Accidental releases of titanium tetrachloride (TiCl4) in the context of major hazards--spill behaviour using REACTPOOL.

Titanium tetrachloride is a highly toxic and corrosive substance that is used widely in the process industries. On accidental release, it creates liquid pools that can either boil or evaporate. The main feature of the liquid pool is the reaction of titanium tetrachloride with water. There are three sources of water available for reaction: free ground water, atmospheric moisture and substrate water. Unfortunately, there is no specific study that examines the liquid phase hydrolysis reaction of titanium tetrachloride. Based on thermodynamic calculations and relevant information found on the topic, it is concluded that liquid titanium tetrachloride reacts exothermically with all three sources of water yielding hydrogen chloride gas and a solid complex of titanium oxychloride. The purpose of this paper is to describe the spill behaviour of titanium tetrachloride reporting a number of results using the REACTPOOL model [T. Kapias, R.F. Griffiths, C. Stefanidis, REACTPOOL: a code implementing a new multi-compound pool model that accounts for chemical reactions and changing composition for spills of water reactive chemicals, J. Hazard. Mater. A81 (2001) 1-18]. It also addresses the dangers involved in cases of accidental release of titanium tetrachloride and reports its properties, referring to toxicity data and other relevant information. The spill behaviour of titanium tetrachloride has been incorporated into REACTPOOL. Model results indicate that the pool behaviour is mainly affected by the amount of free ground water, the wind speed and surface roughness. Although titanium tetrachloride has been involved in a number of major accidents, there are no experimental data relevant to the modelling requirements.

MRI studies of the evaporation of a single liquid droplet from porous surfaces.

A combination of in situ one-dimensional profiling and two-dimensional 1H magnetic resonance imaging has been applied to study the shape and subsequent dynamic evaporation behavior of a single liquid droplet after impact onto a porous surface in a carefully controlled atmosphere. Aspects of the porous media permeability and particle shape are shown to affect considerably the observed drying regime. Variation in the shape, spread ratio, and penetration depth of the liquid droplet following impact are attributed to the different types of porous media used. A comparison of numerical simulations with the MRI data for the droplet shape, spread factor, and penetration depth show good agreement though larger deviations between simulated and experimental results occur in certain cases where the surface of the porous medium is disrupted by the impact of the liquid droplet. Initial results examining the effect of a reduced liquid surface tension show a significantly increased evaporation rate.

Spill behaviour using REACTPOOL. Part II. Results for accidental releases of silicon tetrachloride (SiCl(4)).

Silicon tetrachloride is a toxic, corrosive water reactive substance that is used widely in the process industries. On spillage from containment it creates liquid pools that can either boil or evaporate. The main feature of the pool behaviour is the exothermic reaction with water. There are three sources of water available for reaction: free ground water, substrate water and atmospheric moisture. Hydrogen chloride gas and ortho-silicic acid solid (or silica gel) are produced by the hydrolysis reaction. The purpose of this paper is to describe the dangers involved in cases of accidental releases of silicon tetrachloride, to report its properties, referring to toxicity data, major accidents and mitigation tests. It also describes pool behaviour using REACTPOOL [1]. Model results indicate that the pool behaviour is governed mainly by the amount of water available for reaction. Surface roughness and wind speed also have a significant effect on the results. Results are compared with those for other water reactive chemicals in Part III of this series of papers [3]. The generated cloud will initially contain silicon tetrachloride and hydrogen chloride with numerous processes taking place. Although silicon tetrachloride has been involved in many major hazard incidents, there are no experimental data relevant to the modelling requirements.

Spill behaviour using REACTPOOL. Part III. Results for accidental releases of phosphorus trichloride (PCl(3)) and oxychloride (POCl(3)) and general discussion.

Phosphorus trichloride and oxychloride are aggressive materials, widely used in the process industries. On escape to the atmosphere they create toxic clouds that may cause serious damage to people and to the environment. When spilled onto the ground they create liquid pools that can boil, evaporate or even solidify. The main feature of the pool behaviour is the exothermic reaction of these chemicals with water, which is complicated and depends heavily on the amount of water available for reaction, and as result of which the pool has changing composition and properties. The purpose of this paper is to describe the dangers involved in cases of accidental releases of phosphorus trichloride and oxychloride, to report their properties, referring to toxicity data and major accidents. The spill behaviour of phosphorus trichloride and oxychloride has been incorporated into REACTPOOL [R.F. Kapias, C. Griffiths, J. Haz. Mater.]. Model results indicate that the pool behaviour is strongly affected by the amount of water available for reaction. Surface roughness and wind speed, also have a strong effect on the results. Although there are no experimental data for model validation, it is shown that REACTPOOL gives useful insights into the behaviour of such spills. The paper concludes with a discussion comparing the behaviour for several water reactive chemicals to which REACTPOOL has been applied.

