VTechWorks Repository :: Browsing by Author "Vikesland, Peter J."

Browsing by Author "Vikesland, Peter J."

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Addressing and Assessing Lead Threats in Drinking Water: Non-Leaded Brass, Product Testing, Particulate Lead Occurrence and Effects of the Chloride to Sulfate Mass Ratio on Corrosion
Triantafyllidou, Simoni (Virginia Tech, 2006-09-11)
Growing concern over adverse health effects from low level lead exposure motivated reassessment of lead occurrence in drinking water, from the perspective of 1) possibly eliminating lead from new brass materials, and 2) performance testing of existing products. During the course of this thesis work, it was discovered that several cases of childhood lead poisoning in North Carolina, South Carolina and Washington D.C. occurred from contaminated potable water. That disconcerting finding prompted additional work into 3) deficiencies in existing lead testing of drinking water samples, and 4) impacts of water treatment steps on lead leaching. Meters, components, and fittings manufactured from non-leaded brass (< 0.25 percent lead content) are increasingly specified for use in water distribution systems and premise plumbing, in response to California's Proposition 65 and the proposed Lead Free Drinking Water Act. An in-depth review of the available literature revealed that non-leaded brass releases minimal amounts of lead and other contaminants of concern to drinking water. There is legitimate concern about the corrosion resistance and longevity of these non-leaded alloys in the range of waters that will be encountered in practice. Nonetheless, when the potential impacts to manufacturers, utilities and consumers are considered, non-leaded brasses appear to be attractive albeit at slightly higher cost. For existing leaded brass products, concerns have been raised over potential limitations of performance standards used to certify the products as "safe" in the marketplace. The ANSI/NSF 61 Section 9 test is the industry standard, and its protocol is critically evaluated from the perspective of the leaching solution chemistry. Testing indicated that the protocol water is reasonably representative of a typical water supply. However, some lower pH and lower alkalinity waters can be much more aggressive than the existing section 9 water, and for potable water with these characteristics, problems with higher than desired lead leaching may occur. It may be desirable to tighten the standard's pass/fail lead criterion in order to account for this problem in practice. Several cases of childhood lead poisoning from water have been recently encountered, which prompted environmental assessments. It was visually obvious that some of the lead particles ingested by these children, present in water from the tap, were not completely dissolving in the standard method with weak acid recommended by the US EPA. A laboratory investigation proved that up to 80% particulate lead in water samples could be "missed" by the standard protocol. Unfortunately, tests with simulated gastric fluid revealed that much of this particulate lead would be bioavailable in the presence of chloride, warmer temperatures and lower pH inside the human stomach. It is recommended that water utilities be alert to this possible problem and that environmental assessments of lead poisoned children use stronger digestions to detect lead in water. Several of the lead poisoning instances occurred after the utility changed both disinfectant chemicals (from chlorine to chloramine) and coagulant types. Although authorities initially thought chloramine was the cause based on experiences in Washington D.C., bench scale studies in this work proved that a change in coagulant from aluminum sulfate to either ferric chloride or polyaluminum chloride was in fact the main reason of the lead spikes. The reduction in sulfate and increase in chloride increased the chloride to sulfate mass ratio of the water supply. A higher chloride to sulfate mass ratio triggered much higher (2.3-40 times more) lead leaching from solder connected to copper pipe. The adverse effects of the increase in the ratio could not be eliminated by adding a corrosion inhibitor.
Addressing gaps in the US EPA Lead and Copper Rule: Developing guidance and improving citizen science tools to mitigate corrosion in public water systems and premise plumbing
Kriss, Rebecca Boyce (Virginia Tech, 2023-06-21)
Lead and copper in drinking water are known to pose aesthetic and health concerns for humans and pets. The United States Environmental Protection Agency (US EPA) Lead and Copper Rule (LCR) set 90th percentile action levels for lead (15 ppb) and copper (1.3 mg/L), above which utilities must implement systemwide corrosion control. However, gaps in the US EPA LCR leave at least 10% of residents using municipal water and all private well users vulnerable to elevated lead and copper in their drinking water. To help address these gaps in the LCR, this dissertation 1) Evaluates accuracy of at-home lead in water test kits to help residents identify lead problems, 2) Refines orthophosphate corrosion control guidance to help reduce cuprosolvency, 3) Identifies challenges to mitigating cuprosolvency by raising pH, and 4) Develops guidance that can help residents assess and address cuprosolvency problems. Lead in drinking water can pose a variety of health concerns, particularly for young children. The revised LCR will still leave many residents unprotected from elevated lead in their drinking water and potentially wondering what to do about it. Many consumers concerned about lead may choose to purchase at-home lead in water test kits, but there is no certification authority to ensure their accuracy. Most off-the-shelf tests purchased in this work (12 of 16) were not able to detect dissolved or particulate lead at levels of concern in drinking water (i.e. near the lead action level of 15 ppb) due to high detection limits (5,000-20,000 ppb). Binary type tests, which indicate the presence or absence of lead based on a trigger threshold of 15 ppb, were often effective at detecting dissolved lead, but they failed to detect the presence of leaded particles that often cause high lead exposures in drinking water problems. Some of these problems detecting particles could be reduced using simple at-home acid dissolution with weak household acids such a vinegar or lemon juice. Our analysis points out the strengths and weaknesses of various types of at-home lead in water tests, which could be particularly important considering potential distrust in official results in the aftermath of the Flint Water Crisis. Elevated cuprosolvency, or copper release into drinking water, can be an aesthetic concern due to fixture staining, blue water, and green hair and can pose health concerns for residents and pets. In addition to the general gaps in the LCR described above, compliance sampling in the LCR focuses on older homes at highest risk of elevated lead, rather than the newer homes at highest risk of elevated copper. Problems with elevated copper can sometimes go undetected as a result. Guidance was developed to help proactive utilities address cuprosolvency issues through the addition of orthophosphate corrosion inhibitors or pH adjustment as a function of a water's alkalinity. Linear regressions developed from pipe cuprosolvency tests (R2>0.98) determined a "minimum" orthophosphate dose or a "minimum" pH for a given alkalinity that was expected to almost always reduce copper below the 1.3 mg/L EPA action level in a reasonable length of time. The subjective nature of the terms "almost always" and "reasonable length of time" were quantitatively discussed based on laboratory and field data. Orthophosphate addition was generally very effective at cuprosolvency control. Orthophosphate treatment in copper tube cuprosolvency tests produced cuprosolvency below the action level within the first week of treatment. As expected, orthophosphate treated waters sometimes resulted in higher long-term cuprosolvency than the same waters without orthophosphate corrosion control treatment. This is consistent with the formation of phosphate scales which have an intermediate solubility between the cupric