Browsing by Author "D'Andrilli, Juliana"

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A 21 000-year record of fluorescent organic matter markers in the WAIS Divide ice core
(2017-05) D'Andrilli, Juliana; Foreman, Christine M.; Sigl, Michael; Priscu, John C.; McConnell, Joseph R.
Englacial ice contains a significant reservoir of organic material (OM), preserving a chronological record of materials from Earth's past. Here, we investigate if OM composition surveys in ice core research can provide paleoecological information on the dynamic nature of our Earth through time. Temporal trends in OM composition from the early Holocene extending back to the Last Glacial Maximum (LGM) of the West Antarctic Ice Sheet Divide (WD) ice core were measured by fluorescence spectroscopy. Multivariate parallel factor (PARAFAC) analysis is widely used to isolate the chemical components that best describe the observed variation across three-dimensional fluorescence spectroscopy (excitation–emission matrices; EEMs) assays. Fluorescent OM markers identified by PARAFAC modeling of the EEMs from the LGM (27.0–18.0 kyr BP; before present 1950) through the last deglaciation (LD; 18.0–11.5 kyr BP), to the mid-Holocene (11.5–6.0 kyr BP) provided evidence of different types of fluorescent OM composition and origin in the WD ice core over 21.0 kyr. Low excitation–emission wavelength fluorescent PARAFAC component one (C1), associated with chemical species similar to simple lignin phenols was the greatest contributor throughout the ice core, suggesting a strong signature of terrestrial OM in all climate periods. The component two (C2) OM marker, encompassed distinct variability in the ice core describing chemical species similar to tannin- and phenylalanine-like material. Component three (C3), associated with humic-like terrestrial material further resistant to biodegradation, was only characteristic of the Holocene, suggesting that more complex organic polymers such as lignins or tannins may be an ecological marker of warmer climates. We suggest that fluorescent OM markers observed during the LGM were the result of greater continental dust loading of lignin precursor (monolignol) material in a drier climate, with lower marine influences when sea ice extent was higher and continents had more expansive tundra cover. As the climate warmed, the record of OM markers in the WD ice core changed, reflecting shifts in carbon productivity as a result of global ecosystem response..
Bulk optical characterization of dissolved organic matter from semiarid wheat-based cropping systems
(2017-11) Romero, Carlos M.; Engel, Richard E.; D'Andrilli, Juliana; Chen, Cheng-Sao; Zabinski, Catherine A.; Miller, Perry R.; Wallander, R.
Dissolved organic matter (DOM) plays a critical role in the cycling of nutrients and long-term agricultural sustainability. The composition of DOM in soil is likely altered due to management, yet there is limited knowledge on the effect of long-term cropping on DOM chemical character. Here, we characterized water extractable DOM composition along a gradient of soil organic carbon (SOC) affected by differing cropping and tillage intensity in a semiarid climate of the northern Great Plains, USA. Soil samples (0–10, 10–20, 20–30 cm) were collected from conventional till-fallow winter wheat (Triticum aestivum L.; Ftill-W), no-till spring pea/oilseed-wheat (Pisum sativum L.; Pg/O-W), and no-till continuous wheat (W-W) fields, and analyzed using UV/Vis absorbance and excitation-emission matrix fluorescence spectroscopy. The concentration of DOM decreased with depth and was significantly greater (P < 0.05) under W-W or Pg/O-W than Ftill-W. The absorbance at 254 nm (Abs254), a proxy for DOM aromatic nature, indicated that aromaticity decreased with depth and lower biomass-C inputs (i.e. W-W ≥ Pg/O-W ≥ Ftill-W). Multidimensional parallel factor (PARAFAC) analysis revealed humic-like (C1, C2), monolignol-like (C3), and protein/tannin-like (C4) components with varying fluorescence intensities as a function of cropping system and soil depth. DOM humification, indicated by the humification index (HIX), increased significantly with depth (P < 0.05) and was higher for Ftill-W (2.95) than W-W (2.61) or Pg/O-W (2.28). Overall, DOM became depleted of plant-derived constituents and was enriched by more decomposed, condensed substances in Ftill-W, as compared to W-W or Pg/O-W soils. DOM composition is strongly affected by cropping intensity and such changes are important drivers controlling SOC accretion in arable soils.
Characterization of IHSS Pony Lake fulvic acid dissolved organic matter by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and fluorescence spectroscopy
(2013-12) D'Andrilli, Juliana; Foreman, Christine M.; Marshall, Alan G.; McKnight, Diane M.
