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Geology topics

Brian A. Pellerin

Publications and source records attributed to Brian A. Pellerin.

At least 19 recordsLinked to original sources

Field techniques for fluorescence measurements targeting dissolved organic matter, hydrocarbons, and wastewater in environmental waters: Principles and guidelines for instrument selection, operation and maintenance, quality assurance, and data reporting

The use of field deployable fluorescence sensors by the U.S. Geological Survey has become increasingly common for a wide variety of surface water and groundwater investigations. This report addresses field deployable fluorometers that measure the fluorescence response of various substances in water exposed to incident light generated by the sensor. An introduction to the basic principles of field measurements of fluorescence is provided, as well as technical background information on sensors that target dissolved organic matter, wastewater, and hydrocarbons, including sensor selection, operating principles, key features, and design elements. General deployment, operation and maintenance protocols, quality-assurance techniques, and suggestions for data reporting are presented to facilitate and standardize the collection and accurate communication of data collected by the U.S. Geological Survey across studies, sites, and sensor types. Sensor performance issues and common interferences are also described. An appendix is included to describe sensor calibration criteria and procedures, reporting units, and specific approaches to correct for interferences for fluorescence of dissolved organic matter sensors.

Techniques and Methods

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

Water interactions with soil and vegetation are greatly altered in agricultural watersheds compared to natural landscapes, which impacts sources and fates of organic carbon (OC). While mineral soil horizons in natural ecosystems primarily act as filters for dissolved organic carbon (DOC) leached from organic surface horizons, tilled soils largely lack an organic horizon and their mineral horizons therefore act as a source for both DOC and sediment to surface waters. Irrigated watersheds highlight this difference, as DOC and total suspended sediment (TSS) concentrations simultaneously increase during the low-discharge irrigation season, suggesting that sediment-associated OC may constitute a significant source of DOC. While water-soluble OC (WSOC) from sediments and soils has been found to be compositionally similar to stream DOC, these contributions remain poorly quantified in agricultural streams. To address this, we conducted abiotic solubilization experiments using sediments (suspended and bed) and soils from an irrigated agricultural watershed in northern California, USA. Sediments (R 2 > 0.99) and soils (0.74 < R 2 < 0.89) displayed linear solubilization behaviors over the range of concentrations tested. Suspended sediment from the irrigation season exhibited the largest solubilization efficiency (10.9 ± 1.6% TOC sediment solubilized) and potential (1.79 ± 0.26 mg WSOC g −1 dry sediment), followed by suspended sediment from a winter storm, then bed sediment and soils. Successive solubilization experiments increased the total release of WSOC by ∼50%, but most (88–97%) of the solid-phase OC remained insoluble in water. Using these solubilization potential estimates and measured TSS concentrations, we estimated that WSOC from suspended sediment in streams represented 4–7% of the annual DOC export from the watershed. However, field sediment export is much higher than what is represented by suspended sediment in the water column, therefore field-scale contributions from sediments could be much higher than estimated.

California

Field techniques for the determination of algal pigment fluorescence in environmental waters—Principles and guidelines for instrument and sensor selection, operation, quality assurance, and data reporting

The use of algal fluorometers by the U.S. Geological Survey (USGS) has become increasingly common. The basic principles of algal fluorescence, instrument calibration, interferences, data quantification, data interpretation, and quality control are given in Hambrook Berkman and Canova (2007). Much of the guidance given for instrument maintenance, data storage, and quality assurance in Wagner and others (2006) are also applicable to algal fluorometers, although they are not explicitly discussed. Algal fluorometers have advanced substantially since these guidance documents were published; so that while the basic principles remain unchanged, new guidance is needed. This techniques and methods report is intended to provide additional information on algal fluorescence-sensor calibration, maintenance, measurement, data storage, and quality assurance that meet stated objectives of USGS data-collection efforts. The operations described facilitate and standardize the collection and accurate communication of algal fluorescence data collected by the USGS across studies, sites, and instrument types. This report provides technical background information on algal fluorescence sensors; including specifications, operating principles, key features, and design elements. Maintenance and calibration protocols, quality-assurance techniques, and suggestions for data reporting are presented. Sensor performance issues, common interferences, and strategies for addressing them are also described.

