Interpretation of carbon dioxide diffusion behavior in coals

Storage of carbon dioxide in geological formations is for many countries one of the options to reduce greenhouse gas emissions and thus to satisfy the Kyoto agreements. The CO₂ storage in unminable coal seams has the advantage that it stores CO₂ emissions from industrial processes and can be used to enhance coalbed methane recovery (CO₂-ECBM). For this purpose, the storage capacity of coal is an important reservoir parameter. While the amount of CO₂ sorption data on various natural coals has increased in recent years, only few measurements have been performed to estimate the rate of CO₂ sorption under reservoir conditions. An understanding of gas transport is crucial for processes associated with CO₂ injection, storage and enhanced coalbed methane (ECBM) production.A volumetric experimental set-up has been used to determine the rate of sorption of carbon dioxide in coal particles at various pressures and various grain size fractions. The pressure history during each pressure step was measured. The measurements are interpreted in terms of temperature relaxation and transport/sorption processes within the coal particles. The characteristic times of sorption increase with increasing pressure. No clear dependence of the characteristic time with respect to the particle size was found. At low pressures (below 1 MPa) fast gas diffusion is the prevailing mechanism for sorption, whereas at higher pressures, the slow diffusion process controls the gas uptake by the coal.     

GMM—a gas monitoring module for long-term detection of methane leakage from the seafloor

A new seafloor lander module, the Gas Monitoring Module (GMM), has been developed for continuous and long-term measurements of methane concentration in seawater at the benthic boundary layer, as a result of marine environmental geology and technology synergy. The module is designed to host a series of sensors controlled and managed by a data acquisition and control system able to perform first-level data quality checks. The prototype includes semiconductor methane sensors, an H₂S sensor and a CTD for temperature, salinity, pressure recording, as well as interfaces for additional sensors. The GMM can be linked to submarine cables for real-time data transmission to onshore operators and is suitable for long-term monitoring of natural gas emissions from seafloor or leakages from pipelines and boreholes.     

若尔盖高原沼泽湿地CH4排放研究

若尔盖高原沼泽湿地海拔 3400 m，面积 4038km²，是我国面积最大的高原沼泽湿地分布区。2001年 5～9月的非冰冻期，其主要沼泽类型木里苔草沼泽的CH₄排放通量范围是 0.51～ 8.20 m g/（m ²· h），平均值为 2.87 m g/（m ²· h）；乌拉苔草沼泽CH₄排放通量范围是 0.36～10.04 m g/（m ²· h），平均值为 4.51 m g/（m ²· h）。在空间分布上，不同沼泽类型之间CH₄排放通量具有一定的差异。在季节变化上，没有明显的排放高峰。根据代表性观测点的CH₄平均排放量、日数和沼泽总面积推算，非冰冻期若尔盖高原沼泽湿地CH₄的排放量为 0.052Tg/a。     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

Comparative analysis of continuous radon sensors in underground environments

Four different continuous radon (²²²Rn)-detection systems have been compared in underground environments, namely three subhorizontal tunnels excavated for groundwater exploitation. Within observational uncertainties, all sensors detected the same concentrations of radon in the air of the tunnels, regardless of the methodology used to measure this radioactive gas. In this sense, the choice of continuous long-term radon monitoring sensors in underground tunnels is constrained by factors such as robustness of the instrumentation, power supply and cost, rather than the sensitivity of the detection methodology. This is particularly important for the monitoring of radon in the context of seismo-volcanic surveillance, where the harsh environmental conditions of the monitoring sites and the absence of electrical power supply are key factors to take into account.     

