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Daniel H. Doctor

Publications and source records attributed to Daniel H. Doctor.

At least 37 records · Page 2Linked to original sources
USGS2017

Hypogene caves of the central Appalachian Shenandoah Valley in Virginia

Several caves in the Shenandoah Valley in Virginia show evidence for early hypogenic conduit development with later-enhanced solution under partly confined phreatic conditions guided by geologic structures. Many (but not all) of these caves have been subsequently invaded by surface waters as a result of erosion and exhumation. Those not so affected are relict phreatic caves, bearing no relation to modern drainage patterns. Field and petrographic evidence shows that carbonate rocks hosting certain relict phreatic caves were dolomitized and/or silicified by early hydrothermal fluid migration in zones that served to locally enhance rock porosity, thus providing preferential pathways for later solution by groundwater flow, and making the surrounding bedrock more resistant to surficial weathering to result in caves that reside within isolated hills on the land surface. Features suggesting that deep phreatic processes dominated the development of these relict caves include (1) cave passage morphologies indicative of ascending fluids, (2) cave plans of irregular pattern, reflecting early maze or anastomosing development, (3) a general lack of cave breakdown and cave streams or cave stream deposits, and (4) calcite wall and pool coatings within isolated caves intersecting the local water table, and within unroofed caves at topographic locations elevated well above the lo cal base level. Episodes of deep karstification were likely separated by long periods of geologic time, encompassing multiple phases of sedimentary fill and excavation within caves, and reflect a complex history of deep fluid migration that set the stage for later shallow speleogenesis that continues today.

Virginia↗
USGS2017

New insight into the origin of manganese oxide ore deposits in the Appalachian Valley and Ridge of northeastern Tennessee and northern Virginia, USA

Manganese oxide deposits have long been observed in association with carbonates within the Appalachian Mountains, but their origin has remained enigmatic for well over a century. Ore deposits of Mn oxides from several productive sites located in eastern Tennessee and northern Virginia display morphologies that include botryoidal and branching forms, massive nodules, breccia matrix cements, and fracture fills. The primary ore minerals include hollandite, cryptomelane, and romanèchite. Samples of Mn oxides from multiple localities in these regions were analyzed using electron microscopy, X-ray analysis, Fourier transform infrared spectroscopy, and trace and rare earth element (REE) geochemistry. The samples from eastern Tennessee have biological morphologies, contain residual biopolymers, and exhibit REE signatures that suggest the ore formation was due to supergene enrichment (likely coupled with microbial activity). In contrast, several northern Virginia ores hosted within quartz-sandstone breccias exhibit petrographic relations, mineral morphologies, and REE signatures indicating inorganic precipitation, and a likely hydrothermal origin with supergene overprinting. Nodular accumulations of Mn oxides within weathered alluvial deposits that occur close to breccia-hosted Mn deposits in Virginia show geochemical signatures that are distinct from the breccia matrices and appear to reflect remobilization of earlier-emplaced Mn and concentration within supergene traps. Based on the proximity of all of the productive ore deposits to mapped faults or other zones of deformation, we suggest that the primary source of all of the Mn may have been deep seated, and that Mn oxides with supergene and/or biological characteristics resulted from the local remobilization and concentration of this primary Mn.

Tennessee, Virginia↗
USGS2016

Predicting the occurrence of cave-inhabiting fauna based on features of the earth surface environment

