Properties, functionality and potential applications of novel modified iron nanoparticles for the treatment of 2,4,6-Trichlorophenol

2,4,6-trichlorophenol (TCP) is a pervasive carcinogenic water contaminant found in a wide variety of water and waste systems and is a pertinent model compound of broader aromatic organics, specifically organo-halide pesticides. These compounds are persistent in the environment and show resilience to regular water and waste treatment protocols thus warranting the development and implementation of novel treatment materials for improved contaminant removal. Zero-valent iron (ZVI) has demonstrated the ability to remove or degrade a wide variety of inorganic and organic water contaminants, including chlorophenols, and has been widely applied for in-situ groundwater remediation where contamination is often localised in a low-oxygen environment. ZVI’s broader applications in water treatment have remained mainly limited due to corrosion, particle dispersion, and confinement issues in deployment. This work, therefore, explored the development, functionality, and potential application of new modified nZVI materials (nZVI-Osorb) and assessed their potential to improve iron’s intrinsic functionality while also gauging the material’s viability for TCP remediation in water and waste systems. Materials produced in this thesis were prepared utilising three different embedment procedures (1-pot, multiple additions, oxygen-free). All embedment methods resulted in tightly bound composites featuring high surface areas (340.2-449.1 sq. m/g) with net iron composition ranging from 10% to 29.78% by mass. Electron imaging microscopy verified even dispersion of iron throughout the substrate. Composite materials did not exhibit a delayed rate of atmospheric corrosion over nZVI controls evincing an 18% nZVI0 loss per day until reaching a stabilised concentration (7%) after 48 hrs. nZVI-Osorb composites did produce more favourable iron oxide species which remain conducive to electron transfer from core Fe0 atom. After 50 days, a majority of nZVI in nZVI-Osorb had oxidised to maghemite (30%) and magnetite (26%) compared to control nZVI producing 19% and 12% respectively. Unreactive hematite accounted for 47% of the control and just 36% of the composite. While 1-pot embedment allowed the most substantial control over final iron composition, the oxygen-free method allowed the most reliable preservation of initial nZVI0 concentrations through restricted oxidation. Materials generated through oxygen-free embedment were utilised in the following water treatment trials with TCP. Parameters related to sorption and degradation mechanisms of TCP by nZVI-Osorb were tested in aerobic conditions, e.g. surface and potable water. nZVI-Osorb materials demonstrated high extraction capacity for TCP from aqueous solutions (Qe=1286.4 ±13.5 mg TCP/g Osorb, Qe=1253±106.7 mg TCP/g nZVI-Osorb, pH 5.1, 120mg/L TCP) and followed pseudo second order kinetics. In the broader class of chlorophenols, sorptive affinity mirrored partitioning values with highly substituted chlorophenols displaying the highest sorption capacities. Degradation of TCP by nZVI-Osorb or nZVI controls was not observed due to corrosive hindrance and inadequate reductive capacity, suggesting that materials may not be suitable for highly aerated surface and potable water treatment systems. Environmental conditions pertinent to sorption and degradation mechanisms were evaluated to improve understanding and robustness of functionality in low-oxygen applications, such as wastewater and anaerobic digesters, where nZVI-Osorb treatment is anticipated to be advantageous to TCP sorption and methane production. pH was found to influence sorption dramatically. Acidic solutions below 5 found sorption >90%. This capacity was reduced to <30% when pH was raised above TCP pKa value (6.23) to 7 and above. Further trials found a positive effect on TCP sorption (+7.55%) linked to net pH reduction (5.1 to 3.3) with the addition of secondary acids (volatile fatty acids: acetic, propionic, butyric, 3x 100mg/L) commonly found in anaerobic digester systems. Salinity did not affect TCP sorption. The removal of dissolved and atmospheric oxygen increased total sorption (40ppm-+1.94%, 100ppm- +7.93%, 200ppm- +0.89%, 400mg/L- +14.59%) through reduced iron corrosion and the production of favorable iron oxides, but did not facilitate contaminant degradation. Biodegradation mechanisms for TCP have broadly been established, and new research has supported the improved cometabolic degradation of recalcitrant contaminants like TCP and PCP in nZVI-dosed anaerobic digesters. Model anaerobic digester systems (3.9 g/L nZVI-Osorb, 25mg/L TCP, 240 mg/L acetic, 120mg/L propionic, 120mg/L butyric acid) containing bioreactor sludge (62.5%) were observed through standard water quality diagnostics (pH, ORP, COD, head pressure) for 14 days and suggested that nZVI-Osorb did not inhibit cellular processes. Increased electron activity from iron corrosion and hydrogen gas production, increased overall pH and decreased total ORP in these AD systems. TCP degradation by-products (DCP, CP) were detected in dilute concentrations (<0.01 mg/L) with poor recovery by LC-MS/MS. Results suggest that nZVIOsorb may be well-suited additive for AD systems. This study contributes to knowledge of the properties, functionality, and treatment mechanisms of metal-sorbent composites with a model chlorinated aromatic water contaminant in aerobic and anaerobic environments. The work identifies favourable environmental and process conditions to apply these materials in larger scale applications, particularly, anaerobic digestion and provides support for the continued refinement and improvement of nZVI based remediation systems

