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- 4-Chloro-3-methylphenol – inhalable fraction. Documentation for occupational exposure limits (OEls)
Krystyna Sitarek
- Peracetic acid. Documentation for occupational exposure limits (OEls)
Daria Pakulska, Sławomir Czerczak
- 2-Ethylhexyl acrylate. Determining 2-ethylhexyl acrylate in workplace air with gas chromatography with flame ionization detection (GC-FID)
Agata Wziątek, Katarzyna Janoszka, Jan Gromiec
- Cyclopentane. Determining cyclopentane in workplace air with gas chromatography with mass detection (GC-MS)
Małgorzata Kucharska, Wiktor Wesołowski, Jan Gromiec
- 3,4-Dichloroaniline. Determining 3,4-dichloroaniline with chromatography
Anna Jeżewska
- Diphenylamine. Determining diphenylamine in workplace air with HPLC
Marzena Bonczarowska, Sławomir Brzeźnicki, Jan Gromiec
- Methoxyaniline. Determining in workplace air with HPLC
Marzena Bonczarowska, Sławomir Brzeźnicki, Jan Gromiec
- Molybdenum and its compounds. Method of determining molybdenum and its compounds in workplace air
Ewa Gawęda
- Selenium and its compounds. Method of determining selenium and its compounds in workplace air
Ewa Gawęda
- Skin protection measures for protecting human skin against water and aqueous solutions of detergents, acids and bases
Joanna Kurpiewska, Jolanta Liwkowicz
- The activity of the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment in 2011-2013
Jolanta Skowroń
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4-Chloro-3-methylphenol – inhalable fraction. Documentation for occupational exposure limits (OEls) Krystyna Sitarek
4-Chloro-3-methylphenol (PCMC) is white or pink crystals. It is used as a bactericide, in preservative adhesives, rubber, paint, ink, textiles and leather, cosmetics, pharmaceuticals (heparin and insulin). LD50 after oral administration in rats is 5129 mg/kg for males and 3636 mg/kg for females. PCMC strongly irritates the eyes of rabbits. Following getting into the eye, PCMC has a corrosive effect, causing conjunctivitis, conjunctival ulcers, inflammation of the iris and corneal opacity and ulceration. PCMC also causes skin irritation in humans and rabbits. PCMC is not sensitizing for guinea pigs in the Magnusson-Kligman test. Based on the results of a study in which for 24 months rats were administered PCMC in their feed at daily doses of 0, 21, 103.1 and 558.9 mg/kg (males) and 0, 27.7, 134.3 and 743.5 mg/kg (females), NOAEL was determined for males at 21 mg/kg/day and LOAEL of 103.1 mg/kg/day. The total incidence of unilateral and bilateral degeneration of the seminiferous tubules and the total rate of reduction in the number of sperm in the epididymis were considered.
PCMC administered per os in rats during organogenesis is not teratogenic. PCMC does not reverse mutation in S. typhimurium strains with and without metabolic fraction. There was no increase in the frequency of micronuclei in bone marrow. IARC experts put 4-chloro-3-methylphenol in group D, i.e., substances not classified for carcinogenicity to humans. In Poland and in most other European countries, the value of the maximum permissible concentration of 4-chlo-ro-3-methylphenol in workplace air is not set. In 2005, in Sweden, the standard values of PCMC were TWA 3 mg/m³ and STEL 6 mg/m³ and information that it is an allergen, in The Netherlands in 2003, TWA was 3 mg/m³.
Resulting from the 24-month study on rats, the NOAEL of 21 mg/kg/day was used to calculate the TWA. The Expert Group for Chemical Agents recommended a TWA value of 5 mg/m³ (inha-lable fraction) and notation “A”(a sensitizing agent) "I" (an irritating agent).
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Peracetic acid Documentation for occupational exposure limits (OEls) Ewa Gawęda
Peracetic acid (PAA) most often exists as a mixture, which is in chemical equilibrium with hydrogen peroxide, acetic acid and water. In trade, PAA is present in aqueous solutions, which are clear, colorless liquids with a pungent odor of vinegar. Peracetic acid is mainly used as a disinfectant, bleach or oxidant in preparative chemistry. It is a high production volume chemical. Under occupational conditions, there is a probability of exposure to aqueous solutions of PAA by inhalation as well as by dermal route during such operations as load-ing and unloading, and various industrial uses. Aerosols and vapors of aqueous solutions of PAA exhibit irritation to the respiratory tract and eyes. Workers in acute inhalation exposure may feel strong discomfort and watery eyes due to irritation. Laboratory animals also suffered irritation of eyes and respiratory tract with varying degrees of severity depending on the concentration. Under conditions of exposure to high concentrations followed by chronic inhalation, besides respiratory tract and eye irritation, inflammatory changes in the lungs, decreased weight gain, changes in blood counts and liver inflammation have been observed.