hydroxide in new pipes and the malachite or tenorite scales expected in pipe aging without orthophosphate. A linear regression (R2>0.98) was used to determine the orthophosphate dose needed for a given alkalinity to yield copper below the 1.3 mg/L action level in the pipe segments with the highest, 2nd highest, 3rd highest copper concentrations (100th, 95th, or 90th percentile, n=20 replicates, five each from four manufacturers) after 4 or 22 weeks of pipe aging. This regression was generally in good agreement with a bin approach put forth in the 2015 Consensus Statement from the National Drinking Water Advisory Council, but in some cases the regression predicted that higher orthophosphate doses would be needed. In contrast, due to the greater complexity of the reactions involved, a similar simplistic approach for pH adjustment is not widely applicable. A linear regression predicted that higher "minimum" pH values would be needed to control cuprosolvency compared to those suggested by the 2015 National Drinking Water Advisory Consensus Statement. Results indicate that factors such as the potential for calcite precipitation, pipe age, and significant variability in cuprosolvency from pipes of different manufacturers may warrant further research. Field LCR monitoring data indicated that 90th percentile copper concentrations continued to decline over a period of years or decades when orthophosphate is not used, and our laboratory results demonstrate a few cases where copper levels even increased with time. Consideration of confounding effects from other water quality parameters such as natural organic matter, silica, and sulfate would be necessary before the "minimum" pH criteria could be broadly applied. Guidance was then developed to help address cuprosolvency issues on a single building or single home basis for residents with private wells or those with high copper in municipal systems meeting the LCR. A hierarchy of costs and considerations for various interventions are discussed including replumbing with alternative materials, using bottled water or point use pitcher, tap, or reverse osmosis filters to reduce copper consumption, and using whole house interventions like more conventional orthophosphate addition and pH adjustment, or unproven strategies like granular activated carbon filtration, reverse osmosis treatment, and ion exchange treatment. Laboratory and citizen science testing demonstrated that some inexpensive at-home tests for pH and copper, were accurate enough to serve as inputs for this guidance and could empower consumers to diagnose their problems and consider possible solutions. Citizen science field testing and companion laboratory studies of potential interventions indicate that short-term (<36 weeks) use of pH adjustment, granular activated carbon, anion exchange and reverse osmosis treated water were not effective at forming a protective scale for the resident's water tested. In this case-study, cuprosolvency problems were ultimately related to water chemistry and linked to variability in influent water pH. Overall, this work highlighted weaknesses in the current US EPA Lead and Copper Rule. It attempted to close some of these gaps by assessing the accuracy of at-home citizen science tests for lead and copper detection and developing guidance to support voluntary interventions by utilities or consumers. Ideally, local authorities (utilities, health departments, cooperative extension programs) could adapt this guidance to account for local water quality considerations and support consumers in resolving cuprosolvency issues. This guidance may also serve as a citizen science approach that some consumers could use to make decisions on their own. Future work could extend and improve on these initial efforts.
Addressing the Contribution of Indirect Potable Reuse to Inland Freshwater Salinization
Bhide, Shantanu V.; Grant, Stanley B.; Parker, Emily A.; Rippy, Megan A.; Godrej, Adil N.; Kaushal, Sujay S.; Prelewicz, Gregory; Saji, Niffy; Curtis, Shannon; Vikesland, Peter J.; Maile-Moskowitz, Ayella; Edwards, Marc A.; Lopez, Kathryn; Birkland, Thomas A.; Schenk, Todd (2021-02-02)
Inland freshwater salinity is rising worldwide, a phenomenon called the freshwater salinization syndrome (FSS). We investigate a potential conflict between managing the FSS and indirect potable reuse, the practice of augmenting water supplies through the addition of reclaimed wastewater to surface waters and groundwaters. From time-series data collected over 25 years, we quantify the contributions of three salinity sources—a wastewater reclamation facility and two rapidly urbanizing watersheds—to the rising concentration of sodium (a major ion associated with the FSS) in a regionally important drinking water reservoir in the Mid-Atlantic United States. Sodium mass loading to the reservoir is primarily from watershed runoff during wet weather and reclaimed wastewater during dry weather. Across all timescales evaluated, sodium concentration in the reclaimed wastewater is higher than in outflow from the two watersheds. Sodium in reclaimed wastewater originates from chemicals added during wastewater treatment, industrial and commercial discharges, human excretion, and down-drain disposal of drinking water and sodium-rich household products. Thus, numerous opportunities exist to reduce the contribution of indirect potable reuse to sodium pollution at this site, and the FSS more generally. These efforts will require deliberative engagement with a diverse community of watershed stakeholders and careful consideration of the local political, social, and environmental context.
Advanced Applications of Raman Spectroscopy for Environmental Analyses
Lahr, Rebecca Halvorson (Virginia Tech, 2014-01-09)
Due to an ever-increasing global population and limited resource availability, there is a constant need for detection of both natural and anthropogenic hazards in water, air, food, and material goods. Traditionally a different instrument would be used to detect each class of contaminant, often after a concentration or separation protocol to extract the analyte from its matrix. Raman spectroscopy is unique in its ability to detect organic or inorganic, airborne or waterborne, and embedded or adsorbed analytes within environmental systems. This ability comes from the inherent abilities of the Raman spectrometer combined with concentration, separation, and signal enhancement provided by drop coating deposition Raman (DCDR) and surface-enhanced Raman spectroscopy (SERS). Herein the capacity of DCDR to differentiate between cyanotoxin variants in aqueous solutions was demonstrated using principal component analysis (PCA) to statistically demonstrate spectral differentiation. A set of rules was outlined based on Raman peak ratios to allow an inexperienced user to determine the toxin variant identity from its Raman spectrum. DCDR was also employed for microcystin-LR (MC-LR) detection in environmental waters at environmentally relevant concentrations, after pre-concentration with solid-phase extraction (SPE). In a cellulose matrix, SERS and normal Raman spectral imaging revealed nanoparticle transport and deposition patterns, illustrating that nanoparticle surface coating dictated the observed transport properties. Both SERS spectral imaging and insight into analyte transport in wax-printed paper microfluidic channels will ultimately be useful for microfluidic paper-based analytical device (𝜇PAD) development. Within algal cells, SERS produced 3D cellular images in the presence of intracellularly biosynthesized gold nanoparticles (AuNP), documenting in detail the molecular vibrations of biomolecules at the AuNP surfaces. Molecules involved in nanoparticle biosynthesis were identified at AuNP surfaces within algal cells, thus aiding in mechanism elucidation. The capabilities of Raman spectroscopy are endless, especially in light of SERS tag design, coordinating detection of analytes that do not inherently produce strong Raman vibrations. The increase in portable Raman spectrometer availability will only facilitate cheaper, more frequent application of Raman spectrometry both in the field and the lab. The tremendous detection power of the Raman spectrometer cannot be ignored.
