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 (NO 3 -) 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 d 18 O-NO 3 -isotopes to help interpret the drivers of variable NO 3 -and FDOM concentrations measured in situ. In situ data revealed seasonal, event and diurnal patterns associated with hydrological and biogeochemical processes regulating stream NO 3 -and FDOM concentrations. An observed decrease in NO 3 -concentrations after peak snowmelt runoff and muted response to spring rainfall was consistent with the flushing of a limited supply of NO 3 -(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 NO 3 -variability of 1-2 lmol l -1 after snowpack ablation, presumably due to in-stream uptake prior to leafout. A comparison of NO 3 -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 NO 3 -and -3 to -14% for DOC), but resulted in much larger differences for daily yields (-66 to ?27% for NO 3 -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 NO 3 -and FDOM in streams, and will be Electronic supplementary material The online version of this article (

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 commerciallyavailable 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.

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 km2 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 (r2 = 0.97), providing a highly resolved proxy for DOC throughout the study period. Discrete optical properties including specific UV absorbance (SUVA254), spectral slope (S290–350), 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.

Summary 1. We investigated diurnal nitrate (NO3−) concentration variability in the San Joaquin River using an in situ optical NO3− sensor and discrete sampling during a 5‐day summer period characterized by high algal productivity. Dual NO3− isotopes (δ15NNO3 and δ18ONO3) and dissolved oxygen isotopes (δ18ODO) were measured over 2 days to assess NO3− sources and biogeochemical controls over diurnal time‐scales. 2. Concerted temporal patterns of dissolved oxygen (DO) concentrations and δ18ODO were consistent with photosynthesis, respiration and atmospheric O2 exchange, providing evidence of diurnal biological processes independent of river discharge. 3. Surface water NO3− 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 δ15NNO3 and δ18ONO3 isotopes suggests that algal assimilation and denitrification are not major processes controlling diurnal NO3− variability in the San Joaquin River during the study. The lack of a clear explanation for NO3− variability likely reflects a combination of riverine biological processes and time‐varying physical transport of NO3− from upstream agricultural drains to the mainstem San Joaquin River. 4. The application of an in situ optical NO3− 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.

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