In Poland, a MAC (maximum admissible con-centration) value for PAA has not been estab-lished yet. All over the world, only the Ameri-can Conference of Governmental Industrial Hygienists (ACGIH) proposed a STEL value for peracetic acid at the level of 1.22 mg/m³. It was agreed that the critical health endpoints of aqueous solutions of PAA are the irritation of the eyes and the upper respiratory tract. In studies on rats (Janssen 1989c), RD50 was 8.4 mg/m³. As recommended by the ACGIH, the MAC value should be established within the range of 0.1 – 0.01 RD50. The Expert Group for Chemical Agents established that the MAC value for this compound should be 0.1 RD50, i.e. 0.8 mg/m³. Moreover, based on the molar ratios it was calculated that the proposed MAC value for peracetic acid corresponds to 0.4 mg/m³ of hydrogen peroxide, which is formed during decomposition of peracetic acid. It is the current MAC value for hydrogen peroxide in Poland. Therefore, the adopted MAC value of 0.8 mg/m³ should protect workers against both chemicals. The validity of this MAC value is also confirmed by the results of Fraser, Thorbinson (1986) and McDonagh (1997), which indicate that short-term exposure to PAA at a concentration of 1.56 mg/m³ should not cause unpleasant sensations or immediate irritation of eyes and respiratory tract, but for more sensitive people, prolonged exposure may be uncomfortable. Considering the irritat-ing/corrosive properties of aqueous solutions of peracetic acid, 1.6 mg/m³ has been pro-posed as the value of short-term exposure limit (STEL). Notation "C" (corrosive) has been proposed.
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2-Ethylhexyl acrylate. Determining 2-ethylhexyl acrylate in workplace air with gas chromatography with flame ionization detection (GC-FID) Agata Wziątek, Katarzyna Janoszka, Jan Gromiec
A new procedure has been developed for the assay of 2-ethylhexyl acrylate with gas chromatography. The method is based on: the adsorption of 2-ethylhexyl acrylate on activated charcoal and desorption with 5% acetic acid in carbon disulfide. The resulted solutions are analysed with gas chromatography with flame ionization detection. The working range of the analytical method is 30 ÷ 750 µg/ml (3 ÷ 75 mg/m³ for a 10-L air sample). Limit of quantification: 7.0 µg/ml.
The developed method of determining 2-ethylhexyl acrylate has been recorded as an analytical procedure (see Appendix).
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Cyclopentane. Determining cyclopentane in workplace air with gas chromatography with mass detection (GC-MS) Małgorzata Kucharska, Wiktor Wesołowski, Jan Gromiec
A new procedure has been developed for the assay of cyclopentane using gas chromatog-raphy with mass detection. The method is based on the adsorption of cyclopentane on activated charcoal and desorption with carbon disulfide. The resulted solutions are analysed with gas chromatography with mass detection. The working range of the analytical method is 150 ÷ 5000 µg/ml (300 ÷ 10000 mg/m3 for a 0.5- L air sample and 30 ÷ 1000 mg/m³ for a 5-L air sample). Limit of quantification: 131.2 µg/ml. The developed method of determining cyclopentane has been recorded as an analytical procedure (see Appendix).
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3,4-Dichloroaniline. Determining 3,4-dichloroaniline with chromatography Anna Jeżewska
A new procedure has been developed for the assay of 3,4-dichloroaniline (DCA) using high-performance liquid chromatography with diode array detector. This method is based on the adsorption of DCA on a silica gel, extrac-tion with methanol and chromatographic analysis of the obtained solution. The working range is 0.56 to 11.2 mg/m3 for a 30-L air sample. Limit of quantification (LOQ): 0.53 µg/m³. The developed method of determining 3,4-dichloroaniline has been recorded as an analytical procedure, which is available in the Appendix.
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Diphenylamine. Determining diphenylamine in workplace air with HPLC Marzena Bonczarowska, Sławomir Brzeźnicki, Jan Gromiec
A new procedure has been developed for the assay of diphenylamine with high-performance liquid chromatography with a FLD or UV-VIS detector. The method is based on the adsorption of diphenylamine on glass fibre filters treated with sulfuric acid. The trapped diphenylamine is then extracted with methanol and the resulted solutions are ana-lysed with high performance chromatography with ultraviolet or spectrofluorimetric detection. The working range of the analytical method is 0.4 ÷ 16 mg/m³ for a 100 L air sam-ple. Limit of quantification: 0.00026 µg/ml (FLD) and 0.02 µg/ml (UV-VIS). The developed method of determining diphenylamine has been recorded as an analytical procedure (see Appendix).
