Stable Fe isotopes have only recently been measured in freshwater systems, mainly in meromictic lakes. Here we report the δ56Fe of dissolved, particulate, and sediment Fe in two small dimictic boreal shield headwater lakes: manipulated eutrophic Lake 227, with annual cyanobacterial blooms, and unmanipulated oligotrophic Lake 442. Within the lakes, the range in δ56Fe is large (ca. -0.9 to +1.8‰), spanning more than half the entire range of natural Earth surface samples. Two layers in the water column with distinctive δ56Fe of dissolved (dis) and particulate (spm) Fe were observed, despite differences in trophic states. In the epilimnia of both lakes, a large Δ56Fedis-spm fractionation of 0.4-1‰ between dissolved and particulate Fe was only observed during cyanobacterial blooms in Lake 227, possibly regulated by selective biological uptake of isotopically light Fe by cyanobacteria. In the anoxic layers in both lakes, upward flux from sediments dominates the dissolved Fe pool with an apparent Δ56Fedis-spm fractionation of -2.2 to -0.6‰. Large Δ56Fedis-spm and previously published metagenome sequence data suggest active Fe cycling processes in anoxic layers, such as microaerophilic Fe(II) oxidation or photoferrotrophy, could regulate biogeochemical cycling. Large fractionation of stable Fe isotopes in these lakes provides a potential tool to probe Fe cycling and the acquisition of Fe by cyanobacteria, with relevance for understanding biogeochemical cycling of Earth's early ferruginous oceans.

Stable Fe isotopes have only recently been measured in freshwater systems, mainly in meromictic lakes. Here we report the δ56Fe of dissolved, particulate, and sediment Fe in two small dimictic boreal shield headwater lakes: manipulated eutrophic Lake 227, with annual cyanobacterial blooms, and unmanipulated oligotrophic Lake 442. Within the lakes, the range in δ56Fe is large (ca. -0.9 to +1.8‰), spanning more than half the entire range of natural Earth surface samples. Two layers in the water column with distinctive δ56Fe of dissolved (dis) and particulate (spm) Fe were observed, despite differences in trophic states. In the epilimnia of both lakes, a large Δ56Fedis-spm fractionation of 0.4-1‰ between dissolved and particulate Fe was only observed during cyanobacterial blooms in Lake 227, possibly regulated by selective biological uptake of isotopically light Fe by cyanobacteria. In the anoxic layers in both lakes, upward flux from sediments dominates the dissolved Fe pool with an apparent Δ56Fedis-spm fractionation of -2.2 to -0.6‰. Large Δ56Fedis-spm and previously published metagenome sequence data suggest active Fe cycling processes in anoxic layers, such as microaerophilic Fe(II) oxidation or photoferrotrophy, could regulate biogeochemical cycling. Large fractionation of stable Fe isotopes in these lakes provides a potential tool to probe Fe cycling and the acquisition of Fe by cyanobacteria, with relevance for understanding biogeochemical cycling of Earth's early ferruginous oceans.

Monod growth kinetics predictions of competition outcomes between freshwater cyanobacteria and chlorophytes at low iron (Fe) was tested with dual-species competition experiments. Fe threshold concentrations (FeT) below which growth ceases and growth affinities (slope of Fe concentration vs growth rate near FeT) for three large-bodied cyanobacteria and two chlorophytes in batch cultures showed that cyanobacteria are more efficient at acquiring Fe and predicted that cyanobacteria will dominate chlorophytes at low Fe, similar to an earlier study where cyanobacteria were more efficient at acquiring phosphorus (P) at low P. The prediction of cyanobacteria dominance at low Fe was borne out in serial dilution competition experiments between a pico-cyanobacteria and a third chlorophyte. These results show that Monod kinetics can successfully predict competition outcomes between cyanobacteria and eukaryotic algae in a laboratory setting at low Fe. However, while nutrient acquisition and growth kinetics are clearly important, other factors also influence competition between pico-cyanobacteria, large-bodied cyanobacteria, and eukaryotic algae in natural systems. These factors include the effect of cell surface area/volume ratio on cellular nutrient supply rates, cyanobacteria dependence on membrane transport of Fe+2, Fe+2 supply from anaerobic sediments, buoyancy regulation, and intensive grazing of pico-cyanobacteria.