Spill behaviour using REACTPOOL. Part I. Results for accidental releases of chlorosulphonic acid (HSO(3)Cl).

Chlorosulphonic acid is a toxic, highly reactive and corrosive substance that exists in its liquid form at ambient conditions. Its major hazardous potential comes from the clouds of hydrogen chloride and sulphuric acid mist produced whenever this chemical escapes from containment and is exposed to moisture. It decomposes violently and sometimes explosively in the presence of water, liberating heat. On spillage it creates liquid pools that can either boil or evaporate. There are three sources of water available for reaction: free ground water, substrate water and atmospheric moisture. Hydrogen chloride gas or aqueous solution and sulphuric acid liquid are produced by the hydrolysis reaction. This paper describes the dangers involved in cases of accidental releases of chlorosulphonic acid, referring to its properties, toxicity data and mitigation tests. It also reports results of pool behaviour using REACTPOOL [T. Kapias, R.F. Griffiths, C. Stefanidis, J. Haz. Mat., submitted for publication]. These results indicate that the pool behaviour is governed mainly by the amount of water available for reaction. Surface roughness and wind speed also have a significant effect on the results. A discussion of the results in comparison with those for other water reactive substances is presented in Part III of this series of papers [T. Kapias, R.F. Griffiths, J. Haz. Mat., submitted for publication]. The generated cloud will initially contain chlorosulphonic acid, hydrogen chloride and sulphuric acid with numerous processes taking place. Initially, it is usually denser than air. Although chlorosulphonic acid has been involved in major hazard incidents, there are no experimental data relevant to the modelling requirements. Use of REACTPOOL provides insights into the major hazard role of this substance.

REACTPOOL: a code implementing a new multi-compound pool model that accounts for chemical reactions and changing composition for spills of water reactive chemicals.

All chemicals that react violently with water or in contact with water liberate toxic gas are included in the list of substances covered by the majority of the international legislation on major hazards. This category includes a large number of chemicals that are used widely in the process industries. A survey of accidents that occurred in the last 10 years in the USA shows numerous major incidents that involved spillages of these substances. Even so, there are almost no experimental data on the behaviour of these chemicals on release. Furthermore, there are very few published studies on modelling the behaviour of such spillages, except in the case of hydrogen fluoride. In previous work we reported a new theoretical model [J. Haz. Mat. 62 (1998) 101-129, J. Haz. Mat. 62 (1998) 131-142, J. Haz. Mat. A67 (1999) 9-40], that describes accidental spills of SO(3) and oleum, which are substances with very complex behaviour that belong to this category. It describes both the pool [J. Haz. Mat. 62 (1998) 101-129, J. Haz. Mat. 62 (1998) 131-142] and the cloud behaviour [J. Haz. Mat. A67 (1999) 9-40]. In the work reported here the pool model was modified in a generic form in order to include other water reactive chemicals. REACTPOOL is a new code that can be used for both instantaneous and continuous liquid releases under a wide range of input parameters (steady or varying). It can be used for all liquids irrespective of their volatility and reactivity, and it describes pools consisting of more than one liquid that can have changing composition and properties. The purpose of this paper is to present the general procedure followed in REACTPOOL and to show how the new model has been modified and implemented for substances other than SO(3) and oleum. The modelling procedure has been implemented in a computer code written in Visual Basic, and results of the model have been generated using this code. It should be noted that this model requires validation data, but that the availability of such data awaits the performance of suitable experimental investigations.

Dispersion and thermodynamics of clouds generated from spills of SO3 and oleum.

A new model describing the dispersion behaviour and the processes that occur in a cloud generated from accidental spills of SO3 and oleum has been developed. Such a cloud may initially behave as a dense gas, with several chemical and physical processes occurring in it. There is not usually enough atmospheric moisture in the air passing immediately above the pool for complete and rapid reaction to sulphuric acid mist. Therefore in the early stages, SO3 vapour, H2SO4 vapour and H2SO4 aerosol will be present. At some distance downwind, transition to passive dispersion behaviour will take place and only sulphuric acid aerosol will be present in the cloud. The dense gas model is based on a box type dispersion model. The passive behaviour is described by a Gaussian model that takes into account deposition of the aerosol particles. The model results suggest a number of lines of experimental investigation that are required to provide data for model validation.

