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Zooplankton communities are important components of aquatic food webs in part because they recycle nutrients and carbon. Lacking a complete understanding of the composition of organic material cycled by zooplankton, the breadth of their biogeochemical and ecological contributions to aquatic ecosystems is uncertain. Here, we show that large-bodied zooplankton communities from three diverse biomes across North America release dissolved organic matter (DOM) that is chemically complex. We applied optical techniques and ultrahigh-resolution mass spectrometry to samples of DOM released by zooplankton in leachate incubations and compared these to the composition of aquatic DOM from ambient environments. The leachates captured the DOM released from zooplankton before exposure to environmental conditions that alter its chemical composition. Surprisingly, leachates from all sites contained substantial quantities of all five major fluorescence peaks representing distinct DOM compositions. When averaged, leachates consistently had low optical absorbance and elevated protein-like fluorescence, relative to lake water. Ultrahigh-resolution characterization showed that leachate DOM contained over 7000 detected molecular formulae (MF), many of which were N- and S- rich, with > 10% MF unique to the leachate and not detected in lake DOM. Together, these results help to define the composition of animal DOM inputs, a widely-overlooked end-member in aquatic DOM studies. Given the chemical breadth of zooplankton-derived DOM, this source may partially explain how N- and S- rich, reduced MF persist in these environments. These findings further underscore the rich chemical diversity of linkages between animals and lower trophic levels.

Mercury (Hg) is a naturally occurring element that bonds with organic matter and, when converted to methylmercury, is a potent neurotoxicant. Here we estimate potential future releases of Hg from thawing permafrost for low and high greenhouse gas emissions scenarios using a mechanistic model. By 2200, the high emissions scenario shows annual permafrost Hg emissions to the atmosphere comparable to current global anthropogenic emissions. By 2100, simulated Hg concentrations in the Yukon River increase by 14% for the low emissions scenario, but double for the high emissions scenario. Fish Hg concentrations do not exceed United States Environmental Protection Agency guidelines for the low emissions scenario by 2300, but for the high emissions scenario, fish in the Yukon River exceed EPA guidelines by 2050. Our results indicate minimal impacts to Hg concentrations in water and fish for the low emissions scenario and high impacts for the high emissions scenario., Permafrost locks away the largest reservoir of mercury on the planet, but climate warming threatens to thaw these systems. Here the authors use models to show that unconstrained fossil fuel burning will dramatically increase the amount of mercury released into future ecosystems.

Landcover changes have altered the natural carbon cycle; however, most landcover studies focus on either forest conversion to agriculture or urban, rarely both. We present differences in dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) molecular composition within Upper Mississippi River Basin low order streams and rivers draining one of three dominant landcovers (forest, agriculture, and urban). Streams draining forest and urban landcovers have greater DOC concentrations, likely driven by differences in carbon sourcing, microbial processing, and soil disturbance. Using Fourier transform-ion cyclotron resonance mass spectrometry, 24% of assigned molecular formulae are common across all landcovers. Relative abundances of N-,S- heteroatomic formulae (CHON, CHOS, CHONS) are higher for agricultural and urban streams, with agricultural stream DOM having more N-containing formulae compared to urban stream DOM, which has more S-containing formulae. Higher N-,S- heteroatomic formulae abundance, along with enrichment in aliphatic, N-aliphatic, and highly unsaturated and phenolic (low O/C) compound categories within agricultural and urban stream DOM are likely to result from increased anthropogenic inputs, autochthonous production, and microbial processing associated with agricultural and urban impacts. Reduced N-,S- heteroatomic formulae abundances in forested stream DOM, along with enrichments in condensed aromatics, polyphenolics, and highly unsaturated phenolic (high O/C) compound categories, likely reflect greater contributions from surrounding organic-rich forest soil and vegetation. Overall, landcover change from forested to agriculture lowers DOC concentrations and changes from forested to agriculture or urban increases autochthonous, and presumably more biolabile, DOM contributions with ramifications for stream biogeochemical cycling.

Circumpolar lakes comprise ~ 1.4 million km2 of arctic and subarctic landscapes and are vulnerable to change in vegetation, permafrost distribution, and hydrological conditions in response to climate warming. However, the composition and cycling of dissolved organic matter (DOM) is poorly understood for these lakes because most are remote and unstudied. The goal of this study was to assess timescale and source controls on DOM composition in Canvasback Lake, a shallow, sub-Arctic lake in interior Alaska with similar hydrologic and geomorphic characteristics to about a quarter of circumpolar lake ecosystems. Lake dissolved organic carbon (DOC) concentration varied by as much as 16% from the mean (3.34 mg L−1 change) through diel cycles in spring 2016 to fall 2017 and was accompanied by minor changes in DOM composition. At the seasonal scale, DOC concentration increased from spring through fall to very high concentrations under ice in winter. Decreases in both condensed aromatic and polyphenolic compound classes and lignin carbon-normalized yield, plus increased relative abundance of aliphatic compounds, suggests that DOM composition shifts from a pulse of allochthonous DOM in the spring to more autochthonous under-ice. These changes highlight the seasonally-dynamic nature of DOM in circumpolar lakes that are poorly captured by single-visit lake surveys and underscores the need to measure DOM properties and fate consistently across multiple timescales (i.e. seasonally) to better constrain the role of DOM in lake processes. To further assess DOM sources, a suite of endmember leachates were compared to bulk lake DOM, indicating solely allochthonous inputs are not well reflected in lake DOM, highlighting the role of degradation processes or mixing with autochthonous sources. Thus, Canvasback Lake appears less well connected to terrestrial inputs compared to past studies of northern high-latitude lakes and does not behave as previous boreal lake models suggest.

