Anoxia begets anoxia: A positive feedback to the deoxygenation of temperate lakes.

Declining oxygen concentrations in the deep waters of lakes worldwide pose a pressing environmental and societal challenge. Existing theory suggests that low deep-water dissolved oxygen (DO) concentrations could trigger a positive feedback through which anoxia (i.e., very low DO) during a given summer begets increasingly severe occurrences of anoxia in following summers. Specifically, anoxic conditions can promote nutrient release from sediments, thereby stimulating phytoplankton growth, and subsequent phytoplankton decomposition can fuel heterotrophic respiration, resulting in increased spatial extent and duration of anoxia. However, while the individual relationships in this feedback are well established, to our knowledge, there has not been a systematic analysis within or across lakes that simultaneously demonstrates all of the mechanisms necessary to produce a positive feedback that reinforces anoxia. Here, we compiled data from 656 widespread temperate lakes and reservoirs to analyze the proposed anoxia begets anoxia feedback. Lakes in the dataset span a broad range of surface area (1-126,909 ha), maximum depth (6-370 m), and morphometry, with a median time-series duration of 30 years at each lake. Using linear mixed models, we found support for each of the positive feedback relationships between anoxia, phosphorus concentrations, chlorophyll a concentrations, and oxygen demand across the 656-lake dataset. Likewise, we found further support for these relationships by analyzing time-series data from individual lakes. Our results indicate that the strength of these feedback relationships may vary with lake-specific characteristics: For example, we found that surface phosphorus concentrations were more positively associated with chlorophyll a in high-phosphorus lakes, and oxygen demand had a stronger influence on the extent of anoxia in deep lakes. Taken together, these results support the existence of a positive feedback that could magnify the effects of climate change and other anthropogenic pressures driving the development of anoxia in lakes around the world.

Longer duration of seasonal stratification contributes to widespread increases in lake hypoxia and anoxia.

The concentration of dissolved oxygen (DO) is an important attribute of aquatic ecosystems, influencing habitat, drinking water quality, biodiversity, nutrient biogeochemistry, and greenhouse gas emissions. While average summer DO concentrations are declining in lakes across the temperate zone, much remains unknown about seasonal factors contributing to deepwater DO losses. It is unclear whether declines are related to increasing rates of seasonal DO depletion or changes in seasonal stratification that limit re-oxygenation of deep waters. Furthermore, despite the presence of important biological and ecological DO thresholds, there has been no large-scale assessment of changes in the amount of habitat crossing these thresholds, limiting the ability to understand the consequences of observed DO losses. We used a dataset from >400 widely distributed lakes to identify the drivers of DO losses and quantify the frequency and volume of lake water crossing biologically and ecologically important threshold concentrations ranging from 5 to 0.5 mg/L. Our results show that while there were no consistent changes over time in seasonal DO depletion rates, over three-quarters of lakes exhibited an increase in the duration of stratification, providing more time for seasonal deepwater DO depletion to occur. As a result, most lakes have experienced summertime increases in the amount of water below all examined thresholds in deepwater DO concentration, with increases in the proportion of the water column below thresholds ranging between 0.9% and 1.7% per decade. In the 30-day period preceding the end of stratification, increases were greater at >2.2% per decade and >70% of analyzed lakes experienced increases in the amount of oxygen-depleted water. These results indicate ongoing climate-induced increases in the duration of stratification have already contributed to reduction of habitat for many species, likely increased internal nutrient loading, and otherwise altered lake chemistry. Future warming is likely to exacerbate these trends.

Reactivity, fate and functional roles of dissolved organic matter in anoxic inland waters.

The transit of organic matter (OM) through the aquatic compartment of its global cycle has been intensively studied, traditionally with a focus on the processing and degradation of its dissolved fraction (dissolved organic matter, DOM). Because this is so intimately related to oxidation, the notion tenaciously persists that where oxygen is absent, DOM turnover is markedly slowed. In this Opinion Piece, we outline how diverse processes shape, transform and degrade DOM also in anoxic aquatic environments, and we focus here on inland waters as a particular case study. A suite of biogeochemical DOM functions that have received comparatively little attention may only be expressed in anoxic conditions and may result in enhanced biogeochemical roles of these deoxygenated habitats on a network scale.

Oxidation of Reduced Peat Particulate Organic Matter by Dissolved Oxygen: Quantification of Apparent Rate Constants in the Field.

Peat particulate organic matter (POM) is an important terminal electron acceptor for anaerobic respiration in northern peatlands provided that the electron-accepting capacity of POM is periodically restored by oxidation with O2 during peat oxygenation events. We employed push-pull tests with dissolved O2 as reactant to determine pseudo-first-order rate constants of O2 consumption ( kobs) in anoxic peat soil of an unperturbed Swedish ombrotrophic bog. Dissolved O2 was rapidly consumed in anoxic peat with a mean kobs of 2.91 ± 0.60 h-1, corresponding to an O2 half-life of ∼14 min. POM dominated O2 consumption, as evidenced from approximately 50-fold smaller kobs in POM-free control tests. Inhibiting microbial activity with formaldehyde did not appreciably slow O2 consumption, supporting abiotic O2 reduction by POM moieties, not aerobic respiration, as the primary route of O2 consumption. Peat preoxygenation with dissolved O2 lowered kobs in subsequent oxygen consumption tests, consistent with depletion of reduced moieties in POM. Finally, repeated oxygen consumption tests demonstrated that anoxic peat POM has a high reduction capacity, in excess to 20 µmol electrons donated per gram POM. This work demonstrates rapid abiotic oxidation of reduced POM by O2, supporting that short-term oxygenation events can restore the capacity of POM to accept electrons from anaerobic respiration in temporarily anoxic parts of peatlands.