An 8-year record of gas geochemistry and isotopic composition of methane during baseline sampling at a groundwater observation well in Alberta (Canada)

Variability in baseline groundwater methane concentrations and isotopic compositions was assessed while comparing free and dissolved gas sampling approaches for a groundwater monitoring well in Alberta (Canada) over an 8-year period. Methane concentrations in dissolved gas samples (n?=?12) were on average 4,380?±?2,452 μg/L, yielding a coefficient of variation (CV) >50 %. Methane concentrations in free gas samples (n?=?12) were on average 228,756?±?62,498 ppm by volume, yielding a CV of 27 %. Quantification of combined sampling, sample handling and analytical uncertainties was assessed via triplicate sampling (CV of 19 % and 12 % for free gas and dissolved gas methane concentrations, respectively). Free and dissolved gas samples yielded comparable methane concentration patterns and there was evidence that sampling operations and pumping rates had a marked influence on the obtained methane concentrations in free gas. δ¹³C_CH4 and δ²H_CH4 values of methane were essentially constant (?78.6?±?1.3 and ?300?±?3?‰, respectively) throughout the observation period, suggesting that methane was derived from the same biogenic source irrespective of methane concentration variations. The isotopic composition of methane constitutes a robust and highly valuable baseline parameter and increasing δ¹³C_CH4 and δ²H_CH4 values during repeat sampling may indicate influx of thermogenic methane. Careful sampling and analytical procedures with identical and repeatable approaches are required in baseline-monitoring programs to generate methane concentration and isotope data for groundwater that can be reliably compared to repeat measurements once potential impact from oil and gas development, for example, may occur.     

盐类对甲烷水合物稳定性影响研究进展

甲烷水合物稳定性主要控制着甲烷水合物稳定带的厚度,温度、压力、孔隙水盐度和气体组分等因素影响着水合物稳定带的厚度。甲烷水合物的形成与地层水关系密切,而地层水中的各种盐离子(Cl~-、Na~+、Mg~(2+)、SO_4(~2-)、Ca~(2+))以及过渡金属(Fe、Mn、Cu、Co、Ni等)会影响天然气水合物的形成和分解条件。因此,研究盐类对甲烷水合物的稳定性认识有助于更加深入了解天然气水合物的成藏条件。本文分析了氯化物、硫酸盐、碳酸盐三大盐类对甲烷水合物稳定性的影响:同一盐类不同盐度条件下,随着盐度的增加,甲烷水合物相平衡曲线向低温高压偏移。总结了不同盐类和阴阳离子对甲烷水合物的抑制作用大小:在相同浓度、不同盐类条件下,盐类浓度在1.0~1.5 mol/L时盐类对甲烷水合物的抑制作用大小为MgCl_2CaCl_2Na ClKCl,盐类浓度大于1.5 mol/L时CaCl_2的抑制作用较强;阴离子对甲烷水合物的抑制作用大小争议较大,阳离子中Mg~(2+)对甲烷水合物的抑制作用最强。从目前的研究成果来看,已有数据与实际地质条件还存在一定差距,需要在真实实验条件下加强氯化物-硫酸盐-碳酸盐-甲烷-水体系的详细研究。本文提出,将高压可视反应腔与显微激光拉曼技术相结合,有望准确获取天然气水合物稳定形成时的温压条件,明确盐类和阴阳离子的抑制作用大小,以及盐类和离子特性如何影响水合物的形成和稳定,以便为未来的水合物勘探开发提供参考。     

天然气水合物成因探讨

天然气水合物是未来的能源资源。其分布于极地地区、深海地区及深水湖泊中。在海洋里,天然气水合物主要分布于外大陆边缘和洋岛的周围,其分布与近代火山的分布范围具有一致性。同位素组成表明天然气水合物甲烷主要是由自养产甲烷菌还原CO₂形成的。典型的大陆边缘沉积物有机碳含量低（＜0．5％～1．0％）,不足以产生天然气水合物带高含量的甲烷。赋存天然气水合物的沉积物时代主要为晚中新世-晚上新世,具有一定的时限性,并且天然气水合物与火山灰或火山砂共存,表明其形成与火山-热液体系有一定联系。火山与天然气水合物空间上的一致性表明,天然气水合物甲烷的底物可能主要是由洋底火山喷发带来的CO2。由前人研究结果推断 HCO^－₃在脱去两个O原子的同时,可能发生了亲核重排,羟基 H原子迁移到 C原子上,形成了甲酰基（HCO^－）,使甲烷的第一个 H原子来源于水。探讨了甲烷及其水合物的形成机制,提出了天然气水合物成因模型。     

