Experimental Ecosystem Eutrophication Causes Offsetting Effects on Emissions of CO2, CH4, and N2O from Agricultural Reservoirs.

Despite decades of research and management efforts, eutrophication remains a persistent threat to inland waters. As nutrient pollution intensifies in the coming decades, the implications for aquatic greenhouse gas (GHG) emissions are poorly defined, particularly the responses of individual GHGs: carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O). The biogeochemical controls of each gas can differ, making it difficult to predict the overall effect of nutrient pollution on the net radiative forcing of aquatic ecosystems. Here, we induced eutrophication of small nitrogen (N)-limited agricultural reservoirs and measured changes in diffusive GHG emissions within a before-after-control-impact (BACI) study design during June to September 2021. Each gas exhibited a unique response to 300% increases in primary production, with a shift from an overall CO2 source to a sink, a modest increase in N2O flux, and, unexpectedly, no significant change in CH4 emissions. The lack of net directional change in CO2-equivalent GHG emissions in fertilized reservoirs during the summer contrasts findings from empirical studies of eutrophic lakes. Our findings illustrate the difficulty in extrapolating among different sized ecosystems and suggest that forecast 2-fold increases in agricultural N fertilization by 2050 may not result in consistently elevated GHG emissions during summer, at least from small reservoirs in continental grassland regions.

Dominance of net autotrophy in arid landscape low relief polar lakes, Nunavut, Canada.

The Arctic is the fastest warming biome on the planet, and environmental changes are having striking effects on freshwater ecosystems that may impact the regional carbon cycle. The metabolic state of Arctic lakes is often considered net heterotrophic, due to an assumed supply of allochthonous organic matter that supports ecosystem respiration and carbon mineralization in excess of rates of primary production. However, lake metabolic patterns vary according to regional climatic characteristics, hydrological connectivity, organic matter sources and intrinsic lake properties, and the metabolism of most Arctic lakes is unknown. We sampled 35 waterbodies along a connectivity gradient from headwater to downstream lakes, on southern Victoria Island, Nunavut, in an area characterized by low precipitation, organic-poor soils, and high evaporation rates. We evaluated whether lakes were net autotrophic or heterotrophic during the open water period using an oxygen isotopic mass balance approach. Most of the waterbodies were autotrophic and sites of net organic matter production or close to metabolic equilibrium. Autotrophy was associated with higher benthic primary production, as compared to its pelagic counterpart, due to the high irradiance reaching the bottom and efficient internal carbon and nutrient cycling. Highly connected midstream and downstream lakes showed efficient organic matter cycling, as evidenced by the strong coupling between gross primary production (GPP) and ecosystem respiration, while decoupling was observed in some headwater lakes with significantly higher GPP. The shallow nature of lakes in the flat, arid region of southern Victoria Island supports net autotrophy in most lakes during the open water season. Ongoing climate changes that lengthen the ice-free irradiance period and increase rates of nutrient evapoconcentration may further promote net autotrophy, with uncertain long-term effects for lake functioning.

Salinity causes widespread restriction of methane emissions from small inland waters.

Inland waters are one of the largest natural sources of methane (CH4), a potent greenhouse gas, but emissions models and estimates were developed for solute-poor ecosystems and may not apply to salt-rich inland waters. Here we combine field surveys and eddy covariance measurements to show that salinity constrains microbial CH4 cycling through complex mechanisms, restricting aquatic emissions from one of the largest global hardwater regions (the Canadian Prairies). Existing models overestimated CH4 emissions from ponds and wetlands by up to several orders of magnitude, with discrepancies linked to salinity. While not significant for rivers and larger lakes, salinity interacted with organic matter availability to shape CH4 patterns in small lentic habitats. We estimate that excluding salinity leads to overestimation of emissions from small Canadian Prairie waterbodies by at least 81% ( ~ 1 Tg yr-1 CO2 equivalent), a quantity comparable to other major national emissions sources. Our findings are consistent with patterns in other hardwater landscapes, likely leading to an overestimation of global lentic CH4 emissions. Widespread salinization of inland waters may impact CH4 cycling and should be considered in future projections of aquatic emissions.