Techniques and Methods

Winter flooding to conserve agricultural peat soils in a temperate climate: Effect on greenhouse gas emissions and global warming potential

This study investigated the CO 2 and CH 4 emission rates from agricultural operations on peat soils in the Sacramento-San Joaquin Delta, comparing two common soil management treatments: leaving the field fallow in the winter and flooding the field in winter. Winter flooding is intended to reduce the oxidative loss of soil organic matter to CO 2 , as well as other putative benefits. The goal of the study was to assess if winter flooding lowers overall net carbon loss from the field and if it increases the net CH 4 emissions to a degree that results in a net increase in Global Warming Potential (GWP). The two treatments had similar annual carbon emissions (1.7–1.8 g C/m 2 /d) with the measured annual CO 2 flux rates for both among the highest previously reported, indicating that the flooding treatment did not effectively mitigate subsidence and loss of soil carbon. The flooded treatment had among the highest annual CH 4 emissions previously reported (64.1 mg C/m 2 /d), an order of magnitude greater than that measured on the fallow treatment (5.9 mg C/m 2 /d). Despite the much larger flux of CH 4 from the flooded treatment, when the net carbon export associated with grain harvest and hydrologic transport is included, the differences in the carbon balance and GWP (equivalent to CO 2 emissions of ~775 g C/m 2 /yr) between treatments is insignificant. Total greenhouse gas emissions and GWP of both sites are among the largest previously documented from cultivated peat systems, putting their climatic effect on par with freshwater wetlands, but without the concomitant soil conservation and carbon sequestration benefits of continuous flooding.

Book chapter

Optical properties of water for prediction of wastewater contamination, human-associated bacteria, and fecal indicator bacteria in surface water at three watershed scales

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

Michigan, New York, Ohio, Wisconsin

Technical note—Relative variability of selected turbidity standards and sensors in use by the U.S. Geological Survey

