No description available.

The emergence of antibiotic resistance in riverine systems has become a growing issue worldwide. The use of watershed-scale models is popular with many other water quality issues but not in the case of antibiotic resistance. In this study, we introduce a watershed-scale bacteria fate and transport model to simulate antibiotic resistance in E. coli. This model was developed through amendments to an existing watershed-scale physically based hydrological model (SWAT), and the newly modified model was called SWAT-ARB. The SWAT-ARB model was employed in the receiving environment of a WWTP in the Adyar River basin, India. The SWAT-ARB model simulations of resistant fractions (resistant E. coli concentration/E. coli concentration) in stream water were analyzed by the flow levels with the application of a range of parameter values. It is concluded that the model can be used to test prevailing hypotheses and evaluate the current state of knowledge. For instance, model simulations suggest that the influx of ARB can be a primary driver of antibiotic resistance in rivers compared to ambient antibiotic concentrations. We used the SWAT-ARB model to quantify the impact of climate change on antibiotic resistance. Six climate models were used to obtain the future climates in two distinct scenarios. The model was applied to three watersheds as Adyar basin- India, Crab Creek basin- USA, and upper Viskan basin- Sweden. It was concluded that temperature increase may greatly affect the colder climates (Crab Creek and Viskan) with higher simulated resistant fractions. In case of Adyar basin, resistant fractions are alleviated in high flow conditions, while aggravated in low flow conditions. / Doctor of Philosophy / The antibiotic resistance occurs when bacteria no longer responds to antibiotics. Hence, the diseases that caused by resistant bacteria are harder to treat. These antibiotic resistant bacteria end up in our rivers because of our heavy use of antibiotics in human and animal treatments. Thus, the spread of antibiotic resistance has become a water quality issue in the rivers worldwide. Scientists generally use computer models to understand water quality issues in rivers. These computer models are important because of high cost of monitoring and their use in finding how environment works. Up to the date of this publication, there is no sophisticated enough model to simulate antibiotic resistance in rivers. Hence, we created a river basin scale model to simulate antibiotic resistance. We found that the influx of ARB can be a primary driver of antibiotic resistance in rivers compared to ambient antibiotic concentrations. The model was applied to three watersheds as Adyar basin- India, Crab Creek basin- USA, and upper Viskan basin- Sweden. It was concluded that temperature increase may greatly affect the colder climates (Crab Creek and Viskan) with higher antibiotic resistant bacteria compared to susceptible bacteria.

Rivers are arteries that connect land and sea, and provide a conduit and reactor for allochthonous and autochthonous organic carbon sources (OC) delivered to the coastal ocean. In comparison to marine waters, inland waters quantitatively represent only a fraction of the marine system; however, their importance to global C cycling maybe disproportional to its actual size. Inland systems are subject to multiple sources of OC (autochthonous and allochthonous) that vary individually in space and time with respect to their concentration and potential bacterial bioavailability. This study investigates the impact of high and ambient inorganic nutrient concentrations on the bacterial bioavailability of potential exogenous and internal organic C sources to bacterial decomposition in the Chickahominy River using a long term incubation approach. In addition the elemental composition of each organic C substrate is investigated as a predictor of OC source bioavailability. The results of sole source incubations showed that autochthonous SAV sources were the most labile whereas soil derived OC was the least bioavailable, irrespective of nutrients. However, leaf litter sources showed relatively high bioavailability. The C:N ratios of SAV, Peltandra virginica, Botryococcus braunii, leaf litter, and soil (19.6, 12.4, 15, 29.7, 8.4 respectively) oppose historically accepted theory that autochthonous OC sources with low C:N ratios are a more bioavailable substrate for bacteria than allochthonous OC substrates with higher C:N ratios. The results of this study should provide a better of understanding of the interaction between inorganic nutrients and OC decomposition from allochthonous and autochthonous sources as well and potentially allow model prediction of OC lability based on its elemental signature.