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Methoxyaniline. Determining in workplace air with HPLC Marzena Bonczarowska, Sławomir Brzeźnicki, Jan Gromiec
A new procedure has been developed for the assay of methoxyaniline (anisidine) isomers with high-performance liquid chromatography with a FLD or UV-VIS detector. The method is based on the adsorption of 2-methoxyaniline (2-MA) and 4-methoxyaniline on Amberlite XAD-2. Adsorbed compounds are eluted with aceto-nitrile and derivatized with 9-fluorenylmethyl chloroformate (FMOC CL). The resulted solutions are analysed with high performance chromatography with ultraviolet or spectro-fluorimetric detection. The working range of the analytical method is 0.025 - 1 mg/m³ for a 200-L air sample. Limit of quantification: 0.01 µg/ml (FLD. The developed method of determining methoxy-aniline (anisidine) isomers has been recorded as an analytical procedure (see Appendix).
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Molybdenum and its compounds. Method of determining molybdenum and its compounds in workplace air Ewa Gawęda
This method is used for determining molyb-denum and its compounds in workplace air. It is based on stopping molybdenum on a mem-brane filter, mineralizing the sample with concentrated nitric acid and sulphuric acid and preparing the solution for analysis in diluted nitric acid. Molybdenum in the solution is determined with atomic absorption spectrophotometry with a nitrogen peroxide-acetylene flame. The determination limit of the method is 0.4 mg/m³ (for a 600-L air sample). The developed method of determining molybdenum and its compounds has been recorded as an analytical procedure (see Appendix).
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Selenium and its compounds. Method of determining selenium and its compounds in workplace air Ewa Gawęda
This method is used for determining selenium and its compounds in workplace air. It is based on stopping selenium on a membrane filter, mineralizing the sample with concentrated nitric acid and preparing the solution for analysis in diluted nitric acid. Selenium in the solution is determined with atomic absorption spectrophotometry with an air-acetylene flame. The determination limit of the method is 0.01 mg/m³ (for a 720-L air sample). The developed method of determining selenium and its compounds has been recorded as an analytical procedure (see Appendix).
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Skin protection measures for protecting human skin against water and aqueous solutions of detergents, acids and bases Joanna Kurpiewska, Jolanta Liwkowicz
This article discusses the influence of water, water solutions of detergents on human skin and barrier preparations which protect against these irritating effects. Skin protection measures, hydrophobic barrier creams, are very helpful in preventing occupational der-matoses. This paper presents testing the effec-tiveness of six skin protecting products with technical methods developed at the Central Institute for Labour Protection – National Research Institute. Barrier properties of these products differ significantly so the developed methods help to select the best product. The developed methods of determining hydrophobic skin protection measures have been recorded as analytical procedures, which are available in the Appendix.
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The activity of the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment in 2011-2013 Jolanta Skowroń
In the second phase of the National Pro-gramme “Safety and working conditions im-provement”, 9 meetings of the Commission took place, during which the following items were discussed:
31 documentations for recommended exposure limits of chemical substances prepared by the Expert Group for Chemical Agents
introduction of a definition of aerosol fraction (inhalable, respirable and thoracic) to the regulation for MACs and MAIs, which was associated with changes in Parts A and B of the regulation for 39 chemicals and 19 dusts
adaptation of the national regulation to Directive 2009/161/EC especially for 4 substances: phenol, 1-methyl-2-piroli-dyne, sulphuric acid and hydrogen sul-phide
the report on the working conditions of employees exposed to sulfuric acid(VI) carried out by the State Sanitary Inspec-tion between January and June 2011
methods for determining thoracic fraction of sulfuric acid(VI) in the working environment
requests submitted to the Interdepart-mental Commission for MACs and MAIs by representatives of the Polish industry regarding introducing an additional value for the thoracic fraction of sulfuric acid(VI) of 0.05 mg/m³ in the draft Regulation of the Minister of Labour and Social Policy
interpretation of the results of measure-ments of harmful chemical and physical agents in the working environment
Hhealth effects of exposure to silica in Poland, a strategy of sampling crystalline silica dust in the workplace, methods for determining the concentration of respirable crystalline silica and selecting equipment for respiratory hazards in the form of dust containing free crystalline silica
proposals of the maximum admissible concentration (MAC) for crystalline silica: quartz [14808-60-7], cristobalite [14464-46-1] – respi-rable fraction of 0.05 mg/m3 and 0.1 mg/m³
the proposal of the Commission for Oc-cupational Safety in Mining operating at the State Mining Authority for an exemption of gases present in underground mining: carbon monoxide, nitrogen oxide, sulfur dioxide and hydrogen sulfide from the regulation on maximum admissible concentrations and intensities of agents harmful to health in the working environment
comments on the proposal of an indicative occupational exposure limit (OEL and STEL) for nitrogen dioxide (NO2) by SCOEL reported by KGHM Polish Cop-per SA and the Association of Em-ployers of Polish Copper and passed to SCOEL by the Contact Point
verification of the value of MAC(TWA) and ceiling STEL(C) for the following substances: acetaldehyde, acetic anhydride and chloro(phenyl)methane as, according to the rules adopted by the Interdepartmental Commission for MACs and MAIs, they cannot occur together
two conclusions of the Group of Experts on Microclimate: the introduction of amendments to the Regulation of the Council of Ministers of 24 August 2004 on the list of jobs forbidden for young people and the conditions of their employment at some of these jobs (Journal of Laws of 2004 No 200, pos. 2047 , d. Laws of 2005, No. 136, item. 1145, d. Laws of 2006, No. 107, item. 724) and changes in Annex 2 to the Regulation the Minister of Labour and Social Policy in part C. Microclimate, point No. 2 Cold microclimate
leaving the MAC values for the inhal-able fraction of lead [7439-92-1] and inorganic compounds, with the exception of arsenate (V) lead (II) and chromate (VI) lead (II) (Pb) at the level of 0.05 mg/m3 and the determination of the DSB for lead in the blood of 300 m/L.
