Anthony J. Tesoriero

Mechanism and rate of denitrification in an agricultural watershed: Electron and mass balance along groundwater flow paths

The rate and mechanism of nitrate removal along and between groundwater flow paths were investigated using a series of well nests screened in an unconfined sand and gravel aquifer. Intensive agricultural activity in this area has resulted in nitrate concentrations in groundwater often exceeding drinking water standards. Both the extent and rate of denitrification varied depending on the groundwater flow path. While little or no denitrification occurred in much of the upland portions of the aquifer, a gradual redox gradient is observed as aerobic upland groundwater moves deeper in the aquifer. In contrast, a sharp shallow redox gradient is observed adjacent to a third-order stream as aerobic groundwater enters reduced sediments. An essentially complete loss of nitrate concurrent with increases in excess N2 provide evidence that denitrification occurs as groundwater enters this zone. Electron and mass balance calculations suggest that iron sulfide (e.g., pyrite) oxidation is the primary source of electrons for denitrification. Denitrification rate estimates were based on mass balance calculations using nitrate and excess N2 coupled with groundwater travel times. Travel times were determined using a groundwater flow model and were constrained by chlorofluorocarbon-based age dates. Denitrification rates were found to vary considerably between the two areas where denitrification occurs. Denitrification rates in the deep, upland portions of the aquifer were found to range from <0.01 to 0.14 mM of N per year; rates at the redoxcline along the shallow flow path range from 1.0 to 2.7 mM of N per year. Potential denitrification rates in groundwater adjacent to the stream may be much faster, with rates up to 140 mM per year based on an in situ experiment conducted in this zone.

Nitrogen contamination of surficial aquifers - A growing legacy

The virtual ubiquity of fertilizer-fed agriculture, increasing over several decades, has become necessary to support the global human population. Ironically, widespread use of nitrogen (N) has contaminated another vital resource: surficial fresh groundwater. Further, as nitrous oxide (N2O) is a potent greenhouse gas, anthropogenic manipulation of N budgets has ramifications that can extend far beyond national borders. To get a handle on the size of the problem, Puckett et al. present an approach to track historical contamination and thus analyze trends now and in the past with implications for the future.

Vulnerability of Streams to Legacy Nitrate Sources

The influence of hydrogeologic setting on the susceptibility of streams to legacy nitrate was examined at seven study sites having a wide range of base flow index (BFI) values. BFI is the ratio of base flow to total streamflow volume. The portion of annual stream nitrate loads from base flow was strongly correlated with BFI. Furthermore, dissolved oxygen concentrations in streambed pore water were significantly higher in high BFI watersheds than in low BFI watersheds suggesting that geochemical conditions favor nitrate transport through the bed when BFI is high. Results from a groundwater-surface water interaction study at a high BFI watershed indicate that decades old nitrate-laden water is discharging to this stream. These findings indicate that high nitrate levels in this stream may be sustained for decades to come regardless of current practices. It is hypothesized that a first approximation of stream vulnerability to legacy nutrients may be made by geospatial analysis of watersheds with high nitrogen inputs and a strong connection to groundwater (e.g., high BFI).

Identifying pathways and processes affecting nitrate and orthophosphate inputs to streams in agricultural watersheds

Understanding nutrient pathways to streams will improve nutrient management strategies and estimates of the time lag between when changes in land use practices occur and when water quality effects that result from these changes are observed. Nitrate and orthophosphate (OP) concentrations in several environmental compartments were examined in watersheds having a range of base flow index (BFI) values across the continental United States to determine the dominant pathways for water and nutrient inputs to streams. Estimates of the proportion of stream nitrate that was derived from groundwater increased as BFI increased. Nitrate concentration gradients between groundwater and surface water further supported the groundwater source of nitrate in these high BFI streams. However, nitrate concentrations in stream-bed pore water in all settings were typically lower than stream or upland groundwater concentrations, suggesting that nitrate discharge to streams was not uniform through the bed. Rather, preferential pathways (e.g., springs, seeps) may allow high nitrate groundwater to bypass sites of high biogeochemical transformation. Rapid pathway compartments (e.g., overland flow, tile drains) had OP concentrations that were typically higher than in streams and were important OP conveyers in most of these watersheds. In contrast to nitrate, the proportion of stream OP that is derived from ground water did not systematically increase as BFI increased. While typically not the dominant source of OP, groundwater discharge was an important pathway of OP transport to streams when BFI values were very high and when geochemical conditions favored OP mobility in groundwater.

Quantifying watershed‐scale groundwater loading and in‐stream fate of nitrate using high‐frequency water quality data

We describe a new approach that couples hydrograph separation with high-frequency nitrate data to quantify time-variable groundwater and runoff loading of nitrate to streams, and the net in-stream fate of nitrate at the watershed scale. The approach was applied at three sites spanning gradients in watershed size and land use in the Chesapeake Bay watershed. Results indicate that 58–73% of the annual nitrate load to the streams was groundwater-discharged nitrate. Average annual first-order nitrate loss rate constants (k) were similar to those reported in both modeling and in-stream process-based studies, and were greater at the small streams (0.06 and 0.22 day−1) than at the large river (0.05 day−1), but 11% of the annual loads were retained/lost in the small streams, compared with 23% in the large river. Larger streambed area to water volume ratios in small streams results in greater loss rates, but shorter residence times in small streams result in a smaller fraction of nitrate loads being removed than in larger streams. A seasonal evaluation of k values suggests that nitrate was retained/lost at varying rates during the growing season. Consistent with previous studies, streamflow and nitrate concentrations were inversely related to k. This new approach for interpreting high-frequency nitrate data and the associated findings furthers our ability to understand, predict, and mitigate nitrate impacts on streams and receiving waters by providing insights into temporal nitrate dynamics that would be difficult to obtain using traditional field-based studies.