Perfluoroalkylated substances (PFAS) are persistent contaminants that are widely distributed in the global environment. Despite the fact that these chemicals have been manufactured and used for over 50 years, there has been little scientific and regulatory interest until very recently. An important research priority over the past decade has been to gain a better understanding of the mechanisms and pathways explaining the presence of these compounds in remote regions. One explanation is related to the use and release of volatile precursor compounds which undergo atmospheric transport and are also susceptible to degradation to PFAS through gas phase reactions with radical species. The main purpose of this doctoral thesis was to investigate an alternative explanation, namely the long-range transport (LRT) of PFAS themselves, which have been released into the environment in substantial quantities during manufacturing and product use. Papers I – III explore the LRT potential of perfluorocarboxylic acids and perfluorocarboxylates and demonstrate that both oceanic and atmospheric transport are efficient pathways of dispersion from source to remote regions of the Northern Hemisphere. Oceanic transport of perfluorooctane sulfonate (PFOS) was shown to be an important process in Paper IV as well. The role of precursor transport and degradation to PFOS was also examined in this paper. The most interesting aspect of the fate and transport of PFOS precursors is the rapid response in ambient concentrations exhibited by these compounds in the model simulations following production phase-out. Since precursor compounds are known to degrade to PFOS in vivo, the modeling results demonstrate that this exposure pathway is a plausible explanation for the declining trends in PFOS concentrations reported for marine mammals in some remote environments.

<p>The study and application of materials possessing size dimensions in the nano scale range and, as a result, unique properties have led to the birth of a new field; nanotechnology. Scientists and engineers have discovered and are exploiting the novel physicochemical characteristics of nanoparticles (NPs) to enhance consumer products and technologies in ways superior to their bulk counterparts. Escalating production and use of NPs will unavoidably lead to release and exposure to environmental systems. This introduction of emerging potential contaminant NPs will provide new and interesting challenges for exposure and risk forecasting as well as environmental endurance.</p><p>The ultimate goal of this research is to develop a framework that incorporates experimental and computational efforts to assess and better understand the exposure of metal and metal-oxide NPs released to wastewater treatment plants (WWTPs) and further implications on land application units (LAUs) where biosolids can be applied. The foundation of the computational effort is comprised of Monte Carlo mass balance models that account for the unique processes affecting NP fate and transport through the different technical compartments of a WWTP and LAU. Functional assay and bioreactor experiments in environmental media were used to determine parameters capable of describing the critical processes that impact the fate of NPs in wastewater. </p><p>The results of this research indicate that a simplified, but still environmentally relevant nano-specific exposure assessment is possible through experimentation to parameterize adapted models. Black box modeling efforts, which have been shown in previous studies, show no disadvantage relative to discretization of technical compartments as long as all key transport and fate mechanisms are considered. The distribution coefficient (_), an experimentally determined, time-dependent parameter, can be used to predict the distribution of NPs between the liquid and solid phase in WWTPs. In addition, this parameter can be utilized a step further for the estimation of the more fundamental, time independent attachment efficiency between the NPs and the solids in wastewater. The NP core, size, and surface coating will influence the value of these parameters in addition to the background particle characteristics as the parameters are specific to the environmental system of study. For the metal and metal-oxide NPs studied, preferential overall association of approximately 90% or greater with the solid phase of wastewater was observed and predicted. </p><p>Furthermore, NP transformations including dissolution, redox reactions, and adsorption can potentially impact exposure. For example, experimental results showed that nano-CeO2 is reduced from Ce(IV) to Ce(III) when in contact with wastewater bacteria where Ce2S3 will likely govern the Ce(III) phase in biosolids. From the literature, similar transformations have been observed with Ag and ZnO NPs to Ag2S and ZnS. With respect to TiO2 NPs, studies indicated that due to high insolubility, these NPs would not undergo transformation in WWTPs. The distribution and transformation rate coefficients can then be used in fate models to predict the NP species exposed to aquatic and terrestrial systems and environmentally relevant concentrations released from WWTPs. </p><p>Upon completion of the WWTP model, the predicted concentrations of NPs and NP transformation byproducts released in effluent and biosolids were attainable. A simple mass balance model for NP fate in LAUs was then developed to use this output. Results indicate that NP loading on LAUs would be very low but that build up over time to steady state could result in mass concentrations on the order of the typical level for the background metal in soil. Transport processes of plant uptake and leaching were expected to greatly impact the solid phase concentration of the NPs remaining in the LAU, while rainfall did not impart a significant influence upon variation between low and high annual amounts. The significance of this research is the introduction of a method for NP exposure assessment in WWTPs and subsequently in LAUs. This work describes and quantifies the key processes that will impact Ag, TiO2, CeO2 and ZnO NP fate and transport, which can inform future studies, the modeling community and regulatory agencies.</p> / Dissertation

