High-frequency sensor data capture short-term variability in Fe and Mn concentrations due to hypolimnetic oxygenation and seasonal dynamics in a drinking water reservoir.

The biogeochemical cycles of iron (Fe) and manganese (Mn) in lakes and reservoirs have predictable seasonal trends, largely governed by stratification dynamics and redox conditions in the hypolimnion. However, short-term (i.e., sub-weekly) trends in Fe and Mn cycling are less well-understood, as most monitoring efforts focus on longer-term (i.e., monthly to yearly) time scales. The potential for elevated Fe and Mn to degrade water quality and impact ecosystem functioning, coupled with increasing evidence for high spatiotemporal variability in other biogeochemical cycles, necessitates a closer evaluation of the short-term Fe and Mn dynamics in lakes and reservoirs. We adapted a UV-visible spectrophotometer coupled with a multiplexor pumping system and partial least squares regression (PLSR) modeling to generate high spatiotemporal resolution predictions of Fe and Mn concentrations in a drinking water reservoir (Falling Creek Reservoir, Vinton, VA, USA) equipped with a hypolimnetic oxygenation (HOx) system. We quantified hourly Fe and Mn concentrations during two transitional periods: reservoir turnover (Fall 2020) and HOx initiation (Summer 2021). Our sensor system successfully predicted mean Fe and Mn concentrations and trends, ground-truthed by grab sampling and laboratory analysis. During fall turnover, hypolimnetic Fe and Mn concentrations began to decrease more than two weeks before complete mixing of the reservoir, with rapid equalization of epilimnetic and hypolimnetic Fe and Mn concentrations in less than 48 h after full water column mixing. During the initiation of HOx in Summer 2021, Fe and Mn displayed distinctly different responses to oxygenation, as indicated by the rapid oxidation of soluble Fe but not soluble Mn. This study demonstrates that Fe and Mn concentrations are sensitive to changes in redox conditions induced by stratification and oxygenation, although their responses to these changes differ. We also show that high spatio-temporal resolution predictions of Fe and Mn can improve drinking water monitoring programs and reservoir management practices.

Event-scale hysteresis metrics to reveal processes and mechanisms controlling constituent export from watersheds: A review✰.

Due to the increased availability of high-frequency measurements of stream chemistry provided by in situ sensors, researchers have gained more access to relationships between stream discharge and constituent concentrations (C-Q relationships) at event-scales. Existing studies reveal that event-scale C-Q relationships are mostly non-linear and exhibit temporal lags between peaks (or troughs) of hydrographs and chemographs, resulting in apparent hysteresis effects. In this paper, we summarize and introduce tools and methods in hysteresis analysis, especially the history and progresses of metrics to quantify hysteresis patterns. In addition, this paper provides a typical workflow to conduct event-scale hysteresis analysis, such as how to obtain the access to high-frequency measurements, existing methods to delineate storm events, approaches to classify and quantify hysteresis patterns, possible features/properties controlling hysteresis patterns, statistical methods to identify features at play, and strategies to deliver the inferences from hysteresis analysis. Lastly, we discuss some potential limitations that arise in the workflow and possible future work to address the challenges, including the development of advanced quantitative hysteresis metrics, generalized and standardized tools to delineate events and the integration of hysteresis analysis with numerical modeling. This paper aims to provide a critical overview of technical approaches for hysteresis analysis for researchers and hopefully foster their interests to advance our understanding of complex mechanisms in event-scale hydro-biogeochemical processes.

High-frequency, in situ sampling of field woodchip bioreactors reveals sources of sampling error and hydraulic inefficiencies.

Woodchip bioreactors are a practical, low-cost technology for reducing nitrate (NO3) loads discharged from agriculture. Traditional methods of quantifying their performance in the field mostly rely on low-frequency, time-based (weekly to monthly sampling interval) or flow-weighted sample collection at the inlet and outlet, creating uncertainty in their performance and design by providing incomplete information on flow and water chemistry. To address this uncertainty, two field bioreactors were monitored in the US and New Zealand using high-frequency, multipoint sampling for in situ monitoring of NO3-N concentrations. High-frequency monitoring (sub hourly interval) at the inlet and outlet of both bioreactors revealed significant variability in volumetric removal rates and percent reduction, with percent reduction varying by up to 25 percentage points within a single flow event. Time series of inlet and outlet NO3 showed significant lag in peak concentrations of 1-3 days due to high hydraulic residence time, where calculations from instantaneous measurements produced erroneous estimates of performance and misleading relationships between residence time and removal. Internal porewater sampling wells showed differences in NO3 concentration between shallow and deep zones, and "hot spot" zones where peak NO3 removal co-occurred with dissolved oxygen depletion and dissolved organic carbon production. Tracking NO3 movement through the profile showed preferential flow occurring with slower flow in deeper woodchips, and slower flow further from the most direct flowpath from inlet to outlet. High-frequency, in situ data on inlet and outlet time series and internal porewater solute profiles of this initial work highlight several key areas for future research.

