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Brian A. Bergamaschi

Publications and source records attributed to Brian A. Bergamaschi.

At least 73 records · Page 4Linked to original sources

DOM composition in an agricultural watershed: assessing patterns and variability in the context of spatial scales

Willow Slough, a seasonally irrigated agricultural watershed in the Sacramento River valley, California, was sampled synoptically in order to investigate the extent to which dissolved organic carbon (DOC) concentrations and compositions from throughout the catchment are represented at the mouth. DOC concentrations ranged from 1.8 to 13.9 mg L −1 , with the lowest values in headwater 1st and 2nd order streams, and the highest values associated with flood irrigation. Carbon-normalized vanillyl phenols varied from 0.05 to 0.67 mg 100 mg OC −1 (0.37 mean), indicative of considerable contributions from vascular plants. DOC concentrations and compositions at the mouth appear to be primarily influenced by land use (agriculture) in the lower reaches, and therefore very little of the headwater chemistry (1st and 2nd order streams) can be discerned from the chemistry at or near the mouth (3rd and 4th order streams), indicating the need for synoptic sampling to capture the breadth of organic carbon cycling within a catchment. Field sampling during irrigation showed the large impact that flood irrigation can have on DOC concentrations and compositions, likely a primary cause of significantly elevated Willow Slough DOC concentrations during the summer irrigation season. Optical proxies exhibited varying degrees of correlation with chemical measurements, with strongest relationships to DOC and dissolved lignin ( r 2 = 0.95 and 0.73, respectively) and weaker relationships to carbon-normalized lignin yields and C:V ( r 2 from 0.31 to 0.42). Demonstrating the importance of matching scale to processes, we found no relationship between dissolved lignin concentrations and total suspended sediments (TSS) across all sites, in contrast to the strong relationship observed in weekly samples at the mouth. As DOC concentrations and compositions at the mouth of Willow Slough are closely tied to anthropogenic activities within the catchment, future changes in land-use driven by climate change, water availability, and economic pressures on crop types will also bring about changes in the overall biogeochemistry.

California↗

Sources and characteristics of organic matter in the Clackamas River, Oregon, related to the formation of disinfection by-products in treated drinking water

