Forecasting and Hindcasting PFAS Concentrations in Groundwater Discharging to Streams near a PFAS Production Facility.

Per- and polyfluoroalkyl substances (PFAS) are known to be highly persistent in groundwater, making it vital to develop new approaches to important practical questions such as the time scale for future persistence of PFAS in contaminated groundwater. In the approach presented here, groundwater from beneath streambeds was analyzed for PFAS and age-dated using SF6 and 3H/3He. The results were coupled with groundwater flux measurements in a convolution approach to estimate past and future PFAS concentrations in groundwater discharge to the streams. At our test site near the Cape Fear River (CFR) of North Carolina, PFAS were detected in groundwater up to 43 years old, suggesting that some PFAS entered groundwater immediately or shortly after fluorochemical production began at the nearby Fayetteville Works. Results are consistent with little to no retardation in groundwater for perfluoroethers such as hexafluoropropylene oxide-dimer acid (HFPO-DA) and perfluoro-2-methoxypropanoic acid (PMPA), the two most abundant PFAS, with mean concentrations of 229 and 498 ng/L, respectively. Future PFAS concentrations in groundwater discharge to streams were estimated to remain above current MCL or health advisory levels through at least 2050 or 2060 (using 3H/3He and SF6, respectively). Recent atmospheric deposition data suggest lower but non-negligible amounts of PFAS may continue to enter groundwater, likely further extending PFAS persistence in groundwater and the adjacent CFR. This approach shows promise for giving an overall perspective on persistence of PFAS in groundwater discharge from a broad contaminated area.

Impact of Eastern Redcedar encroachment on water resources in the Nebraska Sandhills.

Worldwide, tree or shrub dominated woodlands have encroached into herbaceous dominated grasslands. While very few studies have evaluated the impact of Eastern Redcedar (redcedar) encroachment on the water budget, none have analyzed the impact on water quality. In this study, we evaluated the impact of redcedar encroachment on the water budget in the Nebraska Sand Hills and how the decreased streamflow would increase nitrate and atrazine concentrations in the Platte River. We calibrated a Soil and Water Assessment Tool (SWAT model) for streamflow, recharge, and evapotranspiration. Using a moving window with a dilate morphological filter, encroachment scenarios of 11.9 %, 16.1 %, 28.0 %, 40.6 %, 57.5 %, 72.5 % and 100 % were developed and simulated by the calibrated model. At 11.9 % and 100 % encroachment, streamflow was reduced by 4.6 % and 45.5 %, respectively in the Upper Middle Loup River, a tributary to the Platte River. Percolation and deep aquifer recharge increased by 27 % and 26 % at 100 % encroachment. Streamflow in the Platte River, a major water source for Omaha and Lincoln, would decrease by 2.6 %, 5.5 % and 10.5 % for 28 %, 57.5 %, and 100 % encroachment of the Loup River watershed, respectively. This reduction in streamflow could increase nitrate and atrazine concentrations in the Platte River by 4 to 15 % and 4 to 30 %, respectively. While the density of redcedar is minimal, it is important to manage their encroachment to prevent reductions in streamflow and potential increases in pollutant concentrations.

Per- and Polyfluoroalkyl Substance (PFAS) Transport from Groundwater to Streams near a PFAS Manufacturing Facility in North Carolina, USA.

We quantified per- and polyfluoroalkyl substance (PFAS) transport from groundwater to five tributaries of the Cape Fear River near a PFAS manufacturing facility in North Carolina (USA). Hydrologic and PFAS data were coupled to quantify PFAS fluxes from groundwater to the tributaries. Up to 29 PFAS were analyzed, including perfluoroalkyl acids and recently identified fluoroethers. Total quantified PFAS (ΣPFAS) in groundwater was 20-4773 ng/L (mean = 1863 ng/L); the range for stream water was 426-3617 ng/L (mean = 1717 ng/L). Eight PFAS constituted 98% of ΣPFAS; perfluoro-2-(perfluoromethoxy)propanoic acid (PMPA) and hexafluoropropylene oxide dimer acid (GenX) accounted for 61%. For PFAS discharge from groundwater to one tributary, values estimated from stream water measurements (18 ± 4 kg/yr) were similar to those from groundwater measurements in streambeds (22-25 ± 5 kg/yr). At baseflow, 32 ± 7 kg/yr of PFAS discharged from groundwater to the five tributaries, eventually reaching the Cape Fear River. Given the PFAS emission timeline at the site, groundwater data suggest the abundant fluoroethers moved through the subsurface to streams in ≪50 yr. Discharge of contaminated groundwater may lead to long-term contamination of surface water and impacts on downstream drinking water supplies. This work addresses a gap in the PFAS literature: quantifying PFAS mass transfer between groundwater and surface water using field data.

