Nitrous acid (HONO) and the nitrite ion represent a particularly important conjugate pair of trace species with regard to heterogeneous behavior within the bulk, and on the surface, of aqueous atmospheric dispersions: this role results from their chemical reactivity, photolysis pathways, solubility, and ambient concentration levels. The actual ratio of NO(2)(-): HONO in solution is determined by the pH and the nitrous acid dissociation constant (pK(a)) which is generally quoted in the literature as 3.27 at 298 K. However there is much disagreement in published works as to the exact value, which should be used in model calculations relevant to the atmosphere. Furthermore even though the nitrite ion is known to absorb solar radiation in the 300-400 nm region and represents a dominant source of *OH radicals in surface seawater, large variations in the measured molar decadic absorption coefficients, epsilon, for nitrite ions (and aqueous HONO) are evident in the literature. In the current study, using a UV-vis spectrometric approach with careful baseline subtraction, the relevant epsilon values for the nitrite ion were determined to be 8.16 +/- 0.08 M(-1) cm(-1) for the npi transitions at 290 nm and 22.1 +/- 0.22 M(-1) cm(-1) at 354 nm. For HONO, the wavelength maximum for the strongest vibronic band in solution was found at 372 nm with an epsilon value of 60.52 +/- 0.6 M(-1) cm(-1). Using the Henderson-Hasselbalch equation and the above data, a value of 2.8 +/- 0.1 is therefore reported here for the pK(a) of nitrous acid. A Newton-Gauss method was then employed to solve a set of nonlinear equations defining the chemical speciation model for HONO in solution using an algorithm written in FORTRAN 90. A model based on a simple one-step protonation worked well for intermediate pHs (6-3) but departed from the experimental observations in highly acidic media. A two-step equilibrium model involving the nitroacidium ion, H(2)ONO(+), gave a much closer fit in the very acidic region, while having little or no effect on the pH 6-3 section of the profile.
The known room-temperature, solution-phase reaction between nitrite ions and iodide ions, which occurs in acidic conditions (pH < 5.5), is shown to be accelerated when neutral aqueous solutions are frozen. The reaction is proposed to occur in liquid "micropockets" within the ice structure at temperatures between the freezing point and the eutectic temperature. The products, nitric oxide and molecular iodine, are known to play significant roles in atmospheric compositional change, and therefore, the results obtained here, which are not dependent on acidification, may impact on observed snowpack chemistry. Investigation of the effect of oxygen on the chemical processing indicates that a chain reaction mechanism is operative.
The effect of freezing on a variety of acidified and neutral, nitrite ion and halide-containing mixtures has been investigated using UV/vis spectroscopy. Several trihalide ions were formed and monitored, including I(2)Cl(-), I(2)Br(-), ICl(2)(-) and IBr(2)(-). A mechanism to explain the observations is given in terms of steps involving INO and the nitroacidium ion, [H(2)ONO](+). The transformation of sea salt components to specific trihalide ions by freezing represents a potentially important process in a polar atmospheric context. This is because the dichloro- and dibromo-trihalide ions can release chlorine- and bromine-containing gases, which are key intermediates in ozone destruction.
• Introduction: The requirement for pre-hospital practitioners to perform additional interventions is ever increasing. In Ireland the training of prehospital practitioners is currently developing and evolving to meet this demand. This requires the use of simulators with the capability to simulate more advanced interventions. • Objectives: We wished to explore the views of pre-hospital care practitioners post participation in a pilot high fidelity simulation in emergency care, to gauge its acceptability, relevance and application. • Method: Pre-hospital care practitioners' participated in 12 full immersion high-fidelity simulated scenarios, over three consecutive days. Live video recording was during the scenarios and replayed during debriefing sessions. The participants completed a voluntary and anonymous evaluation of the training using six statements on a five point Likert scale and free text written comments to three open-ended questions. • Results: The overall response to the training was overwhelming positive with 94.4 % of the participants either strongly agreed or agreed that the course met their learning needs. All agreed that they found the course relevant to their stage of training and that the course will impact beneficially on their clinical practice. • Conclusion: This pilot study has shown that high-fidelity simulation is both applicable and relevant to pre-hospital practitioner.
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