This study characterized the amount and quality of organic matter in the Clackamas River, Oregon, to gain an understanding of sources that contribute to the formation of chlorinated and brominated disinfection by-products (DBPs), focusing on regulated DBPs in treated drinking water from two direct-filtration treatment plants that together serve approximately 100,000 customers. The central hypothesis guiding this study was that natural organic matter leaching out of the forested watershed, in-stream growth of benthic algae, and phytoplankton blooms in the reservoirs contribute different and varying proportions of organic carbon to the river. Differences in the amount and composition of carbon derived from each source affects the types and concentrations of DBP precursors entering the treatment plants and, as a result, yield varying DBP concentrations and species in finished water. The two classes of DBPs analyzed in this study-trihalomethanes (THMs) and haloacetic acids (HAAs)-form from precursors within the dissolved and particulate pools of organic matter present in source water. The five principal objectives of the study were to (1) describe the seasonal quantity and character of organic matter in the Clackamas River; (2) relate the amount and composition of organic matter to the formation of DBPs; (3) evaluate sources of DBP precursors in the watershed; (4) assess the use of optical measurements, including in-situ fluorescence, for estimating dissolved organic carbon (DOC) concentrations and DBP formation; and (5) assess the removal of DBP precursors during treatment by conducting treatability "jar-test" experiments at one of the treatment plants. Data collection consisted of (1) monthly sampling of source and finished water at two drinking-water treatment plants; (2) event-based sampling in the mainstem, tributaries, and North Fork Reservoir; and (3) in-situ continuous monitoring of fluorescent dissolved organic matter (FDOM), turbidity, chlorophyll- a , and other constituents to continuously track source-water conditions in near real-time. Treatability tests were conducted during the four event-based surveys to determine the effectiveness of coagulant and powdered activated carbon (PAC) on the removal of DBP precursors. Sample analyses included DOC, total particulate carbon (TPC), total and dissolved nutrients, absorbance and fluorescence spectroscopy, and, for regulated DBPs, concentrations of THMs and HAAs in finished water and laboratory-based THM and HAA formation potentials (THMFP and HAAFP, respectively) for source water and selected locations throughout the watershed. The results of this study may not be typical given the record and near record amounts of precipitation that occurred during spring that produced streamflow much higher than average in 2010-11. Although there were algal blooms, lower concentrations of chlorophyll- a were observed in the water column during the study period compared to historical data. Concentrations of DBPs in finished (treated) water averaged 0.024 milligrams per liter (mg/L) for THMs and 0.022 mg/L for HAAs; maximum values were about 0.040 mg/L for both classes of DBPs. Although DBP concentrations were somewhat higher within the distribution system, none of the samples collected for this study or for the quarterly compliance monitoring by the water utilities exceeded levels permissible under existing U.S. Environmental Protection Agency (USEPA) regulations: 0.080 mg/L for THMs and 0.060 mg/L for HAAs. DOC concentrations were generally low in the Clackamas River, typically about 1.0-1.5 mg/L. Concentrations in the mainstem occasionally increased to nearly 2.5 mg/L during storms; DOC concentrations in tributaries were sometimes much higher (up to 7.8 mg/L). The continuous in-situ FDOM measurements indicated sharp rises in DOC concentrations in the mainstem following rainfall events; concentrations were relatively stable during summer base flow. Even though the first autumn storm mobilized appreciable quantities of carbon, higher concentrations of DBPs in finished water were observed 3-weeks later, after the ground was saturated from additional rainfall. The majority of the DOC in the lower Clackamas River appears to originate from the upper basin, suggesting terrestrial carbon was commonly the dominant source. Lower-basin tributaries typically contained the highest concentrations of DOC and DBP precursors and contributed substantially to the overall loads in the mainstem during storms. During low-flow periods, tributaries were not major sources of DOC or DBP precursors to the Clackamas River. Although the dissolved fraction of organic carbon contributed the majority of DBP precursors, at times the particulate fraction (inorganic sediment and organic particles including detritus and algal material) contributed a substantial fraction of DBP precursors. Considering just the main-stem sites, on average, 10 percent of THMFP and 32 percent of HAAFP were attributed to particulate carbon. This finding suggests water-treatment methods that remove particles prior to chlorination would reduce finished-water DBP concentrations to some degree. Overall, concentrations of THM and HAA precursors were closely linked to DOC concentrations; laboratory DBP formation potentials (DBPFPs) clearly showed that THMFP and HAAFP were greatest in the downstream tributaries that contained elevated carbon concentrations. However, carbon-normalized "specific" formation potentials for THMs and HAAs (STHMFP and SHAAFP, respectively) revealed changes in carbon character over time that affected the two types of DBP classes differently. HAA precursors were elevated in waters containing aromatic-rich soil-derived material arising from forested areas. In contrast, THM precursors were associated with carbon having a lower aromatic content; highest STHMFP occurred in autumn 2011 in the mainstem from North Fork Reservoir downstream to LO DWTP. This pattern suggests the potential for a link between THM precursors and algal-derived carbon. The highest STHMFP value was measured within North Fork Reservoir, indicating reservoir derived carbon may be important for this class of DBPs. Weak correlations between STHMFP and SHAAFP emphasize that precursor sources for these types of DBPs may be different. This highlights not only that different locations within the watershed produce carbon with different reactivity (specific DBPFP), but also that different management approaches for each class of DBP precursors could be required for control. Treatability tests conducted on source water during four basin-wide surveys demonstrated that an average of about 40 percent of DOC can be removed by coagulation. While the decrease in THMFP following coagulation was similar to DOC, the decrease in HAAFP was much greater (approximately 70 percent), indicating coagulation is particularly effective at removing HAA precursors'likely because of the aromatic nature of the carbon associated with HAA precursors. Several findings from this study have direct implications for managing drinking-water resources and for providing useful information that may help improve treatment-plant operations. For example, the use of in-situ fluorometers that measure FDOM provided an excellent proxy for DOC concentration in this system and revealed short-term, rapid changes in DOC concentration during storm events. In addition, the strong correlation between FDOM values measured in-situ and HAA5 concentrations in finished water may permit estimation of continuous HAA concentrations, as was done here. As part of this study, multiple in-situ FDOM sensors were deployed continuously and in real-time to characterize the composition of dissolved organic matter. Although the initial results were promising, additional research and engineering developments will be needed to demonstrate the full utility of these sensors for this purpose. In conclusion, although DBPFPs were strongly correlated to DOC concentration, some DBPs formed from particulate carbon, including terrestrial leaf material and algal material such as planktonic species of blue-green algae and sloughed filaments, stalks, and cells of benthic algae. Different precursor sources in the watershed were evident from the data, suggesting specific actions may be available to address some of these sources. In-situ measurements of FDOM proved to be an excellent proxy for DOC concentration as well as HAA formation during treatment, which suggests further development and refinement of these sensors have the potential to provide real-time information about complex watershed processes to operators at the drinking-water treatment plants. Follow-up studies could examine the relative roles that terrestrial and algal sources have on the DBP precursor pool to better understand how watershed-management activities may be affecting the transport of these compounds to Clackamas River drinking-water intakes. Given the low concentrations of algae in the water column during this study, additional surveys during more typical river conditions could provide a more complete understanding of how algae contribute DBP precursors. Further development of FDOM-sensor technology can improve our understanding of carbon dynamics in the river and how concentrations may be trending over time. This study was conducted in collaboration with Clackamas River Water and the City of Lake Oswego water utilities. Other research partners included Oregon Health and Science University in Hillsboro, Oregon, Alexin Laboratory in Tigard, Oregon, U.S. Geological Survey National Research Program Laboratory in Denver, Colorado, and the U.S. Geological Survey Water Science Centers in Portland, Oregon, and Sacramento, California. This project was supported with funding from Clackamas River Water, City of Lake Oswego, the U.S. Geological Survey, and the Water Research Foundation.

