Impact of emissions from natural gas production facilities on ambient air quality in the Barnett Shale area: A pilot study

Rapid and extensive development of shale gas resources in the Barnett Shale region of Texas in recent years has created concerns about potential environmental impacts on water and air quality. The purpose of this study was to provide a better understanding of the potential contributions of emissions from gas production operations to population exposure to air toxics in the Barnett Shale region. This goal was approached using a combination of chemical characterization of the volatile organic compound (VOC) emissions from active wells, saturation monitoring for gaseous and particulate pollutants in a residential community located near active gas/oil extraction and processing facilities, source apportionment of VOCs measured in the community using the Chemical Mass Balance (CMB) receptor model, and direct measurements of the pollutant gradient downwind of a gas well with high VOC emissions. Overall, the study results indicate that air quality impacts due to individual gas wells and compressor stations are not likely to be discernible beyond a distance of approximately 100 m in the downwind direction. However, source apportionment results indicate a significant contribution to regional VOCs from gas production sources, particularly for lower-molecular-weight alkanes (<C6). Although measured ambient VOC concentrations were well below health-based safe exposure levels, the existence of urban-level mean concentrations of benzene and other mobile source air toxics combined with soot to total carbon ratios that were high for an area with little residential or commercial development may be indicative of the impact of increased heavy-duty vehicle traffic related to gas production

ImplicationsRapid and extensive development of shale gas resources in recent years has created concerns about potential environmental impacts on water and air quality. This study focused on directly measuring the ambient air pollutant levels occurring at residential properties located near natural gas extraction and processing facilities, and estimating the relative contributions from gas production and motor vehicle emissions to ambient VOC concentrations. Although only a small-scale case study, the results may be useful for guidance in planning future ambient air quality studies and human exposure estimates in areas of intensive shale gas production.     

An exploratory study of air emissions associated with shale gas development and production in the Barnett Shale

Information regarding air emissions from shale gas extraction and production is critically important given production is occurring in highly urbanized areas across the United States. Objectives of this exploratory study were to collect ambient air samples in residential areas within 61 m (200 feet) of shale gas extraction/production and determine whether a “fingerprint” of chemicals can be associated with shale gas activity. Statistical analyses correlating fingerprint chemicals with methane, equipment, and processes of extraction/production were performed. Ambient air sampling in residential areas of shale gas extraction and production was conducted at six counties in the Dallas/Fort Worth (DFW) Metroplex from 2008 to 2010. The 39 locations tested were identified by clients that requested monitoring. Seven sites were sampled on 2 days (typically months later in another season), and two sites were sampled on 3 days, resulting in 50 sets of monitoring data. Twenty-four-hour passive samples were collected using summa canisters. Gas chromatography/mass spectrometer analysis was used to identify organic compounds present. Methane was present in concentrations above laboratory detection limits in 49 out of 50 sampling data sets. Most of the areas investigated had atmospheric methane concentrations considerably higher than reported urban background concentrations (1.8–2.0 ppm_v). Other chemical constituents were found to be correlated with presence of methane. A principal components analysis (PCA) identified multivariate patterns of concentrations that potentially constitute signatures of emissions from different phases of operation at natural gas sites. The first factor identified through the PCA proved most informative. Extreme negative values were strongly and statistically associated with the presence of compressors at sample sites. The seven chemicals strongly associated with this factor (o-xylene, ethylbenzene, 1,2,4-trimethylbenzene, m- and p-xylene, 1,3,5-trimethylbenzene, toluene, and benzene) thus constitute a potential fingerprint of emissions associated with compression.

Implications: Information regarding air emissions from shale gas development and production is critically important given production is now occurring in highly urbanized areas across the United States. Methane, the primary shale gas constituent, contributes substantially to climate change; other natural gas constituents are known to have adverse health effects. This study goes beyond previous Barnett Shale field studies by encompassing a wider variety of production equipment (wells, tanks, compressors, and separators) and a wider geographical region. The principal components analysis, unique to this study, provides valuable information regarding the ability to anticipate associated shale gas chemical constituents.     

