Geology topics

Aron Stubbins

Publications and source records attributed to Aron Stubbins.

12 recordsLinked to original sources

USGS2026

Evaluating drivers of environmental change in a lake sediment core: Insights from spectroscopic metrics of water-extractable organic matter and stable carbon isotopes

Freshwater lakes play a critical role in the global carbon cycle by storing and transforming organic matter (OM) from both terrestrial and aquatic sources. Small lakes in northern temperate regions, despite their limited surface area, disproportionately influence regional carbon budgets. Buried sediments integrate OM inputs over time and archive ecosystem responses to natural and anthropogenic disturbances. However, the direction and magnitude of recent environmental changes on sediment carbon (C) dynamics remain poorly understood. A 23-cm core was collected from a small temperate lake in northeastern USA to evaluate sediment OM content and composition over timescales relevant to historical land-use change, damming, and recovery from acid deposition. Patterns in OM burial and source contributions were revealed via elemental and isotopic analyses of bulk OM and ultraviolet-visible spectrophotometry of water-extractable organic matter (WEOM). The optical metrics expanded observations of likely OM sources beyond the information gained from bulk carbon metrics (total carbon, δ 13 C). The aromaticity of WEOM increased downcore, which is consistent with a shift from increased terrestrial inputs during early logging and damming activity (pre ∼1920) to more microbial-derived OM in recent surficial sediments. Future applications of WEOM optical properties as complements to traditional geochemical metrics can enhance interpretations of lake ecosystem responses recorded in lake sediments to environmental perturbations in temperate lakes.

New York↗

USGS2022

Optical properties of dissolved organic matter in throughfall and stemflow vary across tree species and season in a temperate headwater forest

Tree-derived dissolved organic matter (DOM) comprises a significant carbon flux within forested watersheds. Few studies have assessed the optical properties of tree-derived DOM. To increase understanding of the factors controlling tree-derived DOM quality, we measured DOM optical properties, dissolved organic carbon (DOC) and calcium concentrations in throughfall and stemflow for 17 individual rain events during summer and fall in a temperate deciduous forest in Vermont, United States. DOC and calcium fluxes in throughfall and stemflow were enriched on average 4 to 70 times incident fluxes in rain. A multiway model was developed using absorbance and fluorescence spectroscopy to further characterize DOM optical properties. Throughfall contained a higher percentage of protein-like DOM fluorescence than stemflow while stemflow was characterized by a higher percentage of humic-like DOM fluorescence. DOM absorbance spectral slopes in yellow birch ( Betula alleghaniensis ) stemflow were significantly higher than in sugar maple ( Acer saccharum ) stemflow. DOM optical metrics were not influenced by rainfall volume, but percent protein-like fluorescence increased in throughfall during autumn when leaves senesced. Given the potential influence of tree-derived DOM fluxes on receiving soils and downstream ecosystems, future modeling of DOM transport and soil biogeochemistry should represent the influence of differing DOM quality in throughfall and stemflow across tree species and seasons.

Vermont↗

USGS2022

Using dissolved organic matter fluorescence to predict total mercury and methylmercury in forested headwater streams, Sleepers River, Vermont USA

Aqueous transport of mercury (Hg) across the landscape is closely linked to dissolved organic matter (DOM). Both quantity and quality of DOM affect Hg mobility, as well as the formation and transport of toxic methylmercury (MeHg), but only a limited number of field studies have investigated Hg and MeHg with respect to specific DOM components. We investigated these interactions at the 41-ha forested W-9 catchment at Sleepers River, Vermont, which has a long history of mercury and other biogeochemical research. We examined spatial and temporal patterns of filtered Hg fractions and dissolved organic carbon (DOC) concentration, DOM quality, and major solutes at 12 stream sites within W-9 and the downstream W-3 gage (837 ha) over five sampling campaigns including a large (79 mm) fall storm, spring snowmelt, and three seasonally contrasting base flow periods. Filtered total Hg (THg), MeHg, and DOC concentrations increased in order base flow < snowmelt < fall storm, except that MeHg remained at baseflow levels during snowmelt. Ranges of median concentrations across sites for the five campaigns were THg, <0.2–4.1 ng L −1 ; MeHg, <0.03–0.45 ng L −1 ; and DOC, 0.8–14.0 mg L −1 . Humic-like DOM fluorescence components, as determined by parallel factor analysis (PARAFAC), dominated the fluorescence across sites and sampling campaigns. THg correlated strongly ( r > 0.94) with these humic components, but even more strongly with bulk DOC and absorbance at 254 nm (UV 254 ; r > 0.96), and less strongly with protein-like DOM (0.7 < r < 0.9). MeHg correlated in the same order but less strongly with humic- (0.8 < r < 0.9) and protein-like (0.6 < r < 0.8) DOM. MeHg increased in summer, potentially in response to enhanced microbial production in warmer periods. MeHg formation may have been linked to protein-like DOM, but its transport was linked to humic-like DOM.