Culture, Theory, Data: An Introduction

The introduction to a special issue of New Literary History titled "Culture, Theory, Data," which explores the consequences of computation for cultural theory—and vice-versa. The introduction begins by explaining how we came to a historical juncture where "culture" and "data" seem to be opposed terms. Then it offers some reasons for believing that opposition is beginning to fade, including the emergence of "a new theoretical lingua franca" that draws meaning simultaneously from quantitative and from qualitative disciplines. The authors end by observing that reflection on the intersection of culture and data is particularly urgent in an era of generative language models

Re‐Imagining Inclusion Through the Lens of Disabled Childhoods

The purpose of this article is to contribute new insights to critical disability and disabled children’s childhood studies that center on the valuing of disabled children’s lives—a guiding purpose in the disability justice movement. We use published findings from the Inclusive Early Childhood Service System project, a longitudinal, institutional ethnography of the ways that families and children are organized around categories of disability, which show social inclusions and exclusions before and during the pandemic. These findings illuminate: (a) institutional flexibility for the purpose of social inclusion and isolation during the pandemic as a result of institutional organization; (b) the impact of institutional decisions around closures, remote programs, and support on families’ choices and self‐determination; and (3) the ways safety is differently applied and rationalized for disabled children allowing institutions to exclude disabled children and families. We use critical disability studies and disabled children’s childhood studies to interpret these findings and position the valuing of disabled children’s lives with a call for disability justice actions

R|S Atlas: Identifying Existing Cohort Study Data Resources to Accelerate Epidemiological Research on the Influence of Religion and Spirituality on Human Health

OBJECTIVE: Many studies have documented significant associations between religion and spirituality (R/S) and health, but relatively few prospective analyses exist that can support causal inferences. To date, there has been no systematic analysis of R/S survey items collected in US cohort studies. We conducted a systematic content analysis of all surveys ever fielded in 20 diverse US cohort studies funded by the National Institutes of Health (NIH) to identify all R/S-related items collected from each cohort\u27s baseline survey through 2014. DESIGN: An R|S Ontology was developed from our systematic content analysis to categorise all R/S survey items identified into key conceptual categories. A systematic literature review was completed for each R/S item to identify any cohort publications involving these items through 2018. RESULTS: Our content analysis identified 319 R/S survey items, reflecting 213 unique R/S constructs and 50 R|S Ontology categories. 193 of the 319 extant R/S survey items had been analysed in at least one published paper. Using these data, we created the R|S Atlas (https://atlas.mgh.harvard.edu/), a publicly available, online relational database that allows investigators to identify R/S survey items that have been collected by US cohorts, and to further refine searches by other key data available in cohorts that may be necessary for a given study (eg, race/ethnicity, availability of DNA or geocoded data). CONCLUSIONS: R|S Atlas not only allows researchers to identify available sources of R/S data in cohort studies but will also assist in identifying novel research questions that have yet to be explored within the context of US cohort studies

