Yuehan Lu

Use of ESI-FTICR-MS to Characterize Dissolved Organic Matter in Headwater Streams Draining Forest-Dominated and Pasture-Dominated Watersheds

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proven to be a powerful technique revealing complexity and diversity of natural DOM molecules, but its application to DOM analysis in grazing-impacted agricultural systems remains scarce. In the present study, we presented a case study of using ESI-FTICR-MS in analyzing DOM from four headwater streams draining forest- or pasture-dominated watersheds in Virginia, USA. In all samples, most formulas were CHO compounds (71.8–87.9%), with other molecular series (CHOS, CHON, CHONS, and CHOP (N, S)) accounting for only minor fractions. All samples were dominated by molecules falling in the lignin-like region (H/C = 0.7–1.5, O/C = 0.1–0.67), suggesting the predominance of allochthonous, terrestrial plant-derived DOM. Relative to the two pasture streams, DOM formulas in the two forest streams were more similar, based on Jaccard similarity coefficients and nonmetric multidimensional scaling calculated from Bray-Curtis distance. Formulas from the pasture streams were characterized by lower proportions of aromatic formulas and lower unsaturation, suggesting that the allochthonous versus autochthonous contributions of organic matter to streams were modified by pasture land use. The number of condensed aromatic structures (CAS) was higher for the forest streams, which is possibly due to the controlled burning in the forest-dominated watersheds and suggests that black carbon was mobilized from soils to streams. During 15-day biodegradation experiments, DOM from the two pasture streams was altered to a greater extent than DOM from the forest streams, with formulas with H/C and O/C ranges similar to protein (H/C = 1.5–2.2, O/C = 0.3–0.67), lipid (H/C = 1.5–2.0, O/C = 0–0.3), and unsaturated hydrocarbon (H/C = 0.7–1.5, O/C = 0–0.1) being the most bioreactive groups. Aromatic compound formulas including CAS were preferentially removed during combined light+bacterial incubations, supporting the contention that black carbon is labile to light alterations. Collectively, our data demonstrate that headwater DOM composition contains integrative information on watershed sources and processes, and the application of ESI-FTICR-MS technique offers additional insights into compound composition and reactivity unrevealed by fluorescence and stable carbon isotopic measurements.

Hydrological and land use control of watershed exports of dissolved organic matter in a large arid river basin in northwestern China

We evaluated variation in dissolved organic matter (DOM) export as a function of hydrology and land use from a large arid river basin in northwestern China. Two soil-derived, humic-like (C1 and C2) and three protein-like fluorescence components (C3, C4, and C5) were identified. During high discharges, river water DOM had higher values of DOC concentration, percent humic fluorescence, and humification index, but lower values of fluorescence index and percent protein fluorescence than found at base flow, suggesting that flow paths shifted to shallower depths flushing out topsoil organic matter. Loading of DOC and soil-derived humic fluorescence were driven largely by discharge, with values over 10 times higher during high discharges than at base flow. Furthermore, both δ13C-DOC and C1 at high flows positively correlated with %agricultural lands within 1 km river buffers, demonstrating that near-river agricultural activities enhanced storm export of soil DOM. At base flow, C4 positively correlated with %agricultural lands, showing stimulation of aquatic bacterial carbon production as a result of elevated nutrient inputs from agricultural lands. Percent contributions of humic fluorescence in groundwater varied with well depths in shallow wells, but this pattern was not observed for deeper groundwater, suggesting that humic DOM could serve as a water source tracer indicating deeper aquifers were isolated from river water and shallow groundwater. Together, our data demonstrate that hydrology and land use controlled the sources and amount of riverine DOM in this large agricultural basin and that regulating storm runoff and near-river agricultural activities should be incorporated in ecosystem-based management of water resources.

Climatic and watershed controls of dissolved organic matter variation in streams across a gradient of agricultural land use

Human land use has led to significant changes in the character of dissolved organic matter (DOM) in lotic ecosystems. These changes are expected to have important environmental and ecological consequences. However, high spatiotemporal variability has been reported in previous studies, and the underlying mechanisms remain inadequately understood. This study assessed variation in the properties of stream water DOM within watersheds across a gradient of agricultural land use with grazing pasture lands as the dominant agricultural type in the southeastern United States. We collected water samples under baseflow conditions five times over eight months from a regional group of first- to fourth-order streams. Samples were analyzed for dissolved organic carbon (DOC) concentration, DOM quality based on absorbance and fluorescence properties, as well as DOM biodegradability. We found that air temperature and antecedent hydrological conditions (indicated by antecedent precipitation index and stream water sodium concentrations) positively influenced stream water DOC concentration, DOM fluorescence index, and the proportion of soil-derived, microbial humic fluorescence. This observation suggests that elevated production and release of microbial DOM in soils facilitated by high temperature, in conjunction with strong soil-stream hydrological connectivity, were important drivers for changes in the concentration and composition of stream water DOM. By comparison, watersheds with a high percentage of agricultural land use showed higher DOC concentration, larger proportion of soil-derived, humic-like DOM compounds, and higher DOC biodegradability. These observations reflect preferential mobilization of humic DOM compounds from shallow organic matter-rich soils in agricultural watersheds, likely due to enhanced soil erosion, organic matter oxidation and relatively shallow soil-to-stream flow paths.