The fate and transport of cyanide in groundwater was investigated at gasworks sites in southeastern Australia. Two gasworks sites were investigated during this research: one in Tasmania and the other in Adelaide. The research followed three principal methods of investigation: field work, laboratory work and numerical modelling. The field work was aimed at observing the behaviour of cyanide in highly contaminated groundwater environments. Measured field parameters and laboratory analytical results from groundwater sampling were used to describe the hydrodynamics and hydrochemistry of the groundwater environment, providing a framework for groundwater flow and solute transport modelling. Groundwater and soil samples were also collected for use in laboratory experiments. The results from both field sites indicate contrasting hydrogeological environments, however, inorganic (metallic and non-metallic) and organic contaminants were measured in solution at both sites. The maximum concentrations observed at both sites were up to 5,300 mg/L CN(Total) (Adelaide site) and 21 mg/L CN(Total) (Tasmanian site). Results from geochemical modelling of solutes in groundwater at the field sites indicate that cyanide was predominantly in its free form in solution, with metallo- and alkali-cyanides also present.

abstract: In this work, the vapor transport and aerobic bio-attenuation of compounds from a multi-component petroleum vapor mixture were studied for six idealized lithologies in 1.8-m tall laboratory soil columns. Columns representing different geological settings were prepared using 20-40 mesh sand (medium-grained) and 16-minus mesh crushed granite (fine-grained). The contaminant vapor source was a liquid composed of twelve petroleum hydrocarbons common in weathered gasoline. It was placed in a chamber at the bottom of each column and the vapors diffused upward through the soil to the top where they were swept away with humidified gas. The experiment was conducted in three phases: i) nitrogen sweep gas; ii) air sweep gas; iii) vapor source concentrations decreased by ten times from the original concentrations and under air sweep gas. Oxygen, carbon dioxide and hydrocarbon concentrations were monitored over time. The data allowed determination of times to reach steady conditions, effluent mass emissions and concentration profiles. Times to reach near-steady conditions were consistent with theory and chemical-specific properties. First-order degradation rates were highest for straight-chain alkanes and aromatic hydrocarbons. Normalized effluent mass emissions were lower for lower source concentration and aerobic conditions. At the end of the study, soil core samples were taken every 6 in. Soil moisture content analyses showed that water had redistributed in the soil during the experiment. The soil at the bottom of the columns generally had higher moisture contents than initial values, and soil at the top had lower moisture contents. Profiles of the number of colony forming units of hydrocarbon-utilizing bacteria/g-soil indicated that the highest concentrations of degraders were located at the vertical intervals where maximum degradation activity was suggested by CO2 profiles. Finally, the near-steady conditions of each phase of the study were simulated using a three-dimensional transient numerical model. The model was fit to the Phase I data by adjusting soil properties, and then fit to Phase III data to obtain compound-specific first-order biodegradation rate constants ranging from 0.0 to 5.7x103 d-1. / Dissertation/Thesis / Ph.D. Civil and Environmental Engineering 2012

An awareness of mercury (Hg) contamination in various aquatic environments around the world has increased over the past decade, mostly due to its ability to concentrate in the biota. Because the presence and distribution of Hg in aquatic systems depend on many factors (e.g., pe, pH, salinity, temperature, organic and inorganic ligands, sorbents, etc.), it is crucial to understand its fate and transport in the presence of complexing constituents and natural sorbents, under those different factors. An improved understanding of the subject will support the selection of monitoring, remediation, and restoration technologies. The coupling of equilibrium chemical reactions with transport processes in the model PHREEQC offers an advantage in simulating and predicting the fate and transport of aqueous chemical species of interest. Thus, a great variety of reactive transport problems could be addressed in aquatic systems with boundary conditions of specific interest. Nevertheless, PHREEQC lacks a comprehensive thermodynamic database for Hg. Therefore, in order to use PHREEQC to address the fate and transport of Hg in aquatic environments, it is necessary to expand its thermodynamic database, confirm it and then evaluate it in applications where potential exists for its calibration and continued validation. The objectives of this study were twofold: 1) to develop, expand, and confirm the Hg database of the hydrogeochemical PHREEQC to enhance its capability to simulate the fate of Hg species in the presence of complexing constituents and natural sorbents under different conditions of pH, redox, salinity and temperature; and 2) to apply and evaluate the new database in flow and transport scenarios, at two field test beds: Oak Ridge Reservation, Oak Ridge, TN and Everglades National Park, FL, where Hg is present and is of much concern. Overall, this research enhanced the capability of the PHREEQC model to simulate the coupling of the Hg reactions in transport conditions. It also demonstrated its usefulness when applied to field situations.

