A 3D high-resolution subsurface characteristic (HSC) numerical model to assess migration and distribution of subsurface DNAPLs was developed. Diverse field data, including lithologic, hydrogeologic, petrophysical, and fracture information from both in situ observations and laboratory experiments were utilized for realistic model representation. For the first time, the model integrates hydrogeologic characteristics of both porous (unconsolidated soil (US) and weathered rock (WR)) and fractured rock (FR) media distinctly affecting DNAPLs migration. This allowed for capturing DNAPLs behavior within US, WR, and FR as well as at the boundary between the media, simultaneously. In the 3D HSC model, hypothetical 100-year DNAPLs contamination was simulated, quantitatively analyzing its spatiotemporal distributions by momentum analyses. Twelve sensitivity scenarios examined the impact of WR and FR characteristics on DNAPLs migration, delineating significant roles of WR. DNAPLs primarily resided in WR due to low permeability and limited penetration into FR through sparse inlet fractures. The permeability anisotropy in WR was most influential to determine the DNAPLs fate, surpassing the impacts of FR characteristics, including rock matrix permeability, fracture aperture size, and fracture + rock mean porosity. This study first attempted to apply the field-data-based multiple geological media concept in the DNAPLs prediction model. Consequently, the field-scale effects of WR and media transitions, which have been often overlooked in evaluating DNAPLs contamination, were underscored.

The characterization and evaluation of heat dissipation effects in fractured rock is becoming a priority topic with respect to the potential application of low-temperature thermal remediation in these settings. A three-dimensional numerical model was utilized to investigate heat dissipation-related thermo-hydrological processes in an upper fractured rock layer and a lower impermeable bedrock layer. To identify the factors controlling spatial temperature variances in the fractured rock layer accounting for a scaled heat source and variable groundwater flow, global sensitivity analyses were conducted on the variables using three categories: heat source, groundwater flow, and rock properties. A discrete Latin-hypercube-one-at-a-time method was used to conduct the analyses. A heat dissipation coefficient was proposed to evaluate the correlation between heat dissipation effects and transmissivity based on a case study using the hydrogeological setting of a well-characterized Canadian field site. The results show a significance ranking of three sets of variables controlling heat dissipation processes in both the central and the bottom areas of the heating zone: specifically, heat source > groundwater > rock. The groundwater influx and heat conduction in the rock matrix are key factors determining heat dissipation at the upstream and bottom areas of the heating zone, respectively. The heat dissipation coefficient is closely associated with the transmissivity of the fractured rock in a monotonic relationship. A significant growth rate of the heat dissipation coefficient appears when the transmissivity is between 1 × 10-6 and 2 × 10-5m2/s. The results suggest that the low-temperature thermal remediation can be a promising technique to adapt the significant heat dissipation in highly weathered fractured rock.

Recalcitrant groundwater contamination is a common problem at hazardous waste sites worldwide. Groundwater contamination persists despite decades of remediation efforts at many sites because contaminants sorbed or dissolved within low-conductivity zones can back diffuse into high-conductivity zones, and therefore act as a continuing source of contamination to flowing groundwater. A review of the available literature on remediation of plume persistence due to back diffusion was conducted, and four sites were selected as case studies. Remediation at the sites included pump and treat, enhanced bioremediation, and thermal treatment. Our review highlights that a relatively small number of sites have been studied in sufficient detail to fully evaluate remediation of back diffusion; however, three general conclusions can be made based on the review. First, it is difficult to assess the significance of back diffusion without sufficient data to distinguish between multiple factors contributing to contaminant rebound and plume persistence. Second, high-resolution vertical samples are decidedly valuable for back diffusion assessment but are generally lacking in post-treatment assessments. Third, complete contaminant mass removal from back diffusion sources may not always be possible. Partial contaminant mass removal may nonetheless have potential benefits, similar to partial mass removal from primary DNAPL source zones.

Persistent arsenic (As) pollution sources from anthropogenic activities pose a serious threat to groundwater quality. This work aims to illustrate the application of an innovative remediation technology to remove As from a heavily contaminated fractured aquifer at a historically polluted industrial site. Groundwater circulation well (GCW) technology was tested to significantly increase and accelerate the mobilization and removal of As in the source area. The GCW extracts and re-injects groundwater at different depths of a vertical circulation well. By pumping out and reinjecting in different screen sections of the well, the resulting vertical hydraulic gradients create recirculation cells and affect and mobilize trapped contaminants that cannot be influenced by traditional pumping systems. The first 45-m deep IEG-GCW® system was installed in 2020, equipped with 4 screen sections at different depths and with an above-ground As removal system by oxidation and filtration on Macrolite (Enki). A geomodeling approach supports both remediation and multi-source data interpretation. The first months of operation demonstrate the hydraulic effectiveness of the IEG-GCW® system in the fractured rock aquifer and the ability to significantly enhance As removal compared to conventional pumping wells currently feeding a centralized treatment system. The recirculation flow rate amounts to about 2 m3/h. Water pumped and treated by the GCW system is reintroduced with As concentrations reduced by an average of 20%-60%. During the pilot test, the recirculating system removed 23 kg As whilst the entire central pump-and-treat (P&T) system removed 129 kg, although it treated 100 times more water volume. The P&T plant removed 259 mg As per m3 of pumped and treated groundwater while the GCW removed 4814 mg As per m3 of the treated groundwater. The results offer the opportunity for a more environmentally sustainable remediation approach by actively attacking the contamination source rather than containing the plume.

