Geology topics

Robert G.M. Spencer

Publications and source records attributed to Robert G.M. Spencer.

17 recordsLinked to original sources

USGS2025

Organic matter composition versus microbial source: Controls on carbon loss from fen wetland and permafrost soils

Wetland and permafrost soils contain some of Earth's largest reservoirs of organic carbon, and these stores are threatened by rapid warming across the Arctic. Nearly half of northern wetlands are affected by permafrost. As these ecosystems warm, the cycling of dissolved organic matter (DOM) and the opportunities for microbial degradation are changing. This is particularly evident as the relationship between wetland and permafrost DOM dynamics evolves, especially with the introduction of permafrost-derived DOM into wetland environments. Thus, understanding the interplay of DOM composition and microbial communities from wetlands and permafrost is critical to predicting the impact of released carbon on global carbon cycling. As little is understood about the interactions between wetland active layer and permafrost-derived sources as they intermingle, we conducted experimental bioincubations of mixtures of DOM and microbial communities from two fen wetland depths (shallow: 0–15 cm, and deep: 15–30 cm) and two ages of permafrost soil (Holocene and Pleistocene). We found that the source of microbial inoculum was not a significant driver of dissolved organic carbon (DOC) degradation across treatments; rather, DOM source and specifically, DOM molecular composition, controlled the rate of DOC loss over 100 days of bioincubations. DOC loss across all treatments was negatively correlated with modified aromaticity index, O/C, and the relative abundance of condensed aromatic and polyphenolic formula, and positively correlated with H/C and the relative abundance of aliphatic and peptide-like formula. Pleistocene permafrost-derived DOC exhibited ∼70% loss during the bioincubation driven by its initial molecular-level composition, highlighting its high bioavailability irrespective of microbial source.

Alaska↗

USGS2024

Linking dissolved organic matter composition to landscape properties in wetlands across the United States of America

Wetlands are integral to the global carbon cycle, serving as both a source and a sink for organic carbon. Their potential for carbon storage will likely change in the coming decades in response to higher temperatures and variable precipitation patterns. We characterized the dissolved organic carbon (DOC) and dissolved organic matter (DOM) composition from 12 different wetland sites across the USA spanning gradients in climate, landcover, sampling depth, and hydroperiod for comparison to DOM in other inland waters. Using absorption spectroscopy, parallel factor analysis modeling, and ultra-high resolution mass spectroscopy, we identified differences in DOM sourcing and processing by geographic site. Wetland DOM composition was driven primarily by differences in landcover where forested sites contained greater aromatic and oxygenated DOM content compared to grassland/herbaceous sites which were more aliphatic and enriched in N and S molecular formulae. Furthermore, surface and porewater DOM was also influenced by properties such as soil type, organic matter content, and precipitation. Surface water DOM was relatively enriched in oxygenated higher molecular weight formulae representing HUP High O/C compounds than porewaters, whose DOM composition suggests abiotic sulfurization from dissolved inorganic sulfide. Finally, we identified a group of persistent molecular formulae (3,489) present across all sites and sampling depths (i.e., the signature of wetland DOM) that are likely important for riverine-to-coastal DOM transport. As anthropogenic disturbances continue to impact temperate wetlands, this study highlights drivers of DOM composition fundamental for understanding how wetland organic carbon will change, and thus its role in biogeochemical cycling.

