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Liang, Liyuan

Publications and source records attributed to Liang, Liyuan.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Deposition and characterization of α-Fe 2 O 3 /Pd thin films for neutron reflectometry studies

Here, we report deposition of hematite/Pd thin films on silicon wafers via radio frequency (RF) magnetron sputtering and subsequent characterization for future in situ neutron reflectometry studies. Following deposition, the hematite/Pd thin films were characterized as prepared and after annealing in air for 2h at 400, 500, and 600 °C, respectively. Raman spectroscopy, grazing incidence x-ray diffraction, and neutron reflectometry (NR) were used to characterize the structure and chemical compositions of the thin films. The results indicate that pure α-Fe 2 O 3 (hematite) films were produced, free from other iron oxide phases and impurities. NR data reveal that one intermediate layer between the Pd layer and the hematite layer was formed during sputtering deposition processes. The fitted scattering length density (SLD) of the as-deposited hematite layer is 70% of the theoretical SLD value, indicating that the grains are loosely packed in the RF-deposited hematite films. After annealing at elevated temperatures, the hematite films show increased SLD values but remain comparable to that of preannealed.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Temporal, Spatial, and Temperature Controls on Organic Carbon Mineralization and Methanogenesis in Arctic High-Centered Polygon Soils

Warming temperatures in continuous permafrost zones of the Arctic will alter both hydrological and geochemical soil conditions, which are strongly linked with heterotrophic microbial carbon (C) cycling. Heterogeneous permafrost landscapes are often dominated by polygonal features formed by expanding ice wedges: water accumulates in low centered polygons (LCPs), and water drains outward to surrounding troughs in high centered polygons (HCPs). These geospatial differences in hydrology cause gradients in biogeochemistry, soil C storage potential, and thermal properties. Presently, data quantifying carbon dioxide (CO 2 ) and methane (CH 4 ) release from HCP soils are needed to support modeling and evaluation of warming-induced CO 2 and CH 4 fluxes from tundra soils. This study quantifies the distribution of microbial CO 2 and CH 4 release in HCPs over a range of temperatures and draws comparisons to previous LCP studies. Arctic tundra soils were initially characterized for geochemical and hydraulic properties. Laboratory incubations at −2, +4, and +8°C were used to quantify temporal trends in CO 2 and CH 4 production from homogenized active layer organic and mineral soils in HCP centers and troughs, and methanogen abundance was estimated from mcrA gene measurements. Results showed that soil water availability, organic C, and redox conditions influence temporal dynamics and magnitude of gas production from HCP active layer soils during warming. At early incubation times (2–9 days), higher CO 2 emissions were observed from HCP trough soils than from HCP center soils, but increased CO 2 production occurred in center soils at later times (>20 days). HCP center soils did not support methanogenesis, but CH 4 -producing trough soils did indicate methanogen presence. Consistent with previous LCP studies, HCP organic soils showed increased CO 2 and CH 4 production with elevated water content, but HCP trough mineral soils produced more CH 4 than LCP mineral soils. HCP mineral soils also released substantial CO 2 but did not show a strong trend in CO 2 and CH 4 release with water content. Knowledge of temporal and spatial variability in microbial C mineralization rates of Arctic soils in response to warming are key to constraining uncertainties in predictive climate models.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Molecular Dynamics Simulation of the Structures, Dynamics, and Aggregation of Dissolved Organic Matter

