Pore Water Dissolved Organic Carbon Concentrations Research Articles

Spatial, Seasonal, and Diel Controls of Nitrogen‐Carbon‐Oxygen Cycling During Lake‐Water Infiltration to an Aquifer

AbstractMany freshwater lakes are groundwater flow‐through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake‐bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O2), and dissolved organic carbon (DOC) during lake‐water recharge from a groundwater flow‐through lake. Lake‐water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O2 and DOC concentrations decreased with depth while nitrate (NO3−) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO3− production and transport was seasonally dependent. In winter, NO3− and O2 were exported beyond 100‐cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO3− reduction zones, and diel patterns of O2 and NO3− penetration depths were observed. Microbial community compositions and stable isotope profiles (δ15N[NO3−], δ18O[NO3−], δ18O[O2]) were consistent with apparent C–N–O reaction stoichiometries indicating O2 reduction and nitrification in shallower porewater, followed by varying NO3− reduction at depth. Maximum porewater NO3− concentrations (∼10–20 μM) were limited by infiltrating O2 concentrations and C/N ratios of reacting organic matter. Lake‐water level variations caused changes in shoreline position and porewater velocities, while variations in lake‐water temperature, DOC, and O2 contributed to changes in reaction rates and depth of O2 and NO3− penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

Spatiotemporal dynamics of dissolved organic carbon in a subtropical wetland and their implications for methane emissions

Wetlands represent about one-third of the global soil organic carbon storage and are the largest natural source of atmospheric methane, a powerful greenhouse gas. Understanding the factors that influence the carbon dynamics in wetlands, and their influence on methane emission, is therefore important. Dissolved organic carbon (DOC) is a major form of carbon export from wetlands and plays an essential role in the aquatic carbon cycling process. However, constraints on spatial and temporal dynamics of DOC in vertical peat layers and their relationship to wetland methane emissions are still rare. Here we investigated spatiotemporal changes in porewater DOC concentration and optical properties (SUVA254, E2/E3, E4/E6) in surface (0–10 cm) and deep (20–30 cm, 50–60 cm, 100–110 cm) peat layers in a subtropical wetland complex, central China, with the aim to explore DOC dynamics and their relationship to methane emissions from wetlands. DOC dynamics and environmental controls were investigated in the context of high-resolution environmental monitoring, including air temperature, rainfall, water table depth, water chemistry, and methane emissions. DOC of surface peat layers generally had higher concentrations, higher aromaticity, lower humification, and greater temporal variations compared to deeper peat layers. During summer floods and high water table conditions, DOC concentrations in the surface peat increased significantly, whilst DOC exports from rivers and lakes also increased synchronously. In contrast, DOC concentrations and spectral properties of deep peat layers remained constant across the sampling months and water table fluctuations. Methane emissions were positively correlated with air temperature and DOC concentration in the porewater of surface peat layers, and negatively correlated with water table depth. Our results suggest that DOC concentration in the porewater of surface peat layers may also have affected the flux of methane emission from wetlands.

Production of Labile Protein-Like Dissolved Organic Carbon Associated With Anaerobic Methane Oxidization in the Haima Cold Seeps, South China Sea

Cold seeps where methane-rich fluids escape from the seafloor generally support enormous biomass of chemosynthetic organisms and associated fauna. In addition to transporting a great amount of methane toward the seafloor, cold seeps also contribute to the aged, dissolved organic carbon (DOC) pool in the deep ocean. Here, two sediment cores from the “Haima cold seeps,” northern South China Sea and a nearby reference core were analyzed for pore-water sulfate and DOC concentrations, δ13C of DOC, and optical properties of dissolved organic matter (DOM). High DOC concentrations (0.9–3.7 mM) accompanied by extremely low δ13C values (−43.9 to −76.2‰) suggest the conversion of methane into sedimentary DOC pool in the seep sediments. Parallel factor analysis (PARAFAC) of the fluorescence excitation-emission matrices shows higher fluorescent intensities of labile protein-like components (C2 and C4) and lower fluorescent intensities of refractory humic-like components (C1 and C3) in the seep cores compared to the reference core. The intensity of C2 is positively correlated with DOC concentrations and δ13C-DOC in the seep sediments, suggesting that the labile protein-like DOM was produced by the anaerobic oxidation of methane (AOM). Moreover, low humification index (HIX) and high biological index (BIX) values also indicate intensified production of relatively labile DOM with lower degradation degree in the seep cores compared to the reference core. Hence, we highlight that methane-derived DOC may serve as important carbon and energy sources for heterotrophic microbial communities due to its relatively labile nature.