Volatile organic compounds at two oil and natural gas production well pads in Colorado and Texas using passive samplers

A pilot study was conducted in application of the U.S. Environmental Protection Agency (EPA) Methods 325A/B variant for monitoring volatile organic compounds (VOCs) near two oil and natural gas (ONG) production well pads in the Texas Barnett Shale formation and Colorado Denver–Julesburg Basin (DJB), along with a traffic-dominated site in downtown Denver, CO. As indicated in the EPA method, VOC concentrations were measured for 14-day sampling periods using passive-diffusive tube samplers with Carbopack X sorbent at fenceline perimeter and other locations. VOCs were significantly higher at the DJB well pad versus the Barnett well pad and were likely due to higher production levels at the DJB well pad during the study. Benzene and toluene were significantly higher at the DJB well pad versus downtown Denver. Except for perchloroethylene, VOCs measured at passive sampler locations (PSs) along the perimeter of the Barnett well pad were significantly higher than PSs farther away. At the DJB well pad, most VOC concentrations, except perchloroethylene, were significantly higher prior to operational changes than after these changes were made. Though limited, the results suggest passive samplers are precise (duplicate precision usually ≤10%) and that they can be useful to assess spatial gradients and operational conditions at well pad locations over time-integrated periods.

Implications: Recently enacted EPA Methods 325A/B use passive-diffusive tube samplers to measure benzene at multiple fenceline locations at petrochemical refineries. This pilot study presents initial data demonstrating the utility of Methods 325A/B for monitoring at ONG facilities. Measurements revealed elevated concentrations reflective of production levels and spatial gradients of VOCs relative to source proximity at the Barnett well pad, as well as operational changes at the DJB well pad. Though limited, these findings indicate that Methods 325A/B can be useful in application to characterize VOCs at well pad boundaries.     

Air pollutant emissions from the development,production, and processing of Marcellus Shale natural gas

The Marcellus Shale is one of the largest natural gas reserves in the United States; it has recently been the focus of intense drilling and leasing activity. This paper describes an air emissions inventory for the development, production, and processing of natural gas in the Marcellus Shale region for 2009 and 2020. It includes estimates of the emissions of oxides of nitrogen (NO_x), volatile organic compounds (VOCs), and primary fine particulate matter (≤2.5 µm aerodynamic diameter; PM_2.5) from major activities such as drilling, hydraulic fracturing, compressor stations, and completion venting. The inventory is constructed using a process-level approach; a Monte Carlo analysis is used to explicitly account for the uncertainty. Emissions were estimated for 2009 and projected to 2020, accounting for the effects of existing and potential additional regulations. In 2020, Marcellus activities are predicted to contribute 6–18% (95% confidence interval) of the NO_x emissions in the Marcellus region, with an average contribution of 12% (129 tons/day). In 2020, the predicted contribution of Marcellus activities to the regional anthropogenic VOC emissions ranged between 7% and 28% (95% confidence interval), with an average contribution of 12% (100 tons/day). These estimates account for the implementation of recently promulgated regulations such as the Tier 4 off-road diesel engine regulation and the U.S. Environmental Protection Agency's (EPA) Oil and Gas Rule. These regulations significantly reduce the Marcellus VOC and NO_x emissions, but there are significant opportunities for further reduction in these emissions using existing technologies.

Implications: The Marcellus Shale is one of the largest natural gas reserves in United States. The development and production of this gas may emit substantial amounts of oxides of nitrogen and volatile organic compounds. These emissions may have special significance because Marcellus development is occurring close to areas that have been designated nonattainment for the ozone standard. Control technologies exist to substantially reduce these impacts. PM_2.5 emissions are predicted to be negligible in a regional context, but elemental carbon emissions from diesel powered equipment may be important.     

活性炭纤维生物挂膜脱除硫化氢

生物脱硫法作为一种高效、高实用性的除硫新技术而受到越来越多的关注。以活性炭纤维为微生物载体,通过活性污泥上清液挂膜驯化,考察硫化氢进气量、喷淋量、pH值和硫酸根离子浓度等条件对脱硫效率的影响。研究结果表明,在室温下,硫化氢负荷为90 g/(m3.h),进气浓度控制在3 g/m3,进气量为60 L/h,喷淋量为250～650 L/(m3.d),pH为2～5的条件下,生物活性炭纤维对硫化氢的去除率可保持在98%以上。     