Stable Fe isotopes have only recently been measured in freshwater systems, mainly in meromictic lakes. Here we report the δ56Fe of dissolved, particulate, and sediment Fe in two small dimictic boreal shield headwater lakes: manipulated eutrophic Lake 227, with annual cyanobacterial blooms, and unmanipulated oligotrophic Lake 442. Within the lakes, the range in δ56Fe is large (ca. -0.9 to +1.8‰), spanning more than half the entire range of natural Earth surface samples. Two layers in the water column with distinctive δ56Fe of dissolved (dis) and particulate (spm) Fe were observed, despite differences in trophic states. In the epilimnia of both lakes, a large Δ56Fedis-spm fractionation of 0.4-1‰ between dissolved and particulate Fe was only observed during cyanobacterial blooms in Lake 227, possibly regulated by selective biological uptake of isotopically light Fe by cyanobacteria. In the anoxic layers in both lakes, upward flux from sediments dominates the dissolved Fe pool with an apparent Δ56Fedis-spm fractionation of -2.2 to -0.6‰. Large Δ56Fedis-spm and previously published metagenome sequence data suggest active Fe cycling processes in anoxic layers, such as microaerophilic Fe(II) oxidation or photoferrotrophy, could regulate biogeochemical cycling. Large fractionation of stable Fe isotopes in these lakes provides a potential tool to probe Fe cycling and the acquisition of Fe by cyanobacteria, with relevance for understanding biogeochemical cycling of Earth's early ferruginous oceans.

Stable Fe isotopes have only recently been measured in freshwater systems, mainly in meromictic lakes. Here we report the δ56Fe of dissolved, particulate, and sediment Fe in two small dimictic boreal shield headwater lakes: manipulated eutrophic Lake 227, with annual cyanobacterial blooms, and unmanipulated oligotrophic Lake 442. Within the lakes, the range in δ56Fe is large (ca. -0.9 to +1.8‰), spanning more than half the entire range of natural Earth surface samples. Two layers in the water column with distinctive δ56Fe of dissolved (dis) and particulate (spm) Fe were observed, despite differences in trophic states. In the epilimnia of both lakes, a large Δ56Fedis-spm fractionation of 0.4-1‰ between dissolved and particulate Fe was only observed during cyanobacterial blooms in Lake 227, possibly regulated by selective biological uptake of isotopically light Fe by cyanobacteria. In the anoxic layers in both lakes, upward flux from sediments dominates the dissolved Fe pool with an apparent Δ56Fedis-spm fractionation of -2.2 to -0.6‰. Large Δ56Fedis-spm and previously published metagenome sequence data suggest active Fe cycling processes in anoxic layers, such as microaerophilic Fe(II) oxidation or photoferrotrophy, could regulate biogeochemical cycling. Large fractionation of stable Fe isotopes in these lakes provides a potential tool to probe Fe cycling and the acquisition of Fe by cyanobacteria, with relevance for understanding biogeochemical cycling of Earth's early ferruginous oceans.

Molot LA, Schiff SL, Venkiteswaran JJ, Baulch HM, Higgins SN, Zastepa A, Verschoor MJ, Walters D. 2021. Low sediment redox promotes cyanobacteria blooms across a trophic range: implications for man...

Abstract Two small, oligotrophic lakes at the IISD-Experimental Lakes Area in northwestern Ontario, Canada were fertilized weekly with only phosphorus (P) in the summer and early fall of 2019. The P fertilization rates were high enough (13.3 µ g l −1 added weekly) to produce dense, month-long blooms of N 2 -fixing Dolichospermum species in both lakes within 9–12 weeks after fertilization began, turning them visibly green without the addition of nitrogen. P-only fertilization increased average seasonal chlorophyll a concentrations and cyanobacteria biomass well above the pre-fertilization levels of 2017 and 2018. Nitrogen (N) content in the epilimnion of thermally stratified Lake 304 and the water column of shallow Lake 303 doubled and P storage in the water column temporarily increased during the blooms. These whole-lake fertilization experiments demonstrate that large cyanobacteria blooms can develop rapidly under high P loading without anthropogenic N inputs, suggesting that aggressive N control programs are unlikely to prevent bloom formation and that P controls should remain the cornerstone for cyanobacteria management.

Phytoplankton blooms are a global water quality issue, and successful management depends on understanding their responses to multiple and interacting drivers, including nutrient loading and climate change. Here, we examine a long-term dataset from Lake 227, a site subject to a fertilization experiment (1969–present) with changing nitrogen:phosphorus (N:P) ratios. We applied a process-oriented model, MyLake, and updated the model structure with nutrient uptake kinetics that incorporated shifting N:P and competition among phytoplankton functional groups. We also tested different temperature and P-loading scenarios to examine the interacting effects of climate change and nutrient loading on phytoplankton blooms. The model successfully reproduced lake physics over 48 yr and the timing, overall magnitude, and shifting community structure (diazotrophs vs. non-diazotrophs) of phytoplankton blooms. Intra- and interannual variability was captured more accurately for the P-only fertilization period than for the high N:P and low N:P fertilization periods, highlighting the difficulty of modeling complex blooms even in well-studied systems. A model scenario was also run which removed climate-driven temperature trends, allowing us to disentangle concurrent drivers of blooms. Results showed that increases in water temperature in the spring led to earlier and larger phytoplankton blooms under climate change than under the effects of nutrient fertilization alone. These findings suggest that successful lake management efforts should incorporate the effects of climate change in addition to nutrient reductions, including intensifying and/or expanding monitoring periods and incorporating climate change into uncertainty estimates around future conditions.

