Hydrophilic Species Are the Most Biodegradable Components of Freshwater Dissolved Organic Matter.

Aquatic dissolved organic matter (DOM) is a crucial component of the global carbon cycle, and the extent to which DOM escapes mineralization is important for the transport of organic carbon from the continents to the ocean. DOM persistence strongly depends on its molecular properties, but little is known about which specific properties cause the continuum in reactivity among different dissolved molecules. We investigated how DOM fractions, separated according to their hydrophobicity, differ in biodegradability across three different inland water systems. We found a strong negative relationship between hydrophobicity and biodegradability, consistent for the three systems. The most hydrophilic fraction was poorly recovered by solid-phase extraction (SPE) (3-28% DOC recovery) and was thus selectively missed by mass spectrometry analysis during SPE. The change in DOM composition after incubation was very low according to SPE-ESI (electrospray ionization)-mass spectrometry (14% change, while replicates had 11% change), revealing that this method is sub-optimal to assess DOM biodegradability, regardless of fraction hydrophobicity. Our results demonstrate that SPE-ESI mass spectrometry does not detect the most hydrophilic and most biodegradable species. Hence, they question our current understanding of the relationships between DOM biodegradability and its molecular composition, which is built on the use of this method.

Global increase in methane production under future warming of lake bottom waters.

Lakes are significant emitters of methane to the atmosphere, and thus are important components of the global methane budget. Methane is typically produced in lake sediments, with the rate of methane production being strongly temperature dependent. Local and regional studies highlight the risk of increasing methane production under future climate change, but a global estimate is not currently available. Here, we project changes in global lake bottom temperatures and sediment methane production rates from 1901 to 2099. By the end of the 21st century, lake bottom temperatures are projected to increase globally, by an average of 0.86-2.60°C under Representative Concentration Pathways (RCPs) 2.6-8.5, with greater warming projected at lower latitudes. This future warming of bottom waters will likely result in an increase in methane production rates of 13%-40% by the end of the century, with many low-latitude lakes experiencing an increase of up to 17 times the historical (1970-1999) global average under RCP 8.5. The projected increase in methane production will likely lead to higher emissions from lakes, although the exact magnitude of the emission increase requires more detailed regional studies.

Short-term apparent mutualism drives responses of aquatic prey to increasing productivity.

According to apparent competition theory, sharing a predator should cause indirect interactions among prey that can affect the structure and the dynamics of natural communities. Though shifts in prey dominance and predator resource use along environmental gradients are rather common, empirical evidence on the role of indirect prey-prey interactions through shared predation particularly with increasing productivity, is still scarce. In an 8-week lake mesocosm experiment, we manipulated both the addition of inorganic nutrients and the presence of generalist fish predators (crucian carp, Carassius carassius L.), to test for the effects of indirect interactions through shared predation along a productivity gradient. We found that apparent mutualism (indirect positive interaction) between benthic and pelagic prey strongly affected short-term responses of aquatic food webs to increasing productivity in the presence of a generalist fish. Increasing productivity favoured the relative abundance of benthic prey, following trends in natural productive lake systems. This led to a shift in fish selectivity from pelagic to benthic prey driven by changes in fish behaviour, which resulted in apparent mutualism due to the lower and delayed top-down control of pelagic prey at increasing productivity. Our results show empirical evidence that the coupling of multiple production pathways can lead to strong indirect interactions through shared predation, whereby prey dynamics on short time-scales are highly dependent on the foraging behaviour of generalist predators. This mechanism may play an important role in short-term responses of food webs across environmental gradients.

Investigating the Ionization of Dissolved Organic Matter by Electrospray.