Oregon↗

Groundwater contributions of flow, nitrate, and dissolved organic carbon to the lower San Joaquin River, California, 2006-08

The influence of groundwater on surface-water quality in the San Joaquin River, California, was examined for a 59-mile reach from the confluence with Salt Slough to Vernalis. The primary objective of this study was to quantify the rate of groundwater discharged to the lower San Joaquin River and the contribution of nitrate and dissolved organic carbon concentrations to the river. Multiple lines of evidence from four independent approaches were used to characterize groundwater contributions of nitrogen and dissolved organic carbon. Monitoring wells (in-stream and bank wells), streambed synoptic surveys (stream water and shallow groundwater), longitudinal profile surveys by boat (continuous water-quality parameters in the stream), and modeling (MODFLOW and VS2DH) provided a combination of temporal, spatial, quantitative, and qualitative evidence of groundwater contributions to the river and the associated quality. Monitoring wells in nested clusters in the streambed (in-stream wells) and on both banks (bank wells) along the river were monitored monthly from September 2006 to January 2009. Nitrate concentrations in the bank wells ranged from less than detection—that is, less than 0.01 milligrams per liter (mg/L) as nitrogen (N)—to approximately 13 mg/L as N. Nitrate was not detected at 17 of 26 monitoring wells during the study period. Dissolved organic carbon concentrations among monitoring wells were highly variable, but they generally ranged from 1 to 4 mg/L. In a previous study, 14 bank wells were sampled once in 1988 following their original installation. With few exceptions, specific conductivity and nitrate concentrations measured in this study were virtually identical to those measured 20 years ago. Streambed synoptic measurements were made by using a temporarily installed drive-point piezometer at 113 distinct transects across the stream during 4 sampling events. Nitrate concentrations exceeded the detection limit of 0.01 mg/L as N in 5 percent of groundwater samples collected from the in-stream wells as part of the synoptic surveys. Only 7 of the 113 cross-sectional transects had nitrate concentrations greater than 1 mg/L as N. In contrast, surface waters in the San Joaquin River tended to have nitrate concentrations in the 1–3 mg/L as N range. A zone of lower oxygen (less than 2 mg/L) in the streambed could limit nitrate contributions from regional groundwater flow because nitrate can be converted to nitrogen gas within this zone. Appreciable concentrations of ammonium (average concentration was 1.92 mg/L as N, and 95th percentile was 10.34 mg/L as N) in the shallow groundwater, believed to originate from anoxic mineralization of streambed sediments, could contribute nitrogen to the overlying stream as nitrate following in-stream nitrification, however. Dissolved organic carbon concentrations were highly variable in the shallow groundwater below the river (1 to 6 ft below streambed) and generally ranged between 1 and 5 mg/L, but had maximum concentrations in the 15–25 mg/L range. The longitudinal profile surveys were not particularly useful in identifying groundwater discharge areas. However, the longitudinal approach described in this report was useful as a baseline survey of measured water-quality parameters and for identifying tributary inflows that affect surface-water concentrations of nitrate. Results of the calibrated MODFLOW model indicated that the simulated groundwater discharge rate was approximately 1.0 cubic foot per second per mile (cfs/mi), and the predominant horizontal groundwater flow direction between the deep bank wells was westward beneath the river. The modeled (VS2DH) flux values (river gain versus river loss) were calculated for the irrigation and non-irrigation season, and these fluxes were an order of magnitude less than those from MODFLOW. During the irrigation season, the average river gain was 0.11 cfs/mi, and the average river loss was −0.05 cfs/mi. During the non-irrigation season, the average river gain was 0.10 cfs/mi, and the average river loss was -0.08 cfs/mi. Information on groundwater interactions and water quality collected for this study was used to estimate loads of nitrate and dissolved organic carbon from the groundwater to the San Joaquin River. Estimated loads of dissolved inorganic nitrogen and dissolved organic carbon were calculated by using concentrations measured during four streambed synoptic surveys and the estimated groundwater discharge rate to the San Joaquin River from MODFLOW of 1 cfs/mi. The estimated groundwater loads to the San Joaquin River for dissolved inorganic nitrogen and dissolved organic carbon were 300 and 350 kilograms per day, respectively. These loads represent 9 and 7 percent, respectively, of the estimated instantaneous surface-water loads for dissolved inorganic nitrogen and dissolved organic carbon at the most downstream site, Vernalis, measured during the four streambed synoptic surveys.

