Export of DOC from forested catchments on the Precambrian Shield of Central Ontario: Clues from 13C and 14C

Export of dissolved organic carbon (DOC) from forested catchmentsis governed by competing processes of production, decomposition, sorptionand flushing. To examine the sources of DOC, carbon isotopes (¹⁴Cand ¹³C) were analyzed in DOC from surface waters, groundwatersand soils in a small forested catchment on the Canadian Shield in centralOntario. A significant fraction (greater than 50%) of DOCin major inflows to the lake is composed of carbon incorporated into organicmatter, solubilized and flushed into the stream within the last 40 years. Incontrast, ¹⁴C in groundwater DOC was old indicating extensiverecycling of forest floor derived organic carbon in the soil column beforeelution to groundwater in the lower B and C soil horizons. A small uplandbasin had a wide range in ¹⁴C from old groundwater values atbaseflow under dry basin conditions to relatively modern values during highflow or wetter antecedent conditions. Wetlands export mainly recently fixedcarbon with little seasonal range. DOC in streams entering the small lakemay be composed of two pools; an older recalcitrant pool delivered bygroundwater and a young labile pool derived from recent organic matter.The relative proportion of these two pools changes seasonally due thechanges in the water flowpaths and organic carbon dynamics. Althoughchanges in local climate (temperature and/or precipitation) may alterthe relative proportions of the old and young pools, the older pool islikely to be more refractory to sedimentation and decomposition in thelake setting. Delivery of older pool DOC from the catchment andsusceptibility of this older pool to photochemical decomposition mayconsequently be important in governing the minimum DOC concentrationlimit in lakes.     

Potential effects of leaf litter on water quality in urban watersheds

Leaf litter plays a critical role in regulating ecological functions in headwater forest streams, whereas the effects of leaves on water quality in urbanized streams are not fully understood. This study examined the potential importance of leaf litter for the release and transformations of organic carbon and nutrients in urban streams, and compared the effects with other types of natural organic substrates (periphyton and stream sediment). Nutrients and organic carbon were leached from senescent leaves of 6 tree species in the laboratory with deionized water, and maximal releases, leaching rate constants, composition and bioavailability of the leached dissolved organic carbon (DOC) were determined. Stream substrates (leaf debris, rocks with periphyton, and sediment) were seasonally collected from urban and forest reference streams of the NSF Baltimore Long-term Ecological Research Site and incubated with overlying stream water to estimate areal fluxes of DOC and nitrogen. Leaf litter leaching showed large ranges in maximal releases of DOC (7.0–131 mg g^?1), dissolved organic nitrogen (DON; 0.07–1.39 mg g^?1) and total dissolved phosphorus (TDP; 0.14–0.70 mg g^?1) among tree species. DOC leaching rate constants, carbon to nitrogen ratios, and DOC bioavailability were all correlated with organic matter quality indicated by fluorescence spectroscopy. Results from substrate incubation experiments showed far higher DOC and DON release and nitrate retention with leaf debris than with sediment, or rocks with periphyton. DOC release from leaf debris was positively correlated with stream nitrate retention at residential and urban sites, with the highest values observed during the fall and lowest during the summer. This study suggests the potential importance of leaf litter quantity and quality on fostering DOC and nutrient release and transformations in urban streams. It also suggests that species-specific impacts of leaves should be considered in riparian buffer and stream restoration strategies.     

Vertical pattern and its driving factors in soil extracellular enzyme activity and stoichiometry along mountain grassland belts

Headwater streams are foci for nutrient and energy loading from terrestrial landscapes, in situ nutrient transformations, and downstream transport. Despite the prominent role that headwater streams can have in regulating downstream water quality, the relative importance of processes that can influence nutrient uptake have not been fully compared in heterotrophic aquatic systems. To address this research need, we assessed the seasonality of dissolved organic carbon (DOC) and nitrate (NO₃^?) uptake, compared the relative influence of hydrologic and biogeochemical drivers on observed seasonal trends in nutrient uptake, and estimated the influence of these biological transformations on watershed scale nutrient retention and export. We determined that seasonal reductions in DOC and NO₃^? concentrations led to decreases in the potential for the biotic community to take up nutrients, and that seasonality of DOC and NO₃^? uptake was consistent with the seasonal dynamics of ecosystem metabolism. We calculated that that during the post-snowmelt period (June to August), biotic retention of both dissolved organic carbon and nitrate exceeded export fluxes from this headwater catchment, highlighting the potential for biological processes to regulate downstream water quality.     

