Geology topics

Bryan D. Downing

Publications and source records attributed to Bryan D. Downing.

34 records · Page 2Linked to original sources

USGS2016

Optical properties of dissolved organic matter (DOM): Effects of biological and photolytic degradation

Advances in spectroscopic techniques have led to an increase in the use of optical properties (absorbance and fluorescence) to assess dissolved organic matter (DOM) composition and infer sources and processing. However, little information is available to assess the impact of biological and photolytic processing on the optical properties of original DOM source materials. We measured changes in commonly used optical properties and indices in DOM leached from peat soil, plants, and algae following biological and photochemical degradation to determine whether they provide unique signatures that can be linked to original DOM source. Changes in individual optical parameters varied by source material and process, with biodegradation and photodegradation often causing values to shift in opposite directions. Although values for different source materials overlapped at the end of the 111-day lab experiment, multivariate statistical analyses showed that unique optical signatures could be linked to original DOM source material even after degradation, with 17 optical properties determined by discriminant analysis to be significant (p<0.05) in distinguishing between DOM source and environmental processing. These results demonstrate that inferring the source material from optical properties is possible when parameters are evaluated in combination even after extensive biological and photochemical alteration.

Limnology and Oceanography↗

USGS2015

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.

California↗

USGS2014

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

Accurately quantifying nitrate (NO 3 – ) 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 NO 3 – sensors allowed us to evaluate model performance relative to measured loads in the lower Mississippi River. Patterns in NO 3 – 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 NO 3 – concentrations consistent with a large flush of stored NO 3 – 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 NO 3 – measurements offer additional benefits not available with regression-based or other load estimation techniques.

Louisiana↗

USGS2014

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.

Science of the Total Environment↗

USGS2014

Experimental design and quality assurance: in situ fluorescence instrumentation

Both instrument design and capabilities of fluorescence spectroscopy have greatly advanced over the last several decades. Advancements include solid-state excitation sources, integration of fiber optic technology, highly sensitive multichannel detectors, rapid-scan monochromators, sensitive spectral correction techniques, and improve data manipulation software (Christian et al., 1981, Lochmuller and Saavedra, 1986; Cabniss and Shuman, 1987; Lakowicz, 2006; Hudson et al., 2007). The cumulative effect of these improvements have pushed the limits and expanded the application of fluorescence techniques to numerous scientific research fields. One of the more powerful advancements is the ability to obtain in situ fluorescence measurements of natural waters (Moore, 1994). The development of submersible fluorescence instruments has been made possible by component miniaturization and power reduction including advances in light sources technologies (light-emitting diodes, xenon lamps, ultraviolet [UV] lasers) and the compatible integration of new optical instruments with various sampling platforms (Twardowski et at., 2005 and references therein). The development of robust field sensors skirt the need for cumbersome and or time-consuming filtration techniques, the potential artifacts associated with sample storage, and coarse sampling designs by increasing spatiotemporal resolution (Chen, 1999; Robinson and Glenn, 1999). The ability to obtain rapid, high-quality, highly sensitive measurements over steep gradients has revolutionized investigations of dissolved organic matter (DOM) optical properties, thereby enabling researchers to address novel biogeochemical questions regarding colored or chromophoric DOM (CDOM). This chapter is dedicated to the origin, design, calibration, and use of in situ field fluorometers. It will serve as a review of considerations to be accounted for during the operation of fluorescence field sensors and call attention to areas of concern when making this type of measurement. Attention is also given to ways in which in-water fluorescence measurements have revolutionized biogeochemical studies of CDOM and how those measurements can be used in conjunction with remotely sense satellite data to understand better the biogeochemistry of DOM in aquatic environments.