California↗

Optical techniques for the determination of nitrate in environmental waters: Guidelines for instrument selection, operation, deployment, maintenance, quality assurance, and data reporting

The recent commercial availability of in situ optical sensors, together with new techniques for data collection and analysis, provides the opportunity to monitor a wide range of water-quality constituents on time scales in which environmental conditions actually change. Of particular interest is the application of ultraviolet (UV) photometers for in situ determination of nitrate concentrations in rivers and streams. The variety of UV nitrate sensors currently available differ in several important ways related to instrument design that affect the accuracy of their nitrate concentration measurements in different types of natural waters. This report provides information about selection and use of UV nitrate sensors by the U.S. Geological Survey to facilitate the collection of high-quality data across studies, sites, and instrument types. For those in need of technical background and information about sensor selection, this report addresses the operating principles, key features and sensor design, sensor characterization techniques and typical interferences, and approaches for sensor deployment. For those needing information about maintaining sensor performance in the field, key sections in this report address maintenance and calibration protocols, quality-assurance techniques, and data formats and reporting. Although the focus of this report is UV nitrate sensors, many of the principles can be applied to other in situ optical sensors for water-quality studies.

Techniques and Methods↗

Seeing the light: the effects of particles, dissolved materials, and temperature on in situ measurements of DOM fluorescence in rivers and streams

Field-deployable sensors designed to continuously measure the fluorescence of colored dissolved organic matter (FDOM) in situ are of growing interest. However, the ability to make FDOM measurements that are comparable across sites and over time requires a clear understanding of how instrument characteristics and environmental conditions affect the measurements. In particular, the effects of water temperature and light attenuation by both colored dissolved material and suspended particles may be significant in settings such as rivers and streams. Using natural standard reference materials, we characterized the performance of four commercially-available FDOM sensors under controlled laboratory conditions over ranges of temperature, dissolved organic matter (DOM) concentrations, and turbidity that spanned typical environmental ranges. We also examined field data from several major rivers to assess how often attenuation artifacts or temperature effects might be important. We found that raw (uncorrected) FDOM values were strongly affected by the light attenuation that results from dissolved substances and suspended particles as well as by water temperature. Observed effects of light attenuation and temperature agreed well with theory. Our results show that correction of measured FDOM values to account for these effects is necessary and feasible over much of the range of temperature, DOM concentration, and turbidity commonly encountered in surface waters. In most cases, collecting high-quality FDOM measurements that are comparable through time and between sites will require concurrent measurements of temperature and turbidity, and periodic discrete sample collection for laboratory measurement of DOM.