Practical Guide to Measuring Wetland Carbon Pools and Fluxes.

Wetlands cover a small portion of the world, but have disproportionate influence on global carbon (C) sequestration, carbon dioxide and methane emissions, and aquatic C fluxes. However, the underlying biogeochemical processes that affect wetland C pools and fluxes are complex and dynamic, making measurements of wetland C challenging. Over decades of research, many observational, experimental, and analytical approaches have been developed to understand and quantify pools and fluxes of wetland C. Sampling approaches range in their representation of wetland C from short to long timeframes and local to landscape spatial scales. This review summarizes common and cutting-edge methodological approaches for quantifying wetland C pools and fluxes. We first define each of the major C pools and fluxes and provide rationale for their importance to wetland C dynamics. For each approach, we clarify what component of wetland C is measured and its spatial and temporal representativeness and constraints. We describe practical considerations for each approach, such as where and when an approach is typically used, who can conduct the measurements (expertise, training requirements), and how approaches are conducted, including considerations on equipment complexity and costs. Finally, we review key covariates and ancillary measurements that enhance the interpretation of findings and facilitate model development. The protocols that we describe to measure soil, water, vegetation, and gases are also relevant for related disciplines such as ecology. Improved quality and consistency of data collection and reporting across studies will help reduce global uncertainties and develop management strategies to use wetlands as nature-based climate solutions. Supplementary Information: The online version contains supplementary material available at 10.1007/s13157-023-01722-2.

Carbonate chemistry and carbon sequestration driven by inorganic carbon outwelling from mangroves and saltmarshes.

Mangroves and saltmarshes are biogeochemical hotspots storing carbon in sediments and in the ocean following lateral carbon export (outwelling). Coastal seawater pH is modified by both uptake of anthropogenic carbon dioxide and natural biogeochemical processes, e.g., wetland inputs. Here, we investigate how mangroves and saltmarshes influence coastal carbonate chemistry and quantify the contribution of alkalinity and dissolved inorganic carbon (DIC) outwelling to blue carbon budgets. Observations from 45 mangroves and 16 saltmarshes worldwide revealed that >70% of intertidal wetlands export more DIC than alkalinity, potentially decreasing the pH of coastal waters. Porewater-derived DIC outwelling (81 ± 47 mmol m-2 d-1 in mangroves and 57 ± 104 mmol m-2 d-1 in saltmarshes) was the major term in blue carbon budgets. However, substantial amounts of fixed carbon remain unaccounted for. Concurrently, alkalinity outwelling was similar or higher than sediment carbon burial and is therefore a significant but often overlooked carbon sequestration mechanism.

Heterotrophic aquatic metabolism and sustained carbon dioxide emissions in a mineral-soil wetland restored with treated effluent.

Wetlands are economically valuable ecosystems, in part because they purify wastewater by retaining and processing nutrients, organic matter (OM), and other pollutants. While natural wetlands are highly productive and sequester large pools of carbon (C), it is unclear whether the C cycle of restored treatment wetlands is functionally consistent with natural systems. This knowledge gap limits our appreciation for the role that wetland restoration can play as a natural solution to climate change. Here, we quantified metabolic and C cycling patterns of a restored, multi-basin wetland (Frank Lake, Alberta, Canada) receiving municipal and beef processing plant effluents rich in nutrients and OM. We conducted metabolic measurements in all three basins using dissolved oxygen sensors deployed under ice and in open water. Extreme production and respiration indicated that effluent was largely mineralized and replaced with wetland OM in transit. The heterotrophic status of all basins aligned with a published mass budget demonstrating the aquatic habitat of the wetland was an OM sink under current drought conditions that lengthen effluent processing time. Floating chamber measurements in open water zones confirmed that the wetland was a source of CO2 to the atmosphere. From input to outflow, sustained emissions led to declining pCO2 and a decline in the ratio of dissolved inorganic to organic C. Over 30 years post-restoration, the open water habitats in Frank Lake remain heterotrophic and a net source of CO2, suggesting that the trajectory of aquatic C cycling may be distinct from wetlands restored with non-effluent water sources.