高强紫外球形灯光解氧化硫化氢气体

提出了采用可产臭氧的高强球形紫外灯光解氧化硫化氢气体。考察了硫化氢初始浓度、湿度、含氧量、停留时间对硫化氢去除效率的影响。实验结果表明,硫化氢浓度在低浓度范围内,对硫化氢的去除效率可以达到99％以上。反应体系内气体湿度比含氧量对硫化氢的去除效率的影响更明显。气体湿度控制在45％～60％和反应停留时间控制在6～10s范围内为最佳。高强紫外球形灯处理硫化氢过程分别存在直接光解和臭氧氧化作用及两者的协同作用。     

Oxidation of gas mixtures containing dimethyl sulfide, hydrogen sulfide, and methanethiol using a two-stage biotrickling filter

A biofiltration technique was developed for removing a mixture of hydrogen sulfide (H2S), methanethiol (MeSH), and dimethyl sulfide (Me2S) from waste gases. Since H2S, especially at high concentrations, disturbs the removal of Me2S, two biotrickling filters with different microbes and operating pH levels were connected in series to create a two-stage system. Different loads of these gases were studied in order to determine their impact on the removal capacity of the system. The microbial consortia for these filters were enriched from the sludge of a Finnish refinery with bubbling H2S or Me2S. Acclimation for Me2S took 2 weeks, though no acclimation time was needed for the other gases. The first filter, at a pH of 2, removed most of the H2S and some of the MeSH and Me2S. The second filter, at a pH of approximately 6.5, removed the rest of the MeSH and most of the Me2S. The total maximum loads of the whole two-stage biotrickling filter were 1150 g/m3/day for H2S-S (suffix S indicates the results are counted as sulfur amounts), 879 g/m3/day for Me2S-S, and 66 g/m3/day for MeSH-S treated in a gas mixture. The average removal efficiencies for all gases tested were 99% or higher.     

预处理沼液与餐厨废弃物的厌氧产气发酵特性

为了实现对餐厨废弃物能源化的梯度利用,将沼液进行水浴加热、超声波和曝气等预处理后与餐厨废弃物混合,在中温（35±1）℃条件下进行产氢和产甲烷梯度厌氧发酵实验。考察了不同预处理沼液对产氢率、产氢相缓冲能力、产氢过程可溶性代谢产物成分以及其进行产甲烷发酵的潜力。结果表明,未经处理的沼液与餐厨废弃物混合发酵的产氢率很低,并且相分离不彻底有甲烷产生;各预处理组的产氢率均明显高于未处理组,并很少或几乎没有甲烷产生,其中超声波处理组产氢率最高为52.3 mL·g-1 VS。水浴加热和超声波处理组的产氢流出液经产甲烷发酵,可以获得与餐厨废弃物直接进行产甲烷发酵相当的甲烷产率。这表明,将餐厨废弃物进行产氢和产甲烷梯度厌氧发酵可获得更高的能源化效率。     

高气速间歇式生物过滤去除高负荷H2S

采用生物过滤法,以鸡粪堆肥和PE混合物为填料,在高气速条件下间歇式处理高负荷H2S废气。空床停留时间为20、15、10、6.7和5 s时,入口浓度3 000 mg/m3下的平均去除率分别为100%、100%、96.5%、89.2%和90.5%。高气速EBRT为5 s时,高入口负荷2 147 g/(m3.h)时的去除负荷为2 023 g/(m3.h),去除率达94%。采用Michaelis-Ment-en模型进行生物降解宏观动力学研究,其中Ks为550 mg/m3,Vm为6.8×104g/(m3.d)。结果表明,在实验温度17～24℃,湿度30%～50%下,生物过滤法间歇式处理高气速高负荷H2S的去除性能好。     

白云石的硫化氢高温脱除性能研究

用天然白云石制备了半焙烧白云石和全焙烧白云石，并在固定床上对这些白云石进行硫化氢的高温脱除性能研究，同时考察了反应温度、空速、粒子粒径对白云石脱硫性能的影响。用X射线衍射（XRD）、热重分析（TG）和气体吸附等测试手段，对脱硫剂的物相组成、结构、比表面积和孔容进行了表征。结果表明，白云石是一种很好的吸硫剂。在同样条件下，3种白云石中半焙烧白云石具有最好的脱硫效果；而对于同一种白云石，反应条件的差异也会导致其脱硫效果的变化。白云石的脱硫性能与其微观结构有密切关系。     

白云石的硫化氢高温脱除性能研究

用天然白云石制备了半焙烧白云石和全焙烧白云石,并在固定床上对这些白云石进行硫化氢的高温脱除性栽能研究,同时考察了反应温度、空速、粒子粒径对白云石脱硫性能的影响.用X射线衍射(XRD)、热重分析(TG)和气体吸附等测试手段,对脱硫剂的物相组成、结构、比表面积和孔容进行了表征.结果表明,白云石是一种很好的吸硫剂.在同样条件下,3种白云石中半焙烧白云石具有最好的脱硫效果;而对于同一种白云石,反应条件的差异也会导致其脱硫效果的变化.白云石的脱硫性能与其微观结构有密切关系.     

