Modeling Volatile Chemical Transport, Biodecay, and Emission to Indoor Air

A model is presented for estimating vapor concentrations in buildings because of volatilization from soil contaminated by non- aqueous phase liquids (NAPL) or from dissolved contaminants in ground water. The model considers source depletion, diffusive- dispersive transport of the contaminant of concern (COC) and of oxygen and oxygen-limited COC biodecay. Diffusive-advective transport through foundations and vapor losses caused by foundation cross-flow are considered. Competitive oxygen use by various species is assumed to be proportional to the product of the average dissolved-phase species concentration and a biopreference factor. Laboratory and field data indicate the biopreference factor to be proportional to the organic carbon partition coefficient for the fuel hydrocarbons studied. Predicted indoor air concentrations were sensitive to soil type and subbase permeability. Lower concentrations were predicted for buildings with shallow foundations caused by flushing of contaminants by cross-flow. NAPL source depletion had a large impact on average exposure concentration. Barometric pumping had a minor effect on indoor air emissions for the conditions studied. Risk-based soil cleanup levels were much lower when biodecay was considered because of the existence of a threshold source concentration below which no emissions occur. Computed cleanup levels at NAPL-contaminated sites were strongly dependent on total petroleum hydrocarbon (TPH) content and COC soil concentration. The model was applied to two field sites with gasoline-contaminated ground water. Confidence limits of predicted indoor air concentrations spanned approximately two orders of magnitude considering uncertainty in model parameters. Measured contaminant concentrations in indoor air were within model-predicted confidence limits.     

Variable near-surface deformation along the Commerce segment of the Commerce geophysical lineament, southeast Missouri to southern Illinois, USA

Recent studies have demonstrated a plausible link between surface and near-surface tectonic features and the vertical projection of the Commerce geophysical lineament (CGL). The CGL is a 5- to 10-km-wide zone of basement magnetic and gravity anomalies traceable for more than 600 km, extending from Arkansas through southeast Missouri and southern Illinois and into Indiana. Twelve kilometers of high-resolution seismic reflection data, collected at four sites along a 175-km segment of the CGL projection, are interpreted to show varying amounts of deformation involving Tertiary and some Quaternary sediments. Some of the locally anomalous geomorphic features in the northern Mississippi embayment region (i.e., paleoliquefaction features, anomalous directional changes in stream channels, and areas of linear bluff escarpments) overlying the CGL can be correlated with specific faults and/or narrow zones of deformed (faulted and folded) strata that are imaged on high-resolution seismic reflection data. There is an observable change in near-surface deformation style and complexity progressing from the southwest to the northeast along the trace of the CGL. The seismic reflection data collaborate mapping evidence which suggests that this region has undergone a complex history of deformation, some of which is documented to be as young as Quaternary, during multiple episodes of reactivation under varying stress fields. This work, along with that of other studies presented in this volume, points to the existence of at least one major crustal feature outside the currently defined zone of seismic activity (New Madrid Seismic Zone) that should be considered as a significant potential source zone for seismogenic activity within the midcontinent region of the United States.     

Preserving Ground Water Samples With Hydrochloric Acid Does Not Result in the Formation of Chloroform

Water samples collected for the determination of volatile organic compounds (VOCs) are often preserved with hydrochloric acid (HCl) to inhibit the biotransformation of the analytes of interest until the chemical analyses can he performed. However, it is theoretically possible that residual free chlorine in the HCl can react with dissolved organic carbon (DOC) to form chloroform via the haloform reaction. Analyses of 1501 ground water samples preserved with HCl from the U.S. Geological Survey's National Water-Quality Assessment Program indicate that chloroform was the most commonly detected VOC among 60 VOCs monitored. The DOC concentrations were not significantly larger in samples with detectable chloroform than in those with no delectable chloroform, nor was there any correlation between the concentrations of chloroform and DOC. Furthermore, chloroform was detected more frequently in shallow ground water in urban areas (28.5% of the wells sampled) than in agricultural areas (1.6% of the wells sampled), which indicates that its detection was more related to urban land-use activities than to sample acidification. These data provide strong evidence that acidification with HCl does not lead to the production of significant amounts of chloroform in ground water samples. To verify these results, an acidification study was designed to measure the concentrations of all trihalomethanes (THMs) that can form as a result of HCl preservation in ground water samples and to determine if ascorbic acid (C₆H₈O₆) could inhibit this reaction if it did occur. This study showed that no THMs were formed as a result of HCl acidification, and that ascorbic acid had no discernible effect on the concentrations of THMs measured.     

Illuminating Subsurface Microbial Water Quality Patterns Using Adenosine Triphosphate and Dynamic Time Warping Approaches

Aquifer microbial water quality evaluations are often performed by collecting groundwater samples from monitoring wells. While samples collected from continuously pumped sources are seldom disputed as representative of the aquifer, natural biofilm present in the vicinity of well screens may introduce unwanted microbial artefacts in monitoring wells that are only periodically sampled. The need for well water purging to obtain samples void of these artefacts has been widely recognized. However, purging methods are not standardized; many approaches presume that physico-chemical water quality stability achieved through the removal of 3 to 5 well volumes is indicative of the stability of target analytes. Using a data set collected from a shallow unconfined aquifer in Southern Ontario, Canada, the need for using dedicated approaches that account for the time-dependent nature of microbial water quality changes was demonstrated. Specifically, the utility of adenosine triphosphate (ATP) as a rapid, field-ready biochemical indicator of microbial water quality stability was investigated. This work shows that ATP concentrations reflect time-limited (bio)colloid transport processes that are consistent with other microbial water quality parameters monitored, but different from commonly measured physical and chemical water quality indicators of well purging adequacy. ATP concentrations occasionally fluctuated even after 3 or 4 h of purging, indicating that microbial artefacts attributable to biofilms in the vicinity of the well screen can still persist. The recurrence of characteristic ATP patterns in each well was systematically examined through the novel application of dynamic time warping (DTW), a nonparametric time series analysis approach. These patterns are believed to be linked with seasonal hydrogeological conditions, which warrant consideration in the design and interpretation of subsurface microbial water quality investigations.     

Using model error in response history analysis to evaluate component calibration methods

This research is part of a larger effort to better understand and quantify the epistemic model uncertainty in dynamic response-history simulations. This paper focuses on how calibration methods influence model uncertainty. Structural models in earthquake engineering are typically built up from independently calibrated component models. During component calibration, engineers often use experimental component response under quasi-static loading to find parameters that minimize the error in structural response under dynamic loading. Since the calibration and the simulation environments are different, if a calibration method wants to provide optimal parameters for simulation, it has to focus on features of the component response that are important from the perspective of global structural behavior. Relevance describes how efficiently a calibration method can focus on such important features. A framework of virtual experiments and a methodology is proposed to evaluate the influence of calibration relevance on model error in simulations. The evaluation is demonstrated through a case study with buckling-restrained braced frames (BRBF). Two calibration methods are compared in the case study. The first, highly relevant calibration method is based on stiffness and hardening characteristics of braces; the second, less relevant calibration method is based on the axial force response of braces. The highly relevant calibration method consistently identified the preferable parameter sets. In contrast, the less relevant calibration method showed poor to mediocre performance. The framework and methodology presented here are not limited to BRBF. They have the potential to facilitate and systematize the improvement of component-model calibration methods for any structural system.