Dissolved Methane Concentrations Research Articles

Revealing the kinetic behaviors of hydrate formation on bubble surface with different pressure gradients in deep-sea methane seepage areas of the South China Sea

In the deep-sea methane seepage environment, hydrate formation on the methane bubbles is a crucial pathway for methane transformation, and plays an important role in determining whether seepage methane can enter the surface ocean. While how the pressure determines the hydrate formation process in different water depths remains unclear. In this study, we investigated the formation kinetic characteristics and microstructure evolution of methane hydrate on suspended gas bubbles within varied pressure conditions. The pressure range (4–14 MPa) was in the deep-sea methane seepage environment. The results indicated that pressure obviously affected the hydrate film formation characteristics. As pressure increased, the lateral growth rate of the hydrate film accelerated, the hydrate crystal particles became smaller, and the initial hydrate film surface became smoother. Raman spectroscopy results showed that pressure changes did not obviously alter the microporous evolution on the hydrate film surface, that the gas-phase/water-phase Raman peak area ratio exhibited similar trends. The dissolved methane concentration under different pressure conditions was not the primary factor affecting hydrate thickening, rather, it depended mainly on the driving force. This study is of great significance in revealing the characteristics of methane hydrate formation and methane transfer in the oceanic methane seepage environment.

Hydrate Formation and Methane Mass Transfer Characteristics in Static Systems of Pure Water and Saline Water with Varied Initial Dissolved Methane Concentrations

Hydrate Formation and Methane Mass Transfer Characteristics in Static Systems of Pure Water and Saline Water with Varied Initial Dissolved Methane Concentrations

Methane mitigation via the nitrite-DAMO process induced by nitrate dosing in sewers

Nitrate or nitrite-dependent anaerobic methane oxidation (n-DAMO) is a microbial process that links carbon and nitrogen cycles as a methane sink in many natural environments. This study demonstrates, for the first time, that the nitrite-dependent anaerobic methane oxidation (nitrite-DAMO) process can be stimulated in sewer systems under continuous nitrate dosing for sulfide control. In a laboratory sewer system, continuous nitrate dosing not only achieved complete sulfide removal, but also significantly decreased dissolved methane concentration by ∼50 %. Independent batch tests confirmed the coupling of methane oxidation with nitrate and nitrite reduction, revealing similar methane oxidation rates of 3.68 ± 0.5 mg CH4 L−1 h−1 (with nitrate as electron acceptor) and 3.57 ± 0.4 mg CH4 L−1 h−1 (with nitrite as electron acceptor). Comprehensive microbial analysis unveiled the presence of a subgroup of the NC10 phylum, namely Candidatus Methylomirabilis (n-DAMO bacteria that couples nitrite reduction with methane oxidation), growing in sewer biofilms and surface sediments with relative abundances of 1.9 % and 1.6 %, respectively. In contrast, n-DAMO archaea that couple methane oxidation solely to nitrate reduction were not detected. Together these results indicated the successful enrichment of n-DAMO bacteria in sewerage systems, contributing to approx. 64 % of nitrite reduction and around 50 % of dissolved methane removal through the nitrite-DAMO process, as estimated by mass balance analysis. The occurrence of the nitrite-DAMO process in sewer systems opens a new path to sewer methane emissions.

Mitigated CH4 release of anaerobic waste fermentation is enabled through effluent degassing system equipped with a polydimethylsiloxane membrane contactor

