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Anne M. Kellerman

Publications and source records attributed to Anne M. Kellerman.

7 recordsLinked to original sources

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

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

Anthropogenic landcover impacts fluvial dissolved organic matter composition in the Upper Mississippi River Basin

Landcover changes have altered the natural carbon cycle; however, most landcover studies focus on either forest conversion to agriculture or urban, rarely both. We present differences in dissolved organic carbon (DOC) concentrations and dissolved organic matter (DOM) molecular composition within Upper Mississippi River Basin low order streams and rivers draining one of three dominant landcovers (forest, agriculture, and urban). Streams draining forest and urban landcovers have greater DOC concentrations, likely driven by differences in carbon sourcing, microbial processing, and soil disturbance. Using Fourier transform-ion cyclotron resonance mass spectrometry, 24% of assigned molecular formulae are common across all landcovers. Relative abundances of N-,S- heteroatomic formulae (CHON, CHOS, CHONS) are higher for agricultural and urban streams, with agricultural stream DOM having more N-containing formulae compared to urban stream DOM, which has more S-containing formulae. Higher N-,S- heteroatomic formulae abundance, along with enrichment in aliphatic, N-aliphatic, and highly unsaturated and phenolic (low O/C) compound categories within agricultural and urban stream DOM are likely to result from increased anthropogenic inputs, autochthonous production, and microbial processing associated with agricultural and urban impacts. Reduced N-,S- heteroatomic formulae abundances in forested stream DOM, along with enrichments in condensed aromatics, polyphenolics, and highly unsaturated phenolic (high O/C) compound categories, likely reflect greater contributions from surrounding organic-rich forest soil and vegetation. Overall, landcover change from forested to agriculture lowers DOC concentrations and changes from forested to agriculture or urban increases autochthonous, and presumably more biolabile, DOM contributions with ramifications for stream biogeochemical cycling.

Iowa, Minnesota, Wisconsin

Hydrocarbons to carboxyl-rich alicyclic molecules: A continuum model to describe biodegradation of petroleum-derived dissolved organic matter in contaminated groundwater plumes

Relationships between dissolved organic matter (DOM) reactivity and chemical composition in a groundwater plume containing petroleum-derived DOM (DOM HC ) were examined by quantitative and qualitative measurements to determine the source and chemical composition of the compounds that persist downgradient. Samples were collected from a transect down the core of the plume in the direction of groundwater flow. An exponential decrease in dissolved organic carbon concentration resulting from biodegradation along the transect correlated with a continuous shift in fluorescent DOM HC from shorter to longer wavelengths. Moreover, ultrahigh resolution mass spectrometry showed a shift from low molecular weight (MW) aliphatic, reduced compounds to high MW, unsaturated (alicyclic/aromatic), high oxygen compounds that are consistent with carboxyl-rich alicyclic molecules. The degree of condensed aromaticity increased downgradient, indicating that compounds with larger, conjugated aromatic core structures were less susceptible to biodegradation. Nuclear magnetic resonance spectroscopy showed a decrease in alkyl (particularly methyl) and an increase in aromatic/olefinic structural motifs. Collectively, data obtained from the combination of these complementary analytical techniques indicated that changes in the DOM HC composition of a groundwater plume are gradual, as relatively low molecular weight (MW), reduced, aliphatic compounds from the oil source were selectively degraded and high MW, alicyclic/aromatic, oxidized compounds persisted.

Minnesota

Hydrologic connectivity determines dissolved organic matter biogeochemistry in northern high-latitude lakes

Northern high‐latitude lakes are undergoing climate‐induced changes including shifts in their hydrologic connectivity with terrestrial ecosystems. How this will impact dissolved organic matter (DOM) biogeochemistry remains uncertain. We examined the drivers of DOM composition for lakes in the Yukon Flats Basin in Alaska, an arid region of low relief that is characteristic of over one‐quarter of circumpolar lake area. Utilizing the vascular plant biomarker lignin, chromophoric dissolved organic matter (CDOM), and ultrahigh‐resolution mass spectrometry, we interpreted DOM compositional changes using lake‐water stable isotope (δ 18 O‐H 2 O) composition as a proxy for lake hydrologic connectivity with the landscape. We observed a relative decrease in CDOM in more hydrologically isolated lakes (enriched δ 18 O‐H 2 O) without a corresponding decrease in dissolved organic carbon (DOC) concentration. Although DOC and CDOM were weakly correlated, a significant positive relationship between lignin and CDOM ( r 2 = 0.67) demonstrates that optical parameters are useful for estimating lignin concentration and thus vascular plant contribution to lake DOM. Indicators of allochthonous DOM, including lignin carbon normalized yields, CDOM aromaticity proxies, and relative abundances of polyphenolic and condensed aromatic compound classes, were negatively correlated with δ 18 O‐H 2 O ( r 2 > 0.45), suggesting there is little allochthonous DOM supplied to many of these hydrologically isolated lakes. We conclude that decreased lake hydrologic connectivity, driven by ongoing climate change (i.e., decreased precipitation, warming temperatures), will reduce allochthonous DOM contributions and shift lakes toward lower CDOM systems with ecosystem‐scale ramifications for heat transfer, photochemical reactions, productivity, and ultimately their biogeochemical function.

Alaska

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

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