Dynamics of major and trace elements during seawater intrusion in a coastal sedimentary aquifer impacted by anthropogenic activities.

This study analyzed the dynamics of major ions and trace elements along the groundwater flow path of the coastal sedimentary Todos Santos aquifer in Baja California Sur, Mexico, moderately impacted by anthropogenic activities. The results indicate that the elements Ca2+, Mg2+, Ba2+, Sr2+ and Li+ are mobilized from the aquifer matrix during seawater intrusion, whereas the alkali-elements Na+, K+ and Rb+ are removed from solution, possibly due to cationic exchange process. The anions HCO3- and SO42- and the elements I and B are mobilized due to carbonate mineral weathering, whereas dissolved silica and the halides Br- and F- behave conservatively during salinization. Groundwater NO3- is provided by sewage infiltration. Regarding trace elements behavior, we identify three groups: i) elements that are mobilized during saline intrusion (Fe, Co, V, Se, Re), ii) elements revealing low or no mobilization (Mo, Ni, Cr, Ta, W) and iii) elements that show an undefined tendency (U, As, Ge, Sb, Cu, Mn). The U and NO3- levels in groundwater should be considered carefully because several wells have concentrations close to the permissible levels. This study may be useful as reference for knowing the possible effect of salinization in coastal aquifers under sea level rise scenarios driven by climate change.

Subsurface microbial diversity in deep-granitic-fracture water in Colorado.

A microbial community analysis using 16S rRNA gene sequencing was performed on borehole water and a granite rock core from Henderson Mine, a >1,000-meter-deep molybdenum mine near Empire, CO. Chemical analysis of borehole water at two separate depths (1,044 m and 1,004 m below the mine entrance) suggests that a sharp chemical gradient exists, likely from the mixing of two distinct subsurface fluids, one metal rich and one relatively dilute; this has created unique niches for microorganisms. The microbial community analyzed from filtered, oxic borehole water indicated an abundance of sequences from iron-oxidizing bacteria (Gallionella spp.) and was compared to the community from the same borehole after 2 weeks of being plugged with an expandable packer. Statistical analyses with UniFrac revealed a significant shift in community structure following the addition of the packer. Phospholipid fatty acid (PLFA) analysis suggested that Nitrosomonadales dominated the oxic borehole, while PLFAs indicative of anaerobic bacteria were most abundant in the samples from the plugged borehole. Microbial sequences were represented primarily by Firmicutes, Proteobacteria, and a lineage of sequences which did not group with any identified bacterial division; phylogenetic analyses confirmed the presence of a novel candidate division. This "Henderson candidate division" dominated the clone libraries from the dilute anoxic fluids. Sequences obtained from the granitic rock core (1,740 m below the surface) were represented by the divisions Proteobacteria (primarily the family Ralstoniaceae) and Firmicutes. Sequences grouping within Ralstoniaceae were also found in the clone libraries from metal-rich fluids yet were absent in more dilute fluids. Lineage-specific comparisons, combined with phylogenetic statistical analyses, show that geochemical variance has an important effect on microbial community structure in deep, subsurface systems.

Tracer mass recovery in fractured aquifers estimated from multiple well tests.

Forced-gradient tracer tests in fractured aquifers often report low mass recoveries. In fractured aquifers, fractures intersected by one borehole may not be intersected by another. As a result (1) injected tracer can follow pathways away from the withdrawal well causing low mass recovery and (2) recovered water can follow pathways not connected to the injection well causing significant tracer dilution. These two effects occur along with other forms of apparent mass loss. If the strength of the connection between wells and the amount of dilution can be predicted ahead of time, tracer tests can be designed to optimize mass recovery and dilution. A technique is developed to use hydraulic tests in fractured aquifers to calculate the conductance (strength of connection) between well pairs and to predict mass recovery and amount of dilution during forced gradient tracer tests. Flow is considered to take place through conduits, which connect the wells to each other and to distant sources or sinks. Mass recovery is related to the proportion of flow leaving the injection well and arriving at the withdrawal well, and dilution is related to the proportion of the flow from the withdrawal well that is derived from the injection well. The technique can be used to choose well pairs for tracer tests, what injection and withdrawal rates to use, and which direction to establish the hydraulic gradient to maximize mass recovery and/or minimize dilution. The method is applied to several tracer tests in fractured aquifers in the Clare Valley, South Australia.