Advancing Monitoring and Mitigation of Antibiotic Resistance in Wastewater Treatment Plants and Water Reuse Systems
Majeed, Haniyyah JaRae (Virginia Tech, 2020-10-22)
Wastewater treatment plants (WWTPs) receive a confluence of sewage containing antibiotics, antibiotic resistant bacteria, antibiotic resistance genes (ARGs), and pathogens, thus serving as key point of interest for the surveillance of antibiotic resistance (AR) dissemination. This thesis advances knowledge about the fate of AR indicators throughout treatment and reuse. The field study informs approaches for monitoring AR at a WWTP by characterizing the resistome (i.e., full profile of ARGs) and microbiome across eight sampling events via metagenomic sequencing, complemented by antibiotic data. The WWTP significantly reduced the total load of ARGs and antibiotics, although correlations between ARGs and antibiotics were generally weak. Quantitative polymerase chain reaction was applied to validate the quantitative capacity of metagenomics, whereby we found strong correlations. The influent and effluent to the WWTP were remarkably stable with time, providing further insight into the sampling frequency necessary for adequate surveillance. The laboratory study examined the effects of commonly applied disinfection processes (chlorination, chloramination, and ultraviolet irradiation [UV]) on the inactivation of antibiotic resistant pathogens and corresponding susceptible pathogens in recycled and potable water. Further, we evaluated their regrowth following disinfection by simulating distribution. Acinetobacter baumannii, an environmental opportunistic pathogen, regrew especially well following UV disinfection, although not when a disinfectant residual was present. Enterococcus faecium, a fecal pathogen, did not regrow following any disinfection process. There were no significant differences between water types. The findings of this study emphasize a need to move beyond the framework of assessing treatment efficacy based on the attenuation of fecal pathogens.
Advancing Nanoplasmonics-enabled Regenerative Spatiotemporal Pathogen Monitoring at Bio-interfaces
Garg, Aditya (Virginia Tech, 2024-05-09)
Non-invasive and continuous spatiotemporal pathogen monitoring at biological interfaces (e.g., human tissue) holds promise for transformative applications in personalized healthcare (e.g., wound infection monitoring) and environmental surveillance (e.g., airborne virus surveillance). Despite notable progress, current receptor-based biosensors encounter inherent limitations, including inadequate long-term performance, restricted spatial resolutions and length scales, and challenges in obtaining multianalyte information. Surface-enhanced Raman spectroscopy (SERS) has emerged as a robust analytical method, merging the molecular specificity of Raman spectroscopy's vibrational fingerprinting with the enhanced detection sensitivity from strong light-matter interaction in plasmonic nanostructures. As a receptor-free and noninvasive detection tool capable of capturing multianalyte chemical information, SERS holds the potential to actualize bio-interfaced spatiotemporal pathogen monitoring. Nonetheless, several challenges must be addressed before practical adoption, including the development of plasmonic bio-interfaces, sensitive capture of multianalyte information from pathogens, regeneration of nanogap hotspots for long-term sensing, and extraction of meaningful information from spatiotemporal SERS datasets. This dissertation tackles these fundamental challenges. Plasmonic bio-interfaces were created using innovative nanoimprint lithography-based scalable nanofabrication methods for reliable bio-interfaced spatiotemporal measurements. These plasmonic bio-interfaces feature sensitive, dense, and uniformly distributed plasmonic transducers (e.g., plasmonic nano dome arrays, optically-coupled plasmonic nanodome and nanohole arrays, self-assembled nanoparticle micro patches) on ultra-flexible and porous platforms (e.g., biomimetic polymeric meshes, textiles). Using these plasmonic bio-interfaces, advancements were made in SERS signal transduction, machine-learning-enabled data analysis, and sensor regeneration. Large-area multianalyte spatiotemporal monitoring of bacterial biofilm components and pH was demonstrated in in-vitro biofilm models, crucial for wound biofilm diagnostics. Additionally, novel approaches for sensitive virus detection were introduced, including monitoring spectral changes during viral infection in living biofilms and direct detection of decomposed viral components. Spatiotemporal SERS datasets were analyzed using unsupervised machine-learning methods to extract biologically relevant spatiotemporal information and supervised machine-learning tools to classify and predict biological outcomes. Finally, a sensor regeneration method based on plasmon-induced nanocavitation was developed to enable long-term continuous detection in protein-rich backgrounds. Through continuous implementation of spatiotemporal SERS signal transduction, machine-learning-enabled data analysis, and sensor regeneration in a closed loop, our solution has the potential to enable spatiotemporal pathogen monitoring at the bio-interface.