Global Biogeochemical Cycles↗

USGS2023

Arctic-boreal lakes of interior Alaska dominated by contemporary carbon

Northern high-latitude lakes are critical sites for carbon processing and serve as potential conduits for the emission of permafrost-derived carbon and greenhouse gases. However, the fate and emission pathways of permafrost carbon in these systems remain uncertain. Here, we used the natural abundance of radiocarbon to identify and trace the predominant sources of methane, carbon dioxide, dissolved inorganic and organic carbon in nine lakes within the Yukon Flats National Wildlife Refuge in interior Alaska, a discontinuous permafrost region with high landscape heterogeneity and susceptibility to climate, permafrost, and hydrological changes. We find that although Yukon Flats lakes primarily process young carbon (modern to 1290 ± 60 years before present), permafrost-derived carbon is present in some of the sampled lakes and contributes, at most, 30 ± 10% of the dissolved carbon in lake surface waters. Apportionment of young carbon and legacy carbon (carbon with radiocarbon age ⩾5000 years before present) is decoupled among the dissolved inorganic and organic carbon species, with methane showing a stronger legacy signature. Our observations suggest that permafrost-thaw-related transport of carbon through Yukon Flats lacustrine ecosystems and into the atmosphere is small, and likely regulated by surficial sediments, permafrost distribution, wildfire occurrence, or masked by contemporary carbon processes. The heterogeneity of lakes across our study area and northern landscapes more broadly cautions against using any one region (e.g. Yedoma permafrost lakes) to upscale their contribution across the pan-Arctic.

Alaska↗

USGS2023

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.

Environmental Science & Technology↗

USGS2023

Quantification of wetland vegetation communities features with airborne AVIRIS-NG, UAVSAR, and UAV LiDAR data in Peace-Athabasca Delta

Arctic-boreal wetlands, important ecosystems for biodiversity and ecological services, are experiencing hydrological changes including permafrost thaw, earlier snowmelt, and increased wildfire susceptibility. These changes are affecting wetland productivity, species diversity, and biogeochemical cycles. However, given the diverse forms and structures of wetland vegetation communities, traditional wetland maps generated from lower spatial and spectral resolution satellite imagery lack community-level vegetation classification and miss spatially complex patterns. In this study, we built a cloud-based workflow to map wetland vegetation community of the Peace-Athabasca Delta (PAD), Canada, by leveraging high-resolution (5-m) airborne multi-sensor datasets, namely NASA's Airborne Visible/Infrared Imaging Spectrometer-Next Generation (AVIRIS-NG) and Uninhabited Aerial Vehicle Synthetic Aperture Radar (UAVSAR), and a historical LiDAR archive. Validation of our classifications using ground references indicates that classifications derived from AVIRIS-NG have higher accuracies (≥87.9%) than either UAVSAR (65.6%) or LiDAR (75.9%) for mapping wetland vegetation communities. We also show improved classification accuracy when combining information from multiple sensors. In particular, incorporating AVIRIS-NG and UAVSAR datasets substantially reduced omission errors of wet graminoid and wet shrub classes from 29.6% to 20.5% and from 10.8% to 7.5%, respectively. Combining AVIRIS-NG and LiDAR datasets further improves overall accuracy (+2.2%) for most classifications, especially emergent vegetation, wet graminoid, and wet shrub. The best performing model, using features derived from all three sensors, achieved an overall accuracy of 93.5%. The framework established here can be used to leverage extensive airborne AVIRIS-NG and UAVSAR datasets collected across Alaska and northwest Canada to understand the spatial distribution of Arctic-Boreal wetland vegetation communities.

Remote Sensing of Environment↗

USGS2023

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.

Minnesota, Iowa, North Dakota, South Dakota, Wisco↗

USGS2022

Hydrologic and landscape controls on dissolved organic matter composition across western North American Arctic lakes

Northern high-latitude lakes are hotspots for cycling dissolved organic carbon (DOC) inputs from allochthonous sources to the atmosphere. However, the spatial distribution of lake dissolved organic matter (DOM) is largely unknown across Arctic-boreal regions with respect to the surrounding landscape. We expand on regional studies of northern high-latitude DOM composition by integrating DOC concentrations, optical properties, and molecular-level characterization from lakes spanning the Canadian Taiga to the Alaskan Tundra. Lakes were sampled during the summer from July to early September to capture the growing season. DOM became more optically processed and molecular-level aromaticity increased northward across the Canadian Shield to the southern Arctic and from interior Alaska to the Tundra, suggesting relatively greater DOM incorporation from allochthonous sources. Using water isotopes (δ 18 O-H 2 O), we report a weak overall trend of increasing DOC and decreasing aromaticity in lakes that were hydrologically isolated from the landscape and enriched in δ 18 O-H 2 O, while within-region trends were stronger and varied depending on the landscape. Finally, DOC correlated weakly with chromophoric dissolved organic matter (CDOM) across the study sites, suggesting that autochthonous and photobleached DOM were a major component of the DOC in these regions; however, some of the northernmost and wetland-dominated lakes followed pan-Arctic riverine DOC-CDOM relationships, indicating strong contributions from allochthonous inputs. As many lakes across the North American Arctic are experiencing changes in temperature and precipitation, we expect the proportions of allochthonous and autochthonous DOM to respond with aquatic optical browning with greater landscape connectivity and more internally produced DOM in hydrologically isolated lakes.