Vermont↗

USGS2021

Event scale relationships of DOC and TDN fluxes in throughfall and stemflow diverge from stream exports in a forested catchment

Aquatic fluxes of carbon and nutrients link terrestrial and aquatic ecosystems. Within forests, storm events drive both the delivery of carbon and nitrogen to the forest floor and the export of these solutes from the land via streams. To increase understanding of the relationships between hydrologic event character and the relative fluxes of carbon and nitrogen in throughfall, stemflow and streams, we measured dissolved organic carbon (DOC) and total dissolved nitrogen (TDN) concentrations in each flow path for 23 events in a forested watershed in Vermont, USA. DOC and TDN concentrations increased with streamflow, indicating their export was limited by water transport of catchment stores. DOC and TDN concentrations in throughfall and stemflow decreased exponentially with increasing precipitation, suggesting that precipitation removed a portion of available sources from tree surfaces during the events. DOC and TDN fluxes were estimated for 76 events across a 2-year period. For most events, throughfall and stemflow fluxes greatly exceeded stream fluxes, but the imbalance narrowed for larger storms (>30 mm). The largest 10 stream events exported 40% of all stream event DOC whereas those same 10 events contributed 14% of all throughfall export. Approximately 2–5 times more DOC and TDN was exported from trees during rain events than left the catchment via streams annually. The diverging influence of event size on tree versus stream fluxes has important implications for forested ecosystems as hydrological events increase in intensity and frequency due to climate change.

Vermont↗

USGS2021

Export of photolabile and photoprimable dissolved organic carbon from the Connecticut River

Dissolved organic carbon (DOC) impacts water quality, the carbon cycle, and the ecology of aquatic systems. Understanding what controls DOC is therefore critical for improving large-scale models and best management practices for aquatic ecosystems. The two main processes of DOC transformation and removal, photochemical and microbial DOC degradation, work in tandem to modify and remineralize DOC within natural waters. Here, we examined both the photo- and microbial remineralization of DOC (photolability and biolability), and the indirect phototransformation of DOC into biolabile DOC (photoprimed biolability) for samples that capture the spatiotemporal and hydrological gradients of the Connecticut River watershed. The majority of DOC exported from this temperate watershed was photolabile and the concentration of photolabile DOC correlated with UV absorbance at 254 nm ( r 2 = 0.86). Phototransformation of DOC also increased biolability, and the total photolabile DOC (sum of photolabile and photoprimed biolabile DOC) showed a stronger correlation with UV absorbance at 254 nm (r 2 = 0.92). We estimate that as much as 49% (SD = 3.3%) and 10% (SD = 1.1%) of annual DOC export from the Connecticut River is directly photolabile and photoprimable, respectively. Thus, 2.82 Gg C year −1 (SD = 0.67 Gg C year −1 ) or 1.13 Mg C km −2 year −1 (SD = 0.27 km −2 year −1 ) of total photolabile DOC escapes photochemical degradation within the river network to be exported from the Connecticut River each year.

Connecticut River↗

USGS2021

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↗

USGS2017

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Florida↗

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

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↗

USGS2008

Relating carbon monoxide photoproduction to dissolved organic matter functionality

Aqueous solutions of humic substances (HSs) and pure monomeric aromatics were irradiated to investigate the chemical controls upon carbon monoxide (CO) photoproduction from dissolved organic matter (DOM). HSs were isolated from lakes, rivers, marsh, and ocean. Inclusion of humic, fulvic, hydrophobic organic, and hydrophilic organic acid fractions from these environments provided samples diverse in source and isolation protocol. In spite of these major differences, HS absorption coefficients (a) and photoreactivities (a bleaching and CO production) were strongly dependent upon HS aromaticity ( r 2 >0.90; n = 11), implying aromatic moieties are the principal chromophores and photoreactants within HSs, and by extension, DOM. Carbonyl carbon and CO photoproduction were not correlated, implying that carbonyl moieties are not quantitatively important in CO photoproduction. CO photoproduction efficiency of aqueous solutions of monomeric aromatic compounds that are common constituents of organic matter varied with the nature of ring substituents. Specifically, electron donating groups increased, while electron withdrawing groups decreased CO photoproductivity, supporting our conclusion that carbonyl substituents are not quantitatively important in CO photoproduction. Significantly, aromatic CO photoproduction efficiency spanned 3 orders of magnitude, indicating that variations in the CO apparent quantum yields of natural DOM may be related to variations in aromatic DOM substituent group chemistry.

Environmental Science and Technology↗