Advancing Rural Public Health: From Drinking Water Quality and Health Outcome Meta-analyses to Wastewater-based Pathogen Monitoring
Darling, Amanda Victoria (Virginia Tech, 2024-10-07)
A rural-urban divide in health status and healthcare infrastructure has been well-documented in the U.S., where populations residing in census regions classified as rural often exhibit more negative health outcomes, adverse health behaviors, and have reduced access to affordable and proximal health services, compared to their urban and peri-urban counterparts. However, it is important to note that such disparities vary based on specific rural regions and individual circumstances. Rural areas may face elevated risk factors for infectious diseases such as increased proximity to wildlife and livestock and disproportionately high reliance on private, non-federally regulated, primary drinking water sources. Chronic conditions prevalent in rural communities such as diabetes and hypertension are frequently linked with longer duration and higher severity of symptoms than in urban areas; this association suggests that the risk of exposure to infectious diseases and the likelihood of progression to serious illness and hospitalization may be elevated, although this is not universally the case across all rural settings. Alongside documented urban-rural health disparities, there also exist disparities in the nature and quality of data on health-related behaviors, outcomes, and service provision in rural areas compared to urban and peri-urban regions. In this dissertation, two key environmental matrices –drinking water and wastewater– were highlighted as vectors of information to better estimate levels of contaminant exposures and health outcomes in rural communities. First, baseline data on drinking water contaminant levels and associated health outcome data were highlighted as crucial for refining holistic exposure estimates as well as understanding drinking water related health burdens in rural communities where a larger proportion of households use private drinking water sources, such as well water, that are not federally regulated. Second, systematic sampling and testing of pathogen biomarkers in wastewater to non-invasively measure population-level health status, also known as wastewater based surveillance (WBS) and, depending on the context, wastewater based epidemiology (WBE) is not constrained by disadvantages of clinical testing, e.g., limited health-care access, long travel times to testing facilities, delay between symptom-onset and testing. Thus, expanded implementation of WBS in rural communities is proposed here as a strategy to address data disparities in clinical testing for infectious diseases. Collectively, this dissertation advances knowledge on estimated drinking water contaminant levels, exposures, and associated public health outcomes and corresponding research gaps in rural Appalachian U.S., and elucidates pathways toward best practices and considerations for public-health focused wastewater testing adoption in rural communities. For the latter, the question of whether WBS challenges unique to rural wastewater systems hinder application of WBS in small, rural communities was explored, as well as methods to advance best-practices for rural WBS. To summarize existing publicly available peer-reviewed literature on drinking water contaminants in rural Appalachian U.S., in Chapter 2, a systematic review and meta-analysis of microbial and chemical drinking water contaminants was performed. Key contaminants were identified as being elevated beyond regulatory, health-based, maximum contaminant levels in our meta-analyses from rural drinking water sources in Appalachia, including E coli, lead, arsenic, uranium. Overall, we found data on drinking water source quality under baseline conditions (i.e., rather than post anomalous contamination events such as chemical spills) in rural Appalachian U.S. was sparse relative to widespread media coverage on the issue. Epidemiologic-based research studies that collected both drinking water exposure data and paired health outcome data were also limited. As a result, although some instances of anomalously high levels of drinking water contaminants were identified in rural Appalachia from the published literature, we could not obtain a clear picture of baseline exposures to drinking water contaminants in most rural Appalachian communities, highlight need to address these knowledge gaps. In Chapter 3, to evaluate whether wastewater could serve as a reliable metric for estimating community circulation of viruses and antimicrobial resistance (AMR) markers, even when sourced from aging and low-resource sewer collection networks, a 12-month wastewater monitoring study was conducted in a small, rural sewer conveyance system with pronounced infrastructural challenges. Specifically, the field site under study was compromised with heavy inflow and infiltration (IandI). Detection rates and concentrations of viral, AMR, and human fecal markers were grouped by levels of IandI impact across the sewershed, and location-, date-, and sample- specific variables were assessed for their relative influence on viral, AMR, and human fecal marker signal using generalized linear models (GLMs). We found that while IandI likely adversely impacted the magnitude of wastewater biomarker signal to some extent throughout the sewershed, especially up-sewer at sites with more pronounced IandI, substantial diminishment of wastewater signal at WWTP influent was not observed in response to precipitation events. Thus, our data indicated that WWTP influent sampling alone can still be used to assess and track community circulation of pathogens in heavily IandI impacted systems, particularly for ubiquitously circulating viruses less prone to dilution induced decay. Delineations were also made for what circumstances up-sewer sampling may be necessary to better inform population shedding of pathogens, especially where IandI is prevalent. Various normalization strategies have been proposed to account for sources of variability for deriving population-level pathogen shedding from wastewater, including those introduced by IandI-driven dilution. Thus, in Chapter 4, we evaluated the temporal and spatial variability of viral and AMR marker signal in wastewater at different levels of IandI, both unnormalized and with the adoption of several normalization strategies. We found that normalization using physicochemical-based wastewater strength metrics (chemical oxygen demand, total suspended solids, phosphate, and ammonia) resulted in higher temporal and site-specific variability of SARS-CoV-2 and human fecal biomarker signal compared to unnormalized data, especially for viral and AMR marker signal measured in wastewater from sites with pronounced IandI. Viral wastewater signal normalized to physicochemical wastewater strength metrics and flow data also closely mirrored precipitation trends, suggesting such normalization approaches may more closely scale wastewater trends towards precipitation patterns rather than per capita signal in an IandI compromised system. We also found that in most cases, normalization did not significantly alter the relationship between wastewater trends and clinical infection trends. These findings suggest a degree of caution is warranted for some normalization approaches, especially where precipitation driven IandI is heightened. However, data and findings largely supported the utility of using human fecal markers such as crAssphage for normalizing wastewater signal to address site-specific differences in dilution levels, since viral signal scaled to this metric did not result in strong correlations between precipitation and wastewater trends, higher spatial and temporal variation was not observed, and strong correlations were observed between viral signal and viral infection trends. Finally, in chapter 5, we assessed the relationship between monthly Norovirus GII, Rotavirus, and SARS-CoV-2 wastewater trends with seasonal infection trends for each of the viruses to ascertain whether WBE could be used in a rural sewershed of this size with substantial IandI impacts to track and potentially predict population level infection trends. Though up-sewer, or near-source sampling, at sites with permanent IandI impacts did not exhibit a clear relationship with seasonal infection trends for Rotavirus, SARS-CoV-2, and Norovirus GII, WWTP influent signal and consensus signals aggregated from multiple up-sewer sites largely mirrored expected seasonal trends. Findings also suggested that for more ubiquitous viral targets, such as SARS-CoV-2, viral trends measured at WWTP influent in a small IandI impacted system may still provide a sufficiently useful measure of infection trends to inform the use of WBE (assuming appropriate normalization to sewershed population). These findings elucidate the potential utility and relative robustness of wastewater testing to ascertain community-level circulation of pathogens in small, rural sewersheds even those compromised by extensive IandI inputs. Overall, this dissertation examined drinking water and wastewater as critical metrics for assessing contaminant exposures and infectious disease trends in rural communities, particularly in the context of small, rural communities which tend to have more limited health infrastructure and lower-resource wastewater systems. Overall, findings underscore the need for baseline data on drinking water quality by identifying gaps in current knowledge and calling for further research to better understand drinking water contaminant exposure levels in rural areas. Wastewater as a non-invasive, population-level health metric was evaluated in the context of a small, rural sewer system overall, and by varying observed levels of IandI, as well as associated tradeoffs for normalization adoption. By evaluating these environmental surveillance metrics using both desk-based and field-based research study designs, findings from this dissertation offer valuable insights and practical recommendations for improving baseline drinking water quality monitoring and wastewater pathogen testing, all with the overarching goal of supporting more targeted public health interventions in rural settings.