Noble gas tracing of groundwater/coalbed methane interaction in the San Juan Basin, USA

The San Juan Basin natural gas field, located in northwestern New Mexico and southwestern Colorado in the USA, is a case-type coalbed methane system. Groundwater is thought to play a key role in both biogenic methane generation and the CO₂ sequestration potential of coalbed systems. We show here how noble gases can be used to construct a physical model that describes the interaction between the groundwater system and the produced gas. We collected 28 gas samples from producing wells in the artesian overpressured high production region of the basin together with 8 gas samples from the underpressured low production zone as a control. Stable isotope and major species determination clearly characterize the gas in the high production region as dominantly biogenic in origin, and the underpressured low producing region as having a significant admix of thermogenic coal gas. ³He/⁴He ratios increase from 0.0836R_a at the basin margin to 0.318R_a towards the center, indicating a clear but small mantle He signature in all gases. Coherent fractionation of water-derived ²⁰Ne/³⁶Ar and crustal ⁴He/⁴⁰Ar* are explained by a simple Rayleigh fractionation model of open system groundwater degassing. Low ²⁰Ne concentrations compared to the model predicted values are accounted for by dilution of the groundwater-associated gas by desorbed coalbed methane. This Rayleigh fractionation and dilution model together with the gas production history allows us to quantify the amount of water involved in gas production at each well. The quantified water volumes in both underpressured and overpressured zones range from 1.7 × 10³ m³ to 4.2 × 10⁵ m³, with no clear distinction between over- and underpressured production zones. These results conclusively show that the volume of groundwater seen by coal does not play a role in determining the volume of methane produced by secondary biodegradation of these coalbeds. There is no requirement of continuous groundwater flow for renewing the microbes or nutrient components. We furthermore observe strong mass related isotopic fractionation of ²⁰Ne/²²Ne and ³⁸Ar/³⁶Ar isotopic ratios. This can be explained by a noble gas concentration gradient in the groundwater during gas production, which causes diffusive partial re-equilibration of the noble gas isotopes. It is important for the study of other systems in which extensive groundwater degassing may have occurred to recognize that severe isotopic fractionation of air-derived noble gases can occur when such concentration gradients are established during gas production. Excess air-derived Xe and Kr in our samples are shown to be related to the diluting coalbed methane and can only be accounted for if Xe and Kr are preferentially and volumetrically trapped within the coal matrix and released during biodegradation to form CH₄.     

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.     

Providing interoperability for air quality in-situ sensors observations using GML technology

Geographic information provides the basis for many types of decisions ranging from simple path finding, to the sustainable management of environmental conditions. Producing such information is a time consuming and costly endeavor. Data sharing on the web is an avenue to increase the efficiency of the practices. This paper scientifically examines the new emerging technologies namely, internet, geographic markup language (GML), and observation and measurement models, to construct an interoperable repository for air quality sensors measurements. The paper also elaborates on the design and implementation of a web-based air quality information system (AQIS) for the city of Tehran. In-situ sensors measure ozone (C₃), carbon monoxide (CO), sulfur dioxide (SC₂), nitrogen dioxide (NC₂) and particulate matters (PM) in polluted metropolitans. Providing real-time air quality information can improve the decisions of the pertinent environmental organizations. Using GML for encoding sensors observations makes it possible to build an interoperable repository that is independent of platforms and vendors. Providing query possibilities based on monitoring stations, sensor names (pollutants), date and time intervals, and spatial query on the AQIS interfaces are the major functions of this system. Although standardized, it was concluded that the use of GML as data format increases the size of GML document. In addition, the developed system provides no map based results for the clients. Therefore, it is required to be improved by adding more GIS functions.     

