Mechanistic studies on the degradation of gasoline oxygenates by advanced oxidation technologies and the reaction of 4-methyl-1,2,4-triazoline-3,5-dione with tetracyclopropylethylene

Gasoline oxygenates (MTBE, methyl tert-butyl ether; DIPE, di-isopropyl ether; ETBE, ethyl tert-butyl ether; TAME, tert-amyl ether) are added to gasoline to boost octane and enhance combustion. The combination of large scale use, high water solubility and only minor biodegradability has now resulted in a significant gasoline oxygenate contamination occurring in surface, ground, and drinking water systems. Combination of hydroxyl radical formation and the pyrolytic environment generated by ultrasonic irradiation (665 kHz) leads to the rapid degradation of MTBE and other gasoline oxygenates in aqueous media. ^ The presence of oxygen promotes the degradation processes by rapid reaction with carbon centered radicals indicating radical processes involving O 2 are significant pathways. A number of the oxidation products were identified. The formation of products (alcohols, ketones, aldehydes, esters, peroxides, etc) could be rationalized by mechanisms which involve hydrogen abstraction by OH radical and/or pyrolysis to form carboncentered radicals which react with oxygen and follow standard oxidation chain processes. ^ The reactions of N-substituted R-triazolinediones (RTAD; R = CH 3 or phenyl) have attracted considerable interest because they exhibit a number of unusual mechanistic characteristics that are analogous to the reactions of singlet oxygen (1O2) and offer an easy way to provide C-N bond(s) formation. The reactions of triazolinedione with olefins have been widely studied and aziridinium imides are generally accepted to be the reactive intermediates. ^ We observed the rapid formation of an unusual intermediate upon mixing tetracyclopropylethylene with 4-methyl-1,2,4-triazoline-3,5-dione in CDCl 3. Detailed characterization by NMR (proton, 13C, 2-D NMRs) indicates the intermediate is 5,5,6,6-tetracyclopropyl-3-methyl-5,6-dihydro-oxazolo[3,2- b][1,2,4]-triazolium-2-olate. Such products are extremely rare and have not been studied. Upon warming the intermediate is converted to 2 + 2 diazetidine (major) and ene product (minor). ^ To further explore the kinetics and dynamics of the reaction activation energies were obtained using Arrhenius plots. Activation energies for the formation of the intermediate from reactants, and 2+2 adduct from the intermediate were determined as 7.48 kcal moll and 19.8 kcal mol−1 with their pre-exponential values of 2.24 × 105 dm 3 mol−1 sec−1 and 2.75 × 108 sec−1, respectively, meaning net slow reactions because of low pre-exponential values caused by steric hindrance. ^

Prenatal augmented auditory stimulation and visual system development: Effects of timing on intersensory organization

This study investigated the effects of augmented prenatal auditory stimulation on postnatal visual responsivity and neural organization in bobwhite quail (Colinus virginianus). I delivered conspecific embryonic vocalizations before, during, or after the development of a multisensory, midbrain audiovisual area, the optic tectum. Postnatal simultaneous choice tests revealed that hatchlings receiving augmented auditory stimulation during optic tectum development as embryos failed to show species-typical visual preferences for a conspecific maternal hen 72 hours after hatching. Auditory simultaneous choice tests showed no hatchlings had deficits in auditory function in any of the groups, indicating deficits were specific to visual function. ZENK protein expression confirmed differences in the amount of neural plasticity in multiple neuroanatomical regions of birds receiving stimulation during optic tecturn development, compared to unmanipulated birds. The results of these experiments support the notion that the timing of augmented prenatal auditory stimulation relative to optic tectum development can impact postnatal perceptual organization in an enduring way.^