Removal of hydrogen sulfide gas and landfill leachate treatment using coal bottom ash.

Coal bottom ashes produced from three thermal power plants were used in column and batch experiments to investigate the adsorption capacity of the coal ash. Hydrogen sulfide and leachates collected from three sanitary landfill sites were used as adsorbate gas and solutions, respectively. Experimental results showed that coal bottom ash could remove H2S from waste gas or reduce the concentrations of various pollutants in the leachate. Each gram of bottom ash could remove up to 10.5 mg of H2S. In treating the landfill leachate, increasing ash dosage increased the removal efficiency but decreased the adsorption amount per unit mass of ash. For these tested ashes, the removal efficiencies of chemical oxygen demand (COD), NH3-N, total Kjeldhal nitrogen (TKN), P, Fe3+, Mn2+, and Zn2+ were 36.4-50, 24.2-39.4, 27.0-31.1, 82.2-92.9, 93.8-96.5, 93.7-95.4, and 80.5-82.2%, respectively; the highest adsorption capacities for those parameters were 3.5-5.6, 0.22-0.63, 0.36-0.45, 0.027-0.034, 0.050-0.053, 0.029-0.032, and 0.006 mg/g of bottom ash, respectively. The adsorption of pollutants in the leachate conformed to Freundlich's adsorption model.     

多级串联腐殖土固定床处理氨气硫化氢恶臭气体的机理

设计了腐殖土固定床串联缺氧SBR多级反应器对填埋场臭气与渗滤液进行协同处理,以气体表面负荷、水力负荷、污染物负荷为影响因素进行正交实验,探究腐殖土固定床对氨气与硫化氢的处理效能与去除机理,并运用物料衡算的方法对腐殖土固定床去除氨气的机理进行分析。结果表明：腐殖土固定床对氨气与硫化氢的平均去除率分别为95%与98%,各因素对氨气去除率的影响大小的依次顺序为气体表面负荷>污染物负荷>水力负荷,各因素对硫化氢去除率的影响大小的依次顺序为污染物负荷>气体表面负荷=水力负荷,最佳实验条件为气体表面负荷为7 m·h⁻¹,水力负荷为0.12 m·d⁻¹,氨气负荷为10 mg·(m³·h)⁻¹,硫化氢负荷为2 mg·(m³·h)⁻¹。机理分析的结果表明多级串联腐殖土固定床对氨气去除主要是靠气相与液相的分压差 (浓度差) ,传质受进口氨气浓度、即氨气气相分压影响,此过程中气膜阻力远大于液膜阻力,近似于气膜控制过程,且各级液相氨氮等效形成的分压差距较小、气相与液相的分压差 (浓度差) 与气液有效传质面积逐级减。本研究结果可为现有的填埋场臭气处理技术上发展腐殖土固定床协同处理臭气渗滤液工艺提供参考。     

On the origins of night-time NO at a rural measurement site

Mixing ratios for NO and NO₂ were measured during 1980/1981 at Deuselbach, a rural site in Germany. The data are analyzed with regard to the occurrence of nocturnal NO signals and their origins. Anthropogenic influences arising from road traffic and home heating activities are identified by their dependence on wind direction. An additional non-directional component is found to exist. It shows up most frequently in summer and when it occurs, the NO mixing ratio increases with rising temperature indicating a biological origin of night-time NO. The temporal behavior of night-time NO is usually correlated with that of CO₂ but anticorrelated to that of O₃. This shows that NO is brought upwards to the air intake of the NO_x monitor from lower levels and that the source of the non-directional component of nocturnal NO is the earth's surface. The release of NO from soils is known from other work and this process is probably also responsible for the present observations. A flux estimate agrees with soil fluxes reported by other authors. The accumulation of NO in the surface air layer under stagnant conditions leads to the appearance of a morning peak of NO after sunrise when increased vertical mixing brings NO rich air up to the monitoring level. During summer, the morning peak may override the NO peak expected to occur at noon due to the photodissociation of NO₂.     

