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George R. Aiken

Publications and source records attributed to George R. Aiken.

At least 55 records · Page 3Linked to original sources
USGS2015

Uranium isotopes and dissolved organic carbon in loess permafrost: Modeling the age of ancient ice

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 234 U vs. 238 U ( 234 U/ 238 U) 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 ( 234 U/ 238 U) 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 ( 234 U/ 238 U) 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 ( 234 U/ 238 U) 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 ( 14 C) 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.

Alaska↗
USGS2015

Characterization of hydraulic fracturing flowback water in Colorado: Implications for water treatment

A suite of analytical tools was applied to thoroughly analyze the chemical composition of an oil/gas well flowback water from the Denver–Julesburg (DJ) basin in Colorado, and the water quality data was translated to propose effective treatment solutions tailored to specific reuse goals. Analysis included bulk quality parameters, trace organic and inorganic constituents, and organic matter characterization. The flowback sample contained salts (TDS = 22,500 mg/L), metals (e.g., iron at 81.4 mg/L) and high concentration of dissolved organic matter (DOC = 590 mgC/L). The organic matter comprised fracturing fluid additives such as surfactants (e.g., linear alkyl ethoxylates) and high levels of acetic acid (an additives' degradation product), indicating the anthropogenic impact on this wastewater. Based on the water quality results and preliminary treatability tests, the removal of suspended solids and iron by aeration/precipitation (and/or filtration) followed by disinfection was identified as appropriate for flowback recycling in future fracturing operations. In addition to these treatments, a biological treatment (to remove dissolved organic matter) followed by reverse osmosis desalination was determined to be necessary to attain water quality standards appropriate for other water reuse options (e.g., crop irrigation). The study provides a framework for evaluating site-specific hydraulic fracturing wastewaters, proposing a suite of analytical methods for characterization, and a process for guiding the choice of a tailored treatment approach.

Colorado↗
USGS2015

Photoreduction of Hg(II) and photodemethylation of methylmercury: the key role of thiol sites on dissolved organic matter

This study examined the kinetics of photoreduction of Hg( II ) and photodemethylation of methylmercury (MeHg + ) attached to, or in the presence of, dissolved organic matter (DOM). Both Hg( II ) and MeHg + are principally bound to reduced sulfur groups associated with DOM in many freshwater systems. We propose that a direct photolysis mechanism is plausible for reduction of Hg( II ) bound to reduced sulfur groups on DOM while an indirect mechanism is supported for photodemethylation of MeHg + bound to DOM. UV spectra of Hg( II ) and MeHg + bound to thiol containing molecules demonstrate that the Hg( II )–S bond is capable of absorbing UV-light in the solar spectrum to a much greater extent than MeHg + –S bonds. Experiments with chemically distinct DOM isolates suggest that concentration of DOM matters little in the photochemistry if there are enough reduced S sites present to strongly bind MeHg + and Hg( II ); DOM concentration does not play a prominent role in photodemethylation other than to screen light, which was demonstrated in a field experiment in the highly colored St. Louis River where photodemethylation was not observed at depths ≥10 cm. Experiments with thiol ligands yielded slower photodegradation rates for MeHg + than in experiments with DOM and thiols; rates in the presence of DOM alone were the fastest supporting an intra-DOM mechanism. Hg( II ) photoreduction rates, however, were similar in experiments with only DOM, thiols plus DOM, or only thiols suggesting a direct photolysis mechanism. Quenching experiments also support the existence of an intra-DOM photodemethylation mechanism for MeHg + . Utilizing the difference in photodemethylation rates measured for MeHg + attached to DOM or thiol ligands, the binding constant for MeHg + attached to thiol groups on DOM was estimated to be 10 16.7 .