Electrospray ionization (ESI) operating in the negative mode coupled to high-resolution mass spectrometry is the most popular technique for the characterization of dissolved organic matter (DOM). The vast molecular heterogeneity and the functional group diversity of this complex mixture prevents the efficient ionization of the organic material by a single ionization source, so the presence of uncharacterized material is unavoidable. The extent of this poorly ionizable pool of carbon is unknown, is presumably variable between samples, and can only be assessed by the combination of analysis with a uniform detection method. Charged aerosol detection (CAD), whose response is proportional to the amount of nonvolatile material and is independent from the physicochemical properties of the analytes, is a suitable candidate. In this study, a fulvic acid mixture was fractionated and analyzed by high-pressure liquid chromatography-mass spectrometry in order to investigate the polarity and size distributions of highly and poorly ionizable material in the sample. Additionally, DOM samples of terrestrial and marine origins were analyzed to evaluate the variability of these pools across the land-sea aquatic continuum. The relative response factor values indicated that highly ionizable components of aquatic DOM mixtures are more hydrophilic and have lower molecular weight than poorly ionizable components. Additionally, a discrepancy between the samples of terrestrial and marine origins was found, indicating that marine samples are better represented by ESI than terrestrial samples, which have an abundant portion of hydrophobic poorly ionizable material.

The CO2 -equivalent balance of freshwater ecosystems is non-linearly related to productivity.

Eutrophication of fresh waters results in increased CO2 uptake by primary production, but at the same time increased emissions of CH4 to the atmosphere. Given the contrasting effects of CO2 uptake and CH4 release, the net effect of eutrophication on the CO2 -equivalent balance of fresh waters is not clear. We measured carbon fluxes (CO2 and CH4 diffusion, CH4 ebullition) and CH4 oxidation in 20 freshwater mesocosms with 10 different nutrient concentrations (total phosphorus range: mesotrophic 39 µg/L until hypereutrophic 939 µg/L) and planktivorous fish in half of them. We found that the CO2 -equivalent balance had a U-shaped relationship with productivity, up to a threshold in hypereutrophic systems. CO2 -equivalent sinks were confined to a narrow range of net ecosystem production (NEP) between 5 and 19 mmol O2  m-3  day-1 . Our findings indicate that eutrophication can shift fresh waters from sources to sinks of CO2 -equivalents due to enhanced CO2 uptake, but continued eutrophication enhances CH4 emission and transforms freshwater ecosystems to net sources of CO2 -equivalents to the atmosphere. Nutrient enrichment but also planktivorous fish presence increased productivity, thereby regulating the resulting CO2 -equivalent balance. Increasing planktivorous fish abundance, often concomitant with eutrophication, will consequently likely affect the CO2 -equivalent balance of fresh waters.

Emergence of the Reactivity Continuum of Organic Matter from Kinetics of a Multitude of Individual Molecular Constituents.

The reactivity continuum (RC) model is a powerful statistical approach for describing the apparent kinetics of bulk organic matter (OM) decomposition. Here, we used ultrahigh resolution mass spectrometry data to evaluate the main premise of the RC model, namely that there is a continuous spectrum of reactivity within bulk OM, where each individual reactive type undergoes exponential decay. We performed a 120 day OM decomposition experiment on lake water, with an untreated control and a treatment preexposed to UV light, and described the loss of bulk dissolved organic carbon with RC modeling. The behavior of individual molecular formulas was described by fitting the single exponential model to the change in peak intensities over time. The range of the empirically derived apparent exponential decay coefficients (kexp) was indeed continuous. The character of the corresponding distribution, however, differed from the conceptual expectations, due to the effects of intrinsic averaging, overlaps in formula-specific loss and formation rates, and the limitation of the RC model to include apparently accumulating compounds in the analysis. Despite these limitations, both the RC model-simulated and empirical (mass spectrometry-derived) distributions of kexp captured the effects of preexposure to UV light. Overall, we present experimental evidence that the reactivity continuum within bulk OM emerges from a range of reactivity of numerous individual components. This constitutes direct empirical support for the major assumption behind the RC model of the natural OM decomposition.

Temperature-controlled organic carbon mineralization in lake sediments.