Increasing riverine export of dissolved organic carbon from China

River transport of dissolved organic carbon (DOC) to the ocean is a crucial but poorly quantified regional carbon cycle component. Large uncertainties remaining on the riverine DOC export from China, as well as its trend and drivers of change, have challenged the reconciliation between atmosphere-based and land-based estimates of China's land carbon sink. Here, we harmonized a large database of riverine in-situ measurements and applied a random forest model, to quantify riverine DOC fluxes (F_DOC) and DOC concentrations (C_DOC) in rivers across China. This study proposes the first DOC modeling effort capable of reproducing well the magnitude of riverine C_DOC and F_DOC, as well as its trends, on a monthly scale and with a much wider spatial distribution over China compared to previous studies that mainly focused on annual-scale estimates and large rivers. Results show that over the period 2001–2015, the average C_DOC was 2.25 ± 0.45 mg/L and average F_DOC was 4.04 ± 1.02 Tg/year. Simultaneously, we found a significant increase in F_DOC (+0.044 Tg/year², p = .01), but little change in C_DOC (−0.001 mg/L/year, p > .10). Although the trend in C_DOC is not significant at the country scale, it is significantly increasing in the Yangtze River Basin and Huaihe River Basin (0.005 and 0.013 mg/L/year, p < .05) while significantly decreasing in the Yellow River Basin and Southwest Rivers Basin (−0.043 and −0.014 mg/L/year, p = .01). Changes in hydrology, play a stronger role than direct impacts of anthropogenic activities in determining the spatio-temporal variability of F_DOC and C_DOC across China. However, and in contrast with other basins, the significant increase in C_DOC in the Yangtze River Basin and Huaihe River Basin is attributable to direct anthropogenic activities. Given the dominance of hydrology in driving F_DOC, the increase in F_DOC is likely to continue under the projected increase in river discharge over China resulting from a future wetter climate.     

Mineralisation of dissolved organic matter by heterotrophic stream biofilm communities in a large boreal catchment

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Contribution of plant photosynthates to dissolved organic carbon in a flooded rice soil

Dissolved organic C (DOC) plays important roles in nutrient cycling and methane production in flooded rice ecosystem. The microcosm experiment was carried out to measure directly the contribution of photosynthates to DOC by using a ¹³C pulse-chase labeling technique. DOC was operationally divided into water-extractable organic C (WEOC) and salt-extractable organic C (SEOC) by successive extraction firstly with deionized water and then with 0.25?M K₂SO₄. Total WEOC increased with plant growth, whereas SEOC concentration did not change significantly over the growing season. About 0.037–0.36% (mean 0.16%) of the assimilated ¹³C was incorporated into WEOC immediately after ¹³CO₂ assimilation (Day 0), but only 0–0.025% (mean 0.01%) was incorporated into SEOC. At the end of the growing season, the ¹³C amounts of WEOC substantially decreased, while those of SEOC slightly increased. The estimated net plant C contribution was 21?mg?C?plant^?1 to WEOC and 6?mg?C?plant^?1 to SEOC, corresponding to 33.8% of total WEOC and 20.2% of total SEOC at the end of the growing season, respectively. The results suggest that the incorporation and decomposition of the photosynthesized C occurred rapidly in rice soil which significantly affected the WEOC dynamics, but SEOC appeared to be in equilibrium with the native soil organic matter, receiving less effect from the plant growth.     