One of the most challenging fauna to study in situ is the obligate cave fauna because of the difficulty of sampling. Cave-limited species display patchy and restricted distributions, but it is often unclear whether the observed distribution is a sampling artifact or a true restriction in range. Further, the drivers of the distribution could be local environmental conditions, such as cave humidity, or they could be associated with surface features that are surrogates for cave conditions. If surface features can be used to predict the distribution of important cave taxa, then conservation management is more easily obtained. We examined the hypothesis that the presence of major faunal groups of cave obligate species could be predicted based on features of the earth surface. Georeferenced records of cave obligate amphipods, crayfish, fish, isopods, beetles, millipedes, pseudoscorpions, spiders, and springtails within the area of Appalachian Landscape Conservation Cooperative in the eastern United States (Illinois to Virginia and New York to Alabama) were assigned to 20 x 20 km grid cells. Habitat suitability for these faunal groups was modeled using logistic regression with twenty predictor variables within each grid cell, such as percent karst, soil features, temperature, precipitation, and elevation. Models successfully predicted the presence of a group greater than 65% of the time (mean = 88%) for the presence of single grid cell endemics, and for all faunal groups except pseudoscorpions. The most common predictor variables were latitude, percent karst, and the standard deviation of the Topographic Position Index (TPI), a measure of landscape rugosity within each grid cell. The overall success of these models points to a number of important connections between the surface and cave environments, and some of these, especially soil features and topographic variability, suggest new research directions. These models should prove to be useful tools in predicting the presence of species in understudied areas.

Appalachian Landscape Conservation Cooperative↗
USGS2016

Analysis of hydrologic and geochemical time-series data at James Cave, Virginia: Implications for epikarst influence on recharge in Appalachian karst aquifers

The epikarst, which consists of highly weathered rock in the upper vadose zone of exposed karst systems, plays a critical role in determining the hydrologic and geochemical characteristics of recharge to an underlying karst aquifer. This study utilized time series (2007–2014) of hydrologic and geochemical data of drip water collected within James Cave, Virginia, to examine the influence of epikarst on the quantity and quality of recharge in a mature, doline-dominated karst terrain. Results show a strong seasonality of both hydrology and geochemistry of recharge, which has implications for management of karst aquifers in temperate climatic zones. First, recharge (discharge from the epikarst to the underlying aquifer) reaches a maximum between late winter and early spring, with the onset of the recharge season ranging from as early as December to as late as March during the study period. The timing and duration of the recharge season were found to be a function of precipitation in excess of evapotranspiration on a seasonal time scale. Secondly, seasonally variable residence times for water in the epikarst influence rock-water interaction and, hence, the geochemical characteristics of recharge. Overall, results highlight the strong and complex influence that the epikarst has on karst recharge, which requires long-term and high-resolution data sets to accurately understand and quantify.

Virginia↗
USGS2015

Instrumenting caves to collect hydrologic and geochemical data: case study from James Cave, Virginia

Karst aquifers are productive groundwater systems, supplying approximately 25 % of the world’s drinking water. Sustainable use of this critical water supply requires information about rates of recharge to karst aquifers. The overall goal of this project is to collect long-term, high-resolution hydrologic and geochemical datasets at James Cave, Virginia, to evaluate the quantity and quality of recharge to the karst system. To achieve this goal, the cave has been instrumented for continuous (10-min interval) measurement of the (1) temperature and rate of precipitation; (2) temperature, specific conductance, and rate of epikarst dripwater; (3) temperature of the cave air; and (4) temperature, conductivity, and discharge of the cave stream. Instrumentation has also been installed to collect both composite and grab samples of precipitation, soil water, the cave stream, and dripwater for geochemical analysis. This chapter provides detailed information about the instrumentation, data processing, and data management; shows examples of collected datasets; and discusses recommendations for other researchers interested in hydrologic and geochemical monitoring of cave systems. Results from the research, briefly described here and discussed in more detail in other publications, document a strong seasonality of the start of the recharge season, the extent of the recharge season, and the geochemistry of recharge.