Peatlands, soils and the ocean floor are well-recognized as sites of organic carbon accumulation and represent important global carbon sinks. Although the annual burial of organic carbon in lakes and reservoirs exceeds that of ocean sediments, these inland waters are components of the global carbon cycle that receive only limited attention. Of the organic carbon that is being deposited onto the sediments, a certain proportion will be mineralized and the remainder will be buried over geological timescales. Here we assess the relationship between sediment organic carbon mineralization and temperature in a cross-system survey of boreal lakes in Sweden, and with input from a compilation of published data from a wide range of lakes that differ with respect to climate, productivity and organic carbon source. We find that the mineralization of organic carbon in lake sediments exhibits a strongly positive relationship with temperature, which suggests that warmer water temperatures lead to more mineralization and less organic carbon burial. Assuming that future organic carbon delivery to the lake sediments will be similar to that under present-day conditions, we estimate that temperature increases following the latest scenarios presented by the Intergovernmental Panel on Climate Change could result in a 4-27 per cent (0.9-6.4 Tg C yr(-1)) decrease in annual organic carbon burial in boreal lakes.

Controls of dissolved organic matter quality: evidence from a large-scale boreal lake survey.

Inland waters transport large amounts of dissolved organic matter (DOM) from terrestrial environments to the oceans, but DOM also reacts en route, with substantial water column losses by mineralization and sedimentation. For DOM transformations along the aquatic continuum, lakes play an important role as they retain waters in the landscape allowing for more time to alter DOM. We know DOM losses are significant at the global scale, yet little is known about how the reactivity of DOM varies across landscapes and climates. DOM reactivity is inherently linked to its chemical composition. We used fluorescence spectroscopy to explore DOM quality from 560 lakes distributed across Sweden and encompassed a wide climatic gradient typical of the boreal ecozone. Six fluorescence components were identified using parallel factor analysis (PARAFAC). The intensity and relative abundance of these components were analyzed in relation to lake chemistry, catchment, and climate characteristics. Land cover, particularly the percentage of water in the catchment, was a primary factor explaining variability in PARAFAC components. Likewise, lake water retention time influenced DOM quality. These results suggest that processes occurring in upstream water bodies, in addition to the lake itself, have a dominant influence on DOM quality. PARAFAC components with longer emission wavelengths, or red-shifted components, were most reactive. In contrast, protein-like components were most persistent within lakes. Generalized characteristics of PARAFAC components based on emission wavelength could ease future interpretation of fluorescence spectra. An important secondary influence on DOM quality was mean annual temperature, which ranged between -6.2 and +7.5 °C. These results suggest that DOM reactivity depends more heavily on the duration of time taken to pass through the landscape, rather than temperature. Projected increases in runoff in the boreal region may force lake DOM toward a higher overall amount and proportion of humic-like substances.

Selective chlorination of natural organic matter: identification of previously unknown disinfection byproducts.

Natural organic matter (NOM) serve as precursors for disinfection byproducts (DBPs) in drinking water production making NOM removal essential in predisinfection treatment processes. We identified molecular formulas of chlorinated DBPs after chlorination and chloramination in four Swedish surface water treatment plants (WTPs) using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chlorine-containing formulas were detected before and after disinfection and were therefore classified to identify DBPs. In total, 499 DBPs were detected, of which 230 have not been reported earlier. The byproducts had, as a group, significantly lower ratio of hydrogen to carbon (H/C) and significantly higher average carbon oxidation state (COS), double bond equivalents per carbon (DBE/C) and ratio of oxygen to carbon (O/C) compared to Cl-containing components present before disinfection and CHO formulas in samples taken both before and after disinfection. Electrophilic substitution, the proposed most significant reaction pathway for chlorination of NOM, results in carbon oxidation and decreased H/C while O/C and DBE/C is left unchanged. Because the identified DBPs had significantly higher DBE/C and O/C than the CHO formulas we concluded that chlorination of NOM during disinfection is selective toward components with relatively high double bond equivalency and number of oxygen atoms per carbon. Furthermore, choice of disinfectant, dose, and predisinfection treatment at the different WTPs resulted in distinct patterns in the occurrence of DBP formulas.