Environmental Science: Processes and Impacts↗
USGS2015

Concentrations and distributions of metals associated with dissolved organic matter from the Suwannee River (GA, USA)

Concentrations and distributions of metals in Suwannee River (SR) raw filtered surface water (RFSW) and dissolved organic matter (DOM) processed by reverse osmosis (RO), XAD-8 resin (for humic and fulvic acids [FA]), and XAD-4 resin (for “transphilic” acids) were analyzed by asymmetrical flow field-flow fractionation (AsFlFFF). SR samples were compared with DOM samples from Nelson's Creek (NLC), a wetland-draining stream in northern Michigan; previous International Humic Substances Society (IHSS) FA and RO samples from the SR; and an XAD-8 sample from Lake Fryxell (LF), Antarctica. Despite application of cation exchange during sample processing, all XAD and RO samples contained substantial metal concentrations. AsFlFFF fractograms allowed metal distributions to be characterized as a function of DOM component molecular weight (MW). In SR RFSW, Fe, Al, and Cu were primarily associated with intermediate to higher than average MW DOM components. SR RO, XAD-8, and XAD-4 samples from May 2012 showed similar MW trends for Fe and Al but Cu tended to associate more with lower MW DOM. LF DOM had abundant Cu and Zn, perhaps due to amine groups that should be present due to its primarily algal origins. None of the fractograms showed obvious evidence for mineral nanoparticles, although some very small mineral nanoparticles might have been present at trace concentrations. This research suggests that AsFlFFF is important for understanding how metals are distributed in different DOM samples (including IHSS samples), which may be key to metal reactivity and bioavailability.

Georgia↗
USGS2015

The river as a chemostat: fresh perspectives on dissolved organic matter flowing down the river continuum

A better understanding is needed of how hydrological and biogeochemical processes control dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) composition from headwaters downstream to large rivers. We examined a large DOM dataset from the National Water Information System of the US Geological Survey, which represents approximately 100 000 measurements of DOC concentration and DOM composition at many sites along rivers across the United States. Application of quantile regression revealed a tendency towards downstream spatial and temporal homogenization of DOC concentrations and a shift from dominance of aromatic DOM in headwaters to more aliphatic DOM downstream. The DOC concentration–discharge (C-Q) relationships at each site revealed a downstream tendency towards a slope of zero. We propose that despite complexities in river networks that have driven many revisions to the River Continuum Concept, rivers show a tendency towards chemostasis (C-Q slope of zero) because of a downstream shift from a dominance of hydrologic drivers that connect terrestrial DOM sources to streams in the headwaters towards a dominance of instream and near-stream biogeochemical processes that result in preferential losses of aromatic DOM and preferential gains of aliphatic DOM.

Canadian Journal of Fisheries and Aquatic Sciences↗
USGS2014

Using dissolved organic matter age and composition to detect permafrost thaw in boreal watersheds of interior Alaska

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 Δ 14 C content of hydrophobic acid isolates (Δ 14 C-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 Δ 14 C-HPOA and UV absorbance coefficient at 254 nm ( α 254 ) across all study rivers. Using α 254 as an optical indicator for Δ 14 C-HPOA, we also observed a long-term decline in α 254 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.

Alaska↗
USGS2014

Effects of iron on optical properties of dissolved organic matter

Iron is a source of interference in the spectroscopic analysis of dissolved organic matter (DOM); however, its effects on commonly employed ultraviolet and visible (UV–vis) light adsorption and fluorescence measurements are poorly defined. Here, we describe the effects of iron(II) and iron(III) on the UV–vis absorption and fluorescence of solutions containing two DOM fractions and two surface water samples. In each case, regardless of DOM composition, UV–vis absorption increased linearly with increasing iron(III). Correction factors were derived using iron(III) absorption coefficients determined at wavelengths commonly used to characterize DOM. Iron(III) addition increased specific UV absorbances (SUVA) and decreased the absorption ratios ( E 2 : E 3 ) and spectral slope ratios ( S R ) of DOM samples. Both iron(II) and iron(III) quenched DOM fluorescence at pH 6.7. The degree and region of fluorescence quenching varied with the iron:DOC concentration ratio, DOM composition, and pH. Regions of the fluorescence spectra associated with greater DOM conjugation were more susceptible to iron quenching, and DOM fluorescence indices were sensitive to the presence of both forms of iron. Analyses of the excitation–emission matrices using a 7- and 13-component parallel factor analysis (PARAFAC) model showed low PARAFAC sensitivity to iron addition.