Limnology and Oceanography: Methods↗

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 x 10 4 , and the average VCF (from 10 to 72 h) over all experiments was 12.6 x 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 x 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.

Environmental Toxicology and Chemistry↗

Mercury dynamics in a San Francisco estuary tidal wetland: assessing dynamics using in situ measurements

We used high-resolution in situ measurements of turbidity and fluorescent dissolved organic matter (FDOM) to quantitatively estimate the tidally driven exchange of mercury (Hg) between the waters of the San Francisco estuary and Browns Island, a tidal wetland. Turbidity and FDOM—representative of particle-associated and filter-passing Hg, respectively—together predicted 94 % of the observed variability in measured total mercury concentration in unfiltered water samples (UTHg) collected during a single tidal cycle in spring, fall, and winter, 2005–2006. Continuous in situ turbidity and FDOM data spanning at least a full spring-neap period were used to generate UTHg concentration time series using this relationship, and then combined with water discharge measurements to calculate Hg fluxes in each season. Wetlands are generally considered to be sinks for sediment and associated mercury. However, during the three periods of monitoring, Browns Island wetland did not appreciably accumulate Hg. Instead, gradual tidally driven export of UTHg from the wetland offset the large episodic on-island fluxes associated with high wind events. Exports were highest during large spring tides, when ebbing waters relatively enriched in FDOM, dissolved organic carbon (DOC), and filter-passing mercury drained from the marsh into the open waters of the estuary. On-island flux of UTHg, which was largely particle-associated, was highest during strong winds coincident with flood tides. Our results demonstrate that processes driving UTHg fluxes in tidal wetlands encompass both the dissolved and particulate phases and multiple timescales, necessitating longer term monitoring to adequately quantify fluxes.

California↗

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.

Florida↗

In situ optical water-quality sensor networks - Workshop summary report

Advanced in situ optical water-quality sensors and new techniques for data analysis hold enormous promise for furthering scientific understanding of aquatic systems. These sensors measure important biogeochemical parameters for long deployments, enabling the capture of data at time scales over which they vary most meaningfully. The high-frequency, real-time water-quality data they generate provide opportunities for early warning of water-quality deterioration, trend detection, and science-based decision support. However, developing networks of optical sensors in freshwater systems that report reliable and comparable data across and between sites remains a challenge to the research and monitoring community. To address this, the U. S. Geological Survey (USGS) and the Consortium of Universities for the Advancement of Hydrologic Science, Inc. (CUAHSI) convened a joint 3-day workshop (June 8-10, 2011) at the National Conservation Training Center in Shepardstown, West Virginia, to explore ways to coordinate development of standards and applications for optical sensors, and improve handling, storing, and analyzing the continuous data they produce. The workshop brought together more than 60 scientists, program managers, and vendors from universities, government agencies, and the private sector. Several important outcomes emerged from the presentations and breakout sessions. There was general consensus that making intercalibrated measurements requires that both manufacturers and users better characterize and calibrate the sensors under field conditions. For example, the influence of suspended particles, highly colored water, and temperature on optical sensors remains poorly understood, but consistently accounting for these factors is critical to successful deployment and for interpreting results in different settings. This, in turn, highlights the lack of appropriate standards for sensor calibrations, field checks, and characterizing interferences, as well as methods for data validation, treatment, and analysis of resulting measurements. Participants discussed a wide range of logistical considerations for successful sensor deployments, including key physical infrastructure, data loggers, and remote-communication techniques. Tools to manage, assure, and control quality, and explore large streams of continuous water-quality data are being developed by the USGS, CUAHSI, and other organizations, and will be critical to making full use of these highfrequency data for research and monitoring.