Resistance and resilience of microbial communities--temporal and spatial insurance against perturbations.

Bacteria play fundamental roles for many ecosystem processes; however, little empirical evidence is available on how environmental perturbations affect their composition and function. We investigated how spatial and temporal refuges affect the resistance and resilience of a freshwater bacterioplankton community upon a salinity pulse perturbation in continuous cultures. Attachment to a surface avoided the flushing out of cells and enabled re-colonization of the liquid phase after the perturbation, hence serving as a temporal refuge. A spatial refuge was established by introduction of bacteria from an undisturbed reservoir upstream of the continuous culture vessel, acting analogous to a regional species pool in a metacommunity. The salinity pulse affected bacterial community composition and the rates of respiration and the pattern of potential substrate utilization as well as the correlation between composition and function. Compared with the no-refuge treatment, the temporal refuge shortened return to pre-perturbation conditions, indicating enhanced community resilience. Composition and function were less disturbed in the treatment providing a spatial refuge, suggesting higher resistance. Our results highlight that spatial and temporal dynamics in general and refuges in particular need to be considered for conceptual progress in how microbial metacommunities are shaped by perturbations.

Pronounced seasonal dynamics of freshwater chitinase genes and chitin processing.

Seasonal variation in activity of enzymes involved in polymer degradation, including chitinases, has been observed previously in freshwater environments. However, it is not known whether the seasonal dynamics are due to shifts in the activity of bacteria already present, or shifts in community structure towards emergence or disappearance of chitinolytic organisms. We traced seasonal shifts in the chitinase gene assemblage in a temperate lake and linked these communities to variation in chitinase activity. Chitinase genes from 20 samples collected over a full yearly cycle were characterized by pyrosequencing. Pronounced temporal shifts in composition of the chitinase gene pool (beta diversity) occurred along with distinct shifts in richness (alpha diversity) as well as chitin processing. Changes in the chitinase gene pool correlated mainly with temperature, abundance of crustacean zooplankton and phytoplankton blooms. Also changes in the physical structure of the lake, e.g. stratification and mixing were associated with changes in the chitinolytic community, while differences were minor between surface and suboxic hypolimnetic water. The lake characteristics influencing the chitinolytic community are all linked to changes in organic particles and we suggest that seasonal changes in particle quality and availability foster microbial communities adapted to efficiently degrade them.

Reciprocal subsidies between freshwater and terrestrial ecosystems structure consumer resource dynamics.

Cross-ecosystem movements of material and energy, particularly reciprocal resource fluxes across the freshwater-land interface, have received major attention. Freshwater ecosystems may receive higher amounts of subsidies (i.e., resources produced outside the focal ecosystem) than terrestrial ecosystems, potentially leading to increased secondary production in freshwaters. Here we used a meta-analytic approach to quantify the magnitude and direction of subsidy inputs across the freshwater-land interface and to determine subsequent responses in recipient animals. Terrestrial and freshwater ecosystems differed in the magnitude of subsidies they received, with aquatic ecosystems generally receiving higher subsidies than terrestrial ecosystems. Surprisingly, and despite the large discrepancy in magnitude, the contribution of these subsidies to animal carbon inferred from stable isotope composition did not differ between freshwater and terrestrial ecosystems, likely due to the differences in subsidy quality. The contribution of allochthonous subsidies was highest to primary consumers and predators, suggesting that bottom-up and top-down effects may be affected considerably by the input of allochthonous resources. Future work on subsidies will profit from a food web dynamic approach including indirect trophic interactions and propagating effects.

Terrestrial subsidies to lake food webs: an experimental approach.

