Risk assessment in occupational exposure to formaldehyde: differences between anatomy and pathology laboratories and formaldehyde-resins production

Formaldehyde (CH2O), the most simple and reactive of all aldehydes, is colorless, and readily polymerizing gas at normal temperature. The most extensive use is in production of resins and has an important application as a disinfectant and preservative, reason why relevant workplace exposure may also occur in pathology and anatomy laboratories and in mortuaries. A study was carried out in Portugal, in a formaldehyde production resins factory and in 10 pathology and anatomy laboratories. It was applied a risk assessment methodology based on Queensland University proposal that permitted to perform risk assessment for each activity developed in a work station. This methodology was applied in 83 different activities developed in the laboratories and in 18 activities of the factory. Also, Micronucleus Test was performed in lymphocytes from 30 factory workers and 50 laboratories workers.

Genotoxic effects in occupational exposure to formaldehyde: A study in anatomy and pathology laboratories and formaldehyde-resins production

Background - According to the Report on Carcinogens, formaldehyde ranks 25th in the overall U.S. chemical production, with more than 5 million tons produced each year. Given its economic importance and widespread use, many people are exposed to formaldehyde environmentally and/or occupationally. Presently, the International Agency for Research on Cancer classifies formaldehyde as carcinogenic to humans (Group 1), based on sufficient evidence in humans and in experimental animals. Manyfold in vitro studies clearly indicated that formaldehyde can induce genotoxic effects in proliferating cultured mammalian cells. Furthermore, some in vivo studies have found changes in epithelial cells and in peripheral blood lymphocytes related to formaldehyde exposure. Methods - A study was carried out in Portugal, using 80 workers occupationally exposed to formaldehyde vapours: 30 workers from formaldehyde and formaldehyde-based resins production factory and 50 from 10 pathology and anatomy laboratories. A control group of 85 non-exposed subjects was considered. Exposure assessment was performed by applying simultaneously two techniques of air monitoring: NIOSH Method 2541 and Photo Ionization Detection equipment with simultaneously video recording. Evaluation of genotoxic effects was performed by application of micronucleus test in exfoliated epithelial cells from buccal mucosa and peripheral blood lymphocytes. Results - Time-weighted average concentrations not exceeded the reference value (0.75 ppm) in the two occupational settings studied. Ceiling concentrations, on the other hand, were higher than reference value (0.3 ppm) in both. The frequency of micronucleus in peripheral blood lymphocytes and in epithelial cells was significantly higher in both exposed groups than in the control group (p < 0.001). Moreover, the frequency of micronucleus in peripheral blood lymphocytes was significantly higher in the laboratories group than in the factory workers (p < 0.05). A moderate positive correlation was found between duration of occupational exposure to formaldehyde (years of exposure) and micronucleus frequency in peripheral blood lymphocytes (r = 0.401; p < 0.001) and in epithelial cells (r = 0.209; p < 0.01). Conclusions - The population studied is exposed to high peak concentrations of formaldehyde with a long-term exposure. These two aspects, cumulatively, can be the cause of the observed genotoxic endpoint effects. The association of these cytogenetic effects with formaldehyde exposure gives important information to risk assessment process and may also be used to assess health risks for exposed workers.

Painéis fenólicos para aplicação em fachadas exteriores

Dissertação para obtenção do grau de Mestre em Engenharia Civil

Genotoxicity biomarkers in occupational to formaldehyde in pathology anatomy laboratories

Formaldehyde (FA) the most simple and reactive of all aldehydes, is a colorless, reactive and readily polymerizing gas at normal temperature. It has a pungent, suffocating odour that is recognized by most human subjects at concentrations below 1ppm. According to the Report on Carcinogens, FA ranks 25th in the overall U.S. chemical production with more than 11 billion pounds (5 million tons) produced each year. Is an important industrial compound that is used in the manufacture of synthetic resins and chemical compounds such as lubricants and adhesives. It has also applications as a disinfectant, preservative and is used in cosmetics. Estimates of the number of persons who are occupationally exposed to FA indicate that, at least at low levels, may occur in a wide variety of industries. The occupational settings with most extensive use of formaldehyde is in the production of resins and in anatomy and pathology laboratories. Several studies reported a carcinogenic effect in humans after inhalation of FA, in particular an increased risk for nasopharyngeal cancer. Nowadays, the International Agency for Research on Cancer (IARC) classifies FA as carcinogenic to humans (group 1), on the basis of sufficient evidence in humans and sufficient evidence in experimental animals. Manifold in vitro studies clearly indicated that FA is genotoxic. FA induced various genotoxic effects in proliferatin cultured mammalian cells. A variety of evidence suggests that the primary DNA alterations after FA exposure are DNA-protein crosslinks. Incomplete repair of DPX can lead to the formation of mutations.