Dissolved organic carbon in streams from artificially drained and intensively farmed watersheds in Indiana, USA

Dissolved organic carbon (DOC) in streams draining hydrologically modified and intensively farmed watersheds has not been well examined, despite the importance of these watersheds to water quality issues and the potential of agricultural soils to sequester carbon. We investigated the dynamics of DOC for 14 months during 2006 and 2007 in 6 headwater streams in a heavily agricultural and tile-drained landscape in the midwestern US. We also monitored total dissolved nitrogen (TDN) in the streams and tile drains. The concentrations of DOC in the streams and tile drains ranged from approximately 1–6 mg L^?1, while concentrations of TDN, the composition of which averaged >94% nitrate, ranged from <1 to >10 mg L^?1. Tile drains transported both DOC and TDN to the streams, but tile inputs of dissolved N were diluted by stream water, whereas DOC concentrations were generally greater in the streams than in tile drains. Filamentous algae were dense during summer base flow periods, but did not appear to contribute to the bulk DOC pool in the streams, based on diel monitoring. Short-term laboratory assays indicated that DOC in the streams was of low bioavailability, although DOC from tile drains in summer had bioavailability of 27%. We suggest that these nutrient-rich agricultural streams are well-suited for examining how increased inputs of DOC, a potential result of carbon sequestration in agricultural soils, could influence ecosystem processes.     

Lability of organic carbon in lakes of different trophic status

1. We used first‐order kinetic parameters of biological oxygen demand (BOD), the constant of aerobic decomposition (k) and the asymptotic value of BOD (BOD_ult), to characterise the lability of organic carbon pools in six lakes of different trophic state: L. Naroch, L. Miastro and L. Batorino (Belarus), L. Kinneret (Israel), L. Ladoga (Russia) and L. Mendota (U.S.A.). The relative contributions of labile and refractory organic carbon fractions to the pool of total organic carbon (TOC) in these lakes were quantified. We also determined the amounts of labile organic carbon within the dissolved and particulate TOC pools in the three Belarus lakes. 2. Mean annual chlorophyll concentrations (used as a proxy for lake trophic state) ranged from 2.3 to 50.6 μg L⁻¹, labile organic carbon (OC_L = 0.3BOD_ult) from 0.75 to 2.95 mg C L⁻¹ and k from 0.044 to 0.14 day⁻¹. 3. Our data showed that there were greater concentrations of OC_L but lower k values in more productive lakes. 4. In all cases, the DOC fraction dominated the TOC pool. OC_L was a minor component of the TOC pool averaging about 20%, irrespective of lake trophic state. 5. In all the lakes, most (c. 85%) of the DOC pool was refractory, corresponding with published data based on measurements of bacterial production and DOC depletion. In contrast, a larger fraction (27–55%) of the particulate organic carbon (POC) pool was labile. The relative amount of POC in the TOC pool tended to increase with increasing lake productivity. 6. Long‐term BOD incubations can be valuable in quantifying the rates of breakdown of the combined particulate and dissolved organic carbon pools and in characterising the relative proportions of the labile and recalcitrant fractions of these pools. If verified from a larger number of lakes our results could have important general implications.     

The organic carbon dynamics of a moorland catchment in N. W. England

The carbon cycle was quantified in the catchment of Doe House Gill, which drains high-relief moorland, with thin organic-rich soils (leptosols and podzols) 10–25 cm deep, in northern England. The soil C pool of 8,300 g m^-2 is due mainly to humic acid and older humin. If steady state is assumed, and a single soil C pool, the average ¹⁴C content of the whole soil (93% modern) yields a mean carbon residence time of 800 years, although this varied from 300 to 1,600 years in the four samples studied. Stream water fluxes of dissolved and particulate organic carbon (DOC, POC) were 2.5 and 0.4 g m⁻² a⁻¹ respectively in 2002–2003, lower than values for some other upland streams in the UK. The C pool, flux, and isotope data were used, with the assumption of steady state, to calibrate DyDOC, a model that simulates the soil carbon cycle, including the generation and transport of DOC. According to DyDOC, the litter pool (ca. 100 gC m⁻²) turns over quickly, and most (>90%) of the litter carbon is rapidly mineralised. The soil is calculated to gain only 16 gC m⁻² a⁻¹, and to lose the same amount, about 80% as CO₂ and 20% as DOC. From the DO¹⁴C content of 107.5% modern (due to “bomb carbon”) the model could be calibrated by assuming all DOC to come directly from litter, but DOC is more likely a mixture, derived from more than one soil C pool. The seasonal variability exhibited by stream water DOC concentration (maximum in September, minimum in January) is attributed mainly to variations in rainfall and evapotranspiration, rather than in the metabolic production rate of “potential DOC”. The model predicts that, for a Q ₁₀ of 2, the total soil organic C pool would decrease by about 5% if subjected to warming over 200 years. DyDOC predicts higher DOC fluxes in response to increased litter inputs or warming, and can simulate changes in DOC flux due to variations in sorption to soil solids, that might occur due to acidification and its reversal.     