Advancing the Understanding of Water Distribution System Corrosion: Effects of Chlorine and Aluminum on Copper Pitting, Temperature Gradients on Copper Corrosion, and Silica on Iron Release
Rushing, Jason Clark (Virginia Tech, 2002-07-24)
When severe copper pitting problems impacted customers at a large utility, studies were begun to attempt to diagnose the problem and identify potential solutions. A series of tests were conducted to characterize the nature of pitting. Desktop comparisons of pinhole leak frequency and treatment practices at nearly utilities were also documented to identify treatment factors that might be influencing the initiation and propagation of leaks. Factors identified included the presence of relatively high levels of free chlorine and aluminum in the distribution system. Experiments were conducted to examine the effect of these constituents on copper pitting under stagnant and flow conditions. That led to discovery of a synergistic redox reaction between chlorine, aluminum solids, and copper metal as evidenced by increased chlorine decay rates, non-uniform corrosion, and rising corrosion potentials. Temperature changes had been suspected to increase copper pitting frequency and copper release to drinking water. Experiments examined the effect of temperature gradients on copper pipe corrosion during stagnant conditions. The pipe orientation in relation to the temperature gradient determined whether convective mixing would occur, which influenced temperature gradients within the pipe. This work is the first to demonstrate that temperature gradients lead to thermogalvanic currents, influences copper leaching and scale type. Iron release from corroding water mains is another concern of many water utilities, but little is known about chemistry factors that influence the problem. In laboratory experiments, higher levels of silica caused more iron release to the water and decreased the size of suspended iron particles. Silica levels also changed during the experiment: it decreased through incorporation into a dense scale, and increased by release from cast iron during corrosion. Silica slightly decreased iron corrosion rates near the end of this 6-month test.
Aerosol microdroplets exhibit a stable pH gradient
Wei, Haoran; Vejerano, Eric P.; Leng, Weinan; Huang, Qishen; Willner, Marjorie R.; Marr, Linsey C.; Vikesland, Peter J. (2018-07-10)
Suspended aqueous aerosol droplets (< 50 mu m) are microreactors for many important atmospheric reactions. In droplets and other aquatic environments, pH is arguably the key parameter dictating chemical and biological processes. The nature of the droplet air/water interface has the potential to significantly alter droplet pH relative to bulk water. Historically, it has been challenging to measure the pH of individual droplets because of their inaccessibility to conventional pH probes. In this study, we scanned droplets containing 4-mercaptobenzoic acid-functionalized gold nanoparticle pH nanoprobes by 2D and 3D laser confocal Raman microscopy. Using surface-enhanced Raman scattering, we acquired the pH distribution inside approximately 20-mu m-diameter phosphate-buffered aerosol droplets and found that the pH in the core of a droplet is higher than that of bulk solution by up to 3.6 pH units. This finding suggests the accumulation of protons at the air/water interface and is consistent with recent thermodynamic model results. The existence of this pH shift was corroborated by the observation that a catalytic reaction that occurs only under basic conditions (i.e., dimerization of 4-aminothiophenol to produce dimercaptoazobenzene) occurs within the high pH core of a droplet, but not in bulk solution. Our nanoparticle probe enables pH quantification through the cross-section of an aerosol droplet, revealing a spatial gradient that has implications for acid-base-catalyzed atmospheric chemistry.
Aerosolization and Atmospheric Transformation of Engineered Nanoparticles
Tiwari, Andrea Jean (Virginia Tech, 2014-04-04)
While research on the environmental impacts of engineered nanoparticles (ENPs) is growing, the potential for them to be chemically transformed in the atmosphere has been largely ignored. The overall objective of this work was to assess the atmospheric transformation of carbonaceous nanoparticles (CNPs). The research focuses on C₆₀ fullerene because it is an important member of the carbonaceous nanoparticle (CNP) family and is used in a wide variety of applications. The first specific objective was to review the potential of atmospheric transformations to alter the environmental impacts of CNPs. We described atmospheric processes that were likely to physically or chemically alter aerosolized CNPs and demonstrated their relevance to CNP behavior and toxicity in the aqueous and terrestrial environment. In order to investigate the transformations of CNP aerosols under controlled conditions, we developed an aerosolization technique that produces nano-scale aerosols without using solvents, which can alter the surface chemistry of the aerosols. We demonstrated the technique with carbonaceous (C₆₀) and metal oxide (TiO₂, CeO₂) nanoparticle powders. All resulting aerosols exhibited unimodal size distributions and mode particle diameters below 100 nm. We used the new aerosolization technique to investigate the reaction between aerosolized C₆₀ and atmospherically realistic levels of ozone (O₃) in terms of reaction products, reaction rate, and oxidative stress potential. We identified C₆₀O, C₆₀O2, and C₆₀O3 as products of the C₆₀-O3 reaction. We demonstrated that the oxidative stress potential of C₆₀ may be enhanced by exposure to O3. We found the pseudo-first order reaction rate to be 9 x 10⁻⁶ to 2 x 10⁻⁵ s⁻¹, which is several orders of magnitude lower than the rate for several PAH species under comparable conditions. This research has demonstrated that a thorough understanding of atmospheric chemistry of ENPs is critical for accurate prediction of their environmental impacts. It has also enabled future research in that vein by developing a novel technique to produce nanoscale aerosols from nanoparticle powders. Results of this research will help guide the formulation of appropriate environmental policy concerning the regulation of ENPs.
Aggregation and sedimentation of magnetite nanoparticle clusters
Vikesland, Peter J.; Rebodos, R. L.; Bottero, J. Y.; Rose, J.; Masion, A. (Royal Society of Chemistry, 2016-03-24)
Magnetite nanoparticles are redox active constituents of subsurface and corrosive environments. In this study, we characterized the aggregation and sedimentation behavior of well characterized magnetite nanoparticle clusters using dynamic light scattering (DLS), UV-vis-NIR spectroscopy, and small angle X-ray scattering (SAXS). Both unfunctionalized (NaOH-magnetite) and tetramethylammonium hydroxide (TMAOH-magnetite) surface functionalized nanoparticle clusters were employed. TMAOH-magnetite has a slightly smaller primary nanoparticle radius as determined by TEM (4 ± 0.7 nm vs. 5 ± 0.8 for NaOH-magnetite) and a smaller initial DLS determined cluster radius (<30 nm vs. 100–200 nm for NaOH-magnetite). Interestingly, in spite of its smaller initial nanoparticle cluster size, TMAOH-magnetite undergoes sedimentation more rapidly than NaOH-magnetite. This behavior is consistent with the more rapid aggregation of the smaller TMAOH-magnetite clusters as well as their lower fractal dimension, as determined by SAXS. This study illustrates that both nanoparticle cluster size and fractal dimension should be carefully considered when considering the environmental transport and fate of highly aggregated nanoparticles.