Virginia↗
USGS2015

Karst of the Mid-Atlantic region in Maryland, West Virginia, and Virginia

The Mid-Atlantic region hosts some of the most mature karst landscapes in North America, developed in highly deformed rocks within the Piedmont and Valley and Ridge physiographic provinces. This guide describes a three-day excursion to examine karst development in various carbonate rocks by following Interstate 70 west from Baltimore across the eastern Piedmont, across the Frederick Valley, and into the Great Valley proper. The localities were chosen in order to examine the structural and lithological controls on karst feature development in marble, limestone, and dolostone rocks with an eye toward the implications for ancient landscape evolution, as well as for modern subsidence hazards. A number of caves will be visited, including two commercial caverns that reveal strikingly different histories of speleogenesis. Links between karst landscape development, hydrologic dynamics, and water resource sustainability will also be emphasized through visits to locally important springs. Recent work on quantitative dye tracing, spring water geochemistry, and groundwater modeling reveal the interaction between shallow and deep circulation of groundwater that has given rise to the modern karst landscape. Geologic and karst feature mapping conducted with the benefit of lidar data help reveal the strong bedrock structural controls on karst feature development, and illustrate the utility of geologic maps for assessment of sinkhole susceptibility.

Book chapter↗
USGS2015

Karst mapping in the United States: Past, present and future

The earliest known comprehensive karst map of the entire USA was published by Stringfield and LeGrand (1969), based on compilations of William E. Davies of the U.S. Geological Survey (USGS). Various versions of essentially the same map have been published since. The USGS recently published new digital maps and databases depicting the extent of known karst, potential karst, and pseudokarst areas of the United States of America including Puerto Rico and the U.S. Virgin Islands (Weary and Doctor, 2014). These maps are based primarily on the extent of potentially karstic soluble rock types, and rocks with physical properties conducive to the formation of pseudokarst features. These data were compiled and refined from multiple sources at various spatial resolutions, mostly as digital data supplied by state geological surveys. The database includes polygons delineating areas with potential for karst and that are tagged with attributes intended to facilitate classification of karst regions. Approximately 18% of the surface of the fifty United States is underlain by significantly soluble bedrock. In the eastern United States the extent of outcrop of soluble rocks provides a good first-approximation of the distribution of karst and potential karst areas. In the arid western states, the extent of soluble rock outcrop tends to overestimate the extent of regions that might be considered as karst under current climatic conditions, but the new dataset encompasses those regions nonetheless. This database will be revised as needed, and the present map will be updated as new information is incorporated.

GSA Special Papers↗
USGS2015

Hydrologic and geochemical dynamics of vadose zone recharge in a mantled karst aquifer: Results of monitoring drip waters in Mystery Cave, Minnesota

Caves provide direct access to flows through the vadose zone that recharge karst aquifers. Although many recent studies have documented the highly dynamic processes associated with vadose zone flows in karst settings, few have been conducted in mantled karst settings, such as that of southeastern Minnesota. Here we present some results of a long-term program of cave drip monitoring conducted within Mystery Cave, Minnesota. In this study, two perennial ceiling drip sites were monitored between 1997 and 2001. The sites were located about 90 m (300 ft) apart along the same cave passage approximately 18 m (60 ft) below the surface; 7 to 9 m (20 to 30 ft) of loess and 12 m (40 ft) of flat-lying carbonate bedrock strata overlie the cave. Records of drip rate, electrical conductivity, and water temperature were obtained at 15 minute intervals, and supplemented with periodic sampling for major ion chemistry and water stable isotopes. Patterns in flow and geochemistry emerged at each of the two drip sites that were repeated year after year. Although one site responded relatively quickly (within 2-7 hours) to surface recharge events while the other responded more slowly (within 2-5 days), thresholds of antecedent moisture needed to be overcome in order to produce a discharge response at both sites. The greatest amount of flow was observed at both sites during the spring snowmelt period. Rainfall events less than 10 mm (0.4 in) during the summer months generally did not produce a drip discharge response, yet rapid drip responses were observed following intense storm events after periods of prolonged rainfall. The chemical data from both sites indicate that reservoirs of vadose zone water with distinct chemical signatures mixed during recharge events, and drip chemistry returned to a baseline composition during low flow periods. A reservoir with elevated chloride and sulfate concentrations impacts the slow-response drip site with each recharge event, but does not similarly affect the fast-response drip site. Nitrate concentrations in drip waters were generally less than 4.0 mg/L as NO3- (or less than 1 mg/L as N). Nitrate was either stable or slightly increased with drip rate at the fast-response drip site; in contrast, nitrate concentrations decreased with drip rate at the slow-response drip site.

