Ari Auvinen

Industrial worker exposure to airborne particles during the packing of pigment and nanoscale titanium dioxide

Context: Titanium dioxide (TiO2) factory workers’ source specific exposure and dose to airborne particles was studied extensively for particles between 5 nm and 10 μm in size. Objective: We defined TiO2 industry workers’ quantitative inhalation exposure levels during the packing of pigment TiO2 (pTiO2) and nanoscale TiO2 (nTiO2) material from concentrations measured at work area. Methods: Particle emissions from different work events were identified by linking work activity with the measured number size distributions and mass concentrations of particles. A lung deposit model was used to calculate regional inhalation dose rates in units of particles min−1 and μg min−1 without use of respirators. Results: Workers’ average exposure varied from 225 to 700 μg m−3 and from 1.15 × 104 to 20.1 × 104 cm−4. Over 90% of the particles were smaller than 100 nm. These were mainly soot and particles formed from process chemicals. Mass concentration originated primarily from the packing of pTiO2 and nTiO2 agglomerates. The nTiO2 exposure resulted in a calculated dose rate of 3.6 × 106 min−1 and 32 μg min−1 where 70% of the particles and 85% of the mass was deposited in head airways. Conclusions: The recommended TiO2 exposure limits in mass by NIOSH and in particle number by IFA were not exceeded. We recommend source-specific exposure assessment in order to evaluate the workers’ risks. In nTiO2 packing, mass concentration best describes the workers’ exposure to nTiO2 agglomerates. Minute dose rates enable the simulation of workers’ risks in different exposure scenarios.

A size selective nanoparticle collection device based on diffusion and thermophoresis

There is a growing industry fabricating products that are based on nanoparticles (particle diameter dp≤100 nm). The production of these particles requires detection, classification and characterisation of even smaller particles because of, e.g. preventing unwanted particle emissions from the processes and health issues. Monitoring of the processes is needed on one hand for product quality determinations, on the other hand to ensure safe and particle-free working conditions. Thus simple, fast and reliable measurement devices are needed for particle characterisation.

The Effect of Boundary Conditions on Gas-phase Synthesised Silver Nanoparticles

We have prepared spherical non-agglomerated silver nanoparticles by an evaporation–condensation–dilution/cooling technique. Silver was evaporated from a crucible in a tubular flow reactor. A porous tube diluter was used to quench the carrier gas at the outlet of the reactor to enhance the formation of small particles and to suppress agglomeration and other particle growth mechanisms. The number size distribution of the prepared particles was measured with a differential mobility analyser–condensation nucleus counter combination and the size and the shape of the particles were analysed with transmission electron microscope. The system was modelled using a sectional aerosol dynamics computer code to estimate the importance of different aerosol processes. In all conditions the particles obtained were non-agglomerated and spherical. The mean particle diameter varied from 4 to 10-nm depending on boundary conditions. From the modelling studies it can be concluded that the nucleation rate is the most important parameter controlling the final particle size.

On the transport and speciation of ruthenium in high temperature oxidising conditions

Summary In this paper, the transport and speciation of ruthenium under conditions simulating an air ingress accident was studied. Ruthenium dioxide was exposed to an oxidising environment at high temperatures (>1200 °C) in a tubular flow furnace. At these conditions, volatile ruthenium species were formed. A major part of the released ruthenium was deposited in the tube as RuO2. Depending on the experimental conditions, 12–35 wt. % of the released ruthenium was trapped in the outlet filter as RuO2 particles. At completely dry conditions using stainless steel tubes, only 0.1–0.2 wt. % of the released ruthenium reached the trapping bottle as gaseous RuO4. However, when alumina was applied as tube material or the atmosphere contained some water vapour and silver seed particles, the fraction of gaseous ruthenium reaching the trapping bottle increased to 5 wt. % which is close to thermodynamic equilibrium. This indicates that RuO2 does not catalyse the decomposition of RuO4.

Exposure to CeO2 nanoparticles during flame spray process

Abstract The use of nanotechnology in different fields is increasing rapidly. Engineered nanoparticles (ENPs) may have adverse effect on human health, but little is known about the exposure levels of ENPs at occupational settings. In this study, exposure levels of cerium oxide (CeO2) ENPs were measured during enclosed flame spray process used for coating and surface modification of materials. Particle number concentration, mass concentration, and morphology and composition of the ENPs were studied. The average particle number concentration varied from 4.7·103 to 2.1·105 1/cm3 inside the enclosure, and from 4.6·103 to 1.4·104 1/cm3 outside the enclosure. The average mass concentrations inside and outside the enclosure were 320 and 66 μg/m3, respectively. A batch-type process caused significant variation in the concentrations, especially inside the enclosure. CeO2 ENPs were mainly chainlike aggregates, consisting of spherical 20–40 nm primary particles having crystalline structure. In conclusion, enclosure of the process with efficient ventilation seemed to be an effective means to reduce the exposure to CeO2 ENPs as expected.

