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- Dustiness test methods for nanomaterials
Elżbieta Jankowska, Piotr Sobiech
- Hydrogen peroxide. Documentation
Renata Soćko
- Phosphoryl trichloride. Documentation
Katarzyna Konieczko, Sławomir Czerczak
- Determination of 4,4'-thiobis(6-tert-butyl-3-methylphenol) in workplace air with chromatography
Anna Jeżewska
- Chromatographic determination of tetramethylsuccinonitrile in workplace air
Agnieszka Woźnica
- Amended method for determining iron oxides in workplace air
Jolanta Surgiewicz
- Determination of ethyl bromide in the workplace air by gas chromatography with mass detection (GC-MS)
Wiktor Wesołowski, Małgorzata Kucharska, Jan Gromiec
- Determining vinyl bromide in workplace air with gas chromatography with mass detection (GC-MS)
Małgorzata Kucharska, Wiktor Wesołowski, Jan Gromiec
- Determining 3,7-dimethylocta-2,6-dienal in workplace air with HPLC
Anna Jeżewska
- Determining acrylic acid in workplace air with HPLC
Sławomir Brzeźnicki, Marzena Bonczarowska, Jan Gromiec
- Using gas chromatography with electron capture detection in analysing hexachlorocyclopentadiene in air samples
Joanna Kowalska
- Amended method for determining hydrogen chloride in workplace air
Ewa Gawęda
- Amended method for determining phosphorus pentoxide in workplace air
Ewa Gawęda
- Amended method for determining phosphorus pentachloride in workplace air
Ewa Gawęda
- The activity of the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment in 2012
Jolanta Skowroń 
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Dustiness test methods for nanomaterials
Elżbieta Jankowska, Piotr Sobiech
This article presents issues associated with standard and alternative dustiness test methods for materials with reference to their size fractions (inhalable, thoracic and respirable) according to standard EN 15051: 2006 (PN-EN 15051: 2006). It discusses the principles of classifying the dustiness of materials determined with the standard or alternative methods. The article also discusses developing methods for testing dustiness for nano-
materials, which should embrace both investigations associated with size fractions determined with the gravimetric method and necessary due to the nanospecificity of those materials, i.e., at least determining the number concentration and the size distribution of the nano-objects.
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Hydrogen peroxide. Documentation
Renata Soćko
Hydrogen peroxide is a colourless liquid that is normally handled as an aqueous solu-tion.Hydrogen peroxide is commonly used in industry for disinfecting, bleaching and as a general oxidizing agent. The main use (48%) of hydrogen peroxide in the EU is for bleaching pulp. Other uses include manufacturing chemicals and using it as an intermediate in the synthesis of chemicals such as sodium perborate, sodium percarbonate, hydroquinone, hydrazine, organic peroxides and many others. It is used in bleaching textiles and other products, wastewater and waste gas treatment, disinfection, beverage packing, surface treat-ment, etching and cleaning. Small quantities are used in consumer products such as cosmetics, toothpaste and deodorants.
Hydrogen peroxide causes irritation of the respiratory tract and eyes. Inhalation of high concentrations of the vapour or mist of hydrogen peroxide may cause extreme irritation of the nose and throat. Even short periods of exposure may cause stinging and watering of the eye and exposure to 9.2 mg/m3 has been reported to cause lung irritation in humans. Higher levels of exposure may cause headache, dizziness, vomiting, diarrhoea, tremors, numbness, convulsions, pulmonary oedema, unconsciousness, and shock. Contact of hy-drogen peroxide with the skin can cause severe skin damage.
An irritant of the eyes, mucous membranes, lungs and skin is a critical effect of hydrogen peroxide. The MAC value for hydrogen peroxide was calculated on the basis of the LOAEL (0.83 mg/m3) value and uncertainty factor (Uf= 2). The MAC value of 0.4 mg/m3 is recommended and the value of STEL of 0.8 mg/m3. An additional notation of hydrogen peroxide is C – corrosive compounds.