Conference Paper↗
USGS2015

A semi-automated tool for reducing the creation of false closed depressions from a filled LIDAR-derived digital elevation model

Closed depressions on the land surface can be identified by ‘filling’ a digital elevation model (DEM) and subtracting the filled model from the original DEM. However, automated methods suffer from artificial ‘dams’ where surface streams cross under bridges and through culverts. Removal of these false depressions from an elevation model is difficult due to the lack of bridge and culvert inventories; thus, another method is needed to breach these artificial dams. Here, we present a semi-automated workflow and toolbox to remove falsely detected closed depressions created by artificial dams in a DEM. The approach finds the intersections between transportation routes (e.g., roads) and streams, and then lowers the elevation surface across the roads to stream level allowing flow to be routed under the road. Once the surface is corrected to match the approximate location of the National Hydrologic Dataset stream lines, the procedure is repeated with sequentially smaller flow accumulation thresholds in order to generate stream lines with less contributing area within the watershed. Through multiple iterations, artificial depressions that may arise due to ephemeral flow paths can also be removed. Preliminary results reveal that this new technique provides significant improvements for flow routing across a DEM and minimizes artifacts within the elevation surface. Slight changes in the stream flow lines generally improve the quality of flow routes; however some artificial dams may persist. Problematic areas include extensive road ditches, particularly along divided highways, and where surface flow crosses beneath road intersections. Limitations do exist, and the results partially depend on the quality of data being input. Of 166 manually identified culverts from a previous study by Doctor and Young in 2013, 125 are within 25 m of culverts identified by this tool. After three iterations, 1,735 culverts were identified and cataloged. The result is a reconditioned elevation dataset, which retains the karst topography for further analysis, and a culvert catalog.

Conference Paper↗
USGS2014

Karst geomorphology and hydrology of the Shenandoah Valley near Harrisonburg, Virginia

The karst of the central Shenandoah Valley has characteristics of both shallow and deep phreatic formation. This field guide focuses on the region around Harrisonburg, Virginia, where a number of these karst features and their associated geologic context can be examined. Ancient, widespread alluvial deposits cover much of the carbonate bedrock on the western side of the valley, where shallow karstification has resulted in classical fluviokarst development. However, in upland exposures of carbonate rock, isolated caves exist atop hills not affected by surface processes other than exposure during denudation. The upland caves contain phreatic deposits of calcite and fine-grained sediments. They lack any evidence of having been invaded by surface streams. Recent geologic mapping and LIDAR (light detection and ranging) elevation data have enabled interpretive association between bedrock structure, igneous intrusions, silicification and brecciation of host carbonate bedrock, and the location of several caves and karst springs. Geochemistry, water quality, and water temperature data support the broad categorization of springs into those affected primarily by shallow near-surface recharge, and those sourced deeper in the karst aquifer. The deep-seated karst formation occurred in the distant past where subvertical fracture and fault zones intersect thrust faults and/or cross-strike faults, enabling upwelling of deep-circulating meteoric groundwater. Most caves formed in such settings have been overprinted by later circulation of shallow groundwater, thus removing evidence of the history of earliest inception; however, several caves do preserve evidence of an earlier formation.

