Rethinking Aerobic Respiration in the Hyporheic Zone under Variation in Carbon and Nitrogen Stoichiometry.

Hyporheic zones (HZs)─zones of groundwater-surface water mixing─are hotspots for dissolved organic matter (DOM) and nutrient cycling that can disproportionately impact aquatic ecosystem functions. However, the mechanisms affecting DOM metabolism through space and time in HZs remain poorly understood. To resolve this gap, we investigate a recently proposed theory describing trade-offs between carbon (C) and nitrogen (N) limitations as a key regulator of HZ metabolism. We propose that throughout the extent of the HZ, a single process like aerobic respiration (AR) can be limited by both DOM thermodynamics and N content due to highly variable C/N ratios over short distances (centimeter scale). To investigate this theory, we used a large flume, continuous optode measurements of dissolved oxygen (DO), and spatially and temporally resolved molecular analysis of DOM. Carbon and N limitations were inferred from changes in the elemental stoichiometric ratio. We show sequential, depth-stratified relationships of DO with DOM thermodynamics and organic N that change across centimeter scales. In the shallow HZ with low C/N, DO was associated with the thermodynamics of DOM, while deeper in the HZ with higher C/N, DO was associated with inferred biochemical reactions involving organic N. Collectively, our results suggest that there are multiple competing processes that limit AR in the HZ. Resolving this spatiotemporal variation could improve predictions from mechanistic models, either via more highly resolved grid cells or by representing AR colimitation by DOM thermodynamics and organic N.

A Low-Cost Programmable Reversing Flow Column Apparatus for Investigating Mixing Zones.

This note describes the development and testing of a novel, programmable reversing flow 1D (R1D) experimental column apparatus designed to investigate reaction, sorption, and transport of solutes in aquifers within dynamic reversing flow zones where waters with different chemistries mix. The motivation for constructing this apparatus was to understand the roles of mixing and reaction on arsenic discharging through a tidally fluctuating riverbank. The apparatus can simulate complex transient flux schedules similar to natural flow regimes The apparatus uses an Arduino microcontroller to control flux magnitude through two peristaltic pumps. Solenoid valves control flow direction from two separate reservoirs. In-line probes continually measure effluent electrical conductance, pH, oxidation-reduction potential, and temperature. To understand how sensitive physical solute transport is to deviations from the real hydrograph of the tidally fluctuating river, two experiments were performed using: (1) a simpler constant magnitude, reversing flux direction schedule (RCF); and (2) a more environmentally relevant variable magnitude, reversing flux direction schedule (RVF). Wherein, flux magnitude was ramped up and down according to a sine wave. Modeled breakthrough curves of chloride yielded nearly identical dispersivities under both flow regimes. For the RVF experiment, Peclet numbers captured the transition between diffusion and dispersion dominated transport in the intertidal interval. Therefore, the apparatus accurately simulated conservative, environmentally relevant mixing under transient, variable flux flow regimes. Accurately generating variable flux reversing flow regimes is important to simulate the interaction between flow velocity and chemical reactions where Brownian diffusion of solutes to solid-phase reaction sites is kinetically limited.

Mass fluxes of dissolved arsenic discharging to the Meghna River are sufficient to account for the mass of arsenic in riverbank sediments.

Shallow (<30 m) reducing groundwater commonly contains abundant dissolved arsenic (As) in Bangladesh. We hypothesize that dissolved As in iron (Fe)-rich groundwater discharging to rivers is trapped onto Fe(III)-oxyhydroxides which precipitate in shallow riverbank sediments under the influence of tidal fluctuations. Therefore, the goal of this study is to compare the calculated mass of sediment-bound As that would be sequestered from dissolved groundwater As that discharges through riverbanks of the Meghna River to the observed mass of As trapped within riverbank sediments. To calculate groundwater discharge, a Boussinesq aquifer analytical groundwater flow model was developed and constrained by cyclical seasonal fluctuations in hydraulic heads and river stages observed at three sites along a 13 km reach in central Bangladesh. At all sites, groundwater discharges to the river year-round but most of it passes through an intertidal zone created by ocean tides propagating upstream from the Bay of Bengal in the dry season. The annualized groundwater discharge per unit width at the three sites ranges from 173 to 891 m2/yr (average 540 m2/yr). Assuming that riverbanks have been stable since the Brahmaputra River avulsed far away from this area 200 years ago and dissolved As is completely trapped within riverbank sediments, the mass of accumulated sediment As can be calculated by multiplying groundwater discharge by ambient aquifer As concentrations measured in 1969 wells. Across all sites, the range of calculated sediment As concentrations in the riverbank is 78-849 mg/kg, which is higher than the observed concentrations (17-599 mg/kg). This discovery supports the hypothesis that the dissolved As in groundwater discharge to the river is sufficient to account for the observed buried deposits of As along riverbanks.