As climate warming and precipitation increase at high latitudes, permafrost terrains across the circumpolar north are poised for intensified geomorphic activity and sediment mobilization that are expected to persist for millennia. In previously glaciated permafrost terrain, ice-rich deposits are associated with large stores of reactive mineral substrate. Over geological timescales, chemical weathering moderates atmospheric CO2 levels, raising the prospect that mass wasting driven by terrain consolidation following thaw (thermokarst) may enhance weathering of permafrost sediments and thus climate feedbacks. The nature of these feedbacks depends upon the mineral composition of sediments (weathering sources) and the balance between atmospheric exchange of CO2 vs. fluvial export of carbonate alkalinity (Σ[HCO3-, CO32-]). Working in the fluvially incised, ice-rich glacial deposits of the Peel Plateau in northwestern Canada, we determine the effects of slope thermokarst in the form of retrogressive thaw slump (RTS) activity on mineral weathering sources, CO2 dynamics, and carbonate alkalinity export and how these effects integrate across watershed scales (∼ 2 to 1000 km2). We worked along three transects in nested watersheds with varying connectivity to RTS activity: a 550 m transect along a first-order thaw stream within a large RTS, a 14 km transect along a stream which directly received inputs from several RTSs, and a 70 km transect along a larger stream with headwaters that lay outside of RTS influence. In undisturbed headwaters, stream chemistry reflected CO2 from soil respiration processes and atmospheric exchange. Within the RTS, rapid sulfuric acid carbonate weathering, prompted by the exposure of sulfide- and carbonate-bearing tills, appeared to increase fluvial CO2 efflux to the atmosphere and propagate carbonate alkalinity across watershed scales. Despite covering less than 1 % of the landscape, RTS activity drove carbonate alkalinity to increase by 2 orders of magnitude along the largest transect. Amplified export of carbonate alkalinity together with isotopic signals of shifting DIC and CO2 sources along the downstream transects highlights the dynamic nature of carbon cycling that may typify glaciated permafrost watersheds subject to intensification of hillslope thermokarst. The balance between CO2 drawdown in regions where carbonic acid weathering predominates and CO2 release in regions where sulfides are more prevalent will determine the biogeochemical legacy of thermokarst and enhanced weathering in northern permafrost terrains. Effects of RTSs on carbon cycling can be expected to persist for millennia, indicating a need for their integration into predictions of weathering–carbon–climate feedbacks among thermokarst terrains.

Groundwater carbon (C) supply to lakes and streams is important to understanding the role of inland waters in global and regional cycles and in the functioning of aquatic ecosystems. We provide new...

Carbon dioxide (CO2) emissions from rivers and other inland waters are thought to be a major component of regional and global carbon cycling. In large managed rivers such as the Columbia River, contemporary ecosystem changes such as damming, nutrient enrichment, and increased water residence times may lead to reduced CO2 concentrations (and emissions) due to increased primary production, as has been shown in another large North American river (Upper Mississippi). In this work, spatial patterns of water quality, including dissolved CO2 concentrations, were assessed in the Lower Columbia River (LCR) and major tributaries using underway measurements from a small research vessel during July 2016. We observed near-equilibrium CO2 conditions and overall weak supersaturation of CO2 in the main channel (average 133.8% saturation) and tributaries. We observed only weak correlations between CO2 saturation, chlorophyll a fluorescence, and turbidity, thus not strongly supporting our hypothesis of primary prod...

Riverine ecosystems receive organic matter (OM) from terrestrial sources, internally produce new OM, and biogeochemically cycle and modify organic and inorganic carbon. Major gaps remain in the understanding of the relationships between carbon sources and processing in river systems. Here we synthesize isotopic, elemental, and molecular properties of dissolved organic carbon (DOC), particulate organic carbon (POC), and dissolved inorganic carbon (DIC) in the Upper Mississippi River (UMR) system above Wabasha, MN, including the main stem Mississippi River and its four major tributaries (Minnesota, upper Mississippi, St. Croix, and Chippewa Rivers). Our goal was to elucidate how biological processing modifies the chemical and isotopic composition of aquatic carbon pools during transport downstream in a large river system with natural and man-made impoundments. Relationships between land cover and DOC carbon-isotope composition, absorbance, and hydrophobic acid content indicate that DOC retains terrestrial carbon source information, while the terrestrial POC signal is largely replaced by autochthonous organic matter, and DIC integrates the influence of in-stream photosynthesis and respiration of organic matter. The UMR is slightly heterotrophic throughout the year, but pools formed by low-head navigation dams and natural impoundments promote a shift towards autotrophic conditions, altering aquatic ecosystem dynamics and POC and DIC composition. Such changes likely occur in all major river systems affected by low-head dams and need to be incorporated into our understanding of inland water carbon dynamics and processes controlling CO2 emissions from rivers, as new navigation and flood control systems are planned for future river and water resources management.