Open-File Report↗

Taking the pulse of snowmelt: in situ sensors reveal seasonal, event and diurnal patterns of nitrate and dissolved organic matter variability in an upland forest stream

Highly resolved time series data are useful to accurately identify the timing, rate, and magnitude of solute transport in streams during hydrologically dynamic periods such as snowmelt. We used in situ optical sensors for nitrate (NO3 - ) and chromophoric dissolved organic matter fluorescence (FDOM) to measure surface water concentrations at 30 min intervals over the snowmelt period (March 21–May 13, 2009) at a 40.5 hectare forested watershed at Sleepers River, Vermont. We also collected discrete samples for laboratory absorbance and fluorescence as well as δ 18 O–NO3 - isotopes to help interpret the drivers of variable NO3 - and FDOM concentrations measured in situ. In situ data revealed seasonal, event and diurnal patterns associated with hydrological and biogeochemical processes regulating stream NO3 - and FDOM concentrations. An observed decrease in NO3 - concentrations after peak snowmelt runoff and muted response to spring rainfall was consistent with the flushing of a limited supply of NO3 - (mainly from nitrification) from source areas in surficial soils. Stream FDOM concentrations were coupled with flow throughout the study period, suggesting a strong hydrologic control on DOM concentrations in the stream. However, higher FDOM concentrations per unit streamflow after snowmelt likely reflected a greater hydraulic connectivity of the stream to leachable DOM sources in upland soils. We also observed diurnal NO3 - variability of 1–2 μmol l -1 after snowpack ablation, presumably due to in-stream uptake prior to leafout. A comparison of NO3 - and dissolved organic carbon yields (DOC, measured by FDOM proxy) calculated from weekly discrete samples and in situ data sub-sampled daily resulted in small to moderate differences over the entire study period (-4 to 1% for NO3 - and -3 to -14% for DOC), but resulted in much larger differences for daily yields (-66 to +27% for NO3 - and -88 to +47% for DOC, respectively). Despite challenges inherent in in situ sensor deployments in harsh seasonal conditions, these data provide important insights into processes controlling NO3 - and FDOM in streams, and will be critical for evaluating the effects of climate change on snowmelt delivery to downstream ecosystems.

Vermont↗

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↗

The aquatic real-time monitoring network; in-situ optical sensors for monitoring the nation's water quality

Floods, hurricanes, and longer-term changes in climate and land use can have profound effects on water quality due to shifts in hydrologic flow paths, water residence time, precipitation patterns, connectivity between rivers and uplands, and many other factors. In order to understand and respond to changes in hydrology and water quality, resource managers and policy makers have a need for accurate and early indicators, as well as the ability to assess possible mechanisms and likely outcomes. In-situ optical sensors-those making continuous measurements of constituents by absorbance or fluorescence properties in the environment at timescales of minutes to years-have a long history in oceanography for developing highly resolved concentrations and fluxes, but are not commonly used in freshwater systems. The United States Geological Survey (USGS) has developed the Aquatic Real-Time Monitoring Network, with high-resolution optical data collection for organic carbon, nutrients, and sediment in large coastal rivers, along with continuous measurements of discharge, water temperature, and dissolved inorganic carbon. The collecting of continuous water-quality data in the Nation?s waterways has revealed temporal trends and spatial patterns in constituents that traditional sampling approaches fail to capture, and will serve a critical role in monitoring, assessment and decision-making in a rapidly changing landscape.

Fact Sheet↗

Use and environmental occurrence of pharmaceuticals 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.

Environmental Science & Technology↗

Comparison of XAD with other dissolved lignin isolation techniques and a compilation of analytical improvements for the analysis of lignin in aquatic settings