We present the extensive characterization of Antarctic Pony Lake (PL) dissolved organic matter (DOM), an International Humic Substance Society (IHSS) fulvic acid (FA) reference standard, using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) and excitationâ€“emission matrix fluorescence spectroscopy (EEMS). PLFA is the first reference standard available through IHSS derived solely from a microbial source. A number of factors differentiate PLFA from other IHSS standards, including source material, geographic location, sunlight exposure, freezeâ€“thaw conditions, and other in situ environmental influences. ESI FT-ICR MS and EEMS were used to compare the PLFA microbial DOM compositional signature with the IHSS Suwannee River (SR) FA, a standard frequently studied for environmental DOM analysis. Although CcHhOoNnSs(n = 0, 1, or 2 and s = 0 or 1) constituents were present in both IHSS samples, PLFA contained more N and S molecular species, whereas SRFA was dominated by CcHhOo compounds. Proteinaceous character was detected with both methods, in greater abundance for PLFA, which we attributed to its microbial source material and labile, potentially more reactive nature than SRFA. Characterization from both analytical techniques resulted in complementary data that reinforce the importance of PLFA as an IHSS reference standard that should be utilized for other microbiological environmental DOM comparisons.
Compositional tracking of dissolved organic matter in semiarid wheat-based cropping systems using fluorescence EEMs-PARAFAC and absorbance spectroscopy
(2019-08) Romero, Carlos M.; Engel, Richard E.; D'Andrilli, Juliana; Miller, Perry R.; Wallander, Roseann
We conducted this study to quantify long-term cropping related changes in soil organic carbon (SOC) stocks and characterize the optical properties of dissolved organic matter (DOM) after a decadal on-farm experiment in Montana, USA. Soil samples (0–50 cm) were collected from minimum till (MT) and no-till (NT) fields under fallow-winter wheat (Triticum aestivum L.; F-W) and pea-winter wheat (Pisum sativum L.; P-W) rotations. Stocks of SOC(0–50 cm) averaged 65.6 Mg C ha−1 and 60.6 Mg C ha−1 for P-W and F-W, respectively. The net SOC accretion rate for P-W equated to 0.61 Mg ha−1 yr−1 relative to F-W. We used absorbance spectroscopy and excitation-emission matrices to characterize DOM composition of samples collected from MT F-W and NT P-W. The two cropping systems exhibited similar estimates of aromaticity (absorbance at 254 nm; 0.33–0.39 a.u.) and humification index (1.83–1.86). Parallel factor (PARAFAC) analysis revealed humic-like (C1, C2), monolignol/amino acid-like (C3), and amino acid-/tannin-like (C4) components with equivalent fluorescent intensities among MT F-W and NT P-W. Fluorescence efficiencies increased with depth, suggesting a shift from larger, plant-like material to smaller, microbial-derived precursors. Overall, we found DOM composition to be minimally affected by cropping systems in this semiarid climate of the northern Great Plains.
Differential Incorporation of Bacteria, Organic Matter, and Inorganic Ions Into Lake Ice During Ice Formation
(2019-03) Santibanez, Pamela A.; Michaud, Alexander B.; Vick-Majors, Trista J.; D'Andrilli, Juliana; Hand, Kevin P.; Priscu, John C.
The segregation of bacteria, inorganic solutes, and total organic carbon between liquid water and ice during winter ice formation on lakes can significantly influence the concentration and survival of microorganisms in icy systems and their roles in biogeochemical processes. Our study quantifies the distributions of bacteria and solutes between liquid and solid water phases during progressive freezing. We simulated lake ice formation in mesocosm experiments using water from perennially (Antarctica) and seasonally (Alaska and Montana, United States) ice-covered lakes. We then computed concentration factors and effective segregation coefficients, which are parameters describing the incorporation of bacteria and solutes into ice. Experimental results revealed that, contrary to major ions, bacteria were readily incorporated into ice and did not concentrate in the liquid phase. The organic matter incorporated into the ice was labile, amino acid-like material, differing from the humic-like compounds that remained in the liquid phase. Results from a control mesocosm experiment (dead bacterial cells) indicated that viability of bacterial cells did not influence the incorporation of free bacterial cells into ice, but did have a role in the formation and incorporation of bacterial aggregates. Together, these findings demonstrate that bacteria, unlike other solutes, were preferentially incorporated into lake ice during our freezing experiments, a process controlled mainly by the initial solute concentration of the liquid water source, regardless of cell viability.
DOM composition alters ecosystem function during microbial processing of isolated sources
(2019-01) D'Andrilli, Juliana; Junker, James R.; Smith, Heidi J.; Scholl, Eric A.; Foreman, Christine M.
Dynamics of dissolved organic matter (DOM) in ecosystems are controlled by a suite of interacting physical, chemical, and biological factors. Growing recognition of the associations between microbial communities and metabolism and intrinsic DOM characteristics, highlight the potential importance of microbe-DOM relationships to modulate the role and fate of DOM, yet these relationships are difficult to isolate because they often operate across confounding environmental gradients. In a controlled laboratory incubation (44 days), we integrated DOM bulk and molecular characterization, bacterial abundances, microbial assemblage composition, nutrient concentrations, and cellular respiration to discern the structural dynamics of biological processing among DOM sources from different allochthonous litters (grass, deciduous leaves, and evergreen needles). We identified two periods, consistent among DOM sources, where processing dynamics differed. Further, bulk fluorescent analyses showed shifts from low to high excitation and emission wavelengths, indicating the biological production of more complex/degraded materials over time. Molecular level analyses revealed similar temporal patterns among DOM sources in the production and consumption of individual chemical components varying in reactivity and heteroatomic content. Despite these similarities, total carbon (C) removed and carbon dioxide (CO2) accumulation differed by ~ 20% and 25% among DOM sources. This range in C processing was apparently tied to key chemical properties of the DOM (e.g., initial DOM composition, N content, and labile nature) as well as differential reorganization of the microbial populations that decomposed the DOM. We conclude that the production, transformation, and consumption of C in aquatic ecosystems is strongly dependent on the source and character of DOM as well as the structure of the microbial communities present, both of which change as DOM is processed over time. It is crucial that stream C processing models represent this complexity accurately.