Advanced oxidation of arsenic species in aqueous solutions

Ingestion of arsenic from contaminated water is a serious problem and affects the health of more than 100 million people worldwide. Traditional water purification technologies are generally not effective or cost prohibitive for the removal of arsenic to acceptable levels (≤10 ppb). Current multi-step arsenic removal processes involve oxidation, precipitation and/or adsorption. Advanced Oxidation Technologies (AOTs) may be attractive alternatives to existing treatments. The reactions of inorganic and organic arsenic species with reactive oxygen species were studied to develop a fundamental mechanistic understanding of these reactions, which is critical in identifying an effective and economical technology for treatment of arsenic contaminated water. ^ Detailed studies on the conversion of arsenite in aqueous media by ultrasonic irradiation and TiO2 photocatalytic oxidation (PCO) were conducted, focusing on the roles of hydroxyl radical and superoxide anion radical formed during the irradiation. ·OH plays the key role, while O2 -· has little or no role in the conversion of arsenite during ultrasonic irradiation. The reaction of O2-· does not contribute in the rapid conversion of As(III) when compared to the reaction of As(III) with ·OH radical during TiO2 PCO. Monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) are readily degraded upon TiO2 PCO. DMA is oxidized to MMA as the intermediate and arsenate as the final product. For dilute solutions, TiO2 also may be applicable as an adsorbent for direct removal of arsenic species, namely As(III), As(V), MMA and DMA, all of which are strongly adsorbed, thus eliminating the need for a multi-step treatment process. ^ Phenylarsonic acid (PA) was subjected to gamma radiolysis under hydroxyl radical generating conditions, which showed rapid degradation of PA. Product analysis and computational calculation both indicate the arsenate group is an ortho, para director. Our results indicate · OH radical mediated processes should be effective for the remediation of phenyl substituted arsonic acids. ^ While hydroxyl radical generating methods, specifically AOTs, appear to be promising methods for the treatment of a variety of arsenic compounds in aqueous media, pilot studies and careful economic analyses will be required to establish the feasibility of AOTs applications in the removal of arsenic. ^

Space division multiple access for wireless sensor networks

This dissertation proposed a self-organizing medium access control protocol (MAC) for wireless sensor networks (WSNs). The proposed MAC protocol, space division multiple access (SDMA), relies on sensor node position information and provides sensor nodes access to the wireless channel based on their spatial locations. SDMA divides a geographical area into space divisions, where there is one-to-one map between the space divisions and the time slots. Therefore, the MAC protocol requirement is the sensor node information of its position and a prior knowledge of the one-to-one mapping function. The scheme is scalable, self-maintaining, and self-starting. It provides collision-free access to the wireless channel for the sensor nodes thereby, guarantees delay-bounded communication in real time for delay sensitive applications. This work was divided into two parts: the first part involved the design of the mapping function to map the space divisions to the time slots. The mapping function is based on a uniform Latin square. A Uniform Latin square of order k = m 2 is an k x k square matrix that consists of k symbols from 0 to k-1 such that no symbol appears more than once in any row, in any column, or in any m x in area of main subsquares. The uniqueness of each symbol in the main subsquares presents very attractive characteristic in applying a uniform Latin square to time slot allocation problem in WSNs. The second part of this research involved designing a GPS free positioning system for position information. The system is called time and power based localization scheme (TPLS). TPLS is based on time difference of arrival (TDoA) and received signal strength (RSS) using radio frequency and ultrasonic signals to measure and detect the range differences from a sensor node to three anchor nodes. TPLS requires low computation overhead and no time synchronization, as the location estimation algorithm involved only a simple algebraic operation.

