This dissertation focuses on the structure-function relationships of nanomaterials (NMs) and some of their applications in environmental engineering. The aim is to investigate NMs of different surface chemistries and assess their interactions with biological models, evaluate the weathering impact and degradation parameters to improve polymer coatings, test their efficiency for contaminant removal and provide further understanding in the safe design of nanomaterials. Nanoecotoxicological risk assessment currently suffers from a lack of testing procedures adapted to nanomaterials. Graphene oxide (GO) is a carbon nanomaterial (CNM) that consists of a single layer of carbon atoms arranged in a hexagonal network. It is decorated with a high density of oxygen functional groups including epoxide and hydroxyl moieties on the basal planes and carboxylic and carbonyl groups at the edges. The changes in surface chemistry give GO unique properties that can be tailored for a function. Additionally, because of its simple synthesis and flexible chemistry, GO has been a popular building block of many composite CNMs. In environmental engineering, specifically, water treatment, GO has been studied by itself or as a composite for pollutant removal, biofouling reduction, and as an antimicrobial agent, just to name a few. Like GO, silver (Ag) is another NM widely used in water treatment for its biocidal properties. Despite the recent growth in this field, a fundamental understanding of the function-structure relationships in NMs is still progressing. Through a systematic set of experiments, the structure-properties-function and structure-properties-hazard relationships were investigated. These relationships can be used to establish guidelines to engineer “safe-by-design” functional nanomaterials, where materials are tailored to enhance their function while minimizing their inherent biological or environmental hazard.

Cerebral lateralization describes the asymmetries between the two halves of the brain which results in side-specialized processing of certain functions. This phenomenon provides a selective advantage by promoting enhanced cognitive abilities. However, due to the plastic nature of lateralization, an individual’s lateralization is highly subject to change by many external factors, such as pollution, throughout its life. Additionally, lateralized regions are dependent on different contexts, so lateralized elements do not all experience the same effects. A common pollutant found worldwide is bisphenol-A (BPA), a critical component of many plastics. BPA is a known endocrine disruptor that can agonize and antagonize the functions of sex steroids. Other studies have demonstrated the importance of sex steroids in regulating the development of cerebral lateralization; BPA may similarly affect lateralization. A popular research animal for studying toxicology is the zebrafish. Its advantages include a fully sequenced genome, many human orthologs, and more importantly, expresses lateralized behaviors that are indicative of the strength of its cerebral lateralization. This experiment analyzed the effects of BPA exposure on visual lateralization of zebrafish. Given the role that sex steroids play in moderating lateralization, it was hypothesized that exposing zebrafish to BPA would diminish the strength of lateralization in the brain which would translate into reduced behavioral lateralization. To test this, one group was exposed to 0.01 mg/L BPA for one week and compared against a control group in their eye preference when approaching a visual cue. Two settings, a foraging context and a social context, were utilized to examine the scope of impairment in lateralization. The control group in both settings displayed similar strengths in behavioral lateralization with a left eye preference. However, the lateralized response faded completely with BPA treatment. This experiment demonstrates that BPA induces loss of lateralization and possesses similar impacts on mechanisms controlling investigatory behavior in these two contexts. Wild populations may encounter higher concentrations of BPA, and although there is greater variability in these exposures, this experiment proves that exposure even beyond critical periods of development can impair lateralization. Additional research will have to be conducted to identify the effects of BPA on other lateralized behaviors and sensory modalities to pinpoint the exact mechanisms through which BPA influences lateralization.

This dissertation critically evaluated methodologies and devices for assessing and protecting the health of human populations, with particular emphasis on groundwater remediation and the use of wastewater-based epidemiology (WBE) to inform population health. A meta-analysis and assessment of laboratory-scale treatability studies for removing chlorinated solvents from groundwater found that sediment microcosms operated as continuous-flow columns are preferable to batch bottles when seeking to emulate with high fidelity the complex conditions prevailing in the subsurface in contaminated aquifers (Chapter 2). Compared to monitoring at the field-scale, use of column microcosms also showed (i) improved chemical speciation, and (ii) qualitative predictability of field parameters (Chapter 3). Monitoring of glucocorticoid hormones in wastewater of a university campus showed (i) elevated stress levels particularly at the start of the semester, (ii) on weekdays relative to weekend days (p = 0.05) (161 ± 42 μg d-1 per person, 122 ± 54 μg d-1 per person; p ≤ 0.05), and (iii) a positive association between levels of stress hormones and nicotine (rs: 0.49) and caffeine (0.63) consumption in this student population (Chapter 4). Also, (i) alcohol consumption determined by WBE was in line with literature estimates for this young sub-population (11.3 ± 7.5 g d-1 per person vs. 10.1 ± 0.8 g d-1 per person), whereas caffeine and nicotine uses were below (114 ± 49 g d-1 per person, 178 ± 19 g d-1 per person; 627 ± 219 g d-1 per person, 927 ± 243 g d-1 per person). The introduction of a novel continuous in situ sampler to WBE brought noted benefits relative to traditional time-integrated sampling, including (i) a higher sample coverage (93% vs. 3%), (ii) an ability to captured short-term analyte pulses (e.g., heroin, fentanyl, norbuprenorphine, and methadone), and (iii) an overall higher mass capture for drugs of abuse like morphine, fentanyl, methamphetamine, amphetamine, and the opioid antagonist metabolite norbuprenorphine (p ≤ 0.01). Methods and devices developed in this work are poised to find applications in the remediation sector and in human health assessments.

