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In Lake Erie, toxin-forming harmful algal blooms (HABs) occur following high concentrations of hydrogen peroxide (H 2 O 2 ). Correlation between H 2 O 2 concentrations and HABs revealed knowledge gaps on the controls of H 2 O 2 production in Lake Erie. One way H 2 O 2 is produced is upon absorption of sunlight by the chromophoric fraction of dissolved organic matter (CDOM). Rates of this photochemical production of H 2 O 2 may increase in proportion to the apparent quantum yield of H 2 O 2 ( Φ H 2 O 2 ,λ ) from CDOM. However, the Φ H 2 O 2 ,λ for H 2 O 2 production from CDOM remains too poorly constrained to predict the magnitude and range of photochemically produced H 2 O 2 , particularly in freshwaters like Lake Erie. To address this knowledge gap, the Φ H 2 O 2 ,λ was measured approximately biweekly from June–September 2019 in the western basin of Lake Erie along with supporting analyses ( e.g. , CDOM concentration and composition). The average Φ H 2 O 2 ,λ in Lake Erie was within previously reported ranges. However, the Φ H 2 O 2 ,λ varied 5-fold in space and time. The highest Φ H 2 O 2 ,λ was observed in the Maumee River, a tributary of Lake Erie. In nearshore waters of Lake Erie, the Φ H 2 O 2 ,λ decreased about five-fold from June through September. Integration of the controls of photochemical production of H 2 O 2 in Lake Erie show that the variability in rates of photochemical H 2 O 2 production was predominantly due to the Φ H 2 O 2 ,λ . In offshore waters, CDOM concentration also strongly influenced photochemical H 2 O 2 production. Together, the results confirm prior work suggesting that photochemical production of H 2 O 2 contributes but likely cannot account for all the H 2 O 2 associated with HABs in Lake Erie. 

ABSTRACT In the oligotrophic oceans, key autotrophs depend on “helper” bacteria to reduce oxidative stress from hydrogen peroxide (H 2 O 2 ) in the extracellular environment. H 2 O 2 is also a ubiquitous stressor in freshwaters, but the effects of H 2 O 2 on autotrophs and their interactions with bacteria are less well understood in freshwaters. Naturally occurring H 2 O 2 in freshwater systems is proposed to impact the proportion of microcystin-producing (toxic) and non-microcystin-producing (nontoxic) Microcystis in blooms, which influences toxin concentrations and human health impacts. However, how different strains of Microcystis respond to naturally occurring H 2 O 2 concentrations and the microbes responsible for H 2 O 2 decomposition in freshwater cyanobacterial blooms are unknown. To address these knowledge gaps, we used metagenomics and metatranscriptomics to track the presence and expression of genes for H 2 O 2 decomposition by microbes during a cyanobacterial bloom in western Lake Erie in the summer of 2014. katG encodes the key enzyme for decomposing extracellular H 2 O 2 but was absent in most Microcystis cells. katG transcript relative abundance was dominated by heterotrophic bacteria. In axenic Microcystis cultures, an H 2 O 2 scavenger (pyruvate) significantly improved growth rates of one toxic strain while other toxic and nontoxic strains were unaffected. These results indicate that heterotrophic bacteria play a key role in H 2 O 2 decomposition in Microcystis blooms and suggest that their activity may affect the fitness of some Microcystis strains and thus the strain composition of Microcystis blooms but not along a toxic versus nontoxic dichotomy. IMPORTANCE Cyanobacterial harmful algal blooms (CHABs) threaten freshwater ecosystems globally through the production of toxins. Toxin production by cyanobacterial species and strains during CHABs varies widely over time and space, but the ecological drivers of the succession of toxin-producing species remain unclear. Hydrogen peroxide (H 2 O 2 ) is ubiquitous in natural waters, inhibits microbial growth, and may determine the relative proportions of Microcystis strains during blooms. However, the mechanisms and organismal interactions involved in H 2 O 2 decomposition are unexplored in CHABs. This study shows that some strains of bloom-forming freshwater cyanobacteria benefit from detoxification of H 2 O 2 by associated heterotrophic bacteria, which may impact bloom development. 