Contribution of sedimentary organic matter to arsenic mobilization along a potential natural reactive barrier (NRB) near a river: The Meghna river, Bangladesh.

Elevated dissolved arsenic (As) concentrations in the shallow aquifers of Bangladesh are primarily caused by microbially-mediated reduction of As-bearing iron (Fe) (oxy)hydroxides in organic matter (OM) rich, reducing environments. Along the Meghna River in Bangladesh, interactions between the river and groundwater within the hyporheic zone cause fluctuating redox conditions responsible for the formation of a Fe-rich natural reactive barrier (NRB) capable of sequestering As. To understand the NRB's impact on As mobility, the geochemistry of riverbank sediment (<3 m depth) and the underlying aquifer sediment (up to 37 m depth) was analyzed. A 24-hr sediment-water extraction experiment was performed to simulate interactions of these sediments with oxic river water. The sediment and the sediment-water extracts were analyzed for inorganic and organic chemical parameters. Results revealed no differences between the elemental composition of riverbank and aquifer sediments, which contained 40 ± 12 g/kg of Fe and 7 ± 2 mg/kg of As, respectively. Yet the amounts of inorganic and organic constituents extracted were substantially different between riverbank and aquifer sediments. The water extracted 6.4 ± 16.1 mg/kg of Fe and 0.03 ± 0.02 mg/kg of As from riverbank sediments, compared to 154.0 ± 98.1 mg/kg of Fe and 0.55 ± 0.40 mg/kg of As from aquifer sediments. The riverbank and aquifer sands contained similar amounts of sedimentary organic matter (SOM) (17,705.2 ± 5157.6 mg/kg). However, the water-extractable fraction of SOM varied substantially, i.e., 67.4 ± 72.3 mg/kg in riverbank sands, and 1330.3 ± 226.6 mg/kg in aquifer sands. Detailed characterization showed that the riverbank SOM was protein-like, fresh, low molecular weight, and labile, whereas SOM in aquifer sands was humic-like, older, high molecular weight, and recalcitrant. During the dry season, oxic conditions in the riverbank may promote aerobic metabolisms, limiting As mobility within the NRB.

Absence of ice-bonded permafrost beneath an Arctic lagoon revealed by electrical geophysics.

Relict permafrost is ubiquitous throughout the Arctic coastal shelf, but little is known about it near shore. The presence and thawing of subsea permafrost are vital information because permafrost stores an atmosphere's worth of carbon and protects against coastal erosion. Through electrical resistivity imaging across a lagoon on the Alaska Beaufort Sea coast in summer, we found that the subsurface is not ice-bonded down to ~20 m continually from within the lagoon, across the beach, and underneath an ice-wedge polygon on the tundra. This contrasts with the broadly held idea of a gently sloping ice-bonded permafrost table extending from land to offshore. The extensive unfrozen zone is a marine talik connected to on-land cryopeg. This zone is a potential source and conduit for water and dissolved organic matter, is vulnerable to physical degradation, and is liable to changes in biogeochemical processes that affect carbon cycling and climate feedbacks.

Groundwater as a major source of dissolved organic matter to Arctic coastal waters.

Groundwater is projected to become an increasing source of freshwater and nutrients to the Arctic Ocean as permafrost thaws, yet few studies have quantified groundwater inputs to Arctic coastal waters under contemporary conditions. New measurements along the Alaska Beaufort Sea coast show that dissolved organic carbon and nitrogen (DOC and DON) concentrations in supra-permafrost groundwater (SPGW) near the land-sea interface are up to two orders of magnitude higher than in rivers. This dissolved organic matter (DOM) is sourced from readily leachable organic matter in surface soils and deeper centuries-to millennia-old soils that extend into thawing permafrost. SPGW delivers approximately 400-2100 m3 of freshwater, 14-71 kg of DOC, and 1-4 kg of DON to the coastal ocean per km of shoreline per day during late summer. These substantial fluxes are expected to increase as massive stocks of frozen organic matter in permafrost are liberated in a warming Arctic.