Multiple processes support the significant efflux of carbon dioxide (CO2) from rivers and streams. Attribution of CO2 oversaturation will lead to better quantification of the freshwater carbon cycle and provide insights into the net cycling of nutrients and pollutants. CO2 production is closely related to O2 consumption because of the metabolic linkage of these gases. However, this relationship can be weakened due to dissolved inorganic carbon inputs from groundwater, carbonate buffering, calcification, and anaerobic metabolism. CO2 and O2 concentrations and other water quality parameters were analyzed in two data sets: a synoptic field study and nationwide water quality monitoring data. CO2 and O2 concentrations were strongly negatively correlated in both data sets (ρ = −0.67 and ρ = −0.63, respectively), although the correlations were weaker in high-alkalinity environments. In nearly all samples, the molar oversaturation of CO2 was a larger magnitude than molar O2 undersaturation. We used a dynamically coupled O2CO2 model to show that lags in CO2 air-water equilibration are a likely cause of this phenomenon. Lags in CO2 equilibration also impart landscape-scale differences in the behavior of CO2 between high- and low-alkalinity watersheds. Although the concept of carbonate buffering and how it creates lags in CO2 equilibration with the atmosphere is well understood, it has not been sufficiently integrated into our understanding of CO2 dynamics in freshwaters. We argue that the consideration of carbonate equilibria and its effects on CO2 dynamics are primary steps in understanding the sources and magnitude of CO2 oversaturation in rivers and streams.

Planktonic community respiration (CR) is a major component of aquatic biogeochemical cycling and food web energetics. Accurate, direct characterizations of short-term patterns and drivers of plankton CR are needed to understand aquatic biogeochemical processes and food web functioning. Recent work indicates CR may be commonly underestimated, and may undergo considerable diel changes that are missed using standard methodological approaches. To explore these possibilities, we applied an immediate, in situ, dark incubation approach at ~ 3 h intervals over 2.5 diel cycles in a shallow, productive, sub-arctic lake in interior Alaska, USA. Rates of CR varied 17-fold, strongly coupled to diel oscillations in water temperature. A weak inverse relationship to ~ 3 mg L−1 diel changes in dissolved organic carbon concentrations suggests CR partially modulated the standing stock of organic matter over short timescales. Average rates of CR were ~ 6 to 100-fold greater than published, conventional CR measurements, but comparable to existing free-water estimates of ecosystem respiration for nearby Alaskan lakes. Overall, this study places new weight on the importance of CR in whole-ecosystem biogeochemical transformations by supporting recent suggestions that planktonic CR may be commonly underestimated.

Recent studies have found insignificant or decreasing trends in time-series dissolved organic carbon (DOC) datasets, questioning the assumption that long-term DOC concentrations in surface waters are increasing in response to anthropogenic forcing, including climate change, land use, and atmospheric acid deposition. We used the weighted regressions on time, discharge, and season (WRTDS) model to estimate annual flow-normalized concentrations and fluxes to determine if changes in DOC quantity and quality signal anthropogenic forcing at 10 locations in the Mississippi River Basin. Despite increases in agriculture and urban development throughout the basin, net increases in DOC concentration and flux were significant at only 3 of 10 sites from 1997 to 2013 and ranged between −3.5% to +18% and −0.1 to 19%, respectively. Positive shifts in DOC quality, characterized by increasing specific ultraviolet absorbance at 254 nm, ranged between +8% and +45%, but only occurred at one of the sites with significant DOC quantity increases. Basinwide reductions in atmospheric sulfate deposition did not result in large increases in DOC either, likely because of the high buffering capacity of the soil. Hydroclimatic factors including annual discharge, precipitation, and temperature did not significantly change during the 17-year timespan of this study, which contrasts with results from previous studies showing significant increases in precipitation and discharge over a century time scale. Our study also contrasts with those from smaller catchments, which have shown stronger DOC responses to climate, land use, and acidic deposition. This temporal and spatial analysis indicated that there was a potential change in DOC sources in the Mississippi River Basin between 1997 and 2013. However, the overall magnitude of DOC trends was not large, and the pattern in quantity and quality increases for the 10 study sites was not consistent throughout the basin.