Modeling Allochthonous Dissolved Organic Carbon Mineralization Under Variable Hydrologic Regimes in Boreal Lakes

Here, we explore the interaction between hydrology and the reactivity of allochthonous dissolved organic carbon (DOC_alloch) in determining the potential of DOC_alloch to generate CO₂ through biological and photo-chemical mineralization in boreal lakes. We developed a mechanistic model that integrates the reactivity continuum (RC) concept to reconstruct in-lake mineralization of DOC_alloch under variable hydrologic conditions using empirical measurements of DOC_alloch concentrations and reactivity as model inputs. The model predicts lake DOC_alloch concentration (L-DOC_alloch) and its average overall reactivity \( \left( {\bar{K}_{\text{alloch}} } \right) \), which integrates the distribution of DOC_alloch ages within the lake as a function of the DOC loading (DOC_in), the initial reactivity of this DOC_in (k ₀), and the lake water residence time (WRT). The modeled DOC_alloch mineralization rates and concentrations were in agreement with expectations based on observed and published values of ambient lake DOC concentrations and reactivity. Results from this modeling exercise reveal that the interaction between WRT and k ₀ is a key determinant of the ambient concentration and reactivity of lake DOC_alloch, which represents the bulk of DOC in most of these lakes. The steady-state \( \left( {\bar{K}_{\text{alloch}} } \right) \) also represents the proportion of CO₂ that can be extracted from DOC_alloch during its transit through lakes, and partly explains the patterns in surface water pCO₂ oversaturation that have been observed across gradients of lake size and volume. We estimate that in-lake DOC_alloch mineralization could potentially contribute on average 30–40% of the observed surface carbon dioxide partial pressure (pCO₂) across northern lakes. Applying the RC framework to in-lake DOC_alloch dynamics improves our understanding of DOC_alloch transformation and fate along the aquatic network, and results in a predictable mosaic of DOC reactivity and potential CO₂ emissions across lakes within a landscape.     

Chemical character and origin of organic acids in streams and seepage lakes of central Maine

Organic acids and inorganic chemistry were examined in seventeen seepage lakes, seven streams, and one seep in central Maine. The objectives of this analysis were to determine the quantity and quality of dissolved organic carbon (DOC), and to assess the relationship between organic and inorganic surface water chemistry. Lakes and streams sampled were dilute (average conductivity of 20.3 μS cm^?1) with a wide range of DOC (125–2593 μmol C L^?1). Organic acids in DOC were evaluated by:

DOC fractionation (hydrophobic acids and neutrals, and hydrophilic acids, bases, and neutrals);

DOC isolation followed by FT-IR, base titration, and chemical analyses;

adsorption on solid phase extraction columns; and charge balance studies.

All lakes and streams were dominated by hydrophobic and hydrophilic acids (60 to 92% of DOC). Lakes and streams with low DOC had low hydrophobic to hydrophilic acid ratios (ca 1.2–1.3), regardless of pH and acid neutralizing capacities (ANC), compared to lakes and streams with moderate to high DOC concentrations (ca 1.9–2.4). Based on FT-IR spectroscopy and chemical analysis, organic acids were found to be dominated by a strong carboxylic character. Titration data of isolated DOC allowed accurate prediction of organic anions, which were strongly pH dependent (organic anions ranged from 14 to 198 μeq L^?1). Exchange acidity averaged 11.3, 13.6, and 8.7 μeq mg C^?1 for lake hydrophobic acids, lake hydrophilic acids, and stream hydrophobic acids, respectively. Overall evidence suggested that DOC and organic acid characteristics were related to their carboxylic functional group content and that the nature of these constituents was similar despite the source of origin (upland soils, wetlands, or Sphagnum deposits). Also, contact of soil leachates with B horizons seemed to be a controlling factor in DOC quantity and quality in the lakes and streams studied.     