This manuscript highlights numerous incremental improvements in dissolved lignin measurements over the nearly three decades since CuO oxidation of lignin phenols was first adapted for environmental samples. Intercomparison of the recovery efficiency of three common lignin phenol concentration and isolation techniques, namely XAD, C 18 with both CH 3 OH (C 18 M) and CH 3 CN (C 18 A) used independently for priming and elution steps, and tangential flow filtration (TFF) for a range of aquatic samples including fresh, estuarine and marine waters, was undertaken. With freshwater samples XAD8-1, C 18 M and TFF were all observed to recover ca. 80–90% of the lignin phenols and showed no fractionation effects with respect to diagnostic lignin parameters. With estuarine and marine samples more lignin phenols were recovered with C 18 M and XAD8-1 than TFF because of the increased prevalence of low molecular weight lignin phenols in marine influenced samples. For marine systems, differences were also observed between diagnostic lignin parameters isolated via TFF vs. C 18 M and XAD8-1 as a result of the high molecular weight lignin phenols being less degraded than the bulk. Therefore, it is recommended for future studies of marine systems that only one technique is utilized for ease of intercomparison within studies. It is suggested that for studies solely aimed at recovering bulk dissolved lignin in marine environments that C 18 M and XAD8-1 appear to be more suitable than TFF as they recover more lignin. Our results highlight that, for freshwater samples, all three common lignin phenol concentration and isolation techniques are comparable to whole water concentrated by rotary evaporation (i.e. not isolated) but, that for marine systems, the choice of concentration and isolation techniques needs to be taken into consideration with respect to both lignin concentration and diagnostic parameters. Finally, as the study highlights XAD8-1 to be a suitable method for the isolation of dissolved lignin phenols from aquatic systems (statistically indistinguishable from C 18 M, P < 0.1), lignin data representative of whole waters can be produced for IHSS reference materials or other XAD sample archives.

Organic Geochemistry↗

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)&mdash;a regulated class of DBPs&mdash;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.

Journal of Environmental Quality↗

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% of mainstem 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 (R 2 = 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. Copyright ?? 2010 by the American Society of Agronomy.

Journal of Environmental Quality↗

Public review draft: A method for assessing carbon stocks, carbon sequestration, and greenhouse-gas fluxes in ecosystems of the United States under present conditions and future scenarios

The Energy Independence and Security Act of 2007 (EISA), Section 712, authorizes the U.S. Department of the Interior to develop a methodology and conduct an assessment of the Nation's ecosystems focusing on carbon stocks, carbon sequestration, and emissions of three greenhouse gases (GHGs): carbon dioxide, methane, and nitrous oxide. The major requirements include (1) an assessment of all ecosystems (terrestrial systems, such as forests, croplands, wetlands, shrub and grasslands; and aquatic ecosystems, such as rivers, lakes, and estuaries), (2) an estimation of annual potential capacities of ecosystems to increase carbon sequestration and reduce net GHG emissions in the context of mitigation strategies (including management and restoration activities), and (3) an evaluation of the effects of controlling processes, such as climate change, land use and land cover, and wildlfires. The purpose of this draft methodology for public review is to propose a technical plan to conduct the assessment. Within the methodology, the concepts of ecosystems, carbon pools, and GHG fluxes used for the assessment follow conventional definitions in use by major national and international assessment or inventory efforts. In order to estimate current ecosystem carbon stocks and GHG fluxes and to understand the potential capacity and effects of mitigation strategies, the method will use two time periods for the assessment: 2001 through 2010, which establishes a current ecosystem GHG baseline and will be used to validate the models; and 2011 through 2050, which will be used to assess future potential conditions based on a set of projected scenarios. The scenario framework is constructed using storylines of the Intergovernmental Panel on Climate Change (IPCC) Special Report Emission Scenarios (SRES), along with initial reference land-use and land-cover (LULC) and land-management scenarios. An additional three LULC and land-management mitigation scenarios will be constructed for each storyline to enhance carbon sequestration and reduce GHG fluxes in ecosystems. Input from regional experts and stakeholders will be solicited to construct realistic and meaningful scenarios. The methods for mapping the current LULC and ecosystem disturbances will require the extensive use of both remote-sensing data and in-situ (for example, forest inventory data) to capture and characterize landscape-change events. For future potential LULC and ecosystem disturbances, key drivers such as socioeconomic, policy, and climate assumptions will be used in addition to biophysical data. The product of these analyses will be a series of maps for each future year for each scenario. These annual maps will form the basis for estimating carbon storage and GHG emissions. For terrestrial ecosystems, carbon storage, carbon-sequestration capacities, and GHG emissions under the current and projected future conditions will be assessed using the LULC and ecosystem-disturbance estimates in map format with a spatially explicit biogeochemical ensemble modeling system that incorporates properties of management activities (such as tillage or harvesting) and properties of individual ecosystems (such as elevation, vegetation characteristics, and soil attributes). For aquatic ecosystems, carbon burial in sediments and GHG fluxes are functions of the current and projected future stream flow and sediment transports, and therefore will be assessed using empirical modeling methods. Validation and uncertainty analysis methods described in the methodology will follow established guidelines to assess the quality of the assessment results. The U.S. Environmental Protection Agency's Level II ecoregions map (which delineates 24 ecoregions for the Nation) will be the practical instrument for developing and delivering assessment results. Consequently, the ecoregion will be the reporting unit of the assessment because the mitigation scenarios, assessment results, validation, and uncertainty analysis will be