Virginia↗
USGS2014

Coupled hydrological and biogeochemical processes controlling variability of nitrogen species in streamflow during autumn in an upland forest

Autumn is a season of dynamic change in forest streams of the northeastern United States due to effects of leaf fall on both hydrology and biogeochemistry. Few studies have explored how interactions of biogeochemical transformations, various nitrogen sources, and catchment flow paths affect stream nitrogen variation during autumn. To provide more information on this critical period, we studied (1) the timing, duration, and magnitude of changes to stream nitrate, dissolved organic nitrogen (DON), and ammonium concentrations; (2) changes in nitrate sources and cycling; and (3) source areas of the landscape that most influence stream nitrogen. We collected samples at higher temporal resolution for a longer duration than typical studies of stream nitrogen during autumn. This sampling scheme encompassed the patterns and extremes that occurred during base flow and stormflow events of autumn. Base flow nitrate concentrations decreased by an order of magnitude from 5.4 to 0.7 µmol L −1 during the week when most leaves fell from deciduous trees. Changes to rates of biogeochemical transformations during autumn base flow explained the low nitrate concentrations; in-stream transformations retained up to 72% of the nitrate that entered a stream reach. A decrease of in-stream nitrification coupled with heterotrophic nitrate cycling were primary factors in the seasonal nitrate decline. The period of low nitrate concentrations ended with a storm event in which stream nitrate concentrations increased by 25-fold. In the ensuing weeks, peak stormflow nitrate concentrations progressively decreased over closely spaced, yet similarly sized events. Most stormflow nitrate originated from nitrification in near-stream areas with occasional, large inputs of unprocessed atmospheric nitrate, which has rarely been reported for nonsnowmelt events. A maximum input of 33% unprocessed atmospheric nitrate to the stream occurred during one event. Large inputs of unprocessed atmospheric nitrate show direct and rapid effects on forest streams that may be widespread, although undocumented, throughout nitrogen-polluted temperate forests. In contrast to a week-long nitrate decline during peak autumn litterfall, base flow DON concentrations increased after leaf fall and remained high for 2 months. Dissolved organic nitrogen was hydrologically flushed to the stream from riparian soils during stormflow. In contrast to distinct seasonal changes in base flow nitrate and DON concentrations, ammonium concentrations were typically at or below the detection limit, similar to the rest of the year. Our findings reveal couplings among catchment flow paths, nutrient sources, and transformations that control seasonal extremes of stream nitrogen in forested landscapes.

Vermont↗
USGS2014

Karst in the United States: A digital map compilation and database

This report describes new digital maps delineating areas of the United States, including Puerto Rico and the U.S. Virgin Islands, having karst or the potential for development of karst and pseudokarst. These maps show areas underlain by soluble rocks and also by volcanic rocks, sedimentary deposits, and permafrost that have potential for karst or pseudokarst development. All 50 States contain rocks with potential for karst development, and about 18 percent of their area is underlain by soluble rocks having karst or the potential for development of karst features. The areas of soluble rocks shown are based primarily on selection from State geologic maps of rock units containing significant amounts of carbonate or evaporite minerals. Areas underlain by soluble rocks are further classified by general climate setting, degree of induration, and degree of exposure. Areas having potential for volcanic pseudokarst are those underlain chiefly by basaltic-flow rocks no older than Miocene in age. Areas with potential for pseudokarst features in sedimentary rocks are in relatively unconsolidated rocks from which pseudokarst features, such as piping caves, have been reported. Areas having potential for development of thermokarst features, mapped exclusively in Alaska, contain permafrost in relatively thick surficial deposits containing ground ice. This report includes a GIS database with links from the map unit polygons to online geologic unit descriptions.

