Oxidation and emission of methane in a monomictic lake (Rotsee, Switzerland)

The build-up of methane in the hypolimnion of the eutrophic Lake Rotsee (Lucerne, Switzerland) was monitored over a full year. Sources and sinks of methane in the water column were characterized by measuring concentrations and carbon isotopic composition. In fall, high methane concentrations (up to 1 mM) were measured in the anoxic water layer. In the oxic layer, methane concentrations were much lower and the isotopic composition shifted towards heavy carbon isotopes. Methane oxidation rates peaked at the interface between oxic and anoxic water layers at around 8–10 m depth. The electron balance between the oxidants oxygen, sulphate, and nitrate, and the reductants methane, sulphide and ammonium, matched very well in the chemocline during the stratified season. The profile of carbon isotopic composition of methane showed strong indications for methane oxidation at the chemocline (including the oxycline). Aerobic methane oxidizing bacteria were detected at the interface using fluorescence in situ hybridization. Sequencing the responsible organisms from DGGE bands revealed that aerobic methanotrophs type I closely related to Methylomonas were present. Sulphate consumption occurred at the sediment surface and, only towards the end of the stagnation period, matched with a zone of methane consumption. In any case, the flux of sulphate below the chemocline was not sufficient to oxidize all the methane and other oxidants like nitrate, iron or manganese are necessary for the observed methane oxidation. Although most of the methane was oxidized either aerobically or anaerobically, Lake Rotsee was still a source of methane to the atmosphere with emission rates between 0.2 mg CH₄ m^?2 day^?1 in February and 7 mg CH₄ m^?2 day^?1 in November.     

Treatment of Groundwater Containing Methane – Combination of the Processing Stages Desorption and Filtration

Methane is produced under anaerobic conditions by metabolic processes in microbes and can occur in waters of the types anoxic‐anaerobic (RG 1/2) and anaerobic‐reduced (RG 2). If the concentration of methane lies below 0.2 mg/L, then no special treatment processes are required apart from dosing of oxygen and rapid sand filtration, which are performed to remove iron, manganese, and ammonium. The research results show that a higher concentration of methane must be specially treated. From the point of view of stable deferrisation, oxidation of up to 2 mg/L is tolerable in rapid sand filtration. However, an unusual increase in regrowth potential was observed. For this reason, the oxidation of methane should be reduced to 0.5 mg/L until further experiments yield results on the microbiological stability of treated water. Rapid sand filters for nitrification and demanganisation should have a maximum methane loading of 0.2 mg/L. The experiments show that nitrification first occurs at a methane concentration below 0.1 mg/L. During the working in of demanganisation, the inlet water should be free of methane. Therefore desorption is often required. If there is less than 1 mg/L to be degassed, then desorption can be achieved with overpressure in the oxidiser without any change in the carbonate‐bicarbonate equilibrium. With other systems, such as packed columns, wetted‐wall columns, or percolators, carbon dioxide is removed simultaneously. By means of the coefficients of similarity found, it was shown that methane and carbon dioxide desorb in different proportions depending on the system, and that the discharge of carbon dioxide can be reduced through a decrease in the air/water ratio.     

Geochemical constraints on the methane seep activity in western slope of the middle Okinawa Trough,the East China Sea

Anaerobic oxidation of methane and sulfate reduction was studied in the pore waters of four cores at two stations of the middle Okinawa Trough. Pore water vertical distributions of sulfate, methane, sulfide, total alkalinity, ammonium, and phosphate were determined in this study. Our results show strong linear sulfate concentration gradients of 6.83 mmol/L m?1 in Core A and 5.96 mmol/L m?1 in Core C, which were collected from two stations. Concurrent variations of methane, total alkalinity and hydrogen sulfide all exhibit steep increases with depth at both cores, which indicate active methane seep activities around two stations. Pore water ammonium and phosphate concentrations reveal minor influences of organic matter degradation on sulfate reduction at two stations. Sulfate methane interface(SMI) was extrapolated from linear sulfate profiles in methane seep cores. Shallower SMI depths(A: 4.9 mbsf; C: 5.4 mbsf) indicate strong methane fluxes and active anaerobic oxidation of methane in the underlying sediments.     