Open-File Report↗

A method for assessing carbon stocks, carbon sequestration, and greenhouse-gas fluxes in ecosystems of the United States under present conditions and future scenarios

he Energy Independence and Security Act of 2007 (EISA), Section 712, mandates the U.S. Department of the Interior to develop a methodology and conduct an assessment of the Nation’s ecosystems, focusing on carbon stocks, carbon sequestration, and emissions of three greenhouse gases (GHGs): carbon dioxide, methane, and nitrous oxide. The major requirements include (1) an assessment of all ecosystems (terrestrial systems, such as forests, croplands, wetlands, grasslands/shrublands; and aquatic ecosystems, such as rivers, lakes, and estuaries); (2) an estimate of the annual potential capacities of ecosystems to increase carbon sequestration and reduce net GHG emissions in the context of mitigation strategies (including management and restoration activities); and (3) an evaluation of the effects of controlling processes, such as climate change, land-use and land-cover change, and disturbances such as wildfires. The concepts of ecosystems, carbon pools, and GHG fluxes follow conventional definitions in use by major national and international assessment or inventory efforts. In order to estimate current ecosystem carbon stocks and GHG fluxes and to understand the potential capacity and effects of mitigation strategies, the method will use two time periods for the assessment: 2001 through 2010, which establishes a current ecosystem carbon and GHG baseline and will be used to validate the models; and 2011 through 2050, which will be used to assess potential capacities based on a set of scenarios. The scenario framework will be constructed using storylines of the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emission Scenarios (SRES), along with both reference and enhanced land-use and land-cover (LULC) and land-management parameters. Additional LULC and land-management mitigation scenarios will be constructed for each storyline to increase carbon sequestration and reduce GHG fluxes in ecosystems. Input from regional experts and stakeholders will be solicited to construct these scenarios. The methods for mapping the current LULC and ecosystem disturbances will require the extensive use of both remote-sensing data and field-survey data (for example, forest inventories) to capture and characterize landscape-changing events. For potential LULC changes and ecosystem disturbances, key drivers such as socioeconomic and climate changes will be used in addition to the biophysical data. The result of these analyses will be a series of maps for each future year for each scenario. These annual maps will form the basis for estimating carbon storage and GHG emissions. For terrestrial ecosystems, carbon storage, carbon-sequestration capacities, and GHG emissions under the present conditions and future scenarios will be assessed using the LULC-change and ecosystem-disturbance estimates in map format with a spatially explicit biogeochemical ensemble modeling system that incorporates properties of management activities (such as tillage or harvesting) and properties of individual ecosystems (such as energy exchange, vegetation characteristics, hydrological cycling, and soil attributes). For aquatic ecosystems, carbon burial in sediments and fluxes of GHG are functions of the present and future potential stream flow and sediment transport and will be assessed using empirical hydrological modeling methods. Validation and uncertainty analysis methods described in the methodology will follow established guidelines to assess the quality of the assessment results. The U.S. Environmental Protection Agency’s Level II ecoregions map will be the practical instrument for developing and delivering assessment results. Consequently, the ecoregion (there are 22 modified ecoregions) will be the reporting unit of the assessment because the scenarios, assessment results, validation, and uncertainty analysis will be produced at that scale. The implementation of these methods will require collaborations among various Federal agencies, State agencies, nongovernmental organizations, and the science community. Using the method described in this document, the assessment can be completed in approximately 3 to 4 years. The primary deliverables will be assessment reports containing tables, charts, and maps that will present the estimated GHG parameters annually for 2001 through 2050 by ecosystem, pool, and scenario. The results will permit the evaluation of a range of policies, mitigation options, and research topics, such as the demographic, LULC-change, or climate-change effects on carbon stocks, carbon sequestration, and GHG fluxes in ecosystems.

Scientific Investigations Report↗