Organic matter cycling in a model restored wetland receiving complex effluent.

Wetlands have been used to treat anthropogenic effluents for decades due to their intense biogeochemical processes that transform and uptake nutrients, organic matter, and toxins. Despite these known functions, we lack generalizable knowledge of effluent-derived dissolved organic matter (DOM) cycling in wetlands. Here, we quantify the cycling of DOM in one of Canada's more economically important wetland complexes (Frank Lake, Alberta), restored to hydrologic permanence in the 1980s using urban and agro-industrial effluents. Optical analyses and PARAFAC (parallel factor analysis) modelling showed a clear compositional change from more bioavailable and protein-like DOM at effluent input sites to more aromatic and humic-like at the wetland outflow, likely due to DOM processing and inputs from marsh plants and wetland soils. Microbial incubations showed that effluent DOM was rapidly consumed, with the half-life of DOM increasing from as low as 35 days for effluent, to 462 days at the outflow, as a function of compositional shifts toward aromatic, humic-like material. Long-term averaged dissolved organic carbon (DOC) export was low compared to many wetlands (10.3 ± 2.0 g C m-2 yr-1). Consistent with predictions based on water residence time, our mass balance showed Frank Lake was a net source of DOM across all measured years, but shifted from a source to sink among wet and drought years that respectively shortened or lengthened the water residence and DOM processing times. Overall, Frank Lake processes and transforms effluent DOM, despite being a longer-term net source of DOM to downstream environments. Supplementary Information: The online version contains supplementary material available at 10.1007/s10533-022-01002-x.

CO2 dynamics in a small and old subtropical reservoir in East Asia: Environmental controls driving seasonal and spatial variability.

Inland waters have been increasingly viewed as hotspots for greenhouse gas (GHG) emissions owing to their strong capability to intercept and mineralize carbon from the terrestrial environment. Although small waterbodies in humid subtropical climates have the potential to emit considerable amounts of GHG, their emission patterns have remained understudied. This study involved intensive measurements of carbon dioxide (CO2) emissions from a small reservoir and its upstream and downstream reaches located in subtropical Hong Kong. Our results revealed that a variety of metabolic, hydrological, and hydrochemical processes play a critical role in regulating its CO2 dynamics. The reservoir was an overall source of CO2 to the atmosphere with an average areal flux of 24.6 mmol m-2 d-1, and it occasionally functioned as a sink for atmospheric CO2 under intense solar radiation when primary productivity was high. This flux is on the low side relative to that of global (sub)tropical reservoirs, which was likely attributable to the prolonged history of the reservoir (>150 years) and the occasional undersaturation of CO2 in the water column. We also noticed pronounced differences in the underlying controls of CO2 dynamics between the reservoir and its upstream and downstream reaches, emphasizing the importance of taking into account the distinct characteristics of both lentic and lotic waters when evaluating catchment-scale CO2 fluxes.

Microbial Ecology of Methanotrophy in Streams Along a Gradient of CH4 Availability.

Despite the recognition of streams and rivers as sources of methane (CH4) to the atmosphere, the role of CH4 oxidation (MOX) in these ecosystems remains poorly understood to date. Here, we measured the kinetics of MOX in stream sediments of 14 sites to resolve the ecophysiology of CH4 oxidizing bacteria (MOB) communities. The streams cover a gradient of land cover and associated physicochemical parameter and differed in stream- and porewater CH4 concentrations. Michealis-Menten kinetic parameter of MOX, maximum reaction velocity (V max ), and CH4 concentration at half V max (K S ) increased with CH4 supply. K S values in the micromolar range matched the CH4 concentrations measured in shallow stream sediments and indicate that MOX is mostly driven by low-affinity MOB. 16S rRNA gene sequencing identified MOB classified as Methylococcaceae and particularly Crenothrix. Their relative abundance correlated with pmoA gene counts and MOX rates, underscoring their pivotal role as CH4 oxidizers in stream sediments. Building on the concept of enterotypes, we identify two distinct groups of co-occurring MOB. While there was no taxonomic difference among the members of each cluster, one cluster contained abundant and common MOB, whereas the other cluster contained rare operational taxonomic units (OTUs) specific to a subset of streams. These integrated analyses of changes in MOB community structure, gene abundance, and the corresponding ecosystem process contribute to a better understanding of the distal controls on MOX in streams.

