Verification and intercomparison of reactive transport codes to describe root-uptake

Several mathematical models have been developed to simulate processes and interactions in the plant rhizosphere. Most of these models are based on a rather simplified description of the soil chemistry and interactions of plant roots in the rhizosphere. In particular the feedback loops between exudation, water and solute uptake are mostly not considered, although their importance in the bioavailability of mineral elements for plants has been demonstrated. The aim of this work was to evaluate three existing coupled speciation-transport tools to model rhizosphere processes. In the field of hydrogeochemistry, such␣computational tools have been developed to␣describe acid-base and redox reactions, complexation and ion exchange, adsorption and precipitation of chemical species in soils and aquifers using thermodynamic and kinetic relationships. We implemented and tested a simple rhizosphere model with three geochemical computational tools (ORCHESTRA, MIN3P, and PHREEQC). The first step was an accuracy analysis of the different solution strategies by comparing the numerical results to the analytical solution of solute uptake (K or Ca) by a single cylindrical root. All models are able to reproduce the concentration profiles as well as the uptake flux. The relative error of the simulated concentration profile decreases with increasing distance from the root. The uptake flux was simulated for all codes with less than 5% error for K and less than 0.4% for Ca. The strength of the codes presented in this paper is that they can also be used to investigate more complex and coupled biogeochemical processes in rhizosphere models. This is shown exemplarily with simulations involving both exudation and uptake and the simultaneous uptake of solute and wate

Dissolved noble gases and stable isotopes as tracers of preferential fluid flow along faults in the Lower Rhine Embayment, Germany

Groundwater in shallow unconsolidated sedimentary aquifers close to the Bornheim fault in the Lower Rhine Embayment (LRE), Germany, has relatively low δ2H and δ18O values in comparison to regional modern groundwater recharge, and 4He concentrations up to 1.7 × 10−4 cm3 (STP) g–1 ± 2.2 % which is approximately four orders of magnitude higher than expected due to solubility equilibrium with the atmosphere. Groundwater age dating based on estimated in situ production and terrigenic flux of helium provides a groundwater residence time of ∼107 years. Although fluid exchange between the deep basal aquifer system and the upper aquifer layers is generally impeded by confining clay layers and lignite, this study’s geochemical data suggest, for the first time, that deep circulating fluids penetrate shallow aquifers in the locality of fault zones, implying  that sub-vertical fluid flow occurs along faults in the LRE. However, large hydraulic-head gradients observed across many faults suggest that they act as barriers to lateral groundwater flow. Therefore, the geochemical data reported here also substantiate a conduit-barrier model of fault-zone hydrogeology in unconsolidated sedimentary deposits, as well as corroborating the concept that faults in unconsolidated aquifer systems can act as loci for hydraulic connectivity between deep and shallow aquifers. The implications of fluid flow along faults in sedimentary basins worldwide are far reaching and of particular concern for carbon capture and storage (CCS) programmes, impacts of deep shale gas recovery for shallow groundwater aquifers, and nuclear waste storage sites where fault zones could act as potential leakage pathways for hazardous fluids

Submarine groundwater discharge to Tampa Bay : nutrient fluxes and biogeochemistry of the coastal aquifer

