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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.

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.

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.

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.

Site-specific and regional analysis of time-series hydrologic and geochemical data collected from 15 monitoring wells in the Piceance Basin indicated that a leaking gas well contaminated shallow groundwater with thermogenic methane. The gas well was drilled in 1956 and plugged and abandoned in 1990. Chemical and isotopic data showed the thermogenic methane was not from mixing of gas-rich formation water with shallow groundwater or natural migration of a free-gas phase. Water-level and methane-isotopic data, and video logs from a deep monitoring well, indicated that a shale confining layer ~125 m below the zone of contamination was an effective barrier to upward migration of water and gas. The gas well, located 27 m from the contaminated monitoring well, had ~1000 m of uncemented annular space behind production casing that was the likely pathway through which deep gas migrated into the shallow aquifer. Measurements of soil gas near the gas well showed no evidence of methane emissions from the soil to the atmosphere even though methane concentrations in shallow groundwater (16 to 20 mg/L) were above air-saturation levels. Methane degassing from the water table was likely oxidized in the relatively thick unsaturated zone (~18 m), thus rendering the leak undetectable at land surface. Drilling and plugging records for oil and gas wells in Colorado and proxies for depth to groundwater indicated thousands of oil and gas wells were drilled and plugged in the same timeframe as the implicated gas well, and the majority of those wells were in areas with relatively large depths to groundwater. This study represents one of the few detailed subsurface investigations of methane leakage from a plugged and abandoned gas well. As such, it could provide a useful template for prioritizing and assessing potentially leaking wells, particularly in cases where the leakage does not manifest itself at land surface.

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.

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.

Recent warming at high latitudes has accelerated permafrost thaw, which can modify soil carbon dynamics and watershed hydrology. The flux and composition of dissolved organic matter (DOM) from soils to rivers are sensitive to permafrost configuration and its impact on subsurface hydrology and groundwater discharge. Here, we evaluate the utility of DOM composition and age as a tool for detecting permafrost thaw in three rivers (Beaver, Birch, and Hess Creeks) within the discontinuous permafrost zone of interior Alaska. We observed strong temporal controls on Δ14C content of hydrophobic acid isolates (Δ14C-HPOA) across all rivers, with the most enriched values occurring during spring snowmelt (75 ± 8‰) and most depleted during winter flow (−21 ± 8‰). Radiocarbon ages of winter flow samples ranged from 35 to 445 yr BP, closely tracking estimated median base flow travel times for this region (335 years). During spring snowmelt, young DOM was composed of highly aromatic, high molecular-weight compounds, whereas older DOM of winter flow had lower aromaticity and molecular weight. We observed a significant correlation between Δ14C-HPOA and UV absorbance coefficient at 254 nm (α254) across all study rivers. Using α254 as an optical indicator for Δ14C-HPOA, we also observed a long-term decline in α254 during maximum annual thaw depth over the last decade at the Hess Creek study site. These findings suggest a shift in watershed hydrology associated with increasing active layer thickness. Further development of DOM optical indicators may serve as a novel and inexpensive tool for detecting permafrost degradation in northern watersheds.

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[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.

Ground water occurrence, movement, and its contribution to streamflow were investigated in Loch Vale, an alpine catchment in the Front Range of the Colorado Rocky Mountains. Hydrogeomorphologic mapping, seismic refraction measurements, and porosity and permeability estimates indicate that talus slopes are the primary ground water reservoir, with a maximum storage capacity that is equal to, or greater than, total annual discharge from the basin (5.4 ± 0.8 � 10 6 m 3 ). Although snowmelt and glacial melt provide the majority of annual water flux to the basin, tracer tests and gauging along a stream transect indicate that ground water flowing from talus can account for ≥75% of streamflow during storms and the winter base flow period. The discharge response of talus springs to storms and snowmelt reflects rapid transmittal of water through coarse debris at the talus surface and slower release of water from finer-grained sediments at depth. Ice stored in permafrost (including rock glaciers) is the second largest ground water reservoir in Loch Vale; it represents a significant, but seldom recognized, ground water reservoir in alpine terrain. Mean annual air temperatures are sufficiently cold to support permafrost above 3460 m; however, air temperatures have increased 1.1° to 1.4°C since the early 1990s, consistent with long-term (1976‐2000) increases in air temperature measured at other high-elevation sites in the Front Range, European Alps, and Peruvian Andes. If other climatic factors remain constant, the increase in air temperatures at Loch Vale is sufficient to increase the lower elevational limit of permafrost by 150 to 190 m. Although this could cause a short-term increase in streamflow, it may ultimately result in decreased flow in the future.

