Water-soluble organic carbon release from mineral soils and sediments in an irrigated agricultural system.

Water interactions with soil and vegetation are greatly altered in agricultural watersheds compared to natural landscapes, which impacts sources and fates of organic carbon (OC). While mineral soil horizons in natural ecosystems primarily act as filters for dissolved organic carbon (DOC) leached from organic surface horizons, tilled soils largely lack an organic horizon and their mineral horizons therefore act as a source for both DOC and sediment to surface waters. Irrigated watersheds highlight this difference, as DOC and total suspended sediment (TSS) concentrations simultaneously increase during the low-discharge irrigation season, suggesting that sediment-associated OC may constitute a significant source of DOC. While water-soluble OC (WSOC) from sediments and soils has been found to be compositionally similar to stream DOC, these contributions remain poorly quantified in agricultural streams. To address this, we conducted abiotic solubilization experiments using sediments (suspended and bed) and soils from an irrigated agricultural watershed in northern California, USA. Sediments (R2 > 0.99) and soils (0.74 < R2 < 0.89) displayed linear solubilization behaviors over the range of concentrations tested. Suspended sediment from the irrigation season exhibited the largest solubilization efficiency (10.9 ± 1.6% TOCsediment solubilized) and potential (1.79 ± 0.26 mg WSOC g-1 dry sediment), followed by suspended sediment from a winter storm, then bed sediment and soils. Successive solubilization experiments increased the total release of WSOC by ∼50%, but most (88-97%) of the solid-phase OC remained insoluble in water. Using these solubilization potential estimates and measured TSS concentrations, we estimated that WSOC from suspended sediment in streams represented 4-7% of the annual DOC export from the watershed. However, field sediment export is much higher than what is represented by suspended sediment in the water column, therefore field-scale contributions from sediments could be much higher than estimated.

Decline in Thermal Habitat Conditions for the Endangered Delta Smelt as Seen from Landsat Satellites (1985-2019).

This study uses Landsat 5, 7, and 8 level 2 collection 2 surface temperature to examine habitat suitability conditions spanning 1985-2019, relative to the thermal tolerance of the endemic and endangered delta smelt (Hypomesus transpacificus) and two non-native fish, the largemouth bass (Micropterus salmoides) and Mississippi silverside (Menidia beryllina) in the upper San Francisco Estuary. This product was validated using thermal radiometer data collected from 2008 to 2019 from a validation site on a platform in the Salton Sea (RMSE = 0.78 °C, r = 0.99, R2 = 0.99, p < 0.01, and n = 237). Thermally unsuitable habitat, indicated by annual maximum water surface temperatures exceeding critical thermal maximum temperatures for each species, increased by 1.5 km2 yr-1 for the delta smelt with an inverse relationship to the delta smelt abundance index from the California Department of Fish and Wildlife (r = -0.44, R2 = 0.2, p < 0.01). Quantile and Theil-Sen regression showed that the delta smelt are unable to thrive when the thermally unsuitable habitat exceeds 107 km2. A habitat unsuitable for the delta smelt but survivable for the non-natives is expanding by 0.82 km2 yr-1. Warming waters in the San Francisco Estuary are reducing the available habitat for the delta smelt.

Optical Properties of Water for Prediction of Wastewater Contamination, Human-Associated Bacteria, and Fecal Indicator Bacteria in Surface Water at Three Watershed Scales.

Relations between spectral absorbance and fluorescence properties of water and human-associated and fecal indicator bacteria were developed for facilitating field sensor applications to estimate wastewater contamination in waterways. Leaking wastewater conveyance infrastructure commonly contaminates receiving waters. Methods to quantify such contamination can be time consuming, expensive, and often nonspecific. Human-associated bacteria are wastewater specific but require discrete sampling and laboratory analyses, introducing latency. Human sewage has fluorescence and absorbance properties different than those of natural waters. To assist real-time field sensor development, this study investigated optical properties for use as surrogates for human-associated bacteria to estimate wastewater prevalence in environmental waters. Three spatial scales were studied: Eight watershed-scale sites, five subwatershed-scale sites, and 213 storm sewers and open channels within three small watersheds (small-scale sites) were sampled (996 total samples) for optical properties, human-associated bacteria, fecal indicator bacteria, and, for selected samples, human viruses. Regression analysis indicated that bacteria concentrations could be estimated by optical properties used in existing field sensors for watershed and subwatershed scales. Human virus occurrence increased with modeled human-associated bacteria concentration, providing confidence in these regressions as surrogates for wastewater contamination. Adequate regressions were not found for small-scale sites to reliably estimate bacteria concentrations likely due to inconsistent local sanitary sewer inputs.