In this study, first, a fed-batch biogas fermenter was established using anaerobic digester sludge treating secondary sludge from a municipal wastewater treatment plant and operated for 120 days on glycerol as the sole substrate. Then, the prefiltered effluent of the anaerobic digester unit was loaded subsequently into a stirred-tank coupled with a hollow-fibre, polydimethylsiloxane (PDMS) gas-liquid membrane contactor and a dissolved methane sensor for studying the gas recovery process under continuous biogas supply, consisting of CH4 and CO2 in different proportions (70/30 CH4/CO2 vol.%; 50/50 CH4/CO2 vol.%; 30/70 CH4/CO2 vol.%.). Experiments showed that besides the actual composition of the internal biogas, the ratio (0.5–2) of sweep gas (N2) and effluent (liquid) volumetric flow rates (G/L) could be a crucial operating factor with influence on the degassing efficiency attainable by the 1 m2 PDMS membrane module. Results were compared to the performance of the same PDMS membrane module working with synthetic anaerobic digester effluents, indicating the dissolved methane recoveries observed with the synthetic effluents (>50 %) considerably surpassed those with the real effluent (<20 %) where the dissolved methane concentrations, at G/L of 1, were in the range of 12.4 to 17.3 mg L−1.

Development of a fast‐response system with integrated calibration for high‐resolution mapping of dissolved methane concentration in surface waters

AbstractDissolved gas concentrations in surface waters can have sharp gradients across marine and freshwater environments, which often prove challenging to capture with analytical measurement. Collecting discrete samples for laboratory analysis provides accurate results, but suffers from poor spatial resolution. To overcome this limitation, water equilibrators and gas membrane contactors (GMCs) have been used for the automated underway measurement of dissolved gas concentrations in surface water. However, while water equilibrators can provide continuous measurements, their analytical response times to changes in surface water concentration can be slow, lasting tens of minutes. This leads to spatial imprecisions in the dissolved gas concentration data. Conversely, while GMCs have proven to have much faster analytical response times, often lasting only a few minutes or less, they suffer from poor accuracy and thus require routine calibration. Here we present an analytical system for the high accuracy and high precision spatial mapping of dissolved methane concentration in surface waters. The system integrates a GMC with a cavity ringdown spectrometer for fast analytical response times, with a calibration method involving two Weiss‐style equilibrators and discrete measurements in vials. Data from both the GMC and equilibrators are collected simultaneously, with discrete vial samples collected periodically throughout data collection. We also present a mathematical algorithm integrating all data collected for the routine calibration of the GMC dataset. The algorithm facilitates comparison between the GMC and equilibrator datasets despite the substantial differences in response times (0.7–2.1 and 4.1–17.6 min, respectively). This measurement system was tested with both systematic laboratory experiments and field data collected on a research cruise along the US Atlantic margin. Once calibrated, this system identified numerous sharp peaks of dissolved methane concentration in the US Atlantic margin dataset that would be poorly resolved, or outright missed with previous measurement techniques. Overall, the precision and accuracy for the technique presented here were determined to be 11.2% and 10.4%, respectively, the operating range was 0–1000 ppm methane, and the e‐folding response time to changes in dissolved methane concentration was 0.7–2.1 min.

Methane hydrate phase equilibrium considering dissolved methane concentrations and interfacial geometries from molecular simulations.

Natural gas hydrates, mainly existing in permafrost and on the seabed, are expected to be a new energy source with great potential. The exploitation technology of natural gas hydrates is one of the main focuses of hydrate-related studies. In this study, a large-size liquid aqueous solution wrapping a methane hydrate system was established and molecular dynamics simulations were used to investigate the phase equilibrium conditions of methane hydrate at different methane concentrations and interfacial geometries. It is found that the methane concentration of a solution significantly affects the phase equilibrium of methane hydrates. Different methane concentrations at the same temperature and pressure can lead to hydrate formation or decomposition. At the same temperature and pressure, in a system reaching equilibrium, the size of spherical hydrate clusters is coupled to the solution concentration, which is proportional to the Laplace pressure at the solid-liquid interface. Lower solution concentrations reduce the phase equilibrium temperature of methane hydrates at the same pressure; as the concentration increases, the phase equilibrium temperature gradually approaches the actual phase equilibrium temperature. In addition, the interfacial geometry of hydrates affects the thermodynamic stability of hydrates. The spherical hydrate particles have the highest stability for the same volume. Through this study, we provide a stronger foundation to understand the principles driving hydrate formation/dissociation relevant to the exploitation of methane hydrates.

Phosphonate consumers potentially contributing to methane production in Brazilian soda lakes.

