J. Mainhagu

Characterizing long-term contaminant mass discharge and the relationship between reductions in discharge and reductions in mass for DNAPL source areas

The objective of this study was to characterize the temporal behavior of contaminant mass discharge, and the relationship between reductions in contaminant mass discharge and reductions in contaminant mass, for a very heterogeneous, highly contaminated source-zone field site. Trichloroethene is the primary contaminant of concern, and several lines of evidence indicate the presence of organic liquid in the subsurface. The site is undergoing groundwater extraction for source control, and contaminant mass discharge has been monitored since system startup. The results show a significant reduction in contaminant mass discharge with time, decreasing from approximately 1 to 0.15 kg/d over five years. Two methods were used to estimate the mass of contaminant present in the source area at the initiation of the remediation project. One was based on a comparison of two sets of core data, collected 3.5 years apart, which suggests that a significant (~80%) reduction in aggregate sediment-phase TCE concentrations occurred between sampling events. The second method was based on fitting the temporal contaminant mass discharge data with a simple exponential source-depletion function. Relatively similar estimates, 784 and 993 kg, respectively, were obtained with the two methods. These data were used to characterize the relationship between reductions in contaminant mass discharge (CMDR) and reductions in contaminant mass (MR). The observed curvilinear relationship exhibits a reduction in contaminant mass discharge essentially immediately upon the initiation of mass reduction. This behavior is consistent with a system wherein significant quantities of mass are present in hydraulically poorly accessible domains for which mass removal is influenced by rate-limited mass transfer. The results obtained from the present study are compared to those obtained from other field studies to evaluate the impact of system properties and conditions on mass-discharge and mass-removal behavior. The results indicate that factors such as domain scale, hydraulic-gradient status (induced or natural), and flushing-solution composition had insignificant impact on the CMDR-MR profiles and thus on underlying mass-removal behavior. Conversely, source-zone age, through its impact on contaminant distribution and accessibility, was implicated as a critical factor influencing the nature of the CMDR-MR relationship.

Measuring spatial variability of vapor flux to characterize vadose-zone VOC sources: flow-cell experiments.

A method termed vapor-phase tomography has recently been proposed to characterize the distribution of volatile organic contaminant mass in vadose-zone source areas, and to measure associated three-dimensional distributions of local contaminant mass discharge. The method is based on measuring the spatial variability of vapor flux, and thus inherent to its effectiveness is the premise that the magnitudes and temporal variability of vapor concentrations measured at different monitoring points within the interrogated area will be a function of the geospatial positions of the points relative to the source location. A series of flow-cell experiments was conducted to evaluate this premise. A well-defined source zone was created by injection and extraction of a non-reactive gas (SF6). Spatial and temporal concentration distributions obtained from the tests were compared to simulations produced with a mathematical model describing advective and diffusive transport. Tests were conducted to characterize both areal and vertical components of the application. Decreases in concentration over time were observed for monitoring points located on the opposite side of the source zone from the local-extraction point, whereas increases were observed for monitoring points located between the local-extraction point and the source zone. The results illustrate that comparison of temporal concentration profiles obtained at various monitoring points gives a general indication of the source location with respect to the extraction and monitoring points.

Gravity-driven fingers in fractures: experimental study and dispersion analysis by moment method for a point-source injection.

In this study, we investigate the behavior of a dense contaminant injected from a point-source in a fracture. Our experimental model is a transparent Hele-Shaw cell, 0.5 mm of aperture. A saline solution is injected locally representing the point-source pollution. A Laser Induced Fluorescence (LIF) method provides concentration measurement of the pollution plume. Two propagation patterns have been observed: one and two-finger plumes. If the upper part of the plume is stable over time regardless of the second configuration, the moment when the plume separates into two fingers is highly dependent on both injection flow-rate and contaminant concentration. To further investigate the dispersion process inside the fracture, experimental results are interpreted by the spatial and time moment methods. Resulting dispersivities and plume propagation mean velocity are compared to theoretical values derived from a modified Taylor-Aris dispersion tensor. The longitudinal macro-dispersion obtained suggests an asymptotical behavior of the plume spread regardless of the studied configurations. Experimental local dispersivities derived from time and space moments proved to be close at large times to theoretical values predicted by the density-dependent dispersion tensor (Oltéan et al., 2004). Based on those observations the mechanism behind the separation of the plume into two fingers is believed to be significantly impacted by the pre-asymptotic behavior of the dispersion tensor.