Probing sedimentary DOM in the deepest sector of Earth's surface

It has been suggested that hadal trenches are depocenters of organic matter and hotspots for microbial activities. Here, we measured the concentrations of pore-water dissolved organic carbon (DOC) in the seven short cores retrieved from three trenches (i.e., the Mariana Trench, the Mussau Trench, and the New Britain Trench), and analyzed the optical properties of pore-water dissolved organic matter (DOM) from the axis, forearc, and abyssal sediments in the southern Mariana Trench. The positive correlation between the average DOC concentrations and the in-situ total oxygen uptakes among the three trenches suggests that rate of organic matter degradation and redox condition likely control the downcore pore-water DOC concentrations in hadal sediments. Furthermore, analysis of fluorescence DOM reveals a higher carbon-normalized fluorescence of components emitting in the visible (“humic” and “fulvic”-like) at the Mariana Trench axis than at the abyssal plain and forearc. Together with the downcore increase in humification indices and absorbance ratios at the trench axis cores, this points at a significant accumulation of highly degraded, persistent, low-molecular-weight DOM produced by intensified microbial respiration at the trench axis. To our knowledge, this is the first study that examines the features of pore-water DOM in hadal trenches, which provides additional supports for the argument that microbial activities are enhanced at the trench axis and has implication for understanding DOM cycling in deep-sea sediments.

New progress achieved in seasonal dynamics of dissolved organic carbon of permafrost peatland through Chinese–United States EcoPartnership relationships

AbstractPermafrost peatland plays an important role in the global carbon (C) cycle, and dissolved organic carbon (DOC) is one of the most important components to C budgets in this system. Through the Chinese–United States EcoPartnership program, Dr Xianwei Wang, Li Sun, and Prof Changchun Song et al. from the Northeast Institute of Geography and Agroecology of Chinese Academy of Sciences and Prof Aixin Hou from the Louisiana State University observed dynamics of DOC concentrations and specific ultraviolet absorbance at 254 nm (SUVA254) obtained from soil porewater of permafrost peatlands for two growing seasons in the Great Hing'an Mountains, Northeast China. Soil porewater DOC concentrations varied greatly with depths during the growing season, ranging between 22.08 and 65.02 mg L−1. There was no significant relationship between DOC concentrations and SUVA254. DOC concentrations were higher in autumn and increased as the seasonal thaw depth increased. DOC concentrations of supra‐permafrost water at freeze–thaw boundary were also higher than those at the other soil depths. Temperature and thawing depth had been shown to affect DOC concentrations at different soil depths. Our finding suggests that warming and deepening of the active layer likely increase the DOC productions in the permafrost peatland, which may influence the C balance in these C‐enriched ecosystems.

Molecular Traits of Dissolved Organic Matter in the Subterranean Estuary of a High-Energy Beach: Indications of Sources and Sinks

Advective flows of seawater and fresh groundwater through coastal aquifers form a unique ecohydrological interface, the subterranean estuary (STE). Here, freshly produced marine organic matter and oxygen mix with groundwater, which is low in oxygen and contains aged organic carbon (OC) from terrestrial sources. Along the groundwater flow paths, dissolved organic matter (DOM) is degraded and inorganic electron acceptors are successively used up. Because of the different DOM sources and ages, exact degradation pathways are often difficult to disentangle, especially in high-energy environments with dynamic changes in beach morphology, source composition, and hydraulic gradients. From a case study site on a barrier island in the German North Sea, we present detailed biogeochemical data from freshwater lens groundwater, seawater, and beach porewater samples collected over different seasons. The samples were analyzed for physico-chemistry (e.g., salinity, temperature, dissolved silicate), (reduced) electron acceptors (e.g., oxygen, nitrate, and iron), and dissolved organic carbon (DOC). DOM was isolated and molecularly characterized via soft-ionization ultra-high-resolution mass spectrometry, and molecular formulae were identified in each sample. We found that the islands’ freshwater lens harbors a surprisingly high DOM molecular diversity and heterogeneity, possibly due to patchy distributions of buried peat lenses. Furthermore, a comparison of DOM composition of the endmembers indicated that the Spiekeroog high-energy beach STE conveys chemically modified, terrestrial DOM from the inland freshwater lens to the coastal ocean. In the beach intertidal zone, porewater DOC concentrations, lability of DOM and oxygen concentrations, decreased while dissolved (reduced) iron and dissolved silicate concentrations increased. This observation is consistent with the assumption of a continuous degradation of labile DOM along a cross-shore gradient, even in this dynamic environment. Accordingly, molecular properties of DOM indicated enhanced degradation, and “humic-like” fluorescent DOM fraction increased along the flow paths, likely through accumulation of compounds less susceptible to microbial consumption. Our data indicate that the high-energy beach STE is likely a net sink of OC from the terrestrial and marine realm, and that barrier islands such as Spiekeroog may act as efficient “digestors” of organic matter.