Oxic methane production (OMP) has been reported to significantly contribute to methane emissions from oxic surface waters. Demethylation of organic compounds, photosynthesis-associated methane production, and (bacterio)chlorophyll reduction activity are some of the investigated mechanisms as potential OMP sources related to photosynthetic organisms. Recently, cyanobacteria have often been correlated with methane accumulation and emission in freshwater, marine, and saline systems. The Brazilian Pantanal is the world's largest wetland system, with approximately 10,000 shallow lakes, most of which are highly alkaline and saline extreme environments. We initiated this study with an overall investigation using genetic markers, from which we explored metagenomic and limnological data from the Pantanal soda for five potential OMP pathways. Our results showed a strong positive correlation between dissolved methane concentrations and bloom events. Metagenomic data and nutrients, mainly orthophosphate, nitrogen, iron, and methane concentrations, suggest that the organic phosphorous demethylation pathway has the most potential to drive OMP in lakes with blooms. A specialized bacterial community was identified, including the Cyanobacteria Raphidiopsis, although the bloom does not contain the genes to carry out this process. These data showed enough evidence to infer the occurrence of an OMP pathway at Pantanal soda lakes, including the microbial sources and their relation to the cyanobacterial blooms.

Hydrothermal amorphous silica, barite and orpiment from the crater area of seamount (SM-13) off Nicobar island, Andaman sea: Indications for the development of a new hydrothermal field

The Andaman sea characterized by trench-arc-backarc elements (Andaman-Nicobar island-arc, the Andaman back-arc spreading center, the seamount complex, and the back-arc basin) is a complex active basin and is known for hydrothermal activity in some of the seamounts (subaerial and submarine) of the volcanic arc. In the present study, 13 submarine seamounts (SM1- SM13) in the southern Andaman volcanic arc, extending from 6°47′N: 94°43′E to 7° 56′ N: 94° 2.47′E, were surveyed onboard RV Sindhu Sadhana (November 2021) to find the evidences for the hydrothermal activity. Out of the 13 seamounts, at one crater seamount (SM-13) we have observed evidence for hydrothermal activity characterized by plumes rich in dissolved gases (mainly CO2) in the water column, live chemosymbiotic organisms (Bathymodiolus species), and neoforming minerals such as amorphous silica, barite and orpiment. We observed two plumes rich in dissolved gases (mainly CO2), called GP1 and GP2, in the water column at two different water depths i.e. 400 and 380 mbsl respectively. Geochemical analysis of the water samples shows enhanced TCO2 concentrations within the plumes rich in dissolved gases (mainly CO2) observed in sub-bottom profiler data, however, the dissolved methane concentrations do not show any enrichment when compared with ambient seawater concentrations. Apart from the enhancement in the TCO2 concentrations, pH and total alkalinity data also show fluctuations within the same depth zone which may be attributed to the hydrothermal plume exhausting from the crater seamount. The occurrence of live chemosymbiotic organism Bathymodiolus species indicate an active and continuous supply of H2S. The precipitation of neoforming hydrothermal minerals such as amorphous silica, tabular barite, and orpiment on the surface of the rock samples further supports the hydrothermal activity. Previous studies carried out in 2007 have reported hydrothermal ferromanganese oxides precipitated from low-temperature hydrothermal fluids (Surya prakash et al., 2012) and inferred SM-13 as a dormant submarine volcano (Kamesh Raju et al., 2012). However, after 14 years, we observe volatile emissions to the water column, hydrothermal mineral precipitation and live chemosymbiotic organisms from the same seamount. These observations of the present study infer development of a new hydrothermal field in the least explored Andaman Sea. This study adds up a new active site to the global hydrothermal inventory which may allow better estimation of global hydrothermal flux and its role in oceanic elemental cycle.

