diffuse CO₂ degassing are mainly controlled by environmental factors.     

Biodegradation of CO2, CH4 and volatile organic compounds (VOCs) in soil gas from the Vicano–Cimino hydrothermal system (central Italy)

We investigated the effect of microbial activity on the chemistry of hydrothermal fluids related to the Vicano–Cimino system, central Italy. The database included the composition and δ¹³C CO₂ and δ¹³C CH₄ values for soil gas from an area characterized by intense degassing of fluids having a deep origin. The δ¹³C CH₄ values along vertical profiles in the soil indicated that CH₄ was controlled by microbial oxidation occurring at shallow (< 50 cm) depth, where free O₂ was available. This was consistent with the vertical gradients of CH₄, H₂S and O₂ concentrations. The δ¹³C CO₂ values in soil gas, characterized by a composition similar to that of the hydrothermal fluids, were not significantly influenced by biodegradation. On the contrary, gas strongly affected by air contamination showed a significant δ¹³C CO₂ fractionation. Microbial activity caused strong consumption of hydrothermal alkanes, alkenes, cyclics and hydrogenated halocarbons, whereas benzene was recalcitrant. Oxygenated compounds from hydrocarbon degradation consisted of alcohols, with minor aldehydes, ketones and carboxylic acids. A predominance of alcohols at a high rate of degassing flux, corresponding to a short residence time of hydrothermal gas within the soil, indicated incomplete oxidation. N-bearing compounds were likely produced by humic substances in the soil and/or related to contamination by pesticides, whereas α-pinene traced air entering the soil. The study demonstrates that microbial communities in the soil play an important role for mitigating the release to the atmosphere of C-bearing gases, especially CH₄, through diffuse soil degassing, a mechanism that in central Italy significantly contributes to the discharge of CO₂-rich gas from deep sources.     

Soil–gas monitoring: A tool for fault delineation studies along Hsinhua Fault (Tainan), Southern Taiwan

Many studies have shown the soil gas method to be one of the most reliable investigation tools in the research of earthquake precursory signals and fault delineation. The present research is aimed finding the relationship between soil gas distribution and tectonic systems in the vicinity of the Hsinhua Fault zone in the Tainan area of Southern Taiwan. More than 110 samples were collected along 13 traverses to find the spatial distribution of Rn, He, CO₂ and N₂. The spatial congruence of all the gases shows that N₂ is the most probable carrier gas of He, whereas CO₂ seems to be a good carrier gas of Rn in this area. From the spatial distribution of Rn, He, CO₂ and N₂ the trace of Hsinhua Fault and neotectonic features can be identified. The spatial distribution of studied gases shows a clear anomalous trend ENE–SWS along the Hsinhua Fault.     

Influences of air CO<Subscript>2</Subscript> on hydrochemistry of drip water and implications for paleoclimate study in a stream-developed cave,SW China

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 δ¹³C_DIC 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.     

Stable isotopes of carbon dioxide in soil gas over massive sulfide mineralization at Crandon, Wisconsin

Stable isotope ratios of oxygen and carbon were determined for CO₂ in soil gas in the vicinity of the massive sulfide deposit at Crandon, Wisconsin with the objective of determining the source of anomalously high CO₂ concentrations detected previously by McCarthy et al. (1986). Values of δ¹³C in soil gas CO₂ from depths between 0.5 and 1.0 m were found to range from −12.68‰ to −20.03‰ (PDB). Organic carbon from the uppermost meter of soil has δ¹³C between −24.1 and −25.8‰ (PDB), indicating derivation from plant species with the C₃ (Calvin) type of photosynthetic pathway. Microbial decomposition of the organic carbon and root respiration from C₃ and C₄ (Hatch-Slack) plants, together with atmospheric CO₂ are the likely sources of carbon in soil gas CO₂. Values of δ¹⁸O in soil-gas CO₂ range from 32 to 38‰ (SMOW). These δ¹⁸O values are intermediate between that calculated for CO₂ gas in isotopic equilibrium with local groundwaters and that for atmospheric CO₂. The δ¹⁸O data indicate that atmospheric CO₂ has been incorporated by mixing or diffusion. Any CO₂ generated by microbial oxidation of organic matter has equilibrated its oxygen isotopes with the local groundwaters.The isotopic composition of soil-gas CO₂ taken from directly above the massive sulfide deposit was not distinguishable from that of background samples taken 1 to 2 km away. No enrichment of the δ¹³C value of soil-gas CO₂ was observed, contrary to what would be expected if the anomalous CO₂ were derived from the dissolution of Proterozoic marine limestone country rock or of Paleozoic limestone clasts in glacial till. Therefore, it is inferred that root respiration and decay of C₃ plant material were responsible for most CO₂ generation both in the vicinity of the massive sulfide and in the “background” area, on the occasion of our sampling. Interpretation of our data is complicated by the effects of rainfall, which significantly reduced the magnitude of the CO₂ anomaly. Therefore, we cannot rule out the possible mechanism of carbonate dissolution driven by pyrite oxidation, as proposed by Lovell et al. (1983) and McCarthy et al. (1986). Further work is needed on seasonal and daily variations of CO₂ concentrations and stable isotope ratios in various hydrogeologic and ecologic settings so that more effective sampling strategies can be developed for mineral exploration using soil gases.