Comment on "On the calculation of lake metabolic rates: Diel O2 and 18/16O technique" by Peeters et al. [Water Res. 165 2019, 114990].

Quantifying metabolic rates in lakes and other aquatic ecosystems is a complex task, as methods are continually evolving and are not currently standardized. Recently, Peeters et al. presented a valuable simulated dataset that advances the field by comparing the strengths and limitations of individual and combined metabolic techniques. The authors conclude that calculating metabolic rates from point sampling and mass balancing of surface water oxygen concentration and isotope composition is flawed, because the technique does not capture sub-daily patterns of metabolic variability, which they argue invalidates past applications and interpretations. These conclusions are inconsistent with how the method has been used, and are based on a biased construction of scenarios and interpretation of model results, especially because their parameterization of the stable isotopic model employs input values that appear unrepresentative of most lake conditions. Here, we establish that 1) empirical evidence supports the isotopic approach's suitability to approximate daily or longer metabolic patterns in most lakes. 2) The authors' own simulations show agreement between metabolic estimates from point isotopic measurements and average metabolic rates under most scenarios. 3) The authors' invalidation of isotopic measurements are based on the most extreme model deviations observed in simulated hypereutrophic environments. While we welcome a critical evaluation of the isotopic approach, we argue that isotopic model uncertainty needs to be placed within an appropriate context. We emphasize that isotopic sampling and steady state metabolic modelling has a key role to play in constraining metabolic patterns in the global lake landscape, but that the research questions addressed with the method need to be commensurate with the limitations and uncertainties of the approach.

Unabated Nitrogen Pollution Favors Growth of Toxic Cyanobacteria over Chlorophytes in Most Hypereutrophic Lakes.

Human release of reactive nitrogen (N) to the environment has increased 10-fold since 1860 and is expected to increase by a further ∼75% by 2050. Much of this N enters phosphorus (P)-rich, eutrophic lakes in agricultural and urbanized watersheds. While N pollution of eutrophic lakes can promote toxic cyanobacterial growth, some cases of extreme N loading have led to the dominance of chlorophytes (green algae). As N loads required to shift communities from cyanobacterial to chlorophyte dominance are unclear, we experimentally tested phytoplankton responses to a gradient of N loading in a P-rich lake. Low-to-moderate doses (1-3 mg N L-1 week-1) promoted toxic cyanobacterial dominance and elevated concentrations of the hepatotoxin microcystin. Conversely, loads characteristic of pure urban or agricultural effluents (up to 18 mg N L-1 week-1) led to the dominance of chlorophytes over cyanobacteria and lower microcystin content. This indicates that N loads needed to sustain chlorophyte dominance are uncommon, likely restricted to select shallow lakes directly exposed to urban or agricultural effluents. As most N pollution regimes in P-rich lakes will favor toxic cyanobacterial dominance, restricting future N pollution will help curb further cyanobacterial dominance in lakes both directly and by constraining the capacity for future P loading and climate warming to drive cyanobacterial growth.

Effects of experimental nitrogen fertilization on planktonic metabolism and CO2 flux in a hypereutrophic hardwater lake.