Monitoring of Shallow-Water Methane Seeps at Cape Fiolent (Black Sea)

During the period from 2019 to 2021, complex studies of new shallow-water methane bubble gas emission sites were carried out in the coastal zone near Cape Fiolent (Southwest Coast of Crimea). The studies included determining the hydrocarbon and isotopic composition of bubble gas, measuring the concentration of methane and nutrients in the water in the areas of gas emissions, estimating the value of bubble flows, and measuring hydrophysical parameters over the sip sites compared to background areas. The seasonal type of Cape Fiolent methane seeps was noted, its active phases of gas emissions differed in duration in different years. The increased pore water silica concentration at the seep sites and their localization in the vicinity of freshwater slope springs may indicate its association with submarine freshwater discharge in the area. However, no significant desalination of both pore water and the bottom water layer above the siphons was recorded. Dissolved methane concentrations in pore water at seep sites were two orders of magnitude higher compared to background areas and reached 448 μmol/L. Also high values were obtained for surface water directly above the bubble gas emission points (maximum 353 nmol/L). Multi-hour monitoring of hydrophysical parameters above the active seeps showed a dissolved oxygen decrease compared to the background sites. The maximum difference in O2 concentrations was 3 mg/l. The carbon isotopic composition of bubble gas methane δ13C-CH4 (–62.84…38.27‰) and сarbon dioxide δ13C-CO2 (–16.83…–10.17‰) was corresponded to a mixture of isotopically heavy gas and near-surface isotopically light gas of microbial origin. The question remains open: what are the reasons for the change in the summer active and the cold season passive gas emission phases?

The Role of Thermokarst Lake Expansion in Altering the Microbial Community and Methane Cycling in Beiluhe Basin on Tibetan Plateau.

Highlights The co-occurrence network structure of bacteria was more diverse and complex in sediment than in water, while archaea showed an opposite trend at environment under ice.Microbial diversity increased in MS and SH points, and microbial community composition and microbial network complexity were also different among four points.The diversity of functional gene mcrA and pmoA in water was positively correlated with dissolved methane concentration, and the water dissolved methane concentration was positively correlated with the diversity of functional gene mcrA but not with pmoA in sediment.The under-ice environment plays a vital role in the methane cycling of the thermokarst lake.One of the most significant environmental changes across the Tibetan Plateau (TP) is the rapid lake expansion. The expansion of thermokarst lakes affects the global biogeochemical cycles and local climate regulation by rising levels, expanding area, and increasing water volumes. Meanwhile, microbial activity contributes greatly to the biogeochemical cycle of carbon in the thermokarst lakes, including organic matter decomposition, soil formation, and mineralization. However, the impact of lake expansion on distribution patterns of microbial communities and methane cycling, especially those of water and sediment under ice, remain unknown. This hinders our ability to assess the true impact of lake expansion on ecosystem services and our ability to accurately investigate greenhouse gas emissions and consumption in thermokarst lakes. Here, we explored the patterns of microorganisms and methane cycling by investigating sediment and water samples at an oriented direction of expansion occurred from four points under ice of a mature-developed thermokarst lake on TP. In addition, the methane concentration of each water layer was examined. Microbial diversity and network complexity were different in our shallow points (MS, SH) and deep points (CE, SH). There are differences of microbial community composition among four points, resulting in the decreased relative abundances of dominant phyla, such as Firmicutes in sediment, Proteobacteria in water, Thermoplasmatota in sediment and water, and increased relative abundance of Actinobacteriota with MS and SH points. Microbial community composition involved in methane cycling also shifted, such as increases in USCγ, Methylomonas, and Methylobacter, with higher relative abundance consistent with low dissolved methane concentration in MS and SH points. There was a strong correlation between changes in microbiota characteristics and changes in water and sediment environmental factors. Together, these results show that lake expansion has an important impact on microbial diversity and methane cycling.

