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Abstract Winters in snow-covered regions have warmed, likely shifting the timing and magnitude of nutrient export, leading to unquantified changes in water quality. Intermittent, seasonal, and permanent snow covers more than half of the global land surface. Warming has reduced the cold conditions that limit winter runoff and nutrient transport, while cold season snowmelt, the amount of winter precipitation falling as rain, and rain-on-snow have increased. We used existing geospatial datasets (rain-on-snow frequency overlain on nitrogen and phosphorous inventories) to identify areas of the contiguous United States (US) where water quality could be threatened by this change. Next, to illustrate the potential export impacts of these events, we examined flow and turbidity data from a large regional rain-on-snow event in the United States’ largest river basin, the Mississippi River Basin. We show that rain-on-snow, a major flood-generating mechanism for large areas of the globe (Berghuijs et al 2019 Water Resour. Res. 55 4582–93; Berghuijs et al 2016 Geophys. Res. Lett. 43 4382–90), affects 53% of the contiguous US and puts 50% of US nitrogen and phosphorus pools (43% of the contiguous US) at risk of export to groundwater and surface water. Further, the 2019 rain-on-snow event in the Mississippi River Basin demonstrates that these events could have large, cascading impacts on winter nutrient transport. We suggest that the assumption of low wintertime discharge and nutrient transport in historically snow-covered regions no longer holds. Critically, however, we lack sufficient data to accurately measure and predict these episodic and potentially large wintertime nutrient export events at regional to continental scales. 

Oxygen (O₂) regulates soil reduction‐oxidation processes and therefore modulates biogeochemical cycles. The difficulties associated with accurately characterizing soil O₂variability have prompted the use of soil moisture as a proxy for O₂, as O₂diffusion into soil water is much slower than in soil air. The use of soil moisture alone as a proxy measurement for O₂could result in inaccurate O₂estimations. For example, O₂may remain high during cool months when soil respiration rates are low. We analyzed high‐frequency sensor data (e.g., soil moisture, CO₂, gas‐phase soil pore O₂) with a machine learning technique, the Self‐Organizing Map, to pinpoint suites of soil conditions associated with contrasting O₂regimes. At two riparian sites in northern Vermont, we found that O₂levels varied seasonally, and with soil moisture. For example, 47% of low O₂levels were associated with wet and cool soil conditions, whereas 32% were associated with dry and warm conditions. Contrastingly, the majority (62%) of high O₂conditions occurred under dry and warm conditions. High soil moisture levels did not always lead to low O₂, as 38% of high O₂values occurred under wet and cool conditions. Our results highlight challenges with predicting soil O₂solely based on water content, as variable combinations of soil and hydrologic conditions can complicate the relationship between water content and O₂. This indicates that process‐based ecosystem and denitrification models that rely solely on soil moisture to estimate O₂may need to incorporate other site and climate‐specific drivers to accurately predict soil O₂.

 

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.

 

With mounting scientific evidence demonstrating adverse global climate change (GCC) impacts to water quality, water quality policies, such as the Total Maximum Daily Loads (TMDLs) under the U.S. Clean Water Act, have begun accounting for GCC effects in setting nutrient load‐reduction policy targets. These targets generally require nutrient reductions for attaining prescribed water quality standards (WQS) by setting safe levels of nutrient concentrations that curtail potentially harmful cyanobacteria blooms (CyanoHABs). While some governments require WQS to consider climate change, few tools are available to model the complex interactions between climate change and benthic legacy nutrients. We present a novel process‐based integrated assessment model (IAM) that examines the extent to which synergistic relationships between GCC and legacy Phosphorus release could compromise the ability of water quality policies to attain established WQS. The IAM is calibrated for simulating the eutrophic Missisquoi Bay and watershed in Lake Champlain (2001–2050). Water quality impacts of seven P‐reduction scenarios, including the 64.3% reduction specified under the current TMDL, were examined under 17 GCC scenarios. The TMDL WQS of 0.025 mg/L total phosphorus is unlikely to be met by 2035 under the mandated 64.3% reduction for all GCC scenarios. IAM simulations show that the frequency and severity of summer CyanoHABs increased or minimally decreased under most climate and nutrient reduction scenarios. By harnessing IAMs that couple complex process‐based simulation models, the management of water quality in freshwater lakes can become more adaptive through explicit accounting of GCC effects on both the external and internal sources of nutrients.