Quantification of carbon flow from stable isotope fractionation in rice field soils with different organic matter content

Rice fields are an important source for the greenhouse gas methane produced by acetoclastic and hydrogenotrophic methanogenesis. Fractionation of ¹³C/¹²C can in principle be used to quantify the relative contribution of these pathways, but our knowledge of isotopic fractionation during reduction of CO₂ and turnover of acetate in different methanogenic environments is still scarce. We therefore measured δ¹³C signatures in two types of anoxic Italian rice field soils, one with high and one with low degradable organic matter (OM) content. Both soils were incubated in the presence and absence of methyl fluoride, a specific inhibitor of acetoclastic methanogenesis. Optimization of methyl fluoride concentration resulted in complete inhibition of acetoclastic methanogenesis. CH₄ was then exclusively produced by hydrogenotrophic methanogenesis, allowing determination of the isotopic signatures and fractionation factors specific for this methanogenic pathway. Acetate, which was then no longer consumed, accumulated and was used for determination of the isotopic signature of the fermentatively produced acetate (both total acetate and methyl carbon of acetate). Hence, all isotopic signatures, including fractionation factors were determined for the methanogenic soil. These data, were then used for computation of the relative contribution of the two methanogenic pathways. In the high OM soil, the contribution of acetoclastic methanogenesis to total CH₄ production increased simultaneously with decreasing acetate concentration. In the low OM soil, methanogenesis from H₂/CO₂ was clearly greater than theoretically expected. Furthermore, isotope fractionation of hydrogenotrophic methanogenesis indicated that the in situ energy status of methanogens strongly depended on the availability of organic carbon in the rice field soil system. Collectively, our data show that the study of isotopic fractionation in methanogenic environments allows a deeper insight into the ongoing processes, which may be quite different in the same ecosystem with different content of degradable OM.     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

Reduction of structural Fe(III) in nontronite by methanogen Methanosarcina barkeri

Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H₂/CO₂, methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H₂/CO₂ and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7-13% with H₂/CO₂ as substrate, depending on nontronite concentration (5-10 g/L). The extent was higher when methanol was used as a substrate, reaching 25-33%. Methanogenesis was inhibited by Fe(III) reduction in the H₂/CO₂ culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget.     

城市垃圾填埋场甲烷资源量与利用前景

垃圾填埋气的主要成分为CH4、CO2等气体,可严重污染大气、地下水和生态环境,并对全球气候变暖产生一定的影响;同时填埋气也是一种清洁可再生能源和资源,回收和利用垃圾填埋气可实现环境、安全、能源、资源、经济多重效益。目前,垃圾填埋气的利用主要为甲烷利用。本文介绍了填埋气中甲烷资源量的计算方法,采用一阶动力模型对国内城市垃圾填埋气中的甲烷排放量进行了计算和预测,获得了城市生活垃圾填埋气中甲烷的资源量的范围,并分析了国内垃圾填埋气排放的特点和趋势以及国内外对填埋气利用的途径、方法及效果。结合清洁发展机制（CDM）项目和国情分析了垃圾填埋气的利用前景,并提出了填埋气回收利用的主要问题和建议,为国内城市生活垃圾填埋气的利用提供了有益参考。     

Tracing seafloor methane emissions with benthic foraminifera in the Baiyun Sag of the northern South China Sea