Nitrite reduction using a membrane biofilm reactor (MBfR) in a hypoxic environment with dilute methane under low pressures

Methane-based membrane biofilm reactors (MBfRs) can be an effective solution for nitrogen control in wastewater, but there is limited information on nitrite reduction for dilute wastewater (e.g., municipal wastewater) in hypoxic MBfRs. This study assessed the impacts of dilute (20 %), low-pressure methane (0.35–2.41 kPa) applied to MBfRs at hydraulic retention times (HRTs) of 2–12 h on nitrite removals, dissolved methane concentrations, and the resulting changes in the microbial community. High nitrite flux along with rapid and virtually complete (>99 %) nitrite removals were observed at methane pressures of 1.03–2.41 kPa at HRTs above 4 h, despite the use of diluted methane gas for the MBfR. The lowest methane pressure (0.35 kPa) was also able to achieve up to 98 % nitrite removals but required HRTs of up to 12 h. All scenarios had low dissolved methane concentrations (<10 mg/L), indicating that dilute methane at low supply pressures can effectively remove nitrite while meeting dissolved methane guidelines in treated effluent. Methylococcus genus was the key bacterium in MBfR biofilm grown at different HRTs and methane pressures, along with Methylocystis and other heterotrophic denitrifiers (Terrimonas and Hyphomicrobium). This study indicates that methane-based denitrification MBfRs can be a valuable tool to meet nitrogen limits for dilute wastewater coupled to partial nitrification, while limiting the release of methane to the environment.

The characteristics and influencing factors of dissolved methane concentrations in Chongqing's central urban area in the Three Gorges Reservoir, China.

Methane (CH4) emissions from reservoirs have received widespread attention. The central urban area of Chongqing in the Three Gorges Reservoir area was selected as the study area in 2020. The temporal and spatial distribution of dissolved CH4 concentration and flux, key generation pathways, and influencing factors have been studied. The dissolved CH4 concentration in low-water-level period and impoundment period varied from 0.037~0.12 μmol·L-1 and 0.11~0.23 μmol·L-1, with the average values of (0.066 ± 0.0067) μmol·L-1 and (0.13 ± 0.034) μmol·L-1. The CH4 flux was (0.941 ± 0.217) μmol·m-2·h-1 in low-water-level period and (1.915 ± 0.204) μmol·m-2·h-1 in impoundment period. CH4 was produced by CO2 reduction and acetic acid fermentation, accounting for 17.95% and 82.05% of the total CH4 production, respectively. The dissolved CH4 concentration was significantly positively correlated with DO and NO3--N, and it is opposite with dissolved inorganic carbon. The dissolved CH4 concentration in this study area is affected by water environment (33.42%), inorganic nitrogen (29.60%), organic carbon (23.88%), and inorganic carbon (13.10%), and anthropogenic influences promoted dissolved CH4 concentration.

Biogeochemical Assessment of the Coalbed Methane Source, Migration, and Fate: A Case Study of the Shizhuangnan Block, Southern Qinshui Basin.

The exploration and exploitation of coalbed methane (CBM), an essential unconventional gas resource, have received much attention. In terms of shallow groundwater assessment during CBM production, biogenic methane natural formation in situ and methane migration from deep sources into shallow aquifers need to be of most concern. This study analyzes geochemical surveys including ions, isotopes, and dissolved methane concentrations in 75 CBM coproduced water samples in the southern Qinshui Basin. Most of these water samples are weakly alkaline. Some samples’ negative oxidation/reduction potential (ORP) values reveal that the CBM reservoir water samples are mainly produced from reductive groundwater environments. Cl–, Na+, and HCO3– are the dominant ionic constituents of the water samples, which are usually associated with dissolved methane concentrations. The biogeochemical parameters and isotopic features provide an opportunity to assess the origin, migration, and oxidation of biogenic or thermogenic methane. Some water samples suggest biogenic methane formation in situ characterized by negligible SO42– and NO3– concentrations and low δ13CCH4. Only a few water samples indicate the migration of biogenic methane into shallow aquifers without oxidation based on elevated SO42–, NO3–, and δ13CDIC and low δ13CCH4. A few cases characterized by elevated δ13CCH4, negative δ13CDIC values, and negligible SO42– and methane concentrations suggest the oxidation of biogenic methane rather than the migration of thermogenic methane. A significant number of cases mean methane migration to shallow aquifers. Partial oxidation of thermogenic or mixed methane is evaluated by negligible SO42–, NO3–, and methane concentrations and elevated δ13CCH4. Dissolved methane isotopic compositions and aqueous biogeochemical features help study methane formation and potential migration in shallow groundwater.