VAPORISATION RATES OF CsOH AND CsI IN CONDITIONS SIMULATING A SEVERE NUCLEAR ACCIDENT

Abstract The vaporisation rates of volatile fission product compounds are critical parameters for modelling aerosol formation following a severe nuclear accident. The vaporisation of CsOH and CsI was studied in a pure steam atmosphere at ambient pressure (85– 89 kPa ) by increasing the temperature of the flow furnace up to 1000°C. For this purpose, samples were doped with a small amount of radioactive tracer. The vaporisation rate was then determined from the decrease in sample activity with time, using a germanium gamma detector placed outside the furnace. Calculated vaporisation rates obtained by solving complete velocity, temperature and vapour concentration profiles surrounding the sample with FLUENT CFD-software, were in reasonable agreement with the data. A simple engineering calculation agrees almost perfectly with the FLUENT results, if a constant value, Sh≈8, for the Sherwood number is used.

Production and characterization of plutonium dioxide particles as a quality control material for safeguards purposes.

Plutonium (Pu) dioxide particles were produced from certified reference material (CRM) 136 solution (CRM 136-plutonium isotopic standard, New Brunswick Laboratory, Argonne, IL, U.S.A., 1987) using an atomizer system on December 3, 2009 after chemical separation of americium (Am) on October 27, 2009. The highest density of the size distribution of the particles obtained from 312 particles on a selected impactor stage was in the range of 0.7-0.8 μm. The flattening degree of 312 particles was also estimated. The isotopic composition of Pu and uranium (U) and the amount of Am were estimated by thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICPMS), and α-spectrometry. Within uncertainties the isotopic composition of the produced particles is in agreement with the expected values, which were derived from the decay correction of the Pu isotopes in the CRM 136. The elemental ratio of Am to Pu in the produced particles was determined on the 317th and 674th day after Am separation, and the residual amount of Am in the solution was estimated. The analytical results of single particles by micro-Raman-scanning electron microscopy (SEM)-energy-dispersive X-ray spectrometry (EDX) indicate that the produced particles are Pu dioxide. Our initial attempts to measure the density of two single particles gave results with a spread value accompanied by a large uncertainty.

Development of a highly controlled gas-phase nanoparticle generator for inhalation exposure studies.

We have developed a gas-phase nanoparticle generator that produces stable and well-defined size distributions for TiO2. The online analyses of the gas-phase compounds and total number concentration of the generated particles as well as the off-line analysis of the filter samples confirmed the stability of the production. The major advantage of this reactor is that the test substance is directly in the aerosol phase, and thus no preprocessing is needed. This eliminates the physicochemical changes between bulk and administrated material during storing or processing. This system is easy to adjust to different experimental setups and precursors. As a result, well-characterized nanomaterials for inhalation exposure studies can be produced. At mass concentration of 30 mg/Nm3, the count mean diameter was 126 nm (geometric SD 1.6), mass mean diameter was 161 nm (2.0), mass median aerodynamic diameter was 125 nm, and the concentrations of harmful gas-phase by-products remained low. The produced powder consisted of crystals of anatase (77 vol%) and brookite (23 vol%), and its specific surface area was 69 m2/g.

Chlorine release from hypalon cable insulation during severe nuclear reactor accidents

Pyrolytic dehydrochlorination of the electrical cable insulation Hypalon was studied as a function of time and temperature. The chlorine evolution was determined separately by means of on-line activity measurements and by neutron activation analysis in the temperature range 200°C to 300°C, with one test conducted at 500°C. The object of the research was to determine the chlorine release and the chlorine release fraction as a function of temperature. The data obtained were needed to formulate conclusions regarding the release mechanisms of chlorine. Estimates of the amount of hydrochloric acid released to the containment building in a severe reactor accident were also calculated. It can be concluded that the amount of chlorine release from the Hypalon cable is significant and will have an effect on iodine behavior in a severe accident.

Radiolytical oxidation of gaseous iodine by beta radiation

Abstract Iodine is one of the most radiotoxic fission product released from fuel during a severe nuclear power plant accident. Within the containment building, iodine compounds can react e.g. on the painted surfaces and form gaseous organic iodides. In this study, it was found out that gaseous methyl iodide (CH3I) is oxidised when exposed to beta radiation in an oxygen containing atmosphere. As a result, nucleation of aerosol particles takes place and the formation of iodine oxide particles is suggested. These particles are highly hygroscopic. They take up water from the air humidity and iodine oxides dissolve within the droplets. In order to mitigate the possible source term, it is of interest to understand the effect of beta radiation on the speciation of iodine.