Changes in the concentrations of atmospheric greenhouse gases are an important part of the global climate forcing. The hypothesis that benthic foraminifera are useful proxies of local methane emission from the seafloor has been verified on sediment cores by numerous studies. The calcium carbonate (CaCO₃) content and the high-resolution carbon and oxygen isotope composition of the benthic foraminifera from the core 08CF7, from the northeastern Shenhu gas hydrate drilling area in the Baiyun Sag of the northern South China Sea were analyzed, and the benthic foraminifera’s evidence for methane release from gas hydrate decomposition are presented here for the first time. Two rapid obvious carbon isotope negative excursions were observed in the oxygen isotope stage boundaries 5d/5c and 6/5e (penultimate deglaciation, about 130 ka) of the cold-to-warm climatic transition period. The largest negative value of δ¹³C is about ?2.95 ‰, and the whole change of carbon and oxygen isotope is strikingly similar and is in consonance with the atmospheric methane concentration recorded by the Vostok ice core and the carbon isotopic record from Lake Baikal. Combining these results with the analysis of the geological conditions of the study area and the fact that gas hydrate exists in the surrounding area, it can be concluded that the carbon isotope negative excursions of the benthic foraminifera in the northern South China Sea are associated with methane release from gas hydrate decomposition due to deglacial climate warming. By recording the episodes of massive gas hydrate decomposition closely linked with the northern hemisphere temperatures during major warming periods, the new δ¹³C record from the Baiyun Sag provides further evidence for the potential impact of gas hydrate reservoir on rapid deglacial rises of atmospheric methane levels.     

A theoretical model for gas adsorption-induced coal swelling

Swelling and shrinkage (volumetric change) of coal during adsorption and desorption of gas is a well-known phenomenon. For coalbed methane recovery and carbon sequestration in deep, unminable coal beds, adsorption-induced coal volumetric change may cause significant reservoir permeability change. In this work, a theoretical model is derived to describe adsorption-induced coal swelling at adsorption and strain equilibrium. This model applies an energy balance approach, which assumes that the surface energy change caused by adsorption is equal to the elastic energy change of the coal solid. The elastic modulus of the coal, gas adsorption isotherm, and other measurable parameters, including coal density and porosity, are required in this model. Results from the model agree well with experimental observations of swelling. It is shown that the model is able to describe the differences in swelling behaviour with respect to gas species and at very high gas pressures, where the coal swelling ratio reaches a maximum then decreases. Furthermore, this model can be used to describe mixed-gas adsorption induced-coal swelling, and can thus be applied to CO₂-enhanced coalbed methane recovery.     

1981–2020 winter ozone trends,Erzgebirge, Central Europe

Tropospheric ozone (O₃) acts as greenhouse gas and air pollutant. Over the last 100 years, tropospheric O₃ levels increased above background by factor 2.5 in the northern hemisphere and by factor 3–4 across Europe. The gas poses a potential risk to forest ecosystems in many mountain areas. There, O₃ concentrations result from long-range transport and are influenced by removal processes (dry deposition, gas phase and cloud removal, reduction on wet aerosols). Most trend studies analyzed annual-mean concentrations. We focus on winter O₃ trends at high altitudes in the German/Czech Erzgebirge (period 1981–2020) to avoid major noise from photochemical reactions and to better explain recent O₃ behavior in Central Europe. Hourly air quality and meteorological data from four stations (Carlsfeld, CAR; Fichtelberg, FIB; Schwartenberg, SWB; Zinnwald, ZIW) were used to analyze O₃ trends. The data can explain the complex O₃ formation and removal behavior.Three distinct periods of O₃-concentration trends can be discerned: i) Until the late 1980s, characterized by relatively low O₃ concentrations. ii) Dramatic transformation in the 1990s with changing air pollution in Central Europe. Strong O₃-concentration increase at FIB is corroborated by data from CAR and ZIW. iii) Stabilization as of 1997/98, when O₃ concentrations remained at the same level for all four stations, despite general regional air pollution decrease. Key results are:a) Winter O₃ trends mainly depend on O₃ concentration of air masses transported to the stations and on the O₃-removal potential (ORP) of clouds, not on local formation processes.b) ORP differs between clouds and fog, depending on droplet chemical composition. Fog from the North Bohemian Basin showed the highest ORP due to reaction with liquid phase S(IV). However, O₃ reactions with O₂⁻ in fog droplets showed high ORP, too, depending on cloud-water pH values and NO_x concentrations.c) So-called “Bohemian fog” decreased, and with it related ORP, while that of clouds from westerly and northwesterly air masses remained nearly unchanged since 1997/98.d) Decreasing ORP in clouds and fog (= higher O₃ concentration) oppose decreasing O₃ concentrations in westerly air masses. Both effects lead to unchanged O₃ levels in the Erzgebirge since 1997/98.     