Dissolved organic matter (DOM) plays a significant role in the transport and transformation of pollutants in the aquatic environment. However, the experimental characterization of DOM has been limited mainly to bulk properties, and the molecular-level interactions among various components of DOM remain to be fully characterized. In this study, we use molecular dynamics (MD) simulations to probe the structural properties of model DOM systems at atomic detail. The 200 ns simulations, validated by available experimental data, reveal processes and mechanisms by which chemical species (cations, peptides, lipids, lignin, carbohydrates, and some low-molecular-weight aliphatic and aromatic compounds) aggregate to form complex DOM. The DOM aggregates are dynamic, consisting of a hydrophobic core and amphiphilic exterior. The lipid tails and other hydrophobic fragments form the core, with hydrophilic and amphiphilic groups exposed to water, making DOM accessible to both polar and nonpolar species. Thus, the lipid component acts as a nucleator, whereas cations (especially Ca 2+ ) connect the molecular fragments on the surface by coordinating with the O-containing functional groups of DOM. The structural details revealed here provide new insights including surface accessible atoms, overall assemblage, and interactions among the molecules of DOM for understanding the kinetics and mechanisms through which DOM interacts with metal and other contaminants.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Electrochemical properties of the interaction between cytochrome c and a hematite nanowire array electrode

We investigate the interaction of horse heart cytochrome c (cyt c ) with hematite nanowire array electrodes by cyclic voltammetry to study the electron transfer between redox active proteins and mineral surfaces. Using this model system, we quantify electron transfer rates between cyt c and hematite under varying electric potential and pH conditions. The results are consistent with two cyt c conformations adsorbed at the hematite surface: the native and a partially unfolded form. The partially unfolded protein maintained redox activity, but at a lower redox potential than the native protein. Adsorption of cyt c allowed direct electron transfer between cyt c and hematite, with an interfacial electron transfer rate, k ° ET , of 0.4 s -1 for the native form and 0.55 s -1 for the partially unfolded protein at pH 7.07. At pH 4.66, protein adsorption decreased compared to neutral pH and the fraction of partially unfolded protein increased. Additionally, the diffusion controlled electron transfer rate between hematite and the electron shuttling compound anthraquinone-2,6-disulfonate (AQDS) was determined to be k ° ET = 8.0·10 -3 cm·s -1 at pH 7.07. In conclusion, modulation of electron transfer rates as a result of conformational changes by redox active proteins has broad implications for describing chemical transformations at biological-mineral interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Molecular Insights into Arctic Soil Organic Matter Degradation under Warming

Molecular composition of the Arctic soil organic carbon (SOC) and its susceptibility to microbial degradation are uncertain due to heterogeneity and unknown SOC compositions. Using ultrahigh resolution mass spectrometry, we determined the susceptibility and compositional changes of extractable dissolved organic matter (EDOM) in an anoxic warming incubation experiment (up to 122 days) with a tundra soil from Alaska, United States. EDOM was extracted with 10 mM NH4HCO3 from both the organic and mineral-layer soils during incubation at either –2 or 8°C. Based on their O:C and H:C ratios, EDOM molecular formulas were qualitatively grouped into nine biochemical classes of compounds, among which lignin-like compounds dominated both the organic and mineral soils and were the most stable, whereas amino sugars, peptides and carbohydrate-like compounds were the most biologically labile. These results corresponded with shifts in EDOM elemental composition, in which the ratios of O:C and N:C decreased, while average C content in EDOM, molecular mass, and aromaticity increased after 122 days of incubation. This research demonstrates that certain EDOM molecules, such as amino sugars, peptides, and carbohydrate-like compounds, are disproportionately more susceptible to microbial degradation than others in the soil, and these results should be considered in SOC degradation models to improve predictions of Arctic climate feedbacks.

Chen, Hongmei↗
DOE OSTI2017

Microbial Community and Functional Gene Changes in Arctic Tundra Soils in a Microcosm Warming Experiment