Modeling field-scale multiple tracer injection at a low-level waste disposal site in fractured rocks: effect of multiscale heterogeneity and source term uncertainty on conceptual understanding of mass transfer processes.

Multiple factors may affect the scale-up of laboratory multi-tracer injection into structured porous media to the field. Under transient flow conditions and with multiscale heterogeneities in the field, previous attempts to scale-up laboratory experiments have not answered definitely the questions about the governing mechanisms and the spatial extent of the influence of small-scale mass transfer processes such as matrix diffusion. The objective of this research is to investigate the effects of multiscale heterogeneity, mechanistic and site model conceptualization, and source term density effect on elucidating and interpreting tracer movement in the field. Tracer release and monitoring information previously obtained in a field campaign of multiple, conservative tracer injection under natural hydraulic gradients at a low-level waste disposal site in eastern Tennessee, United States, is used for the research. A suite of two-pore-domain, or fracture-matrix, groundwater flow and transport models are calibrated and used to conduct model parameter and prediction uncertainty analyses. These efforts are facilitated by a novel nested Latin-hypercube sampling technique. Our results verify, at field scale, a multiple-pore-domain, multiscale mechanistic conceptual model that was used previously to interpret only laboratory observations. The results also suggest that, integrated over the entire field site, mass flux rates attributable to small-scale mass transfer are comparable to that of field-scale solute transport. The uncertainty analyses show that fracture spacing is the most important model parameter and model prediction uncertainty is relatively higher at the interface between the preferred flow path and its parent bedrock. The comparisons of site conceptual models indicate that the effect of matrix diffusion may be confined to the immediate neighborhood of the preferential flow path. Finally, because the relatively large amount of tracer needed for field studies, it is likely that source term density effect may exaggerate or obscure the effect of matrix diffusion on the movement of tracers from the preferred flow path into the bedrock.

Analysis of a vertical dipole tracer test in highly fractured rock.

The results of a vertical dipole tracer experiment performed in highly fractured rocks of the Clare Valley, South Australia, are presented. The injection and withdrawal piezometers were both screened over 3 m and were separated by 6 m (midpoint to midpoint). Due to the long screen length, several fracture sets were intersected, some of which do not connect the two piezometers. Dissolved helium and bromide were injected into the dipole flow field for 75 minutes, followed by an additional 510 minutes of flushing. The breakthrough of helium was retarded relative to bromide, as was expected due to the greater aqueous diffusion coefficient of helium. Also, only -25% of the total mass injected of both tracers was recovered. Modeling of the tracer transport was accomplished using an analytical one-dimensional flow and transport model for flow through a fracture with diffusion into the matrix. The assumptions made include: streamlines connecting the injection and withdrawal point can be modeled as a dipole of equal strength, flow along each streamline is one dimensional, and there is a constant Peclet number for each streamline. In contrast to many other field tracer studies performed in fractured rock, the actual travel length between piezometers was not known. Modeling was accomplished by fitting the characteristics of the tracer breakthrough curves (BTCs), such as arrival times of the peak concentration and the center of mass. The important steps were to determine the fracture aperture (240 microm) based on the parameters that influence the rate of matrix diffusion (this controls the arrival time of the peak concentration); estimating the travel distance (11 m) by fitting the time of arrival of the centers of mass of the tracers; and estimating fracture dispersivity (0.5 m) by fitting the times that the inflection points occurred on the front and back limbs of the BTCs. This method works even though there was dilution in the withdrawal well, the amount of which can be estimated by determining the value that the modeled concentrations need to be reduced to fit the data (approximately 50%). The use of two tracers with different diffusion coefficients was not necessary, but it provides important checks in the modeling process because the apparent retardation between the two tracers is evidence of matrix diffusion and the BTCs of both tracers need to be accurately modeled by the best fit parameters.