Hydrogeologic setting overrides any influence of wildfire on pore water dissolved organic carbon concentration and quality at a boreal fen

AbstractWestern Boreal Canada could experience drier hydrometeorological conditions under future climatic changes, and the drying of nonpermafrost peatlands can lead to higher frequency and extent of wildfires. Despite increasing pressures, our understanding of the impact of fire on dissolved organic carbon (DOC) concentration and quality across boreal peatlands is not consistent. This study capitalizes on the rare opportunity of having 3 years of prefire and 3 years of postfire DOC data at a treed, moderate‐rich fen in the Western Boreal Plain, northern Alberta, to investigate wildfire effects on peatland DOC dynamics. We investigated whether a wildfire facilitated any changes in the pore water DOC concentration and quality. There was very little impact of the fire directly, with no significant changes in DOC concentrations postfire. We highlight that DOC patterns are more likely to be controlled by local hydrogeological factors than any effect of fire. Fall hydrological conditions and subsequent winter storage processes impose a strong control on DOC concentrations the following year. We suggest that the presence or absence of concrete ground frost in the fen (determined by fall water table position) influences overwinter storage changes, controlling the effect that DOC‐poor snowmelt may have on pore water concentrations. However, an increase in SUVA254 was found 2 years postfire, indicating an increase in aromaticity. These results highlight the need for careful consideration of the local hydrogeologic setting and hydrological regime when predicting and analysing trends in DOC concentrations and quality.

Hydrological control of dissolved organic carbon dynamics in a rehabilitated <i>Sphagnum</i>-dominated peatland: a water-table based modelling approach

Abstract. Hydrological disturbances could increase dissolved organic carbon (DOC) exports through changes in runoff and leaching, which reduces the potential carbon sink function of peatlands. The objective of this study was to assess the impact of hydrological restoration on hydrological processes and DOC dynamics in a rehabilitated Sphagnum-dominated peatland. A conceptual hydrological model calibrated on the water table and coupled with a biogeochemical module was applied to La Guette peatland (France), which experienced a rewetting initiative on February 2014. The model (eight calibrated parameters) reproduced water-table (0.1<NS<0.61) and pore-water DOC concentrations (2<RMSE<11 mg L−1) in a time series (1 April 2014 to 15 December 2017) in two contrasting locations (rewetted and control) in the peatland. Hydrological restoration was found to impact the water balance through a decrease in slow deep drainage and an increase in fast superficial runoff. Observed DOC concentrations were higher in summer in the rewetted location compared to the control area and were linked to a difference in dissolved organic matter composition analyzed by fluorescence. Hydrological conditions, especially the severity of the water-table drawdown in summer, were identified as the major factor controlling DOC-concentration dynamics. The results of the simulation suggest that the hydrological restoration did not affect DOC loads, at least in a short-term period (3 years). However, it impacted the temporal dynamics of DOC exports, which were the most episodic and were mainly transported through fast surface runoff in the area affected by the restoration, while slow deep drainage dominated DOC exports in the control area. In relation to dominant hydrological processes, exported DOC is expected to be derived from more recent organic matter in the top peat layer in the rewetted area, compared to the control area. Since it is calibrated on water-table and DOC concentration, the model presented in this study proved to be a relevant tool in identifying the main hydrological processes and factors controlling DOC dynamics in different areas of the same peatland. It is also a suitable alternative to a discharge-calibrated catchment model when the outlet is not easy to identify or to monitor.

