Chemicals of emerging concern in coastal aquifers: Assessment along the land-ocean interface.

Submarine Groundwater Discharge (SGD) is recognized as a relevant source of pollutants to the sea, but little is known about its relevance as a source of chemicals of emerging concern (CECs). Here, both the presence and distribution of a wide range of CECs have been evaluated in the most comprehensive manner to date, in a well-characterized Mediterranean coastal aquifer near Barcelona (Spain). Samples from coastal groundwater and seawater allowed for the unique spatial characterization of the pollutants present in the land-ocean interface, an outstanding research gap that required attention. The main goals were (1) to determine CECs in the aquifer, so as to evaluate the SGD as a relevant source of marine pollution, and (2) to identify new tracers to improve our understanding of SGD dynamics. To this end, 92 CECs were located in the aquifer by using wide-scope analytical target methodologies (>2000 chemicals). Among them, the perfluoroalkyl and polyfluoroalkyl substances (PFAS), along with the pharmaceuticals carbamazepine and topiramate, were revealed to be good markers for tracing anthropogenic contamination in ground- and seawater, in concrete situations (e.g., highly contaminated sites). Additionally, non-target analysis expanded the number of potential tracers, making it a promising tool for identifying both the source and the fate of pollutants.

Tritium transport in non-saturated concrete under temperature fluctuations.

This work studies the effect of the environmental conditions on tritium transport in concrete cells storing radioactive waste. Water with high concentration of tritium was leaking from drains situated in these concrete cells, which indicates flow of water and tritium transport in these cells. 2D numerical models together with temperature and humidity measurements suggested that this leak of tritiated water is caused by a combination of thermo-hydraulic processes occurring in the unsaturated concrete, that comprise capillary rise from the groundwater, evaporation and condensation due to temperature gradients caused by seasonal temperature fluctuations outside. Following this conceptual model, numerical models have been developed to study the tritium transport in the concrete. Model results show that tritium concentration varies according to evaporation and condensation processes inside the concrete cell. An analysis of tritium fluxes revealed that differences in transport mechanisms in liquid and gas can cause concentration gradients of tritium in zones of high water content very different or even opposite to those in zones with low water content. From our numerical calculations, we conclude that there is no release of tritiated water to the groundwater.

Vapor flow control in dune sediments under dry bare soil conditions.

The study presents daily values of inward and outward vapor flux crossing the soil-atmosphere boundary in dependence on meteorological parameters and soil moisture. Measurements of vapor flux, soil moisture and meteorological parameters were evaluated during days without rainfall between 2015 and 2019. Vapor flux data were obtained at 1 min intervals by a precision lysimeter installed in the Doñana National Park, southwest Spain. Meteorological data were measured on-site at 10-min intervals, including temperature, relative humidity, wind velocity and net radiation. After manual and automatic noise elimination of the lysimeter data, time series of a summer and winter period were generated for selected relevant parameters. Furthermore, daily cumulative data of inward and outward vapor flux were calculated for the entire period and analyzed for their control by meteorological parameters and soil moisture. Results show moderate correlations of daily outward vapor flux on the diurnal amplitudes of temperature and humidity whereas daily inward vapor indicates moderate correlations with temperature and soil moisture. A correction coefficient for potential evaporation to estimate actual evaporation was determined based on soil moisture and air temperature.

Analytical Solution to Assess the Induced Seismicity Potential of Faults in Pressurized and Depleted Reservoirs.

Displaced faults crossing the reservoir could significantly increase the induced earthquake frequency in geo-energy projects. Understanding and predicting the stress variation in such cases is essential to minimize the risk of induced seismicity. Here, we adopt the inclusion theory to develop an analytical solution for the stress response to pore pressure variations within the reservoir for both permeable and impermeable faults with offset ranging from zero to the reservoir thickness. By analyzing fault stability changes due to reservoir pressurization/depletion under different scenarios, we find that (1) the induced seismicity potential of impermeable faults is always larger than that of permeable faults under any initial and injection conditions-the maximum size of the fault undergoing failure is 3-5 times larger for impermeable than for permeable faults; (2) stress concentration at the corners results in the occurrence of reversed slip in normal faults with a normal faulting stress regime; (3) while fault offset has no impact on the slip potential for impermeable faults, the slip potential increases with the offset for permeable faults, which indicates that non-displaced permeable faults constitute a safer choice for site selection; (4) an impermeable fault would rupture at a lower deviatoric stress, and at a smaller pressure buildup than a permeable one; and (5) the induced seismicity potential is overestimated and the injectivity underestimated if the stress arching (i.e., the poromechanical coupling) is neglected. This analytical solution is a useful tool for site selection and for supporting decision making during the lifetime of geo-energy projects.

