Up to 25 percent of the operating budget for contaminated site restoration projects is spent on site characterization, including long-term monitoring of contaminant concentrations. The sensitivity, selectivity, and reproducibility of analytical methods have improved to the point where sampling techniques bear the primary responsibility for the accuracy and precision of the data. Most samples represent discrete concentrations in time and space; with sampling points frequently limited in both dimensions, sparse data sets are heavily extrapolated and the quality of data further limited.

Methods are presented for characterizing contaminants in water (groundwater and surface waters) and indoor air. These techniques are integrative, providing information averaged over time and/or space, as opposed to instantaneous point measurements. Contaminants are concentrated from the environment, making these methods applicable to trace contaminants. These methods have the potential to complement existing techniques, providing the practitioner with opportunities to reduce costs and improve the quality of the data used in decision making.

A conceptual model for integrative sampling of environmental waters is developed and a literature review establishes an advantage in precision for active samplers. A programmable sampler was employed to measure the concentration of chromate in a shallow aquifer exhibiting time-dependent contaminant concentrations, providing a unique data set and sustainability benefits. The analysis of heat exchanger condensate, a waste stream generated by air conditioning, is demonstrated in a non-intrusive method for indoor air quality assessment. In sum, these studies present new opportunities for effective, sustainable environmental characterization.

Vapor intrusion (VI), can pose health risks to building occupants. Assessment and mitigation at VI impacted sites have been guided by a site conceptual model (SCM) in which vapors originate from subsurface sources, diffuse through soil matrix and enter into a building by gas flow across foundation cracks. Alternative VI pathways and groundwater table fluctuations are not often considered.

Alternative VI pathways, involving vapor transport along sewer lines and other subsurface infrastructure, have recently been found to be significant contributors to VI impacts at some sites. This study evaluated approaches for identifying and characterizing the significance of alternative VI pathways and assessed the effectiveness of conventional mitigation at a site with an alternative VI pathway that can be manipulated to be on or off. The alternative pathway could not be identified using conventional pathway assessment procedures and can only be discovered under controlled pressure method (CPM) conditions. Measured emission rates were two orders of magnitude greater than screening model estimates and sub-foundation vertical soil gas profiles changed and were no longer consistent with the conventional VI conceptual model when the CPM test was conducted. The pipe flow VI pathway reduced the vacuum performance of the sub-slab depressurization (SSD) VI mitigation system, but the SSD system still provided sufficient protection to the house.

The relationship between groundwater table fluctuations and subsurface vapor emissions and transport is examined using multi-year data from the field site, and is studied in the laboratory. In addition, a broader range of conditions is examined through use of modeling validated with the experimental data. The results indicate that fluctuating groundwater tables will lead to amplified volatile organic chemical (VOC) emissions from groundwater to soil surface relative to steady water table elevation, however, the magnitude of this amplification is less concerned when long-term water fluctuation present. No clear correlations were found between VOC emissions and water table changes at the study site where annual water table fluctuations of about 0.3 m existed. Significant VOC emission amplifications by water table fluctuation would be expected under shallow groundwater conditions according to model analysis results.

This dissertation focused on the development and application of state-of-the-art monitoring tools and analysis methods for tracking the fate of trace level contaminants in the natural and built water environments, using fipronil as a model; fipronil and its primary degradates (known collectively as fiproles) are among a group of trace level emerging environmental contaminants that are extremely potent arthropodic neurotoxins. The work further aimed to fill in data gaps regarding the presence and fate of fipronil in engineered water systems, specifically in a wastewater treatment plant (WWTP), and in an engineered wetland. A review of manual and automated “active” water sampling technologies motivated the development of two new automated samplers capable of in situ biphasic extraction of water samples across the bulk water/sediment interface of surface water systems. Combined with an optimized method for the quantification of fiproles, the newly developed In Situ Sampler for Biphasic water monitoring (IS2B) was deployed along with conventional automated water samplers, to study the fate and occurrence of fiproles in engineered water environments; continuous sampling over two days and subsequent analysis yielded average total fiprole concentrations in wetland surface water (9.9 ± 4.6 to 18.1 ± 4.6 ng/L) and wetland sediment pore water (9.1 ± 3.0 to 12.6 ± 2.1 ng/L). A mass balance of the WWTP located immediately upstream demonstrated unattenuated breakthrough of total fiproles through the WWTP with 25 ± 3 % of fipronil conversion to degradates, and only limited removal of total fiproles in the wetland (47 ± 13%). Extrapolation of local emissions (5–7 g/d) suggests nationwide annual fiprole loadings from WWTPs to U.S. surface waters on the order of about one half to three quarters of a metric tonne. The qualitative and quantitative data collected in this work have regulatory implications, and the sampling tools and analysis strategies described in this thesis have broad applicability in the assessment of risks posed by trace level environmental contaminants.