We explored the underlying patterns of temporal stream CO2 partial pressure (pCO2) variability using high-frequency sensors in seven disparate headwater streams distributed across the northern hemisphere. We also compared this dataset of >40,000 pCO2 records with other published records from lotic systems. Individual stream sites exhibited relatively distinct pCO2 patterns over time with few consistent traits across sites. Some sites showed strong diel variability, some exhibited increasing pCO2 with increasing discharge, whereas other streams had reduced pCO2 with increasing discharge or no clear response to changes in flow. The only “universal” signature observed in headwater streams was a late summer pCO2 maxima that was likely driven by greatest rates of organic matter respiration due to highest annual temperatures. However, we did not observe this seasonal pattern in a southern hardwood forest site, likely because the region was transitioning from a severe drought. This work clearly illustrates the heterogeneous nature of headwater streams, and highlights the idiosyncratic nature of a non-conservative solute that is jointly influenced by physics, hydrology, and biology. We suggest that future researchers carefully select sensor locations (within and among streams) and provide additional contextual information when attempting to explain pCO2 patterns.

Northern rivers connect a land area of approximately 20.5 million km2 to the Arctic Ocean and surrounding seas. These rivers account for ~10% of global river discharge and transport massive quantities of dissolved and particulate materials that reflect watershed sources and impact biogeochemical cycling in the ocean. In this paper, multiyear data sets from a coordinated sampling program are used to characterize particulate organic carbon (POC) and particulate nitrogen (PN) export from the six largest rivers within the pan-Arctic watershed (Yenisey, Lena, Ob', Mackenzie, Yukon, Kolyma). Together, these rivers export an average of 3055 × 109 g of POC and 368 × 109 g of PN each year. Scaled up to the pan-Arctic watershed as a whole, fluvial export estimates increase to 5767 × 109 g and 695 × 109 g of POC and PN per year, respectively. POC export is substantially lower than dissolved organic carbon export by these rivers, whereas PN export is roughly equal to dissolved nitrogen export. Seasonal patterns in concentrations and source/composition indicators (C:N, δ13C, Δ14C, δ15N) are broadly similar among rivers, but distinct regional differences are also evident. For example, average radiocarbon ages of POC range from ~2000 (Ob') to ~5500 (Mackenzie) years before present. Rapid changes within the Arctic system as a consequence of global warming make it challenging to establish a contemporary baseline of fluvial export, but the results presented in this paper capture variability and quantify average conditions for nearly a decade at the beginning of the 21st century.

The Upper Mississippi River, engineered for river navigation in the 1930s, includes a series of low-head dams and navigation pools receiving elevated sediment and nutrient loads from the mostly agricultural basin. Using high-resolution, spatially resolved water quality sensor measurements along 1385 river kilometers, we show that primary productivity and organic matter accumulation affect river carbon dioxide and methane emissions to the atmosphere. Phytoplankton drive CO2 to near or below atmospheric equilibrium during the growing season, while anaerobic carbon oxidation supports a large proportion of the CO2 and CH4 production. Reductions of suspended sediment load, absent of dramatic reductions in nutrients, will likely further reduce net CO2 emissions from the river. Large river pools, like Lake Pepin, which removes the majority of upstream sediments, and large agricultural tributaries downstream that deliver significant quantities of sediments and nutrients, are likely to persist as major geographical drivers of greenhouse gas emissions.

In terrestrial and marine ecosystems, remote sensing has been used to estimate gross primary productivity (GPP) for decades, but few applications exist for shallow freshwater ecosystems.Here we show field-based GPP correlates with satellite and airborne lake color across a range of optically and limnologically diverse lakes in interior Alaska. A strong relationship between in situ GPP derived from stable oxygen isotopes (δ18O) and space-based lake color from satellites (e.g. Landsat-8, Sentinel-2 and CubeSats) and airborne imagery (AVIRIS-NG) demonstrates the potential power of this technique for improving spatial and temporal monitoring of lake GPP when coupled with additional field validation measurements across different systems. In shallow waters clear enough for sunlight to reach lake bottoms, both submerged vegetation (macrophytes and algae) and phytoplankton likely contribute to GPP. The stable isotopes and remotely sensed shallow lake color used here integrate both components. These results demonstrate the utility of lake color as a feasible means for mapping lake GPP from remote sensing. This novel methodology estimates GPP from remote sensing in shallow lakes by combining field measurements of oxygen isotopes with airborne, satellite and CubeSat imagery. This use of lake color for providing insight into ecological processes of shallow lakes is recommended, especially for remote arctic and boreal landscapes.

This study used automated enzymatic activity measurements conducted from a mobile research vessel to detect the spatial variability of beta‑d‑glucuronidase (GLUC) activity in large freshwater bodies. The ship-borne observations provided the first high-resolution spatial data of GLUC activity in large water bodies as rapid indication of fecal pollution and were used to identify associations with hydrological conditions and land use. The utility of this novel approach for water quality screening was evaluated by surveys of the Columbia River, the Mississippi River and the Yahara Lakes, covering up to a 500 km river course and 50 km

