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.

Agricultural land use changes stream dissolved organic matter via altering soil inputs to streams.

Agricultural land use leads to significant changes in both the quality (e.g., sources and compositions) and quantity of dissolved organic matter (DOM) exported from terrestrial to aquatic ecosystems. However, the effect of agricultural activities often interacts with those of hydroclimatic drivers, making it difficult to delineate agriculture-induced changes and identify associated mechanisms. Using partial least square path modeling (PLS-PM), we examined the relative importance of agricultural land use, stream order, precipitation, and temperature in mediating allochthonous versus autochthonous sources and pathways that influenced stream DOM quality and quantity. We analyzed stream water DOM from 15 small streams draining watersheds across a gradient of agricultural land use in Southeast USA for about one year. For DOM quantity, agricultural land use increased the export of DOC and various DOM pools (terrestrial humic, microbial humic, and protein-like DOM) from land to streams, and for DOM quality, agricultural streams showed greater proportions of microbial humic compounds than forested streams. The PLS-PM model for DOM quantity accounted for 75.5% of total variance and identified that agricultural land use increased stream water DOM quantity primarily through increasing allochthonous inputs, which can be attributed to shallower flow paths in agricultural watersheds that enabled the export of organic materials from the upper, organic-rich soil horizon. PLS-PM models for DOM quality only explained ~13% of the total variance, highlighting the complex dynamics between environmental drivers and stream water DOM. Relative to commonly used multivariate statistic modeling (e.g., redundancy analysis (RDA)), PLS-PM models offer the advantages of identifying the primary pathway by which agricultural lands alter freshwater DOM and quantifying the relative importance of interactive effects of agriculture and hydroclimatic drivers. Therefore, structural equation modeling is a powerful tool that should be more widely adopted to distinguish among multiple drivers and mechanisms regulating freshwater biogeochemistry.

Current Magnitude and Mechanisms of Groundwater Discharge in the Arctic: Case Study from Alaska.

To better understand groundwater-surface water dynamics in high latitude areas, we conducted a field study at three sites in Alaska with varying permafrost coverage. The natural groundwater tracer ((222)Rn, radon) was used to evaluate groundwater discharge, and electrical resistivity tomography (ERT) was used to examine subsurface mixing dynamics. Different controls govern groundwater discharge at these sites. In areas with sporadic permafrost (Kasitsna Bay), the major driver of submarine groundwater discharge is tidal pumping, due to the large tidal oscillations, whereas at Point Barrow, a site with continuous permafrost and small tidal amplitudes, fluxes are mostly affected by seasonal permafrost thawing. Extended areas of low resistivity in the subsurface alongshore combined with high radon in surface water suggests that groundwater-surface water interactions might enhance heat transport into deeper permafrost layers promoting permafrost thawing, thereby enhancing groundwater discharge.