Search

Photochemical production of hydrogen peroxide (H2O2) may not the dominant source of H2O2 in Lake Erie, where toxin-forming harmful algal blooms follow high concentrations of H2O2.

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.

On behalf of the journal, AGU, and the scientific community, the editors of Geophysical Research Letters would like to sincerely thank those who reviewed manuscripts for us in 2021. The hours reading and commenting on manuscripts not only improve the manuscripts, but also increase the scientific rigor of future research in the field. With the advent of AGU's data policy, many reviewers have also helped immensely to evaluate the accessibility and availability of data, and many have provided insightful comments that helped to improve the data presentation and quality. We greatly appreciate the assistance of the reviewers in advancing open science, which is a key objective of AGU's data policy. We particularly appreciate the timely reviews in light of the demands imposed by the rapid review process at Geophysical Research Letters. The COVID pandemic continued to impose additional stresses on the review process, as many reviewers had to juggle increased family commitments, hours of online meetings, remote work and instruction, lack of physical access to library resources, and other hardships, to maintain the quality and timeliness of their reviews. We received 4,832 submissions in 2021 and 5,232 reviewers contributed to their evaluation by providing 8,874 reviews in total. Although we witnessed an increase in the number of submissions, the average number of days to complete a review increased only slightly! That says a lot about the diligence of our reviewers. We deeply appreciate their contributions in these challenging times.

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 analysed for gene expression and DOM chemical composition. Microbial gene expression (metatranscriptomics) in light and dark treatments diverged substantially after 4 h. Gene expression suggested that sunlight exposure of DOM initially stimulated microbial growth by (i) replacing the function of enzymes that degrade higher molecular weight DOM such as enzymes for aromatic carbon degradation, oxygenation, and decarboxylation, and (ii) 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.

Solar radiation initiates photochemical oxidation of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) in inland waters, contributing to their carbon dioxide emissions to the atmosphere. Models can determine photochemical DIC production over large spatiotemporal scales and assess its role in aquatic C cycling. The apparent quantum yield (AQY) spectrum for photochemical DIC production, defined as mol DIC produced per mol chromophoric dissolved organic matter-absorbed photons, is a critical model parameter. In previous studies, the principle for the determination of AQY spectra is the same but methodological specifics differ, and the extent to which these differences influence AQY spectra and simulated aquatic DIC photoproduction is unclear. Here, four laboratories determined AQY spectra from water samples of eight inland waters that are situated in Alaska, Finland, and Sweden and span a nearly 10-fold range in DOM absorption coefficients. All AQY values fell within the range previously reported for inland waters. The inter-laboratory coefficient of variation (CV) for wavelength-integrated AQY spectra (300–450 nm) averaged 38% ± 3% SE, and the inter-water CV averaged 63% ± 1%. The inter-laboratory CV for simulated photochemical DIC production (conducted for the five Swedish lakes) averaged 49% ± 12%, and the inter-water CV averaged 77% ± 10%. This uncertainty is not surprising given the complexities and methodological choices involved in determining DIC AQY spectra and needs to be considered when applying photochemical rate modeling. Thus, we also highlight current methodological limitations and suggest future improvements for DIC AQY determination to reduce inter-laboratory uncertainty. peerReviewed

NMR spectroscopy is widely used in the field of aquatic biogeochemistry to examine the chemical structure of dissolved organic matter (DOM). Most aquatic DOM analyzed by proton NMR (1 H NMR) is concentrated mainly by freeze-drying prior to analysis to combat low concentrations, frequently

Changes in stratospheric ozone and climate over the past 40-plus years have altered the solar ultraviolet (UV) radiation conditions at the Earth’s surface. Ozone depletion has also contributed to climate change across the Southern Hemisphere. These changes are interacting in complex ways to affect human health, food and water security, and ecosystem services. Many adverse effects of high UV exposure have been avoided thanks to the Montreal Protocol with its Amendments and Adjustments, which have effectively controlled the production and use of ozone-depleting substances. This international treaty has also played an important role in mitigating climate change. Climate change is modifying UV exposure and affecting how people and ecosystems respond to UV; these effects will become more pronounced in the future. The interactions between stratospheric ozone, climate and UV radiation will therefore shift over time; however, the Montreal Protocol will continue to have far-reaching benefits for human well-being and environmental sustainability.

Global change influences biogeochemical cycles within and between environmental compartments (i.e., the cryosphere, terrestrial and aquatic ecosystems, and the atmosphere). A major effect of global change on carbon cycling is altered exposure of natural organic matter (NOM) to solar radiation, particularly solar UV radiation. In terrestrial and aquatic ecosystems, NOM is degraded by UV and visible radiation, resulting in the emission of carbon dioxide (CO2) and carbon monoxide, as well as a range of products that can be more easily degraded by microbes (photofacilitation). On land, droughts and land-use change can reduce plant cover causing an increase in exposure of plant litter to solar radiation. The altered transport of soil organic matter from terrestrial to aquatic ecosystems also can enhance exposure of NOM to solar radiation. An increase in emission of CO2 from terrestrial and aquatic ecosystems due to the effects of global warming, such as droughts and thawing of permafrost soils, fuels a positive feedback on global warming. This is also the case for greenhouse gases other than CO2, including methane and nitrous oxide, that are emitted from terrestrial and aquatic ecosystems. These trace gases also have indirect or direct impacts on stratospheric ozone concentrations. The interactive effects of UV radiation and climate change greatly alter the fate of synthetic and biological contaminants. Contaminants are degraded or inactivated by direct and indirect photochemical reactions. The balance between direct and indirect photodegradation or photoinactivation of contaminants is likely to change with future changes in stratospheric ozone, and with changes in runoff of coloured dissolved organic matter due to climate and land-use changes. Fil: Sulzberger, B.. Swiss Federal Institute of Aquatic Science and Technology; Suiza Fil: Austin, Amy Theresa. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Instituto de Investigaciones Fisiológicas y Ecológicas Vinculadas a la Agricultura. Universidad de Buenos Aires. Facultad de Agronomía. Instituto de Investigaciones Fisiológicas y Ecológicas Vinculadas a la Agricultura; Argentina Fil: Cory, R. M.. University of Michigan; Estados Unidos Fil: Zepp, R. G.. United States Environmental Protection Agency; Estados Unidos Fil: Paul, N. D.. Lancaster University; Reino Unido