Air Quality in Mexico City: Spatial and Temporal Variations of Particulate Polycyclic Aromatic Hydrocarbons and Source Apportionment of Gasoline-Versus-Diesel Vehicle Emissions
Thornhill, Dwight Anthony Corey (Virginia Tech, 2007-07-26)
The Mexico City Metropolitan Area (MCMA) is one of the largest cities in the world, and as with many megacities worldwide, it experiences serious air quality and pollution problems, especially with ozone and particulate matter. Ozone levels exceed the health-based standard, which is equivalent to the U.S. standard, on approximately 80% of all days, and concentrations of particulate matter 10 μm and smaller (PM10) exceed the standard on more than 40% of all days in most years. Particulate polycyclic aromatic hydrocarbons (PAHs) are a class of semi-volatile compounds that are formed during combustion and many of these compounds are known or suspected carcinogens. Recent studies on PAHs in Mexico City indicate that very high concentrations have been observed there and may pose a serious health hazard. The first part of this thesis describes results from the Megacities Initiative: Local and Regional Observations (MILAGRO) study in Mexico City in March 2006. During this field campaign, we measured PAH and aerosol active surface area (AS) concentrations at six different locations throughout the city using the Aerodyne Mobile Laboratory (AML). The different sites encompassed a mix of residential, commercial, industrial, and undeveloped land use. The goals of this research were to describe spatial and temporal patterns in PAH and AS concentrations, to gain insight into sources of PAHs, and to quantify the relationships between PAHs and other pollutants. We observed that the highest measurements were generally found at sites with dense traffic networks. Also, PAH concentrations varied considerably in space. An important implication of this result is that for risk assessment studies, a single monitoring site will not adequately represent an individual's exposure. Source identification and apportionment are essential for developing effective control strategies to improve air quality and therefore reduce the health impacts associated with fine particulate matter and PAHs. However, very few studies have separated gasoline- versus diesel-powered vehicle emissions under a variety of on-road driving conditions. The second part of this thesis focuses on distinguishing between the two types of engine emissions within the MCMA using positive matrix factorization (PMF) receptor modeling. The Aerodyne Mobile Laboratory drove throughout the MCMA in March 2006 and measured on-road concentrations of a large suite of gaseous and particulate pollutants, including carbon dioxide, carbon monoxide (CO), nitric oxide (NO), benzene (C6H6), formaldehyde (HCHO), ammonia (NH3), fine particulate matter (PM2.5), PAHs, and black carbon (BC). These pollutant species served as the input data for the receptor model. Fuel-based emission factors and annual emissions within Mexico City were then calculated from the source profiles of the PMF model and fuel sales data. We found that gasoline-powered vehicles were responsible for 90% of mobile source CO emissions and 85% of VOCs, while diesel-powered vehicles accounted for almost all of NO emissions (99.98%). Furthermore, the annual emissions estimates for CO and VOC were lower than estimated during the MCMA-2003 field campaign. The number of megacities is expected to grow dramatically in the coming decades. As one of the world's largest megacities, Mexico City serves as a model for studying air quality problems in highly populated, extremely polluted environments. The results of this work can be used by policy makers to improve air quality and reduce related health risks in Mexico City and other megacities.
Airborne Nanoparticles: Generation, Characterization, and Occupational Exposure
Yeganeh Talab, Behnoush (Virginia Tech, 2007-03-14)
Despite the rapid growth in nanotechnology, very little is known about the unintended health or environmental effects of manufactured nanomaterials. The development of nanotechnology risk assessments and regulations requires quantitative information on the potential for exposure to nanomaterials. In addition, to facilitate life-cycle assessments and inhalation toxicology studies, robust methods are needed to generate aerosolized engineered nanoparticles. We conducted a set of field studies to measure the fine particle mass concentrations (PM2.5) as well as nanoparticle number concentrations and size distributions in two nanomaterial manufacturing facilities. Measurements were performed near the reactor, in the breathing zone, and at a background site. Increases in PM2.5 and particle number concentrations were associated with physical handling of nanomaterials. The highest PM2.5 concentration observed was 2700 ug m-3 during sweeping of the reactor in the commercial plant. In most cases, an increase in the number of sub-100 nm particles accounted for the increase in total number concentrations. The results of this research can be used to develop guidelines for workplace regulations to minimize workers' exposure to nanoparticles. Furthermore, we used an atomizer to aerosolize C60 aggregates from a fullerene-water suspension. Measurement of particle size distributions and number concentrations showed that increasing the initial fullerene concentration resulted in increased number of aerosolized particles, while the average size of particles remained relatively constant. To return the aerosolized fullerenes into water, we passed the aerosol sample through an impinger. Reducing the flow rate through the impinger resulted in an increase in the collection efficiency of airborne nanoparticles.
Antibiotic Resistance Characterization in Human Fecal and Environmental Resistomes using Metagenomics and Machine Learning
Gupta, Suraj (Virginia Tech, 2021-11-03)
Antibiotic resistance is a global threat that can severely imperil public health. To curb the spread of antibiotic resistance, it is imperative that efforts commensurate with a “One Health” approach are undertaken. Given that interconnectivities among ecosystems can serve as conduits for the proliferation and dissemination of antibiotic resistance, it is increasingly being recognized that a robust global environmental surveillance framework is required to promote One Health. The ideal aim would be to develop approaches that inform global distribution of antibiotic resistance, help prioritize monitoring targets, present robust data analysis frameworks to profile resistance, and ultimately help build strategies to curb the dissemination of antibiotic resistance. The work described in this dissertation was aimed at evaluating and developing different data analysis paradigms and their applications in investigating and characterizing antibiotic resistance across different resistomes. The applications presented in Chapter 2 illustrate challenges associated with various environmental data types (especially metagenomics data) and present a path to advance incorporation of data analytics approaches in Environmental Science and Engineering research and applications. Chapter 3 presents a novel approach, ExtrARG, that identifies discriminatory ARGs among resistomes based on factors of interest. The results in Chapter 4 provide insight into the global distribution of ARGs across human fecal and sewage resistomes across different socioeconomics. Chapter 5 demonstrates a data analysis paradigm using machine learning algorithms that helps bridge the gap between information obtained via culturing and metagenomic sequencing. Lastly, the results of Chapter 6 illustrates the contribution of phages to antibiotic resistance. Overall, the findings provide guidance and approaches for profiling antibiotic resistance using metagenomics and machine learning. The results reported further expand the knowledge on the distribution of antibiotic resistance across different resistomes.
Antimicrobial Resistance Mitigation [ARM] Concept Paper
Vikesland, Peter J.; Alexander, Kathleen A.; Badgley, Brian D.; Krometis, Leigh-Anne H.; Knowlton, Katharine F.; Gohlke, Julia M.; Hall, Ralph P.; Hawley, Dana M.; Heath, Lenwood S.; Hession, W. Cully; Hull, Robert Bruce IV; Moeltner, Klaus; Ponder, Monica A.; Pruden, Amy; Schoenholtz, Stephen H.; Wu, Xiaowei; Xia, Kang; Zhang, Liqing (Virginia Tech, 2017-05-15)
The development of viable solutions to the global threat of antimicrobial resistance requires a transdisciplinary approach that simultaneously considers the clinical, biological, social, economic, and environmental drivers responsible for this emerging threat. The vision of the Antimicrobial Resistance Mitigation (ARM) group is to build upon and leverage the present strengths of Virginia Tech in ARM research and education using a multifaceted systems approach. Such a framework will empower our group to recognize the interconnectedness and interdependent nature of this threat and enable the delineation, development, and testing of resilient approaches for its mitigation. We seek to develop innovative and sustainable approaches that radically advance detection, characterization, and prevention of antimicrobial resistance emergence and dissemination in human-dominated and natural settings...
