Deep denitrification: Stream and groundwater biogeochemistry reveal contrasted but connected worlds above and below.

Excess nutrients from agricultural and urban development have created a cascade of ecological crises around the globe. Nutrient pollution has triggered eutrophication in most freshwater and coastal ecosystems, contributing to a loss in biodiversity, harm to human health, and trillions in economic damage every year. Much of the research conducted on nutrient transport and retention has focused on surface environments, which are both easy to access and biologically active.

Stratification of reactivity determines nitrate removal in groundwater.

Biogeochemical reactions occur unevenly in space and time, but this heterogeneity is often simplified as a linear average due to sparse data, especially in subsurface environments where access is limited. For example, little is known about the spatial variability of groundwater denitrification, an important process in removing nitrate originating from agriculture and land use conversion. Information about the rate, arrangement, and extent of denitrification is needed to determine sustainable limits of human activity and to predict recovery time frames.

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 NO decreases ranging from 0.3 to 0.

Dating groundwater with dissolved silica and CFC concentrations in crystalline aquifers.

Estimating intermediate water residence times (a few years to a century) in shallow aquifers is critical to quantifying groundwater vulnerability to nutrient loading and estimating realistic recovery timelines. While intermediate groundwater residence times are currently determined with atmospheric tracers such as chlorofluorocarbons (CFCs), these analyses are costly and would benefit from other tracer approaches to compensate for the decreasing resolution of CFC methods in the 5-20 years range. In this context, we developed a framework to assess the capacity of dissolved silica (DSi) to inform residence times in shallow aquifers.

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 5km 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.

Unmasking Amides: Ruthenium-Catalyzed Protodecarbonylation of N-Substituted Phthalimide Derivatives.

The unprecedented transformation of a wide range of synthetically appealing phthalimides into amides in a single-step operation has been achieved in high yields and short reaction times using a ruthenium catalyst. Mechanistic studies revealed a unique, homogeneous pathway involving five-membered ring opening and CO release with water being the source of protons.

Field Continuous Measurement of Dissolved Gases with a CF-MIMS: Applications to the Physics and Biogeochemistry of Groundwater Flow.

In the perspective of a temporal and spatial exploration of aquatic environments (surface and groundwater), we developed a technique for field continuous measurements of dissolved gases with a precision better than 1% for N, O, CO, He, Ar, 2% for Kr, 8% for Xe, and 3% for CH, NO and Ne. With a large resolution (from 1 × 10 to 1 × 10 ccSTP/g) and a capability of high frequency analysis (1 measure every 2 s), the CF-MIMS (Continuous Flow Membrane Inlet Mass Spectrometer) is an innovative tool allowing the investigation of a large panel of hydrological and biogeochemical processes in aquatic systems. Based on the available MIMS technology, this study introduces the development of the CF-MIMS (conception for field experiments, membrane choices, ionization) and an original calibration procedure allowing the quantification of mass spectral overlaps and temperature effects on membrane permeability.

Groundwater Isolation Governs Chemistry and Microbial Community Structure along Hydrologic Flowpaths.

This study deals with the effects of hydrodynamic functioning of hard-rock aquifers on microbial communities. In hard-rock aquifers, the heterogeneous hydrologic circulation strongly constrains groundwater residence time, hydrochemistry, and nutrient supply. Here, residence time and a wide range of environmental factors were used to test the influence of groundwater circulation on active microbial community composition, assessed by high throughput sequencing of 16S rRNA.

Impact of climate changes during the last 5 million years on groundwater in basement aquifers.

Climate change is thought to have major effects on groundwater resources. There is however a limited knowledge of the impacts of past climate changes such as warm or glacial periods on groundwater although marine or glacial fluids may have circulated in basements during these periods. Geochemical investigations of groundwater at shallow depth (80-400 m) in the Armorican basement (western France) revealed three major phases of evolution: (1) Mio-Pliocene transgressions led to marine water introduction in the whole rock porosity through density and then diffusion processes, (2) intensive and rapid recharge after the glacial maximum down to several hundred meters depths, (3) a present-day regime of groundwater circulation limited to shallow depth.