Seismic performance of hybrid fiber reinforced polymer-concrete pier columns

As part of a multi-university research program funded by NSF, a comprehensive experimental and analytical study of seismic behavior of hybrid fiber reinforced polymer (FRP)-concrete column is presented in this dissertation. Experimental investigation includes cyclic tests of six large-scale concrete-filled FRP tube (CFFT) and RC columns followed by monotonic flexural tests, a nondestructive evaluation of damage using ultrasonic pulse velocity in between the two test sets and tension tests of sixty-five FRP coupons. Two analytical models using ANSYS and OpenSees were developed and favorably verified against both cyclic and monotonic flexural tests. The results of the two methods were compared. A parametric study was also carried out to investigate the effect of three main parameters on primary seismic response measures. The responses of typical CFFT columns to three representative earthquake records were also investigated. The study shows that only specimens with carbon FRP cracked, whereas specimens with glass or hybrid FRP did not show any visible cracks throughout cyclic tests. Further monotonic flexural tests showed that carbon specimens both experienced flexural cracks in tension and crumpling in compression. Glass or hybrid specimens, on the other hand, all showed local buckling of FRP tubes. Compared with conventional RC columns, CFFT column possesses higher flexural strength and energy dissipation with an extended plastic hinge region. Among all CFFT columns, the hybrid lay-up demonstrated the highest flexural strength and initial stiffness, mainly because of its high reinforcement index and FRP/concrete stiffness ratio, respectively. Moreover, at the same drift ratio, the hybrid lay-up was also considered as the best in term of energy dissipation. Specimens with glassfiber tubes, on the other hand, exhibited the highest ductility due to better flexibility of glass FRP composites. Furthermore, ductility of CFFTs showed a strong correlation with the rupture strain of FRP. Parametric study further showed that different FRP architecture and rebar types may lead to different failure modes for CFFT columns. Transient analysis of strong ground motions showed that the column with off-axis nonlinear filament-wound glass FRP tube exhibited a superior seismic performance to all other CFFTs. Moreover, higher FRP reinforcement ratios may lead to a brittle system failure, while a well-engineered FRP reinforcement configuration may significantly enhance the seismic performance of CFFT columns.

Contingency, contiguity, and development: The ontogeny of contingency learning in northern bobwhite (Colinus virginianus) chicks

The purpose of this study was to investigate the ontogeny of auditory learning via operant contingency in Northern bobwhite (Colinus virginianus ) hatchlings and possible interaction between attention, orienting and learning during early development. Chicks received individual 5 min training sessions in which they received a playback of a bobwhite maternal call at a single delay following each vocalization they emitted. Playback was either from a single randomly chosen speaker or switched back and forth semi-randomly between two speakers during training. Chicks were tested 24 hrs later in a simultaneous choice test between the familiar and an unfamiliar maternal call. It was found that day-old chicks showed a significant time-specific decrement in auditory learning when trained with delays in the range of 470–910 ms between their vocalizations and call playback only when training involved two speakers. Two-day-old birds showed an even more sustained disruption of learning than day-old chicks, whereas three-day-old chicks showed a pattern of intermittent interference with their learning when trained at such delays. A similar but less severe decrement in auditory learning was found when chicks were provided with motor training in which playback was contingent upon chicks entering and exiting one of two colored squares placed on the floor of the arena. Chicks provided with playback of the call at randomly chosen delays each time they vocalized exhibited large fluctuations in their responsivity to the auditory stimulus as a function of delay—fluctuations which were correlated significantly with measures of chick learning, particularly at two-days-of-age. When playback was limited to a single location chicks no longer showed a time-specific disruption of their learning of the auditory stimulus. Sequential analyses revealed several patterns suggesting that an attentional process similar or analogous to attentional blink may have contributed both to the observed fluctuations in chick responsivity to the auditory stimulus as a function of delay and to the time-specific learning deficit shown by chicks provided with two-speaker training. The study highlights that learning can be substantially modulated by processes of orienting and attention and has a number of important implications for research within cognitive neuroscience, animal behavior and learning.