n-Hexane hydroisomerisation over bifunctional Pt/MCM-22 catalysts. Influence of the mode of Pt introduction

Three different methods were used to introduce 1.0 wt.% of Pt in bifunctional Pt/MCM-22 zeolite catalysts: ion exchange with Pt(NH3)(4)(2+), incipient wetness impregnation with PtCl6H2 and mechanical mixture with Pt/Al2O3. The Pt dispersion was estimated by transmission electron microscopy and the hydrogenating activity with toluene hydrogenation at 110 degrees C. From these experiments, it can be concluded that with the ion exchanged sample, platinum was located within the inner micropores and on the outer surface, whereas with the impregnated one, platinum was essentially on the outer surface under the form of large particles. With all the samples there is a fast initial decrease in the activity for n-hexane hydroisomerisation at 250 degrees C. With exchanged and impregnated samples, this decrease is followed by a plateau, the activity value being then higher with impregnated sample. For the sample prepared by mechanical mixture a continuous decrease in activity can be observed. All these differences can be related with the distinct locations of Pt.

Development of a penetration test for timber impregnation products for use in old buildings

This paper studies the application of commercial biocides to old maritime pine timber structures (Pinus pinaster Ait.) that have previously been impregnated with other products. A method was developed in the laboratory to be used in situ to determine the impregnation depth achieved by a new generation biocide product applied to timber from an old building. This timber had once been treated with an unknown product difficult to characterize without extensive analysis. The test was initially developed in laboratory conditions and later tested on elements of the roof structure of an 18th century building. In both cases the results were promising and mutually consistent with penetration depths for some treatments reaching 2.0 cm. The application in situ proved the tests viability and simplicity of execution giving a clear indication on the feasibility of possible re-treatments.

Occupational exposure to formaldehyde: effects of years of exposure in the frequency of micronucleus

Formaldehyde: an important industrial compound used in the manufacture of synthetic resins and chemical compounds such as lubricants and adhesives; also applied as a disinfectant, preservative and in cosmetics productions; relevant workplace exposure to FA also occurs in anatomy, pathology and in mortuaries; classified by IARC as carcinogenic to humans (Group 1), based on sufficient evidence in humans and experimental animals; manifold in vitro studies indicated that FA can induce genotoxic effects in proliferating cultured mammalian cells. Aim of the study: to evaluate if years of exposure induced a genotoxic biomarkers increase, namely MN in lymphocytes and buccal cells, in workers occupationally exposed to FA (factory and pathology anatomy laboratory).

Micronuclei in peripheral blood lymphocytes in formaldehyde occupationally exposed workers

Formaldehyde (CH2O) the most simple and reactive of all aldehydes, is a colorless, reactive and readily polymerizing gas at normal temperature. It has a pungent, suffocating odour that is recognized by most human subjects at concentrations below 1 ppm. According to the Report on Carcinogens, formaldehyde (FA) ranks 25th in the overall U.S. chemical production with more than 11 billion pounds (5 million tons) produced each year. Is an important industrial compound that is used in the manufacture of synthetic resins and chemical compounds such as lubricants and adhesives. It has also applications as a disinfectant, preservative and is used in cosmetics. Estimates of the number of persons who are occupationally exposed to FA indicate that, at least at low levels, may occur in a wide variety of industries. The occupational settings with most extensive use of formaldehyde is in the production of resins and in anatomy and pathology laboratories. Several studies reported a carcinogenic effect in humans after inhalation of FA, in particular an increased risk for nasopharyngeal cancer. Nowadays, the International Agency for Research on Cancer (IARC) classifies FA as carcinogenic to humans (group 1), on the basis of sufficient evidence in humans and sufficient evidence in experimental animals. Manifold in vitro studies clearly indicated that FA is genotoxic. FA induced various genotoxic effects in proliferatin cultured mammalian cells. A variety of evidence suggests that the primary DNA alterations after FA exposure are DNA-protein crosslinks (DPX). Incomplete repair of DPX can lead to the formation of mutations.

Development of an in situ penetration test for the uptake of preservatives in applied wood

This paper concerns the study of biocides application in old timber structures of maritime pine (Pinus pinaster Ail.), previously impregnated with other products. A method was developed in laboratory to determine in situ the penetration depth of a product applied superficially. As initial treatment, three traditional products for sawn timber for buildings were used and, for new treatments, two newer, more environmentally benign products were used. Their ability to penetrate the pre-treated surfaces was evaluated after 1, 2 and 3 applications at 24 hours intervals and the results obtained are presented. Finally, the applicability of the developed test to the in-situ evaluation of timber structures is also discussed.