Initial community and environment determine the response of bacterial communities to dispersant and oil contamination.

Bioremediation of seawater by natural bacterial communities is one potential response to coastal oil spills, but the success of the approach may vary, depending on geographical location, oil composition and the timing of spill. The short term response of coastal bacteria to dispersant, oil and dispersed oil was characterized using 16S rRNA gene tags in two mesocosm experiments conducted two months apart. Despite differences in the amount of oil-derived alkanes across the treatments and experiments, increases in the contributions of hydrocarbon degrading taxa and decreases in common estuarine bacteria were observed in response to dispersant and/or oil. Between the two experiments, the direction and rates of changes in particulate alkane concentrations differed, as did the magnitude of the bacterial response to oil and/or dispersant. Together, our data underscore large variability in bacterial responses to hydrocarbon pollutants, implying that bioremediation success varies with starting biological and environmental conditions.

Evaluating Differences in Transport Behavior of Sodium Chloride and Brilliant Blue FCF in Sand Columns

Groundwater tracers such as sodium chloride (NaCl) and the food color brilliant blue FCF (BBF) had been widely used to evaluate flow dynamics, but the possible discrepancy of transport dynamics between the two tracers through a same medium remains obscure. In order to fill this knowledge gap, we combined laboratory experiments and model analysis for transport of the above tracers. We first conducted three progressive experiments, including (1) transport experiments of NaCl and BBF through saturated sand columns packed with uniform glass beads; (2) transport experiments of the two tracers through silica sand columns as a function of travel distances and flow rates; and (3) a long-term adsorption experiment exploring the adsorption of the two tracers to silica sands. All laboratory results show that NaCl exhibits slower and smaller peaks in tracer breakthrough curves than BBF. Further model analysis using the standard advection-dispersion equation (with a retardation coefficient to account for equilibrium sorption) demonstrates that the NaCl plume has a larger dispersion coefficient than that of BBF. Both the laboratory and a pseudo-kinetic model also reveal that NaCl might be observed more by the medium than BBF. Therefore, although NaCl is well known to be a more conservative tracer than BBF, our laboratory and numerical experiments suggest the opposite. NaCl can be less conservative than BBF through laboratory-scale sand columns, probably due to (1) stronger sorption of NaCl to silica sand, and/or (2) relatively stronger mass exchange between mobile and immobile zones in macroscopically homogeneous porous media.

Sensitivity of sediment geochemical proxies to coring location and corer type in a large lake: Implications for paleolimnological reconstruction

We compared a suite of geochemical proxies in sediment cores collected in 1982, 1988, 1991, and 2003 from sites near the depocenter of Lake Erie to evaluate the reliability of paleoenvironmental reconstructions derived from lacustrine sediments. Our proxies included the concentrations and carbon isotopic compositions of organic and inorganic carbon (TOC, CaCO3, δ13Corg, and δ13CCaCO3), augmented by organic C to total N ratios (Corg:Ntot), δ15N, and carbonate δ18O values (δ18OCaCO3). The three coring sites were clustered within 12 km; two types of corers—a Box corer and a Benthos gravity corer—were used for the 1991 sampling campaign. The variance of most proxies was accounted for not only by temporal environmental changes but also by coring locations and corer type, indicating that sediment spatial heterogeneity and differences in sediment recovery due to the use of different corers also played a part in determining the geochemical compositions of these cores. The TOC, δ13Corg, and δ13CCaCO3 values showed decadal temporal patterns that were consistent between the multiple sampling campaigns. In contrast, the δ15N, Corg:Ntot, CaCO3, and δ18OCaCO3 exhibited across-core differences in their temporal variations, making it difficult to extract consistent environment information from different cores. Our findings suggest that in addition to temporal environmental changes, high-resolution paleolimnological reconstruction is sensitive to many factors that could include spatial sediment heterogeneity, discontinuous sedimentation processes, bioturbation, sediment dating uncertainty, and artifacts associated with analytical and coring procedures. Therefore, multiple-core sampling and analysis are important in reliably reconstructing environmental changes, particularly for large, heterogeneous lacustrine basins.

River network saturation concept: factors influencing the balance of biogeochemical supply and demand of river networks

River networks modify material transfer from land to ocean. Understanding the factors regulating this function for different gaseous, dissolved, and particulate constituents is critical to quantify the local and global effects of climate and land use change. We propose the River Network Saturation (RNS) concept as a generalization of how river network regulation of material fluxes declines with increasing flows due to imbalances between supply and demand at network scales. River networks have a tendency to become saturated (supply ≫ demand) under higher flow conditions because supplies increase faster than sink processes. However, the flow thresholds under which saturation occurs depends on a variety of factors, including the inherent process rate for a given constituent and the abundance of lentic waters such as lakes, ponds, reservoirs, and fluvial wetlands within the river network. As supply increases, saturation at network scales is initially limited by previously unmet demand in downstream aquatic ecosystems. The RNS concept describes a general tendency of river network function that can be used to compare the fate of different constituents among river networks. New approaches using nested in situ high-frequency sensors and spatially extensive synoptic techniques offer the potential to test the RNS concept in different settings. Better understanding of when and where river networks saturate for different constituents will allow for the extrapolation of aquatic function to broader spatial scales and therefore provide information on the influence of river function on continental element cycles and help identify policy priorities.