Measuring air-water interfacial area for soils using the mass balance surfactant-tracer method.

There are several methods for conducting interfacial partitioning tracer tests to measure air-water interfacial area in porous media. One such approach is the mass balance surfactant tracer method. An advantage of the mass-balance method compared to other tracer-based methods is that a single test can produce multiple interfacial area measurements over a wide range of water saturations. The mass-balance method has been used to date only for glass beads or treated quartz sand. The purpose of this research is to investigate the effectiveness and implementability of the mass-balance method for application to more complex porous media. The results indicate that interfacial areas measured with the mass-balance method are consistent with values obtained with the miscible-displacement method. This includes results for a soil, for which solid-phase adsorption was a significant component of total tracer retention.

Using vapor phase tomography to measure the spatial distribution of vapor concentrations and flux for vadose-zone VOC sources

A test was conducted at a chlorinated-solvent contaminated site in Tucson, AZ, to evaluate the effectiveness of vapor-phase tomography (VPT) for characterizing the distribution of volatile organic contaminants (VOC) in the vadose zone. A soil vapor extraction (SVE) system has been in operation at the site since 2007. Vapor concentration and vacuum pressure were measured at four different depths in each of the four monitoring wells surrounding the extraction well. The test provided a 3D characterization of local vapor concentrations under induced-gradient conditions. Permeability data obtained from analysis of borehole logs were used along with pressure and the vapor-concentration data to determine VOC mass flux within the test domain. A region of higher mass flux was identified in the deepest interval of the S-SW section of the domain, indicating the possible location of a zone with greater contaminant mass. These results are consistent with the TCE-concentration distribution obtained from sediment coring conducted at the site. In contrast, the results of a standard soil gas survey did not indicate the presence of a zone with greater contaminant mass. These results indicate that the VPT test provided a robust characterization of VOC concentration and flux distribution at the site.

Application of phytoscreening to three hazardous waste sites in Arizona

The great majority of prior phytoscreening applications have been conducted in humid and temperate environments wherein groundwater is relatively shallow (~1-6m deep). The objective of this research is to evaluate its use in semi-arid environments for sites with deeper groundwater (>10m). To that end, phytoscreening is applied to three chlorinated-solvent hazardous-waste sites in Arizona. Contaminant concentrations were quantifiable in tree-tissue samples collected from two of the sites (Nogales, Park-Euclid). Contaminant concentrations were detectable, but not quantifiable, for the third site. Tree-tissue concentrations of tetrachloroethene (PCE) ranged from approximately 400-5000ug/kg wet weight for burrobrush, cottonwood, palo verde, and velvet mesquite at the Nogales site. In addition to standard trunk-core samples, leaf samples were collected to test the effectiveness of a less invasive sampling method. Leaf-sample concentrations were quantifiable, but several times lower than the corresponding core-sample concentrations. Comparison of results obtained for the test sites to those reported in the literature suggest that tree species is a major factor mediating observed results. One constraint faced for the Arizona sites was the relative scarcity of mature trees available for sampling, particularly in areas adjacent to industrial zones. The results of this study illustrate that phytoscreening can be used effectively to characterize the presence of groundwater contamination for semi-arid sites with deeper groundwater.

Transfer of Heavy Metals from Soils to Vegetables and Associated Human Health Risk in Selected Sites in Pakistan

Contamination of the food chain with heavy metals is considered as one of the major environmental pathways of human exposure to metals leading to potential health risks. This study aimed to investigate the concentrations of heavy metals such as copper (Cu), zinc (Zn), chromium (Cr), nickel (Ni), and manganese (Mn) in agricultural soils and food crops (fruit, leaf, and root vegetables), and their associated health risks to the local population in selected southern districts of Khyber Pakhtunkhwa Province, Pakistan. The concentrations of the selected metals in soil varied over a wide range, in the following decreasing order: Mn > Zn > Cr > Ni > Cu. The bioaccumulation of metals in vegetables was within the permissible risk limits, except for Cr which showed higher contamination in all the tested food crops. The trend of metal transfer factors for different vegetables was in the order of Cu > Ni > Cr > Mn > Zn, while the calculated daily intake of metals (DIM) in adults and children through consumption of food crops was in the decreasing order of Mn > Zn > Ni > Cr > Cu. The health risk index (HRI) values for the heavy metals for both adults and children were less than 1. Therefore, no significant health risk is anticipated for the local consumers through ingestion of these food crops.