The chemical succession in anoxic lake waters as source of molecular diversity of organic matter.

The aquatic networks that connect soils with oceans receive each year 5.1 Pg of terrestrial carbon to transport, bury and process. Stagnant sections of aquatic networks often become anoxic. Mineral surfaces attract specific components of organic carbon, which are released under anoxic conditions to the pool of dissolved organic matter (DOM). The impact of the anoxic release on DOM molecular composition and reactivity in inland waters is unknown. Here, we report concurrent release of iron and DOM in anoxic bottom waters of northern lakes, removing DOM from the protection of iron oxides and remobilizing previously buried carbon to the water column. The deprotected DOM appears to be highly reactive, terrestrially derived and molecularly distinct, generating an ambient DOM pool that relieves energetic constraints that are often assumed to limit carbon turnover in anoxic waters. The Fe-to-C stoichiometry during anoxic mobilization differs from that after oxic precipitation, suggesting that up to 21% of buried OM escapes a lake-internal release-precipitation cycle, and can instead be exported downstream. Although anoxic habitats are transient and comprise relatively small volumes of water on the landscape scale, our results show that they may play a major role in structuring the reactivity and molecular composition of DOM transiting through aquatic networks and reaching the oceans.

Intermittent meromixis controls the trophic state of warming deep lakes.

Vertical mixing modulates nutrient dynamics in lakes. However, surface warming reduces the range of vertical mixing and the probability of full circulation events. Important consequences of reduced vertical mixing include the sequestration of phosphorus (P) within a stagnant zone and the promotion of oligotrophication. Nevertheless, warming-induced shifts from full to partial mixing (meromixis) are not permanent and are partially reversible during exceptionally cold or windy winters. In this study, we investigated how intermittent meromixis affects lake P budgets. We examined the P cycle of a perialpine lake with variable mixing depths by pairing sedimentation and release flux measurements with sedimentary archives. We found that the amount of dissolved P surpassed that of the potentially mobile P in the sediments by a 13:1 ratio. At least 55% of the settled P was rapidly released to bottom waters isolated from flushing, illustrating the general biogeochemical mechanism that promotes deep-water P storage when lakes undergo warming. This storage process is abruptly inverted when meromixis suddenly retreats, deeper mixing introduces P pulses to the surface waters, thereby promoting phytoplankton proliferation. Our estimates showed that lakes containing up to 40% of the global freshwater volume could shift towards intermittent meromixis if the atmospheric warming trend continues. Thus, these lakes might accumulate 0-83% of their P load in irregularly circulating waters and are prone to large P pulses.

Extracellular Electron Transfer May Be an Overlooked Contribution to Pelagic Respiration in Humic-Rich Freshwater Lakes.

Humic lakes and ponds receive large amounts of terrestrial carbon and are important components of the global carbon cycle, yet how their redox cycling influences the carbon budget is not fully understood. Here we compared metagenomes obtained from a humic bog and a clear-water eutrophic lake and found a much larger number of genes that might be involved in extracellular electron transfer (EET) for iron redox reactions and humic substance (HS) reduction in the bog than in the clear-water lake, consistent with the much higher iron and HS levels in the bog. These genes were particularly rich in the bog's anoxic hypolimnion and were found in diverse bacterial lineages, some of which are relatives of known iron oxidizers or iron-HS reducers. We hypothesize that HS may be a previously overlooked electron acceptor and that EET-enabled redox cycling may be important in pelagic respiration and greenhouse gas budget in humic-rich freshwater lakes.

Reduction-oxidation cycles of organic matter increase bacterial activity in the pelagic oxycline.

Dissolved organic matter (DOM) in aquatic ecosystems contains redox-active moieties, which are prone to oxidation and reduction reactions. Oxidized moieties feature reduction potentials Eh , so that the moieties may be used as terminal electron acceptors (TEAs) in microbial respiration with a thermodynamic energy yield between nitrate and sulfate reduction. Here, we study the response of pelagic freshwater bacteria to exposure to native DOM with varying availabilities of oxidized moieties and hence redox state. Our results show that the prevalence of oxidized DOM favors microbial production and growth in anoxic waters. Reduced DOM in stratified lakes may be oxidized when fluctuations of the oxycline expose DOM in previously anoxic water to epilimnetic oxygen. The resulting oxidized DOM may be rapidly used as TEAs in microbial respiration during subsequent periods of anoxia. We further investigate if the prevalence of these organic electron sinks in anaerobic incubations can induce changes in the microbial community. Our results reveal that DOM traversing transient redox interfaces selects for species that profit from such spatially confined and cyclically restored TEA reservoirs.