Cross-ecosystem movements of material and energy are ubiquitous. Aquatic ecosystems typically receive material that also includes organic matter from the surrounding catchment. Terrestrial-derived (allochthonous) organic matter can enter aquatic ecosystems in dissolved or particulate form. Several studies have highlighted the importance of dissolved organic carbon to aquatic consumers, but less is known about allochthonous particulate organic carbon (POC). Similarly, most studies showing the effects of allochthonous organic carbon (OC) on aquatic consumers have investigated pelagic habitats; the effects of allochthonous OC on benthic communities are less well studied. Allochthonous inputs might further decrease primary production through light reduction, thereby potentially affecting autotrophic resource availability to consumers. Here, an enclosure experiment was carried out to test the importance of POC input and light availability on the resource use in a benthic food web of a clear-water lake. Corn starch (a C(4) plant) was used as a POC source due to its insoluble nature and its distinct carbon stable isotope value (δ(13)C). The starch carbon was closely dispersed over the bottom of the enclosures to study the fate of a POC source exclusively available to sediment biota. The addition of starch carbon resulted in a clear shift in the isotopic signature of surface-dwelling herbivorous and predatory invertebrates. Although the starch carbon was added solely to the sediment surface, the carbon originating from the starch reached zooplankton. We suggest that allochthonous POC can subsidize benthic food webs directly and can be further transferred to pelagic systems, thereby highlighting the importance of benthic pathways for pelagic habitats.

Organic Matter Degradation across Ecosystem Boundaries: The Need for a Unified Conceptualization.

The global carbon cycle connects organic matter (OM) pools in soil, freshwater, and marine ecosystems with the atmosphere, thereby regulating their size and reactivity. Due to the complexity of biogeochemical processes and historically compartmentalized disciplines, ecosystem-specific conceptualizations of OM degradation have emerged independently of developments in other ecosystems. Recent discussions regarding the relative importance of molecular composition and ecosystem properties on OM degradation have diverged in opposing directions across subdisciplines, leaving our understanding inconsistent. Ecosystem-dependent theories are problematic since properties unique to an ecosystem may change in response to anthropogenic stressors, including climate change. The next breakthrough in our understanding of OM degradation requires a shift in focus towards developing a unified theory of controls on OM across ecosystems.

Predicting lake dissolved organic carbon at a global scale.

The pool of dissolved organic carbon (DOC), is one of the main regulators of the ecology and biogeochemistry of inland water ecosystems, and an important loss term in the carbon budgets of land ecosystems. We used a novel machine learning technique and global databases to test if and how different environmental factors contribute to the variability of in situ DOC concentrations in lakes. In order to estimate DOC in lakes globally we predicted DOC in each lake with a surface area larger than 0.1 km2. Catchment properties and meteorological and hydrological features explained most of the variability of the lake DOC concentration, whereas lake morphometry played only a marginal role. The predicted average of the global DOC concentration in lake water was 3.88 mg L-1. The global predicted pool of DOC in lake water was 729 Tg from which 421 Tg was the share of the Caspian Sea. The results provide global-scale evidence for ecological, climate and carbon cycle models of lake ecosystems and related future prognoses.

Regional diversity of complex dissolved organic matter across forested hemiboreal headwater streams.

Dissolved organic matter (DOM) from soils enters the aquatic environment via headwater streams. Thereafter, it is gradually transformed, removed by sedimentation, and mineralised. Due to the proximity to the terrestrial source and short water residence time, the extent of transformation is minimal in headwaters. DOM has variable composition across inland waters, but the amount of variability in the terrestrial end member is unknown. This gap in knowledge is crucial considering the potential impact large variability would have on modelling DOM degradation. Here, we used a novel liquid chromatography -mass spectrometry method to characterise DOM in 74 randomly selected, forested headwater streams in an 87,000 km2 region of southeast Sweden. We found a large degree of sample similarity across this region, with Bray-Curtis dissimilarity values averaging 8.4 ± 3.0% (mean ± SD). The identified variability could be reduced to two principle coordinates, correlating to varying groundwater flow-paths and regional mean temperature. Our results indicate that despite reproducible effects of groundwater geochemistry and climate, the composition of DOM is remarkably similar across catchments already as it leaves the terrestrial environment, rather than becoming homogeneous as different headwaters and sub-catchments mix.