Mechanistic studies on the advanced oxidation and photochemical transformation of cyanotoxins (microcystins)

The increased occurrence of cyanobacteria (blue-green algae) blooms and the production of associated cyanotoxins have presented a threat to drinking water sources. Among the most common types of cyanotoxins found in potable water are microcystins (MCs), a family of cyclic heptapeptides containing substrates. MCs are strongly hepatotoxic and known to initiate tumor promoting activity. The presence of sub-lethal doses of MCs in drinking water is implicated as one of the key risk factors for an unusually high occurrence of primary liver cancer. ^ A variety of traditional water treatment methods have been attempted for the removal of cyanotoxins, but with limited success. Advanced Oxidation Technologies (AOTs) are attractive alternatives to traditional water treatments. We have demonstrated ultrasonic irradiation and UV/H2O2 lead to the degradation of cyanotoxins in drinking water. These studies demonstrate AOTs can effectively degrade MCs and their associated toxicity is dramatically reduced. We have conducted detailed studies of different degradation pathways of MCs and conclude that the hydroxyl radical is responsible for a significant fraction of the observed degradation. Results indicate preliminary products of the sonolysis of MCs are due to the hydroxyl radical attack on the benzene ring and substitution and cleavage of the diene of the Adda peptide residue. AOTs are attractive methods for treatment of cyanotoxins in potable water supplies. ^ The photochemical transformation of MCs is important in the environmental degradation of MCs. Previous studies implicated singlet oxygen as a primary oxidant in the photochemical transformation of MCs. Our results indicate that singlet oxygen predominantly leads to degradation of the phycocyanin, pigments of blue green algae, hence reducing the degradation of MCs. The predominant process involves isomerization of the diene (6E to 6Z) in the Adda side chain via photosensitized isomerization involving the photoexcited phycocyanin. Our results indicate that photosensitized processes play a key role in the environmental fate and elimination of MCs in the natural waters. ^

Interactions of different arsenic species with thols: Chemical and biological implications

Arsenic has been classified as a group I carcinogen. It has been ranked number one in the CERCLA priority list of hazardous substances due to its frequency, toxicity and potential for human exposure. Paradoxically, arsenic has been employed as a successful chemotherapeutic agent for acute promyelocytic leukemia and has found some success in multiple myeloma. Since arsenic toxicity and efficacy is species dependent, a speciation method, based on the complementary use of reverse phase and cation exchange chromatography, was developed. Inductively coupled plasma mass spectrometer (ICP-MS), as an element specific detector, and electrospray ionization mass spectrometer (ESI-MS), as a molecule specific detector, were employed. Low detection limits in the µg. L−1 range on the ICP-MS and mg. L−1 range on the ESI-MS were obtained. The developed methods were validated against each other through the use of a Deming plot. With the developed speciation method, the effects of both pH on the stability of As species and reduced glutathione (GSH) concentration on the formation and stability of arsenic glutathione complexes were studied. To identify arsenicals in multiple myeloma (MM) cell lines post arsenic trioxide (ATO) and darinaparsin (DAR) incubation, an extraction method based on the use of ultrasonic probe was developed. Extraction tools and solvents were evaluated and the effect of GSH concentration on the quantitation of arsenic glutathione (As-GSH) complexes in MM cell extracts was studied. The developed method was employed for the identification of metabolites in DAR incubated cell lines where the effect of extraction pH, DAR incubation concentration and incubation time on the relative distribution of the As metabolites was assessed. A new arsenic species, dimethyarsinothioyl glutathione (DMMTA V-GS), a pentavalent thiolated arsenical, was identified in the cell extracts through the use of liquid chromatography tandem mass spectrometry. The formation of the new metabolite in the extracts was dependent on the decomposition of s-dimethylarsino glutathione (DMA(GS)). These results have major implications in both the medical and toxicological fields of As because they involve the metabolism of a chemotherapeutic agent and the role sulfur compounds play in this mechanism.