Through the PolarTREC program that pairs US educators with field researchers in polar regions, our team has been collaborating on K-12 and undergraduate curriculum development and outreach activiti...

On behalf of the journal, AGU, and the scientific community, the editors would like to sincerely thank those who reviewed the manuscripts for Geophysical Research Letters in 2020. The hours reading and commenting on manuscripts not only improve the manuscripts but also increase the scientific rigor of future research in the field. We particularly appreciate the timely reviews in light of the demands imposed by the rapid review process at Geophysical Research Letters. The COVID pandemic imposed additional stresses on the review process, as many reviewers had to juggle increased family commitments, hours of online meetings, remote work and instruction, lack of physical access to library resources, and other hardships to maintain the quality and timeliness of their reviews. Although we witnessed an increase in the number of submissions, the average number of days to complete a review increased by less than one day!! That says a lot about the diligence of our reviewers. We deeply appreciate their contributions in these challenging times. With the advent of AGU's data policy, many reviewers have also helped immensely to evaluate the accessibility and availability of data, and many have provided insightful comments that helped to improve the data presentation and quality. We greatly appreciate the assistance of the reviewers in advancing open science, which is a key objective of AGU's data policy. Individuals in italics provided three or more reviews for Geophysical Research Letters during the year. In total, 5,177 referees contributed to 8,786 individual reviews. Thank you again. We look forward to the coming year of exciting advances in the field and communicating those advances to our community and to the broader public.

Photomineralization, the transformation of dissolved organic carbon (DOC) to CO2 by sunlight, is an important source of CO2 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.

In sunlit waters, photodegradation of dissolved organic matter (DOM) yields completely oxidized carbon (i.e., CO2) 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 CO2 (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 18O2 into DOM isolated from Alaskan Arctic surface waters using high-resolution mass spectrometry. Complete and partial photo-oxidation of DOM was also quantified as CO2 production and O2 consumption. The majority of 18O-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 O2 is required to produce one mol of CO2. 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.

Watershed urbanization introduces a variety of physical, chemical, and thermal stressors to receiving streams and leads to well-documented declines in the diversity of fish and macroinverte...

Hydroxyl radical ( OH) is a highly reactive oxidant of dissolved organic carbon (DOC) in the environment. OH production in the dark was observed through iron and DOC mediated Fenton reactions in natural environments. Specifically, when dissolved oxygen (O2) was added to low oxygen and anoxic soil waters in arctic Alaska, OH was produced in proportion to the concentrations of reduced iron (Fe(II)) and DOC. Here we demonstrate that Fe(II) was the main electron donor to O2 to produce OH. In addition to quantifying OH production, hydrogen peroxide (H2O2) was detected in soil waters as a likely intermediate in OH production from oxidation of Fe(II). For the first time in natural systems we detected carbon dioxide (CO2) production from OH oxidation of DOC. More than half of the arctic soil waters tested showed production of CO2 under conditions conducive for production of OH. Findings from this study strongly suggest that DOC is the main sink for OH, and that OH can oxidize DOC to yield CO2. Thus, this iron-mediated, dark chemical oxidation of DOC may be an important component of the arctic carbon cycle.

Membrane fouling by dissolved organic matter (DOM), especially microbially-derived DOM, is a major challenge for ultrafiltration (UF) membranes in water purification. Fouling may be mitigated by pretreating feed waters; however, there are no comprehensive studies that compare the fouling reduction efficacies across different pretreatment processes. Further, there is a limited understanding of the relationship between fouling reduction efficacy and microbially-derived DOM removal from source waters. Accordingly, the objectives of this study were to: (i) evaluate and compare the efficacies of five pretreatment processes in reducing UF membrane fouling by DOM; and (ii) investigate whether a relationship exists between membrane fouling reduction and microbially-derived DOM removal by pretreatment processes. We investigated seven water sources and a polyvinylidene fluoride hollow-fiber UF membrane using bench-scale fouling tests. Dissolved organic carbon content, ultraviolet absorbance and fluorescence excitation-emission matrix spectroscopy were used to assess DOM concentration and composition. Alum and ferric chloride coagulation were the most effective pretreatment processes in reducing membrane fouling, anion exchange was moderately effective, and PAC adsorption and chlorine pre-oxidation were the least effective. Consistent with previous studies, microbially-derived DOM was the major contributor to UF membrane fouling regardless of water source or pretreatment type. Fouling reduction was strongly correlated with the reduction of microbially-derived DOM in foulant layers but not from source waters. This result indicates that a fraction of the total microbially-derived DOM in feed waters was responsible for UF fouling. Overall, pretreatment processes that remove microbially-derived DOM are well-suited for UF membrane fouling reduction.