Biologically driven DOC release from peatlands during recovery from acidification

Peatlands store 1/3 of global soil carbon, destabilisation of which contributes much to the recent increase in DOC (dissolved organic carbon) in freshwater ecosystems. One suggested mechanism for the enhanced decomposition of peat and the releases of DOC is recovery from acidification. However, no biological role in the process has yet been identified. Here we report extracellular enzyme activities and microbial composition in peatlands of Korea, the UK, Japan and Indonesia, and find higher pH to promote phenol oxidase activities, greater abundances in Actinobacteria and fungi, and enhanced pore-water DOC concentrations. Our pH manipulation experiments also showed that increase in pH enhanced phenol oxidase activity and DOC production with greater Actinobacterial and fungal abundances. Finally, knockout or addition of phenol oxidase dramatically changed DOC and phenolic production, indicating the central role of phenol oxidase in DOC mobilisation. Our findings provide evidence to support a previously unrecognized biological mechanism through which pH increases activate phenol oxidase, accelerating the release of DOC and phenolics.

Spatial Variation in Sediment Organic Carbon Distribution across the Alaskan Beaufort Sea Shelf

In September 2009, a series of sediment cores were collected across the Alaskan Beaufort Sea shelf-slope. Sediment and porewater organic carbon (OC) concentrations and stable carbon isotope ratios (δ13C) were measured to investigate spatial variations in sediment organic matter (OM) sources and distribution of these materials across the shelf. Cores were collected along three main nearshore (shelf) to offshore (slope) sampling lines (transects) from east-to-west along the North Slope of Alaska: Hammerhead (near Camden Bay), Thetis Island (near Prudhoe Bay), and Cape Halkett (towards Point Barrow). Measured sediment organic carbon (TOC) and porewater dissolved organic carbon (DOC) concentrations and their respective δ13C values were used to investigate the relative contribution of different OM sources to sediment OC pool cycled at each location. Sources of OM considered included: water column-sourced phytodetritus, deep sediment methane (CH4), and terrestrial, tundra/river-sourced OM. Results of these measurements, when coupled with results from previous research and additional analyses of sediment and porewater composition, show a pattern of spatial variation in sediment OC concentrations, OM source contributions, and OM cycled along the Alaskan Beaufort Sea shelf. In general, measured sediment total organic carbon (TOC) concentrations, δ13CTOC values, porewater DOC concentrations, and δ13CDOC values are consistent with an east-to-west transport of modern Holocene sediments with higher OC concentrations primarily sourced from relatively labile terrestrial, tundra OM sources and phytodetritus along the Alaskan Beaufort shelf. Sediment transport along the shelf results in the medium-to-long term accumulation and burial of sediment OM focused to the west which in turn results in higher biogenic CH4 production rates and higher upward CH4 diffusion through the sediments resulting in CH4−AMO-sourced contribution to sediment OC westward along the shelf. Understanding current OM sources and distributions along the Alaskan Beaufort shelf is important for enhancing models of carbon cycling in Arctic coastal shelf systems. This will help support the prediction of the climate response of the Arctic created in the face of future warming scenarios.

Responses of CO2 emission and pore water DOC concentration to soil warming and water table drawdown in Zoige Peatlands

Peatlands in Zoige Plateau contains more than half of peatland carbon stock in China. This part of carbon is losing with climate change through dissolved organic carbon (DOC) export and carbon dioxide (CO2) emissions, both of which are vulnerable to the environmental changes, especially on the Zoige Plateau with a pace of twice the observed rate of global climate warming. This research aimed to understand how climate change including soil warming, rainfall reduction and water table change affect CO2 emissions and whether the trends of changes in CO2 emission are consistent with those of pore water DOC concentration. A mesocosm experiment was designed to investigate the CO2 emission and pore water DOC during the growing seasons of 2009–2010 under scenarios of passive soil warming, 20% rainfall reduction and changes to the water table levels. The results showed a positive relationship between CO2 emission and DOC concentration. For single factor effect, we found no significant relationship between water table and CO2 emission or DOC concentration. However, temperature at 5 cm depth was found to have positive linear relationship with CO2 emission and DOC concentration. The combined effect of soil warming and rainfall reduction increased CO2 emission by 96.8%. It suggested that the drying and warming could stimulate potential emission of CO2. Extending this result to the entire peatland area in Zoige Plateau translates into 0.45 Tg CO2 emission per year over a growing season. These results suggested that the dryer and warmer Zoige Plateau will increase CO2 emission. We also found the contribution rate of DOC concentration to CO2 emission was increased by 12.1% in the surface layer and decreased by 13.8% in the subsurface layer with combined treatment of soil warming and rainfall reduction, which indicated that the warmer and dryer environmental conditions stimulate surface peat decomposition process.