Continual long-term monitoring of methane in wells above the Utica Shale using total dissolved gas pressure probes

Monitoring of dissolved methane concentrations in groundwater is required to identify impacts from oil and gas development and to understand temporal variability under background conditions. Currently, long-term (i.e., multiyear) monitoring is performed via periodic groundwater sampling; hence, the data are temporally limited and can suffer from degassing losses in-well and at surface for groundwater with high dissolved gas concentrations. The application of total dissolved gas pressure (PTDG) probes for long-term monitoring of methane-rich groundwater was investigated for >2 years in three monitoring wells in a low-permeability bedrock aquifer above the Utica Shale, Canada. The advantage of these probes is that they allow for continual in situ monitoring. A hydraulic packer was installed in each well, below which PTDG and water pressure were measured every 15 or 30 min. The major dissolved gas species composition, required to calculate methane concentrations from PTDG, was determined from groundwater samples collected approximately bimonthly. Methane was the dominant gas in each well (~80–97%), with relatively consistent composition over time, indicating PTDG provided a reasonable proxy for methane concentrations. All three wells had high PTDG (reaching 53.0 m H2O), with PTDG-derived methane concentrations (34–156 mg/L) much higher (3–12 times) and relatively more stable than determined by conventional groundwater analysis. PTDG monitoring also revealed substantial short-term changes during pumping and between sampling events (up to 4 m H2O), possibly associated with background variability. Limitations and technical remedies are discussed. This study demonstrates that PTDG probes can be a valuable tool for monitoring methane-rich groundwater.

Spatial and temporal variability of dissolved methane concentrations and diffusive emissions in the Three Gorges Reservoir

Methane (CH4) emissions from freshwater aquatic systems such as rivers and reservoirs are an important component of the global methane budget. However, the estimation can be largely affected by the spatial and temporal resolutions of measurements. Especially, the lack of high-resolution studies in the Three Gorges Reservoir (TGR), one of the largest reservoirs in the world, has led to a longstanding debate on its CH4 emissions. In this study, the spatial distribution and seasonal variations of dissolved CH4 concentrations were measured using a fast-response automated gas equilibrator in the TGR. We observed large spatiotemporal variations of dissolved CH4 (mean ± SD: 0.26 ± 0.19 μM in summer and 0.24 ± 0.17 μM in winter). Higher concentrations with stronger variations were found in the upstream than in the section close to the Three Gorges Dam. The dissolved CH4 concentration in the TGR was mainly influenced by sewage discharge, sedimentation, topographical conditions, tributaries, and spatial and seasonal variations in hydrodynamics. Regression analyses suggest that the concentration can be characterized by sewage discharge, water depth, and electrical conductivity to a certain extent. Mean diffusive CH4 fluxes from the TGR in summer and winter were 16.2 mg m−2 d−1 and 3.1 mg m−2 d−1, respectively. Downsampling simulations show that scaling dissolved CH4 in the TGR from one site likely involves large errors, and at least ∼38 sites and ∼52–58 sites are needed to achieve an accurate estimate in summer and winter, respectively. Due to the large spatial and temporal heterogeneity, high-resolution measurements are key to improving the reliability of CH4 estimates and assessing the contribution of the TGR to regional and global CH4 budgets.

Improved Membrane Inlet Mass Spectrometer Method for Measuring Dissolved Methane Concentration and Methane Production Rate in a Large Shallow Lake

