Excitation-emission matrixes (EEMs) of 379 dissolved organic matter (DOM) samples from diverse aquatic environments were modeled by parallel factor analysis (PARAFAC). Thirteen components likely representing groups of similarly fluorescing moieties were found to explain the variation in this data set. Seven of the thirteen components were identified as quinone-like based on comparison of their excitation and emission spectra to spectra of model quinones. These quinone-like fluorophores were found to vary in redox state and degree of conjugation. Two components were identified as amino acid-like based on comparison to tyrosine and tryptophan fluorescence spectra. The other four components are not yet associated with any class of molecules. The quinone-like fluorophores account for about 50% of the fluorescence for every sample analyzed, showing that quinone-like fluorophores are an important and ubiquitous fluorescing moiety and in natural waters. Further, the distribution of the quinone-like fluorophores was evaluated as a function of environmental and laboratory redox gradients. Under reducing conditions, the contribution of the reduced quinone-like fluorophores increased concurrentwith a decrease in the oxidized quinone-like fluorophores, indicating that DOM fluorescence is a function of redox state of quinone-like moieties. Lastly, a ratio of two quinone-like fluorophores was found to explain the variation in the fluorescence index. These results provide new insight into the redox reactivity of DOM and have implications for the application of fluorescence spectroscopy as a tool to characterize DOM.

Carbon in thawing permafrost soils may have global impacts on climate change; however, the factors that control its processing and fate are poorly understood. The dominant fate of dissolved organic carbon (DOC) released from soils to inland waters is either complete oxidation to CO2 or partial oxidation and river export to oceans. Although both processes are most often attributed to bacterial respiration, we found that photochemical oxidation exceeds rates of respiration and accounts for 70 to 95% of total DOC processed in the water column of arctic lakes and rivers. At the basin scale, photochemical processing of DOC is about one-third of the total CO2 released from surface waters and is thus an important component of the arctic carbon budget.

[1] Source, transformation, and preservation mechanisms of dissolved organic matter (DOM) remain elemental questions in contemporary marine and aquatic sciences and represent a missing link in models of global elemental cycles. Although the chemical character of DOM is central to its fate in the global carbon cycle, DOM characterizations in long-term ecological research programs are rarely performed. We analyzed the variability in the quality of 134 DOM samples collected from 12 Long Term Ecological Research stations by quantification of organic carbon and nitrogen concentration in addition to analysis of UV-visible absorbance and fluorescence spectra. The fluorescence spectra were further characterized by parallel factor analysis. There was a large range in both concentration and quality of the DOM, with the dissolved organic carbon (DOC) concentration ranging from less than 1 mgC/L to over 30 mgC/L. The ranges of specific UV absorbance and fluorescence parameters suggested significant variations in DOM composition within a specific study area, on both spatial and temporal scales. There was no correlation between DOC concentration and any DOM quality parameter, illustrating that comparing across biomes, large variations in DOM quality are not necessarily associated with corresponding large ranges in DOC concentrations. The data presented here emphasize that optical properties of DOM can be highly variable and controlled by different physical (e.g., hydrology), chemical (e.g., photoreactivity/redox conditions), and biological (e.g., primary productivity) processes, and as such can have important ecological consequences. This study demonstrates that relatively simple DOM absorbance and/or fluorescence measurements can be incorporated into long-term ecological research and monitoring programs, resulting in advanced understanding of organic matter dynamics in aquatic ecosystems.

Abstract. The Arctic is a water-rich region, with freshwater systems covering about 16 % of the northern permafrost landscape. Permafrost thaw creates new freshwater ecosystems, while at the same time modifying the existing lakes, streams, and rivers that are impacted by thaw. Here, we describe the current state of knowledge regarding how permafrost thaw affects lentic (still) and lotic (moving) systems, exploring the effects of both thermokarst (thawing and collapse of ice-rich permafrost) and deepening of the active layer (the surface soil layer that thaws and refreezes each year). Within thermokarst, we further differentiate between the effects of thermokarst in lowland areas vs. that on hillslopes. For almost all of the processes that we explore, the effects of thaw vary regionally, and between lake and stream systems. Much of this regional variation is caused by differences in ground ice content, topography, soil type, and permafrost coverage. Together, these modifying factors determine (i) the degree to which permafrost thaw manifests as thermokarst, (ii) whether thermokarst leads to slumping or the formation of thermokarst lakes, and (iii) the manner in which constituent delivery to freshwater systems is altered by thaw. Differences in thaw-enabled constituent delivery can Published by Copernicus Publications on behalf of the European Geosciences Union. J. E. Vonk et al.: Effects of permafrost thaw on Arctic aquatic ecosystemsbe considerable, with these modifying factors determining, for example, the balance between delivery of particulate vs. dissolved constituents, and inorganic vs. organic materials. Changes in the composition of thaw-impacted waters, coupled with changes in lake morphology, can strongly affect the physical and optical properties of thermokarst lakes. The ecology of thaw-impacted lakes and streams is also likely to change; these systems have unique microbiological communities, and show differences in respiration, primary production, and food web structure that are largely driven by differences in sediment, dissolved organic matter, and nutrient delivery. The degree to which thaw enables the delivery of dissolved vs. particulate organic matter, coupled with the composition of that organic matter and the morphology and stratification characteristics of recipient systems will play an important role in determining the balance between the release of organic matter as greenhouse gases (CO 2 and CH 4 ), its burial in sediments, and its loss downstream. The magnitude of thaw impacts on northern aquatic ecosystems is increasing, as is the prevalence of thaw-impacted lakes and streams. There is therefore an urgent need to quantify how permafrost thaw is affecting aquatic ecosystems across diverse Arctic landscapes, and the implications of this change for further climate warming.