Insights from using in-situ ultraviolet-visible spectroscopy to assess nitrogen treatment and subsurface dynamics in a regenerative stormwater conveyance (RSC) system.

Regenerative stormwater conveyance (RSC) is a recently developed stormwater control measure that marries the concepts of bioretention and stream restoration. RSC mitigates stormwater runoff by converting surface flow to subsurface seepage using a series of pools and riffles built over a sand media bed. Subsurface seepage flows through media and exits the RSC beneath the outlet weir. Previous studies on RSC pollutant mitigation have focused on surface flow discharges from the RSC. To date, no known research has been conducted on the potential pollutant contributions of RSC seepage, despite the fact that this water also enters receiving waters. This research used Multi-Point Sampling coupled with in-situ ultraviolet-visual spectroscopy to measure nitrogen in seepage during simulated storm events (n = 9) at a field-scale RSC in Raleigh, North Carolina. Calibrations between light absorbance and concentrations were acceptable (Nash-Sutcliffe coefficient > 0.65) for nitrate and total ammoniacal nitrogen (TAN) and very good (Nash-Sutcliffe coefficient > 0.90) for total Kjehdahl nitrogen (TKN). Early storm simulations revealed some initial nutrient flushing from the substrate, which subsided by the third simulation. Overall, subsurface seepage nitrate, TAN, and TKN concentrations were lower by 29%, 57%, and 4% relative to storm inflow concentrations, respectively. Computed subsurface nitrogen concentrations demonstrated temporal variability, highlighting dynamic transport and biogeochemical transformations in saturated and unsaturated conditions. Nitrogen concentrations were lower in seepage than in surface flow; however, due to the high volume of runoff converted to seepage, nitrogen loads discharged in seepage can be larger than those of surface flow. Further research is needed to examine subsurface pollutant reductions under varying hydrologic and seasonal conditions.

Drying-Rewetting Cycles Affect Nitrate Removal Rates in Woodchip Bioreactors.

Woodchip bioreactors are widely used to control nitrogen export from agriculture using denitrification. There is abundant evidence that drying-rewetting (DRW) cycles can promote enhanced metabolic rates in soils. A 287-d experiment investigated the effects of weekly DRW cycles on nitrate (NO) removal in woodchip columns in the laboratory receiving constant flow of nitrated water. Columns were exposed to continuous saturation (SAT) or to weekly, 8-h drying-rewetting (8 h of aerobiosis followed by saturation) cycles (DRW). Nitrate concentrations were measured at the column outlets every 2 h using novel multiplexed sampling methods coupled to spectrophotometric analysis. Drying-rewetting columns showed greater export of total and dissolved organic carbon and increased NO removal rates. Nitrate removal rates in DRW columns increased by up to 80%, relative to SAT columns, although DRW removal rates decreased quickly within 3 d after rewetting. Increased NO removal in DRW columns continued even after 39 DRW cycles, with ∼33% higher total NO mass removed over each weekly DRW cycle. Data collected in this experiment provide strong evidence that DRW cycles can dramatically improve NO removal in woodchip bioreactors, with carbon availability being a likely driver of improved efficiency. These results have implications for hydraulic management of woodchip bioreactors and other denitrification practices.

Addressing the fouling of in situ ultraviolet-visual spectrometers used to continuously monitor water quality in brackish tidal marsh waters.

The introduction of portable in situ ultraviolet-visual spectrometers has made possible the collection of water quality parameters at a high frequency in dynamic systems such as tidal marshes. The usefulness of this technology is inhibited by fouling of the instrument's optics. In this study, a spectrometer fitted with manufacturer-recommended compressed air optical cleaning was installed in a brackish marsh to determine if fouling interfered with measurements between bi-weekly servicing. During a 2-wk period, the absorbance measured in air at 220 nm increased from 9 to 549 m, indicating major fouling. An antifouling system was developed that reduced the time of exposure of the optics to stream water and used a pressurized fresh water cleaning. After implementation of the system, the absorbance in air increased to at most 63 m after 2 wk of data collection. The dramatic reduction in fouling will allow quality long-term data to be collected using this technology.