Microbial decomposition of soil organic carbon (SOC) in the thawing Arctic permafrost is one of the most important, but poorly understood, processes in determining the greenhouse gases feedback of tundra ecosystems to climate. Here in this paper, we examine changes in microbial community structure during an anoxic incubation at either –2 or 8 °C for up to 122 days using both an organic and a mineral soil collected from the Barrow Environmental Observatory in northern Alaska, USA. Soils were characterized for SOC chemistry, and GeoChips were used to determine microbial community structure and functional genes associated with C degradation and Fe(III) reduction. We observed notable decreases in functional gene diversity (at P < 0.05) in response to warming at 8 °C, particularly in the organic soil. A number of genes associated with SOC degradation, fermentation, methanogenesis, and iron cycling decreased significantly (P < 0.05) after 122 days of incubation, which coincided well with decreasing labile SOC content, soil respiration, methane production, and iron reduction. The soil type (i.e., organic vs. mineral) and the availability of labile SOC were among the most significant environmental factors impacting the functional community structure. In contrast, the functional structure was largely unchanged in the –2 °C incubation due to low microbial activity resulting in less competition or exclusion. These results demonstrate the vulnerability of SOC in Arctic tundra to warming, facilitated by iron reduction and methanogenesis, and the importance of microbial communities in moderating such vulnerability.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Photochemical reactions between mercury (Hg) and dissolved organic matter decrease Hg bioavailability and methylation

Atmospheric deposition of mercury (Hg) to surface water is one of the dominant sources of Hg in aquatic environments and ultimately drives methylmercury (MeHg) toxin accumulation in fish. It is known that freshly deposited Hg is more readily methylated by microorganisms than aged or preexisting Hg; however the underlying mechanism of this process is unclear. Here we report that Hg bioavailability is decreased by photochemical reactions between Hg and dissolved organic matter (DOM) in water. Photo-irradiation of Hg-DOM complexes results in loss of Sn(II)-reducible (i.e. reactive) Hg and up to an 80% decrease in MeHg production by the methylating bacterium Geobacter sulfurreducens PCA. Loss of reactive Hg proceeded at a faster rate with a decrease in the Hg to DOM ratio and is attributed to the possible formation of mercury sulfide (HgS). Lastly, these results suggest a new pathway of abiotic photochemical formation of HgS in surface water and provide a mechanism whereby freshly deposited Hg is readily methylated but, over time, progressively becomes less available for microbial uptake and methylation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Warming increases methylmercury production in an Arctic soil

The rapid temperature rise in Arctic permafrost concerns not only the degradation of stored soil organic carbon (SOC) and climate feedback, but also the production and bioaccumulation of methylmercury (MeHg) that may endanger humans, as well as wildlife in terrestrial, aquatic, and marine ecosystems. Decomposition of SOC provides an energy source for microbial methylation, although little is known how rapid permafrost thaw affects Hg methylation and how SOC degradation is coupled to MeHg biosynthesis. We describe rates of MeHg production in Arctic soils from an 8-month warming microcosm experiment under anoxic conditions. MeHg production increased >10 fold in both organic- and the mineral-rich soil layers at a warmer temperature (8 C) compared to a sub-zero temperature ( 2 C). MeHg production was positively correlated to methane and ferrous ion concentrations, suggesting that Hg methylation is coupled with methanogenesis and iron reduction. Labile SOC, such as reducing sugars and alcohol, were particularly effective in fueling the initial rapid biosynthesis of MeHg. In freshly amended Hg we found that there was more bioavailable than existing Hg in the mineral soil. Finally, the data indicate that climate warming and permafrost thaw could greatly enhance MeHg production, thereby impacting Arctic aquatic and marine ecosystems through biomagnification in the food web.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Effect of warming on the degradation and production of low-molecular-weight labile organic carbon in an Arctic tundra soil