Influence of watershed characteristics on streambed hydraulic conductivity across multiple stream orders.

Streambeds are critical hydrological interfaces: their physical properties regulate the rate, timing, and location of fluxes between aquifers and streams. Streambed vertical hydraulic conductivity (Kv) is a key parameter in watershed models, so understanding its spatial variability and uncertainty is essential to accurately predicting how stresses and environmental signals propagate through the hydrologic system. Most distributed modeling studies use generalized Kv estimates from column experiments or grain-size distribution, but Kv may include a wide range of orders of magnitude for a given particle size group. Thus, precisely predicting Kv spatially has remained conceptual, experimental, and/or poorly constrained. This usually leads to increased uncertainty in modeling results. There is a need to shift focus from scaling up pore-scale column experiments to watershed dimensions by proposing a new kind of approach that can apply to a whole watershed while incorporating spatial variability of complex hydrological processes. Here we present a new approach, Multi-Stemmed Nested Funnel (MSNF), to develop pedo-transfer functions (PTFs) capable of simulating the effects of complex sediment routing on Kv variability across multiple stream orders in Frenchman Creek watershed, USA. We find that using the product of Kv and drainage area as a response variable reduces the fuzziness in selecting the "best" PTF. We propose that the PTF can be used in predicting the ranges of Kv values across multiple stream orders.

Recognition of Regional Water Table Patterns for Estimating Recharge Rates in Shallow Aquifers.

We propose a new method for groundwater recharge rate estimation in regions with stream-aquifer interactions, at a linear scale on the order of 10 km and more. The method is based on visual identification and quantification of classically recognized water table contour patterns. Simple quantitative analysis of these patterns can be done manually from measurements on a map, or from more complex GIS data extraction and curve fitting. Recharge rate is then estimated from the groundwater table contour parameters, streambed gradients, and aquifer transmissivity using an analytical model for groundwater flow between parallel perennial streams. Recharge estimates were obtained in three regions (areas of 1500, 2200, and 3300 km2 ) using available water table maps produced by different methods at different times in the area of High Plains Aquifer in Nebraska. One region is located in the largely undeveloped Nebraska Sand Hills area, while the other two regions are located at a transition zone from Sand Hills to loess-covered area and include areas where groundwater is used for irrigation. Obtained recharge rates are consistent with other independent estimates. The approach is useful and robust diagnostic tool for preliminary estimates of recharge rates, evaluation of the quality of groundwater table maps, identification of priority areas for further aquifer characterization and expansion of groundwater monitoring networks prior to using more detailed methods.

Gas-Tracer Experiment for Evaluating the Fate of Methane in a Coastal Plain Stream: Degassing versus in-Stream Oxidation.

Methane emissions from streams and rivers have recently been recognized as an important component of global greenhouse budgets. Stream methane is lost as evasion to the atmosphere or in-stream methane oxidation. Previous studies have quantified evasion and oxidation with point-scale measurements. In this study, dissolved gases (methane, krypton) were injected into a coastal plain stream in North Carolina to quantify stream CH4 losses at the watershed scale. Stream-reach modeling yielded gas transfer and oxidation rate constants of 3.2 ± 0.5 and 0.5 ± 1.5 d-1, respectively, indicating a ratio of about 6:1. The resulting evasion and oxidation rates of 2.9 mmol m-2 d-1 and 1,140 nmol L-1 d-1, respectively, lie within ranges of published values. Similarly, the gas transfer velocity (K600) of 2.1 m d-1 is consistent with other gas tracer studies. This study illustrates the utility of dissolved-gas tracers for evaluating stream methane fluxes. In contrast to point measurements, this approach provides a larger watershed-scale perspective. Further work is needed to quantify the magnitude of these fluxes under varying conditions (e.g., stream temperature, nutrient load, gradient, flow rate) at regional and global scales before reliable bottom-up estimates of methane evasion can be determined at global scales.

A Tube Seepage Meter for In Situ Measurement of Seepage Rate and Groundwater Sampling.

We designed and evaluated a "tube seepage meter" for point measurements of vertical seepage rates (q), collecting groundwater samples, and estimating vertical hydraulic conductivity (K) in streambeds. Laboratory testing in artificial streambeds show that seepage rates from the tube seepage meter agreed well with expected values. Results of field testing of the tube seepage meter in a sandy-bottom stream with a mean seepage rate of about 0.5 m/day agreed well with Darcian estimates (vertical hydraulic conductivity times head gradient) when averaged over multiple measurements. The uncertainties in q and K were evaluated with a Monte Carlo method and are typically 20% and 60%, respectively, for field data, and depend on the magnitude of the hydraulic gradient and the uncertainty in head measurements. The primary advantages of the tube seepage meter are its small footprint, concurrent and colocated assessments of q and K, and that it can also be configured as a self-purging groundwater-sampling device.