Kenna D. Butler

Measurement of dissolved organic matter fluorescence in aquatic environments: an interlaboratory comparison.

The fluorescent properties of dissolved organic matter (DOM) are often studied in order to infer DOM characteristics in aquatic environments, including source, quantity, composition, and behavior. While a potentially powerful technique, a single widely implemented standard method for correcting and presenting fluorescence measurements is lacking, leading to difficulties when comparing data collected by different research groups. This paper reports on a large-scale interlaboratory comparison in which natural samples and well-characterized fluorophores were analyzed in 20 laboratories in the U.S., Europe, and Australia. Shortcomings were evident in several areas, including data quality-assurance, the accuracy of spectral correction factors used to correct EEMs, and the treatment of optically dense samples. Data corrected by participants according to individual laboratory procedures were more variable than when corrected under a standard protocol. Wavelength dependency in measurement precision and accuracy were observed within and between instruments, even in corrected data. In an effort to reduce future occurrences of similar problems, algorithms for correcting and calibrating EEMs are described in detail, and MATLAB scripts for implementing the studys protocol are provided. Combined with the recent expansion of spectral fluorescence standards, this approach will serve to increase the intercomparability of DOM fluorescence studies.

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.

Pan-arctic trends in terrestrial dissolved organic matter from optical measurements

Climate change is causing extensive warming across arctic regions resulting in permafrost degradation, alterations to regional hydrology, and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275-295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of ‘terrestrial humic-like’ versus ‘marine humic-like’ fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in lignin composition across rivers and seasons. Our findings suggest that synoptic, high-resolution optical measurements can provide improved understanding of northern high-latitude organic matter cycling and flux, and prove an important technique for capturing future climate-driven changes.

Identifying fluorescent pulp mill effluent in the Gulf of Maine and its watershed

Using fluorescence spectroscopy and parallel factor analysis (PARAFAC) we characterized and modeled the fluorescence properties of dissolved organic matter (DOM) in samples from the Penobscot River, Androscoggin River, Penobscot Bay, and the Gulf of Maine (GoM). We analyzed excitation-emission matrices (EEMs) using an existing PARAFAC model (Cory and McKnight, 2005) and created a system-specific model with seven components (GoM PARAFAC). The GoM PARAFAC model contained six components similar to those in other PARAFAC models and one unique component with a spectrum similar to a residual found using the Cory and McKnight (2005) model. The unique component was abundant in samples from the Androscoggin River immediately downstream of a pulp mill effluent release site. The detection of a PARAFAC component associated with an anthropogenic source of DOM, such as pulp mill effluent, demonstrates the importance for rigorously analyzing PARAFAC residuals and developing system-specific models.

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 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.

Removal of terrestrial DOC in aquatic ecosystems of a temperate river network

Surface waters play a potentially important role in the global carbon balance. Dissolved organic carbon (DOC) fluxes are a major transfer of terrestrial carbon to river systems, and the fate of DOC in aquatic systems is poorly constrained. We used a unique combination of spatially distributed sampling of three DOC fractions throughout a river network and modeling to quantify the net removal of terrestrial DOC during a summer base flow period. We found that aquatic reactivity of terrestrial DOC leading to net loss is low, closer to conservative chloride than to reactive nitrogen. Net removal occurred mainly from the hydrophobic organic acid fraction, while hydrophilic and transphilic acids showed no net change, indicating that partitioning of bulk DOC into different fractions is critical for understanding terrestrial DOC removal. These findings suggest that river systems may have only a modest ability to alter the amounts of terrestrial DOC delivered to coastal zones.

Long‐term anoxia and release of ancient, labile carbon upon thaw of Pleistocene permafrost

USGS through the Climate and Land Use Change Mission Area and the NRC postdoc program; Montana State University Vice President of Research and College of Agriculture; the Montana Agricultural Experiment Station; National Science Foundation (EAR 0630257)

Toward a quantitative and empirical dissolved organic carbon budget for the Gulf of Maine, a semienclosed shelf sea

A time series of organic carbon export from Gulf of Maine (GoM) watersheds was compared to a time series of biological, chemical, bio-optical, and hydrographic properties, measured across the GoMbetween Yarmouth, NS, Canada, and Portland, ME, U.S. Optical proxies were used to quantify the dissolved organic carbon (DOC) and particulate organic carbon in the GoM. The Load Estimator regression model applied to river discharge data demonstrated that riverine DOC export (and its decadal variance) has increased over the last 80 years. Several extraordinarily wet years (2006–2010) resulted in a massive pulse of chromophoric dissolved organic matter (CDOM; proxy for DOC) into the western GoM along with unidentified optically scattering material (<0.2μmdiameter). A survey of DOC in the GoM and Scotian Shelf showed the strong influence of the Gulf of Saint Lawrence on the DOC that enters the GoM. A deep plume of CDOM-rich water was observed near the coast of Maine which decreased in concentration eastward. The Forel-Ule color scale was derived and compared to the same measurements made in 1912–1913 by Henry Bigelow. Results show that the GoM has yellowed in the last century, particularly in the region of the extension of the Eastern Maine Coastal Current. Time lags between DOC discharge and its appearance in the GoM increased with distance from the river mouths. Algae were also a significant source of DOC but not CDOM. Gulf-wide algal primary production has decreased. Increases in precipitation and DOC discharge to the GoM are predicted over the next century.

Dissolved organic matter composition of Arctic rivers: Linking permafrost and parent material to riverine carbon

Recent climate change in the Arctic is driving permafrost thaw, which has important implications for regional hydrology and global carbon dynamics. Permafrost is an important control on groundwater dynamics and the amount and chemical composition of dissolved organic matter (DOM) transported by high-latitude rivers. The consequences of permafrost thaw for riverine DOM dynamics will likely vary across space and time, due in part to spatial variation in ecosystem properties in Arctic watersheds. Here we examined watershed controls on DOM composition in 69 streams and rivers draining heterogeneous landscapes across a broad region of Arctic Alaska. We characterized DOM using bulk dissolved organic carbon (DOC) concentration, optical properties, and chemical fractionation and classified watersheds based on permafrost characteristics (mapping of parent material and ground ice content, modeling of thermal state) and ecotypes. Parent material and ground ice content significantly affected the amount and composition of DOM. DOC concentrations were higher in watersheds underlain by fine-grained loess compared to watersheds underlain by coarse-grained sand or shallow bedrock. DOC concentration was also higher in rivers draining ice-rich landscapes compared to rivers draining ice-poor landscapes. Similarly, specific ultraviolet absorbance (SUVA254, an index of DOM aromaticity) values were highest in watersheds underlain by fine-grained deposits or ice-rich permafrost. We also observed differences in hydrophobic organic acids, hydrophilic compounds, and DOM fluorescence across watersheds. Both DOC concentration and SUVA254 were negatively correlated with watershed active layer thickness, as determined by high-resolution permafrost modeling. Together, these findings highlight how spatial variations in permafrost physical and thermal properties can influence riverine DOM.

Unifying concepts linking dissolved organic matter composition to persistence in aquatic ecosystems

The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ13C-dissolved organic carbon (DOC) and Δ14C-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern Δ14C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA254), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ13C-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific Ocean and Antarctic lakes) exhibited distinct molecular composition due to differences in extent of degradation. Across all sites and end-members studied, we find a consistent shift in composition with aging, highlighting the persistence of certain biomolecules concurrent with degradation time.