Hardwater lakes are common in human-dominated regions of the world and often experience pollution due to agricultural and urban effluent inputs of inorganic and organic nitrogen (N). Although these lakes are landscape hotspots for CO2 exchange and food web carbon (C) cycling, the effect of N enrichment on hardwater lake food web functioning and C cycling patterns remains unclear. Specifically, it is unknown if different eutrophication scenarios (e.g., modest non point vs. extreme point sources) yield consistent effects on auto- and heterotrophic C cycling, or how biotic responses interact with the inorganic C system to shape responses of air-water CO2 exchange. To address this uncertainty, we induced large metabolic gradients in the plankton community of a hypereutrophic hardwater Canadian prairie lake by adding N as urea (the most widely applied agricultural fertilizer) at loading rates of 0, 1, 3, 8 or 18 mg N L-1 week-1 to 3240-L, in-situ mesocosms. Over three separate 21-day experiments, all treatments of N dramatically increased phytoplankton biomass and gross primary production (GPP) two- to six-fold, but the effects of N on autotrophs plateaued at ~3 mg N L-1. Conversely, heterotrophic metabolism increased linearly with N fertilization over the full treatment range. In nearly all cases, N enhanced net planktonic uptake of dissolved inorganic carbon (DIC), and increased the rate of CO2 influx, while planktonic heterotrophy and CO2 production only occurred in the highest N treatments late in each experiment, and even in these cases, enclosures continued to in-gas CO2. Chemical effects on CO2 through calcite precipitation were also observed, but similarly did not change the direction of net CO2 flux. Taken together, these results demonstrate that atmospheric exchange of CO2 in eutrophic hardwater lakes remains sensitive to increasing N loading and eutrophication, and that even modest levels of N pollution are capable of enhancing autotrophy and CO2 in-gassing in P-rich lake ecosystems.

Surface water CO2 concentration influences phytoplankton production but not community composition across boreal lakes.

Recent experimental evidence suggests that changes in the partial pressure of CO2 (pCO2 ), in concert with nutrient fertilisation, may result in increased primary production and shifted phytoplankton community composition that favours species lacking adaptations to low CO2 environments. It is not clear whether these results apply in ambient freshwaters, which are already often supersaturated in CO2 , and where phytoplankton structure and activity are under complex control of diverse local and regional factors. Here, we use a large-scale comparative study of 69 boreal lakes to explore the influence of existing CO2 gradients (c. 50-2300 µatm) on phytoplankton community composition and biomass production. While community composition did not respond to pCO2 gradients, gross primary production was enhanced, but only in lakes already supersaturated in CO2 , demonstrating that environmental context is key in determining pCO2 -phytoplankton interactions. We further argue that increased atmospheric CO2 is unlikely to influence phytoplanktonic composition and production in northern lakes.

Decrease in CO2 efflux from northern hardwater lakes with increasing atmospheric warming.

Boreal lakes are biogeochemical hotspots that alter carbon fluxes by sequestering particulate organic carbon in sediments and by oxidizing terrestrial dissolved organic matter to carbon dioxide (CO2) or methane through microbial processes. At present, such dilute lakes release ∼1.4 petagrams of carbon annually to the atmosphere, and this carbon efflux may increase in the future in response to elevated temperatures and increased hydrological delivery of mineralizable dissolved organic matter to lakes. Much less is known about the potential effects of climate changes on carbon fluxes from carbonate-rich hardwater and saline lakes that account for about 20 per cent of inland water surface area. Here we show that atmospheric warming may reduce CO2 emissions from hardwater lakes. We analyse decadal records of meteorological variability, CO2 fluxes and water chemistry to investigate the processes affecting variations in pH and carbon exchange in hydrologically diverse lakes of central North America. We find that the lakes have shifted progressively from being substantial CO2 sources in the mid-1990s to sequestering CO2 by 2010, with a steady increase in annual mean pH. We attribute the observed changes in pH and CO2 uptake to an atmospheric-warming-induced decline in ice cover in spring that decreases CO2 accumulation under ice, increases spring and summer pH, and enhances the chemical uptake of CO2 in hardwater lakes. Our study suggests that rising temperatures do not invariably increase CO2 emissions from aquatic ecosystems.

Oxic water column methanogenesis as a major component of aquatic CH4 fluxes.

Methanogenesis has traditionally been assumed to occur only in anoxic environments, yet there is mounting, albeit indirect, evidence of methane (CH4) production in oxic marine and freshwaters. Here we present the first direct, ecosystem-scale demonstration of methanogenesis in oxic lake waters. This methanogenesis appears to be driven by acetoclastic production, and is closely linked to algal dynamics. We show that oxic water methanogenesis is a significant component of the overall CH4 budget in a small, shallow lake, and provide evidence that this pathway may be the main CH4 source in large, deep lakes and open oceans. Our results challenge the current global understanding of aquatic CH4 dynamics, and suggest a hitherto unestablished link between pelagic CH4 emissions and surface-water primary production. This link may be particularly sensitive to widespread and increasing human influences on aquatic ecosystem primary productivity.