Climate change effects on peatland decomposition and porewater dissolved organic carbon biogeochemistry

Carbon accumulation and storage is a defining characteristic of peatland ecosystems. Decomposition of peat releases dissolved organic carbon (DOC) to receiving waters and can be an important fraction of the peatland carbon budget, along with being an important modifier of downstream water quality. Changes in temperature and hydrological processes under future climate scenarios are expected to impact decomposition processes in peatlands with unclear ramifications for both the quantity and the quality of the DOC released. We experimentally examined the individual and interactive effects of increased temperature, elevated atmospheric carbon dioxide concentration, and lower water table position on peatland decomposition and the quantity and quality of porewater DOC in intact, replicated peat monoliths in a full factorial design. Decomposition rates and porewater DOC concentrations significantly increased under elevated temperature conditions; however, the quality of this carbon was variable, showing signs of both increased lability and recalcitrance. Lowered water table treatments also increased decomposition rates, although the high water conditions prompted greater porewater DOC concentrations and lability. It is expected that elevated decomposition rates under future climate scenarios will alter porewater DOC quantity in peatlands; however, we suggest that contributions from the aboveground system are needed to fully understand changes in DOC quality and subsequent ecosystem dynamics.

Influence of Water Table Depth on Pore Water Chemistry and Trihalomethane Formation Potential in Peatlands.

Drained peatland catchments are reported to produce more colored, dissolved organic carbon (DOC)-rich water, presenting problems for potable water treatment. The blocking of peatland drainage ditches to restore the water table is increasingly being considered as a strategy to address this deterioration in water quality. However, the effect of ditch blocking on the potential of DOC to form trihalomethanes (THMs) has not been assessed. In this study, the effect of peat rewetting on pore water DOC concentration and characteristics (including THM formation potential [THMFP]) was assessed over 12 months using peat cores collected from two drained peatland sites. The data show little evidence of differences in DOC concentration or characteristics between the different treatments. The absence of any difference in the THMFP of pore water between treatments suggests that, in the short term at least, ditch blocking may not have an effect on the THMFP of waters draining peatland catchments.

Variations in dissolved organic carbon concentrations across peatland hillslopes

Peatlands are important terrestrial carbon stores and dissolved organic carbon (DOC) is one of the most important contributors to carbon budgets in peatland systems. Many studies have investigated factors affecting DOC concentration in peatland systems, yet hillslope position has been thus far overlooked as a variable that could influence DOC cycling. This study investigates the importance of hillslope position with regard to DOC cycling. Two upland peat hillslopes were studied in the Peak District, UK, to determine what impact, if any, hillslope position had upon DOC concentration. Hillslope position was found to be a significant factor affecting variation in soil pore water DOC concentration, with bottom-slope positions having significantly lower DOC concentrations than up-slope because of dilution of DOC as water moves down-slope and is flushed out of the system via lateral throughflow. Water table drawdown on steeper mid-slopes increased DOC concentrations through increased DOC production and extended residence times allowing a build-up of humic-rich DOC compounds. Hillslope position did not significantly affect DOC concentrations in surface runoff water because of the dilution of near-surface soil pore water by precipitation inputs, while stream water had similar water chemistry properties to soil pore water under low-flow conditions.

Performance of Denitrifying Stormwater Biofilters Under Intermittent Conditions

Denitrifying stormwater biofiltration systems that include submerged zones containing organic carbon sources can alleviate eutrophication by reducing nitrogen loadings from stormwater runoff. The objective of this research was to evaluate performance of denitrifying biofilters containing wood chip medium under varying dynamic loading rates and antecedent dry conditions (ADCs). Results showed that during ADCs, dissolved organic carbon (DOC) concentrations increased in pore water due to dissolution of the wood chip medium. During a storm event, nitrate (NO3−) removal was enhanced due to high pore water DOC concentrations and mixing of NO3− from the influent with pore water; however, as DOC was gradually flushed out of the biofilter, higher effluent NO3− concentrations were observed over time. At lower hydraulic loading rates, effluent NO3− concentrations were low due to sufficient hydraulic residence time for denitrification. For all storm events tested, an overall NO3− mass removal efficiency of 85% was achieved. Sulfate reduction was observed at long ADCs (up to 30 days). Phosphate release was observed when NO3− was absent from the effluent, possibly due to dissolution of iron oxyhydroxides under low redox conditions. Findings from this study are being used to develop a mathematical model of nitrogen removal in denitrifying stormwater biofilters.