Global Biogeochemical Cycles↗

USGS2019

Dissolved organic carbon turnover in permafrost-influenced watersheds of interior Alaska: Molecular insights and the priming effect

Increased permafrost thaw due to climate change in northern high-latitudes has prompted concern over impacts on soil and stream biogeochemistry that affect the fate of dissolved organic carbon (DOC). Few studies to-date have examined the link between molecular composition and biolability of dissolved organic matter (DOM) mobilized from different soil horizons despite its importance in understanding carbon turnover in aquatic systems. Additionally, the effect of mixed DOM sources on microbial metabolism (e.g., priming) is not well understood. No studies to-date have addressed potential priming effects in northern high-latitude or permafrost-influenced aquatic ecosystems, yet these ecosystems may be hot spots of priming where biolabile, ancient permafrost DOC mixes with relatively stable, modern stream DOC. To assess biodegradability and priming of DOC in permafrost-influenced streams, we conducted 28 day bioincubation experiments utilizing a suite of stream samples and leachates of fresh vegetation and different soil horizons, including permafrost, from Interior Alaska. The molecular composition of unamended DOM samples at initial and final time points was determined by ultrahigh resolution mass spectrometry. Initial molecular composition was correlated to DOC biodegradability, particularly the contribution of energy-rich aliphatic compounds, and stream microbial communities utilized 50–56% of aliphatics in permafrost-derived DOM within 28 days. Biodegradability of DOC followed a continuum from relatively stable stream DOC to relatively biolabile DOC derived from permafrost, active layer organic soil, and vegetation leachates. Microbial utilization of DOC was ∼3–11% for stream bioincubations and ranged from 9% (active layer mineral soil-derived) to 66% (vegetation-derived) for leachate bioincubations. To investigate the presence or absence of a priming effect, bioincubation experiments included treatments amended with 1% relative carbon concentrations of simple, biolabile organic carbon substrates (i.e., primers). The amount of DOC consumed in primed treatments was not significantly different from the control in any of the bioincubation experiments after 28 days, making it apparent that the addition of biolabile permafrost-derived DOC to aquatic ecosystems will likely not enhance the biodegradation of relatively modern, stable DOC sources. Thus, future projections of carbon turnover in northern high-latitude region streams may not have to account for a priming effect.

Alaska↗

USGS2019

Identifying the molecular signatures of agricultural expansion in Amazonian headwater streams

Agricultural impacts on aquatic ecosystems are well-studied, however, most research has focused on temperate regions, whereas the forefront of agricultural expansion is currently in the tropics. At the vanguard of this growth is the boundary between the Amazon and Cerrado biomes in Brazil, driven primarily by expansion of soybean and corn croplands. Here we examine the impacts of cropland expansion on receiving lowland Amazon Basin headwater streams in terms of dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition via ultra-high resolution mass spectrometry. Streams draining croplands had lower DOC concentrations and DOM molecular signatures enriched in N- and S-containing formula in comparison to forested streams. Cropland streams were also enriched in aliphatic, peptide-like and highly unsaturated and phenolic (low O/C) compound categories in comparison to forest streams (enriched in polyphenolics, condensed aromatics and highly unsaturated and phenolic (high O/C) compound categories) indicative of the shifting of sources from organic-rich surface soils and litter layers to autochthonous and more microbial biomass. Distinct molecular assemblages were strongly correlated with cropland and forest catchments, highlighting headwater streams as sentinels for detecting change. On investigation of unique molecular formulae present in only cropland sites, four cropland markers provided the ability to track agricultural impacts in the region. Overall, these patterns indicate reduced organic matter inputs in croplands and greater microbial degradation at these sites leading to declining DOC concentrations, and DOM of more microbial character in receiving streams that is more biolabile, with clear ramifications for downstream ecology and biogeochemical cycles.