Two -way direction of influence in mother-infant interaction as denoted by concurrent reciprocal learning processes

This series of 5 single-subject studies used the operant conditioning paradigm to investigate, within the two-way influence process, how (a) contingent infant attention can reinforce maternal verbal behaviors during a period of mother-infant interaction and under subsequent experimental manipulation. Differential reinforcement was used to determine if it is possible that an infant attending to the mother (denoted by head-turns towards the image of the mother plus eye contact) increases (reinforces) the mother's verbal response (to a cue from the infant) upon which the infant behavior is contingent. There was also (b) an evaluation during the contrived parent-infant interaction for concurrent operant learning of infant vocal behavior via contingent verbal responding (reinforcement) implemented by the mother. Further, it was noted (c) whether or not the mother reported being aware that her responses were influenced by the infant's behavior. Findings showed: the operant conditioning of the maternal verbal behaviors were reinforced by contingent infant attention; and the operant conditioning of infant vocalizations was reinforced by contingent maternal verbal behaviors. No parent reported (1) being aware of the increase in their verbal response reinforced during operant conditioning of parental behavior nor a decrease in those responses during the DRA reversal phase, or (2) noticing a contingency between infant's and mother's response. By binomial 1-tail tests, the verbal-behavior patterns of the 5 mothers were conditioned by infant reinforcement (p < 0.02) and, concurrently, the vocal-response patterns of the 5 infants were conditioned by maternal reinforcement (p < 0.02). A program of systematic empirical research on the determinants of concurrent conditioning within mother-child interaction may provide a way to evaluate the differential effectiveness of interventions aimed at improving parent-child interactions. The work conducted in the present study is one step in this direction. ^

A model for continuous measurement of drilled shaft diameter during construction

Non-Destructive Testing (NDT) of deep foundations has become an integral part of the industry's standard manufacturing processes. It is not unusual for the evaluation of the integrity of the concrete to include the measurement of ultrasonic wave speeds. Numerous methods have been proposed that use the propagation speed of ultrasonic waves to check the integrity of concrete for drilled shaft foundations. All such methods evaluate the integrity of the concrete inside the cage and between the access tubes. The integrity of the concrete outside the cage remains to be considered to determine the location of the border between the concrete and the soil in order to obtain the diameter of the drilled shaft. It is also economic to devise a methodology to obtain the diameter of the drilled shaft using the Cross-Hole Sonic Logging system (CSL). Performing such a methodology using the CSL and following the CSL tests is performed and used to check the integrity of the inside concrete, thus allowing the determination of the drilled shaft diameter without having to set up another NDT device.^ This proposed new method is based on the installation of galvanized tubes outside the shaft across from each inside tube, and performing the CSL test between the inside and outside tubes. From the performed experimental work a model is developed to evaluate the relationship between the thickness of concrete and the ultrasonic wave properties using signal processing. The experimental results show that there is a direct correlation between concrete thicknesses outside the cage and maximum amplitude of the received signal obtained from frequency domain data. This study demonstrates how this new method to measuring the diameter of drilled shafts during construction using a NDT method overcomes the limitations of currently-used methods. ^ In the other part of study, a new method is proposed to visualize and quantify the extent and location of the defects. It is based on a color change in the frequency amplitude of the signal recorded by the receiver probe in the location of defects and it is called Frequency Tomography Analysis (FTA). Time-domain data is transferred to frequency-domain data of the signals propagated between tubes using Fast Fourier Transform (FFT). Then, distribution of the FTA will be evaluated. This method is employed after CSL has determined the high probability of an anomaly in a given area and is applied to improve location accuracy and to further characterize the feature. The technique has a very good resolution and clarifies the exact depth location of any void or defect through the length of the drilled shaft for the voids inside the cage. ^ The last part of study also evaluates the effect of voids inside and outside the reinforcement cage and corrosion in the longitudinal bars on the strength and axial load capacity of drilled shafts. The objective is to quantify the extent of loss in axial strength and stiffness of drilled shafts due to presence of different types of symmetric voids and corrosion throughout their lengths.^