The fate of soil organic carbon (SOC) stored in the Arctic permafrost is a key concern as temperatures continue to rise in the northern hemisphere. Studies and conceptual models suggest that SOC degradation is affected by the composition of SOC, but it is unclear exactly what portions of SOC are vulnerable to rapid breakdown and what mechanisms may be controlling SOC degradation upon permafrost thaw. Here, we examine the dynamic consumption and production of labile SOC in an anoxic incubation experiment using soil samples from the active layer at the Barrow Environmental Observatory, Barrow, Alaska, USA. Free-reducing sugars, alcohols, and low-molecular-weight (LMW) organic acids were analyzed during incubation at either –2 or 8 °C for up to 240 days. Results show that simple sugar and alcohol SOC largely account for the initial rapid release of CO 2 and CH 4 through anaerobic fermentation, whereas the fermentation products, acetate and formate, are subsequently utilized as primary substrates for methanogenesis. Iron(III) reduction is correlated to acetate production and methanogenesis, suggesting its important role as an electron acceptor in tundra SOC respiration. These observations are further supported in a glucose addition experiment, in which rapid CO 2 and CH 4 production occurred concurrently with rapid production and consumption of labile organics such as acetate. However, addition of tannic acid, as a more complex organic substrate, showed little influence on the overall production of CO 2 and CH 4 and organic acids. Together our study shows that LMW labile organics in SOC control the initial rapid release of green-house gases upon warming. We thus present a conceptual framework for the labile SOC transformations and their relations to fermentation, iron reduction and methanogenesis, thereby providing the basis for improved model prediction of climate feedbacks in the Arctic.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Geochemical drivers of organic matter decomposition in Arctic tundra soils

Climate change is warming tundra ecosystems in the Arctic, resulting in the decomposition of previously-frozen soil organic matter (SOM) and release of carbon (C) to the atmosphere; however, the processes that control SOM decomposition and C emissions remain highly uncertain. In this study, we evaluate geochemical factors that influence anaerobic production of carbon dioxide (CO 2 ) and methane (CH 4 ) in the active layers of four ice-wedge polygons. Surface and soil pore waters were collected during the annual thaw season over a two-year period in an area containing waterlogged, low-centered polygons and well-drained, high-centered polygons. We report spatial and seasonal patterns of dissolved gases in relation to the geochemical properties of Fe and organic C as determined using spectroscopic and chromatographic techniques. Iron was present as Fe(II) in soil solution near the permafrost boundary but enriched as Fe(III) in the middle of the active layer, similar to dissolved aromatic-C and organic acids. Dissolved CH 4 increased relative to dissolved CO 2 with depth and varied with soil moisture in the middle of the active layer in patterns that were positively correlated with the proportion of dissolved Fe(III) in transitional and low-centered polygon soils but negatively correlated in the drier flat- and high-centered polygons. These results suggest that microbial-mediated Fe oxidation and reduction influence respiration/fermentation of SOM and production of substrates (e.g., low-molecular-weight organic acids) for methanogenesis. As a result, we infer that geochemical differences induced by water saturation dictate microbial products of SOM decomposition, and Fe geochemistry is an important factor regulating methanogenesis in anoxic tundra soils.

58 GEOSCIENCES↗
DOE OSTI2015

Pathways of anaerobic organic matter decomposition in tundra soils from Barrow, Alaska

Arctic tundra soils store a large quantity of organic carbon that is susceptible to decomposition and release to the atmosphere as methane (CH 4 ) and carbon dioxide (CO 2 ) under a warming climate. Anaerobic processes that generate CH 4 and CO 2 remain unclear because previous studies have focused on aerobic decomposition pathways. To predict releases of CO 2 and CH 4 from tundra soils, it is necessary to identify pathways of soil organic matter decomposition under the anoxic conditions that are prevalent in Arctic ecosystems. Here molecular and spectroscopic techniques were used to monitor biological degradation of water-extractable organic carbon (WEOC) during anoxic incubation of tundra soils from a region of continuous permafrost in northern Alaska. Organic and mineral soils from the tundra active layer were incubated at –2, +4, or +8°C for up to 60 days to mimic the short-term thaw season. Results suggest that, under anoxic conditions, fermentation converted complex organic molecules into simple organic acids that were used in concomitant Fe-reduction and acetoclastic methanogenesis reactions. Nonaromatic compounds increased over time as WEOC increased. Organic acid metabolites initially accumulated in soils but were mostly depleted by day 60 because organic acids were consumed to produce Fe(II), CO 2 , and CH 4 . We conclude that fermentation of nonprotected organic matter facilitates methanogenesis and Fe reduction reactions, and that the proportion of organic acids consumed by methanogenesis increases relative to Fe reduction with increasing temperature. As a result, the decomposition pathways observed in this study are important to consider in numerical modeling of greenhouse gas production in the Arctic.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2015

Formation of soluble mercury oxide coatings: Transformation of elemental mercury in soils

In this study, the impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reacting with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.