Dissolved organic carbon and nitrate concentrations in streams: a useful index indicating carbon and nitrogen availability in catchments

Dissolved organic carbon (DOC) and NO₃^– are important forms of C and N in stream water. Hypotheses concerning relationships between DOC and NO₃^– concentrations have been proposed, but there are no reports demonstrating a relationship between them in stream water. We observed 35 natural streams in the Lake Biwa watershed, central Japan, and found an inverse relationship between DOC and NO₃^– concentrations. This relationship was also found in observations of their seasonal variations in the Lake Biwa watershed. Moreover, this relationship was also found to apply to watersheds in other regions in Japan. These results suggest that forest biogeochemical processes which control DOC and NO₃^– concentrations in Japanese streams are closely related. Excess N availability together with a C (energy) deficit in a soil environment may explain this relationship. DOC and NO₃^– concentrations in streams will thus be a useful index indicating C and N availability in catchments.     

Characteristics of DOC Exported from Northern Hardwood Forests Receiving Chronic Experimental NO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack> Deposition

Abstract Sugar maple (Acer saccharum Marsh.)-dominated northern hardwood forests of the Great Lakes Region commonly receive elevated levels of atmospheric nitrate (NO₃⁻) deposition, which can alter belowground carbon (C) cycling. Past research has demonstrated that chronic experimental NO₃⁻ deposition (3 g N m⁻² y⁻¹ above ambient) elicits a threefold increase in the leaching loss of dissolved organic carbon (DOC). Here, we used DOC collected from tension-cup lysimeters to test whether increased DOC export under experimental NO₃⁻ deposition originated from forest floor or mineral soil organic matter (SOM). We used DOC radiocarbon dating to quantify C sources and colorimetric assays to measure DOC aromaticity and soluble polyphenolic content. Our results demonstrated that DOC exports are primarily derived from new C (<50-years-old) in the forest floor under both ambient and experimental NO₃⁻ deposition. Experimental NO₃⁻ deposition increased soluble polyphenolic content from 25.03 ± 4.26 to 49.19 ± 4.23 μg phenolic C mg DOC⁻¹, and increased total aromatic content as measured by specific UV absorbance. However, increased aromatic compounds represented a small fraction (<10%) of the total observed increased DOC leaching. In combination, these findings suggest that experimental NO₃⁻ deposition has altered the production or retention as well as phenolic content of DOC formed in forest floor, however exact mechanisms are uncertain. Further elucidation of the mechanism(s) controlling enhanced DOC leaching is important for understanding long-term responses of Great Lakes forests to anthropogenic N deposition and the consequences of those responses for aquatic ecosystems.     

Sources and export fluxes of inorganic and organic carbon and nutrient species from the seasonally ice-covered Yukon River

Climate and environmental changes are having profound impacts on Arctic river basins, but the biogeochemical response remains poorly understood. To examine the effect of ice formation on temporal variations in composition and fluxes of carbon and nutrient species, monthly water and particulate samples collected from the lower Yukon River between July 2004 and September 2005 were measured for concentrations of organic and inorganic C, N, and P, dissolved silicate (Si(OH)₄), and stable isotope composition (δD and δ¹⁸O). All organic carbon and nutrient species had the highest concentration during spring freshet and the lowest during the winter season under the ice, indicating dominant sources from snowmelt and flushing of soils in the drainage basin. In contrast, inorganic species such as dissolved inorganic carbon (DIC) and Si(OH)₄ had the highest concentrations in winter and the lowest during spring freshet, suggesting dilution during snowmelt and sources from groundwater and leaching/weathering of mineral layer. The contrasting relation with discharge between organic, such as dissolved organic carbon (DOC), and inorganic, such as DIC and Si(OH)₄, indicates hydrological control of solute concentration but different sources and transport mechanisms for organic and inorganic carbon and nutrient species. Concentration of DOC also shows an inter-annual variability with higher DOC in 2005 (higher stream flow) than 2004 (lower stream flow). Average inorganic N/P molar ratio was 110?±?124, with up to 442 under the ice and 38–70 during the ice-open season. While dissolved organic matter had a higher C/N ratio under the ice (45–62), the particulate C/N ratio was lower during winter (21–26) and spring freshet (19). Apparent fractionation factors of C, N, P, Si and δD and δ¹⁸O between ice and river water varied considerably, with high values for inorganic species such as DIC and Si(OH)₄ (45 and 9550, respectively) but lower values for DOC (4.7). River ice formation may result in fractionation of inorganic and organic solutes and the repartitioning of seasonal flux of carbon and nutrient species. Annual export flux from the Yukon River basin was 1.6?×?10¹² g-DOC, 4.4?×?10¹² g-DIC, and 0.89?×?10¹² g-POC during 2004–2005. Flux estimation without spring freshet sampling results in considerable underestimation for organic species but significant overestimation for inorganic species regardless of the flux estimation methods used. Without time-series sampling that includes frozen season, an over- or under-estimation in carbon and nutrient fluxes will occur depending on chemical species. Large differences in carbon export fluxes between studies and sampling years indicate that intensive sampling together with long-term observations are needed to determine the response of the Yukon River to a changing climate.     

