Geology topics

Kenna D. Butler

Publications and source records attributed to Kenna D. Butler.

At least 19 recordsLinked to original sources

USGS2018

Comparison of the chemical composition of dissolved organic matter in three lakes in Minnesota

New information on the chemical composition of dissolved organic matter (DOM) in three lakes in Minnesota has been gained from spectral editing and two-dimensional nuclear magnetic resonance (NMR) methods, indicating the effects of lake hydrological settings on DOM composition. Williams Lake (WL), Shingobee Lake (SL), and Manganika Lake (ML) had different source inputs, and the lake water residence time (WRT) of WL was markedly longer than that of SL and ML. The hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions combined comprised >50% of total DOM in these lakes, and contained carboxyl-rich alicyclic molecules (CRAM), aromatics, carbohydrates, and N-containing compounds. The previously understudied TPIA fractions contained fewer aromatics, more oxygen-rich CRAM, and more N-containing compounds compared to the corresponding HPOA. CRAM represented the predominant component in DOM from all lakes studied, and more so in WL than in SL and ML. Aromatics including lignin residues and phenols decreased in relative abundances from ML to SL and WL. Carbohydrates and N-containing compounds were minor components in both HPOA and TPIA and did not show large variations among the three lakes. The increased relative abundances of CRAM in DOM from ML, SL to WL suggested the selective preservation of CRAM with increased residence time.

Minnesota↗

USGS2018

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 (δ 13 C-dissolved organic carbon (DOC) and Δ 14 C-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 Δ 14 C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA 254 ), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ 13 C-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.

Environmental Science & Technology↗

USGS2018

Evidence for major input of riverine organic matter into the ocean

The changes in the structure of XAD-8 isolated dissolved organic matter (DOM) samples along a river (Penobscot River) to estuary (Penobscot Bay) to ocean (across the Gulf of Maine) transect and from the Pacific Ocean were investigated using selective and two dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy coupled with elemental and carbon isotope analysis. The results provide important insights into the nature of relatively stable structures in the river-to-ocean continuum and the enigma of the fate of terrestrial DOM in the marine system. First, lignin and carboxyl-rich alicyclic molecules (CRAMs), which are indistinguishable from mass spectrometry, were clearly differentiated with NMR spectroscopy. NMR unambiguously showed that CRAMs persisted along the river-to-ocean transect and in the Pacific Ocean, while lignin residues dramatically decreased in abundance from the river to the coastal ocean and the Pacific Ocean. The results challenge a previous conclusion that lignin-derived compounds are refractory and can accumulate in the coastal ocean. The loss of terrestrial plant-derived aromatic compounds such as lignin and tannin residues throughout the sequence of riverine, coastal, and open ocean DOM extracts could also partially explain the decreasing organic carbon recovery by XAD-8 isolation and the change in carbon stable isotope composition from riverine DOM (δ 13 C −27.6‰) to ocean DOM (δ 13 C −23.0‰) extracts. The observation, from advanced NMR, of similar CRAM molecules in XAD-8 isolated DOM samples from the Penobscot River to the Penobscot Bay and from the ocean refutes a previous conclusion that XAD-isolated DOM samples from seawater and river are distinctly different. The alicyclic structural features of CRAMs and their presence as the major structural units in DOM extracts from the Penobscot River to Gulf of Maine transect, together with the deduced old 14 C age of CRAMs in the ocean, imply that terrestrial CRAMs may persist on timescales long enough to be transported into the ocean.

Organic Geochemistry↗

USGS2016

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 (SUVA 254 , 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 SUVA 254 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.

Global Biogeochemical Cycles↗

USGS2016

DOM composition and transformation in boreal forest soils: The effects of temperature and organic-horizon decomposition state

The boreal region stores large amounts of organic carbon (C) in organic-soil horizons, which are vulnerable to destabilization via warming and disturbance. Decomposition of soil organic matter (SOM) contributes to the production and turnover of dissolved organic matter (DOM). While temperature is a primary control on rates of SOM and DOM cycling, little is known about temperature effects on DOM composition in soil leachate. Here we conducted a 30 day incubation to examine the effects of temperature (20 versus 5°C) and SOM decomposition state (moss versus fibric versus amorphous horizons) on DOM composition in organic soils of interior Alaska. We characterized DOM using bulk dissolved organic C (DOC) concentration, chemical fractionation, optical properties, and ultrahigh-resolution mass spectrometry. We observed an increase in DOC concentration and DOM aromaticity in the 20°C treatment compared to the 5°C treatment. Leachate from fibric horizons had higher DOC concentration than shallow moss or deep amorphous horizons. We also observed chemical shifts in DOM leachate over time, including increases in hydrophobic organic acids, polyphenols, and condensed aromatics and decreases in low-molecular weight hydrophilic compounds and aliphatics. We compared ultrahigh-resolution mass spectrometry and optical data and observed strong correlations between polyphenols, condensed aromatics, SUVA 254 , and humic-like fluorescence intensities. These findings suggest that biolabile DOM was preferentially mineralized, and the magnitude of this transformation was determined by kinetics (i.e., temperature) and substrate quality (i.e., soil horizon). With future warming, our findings indicate that organic soils may release higher concentrations of aromatic DOM to aquatic ecosystems.