Open-File Report↗
USGS2014

Automated determination of the stable carbon isotopic composition (δ 13 C) of total dissolved inorganic carbon (DIC) and total nonpurgeable dissolved organic carbon (DOC) in aqueous samples: RSIL lab codes 1851 and 1852

The purposes of the Reston Stable Isotope Laboratory (RSIL) lab codes 1851 and 1852 are to determine the total carbon mass and the ratio of the stable isotopes of carbon (δ 13 C) for total dissolved inorganic carbon (DIC, lab code 1851) and total nonpurgeable dissolved organic carbon (DOC, lab code 1852) in aqueous samples. The analysis procedure is automated according to a method that utilizes a total carbon analyzer as a peripheral sample preparation device for analysis of carbon dioxide (CO 2 ) gas by a continuous-flow isotope ratio mass spectrometer (CF-IRMS). The carbon analyzer produces CO 2 and determines the carbon mass in parts per million (ppm) of DIC and DOC in each sample separately, and the CF-IRMS determines the carbon isotope ratio of the produced CO 2 . This configuration provides a fully automated analysis of total carbon mass and δ 13 C with no operator intervention, additional sample preparation, or other manual analysis. To determine the DIC, the carbon analyzer transfers a specified sample volume to a heated (70 °C) reaction vessel with a preprogrammed volume of 10% phosphoric acid (H 3 PO 4 ), which allows the carbonate and bicarbonate species in the sample to dissociate to CO 2 . The CO 2 from the reacted sample is subsequently purged with a flow of helium gas that sweeps the CO 2 through an infrared CO 2 detector and quantifies the CO 2 . The CO 2 is then carried through a high-temperature (650 °C) scrubber reactor, a series of water traps, and ultimately to the inlet of the mass spectrometer. For the analysis of total dissolved organic carbon, the carbon analyzer performs a second step on the sample in the heated reaction vessel during which a preprogrammed volume of sodium persulfate (Na 2 S 2 O 8 ) is added, and the hydroxyl radicals oxidize the organics to CO 2 . Samples containing 2 ppm to 30,000 ppm of carbon are analyzed. The precision of the carbon isotope analysis is within 0.3 per mill for DIC, and within 0.5 per mill for DOC.

Techniques and Methods↗
USGS2013

Comparison of age distributions estimated from environmental tracers by using binary-dilution and numerical models of fractured and folded karst: Shenandoah Valley of Virginia and West Virginia, USA

Measured concentrations of environmental tracers in spring discharge from a karst aquifer in the Shenandoah Valley, USA, were used to refine a numerical groundwater flow model. The karst aquifer is folded and faulted carbonate bedrock dominated by diffuse flow along fractures. The numerical model represented bedrock structure and discrete features (fault zones and springs). Concentrations of 3 H, 3 He, 4 He, and CFC-113 in spring discharge were interpreted as binary dilutions of young (0–8 years) water and old (tracer-free) water. Simulated mixtures of groundwater are derived from young water flowing along shallow paths, with the addition of old water flowing along deeper paths through the model domain that discharge to springs along fault zones. The simulated median age of young water discharged from springs (5.7 years) is slightly older than the median age estimated from 3 H/ 3 He data (4.4 years). The numerical model predicted a fraction of old water in spring discharge (0.07) that was half that determined by the binary-dilution model using the 3 H/ 3 He apparent age and 3 H and CFC-113 data (0.14). This difference suggests that faults and lineaments are more numerous or extensive than those mapped and included in the numerical model.

Virginia;West Virginia↗
USGS2013

An evaluation of automated GIS tools for delineating karst sinkholes and closed depressions from 1-meter LIDAR-derived digital elevation data

