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- All Subjects: Analytical Chemistry
- Creators: Herckes, Pierre
- Creators: Shock, Everett
Here, a mathematical model of dielectrophoretic data is presented to connect analyte properties with data features, including the intercept and slope, enabling DEP to be used in applications which require this information. The promise of DEP to distinguish between analytes with small differences is illustrated with antibiotic resistant bacteria. The DEP system is shown to differentiate between methicillin-resistant and susceptible Staphylococcus aureus. This differentiation was achieved both label free and with bacteria that had been fluorescently-labeled. Klebsiella pneumoniae carbapenemase-positive and negative Klebsiella pneumoniae were also distinguished, demonstrating the differentiation for a different mechanism of antibiotic resistance. Differences in dielectrophoretic behavior as displayed by S. aureus and K. pneumoniae were also shown by Staphylococcus epidermidis. These differences were exploited for a separation in space of gentamicin-resistant and -susceptible S. epidermidis. Besides establishing the ability of DEP to distinguish between populations with small biophysical differences, these studies illustrate the possibility for the use of DEP in applications such as rapid diagnostics.
Both gradient separation techniques and dielectrophoresis can solve some of the difficulties presented by complex biological samples, thanks to selective capture, isolation, and concentration of analytes. By merging dielectrophoresis with a gradient separation-based approach, gradient insulator dielectrophoresis (g-iDEP) promises benefits in the form of rapid and specific separation of extremely similar bioparticles. High-resolution capture can be achieved by exploiting variations in the characteristic physical properties of cells and other bioparticles.
Novel implementation and application of the technique has demonstrated the isolation and concentration of blood cells from a complex biological sample, differentiation of bacterial strains within a single species, and separation of antibiotic-resistant and antibiotic-susceptible bacteria. Furthermore, this approach allows simultaneous concentration of analyte, facilitating detection and downstream analysis. A theoretical description of the resolving capabilities of g-iDEP was also developed. This theory explores the relationship between experimental parameters and resolution. Results indicate the possibility of differentiating particles with dielectrophoretic mobilities that differ by as little as one part in 100,000,000, or electrophoretic mobilities differing by as little as one part in 100,000. These results indicate the potential g-iDEP holds in terms of both separatory power and the possibility for diagnostic applications.
Novel, sensitive methods of measuring NDMA in air were developed based on Solid Phase Extraction (SPE) and Solid Phase Microextraction (SPME) coupled to Gas Chromatography-Mass Spectrometry (GC-MS). The two measuring techniques were evaluated in laboratory experiments. SPE-GC-MS was applicable in ambient air sampling and NDMA in ambient air was found in the 0.1-13.0 ng/m3 range.
NDMA photolysis, the main degradation atmospheric pathway, was studied in the atmospheric aqueous phase. Water soluble organic carbon (WSOC) was found to have more impact than inorganic species on NDMA photolysis by competing with NDMA for photons and therefore could substantially increase the NDMA lifetime in the atmosphere. The optical properties of atmospheric WSOC were investigated in aerosol, fog and cloud samples and showed WSOC from atmospheric aerosols has a higher mass absorption efficiency (MAE) than organic matter in fog and cloud water, resulting from a different composition, especially in regards of volatile species, that are not very absorbing but abundant in fogs and clouds.
NDMA formation kinetics during chloramination were studied in aqueous samples including wastewater, surface water and ground water, at two monochloramine concentrations. A simple second order NDMA formation model was developed using measured NDMA and monochloramine concentrations at select reaction times. The model fitted the NDMA formation well (R2 >0.88) in all water matrices. The proposed model was then optimized and applied to fit the data of NDMA formation from natural organic matter (NOM) and model precursors in previously studies. By determining the rate constants, the model was able to describe the effect of water conditions such as DOC and pH on NDMA formation.
Plasticizers are plastic additives used to enhance the physical properties of plastic and are ubiquitous in the environment. A class of plasticizer compounds called phthalate esters that are not fully eliminated in wastewater treatment facilities are relevant to the ecological health of downstream ecosystems and urban areas due to their ecotoxicity, tendency for soil accumulation, and the emerging concern about their effects on public health. However, plasticizer concentrations in a constructed wetland environment have rarely been studied in the United States, prompting the need for a method of plasticizer quantification in the Tres Rios Constructed Wetlands which are sustained by the effluent of the 91st Avenue Wastewater Treatment Plant in Phoenix, Arizona. The concentrations of four common plasticizer compounds (dimethyl: DMP, diethyl: DEP, di-n-butyl: DnBP, and bis(2-ethylhexyl): DEHP phthalate) at five sites across the wetland surface water were quantified using solid-phase extraction followed by gas chromatography coupled with mass spectrometry (GC/MS). The sampling period included four sample sets taken from March 2022 to September 2022, which gave temporal data in addition to spatial concentration data. Quantification and quality control were performed using internal standard calibration, replicate samples, and laboratory blanks. Higher molecular weight phthalates accumulated in the wetland surface water at significantly higher average concentrations than those of lower molecular weight at a 95% confidence level, ranging from 8 ng/L to 7349 ng/L and 4 ng/L to 27876 ng/L for DnBP and DEHP, respectively. Concentrations for dimethyl phthalate and diethyl phthalate were typically less than 50 ng/L and were often below the method detection limit. Average concentrations of DnBP and DEHP were significantly higher during periods of high temperatures and arid conditions. The spatial distribution of phthalates was analyzed. Most importantly, a method for successful ultra-trace quantification of plasticizers at Tres Rios was established. These results confirm the presence of plasticizers at Tres Rios and a significant seasonal increase in their surface water concentrations. The developed analytical procedure provides a solid foundation for the Wetlands Environmental Ecology Lab at ASU to further investigate plasticizers and contaminants of emerging concern and determine their ultimate fate through volatilization, sorption, photodegradation, hydrolysis, microbial biodegradation, and phytoremediation studies.
Quantifying halogen presence and speciation in particulate matter is crucial given the role atmospheric particulates play in transport and cycling. While some halogens (fluorine and chlorine) are often included in aerosol studies, iodine and bromine have rarely been examined, especially outside of a marine environment. Focus on this environment is, in part, due to the existence of biogenic marine sources for both halogens. However, examining iodine and bromine in an urban environment has the potential to provide key insights into the transport and processing of these species in the atmosphere. As Tempe is set within a desert environment, bromine concentration is expected to be relatively high due to its presence in Earth’s crust, while iodine is expected to exist in higher concentrations near the coast. To detect presence and concentration, ICP-MS analysis was performed on samples taken in Tempe, AZ as well as sites in Bakersfield, CA and Davis, CA, which yielded preliminary results in line with these expectations. A secondary set of samples were taken in Tempe, AZ during dust storms, haboobs, and winter holidays. CIC was used to determine the organic fraction. In doing so, this study aims to identify species present in an urban environment as well as potential transportation pathways.
This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.
An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.