Simulation of photoreactive transients and of photochemical transformation of organic pollutants in sunlit boreal lakes across 14 degrees of latitude: A photochemical mapping of Sweden.

Lake water constituents, such as chromophoric dissolved organic matter (CDOM) and nitrate, absorb sunlight which induces an array of photochemical reactions. Although these reactions are a substantial driver of pollutant degradation in lakes they are insufficiently understood, in particular on large scales. Here, we provide for the first time comprehensive photochemical maps covering a large geographic region. Using photochemical kinetics modeling for 1048 lakes across Sweden we simulated the steady-state concentrations of four photoreactive transient species, which are continuously produced and consumed in sunlit lake waters. We then simulated the transient-induced photochemical transformation of organic pollutants, to gain insight into the relevance of the different photoreaction pathways. We found that boreal lakes were often unfavorable environments for photoreactions mediated by hydroxyl radicals (OH) and carbonate radical anions (CO3-), while photoreactions mediated by CDOM triplet states (3CDOM*) and, to a lesser extent, singlet oxygen (1O2) were the most prevalent. These conditions promote the photodegradation of phenols, which are used as plastic, medical drug and herbicide precursors. When CDOM concentrations increase, as is currently commonly the case in boreal areas such as Sweden, 3CDOM* will also increase, promoting its importance in photochemical pathways even more.

Organic carbon burial in global lakes and reservoirs.

Burial in sediments removes organic carbon (OC) from the short-term biosphere-atmosphere carbon (C) cycle, and therefore prevents greenhouse gas production in natural systems. Although OC burial in lakes and reservoirs is faster than in the ocean, the magnitude of inland water OC burial is not well constrained. Here we generate the first global-scale and regionally resolved estimate of modern OC burial in lakes and reservoirs, deriving from a comprehensive compilation of literature data. We coupled statistical models to inland water area inventories to estimate a yearly OC burial of 0.15 (range, 0.06-0.25) Pg C, of which ~40% is stored in reservoirs. Relatively higher OC burial rates are predicted for warm and dry regions. While we report lower burial than previously estimated, lake and reservoir OC burial corresponded to ~20% of their C emissions, making them an important C sink that is likely to increase with eutrophication and river damming.

Interactions of bacteria and fungi on decomposing litter: differential extracellular enzyme activities.

Fungi and bacteria are key agents in plant litter decomposition in freshwater ecosystems. However, the specific roles of these two groups and their interactions during the decomposition process are unclear. We compared the growth and patterns of degradative enzymes expressed by communities of bacteria and fungi grown separately and in coexistence on Phragmites leaves. The two groups displayed both synergistic and antagonistic interactions. Bacteria grew better together with fungi than alone. In addition, there was a negative effect of bacteria on fungi, which appeared to be caused by suppression of fungal growth and biomass accrual rather than specifically affecting enzyme activity. Fungi growing alone had a high capacity for the decomposition of plant polymers such as lignin, cellulose, and hemicellulose. In contrast, enzyme activities were in general low when bacteria grew alone, and the activity of key enzymes in the degradation of lignin and cellulose (phenol oxidase and cellobiohydrolase) was undetectable in the bacteria-only treatment. Still, biomass-specific activities of most enzymes were higher in bacteria than in fungi. The low total activity and growth of bacteria in the absence of fungi in spite of apparent high enzymatic efficiency during the degradation of many substrates suggest that fungi provide the bacteria with resources that the bacteria were not able to acquire on their own, most probably intermediate decomposition products released by fungi that could be used by bacteria.