内陆水体好氧甲烷氧化过程研究进展

内陆水体是全球碳循环的关键组成部分,是大气中甲烷(CH4)的重要来源,每年从内陆淡水与自然湿地排放进入大气的CH4约为185～357 Tg/a.通常,内陆水体中CH4主要由分布于水层底部的厌氧区或沉积层内的产甲烷菌介导产生,其向水层表面传输的过程中易被甲烷氧化菌所氧化.甲烷氧化菌可分为好氧甲烷氧化菌和厌氧甲烷氧化菌,有...     

Anaerobic methane oxidation: Rate depth distributions in Skan Bay sediments

A radiotracer method that measures rates of oxidation of methane to carbon dioxide has been applied to anoxic marine sediments. The results confirm the occurrence of anaerobic methane oxidation and agree with model predictions of a zone of intense anaerobic methane oxidation at the base of the sulfate-reducing zone.     

Effect of Resuspension on the Release of Heavy Metals and Water Chemistry in Anoxic and Oxic Sediments

Two types of river sediments with contrasting characteristics (anoxic or oxic) were resuspended and the release of heavy metals and changes in water chemistry were investigated. During resuspension of the anoxic sediment, the dissolved oxygen (DO) concentration and redox potential of the water layer decreased abruptly within the first 1 min, followed by increases toward the end of the resuspension period. Heavy metals were released rapidly in the first 6 h, probably due to the oxidation of acid volatile sulfide (AVS) of the anoxic sediment, and then the aqueous phase concentrations of the heavy metals decreased due to resorption onto the sediment until the 12‐h point. During resuspension of the oxic sediment, the DO concentration and redox potential remained relatively constant in the oxic ranges. The heavy metals were released from the oxic sediment gradually during a 24‐h resuspension period. The temporal maximum concentrations of Ni, Cu, Zn, and Cd in the aqueous phases in both experiments frequently exceeded the USEPA water quality criteria or the water quality guidelines of Australia and New Zealand. This suggests that a resuspension event could bring about temporal water quality deterioration in the two sediment environments.     

Methane biotransformation in the ocean and its effects on climate change: A review

Methane is a potent greenhouse gas. Continental margins contain large reservoirs of methane as solid gas hydrate and the dissolved and gaseous forms of methane. Submarine methane seeps along the global continental margins, including the coastal seas, have been estimated to contribute 0.01 to 0.05 Gt of carbon to the atmosphere annually, accounting for between 1% and 5% of the global methane emissions to the atmosphere. Much of this methane is exhausted via microbial anaerobic methane oxidation. Methane biotransformation in the ocean has effects on global climate change. This review mainly introduces the mechanisms of methanogenesis and methane oxidation and describes new findings that will provide information that will improve the understanding of the balance in terms of the generation, migration and consumption of methane in marine environments. Moreover, this review provides new insights into methane biogeochemical cycles and the effects of marine methane budgets on global climate.     

Equilibrium and disequilibrium degassing of a phonolitic melt (Vesuvius AD 79 “white pumice”) simulated by decompression experiments

Equilibrium and disequilibrium degassing of a volatile phase from a magma of K-phonolitic composition was investigated to assess its behavior upon ascent. Decompression experiments were conducted in Ar-pressurized externally heated pressure vessels at superliquidus temperature (1050 °C), in the pressure range 10–200 MPa using pure water as fluid phase. All experiments were equilibrated at 200 MPa and then decompressed to lower pressures with rates varying from 0.0028 to 4.8 MPa/s. Isobaric saturation experiments were performed at the same temperature and at 900–950 °C to determine the equilibrium water solubility in the pressure range 30–250 MPa. The glasses obtained from decompression experiments were analyzed for their dissolved water content, vesicularity and bubble size distribution. All decompressed samples presented a first event of bubble nucleation at the capsule–melt interface. Homogeneous bubble nucleation in the melt only occurred in fast-decompressed experiments (4.8 and 1.7 MPa/s), for ΔP ≅ 100 MPa. For these decompression rates high water over-saturations were maintained until a rapid exsolution was triggered at ΔP > 150 MPa. For slower rates (0.0028, 0.024, 0.17 MPa/s) the degassing of the melt took place by diffusive growth of the bubbles nucleating at the capsule–melt interface. This process sensibly reduced water over-saturation in the melt, preventing homogeneous nucleation to occur. For decompression rates of 0.024 and 0.17 MPa/s low water over-saturations were attained in the melt, gradually declining toward equilibrium concentrations at low pressures. A near-equilibrium degassing path was observed for a decompression rate of 0.0028 MPa/s. Experimental data combined with natural pumice textures suggest that both homogeneous and heterogeneous bubble nucleations occurred in the phonolitic magma during the AD 79 Vesuvius plinian event. Homogeneous bubble nucleation probably occurred at a depth of ∼ 3 km, in response to a fast decompression of the magma during the ascent.     