A 5-year study of the impact of peatland revegetation upon DOC concentrations

Summary Peatlands are among the largest long-term soil carbon stores on the globe, but their degradation can lead to significant carbon losses. Therefore, restoration of peatlands has received considerable attention but the impact of revegetation upon critical water quality parameters has not been assessed. In this paper we consider a 5-year study of three restored sites in comparison to both an unrestored, bare peat control and to a vegetated control that did not require restoration. The soil porewater dissolved organic carbon concentration (DOC) was measured (6 replicates) for each restoration treatment and each control. The soil water measurements were made in the context of measuring the depth to water table; soil water pH and conductivity; and DOC concentration in surface runoff for the same restored and control treatment. The study showed that the average soil porewater DOC concentration on the restored sites rose significantly over the 5 year study representing a 34% increase relative to the vegetated control and an 11% increase relative to the unrestored, bare control. Soil pore water concentrations were not significantly different from surface runoff DOC concentrations, and therefore restoration as conducted by this study would have contributed to water quality deterioration in the catchment. However, had water table restoration been conducted alongside revegetation then a significant decline in DOC concentrations could have been realised.

Peat porewater dissolved organic carbon concentration and lability increase with warming: a field temperature manipulation experiment in a poor-fen

Studies conducted across northern Europe and North America have shown increases in dissolved organic carbon (DOC) in aquatic systems in recent decades. While there is little consensus as to the exact mechanisms for the increases in DOC, hypotheses converge on such climate change factors as warming, increased precipitation variability, and changes in atmospheric deposition. In this study, we tested the effects of warming on peat porewater composition by actively warming a peatland with infrared lamps mounted 1.24 m above the peat surface for 3 years. Mean growing season peat temperatures in the warmed plots (n = 5) were 1.9 ± 0.4 °C warmer than the control plots at 5 cm depth (t statistic = 5.03, p = 0.007). Mean porewater DOC concentrations measured throughout the growing season were 15 % higher in the warmed plots (73.4 ± 3.2 mg L−1) than in the control plots (63.7 ± 2.1 mg L−1) at 25 cm (t = 4.69, p < 0.001). Furthermore, DOC from the warmed plots decayed nearly twice as fast as control plot DOC in laboratory incubations, and exhibited lower aromaticity than control plot porewater (reduction in SUVA254 in heated plots compared with control plots). Dissolved organic nitrogen (DON) concentrations tracked DOC patterns as expected, but the amount of dissolved N per unit C decreased with warming. Previous work has shown that warming increased net primary production at this site, and together with measured increases in the activities of chitinases and glucosidases we suggest that the increased DOC concentrations observed with warming were derived in part from microbial-plant interactions in the rhizosphere. We also detected more nitrogen containing compounds with higher double bond equivalents (DBE) unique to the warmed plots, within the pool of biomolecules able to deprotonate (16 % of all compounds identified using ultrahigh resolution ion electrospray mass spectrometry); we suggest these compounds could be the products of increased plant, microbial, and enzyme activity occurring with warming. With continued warming in peatlands, an increase in relatively labile DOC concentrations could contribute to dissolved exports of DOC in runoff, and would likely contribute to the pool of efficient electron donors (and acceptors) in the production of CO2 and CH4 in terrestrial and aquatic environments.

Hot Spots and Hot Moments of Dissolved Organic Carbon Export and Soil Organic Carbon Storage in the Shale Hills Catchment

