Degradation and fate of 2,4-dinitroanisole (DNAN) and its intermediates treated with Mg/Cu bimetal: Surface examination with XAS, DFT, and LDI-MS.

A novel Mg-based bimetal reagent (Mg/Cu) was used as an enhanced reductive system to degrade insensitive munition 2,4-dinitroanisole (DNAN), a contaminant found in energetic-laden waste. Degradation of DNAN was significantly impacted by dissolved oxygen and studied in anoxic and oxic bimetal systems (i.e., purging with N2, air, or O2 gas). Degradation occurred through sequential nitroreduction: first one nitro group was reduced (ortho or para) to form short-lived intermediates 2-amino-4-nitroanisole or 4-amino-2-nitroanisole (2-ANAN or 4-ANAN), and then subsequent reduction of the other nitro group formed 2,4-diaminoanisole (DAAN). The nitro-amino intermediates demonstrated regioselective reduction in the ortho position to 2-ANAN; Regioselectivity was also impacted by the anoxic/oxic environment. Under O2-purging DNAN degradation rate was slightly enhanced, but most notably O2 significantly accelerated DAAN generation. DAAN also further degraded only in the oxygenated Mg/Cu system. Adsorption of DNAN byproducts to the reagent occurred regardless of anoxic/oxic condition, resulting in a partition of carbon mass between the adsorbed phase (27%-35%) and dissolved phase (59%-72%). Additional surface techniques were applied to investigate contaminant interaction with Cu. Density functional theory (DFT) calculations identified preferential adsorption structures for DNAN on Cu with binding through two O atoms of one or both nitro groups. X-ray absorption spectroscopy (XAS) measurements determined the oxidation state of catalytic metal Cu and formation of a Cu-O-N bond during treatment. Laser desorption ionization mass spectrometry (LDI-MS) measurements also identified intermediate 2-ANAN adsorbed to the bimetal surface.

Oxidative degradation of nitroguanidine (NQ) by UV-C and oxidants: Hydrogen peroxide, persulfate and peroxymonosulfate.

Nitroguanidine (NQ), a component used in insensitive munitions formulations, has high solubility which often leads to highly contaminated wastewater streams. In this work, batch experiments were conducted to investigate and compare the NQ degradation by UV-based advanced oxidation processes (AOPs); hydrogen peroxide (H2O2), persulfate (PS) and peroxymonosulfate (PMS) were selected as oxidants. A preliminary evaluation of AOPs kinetics, byproducts, and potential degradation pathways were carried out and compared to NQ degradation by direct UV-C photolysis. The effects of oxidant dosage, NQ concentrations and pH were evaluated by determining the respective kinetic constants of degradation. Among the treatments applied, UV/PS showed to be a promising and effective alternative leading to faster rates of degradation respect to both oxidant dosage (25 mM) and initial NQ concentrations (≤24 mM). Nevertheless, the degradation rate of NQ by UV/PS appeared to be affected strongly by the initial pH compared to UV/H2O2 and UV/PMS, with the lowest rate overall at pH ≥ 8.0. In addition, the main byproducts from NQ degradation, guanidine and cyanamide, showed to be involved in further degradation steps only with UV/PS and UV/PMS suggesting higher degradation effectiveness of these oxidants compared UV/H2O2 and UV alone.

Characterization of Mg-based bimetal treatment of insensitive munition 2,4-dinitroanisole.

The manufacturing of insensitive munition 2,4-dinitroanisole (DNAN) generates waste streams that require treatment. DNAN has been treated previously with zero-valent iron (ZVI) and Fe-based bimetals. Use of Mg-based bimetals offers certain advantages including potential higher reactivity and relative insensitivity to pH conditions. This work reports preliminary findings of DNAN degradation by three Mg-based bimetals: Mg/Cu, Mg/Ni, and Mg/Zn. Treatment of DNAN by all three bimetals is highly effective in aqueous solutions (> 89% removal) and wastewater (> 91% removal) in comparison with treatment solely with zero-valent magnesium (ZVMg; 35% removal). Investigation of reaction byproducts supports a partial degradation pathway involving reduction of the ortho or para nitro to amino group, leading to 2-amino-4-nitroanisole (2-ANAN) and 4-amino-2-nitroanisole (4-ANAN). Further reduction of the second nitro group leads to 2,4-diaminoanisole (DAAN). These byproducts are detected in small quantities in the aqueous phase. Carbon mass balance analysis suggests near-complete closure (91%) with 12.4 and 78.4% of the total organic carbon (TOC) distributed in the aqueous and mineral bimetal phases, respectively. Post-treatment surface mineral phase analysis indicates Mg(OH)2 as the main oxidized species; oxide formation does not appear to impair treatment.

Detection of uric acid stones in the ureter using low- and conventional-dose computed tomography.