Monitoring Turbidity in San Francisco Estuary and Sacramento-San Joaquin Delta Using Satellite Remote Sensing.

This study utilizes satellite data to investigate water quality conditions in the San Francisco Estuary and its upstream delta, the Sacramento-San Joaquin River Delta. To do this, this study derives turbidity from the European Space Agency satellite Sentinel-2 acquired from September 2015 to June 2019 and conducts a rigorous validation with in situ measurements of turbidity from optical sensors at continuous monitoring stations. This validation includes 965 matchup comparisons between satellite and in situ sensor data across 22 stations, yielding R 2 = 0.63 and 0.75 for Nephelometric Turbidity Unit and Formazin Nephelometric Unit (FNU) stations, respectively. This study then applies remote sensing to evaluate patterns in turbidity during the Suisun Marsh Salinity Control Gates Action ("Gates action"), a pilot study designed to increase habitat access and quality for the endangered Delta Smelt. The basic strategy was to direct more freshwater into Suisun Marsh, creating more low salinity habitat that would then have higher (and more suitable) turbidity than upstream river channels. For all seven acquisitions considered from June 29 to September 27, 2018, turbidity conditions in Bays and Sloughs subregions were consistently higher (and more suitable) (26-47 FNU) than what was observed in the upstream River region (13-25 FNU). This overall pattern was observed when comparing images acquired during similar tidal stages and heights.

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.

Spatial variability of phytoplankton in a shallow tidal freshwater system reveals complex controls on abundance and community structure.

Estuaries worldwide are undergoing changes to patterns of aquatic productivity because of human activities that alter flow, impact sediment delivery and thus the light field, and contribute nutrients and contaminants like pesticides and metals. These changes can influence phytoplankton communities, which in turn can alter estuarine food webs. We used multiple approaches-including high-resolution water quality mapping, synoptic sampling, productivity and nitrogen uptake rates, Lagrangian parcel tracking, enclosure experiments and bottle incubations-over a short time period to take a "spatial snapshot" of conditions in the northern region of the San Francisco Estuary (California, USA) to examine how environmental drivers like light availability, nutrients, water residence time, and contaminants affect phytoplankton abundance and community attributes like size distribution, taxonomic structure, and nutrient uptake rates. Zones characterized by longer residence time (15-60 days) had higher chlorophyll-a concentrations (9 ±â€¯4 µg L-1) and were comprised primarily of small phytoplankton cells (<5 µm, 74 ±â€¯8%), lower ammonium concentrations (1 ±â€¯0.8 µM), higher nitrate uptake rates, and higher rates of potential carbon productivity. Conversely, zones characterized by shorter residence time (1-14 days) had higher ammonium concentration (13 ±â€¯5 µM) and lower chlorophyll-a concentration (5 ±â€¯1 µg L-1) with diatoms making up a larger percent contribution. Longer residence time, however, did not result in the accumulation of large (>5 µm) cells considered important to pelagic food webs. Rather, longer residence time zones had a phytoplankton community comprised primarily of small cells, particularly picocyanobacteria that made up 38 ±â€¯17% of the chlorophyll-a - nearly double the concentration seen in shorter residence time zones (22 ±â€¯7% picocyanobacterial of chlorophyll-a). Our results suggest that water residence time in estuaries may have an effect as large or larger than that experimentally demonstrated for light, contaminants, or nutrients.

Effects of solid-liquid separation and storage on monensin attenuation in dairy waste management systems.