Amazon River basin, Tanguro Ranch, Xinga River↗

USGS2017

Irrigation as a fuel pump to freshwater ecosystems

We generated a detailed time series of total dissolved hydrolyzable amino acids (DHAA) in a watershed dominated by irrigated agriculture in northern California, USA to investigate the roles of hydrologic and seasonal changes on the composition of dissolved organic matter (DOM). DHAA are sensitive indicators of the degradation state and reactivity of DOM. DHAA concentrations ranged from 0.55 to 9.96 μM (median 3.51 ± 1.80 μM), with expected peaks during high-discharge storms and unexpected high values throughout the low-discharge irrigation season. Overall, summer irrigation was a critical hydrologic regime for DOM cycling since it mobilized DOM similar in concentration and reactivity to DOM released during storms. Together, irrigation and storm flows exported DOM with (1) the largest DHAA contributions to the dissolved organic carbon and the dissolved organic nitrogen pools, (2) the largest proportion of basic amino acids, and (3) the lowest degradation extent based on multiple indices. In this highly disturbed terrestrial system, UV–vis absorbance did not correlate with DHAA concentrations, while classic interpretations of common amino acid indicators (e.g., proportion of basic amino acids, degradation index, percent of non-protein amino acids) were prone to conflicting characterizations of DOM reactivity. Therefore, a new parameter (processing ratio, PR) derived from individual amino acid concentrations was developed that demonstrated a strong potential for mechanistic-driven characterization of the extent of DOM diagenesis in freshwaters. Irrigated agriculture altered stream biogeochemistry by releasing a continuous supply of reactive DOM (lowest PR values), thereby providing an additional energy source to downstream ecosystems.

California↗

USGS2015

Biodegradability of dissolved organic carbon in permafrost soils and aquatic systems: a meta-analysis

As Arctic regions warm and frozen soils thaw, the large organic carbon pool stored in permafrost becomes increasingly vulnerable to decomposition or transport. The transfer of newly mobilized carbon to the atmosphere and its potential influence upon climate change will largely depend on the degradability of carbon delivered to aquatic ecosystems. Dissolved organic carbon (DOC) is a key regulator of aquatic metabolism, yet knowledge of the mechanistic controls on DOC biodegradability is currently poor due to a scarcity of long-term data sets, limited spatial coverage of available data, and methodological diversity. Here, we performed parallel biodegradable DOC (BDOC) experiments at six Arctic sites (16 experiments) using a standardized incubation protocol to examine the effect of methodological differences commonly used in the literature. We also synthesized results from 14 aquatic and soil leachate BDOC studies from across the circum-arctic permafrost region to examine pan-arctic trends in BDOC. An increasing extent of permafrost across the landscape resulted in higher DOC losses in both soil and aquatic systems. We hypothesize that the unique composition of (yedoma) permafrost-derived DOC combined with limited prior microbial processing due to low soil temperature and relatively short flow path lengths and transport times, contributed to a higher overall terrestrial and freshwater DOC loss. Additionally, we found that the fraction of BDOC decreased moving down the fluvial network in continuous permafrost regions, i.e. from streams to large rivers, suggesting that highly biodegradable DOC is lost in headwater streams. We also observed a seasonal (January–December) decrease in BDOC in large streams and rivers, but saw no apparent change in smaller streams or soil leachates. We attribute this seasonal change to a combination of factors including shifts in carbon source, changing DOC residence time related to increasing thaw-depth, increasing water temperatures later in the summer, as well as decreasing hydrologic connectivity between soils and surface water as the thaw season progresses. Our results suggest that future climate warming-induced shifts of continuous permafrost into discontinuous permafrost regions could affect the degradation potential of thaw-released DOC, the amount of BDOC, as well as its variability throughout the Arctic summer. We lastly recommend a standardized BDOC protocol to facilitate the comparison of future work and improve our knowledge of processing and transport of DOC in a changing Arctic.