Epidemiology of hypothermia: fatalities and hospitalisations in New Zealand.

BACKGROUND: Hypothermia occurs within domestic and non-residential settings. Most epidemiological data originate from the northern hemisphere, with little data being generally available concerning cases from New Zealand and Australia. AIMS: The National Health Statistics Centre (New Zealand) records hospital discharges and deaths. This study isolated hypothermia cases, to quantify its incidence and identify risk groups. METHODS: The morbidity and mortality files for the years 1979-86 (cases = 3,808,717) and 1977-86 (cases = 259,325; respectively) were searched by three investigators. RESULTS: Hypothermia hospitalisations were identified (6.9 per 100,000 per year). There were 176 deaths from hypothermia, representing 0.07% of the 259,325 deaths from all causes for the same period (0.537 per 100,000 people per year); of these fatalities, 72.2% were classified as domestic, and 27.8% as non-residential; of the domestic fatalities, 86.6% were 65 + years and 35.5% of these were male. Within the non-residential category, 75.5% were aged 13-65, of which 94.6% were male. The hospitalisation incidence was 12.7 times the fatality incidence, with the majority of hospitalisations being of domestic origin (88.4% of total), and occurring mostly within the lower and upper age extremes. Neonatal domestic hypothermia accounted for 72.6% of all domestic hospitalisations, and the elderly constituted 72.0% of the remaining cases. The proportion of New Zealand fatalities caused by hypothermia was 0.067%; lower than reported in the United Kingdom. CONCLUSIONS: The two main non-neonatal groups contributing to cases of hypothermia were males aged 13-65 years, and the elderly. In the aged, the proportion of hypothermia-related deaths was no different from that associated with other disorders, however, the case-fatality ratio was three times greater, highlighting the need for improving prevention and management strategies.

Racial differences in platelet cytosolic calcium and calcitropic hormones in normotensive subjects.

Elevated levels of serum parathyroid hormone (PTH) and platelet cytosolic free calcium ([Ca2+]i) have been reported in subjects with essential hypertension. In addition, there is a positive correlation between serum PTH and platelet [Ca2+]i in white subjects with essential hypertension. Black normotensive subjects have relatively higher levels of serum PTH when compared to white normotensive subjects. To investigate the possibility that elevated serum PTH levels in black normotensives may contribute to elevated platelet [Ca2+]i, calcitropic hormone profiles and platelet [Ca2+]i were determined in 31 black normotensive subjects and 34 age-matched white normotensive subjects. There was no difference between the two groups in total serum calcium, plasma ionized calcium, or creatinine clearance. However, serum PTH was significantly elevated (P < .02) in the black normotensive group. Serum 1,25(OH)2 vitamin D levels were similar between the two groups whereas serum 25(OH) vitamin D levels were significantly lower (P < .001) in the blacks. The 24 h urinary excretion of Ca was also lower (P < .05) in the black normotensive group. Basal platelet [Ca2+]i was significantly lower (P < .05) in black normotensive than in white normotensive subjects. Serum PTH levels did not correlate with platelet [Ca2+]i in either group, or in the groups combined. These results demonstrate that the higher serum PTH concentrations in black normotensives is not associated with higher platelet [Ca2+]i, as is the case in white hypertensive patients.

The acute effects of glucosidase inhibition on post-meal glucose increments in insulin-dependent diabetics.

The effects of glucosidase inhibition on postprandial glucose tolerance was studied in 11 insulin-dependent diabetics. In comparison with placebo, 50 mg miglitol was able to lower the incremental glucose response significantly at 30 minutes and 60 minutes when insulin was injected: (i) 30 minutes before the meal (2,3 +/- 0,5 mmol/l v. 0,37 +/- 0,2 mmol/l; P less than 0,001; and 5,0 +/- 0,7 mmol/l v. 1,1 +/- 0,8 mmol/l; P less than 0,001); and (ii) immediately before the meal (2,3 +/- 0,5 mmol/l v. 2,2 +/- 0,9 mmol/l; P less than 0,001) respectively. The incremental glucose area under the curve when insulin was injected 30 minutes before breakfast was also significantly reduced on miglitol in comparison with placebo (0,67 +/- 0,15 mmol/l v. 0,16 +/- 0,14 mmol/l; P less than 0,01). The effect of miglitol was more evident when insulin was injected 30 minutes before rather than immediately before the meal. No significant adverse effects were encountered. It is concluded that: (i) miglitol safely reduces the early post-meal glucose increments in insulin-dependent diabetics; and (ii) its effect enhances the hypoglycaemic response of an appropriately timed injection of insulin.