Water column methane oxidation adjacent to an area of active hydrate dissociation,Eel river Basin

The role of methane clathrate hydrates in the global methane budget is poorly understood because little is known about how much methane from decomposing hydrates actually reaches the atmosphere. In an attempt to quantify the role of water column methanotrophy (microbial methane oxidation) as a control on methane release, we measured water column methane profiles (concentration and δ¹³C) and oxidation rates at eight stations in an area of active methane venting in the Eel River Basin, off the coast of northern California. The oxidation rate measurements were made with tracer additions of ³H-CH₄.Small numbers of instantaneous rate measurements are difficult to interpret in a dynamic, advecting coastal environment, but combined with the concentration and stable isotope measurements, they do offer insights into the importance of methanotrophy as a control on methane release. Fractional oxidation rates ranged from 0.2 to 0.4% of ambient methane per day in the deep water (depths >370 m), where methane concentration was high (20–300 nM), to near-undetectable rates in the upper portion of the water column (depths <370 m), where methane concentration was low (3–10 nM). Methane turnover time averaged 1.5 yr in the deep water but was on the order of decades in the upper portion of the water column. The depth-integrated water column methane oxidation rates for the deep water averaged 5.2 mmol CH₄ m⁻² yr⁻¹, whereas the upper portion of the water column averaged only 0.14 mmol CH₄ m⁻² yr⁻¹; the depth-integrated oxidation rate for deep water in the 25-km² area encompassing the venting field averaged 2 × 10⁶ g CH₄ yr⁻¹. Stable isotope values (δ¹³C-CH₄) for individual samples ranged from −34 to −52‰ (vs. PDB, Peedee belemnite standard) in the region. These values are isotopically enriched relative to hydrates in the region (δ¹³C-CH₄ about −57 to −69‰), further supporting our observations of extensive methane oxidation in this environment.     

Hazardous gas emissions from the flanks of the quiescent Colli Albani volcano (Rome,Italy)

Gas hazard was evaluated in the three most important cold gas emission zones on the flanks of the quiescent Colli Albani volcano. These zones are located above structural highs of the buried carbonate basement which represents the main regional aquifer and the main reservoir for gas rising from depth. All extensional faults affecting the limestone reservoir represent leaking pathways along which gas rises to the surface and locally accumulates in shallow permeable horizons forming pressurized pockets that may produce gas blowout when reached by wells. The gas, mainly composed of CO₂ (>90 vol.%), contains appreciable quantities of H₂S (0.35–6 vol.%), and both represent a potentially high local hazard. Both gases are denser than air and accumulate near ground where they may reach hazardous concentrations, and lethal accidents frequently occur to animals watering at local ponds. In order to evaluate the rate of degassing and the related hazard, CO₂ and H₂S diffuse soil flux surveys have been repeatedly carried out using an accumulation chamber. The viscous gas flux of some important discrete emissions has been evaluated and the CO₂ and H₂S air concentration measured by portable devices and by Tunable Diode Laser profiles. The minimum potential lethal concentration of the two gases (250 ppm for H₂S and 8 vol.% for CO₂) is 320 times higher for CO₂, whereas the CO₂/H₂S concentration ratio in the emitted natural gas is significantly lower (15–159). This explains why H₂S reaches hazardous, even lethal, concentrations more frequently than CO₂. A relevant hazard exists for both gases in the depressed zones (channels, excavations) particularly in the non-windy early hours of the day.