In mining engineering, crack distribution has a considerable influence on the mechanical behavior and stability of the surrounding rock mass. Using the granite of the Sanshandao gold mine as experimental samples, the deformation and failure of fractured rock were analyzed based on a rock uniaxial compression test with acoustic emission monitoring. We analyzed the characteristics of different stages of rock sample deformation, and evaluated the failure mode of seven types of rock samples. The results show that the cracks had a considerable impact on rock sample strength and mechanical behavior, and the strength of intact rock was the highest, while that of the sample with parallel double cracks was the lowest. The acoustic emission parameters, AF, RA, and lg(AF/RA), have different change trends in different stages of rock deformation and failure. Based on these change trends, the failure modes of rock samples with different crack distributions were identified. Additionally, for the rock samples with seven types of crack distribution, a sudden or progressive failure caused by the b-value curves was observed. The research findings provide a database for deep surrounding rock stability in the study area and provide suggestions for failure prediction.

Fractured rock aquifers are susceptible to contamination, with metal(loid)s rapidly migrating from poorly developed overburden to the fractured rock vadose zone and thus into groundwater. Compared to typical porous aquifers, retention effects within the rock matrix are small, and rapid advection along fractures leads to a higher risk of groundwater contamination. However, the highly complex anisotropic pathways of natural fractures hinder research in this field. To construct reproducible fractures, this study used 3D printing following Computed X-ray Microtomography (μCT) scans of a fractured rock collected in a natural limestone aquifer. Stimulated metalloid release was observed in the fractured rock during column leaching, and the leachate concentrations of arsenic (As) and antimony (Sb) increased by up to 17.5 and 36.4 times, respectively, compared with the porous vadose zone. Fluctuations in fracture metalloid release patterns in dissolved and adsorbed phases were attributed to retention and filtration effects induced by soil particles within fractures. Geophysical properties of the porous overburden, especially the aggregation characteristics, greatly affected the non-equilibrium leaching behavior of As, but had a limited effect on the near-equilibrium leaching of Sb, which was explored by modifying the surficial soil layer with either montmorillonite clay or charcoal. The results of this study provide a novel method and useful information for modeling and risk assessment of fractured rock aquifers.

Colloid transport in fractured rock formations is an important process impacting the fate of pollutants in the subsurface. Despite intensive and outstanding research on their transport phenomena, the impact of small-scale surface heterogeneity on colloid behavior at the fracture scale remains difficult to assess. In particular, there is relatively little direct experimental evidence on the impact of natural fracture surface heterogeneity on colloid transport. To investigate this, we developed an experimental setup allowing the direct visualization of fluorescent colloid transport in a flow cell containing a natural chalk rock sample while simultaneously monitoring effluent colloid concentrations. We used samples containing both a natural fracture surface and an artificially made smooth surface from the same chalk core. We characterized the roughness and chemical composition of both surface types and numerically calculated each surface\'s velocity field. From the experiments, we obtained direct images of colloid transport over the surfaces, from which we calculated their dispersion coefficients and quantified the residual deposition of colloids on the rock surface. We also measured the colloid breakthrough curves by collecting eluent samples from the flow cell outlet. The natural fracture surface exhibited larger physical and chemical heterogeneity than the smooth, artificially generated surface. The aperture variability across the natural surface led to preferential flow and colloid transport which was qualitatively apparent in the fluorescent images. The colloid transport patterns matched the calculated velocity fields well, directly linking the surface topography and aperture variation to colloid transport. Compared to the artificially made surface, the natural surface also showed higher dispersion coefficients, which corresponded to the colloids\' earlier breakthrough from the flow cell. While we found differences between the elemental composition of the natural and artificially smooth surfaces, we could not observe their impact on the colloids\' surface attachment and retention. The main novelty in this work is the coupling of direct colloid transport imaging, breakthrough curve measurements, and colloid surface deposition analyses, in a flow cell containing a natural carbonate rock sample. Our experimental setup can be used to further investigate the link between surface heterogeneity, both chemical and physical, and colloid transport and deposition in natural rock fractures.

