Impact of dry density and incomplete saturation on microbial growth in bentonite clay for nuclear waste storage.

AIMS: Many countries are in the process of designing a deep geological repository (DGR) for long-term storage of used nuclear fuel. For several designs, used fuel containers will be placed belowground, with emplacement tunnels being backfilled using a combination of highly compacted powdered bentonite clay buffer boxes surrounded by a granulated "gapfill" bentonite. To limit the potential for microbiologically influenced corrosion of used fuel containers, identifying conditions that suppress microbial growth is critical for sustainable DGR design. This study investigated microbial communities in powdered and gapfill bentonite clay incubated in oxic pressure vessels at dry densities between 1.1 g cm-3 (i.e. below repository target) and 1.6 g cm-3 (i.e. at or above repository target) as a 1-year time series. RESULTS: Our results showed an initial (i.e. 1 month) increase in the abundance of culturable heterotrophs associated with all dry densities <1.6 g cm-3, which reveals growth during transient low-pressure conditions associated with the bentonite saturation process. Following saturation, culturable heterotroph abundances decreased to those of starting material by the 6-month time point for all 1.4 and 1.6 g cm-3 pressure vessels, and the most probable numbers of culturable sulfate-reducing bacteria (SRB) remained constant for all vessels and time points. The 16S rRNA gene sequencing results showed a change in microbial community composition from the starting material to the 1-month time point, after which time most samples were dominated by sequences associated with Pseudomonas, Bacillus, Cupriavidus, and Streptomyces. Similar taxa were identified as dominant members of the culture-based community composition, demonstrating that the dominant members of the clay microbial communities are viable. Members of the spore-forming Desulfosporosinus genus were the dominant SRB for both clay and culture profiles. CONCLUSIONS: After initial microbial growth while bentonite was below target pressure in the early phases of saturation, microbial growth in pressure vessels with dry densities of at least 1.4 g cm-3 was eventually suppressed as bentonite neared saturation.

Multicomponent Synthesis of Poly(α-aminophosphine chalcogenide)s and Subsequent Depolymerization.

Multicomponent reactions of primary phosphines (R-PH2), diimines (R'-N═C(H)-R-(H)C═N-R'), and chalcogens (O2, S8) generate poly(α-aminophosphine chalcogenide)s (4-7) through step-growth polymerization. Characterization of the linear polymers using 31P{1H} diffusion-ordered NMR spectroscopy (DOSY) experiments aided in determining the molecular weight (Mw) of the material. Subjecting the polyphosphine oxide or sulfide to reducing conditions in the presence of a Lewis acid resulted in complete depolymerization of the polymers, quantitatively releasing the 1° phosphine and diimine (2) starting materials, with concomitant reduction of diimine to diamine (9).

Reactivity of Primary Phosphines and Primary Phosphine Sulfides towards Imines.

Reactivity of primary phosphines with two stoichiometric equivalents of imine results in the formation of bis-α-aminophosphines (2 a-e), which can be subsequently oxidized in the presence of S8 or H2 O2 to generate air stable bis-α-aminophosphine sulfides (2 b-m(S/O)). To elucidate the mechanism of this three-component reaction, Hammett analysis, kinetic isotope effect (KIE), and trapping experiments were performed. Ultimately a P(V)-P(III) tautomerization is invoked, followed by nucleophilic attack by the P(III) species to generate the desired products.

Endoscopic Submucosal Dissection for Resolution of a Symptomatic Pancreatic Rest in a Pediatric Patient: A Case Report and Literature Review.

The pancreatic rest, aberrant, or heterotopic pancreas is a normal function pancreas found in the submucosal layer of the greater curvature of the gastric antrum and occasionally in the duodenum. Most of the patients are asymptomatic and the finding is usually incidental. We describe the case of a child with abdominal pain and history of recurrent ulcers that necessitated esophagogastroduodenoscopy and further evaluation with endoscopic ultrasound that confirmed a submucosal lesion consistent with a pancreatic rest. Endoscopic submucosal dissection was performed without complication, and complete symptom resolution was achieved after dissection of the pancreatic rest.