Vapor intrusion (VI) pathway assessment often involves the collection and analysis of groundwater, soil gas, and indoor air data. There is temporal variability in these data, but little is understood about the characteristics of that variability and how it influences pathway assessment decision-making. This research included the first-ever collection of a long-term high-frequency indoor air data set at a house with VI impacts overlying a dilute chlorinated solvent groundwater plume. It also included periodic synoptic snapshots of groundwater and soil gas data and high-frequency monitoring of building conditions and environmental factors. Indoor air trichloroethylene (TCE) concentrations varied over three orders-of-magnitude under natural conditions, with the highest daily VI activity during fall, winter, and spring months. These data were used to simulate outcomes from common sampling strategies, with the result being that there was a high probability (up to 100%) of false-negative decisions and poor characterization of long-term exposure. Temporal and spatial variability in subsurface data were shown to increase as the sampling point moves from source depth to ground surface, with variability of an order-of-magnitude or more for sub-slab soil gas. It was observed that indoor vapor sources can cause subsurface vapor clouds and that it can take days to weeks for soil gas plumes created by indoor sources to dissipate following indoor source removal. A long-term controlled pressure method (CPM) test was conducted to assess its utility as an alternate approach for VI pathway assessment. Indoor air concentrations were similar to maximum concentrations under natural conditions (9.3 μg/m3 average vs. 13 μg/m3 for 24 h TCE data) with little temporal variability. A key outcome was that there were no occurrences of false-negative results. Results suggest that CPM tests can produce worst-case exposure conditions at any time of the year. The results of these studies highlight the limitations of current VI pathway assessment approaches and demonstrate the need for robust alternate diagnostic tools, such as CPM, that lead to greater confidence in data interpretation and decision-making.

Hydrocarbon spill site cleanup is challenging when contaminants are present in lower permeability layers. These are difficult to remediate and may result in long-term groundwater impacts. The research goal is to investigate strategies for long-term reduction of contaminant emissions from sources in low permeability layers through partial source treatment at higher/lower permeability interfaces. Conceptually, this provides a clean/reduced concentration zone near the interface, and consequently a reduced concentration gradient and flux from the lower permeability layer. Treatment by in-situ chemical oxidation (ISCO) was evaluated using hydrogen peroxide (H2O2) and sodium persulfate (Na2S2O8). H2O2 studies included lab and field-scale distribution studies and lab emission reduction experiments. The reaction rate of H2O2 in soils was so fast it did not travel far (<1 m) from delivery points under typical flow conditions. Oxygen gas generated and partially trapped in soil pores served as a dissolved oxygen (DO) source for >60 days in field and lab studies. During that period, the laboratory studies had reduced hydrocarbon impacts, presumably from aerobic biodegradation, which rebounded once the O2 source depleted. Therefore field monitoring should extend beyond the post-treatment elevated DO. Na2S2O8 use was studied in two-dimensional tanks (122-cm tall, 122-cm wide, and 5-cm thick) containing two contrasting permeability layers (three orders of magnitude difference). The lower permeability layer initially contained a dissolved-sorbed contaminant source throughout this layer, or a 10-cm thick non-aqueous phase liquid (NAPL)-impacted zone below the higher/lower permeability interface. The dissolved-sorbed source tank was actively treated for 14 d. Two hundred days after treatment, the emission reduction of benzene, toluene, ethylbenzene, and p-xylene (BTEX) were 95-99% and methyl tert-butyl ether (MTBE) was 63%. The LNAPL-source tank had three Na2S2O8 and two sodium hydroxide (NaOH) applications for S2O82- base activation. The resulting emission reductions for BTEX, n-propylbenzene, and 1,3,5 trymethylbenzene were 55-73%. While less effective at reducing emissions from LNAPL sources, the 14-d treatment delivered sufficient S2O82- though diffusion to remediate BTEX from the 60 cm dissolved-sorbed source. The overall S2O82- utilization in the dissolved source experiment was calculated by mass balance to be 108-125 g S2O82-/g hydrocarbon treated.