Plutonium (Pu) in the subsurface environment can transport in different oxidation states as an aqueous solute or as colloidal particles. The transport behavior of Pu is affected by the relative abundances of these species and can be difficult to predict when they simultaneously exist. This study investigates the concurrent transport of Pu intrinsic colloids, Pu(IV)(aq) and Pu(V-VI)(aq) through a combination of controlled experiments and semi-analytical dual-porosity transport modeling. Pu transport experiments were conducted in a fractured granite at high and low flow rates to elucidate sorption processes and their scaling behavior. In the experiments, Pu(IV)(aq) was the least mobile of the Pu species, Pu(V-VI)(aq) had intermediate mobility, and the colloidal Pu, which consisted mainly of precipitated and/or hydrolyzed Pu(IV), was the most mobile. The semi-analytical modeling revealed that the sorption of each Pu species was rate-limited, as the sorption could not be described by assuming local equilibrium in the experiments. The model was able to describe the sorption of the different Pu species that occurring either on fracture surfaces, in the pores of the rock matrix, or simultaneously in both locations. While equally good fits to the data could be achieved using any of these assumptions, a fracture-dominated process was considered to be the most plausible because it provided the most reasonable estimates of sorption rate constants. Importantly, a key result of this work is that the sorption rate constant of all Pu species tends to decrease with increasing time scales, which implies that Pu will tend to be more mobile at longer time scales than observations at shorter time scales suggest. This result has important implications for predicting the environmental impacts of Pu in the safety assessments of geologic repositories for radioactive waste disposal, and we explore potential mechanistic bases for upscaling the sorption rate constants to time and distance scales that cannot be practically evaluated in experiments.

The potential neurotoxic and carcinogenic effects of the explosives compound RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) on human health requires groundwater remediation strategies to meet low cleanup goals. Bioremediation of RDX is feasible through biostimulation of native microbes with an organic carbon donor but may be less efficient, or not occur at all, in the presence of the common co-contaminants perchlorate and nitrate. Laboratory tests compared biostimulation with bioaugmentation to achieve anaerobic degradation of RDX, perchlorate, and nitrate; a field pilot test was then conducted in a fractured rock aquifer with the selected bioaugmentation approach. Insignificant reduction of RDX, perchlorate, or nitrate was observed by the native microbes in microcosms, with or without biostimulation by addition of lactate. Tests of the RDX-degrading ability of the microbial consortium WBC-2, originally developed for dehalogenation of chlorinated volatile organic compounds, showed first-order biodegradation rate constants ranging from 0.57 to 0.90 per day (half-lives 1.2 to 0.80 days). WBC-2 sustained degradation without daughter product accumulation when repeatedly amended with RDX and lactate for a year. In microcosms with groundwater containing perchlorate and nitrate, RDX degradation began without delay when bioaugmented with 10% WBC-2. Slower RDX degradation occurred with 3% or 5% WBC-2 amendment, indicating a direct relation with cell density. Transient RDX daughter compounds included methylene dinitramine, MNX, and DNX. With WBC-2 amendment, nitrate concentrations immediately decreased to near or below detection, and perchlorate degradation occurred with half-lives of 25-34 days. Single-well injection tests with WBC-2 and lactate showed that the onset of RDX degradation coincided with the onset of sulfide production, which was affected by the initial perchlorate concentration. Biodegradation rates in the pilot injection tests agreed well with those measured in the microcosms. These results support bioaugmentation with an anaerobic culture as a remedial strategy for sites contaminated with RDX, nitrate, and perchlorate.

Time series analyses are a crucial tool for uncovering the patterns and processes shaping microbial communities and their functions, especially in aquatic ecosystems. Subsurface aquatic environments are perceived to be more stable than surface oceans and lakes, due to the lack of sunlight, the absence of photosysnthetically-driven primary production, low temperature variations, and oligotrophic conditions. However, periodic groundwater recharge should affect the structure and succession of groundwater microbiomes. To disentangle the long-term temporal changes in bacterial communities of shallow fractured bedrock groundwater, and identify the drivers of the observed patterns, we analysed bacterial 16S rRNA gene sequencing data for samples collected monthly from three groundwater wells over a six-year period (n = 230) along a hillslope recharge area. We showed that the bacterial communities in the groundwater of limestone-mudstone alternations were not stable over time and exhibited non-linear dissimilarity patterns which corresponded to periods of groundwater recharge. Further, we observed an increase in dissimilarity over time (generalized additive model P < 0.001) indicating that the successive recharge events result in communities that are increasingly more dissimilar to the initial reference time point. The sampling period was able to explain up to 29.5% of the variability in bacterial community composition and the impact of recharge events on the groundwater microbiome was linked to the strength of the recharge and local environmental selection. Many groundwater bacteria originated from the recharge-related sources (mean = 66.5%, SD = 15.1%) and specific bacterial taxa were identified as being either enriched or repressed during recharge events. Overall, similar to surface aquatic environments, the microbiomes in shallow fractured-rock groundwater vary through time, though we revealed groundwater recharges as unique driving factors for these patterns. The high temporal resolution employed here highlights the dynamics of bacterial communities in groundwater, which is an essential resource for the provision of clean drinking water; understanding the biological complexities of these systems is therefore crucial.