Environmental release of veterinary pharmaceuticals has been of regulatory concern for more than a decade. Monensin is a feed additive antibiotic that is prevalent throughout the dairy industry and is excreted in dairy waste. This study investigates the potential of dairy waste management practices to alter the amount of monensin available for release into the environment. Analysis of wastewater and groundwater from two dairy farms in California consistently concluded that monensin is most present in lagoon water and groundwater downgradient of lagoons. Since the lagoons represent a direct source of monensin to groundwater, the effect of waste management, by mechanical screen separation and lagoon aeration, on aqueous monensin concentration was investigated through construction of lagoon microcosms. The results indicate that monensin attenuation is not improved by increased solid-liquid separation prior to storage in lagoons, as monensin is rapidly desorbed after dilution with water. Monensin is also shown to be easily degraded in lagoon microcosms receiving aeration, but is relatively stable and available for leaching under typical anaerobic lagoon conditions.

Using Continuous Underway Isotope Measurements To Map Water Residence Time in Hydrodynamically Complex Tidal Environments.

Stable isotopes present in water (δ2H, δ18O) have been used extensively to evaluate hydrological processes on the basis of parameters such as evaporation, precipitation, mixing, and residence time. In estuarine aquatic habitats, residence time (τ) is a major driver of biogeochemical processes, affecting trophic subsidies and conditions in fish-spawning habitats. But τ is highly variable in estuaries, owing to constant changes in river inflows, tides, wind, and water height, all of which combine to affect τ in unpredictable ways. It recently became feasible to measure δ2H and δ18O continuously, at a high sampling frequency (1 Hz), using diffusion sample introduction into a cavity ring-down spectrometer. To better understand the relationship of τ to biogeochemical processes in a dynamic estuarine system, we continuously measured δ2H and δ18O, nitrate and water quality parameters, on board a small, high-speed boat (5 to >10 m s-1) fitted with a hull-mounted underwater intake. We then calculated τ as is classically done using the isotopic signals of evaporation. The result was high-resolution (∼10 m) maps of residence time, nitrate, and other parameters that showed strong spatial gradients corresponding to geomorphic attributes of the different channels in the area. The mean measured value of τ was 30.5 d, with a range of 0-50 d. We used the measured spatial gradients in both τ and nitrate to calculate whole-ecosystem uptake rates, and the values ranged from 0.006 to 0.039 d-1. The capability to measure residence time over single tidal cycles in estuaries will be useful for evaluating and further understanding drivers of phytoplankton abundance, resolving differences attributable to mixing and water sources, explicitly calculating biogeochemical rates, and exploring the complex linkages among time-dependent biogeochemical processes in hydrodynamically complex environments such as estuaries.

High-Resolution Remote Sensing of Water Quality in the San Francisco Bay-Delta Estuary.

The San Francisco Bay-Delta Estuary watershed is a major source of freshwater for California and a profoundly human-impacted environment. The water quality monitoring that is critical to the management of this important water resource and ecosystem relies primarily on a system of fixed water-quality monitoring stations, but the limited spatial coverage often hinders understanding. Here, we show how the latest technology in visible/near-infrared imaging spectroscopy can facilitate water quality monitoring in this highly dynamic and heterogeneous system by enabling simultaneous depictions of several water quality indicators at very high spatial resolution. The airborne portable remote imaging spectrometer (PRISM) was used to derive high-spatial-resolution (2.6 × 2.6 m) distributions of turbidity, and dissolved organic carbon (DOC) and chlorophyll-a concentrations in a wetland-influenced region of this estuary. A filter-passing methylmercury vs DOC relationship was also developed using in situ samples and enabled the high-spatial-resolution depiction of surface methylmercury concentrations in this area. The results illustrate how high-resolution imaging spectroscopy can inform management and policy development in important inland and estuarine water bodies by facilitating the detection of point- and nonpoint-source pollution, and by providing data to help assess the complex impacts of wetland restoration and climate change on water quality and ecosystem productivity.

Mississippi River nitrate loads from high frequency sensor measurements and regression-based load estimation.