The challenges associated with field measurements of turbidity are well known and result primarily from differences in reported values that depend on instrument design and the resulting need for reporting units that are specific to those designs. A critical challenge for making comparable turbidity measurements is the selection and use of appropriate turbidity standards for sensor calibration. The accepted primary standards for turbidity measurements use formazin made from scratch; all others should relate back to readings obtained using standard formazin. However, because turbidity is a qualitative property of water, comparing standards is not as simple as it is for many chemical measurements. The U.S. Geological Survey “National Field Manual for the Collection of Water-Quality Data” currently allows for the use of two standards, formazin and polymer beads, for the calibration of field turbidimeters. Another challenge for making comparable turbidity measurements is selection of turbidity sensors. A turbidity sensor commonly used in the U.S. Geological Survey, the Yellow Springs Instruments (YSI) 6136, has been replaced by the manufacturer with the YSI EXO turbidity sensor. Both sensors operate on the same principles but have slight design differences that result in readings that are not directly comparable on a 1:1 basis. Differences in calibration standards and sensors are a cause of concern in ongoing studies that require switching calibration standards or sensor types, and for comparisons of data collected with sensors calibrated by using different calibration standards, different sensor types, or both. The objectives of this study were to evaluate the response of two YSI turbidity sensors in both formazin-based standards (StablCal) and polymer turbidity standards (in this case YSI brand; however, other brands are available) and to compare the performance of the YSI EXO and YSI 6136 turbidity sensors under similar laboratory and environmental (field) conditions. To quantify these differences, a series of laboratory and field side-by-side comparisons were conducted. Nine field comparisons of YSI EXO and YSI 6136 sensors were performed at site locations in Kansas and Virginia. Two field comparisons of StablCal and polymer calibration standards were performed in Kansas, both using YSI EXO turbidity sensors. Five laboratory comparisons between the YSI EXO and YSI 6136 turbidity sensors were performed, and seven laboratory comparisons between StablCal and polymer turbidity standards were performed using YSI EXO turbidity sensors. The results can help the USGS and others better understand how turbidity data can differ depending on the sensors and calibration standards used. Key findings and conclusions include the following— Regardless of the comparison, strong linear associations were typically found across all measures of turbidity under field and laboratory conditions, but linear associations were not necessarily 1:1 and varied by type of standard, type of sensor, and field and laboratory conditions. The mean relative percentage differences for all but a few comparisons were greater than 10 percent but less than 30 percent. However, differences were inconsistent across the laboratory and field conditions measured in this study, precluding the ability to formulate definitive statements of consistent directional bias depending on the type of standard or sensor used. Across all tests and a range of 0 to 1,000 formazin nephelometric units (FNU), no consistent bias between the YSI EXO and YSI 6136 turbidity sensors was observed, but either regression relations were near 1:1 or the YSI EXO turbidity readings were lower than those measured with the YSI 6136. Relative percentage differences typically exceeded the 10- and 30-percent benchmarks. However, most (about 95 percent) of the absolute differences between turbidity values measured with the YSI EXO and those measured with the YSI 6136 sensors were less than 20 FNU. In laboratory experiments, when turbidity was “constant,” the absolute difference between YSI EXO and YSI 6136-measured turbidity values ranged from near 0 FNU to nearly 400 FNU (over a range of 0 to 1,000 FNU). Substantial variability in turbidity measurements makes comparison between standards and sensor types challenging. Given the inherent variability in turbidity measurements and the lack of consistent bias between calibration standards or sensors, changing methods during an ongoing study would compromise the comparability of the data. The effect of changing methods ultimately depends on study objectives. If method changes are required, laboratory- and field-based comparisons across a range of conditions ideally would be conducted to determine whether site-specific biases can be identified.

Open-File Report

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

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

California

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

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

California

Monitoring the Riverine Pulse: Applying high-frequency nitrate data to advance integrative understanding of biogeochemical and hydrological processes

Widespread deployment of sensors that measure river nitrate (NO3-) concentrations has led to many recent publications in water resources journals including review papers focused on data quality assurance, improved load calculations, and better nutrient management. The principal objective of this paper is to review and synthesize studies of high-frequency NO3- data that have aimed to improve understanding of the hydrologic and biogeochemical processes underlying episodic, diel, and long-term stream NO3- dynamics. Investigations have provided unprecedented detail on hysteresis and flushing patterns during high flow, seasonal variation during baseflow, and responses to multi-year climate variation. Analyses of high-frequency data have led to notable advances in understanding how climate variation affects spatial and temporal NO3- patterns, especially dry-wet cycles and antecedent moisture. Further advances have been limited by few investigations that include high-frequency measurements outside the channel and the short duration of many records. High-frequency data for multiple constituents have provided new insight to the relative roles of hydrology and biogeochemistry as highlighted by studies of the roles of autotrophic uptake, denitrification, riparian evapotranspiration, and temperature-driven changes in viscosity as drivers of diel patterns. Comparisons of short-duration high-frequency data with long-duration low frequency data have described similarities and differences in concentration – discharge patterns and highlighted the role of legacy stores. Investigators have applied innovative analysis approaches not previously possible with low-frequency or temporally-irregular data. Future availability of long-duration high-frequency data will provide new insight to processes, resulting in improved conceptual models and a deeper understanding of the role of climate variation.