Endoscopic Management of the Ascending Colon Perforation Secondary to a Rare-Earth Magnets Ingestion in a Pediatric Patient.

Rare magnets (neodymium magnets) are high-powered magnets known to cause intestinal perforation if the intestinal mucosa is trapped in between 2 or several magnets. A bowel perforation in pediatric patients secondary to magnets is usually managed with a surgical intervention that might require enterectomy. We report a case of an 11-year-old boy who presented with abdominal pain and a finding on abdominal x-ray of radiopaque foreign bodies located in the ascending colon. He underwent colonoscopy with a finding of embedded magnets with a colonic perforation. The colonoscopy revealed embedded magnets in the colonic mucosa that were colonoscopically removed, and then, the perforated site was successfully managed with endoclipping of the perforation site in the ascending colon.

Fidget Spinner Ingestions in Children-A Problem that Spun Out of Nowhere.

The Consumer Product Safety Risk Management System's injury and potential injury database records 13 cases of fidget spinner ingestion since 2016. In addition to a database query, we report 3 additional cases of fidget spinner ingestion to describe patient presentations and subsequent management strategies.

Human Papilloma Viruses and Breast Cancer - Assessment of Causality.

High risk human papilloma viruses (HPVs) may have a causal role in some breast cancers. Case-control studies, conducted in many different countries, consistently indicate that HPVs are more frequently present in breast cancers as compared to benign breast and normal breast controls (odds ratio 4.02). The assessment of causality of HPVs in breast cancer is difficult because (i) the HPV viral load is extremely low, (ii) HPV infections are common but HPV associated breast cancers are uncommon, and (iii) HPV infections may precede the development of breast and other cancers by years or even decades. Further, HPV oncogenesis can be indirect. Despite these difficulties, the emergence of new evidence has made the assessment of HPV causality, in breast cancer, a practical proposition. With one exception, the evidence meets all the conventional criteria for a causal role of HPVs in breast cancer. The exception is "specificity." HPVs are ubiquitous, which is the exact opposite of specificity. An additional reservation is that the prevalence of breast cancer is not increased in immunocompromised patients as is the case with respect to HPV-associated cervical cancer. This indicates that HPVs may have an indirect causal influence in breast cancer. Based on the overall evidence, high-risk HPVs may have a causal role in some breast cancers.

Effect of water chemistry on the dissolution rate of the lead corrosion product hydrocerussite.

Hydrocerussite (Pb3(CO3)2(OH)2) is widely observed as a corrosion product in drinking water distribution systems. Its equilibrium solubility and dissolution rate can control lead concentrations in drinking water. The dissolution rate of hydrocerussite was investigated as a function of pH, dissolved inorganic carbon (DIC), and orthophosphate concentrations at conditions relevant to drinking water distribution using continuously stirred tank reactors (CSTRs). In the absence of DIC and orthophosphate, the dissolution rate decreased with increasing pH. Addition of DIC inhibited the dissolution of hydrocerussite. The addition of orthophosphate significantly decreased the dissolution rate of hydrocerussite. At conditions with orthophosphate and without DIC, a lead(II) phosphate solid hydroxylpyromorphite (Pb5(PO4)3OH) was observed after reaction, and orthophosphate's inhibitory effect can be attributed to the formation of this low-solubility lead(II) phosphate solid. In the presence of both orthophosphate and DIC, no lead(II) phosphate solid was observed, but the rate was still lowered by the presence of orthophosphate, which might be due to the adsorption of orthophosphate to block reactive sites on the hydrocerussite surface. For systems in which hydroxylpyromorphite was present, the steady-state effluent lead concentrations from the CSTRs were close to the predicted equilibrium solubility of hydroxylpyromorphite. In the absence of orthophosphate rapid equilibration of hydrocerussite was observed.

Adsorption of water and ethanol in MFI-type zeolites.