Seismic Performance of Hybrid Fiber Reinforced Polymer-Concrete Pier Columns

As part of a multi-university research program funded by NSF, a comprehensive experimental and analytical study of seismic behavior of hybrid fiber reinforced polymer (FRP)-concrete column is presented in this dissertation. Experimental investigation includes cyclic tests of six large-scale concrete-filled FRP tube (CFFT) and RC columns followed by monotonic flexural tests, a nondestructive evaluation of damage using ultrasonic pulse velocity in between the two test sets and tension tests of sixty-five FRP coupons. Two analytical models using ANSYS and OpenSees were developed and favorably verified against both cyclic and monotonic flexural tests. The results of the two methods were compared. A parametric study was also carried out to investigate the effect of three main parameters on primary seismic response measures. The responses of typical CFFT columns to three representative earthquake records were also investigated. The study shows that only specimens with carbon FRP cracked, whereas specimens with glass or hybrid FRP did not show any visible cracks throughout cyclic tests. Further monotonic flexural tests showed that carbon specimens both experienced flexural cracks in tension and crumpling in compression. Glass or hybrid specimens, on the other hand, all showed local buckling of FRP tubes. Compared with conventional RC columns, CFFT column possesses higher flexural strength and energy dissipation with an extended plastic hinge region. Among all CFFT columns, the hybrid lay-up demonstrated the highest flexural strength and initial stiffness, mainly because of its high reinforcement index and FRP/concrete stiffness ratio, respectively. Moreover, at the same drift ratio, the hybrid lay-up was also considered as the best in term of energy dissipation. Specimens with glassfiber tubes, on the other hand, exhibited the highest ductility due to better flexibility of glass FRP composites. Furthermore, ductility of CFFTs showed a strong correlation with the rupture strain of FRP. Parametric study further showed that different FRP architecture and rebar types may lead to different failure modes for CFFT columns. Transient analysis of strong ground motions showed that the column with off-axis nonlinear filament-wound glass FRP tube exhibited a superior seismic performance to all other CFFTs. Moreover, higher FRP reinforcement ratios may lead to a brittle system failure, while a well-engineered FRP reinforcement configuration may significantly enhance the seismic performance of CFFT columns.

The Effect of Prenatal Auditory Enrichment on Perceptual Narrowing in Bobwhite Quail Neonates

The development of species-typical perceptual preferences has been shown to depend on a variety of socially and ecologically derived sensory stimulation during both the pre- and postnatal periods. The prominent mechanism behind the development of these seemingly innate tendencies in young organisms has been hypothesized to be a domain-general pan-sensory selectivity process referred to as perceptual narrowing, whereby regularly experienced sensory stimuli are honed in upon, while simultaneously losing the ability to effectively discriminate between atypical or unfamiliar sensory stimulation. Previous work with precocial birds has been successful in preventing the development of species-typical perceptual preferences by denying the organism typical levels of social and/or self-produced stimulation. The current series of experiments explored the mechanism of perceptual narrowing to assess the malleability of a species-typical auditory preference in avian embryos. By providing a variety of different unimodal and bimodal presentations of a mixed-species vocalizations at the onset of prenatal auditory function, the following project aimed to 1) keep the perceptual window from narrowing, thereby interfering with the development of a species-typical auditory preference, 2) investigate how long differential prenatal stimulation can keep the perceptual window open postnatally, 3) explore how prenatal auditory enrichment effected preferences for novelty, and 4) assess whether prenatal auditory perceptual narrowing is affected by modality specific or amodal stimulus properties during early development. Results indicated that prenatal auditory enrichment significantly interferes with the emergence of a species-typical auditory preference and increases openness to novelty, at least temporarily. After accruing postnatal experience in an environment rich with species-typical auditory and multisensory cues, the effect of prenatal auditory enrichment rapidly was found to rapidly fade. Prenatal auditory enrichment with extraneous non-synchronous light exposure was shown to both keep the perceptual narrowing window open and impede learning in the postnatal environment, following hatching. Results are discussed in light of the role experience plays in perceptual narrowing during the perinatal period.