Dynamic processing of DOM: Insight from exometabolomics, fluorescence spectroscopy, and mass spectrometry
(2018-06) Smith, Heidi J.; Tigges, Michelle M.; D'Andrilli, Juliana; Parker, Albert E.; Bothner, Brian; Foreman, Christine M.
Dissolved organic matter (DOM) in freshwater environments is an important source of organic carbon, supporting bacterial respiration. Frozen environments cover vast expanses of our planet, with glaciers and ice-sheets storing upwards of 6 petagrams of organic carbon. It is generally believed that DOM liberated from ice stimulates downstream environments. If true, glacial DOM is an important component of global carbon cycling. However, coupling the release of DOM to microbial activity is challenging due to the molecular complexity of DOM and the metabolic connectivity within microbial communities. Using a single environmentally relevant organism, we demonstrate that processing of compositionally diverse DOM occurs, but, even though glacially derived DOM is chemically labile, it is unable to support sustained respiration. In view of projected changes in glacier DOM export, these findings imply that biogeochemical impacts on downstream environments will depend on the reactivity and heterogeneity of liberated DOM, as well as the timescale.
Subsurface In Situ Detection of Microbes and Diverse Organic Matter Hotspots in the Greenland Ice Sheet
(2020) Malaska, Michael J.; Bhartia, Rohit; Manatt, Kenneth S.; Priscu, John C.; Abbey, William J.; Mellerowicz, Boleslaw; Palmowski, Joseph; Paulsen, Gale L.; Zacny, Kris; Eshelman, Evan J.; D'Andrilli, Juliana
We used a deep-ultraviolet fluorescence mapping spectrometer, coupled to a drill system, to scan from the surface to 105 m depth into the Greenland ice sheet. The scan included firn and glacial ice and demonstrated that the instrument is able to determine small (mm) and large (cm) scale regions of organic matter concentration and discriminate spectral types of organic matter at high resolution. Both a linear point cloud scanning mode and a raster mapping mode were used to detect and localize microbial and organic matter “hotspots” embedded in the ice. Our instrument revealed diverse spectral signatures. Most hotspots were <20 mm in diameter, clearly isolated from other hotspots, and distributed stochastically; there was no evidence of layering in the ice at the fine scales examined (100 μm per pixel). The spectral signatures were consistent with organic matter fluorescence from microbes, lignins, fused-ring aromatic molecules, including polycyclic aromatic hydrocarbons, and biologically derived materials such as fulvic acids. In situ detection of organic matter hotspots in ice prevents loss of spatial information and signal dilution when compared with traditional bulk analysis of ice core meltwaters. Our methodology could be useful for detecting microbial and organic hotspots in terrestrial icy environments and on future missions to the Ocean Worlds of our Solar System.
An ultrahigh-resolution mass spectrometry index to estimate natural organic matter lability
(2015-12) D'Andrilli, Juliana; Cooper, William T.; Foreman, Christine M.; Marshall, Alan G.
Rationale: Determining the chemical constituents of natural organic matter (NOM) by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICRMS) remains the ultimate measure for probing its source material, evolution, and transport; however, lability and the fate of organic matter (OM) in the environment remain controversial. FTICRMS-derived elemental compositions are presented in this study to validate a new interpretative method to determine the extent of NOM lability from various environments. Methods: FTICRMS data collected over the last decade from the same 9.4 tesla instrument using negative electrospray ionization at the National High Magnetic Field Laboratory in Tallahassee, Florida, was used to validate the application of a NOM lability index. Solid-phase extraction cartridges were used to isolate the NOM prior to FTICRMS; mass spectral peaks were calibrated internally by commonly identified NOM homologous series, and molecular formulae were determined for NOM composition and lability analysis. Results: A molecular lability boundary (MLB) was developed from the FTICRMS molecular data, visualized from van Krevelen diagrams, dividing the data into more and less labile constituents. NOM constituents above the MLB at H/C ≥1.5 correspond to more labile material, whereas NOM constituents below the MLB, H/C <1.5, exhibit less labile, more recalcitrant character. Of all marine, freshwater, and glacial environments considered for this study, glacial ecosystems were calculated to contain the most labile OM. Conclusions: The MLB extends our interpretation of FTICRMS NOM molecular data to include a metric of lability, and generally ranked the OM environments from most to least labile as glacial > marine > freshwater. Applying the MLB is useful not only for individual NOM FTICRMS studies, but also provides a lability threshold to compare and contrast molecular data with other FTICRMS instruments that survey NOM from around the world.