In sunlit waters, photochemical alteration of dissolved organic carbon (DOC) impacts the microbial respiration of DOC to CO2. This coupled photochemical and biological degradation of DOC is especially critical for carbon budgets in the Arctic, where thawing permafrost soils increase opportunities for DOC oxidation to CO2 in surface waters, thereby reinforcing global warming. Here we show how and why sunlight exposure impacts microbial respiration of DOC draining permafrost soils. Sunlight significantly increases or decreases microbial respiration of DOC depending on whether photo-alteration produces or removes molecules that native microbial communities used prior to light exposure. Using high-resolution chemical and microbial approaches, we show that rates of DOC processing by microbes are likely governed by a combination of the abundance and lability of DOC exported from land to water and produced by photochemical processes, and the capacity and timescale that microbial communities have to adapt to metabolize photo-altered DOC., The role of dissolved organic carbon (DOC) photo-alteration in the microbial respiration of DOC to CO2 is unclear. Here, the authors show that the impact of this mechanism depends on whether photo-alteration of DOC produces or removes molecules used by native microbial communities prior to light exposure.

Evidence suggests that reactive oxygen species (ROS) are important in transforming the chemical composition of the large pool of terrestrially-derived dissolved organic matter (DOM) exported from land to water annually. However, due to the challenges inherent in isolating the effects of individual ROS on DOM composition, the role of ROS in the photochemical alteration of DOM remains poorly characterized. In this work, terrestrial DOM was independently exposed to singlet oxygen (1O2), and superoxide ( O 2 - under controlled laboratory conditions). Using ultra-high resolution mass spectrometry to track molecular level alterations of DOM by ROS, these findings suggest exposure to 1O2 (generated using Rose Bengal and visible light) removed formulas with an O/C > 0.3, and primarily resulted in DOM comprised of formulas with higher oxygen content, while O 2 - exposure (from KO2 in DMSO) removed formulas with O/C 1.5). Comparison of DOM altered by ROS in this study to riverine and coastal DOM showed that (20–80%) overlap in formulas, providing evidence for the role of ROS in shaping the composition of DOM exported from rivers to oceans.

Human activities are causing a global proliferation of cyanobacterial harmful algal blooms (CHABs), yet we have limited understanding of how these events affect freshwater bacterial communities. Using weekly data from western Lake Erie in 2014, we investigated how the cyanobacterial community varied over space and time, and whether the bloom affected non-cyanobacterial (nc-bacterial) diversity and composition. Cyanobacterial community composition fluctuated dynamically during the bloom, but was dominated by Microcystis and Synechococcus OTUs. The bloom's progression revealed potential impacts to nc-bacterial diversity. Nc-bacterial evenness displayed linear, unimodal, or no response to algal pigment levels, depending on the taxonomic group. In addition, the bloom coincided with a large shift in nc-bacterial community composition. These shifts could be partitioned into components predicted by pH, chlorophyll a, temperature, and water mass movements. Actinobacteria OTUs showed particularly strong correlations to bloom dynamics. AcI-C OTUs became more abundant, while acI-A and acI-B OTUs declined during the bloom, providing evidence of niche partitioning at the sub-clade level. Thus, our observations in western Lake Erie support a link between CHABs and disturbances to bacterial community diversity and composition. Additionally, the short recovery of many taxa after the bloom indicates that bacterial communities may exhibit resilience to CHABs. This article is protected by copyright. All rights reserved.

Author(s): Rajaram, H; Diffenbaugh, N; Camargo, S; Cardenas, MB; Carey, R; Cobb, K; Cory, R; Cronin, M; Dombard, A; Donohue, K; Flesch, L; Giannini, A; Hayes, G; Hogg, A; Ilyina, T; Ivanov, V; Jacobsen, S; Korte, M; Lu, G; Morlighem, M; Magnusdottir, G; Newman, A; Opher, M; Passalacqua, P; Patricola, C; Ritsema, J; Sprintall, J; Su, H; Thornton, J; Williams, P; Yau, A | Abstract: On behalf of the journal, AGU, and the scientific community, the Editors would like to sincerely thank those who reviewed manuscripts for Geophysical Research Letters in 2018. The hours reading and commenting on manuscripts not only improves the manuscripts but also increases the scientific rigor of future research in the field. We particularly appreciate the timely reviews, in light of the demands imposed by the rapid review process at Geophysical Research Letters. With the revival of the “major revisions” decisions, we appreciate the reviewers' efforts on multiple versions of some manuscripts. Many of those listed below went beyond and reviewed three or more manuscripts for our journal, and those are indicated in italics. In total, 4,484 referees contributed to 7,557 individual reviews in journal. Thank you again. We look forward to the coming year of exciting advances in the field and communicating those advances to our community and to the broader public.