Book chapter↗

USGS2013

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↗

USGS2013

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↗

USGS2013

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↗

USGS2012

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↗

USGS2012

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↗

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↗

USGS2011

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↗

USGS2010

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↗

USGS2009

High-frequency in situ optical measurements during a storm event: Assessing relationships between dissolved organic matter, sediment concentrations, and hydrologic processes

Dissolved organic matter (DOM) dynamics during storm events has received considerable attention in forested watersheds, but the extent to which storms impart rapid changes in DOM concentration and composition in highly disturbed agricultural watersheds remains poorly understood. In this study, we used identical in situ optical sensors for DOM fluorescence (FDOM) with and without filtration to continuously evaluate surface water DOM dynamics in a 415 km 2 agricultural watershed over a 4 week period containing a short-duration rainfall event. Peak turbidity preceded peak discharge by 4 h and increased by over 2 orders of magnitude, while the peak filtered FDOM lagged behind peak turbidity by 15 h. FDOM values reported using the filtered in situ fluorometer increased nearly fourfold and were highly correlated with dissolved organic carbon (DOC) concentrations (r 2 = 0.97), providing a highly resolved proxy for DOC throughout the study period. Discrete optical properties including specific UV absorbance (SUVA 254 ), spectral slope (S 290–350 ), and fluorescence index (FI) were also strongly correlated with in situ FDOM and indicate a shift toward aromatic, high molecular weight DOM from terrestrially derived sources during the storm. The lag of the peak in FDOM behind peak discharge presumably reflects the draining of watershed soils from natural and agricultural landscapes. Field and experimental evidence showed that unfiltered FDOM measurements underestimated filtered FDOM concentrations by up to ∼60% at particle concentrations typical of many riverine systems during hydrologic events. Together, laboratory and in situ data provide insights into the timing and magnitude of changes in DOM quantity and quality during storm events in an agricultural watershed, and indicate the need for sample filtration in systems with moderate to high suspended sediment loads.

Journal of Geological Research↗

USGS2009

Assessing the sources and magnitude of diurnal nitrate variability in the San Joaquin River (California) with an in situ optical nitrate sensor and dual nitrate isotopes

1. We investigated diurnal nitrate (NO 3 − ) concentration variability in the San Joaquin River using an in situ optical NO 3 − sensor and discrete sampling during a 5‐day summer period characterized by high algal productivity. Dual NO 3 − isotopes (δ 15 N NO3 and δ 18 O NO3 ) and dissolved oxygen isotopes (δ 18 O DO ) were measured over 2 days to assess NO 3 − sources and biogeochemical controls over diurnal time‐scales. 2. Concerted temporal patterns of dissolved oxygen (DO) concentrations and δ 18 O DO were consistent with photosynthesis, respiration and atmospheric O 2 exchange, providing evidence of diurnal biological processes independent of river discharge. 3. Surface water NO 3 − concentrations varied by up to 22% over a single diurnal cycle and up to 31% over the 5‐day study, but did not reveal concerted diurnal patterns at a frequency comparable to DO concentrations. The decoupling of δ 15 N NO3 and δ 18 O NO3 isotopes suggests that algal assimilation and denitrification are not major processes controlling diurnal NO 3 − variability in the San Joaquin River during the study. The lack of a clear explanation for NO 3 − variability likely reflects a combination of riverine biological processes and time‐varying physical transport of NO 3 − from upstream agricultural drains to the mainstem San Joaquin River. 4. The application of an in situ optical NO 3 − sensor along with discrete samples provides a view into the fine temporal structure of hydrochemical data and may allow for greater accuracy in pollution assessment.

Freshwater Biology↗

USGS2008

Assessing contribution of DOC from sediments to a drinking-water reservoir using optical profiling

Understanding the sources of dissolved organic carbon (DOC) in drinking-water reservoirs is an important management issue because DOC may form disinfection by-products, interfere with disinfection, or increase treatment costs. DOC may be derived from a host of sources-algal production of DOC in the reservoir, marginal production of DOC from mucks and vascular plants at the margins, and sediments in the reservoir. The purpose of this study was to assess if release of DOC from reservoir sediments containing ferric chloride coagulant was a significant source of DOC to the reservoir. We examined the source-specific contributions of DOC using a profiling system to measure the in situ distribution of optical properties of absorption and fluorescence at various locations in the reservoir. Vertical optical profiles were coupled with discrete water samples measured in the laboratory for DOC concentration and optical properties: absorption spectra and excitation emission matrix spectra (EEMs). Modeling the in situ optical data permitted estimation of the bulk DOC profile in the reservoir as well as separation into source-specific contributions. Analysis of the source-specific profiles and their associated optical characteristics indicated that the sedimentary source of DOC to the reservoir is significant and that this DOC is labile in the reservoir. We conclude that optical profiling is a useful technique for understanding complex biogeochemical processes in a reservoir.

Lake and Reservoir Management↗