58 GEOSCIENCES↗
DOE OSTI2015

Thiol-facilitated cell export and desorption of methylmercury by anaerobic bacteria

Neurotoxic methylmercury (MeHg), formed by anaerobic bacteria, is shown to be rapidly excreted from the cell, but the mechanism of this process is unclear. Using both Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132 strains, we investigated the factors affecting export and distribution of MeHg in mercury methylation and MeHg sorption-desorption assays. Thiols, such as cysteine, were found to greatly facilitate desorption and export of MeHg, particularly by PCA cells. However, in cysteine-free assays (4 h) >90% of the synthesized MeHg was associated with PCA, among which ~73% was sorbed on the cell surface and 19% remained inside the cells. In comparison, a majority of the MeHg (70%) was exported by ND132, leaving ~20% of the MeHg sorbed on the surface and 10% inside the cells. When MeHg was added directly to the cell suspensions, ND132 adsorbed much lower MeHg but took up more MeHg inside cells than PCA did. These results demonstrate that MeHg export is bacteria strain-specific, time dependent, and is influenced by thiols, implicating important roles of ligand complexation in facilitating MeHg production and mobilization in the environment.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Degradation of trichloroethene with a noval ball milled Fe-C nanocomposite

Nanoscale zero-valent iron (NZVI) is effective in reductively degrading dense non-aqueous phase liquids (DNAPLs), such as trichloroethene (TCE), in groundwater (i.e., dechlorination) although the NZVI technology itself still suffers from high material costs and inability to target hydrophobic contaminants in source zones. To address these problems, we developed a novel, inexpensive iron-carbon (Fe-C) nanocomposite material by simultaneously milling micron-size iron and activated carbon powder. Microscopic and X-ray diffraction (XRD) characterization of the composite material revealed that nanoparticles of Fe were dispersed in activated carbon and a new iron carbide phase was formed. Bench-scale studies showed that this material instantaneously sorbed >90% of TCE from aqueous solutions and subsequently decomposed TCE into non-chlorinated products. Compared to milled Fe, Fe-C nanocomposite dechlorinated TCE at a slightly slower rate and favored the production of ethene over other TCE degradation products such as C 3 -C 6 compounds. When placed in hexane-water mixture, the Fe-C nanocomposite materials are preferentially partitioned into the organic phase, indicating the ability of the composite materials to target DNAPL during remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Indexing Permafrost Soil Organic Matter Degradation Using High-Resolution Mass Spectrometry

Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon cycling, although the molecular details of these transformations remain unclear. This study reports the application of ultrahigh resolution mass spectrometry to profile the molecular composition of SOM and its degradation during a simulated warming experiment. A soil sample, collected near Barrow, Alaska, USA, was subjected to a 40-day incubation under anoxic conditions and analyzed before and after the incubation to determine changes of SOM composition. A CHO index based on molecular C, H, and O data was utilized to codify SOM components according to their observed degradation potentials. Compounds with a CHO index score between –1 and 0 in a water-soluble fraction (WSF) demonstrated high degradation potential, with a highest shift of CHO index occurred in the N-containing group of compounds, while similar stoichiometries in a base-soluble fraction (BSF) did not. Additionally, compared with the classical H:C vs O:C van Krevelen diagram, CHO index allowed for direct visualization of the distribution of heteroatoms such as N in the identified SOM compounds. We demonstrate that CHO index is useful not only in characterizing arctic SOM at the molecular level but also enabling quantitative description of SOM degradation, thereby facilitating incorporation of the high resolution MS datasets to future mechanistic models of SOM degradation and prediction of greenhouse gas emissions.

Environmental Molecular Sciences Laboratory↗