NMR spectroscopy is widely used in the field of aquatic biogeochemistry to examine the chemical structure of dissolved organic matter (DOM). Most aquatic DOM analyzed by proton NMR (

Chemical characteristics of dissolved organic matter (DOM) extracted from an ombrotrophic bog in northern Minnesota by two methods – XAD-8 and DEAE-cellulose – were compared using 13C NMR spectroscopy, excitation–emission matrix fluorescence spectroscopy (EEMS), and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). DOM extracted with XAD-8, a relatively hydrophobic sorbent, had a larger 13C NMR signal in the aromatic carbon region, but DOM extracted by DEAE-cellulose, a weak anion exchanger, had a larger signal in the carboxylic carbon region. DOM extracts prepared by the two methods were similar in their overall chemical characteristics that serve as proxies for organic matter sources. For example, only small differences were observed in the fluorescence index (FI) values of the extracts, and all values were within the range expected for terrestrially-derived DOM. EEMS spectra of both extracts had “humic-like” peak A areas smaller than that of standard reference Suwannee River fulvic acid. Of 2801 distinct chemical formulas assigned during FT-ICR MS analysis of the two extracts, 66% were present in both; 15% were unique to the XAD-8 extract, and 19% were unique to the DEAE-cellulose extract. Van Krevelen plots showed that the DEAE-cellulose extract had more tannin-like and condensed aromatic entities and formulas with higher O/C ratios, whereas the XAD-8 extract had more lignin-like material and formulas with higher H/C ratios. Overall, differences in chemical characteristics of the extracts reflect the mechanisms by which the extractants operate.

We investigated how absorption of sunlight by chromophoric dissolved organic matter (CDOM) controls the degradation and export of DOM from Imnavait Creek, a beaded stream in the Alaskan Arctic. We measured concentrations of dissolved organic carbon (DOC), as well as concentrations and characteristics of CDOM and fluorescent dissolved organic matter (FDOM), during ice-free periods of 2011–2012 in the pools of Imnavait Creek and in soil waters draining to the creek. Spatial and temporal patterns in CDOM and FDOM in Imnavait Creek were analyzed in conjunction with measures of DOM degradation by sunlight and bacteria and assessments of hydrologic residence times and in situ UV exposure. CDOM was the dominant light attenuating constituent in the UV and visible portion of the solar spectrum, with high attenuation coefficients ranging from 86 ± 12 m−1 at 305 nm to 3 ± 1 m−1 in the photosynthetically active region (PAR). High rates of light absorption and thus light attenuation by CDOM contributed to thermal stratification in the majority of pools in Imnavait Creek under low-flow conditions. In turn, thermal stratification increased the residence time of water and DOM, and resulted in a separation of water masses distinguished by contrasting UV exposure (i.e., UV attenuation by CDOM with depth resulted in bottom waters receiving less UV than surface waters). When the pools in Imnavait Creek were stratified, DOM in the pool bottom water closely resembled soil water DOM in character, while the concentration and character of DOM in surface water was reproduced by experimental photo-degradation of bottom water. These results, in combination with water column rates of DOM degradation by sunlight and bacteria, suggest that photo-degradation is the dominant process controlling DOM fate and export in Imnavait Creek. A conceptual model is presented showing how CDOM amount and lability interact with incident UV light and water residence time to determine whether photo-degradation is "light-limited" or "substrate-limited". We suggest that degradation of DOM in CDOM-rich streams or ponds similar to Imnavait is typically light-limited under most flow conditions. Thus, export of DOM from this stream will be less under conditions that increase the light available for DOM photo-degradation (i.e., low flows, sunny days).

Northern circumpolar permafrost soils contain roughly twice the amount of carbon stored in the atmosphere today, but the majority of this soil organic carbon is perennially frozen. Climate warming in the arctic is thawing permafrost soils and mobilizing previously frozen dissolved organic matter (DOM) from deeper soil layers to nearby surface waters. Previous studies have reported that ancient DOM draining deeper layers of permafrost soils was more susceptible to degradation by aquatic bacteria compared to modern DOM draining the shallow active layer of permafrost soils, and have suggested that DOM chemical composition may be an important control for the lability of DOM to bacterial degradation. However, the compositional features that distinguish DOM drained from different depths in permafrost soils are poorly characterized. Thus, the objective of this study was to characterize the chemical composition of DOM drained from different depths in permafrost soils, and relate these compositional differences to its susceptibility to biological degradation. DOM was leached from the shallow organic mat and the deeper permafrost layer of soils within the Imnavait Creek watershed on the North Slope of Alaska. DOM draining both soil layers was characterized in triplicate by coupling ultra-high resolution mass spectrometry, 13C solid-state NMR, and optical spectroscopy methods with multi-variate statistical analyses. Reproducibility of replicate mass spectra was high, and compositional differences resulting from interfering species or isolation effects were significantly smaller than differences between DOM drained from each soil layer. All analyses indicated that DOM leached from the shallower organic mat contained higher molecular weight, more oxidized, and more unsaturated aromatic species compared to DOM leached from the deeper permafrost layer. Bacterial production rates and bacterial efficiencies were significantly higher for permafrost compared to organic mat DOM; however, respiration rates were similar between DOM sources. Increased release of permafrost DOM from arctic soils to surface waters will change the chemical composition of DOM and its lability to bacteria, but this study suggests that these shifts in DOM composition and lability may not increase the carbon dioxide produced by bacterial respiration of permafrost DOM exported to arctic surface waters compared to DOM currently draining the shallow active layer.

