Large Fractionation in Iron Isotopes Implicates Metabolic Pathways for Iron Cycling in Boreal Shield Lakes.

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

Temperature Dependence of Photodegradation of Dissolved Organic Matter to Dissolved Inorganic Carbon and Particulate Organic Carbon.

Photochemical transformation of dissolved organic matter (DOM) has been studied for more than two decades. Usually, laboratory or "in-situ" experiments are used to determine photodegradation variables. A common problem with these experiments is that the photodegradation experiments are done at higher than ambient temperature. Five laboratory experiments were done to determine the effect of temperature on photochemical degradation of DOM. Experimental results showed strong dependence of photodegradation on temperature. Mathematical modeling of processes revealed that two different pathways engaged in photochemical transformation of DOM to dissolved inorganic carbon (DIC) strongly depend on temperature. Direct oxidation of DOM to DIC dominated at low temperatures while conversion of DOM to intermediate particulate organic carbon (POC) prior to oxidation to DIC dominated at high temperatures. It is necessary to consider this strong dependence when the results of laboratory experiments are interpreted in regard to natural processes. Photodegradation experiments done at higher than ambient temperature will necessitate correction of rate constants.

Interaction of extrinsic chemical factors affecting photodegradation of dissolved organic matter in aquatic ecosystems.

Photochemical degradation of dissolved organic matter (DOM) plays an important role in the carbon cycle. Irradiation experiments were conducted to evaluate the influence of chemical factors, specifically those expected to be altered in natural waters by atmospheric acid deposition, on photodegradation of DOM. These included pH, nitrate, iron and calcium. The experiments were carried out using stream and lake water samples with a wide range of dissolved organic carbon (DOC) concentration. Decreasing DOC concentration along with decreasing absorbance was observed during three-week exposures to natural solar radiation as well as during laboratory experiments with artificial solar radiation. The pH of the samples significantly affected degradation rates of DOM especially with elevated iron, while no influence of nitrate or calcium concentration was observed. Addition of Fe(III) did not significantly affect photodegradation and photobleaching rate constants in samples at circumneutral pH. Acid pH increased photodegradation rates. The results suggest that photodegradation rates of DOM will decrease during recovery from acidification. Hence, lower photodegradation rates may be responsible for increases in DOM observed in some regions of North America and Europe.

Humic substances-part 7: the biogeochemistry of dissolved organic carbon and its interactions with climate change.

