Storm events dominate riverine loads of dissolved organic carbon (DOC) and nitrate and are expected to increase in frequency and intensity in many regions due to climate change. We deployed three high‐frequency (15 min) in situ absorbance spectrophotometers to monitor DOC and nitrate concentration for 126 storms in three watersheds with agricultural, urban, and forested land use/land cover. We examined intrastorm hysteresis and the influences of seasonality, storm size, and dominant land use/land cover on storm DOC and nitrate loads. DOC hysteresis was generally anticlockwise at all sites, indicating distal and plentiful sources for all three streams despite varied DOC character and sources. Nitrate hysteresis was generally clockwise for urban and forested sites, but anticlockwise for the agricultural site, indicating an exhaustible, proximal source of nitrate in the urban and forested sites, and more distal and plentiful sources of nitrate in the agricultural site. The agricultural site had significantly higher storm nitrate yield per water yield and higher storm DOC yield per water yield than the urban or forested sites. Seasonal effects were important for storm nitrate yield in all three watersheds and farm management practices likely caused complex interactions with seasonality at the agricultural site. Hysteresis indices did not improve predictions of storm nitrate yields at any site. We discuss key lessons from using high‐frequency in situ optical sensors.

Catchment nutrient export, especially during high flow events, can influence ecological processes in receiving waters by altering nitrogen (N) and phosphorus (P) concentrations and relative amounts (stoichiometry). Event-scale N and P export dynamics may be significantly altered by land use/land cover (LULC) and season. Consequently, to manage water resources, it is important to understand how LULC and season interact to influence event N and P export. In situ, high-frequency spectrophotometers allowed us to continuously and concurrently monitor nitrate (NO 3 −) and soluble reactive P (SRP) concentrations and therefore examine event-scale NO 3 − and SRP export dynamics. Here we analyzed event NO 3 − and SRP concentration-discharge hysteresis patterns and yields for >400 events to evaluate how LULC and seasonality influence event NO 3 − and SRP export dynamics in three low-order watersheds with different primary LULCs (agricultural, forested, and urban). Differences among event NO 3 − and SRP hysteresis patterns suggest these nutrients have different source areas and dominant transport pathways that were impacted by both LULC and seasonality. Unexpectedly, we observed similar seasonal patterns in event NO 3 − :SRP stoichiometry among LULCs, with the most N-enriched events occurring in spring, and event stoichiometry approaching Redfield N:P ratios in the fall. However, seasonal stoichiometry patterns were driven by unique seasonal NO 3 − and SRP export patterns at each site. Overall these findings suggest LULC and seasonality interact to alter the timing and magnitude of event NO 3 − and SRP exports, leading to seasonal patterns in event NO 3 − to SRP stoichiometry that may influence ecological processes, such as productivity, in receiving waters. Plain Language Summary High flow events transport relatively large quantities of nitrogen (N) and phosphorus (P) to streams and downstream waterbodies where they may stimulate algal blooms and degrade water quality. We evaluated how land uses and seasons alter event nutrient transport. We monitored >400 events with sensors in streams with contrasting land uses. Event N and P concentration patterns differed from each other suggesting dissolved N and P were transported from different locations in the landscape. Further, the agricultural and urban streams received more dissolved N and P than the forested stream. This likely results from fertilizer applications in excess of crop (agricultural and lawn grass) needs and landscape modifications, such as drainage systems and impervious surfaces, that limit soils and vegetation from removing nutrients from runoff. Lastly, season influenced the ratio of dissolved N to P delivery, with spring events transporting the most N relative to P and fall events transporting the least. Overall, land use and season uniquely influenced event nutrient transport. Management strategies to reduce algal blooms in downstream waterbodies must consider interactions among land use, nutrient type, and season. However, ratios of N to P may change seasona...

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TitleWood export varies among decadal, annual, seasonal, and daily scale hydrologic regimes in a large, Mediterranean climate, mountain river watershed Data AvailabilityThe data associated with this publication are available upon request.

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Accurate riverine phosphorus concentration measurements are often critical to meet watershed management goals. Phosphorus monitoring programs often rely on proxy variables such as turbidity and discharge and have limited ability to accurately estimate concentrations of dissolved phosphorus fractions that are most bioavailable. Optical water quality sensors can make subhourly measurements and have been shown to reduce uncertainty in load estimates and reveal high-frequency storm dynamics for nitrate and dissolved organic carbon. We evaluated the utility of in situ UV-Visible spectrophotometers to predict total, dissolved, and soluble reactive phosphorus concentrations in streams draining agricultural, urban, and forested land use/land covers. We present the first statistically validated application of optical water quality sensors to demonstrate how sensors may perform in predicting phosphorus fraction concentrations through training set models. Total phosphorus predictions from UV-Visible spectra were optimal when models were site-specific, and the proportion of variance explained was generally as high as or higher than the results of other studies that rely only on discharge and turbidity. However, root mean square errors for total phosphorus models were relatively high compared to the median concentrations at each site. Models to predict dissolved and soluble reactive phosphorus concentrations explained a greater proportion of the variance than any other known proxy variable technique, and results varied by land use/land cover. Though accuracy limitations remain, this approach has potential to predict concurrent total, dissolved, and soluble reactive phosphorus concentrations at a high frequency for many applications in water quality research and management communities.

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