We assessed spatial and temporal patterns of dissolved organic carbon (DOC) lability and composition throughout the alluvial aquifer of the 16 km2 Nyack Floodplain in northwest Montana, USA. Water influx to the aquifer derives almost exclusively from the Middle Fork of the Flathead River, and water residence times within the aquifer range from days to months. Across seasons and channel discharge conditions, we measured DOC concentration, lability, and optical properties of aquifer water sampled from 12 wells, both near and ~3 m below the water table. Concentrations of DOC were typically low (542 ± 22.7 µg L−1; mean ± se), and the percentage of labile DOC averaged 18 ± 12% during 3 day laboratory assays. Parallel factor analysis of fluorescence excitation-emission matrices revealed two humic-like and two amino acid-like fluorescence groups. Total DOC, humic-like components, and specific UV absorbance decreased with water residence time, consistent with sorption to aquifer sediments. However, labile DOC (both concentration and fraction) increased with water residence time, suggesting a concurrent influx or production of labile DOC. Thus, although the carbon-poor, oxygen-rich aquifer is a net sink for DOC, recalcitrant DOC appears to be replaced with more labile DOC along aquifer flow paths. Our observation of DOC production in long flow paths contrasts with studies of hyporheic DOC consumption along short (centimeters to meters) flow paths and highlights the importance of understanding the role of labile organic matter production and/or influx in alluvial aquifer carbon cycling.

Illuminating the pathway to destruction Arctic lakes are an important source of atmospheric CO 2 and therefore play a role in climate change. It is thus vital to know how the rapid Arctic warming will affect them. Cory et al. now show that light is the biggest culprit in the breakdown of carbon from thawing permafrost soils (see the Perspective by Tranvik). This carbon then moves out into Arctic lakes and streams. Contrary to previous expectations, these photochemical processes cause much more destruction of the organic molecules in fresh water than bacterial respiration does. Science , this issue p. 925 ; see also p. 870

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% of stream water DOC was biodegraded by microorganisms, including 31–45% of the humic DOC. This bioreactive DOM separated into two different groups: (1) H/C centered at 1.5 with O/C 0.1–0.5 or (2) low H/C of 0.5–1.0 spanning O/C 0.2–0.7 that were positively correlated (Spearman ranking) with chromophoric and fluorescent DOM (CDOM and FDOM, respectively). DOM that was more recalcitrant and resistant to microbial degradation aligned tightly in the center of the van Krevelen space (H/C 1.0–1.5, O/C 0.25–0.6) and negatively correlated (Spearman ranking) with CDOM and FDOM. These findings were supported further by principal component analysis and 2-D correlation analysis of the relative magnitudes of the mass spectral peaks assigned to molecular formulas. This study demonstrates that our approach of processing stream water through bioreactors followed by EEMs and FTICR-MS analyses, in combination with multivariate statistical analysis, allows for precise, robust characterization of compound bioreactivity and associated molecular level composition.

Human activities are causing a global proliferation of cyanobacterial harmful algal blooms (CHABs), yet we have limited understanding of how these events affect freshwater bacterial communities. Using weekly data from western Lake Erie in 2014, we investigated how the cyanobacterial community varied over space and time, and whether the bloom affected non-cyanobacterial (nc-bacterial) diversity and composition. Cyanobacterial community composition fluctuated dynamically during the bloom, but was dominated by Microcystis and Synechococcus OTUs. The bloom's progression revealed potential impacts to nc-bacterial diversity. Nc-bacterial evenness displayed linear, unimodal, or no response to algal pigment levels, depending on the taxonomic group. In addition, the bloom coincided with a large shift in nc-bacterial community composition. These shifts could be partitioned into components predicted by pH, chlorophyll a, temperature, and water mass movements. Actinobacteria OTUs showed particularly strong correlations to bloom dynamics. AcI-C OTUs became more abundant, while acI-A and acI-B OTUs declined during the bloom, providing evidence of niche partitioning at the sub-clade level. Thus, our observations in western Lake Erie support a link between CHABs and disturbances to bacterial community diversity and composition. Additionally, the short recovery of many taxa after the bloom indicates that bacterial communities may exhibit resilience to CHABs.

Photochemical degradation of dissolved organic matter (DOM) to carbon dioxide (CO2) and partially oxidized compounds is an important component of the carbon cycle in the Arctic. Thawing permafrost soils will change the chemical composition of DOM exported to arctic surface waters, but the molecular controls on DOM photodegradation remain poorly understood, making it difficult to predict how inputs of thawing permafrost DOM may alter its photodegradation. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer of arctic soils to complete and partial photo-oxidation and investigated changes in the chemical composition of each DOM source following sunlight exposure. Permafrost and organic mat DOM had similar lability to photomineralization despite substantial differences in initial chemical composition. Concurrent losses of carboxyl moieties and shifts in chemical composition during photodegradation indicated that photodecarboxylation could account for 40-90% of DOM photomineralized to CO2. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic moieties with antioxidant properties. These results suggest that photodegradation will likely continue to be an important control on DOM fate in arctic freshwaters as the climate warms and permafrost soils thaw.