Accurately quantifying nitrate (NO3-) loading from the Mississippi River is important for predicting summer hypoxia in the Gulf of Mexico and targeting nutrient reduction within the basin. Loads have historically been modeled with regression-based techniques, but recent advances with high frequency NO3- sensors allowed us to evaluate model performance relative to measured loads in the lower Mississippi River. Patterns in NO3- concentrations and loads were observed at daily to annual time steps, with considerable variability in concentration-discharge relationships over the two year study. Differences were particularly accentuated during the 2012 drought and 2013 flood, which resulted in anomalously high NO3- concentrations consistent with a large flush of stored NO3- from soil. The comparison between measured loads and modeled loads (LOADEST, Composite Method, WRTDS) showed underestimates of only 3.5% across the entire study period, but much larger differences at shorter time steps. Absolute differences in loads were typically greatest in the spring and early summer critical to Gulf hypoxia formation, with the largest differences (underestimates) for all models during the flood period of 2013. In additional to improving the accuracy and precision of monthly loads, high frequency NO3- measurements offer additional benefits not available with regression-based or other load estimation techniques.

Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter.

Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5×10(-3)m(2)mol(-1) (s.d. 3.5×10(-3)) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg-DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

Dissolved organic matter reduces algal accumulation of methylmercury.

Dissolved organic matter (DOM) significantly decreased accumulation of methylmercury (MeHg) by the diatom Cyclotella meneghiniana in laboratory experiments. Live diatom cells accumulated two to four times more MeHg than dead cells, indicating that accumulation may be partially an energy-requiring process. Methylmercury enrichment in diatoms relative to ambient water was measured by a volume concentration factor (VCF). Without added DOM, the maximum VCF was 32 × 10(4) , and the average VCF (from 10 to 72 h) over all experiments was 12.6 × 10(4) . At very low (1.5 mg/L) added DOM, VCFs dropped by approximately half. At very high (20 mg/L) added DOM, VCFs dropped 10-fold. Presumably, MeHg was bound to a variety of reduced sulfur sites on the DOM, making it unavailable for uptake. Diatoms accumulated significantly more MeHg when exposed to transphilic DOM extracts than hydrophobic ones. However, algal lysate, a labile type of DOM created by resuspending a marine diatom in freshwater, behaved similarly to a refractory DOM isolate from San Francisco Bay. Addition of 67 µM L-cysteine resulted in the largest drop in VCFs, to 0.28 × 10(4) . Although the DOM composition influenced the availability of MeHg to some extent, total DOM concentration was the most important factor in determining algal bioaccumulation of MeHg.

Tidally driven export of dissolved organic carbon, total mercury, and methylmercury from a mangrove-dominated estuary.

The flux of dissolved organic carbon (DOC) from mangrove swamps accounts for 10% of the global terrestrial flux of DOC to coastal oceans. Recent findings of high concentrations of mercury (Hg) and methylmercury (MeHg) in mangroves, in conjunction with the common co-occurrence of DOC and Hg species, have raised concerns that mercury fluxes may also be large. We used a novel approach to estimate export of DOC, Hg, and MeHg to coastal waters from a mangrove-dominated estuary in Everglades National Park (Florida, USA). Using in situ measurements of fluorescent dissolved organic matter as a proxy for DOC, filtered total Hg, and filtered MeHg, we estimated the DOC yield to be 180 (±12.6) g C m(-2) yr(-1), which is in the range of previously reported values. Although Hg and MeHg yields from tidal mangrove swamps have not been previously measured, our estimated yields of Hg species (28 ± 4.5 µg total Hg m(-2) yr(-1) and 3.1 ± 0.4 µg methyl Hg m(-2) yr(-1)) were five times greater than is typically reported for terrestrial wetlands. These results indicate that in addition to the well documented contributions of DOC, tidally driven export from mangroves represents a significant potential source of Hg and MeHg to nearby coastal waters.

Use and environmental occurrence of antibiotics in freestall dairy farms with manured forage fields.