This paper is not subject to U.S. copyright. The definitive version was published in Marine Chemistry 104 (2007): 85-97, doi:10.1016/j.marchem.2006.10.012.To separately quantify the roles of fresh and saline submarine groundwater discharge (SGD), relative to that of rivers, in transporting nutrients to Tampa Bay, Florida, we used three approaches (Darcy's Law calculations, a watershed water budget, and a 222Rn mass-balance) to estimate rate of SGD from the Pinellas peninsula. Groundwater samples were collected in 69 locations in the coastal aquifer to examine biogeochemical conditions, nutrient concentrations and stoichiometry, and salinity structure. Salinity structure was also examined using stationary electrical resistivity measurements. The coastal aquifer along the Pinellas peninsula was chemically reducing in all locations sampled, and that condition influences nitrogen (N) form and mobility of N and PO43−. Concentrations of NH4+, PO43− and ratio of dissolved inorganic N (DIN) to PO43− were all related to measured oxidation/reduction potential (pε) of the groundwater. Ratio of DIN: PO43− was below Redfield ratio in both fresh and saline groundwater. Nitrogen occurred almost exclusively in reduced forms, NH4+ and dissolved organic nitrogen (DON), suggesting that anthropogenic N is exported from the watershed in those forms. In comparison to other SGD studies, rate of PO43− flux in the seepage zone (μM m− 2 d− 1) in Tampa Bay was higher than previous estimates, likely due to 1) high watershed population density, 2) chemically reducing conditions, and 3) high ion concentrations in fresh groundwater. Estimates of freshwater groundwater flux indicate that the ratio of groundwater discharge to stream flow is not, vert, similar 20 to 50%, and that the magnitudes of both the total dissolved nitrogen and PO43− loads due to fresh SGD are not, vert, similar 40 to 100% of loads carried by streams. Estimates of SGD based on radon inventories in near-shore waters were 2 to 5 times greater than the estimates of freshwater groundwater discharge, suggesting that brackish and saline SGD is also an important process in Tampa Bay and results in flux of regenerated N and P from sediment to surface water.This work was supported by a USGS Mendenhall Postdoctoral Fellowship to K.D.K. and by the USGS Coastal and Marine Geology Program's (CMGP) Tampa Bay Project

Hybrid off-river augmentation system as an alternative raw water resource: the hydrogeochemistry of abandoned mining ponds

The use of water from abandoned mining ponds under a hybrid off-river augmentation system (HORAS) has been initiated as an alternative water resource for raw water. However, it raises the questions over the safety of the use of such waters. In this study, the hydrogeochemical analysis of the waters is presented to assess the degree to which the water has been contaminated. Comparisons were made between sampling sites, i.e. abandoned mining ponds, active sand mining ponds and the receiving streams within Bestari Jaya, Selangor River basin. The aqueous geochemistry analysis showed different hydrochemical signatures of major elements between sites, indicating different sources of minerals in the water. Discharges from the sand mining ponds were found to contain elevated availability of dissolved concentrations of iron, manganese, lead, copper and zinc, among others. However, the quality of the water (from the main river) that is supplied for potable water consumption is at a satisfactory level despite being partly sourced from the abandoned mining ponds. In fact, all the metal concentrations detected were well below the Malaysia Ministry of Health guideline limits for untreated raw water. In addition, the results of the geochemical index analysis (i.e. geoaccumulation index, enrichment factor and modified contamination factor) showed that the rivers and abandoned mining ponds were generally unpolluted with respect to the metals found in sediments

Mineralogical attenuation for metallic remediation in a passive system for mine water treatment

Passive systems with constructed wetlands have been consistently used to treat mine water from abandoned mines. Long-term and cost-effective remediation is a crucial expectation for these water treatment facilities. To achieve that, a complex chain of physical, chemical, biological, and mineralogical mechanisms for pollutants removal must be designed to simulate natural attenuation processes. This paper aims to present geochemical and mineralogical data obtained in a recently constructed passive system (from an abandoned mine, Jales, Northern Portugal). It shows the role of different solid materials in the retention of metals and arsenic, observed during the start-up period of the treatment plant. The mineralogical study focused on two types of materials: (1) the ochre-precipitates, formed as waste products from the neutralization process, and (2) the fine-grained minerals contained in the soil of the wetlands. The ochre-precipitates demonstrated to be poorly ordered iron-rich material, which gave rise to hematite upon artificial heating. The heating experiments also provided mineralogical evidence for the presence of an associated amorphous arsenic-rich compound. Chemical analysis on the freshly ochre-precipitates revealed high concentrations of arsenic (51,867 ppm) and metals, such as zinc (1,213 ppm) and manganese (821 ppm), indicating strong enrichment factors relative to the water from which they precipitate. Mineralogical data obtained in the soil of the wetlands indicate that chlorite, illite, chlorite–vermiculite and mica–vermiculite mixedlayers, vermiculite, kaolinite and goethite are concentrated in the fine-grained fractions (<20 and <2 μm). The chemical analyses show that high levels of arsenic (up to 3%) and metals are also retained in these fractions, which may be enhanced by the low degree of order of the clay minerals as suggested by an XRD study. The obtained results suggest that, although the treatment plant has been receiving water only since 2006, future performance will be strongly dependent on these identified mineralogical pollutant hosts.Fundação para a Ciência e a Tecnologia (FCT