The biogeochemistry of a manganese-rich Scottish sea loch: Implications for the study of anoxic nitrification

The anoxic oxidation of ammonia by manganese oxides is a newly recognised pathway for the production of N₂ in sedimentary environments, potentially contributing a significant loss of nitrogen from the world's oceans. Due to the complex recycling of redox species in marine sediments this process is difficult to discern in the natural environment, and is consequently poorly understood. The potential for anoxic nitrification coupled to manganese reduction was investigated through field research and laboratory incubation experiments. Field data from Loch Fyne, a manganese-rich site, did not provide conclusive evidence for anoxic nitrification, although minor accumulation of nitrate was observed in anoxic pore-waters. Incubation of Loch Fyne sediments showed anoxic nitrification to occur, with accumulation of both nitrate and nitrite coincident with removal of ammonia under anoxia, although these observations were not reproduced in repeat experiments. The laboratory evidence for anoxic nitrification confirms the reaction is possible in marine sediments; however, the wider significance of anoxic nitrification remains uncertain. Contrary to previous assumptions about anoxic nitrification, results suggest the reaction may not be dependent on total manganese concentrations and may be inhibited by conventional heterotrophic manganese reduction in manganese-rich sediments.     

Elemental sulfur in northern South China Sea sediments and its significance

Elemental sulfur(ES) is one of the intermediates in the inorganic sulfur cycle and thus plays a key role in the fractionation of stable sulfur isotopes in different reservoirs and the marine environment. In this study, solid ES is discovered in sediments near the Jiulong Methane Reef in the northern South China Sea by scanning electron microscopy and Raman spectroscopy. Combining the morphology and distribution of ES, pyrite concentrations, and sulfur isotopes, we conclude that:(1) solid ES coexists with pyrite microcrystals and sulfide(oxyhydr)oxides as well as clay minerals, and they are mainly distributed on the surface of mineral aggregates;(2) ES mainly occurs within and near the sulfate-methane transition zone(SMTZ) despite little morphological diversity;(3) ES formation might be related to hydrogen sulfide oxidation and is therefore linked with fluctuations in the SMTZ. Within the SMTZ, hydrogen sulfide is produced and pyrite precipitates because of enhanced anaerobic oxidation of methane coupled with dissimilatory sulfate reduction. This enhances the efficiency of the inorganic sulfur cycle and provides favorable conditions for ES formation. The discovery of solid ES in sediments near the Jiulong Methane Reef suggests an important relationship with SMTZ fluctuations that could have implications for the evolution of methane hydrate in the South China Sea.     

Modeling nitrogen–carbon cycling and oxygen consumption in bottom sediments

A model framework is presented for simulating nitrogen and carbon cycling at the sediment–water interface, and predicting oxygen consumption by oxidation reactions inside the sediments. Based on conservation of mass and invoking simplifying assumptions, a coupled system of diffusive–reactive partial differential equations is formulated for two-layer conceptual model of aerobic–anaerobic sediments. Oxidation reactions are modeled as first-order rate processes and nitrate is assumed to be consumed entirely in the anoxic portion of the sediments. The sediments are delineated into a thin oxygenated surface layer whose thickness is equal to the oxygen penetration depth, and a lower, but much thicker anoxic layer. The sediments are separated from the overlying water column by a relatively thin boundary layer through which mass transfer is diffusion controlled. Transient solutions are derived using the method of Laplace transform and Green’s function, which relate pore-water concentrations of the constituents to their concentrations in the bulk water and to the flux of decomposable settling organic matter. Steady-state pore-water concentrations are also obtained including expressions for the extent of methane saturation zone and methane gas flux. A relationship relating the sediment oxygen demand (SOD) to bulk water oxygen is derived using the two-film concept, which in combination with the depth-integrated solutions forms the basis for predicting the extent of oxygen penetration in the sediment. Iterative procedure and simplification thereof are proposed to estimate the extent of methane saturation zone and thickness of the aerobic layer as functions of time. Sensitivity of steady-state solutions to key parameters illustrates sediment processes interactions and synergistic effects. Simulations indicate that for a relatively thin diffusive boundary layer, d, oxygen uptake is limited by biochemical processes inside the sediments, whereas for a thick boundary layer oxygen transfer through the diffusive boundary layer is limiting. The results show an almost linear relationship between steady-state sediment oxygen demand and bulk water oxygen. For small d methane and nitrogen fluxes are sediment controlled, whereas for large d they are controlled by diffusional transfer through the boundary layer. It is shown that the two-layer model solution converges to the one-layer model (anaerobic layer) solution as the thickness of the oxygenated layer approaches zero, and that the transient solutions approach asymptotically their corresponding steady-state solutions.     