The Commission proposed to the Minister of Labour and Social Policy the following changes in the list of MAC and MAI values:
introduction in Annex 1 in parts A and B of a list of definitions of inhalable, respirable and thoracic fraction
introduction in Annex No. 1 in Part A of a list of changes for 39 chemicals and 19 dusts in the context of the definition of aerosols fraction
introduction in Annex 1 in Part A of a list of occupational exposure limit values of 9 new chemical agents harmful to health
introduction in Annex 1 in Part A and B of a list of changes in maximum admissible concentrations for 22 chemi-cals
introduction in Annex 2 in Part C of changes for cold microclimate
interdepartmental Commission for MACs and MAIs does not have the evidence base to determine the distinct values of MAC(TWA)/STEL for gases present in underground mining: carbon dioxide, carbon monoxide, nitrogen oxide, sulfur dioxide and hydrogen sulfide
the need to analyse the regulation of the Council of Ministers on the list of jobs forbidden for young people and the con-ditions of their employment at some of these jobs in terms of changes in the cold microclimate and other factors.
In 2011-2013, 12 issues (67-78) of Commission's quarterly "Principles and Methods of Assessing the Working Environment”.
The results of the Commission's activities were presented in 14 publications at the national level and 1 international publication, at 6 national conferences and on the website of the Bureau of Chemical Bulletin "Chemistry, Health, Environment", available on online (December 2013) at http://www.chemikalia.gov.pl/biuletyn_biura.php.
In 2013, the Commission met at three sessions, in which 9 documentations for recommended exposure limits of chemical substances were discussed. Moreover, the Commission dis-cussed:
– the results of environmental research conducted by the State Sanitary Inspec-tion (in 2011 and 2012) for the chemicals that the Interdepartmental Commission was to discuss in 2013
– the introduction to Annex 1 of Part B changes in the admissible concentration of respirable crystalline silica
– the change in the recommended value for lead in blood (DSB) and the value for lead in blood in the Regulation of the Minister of Health of 30 December 2004
– the changes in Annex 2 of the Regula-tion the Minister of Labour and Social Policy on maximum admissible concentrations and intensities of agents harmful to health in the working environment in Part C. Microclimate, point No. 2 Cold microclimate.
The Commission proposed to the Minister of Labour and Social Policy the following changes in the list of MAC and MAI values:
adding three new chemical substances to the list of MAC values: diphenylamine (inhalable fraction), 4-chloro-3-methyl-phenol (inhalable fraction), peracetic acid
changing MAC values for three chemi-cals: acetic anhydride, dimethyl phthalate (inhalable fraction), N-methylaniline and respirable silica
changing in Annex 2, Part C. Microcli-mate, point No. 2 Cold microclimate.
Within the framework of interdepartmental consultations of the draft regulation on maximum admissible concentrations and intensi-ties of agents harmful to health in the working environment (draft of 18 June 2013), the Secre-tariat of the Commission prepared opinions on the comments made by the Ministry of Economy, Chief Labour Inspector , Ministry of Foreign Affairs, Central Mining Institute and Ministry of Environment.
Four issues of the “Principles and Methods of Assessing the Working Environment” were published in 2013; they included 16 documentations for recommended exposure limits for chemicals, 16 methods for assessing the concentration of chemicals in the working environment, report on the activities of the Interdepartmental Commission for MAC and MAI in 2012, 4 original articles and indexes of published articles, monographic documentations and methods for determining concentrations of chemical substances in the air.
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