Studies worldwide have shown that mercury (Hg) is a ubiquitouscontaminant, reaching even the most remote environments such ashigh-altitude lakes via atmospheric pathways. However, very fewstudies have been conducted to assess Hg contamination levels ofthese systems. We sampled 90 mid-latitude, high-altitude lakes from seven national parks in the western United States during afour-week period in September 1999. In addition to the synoptic survey, routine monitoring and experimental studies were conducted at one of the lakes (Mills Lake) to quantify MeHg fluxrates and important process rates such as photo-demethylation. Results show that overall, high-altitude lakes have low total mercury (HgT) and methylmercury (MeHg) levels (1.07 and 0.05 ng L-1, respectively), but a very good correlation of Hg to MeHg (r2= 0.82) suggests inorganic Hg(II) loading is a primary controlling factor of MeHg levels in dilute mountain lakes. Positive correlations were also observed for dissolved organic carbon (DOC) and both Hg and MeHg, although to a much lesser degree. Levels of MeHg were similar among the seven national parks, with the exception of Glacier National Park where lowerconcentrations were observed (0.02 ng L-1), and appear to berelated to naturally elevated pH values there. Measured rates ofMeHg photo-degradation at Mills Lake were quite fast, and thisprocess was of equal importance to sedimentation and stream flowfor removing MeHg. Enhanced rates of photo-demethylation are likely an important reason why high-altitude lakes, with typically high water clarity and sunlight exposure, are low in MeHg.

[1] Carbon dioxide (CO2) and methane (CH4) emissions are important, but poorly quantified, components of riverine carbon (C) budgets. This is largely because the data needed for gas flux calculations are sparse and are spatially and temporally variable. Additionally, the importance of C gas emissions relative to lateral C exports is not well known because gaseous and aqueous fluxes are not commonly measured on the same rivers. We couple measurements of aqueous CO2 and CH4 partial pressures (pCO2, pCH4) and flux across the water-air interface with gas transfer models to calculate subbasin distributions of gas flux density. We then combine those flux densities with remote and direct observations of stream and river water surface area and ice duration, to calculate C gas emissions from flowing waters throughout the Yukon River basin. CO2 emissions were 7.68 Tg C yr−1 (95% CI: 5.84 −10.46), averaging 750 g C m−2 yr−1 normalized to water surface area, and 9.0 g C m−2 yr−1 normalized to river basin area. River CH4 emissions totaled 55 Gg C yr−1 or 0.7% of the total mass of C emitted as CO2 plus CH4 and ∼6.4% of their combined radiative forcing. When combined with lateral inorganic plus organic C exports to below head of tide, C gas emissions comprised 50% of total C exported by the Yukon River and its tributaries. River CO2 and CH4 derive from multiple sources, including groundwater, surface water runoff, carbonate equilibrium reactions, and benthic and water column microbial processing of organic C. The exact role of each of these processes is not yet quantified in the overall river C budget.

[1] Northern high-latitude rivers transport large amounts of terrestrially derived dissolved organic matter (DOM) from boreal and arctic ecosystems to coastal areas and oceans. Current knowledge of the biodegradability of DOM in these rivers is limited, particularly for large rivers discharging to the Arctic Ocean. We conducted a seasonally comprehensive study of biodegradable dissolved organic carbon (BDOC) dynamics in the Yukon River and two of its tributaries in Alaska, USA. Distinct seasonal patterns of BDOC, consistent across a wide range of watershed size, indicate BDOC is transported year-round. Relative biodegradability (%BDOC) was greatest during winter, and decreased into spring and summer. Due to large seasonal differences in DOC concentration, the greatest concentrations of BDOC (mg C L−1) occurred during spring freshet, followed by winter and summer. While chemical composition of DOM was an important driver of BDOC, the overriding control of BDOC was mineral nutrient availability due to wide shifts in carbon (C) and nitrogen (N) stoichiometry across seasons. We calculated seasonal and annual loads of BDOC exported by the Yukon River by applying measured BDOC concentrations to daily water discharge values, and also by applying an empirical correlation between %BDOC and the ratio of DOC to dissolved inorganic N (DIN) to total DOC loads. The Yukon River exports ∼0.2 Tg C yr−1 as BDOC that is decomposable within 28 days. This corresponds to 12–18% of the total annual DOC export. Furthermore, we calculate that the six largest arctic rivers, including the Yukon River, collectively export ∼2.3 Tg C yr−1 as BDOC to the Arctic Ocean.