We summarize the results of a recent interagency assessment of land carbon dynamics in Alaska, in which carbon dynamics were estimated for all major terrestrial and aquatic ecosystems for the historical period (1950-2009) and a projection period (2010-2099). Between 1950 and 2009, upland and wetland (i.e., terrestrial) ecosystems of the state gained 0.4 Tg C/yr (0.1% of net primary production, NPP), resulting in a cumulative greenhouse gas radiative forcing of 1.68 × 10-3 W/m2 . The change in carbon storage is spatially variable with the region of the Northwest Boreal Landscape Conservation Cooperative (LCC) losing carbon because of fire disturbance. The combined carbon transport via various pathways through inland aquatic ecosystems of Alaska was estimated to be 41.3 Tg C/yr (17% of terrestrial NPP). During the projection period (2010-2099), carbon storage of terrestrial ecosystems of Alaska was projected to increase (22.5-70.0 Tg C/yr), primarily because of NPP increases of 10-30% associated with responses to rising atmospheric CO2 , increased nitrogen cycling, and longer growing seasons. Although carbon emissions to the atmosphere from wildfire and wetland CH4 were projected to increase for all of the climate projections, the increases in NPP more than compensated for those losses at the statewide level. Carbon dynamics of terrestrial ecosystems continue to warm the climate for four of the six future projections and cool the climate for only one of the projections. The attribution analyses we conducted indicated that the response of NPP in terrestrial ecosystems to rising atmospheric CO2 (~5% per 100 ppmv CO2 ) saturates as CO2 increases (between approximately +150 and +450 ppmv among projections). This response, along with the expectation that permafrost thaw would be much greater and release large quantities of permafrost carbon after 2100, suggests that projected carbon gains in terrestrial ecosystems of Alaska may not be sustained. From a national perspective, inclusion of all of Alaska in greenhouse gas inventory reports would ensure better accounting of the overall greenhouse gas balance of the nation and provide a foundation for considering mitigation activities in areas that are accessible enough to support substantive deployment.

Ground ice is abundant in the upper permafrost throughout the Arctic and fundamentally affects terrain responses to climate warming. Ice wedges, which form near the surface and are the dominant type of massive ice in the Arctic, are particularly vulnerable to warming. Yet, processes controlling ice-wedge degradation and stabilization are poorly understood. Here we quantified ice-wedge volume and degradation rates, compared ground-ice characteristics and thermal regimes across a sequence of five degradation and stabilization stages, and evaluated biophysical feedbacks controlling permafrost stability near Prudhoe Bay, Alaska. Mean ice-wedge volume in the top 3 m of permafrost was 21%. Imagery from 1949 to 2012 showed thermokarst extent (area of water-filled troughs) was relatively small from 1949 (0.9%) to 1988 (1.5%), abruptly increased by 2004 (6.3%), and increased slightly by 2012 (7.5%). Mean annual surface temperatures varied by 4.9 °C among degradation and stabilization stages, and by 9.9 °C from polygon center to deep lake bottom. Mean thicknesses of the active layer, ice-poor transient layer, ice-rich intermediate layer, thermokarst-cave ice, and wedge ice varied substantially among stages. In early stages, thaw settlement caused water to impound in thermokarst troughs, creating positive feedbacks that increased net radiation, soil heat flux, and soil temperatures. Plant growth and organic-matter accumulation in the degraded troughs provided negative feedbacks that allowed ground ice to aggrade and heave the surface, thus reducing surface water depth and soil temperatures in later stages. The ground ice dynamics and ecological feedbacks greatly complicate efforts to assess permafrost responses to climate change.

Northern permafrost soils store a vast reservoir of carbon, nearly twice that of the present atmosphere. Current and projected climate warming threatens widespread thaw of these frozen, organic carbon (OC)-rich soils. Upon thaw, mobilized permafrost OC in dissolved and particulate forms can enter streams and rivers, which are important processors of OC and conduits for carbon dioxide (CO2) to the atmosphere. Here, we demonstrate that ancient dissolved organic carbon (DOC) leached from 35,800 y B.P. permafrost soils is rapidly mineralized to CO2. During 200-h experiments in a novel high-temporal-resolution bioreactor, DOC concentration decreased by an average of 53%, fueling a more than sevenfold increase in dissolved inorganic carbon (DIC) concentration. Eighty-seven percent of the DOC loss to microbial uptake was derived from the low-molecular-weight (LMW) organic acids acetate and butyrate. To our knowledge, our study is the first to directly quantify high CO2 production rates from permafrost-derived LMW DOC mineralization. The observed DOC loss rates are among the highest reported for permafrost carbon and demonstrate the potential importance of LMW DOC in driving the rapid metabolism of Pleistocene-age permafrost carbon upon thaw and the outgassing of CO2 to the atmosphere by soils and nearby inland waters.