ARGem: a new metagenomics pipeline for antibiotic resistance genes: metadata, analysis, and visualization
Liang, Xiao; Zhang, Jingyi; Kim, Yoonjin; Ho, Josh; Liu, Kevin; Keenum, Ishi M.; Gupta, Suraj; Davis, Benjamin; Hepp, Shannon L.; Zhang, Liqing; Xia, Kang; Knowlton, Katharine F.; Liao, Jingqiu; Vikesland, Peter J.; Pruden, Amy; Heath, Lenwood S. (Frontiers, 2023-09-15)
Antibiotic resistance is of crucial interest to both human and animal medicine. It has been recognized that increased environmental monitoring of antibiotic resistance is needed. Metagenomic DNA sequencing is becoming an attractive method to profile antibiotic resistance genes (ARGs), including a special focus on pathogens. A number of computational pipelines are available and under development to support environmental ARG monitoring; the pipeline we present here is promising for general adoption for the purpose of harmonized global monitoring. Specifically, ARGem is a user-friendly pipeline that provides full-service analysis, from the initial DNA short reads to the final visualization of results. The capture of extensive metadata is also facilitated to support comparability across projects and broader monitoring goals. The ARGem pipeline offers efficient analysis of a modest number of samples along with affordable computational components, though the throughput could be increased through cloud resources, based on the user’s configuration. The pipeline components were carefully assessed and selected to satisfy tradeoffs, balancing efficiency and flexibility. It was essential to provide a step to perform short read assembly in a reasonable time frame to ensure accurate annotation of identified ARGs. Comprehensive ARG and mobile genetic element databases are included in ARGem for annotation support. ARGem further includes an expandable set of analysis tools that include statistical and network analysis and supports various useful visualization techniques, including Cytoscape visualization of co-occurrence and correlation networks. The performance and flexibility of the ARGem pipeline is demonstrated with analysis of aquatic metagenomes. The pipeline is freely available at https://github.com/xlxlxlx/ARGem.
Assessing Vulnerabilities to the Spread of Pathogens and Antibiotic Resistance in Agricultural and Water Systems Using Culture-, Molecular-, and Metagenomic-based Techniques
Keenum, Ishi M. (Virginia Tech, 2021-09-09)
As climate change exacerbates water scarcity and alters available water and fertilizer resources, it is vital that take appropriate measures to ensure sustainable treatment of water, wastewater, and other waste streams that are protective of public health and support recovery and reuse of water and nutrients. The overarching theme of this dissertation is the advancement of next-generation DNA sequencing (NGS) and computational tools for achieving these goals. A suite of relevant fecal and environmental opportunistic pathogens are examined using both culture-based and NGS-based methods. Of particular concern to this research was not only the attenuation and inactivation of pathogens, but also ensuring that optimal treatment approaches reduce antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs). Key systems that were the focus of this effort included nutrient reuse (wastewater-derived biosolids and cattle-derived manure), water reuse, and drinking water systems disrupted by a major hurricane. A field study was carried out to survey a suite of pathogens from source-to tap in six small drinking water systems in Puerto Rico six months after Hurricane Maria. The study revealed that pathogenic Leptospira DNA was detected in all systems that were reliant on surface water. On the other hand, Salmonella spp. was detected in surface and groundwater sources and some distribution system waters both by culture and PCR. The study provided comparison of molecular-, microscopic-, and culture-based analysis for pathogen detection and highlighted the need for disaster preparedness for small water systems, including back-up power supply and access to chlorination as soon as possible after a natural disaster. A second field-study examined wastewater derived solids across an international transect of wastewater treatment plants in order to gain insight into the range of ARG concentrations encountered. It was found that, while total ARGs did not vary between treatment or continent of origin, clinically-relevant ARGs (i.e., ARGs encoding resistance to important classes of antibiotics used in humans) were significantly higher in solids derived from Asian wastewater treatment plants. Estimated loading rates of ARGs to soil under a scenario of land application were determined, highlighting in all cases that they are orders of magnitude higher than in the aqueous effluent. Livestock manure, derived from control cattle and cattle undergoing typical antibiotic treatment, and corresponding composts were also evaluated as common soil amendments in a separate study. In this study, the amendments were applied to two soil types in a greenhouse setting, in order to compare the resulting carriage of ARGs on a root (radish) versus leafy (lettuce) vegetable. Remarkably, radishes were found to harbor the highest relative abundance of total ARGs enumerated by metagenomics, even higher than corresponding soils or manures. Although the total microbial load will be lower on a harvested vegetable, the results suggest that the vegetable surface environment can differentially favor the survival of ARBs. The role of wastewater and water reuse treatment processes in reducing ARB and ARGs was also investigated at field-scale. Two independent wastewater treatment plants both substantially reduced total ARG relative and absolute abundance through biological treatment and settling according to metagenomic analysis. The subsequent water reuse treatment train of one system produced water for non- potable purposes and found further reduction in ARGs after chlorination, but a five hundred percent increase in the relative abundance of ARGs in the subsequent distribution system. In the second plant, which employed a membrane-free ozone-biologically-activated carbon-granular activated carbon treatment train for indirect potable reuse, there were notable increases in total ARG relative abundance following ozonation and chlorination. However, these numbers attenuated below background aquifer levels before recharge. Culture-based analysis of these systems targeting resistant ESKAPE pathogens (Escherichia coil, Staphylococcus aureus, Klebsiella spp., Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterococcus spp.) indicated similar trends as the metagenomic ARG analysis for both systems, but was challenged by sub-optimal media for wastewater samples and low confirmation rates, limiting statistical analysis. In order to advance the application of NGS, molecular, and associated bioinformatic tools for monitoring pathogens and antibiotic resistance in environmental systems, newly emerging methods and field standards for antibiotic resistance assessment were also evaluated. Hybrid assembly, the assembly for both short and long metagenomic sequencing reads, were assessed with an in silico framework in order to determine which available assemblers produced the most accurate and long contigs. Hybrid assembly was found to produce longer and more accurate assemblies at all coverages by reducing error as compared to short read assembly, though the outputs differed in composition from long read assembly. Where it is possible, it is beneficial to sequence using both long- and short-read NGS technologies and employ hybrid assembly, but further validation is recommended. Genome resolved metagenomics has also emerged as a strategy to recover individual bacterial genomes from the mixed metagenomic samples though this is often not well validated. In order to address this, genomes were assembled from reclaimed water systems and were compared against whole-genome sequences of antibiotic resistant E.coli isolates. Metagenome-derived genomes were found to produce similar profiles in wastewater treatment plant influents. A final theme to this dissertation addresses the need to standardize targets, methodologies, and reporting of antibiotic resistance in the environment. A systematic literature review was conducted on assays for the enumeration of key ARGs across aquatic environments and recommendations are summarized for the production of comparable data. In sum, this dissertation advances knowledge about the occurrence of pathogens, ARB, and ARGs across aquatic and agricultural systems and across several countries. Advances are made in the application of NGS tools for environmental monitoring of antibiotic resistance and other targets and a path forward is recommended for continued improvement as both DNA sequencing technologies and computational methodologies continue to rapidly advance.