We measured mercury (Hg) concentrations and calculated export and yield from the Yukon River Basin (YRB) to quantify Hg flux from a large, permafrost-dominated, high-latitude watershed. Exports of Hg averaged 4400 kg Hg yr(-1). The average annual yield for the YRB during the study period was 5.17 μg m(-2) yr(-1), which is 3-32 times more than Hg yields reported for 8 other major northern hemisphere river basins. The vast majority (90%) of Hg export is associated with particulates. Half of the annual export of Hg occurred during the spring with about 80% of 34 samples exceeding the U.S. EPA Hg standard for adverse chronic effects to biota. Dissolved and particulate organic carbon exports explained 81% and 50%, respectively, of the variance in Hg exports, and both were significantly (p < 0.001) correlated with water discharge. Recent measurements indicate that permafrost contains a substantial reservoir of Hg. Consequently, climate warming will likely accelerate the mobilization of Hg from thawing permafrost increasing the export of organic carbon associated Hg and thus potentially exacerbating the production of bioavailable methylmercury from permafrost-dominated northern river basins.

[1] Loads and yields of suspended sediment and carbonate were measured and modeled at three locations on the Yukon, Tanana, and Porcupine Rivers in Alaska during water years 2001–2005 (1 October 2000 to 30 September 2005). Annual export of suspended sediment and carbonate upstream from the Yukon Delta averaged 68 Mt a−1 and 387 Gg a−1, respectively, with 50% of the suspended sediment load originating in the Tanana River Basin and 88% of the carbonate load originating in the White River Basin. About half the annual suspended sediment export occurred during spring, and half occurred during summer-autumn, with very little export in winter. On average, a minimum of 11 Mt a−1 of suspended sediment is deposited in floodplains between Eagle, Alaska, and Pilot Station, Alaska, on an annual basis, mostly in the Yukon Flats. There is about a 27% loss in the carbonate load between Eagle and Yukon River near Stevens Village, with an additional loss of about 29% between Stevens Village and Pilot Station, owing to a combination of deposition and dissolution. Comparison of current and historical suspended sediment loads for Tanana River suggests a possible link between suspended sediment yield and the Pacific decadal oscillation.

[1] The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long-term DOC monitoring data. Intensive sampling across the historically under-sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean.

The radionuclide210Pb shows significant geographic variations in the extent of its removal from the open ocean water column. This “texture of scavenging” is defined by mapping: (1) the integrated deficiency of210Pb in the water column, relative to its supply from the atmosphere and from in situ decay of dissolved226Ra, and (2) inventories of excess210Pb in deep-sea sediments. The ratio of210Pb deficiency to its supply, termed the scavenging effectiveness, is ∼ 20% in the North Equatorial Pacific and ∼ 50% in the North Atlantic. This variation is related to the combined effects of uptake of210Pb onto sinking particles and lateral transport of210Pb to areas of more intense removal. Sediment inventories of excess210Pb, normalized to the210Pb deficiency in the overlying water column, permit evaluation of the relative importance of these effects. In the North Equatorial Pacific virtually all of the210Pb removed from the water column is present in the underlying sediments but in the mid-latitude North Atlantic, the sediments comprise only about 50% of the210Pb removed. The deficiencies of210Pb in the mid-latitude North Atlantic sediments south of 50°N are qualitatively offset by surpluses in high-latitude sediments north of 50°N. Higher primary productivity and new production in the surface waters of the high-latitude North Atlantic and North Equatorial Pacific, relative to the oligotrophic central North Atlantic, may account for the greater fluxes of210Pb to bottom sediments in those areas.

[1] Loads and yields of dissolved and particulate nitrogen (N) and phosphorus (P) were measured and modeled at three locations on the Yukon River (YR) and on the Tanana and Porcupine Rivers in Alaska during 2001–2005. Total export of N and P upstream of Yukon Delta averaged 120 Gg N a−1 and 56 Gg P a−1, respectively, with 43.5% of total N (TN) as dissolved organic N, and 98% of total P (TP) as particulate phosphorus. Approximately half of the annual export of TN and TP occurred during spring. Hydrologic yields of TN (5.6–13.3 mmol N m−2 a−1) and TP (0.8–9.0 mmol P m−2 a−1) were least in the Porcupine basin and greatest in the Tanana basin and were proportional to water yield. Comparison of current and historical dissolved organic matter (DOM) export from the basin indicates decreased DON export with respect to total water discharge during summer and autumn in recent decades. Any possible climate-related change in annual water discharge will result in proportional changes in N and P export.