Environmental releases of antibiotics from concentrated animal feeding operations (CAFOs) are of increasing regulatory concern. This study investigates the use and occurrence of antibiotics in dairy CAFOs and their potential transport into first-encountered groundwater. On two dairies we conducted four seasonal sampling campaigns, each across 13 animal production and waste management systems and associated environmental pathways: application to animals, excretion to surfaces, manure collection systems, soils, and shallow groundwater. Concentrations of antibiotics were determined using on line solid phase extraction (OLSPE) and liquid chromatography-tandem mass spectrometry (LC/MS/MS) with electrospray ionization (ESI) for water samples, and accelerated solvent extraction (ASE) LC/MS/MS with ESI for solid samples. A variety of antibiotics were applied at both farms leading to antibiotics excretion of several hundred grams per farm per day. Sulfonamides, tetracyclines, and their epimers/isomers, and lincomycin were most frequently detected. Yet, despite decades of use, antibiotic occurrence appeared constrained to within farm boundaries. The most frequent antibiotic detections were associated with lagoons, hospital pens, and calf hutches. When detected below ground, tetracyclines were mainly found in soils, whereas sulfonamides were found in shallow groundwater reflecting key differences in their physicochemical properties. In manure lagoons, 10 compounds were detected including tetracyclines and trimethoprim. Of these 10, sulfadimethoxine, sulfamethazine, and lincomycin were found in shallow groundwater directly downgradient from the lagoons. Antibiotics were sporadically detected in field surface samples on fields with manure applications, but not in underlying sandy soils. Sulfadimethoxine and sulfamethazine were detected in shallow groundwater near field flood irrigation gates, but at highly attenuated levels.

Microbial degradation of plant leachate alters lignin phenols and trihalomethane precursors.

Although the importance of vascular plant-derived dissolved organic carbon (DOC) in freshwater systems has been studied, the role of leached DOC as precursors of disinfection byproducts (DBPs) during drinking water treatment is not well known. Here we measured the propensity of leachates from four crops and four aquatic macrophytes to form trihalomethanes (THMs)-a regulated class of DBPs-before and after 21 d of microbial degradation. We also measured lignin phenol content and specific UV absorbance (SUVA(254)) to test the assumption that aromatic compounds from vascular plants are resistant to microbial degradation and readily form DBPs. Leaching solubilized 9 to 26% of total plant carbon, which formed 1.93 to 6.72 mmol THM mol C(-1). However, leachate DOC concentrations decreased by 85 to 92% over the 21-d incubation, with a concomitant decrease of 67 to 92% in total THM formation potential. Carbon-normalized THM yields in the residual DOC pool increased by 2.5 times on average, consistent with the preferential uptake of nonprecursor material. Lignin phenol concentrations decreased by 64 to 96% over 21 d, but a lack of correlation between lignin content and THM yields or SUVA(254) suggested that lignin-derived compounds are not the source of increased THM precursor yields in the residual DOC pool. Our results indicate that microbial carbon utilization alters THM precursors in ecosystems with direct plant leaching, but more work is needed to identify the specific dissolved organic matter components with a greater propensity to form DBPs and affect watershed management, drinking water quality, and human health.

Determining sources of dissolved organic carbon and disinfection byproduct precursors to the McKenzie River, Oregon.

This study was conducted to determine the main sources of dissolved organic carbon (DOC) and disinfection byproduct (DBP) precursors to the McKenzie River, Oregon (USA). Water samples collected from the mainstem, tributaries, and reservoir outflows were analyzed for DOC concentration and DBP formation potentials (trihalomethanes [THMFPs] and haloacetic acids [HAAFPs]). In addition, optical properties (absorbance and fluorescence) of dissolved organic matter (DOM) were measured to provide insight into DOM composition and assess whether optical properties are useful proxies for DOC and DBP precursor concentrations. Optical properties indicative of composition suggest that DOM in the McKenzie River mainstem was primarily allochthonous--derived from soils and plant material in the upstream watershed. Downstream tributaries had higher DOC concentrations than mainstem sites (1.6 +/- 0.4 vs. 0.7 +/- 0.3 mg L(-1)) but comprised < 5% ofmainstem flows and had minimal effect on overall DBP precursor loads. Water exiting two large upstream reservoirs also had higher DOC concentrations than the mainstem site upstream of the reservoirs, but optical data did not support in situ algal production as a source of the added DOC during the study. Results suggest that the first major rain event in the fall contributes DOM with high DBP precursor content. Although there was interference in the absorbance spectra in downstream tributary samples, fluorescence data were strongly correlated to DOC concentration (R2 = 0.98), THMFP (R2 = 0.98), and HAAFP (R2 = 0.96). These results highlight the value of using optical measurements for identifying the concentration and sources of DBP precursors in watersheds, which will help drinking water utilities improve source water monitoring and management programs.