Journal of Geophysical Research: Biogeosciences↗

USGS2016

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 GoM between 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 (<0.2 μm diameter). 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.

Gulf of Maine↗

USGS2016

Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

Seasonal (spring freshet, summer–autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV–visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64–74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63–77%) and TPIA (54–78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OC np , OC np O and C q , 13–17% of HPOA and 15–20% of TPIA) and isolated O–CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (&sim;5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C–O and O–C–O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

Alaska, Yukon↗

USGS2015

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

The fate of permafrost carbon upon thaw will drive feedbacks to climate warming. Here we consider the character and context of dissolved organic carbon (DOC) in yedoma permafrost cores from up to 20 m depth in central Alaska. We observed high DOC concentrations (4 to 129 mM) and consistent low molecular weight organic acid concentrations in three cores. We estimate a DOC production rate of 12 µmol DOC m −2 yr −1 based on model ages of up to ~200 kyr derived from uranium isotopes. Acetate C accounted for 24 ± 1% of DOC in all samples. This proportion suggests long-term anaerobiosis and is likely to influence thaw outcomes due to biolability of acetate upon release in many environments. The combination of uranium isotopes, ammonium concentrations, and calcium concentrations explained 86% of the variation in thaw water DOC concentrations, suggesting that DOC production may be related to both reducing conditions and mineral dissolution over time.

Geophysical Research Letters↗

USGS2015

Importance of the colmation layer in the transport and removal of cyanobacteria, viruses, and dissolved organic carbon during natural lake-bank filtration

This study focused on the importance of the colmation layer in the removal of cyanobacteria, viruses, and dissolved organic carbon (DOC) during natural bank filtration. Injection-and-recovery studies were performed at two shallow (0.5 m deep), sandy, near-shore sites at the southern end of Ashumet Pond, a waste-impacted, kettle pond on Cape Cod, MA, that is subject to periodic blooms of cyanobacteria and continuously recharges a sole-source drinking-water aquifer. The experiment involved assessing the transport behaviors of bromide (conservative tracer), Synechococcus sp. IU625 (cyanobacterium, 2.6 ± 0.2 µm), AS-1 (tailed cyanophage, 110 nm long), MS2 (coliphage, 26 nm diameter), and carboxylate-modified microspheres (1.7 µm diameter) introduced to the colmation layer using a bag-and-barrel (Lee-type) seepage meter. The injectate constituents were tracked as they were advected across the pond water–groundwater interface and through the underlying aquifer sediments under natural-gradient conditions past push-point samplers placed at &sim;30-cm intervals along a 1.2-m-long, diagonally downward flow path. More than 99% of the microspheres, IU625, MS2, AS-1, and &sim;44% of the pond DOC were removed in the colmation layer (upper 25 cm of poorly sorted bottom sediments) at two test locations characterized by dissimilar seepage rates (1.7 vs. 0.26 m d −1 ). Retention profiles in recovered core material indicated that >82% of the attached IU625 were in the top 3 cm of bottom sediments. The colmation layer was also responsible for rapid changes in the character of the DOC and was more effective (by three orders of magnitude) at removing microspheres than was the underlying 20-cm-thick segment of sediment.

Massachusetts↗

USGS2015

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.

Massachusetts↗

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&permil;) and most depleted during winter flow (−21 ± 8&permil;). 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

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

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↗

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↗

USGS2012

Biodegradability of dissolved organic carbon in the Yukon River and its tributaries: Seasonality and importance of inorganic nitrogen

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 &sim;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 &sim;2.3 Tg C yr −1 as BDOC to the Arctic Ocean.