OBJECTIVE: To determine the ability of low- and conventional-dose computed tomography (CT) in identification of uric acid stones, which are of lower density than calcium oxalate stones. MATERIALS AND METHODS: Uric acid stones (3, 5, and 7 mm) were randomly placed in human cadaveric ureters and scanned using conventional 140-mAs and low-dose 70-, 50-, 30-, 15-, 7.5-, and 5-mAs settings. A single-blinded radiologist reviewed a total of 523 scanned stone images. Sensitivity and specificity were compared among different settings and stone sizes. RESULTS: Imaging using 140-, 70-, 50-, 30-, 15-, 7.5-, and 5-mAs settings resulted in 97%, 97%, 96%, 93%, 83%, 83%, and 69% sensitivity and 92%, 92%, 91%, 89%, 88%, 91%, and 94% specificity, respectively. There was a significant difference in sensitivity between 140 mAs and 15, 7.5, and 5 mAs (P = .011, P = .011, and P <.001, respectively). Sensitivity for 3-, 5-, and 7-mm stones was 83%, 90%, and 93%, respectively. At ≤ 15 mAs, 3-mm stones had a higher rate of false negatives (P <.001). CONCLUSION: Both low- and conventional-dose CTs demonstrate excellent sensitivity and specificity for the detection of ureteral uric acid stones. However, low-dose CT at ≤ 15 mAs resulted in reduced detection of uric acid stones.

Sedation, analgesia, and local anesthesia: a review for general and interventional radiologists.

Radiologists, like other physicians, need to know how to use sedatives, analgesics, and local anesthetics; however, their exposure to patients requiring discomfort control is limited, not just during residency but also in postgraduate practice. The purpose of this article is to provide a reference guide for radiologists who need pertinent and ready information on discomfort control. The authors discuss policies and standards that the Joint Commission has established for sedation providers; also discussed are the clinical pharmacology and dosage recommendations for the sedative, analgesic, anesthetic, and reversal agents that radiologists are most likely to use. Monitored anesthesia care and patient-controlled analgesia pumps, and in what circumstances they may be appropriate, are discussed. Anesthesia consultations are not uncommon when a nonanesthesiologist needs either of these services. Stiff chest syndrome, serotonin release syndrome, and systemic toxicity due to local anesthesia, all life-threatening conditions that sedation and analgesia providers may encounter, are discussed. The causes of these conditions and their necessary treatments are included in the discussion, along with cases in which a nonanesthesiologist may need an anesthesia consultation. It is important to understand that the control of pain and anxiety are not mutually exclusive but can occur either separately or together; when an agent that controls anxiety and an agent that controls pain are given together, the overall effect is synergistic. It is also important to understand the concept of multimodal analgesia; this is the use of opioids and nonopioids together to take full advantage of the analgesic effects of each component while minimizing potential side effects. Radiologists are fully capable of providing effective and safe pain control on their own and with the assistance of an anesthesiologist.

Contrast media in breast imaging.

Although mammography is the standard imaging modality for detection of breast cancer, magnetic resonance (MR) imaging is a valuable adjunct and, in certain cases, is the imaging of choice. Contrast-enhanced breast MR imaging provides a noninvasive means of staging disease, assessing posttreatment response, and screening of high-risk patients with genetic predispositions. Additional indications for MR mammography include lesion characterization, contralateral breast evaluation in patients with proved malignancy, and identifying primary malignancy in patients with axillary nodal disease. There are several competing factors that influence the quality of the study. Finding the right balance is the key to providing high-quality images that can be accurately interpreted.

Use of atomic force microscopy for morphological and morphometric analyses of acrosome intact and acrosome-reacted human sperm.

The objective of this study was to use atomic force microscopy (AFM), with submicron resolution, for morphophologic and morphometric analyses of acrosome intact and acrosome-reacted human sperm heads. A mixed population of acrosome intact and reacted sperm was produced by treating capacitated sperm with A23187, which induced the acrosome reaction in approximately 50% of total sperm population. This A23187-treated sperm suspension was then plated onto a coverslip and acrosome reacted sperm were preidentified by their specific staining with rhodamine-conjugated Concanavalin A. The sperm coverslip was then air-dried and scanned by a Nanoscope IIIa atomic force microscope, using the contact mode. Top and side view images processed through the illuminate mode revealed three dimensional sperm head contour, with the highest point situated in the head posterior in both acrosome intact and acrosome reacted sperm. Maximum height, length, and width measured in 50 acrosome intact and 50 acrosome-reacted sperm were the same in both populations. However, head length at half maximum height was significantly decreased in acrosome reacted sperm (2.99 +/- 0.24 microm vs. 3.56 +/- 0.32 microm of acrosome intact sperm), due to the sudden change of the height contour from the maximum peak to the anterior tip of acrosome-reacted sperm. Our results described here can therefore be used to differentiate acrosome intact and reacted sperm from each other. This would allow future studies on subcellular changes, related to the acrosome reaction, at the submicron resolution level under more physiological conditions, since AFM does not require fixing or staining of the samples.