Does It Pay Off to Explicitly Link Functional Gene Expression to Denitrification Rates in Reaction Models?

Environmental omics and molecular-biological data have been proposed to yield improved quantitative predictions of biogeochemical processes. The abundances of functional genes and transcripts relate to the number of cells and activity of microorganisms. However, whether molecular-biological data can be quantitatively linked to reaction rates remains an open question. We present an enzyme-based denitrification model that simulates concentrations of transcription factors, functional-gene transcripts, enzymes, and solutes. We calibrated the model using experimental data from a well-controlled batch experiment with the denitrifier Paracoccous denitrificans. The model accurately predicts denitrification rates and measured transcript dynamics. The relationship between simulated transcript concentrations and reaction rates exhibits strong non-linearity and hysteresis related to the faster dynamics of gene transcription and substrate consumption, relative to enzyme production and decay. Hence, assuming a unique relationship between transcript-to-gene ratios and reaction rates, as frequently suggested, may be an erroneous simplification. Comparing model results of our enzyme-based model to those of a classical Monod-type model reveals that both formulations perform equally well with respect to nitrogen species, indicating only a low benefit of integrating molecular-biological data for estimating denitrification rates. Nonetheless, the enzyme-based model is a valuable tool to improve our mechanistic understanding of the relationship between biomolecular quantities and reaction rates. Furthermore, our results highlight that both enzyme kinetics (i.e., substrate limitation and inhibition) and gene expression or enzyme dynamics are important controls on denitrification rates

Estimating Groundwater Recharge in Fully Integrated pde-Based Hydrological Models

Groundwater recharge is the main forcing of regional groundwater flow. In traditional partial-differential-equation (pde)-based models that treat aquifers as separate compartments, groundwater recharge needs to be defined as a boundary condition or it is a coupling condition to other compartments. Integrated models that treat the vadose and phreatic zones as a continuum allow for a more sophisticated calculation of subsurface fluxes, as feedbacks between both zones are captured. However, they do not contain an explicit groundwater-recharge term so it needs to be estimated by post-processing. Groundwater recharge consists of changes in groundwater storage and of the flux crossing the water table, which can be calculated based on hydraulic gradients. We introduce a method to evaluate the change of groundwater storage by a time-cumulative water balance over the depth section of water table fluctuations, avoiding the use of a specific yield. We demonstrate the approach first by a simple 1-D vertical model that does not allow for lateral outflow and illustrates the ambiguity of computing groundwater recharge by different methods. We then apply the approach to a 3-D model with a complex topography and subsurface structure. The latter example shows that groundwater recharge is highly variable in space and time with notable differences between regional and local estimates. Local heterogeneity of topography or subsurface properties results in complex redistribution patterns of groundwater. In fully integrated models, river-groundwater exchange flow may severely bias the estimate of groundwater recharge. We, therefore, advise masking out groundwater recharge at river locations

Comparison of Instantaneous and Constant-Rate Stream Tracer Experiments Through Parametric Analysis of Residence Time Distributions

Artificial tracers are frequently employed to characterize solute residence times in stream systems and infer the nature of water retention. When the duration of tracer application is different between experiments, tracer breakthrough curves at downstream locations are difficult to compare directly. We explore methods for deriving stream solute residence time distributions (RTD) from tracer test data, allowing direct, non-parametric comparison of results from experiments of different durations. Paired short- and long-duration field experiments were performed using instantaneous and constant-rate tracer releases, respectively. The experiments were conducted in two study reaches that were morphologically distinct in channel structure and substrate size. Frequency- and time domain deconvolution techniques were used to derive RTDs from the resulting tracer concentrations. Comparisons of results between experiments of different duration demonstrated few differences in hydrologic retention characteristics inferred from short- and long-term tracer tests. Because non-parametric RTD analysis does not presume any shape of the distribution, it is useful for comparisons across tracer experiments with variable inputs and for validations of fundamental transport model assumptions

Spatial and temporal evolution of groundwater arsenic contamination in the Red River delta, Vietnam: Interplay of mobilisation and retardation processes

Geogenic arsenic (As) contamination of groundwater poses a major threat to global health, particularly in Asia. To mitigate this exposure, groundwater is increasingly extracted from low-As Pleistocene aquifers. This, however, disturbs groundwater flow and potentially draws high-As groundwater into low-As aquifers. Here we report a detailed characterisation of the Van Phuc aquifer in the Red River Delta region, Vietnam, where high-As groundwater from a Holocene aquifer is being drawn into a low-As Pleistocene aquifer. This study includes data from eight years (2010–2017) of groundwater observations to develop an understanding of the spatial and temporal evolution of the redox status and groundwater hydrochemistry. Arsenic concentrations were highly variable (0.5–510 μg/L) over spatial scales of <200 m. Five hydro(geo)chemical zones (indicated as A to E) were identified in the aquifer, each associated with specific As mobilisation and retardation processes. At the riverbank (zone A), As is mobilised from freshly deposited sediments where Fe(III)-reducing conditions occur. Arsenic is then transported across the Holocene aquifer (zone B), where the vertical intrusion of evaporative water, likely enriched in dissolved organic matter, promotes methanogenic conditions and further release of As (zone C). In the redox transition zone at the boundary of the two aquifers (zone D), groundwater arsenic concentrations decrease by sorption and incorporations onto Fe(II) carbonates and Fe(II)/Fe(III) (oxyhydr)oxides under reducing conditions. The sorption/incorporation of As onto Fe(III) minerals at the redox transition and in the Mn(IV)-reducing Pleistocene aquifer (zone E) has consistently kept As concentrations below 10 μg/L for the studied period of 2010–2017, and the location of the redox transition zone does not appear to have propagated significantly. Yet, the largest temporal hydrochemical changes were found in the Pleistocene aquifer caused by groundwater advection from the Holocene aquifer. This is critical and calls for detailed investigations