LiDAR (Light Detection and Ranging) surveys of karst terrains provide high-resolution digital elevation models (DEMs) that are particularly useful for mapping sinkholes. In this study, we used automated processing tools within ArcGIS (v. 10.0) operating on a 1.0 m resolution LiDAR DEM in order to delineate sinkholes and closed depressions in the Boyce 7.5 minute quadrangle located in the northern Shenandoah Valley of Virginia. The results derived from the use of the automated tools were then compared with depressions manually delineated by a geologist. Manual delineation of closed depressions was conducted using a combination of 1.0 m DEM hillshade, slopeshade, aerial imagery, and Topographic Position Index (TPI) rasters. The most effective means of visualizing depressions in the GIS was using an overlay of the partially transparent TPI raster atop the slopeshade raster at 1.0 m resolution. Manually identified depressions were subsequently checked using aerial imagery to screen for false positives, and targeted ground-truthing was undertaken in the field. The automated tools that were utilized include the routines in ArcHydro Tools (v. 2.0) for prescreening, evaluating, and selecting sinks and depressions as well as thresholding, grouping, and assessing depressions from the TPI raster. Results showed that the automated delineation of sinks and depressions within the ArcHydro tools was highly dependent upon pre-conditioning of the DEM to produce "hydrologically correct" surface flow routes. Using stream vectors obtained from the National Hydrologic Dataset alone to condition the flow routing was not sufficient to produce a suitable drainage network, and numerous artificial depressions were generated where roads, railways, or other manmade structures acted as flow barriers in the elevation model. Additional conditioning of the DEM with drainage paths across these barriers was required prior to automated 2delineation of sinks and depressions. In regions where the DEM had been properly conditioned, the tools for automated delineation performed reasonably well as compared to the manually delineated depressions, but generally overestimated the number of depressions thus necessitating manual filtering of the final results. Results from the TPI thresholding analysis were not dependent on DEM pre-conditioning, but the ability to extract meaningful depressions depended on careful assessment of analysis scale and TPI thresholding.

Conference Paper↗
USGS2012

Spatial analysis of geologic and hydrologic features relating to sinkhole occurrence in Jefferson County, West Virginia

In this study the influence of geologic features related to sinkhole susceptibility was analyzed and the results were mapped for the region of Jefferson County, West Virginia. A model of sinkhole density was constructed using Geographically Weighted Regression (GWR) that estimated the relations among discrete geologic or hydrologic features and sinkhole density at each sinkhole location. Nine conditioning factors on sinkhole occurrence were considered as independent variables: distance to faults, fold axes, fracture traces oriented along bedrock strike, fracture traces oriented across bedrock strike, ponds, streams, springs, quarries, and interpolated depth to groundwater. GWR model parameter estimates for each variable were evaluated for significance, and the results were mapped. The results provide visual insight into the influence of these variables on localized sinkhole density, and can be used to provide an objective means of weighting conditioning factors in models of sinkhole susceptibility or hazard risk.

West Virginia↗
USGS2011

How reservoirs alter drinking water quality: Organic matter sources, sinks, and transformations

Within reservoirs, production, transformation, and loss of dissolved organic matter (DOM) occur simultaneously. While the balance between production and loss determines whether a reservoir is a net sink or source of DOM, changes in chemical composition are also important because they affect DOM reactivity with respect to disinfection by-product (DBP) formation. The composition of the DOM pool also provides insight into DOM sources and processing, which can inform reservoir management. We examined the concentration and composition of DOM in San Luis Reservoir, a large off-stream impoundment of the California State Water Project. We used a wide array of DOM chemical tracers including dissolved organic carbon (DOC) concentration, trihalomethane and haloacetic acid formation potentials (THMFP and HAAFP, respectively), absorbance properties, isotopic composition, lignin phenol content, and structural groupings determined by 13 C nuclear magnetic resonance (NMR). There were periods when the reservoir was a net source of DOC due to the predominance of algal production (summer), a net sink due to the predominance of degradation (fall–winter), and balanced between production and consumption (spring). Despite only moderate variation in bulk DOC concentration (3.0–3.6 mg C/L), changes in DOM composition indicated that terrestrial-derived material entering the reservoir was being degraded and replaced by aquatic-derived DOM produced within the reservoir. Substantial changes in the propensity of the DOM pool to form THMs and HAAs illustrate that the DBP precursor pool was not directly coupled to bulk DOC concentration and indicate that algal production is an important source of DBP precursors. Results suggest reservoirs have the potential to attenuate DOM amount and reactivity with respect to DBP precursors via degradative processes; however, these benefits can be decreased or even negated by the production of algal-derived DOM.

California↗