Natural water bodies, such as lakes, rivers, and oceans, are important sources of atmospheric methane (CH4). Therefore, quantitative and accurate determination of the dissolved CH4 concentration in water is of great significance for studying CH4 emissions and providing an in-depth understanding of the carbon cycle. Headspace gas chromatography (HGC) is the traditional method for measuring CH4 in water. Despite its long success, it has a lot of problems in use, such as complex pretreatment and a long measurement time, and it is not suitable for the CH4 determination of a large number of samples. In view of these shortcomings, a more convenient and efficient method based on membrane inlet mass spectrometry (MIMS) for quantitative measurements of the dissolved CH4 concentration in water was established. In our study, the standard curves showed that the method had high accuracy, both at low and high CH4 concentrations. After a laboratory test, to evaluate the sensitivity of this method, samples were collected from a large shallow lake (Lake Taihu). Both the HGC method and MIMS method were used to determine the dissolved CH4 to compare these two methods. The small difference in CH4 concentration obtained from the MIMS and HGC methods and the significant correlation between the CH4 concentrations derived from the MIMS method with those derived from the HGC method showed that the MIMS method could replace the HGC method in the determination of dissolved CH4 in natural waters. In addition, we also measured the sediment CH4 production rates in three different areas of Lake Taihu using a laboratory incubation experiment. During the experiment, significant CH4 accumulations were observed, indicating that sediment CH4 production was an important source of dissolved CH4 in the water column. Our study concluded that the MIMS method was sufficient and a better alternative than the HGC method owing to its capacity to measure a broad range of values plus the fact that it was relatively easy to use with less manipulation of the samples.

Detailed Patterns of Methane Distribution in the German Bight

Although methane is a widely studied greenhouse gas, uncertainties remain with respect to the factors controlling its distribution and diffusive flux into the atmosphere, especially in highly dynamic coastal waters. In the southern North Sea, the Elbe and Weser rivers are two major tributaries contributing to the overall methane budget of the southern German Bight. In June 2019, we continuously measured methane and basic hydrographic parameters at a high temporal and spatial resolution (one measurement per minute every 200–300 m) on a transect between Cuxhaven and Helgoland. These measurements revealed that the overall driver of the coastal methane distribution is the dilution of riverine methane-rich water with methane-poor marine water. For both the Elbe and Weser, we determined an input concentration of 40–50 nmol/L compared to only 5 nmol/L in the marine area. Accordingly, we observed a comparatively steady dilution pattern of methane concentration toward the marine realm. Moreover, small-scale anomalous patterns with unexpectedly higher dissolved methane concentrations were discovered at certain sites and times. These patterns were associated with the highly significant correlations of methane with oxygen or turbidity. However, these local anomalies were not consistent over time (days, months). The calculated diffusive methane flux from the water into the atmosphere revealed local values approximately 3.5 times higher than background values (median of 36 and 128 μmol m–2 d–1). We evaluate that this occurred because of a combination of increasing wind speed and increasing methane concentration at those times and locations. Hence, our results demonstrate that improved temporal and spatial resolution of methane measurements can provide a more accurate estimation and, consequently, a more functional understanding of the temporal and spatial dynamics of the coastal methane flux.

Physical Disturbance by Bottom Trawling Suspends Particulate Matter and Alters Biogeochemical Processes on and Near the Seafloor

Bottom trawling is known to affect benthic faunal communities but its effects on sediment suspension and seabed biogeochemistry are less well described. In addition, few studies have been carried out in the Baltic Sea, despite decades of trawling in this unique brackish environment and the frequent occurrence of trawling in areas where hypoxia and low and variable salinity already act as ecosystem stressors. We measured the physical and biogeochemical impacts of an otter trawl on a muddy Baltic seabed. Multibeam bathymetry revealed a 36 m-wide trawl track, comprising parallel furrows and sediment piles caused by the trawl doors and shallower grooves from the groundgear, that displaced 1,000 m3 (500 t) sediment and suspended 9.5 t sediment per km of track. The trawl doors had less effect than the rest of the gear in terms of total sediment mass but per m2 the doors had 5× the displacement and 2× the suspension effect, due to their greater penetration and hydrodynamic drag. The suspended sediment spread &amp;gt;1 km away over the following 3–4 days, creating a 5–10 m thick layer of turbid bottom water. Turbidity reached 4.3 NTU (7 mgDW L–1), 550 m from the track, 20 h post-trawling. Particulate Al, Ti, Fe, P, and Mn were correlated with the spatio-temporal pattern of suspension. There was a pulse of dissolved N, P, and Mn to a height of 10 m above the seabed within a few hundred meters of the track, 2 h post-trawling. Dissolved methane concentrations were elevated in the water for at least 20 h. Sediment biogeochemistry in the door track was still perturbed after 48 h, with a decreased oxygen penetration depth and nutrient and oxygen fluxes across the sediment-water interface. These results clearly show the physical effects of bottom trawling, both on seabed topography (on the scale of km and years) and on sediment and particle suspension (on the scale of km and days-weeks). Alterations to biogeochemical processes suggest that, where bottom trawling is frequent, sediment biogeochemistry may not have time to recover between disturbance events and elevated turbidity may persist, even outside the trawled area.