Analysis of trichloroethene vapour in soil-gas samples using solid-sorbent tubes with gas chromatography/mass spectrometry

A sampling method for the determination of chlorinated contaminant vapor concentrations present in the vadose zone, specifically TCE, has been developed, and was applied at the Tucson International Airport Authority (TIAA) Superfund site. The method, modified from the NIOSH Manual of Analytical Methods (NMAM) # 1022 for ambient-air sampling of TCE, is targeted to situations requiring cost effective sample collection, particularly for cases when concentrations are at or below maximum contaminant levels (MCLs). In the modified NIOSH method, TCE vapor is sampled using a solid sorbent tube. Gas Chromatography with Mass Spectrometry is used to confirm and quantify the presence of TCE. The results of laboratory tests demonstrate a maximum TCE vapor load of approximately 22 mg before breakthrough to the secondary sorbent tube section, and an extraction efficiency of approximately 97%. The results of a performance comparison test conducted in the field demonstrated that concentrations obtained with the sorbent tube samplers (~5 ug/L) were similar to those obtained with the use of standard Summa canisters (~3 ug/L). The quantitative detection limit for the new method was 0.03 ug/L under the operative conditions, a significant improvement to current regulatory analytical methods. The results indicate that use of the sorbent tube method will be effective for vapor sample collection at VOC-contaminated sites, particularly in characterizing low concentrations.

Estimating initial contaminant mass based on fitting mass-depletion functions to contaminant mass discharge data: Testing method efficacy with SVE operations data

The mass of contaminant present at a site, particularly in the source zones, is one of the key parameters for assessing the risk posed by contaminated sites, and for setting and evaluating remediation goals and objectives. This quantity is rarely known and is challenging to estimate accurately. This work investigated the efficacy of fitting mass-depletion functions to temporal contaminant mass discharge (CMD) data as a means of estimating initial mass. Two common mass-depletion functions, exponential and power functions, were applied to historic soil vapor extraction (SVE) CMD data collected from 11 contaminated sites for which the SVE operations are considered to be at or close to essentially complete mass removal. The functions were applied to the entire available data set for each site, as well as to the early-time data (the initial 1/3 of the data available). Additionally, a complete differential-time analysis was conducted. The latter two analyses were conducted to investigate the impact of limited data on method performance, given that the primary mode of application would be to use the method during the early stages of a remediation effort. The estimated initial masses were compared to the total masses removed for the SVE operations. The mass estimates obtained from application to the full data sets were reasonably similar to the measured masses removed for both functions (13 and 15% mean error). The use of the early-time data resulted in a minimally higher variation for the exponential function (17%) but a much higher error (51%) for the power function. These results suggest that the method can produce reasonable estimates of initial mass useful for planning and assessing remediation efforts.

Effective integrated frameworks for assessing mining sustainability

The objectives of this research are to review existing methods used for assessing mining sustainability, analyze the limited prior research that has evaluated the methods, and identify key characteristics that would constitute an enhanced sustainability framework that would serve to improve sustainability reporting in the mining industry. Five of the most relevant frameworks were selected for comparison in this analysis, and the results show that there are many commonalities among the five, as well as some disparities. In addition, relevant components are missing from all five. An enhanced evaluation system and framework were created to provide a more holistic, comprehensive method for sustainability assessment and reporting. The proposed framework has five components that build from and encompass the twelve evaluation characteristics used in the analysis. The components include Foundation, Focus, Breadth, Quality Assurance, and Relevance. The enhanced framework promotes a comprehensive, location-specific reporting approach with a concise set of well-defined indicators. Built into the framework is quality assurance, as well as a defined method to use information from sustainability reports to inform decisions. The framework incorporates human health and socioeconomic aspects via initiatives such as community-engaged research, economic valuations, and community-initiated environmental monitoring.