Gas transport in the unsaturated zone affects contaminant flux and remediation, interpretation of groundwater travel times from atmospheric tracers, and mass budgets of environmentally important gases. Although unsaturated zone transport of gases is commonly treated as dominated by diffusion, the characteristics of transport in deep layered sediments remain uncertain. In this study, we use a multimodel approach to analyze results of a gas-tracer (SF6) test to clarify characteristics of gas transport in deep unsaturated alluvium. Thirty-five separate models with distinct diffusivity structures were calibrated to the tracer-test data and were compared on the basis of Akaike Information Criteria estimates of posterior model probability. Models included analytical and numerical solutions. Analytical models provided estimates of bulk-scale apparent diffusivities at the scale of tens of meters. Numerical models provided information on local-scale diffusivities and feasible lithological features producing the observed tracer breakthrough curves. The combined approaches indicate significant anisotropy of bulk-scale diffusivity, likely associated with high-diffusivity layers. Both approaches indicated that diffusivities in some intervals were greater than expected from standard models relating porosity to diffusivity. High apparent diffusivities and anisotropic diffusivity structures were consistent with previous observations at the study site of rapid lateral transport and limited vertical spreading of gas-phase contaminants. Additional processes such as advective oscillations may be involved. These results indicate that gases in deep, layered unsaturated zone sediments can spread laterally more quickly, and produce higher peak concentrations, than predicted by homogeneous, isotropic diffusion models.

Organic carbon (OC) burial in lacustrine sediments represents an important sink in the global carbon cycle; however, large-scale OC burial rates are poorly constrained, primarily because of the sparseness of available data sets. Here we present an analysis of OC burial rates in water bodies of the conterminous U.S. (CONUS) that takes advantage of recently developed national-scale data sets on reservoir sedimentation rates, sediment OC concentrations, lake OC burial rates, and water body distributions. We relate these data to basin characteristics and land use in a geostatistical analysis to develop an empirical model of OC burial in water bodies of the CONUS. Our results indicate that CONUS water bodies sequester 20.8 (95% CI: 9.4-65.8) Tg C yr(-1), and spatial patterns in OC burial are strongly influenced by water body type, size, and abundance; land use; and soil and vegetation characteristics in surrounding areas. Carbon burial is greatest in the central and southeastern regions of the CONUS, where cultivation and an abundance of small water bodies enhance accumulation of sediment and OC in aquatic environments.

Inland waters are an important component of the global carbon cycle through transport, storage, and direct emissions of CO2 and CH4 to the atmosphere. Despite predictions of high physical gas exchange rates due to turbulent flows and ubiquitous supersaturation of CO2—and perhaps also CH4—patterns of gas emissions are essentially undocumented for high mountain ecosystems. Much like other headwater networks around the globe, we found that high-elevation streams in Rocky Mountain National Park, USA, were supersaturated with CO2 during the growing season and were net sources to the atmosphere. CO2 concentrations in lakes, on the other hand, tended to be less than atmospheric equilibrium during the open water season. CO2 and CH4 emissions from the aquatic conduit were relatively small compared to many parts of the globe. Irrespective of the physical template for high gas exchange (high k), we found evidence of CO2 source limitation to mountain streams during the growing season, which limits overall CO2 emissions. Our results suggest a reduced importance of aquatic ecosystems for carbon cycling in high-elevation landscapes having limited soil development and high CO2 consumption via mineral weathering.

The residence time of ice in permafrost is an indicator of past climate history, and of the resilience and vulnerability of high-latitude ecosystems to global change. Development of geochemical indicators of ground-ice residence times in permafrost will advance understanding of the circumstances and evidence of permafrost formation, preservation, and thaw in response to climate warming and other disturbance. We used uranium isotopes to evaluate the residence time of segregated ground ice from ice-rich loess permafrost cores in central Alaska. Activity ratios of 234U vs. 238U (234U/238U) in water from thawed core sections ranged between 1.163 and 1.904 due to contact of ice and associated liquid water with mineral surfaces over time. Measured (234U/238U) values in ground ice showed an overall increase with depth in a series of five neighboring cores up to 21 m deep. This is consistent with increasing residence time of ice with depth as a result of accumulation of loess over time, as well as characteristic ice morphologies, high segregated ice content, and wedge ice, all of which support an interpretation of syngenetic permafrost formation associated with loess deposition. At the same time, stratigraphic evidence indicates some past sediment redistribution and possibly shallow thaw among cores, with local mixing of aged thaw waters. Using measures of surface area and a leaching experiment to determine U distribution, a geometric model of (234U/238U) evolution suggests mean ages of up to ∼200 ky BP in the deepest core, with estimated uncertainties of up to an order of magnitude. Evidence of secondary coatings on loess grains with elevated (234U/238U) values and U concentrations suggests that refinement of the geometric model to account for weathering processes is needed to reduce uncertainty. We suggest that in this area of deep ice-rich loess permafrost, ice bodies have been preserved from the last glacial period (10–100 ky BP), despite subsequent fluctuations in climate, fire disturbance and vegetation. Radiocarbon (14C) analysis of dissolved organic carbon (DOC) in thaw waters supports ages greater than ∼40 ky BP below 10 m. DOC concentrations in thaw waters increased with depth to maxima of >1000 ppm, despite little change in ice content or cryostructures. These relations suggest time-dependent production of old DOC that will be released upon permafrost thaw at a rate that is mediated by sediment transport, among other factors.