Dissolved organic carbon (DOC) export from watersheds and soil organic carbon (SOC) storage are intimately linked in the terrestrial carbon cycle. However, predictions of hot spots and hot moments of DOC and SOC in watersheds remain uncertain because of high spatiotemporal variability and changing controls. In this study, we investigated the linkage between SOC storage and landform units across the 7.9‐ha Shale Hills Critical Zone Observatory (CZO) and its implications for potential hot spots of DOC. We also examined the trends of DOC in soil pore water along two hillslopes of contrasting soils and topography and the impacts of rainfall, stream discharge, and stream temperature on DOC export to identify possible hot moments. Based on the SOC distribution throughout the entire catchment, swales (particularly south‐facing swales) were identified as hot spots because they exhibited significantly higher SOC storage and more active hydrology as compared to the rest of the catchment. Along the two hillslopes reported here, average soil pore water DOC concentrations were noticeably higher (35 ± 12%) along the swale as compared to the planar hillslope. Soil pore water DOC concentrations were elevated at the soil–bedrock interface at the ridgetop and at the Bw–Bt horizon interface in the valley floor, suggesting transport‐driven hot spots along restrictive layer interfaces. Stream water DOC concentration at the catchment outlet averaged 6.2 ± 5.3 mg L−1 from May 2008 to October 2010, which was significantly correlated with stream discharge and stream water temperature. Transport‐driven hot moments of stream water DOC were observed during the periods of snowmelt and late summer to early fall wet‐up, which together contributed ∼55% of total stream water DOC exported in 2009. This reflected the control of DOC export by flushing (linked to discharge) and biological activity (related to temperature) and its variation during different seasons of a year. This study showcased the impacts of complex soil and topography interactions—coupled with changing weather and seasonal biological activity—on the spatiotemporal dynamics of DOC export in a temperate forested catchment and its link to SOC distribution.

Seasonal ice and hydrologic controls on dissolved organic carbon and nitrogen concentrations in a boreal‐rich fen

Boreal wetland carbon cycling is vulnerable to climate change in part because hydrology and the extent of frozen ground have strong influences on plant and microbial functions. We examined the response of dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) across an experimental manipulation of water table position (both raised and lowered water table treatments) in a boreal‐rich fen in interior Alaska. DOC and TDN responses to water table manipulation exhibited an interaction with seasonal ice dynamics. We observed consistently higher DOC and TDN concentrations in the lowered water table treatment (71.7 ± 6.5 and 3.0 ± 0.3 mg−L) than in both the control (55.6 ± 5.1 and 2.3 ± 0.2 mg−L) and raised (49.1 ± 4.3 and 1.9 ± 0.1 mg L−1, respectively) water table treatments. Across all plots, pore water DOC concentrations at 20 cm increased as the depth to water table increased (R2 = 0.43, p &lt; 0.001). DOC concentrations also increased as the seasonal thaw depth increased, with solutes increasing most rapidly in the drained plot (R2 = 0.62, p &lt; 0.001). About half of the TDN pool was composed of dissolved organic N (DON). Inorganic N and DON were both highly correlated with changes in DOC, and their respective constraints to mineralization are discussed. These results demonstrate that a declining water table position and dryer conditions affect thaw depth and peat temperatures, and interactions among these ecosystem properties will likely increase DOC and TDN loading and potential for export in these systems.

Mercury Cycling in Stream Ecosystems. 2. Benthic Methylmercury Production and Bed Sediment−Pore Water Partitioning

Mercury speciation, controls on methylmercury (MeHg) production, and bed sediment-pore water partitioning of total Hg (THg) and MeHg were examined in bed sediment from eight geochemically diverse streams where atmospheric deposition was the predominant Hg input. Across all streams, sediment THg concentrations were best described as a combined function of sediment percent fines (%fines; particles < 63 microm) and organic content. MeHg concentrations were best described as a combined function of organic content and the activity of the Hg(II)-methylating microbial community and were comparable to MeHg concentrations in streams with Hg inputs from industrial and mining sources. Whole sediment tin-reducible inorganic reactive Hg (Hg(II)R) was used as a proxy measure for the Hg(II) pool available for microbial methylation. In conjunction with radiotracer-derived rate constants of 203Hg(II) methylation, Hg(II)R was used to calculate MeHg production potential rates and to explain the spatial variability in MeHg concentration. The %Hg(II)R (of THg) was low (2.1 +/- 5.7%) and was inversely related to both microbial sulfate reduction rates and sediment total reduced sulfur concentration. While sediment THg concentrations were higher in urban streams, %MeHg and %Hg(II)R were higher in nonurban streams. Sediment pore water distribution coefficients (log Kd's) for both THg and MeHg were inversely related to the log-transformed ratio of pore water dissolved organic carbon (DOC) to bed sediment %fines. The stream with the highest drainage basin wetland density also had the highest pore water DOC concentration and the lowest log Kd's for both THg and MeHg. No significant relationship existed between overlying water MeHg concentrations and those in bed sediment or pore water, suggesting upstream sources of MeHg production may be more important than local streambed production as a driver of water column MeHg concentration in drainage basins that receive Hg inputs primarily from atmospheric sources.