High Voltage: The Molecular Properties of Redox-Active Dissolved Organic Matter in Northern High-Latitude Lakes.

Redox-active functional groups in dissolved organic matter (DOM) are crucial for microbial electron transfer and methane emissions. However, the extent of aquatic DOM redox properties across northern high-latitude lakes and their relationships with DOM composition have not been thoroughly described. We quantified electron donating capacity (EDC) and electron accepting capacity (EAC) in lake DOM from Canada to Alaska and assessed their relationships with parameters from absorbance, fluorescence, and ultrahigh resolution mass spectrometry (FT-ICR MS) analyses. EDC and EAC are strongly tied to aromaticity and negatively related to aliphaticity and protein-like content. Redox-active formulae spanned a range of aromaticity, including highly unsaturated phenolic formulae, and correlated negatively with many aliphatic N and S-containing formulae. This distribution illustrates the compositional diversity of redox-sensitive functional groups and their sensitivity to ecosystem properties such as local hydrology and residence time. Finally, we developed a reducing index (RI) to predict EDC in aquatic DOM from FT-ICR MS spectra and assessed its robustness using riverine DOM. As the hydrology of the northern high-latitudes continues to change, we expect differences in the quantity and partitioning of EDC and EAC within these lakes, which have implications for local water quality and methane emissions.

Aquatic carbon cycling in the conterminous United States and implications for terrestrial carbon accounting.

Inland water ecosystems dynamically process, transport, and sequester carbon. However, the transport of carbon through aquatic environments has not been quantitatively integrated in the context of terrestrial ecosystems. Here, we present the first integrated assessment, to our knowledge, of freshwater carbon fluxes for the conterminous United States, where 106 (range: 71-149) teragrams of carbon per year (TgC⋅y(-1)) is exported downstream or emitted to the atmosphere and sedimentation stores 21 (range: 9-65) TgC⋅y(-1) in lakes and reservoirs. We show that there is significant regional variation in aquatic carbon flux, but verify that emission across stream and river surfaces represents the dominant flux at 69 (range: 36-110) TgC⋅y(-1) or 65% of the total aquatic carbon flux for the conterminous United States. Comparing our results with the output of a suite of terrestrial biosphere models (TBMs), we suggest that within the current modeling framework, calculations of net ecosystem production (NEP) defined as terrestrial only may be overestimated by as much as 27%. However, the internal production and mineralization of carbon in freshwaters remain to be quantified and would reduce the effect of including aquatic carbon fluxes within calculations of terrestrial NEP. Reconciliation of carbon mass-flux interactions between terrestrial and aquatic carbon sources and sinks will require significant additional research and modeling capacity.

Ancient low-molecular-weight organic acids in permafrost fuel rapid carbon dioxide production upon thaw.

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.

Inland waters and their role in the carbon cycle of Alaska.

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.

Organic Carbon Burial in Lakes and Reservoirs of the Conterminous United States.

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.

Ebullitive methane emissions from oxygenated wetland streams.

Stream and river carbon dioxide emissions are an important component of the global carbon cycle. Methane emissions from streams could also contribute to regional or global greenhouse gas cycling, but there are relatively few data regarding stream and river methane emissions. Furthermore, the available data do not typically include the ebullitive (bubble-mediated) pathway, instead focusing on emission of dissolved methane by diffusion or convection. Here, we show the importance of ebullitive methane emissions from small streams in the regional greenhouse gas balance of a lake and wetland-dominated landscape in temperate North America and identify the origin of the methane emitted from these well-oxygenated streams. Stream methane flux densities from this landscape tended to exceed those of nearby wetland diffusive fluxes as well as average global wetland ebullitive fluxes. Total stream ebullitive methane flux at the regional scale (103 Mg C yr(-1) ; over 6400 km(2) ) was of the same magnitude as diffusive methane flux previously documented at the same scale. Organic-rich stream sediments had the highest rates of bubble release and higher enrichment of methane in bubbles, but glacial sand sediments also exhibited high bubble emissions relative to other studied environments. Our results from a database of groundwater chemistry support the hypothesis that methane in bubbles is produced in anoxic near-stream sediment porewaters, and not in deeper, oxygenated groundwaters. Methane interacts with other key elemental cycles such as nitrogen, oxygen, and sulfur, which has implications for ecosystem changes such as drought and increased nutrient loading. Our results support the contention that streams, particularly those draining wetland landscapes of the northern hemisphere, are an important component of the global methane cycle.