Catalytic combustion of toluene on Pt zeolite coated cordierite foams

The catalytic properties of Pt based cordierite foam catalysts have been evaluated in catalytic combustion of toluene (800 ppm in air). The catalysts contain identical Pt content (0.1%) which was introduced by three different ways: Pt ion exchange on MFI zeolite and then coating on the foam; Pt ion exchange after zeolite coating and finally Pt directly wet impregnated on the cordierite foam. The catalytic behaviour of Pt foam based catalysts was compared with that of PtMFI zeolite under powder form. Pt exchanged MFI supported on the cordierite foams present an improvement of activity for toluene combustion of about 50 degrees C on the light off temperature (T-50%). The enhanced performance of the structured catalysts is due not only to the open structure of foams and homogeneous thin layers catalyst deposited on their cell walls, but also to the fact that the size and location of Pt particles present in MFI zeolite are changed during the dipping step. Indeed, as prepared Pt samples and those used in the preparation of the slurry were observed by transmission electron microscopy revealing that the chemical interaction of PtMFI zeolite with the binder and detergent, both present in the slurry, leads to an increase of Pt particles size which were found to migrate from internal pores to the external surface of zeolite crystallites thereby increasing catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

Study of Pt/MCM-22 based catalysts in the transformation of n-hexane: effect of rare earth elements and mode of platinum introduction

The bifunctional transformation of n-hexane was carried out over Pt/MCM-22 based catalysts. MCM-22 was synthesized and submitted to ion exchange with rare earth nitrate solutions of La, Nd and Yb, followed by Pt introduction. Three different methods were used to introduce about 1 wt% of Pt in the zeolite: ion exchange, incipient wetness impregnation and mechanical mixture with Pt/Al(2)O(3). The bifunctional catalysts were characterized by transmission electron microscopy and by the model reaction of toluene hydrogenation. These experiments showed that, in the ion exchanged sample, Pt is located both within the inner micropores and on the outer surface, whereas in the impregnated one, the metal is essentially located on the outer surface under the form of large particles. The presence of RE elements increases the hydrogenating activity of Pt/MCM-22 since the location of these species at the vicinity of metal particles causes modification on its electronic properties. Whatever the mode of Pt introduction, a fast initial decrease in conversion is observed for n-hexane transformation, followed by a plateau related to the occurrence of the catalytic transformations at the hemicages located at the outer surface of the crystals. The effect of rare earth elements on the hydrogenating function leads to a lower selectivity in dibranched isomers and increased amounts of light products.

Exposure and genotoxicity assessment methodologies: the case of formaldehyde occupational exposure

Formaldehyde (FA) ranks 25th in the overall U.S. chemical production, with more than 5 million tons produced each year. Given its economic importance and widespread use, many people are exposed to FA occupationally. Recently, based on the correlation with nasopharyngeal cancer in humans, the International Agency for Research on Cancer (IARC) confirmed the classification of FA as a Group I substance. Considering the epidemiological evidence of a potential association with leukemia, the IARC has concluded that FA can cause this lymphoproliferative disorder. Our group has developed a method to assess the exposure and genotoxicity effects of FA in two different occupational settings, namely FAbased resins production and pathology and anatomy laboratories. For exposure assessment we applied simultaneously two different techniques of air monitoring: NIOSH Method 2541 and Photo Ionization Detection Equipment with simultaneously video recording. Genotoxicity effects were measured by cytokinesis-blocked micronucleus assay in peripheral blood lymphocytes and by micronucleus test in exfoliated oral cavity epithelial cells, both considered target cells. The two exposure assessment techniques show that in the two occupational settings peak exposures are still occurring. There was a statistical significant increase in the micronucleus mean of epithelial cells and peripheral lymphocytes of exposed individuals compared with controls. In conclusion, the exposure and genotoxicity effects assessment methodologies developed by us allowed to determine that these two occupational settings promote exposure to high peak FA concentrations and an increase in the micronucleus mean of exposed workers. Moreover, the developed techniques showed promising results and could be used to confirm and extend the results obtained by the analytical techniques currently available.

Teor crítico de cloretos para iniciação da corrosão do aço no betão: influência do estado de superfície da armadura

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica - Processos Químicos

Biodiesel production over lithium modified lime catalysts: activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca = 03 atomic ratio). The catalysts were calcined at 575 degrees C and 800 degrees C, for 5 h, to remove nitrate ions before reaction. The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)(2). The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO. In the tested condition (W-cat/W-oil = 5%; CH3OH/oil = 12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4 h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability. (C) 2013 Elsevier B.V. All rights reserved.

Catálise de hydrocraking baseado em zeólitos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química