The Impact of the Degree of Aquifer Confinement and Anisotropy on Tidal Pulse Propagation.

Oceanic tidal fluctuations which propagate long distances up coastal rivers can be exploited to constrain hydraulic properties of riverbank aquifers. These estimates, however, may be sensitive to degree of aquifer confinement and aquifer anisotropy. We analyzed the hydraulic properties of a tidally influenced aquifer along the Meghna River in Bangladesh using: (1) slug tests combined with drilling logs and surface resistivity to estimate Transmissivity (T); (2) a pumping test to estimate T and Storativity (S) and thus Aquifer Diffusivity (DPT ); and (3) the observed reduction in the amplitude and velocity of a tidal pulse to calculate D using the Jacob-Ferris analytical solution. Average Hydraulic Conductivity (K) and T estimated with slug tests and borehole lithology were 27.3 m/d and 564 m2 /d, respectively. Values of T and S determined from the pumping test ranged from 400 to 500 m2 /d and 1 to 5 × 10-4 , respectively with DPT ranging from 9 to 40 × 105 m2 /d. In contrast, D estimated from the Jacob-Ferris model ranged from 0.5 to 9 × 104 m2 /d. We hypothesized this error resulted from deviations of the real aquifer conditions from those assumed by the Jacob-Ferris model. Using a 2D numerical model tidal pulses were simulated across a range of conditions and D was calculated with the Jacob-Ferris model. Moderately confined (Ktop /Kaquifer < 0.01) or anisotropic aquifers (Kx /Kz > 10) yield D within a factor of 2 of the actual value. The order of magnitude difference in D between pumping test and Jacob-Ferris model at our site argues for little confinement or anisotropy.

An efficient quasi-3D particle tracking-based approach for transport through fractures with application to dynamic dispersion calculation.

The quantitative study of transport through fractured media has continued for many decades, but has often been constrained by observational and computational challenges. Here, we developed an efficient quasi-3D random walk particle tracking (RWPT) algorithm to simulate solute transport through natural fractures based on a 2D flow field generated from the modified local cubic law (MLCL). As a reference, we also modeled the actual breakthrough curves (BTCs) through direct simulations with the 3D advection-diffusion equation (ADE) and Navier-Stokes equations. The RWPT algorithm along with the MLCL accurately reproduced the actual BTCs calculated with the 3D ADE. The BTCs exhibited non-Fickian behavior, including early arrival and long tails. Using the spatial information of particle trajectories, we further analyzed the dynamic dispersion process through moment analysis. From this, asymptotic time scales were determined for solute dispersion to distinguish non-Fickian from Fickian regimes. This analysis illustrates the advantage and benefit of using an efficient combination of flow modeling and RWPT.

An analytical approach for flow analysis in aquifers with spatially varying top boundary.

Analytical models of groundwater flow with a spatially varying elevation of a top boundary are widely used. However, a vast majority of previous analytical studies truncated the irregularly shaped top section with little to no analyses of the shortcomings of the approximate solutions for the resulting rectangles or parallelepipeds. We present an analytical approach based on a perturbation technique that treats complete domains. It is especially accurate near the top boundary, where fluid circulation is most pronounced and higher accuracy is typically needed, such as in regional or hyporheic systems flow. The approach is illustrated by analyzing flow for a Tóthian unit basin.

Transport zonation limits coupled nitrification-denitrification in permeable sediments.

Measurement of biogeochemical processes in permeable sediments (including the hyporheic zone) is difficult because of complex multidimensional advective transport. This is especially the case for nitrogen cycling, which involves several coupled redox-sensitive reactions. To provide detailed insight into the coupling between ammonification, nitrification and denitrification in stationary sand ripples, we combined the diffusion equilibrium thin layer (DET) gel technique with a computational reactive transport biogeochemical model. The former approach provided high-resolution two-dimensional distributions of NO3(-) and (15)N-N2 gas. The measured two-dimensional profiles correlate with computational model simulations, showing a deep pool of N2 gas forming, and being advected to the surface below ripple peaks. Further isotope pairing calculations on these data indicate that coupled nitrification-denitrification is severely limited in permeable sediments because the flow and transport field limits interaction between oxic and anoxic pore water. The approach allowed for new detailed insight into subsurface denitrification zones in complex permeable sediments.

Effect of permeable biofilm on micro- and macro-scale flow and transport in bioclogged pores.