Environmental occurrence and shallow ground water detection of the antibiotic monensin from dairy farms.

Pharmaceuticals used in animal feeding operations have been detected in various environmental settings. There is a growing concern about the impact on terrestrial and aquatic organisms and the development of antibiotic-resistant strains of microorganisms. Pharmaceutical use in milking cows is relatively limited compared with other livestock operations, except for the ionophore monensin, which is given to lactating cows as a feed. By weight, monensin can be the most significant antibiotic used in a dairy farm. This study investigates the potential of monensin to move from dairy operations into the surrounding ground water. Using two dairy farms in California as study sites, we twice collected samples along the environmental pathway-from flush lanes, lagoon waters, and shallow ground water beneath the dairies and beneath its associated manured fields. Monensin concentrations were determined using solid-phase extraction and liquid chromatography-tandem mass spectrometry with positive electrospray ionization. Monensin was detected in all of the flush lane and lagoon water samples. Theoretical maximum concentration estimated from the actual dosing rate and the theoretical excretion rate assuming no attenuation was one order of magnitude greater than observed concentrations, suggesting significant attenuation in the manure collection and storage system. Monensin was also detected, at levels ranging from 0.04 to 0.39 microg L(-1), in some of the ground water samples underneath the production area of the dairy but not from the adjacent manured fields. Concentrations in ground water immediately downgradient of the lagoons were one to two orders of magnitude lower than the concentrations detected in lagoons, suggesting attenuation in the subsurface. The data suggest the possibility of monensin transport into shallow (2-5 m) alluvial ground water from dairy management units, including manure storage lagoons and freestalls occupied by heifers, lactating cows, and dry cows.

Land management impacts on dairy-derived dissolved organic carbon in ground water.

Dairy operations have the potential to elevate dissolved organic carbon (DOC) levels in ground water, where it may interact with organic and inorganic contaminants, fuel denitrification, and may present problems for drinking water treatment. Total and percent bioavailable DOC and total and carbon-specific trihalomethane (THM) formation potential (TTHMFP and STHMFP, respectively) were determined for shallow ground water samples from beneath a dairy farm in the San Joaquin Valley, California. Sixteen wells influenced by specific land management areas were sampled over 3 yr. Measured DOC concentrations were significantly elevated over the background as measured at an upgradient monitoring well, ranging from 13 to 55 mg L(-1) in wells downgradient from wastewater ponds, 8 to 30 mg L(-1) in corral wells, 5 to 12 mg L(-1) in tile drains, and 4 to 15 mg L(-1) in wells associated with manured fields. These DOC concentrations were at the upper range or greatly exceeded concentrations in most surface water bodies used as drinking water sources in California. DOC concentrations in individual wells varied by up to a factor of two over the duration of this study, indicating a dynamic system of sources and degradation. DOC bioavailability over 21 d ranged from 3 to 10%, comparable to surface water systems and demonstrating the potential for dairy-derived DOC to influence dissolved oxygen concentrations (nearly all wells were hypoxic to anoxic) and denitrification. TTHMFP measurements across all management units ranged from 141 to 1731 microg L(-1), well in excess of the maximum contaminant level of 80 microg L(-1) established by the Environmental Protection Agency. STHMFP measurements demonstrated over twofold variation ( approximately 4 to approximately 8 mmol total THM/mol DOC) across the management areas, indicating the dependence of reactivity on DOC composition. The results indicate that land management strongly controls the quantity and quality of DOC to reach shallow ground water and hence should be considered when managing ground water resources and in any efforts to mitigate contamination of ground water with carbon-based contaminants, such as pesticides and pharmaceuticals.

Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon.

Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.