Biogeochemical processes controlling methane in gassy coastal sediments—Part 2: groundwater flow control of acoustic turbidity in Eckernförde Bay Sediments

To understand the origin of the methane distributions in sediments of Eckernförde Bay, three sites were sampled in May 1994 for determination of methane, sulfate and chloride concentrations in the sediment porewaters. In much of the Bay, bubbles of biogenic methane gas within the sediments lead to widespread ‘acoustic turbidity’ seen in acoustic surveys, masking the sedimentary structure below the gassy horizon. Acoustic windows, where the gas does not appear to be present, occur in several locations in the Bay, often surrounded by acoustically turbid sediments. Pockmarks, shallow depressions in the sediment, are also found in Bay sediments and may show acoustic turbidity at even shallower depths below the interface than surrounding sediments. One site of each type was sampled in this study. The site probably representative of much of the bay below 20 m water depth, revealed methane saturated conditions by about 75 cm depth below the interface, confirming inferences from acoustic scattering data that free gas was present in the sediment. Above this, the methane concentration profile was concave-upward, indicative of methane oxidation in the overlying, sulfate-reducing sediments. These porewaters showed a slightly decreasing chlorinity with depth. At an acoustic window site, methane concentrations rose to a maximum at about 125 cm depth, but did not reach saturation. Below this depth they decreased in a concave-down pattern. Chloride concentrations decreased markedly with depth, indicative of vertical freshwater flow from below. The third site was a pockmark exhibiting very shallow acoustic turbidity at about 25 cm depth. Here methane concentrations rose to exceed saturation within 25 cm depth below the interface and the porewaters became almost fresh by 1.5 m depth, indicative of a stronger flow of freshwater from below. These groundwater flows have competing effects on the methane inventory. They help exclude sulfate from the sediment, allowing the earlier/shallower onset of methanogenesis, but they also aid loss of methane through advection. A diagenetic model that couples the biogeochemistry of sulfate and methane is used to explain the presence or absence of methane gas in these sediments in relation to the flow rate of fresh groundwater from below. Model results indicate that acoustic windows within otherwise acoustically turbid sediments of the bay are likely due to relatively higher rates of vertical advection of fresh groundwater. The gassy pockmark, however, with an even higher vertical advection rate, seems to require the input of additional reactive organic carbon to explain its vertical methane distribution.     

Sand veins and MISS from the Mesoproterozoic black shale (ca. 1.7 Ga) in North China: Implication for methane degassing from microbial mats

The Mesoproterozoic Chuanlinggou Formation (ca. 1.7 Ga) consists mainly of dark-gray to black shales that are widespread in the North China Platform. Abundant centimeter-scale sand veins are present within the shale layers of this unit, particularly in the middle part. Sand veins display ptygmatic shapes, perpendicular or with a high angle to bedding planes. They penetrate the black shale layers but are often terminated by thin, lenticular sandstone beds, forming small-scale ‘tepee-like’ structures. On bedding planes, sand veins are expressed as small ridges with 1–3 mm positive relief. Lack of polygonal shapes and their occurrence in thinly laminated, relatively deep-water shales preclude an origin from sand-filled desiccation cracks. Instead, their close association with microbially induced sedimentary structures (MISS) such as micro-wrinkles and gas blisters, putative bacterial fossils (possibly coccoidal cyanobacteria) and framboidal pyrites, suggests that they were formed by degassing of methane from microbial mat decay. Methane gas disrupted overlying sedimentary layers, creating fractures open to seawater. Fine-grained quartz sands, which were transported into the depositional environment by strong winds, filled the fractures. Sand-filled fractures were shortened and folded during burial compaction, forming ptygmatic shapes. The presence of dispersed dolomite and siderite in these sand veins suggests authigenic carbonate precipitation from anaerobic oxidation of methane (AOM). Sand veins are intensely distributed within the Chuanlinggou Formation and are spatially widespread in the North China Platform. If their methane origin is confirmed, they may have important implications for the Mesoproterozoic paleoclimate. With anoxic oceans and low seawater sulfate concentration during the Mesoproterozoic, methane release from microbial mat decay and/or microbial methanogenesis during shallow burial may have been proportionally higher than that of the modern marine environments, with resultant increase in the relative importance of methane in maintaining the Mesoproterozoic greenhouse climate.     