Environmental Science & Technology↗
USGS2014

Influences of glacial melt and permafrost thaw on the age of dissolved organic carbon in the Yukon River basin

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 Δ 14 C-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 Δ 14 C 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.

Alaska↗
USGS2014

Spatial distribution of mercury in southeastern Alaskan streams influenced by glaciers, wetlands, and salmon

Southeastern Alaska is a remote coastal-maritime ecosystem that is experiencing increased deposition of mercury (Hg) as well as rapid glacier loss. Here we present the results of the first reported survey of total and methyl Hg (MeHg) concentrations in regional streams and biota. Overall, streams draining large wetland areas had higher Hg concentrations in water, mayflies, and juvenile salmon than those from glacially-influenced or recently deglaciated watersheds. Filtered MeHg was positively correlated with wetland abundance. Aqueous Hg occurred predominantly in the particulate fraction of glacier streams but in the filtered fraction of wetland-rich streams. Colonization by anadromous salmon in both glacier and wetland-rich streams may be contributing additional marine-derived Hg. The spatial distribution of Hg in the range of streams presented here shows that watersheds are variably, yet fairly predictably, sensitive to atmospheric and marine inputs of Hg.

Alaska↗
USGS2014

An intercomparison of three methods for the large-scale isolation of oceanic dissolved organic matter

Dissolved organic matter (DOM) was isolated from large volumes of deep (674 m) and surface (21 m) ocean water via reverse osmosis/electrodialysis (RO/ED) and two solid-phase extraction (SPE) methods (XAD-8/4 and PPL) at the Natural Energy Laboratory of Hawaii Authority (NELHA). By applying the three methods to common water samples, the efficiencies of XAD, PPL and RO/ED DOM isolation were compared. XAD recovered 42% of dissolved organic carbon (DOC) from deep water (25% with XAD-8; 17% with XAD-4) and 30% from surface water (16% with XAD-8; 14% with XAD-4). PPL recovered 61 ± 3% of DOC from deep water and 61% from surface water. RO/ED recovered 82 ± 3% of DOC from deep water, 14 ± 3% of which was recovered in a sodium hydroxide rinse, and 75 ± 5% of DOC from surface water, with 12 ± 2% in the sodium hydroxide rinse. The highest recoveries of all were achieved by the sequential isolation of DOC, first with PPL and then via RO/ED. This combined technique recovered 98% of DOC from a deep water sample and 101% of DOC from a surface water sample. In total, 1.9, 10.3 and 1.6 g-C of DOC were collected via XAD, PPL and RO/ED, respectively. Rates of DOC recovery using the XAD, PPL and RO/ED methods were 10, 33 and 10 mg-C h − 1 , respectively. Based upon C/N ratios, XAD isolates were heavily C-enriched compared with water column DOM, whereas RO/ED and PPL ➔ RO/ED isolate C/N values were most representative of the original DOM. All techniques are suitable for the isolation of large amounts of DOM with purities suitable for most advanced analytical techniques. Coupling PPL and RO/ED techniques may provide substantial progress in the search for a method to quantitatively isolate oceanic DOC, bringing the entirety of the DOM pool within the marine chemist's analytical window.