BACKGROUND, AIM, AND SCOPE: Dissolved organic matter, measured as dissolved organic carbon (DOC), is an important component of aquatic ecosystems and of the global carbon cycle. It is known that changes in DOC quality and quantity are likely to have ecological repercussions. This review has four goals: (1) to discuss potential mechanisms responsible for recent changes in aquatic DOC concentrations; (2) to provide a comprehensive overview of the interactions between DOC, nutrients, and trace metals in mainly boreal environments; (3) to explore the impact of climate change on DOC and the subsequent effects on nutrients and trace metals; and (4) to explore the potential impact of DOC cycling on climate change. MAIN FEATURES: We review recent research on the mechanisms responsible for recent changes in aquatic DOC concentrations, DOC interactions with trace metals, N, and P, and on the possible impacts of climate change on DOC in mainly boreal lakes. We then speculate on how climate change may affect DOC export and in-lake processing and how these changes might alter nutrient and metal export and processing. Furthermore, the potential impacts of changing DOC cycling patterns on climate change are examined. RESULTS: It has been noted that DOC concentrations in lake and stream waters have increased during the last 30 years across much of Europe and North America. The potential reasons for this increase include increasing atmospheric CO(2) concentration, climate warming, continued N deposition, decreased sulfate deposition, and hydrological changes due to increased precipitation, droughts, and land use changes. Any change in DOC concentrations and properties in lakes and streams will also impact the acid-base chemistry of these waters and, presumably, the biological, chemical, and photochemical reactions taking place. For example, the interaction of trace metals with DOC may be significantly altered by climate change as organically complexed metals such as Cu, Fe, and Al are released during photo-oxidation of DOC. The production and loss of DOC as CO(2) from boreal lakes may also be affected by changing climate. Climate change is unlikely to be uniform spatially with some regions becoming wetter while others become drier. As a result, rates of change in DOC export and concentrations will vary regionally and the changes may be non-linear. DISCUSSION: Climate change models predict that higher temperatures are likely to occur over most of the boreal forests in North America, Europe, and Asia over the next century. Climate change is also expected to affect the severity and frequency of storm and drought events. Two general climate scenarios emerge with which to examine possible DOC trends: warmer and wetter or warmer and drier. Increasing temperature and hydrological changes (specifically, runoff) are likely to lead to changes in the quality and quantity of DOC export from terrestrial sources to rivers and lakes as well as changes in DOC processing rates in lakes. This will alter the quality and concentrations of DOC and its constituents as well as its interactions with trace metals and the availability of nutrients. In addition, export rates of nutrients and metals will also change in response to changing runoff. Processing of DOC within lakes may impact climate depending on the extent to which DOC is mineralized to dissolved inorganic carbon (DIC) and evaded to the atmosphere or settles as particulate organic carbon (POC) to bottom sediments and thereby remaining in the lake. The partitioning of DOC between sediments and the atmosphere is a function of pH. Decreased DOC concentrations may also limit the burial of sulfate, as FeS, in lake sediments, thereby contributing acidity to the water by increasing the formation of H(2)S. Under a warmer and drier scenario, if lake water levels fall, previously stored organic sediments may be exposed to greater aeration which would lead to greater CO(2) evasion to the atmosphere. The interaction of trace metals with DOC may be significantly altered by climate change. Iron enhances the formation of POC during irradiation of lake water with UV light and therefore may be an important pathway for transfer of allochthonous DOC to the sediments. Therefore, changing Fe/DOC ratios could affect POC formation rates. If climate change results in altered DOC chemistry (e.g., fewer and/or weaker binding sites) more trace metals could be present in their toxic and bioavailable forms. The availability of nutrients may be significantly altered by climate change. Decreased DOC concentrations in lakes may result in increased Fe colloid formation and co-incident loss of adsorbable P from the water column. CONCLUSIONS: Climate change expressed as changes in runoff and temperature will likely result in changes in aquatic DOC quality and concentration with concomitant effects on trace metals and nutrients. Changes in the quality and concentration of DOC have implications for acid-base chemistry and for the speciation and bioavailability of certain trace metals and nutrients. Moreover, changes in DOC, metals, and nutrients are likely to drive changes in rates of C evasion and storage in lake sediments. RECOMMENDATIONS AND PERSPECTIVES: The key controls on allochthonous DOC quality, quantity, and catchment export in response to climate change are still not fully understood. More detailed knowledge of these processes is required so that changes in DOC and its interactions with nutrients and trace metals can be better predicted based on changes caused by changing climate. More studies are needed concerning the effects of trace metals on DOC, the effects of changing DOC quality and quantity on trace metals and nutrients, and how runoff and temperature-related changes in DOC export affect metal and nutrient export to rivers and lakes.

Spectrofluorometric properties of dissolved organic matter from Central and Southern Ontario streams and the influence of iron and irradiation.

Fluorescence measurements were used to compare characteristics of dissolved organic matter (DOM) from distinctly different origins: boreal, agricultural and urban streams as well as a storm runoff pond and the outlet of a tertiary wastewater treatment plant. The primary goal was to determine if differences among stream types could be detected using DOM fluorescence in lieu of isolated fulvic acids (FA). Differences in peak excitation and peak emission wavelengths, fluorescence integrated over the 3-D matrix volume integrated fluorescence (VIF), and in a fluorescence index (FI) were examined. In general, peak fluorescence excitation and emission wavelengths as well as FI best distinguished DOM from the various origins. Results suggested that DOM from the boreal streams was of a higher molecular weight and more complex than that of agricultural and urban streams. The effects of irradiation as well as Fe on fluorescence of natural stream waters were also investigated, both of which decreased the ability of optical properties to distinguish DOM source.

Variation in iron, aluminum and dissolved organic carbon mass transfer coefficients in lakes.

Steady-state mass balance models have been successfully used to predict annual loads and concentrations of numerous substances in lakes. A major limitation of the model is that the value of the mass transfer coefficient, nu(X), for some substance, X, is assumed constant and is taken as a mean value of a set of calibration lakes. The range in mean values between lakes for nu(X) is typically two- to three-fold. Thus, there is some potential for error in model predictions if the true but unknown value for a given lake differs from the mean, calibration value. Moreover, the use of a region-specific value for nu(X) for all lakes in a region means that when environmental conditions change, the model will have to be re-calibrated requiring many more years of monitoring. In this study, mass balances for two substances, total iron and aluminum, are presented along with simple empirical relationships that predict mass transfer coefficients for iron as a function of dissolved organic carbon (DOC) concentration and aluminum as a function of DOC and pH. The relationships, which are consistent with current understanding of iron and aluminum behavior, account for >90% of the variation in nu(X). Improvements in mass balance model predictions are expected when these coefficients are used in place of constant values.