This dissertation explores the use of bench-scale batch microcosms in remedial design of contaminated aquifers, presents an alternative methodology for conducting such treatability studies, and - from technical, economical, and social perspectives - examines real-world application of this new technology. In situ bioremediation (ISB) is an effective remedial approach for many contaminated groundwater sites. However, site-specific variability necessitates the performance of small-scale treatability studies prior to full-scale implementation. The most common methodology is the batch microcosm, whose potential limitations and suitable technical alternatives are explored in this thesis. In a critical literature review, I discuss how continuous-flow conditions stimulate microbial attachment and biofilm formation, and identify unique microbiological phenomena largely absent in batch bottles, yet potentially relevant to contaminant fate. Following up on this theoretical evaluation, I experimentally produce pyrosequencing data and perform beta diversity analysis to demonstrate that batch and continuous-flow (column) microcosms foster distinctly different microbial communities. Next, I introduce the In Situ Microcosm Array (ISMA), which took approximately two years to design, develop, build and iteratively improve. The ISMA can be deployed down-hole in groundwater monitoring wells of contaminated aquifers for the purpose of autonomously conducting multiple parallel continuous-flow treatability experiments. The ISMA stores all sample generated in the course of each experiment, thereby preventing the release of chemicals into the environment. Detailed results are presented from an ISMA demonstration evaluating ISB for the treatment of hexavalent chromium and trichloroethene. In a technical and economical comparison to batch microcosms, I demonstrate the ISMA is both effective in informing remedial design decisions and cost-competitive. Finally, I report on a participatory technology assessment (pTA) workshop attended by diverse stakeholders of the Phoenix 52nd Street Superfund Site evaluating the ISMA's ability for addressing a real-world problem. In addition to receiving valuable feedback on perceived ISMA limitations, I conclude from the workshop that pTA can facilitate mutual learning even among entrenched stakeholders. In summary, my doctoral research (i) pinpointed limitations of current remedial design approaches, (ii) produced a novel alternative approach, and (iii) demonstrated the technical, economical and social value of this novel remedial design tool, i.e., the In Situ Microcosm Array technology.

In situ remediation of contaminated aquifers, specifically in situ bioremediation (ISB), has gained popularity over pump-and-treat operations. It represents a more sustainable approach that can also achieve complete mineralization of contaminants in the subsurface. However, the subsurface reality is very complex, characterized by hydrodynamic groundwater movement, geological heterogeneity, and mass-transfer phenomena governing contaminant transport and bioavailability. These phenomena cannot be properly studied using commonly conducted laboratory batch microcosms lacking realistic representation of the processes named above. Instead, relevant processes are better understood by using flow-through systems (sediment columns). However, flow-through column studies are typically conducted without replicates. Due to additional sources of variability (e.g., flow rate variation between columns and over time), column studies are expected to be less reproducible than simple batch microcosms. This was assessed through a comprehensive statistical analysis of results from multiple batch and column studies. Anaerobic microbial biotransformations of trichloroethene and of perchlorate were chosen as case studies. Results revealed that no statistically significant differences were found between reproducibility of batch and column studies. It has further been recognized that laboratory studies cannot accurately reproduce many phenomena encountered in the field. To overcome this limitation, a down-hole diagnostic device (in situ microcosm array - ISMA) was developed, that enables the autonomous operation of replicate flow-through sediment columns in a realistic aquifer setting. Computer-aided design (CAD), rapid prototyping, and computer numerical control (CNC) machining were used to create a tubular device enabling practitioners to conduct conventional sediment column studies in situ. A case study where two remediation strategies, monitored natural attenuation and bioaugmentation with concomitant biostimulation, were evaluated in the laboratory and in situ at a perchlorate-contaminated site. Findings demonstrate the feasibility of evaluating anaerobic bioremediation in a moderately aerobic aquifer. They further highlight the possibility of mimicking in situ remediation strategies on the small-scale in situ. The ISMA is the first device offering autonomous in situ operation of conventional flow-through sediment microcosms and producing statistically significant data through the use of multiple replicates. With its sustainable approach to treatability testing and data gathering, the ISMA represents a versatile addition to the toolbox of scientists and engineers.