Water and ethanol vapor adsorption phenomena are investigated systematically on a series of MFI-type zeolites: silicalite-1 samples synthesized via both alkaline (OH(-)) and fluoride (F(-)) routes, and ZSM-5 samples with different Si/Al ratios as well as different charge-balancing cations. Full isotherms (0.05-0.95 activity) over the range 25-55 °C are presented, and the lowest total water uptake ever reported in the literature is shown for silicalite-1 made via a fluoride-mediated route wherein internal silanol defects are significantly reduced. At a water activity level of 0.95 (35 °C), the total water uptake by silicalite-1 (F(-)) was found to be 0.263 mmol/g, which was only 12.6%, 9.8%, and 3.3% of the capacity for silicalite-1 (OH(-)), H-ZSM-5 (Si/Al:140), and H-ZSM-5 (Si/Al:15), respectively, under the same conditions. While water adsorption shows distinct isotherms for different MFI-type zeolites due to the difference in the concentration, distribution, and types of hydrophilic sites, the ethanol adsorption isotherms present relatively comparable results because of the overall organophilic nature of the zeolite framework. Due to the dramatic differences in the sorption behavior with the different sorbate-sorbent pairs, different models are applied to correlate and analyze the sorption isotherms. An adsorption potential theory was used to fit the water adsorption isotherms on all MFI-type zeolite adsorbents studied. The Langmuir model and Sircar's model are applied to describe ethanol adsorption on silicalite-1 and ZSM-5 samples, respectively. An ideal ethanol/water adsorption selectivity (α) was estimated for the fluoride-mediated silicalite-1. At 35 °C, α was estimated to be 36 for a 5 mol % ethanol solution in water increasing to 53 at an ethanol concentration of 1 mol %. The adsorption data demonstrate that silicalite-1 made via the fluoride-mediated route is a promising candidate for ethanol extraction from dilute ethanol-water solutions.

Effect of gamma irradiation on gas-ionic liquid and water-ionic liquid interfacial stability.

The effect of γ-radiation on gas-ionic liquid (IL) and water-IL interfacial stability was investigated. Three phosphonium-based ILs, which vary considerably in their viscosity, conductivity and miscibility with water, were examined. The gas phase above the IL samples (headspace gas) was analyzed using gas chromatography with a mass spectrometer detector while the changes in the IL and aqueous phases were followed by conductivity measurements and Raman spectroscopy. For the gas-IL systems, the headspace samples showed trace amounts of the radiolytic decomposition products of the ILs that were small and volatile enough to become airborne. The type of cover gas, air or Ar, had no effect on the gas speciation. Negligible changes in the conductivity and the Raman spectra of the IL phase due to irradiation indicate that γ-irradiation induces negligible chemical changes in the IL phase when it is in contact with a gas phase. For the water-IL systems, the initially immiscible layers slowly developed an interfacial emulsion layer, even in the absence of radiation. This layer started at the water-IL interface and then grew downwards, eventually converting the entire IL phase to an emulsion. Gamma-irradiation accelerated the conversion of the IL phase to an emulsion. The development of the emulsion layer was accompanied by changes in the conductivity and the Raman spectra of both the IL and water phases. Based on these results, a mechanism involving the formation of micelles at, or near, the water-IL interface has been proposed to explain the development of an emulsion layer. We also suggest that radiolytic decomposition of ILs produces surfactants that can accumulate at the interface and, even at low concentrations, accelerate the emulsification process.

Bacterial enteritis as a risk factor for childhood intussusception: a retrospective cohort study.

OBJECTIVE: To assess the relationship between bacterial enteritis and intussusception. STUDY DESIGN: The Patient Administration Systems and Biostatistics Activity database from January 2002 to December 2005 was examined for clinic visits or hospital admission to a Department of Defense medical facility for children age 0-5 years. The study included the International Statistical Classification of Diseases and Related Health Problems diagnosis-related group (DRG) codes for infections with Yersinia enterocolitica, Escherichia coli, Shigella species, Salmonella species, and Campylobacter. Identified patients were then assessed for the intussusception DRG code for 0-180 days postinfection. The total number of children enrolled in military treatment facilities in the same age group (denominator) was obtained. RESULTS: Bacterial enteritis significantly increased the relative risk of intussusception. An increased risk was found following infection with Salmonella, E coli, Shigella, and Campylobacter. The relative risk for intussusception following any bacterial enteritis was 40.6 (95% confidence interval = 28.6-57.5; P < .0001). CONCLUSIONS: Bacterial enteritis is a significant risk factor for the subsequent development of intussusception in children.