Biogeosciences↗

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↗

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

Anthropogenic aerosols as a source of ancient dissolved organic matter in glaciers

Glacier-derived dissolved organic matter represents a quantitatively significant source of ancient, yet highly bioavailable carbon to downstream ecosystems. This finding runs counter to logical perceptions of age–reactivity relationships, in which the least reactive material withstands degradation the longest and is therefore the oldest. The remnants of ancient peatlands and forests overrun by glaciers have been invoked as the source of this organic matter. Here, we examine the radiocarbon age and chemical composition of dissolved organic matter in snow, glacier surface water, ice and glacier outflow samples from Alaska to determine the origin of the organic matter. Low levels of compounds derived from vascular plants indicate that the organic matter does not originate from forests or peatlands. Instead, we show that the organic matter on the surface of the glaciers is radiocarbon depleted, consistent with an anthropogenic aerosol source. Fluorescence spectrophotometry measurements reveal the presence of protein-like compounds of microbial or aerosol origin. In addition, ultrahigh-resolution mass spectrometry measurements document the presence of combustion products found in anthropogenic aerosols. Based on the presence of these compounds, we suggest that aerosols derived from fossil fuel burning are a source of pre-aged organic matter to glacier surfaces. Furthermore, we show that the molecular signature of the organic matter is conserved in snow, glacier water and outflow, suggesting that the anthropogenic carbon is exported relatively unchanged in glacier outflows.

Nature Geoscience↗

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↗

USGS2010

Microbial degradation of plant leachate alters lignin phenols and trihalomethane precursors

Although the importance of vascular plant-derived dissolved organic carbon (DOC) in freshwater systems has been studied, the role of leached DOC as precursors of disinfection byproducts (DBPs) during drinking water treatment is not well known. Here we measured the propensity of leachates from four crops and four aquatic macrophytes to form trihalomethanes (THMs)—a regulated class of DBPs—before and after 21 d of microbial degradation. We also measured lignin phenol content and specific UV absorbance (SUVA 254 ) to test the assumption that aromatic compounds from vascular plants are resistant to microbial degradation and readily form DBPs. Leaching solubilized 9 to 26% of total plant carbon, which formed 1.93 to 6.72 mmol THM mol C -1 However, leachate DOC concentrations decreased by 85 to 92% over the 21-d incubation, with a concomitant decrease of 67 to 92% in total THM formation potential. Carbon-normalized THM yields in the residual DOC pool increased by 2.5 times on average, consistent with the preferential uptake of nonprecursor material. Lignin phenol concentrations decreased by 64 to 96% over 21 d, but a lack of correlation between lignin content and THM yields or SUVA 254 suggested that lignin-derived compounds are not the source of increased THM precursor yields in the residual DOC pool. Our results indicate that microbial carbon utilization alters THM precursors in ecosystems with direct plant leaching, but more work is needed to identify the specific dissolved organic matter components with a greater propensity to form DBPs and affect watershed management, drinking water quality, and human health.

Journal of Environmental Quality↗

USGS2009

Fluorescence-based proxies for lignin in freshwater dissolved organic matter

Lignin phenols have proven to be powerful biomarkers in environmental studies; however, the complexity of lignin analysis limits the number of samples and thus spatial and temporal resolution in any given study. In contrast, spectrophotometric characterization of dissolved organic matter (DOM) is rapid, noninvasive, relatively inexpensive, requires small sample volumes, and can even be measured in situ to capture fine-scale temporal and spatial detail of DOM cycling. Here we present a series of cross-validated Partial Least Squares models that use fluorescence properties of DOM to explain up to 91% of lignin compositional and concentration variability in samples collected seasonally over 2 years in the Sacramento River/San Joaquin River Delta in California, United States. These models were subsequently used to predict lignin composition and concentration from fluorescence measurements collected during a diurnal study in the San Joaquin River. While modeled lignin composition remained largely unchanged over the diurnal cycle, changes in modeled lignin concentrations were much greater than expected and indicate that the sensitivity of fluorescence-based proxies for lignin may prove invaluable as a tool for selecting the most informative samples for detailed lignin characterization. With adequate calibration, similar models could be used to significantly expand our ability to study sources and processing of DOM in complex surface water systems.

Journal of Geophysical Research G: Biogeosciences↗