Oxidation of fugitive methane in ground water linked to bacterial sulfate reduction

When fugitive methane migrates upward along boreholes of oil and gas wells, it may migrate into shallow ground water or pass through overlying soil to the atmosphere. Prior to this study, there was little information on the fate of fugitive methane that migrates into ground water. In a field study near Lloydminster, Alberta, Canada, we found hydrogeochemical evidence that fugitive methane from an oil well migrated into a shallow aquifer but has been attenuated by dissimilatory bacterial sulfate reduction at low temperature ( approximately 5 degrees C) under anaerobic conditions. Evidence includes spatial and temporal trends in concentrations of methane and sulfate in ground water and associated trends in concentrations of bicarbonate and sulfide. Within 10 m of the oil well, sulfate concentrations were low, and sulfate was enriched in both 34S and 18O. Sulfate concentrations had a strong positive correlation with delta13C values of bicarbonate, and sulfide was depleted in 34S compared to sulfate. These data indicate that bacterial sulfate reduction occurred near the production well. Near the oil well, elevated concentrations of bicarbonate were observed, and the bicarbonate was depleted in 13C. Modeling indicates that the main source of this excess 13C-depleted bicarbonate is oxidized methane. In concert with the sulfate concentration and isotope data, these results support an interpretation that in situ bacterial oxidation of methane has occurred, linked to bacterial sulfate reduction. Bacterial sulfate reduction may play a major role in bioattenuation of fugitive natural gas in ground water in western Canada.     

Methane in the hyporheic zone of a small lowland stream (Sitka, Czech Republic)

Methane concentrations and selected chemical parameters in interstitial water were examined along subsurface flowpath in two subsystems (hyporheic and parafluvial sediments) in the Sitka stream, Czech Republic. Interstitial methane concentrations exhibited a distinct spatial pattern. In the hyporheic downwelling zone where the sediments are relatively well oxygenated due to high hydrologic exchange with the surface water, low interstitial methane concentrations, averaging 9.3 μg CH₄/l, were found. In contrast, upwelling sediments and parafluvial sediments (active channel sediments lateral to the wetted channel) had significantly higher methane concentrations (p < 0.05, and p < 0.01, respectively), averaging 43.2 μg CH₄/l and 160.5 μg CH₄/l, respectively. Dissolved oxygen was the highest where surface water entered hyporheic/parafluvial sediments and decreased with water residence time in the sediments (p < 0.01). Nitrate concentrations decreased along the flowpath and were significantly lower at downstream end of the riffle (p < 0.001). Sulfate concentrations also show a slight decline with the water residence time, but differences were not significant. Effect of both nitrate and sulfate on methanogenesis is also discussed. The interstitial methane concentration significantly increased with surface water temperature (p < 0.001) and was negatively correlated with redox potential (p < 0.01) and dissolved oxygen (p < 0.05).     

Sauerstoffzehrungsraten von Profundalsediment des Bodensee-Obersees unter oxischen und anoxischen Bedingungen

Oxygen uptake rates by the sediment have been determined in a natural stratified sediment-water system from Lake Constance (Obersee, max. depth). After oxic preconditioning of the system the uptake rates ranged between 855 and 1,062 mg·m^?2·d^?1; after anoxic preconditioning of the system they ranged between 3,405 and 3,794 mg·m^?2·d^?1. These data, and the electron activity buffer capacity and oxygen consumption intensity as found in Lake Constance profundal water, show that the oxic-anoxic transition will happen here at the earliest after 142 days (about 4.5 months) of total oxygen isolation. Reoxygenation requires at least 3.7 times higher O₂ input than supposed for a ‘normal’ winter circulation in Obersee.     