In sunlit waters, photodegradation of dissolved organic matter (DOM) yields completely oxidized carbon ( i.e. , CO 2 ) as well as a suite of partially oxidized compounds formed from oxygen incorporation ( i.e. , partial photo-oxidation). Of these two groups of DOM photo-products, more studies focus on CO 2 (a greenhouse gas) than on partially oxidized DOM, which is likely a diverse group of compounds with poorly constrained roles in aquatic carbon cycling or biogeochemistry. The objective of this study is to address knowledge gaps on the prevalence, products, and pathways of DOM partial photo-oxidation. Here we traced the photochemical incorporation of isotopically labelled 18 O 2 into DOM isolated from Alaskan Arctic surface waters using high-resolution mass spectrometry. Complete and partial photo-oxidation of DOM was also quantified as CO 2 production and O 2 consumption. The majority of 18 O-containing partial oxidation photo-products were classified as carboxylic rich alicyclic molecules (CRAM) and overlapped in composition with previously reported photo-products known to result from the oxidation of DOM by singlet oxygen. These results support a previously proposed hypothesis that photo-oxidation by singlet oxygen may contribute to the formation of CRAM, a compound class of DOM ubiquitously observed in surface waters. The novel application of an isotopic tracer for oxygen incorporation with a mass balance approach to quantify complete and partial photo-oxidation of DOM revealed that less than one mol of O 2 is required to produce one mol of CO 2 . A sensitivity analysis based on this new knowledge demonstrated that the magnitude of DOM partial photo-oxidation may be underestimated by up to four-fold. Consequently, partial photo-oxidation likely plays a more prominent role in shaping DOM composition in sunlit waters of the Arctic than previously understood. Therefore, partial photo-oxidation should be increasingly incorporated into the experimental framework of studies focused on DOM composition in surface waters. 

Microbes and sunlight convert terrigenous dissolved organic matter (DOM) in surface waters to greenhouse gases. Prior studies show contrasting results about how biological and photochemical processes interact to contribute to the degradation of DOM. In this study, DOM leached from the organic layer of tundra soil was exposed to natural sunlight or kept in the dark, incubated in the dark with the natural microbial community, and analyzed for gene expression and DOM chemical composition. Microbial gene expression (metatranscriptomics) in light and dark treatments diverged substantially after 4 hours. Gene expression suggested that sunlight exposure of DOM initially stimulated microbial growth by (a) replacing the function of enzymes that degrade higher molecular weight DOM such as enzymes for aromatic carbon degradation, oxygenation, and decarboxylation, and (b) releasing low molecular weight compounds and inorganic nutrients from DOM. However, growth stimulation following sunlight exposure of DOM came at a cost. Sunlight depleted the pool of aromatic compounds that supported microbial growth in the dark treatment, ultimately causing slower growth in the light treatment over 5 days. These first measurements of microbial metatranscriptomic responses to photo-alteration of DOM provide a mechanistic explanation for how sunlight exposure of terrigenous DOM alters microbial processing and respiration of DOM. 

Photomineralization, the transformation of dissolved organic carbon (DOC) to CO 2 by sunlight, is an important source of CO 2 in arctic surface waters. However, quantifying the role of photomineralization in inland waters is limited by the understanding of hydrologic controls on this process. To bridge this gap, this study evaluates mixing limitations, i.e. , whether and by how much vertical mixing limits the depth-integrated photomineralization rate, in freshwater systems. We developed a conceptual model to qualitatively assess mixing limitations across the range of light attenuation and hydrologic conditions observed in freshwaters. For the common case of exponential light attenuation over depth, we developed a mathematical model to quantify mixing limitation, and used this model to assess a range of arctic freshwater systems. The results demonstrate that mixing limitations are important when there is significant light attenuation by suspended sediment (SS), which is the case in some arctic, boreal and temperate waters. Mixing limitation is pronounced when light attenuation over depth is strong and when the photomineralization rate at the water surface exceeds the vertical mixing rate. Arctic streams and rivers have strong vertical mixing relative to surface photomineralization, such that model results demonstrate no mixing limitation regardless of how much SS is present. Our analysis indicates that well-mixed assumptions used in prior work are valid in many, but not all, arctic surface waters. The effects of mixing limitations in reducing the photomineralization rate must be considered in arctic lakes with high SS concentrations. 

Exposure of dissolved organic matter (DOM) to sunlight can increase or decrease the fraction that is biodegradable (BDOM), but conceptual models fail to explain this dichotomy. We investigated the effect of sunlight exposure on BDOM, addressing three knowledge gaps: (1) how fractions of DOM overlap in their susceptibility to degradation by sunlight and microbes, (2) how the net effect of sunlight on BDOM changes with photon dose, and (3) how rates of DOM photodegradation and biodegradation compare in a stream. Stream waters were exposed to sunlight, and then fed through bioreactors designed to separate labile and semi‐labile pools within BDOM. The net effects of photodegradation on DOM biodegradability, while generally positive, represented the balance between photochemical production and removal of BDOM that was mediated by photon dose. By using sunlight exposure times representative of sunlight exposures in a headwater stream and bioreactors colonized with natural communities and scaled to whole‐stream dynamics, we were able to relate our laboratory findings to the stream. The impact of sunlight exposure on rates of DOM biodegradation in streams was calculated using rates of light absorption by chromophoric DOM, apparent quantum yields for photomineralization and photochemical alteration of BDOM, and mass transfer coefficients for labile and semi‐labile DOM. Rates of photochemical alteration of labile DOM were an order of magnitude lower than rates of biodegradation of labile DOM, but for semi‐labile DOM, these rates were similar, suggesting that sunlight plays a substantial role in the fate of semi‐labile DOM in streams.