WIREs Water

Temporal variability in nitrate – discharge relationships in large rivers as revealed by high frequency data

Little is known about temporal variability in nitrate concentration responses to changes in discharge on intraannual time scales in large rivers. To investigate this knowledge gap, we used a six‐year data set of daily surface water nitrate concentration and discharge averaged from near‐continuous monitoring at U.S. Geological Survey gaging stations on the Connecticut, Potomac, and Mississippi Rivers, three large rivers that contribute substantial nutrient pollution to important estuaries. Interannually, a comparison of nitrate concentration‐discharge (c‐Q) relationships between a traditional discrete grab sample data set and the near‐continuous data set revealed differing c‐Q slopes, which suggests that sample frequency can impact how we ultimately characterize hydrologic systems. Intraannually, we conducted correlation analyses over 30‐day windows to isolate the strength and direction of monthly c‐Q relationships. Monthly c‐Q slopes in the Potomac were positive (enrichment/mobilization response) in summer and fall and negative (dilution response) and weakly chemostatic (nonsignificant near‐zero c‐Q slope) in winter and spring, respectively. The Connecticut displayed a dilution response year‐round, except summer when it was weakly chemostatic. Mississippi c‐Q slopes were weakly chemostatic in all seasons and showed inconsistent responses to discharge fluctuations. The c‐Q dynamics in the Potomac and Connecticut were correlated ( R > 0.3) to river temperature, flow percentile, and calendar day. Minimal correlation in the Mississippi suggests that the large basin area coupled with spatiotemporally variable anthropogenic forcings from substantial land use development created stochastic short‐term c‐Q relationships. Additional work using high‐frequency sensors across large river networks can improve our understanding of spatial source input dynamics in these natural‐human coupled systems.

Water Resources Research

U.S. Geological Survey continuous monitoring workshop—Workshop summary report

Executive Summary The collection of high-frequency (in other words, “continuous”) water data has been made easier over the years because of advances in technologies to measure, transmit, store, and query large, temporally dense datasets. Commercially available, in-situ sensors and data-collection platforms—together with new techniques for data analysis—provide an opportunity to monitor water quantity and quality at time scales during which meaningful changes occur. The U.S. Geological Survey (USGS) Continuous Monitoring Workshop was held to build stronger collaboration within the Water Mission Area on the collection, interpretation, and application of continuous monitoring data; share technical approaches for the collection and management of continuous data that improves consistency and efficiency across the USGS; and explore techniques and tools for the interpretation of continuous monitoring data, which increases the value to cooperators and the public. The workshop was organized into three major themes: Collecting Continuous Data, Understanding and Using Continuous Data, and Observing and Delivering Continuous Data in the Future. Presentations each day covered a variety of related topics, with a special session at the end of each day designed to bring discussion and problem solving to the forefront. The workshop brought together more than 70 USGS scientists and managers from across the Water Mission Area and Water Science Centers. Tools to manage, assure, control quality, and explore large streams of continuous water data are being developed by the USGS and other organizations and will be critical to making full use of these high-frequency data for research and monitoring. Disseminating continuous monitoring data and findings relevant to critical cooperator and societal issues is central to advancing the USGS networks and mission. Several important outcomes emerged from the presentations and breakout sessions.

Open-File Report

High frequency data exposes nonlinear seasonal controls on dissolved organic matter in a large watershed

We analyzed a five year, high frequency time series generated by an in situ fluorescent dissolved organic matter (fDOM) sensor installed near the Connecticut River’s mouth, investigating high temporal resolution DOM dynamics in a larger watershed and longer time series than previously addressed. We identified a gradient between large, saturating summer fDOM responses to discharge and linear, subdued responses during colder months. Seasonal response patterns were not consistent with multiple linear regression. Alternatively, we binned measurements across the yearly cycle using environmental indices, such as temperature, and applied moving regression, a novel approach which produced superior fits to calendar day binning. Spatially averaged watershed soil temperature at 10 cm was the best overall index of discharge-fDOM response. DOM fractionation showed fDOM was primarily a surrogate for hydrophobic organic acid (HPOA) concentrations. HPOAs were highly correlated with discharge, but hydrophilics (HPIs) were not. Discharge dependent DOM concentrations driven by the HPOA fraction may be controlled by soil temperature and water table position relative to organic and mineral soil horizons. HPI concentrations were correlated with average watershed soil temperature at 10 cm but were rather stationary throughout the year, further indicating a consistent groundwater source for this nonfluorescent DOM. We present a resolved subseasonal empirical model of DOM concentrations and fluxes, showing that riverine DOM flux and quality depend heavily on seasonal terrestrial carbon dynamics and hydrologic flow paths. High frequency monitoring reveals readily discernible patterns demonstrating that upland biogeochemical signals are maintained even at this large watershed scale.