Photochemical production of methane in natural waters: implications for its present and past oceanic source

We conducted irradiation experiments with riverine, estuarine, and marine water samples to investigate the possibility of photochemical methane (CH4) formation. CH4 photoproduction was undetectable under oxic conditions or in the absence of methyl radical precursors indicating that its photochemical formation is negligible in the present ocean. Significant photochemical CH4 production was observed in the presence of a methyl radical precursor such as acetone under strictly anoxic conditions. Our results indicate an indirect formation mechanism with coloured dissolved organic matter acting as photosensitizer. We suggest that photochemical CH4 formation might have occurred in the anoxic ocean surface layer of the Archean prior to the onset of O2 accumulation in the atmosphere at around 2300 million years ago. Oceanic CH4 photoproduction via methyl radical (CH3) precursors and its subsequent release to the atmosphere may have contributed to high CH4 mixing ratios in the Archean atmosphere.     

Adsorption-oxidation of hydrogen sulfide on activated carbon fibers: effect of the composition and the relative humidity of the gas phase

The removal of hydrogen sulfide by oxidation-adsorption on two type carbon fibers, Actitex FC1201 and RS1301, was studied. Two kinetic steps where identified. During the first step, the degradation appears to be limited by the oxidation reaction. In the second kinetic step, the by-products inhibit the hydrogen sulfide degradation. This leads to a limitation in the carbon site's accessibility and to a lower kinetic. The Langmuir-Hinshelwood model was used to correlate the experimental results and to estimate the kinetic (k) and the Langmuir adsorption (K) constants. For FC1201 fibers, the kinetic constant (k) is five time higher and the adsorption constant is five time lower compared to the RS1301 fibers. The role of the humidity was found to be highly beneficial for the removal of hydrogen sulfide. Especially in the second kinetic step, where it removes the by-product formed and therefore delays the occurrence of this low kinetic step. The kinetic constant (k) is strongly influenced by humidity while the Langmuir adsorption constant (K) seems independent. The effect of the nature of the gas phase on the reaction kinetic was also studied. Under a dry atmosphere, we note that the oxidation-reaction occurs even if the gaseous oxygen is not present. This oxidation is due to the oxygen surface function of the carbon fibers. Moreover, the degradation kinetic is faster under a dry nitrogen atmosphere. The presence of water traces leads to the acidification of the carbon surface, under oxygen or carbon dioxide atmospheres, and hence limits the hydrogen sulfide dissociation. In a humid atmosphere, the oxygen or carbon dioxide leads to a faster reaction kinetic. The acidification of the carbon surface is largely counterbalanced by the dissolution of the by-products.     

Ten years of atmospheric methane observations at a high elevation site in Western China

In this paper, the continuous (1994–2001) and discrete air sample (1991–2001) measurements of atmospheric CH₄ from the Waliguan Baseline Observatory located in western China (36°17′N, 100°54′E, 3816 m asl) are presented and characterized. The CH₄ time series show large episodic events on the order of 100 ppb throughout the year. During spring, a diurnal cycle with average amplitude of 7 ppb and a morning maximum and late afternoon minimum is observed. In winter, a diurnal cycle with average amplitude of 14 ppb is observed with an afternoon maximum and morning minimum. Unlike most terrestrial observational sites, no obvious diurnal patterns are present during the summer or autumn. A background data selection procedure was developed based on local horizontal and vertical winds. A selected hourly data set representative of “baseline” conditions was derived with approximately 50% of the valid hourly data. The range of CH₄ mixing ratios, annual means, annual increases and mean annual cycle at Waliguan during the 1992–2001 were derived from discrete and continuous data representative of “baseline” conditions and compared to air samples collected at other Northern Hemisphere sites. The range of CH₄ monthly means of 1746–1822 ppb, average annual means of 1786.7±10.8 ppb and mean annual increase of 4.5±4.2 ppb yr⁻¹ at Waliguan were inline with measurements from sites located between 30° and 60°N. There were variations observed in the CH₄ annual increase patterns at Waliguan that were slightly different from the global pattern. The mean CH₄ annual cycle at Waliguan shows an unusual pattern of two gentle peaks in summer and February along with two small valleys in early winter and spring and a mean peak-to-peak amplitude of 11 ppb, much smaller than amplitudes observed at most other mid- and high-northern latitude sites. The Waliguan CH₄ data are strongly influenced by continental Asian CH₄ emissions and provide key information for global atmospheric CH₄ models.     