Bioinformatic Analysis of Wastewater Metagenomes Reveals Microbial Ecological and Evolutionary Phenomena Underlying Associations of Antibiotic Resistance with Antibiotic Use
Brown, Connor L. (Virginia Tech, 2024-01-17)
Antibiotic resistance (AR) is a pervasive crisis that is intricately woven into social and environmental systems. Its escalation is fueled by factors such overuse, poverty, climate change, and the heightened interconnectedness characteristic of our era of globalization. In this dissertation, the impact of antibiotic usage is addressed from the perspective of wastewater-based surveillance (WBS) at the wastewater treatment plant (WWTP) and microbial ecology. Antibiotic usage and contamination was found to influence the prevalence of antibiotic resistance genes (ARGs) and resistant bacteria in both lab-scale and full-scale wastewater treatment settings. Through application of novel bioinformatic approaches developed herein, metagenomics revealed associations between sewage-associated microbes and community antibiotic use that were in part mediated by microbial ecological processes and horizontal gene transfer (HGT). In sum, this dissertation increases the arsenal of bioinformatic tools for AR surveillance in wastewater environments and advances knowledge with respect to the contribution of antibiotic use to the spread of antibiotic resistance at the community-scale. Three studies served to evaluate and/or develop bioinformatic resources for molecular characterization of AR in wastewater. Hybrid assembly combining emerging long read DNA sequencing and short read sequencing was evaluated and found to improve accuracy relative to assembly of long or short reads alone. A novel database of mobile genetic element (MGE) marker genes, mobileOG-db, was compiled in order to address short-comings with pre-existing resources. A pipeline for detecting HGT in metagenomes, Kairos, was created in order to facilitate the detection of HGT in metagenome assemblies which greatly amplified coverage of ARGs. In Chapter 5, a lab-scale study of WWTP bioreactors revealed that elevated antibiotic contamination was correlated with increased prevalence of corresponding ARGs. In addition, multiple in situ HGT events of ARGs encoding resistance to the elevated antibiotics were predicted, including one HGT event likely mediated by a novel bacteriophage. In Chapter 6, influent and effluent from a full-scale municipal WWTP were collected twice-weekly for one year and subjected to deep shotgun metagenomic sequencing. In parallel, collaboration with clinicians enabled statistical modeling of antibiotic usage and resistance, revealing associations between antibiotic prescriptions patterns in the region and resistance at the WWTP. Finally, Chapter 7 details bioinformatic recovery of diverse extended spectrum beta-lactamase gene recovery from the influent and effluent metagenomes, shedding light on the dynamics of circulating resistance genes. In sum, this dissertation identifies bioinformatic evidence for the selection of AR in wastewater environments as a result of antibiotic use in the community and advances hypotheses for explaining the mechanisms of the observed phenomena.
Biomarkers of Lipid Oxidation in the Oral Cavity
Vereb, Heather A. (Virginia Tech, 2011-10-14)
Measuring lipid oxidation is useful as a means of monitoring oxidative stress, such as that induced by clinical conditions or environmental exposure. Characteristic volatile compounds, often with low threshold odors, are secondary products of lipid oxidation reactions. Metallic flavor in food and beverages has been linked with oxidation of lipids in the oral cavity. Breath, an emerging medium for analysis of internal condition, is one means of measuring the metal-induced lipid oxidation responsible for this flavor. This project analyzes the breath of human subjects, as well as lipid oxidation of in vitro samples to identify compounds responsible for producing metallic flavor, which result from the oxidation of lipids in the oral cavity. Because these analytes are found at extremely low (picomolar to nanomolar) concentrations, preconcentration of samples prior to gas chromatography-mass spectrometry analysis is crucial. This study utilizes both solid phase microextraction (SPME) and micromachined silicon micropreconcentrators to concentrate compounds in breath to optimize analysis.
Biomimetic Transparent Nanoplasmonic Meshes by Reverse-Nanoimprinting for Bio-Interfaced Spatiotemporal Multimodal SERS Bioanalysis
Garg, Aditya; Mejia, Elieser; Nam, Wonil; Vikesland, Peter J.; Zhou, Wei (Wiley-V C H Verlag, 2022-11)
Multicellular systems, such as microbial biofilms and cancerous tumors, feature complex biological activities coordinated by cellular interactions mediated via different signaling and regulatory pathways, which are intrinsically heterogeneous, dynamic, and adaptive. However, due to their invasiveness or their inability to interface with native cellular networks, standard bioanalysis methods do not allow in situ spatiotemporal biochemical monitoring of multicellular systems to capture holistic spatiotemporal pictures of systems-level biology. Here, a high-throughput reverse nanoimprint lithography approach is reported to create biomimetic transparent nanoplasmonic microporous mesh (BTNMM) devices with ultrathin flexible microporous structures for spatiotemporal multimodal surface-enhanced Raman spectroscopy (SERS) measurements at the bio-interface. It is demonstrated that BTNMMs, supporting uniform and ultrasensitive SERS hotspots, can simultaneously enable spatiotemporal multimodal SERS measurements for targeted pH sensing and non-targeted molecular detection to resolve the diffusion dynamics for pH, adenine, and Rhodamine 6G molecules in agarose gel. Moreover, it is demonstrated that BTNMMs can act as multifunctional bio-interfaced SERS sensors to conduct in situ spatiotemporal pH mapping and molecular profiling of Escherichia coli biofilms. It is envisioned that the ultrasensitive multimodal SERS capability, transport permeability, and biomechanical compatibility of the BTNMMs can open exciting avenues for bio-interfaced multifunctional sensing applications both in vitro and in vivo.

Browsing by Author "Vikesland, Peter J."

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