Environmental Science and Technology

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

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

California

Irrigation as a fuel pump to freshwater ecosystems

We generated a detailed time series of total dissolved hydrolyzable amino acids (DHAA) in a watershed dominated by irrigated agriculture in northern California, USA to investigate the roles of hydrologic and seasonal changes on the composition of dissolved organic matter (DOM). DHAA are sensitive indicators of the degradation state and reactivity of DOM. DHAA concentrations ranged from 0.55 to 9.96 μM (median 3.51 ± 1.80 μM), with expected peaks during high-discharge storms and unexpected high values throughout the low-discharge irrigation season. Overall, summer irrigation was a critical hydrologic regime for DOM cycling since it mobilized DOM similar in concentration and reactivity to DOM released during storms. Together, irrigation and storm flows exported DOM with (1) the largest DHAA contributions to the dissolved organic carbon and the dissolved organic nitrogen pools, (2) the largest proportion of basic amino acids, and (3) the lowest degradation extent based on multiple indices. In this highly disturbed terrestrial system, UV–vis absorbance did not correlate with DHAA concentrations, while classic interpretations of common amino acid indicators (e.g., proportion of basic amino acids, degradation index, percent of non-protein amino acids) were prone to conflicting characterizations of DOM reactivity. Therefore, a new parameter (processing ratio, PR) derived from individual amino acid concentrations was developed that demonstrated a strong potential for mechanistic-driven characterization of the extent of DOM diagenesis in freshwaters. Irrigated agriculture altered stream biogeochemistry by releasing a continuous supply of reactive DOM (lowest PR values), thereby providing an additional energy source to downstream ecosystems.

California

Designing a high-frequency nutrient and biogeochemical monitoring network for the Sacramento–San Joaquin Delta, northern California

Executive Summary This report is the third in a series of three reports that provide information about how high-frequency (HF) nutrient monitoring may be used to assess nutrient inputs and dynamics in the Sacramento–San Joaquin Delta, California (Delta). The purpose of this report is to provide the background, principles, and considerations for designing an HF nutrient-monitoring network for the Delta to address high-priority, nutrient-management questions. The report starts with discussion of the high-priority management questions to be addressed, continues through discussion of the questions and considerations that place demands and constraints on network design, discusses the principles applicable to network design, and concludes with the presentation of three example nutrient-monitoring network designs for the Delta. For three example network designs, we assess how they would address high-priority questions that have been identified by the Delta Regional Monitoring Program (Delta Regional Monitoring Program Technical Advisory Committee, 2015). This report, along with the other two reports of this series (Kraus and others, 2017; Downing and others, 2017), was drafted in cooperation with the Delta Regional Monitoring Program to help scientists, managers, and planners understand how HF data improve our understanding of nutrient sources and sinks, drivers, and effects in the Delta. The first report in the series (Kraus and others, 2017) provides an introduction to the reasons for and fundamental concepts behind using HF monitoring measurements, including a brief summary of nutrient status and trends in the Delta and an extensive literature review showing how and where other research and monitoring programs have used HF monitoring to improve our understanding of nutrient cycling. The report covers the various technologies available for HF nutrient monitoring and presents the different ways HF monitoring instrumentation may be used for both fixed station and spatial assessments. Finally, it presents numerous examples of how HF measurements are currently (2017) being used in the Delta to examine how nutrients and nutrient cycling are related to aquatic habitat conditions. The second report in the series (Downing and others, 2017) summarizes information about HF nutrient and associated biogeochemical monitoring in the north Delta. The report synthesizes data available from the nutrient and water quality monitoring network currently (2017) operated by the U.S. Geological Survey in this ecologically important region of the Delta. In the report, we present and discuss the available data at various timescales—first at the monthly, seasonal, and inter-annual timescales; and, second, for comparison, at the tidal and event timescales. As expected, we determined that there is substantial variability in nitrate concentrations at short timescales, such as within a few hours, but also significant variability at longer timescales such as months or years. This high variability affects calculation of fluxes and loads, indicating that HF monitoring is necessary for understanding and assessing flux-based processes and outcomes in Delta tidal environments.