生物膜法净化中浓度硫化氢的研究

基于中浓度H2S的生物治理研究较少的现状,利用生物膜法进行了以活性炭为填料净化中浓度H2S适宜条件的研究.考察了温度、营养液喷淋量、空塔气速、H2S初始浓度及pH与H2S净化效率的关系.结果表明,适宜条件为温度30 ℃、营养液喷淋量10 L/h、空塔气速0.16 m3/h、H2S初始质量浓度低于60 mg/m3和pH为2.0.在适宜条件下,生物膜填料塔对H2S的净化效率可达到90%以上.     

Sensor transition failure in the high flow sampler: Implications for methane emission inventories of natural gas infrastructure

Quantification of leaks from natural gas (NG) infrastructure is a key step in reducing emissions of the greenhouse gas methane (CH₄), particularly as NG becomes a larger component of domestic energy supply. The U.S. Environmental Protection Agency (EPA) requires measurement and reporting of emissions of CH₄ from NG transmission, storage, and processing facilities, and the high-flow sampler (or high-volume sampler) is one of the tools approved for this by the EPA. The Bacharach Hi-Flow Sampler (BHFS) is the only commercially available high-flow instrument, and it is also used throughout the NG supply chain for directed inspection and maintenance, emission factor development, and greenhouse gas reduction programs. Here we document failure of the BHFS to transition from a catalytic oxidation sensor used to measure low NG (~5% or less) concentrations to a thermal conductivity sensor for higher concentrations (from ~5% to 100%), resulting in underestimation of NG emission rates. Our analysis includes both our own field testing and analysis of data from two other studies (Modrak et al., 2012; City of Fort Worth, 2011). Although this failure is not completely understood, and although we do not know if all BHFS models are similarly affected, sensor transition failure has been observed under one or more of these conditions: (1) Calibration is more than ~2 weeks old; (2) firmware is out of date; or (3) the composition of the NG source is less than ~91% CH₄. The extent to which this issue has affected recent emission studies is uncertain, but the analysis presented here suggests that the problem could be widespread. Furthermore, it is critical that this problem be resolved before the onset of regulations on CH₄ emissions from the oil and gas industry, as the BHFS is a popular instrument for these measurements.

Implications: An instrument commonly used to measure leaks in natural gas infrastructure has a critical sensor transition failure issue that results in underestimation of leaks, with implications for greenhouse gas emissions estimates as well as safety.     

Combination of photoacoustic detector with gas diffusion probes for the measurement of methane concentration gradients in submerged paddy soil

Dissolved methane was monitored by means of a diffusion probe in combination with a photoacoustic (PA) detector cell placed in the cavity of a liquid nitrogen-cooled CO laser. The detection limit of the photoacoustic detector was 1 ppbv methane (≈ 2 μM in aqueous solution), the time response was 60 s, the spatial resolution was 1.36 mm. These limits were determined by the acoustic noise and the configuration of the diffusion probe. The combination of PA detector with gas diffusion probes was found to be useful for monitoring gaseous compounds. However, the membrane material of the diffusion probe was critical. Silicone as membrane material was useful only for measurement of CH₄. Goretex as membrane material was applicable to measurement of dimethylsulfide (DMS), but did not give a stable signal for trimethylamine (TMA).

Vertical concentration profiles of CH₄ in anoxic paddy soil agreed well with earlier results obtained with a gas chromatograph as detector. Methane was produced in anoxic soil layers below 8–10 mm depth and diffused upwards to the surface through a layer of CH₄-consuming bacteria situated at about 2 mm depth. In the oxic upper 2 mm soil layer the concentration of CH₄ decreased below the detection limit of our system. Methane-containing gas bubbles that were embedded in the soil were detected by a steep increase of the CH₄ signal. The combination of PA detector and gas diffusion probe was found to be a useful tool to measure CH₄ gradients in submerged soil or sediment with high temporal and spatial resolution, thus allowing the localization and quantification of CH₄ production and CH₄ oxidation rates within the soil profile.