Radioactive cesium (137Cs), released from nuclear power plants and nuclear accidental releases, is a problem due to difficulties regarding its removal. Efforts have been focused on removing cesium and the remediation of the contaminated environment. Traditional treatment techniques include Prussian blue and nano zero-valent ion (nZVI) and nano-Fe/Cu particles to remove Cs from water; however, they are not efficient at removing Cs when present at low concentrations of about 10 parts-per-billion (ppb), typical of concentrations found in the radioactive contaminated sites.

The objective of this study was to develop an innovative and simple method to remove Cs+ present at low concentrations by engineering a proteoliposome transporter composed of an uptake protein reconstituted into a liposome vesicle. To achieve this, the uptake protein, Kup, from E. coli, was isolated through protein extraction and purification procedures. The new and simple extraction methodology developed in this study was highly efficient and resulted in purified Kup at ~1 mg/mL. A new method was also developed to insert purified Kup protein into the bilayers of liposome vesicles. Finally, removal of CsCl (10 and 100 ppb) was demonstrated by spiking the constructed proteoliposome in lab-fortified water, followed by incubation and ultracentrifugation, and measuring Cs+ with inductively coupled plasma mass spectrometry (ICP-MS).

The ICP-MS results from testing water contaminated with 100 ppb CsCl, revealed that adding 0.1 – 8 mL of Kup proteoliposome resulted in 0.29 – 12.7% Cs removal. Addition of 0.1 – 2 mL of proteoliposome to water contaminated with 10 ppb CsCl resulted in 0.65 – 3.43% Cs removal. These removal efficiencies were greater than the control, liposome with no protein.

A linear relationship was observed between the amount of proteoliposome added to the contaminated water and removal percentage. Consequently, by adding more volumes of proteoliposome, removal can be simply improved. This suggests that with ~ 60-70 mL of proteoliposome, removal of about 90% can be achieved. The novel technique developed herein is a contribution to emerging technologies in the water and wastewater treatment industry.

Adenoviruses cause gastrointestinal illnesses and have been listed on the U.S. EPA’s Contaminant Candidate Lists (CCL). They are highly resistant to ultraviolet (UV) inactivation. Advanced oxidation processes (AOPs) are known to improve inactivation of microorganisms and simultaneously oxidize organics. The bacteriophage P22 was selected as a surrogate for adenoviruses due to their physical and genetic similarities.

The main objective of this study was to compare the synergic disinfection potential of titanium dioxide (TiO2) or peracetic acid (PAA) with UV for viruses and bacteria in water.

Both bench-scale and pilot-scale evaluation was done. A bench-scale collimated beam was included to evaluate the inactivation of P22 and E. coli by UV with and without TiO2 or PAA. A Purifics Photo-Cat system which is an integrated UV/ceramic membrane reactor was used for the pilot-scale TiO2-UV AOP experiments. For pilot-scale PAA-UV AOP experiments, an in-line D222 UV reactor unit provided by NeoTech Aqua Solutions, Inc. was used.

TiO2 doses of 1, 10, and 40 mg/L were applied in the collimated beam and the Photo-Cat system. Higher TiO2 doses resulted in a higher inactivation in the Photo-Cat and lower inactivation in the collimated beam apparatus. Adding 40 mg/L of TiO2 in the photo-Cat system improved P22 inactivation by 25% while it slightly decreased P22 inactivation in collimated beam apparatus.

PAA doses of 0.25 or 0.5 ppm were continuously injected upstream of the UV light and a 53% or 90% increase in inactivation was observed for E. coli, respectively, as compared to UV alone. However, P22 required higher dose with PAA-UV AOP and PAA concentrations of 1 or 10 ppm resulted in an 18% and 70% increase in the inactivation respectively, as compared to UV alone. Interestingly, when the same condition was applied to water with more organics (UVT 79%), E. coli exhibited the same level of susceptibility to PAA-UV AOP while P22 inactivation decreased.

The results provide new insight on the effectiveness and applicability of adding AOP to UV for microbial inactivation in water. PAA-UV AOP can potentially enhance existing UV disinfection systems with minimal chemical addition, and a simple retrofit to existing UV units.

Activated Carbon has been used for decades to remove organics from water at large scale in municipal water treatment as well as at small scale in Point of Use (POU) and Point of Entry (POE) water treatment. This study focused on Granular Activated Carbon (GAC) and also activated Carbon Block (CB) were studied.

This thesis has three related elements for organics control in drinking water. First, coagulation chemistry for Alum and Aluminum Chlorohydrate (ACH) was optimized for significant organics removal to address membrane fouling issue at a local municipal water treatment plant in Arizona. Second, Rapid Small Scale Column Tests were conducted for removal of Perfluorinated compounds (PFC), PFC were present in groundwater at a local site in Arizona at trace levels with combined concentration of Perfluorooctaneoic Acid (PFOA) and Perfloorooctanesulfonic Acid (PFOS) up to 245 ng/L. Groundwater from the concerned site is used as drinking water source by a private utility. PFC Removal was evaluated for different GAC, influent concentrations and particle sizes. Third, a new testing protocol (Mini Carbon Block (MCB)) for bench scale study of POU water treatment device, specifically carbon block filter was developed and evaluated. The new bench scale decreased the hydraulic requirements by 60 times approximately, which increases the feasibility to test POU at a lab scale. It was evaluated for a common POU organic contaminant: Chloroform, and other model contaminants.

10 mg/L of ACH and 30 mg/L of Alum with pH adjustment were determined as optimal coagulant doses. Bituminous coal based GAC was almost three times better than coconut shell based GAC for removing PFC. Multiple tests with MCB suggested no short circuiting and consistent performance for methylene blue though chloroform removal tests underestimated full scale carbon block performance but all these tests creates a good theoretical and practical fundament for this new approach and provides directions for future researchers.