Rebuttal to correspondence on “Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques”
No abstract available.
Environmental Science & Technology↗
Geology topics
David C. Podgorski
Publications and source records attributed to David C. Podgorski.
Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques
The effect of extraction methods on detecting hydrocarbon oxidation products (HOPs) in groundwater remains unclear. HOPs are polar, water-soluble byproducts of petroleum biodegradation. Our previous work showed that liquid–liquid extraction (LLE), a method commonly used in regulatory monitoring, has a significantly lower extraction efficiency for HOPs compared to solid-phase extraction (SPE). In this study, we evaluate the analytical limitations and compositional selectivity of LLE and SPE using groundwater samples from the Bemidji, MN, crude oil spill site. Optical properties were characterized using excitation–emission matrix spectroscopy (EEMs), and a three-component PARAFAC model was validated, showing consistent trends across both extracts and whole water samples. Ultrahigh-resolution mass spectrometry (UHR-MS) revealed that LLE selectively recovered aliphatic-like compounds but underrepresented more polar oxygenated HOPs. In contrast, SPE methods were more effective at isolating highly oxidized compound classes. These differences were consistent across a gradient of contamination. Overall, the LLE was less precise and less representative of polar HOPs, introducing bias in the characterization of HOPs. This study is the first to quantitatively demonstrate the compositional selectivity and analytical bias of LLE versus SPE for HOPs using combined EEM-PARAFAC and UHR-MS techniques, with implications for long-term monitoring and site assessment protocols.
Environmental Science and Technology↗
Toxicity of crude oil-derived polar unresolved complex mixtures to Pacific herring embryos: Insights beyond polycyclic aromatic hydrocarbons
Crude oil toxicity to early life stage fish is commonly attributed to polycyclic aromatic hydrocarbons (PAHs). However, it remains unclear how the polar unresolved complex mixture (UCM), which constitutes the bulk of the water-soluble fraction of crude oil, contributes to crude oil toxicity. Additionally, the role of photomodification-induced toxicity in relation to the polar UCM is not well understood. This study addresses these knowledge gaps by assessing the toxicity of two laboratory generated polar UCMs from Cook Inlet crude oil, representing the readily water-soluble fraction of crude oil and photoproduced hydrocarbon oxidation products (HOPs), to Pacific herring ( Clupea pallasii ) embryos. A small-scale semi-static exposure design was utilized with a range of polar UCM concentrations (0.5–14 mg/L) in nonvolatile dissolved organic carbon (NVDOC) units, quantifying the entire polar UCM. Compositional analyses revealed a photochemical-driven shift toward more complex aromatic compositions, naphthenic acids, and no detectable levels of PAHs (above 0.3 μg/L). Exposure to the dark polar UCM resulted in higher mortality than exposure to the light polar UCM. Both dark and light polar UCMs induced developmental abnormalities commonly attributed to the PAH fraction, including edema, reduced heart rate, body axis defects, and decreased body lengths, with these effects observed at the lowest dose group (0.5 mg/L NVDOC). These responses suggest photomodification-induced toxicity is driven by exposure to increased concentrations of dissolved HOPs rather than photochemical induced compositional changes. Gene expression analyses focusing on xenobiotic metabolism and cardiac morphogenesis yielded results consistent with previous studies examining the biological mechanisms of crude oil toxicity. In summary, these phenotypic and genotypic responses in Pacific herring embryos indicate that the polar UCM is a significant driver of crude oil toxicity. These findings emphasize the importance of considering the polar UCM in future studies, metric reporting, and risk assessments related to crude oil toxicity.
Science of the Total Environment↗
Photochemical mobilization of dissolved hydrocarbon oxidation products from petroleum contaminated soil into a shallow aquifer activate human nuclear receptors
Elevated non-volatile dissolved organic carbon (NVDOC) concentrations in groundwater monitoring wells under oil-contaminated hydrophobic soils originating from a pipeline rupture at the National Crude Oil Spill & Natural Attenuation Research Site near Bemidji, MN are documented.. We hypothesized the elevated NVDOC is comprised of water-soluble photooxidation products transported from the surface to the aquifer. We use field and laboratory samples in combination with complementary analytical methods to test this hypothesis and determine the biological response to these products. Observations from optical spectroscopy and ultrahigh-resolution mass spectrometry reveal a significant correlation between the chemical composition of NVDOC leached from photochemically weathered soils and groundwater monitoring wells with high NVDOC concentrations measured in the aquifer beneath the contaminated soil. Conversely, the chemical composition from the uncontaminated soil photoleachate, matches the NVDOC observed in the uncontaminated wells. Contaminated groundwater and photodissolution leachates from contaminated soil activated biological targets indicative of xenobiotic metabolism and exhibited potential for adverse effects. Newly formed hydrocarbon oxidation products (HOPs) from fresh oil could be distinguished from those downgradient. This study illustrates another pathway for dissolved HOPs to infiltrate groundwater and potentially affect human health and the environment.