Dissolved organic matter (DOM) represents a mixture of organic molecules that vary due to different source materials and degree of processing. Characterizing how DOM composition evolves along the aquatic continuum can be difficult. Using a size‐exclusion chromatography technique (liquid chromatography‐organic carbon detection [LC‐OCD]), we assessed the variability in DOM composition from both surface and groundwaters across a number of Canadian ecozones (mean annual temperature spanning −10°C to +6°C). A wide range in DOM concentration was found from 0.2 to 120 mg C L−1. Proportions of different size‐based groupings across ecozones were variable, yet similarities between specific waterbody types, regardless of location, suggest commonality in the processes dictating DOM composition. A principal component analysis identified 70% of the variation in LC‐OCD derived DOM compositions could be explained by the waterbody type. We find that DOM composition within a specific waterbody type is similar regardless of the differences in climate or surrounding vegetation where the sample originated from.

Dissolved organic matter (DOM) is a ubiquitous component of aquatic systems, impacting aquatic health and drinking water quality. These impacts depend on the mixture of organic molecules that comprise DOM. Changing climates are altering both the amount and character of DOM being transported from the terrestrial system into adjacent surface waters, yet DOM composition is not monitored as often as overall concentration. Many DOM characterization methods exist, confounding comparison of DOM composition across different studies. The objective of this research is to determine which parameters in a suite of relatively simple and common DOM characterization techniques explain the most variability in DOM composition from surface and groundwater sites. Further, we create a simple visualization tool to easily compare compositional differences in DOM. A large number of water samples (n = 250) was analyzed from six Canadian ecozones for DOM concentration, ultraviolet-visible light absorbance, molecular size, and elemental ratios. Principal component analyses was used to identify quasi-independent DOM compositional parameters that explained the highest variability in the dataset: spectral slope, specific-UV absorbance at 255nm, humic substances fraction, and dissolved organic carbon to dissolved organic nitrogen ratio. A ‘Composition Wheel’ was created by plotting these four parameters as a polygon. Our results find similarities in DOM composition irrespective of site differences in vegetation and climate. Further, two main end-member Composition Wheel shapes were revealed that correspond to DOM in organic-rich groundwaters and DOM influenced by photodegradation. The Composition Wheel approach uses easily visualized differences in polygon shape to quantify how DOM evolves by natural processes along the aquatic continuum and to track sources and degradation of DOM.

Dissolved Organic Matter (DOM) represents a mixture of organic molecules that vary due to different source materials and degree of processing. Characterizing how DOM composition evolves along the aquatic continuum can be difficult. Using a size-exclusion chromatography technique (LC-OCD), we assessed the variability in DOM composition from both surface and groundwaters across a number of Canadian ecozones (mean annual temperature spanning -10 to +6 C). A wide range in DOM concentration was found from 0.2 to 120 mg C/L. Proportions of different size-based groupings across ecozones were variable, yet similarities between specific water-body types, regardless of location, suggest commonality in the processes dictating the evolution of DOM composition. A principal-component analysis identified 70% of the variation in LC-OCD derived DOM compositions could be explained by the water-body type. We find that water-body type has a greater influence on DOM composition than differences in climate or surrounding vegetation.

Aquatic environments with high levels of dissolved ferrous iron and low levels of sulfate serve as an important systems for exploring biogeochemical processes relevant to the early Earth. Boreal Shield lakes, which number in the tens of millions globally, commonly develop seasonally anoxic waters that become iron rich and sulfate poor, yet the iron-sulfur microbiology of these systems has been poorly examined. Here we use genome-resolved metagenomics and enrichment cultivation to explore the metabolic diversity and ecology of anoxygenic photosynthesis and iron/sulfur cycling in the anoxic water columns of three Boreal Shield lakes. We recovered four high-completeness and low-contamination draft genome bins assigned to the class Chlorobia (formerly phylum Chlorobi) from environmental metagenome data and enriched two novel sulfide-oxidizing species, also from the Chlorobia. The sequenced genomes of both enriched species, including the novel "Candidatus Chlorobium canadense", encoded the cyc2 gene that is associated with photoferrotrophy among cultured Chlorobia members, along with genes for phototrophic sulfide oxidation. One environmental genome bin also encoded cyc2. Despite the presence of cyc2 in the corresponding draft genome, we were unable to induce photoferrotrophy in "Ca. Chlorobium canadense". Genomic potential for phototrophic sulfide oxidation was more commonly detected than cyc2 among environmental genome bins of Chlorobia, and metagenome and cultivation data suggested the potential for cryptic sulfur cycling to fuel sulfide-based growth. Overall, our results provide an important basis for further probing the functional role of cyc2 and indicate that anoxygenic photoautotrophs in Boreal Shield lakes could have underexplored photophysiology pertinent to understanding Earth's early microbial communities.