Phytoplankton-specific response to enrichment of phosphorus-rich surface waters with ammonium, nitrate, and urea.

Supply of anthropogenic nitrogen (N) to the biosphere has tripled since 1960; however, little is known of how in situ response to N fertilisation differs among phytoplankton, whether species response varies with the chemical form of N, or how interpretation of N effects is influenced by the method of analysis (microscopy, pigment biomarkers). To address these issues, we conducted two 21-day in situ mesocosm (3140 L) experiments to quantify the species- and genus-specific responses of phytoplankton to fertilisation of P-rich lake waters with ammonium (NH(4)(+)), nitrate (NO(3)(-)), and urea ([NH(2)](2)CO). Phytoplankton abundance was estimated using both microscopic enumeration of cell densities and high performance liquid chromatographic (HPLC) analysis of algal pigments. We found that total algal biomass increased 200% and 350% following fertilisation with NO(3)(-) and chemically-reduced N (NH(4)(+), urea), respectively, although 144 individual taxa exhibited distinctive responses to N, including compound-specific stimulation (Planktothrix agardhii and NH(4)(+)), increased biomass with chemically-reduced N alone (Scenedesmus spp., Coelastrum astroideum) and no response (Aphanizomenon flos-aquae, Ceratium hirundinella). Principle components analyses (PCA) captured 53.2-69.9% of variation in experimental assemblages irrespective of the degree of taxonomic resolution of analysis. PCA of species-level data revealed that congeneric taxa exhibited common responses to fertilisation regimes (e.g., Microcystis aeruginosa, M. flos-aquae, M. botrys), whereas genera within the same division had widely divergent responses to added N (e.g., Anabaena, Planktothrix, Microcystis). Least-squares regression analysis demonstrated that changes in phytoplankton biomass determined by microscopy were correlated significantly (p<0.005) with variations in HPLC-derived concentrations of biomarker pigments (r(2) = 0.13-0.64) from all major algal groups, although HPLC tended to underestimate the relative abundance of cyanobacteria. Together, these findings show that while fertilisation of P-rich lakes with N can increase algal biomass, there is substantial variation in responses of genera and divisions to specific chemical forms of added N.

The effects of phosphorus additions on the sedimentation of contaminants in a uranium mine pit-lake.

We investigated the usefulness of phytoplankton for the removal of surface water contaminants. Nine large mesocosms (92.2m(3)) were suspended in the flooded DJX uranium pit at Cluff Lake (Saskatchewan, Canada), and filled with highly contaminated mine water. Each mesocosm was fertilized with a different amount of phosphorus throughout the 35 day experiment to stimulate phytoplankton growth, and to create a range in phosphorus load (g) to examine how contaminants may be affected by different nutrient regimes. Algal growth was rapid in fertilized mesocosms (as demonstrated by chlorophyll a profiles). As phosphorus loads increased there were significant declines (p<0.05) in the surface water concentrations of As, Co, Cu, Mn, Ni, and Zn. This decline was near significant for uranium (p=0.065). The surface water concentrations of Ra-226, Mo, and Se showed no relationship to phosphorus load. Contaminant concentrations in sediment traps suspended at the bottom of each mesocosm generally showed the opposite trend to that observed in the surface water, with most contaminants (As, Co, Cu, Mn, Ni, Ra-226, U, and Zn) exhibiting a significant positive relationship (p<0.05) with phosphorus load. Selenium and Mo did not respond to nutrient treatments. Our results suggest that phytoremediation has the potential to lower many surface water contaminants through the sedimentation of phytoplankton. Based on our results, we estimate that the Saskatchewan Surface Water Quality Objectives (SSWQO) for DJX pit would be met in approximately 45 weeks for Co, 65 weeks for Ni, 15 weeks for U, and 5 weeks for Zn.