Suwannee River fulvic acid (SRFA) was dialyzed through a 100-500 molecular weight cutoff dialysis membrane, and the dialysate and retentate were analyzed by UV-visible absorption and high-resolution Orbitrap mass spectrometry (MS). A significant fraction (36% based on dissolved organic carbon) of SRFA passed through the dialysis membrane. The fraction of SRFA in the dialysate had a different UV-visible absorption spectrum and was enriched in low molecular weight molecules with a more aliphatic composition relative to the initial SRFA solution. Comparison of the SRFA spectra collected by Orbitrap MS and Fourier transform ion cyclotron resonance MS (FT-ICR MS) demonstrated that the mass accuracy of the Orbitrap MS is sufficient for determination of unique molecular formulas of compounds with masses

We investigated the biological lability of fluorescent dissolved organic matter (FDOM) from a temperate Piedmont stream. Plug-flow bioreactors, colonized and maintained with natural stream water, were used to determine the concentrations of stream-water biodegradable dissolved organic carbon (BDOC) and relative concentrations of FDOM within operationally defined biodegradability classes. Labile molecules with turnover times of hours are metabolized within the stream reach where they originated; semi-labile molecules with turnover times of days travel out of the reach and are transported downstream before being metabolized; and a more recalcitrant class with a longer but undetermined turnover time flows through the river network without being metabolized. Between 26% and 31% of the DOC was biodegradable, with 8.6% labile and the balance semi-labile. Humic-like FDOM was a proxy for more recalcitrant DOM, exhibiting a ± 2% change as a function of increased bioreactor residence time. Humic-like FDOM represents only the more recalcitrant and perhaps the more hydrophobic constituents and not the ecologically important semi-labile humic substances within the BDOC pool. Tyrosine-like and tryptophan-like FDOM constituents included not only labile DOM, but also semi-labile, and more recalcitrant moieties. For example, 13% of the tryptophan-like FDOM was labile, 14% was semi-labile, and 73% was more recalcitrant, while tyrosine-like FDOM was 100% biodegraded and the majority (44–69%) was classified as labile. Collectively our results challenge some previous assessments of FDOM lability classifications and highlight the need to connect fluorescence characteristics of DOM to residence times of different carbon pools that spiral through a river network.

To study the effects of complex environmental media on silver nanoparticle (AgNP) toxicity, AgNPs were added to microcosms with freshwater sediments and two species of aquatic plants (Potamogeton diversifolius and Egeria densa), followed by toxicity testing with microcosm surface water. Microcosms were designed with four environmental matrices in order to determine the contribution of each environmental compartment to changes in toxicity: water only (W), water + sediment (WS), water + plants (WP), and water + plants + sediment (WPS). Silver treatments included AgNPs with two different coatings, gum arabic (GA-AgNPs) or polyvinylpyrollidone (PVP-AgNPs), as well as AgNO(3). Water samples taken from the microcosms at 24 h postdosing were used in acute toxicity tests with two standard model organisms, early life stage zebrafish (Danio rerio) and Daphnia magna. Speciation of Ag in these samples was analyzed using Ag L3-edge X-ray absorption near edge spectroscopy (XANES). Silver speciation patterns for the nanoparticle treatments varied significantly by coating type. While PVP-AgNPs were quite stable and resisted transformation across all matrices (>92.4% Ag(0)), GA-AgNP speciation patterns suggest significantly higher transformation rates, especially in treatments with plants (

A multiyear field study was undertaken on Lake Superior to investigate singlet oxygen ((1)O(2)) photoproduction. Specifically, trends within the lake were examined, along with an assessment of whether correlations existed between chromophoric dissolved organic matter (CDOM) characteristics and (1)O(2) production rates and quantum yields. Quantum yield values were determined and used to estimate noontime surface (1)O(2) steady-state concentrations ([(1)O(2)](ss)). Samples were subdivided into three categories based on their absorbance properties (a300): riverine, river-impacted, or open lake sites. Using calculated surface [(1)O(2)](ss), photochemical half-lives under continuous summer sunlight were calculated for cimetidine, a pharmaceutical whose reaction with (1)O(2) has been established, to be on the order of hours, days, and a week for the riverine, river-impacted, and open lake waters, respectively. Of the CDOM properties investigated, it was found that dissolved organic carbon (DOC) and a300 were the best parameters for predicting production rates of [(1)O(2)](ss). For example, given the correlations found, one could predict [(1)O(2)](ss) within a factor of 4 using a300 alone. Changes in the quantum efficiency of (1)O(2) production upon dilution of river water samples with lake water samples demonstrated that the CDOM found in the open lake is not simply diluted riverine organic matter. The open lake pool was characterized by low absorption coefficient, low fluorescence, and low DOC, but more highly efficient (1)O(2) production and predominates the Lake Superior system spatially. This study establishes that parameters that reflect the quantity of CDOM (e.g., a300 and DOC) correlate with (1)O(2) production rates, while parameters that characterize the absorbance spectrum (e.g., spectral slope coefficient and E2:E3) correlate with (1)O(2) production quantum yields.

The environmental dynamics of dissolved organic matter (DOM) were characterized for a shallow, subtropical, seagrass-dominated estuarine bay, namely Florida Bay, USA. Large spatial and seasonal variations in DOM quantity and quality were assessed using dissolved organic C (DOC) measurements and spectrophotometric properties including excitation emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC). Surface water samples were collected monthly for 2 years across the bay. DOM characteristics were statistically different across the bay, and the bay was spatially characterized into four basins based on chemical characteristics of DOM as determined by EEM-PARAFAC. Differences between zones were explained based on hydrology, geomorphology, and primary productivity of the local seagrass community. In addition, potential disturbance effects from a very active hurricane season were identified. Although the overall seasonal patterns of DOM variations were not significantly affected on a bay-wide scale by this disturbance, enhanced freshwater delivery and associated P and DOM inputs (both quantity and quality) were suggested as potential drivers for the appearance of algal blooms in high impact areas. The application of EEM-PARAFAC proved to be ideally suited for studies requiring high sample throughput methods to assess spatial and temporal ecological drivers and to determine disturbance-induced impacts in aquatic ecosystems.