The increasing prevalence of cyanobacteria-dominated harmful algal blooms is strongly associated with nutrient loading and changing climatic patterns. Changes to precipitation frequency and intensity, as predicted by current climate models, are likely to affect bloom development and composition through changes in nutrient fluxes and water column mixing. However, few studies have directly documented the effects of extreme precipitation events on cyanobacterial composition, biomass, and toxin production. We tracked changes in a eutrophic reservoir following an extreme precipitation event, describing an atypically early toxin-producing cyanobacterial bloom and successional progression of the phytoplankton community, toxins, and geochemistry. An increase in bioavailable phosphorus by more than 27-fold in surface waters preceded notable increases in Aphanizomenon flos-aquae throughout the reservoir approximately 2 weeks postevent and ∼5 weeks before blooms typically occur. Anabaenopeptin-A and three microcystin congeners (microcystin-LR, -YR, and -RR) were detected at varying levels across sites during the bloom period, which lasted between 3 and 5 weeks. These findings suggest extreme rainfall can trigger early cyanobacterial bloom initiation, effectively elongating the bloom season period of potential toxicity. However, effects will vary depending on factors including the timing of rainfall and reservoir physical structure.

Abstract The increasing prevalence of cyanobacteria-dominated harmful algal blooms is strongly associated with nutrient loading and changing climatic patterns. Changes to precipitation frequency and intensity, as predicted by current climate models, are likely to affect bloom development and composition through changes in nutrient fluxes and water column mixing. However, few studies have directly documented the effects of extreme precipitation events on cyanobacterial composition, biomass, and toxin production. We tracked changes in a eutrophic reservoir following an extreme precipitation event, describing an atypically early toxin-producing cyanobacterial bloom, successional progression of the phytoplankton community, toxins, and geochemistry. An increase in bioavailable phosphorus by more than 27-fold in surface waters preceded notable increases in Aphanizomenon flos-aquae throughout the reservoir approximately 2 weeks post flood and ~5 weeks before blooms typically occur. Anabaenopeptin-A and three microcystin congeners (microcystin-LR, -YR, and -RR) were detected at varying levels across sites during the bloom period, which lasted between 3 and 5 weeks. Synthesis and applications: These findings suggest extreme rainfall can trigger early cyanobacterial bloom initiation, effectively elongating the bloom season period of potential toxicity. However, effects will vary depending on factors including the timing of rainfall and reservoir physical structure. In contrast to the effects of early season extreme rainfall, a mid-summer runoff event appeared to help mitigate the bloom in some areas of the reservoir by increasing flushing.

Hydrologic models partition flows into surface and subsurface pathways, but their calibration is typically conducted only against streamflow. Here we argue that unless model outcomes are constrained using flow pathway data, multiple partitioning schemes can lead to the same streamflow. This point becomes critical for biogeochemical modeling as individual flow paths may yield unique chemical signatures. We show how information on flow pathways can be used to constrain hydrologic flow partitioning and how improved partitioning can lead to better water quality predictions. As a case study, an agricultural basin in Ontario is used to demonstrate that using tile discharge data could increase the performance of both the hydrology and the nitrogen transport models. Watershed‐scale tile discharge was estimated based on sparse tile data collected at some tiles using a novel regression‐based approach. Through a series of calibration experiments, we show that utilizing tile flow signatures as calibration criteria improves model performance in the prediction of nitrate loads in both the calibration and validation periods. Predictability of nitrate loads is improved even with no tile flow data and by model calibration only against an approximate understanding of annual tile flow percent. However, despite high values of goodness‐of‐fit metrics in this case, temporal dynamics of predictions are inconsistent with reality. For instance, the model predicts significant tile discharge in summer with no tile flow occurrence in the field. Hence, the proposed tile flow upscaling approach and the partitioning‐constrained model calibration are vital steps toward improving the predictability of biogeochemical models in tiled landscapes.

© American Geophysical Union: Shafii, M., Basu, N., Craig, J. R., Schiff, S. L., & Van Cappellen, P. (2017). A diagnostic approach to constraining flow partitioning in hydrologic models using a multiobjective optimization framework. Water Resources Research, 53(4), 3279–3301. https://doi.org/10.1002/2016WR019736