Evaluation of self-combustion risk in tire derived aggregate fills.

Lightweight tire derived aggregate (TDA) fills are a proven recycling outlet for waste tires, requiring relatively low cost waste processing and being competitively priced against other lightweight fill alternatives. However its value has been marred as several TDA fills have self-combusted during the early applications of this technique. An empirical review of these cases led to prescriptive guidelines from the ASTM aimed at avoiding this problem. This approach has been successful in avoiding further incidents of self-combustion. However, at present there remains no rational method available to quantify self-combustion risk in TDA fills. This means that it is not clear which aspects of the ASTM guidelines are essential and which are accessory. This hinders the practical use of TDA fills despite their inherent advantages as lightweight fill. Here a quantitative approach to self-combustion risk evaluation is developed and illustrated with a parametric analysis of an embankment case. This is later particularized to model a reported field self-combustion case. The approach is based on the available experimental observations and incorporates well-tested methodological (ISO corrosion evaluation) and theoretical tools (finite element analysis of coupled heat and mass flow). The results obtained offer clear insights into the critical aspects of the problem, allowing already some meaningful recommendations for guideline revision.

Bacterial transformation and biodegradation processes simulation in horizontal subsurface flow constructed wetlands using CWM1-RETRASO.

The performance and reliability of the CWM1-RETRASO model for simulating processes in horizontal subsurface flow constructed wetlands (HSSF CWs) and the relative contribution of different microbial reactions to organic matter (COD) removal in a HSSF CW treating urban wastewater were evaluated. Various different approaches with diverse influent configurations were simulated. According to the simulations, anaerobic processes were more widespread in the simulated wetland and contributed to a higher COD removal rate [72-79%] than anoxic [0-1%] and aerobic reactions [20-27%] did. In all the cases tested, the reaction that most contributed to COD removal was methanogenesis [58-73%]. All results provided by the model were in consonance with literature and experimental field observations, suggesting a good performance and reliability of CWM1-RETRASO. According to the good simulation predictions, CWM1-RETRASO is the first mechanistic model able to successfully simulate the processes described by the CWM1 model in HSSF CWs.

Experimental and modeling investigation of multicomponent reactive transport in porous media.

We present an experimental and modeling study of solute transport in porous media in the presence of mixing-induced precipitation of a solid phase. Conservative and reactive transport experiments were performed in a quasi-two-dimensional laboratory flow cell, filled with homogeneous and heterogeneous porous media. Conservative experiments were performed by injecting solutions containing sodium chloride and calcium chloride into the domain. In reactive transport experiments, inlet solutions of calcium chloride and sodium carbonate were injected in parallel, resulting in calcium carbonate precipitation where the solutions mix. Experimental results were used as a benchmark to examine the performance of a reactive transport numerical model. Good agreement between model predictions and experimental results was obtained for the conservative transport experiments. The reactive transport experiments featured the formation of a calcium carbonate mineral phase within the mixing zone between the two solutions, which controlled the spatial evolution of calcium carbonate in the domain. Numerical simulations performed on high resolution grids for both the homogeneous and heterogeneous porous systems underestimated clogging of the system. Although qualitative agreement between model results and experimental observations was obtained, accurate model predictions of the spatial evolution of calcium concentrations at sample points within the flow cell could not be achieved.

Analysis of a deep well recharge experiment by calibrating a reactive transport model with field data.

This paper describes the modeling of the hydrogeochemical effects of deep well recharge of oxic water into an anoxic pyrite-bearing aquifer. Kinetic expressions have been used for mineral dissolution-precipitation rates and organic matter oxidation. Hydrological and chemical parameters of the model were calibrated to field measurements. The results showed that oxidation of pyrite (FeS(2)) and, to a lesser extent, organic matter dominate the changes in quality of the recharged water during its passage through the aquifer. The recharge leads to the consumption of oxygen and nitrate and the formation of sulfate and ferrihydrite. Complexation reactions, cation exchange and precipitation and dissolution of calcite, siderite and rhodochrosite were also identified through the modeling. Despite problems of non-uniqueness of the calibrated parameters, the model was used successfully to depict the geochemical processes occurring in the aquifer. Non-uniqueness can be avoided by constraining the model as much as possible to measurements and/or data from literature, although they cannot be considered always as fixed values and should be considered as stochastic variables instead.