Hydrologic exports of dissolved inorganic and organic carbon (DIC and DOC) reflect permafrost conditions in arctic and subarctic river basins. DIC yields, in particular, increase with decreased permafrost extent. We investigated the influence of permafrost extent on DIC and DOC yield in a tributary of the Yukon River, where the upper watershed has continuous permafrost and the lower watershed has discontinuous permafrost. Our results indicate that DIC versus DOC predominance switches with interannual changes in water availability and flow routing in intermediate-size watersheds having mixed permafrost coverage. Large water yield and small concentrations from mountainous headwaters and small water yield and high concentrations from lowlands produced similar upstream and downstream carbon yields. However, DOC export exceeded DIC export during high flow 2011, whereas DIC predominated during low flow 2010. The majority of exported carbon was derived from near-surface organic sources when landscapes were wet or frozen and from mineralized subsurface sources when infiltration increased.

A natural gradient SF 6 tracer experiment provided an unprecedented evaluation of long distance gas transport in the deep unsaturated zone (UZ) under controlled (known) conditions. The field-scale gas tracer test in the 110-m-thick UZ was conducted at the U.S. Geological Survey’s Amargosa Desert Research Site (ADRS) in southwestern Nevada. A history of anomalous (theoretically unexpected) contaminant gas transport observed at the ADRS, next to the first commercial low-level radioactive waste disposal facility in the United States, provided motivation for the SF 6 tracer study. Tracer was injected into a deep UZ borehole at depths of 15 and 48 m, and plume migration was observed in a monitoring borehole 9 m away at various depths (0.5–109 m) over the course of 1 yr. Tracer results yielded useful information about gas transport as applicable to the spatial scales of interest for off-site contaminant transport in arid unsaturated zones. Modeling gas diffusion with standard empirical expressions reasonably explained SF 6 plume migration, but tended to underpredict peak concentrations for the field-scale experiment given previously determined porosity information. Despite some discrepancies between observations and model results, rapid SF 6 gas transport commensurate with previous contaminant migration was not observed. The results provide ancillary support for the concept that apparent anomalies in historic transport behavior at the ADRS are the result of factors other than nonreactive gas transport properties or processes currently in effect in the undisturbed UZ.

Responses of near-surface permafrost and glacial ice to climate change are of particular significance for understanding long-term effects on global carbon cycling and carbon export by high-latitude northern rivers. Here we report Δ14C-dissolved organic carbon (DOC) values and dissolved organic matter optical data for the Yukon River, 15 tributaries of the Yukon River, glacial meltwater, and groundwater and soil water end-member sources draining to the Yukon River, with the goal of assessing mobilization of aged DOC within the watershed. Ancient DOC was associated with glacial meltwater and groundwater sources. In contrast, DOC from watersheds dominated by peat soils and underlain by permafrost was typically enriched in Δ14C indicating that degradation of ancient carbon stores is currently not occurring at large enough scales to quantitatively influence bulk DOC exports from those landscapes. On an annual basis, DOC exported was predominantly modern during the spring period throughout the Yukon River basin and became older through summer-fall and winter periods, suggesting that contributions of older DOC from soils, glacial meltwaters, and groundwater are significant during these months. Our data indicate that rapidly receding glaciers and increasing groundwater inputs will likely result in greater contributions of older DOC in the Yukon River and its tributaries in coming decades.

A nested sampling network on the Colorado (CR) and Missouri Rivers (MR) provided data to assess impacts of large-scale reservoir systems and climate on carbon export. The Load Estimator (LOADEST) model was used to estimate both dissolved inorganic and organic carbon (DIC and DOC) fluxes for a total of 22 sites along the main stems of the CR and MR. Both the upper CR and MR DIC and DOC fluxes increased longitudinally, but the lower CR fluxes decreased while the lower MRs continued to increase. We examined multiple factors through space and time that help explain these flux patterns. Seasonal variability in precipitation and temperature, along with site-level concentration versus discharge relationships proved to be significant factors explaining much of the difference among sites located below reservoirs as compared to sites located in more free-flowing segments of the river. The characterization of variability in carbon exports over space and time provides a basis for understanding carbon cycling and transport within river basins affected by large reservoir systems, particular in arid-to semi-arid ecosystems.

Aquatic ecosystems are important components of landscape carbon budgets. In lake-rich landscapes, both lakes and streams may be important sources of carbon gases (CO2 and CH4) to the atmosphere, but the processes that control gas concentrations and emissions in these interconnected landscapes have not been adequately addressed. We use multiple data sets that vary in their spatial and temporal extent during 2001–2012 to investigate the carbon gas source strength of streams in a lake-rich landscape and to determine the contribution of lakes, metabolism, and groundwater to stream CO2 and CH4. We show that streams emit roughly the same mass of CO2 (23.4 Gg C yr−1; 0.49 mol CO2 m−2 d−1) as lakes at a regional scale (27 Gg C yr−1) and that stream CH4 emissions (189 Mg C yr−1; 8.46 mmol CH4 m−2 d−1) are an important component of the regional greenhouse gas balance. Gas transfer velocity variability (range = 0.34 to 13.5 m d−1) contributed to the variability of gas flux in this landscape. Groundwater inputs and in-stream metabolism control stream gas supersaturation at the landscape scale, while carbon cycling in lakes and deep groundwaters does not control downstream gas emissions. Our results indicate the need to consider connectivity of all aquatic ecosystems (lakes, streams, wetlands, and groundwater) in lake-rich landscapes and their connections with the terrestrial environment in order to understand the full nature of the carbon cycle.