Contaminants of emerging concern (CECs) are an unregulated suite of constituents frequently detected in environmental waters, which possess the potential to cause a host of reproductive and developmental problems in humans and wildlife. Degradation pathways of several CECs are well-characterized in idealized laboratory settings, but CEC fate and transport in complex field settings is poorly understood. In the present study I use a multi-tracer solute injection to study and quantify physical transport and photodegradation in a wastewater effluent-impacted stream in Ankeny, Iowa. Conservative tracers are used to quantify physical transport processes in the stream. Use of reactive fluorescent tracers allows for isolation of the relative contribution of photodegradation within the system. Field data were used to calibrate a one-dimensional transport model, and forward modeling was then used to predict the transport of sulfamethoxazole, an antibiotic in the effluent which is susceptible to photolysis. Results show that accurate predictions of reactive CECs at the scale of stream reaches can be made using the fate and transport model based on field tracer studies. Results of this study demonstrate a framework that can be used to couple field tracer and laboratory CEC studies to accurately predict the transport and fate of CECs in streams.

Karst waters serve as important water sources in rural Appalachia and are well-connected to surface waters, making them susceptible to anthropogenic contamination, including by fecal indicator bacteria which represent a public health risk. This work designed and implemented a watershed-scale monitoring program for a 26 km2 sinking stream system in southwest Virginia to determine the fate and transport of E. coli in the system. This hydrologically complex watershed is predominantly agricultural and includes multiple key surface water sinks that enter Smokehole Cave and emerge at Smokehole Spring. Field campaigns at surface sites and within Smokehole Cave included bacteriological sampling, hydrologic measurement, and dye tracing. Field data was synthesized to: 1) examine variations in E. coli concentrations in the watershed during varying flows/seasonal conditions; and 2) calculate E. coli growth/decay coefficients for the karst system during different flow/antecedent conditions. E. coli concentrations at Smokehole Spring consistently peaked days after peak hydrologic stage. Flow conditions and storm event response were the largest drivers of E. coli transport through the system. Dye trace results revealed that water from sinks can be stored or move slowly through the karst system, resurging during storm events. E. coli was calculated to decay within the karst system, with a half-life of about 5-120 days which is longer than the travel time of water through the cave of approximately 0.5-2 days. Findings indicate that E. coli transport in Appalachian karst systems is hydrologically driven, roadside spring water collection is not recommended, and bacterial treatment is encouraged if performed. Targeted land-management practices should be explored to decrease E. coli loadings in karst waters. / Master of Science / Karst (cave) waters serve as important water sources in rural Appalachia and are well-connected to surface waters, making them susceptible to contamination from human or animal waste – a public health risk. A field monitoring program was conducted in an agriculturally impacted stream and cave system in southwest Virginia to determine how E. coli, a bacteria found in the waste of humans and other animals, moves through the system. There are several places where surface water sinks into the cave system, eventually entering Smokehole Cave and emerging at Smokehole Spring. Field data collection was performed at surface sites and within Smokehole Cave including sampling for E. coli, water flow measurements, and dye tracing. Field data was combined to 1) examine variations in E. coli concentrations during varying flows/seasonal conditions and 2) calculate E. coli growth/decay coefficients for the cave system during different flow and soil moisture conditions. It was found that E. coli concentrations at Smokehole Spring consistently peaked days after the water depth. Flow conditions and storm events were the largest drivers in E. coli movement through the system. Dye trace results revealed that water from sinks can be stored or moves slowly through the cave system and resurges during storm events. E. coli was found to decay within the cave system. Findings indicate that E. coli movement in Appalachian cave systems is driven by storm events, roadside spring water collection is not recommended, and bacteria treatment is recommended if performed. Cave-specific land-management practices are recommended to keep E. coli from entering cave waters.