California

Clearing the waters: Evaluating the need for site-specific field fluorescence corrections based on turbidity measurements

In situ fluorescent dissolved organic matter (fDOM) measurements have gained increasing popularity as a proxy for dissolved organic carbon (DOC) concentrations in streams. One challenge to accurate fDOM measurements in many streams is light attenuation due to suspended particles. Downing et al. (2012) evaluated the need for corrections to compensate for particle interference on fDOM measurements using a single sediment standard in a laboratory study. The application of those results to a large river improved unfiltered field fDOM accuracy. We tested the same correction equation in a headwater tropical stream and found that it overcompensated fDOM when turbidity exceeded ∼300 formazin nephelometric units (FNU). Therefore, we developed a site-specific, field-based fDOM correction equation through paired in situ fDOM measurements of filtered and unfiltered streamwater. The site-specific correction increased fDOM accuracy up to a turbidity as high as 700 FNU, the maximum observed in this study. The difference in performance between the laboratory-based correction equation of Downing et al. (2012) and our site-specific, field-based correction equation likely arises from differences in particle size distribution between the sediment standard used in the lab (silt) and that observed in our study (fine to medium sand), particularly during high flows. Therefore, a particle interference correction equation based on a single sediment type may not be ideal when field sediment size is significantly different. Given that field fDOM corrections for particle interference under turbid conditions are a critical component in generating accurate DOC estimates, we describe a way to develop site-specific corrections.

Limnology and Oceanography: Methods

Spatial and temporal patterns of dissolved organic matter quantity and quality in the Mississippi River Basin, 1997–2013

Recent studies have found insignificant or decreasing trends in time-series dissolved organic carbon (DOC) datasets, questioning the assumption that long-term DOC concentrations in surface waters are increasing in response to anthropogenic forcing, including climate change, land use, and atmospheric acid deposition. We used the weighted regressions on time, discharge, and season (WRTDS) model to estimate annual flow-normalized concentrations and fluxes to determine if changes in DOC quantity and quality signal anthropogenic forcing at 10 locations in the Mississippi River Basin. Despite increases in agriculture and urban development throughout the basin, net increases in DOC concentration and flux were significant at only 3 of 10 sites from 1997 to 2013 and ranged between −3.5% to +18% and −0.1 to 19%, respectively. Positive shifts in DOC quality, characterized by increasing specific ultraviolet absorbance at 254 nm, ranged between +8% and +45%, but only occurred at one of the sites with significant DOC quantity increases. Basinwide reductions in atmospheric sulfate deposition did not result in large increases in DOC either, likely because of the high buffering capacity of the soil. Hydroclimatic factors including annual discharge, precipitation, and temperature did not significantly change during the 17-year timespan of this study, which contrasts with results from previous studies showing significant increases in precipitation and discharge over a century time scale. Our study also contrasts with those from smaller catchments, which have shown stronger DOC responses to climate, land use, and acidic deposition. This temporal and spatial analysis indicated that there was a potential change in DOC sources in the Mississippi River Basin between 1997 and 2013. However, the overall magnitude of DOC trends was not large, and the pattern in quantity and quality increases for the 10 study sites was not consistent throughout the basin.

Hydrological Processes

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