An Advanced Trajectory-Based Operations Prototype Tool and Focus Group Evaluation

Trajectory-based operations (TBO) is a key concept in the Next Generation Air Transportation System transformation of the National Airspace System (NAS) that will increase the predictability and stability of traffic flows, support a common operational picture through the use of digital data sharing, facilitate more effective collaborative decision making between airspace users and air navigation service providers, and enable increased levels of integrated automation across the NAS. The National Aeronautics and Space Administration (NASA) has been developing trajectory-based systems to improve the efficiency of the NAS during specific phases of flight and is now also exploring Advanced 4-Dimensional Trajectory (4DT) operational concepts that will integrate these technologies and incorporate new technology where needed to create both automation and procedures to support gate-to-gate TBO. A TBO Prototype simulation toolkit has been developed that demonstrates initial functionality that may reside in an Advanced 4DT TBO concept. Pilot and controller subject matter experts (SMEs) were brought to the Air Traffic Operations Laboratory at NASA Langley Research Center for discussions on an Advanced 4DT operational concept and were provided an interactive demonstration of the TBO Prototype using four example scenarios. The SMEs provided feedback on potential operational, technological, and procedural opportunities and concerns. After viewing the interactive demonstration scenarios, the SMEs felt the operational capabilities demonstrated would be useful for performing TBO while maintaining situation awareness and low mental workload. The TBO concept demonstrated produced defined routings around weather which resulted in a more organized, consistent flow of traffic where it was clear to both the controller and pilot what route the aircraft was to follow. In general, the controller SMEs felt that traffic flow management should be responsible for generating and negotiating the operational constraints demonstrated, in cooperation with the Air Traffic Control System Command Center, while air traffic control should be responsible for the implementation of those constraints. The SMEs also indicated that digital data communications would be very beneficial for TBO operations and would result in less workload due to reduced communications, would eliminate issues due to language barriers and frequency problems, and would make receiving, loading, accepting, and executing clearances easier, less ambiguous, and more expeditious. This paper describes an Advanced 4DT operational concept, the TBO Prototype, the demonstration scenarios and methods used, and the feedback obtained from the pilot and controller SMEs in this focus group evaluation

The stem cell organisation, and the proliferative and gene expression profile of Barrett's epithelium, replicates pyloric-type gastric glands

Objective: Barrett's oesophagus shows appearances described as ‘intestinal metaplasia’, in structures called ‘crypts’ but do not typically display crypt architecture. Here, we investigate their relationship to gastric glands. Methods: Cell proliferation and migration within Barrett's glands was assessed by Ki67 and iododeoxyuridine (IdU) labelling. Expression of mucin core proteins (MUC), trefoil family factor (TFF) peptides and LGR5 mRNA was determined by immunohistochemistry or by in situ hybridisation, and clonality was elucidated using mitochondrial DNA (mtDNA) mutations combined with mucin histochemistry. Results: Proliferation predominantly occurs in the middle of Barrett's glands, diminishing towards the surface and the base: IdU dynamics demonstrate bidirectional migration, similar to gastric glands. Distribution of MUC5AC, TFF1, MUC6 and TFF2 in Barrett's mirrors pyloric glands and is preserved in Barrett's dysplasia. MUC2-positive goblet cells are localised above the neck in Barrett's glands, and TFF3 is concentrated in the same region. LGR5 mRNA is detected in the middle of Barrett's glands suggesting a stem cell niche in this locale, similar to that in the gastric pylorus, and distinct from gastric intestinal metaplasia. Gastric and intestinal cell lineages within Barrett's glands are clonal, indicating derivation from a single stem cell. Conclusions: Barrett's shows the proliferative and stem cell architecture, and pattern of gene expression of pyloric gastric glands, maintained by stem cells showing gastric and intestinal differentiation: neutral drift may suggest that intestinal differentiation advances with time, a concept critical for the understanding of the origin and development of Barrett's oesophagus