Predicting Redox Conditions in Groundwater at a Regional Scale.

Defining the oxic-suboxic interface is often critical for determining pathways for nitrate transport in groundwater and to streams at the local scale. Defining this interface on a regional scale is complicated by the spatial variability of reaction rates. The probability of oxic groundwater in the Chesapeake Bay watershed was predicted by relating dissolved O2 concentrations in groundwater samples to indicators of residence time and/or electron donor availability using logistic regression. Variables that describe surficial geology, position in the flow system, and soil drainage were important predictors of oxic water. The probability of encountering oxic groundwater at a 30 m depth and the depth to the bottom of the oxic layer were predicted for the Chesapeake Bay watershed. The influence of depth to the bottom of the oxic layer on stream nitrate concentrations and time lags (i.e., time period between land application of nitrogen and its effect on streams) are illustrated using model simulations for hypothetical basins. Regional maps of the probability of oxic groundwater should prove useful as indicators of groundwater susceptibility and stream susceptibility to contaminant sources derived from groundwater.

Low transient storage and uptake efficiencies in seven agricultural streams: implications for nutrient demand

We used mass load budgets, transient storage modeling, and nutrient spiraling metrics to characterize nitrate (NO), ammonium (NH), and inorganic phosphorus (SRP) demand in seven agricultural streams across the United States and to identify in-stream services that may control these conditions. Retention of one or all nutrients was observed in all but one stream, but demand for all nutrients was low relative to the mass in transport. Transient storage metrics (/, , , and ) correlated with NO retention but not NH or SRP retention, suggesting in-stream services associated with transient storage and stream water residence time could influence reach-scale NO demand. However, because the fraction of median reach-scale travel time due to transient storage () was ≤1.2% across the sites, only a relatively small demand for NO could be generated by transient storage. In contrast, net uptake of nutrients from the water column calculated from nutrient spiraling metrics were not significant at any site because uptake lengths calculated from background nutrient concentrations were statistically insignificant and therefore much longer than the study reaches. These results suggest that low transient storage coupled with high surface water NO inputs have resulted in uptake efficiencies that are not sufficient to offset groundwater inputs of N. Nutrient retention has been linked to physical and hydrogeologic elements that drive flow through transient storage areas where residence time and biotic contact are maximized; however, our findings indicate that similar mechanisms are unable to generate a significant nutrient demand in these streams relative to the loads.

Predicting redox-sensitive contaminant concentrations in groundwater using random forest classification

Machine learning techniques were applied to a large (n > 10,000) compliance monitoring database to predict the occurrence of several redox-active constituents in groundwater across a large watershed. Specifically, random forest classification was used to determine the probabilities of detecting elevated concentrations of nitrate, iron, and arsenic in the Fox, Wolf, Peshtigo, and surrounding watersheds in northeastern Wisconsin. Random forest classification is well suited to describe the nonlinear relationships observed among several explanatory variables and the predicted probabilities of elevated concentrations of nitrate, iron, and arsenic. Maps of the probability of elevated nitrate, iron, and arsenic can be used to assess groundwater vulnerability and the vulnerability of streams to contaminants derived from groundwater. Processes responsible for elevated concentrations are elucidated using partial dependence plots. For example, an increase in the probability of elevated iron and arsenic occurred when well depths coincided with the glacial/bedrock interface, suggesting a bedrock source for these constituents. Furthermore, groundwater in contact with Ordovician bedrock has a higher likelihood of elevated iron concentrations, which supports the hypothesis that groundwater liberates iron from a sulfide-bearing secondary cement horizon of Ordovician age. Application of machine learning techniques to existing compliance monitoring data offers an opportunity to broadly assess aquifer and stream vulnerability at regional and national scales and to better understand geochemical processes responsible for observed conditions.

Estimates of nitrate loads and yields from groundwater to streams in the Chesapeake Bay watershed based on land use and geology

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Estimating Discharge and Nonpoint Source Nitrate Loading to Streams From Three End‐Member Pathways Using High‐Frequency Water Quality Data

The myriad hydrologic and biogeochemical processes taking place in watersheds occurring across space and time are integrated and reflected in the quantity and quality of water in streams and rivers. Collection of high-frequency water quality data with sensors in surface waters provides new opportunities to disentangle these processes and quantify sources and transport of water and solutes in the coupled groundwater-surface water system. A new approach for separating the streamflow hydrograph into three components was developed and coupled with high-frequency nitrate data to estimate time-variable nitrate loads from chemically dilute quick flow, chemically concentrated quick flow, and slowflow groundwater end-member pathways for periods of up to 2 years in a groundwater-dominated and a quick-flow-dominated stream in central Wisconsin, using only streamflow and in-stream water quality data. The dilute and concentrated quick flow end-members were distinguished using high-frequency specific conductance data. Results indicate that dilute quick flow contributed less than 5% of the nitrate load at both sites, whereas 89 ± 8% of the nitrate load at the groundwater-dominated stream was from slowflow groundwater, and 84 ± 25% of the nitrate load at the quick-flow-dominated stream was from concentrated quick flow. Concentrated quick flow nitrate concentrations varied seasonally at both sites, with peak concentrations in the winter that were 2–3 times greater than minimum concentrations during the growing season. Application of this approach provides an opportunity to assess stream vulnerability to nonpoint source nitrate loading and expected stream responses to current or changing conditions and practices in watersheds.