[1] Dissolved organic matter (DOM) originating from the extensive Arctic tundra is an important source of organic material to the Arctic Ocean. Chemical characteristics of whole water dissolved organic matter (DOM) and the fulvic acid fraction of DOM were studied from nine surface waters in the Arctic region of Alaska to gain insight into the extent of microbial and photochemical transformation of this DOM. All the fulvic acids had a strong terrestrial/higher plant signature, with uniformly depleted d 13C values of À28%, and low fluorescence indices around 1.3. Several of the measured chemical characteristics of the Arctic fulvic acids were related to water residence time, a measure of environmental exposure to sunlight and microbial activity. For example, fulvic acids from Arctic streams had higher aromatic contents, higher specific absorbance values, lower nitrogen content, lower amino acid-like fluorescence and were more depleted in d 15 N relative to fulvic acids isolated from lake and coastal surface waters. The differences in the nitrogen signature between the lake and coastal fulvic acids compared to the stream fulvic acids indicated that microbial contributions to the fulvic acid pool increased with increasing water residence time. The photo-lability of the fulvic acids was positively correlated with water residence time, suggesting that the fulvic acids isolated from source waters with larger water residence times (i.e., lakes and coastal waters) have experienced greater photochemical degradation than the stream fulvic acids. In addition, many of the initial differences in fulvic acid chemical characteristics across the gradient of water residence times were consistent with changes observed in fulvic acid photolysis experiments. Taken together, results from this study suggest that photochemical processes predominantly control the chemical character of fulvic acids in Arctic surface waters. Our findings show that hydrologic transport in addition to biogeochemical alteration of the organic matter must be considered in order to predict the ultimate fate of Arctic DOM.

Recent climate change has increased arctic soil temperatures and thawed large areas of permafrost, allowing for microbial respiration of previously frozen C. Furthermore, soil destabilization from melting ice has caused an increase in thermokarst failures that expose buried C and release dissolved organic C (DOC) to surface waters. Once exposed, the fate of this C is unknown but will depend on its reactivity to sunlight and microbial attack, and the light available at the surface. In this study we manipulated water released from areas of thermokarst activity to show that newly exposed DOC is >40% more susceptible to microbial conversion to CO 2 when exposed to UV light than when kept dark. When integrated over the water column of receiving rivers, this susceptibility translates to the light-stimulated bacterial activity being on average from 11% to 40% of the total areal activity in turbid versus DOC-colored rivers, respectively. The range of DOC lability to microbes seems to depend on prior light exposure, implying that sunlight may act as an amplification factor in the conversion of frozen C stores to C gases in the atmosphere.carbon cycling | photochemistry | dissolved organic matter | bacterial community composition | stream

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.

Abstract. The Arctic is a water-rich region, with freshwater systems covering 16 % of the northern permafrost landscape. The thawing of this permafrost creates new freshwater ecosystems, while at the same time modifying the existing lakes, streams, and rivers that are impacted by thaw. Here, we describe the current state of knowledge regarding how permafrost thaw affects lentic and lotic systems, exploring the effects of both thermokarst (thawing and collapse of ice-rich permafrost) and deepening of the active layer (the surface soil layer that thaws and refreezes each year). Within thermokarst, we further differentiate between the effects of thermokarst in lowland areas, vs. that on hillslopes. For almost all of the processes that we explore, the effects of thaw vary regionally, and between lake and stream systems. Much of this regional variation is caused by differences in ground ice content, topography, soil type, and permafrost coverage. Together, these modifying variables determine the degree to which permafrost thaw manifests as thermokarst, whether thermokarst leads to slumping or the formation of thermokarst lakes, and the manner in which constituent delivery to freshwater systems is altered by thaw. Differences in thaw-enabled constituent delivery can be considerable, with these modifying variables determining, for example, the balance between delivery of particulate vs. dissolved constituents, and inorganic vs. organic materials. Changes in the composition of thaw-impacted waters, coupled with changes in lake morphology, can strongly affect the physical and optical properties of thermokarst lakes. The ecology of thaw-impacted systems is also likely to change, with thaw-impacted lakes and streams having unique microbiological communities, and showing differences in respiration, primary production, and food web structure that are largely driven by differences in sediment, dissolved organic matter and nutrient delivery. The degree to which thaw enables the delivery of dissolved vs. particulate organic matter, coupled with the composition of that organic matter and the morphology and stratification characteristics of recipient systems will play an important role in determining the balance between the release of organic matter as greenhouse gases (CO2 and CH4), its burial in sediments, and its loss downstream. The magnitude of thaw impacts on northern aquatic ecosystems is increasing, as is the prevalence of thaw-impacted lakes and streams. There is therefore an urgent need to address the key gaps in understanding in order to predict the full effects of permafrost thaw on aquatic ecosystems throughout the Arctic, and their consequential feedbacks to climate.