Marine Chemistry↗
USGS2013

Controls on dissolved organic carbon quantity and chemical character in temperate rivers of North America

Understanding the processes controlling the transfer and chemical composition of dissolved organic carbon (DOC) in freshwater systems is crucial to understanding the carbon cycle and the effects of DOC on water quality. Previous studies have identified watershed-scale controls on bulk DOC flux and concentration among small basins but fewer studies have explored controls among large basins or simultaneously considered the chemical composition of DOC. Because the chemical character of DOC drives riverine biogeochemical processes such as metabolism and photodegradation, accounting for chemical character in watershed-scale studies will improve the way bulk DOC variability in rivers is interpreted. We analyzed DOC quantity and chemical character near the mouths of 17 large North American rivers, primarily between 2008 and 2010, and identified watershed characteristics that controlled variability. We quantified DOC chemical character using both specific ultraviolet absorbance at 254 nm (SUVA 254 ) and XAD-resin fractionation. Mean DOC concentration ranged from 2.1 to 47 mg C L −1 and mean SUVA 254 ranged from 1.3 to 4.7 L mg C −1 m −1 . We found a significant positive correlation between basin wetland cover and both bulk DOC concentration ( R 2 = 0.78; p < 0.0001) and SUVA 254 ( R 2 = 0.91; p < 0.0001), while other land use characteristics were not correlated. The strong wetland relationship with bulk DOC concentration is similar to that found by others in small headwater catchments. However, two watersheds with extremely long surface water residence times, the Colorado and St. Lawrence, diverged from this wetland relationship. These results suggest that the role of riverine processes in altering the terrestrial DOC signal at the annual scale was minimal except in river systems with long surface water residence times. However, synoptic DOC sampling of both quantity and character throughout river networks will be needed to more rigorously test this finding. The inclusion of DOC chemical character will be vital to achieving a more complete understanding of bulk DOC dynamics in large river systems.

Global Biogeochemical Cycles↗
USGS2013

Chromophoric dissolved organic matter export from U.S. rivers

Chromophoric dissolved organic matter (CDOM) fluxes and yields from 15 major U.S. rivers draining an assortment of terrestrial biomes are presented. A robust relationship between CDOM and dissolved organic carbon (DOC) loads is established (e.g., a 350 versus DOC; r 2 = 0.96, p < 0.001). Calculated CDOM yields are also correlated to watershed percent wetland (e.g. a 350 ; r 2 = 0.81, p < 0.001) providing a method for the estimation of CDOM export from ungauged watersheds. A large variation in CDOM yields was found across the rivers. The two rivers in the north-eastern U.S. (Androscoggin and Penobscot), the Edisto draining into the South Atlantic Bight, and some rivers draining into the Gulf of Mexico (Atchafalaya and Mobile) exhibit the highest CDOM yields, linked to extensive wetlands in these watersheds. If the Edisto CDOM yield is representative of other rivers draining into the South Atlantic Bight, this would result in a CDOM load equivalent to that of the Mississippi from a region of approximately 10% of the Mississippi watershed, indicating the importance of certain regions with respect to the role of terrigenous CDOM in ocean color budgets.

Geophysical Research Letters↗
USGS2013

Enhanced transfer of terrestrially derived carbon to the atmosphere in a flooding event

Rising CO 2 concentration in the atmosphere, global climate change, and the sustainability of the Earth's biosphere are great societal concerns for the 21st century. Global climate change has, in part, resulted in a higher frequency of flooding events, which allow for greater exchange between soil/plant litter and aquatic carbon pools. Here we demonstrate that the summer 2011 flood in the Mississippi River basin, caused by extreme precipitation events, resulted in a “flushing” of terrestrially derived dissolved organic carbon (TDOC) to the northern Gulf of Mexico. Data from the lower Atchafalaya and Mississippi rivers showed that the DOC flux to the northern Gulf of Mexico during this flood was significantly higher than in previous years. We also show that consumption of radiocarbon-modern TDOC by bacteria in floodwaters in the lower Atchafalaya River and along the adjacent shelf contributed to northern Gulf shelf waters changing from a net sink to a net source of CO 2 to the atmosphere in June and August 2011. This work shows that enhanced flooding, which may or may not be caused by climate change, can result in rapid losses of stored carbon in soils to the atmosphere via processes in aquatic ecosystems.