[1] Boreal ecosystems represent a large carbon (C) reservoir and a substantial source of greenhouse gases. Hydrologic conditions dictate whether C leached from boreal soils is processed in catchments or flushed to less productive environments via the stream. This study quantified hydrologic and biogeochemical C loss from a boreal catchment underlain by frozen silt, where flowpaths may deepen as the active layer thaws over the summer. We hypothesized a decrease in the magnitude of C mineralization over the summer associated with changing flowpaths and decreasing hydrologic connectivity, organic matter lability, and nitrogen (N) availability. Conservative tracers were used to partition C and N loss between catchment export and biogeochemical processing. Coupling tracers with tributary and porewater chemistry indicated C and N cycling in soil flowpaths, with an exponential decrease over the summer. Nitrate was primarily reduced in hillslope flowpaths and the lack of N reaching the stream appeared to limit C mineralization. Stream export accounted for the greatest loss of C, removing 247 and 113 mol hr−1 in the early and late summer, respectively. Reactivity was related to hydrologic connectivity between the soils and stream, which was greatest early in the summer and following a large flood. While a warming climate may increase storage potential in thawed soils, the early-season flush of labile material and late-season runoff through mineral flowpaths may maintain high C export rates. Therefore, we highlight physical export as a dominant cause of aqueous C loss from silty catchments as the Arctic continues to thaw.

[1] Boreal ecosystems store significant quantities of organic carbon (C) that may be vulnerable to degradation as a result of a warming climate. Despite their limited coverage on the landscape, streams play a significant role in the processing, gaseous emission, and downstream export of C, and small streams are thought to be particularly important because of their close connection with the surrounding landscape. However, ecosystem carbon studies do not commonly incorporate the role of the aquatic conduit. We measured carbon dioxide (CO2) and methane (CH4) concentrations and emissions in a headwater stream network of interior Alaska underlain by permafrost to assess the potential role of stream gas emissions in the regional carbon balance. First-order streams exhibited the greatest variability in fluxes of CO2 and CH4, and the greatest mean pCO2. High-resolution time series of stream pCO2 and discharge at two locations on one first-order stream showed opposing pCO2 responses to storm events, indicating the importance of hydrologic flowpaths connecting CO2-rich soils with surface waters. Repeated longitudinal surveys on the stream showed consistent areas of elevated pCO2 and pCH4, indicative of discrete hydrologic flowpaths delivering soil water and groundwater having varying chemistry. Up-scaled basin estimates of stream gas emissions suggest that streams may contribute significantly to catchment-wide CH4 emissions. Overall, our results indicate that while stream-specific gas emission rates are disproportionately high relative to the terrestrial landscape, both stream surface area and catchment normalized emission rates were lower than those documented for the Yukon River Basin as a whole. This may be due to limitations of C sources and/or C transport to surface waters.

The magnitude of Alaska (AK) inland waters carbon (C) fluxes is likely to change in the future due to amplified climate warming impacts on the hydrology and biogeochemical processes in high latitude regions. Although current estimates of major aquatic C fluxes represent an essential baseline against which future change can be compared, a comprehensive assessment for AK has not yet been completed. To address this gap, we combined available data sets and applied consistent methodologies to estimate river lateral C export to the coast, river and lake carbon dioxide (CO2 ) and methane (CH4 ) emissions, and C burial in lakes for the six major hydrologic regions in the state. Estimated total aquatic C flux for AK was 41 Tg C/yr. Major components of this total flux, in Tg C/yr, were 18 for river lateral export, 17 for river CO2 emissions, and 8 for lake CO2 emissions. Lake C burial offset these fluxes by 2 Tg C/yr. River and lake CH4 emissions were 0.03 and 0.10 Tg C/yr, respectively. The Southeast and South central regions had the highest temperature, precipitation, terrestrial net primary productivity (NPP), and C yields (fluxes normalized to land area) were 77 and 42 g C·m-2 ·yr-1 , respectively. Lake CO2 emissions represented over half of the total aquatic flux from the Southwest (37 g C·m-2 ·yr-1 ). The North Slope, Northwest, and Yukon regions had lesser yields (11, 15, and 17 g C·m2 ·yr-1 ), but these estimates may be the most vulnerable to future climate change, because of the heightened sensitivity of arctic and boreal ecosystems to intensified warming. Total aquatic C yield for AK was 27 g C·m-2 ·yr-1 , which represented 16% of the estimated terrestrial NPP. Freshwater ecosystems represent a significant conduit for C loss, and a more comprehensive view of land-water-atmosphere interactions is necessary to predict future climate change impacts on the Alaskan ecosystem C balance.