Minnesota↗
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↗
Stream dissolved organic matter in permafrost regions shows surprising compositional similarities but negative priming and nutrient effects
Permafrost degradation is delivering bioavailable dissolved organic matter (DOM) and inorganic nutrients to surface water networks. While these permafrost subsidies represent a small portion of total fluvial DOM and nutrient fluxes, they could influence food webs and net ecosystem carbon balance via priming or nutrient effects that destabilize background DOM. We investigated how addition of biolabile carbon (acetate) and inorganic nutrients (nitrogen and phosphorus) affected DOM decomposition with 28‐day incubations. We incubated late‐summer stream water from 23 locations nested in seven northern or high‐altitude regions in Asia, Europe, and North America. DOM loss ranged from 3% to 52%, showing a variety of longitudinal patterns within stream networks. DOM optical properties varied widely, but DOM showed compositional similarity based on Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) analysis. Addition of acetate and nutrients decreased bulk DOM mineralization (i.e., negative priming), with more negative effects on biodegradable DOM but neutral or positive effects on stable DOM. Unexpectedly, acetate and nutrients triggered breakdown of colored DOM (CDOM), with median decreases of 1.6% in the control and 22% in the amended treatment. Additionally, the uptake of added acetate was strongly limited by nutrient availability across sites. These findings suggest that biolabile DOM and nutrients released from degrading permafrost may decrease background DOM mineralization but alter stoichiometry and light conditions in receiving waterbodies. We conclude that priming and nutrient effects are coupled in northern aquatic ecosystems and that quantifying two‐way interactions between DOM properties and environmental conditions could resolve conflicting observations about the drivers of DOM in permafrost zone waterways.
Global Biogeochemical Cycles↗
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↗
Life at the frozen limit: Microbial carbon metabolism across a Late Pleistocene permafrost chronosequence
Permafrost is an extreme habitat yet it hosts microbial populations that remain active over millennia. Using permafrost collected from a Pleistocene chronosequence (19 to 33 ka), we hypothesized that the functional genetic potential of microbial communities in permafrost would reflect microbial strategies to metabolize permafrost soluble organic matter (OM) in situ over geologic time. We also hypothesized that changes in the metagenome across the chronosequence would correlate with shifts in carbon chemistry, permafrost age, and paleoclimate at the time of permafrost formation. We combined high-resolution characterization of water-soluble OM by Fourier-transform ion-cyclotron-resonance mass spectrometry (FT-ICR MS), quantification of organic anions in permafrost water extracts, and metagenomic sequencing to better understand the relationships between the molecular-level composition of potentially bioavailable OM, the microbial community, and permafrost age. Both age and paleoclimate had marked effects on both the molecular composition of dissolved OM and the microbial community. The relative abundance of genes associated with hydrogenotrophic methanogenesis, carbohydrate active enzyme families, nominal oxidation state of carbon (NOSC), and number of identifiable molecular formulae significantly decreased with increasing age. In contrast, genes associated with fermentation of short chain fatty acids (SCFAs), the concentration of SCFAs and ammonium all significantly increased with age. We present a conceptual model of microbial metabolism in permafrost based on fermentation of OM and the buildup of organic acids that helps to explain the unique chemistry of ancient permafrost soils. These findings imply long-term in situ microbial turnover of ancient permafrost OM and that this pooled biolabile OM could prime ancient permafrost soils for a larger and more rapid microbial response to thaw compared to younger permafrost soils.
Alaska↗
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↗
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↗
Examining the extraction efficiency of petroleum-derived dissolved organic matter in contaminated groundwater plumes
The extraction efficiency of petroleum-derived dissolved organic matter (DOM) was examined for groundwater samples from an aquifer contaminated with crude oil. Four different types of extraction were used to determine which method is best suited for the analysis of potentially toxic petroleum-derived DOM. The four types were a liquid-liquid extraction (LLE) with dichloromethane (EPA method 3510C), and three solid-phase extraction (SPE) stationary phases that are routinely used for extraction of polar analytes from water. For the LLE, that is selective for non-polar compounds, the extraction efficiency of petroleum-derived DOM decreased downgradient as the petroleum-derived DOM becomes increasingly polar due to biodegradation. In contrast, the average extraction efficiency by the SPE methods was greater than 65 % across the gradient. The results showed that SPE is more efficient for extracting petroleum-derived DOM at hydrocarbon-contaminated sites. The use of a method with greater extraction efficiency for partially-oxidized hydrocarbons may prove useful in determining relationships between their composition and structure and potential for risks to human health or the environment.
Ground Water Monitoring and Remediation↗
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↗
Examining natural attenuation and acute toxicity of petroleum-derived dissolved organic matter with optical spectroscopy
Groundwater samples containing petroleum-derived dissolved organic matter (DOM HC ) originating from the north oil body within the National Crude Oil Spill Fate and Natural Attenuation Research Site near Bemidji, MN, USA were analyzed by optical spectroscopic techniques (i.e., absorbance and fluorescence) to assess relationships that can be used to examine natural attenuation and toxicity of DOM HC in contaminated groundwater. A strong correlation between the concentration of dissolved organic carbon (DOC) and absorbance at 254 nm ( a 254 ) along a transect of the DOM HC plume indicates that a 254 can be used to quantitatively assess natural attenuation of DOM HC . Fluorescence components, identified by parallel factor (PARAFAC) analysis, show that the composition of the DOM HC beneath and adjacent to the oil body is dominated by aliphatic, low O/C compounds (“protein-like” fluorescence) and that the composition gradually evolves to aromatic, high O/C compounds (“humic-/fulvic-like” fluorescence) as a function of distance downgradient from the oil body. Finally, a direct, positive correlation between optical properties and Microtox acute toxicity assays demonstrates the utility of these combined techniques in assessing the spatial and temporal natural attenuation and toxicity of the DOM HC in petroleum-impacted groundwater systems.
Environmental Science & Technology↗
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↗
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↗