Simulations of coupled flow around and inside biofilms in pores were conducted to study the effect of porous biofilm on micro- and macro-scale flow and transport. The simulations solved the Navier-Stokes equations coupled with the Brinkman equation representing flow in the pore space and biofilm, respectively, and the advection-diffusion equation. Biofilm structure and distribution were obtained from confocal microscope images. The bulk permeability (k) of bioclogged porous media depends on biofilm permeability (kbr) following a sigmoidal curve on a log-log scale. The upper and lower limits of the curve are the k of biofilm-free media and of bioclogged media with impermeable biofilms, respectively. On the basis of this, a model is developed that predicts k based solely on kbr and biofilm volume ratio. The simulations show that kbr has a significant impact on the shear stress distribution, and thus potentially affects biofilm erosion and detachment. The sensitivity of flow fields to kbr directly translated to effects on the transport fields by affecting the relative distribution of where advection and diffusion dominated. Both kbr and biofilm volume ratio affect the shape of breakthrough curves.

Nutrient inputs from submarine groundwater discharge on the Santiago reef flat, Bolinao, Northwestern Philippines.

Submarine groundwater discharge (SGD) on the reef flat of Bolinao, Pangasinan (Philippines) was mapped using electrical resistivity, 222Rn, and nutrient concentration measurements. Nitrate levels as high as 126 µM, or 1-2 orders of magnitude higher than ambient concentrations, were measured in some areas of the reef flat. Nutrient fluxes were higher during the wet season (May-October) than the dry season (November-April). Dissolved inorganic nitrogen (DIN=NO3+NO2+NH4) and soluble reactive phosphorus (SRP) fluxes during the wet season were 4.4 and 0.2 mmoles m(-2) d(-1), respectively. With the increase population size and anthropogenic activities in Bolinao, an enhancement of SGD-derived nitrogen levels is likely. This could lead to eutrophic conditions in the otherwise oligotrophic waters surrounding the Santiago reef flat.

Geoelectrical imaging of hyporheic exchange and mixing of river water and groundwater in a large regulated river.

Hyporheic mixing and surface water-groundwater interactions are critical processes in aquatic environments. Yet, there is a lack of methods for assessing the spatial extent and distribution of these mixing zones. This study applied time-lapse electrical resistivity (ER) imaging in a 60-m wide and 0.7-m deep alluvial river whose stage periodically varied by 0.7 m due to dam operations to assess dynamic hyporheic mixing and surface water-groundwater interactions. Sixteen channel-spanning repeat ER tomograms (2D sections) over one flood cycle captured the dynamic ER distribution. We mapped a laterally discontinuous hyporheic zone, which had mainly river water circulating through it, several meters into the bed. Underneath the hyporheic zone was a transitional mixing zone intermittently flushed by mixing river water and deep groundwater. Minimally mixed groundwater dominated the deepest areas. ER imaging allows for unraveling hyporheic and deep mixing zone dynamics in large regulated rivers.

Effects of multiscale anisotropy on basin and hyporheic groundwater flow.

Various subsurface flow systems exhibit a combination of small-scale to large-scale anisotropy in hydraulic conductivity (K). The large-scale anisotropy results from systematic trends (e.g., exponential decrease or increase) of K with depth. We present a general two-dimensional solution for calculation of topography-driven groundwater flow considering both small- and large-scale anisotropy in K. This solution can be applied to diverse systems with arbitrary head distribution and geometry of the water table boundary, such as basin or hyporheic flow. In a special case, this solution reduces to the well-known Tóth model of uniform isotropic basin. We introduce an integral measure of flushing intensity that quantifies flushing at different depths. Using this solution, we simulate heads and streamlines and provide analyses of flow structure in the flow domain, relevant to basin analyses or hyporheic flow. It is shown that interactions between small-scale anisotropy and large-scale anisotropy strongly control the flow structure. In the classic Tóth flow model, the flushing intensity curves exhibit quasi-exponential decrease with depth. The new measure is capable of capturing subtle changes in the flow structure. Our study shows that both small- and large-scale anisotropy characteristics have substantial effects that need to be integrated into analysis of topography-driven flow.

A simple constant-head injection test for streambed hydraulic conductivity estimation.

A fast, efficient constant-head injection test (CHIT) for in situ estimation of hydraulic conductivity (K) of sandy streambeds is presented. This test uses constant-head hydraulic injection through a manually driven piezometer. Results from CHIT compare favorably to estimates from slug testing and grain-size analysis. The CHIT combines simplicity of field performance, data interpretation, and accuracy of K estimation in flowing streams.