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Robert S. Eckard

Publications and source records attributed to Robert S. Eckard.

5 recordsLinked to original sources

Organic matter integration, overprinting, and the relative fraction of optically active organic carbon in a human-impacted watershed

Rivers continually integrate terrestrial organic matter (OM) into their waters, in a process that transfers 1.9 Pg C yr –1 as the primary linkage between oceanic and terrestrial carbon cycles. Yet rivers are not simple, conservative OM integrators. Patchy local land uses (wetlands, bogs, agriculture) release OM that can disproportionately alter river biogeochemistry and overprint upstream carbon. These releases are quantifiable at the plot scale but remain unpredictable across river reaches and watersheds, critically inhibiting our ability to scale up terrestrial-aquatic linkages to regional/global carbon cycling models. We evaluated OM overprinting distance along a human-influenced watershed to quantify river integration of terrestrial OM and to bridge the quantification gap between habitats and waterway biogeochemistry. We investigated changes in dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition (lignin phenols, fluorescence excitation-emission spectra using parallel factor analysis [PARAFAC], and the relative fraction of optically active DOM [EEM DOC ]). DOC concentrations increased continually ( p < 0.001) downstream, from median 1.0 mg L –1 at 30 km (headwaters) to 3.3 mg L –1 at the river mouth. This rate of increase corresponded to a DOC overprinting distance—the longitudinal distance over which DOC concentrations double—of 13 km. Mainstem DOC overprinting distance ranged from 8 km (winter, rainy season) to 21 km (summer, dry season with irrigation), highlighting stronger overprinting during increased hydraulic connectivity. Stronger overprinting also correlated to higher EEM DOC ( p < 0.001). Overprinting distance effectively quantifies river integration of DOM along the terrestrial-aquatic interface, helping to refine bottom-up carbon cycle estimates, inform upscaling of site-specific fluxes, and to track land use and climate influence on river biogeochemistry.

California

Trihalomethane precursors: Land use hot spots, persistence during transport, and management options

To meet drinking water regulations, rather than investing in costly treatment plant operations, managers can look for ways to improve source water quality; this requires understanding watershed sources and fates of constituents of concern. Trihalomethanes (THMs) are one of the major classes of regulated disinfection byproducts, formed when a specific fraction of the organic carbon pool—referred to as THM precursors—reacts with chorine and/or bromine during treatment. Understanding the source, fate, timing and duration of the organic compounds that react to form THMs will allow identification of targeted and effective management actions. In this study we evaluated THM precursor contributions from multiple land use categories and hydrologic contexts, including novel data for urban land uses that demonstrate strong potential to release water with high THM formation potential (THMFP; median 618 μg L −1 ): greater than storm runoff integrated across a mixed-use (1/3 natural, 2/3 agricultural) watershed (median 460 μg L −1 ), irrigation runoff from agricultural systems (357 μg L −1 ), or runoff from a natural forested (median 123 μg L −1 ) and shrubland/grassland (median 259 μg L −1 ) watersheds. While individual storm events released high THM precursor concentrations over short periods, dry season agricultural irrigation as well as urban landscapes have the potential to release water high in THM precursors for several months. Experimental bioassays and sampling along 333 miles of the California Aqueduct confirmed bioavailability and photooxidation potential of less than 10% for THM precursors, suggesting that rivers with residence times of days to weeks may act as THM precursor conduits, shuttling THM precursors from hundreds of miles away to drinking water intakes with minimal degradation. This finding has considerable implications for water managers, who may therefore consider THM precursor management strategies that target even sources located far upstream.

California

Dissolved organic matter compositional change and biolability during two storm runoff events in a small sgricultural watershed

Agricultural watersheds are globally pervasive, supporting fundamentally different organic matter source, composition, and concentration profiles in comparison to natural systems. Similar to natural systems, agricultural storm runoff exports large amounts of organic carbon from agricultural land into waterways. But intense management of upper soil layers, waterway channelization, wetland and riparian habitat removal, and postharvest vegetation removal promise to uniquely drive organic matter release to waterways. During a winter first flush and a subsequent storm event, this study investigated the influence of a small agricultural watershed on dissolved organic matter (DOM) source, composition, and biolability. Storm water discharge released strongly terrestrial yet biolabile (23 to 32%) dissolved organic carbon (DOC). Following a 21 day bioassay, a parallel factor analysis identified an 80% reduction in a protein-like (phenylpropyl) component (C2) that was previously correlated to lignin phenol concentration, and a 10% reduction in a humic-like, terrestrially sourced component (C4). Storm-driven releases tripled DOC concentration (from 2.8 to 8.7 mg L −1 ) during the first flush event in comparison to base flow and were terrestrially sourced, with an eightfold increase in vascular plant derived lignin phenols (23.0 to 185 μg L −1 ). As inferred from system hydrology, lignin composition, and nitrate as a groundwater tracer, an initial pulse of dilute water from the upstream watershed caused a counterclockwise DOC hysteresis loop. DOC concentrations peaked after 3.5 days, with the delay between peak discharge and peak DOC attributed to storm water hydrology and a period of initial water repellency of agricultural soils, which delayed DOM leaching.

California

Fluorescence-based proxies for lignin in freshwater dissolved organic matter

Lignin phenols have proven to be powerful biomarkers in environmental studies; however, the complexity of lignin analysis limits the number of samples and thus spatial and temporal resolution in any given study. In contrast, spectrophotometric characterization of dissolved organic matter (DOM) is rapid, noninvasive, relatively inexpensive, requires small sample volumes, and can even be measured in situ to capture fine-scale temporal and spatial detail of DOM cycling. Here we present a series of cross-validated Partial Least Squares models that use fluorescence properties of DOM to explain up to 91% of lignin compositional and concentration variability in samples collected seasonally over 2 years in the Sacramento River/San Joaquin River Delta in California, United States. These models were subsequently used to predict lignin composition and concentration from fluorescence measurements collected during a diurnal study in the San Joaquin River. While modeled lignin composition remained largely unchanged over the diurnal cycle, changes in modeled lignin concentrations were much greater than expected and indicate that the sensitivity of fluorescence-based proxies for lignin may prove invaluable as a tool for selecting the most informative samples for detailed lignin characterization. With adequate calibration, similar models could be used to significantly expand our ability to study sources and processing of DOM in complex surface water systems.

Journal of Geophysical Research G: Biogeosciences

Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L -1 within the Sacramento River to 39.9 mg L -1 at the outfall from an island drain (median 3.0 mg L -1 ), while lignin concentrations ranged from 3.0 &mu;L -1 within the Sacramento River to 111 &mu;L -1 at the outfall from an island drain (median 11.6 &mu;L -1 ). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC) -1 at an island drain to 0.84 mg (100 mg OC) -1 for a wetland (median 0.36 mg (100 mg OC) -1 ), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized landscape features, and is also the first to indicate a significant negative correlation between lignin and DOC bioavailability within environmental samples. Based upon observed trends: (1) Delta features exhibit significant spatial variability in organic chemical composition, and (2) localized Delta features appear to exert strong controls on terrigenous DOC as it passes through the Delta and is exported into the Pacific Ocean.

California