Protein oxidative modifications during electrospray ionization: solution phase electrochemistry or corona discharge-induced radical attack?

The exposure of solution-phase proteins to reactive oxygen species (ROS) causes oxidative modifications, giving rise to the formation of covalent +16 Da adducts. Electrospray ionization (ESI) mass spectrometry (MS) is the most widely used method for monitoring the extent of these modifications. Unfortunately, protein oxidation can also take place as an experimental artifact during ESI, such that it may be difficult to assess the actual level of oxidation in bulk solution. Previous work has demonstrated that ESI-induced oxidation is highly prevalent when operating at strongly elevated capillary voltage V(0) (e.g., +8 kV) and with oxygen nebulizer gas in the presence of a clearly visible corona discharge. Protein oxidation under these conditions is commonly attributed to OH radicals generated in the plasma of the discharge. On the other hand, charge balancing oxidation reactions are known to take place at the metal/liquid interface of the emitter. Previous studies have not systematically explored whether such electrochemical processes could be responsible for the formation of oxidative +16 Da adducts instead of (or in combination with) plasma-generated ROS. Using hemoglobin as a model system, this work illustrates the occurrence of extensive protein oxidation even under typical operating conditions (e.g., V(0) = 3.5 kV, N(2) nebulizer gas). Surprisingly, measurements of the current flowing in the ESI circuit demonstrate that a weak corona discharge persists for these relatively gentle settings. On the basis of comparative experiments with nebulizer gases of different dielectric strength, it is concluded that ROS generated under discharge conditions are solely responsible for ESI-induced protein oxidation. This result is corroborated through off-line electrolysis experiments designed to mimic the electrochemical processes taking place during ESI. Our findings highlight the necessity of using easily oxidizable internal standards in biophysical or biomedical ESI-MS studies where knowledge of protein oxidation in bulk solution is desired. Strategies for eliminating ESI-induced oxidation artifacts are discussed.

Analyzing the influence of alloying elements and impurities on the localized reactivity of titanium grade-7 by scanning electrochemical microscopy.

Scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX) was applied to investigate the grain boundaries on ASTM grade-7 titanium (Ti-7) with a freshly polished surface, and the results showed that the alloying element, Pd, and the impurity, Fe, cosegregated to grain boundaries. Scanning electrochemical microscopy (SECM) was used to study the variations in reactivity on Ti-7 exposed to an aerated neutral solution of 0.1 M NaCl. Locations that possessed an enhanced reactivity compared to the oxide-covered (TiO(2)) surface of the grains on SECM images were proposed to be the boundaries. These areas were further activated by the application of a cathodic bias, and interconnection of the active locations allowed the construction of "grain boundary maps". Variations in surface reactivity were quantitatively analyzed by fitting probe approach curves (PACs) to curves simulated with a model based on finite element analyses using the platform of COMSOL multiphysics software. The difference in reactivity between active grain boundaries and oxide-covered grains was up to a factor of 100 on freshly polished surfaces. This difference decreased to a factor of 10-15 after longer-term exposure of the Ti-7 to the aerated solution, indicating partial passivation of the Pd/Fe-stabilized beta-phase in the grain boundaries. PAC analyses of oxide-covered grains showed that the reactivity increased logarithmically as the bias potential to the Ti-7 was decreased, consistent with reduction of the insulating TiO(2) layer to a more conductive TiOOH layer.

Evaluation of a sequential extraction process used for determining mercury binding mechanisms to coal combustion byproducts.