Impact of Heterogeneity on Oxygen Transfer in a Fluctuating Capillary Fringe

We performed quasi‐two‐dimensional flow through laboratory experiments to study the effect of a coarse‐material inclusion, located in the proximity of the water table, on flow and oxygen transfer in the capillary fringe. The experiments investigate different phases of mass transfer from the unsaturated zone to anoxic groundwater under both steady‐state and transient flow conditions, the latter obtained by fluctuating the water table. Monitoring of flow and transport in the different experimental phases was performed by visual inspection of the complex flow field using a dye tracer solution, measurement of oxygen profiles across the capillary fringe, and determination of oxygen fluxes in the effluent of the flow‐through chamber. Our results show significant effects of the coarse‐material inclusion on oxygen transfer during the different phases of the experiments. At steady state, the oxygen flux across the unsaturated/saturated interface was considerably enhanced due to flow focusing in the fully water‐saturated coarse‐material inclusion. During drainage, a zone of higher water saturation formed in the fine material overlying the coarse lens. The entrapped oxygen‐rich aqueous phase contributed to the total amount of oxygen supplied to the system when the water table was raised back to its initial level. In case of imbibition, pronounced air entrapment occurred in the coarse lens, causing oxygen to partition between the aqueous and gaseous phases. The oxygen mass supplied to the anoxic groundwater following the imbibition event was found to be remarkably higher (approximately seven times) in the heterogeneous system compared with a similar experiment performed in a homogeneous porous medium.     

Methane efflux from marine sediments in passive and active margins: Estimations from bioenergetic reaction–transport simulations

A simplified version of a kinetic–bioenergetic reaction model for anaerobic oxidation of methane (AOM) in marine sediments [Dale, A.W., Regnier, P., Van Cappellen, P., 2006. Bioenergetic controls on anaerobic oxidation of methane (AOM) in coastal marine sediments: a theoretical analysis. Am. J. Sci. 306, 246–294.] is used to assess the impact of transport processes on biomass distributions, AOM rates and methane release fluxes from the sea floor. The model explicitly represents the functional microbial groups and the kinetic and bioenergetic limitations of the microbial metabolic pathways involved in AOM. Model simulations illustrate the dominant control exerted by the transport regime on the activity and abundance of AOM communities. Upward fluid flow at active seep systems restricts AOM to a narrow subsurface reaction zone and sustains high rates of methane oxidation. In contrast, pore-water transport dominated by molecular diffusion leads to deeper and broader zones of AOM, characterized by much lower rates and biomasses. Under steady-state conditions, less than 1% of the upward dissolved methane flux reaches the water column, irrespective of the transport regime. However, a sudden increase in the advective flux of dissolved methane, for example as a result of the destabilization of methane hydrates, causes a transient efflux of methane from the sediment. The benthic efflux of dissolved methane is due to the slow growth kinetics of the AOM community and lasts on the order of 60 years. This time window is likely too short to allow for a significant escape of pore-water methane following a large scale gas hydrate dissolution event such as the one that may have accompanied the Paleocene/Eocene Thermal Maximum (PETM).     

A laboratory study of the biogeochemical cycling of Fe,Mn, Zn and Cu across the sediment-water interface of a productive lake

Laboratory incubation experiments were carried out on sediment cores collected from Esthwaite Water, U.K., during April 1987, when the sediments displayed a characteristic surface (1.5 to 2 cm) oxide floc. The experiments were undertaken at 10°C, in the dark, under variable redox and pH conditions for periods of ~ 720 h (30 d). In some cases, realistic amounts of decomposing lake algae were added to simulate the deposition of an algal bloom. Pore waters and overlying waters were obtained from the incubated sediment cores at various time intervals and the samples analysed for pH and dissolved Fe, Mn, Zn and Cu by AAS. The results demonstrated that trace metal concentrations at the sediment-water interface can show rapid, pulsed responses to episodic events associated with controlling factors such as algal deposition and mixing conditions. The variations in dissolved Fe and Mn concentrations could generally be explained by their well known redox behaviour. Appreciable loss of Mn from solution under conditions of well-developed anoxia was consistent with adsorption of Mn²⁺ by FeS. Cu and Zn were both rapidly (24 h) released into solution during incubation of sediment cores prior to the development of anoxia in the overlying waters. Their most likely sources were the reductive remobilization of Mn oxides and the decomposition of organic matter. The addition of decomposing algae to a series of cores resulted in even higher interfacial dissolved concentrations of Cu and Zn, probably through acting as a supplementary source of the metals and through increased oxide dissolution. Switching from anoxic to oxic conditions also rapidly increased dissolved Cu and Zn concentrations, possibly due to their release during the oxidation of metal sulphides. The enhanced releases of dissolved Cu and Zn were generally short-lived with removal being attributed to the formation of sulphides during anoxia and to adsorption by Fe and Mn oxides under oxic conditions.