Geophysical Research Letters↗
USGS2013

Abundance, size distributions and trace-element binding of organic and iron-rich nanocolloids in Alaskan rivers, as revealed by field-flow fractionation and ICP-MS

Water samples were collected from six small rivers in the Yukon River basin in central Alaska to examine the role of colloids and organic matter in the transport of trace elements in Northern high latitude watersheds influenced by permafrost. Concentrations of dissolved organic carbon (DOC), selected elements (Al, Si, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Ba, Pb, U), and UV-absorbance spectra were measured in 0.45 μm filtered samples. ‘Nanocolloidal size distributions’ (0.5–40 nm, hydrodynamic diameter) of humic-type and chromophoric dissolved organic matter (CDOM), Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pb were determined by on-line coupling of flow field-flow fractionation (FFF) to detectors including UV-absorbance, fluorescence, and ICP-MS. Total dissolved and nanocolloidal concentrations of the elements varied considerably between the rivers and between spring flood and late summer base flow. Data on specific UV-absorbance (SUVA), spectral slopes, and the nanocolloidal fraction of the UV-absorbance indicated a decrease in aromaticity and size of CDOM from spring flood to late summer. The nanocolloidal size distributions indicated the presence of different ‘components’ of nanocolloids. ‘Fulvic-rich nanocolloids’ had a hydrodynamic diameter of 0.5–3 nm throughout the sampling season; ‘organic/iron-rich nanocolloids’ occurred in the <8 nm size range during the spring flood; whereas ‘iron-rich nanocolloids’ formed a discrete 4–40 nm components during summer base flow. Mn, Co, Ni, Cu and Zn were distributed between the nanocolloid components depending on the stability constant of the metal (+II)–organic complexes, while stronger association of Cr to the iron-rich nanocolloids was attributed to the higher oxidation states of Cr (+III or +IV). Changes in total dissolved element concentrations, size and composition of CDOM, and occurrence and size of organic/iron and iron-rich nanocolloids were related to variations in their sources from either the upper organic-rich soil or the deeper mineral layer, depending on seasonal variations in hydrological flow patterns and permafrost dynamics.

Alaska↗
USGS2013

Export of dissolved organic carbon from the Penobscot River basin in north-central Maine

Dissolved organic carbon (DOC) flux from the Penobscot River and its major tributaries in Maine was determined using continuous discharge measurements, discrete water sampling, and the LOADEST regression software. The average daily flux during 2004–2007 was 71 kg C ha −1 yr −1 (392 Mt C d −1 ), an amount larger than measured in most northern temperate and boreal rivers. Distinct seasonal variation was observed in the relation between concentration and discharge (C–Q). During June through December (summer/fall), there was a relatively steep positive C–Q relation where concentration increased by a factor of 2–3 over the approximately 20-fold range of observed stream discharge for the Penobscot River near Eddington, Maine. In contrast, during January through May (winter/spring), DOC concentration did not increase with increasing discharge. In addition, we observed a major shift in the C–Q between 2004–2005 and 2006–2007, apparently resulting from unprecedented rainfall, runoff, and soil flushing beginning in late fall 2005. The relative contribution to the total Penobscot River basin DOC flux from each tributary varied dramatically by season, reflecting the role of large regulated reservoirs in certain basins. DOC concentration and flux per unit watershed area were highest in tributaries containing the largest areas in palustrine wetlands. Tributary DOC concentration and flux was positively correlated to percentage wetland area. Climatic or environmental changes that influence the magnitude or timing of river discharge or the abundance of wetlands will likely affect the export of DOC to the near-coastal ocean.