Bioavailability of dissolved organic matter varies with anthropogenic landcover in the Upper Mississippi River Basin.

Anthropogenic conversion of forests and wetlands to agricultural and urban landcovers impacts dissolved organic matter (DOM) within streams draining these catchments. Research on how landcover conversion impacts DOM molecular level composition and bioavailability, however, is lacking. In the Upper Mississippi River Basin (UMRB), water from low-order streams and rivers draining one of three dominant landcovers (forest, agriculture, urban) was incubated for 28 days to determine bioavailable DOC (BDOC) concentrations and changes in DOM composition. The BDOC concentration averaged 0.49 ± 0.30 mg L-1 across all samples and was significantly higher in streams draining urban catchments (0.72 ± 0.34 mg L-1) compared to streams draining agricultural (0.28 ± 0.15 mg L-1) and forested (0.47 ± 0.17 mg L-1) catchments. Percent BDOC was significantly greater in urban (10% ± 4.4%) streams compared to forested streams (5.6% ± 3.2%), corresponding with greater relative abundances of aliphatic and N-containing aliphatic compounds in urban streams. Aliphatic compound relative abundance decreased across all landcovers during the bioincubation (average -4.1% ± 10%), whereas polyphenolics and condensed aromatics increased in relative abundance across all landcovers (average of +1.4% ± 5.9% and +1.8% ± 10%, respectively). Overall, the conversion of forested to urban landcover had a larger impact on stream DOM bioavailability in the UMRB compared to conversion to agricultural landcover. Future research examining the impacts of anthropogenic landcover conversion on stream DOM composition and bioavailability needs to be expanded to a range of spatial scales and to different ecotones, especially with continued landcover alterations.

Mercury export from the Yukon River Basin and potential response to a changing climate.

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.

Potential impacts of mercury released from thawing permafrost.

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.

Spatial patterns of enzymatic activity in large water bodies: Ship-borne measurements of beta-D-glucuronidase activity as a rapid indicator of microbial water quality.

This study used automated enzymatic activity measurements conducted from a mobile research vessel to detect the spatial variability of beta­d­glucuronidase (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 km2 lake area. The ship-borne measurements of GLUC activity correlated with standard E. coli analyses (R2 = 0.71) and revealed the effects of (1) precipitation events and urban run-off on GLUC activity in surface waters, (2) localized point inlets of potential fecal pollution and (3) increasing GLUC signals along gradients of urbanization. We propose that this ship-borne water quality screening to be integrated into future water inventory programs as an initial or complementary tool (besides established fecal indicator parameters), due to its ability to provide near real-time spatial information on potential fecal contamination of large surface water resources and therefore being helpful to greatly reduce potential human health risks.

A reservoir of nitrate beneath desert soils.

A large reservoir of bioavailable nitrogen (up to approximately 10(4) kilograms of nitrogen per hectare, as nitrate) has been previously overlooked in studies of global nitrogen distribution. The reservoir has been accumulating in subsoil zones of arid regions throughout the Holocene. Consideration of the subsoil reservoir raises estimates of vadose-zone nitrogen inventories by 14 to 71% for warm deserts and arid shrublands worldwide and by 3 to 16% globally. Subsoil nitrate accumulation indicates long-term leaching from desert soils, impelling further evaluation of nutrient dynamics in xeric ecosystems. Evidence that subsoil accumulations are readily mobilized raises concern about groundwater contamination after land-use or climate change.