Global Biogeochemical Cycles↗

USGS2012

Dissolved organic carbon and chromophoric dissolved organic matter properties of rivers in the USA

Dissolved organic carbon (DOC) concentration and chromophoric dissolved organic matter (CDOM) parameters were measured over a range of discharge in 30 U.S. rivers, covering a diverse assortment of fluvial ecosystems in terms of watershed size and landscape drained. Relationships between CDOM absorption at a range of wavelengths (a 254 , a 350 , a 440 ) and DOC in the 30 watersheds were found to correlate strongly and positively for the majority of U.S. rivers. However, four rivers (Colorado, Colombia, Rio Grande and St. Lawrence) exhibited statistically weak relationships between CDOM absorption and DOC. These four rivers are atypical, as they either drain from the Great Lakes or experience significant impoundment of water within their watersheds, and they exhibited values for dissolved organic matter (DOM) parameters indicative of autochthonous or anthropogenic sources or photochemically degraded allochthonous DOM and thus a decoupling between CDOM and DOC. CDOM quality parameters in the 30 rivers were found to be strongly correlated to DOM compositional metrics derived via XAD fractionation, highlighting the potential for examining DOM biochemical quality from CDOM measurements. This study establishes the ability to derive DOC concentration from CDOM absorption for the majority of U.S. rivers, describes characteristics of riverine systems where such an approach is not valid, and emphasizes the possibility of examining DOM composition and thus biogeochemical function via CDOM parameters. Therefore, the usefulness of CDOM measurements, both laboratory-based analyses and in situ instrumentation, for improving spatial and temporal resolution of DOC fluxes and DOM dynamics in future studies is considerable in a range of biogeochemical studies.

Journal of Geophysical Research G: Biogeosciences↗

USGS2012

An initial investigation into the organic matter biogeochemistry of the Congo River

The Congo River, which drains pristine tropical forest and savannah and is the second largest exporter of terrestrial carbon to the ocean, was sampled in early 2008 to investigate organic matter (OM) dynamics in this historically understudied river basin. We examined the elemental (%OC, %N, C:N), isotopic (δ 13 C, Δ 14 C, δ 15 N) and biochemical composition (lignin phenols) of coarse particulate (>63 μm; CPOM) and fine particulate (0.7–63 μm; FPOM) OM and DOC, δ 13 C, Δ 14 C and lignin phenol composition with respect to dissolved OM (<0.7 μm; DOM) from five sites in the Congo River Basin. At all sample locations the organic carbon load was dominated by the dissolved phase (~82–89% of total organic carbon) and the total suspended sediment load was principally fine particulate material (~81–91% fine suspended sediment). Distinct compositional and isotopic differences were observed between all fractions. Congo CPOM, FPOM and DOM all originated from vegetation and soil inputs as evidenced by elemental, isotopic and lignin phenol data, however FPOM was derived from much older carbon pools (mean Δ 14 C = -62.2 ± -13.2&permil;, n = 5) compared to CPOM and DOM (mean Δ 14 C = 55.7 ± 30.6&permil;, n = 4 and 73.4 ± 16.1&permil;, n = 5 respectively). The modern radiocarbon ages for DOM belie a degraded lignin compositional signature (i.e. elevated acid:aldehyde ratios (Ad:Al) relative to CPOM and FPOM), and indicate that the application of OM degradation patterns derived from particulate phase studies to dissolved samples needs to be reassessed: these elevated ratios are likely attributable to fractionation processes during solubilization of plant material. The relatively low DOM carbon-normalized lignin yields (Λ8; 0.67–1.12 (mg(100 mg OC) -1 )) could also reflect fractionation processes, however, they have also been interpreted as an indication of significant microbial or algal sources of DOM. CPOM appears to be well preserved higher vascular plant material as evidenced by its modern radiocarbon age, elevated C:N (17.2–27.1) and Λ8 values (4.56–7.59 (mg(100 mg OC) -1 )). In relation to CPOM, the aged FPOM fraction (320–580 ybp 14 C ages) was comparatively degraded, as demonstrated by its nitrogen enrichment (C:N 11.4–14.3), lower Λ8 (2.80–4.31 (mg(100 mg OC) -1 )) and elevated lignin Ad:Al values similar to soil derived OM. In this study we observed little modification of the OM signature from sample sites near the cities of Brazzaville and Kinshasa to the head of the estuary (~350 km) highlighting the potential for future studies to assess seasonal and long-term OM dynamics from this logistically feasible location and derive relevant information with respect to OM exported to the Atlantic Ocean. The relative lack of OM data for the Congo River Basin highlights the importance of studies such as this for establishing baselines upon which to gauge future change.

Congo River↗