[1] Loads and yields of dissolved and particulate organic and inorganic carbon (DOC, POC, DIC, PIC) were measured and modeled at three locations on the Yukon River (YR) and on the Tanana and Porcupine rivers (TR, PR) in Alaska during 2001–2005. Total YR carbon export averaged 7.8 Tg C yr−1, 30% as OC and 70% as IC. Total C yields (0.39–1.03 mol C m−2 yr−1) were proportional to water yields (139–356 mm yr−1; r2 = 0.84) at all locations. Summer DOC had an aged component (fraction modern (FM) = 0.94–0.97), except in the permafrost wetland-dominated PR, where DOC was modern. POC had FM = 0.63–0.70. DOC had high concentration, high aromaticity, and high hydrophobic content in spring and low concentration, low aromaticity, and high hydrophilic content in winter. About half of annual DOC export occurred during spring. DIC concentration and isotopic composition were strongly affected by dissolution of suspended carbonates in glacial meltwater during summer.

[1] Climate warming is having a dramatic effect on the vegetation distribution and carbon cycling of terrestrial subarctic and arctic ecosystems. Here, we present hydrologic evidence that warming is also affecting the export of dissolved organic carbon and bicarbonate (DOC and HCO3−) at the large basin scale. In the 831,400 km2 Yukon River basin, water discharge (Q) corrected DOC export significantly decreased during the growing season from 1978–80 to 2001–03, indicating a major shift in terrestrial to aquatic C transfer. We conclude that decreased DOC export, relative to total summer through autumn Q, results from increased flow path, residence time, and microbial mineralization of DOC in the soil active layer and groundwater. Counter to current predictions, we argue that continued warming could result in decreased DOC export to the Bering Sea and Arctic Ocean by major subarctic and arctic rivers, due to increased respiration of organic C on land.

[1] High-elevation lakes in the western United States are sensitive to atmospheric deposition of sulfur and nitrogen due to fast hydrologic flushing rates, short growing seasons, an abundance of exposed bedrock, and a lack of well-developed soils. This sensitivity is reflected in the dilute chemistry of the lakes, which was documented in the U.S. Environmental Protection Agency's Western Lake Survey of 1985. Sixty-nine lakes in seven national parks sampled during the 1985 survey were resampled during fall 1999 to investigate possible decadal-scale changes in lake chemistry. In most lakes, SO4 concentrations were slightly lower in 1999 than in 1985, consistent with a regional decrease in precipitation SO4 concentrations and in SO2 emissions in the western United States. Nitrate concentrations also tended to be slightly lower in 1999 than in 1985, in contrast with generally stable or increasing inorganic N deposition in the west. Differences in alkalinity were variable among parks but were relatively consistent within each park. Possible effects of annual and seasonal-scale variations in precipitation amount on lake chemistry were evaluated based on climate data available for the parks and an analysis of climatic effects at two research watersheds with long-term records. Results suggest that rain prior to sampling in 1985 may have caused elevated NO3 in some lakes due to direct runoff of precipitation and flushing of NO3 from alpine soils, which may explain some of the decrease in NO3 concentrations observed in survey lakes.

We investigated the effects of sulfate concentration on sulfate reduction and net S storage in lake sediments using34S as a tracer. The water overlying intact sediment cores from the hypolimnion of Mares Pond, MA, was replaced with two Na234SO4 solutions at either ambient (70 μM) or elevated (260 μM) sulfate concentrations. The δ34S of the added sulfate was 4974 ‰. Over two months, the net sulfate reduction rate in the ambient sulfate treatment was zero, while the net rate for the high sulfate treatment was 140 μmoles/m2/d. The water overlying the cores was kept under oxic conditions and the sediment received no fresh carbon inputs, thus the net rate reported may underestimate the in situ rate. Gross sulfate reduction rates calculated by isotope dilution were approximately 350 μmoles/m2/d for both treatments. While the calculation of gross sulfate reduction rates in intact sediment cores can be complicated by differential diffusion of34S and32S, isotopic fractionation, and the possible formation of ester sulfates, we believe these effects to be small. The results suggest that sulfate reduction is not strongly sulfate-limited in Mares Pond. The difference in net sulfate reduction rates between treatments resulted from a decrease in sulfide oxidation and suggests the importance of reoxidation in controlling net S storage in lake sediments. In both treatments the CRS and organic S fractions were measurably labelled in34S. Below the sediment surface, the CRS fraction was the more heavily labelled storage product for reduced sulfides.