Alexandre Boisson

Reaction chain modeling of denitrification reactions during a push–pull test

Field quantitative estimation of reaction kinetics is required to enhance our understanding of biogeochemical reactions in aquifers. We extended the analytical solution developed by Haggerty et al. (1998) to model an entire 1st order reaction chain and estimate the kinetic parameters for each reaction step of the denitrification process. We then assessed the ability of this reaction chain to model biogeochemical reactions by comparing it with experimental results from a push-pull test in a fractured crystalline aquifer (Ploemeur, French Brittany). Nitrates were used as the reactive tracer, since denitrification involves the sequential reduction of nitrates to nitrogen gas through a chain reaction (NO3(-)→NO2(-)→NO→N2O→N2) under anaerobic conditions. The kinetics of nitrate consumption and by-product formation (NO2(-), N2O) during autotrophic denitrification were quantified by using a reactive tracer (NO3(-)) and a non-reactive tracer (Br(-)). The formation of reaction by-products (NO2(-), N2O, N2) has not been previously considered using a reaction chain approach. Comparison of Br(-) and NO3(-) breakthrough curves showed that 10% of the injected NO3(-) molar mass was transformed during the 12 h experiment (2% into NO2(-), 1% into N2O and the rest into N2 and NO). Similar results, but with slower kinetics, were obtained from laboratory experiments in reactors. The good agreement between the model and the field data shows that the complete denitrification process can be efficiently modeled as a sequence of first order reactions. The 1st order kinetics coefficients obtained through modeling were as follows: k1=0.023 h(-1), k2=0.59 h(-1), k3=16 h(-1), and k4=5.5 h(-1). A next step will be to assess the variability of field reactivity using the methodology developed for modeling push-pull tracer tests.

Autotrophic denitrification supported by biotite dissolution in crystalline aquifers: (2) transient mixing and denitrification dynamic during long-term pumping

We investigated the mixing and dynamic of denitrification processes induced by long-term pumping in the crystalline aquifer of Ploemeur (Brittany, France). Hydrological and geochemical parameters have been continuously recorded over 15 boreholes in 5km2 on a 25-year period. This extensive spatial and temporal monitoring of conservative as well as reactive compounds is a key opportunity to identify aquifer-scale transport and reactive processes in crystalline aquifers. Time series analysis of the conservative elements recorded at the pumped well were used to determine mixing fractions from different compartments of the aquifer on the basis of a Principal Component Analysis approach coupled with an end-member mixing analysis. We could reveal that pumping thus induces a thorough reorganization of fluxes known as capture, favoring infiltration and vertical fluxes in the recharge zone, and upwelling of deep and distant water at long-term time scales. These mixing fractions were then used to quantify the extent of denitrification linked to pumping. Based on the results from batch experiments described in a companion paper, our computations revealed that i) autotrophic denitrification processes are dominant in this context where carbon sources are limited, that ii) nitrate reduction does not only come from the oxidation of pyrite as classically described in previous studies analyzing denitrification processes in similar contexts, and that iii) biotite plays a critical role in sustaining the nitrate reduction process. Both nitrate reduction, sulfate production as well as fluor release ratios support the hypothesis that biotite plays a key role of electron donor in this context. The batch-to-site similarities support biotite availability and the role by bacterial communities as key controls of nitrate removal in such crystalline aquifers. However, the long term data monitoring also indicates that mixing and reactive processes evolve extremely slowly at the scale of the decade.

Autotrophic denitrification supported by biotite dissolution in crystalline aquifers (1): New insights from short-term batch experiments

We investigate denitrification mechanisms through batch experiments using crushed rock and groundwater from a granitic aquifer subject to long term pumping (Ploemeur, France). Except for sterilized experiments, extensive denitrification reaction induces NO3 decreases ranging from 0.3 to 0.6mmol/L. Carbon concentrations, either organic or inorganic, remain relatively stable and do not document potential heterotrophic denitrification. Batch experiments show a clear effect of mineral dissolution which is documented through cation (K, Na, Ca) and Fluoride production. These productions are tightly related to denitrification progress during the experiment. Conversely, limited amounts of SO4, systematically lower than autotrophic denitrification coupled to sulfur oxidation stoichiometry, are produced during the experiments which indicates that sulfur oxidation is not likely even when pyrite is added to the experiments. Analysis of cation ratios, both in isolated minerals of the granite and within water of the batch, allow the mineral dissolution during the experiments to be quantified. Using cation ratios, we show that batch experiments are characterized mainly by biotite dissolution. As biotite contains 21 to 30% of Fe and 0.3 to 1.7% of F, it constitutes a potential source for these two elements. Denitrification could be attributed to the oxidation of Fe(II) contained in biotite. We computed the amount of K and F produced through biotite dissolution when entirely attributing denitrification to biotite dissolution. Computed amounts show that this process may account for the observed K and F produced. We interpret these results as the development of microbial activity which induces mineral dissolution in order to uptake Fe(II) which is used for denitrification. Although pyrite is probably available, SO4 and cation measurements favor a large biotite dissolution reaction which could account for all the observed Fe production. Chemical composition of groundwater produced from the Ploemeur site indicates similar denitrification processes although original composition shows mainly plagioclase dissolution.

Insights about transport mechanisms and fracture flow channeling from multi-scale observations of tracer dispersion in shallow fractured crystalline rock

In fractured media, solute transport is controlled by advection in open and connected fractures and by matrix diffusion that may be enhanced by chemical weathering of the fracture walls. These phenomena may lead to non-Fickian dispersion characterized by early tracer arrival time, late-time tailing on the breakthrough curves and potential scale effect on transport processes. Here we investigate the scale dependency of these processes by analyzing a series of convergent and push-pull tracer experiments with distance of investigation ranging from 4m to 41m in shallow fractured granite. The small and intermediate distances convergent experiments display a non-Fickian tailing, characterized by a -2 power law slope. However, the largest distance experiment does not display a clear power law behavior and indicates possibly two main pathways. The push-pull experiments show breakthrough curve tailing decreases as the volume of investigation increases, with a power law slope ranging from -3 to -2.3 from the smallest to the largest volume. The multipath model developed by Becker and Shapiro (2003) is used here to evaluate the hypothesis of the independence of flow pathways. The multipath model is found to explain the convergent data, when increasing local dispersivity and reducing the number of pathways with distance which suggest a transition from non-Fickian to Fickian transport at fracture scale. However, this model predicts an increase of tailing with push-pull distance, while the experiments show the opposite trend. This inconsistency may suggest the activation of cross channel mass transfer at larger volume of investigation, which leads to non-reversible heterogeneous advection with scale. This transition from independent channels to connected channels when the volume of investigation increases suggest that both convergent and push-pull breakthrough curves can inform the existence of characteristic length scales.