Anaerobic membrane bioreactor model for design and prediction of domestic wastewater treatment process performance

Anaerobic treatment of municipal wastewater that produces energy and low levels of biosolids for disposal has the potential to replace conventional aerobic processes. Here we propose a generic model for anaerobic membrane bioreactors (AnMBRs) that incorporates hydrolysis and dispersed growth microbial metabolism of particulate and soluble substrates, including a size-exclusion constraint based upon the pore size of submerged membranes. The model can be expanded to include attached growth systems, such as anaerobic fluidized bed reactors (AFBRs) within the staged anaerobic fluidized membrane bioreactor (SAF-MBR) system. Model development entailed: (1) acquisition of key kinetic metabolic parameters based on independent batch studies, (2) creation of a matrix of metabolic processes, and (3) development of a model that describes the relevant mass balances in the system. The utility of the model is demonstrated for dynamic simulations of a pilot-scale second generation SAF-MBR treating municipal wastewater (SAF-MBR 2.0). System outputs include the COD of the system effluent (= permeate), recirculated bulk COD and MLSS, gas production rate and composition, and dissolved methane concentration. These parameters are critical for system design and assessment. Predictions of performance by a pilot-scale system agreed well with monitored values, typically with less than 10% error, indicating that the developed model and independent batch assays for model calibration can enable reliable systems-level performance simulations.

Inter-Comparison of the Spatial Distribution of Methane in the Water Column From Seafloor Emissions at Two Sites in the Western Black Sea Using a Multi-Technique Approach

Understanding the dynamics and fate of methane (CH4) release from oceanic seepages on margins and shelves into the water column, and quantifying the budget of its total discharge at different spatial and temporal scales, currently represents a major scientific undertaking. Previous works on the fate of methane escaping from the seafloor underlined the challenge in both, estimating its concentration distribution and identifying gradients. In April 2019, the Envri Methane Cruise has been conducted onboard the R/V Mare Nigrum in the Western Black Sea to investigate two shallow methane seep sites at ∼120 m and ∼55 m water depth. Dissolved CH4 measurements were conducted with two continuous in-situ sensors: a membrane inlet laser spectrometer (MILS) and a commercial methane sensor (METS) from Franatech GmbH. Additionally, discrete water samples were collected from CTD-Rosette deployment and standard laboratory methane analysis was performed by gas chromatography coupled with either purge-and-trap or headspace techniques. The resulting vertical profiles (from both in situ and discrete water sample measurements) of dissolved methane concentration follow an expected exponential dissolution function at both sites. At the deeper site, high dissolved methane concentrations are detected up to ∼45 m from the seabed, while at the sea surface dissolved methane was in equilibrium with the atmospheric concentration. At the shallower site, sea surface CH4 concentrations were four times higher than the expected equilibrium value. Our results seem to support that methane may be transferred from the sea to the atmosphere, depending on local water depths. In accordance with previous studies, the shallower the water, the more likely is a sea-to-atmosphere transport of methane. High spatial resolution surface data also support this hypothesis. Well localized methane enriched waters were found near the surface at both sites, but their locations appear to be decoupled with the ones of the seafloor seepages. This highlights the need of better understanding the processes responsible for the transport and transformation of the dissolved methane in the water column, especially in stratified water masses like in the Black Sea.