Maine↗
USGS2012

Relationships between Δ 14 C and the molecular quality of dissolved organic carbon in rivers draining to the coast from the conterminous United States

Dissolved organic carbon (DOC) in natural waters possesses chemical and molecular qualities indicative of its source and age. The apportionment of DOC by age into millennial and decadal pools is necessary to understand the temporal connection between terrestrial and aquatic ecosystems in the global carbon cycle. We measured Δ 14 C-DOC and chemical composition indices (specific ultraviolet absorbance (SUVA 254 ), fluorescence index (FI), hydrophobic organic acid fraction (HPOA) content) for 15 large river basins in the conterminous United States. Across all rivers the average proportion of HPOA in DOC correlated strongly with SUVA 254 (r 2 = 0.93 p < 0.001). Individual Δ 14 C-DOC ranged from a low of −92.9‰ (726 y.b.p.) in the Colorado River to 73.4‰ (>Modern) in the Altamaha River for the year 2009. When adjusted by total discharge, these U.S. Rivers export modern carbon at between 34 and 46‰, a signal dominated by the Mississippi River. The variation in Δ 14 C correlates to indices of the aromaticity of the DOC measured by the SUVA 254 (r 2 = 0.87, p < 0.001), and FI (r 2 = 0.6; p < 0.001) as well as differences in annual river discharge (r 2 = 0.46, p < 0.006). SUVA 254 was further correlated to broad scale vegetation phenology estimated from the Enhanced Vegetation Index derived from the NASA Moderate Resolution Imaging Spectrometer (MODIS). We show that basins with high discharge, high proportions of vegetation cover, and low human population densities export DOC enriched in aromatic material that corresponds to recently fixed atmospheric CO 2 . Conversely old DOC is exported from low discharge watersheds draining arid regions, and watersheds more strongly impacted by humans. The potential influence from fossil carbon from human inputs to aquatic systems may be important and requires more research.

Global Biogeochemical Cycles↗
USGS2012

Dissolved organic matter composition of winter flow in the Yukon River basin: Implications of permafrost thaw and increased groundwater discharge

Groundwater discharge to rivers has increased in recent decades across the circumpolar region and has been attributed to thawing permafrost in arctic and subarctic watersheds. Permafrost-driven changes in groundwater discharge will alter the flux of dissolved organic carbon (DOC) in rivers, yet little is known about the chemical composition and reactivity of dissolved organic matter (DOM) of groundwater in permafrost settings. Here, we characterize DOM composition of winter flow in 60 rivers and streams of the Yukon River basin to evaluate the biogeochemical consequences of enhanced groundwater discharge associated with permafrost thaw. DOC concentration of winter flow averaged 3.9 ± 0.5 mg C L −1 , yet was highly variable across basins (ranging from 20 mg C L −1 ). In comparison to the summer-autumn period, DOM composition of winter flow had lower aromaticity (as indicated by specific ultraviolet absorbance at 254 nm, or SUVA 254 ), lower hydrophobic acid content, and a higher proportion of hydrophilic compounds (HPI). Fluorescence spectroscopy and parallel factor analysis indicated enrichment of protein-like fluorophores in some, but not all, winter flow samples. The ratio of DOC to dissolved organic nitrogen, an indicator of DOM biodegradability, was positively correlated with SUVA 254 and negatively correlated with the percentage of protein-like compounds. Using a simple two-pool mixing model, we evaluate possible changes in DOM during the summer-autumn period across a range of conditions reflecting possible increases in groundwater discharge. Across three watersheds, we consistently observed decreases in DOC concentration and SUVA254 and increases in HPI with increasing groundwater discharge. Spatial patterns in DOM composition of winter flow appear to reflect differences in the relative contributions of groundwater from suprapermafrost and subpermafrost aquifers across watersheds. Our findings call for more explicit consideration of DOC loss and stabilization pathways associated with changing subsurface hydrology in watersheds underlain by thawing permafrost.

Global Biogeochemical Cycles↗