The extent and variability of water storage and residence times throughout the open water season in beaded arctic streams are poorly understood. Data collected in Imnavait Creek, a beaded stream located north of the Brooks Range in Alaska, were used to better understand the effects of in-pool and riparian storage on heat and mass movement through beaded streams. Temperature data of high spatial resolution within the pools and surrounding sediments were used with volumetric discharge and electrical conductivity to identify storage areas within the pools, banks, and other marshy areas within the riparian zone, including subsurface flow paths that connect the pools. These subsurface flows were found to alter water conductivity and the character of dissolved organic matter (DOM) in short reaches (10 s of m) while influencing the chemistry of downstream pools. During low flow periods, persistent stratification occurred within the pools due to absorption of solar radiation by DOM coupled with permafrost below and low wind stress at the pool surface. Additionally, one of the shallow pools (

A nitrogen-rich segment in a fulvic acid (FA) from Pony Lake, a coastal pond in Antarctica, was investigated by (15)N and (13)C{(14)N} solid-state NMR techniques. As reported previously, the (13)C{(14)N} spectrum of C bonded to N exhibits a peak at 157 ppm that is assigned to an sp(2)-hybridized carbon bonded to at least two nitrogen atoms. This segment contains 48% of all N in the sample. (15)N NMR shows distinct signals, 20 ppm upfield and downfield from the typical peptide resonance; dipolar dephasing confirmed that they are due to protonated N. The well-resolved downfield peak, which accounts for 1/4 of the spectral area, cannot be assigned to aromatic heterocycles, such as purines, because the fraction of aromatic C bonded to N in this sample is very small. Analysis of (15)N chemical-shift trends and (15)N NMR of model compounds, such as arginine and its derivatives, excludes assignment to a guanidinium ion or to substituted guanidino groups. Similarly, ureido groups, -NH-CO-NH-, that are not bonded to a second C = O do not match the observed (15)N peaks in the FA, since both N resonate upfield from the peptide resonance. On the other hand, all chemical shifts are matched within the observed range by the -C(alkyl)-NH-CO-NH-CO-C structure found in two nonaromatic heterocycles, hydantoin and dihydrouracil. The five-membered hydantoin ring, which is found in the purine metabolite allantoin, provides a better match than the six-membered dihydrouracil ring. Regular uracil or thymine fails to produce adequate agreement with observed chemical shifts.

Traditional methods for investigating stream solute biogeochemistry measure longitudinal rates of uptake by increasing either the concentration or isotopic composition of solutes. These methods cannot be applied to dissolved organic matter (DOM) because we cannot replicate the heterogeneous native DOM pool. We explored an alternative approach, attempting to displace or enhance benthic uptake of native DOM by supplying an exogenous source of labile carbon or by enriching the stream with inorganic nitrogen. This approach allows us to measure uptake rates of enriched solutes, as well as changes in the concentration and composition of native DOM resulting from the experimental manipulations. We examined DOM composition using fluorescence characterization. We were able to elicit changes in the chemical composition of native DOM by differentially altering the dynamics of autotrophic production and heterotrophic uptake within the second-order reach of Walker Branch, a well-studied stream in eastern Tennessee. Supplying heterotrophs with labile carbon resulted in an increase in fluorescence associated with terrestrially derived DOM. Stimulating algae by adding inorganic nitrogen increased autochthonous production and indirectly displaced heterotrophic demand for terrestrial DOM due to increased in-stream production of bioavailable DOM. While we were able to alter the composition of the native DOM pool, we observed little change in DOM concentrations. The ability to differentiate between DOM subcomponents provides insight into processes controlling DOM production and consumption that cannot be gained by treating DOM as a single bulk pool.

A major impediment to understanding the biology of microorganisms inhabiting Antarctic environments is the logistical constraint of conducting field work primarily during the summer season. However, organisms that persist throughout the year encounter severe environmental changes between seasons. In an attempt to bridge this gap, we collected ice core samples from Pony Lake in early November 2004 when the lake was frozen solid to its base, providing an archive for the biological and chemical processes that occurred during winter freezeup. The ice contained bacteria and virus-like particles, while flagellated algae and ciliates over-wintered in the form of inactive cysts and spores. Both bacteria and algae were metabolically active in the ice core melt water. Bacterial production ranged from 1.8 to 37.9 μg C L−1 day−1. Upon encountering favorable growth conditions in the melt water, primary production ranged from 51 to 931 μg C L−1 day−1. Because of the strong H2S odor and the presence of closely related anaerobic organisms assigned to Pony Lake bacterial 16S rRNA gene clones, we hypothesize that the microbial assemblage was strongly affected by oxygen gradients, which ultimately restricted the majority of phylotypes to distinct strata within the ice column. This study provides evidence that the microbial community over-winters in the ice column of Pony Lake and returns to a highly active metabolic state when spring melt is initiated.