Leaching of mercury from coal combustion byproducts is a concern because of the toxicity of mercury. Leachability of mercury can be assessed by using sequential extraction procedures. Sequential extraction procedures are commonly used to determine the speciation and mobility of trace metals in solid samples and are designed to differentiate among metals bound by different mechanisms and to different solid phases. This study evaluated the selectivity and effectiveness of a sequential extraction process used to determine mercury binding mechanisms to various materials. A six-step sequential extraction process was applied to laboratory-synthesized materials with known mercury concentrations and binding mechanisms. These materials were calcite, hematite, goethite, and titanium dioxide. Fly ash from a full-scale power plant was also investigated. The concentrations of mercury were measured using inductively coupled plasma (ICP) mass spectrometry, whereas the major elements were measured by ICP atomic emission spectrometry. The materials were characterized by X-ray powder diffraction and scanning electron microscopy with energy dispersive spectroscopy. The sequential extraction procedure provided information about the solid phases with which mercury was associated in the solid sample. The procedure effectively extracted mercury from the target phases. The procedure was generally selective in extracting mercury. However, some steps in the procedure extracted mercury from nontarget phases, and others resulted in mercury redistribution. Iron from hematite and goethite was only leached in the reducible and residual extraction steps. Some mercury associated with goethite was extracted in the ion exchangeable step, whereas mercury associated with hematite was extracted almost entirely in the residual step. Calcium in calcite and mercury associated with calcite were primarily removed in the acid-soluble extraction step. Titanium in titanium dioxide and mercury adsorbed onto titanium dioxide were extracted almost entirely in the residual step.

Nutritional supplementation with transforming growth factor-beta, glutamine, and short chain fatty acids minimizes methotrexate-induced injury.

OBJECTIVE: Gastrointestinal (GI) damage caused by methotrexate (MTX) results in mucosal injury, bacterial invasion, and activation of an immune system that is reduced in function. Diets enriched with glutamine, short chain fatty acids (SCFAs), and transforming growth factor (TGF)-beta have demonstrated decreased infection, weight loss, and GI damage in Crohn disease. We, therefore, sought to study the cytoprotective effects of a diet enriched in glutamine, TGF-beta, and SFCAs (Modulen) in Fischer 344 rats exposed to MTX. METHODS: Rats were divided into five groups: two receiving normal saline and three receiving MTX and fed either normal chow, Modulen supplemented chow starting with the first MTX dose, or Modulen supplemented chow beginning 3 days before MTX injection. Rats were weighed daily. On day 5, albumin and bicarbonate levels were drawn, and rats were killed for examination of their intestinal mucosa by a pathologist unaware of groupings. RESULTS: Rats pretreated with Modulen supplemented chow maintained weight (2.6 vs, 12.3 g weight loss), albumin levels (3.13 vs, 2.43 mg/dL), and bicarbonate levels (23.8 vs. 18.1 mg/dL) as compared with rats fed normal chow throughout MTX treatment (P < 0.05). Pretreatment with Modulen also protected against crypt cell loss, villus atrophy, crypt abscesses, crypt/villus ratio, and overall histologic damage (P < 0.05). CONCLUSION: When administered before and during MTX treatment, Modulen supplementation provided statistically significant protection against weight loss, hypoalbuminemia, acidosis, and GI damage in a rat model. Future animal research of Modulen's protective effects with other chemotherapeutic agents is needed before human trials.

A pilot study using total colonic manometry in the surgical evaluation of pediatric functional colonic obstruction.

BACKGROUND/PURPOSE: Total colonic manometry (TCM) can directly measure intraluminal pressures and contractile function of the entire colon. The utility of TCM to guide the surgical management of functional colonic obstruction has not been reported. METHODS: Total colonic manometry was performed on all patients referred for surgical evaluation of refractory functional colonic obstruction. Manometric tracings were obtained while fasting, after feeding, and after pharmacologic stimulation. RESULTS: Nine patients were referred for refractory colonic obstruction. The mean age was 4.8 years, and the mean duration of follow-up was 29 months. Two patients had functional obstruction after repair of Hirschsprung's disease, and 7 patients had idiopathic functional obstruction. In the idiopathic group, 4 distinct motility patterns were identified: (1) normal colonic motility, (2) dysmotility with massive distension, (3) persistent segmental dysmotility, and (4) global neuropathy/myopathy. Both Hirschsprung's patients showed globally abnormal motility. Surgical management was guided by TCM results. There was significant improvement in bowel function and weight gain after manometry-guided intervention. An unnecessary laparotomy was avoided in 2 patients. CONCLUSIONS: TCM can be valuable in deciding the need for and timing of diversion, the extent of resection required, and the suitability of the patient for restoring bowel continuity in refractory functional obstruction.