Contrasting nutrient exports from a forested and an agricultural catchment in south-eastern Australia

Dissolved organic carbon (DOC) and total and inorganic nitrogen and phosphorus concentrations were determined over 3 years in headwater streams draining two adjacent catchments. The catchments are currently under different land use; pasture/grazing vs plantation forestry. The objectives of the work were to quantify C and nutrient export from these landuses and elucidate the factors regulating export. In both catchments, stream water dissolved inorganic nutrient concentrations exhibited strong seasonal variations. Concentrations were highest during runoff events in late summer and autumn and rapidly declined as discharge increased during winter and spring. The annual variation of stream water N and P concentrations indicated that these nutrients accumulated in the catchments during dry summer periods and were flushed to the streams during autumn storm events. By contrast, stream water DOC concentrations did not exhibit seasonal variation. Higher DOC and NO₃ ⁻ concentrations were observed in the stream of the forest catchment, reflecting greater input and subsequent breakdown of leaf-litter in the forest catchment. Annual export of DOC was lower from the forested catchment due to the reduced discharge from this catchment. In contrast however, annual export of nitrate was higher from the forest catchment suggesting that there was an additional NO₃ ⁻ source or reduction of a NO₃ ⁻ sink. We hypothesize that the denitrification capacity of the forested catchment has been significantly reduced as a consequence of increased evapotranspiration and subsequent decrease in streamflow and associated reduction in the near stream saturated area.     

Effects of desiccation and rewetting on the release and decomposition of dissolved organic carbon from benthic macroalgae

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Soil carbon and belowground carbon balance of a short‐rotation coppice: assessments from three different approaches

Uncertainty in soil carbon (C) fluxes across different land‐use transitions is an issue that needs to be addressed for the further deployment of perennial bioenergy crops. A large‐scale short‐rotation coppice (SRC) site with poplar (Populus) and willow (Salix) was established to examine the land‐use transitions of arable and pasture to bioenergy. Soil C pools, output fluxes of soil CO₂, CH₄, dissolved organic carbon (DOC) and volatile organic compounds, as well as input fluxes from litter fall and from roots, were measured over a 4‐year period, along with environmental parameters. Three approaches were used to estimate changes in the soil C. The largest C pool in the soil was the soil organic carbon (SOC) pool and increased after four years of SRC from 10.9 to 13.9 kg C m^?2. The belowground woody biomass (coarse roots) represented the second largest C pool, followed by the fine roots (Fr). The annual leaf fall represented the largest C input to the soil, followed by weeds and Fr. After the first harvest, we observed a very large C input into the soil from high Fr mortality. The weed inputs decreased as trees grew older and bigger. Soil respiration averaged 568.9 g C m^?2 yr^?1. Leaching of DOC increased over the three years from 7.9 to 14.5 g C m^?2. The pool‐based approach indicated an increase of 3360 g C m^?2 in the SOC pool over the 4‐year period, which was high when compared with the ?27 g C m^?2 estimated by the flux‐based approach and the ?956 g C m^?2 of the combined eddy‐covariance + biometric approach. High uncertainties were associated to the pool‐based approach. Our results suggest using the C flux approach for the assessment of the short‐/medium‐term SOC balance at our site, while SOC pool changes can only be used for long‐term C balance assessments.     