Hydroxyl radical (&bull, OH) is produced in soils from oxidation of reduced iron (Fe(II)) by dissolved oxygen (O2) and can oxidize dissolved organic carbon (DOC) to carbon dioxide (CO2). Understanding the role of &bull, OH on CO2 production in soils requires knowing whether Fe(II) production or O2 supply to soils limits &bull, OH production. To test the relative importance of Fe(II) production versus O2 supply, we measured changes in Fe(II) and O2 and in situ &bull, OH production during simulated precipitation events and during common, waterlogged conditions in mesocosms from two landscape ages and the two dominant vegetation types of the Arctic. The balance of Fe(II) production and consumption controlled &bull, OH production during precipitation events that supplied O2 to the soils. During static, waterlogged conditions, &bull, OH production was controlled by O2 supply because Fe(II) production was higher than its consumption (oxidation) by O2. An average precipitation event (4 mm) resulted in 200 &micro, mol &bull, OH m&minus, 2 per day produced compared to 60 &micro, 2 per day produced during waterlogged conditions. These findings suggest that the oxidation of DOC to CO2 by &bull, OH in arctic soils, a process potentially as important as microbial respiration of DOC in arctic surface waters, will depend on the patterns and amounts of rainfall that oxygenate the soil.

Fluorescent dissolved organic matter (DOM), a fraction of chromophoric DOM, has been known to be produced in the deep ocean and has been considered to be bio-refractory. However, the factors controlling fluorescence properties of DOM in the deep ocean are still not well understood. In this study, we determined the fluorescence properties of DOM in the deep waters of the Okhotsk Sea and the northwestern North Pacific Ocean using excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC). One protein-like, two humic-like components, and one uncertain component, that might be derived from a fluorometer artifact, were identified by EEM-PARAFAC. Fluorescence intensity levels of the protein-like component were highest in the surface waters, decreased with depth, but did not change systematically in the bathypelagic layer (1000 m - bottom). Fluorescence characteristics of the two humic-like components were similar to those traditionally defined as marine and terrestrial humic-like fluorophores, respectively. The fluorescence intensity levels of the two humic-like components were lowest in the surface waters, increased with depth in the mesopelagic layer (200 - 1000 m), and then slightly decreased with depth in the bathypelagic layer. The ratio of the two humic-like components remained in a relatively narrow range in the bathypelagic layer compared to that in the surface layer, suggesting a similar composition of humic-like fluorophores in this layer. In addition, the fluorescence intensities of the two humic-like components were linearly correlated to apparent oxygen utilization (AOU) in the bathypelagic layer, suggesting that both humic-like components are produced in situ as organic matter is oxidized biologically. These findings imply that optical characteristics of humic-like fluorophores once formed might not be altered further biologically or geochemically in the deep ocean. On the other hand, relationships of fluorescence intensities with AOU and Fe(III) solubility were different between the two humic-like components in the mesopelagic layer, suggesting different environmental dynamics and biogeochemical roles for the two humic-like components.

In their article, “New light on a dark subject: On the use of fluorescence data to deduce redox states of natural organic matter,” Macalady and Walton-Day (2009) subjected natural organic matter (NOM) samples to oxidation, reduction, and photochemical transformation. Fluorescence spectra were obtained on samples, which were diluted “to bring maximum uvvisible absorbance values below 1.0.” The spectra were fit to the Cory and McKnight (2005) parallel factor analysis (PARAFAC) model, and consistent variation in the redox state of quinone-like moieties was not detected. Based on these results they concluded that fitting fluorescence spectra to the Cory and McKnight (2005) PARAFAC model to obtain information about the redox state of quinone-like moieties in NOM is problematic. Recognizing that collection and correction of fluorescence spectra requires consideration of many factors, we investigated the potential for inner-filter effects to obscure the ability of fluorescence spectroscopy to quantify the redox state of quinone-like moieties. We collected fluorescence spectra on Pony Lake and Suwannee River fulvic acid standards that were diluted to cover a range of absorbance wavelengths, and fit these spectra to the Cory and McKnight (2005) PARAFAC model. Our results suggest that, in order for the commonly used inner-filter correction to effectively remove inner-filter effects, samples should be diluted such that the absorbance at 254 nm is less than 0.3 prior to the collection of fluorescence spectra. This finding indicates that inner-filter effects may have obscured changes in the redox signature of fluorescence spectra of the highly absorbing samples studied by Macalady and Walton-Day (2009).

Fluorescence spectroscopy has been extensively employed to characterize the source, age, and reactivity of aquatic dissolved organic matter (DOM). However, there is no consensus on the protocols for collecting and correcting DOM fluorescence spectra for the instrument-specific response associated with each component on a fluorometer involved in the excitation of DOM and the resulting detection of DOM emission. The central objective of this study was to evaluate the removal of instrument-specific response from DOM fluorescence spectra collected on three different fluorometers using manufacturer-provided emission and excitation correction files. We evaluated criteria and protocols for comparison of removal of instrument response, using quinine sulfate, a well-characterized fluorophore, as well as the International Humic Substance Society's microbially and terrestrially derived reference end-member fulvic acids: Pony Lake and Suwannee River fulvic acids, respectively. Our results demonstrate that sample spectra collected on different fluorometers differed significantly before correction. Although the effectiveness of manufacturer-provided correction factors in removal of instrument response from sample spectra varied by instrument, spectral overlap of the same sample on multiple instruments improved after correction. Our results suggest that conclusions based on analysis of trends within a dataset of DOM fluorescence spectra should be expected to be independent of the fluorometer employed.