Hydrologic Drivers and Seasonality of Dissolved Organic Carbon Concentration, Nitrogen Content, Bioavailability, and Export in a Forested New England Stream

We present the results of a full year of high-resolution monitoring of hydrologic event-driven export of stream dissolved organic matter (DOM) from the forested Bigelow Brook watershed in Harvard Forest, Massachusetts, USA. A combination of in situ fluorescent dissolved organic matter (FDOM) measurement, grab samples, and bioassays was utilized. FDOM was identified as a strong indicator of concentration for dissolved organic carbon (DOC, r ² = 0.96), dissolved organic nitrogen (DON, r ² = 0.81), and bioavailable DOC (BDOC, r ² = 0.81). Relationships between FDOM and concentration were utilized to improve characterization of patterns of hydrological event-driven export and the quantification of annual export. This characterization was possible because DOM composition remained relatively consistent seasonally; however, a subtle shift to increased fluorescence per unit absorbance was observed for summer and fall seasons and percent BDOC did increase slightly with increasing concentrations. The majority of export occurred during pulsed hydrological events, so the greatest impact of bioavailable exports may be on downstream aquatic ecosystems. Export from individual events was highly seasonal in nature with the highest flow weighted mean concentrations (DOC_FW) being observed in late summer and fall months, but the highest total export being observed for larger winter storms. Seasonal trends in DOC export coincide with weather driven changes in surface and subsurface flow paths, potential for depletion and rebuilding of a flushable soil organic matter pool, and the availability of terrestrial carbon sources such as leaf litter. Our approach and findings demonstrate the utility of high frequency FDOM measurement to improve estimates of intra-annual temporal trends of DOM export.     

Vulnerability of wetland soil carbon stocks to climate warming in the perhumid coastal temperate rainforest

The perhumid coastal temperate rainforest (PCTR) of southeast Alaska has some of the densest soil organic carbon (SOC) stocks in the world (>300 Mg C ha^?1) but the fate of this SOC with continued warming remains largely unknown. We quantified dissolved organic carbon (DOC) and carbon dioxide (CO₂) yields from four different wetland types (rich fen, poor fen, forested wetland and cedar wetland) using controlled laboratory incubations of surface (10 cm) and subsurface (25 cm) soils incubated at 8 and 15 °C for 37 weeks. Furthermore, we used fluorescence characterization of DOC and laboratory bioassays to assess how climate-induced soil warming may impact the quality and bioavailability of DOC delivered to fluvial systems. Soil temperature was the strongest control on SOC turnover, with wetland type and soil depth less important in controlling CO₂ flux and extractable DOC. The high temperature incubation increased average CO₂ yield by ~40 and ~25% for DOC suggesting PCTR soils contain a sizeable pool of readily biodegradable SOC that can be mineralized to DOC and CO₂ with future climate warming. Fluxes of CO₂ were positively correlated to both extractable DOC and percent bioavailable DOC during the last few months of the incubation suggesting mineralization of SOC to DOC is a strong control of soil respiration rates. Whether the net result is increased export of either carbon form will depend on the balance between the land to water transport of DOC and the ability of soil microbial communities to mineralize DOC to CO₂.     

Environmental variability in the reactivity of freshwater dissolved organic carbon to UV-B

Reductions in the global stratospheric ozone layer arethought to be increasing the amount of ultraviolet B (UV-B) radiationreaching the planets surface and may be affecting the chemistry ofdissolved organic carbon (DOC) in surface waters. We studied theabundance of chromophores in DOC collected in four different aquaticenvironments in southwestern Nova Scotia using ¹³C nuclearmagnetic resonance (¹³C NMR) spectroscopy. We showed a clearseasonal pattern in the distribution of structural carbon related tolight-sensitive chromophores. There seemed to be little variation in theUV-B related chemical structure of DOC between lakes and streams, thoughwater from a bog pool showed large differences from the other samples. Thesepatterns of potential UV-B reactivity tend to be dampened however, byvariations in DOC concentrations which also occur seasonally.