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Phosphoryl trichloride. Documentation
Katarzyna Konieczko, Sławomir Czerczak
Phosphoryl trichloride is a clear, colourless to yellow, fuming liquid with a pungent and musty odor. It hydrolyses in water or moist air to hydrogen chloride and orthophosphoric acid. Phosphoryl trichloride is widely used to manufacture alkil and aryl orthophosphate triesters. It is used for plasticizers, flame retardants, hydraulic fluids, insecticides, pharmaceuticals, gasoline additives and dye intermediates. Phosphoryl trichloride is also used as a chlorinating agent, catalyst, cryoscopy solvent and dopant for semiconductor grade silicon. A critical effect of exposure to phosphoryl trichloride is a strong irritation of eyes and the upper respiratory tract. Based on available data no NOAEL nor LOAEL values could be calculated. With regard to rapid hydrolysis of phosphoryl trichloride to hydrochloric acid and orthophos-phoric acid, establishing occupational exposure limits based on existing MAC (TWA) values for these hydrolysis products was proposed. Taking into account the method of determining phosphoryl trichloride in workplace air, relating to orthophos-phoric acid, a MAC (TWA) value of 1 mg/m3 and a STEL value of 2 mg/m3 were proposed by analogy to orthophosphoric acid. C notation, indicating corrosive action of phosphoryl trichloride, was assigned. There are no grounds for establishing a BEI value.
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Determination of 4,4'-thiobis(6-tert-butyl-3-methylphenol) in workplace air with chromatography
Anna Jeżewska
A new procedure has been developed for the assay of 4,4'-thiobis(6-tert-butyl-3-methylphenol) (TBBC) using high-performance liquid chromatography with a diode array detector. This method is based on the adsorption of TBBC a polypropylene filters, extraction with methanol and chromatographic analysis of the obtained solution. The working range is 1 to 20 mg/m3 for a 100-L air sample. Limit of quantification: 2.5 µg/m3.
The developed method of determining 4,4'-thiobis(6-tert-butyl-3-methylphenol) has been recorded as an analytical procedure, which is available in the Appendix.
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Chromatographic determination of tetramethylsuccinonitrile in workplace air
Agnieszka Woźnica
A new procedure has been developed for the determination of tetramethylsuccinonitrile using gas chromatography with a flame ionisation detector. This method is based on the adsorption of tetramethylsuccinonitrile on silica gel, desorption with methanol and chromatographic analysis of the obtained solution. The working range is 0.26 to 5.2 mg/m3 for a 40-L air sample. Limit of quantification: 0.14 µg/m3.
The developed method of determining tetramethylsuccinonitrile has been recorded as an analytical procedure, which is available in the Appendix.
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Amended method for determining iron oxides in workplace air
Jolanta Surgiewicz
This method is based on collecting iron oxides on a membrane filter, mineralizing the sample with concentrated nitric acid and preparing the solution for analysis in diluted nitric acid. Iron oxides in the solution are determined as iron with flame atomic absorption spectrometry. The detection limit for iron oxides in this method is 0.35 mg/m3.
The developed method of determining iron oxides has been recorded as an analytical procedure, which is available in the Appendix.
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Determination of ethyl bromide in the workplace air by gas chromatography with mass detection (GC-MS)
Wiktor Wesołowski, Małgorzata Kucharska, Jan Gromiec
A new procedure has been developed for the assay of ethyl bromide with gas chromatography with mass detection (GC-MS). The method is based on the adsorption of ethyl bromide on petroleum charcoal and desorption with 10% acetone in toluene.
The resulting solutions are analysed with GC-MS.
The working range of this analytical method is from 10 to 1500 µg/ml (1 to 150 mg/m3 for a 10-L air sample). Limit of quantification: 1.76 µg/ml.
The developed method of determining ethyl bromide has been recorded as an analytical procedure, which is available in the Appendix.
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Determining vinyl bromide 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 vinyl bromide (bromoethen) with gas chromatography with mass detection (GC-MS). The method is based on the adsorption of vinyl bromide on petroleum charcoal and desorption with 10% acetone in toluene. The resulted solutions are analysed with GC-MS. The working range of the analytical method is from 0.08 to 12 µg/ml (0.008 to 1.2 mg/m3 for a 10-L air sample). Limit of quantification: 0.0337 µg/ml.
The developed method of determining vinyl bromide has been recorded as an analytical procedure, which is available in the Appendix.
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Determining 3,7-dimethylocta-2,6-dienal in workplace air with HPLC
Anna Jeżewska
A new procedure has been developed for the assay of 3,7-dimethylocta-2,6-dienal (citral) with high-performance liquid chromatography with an diode array detector. This method is based on the adsorption of 3,7-dimethyl-2,6-octadienal vapors on a silica gel, desorption with methanol and chromatographic analysis of the obtained solution. The working range is 2.7 to 5.4 mg/m3 for a 24-L air sample. Limit of quantification: 1.9 µg/m3.
The developed method of determining 3,7-di-methyl-2,6-octadienal has been recorded as an analytical procedure, which is available in the Appendix.
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Determining acrylic acid in workplace air with HPLC
Sławomir Brzeźnicki, Marzena Bonczarowska, Jan Gromiec
A new procedure has been developed for the assay of acrylic acid with high-performance liquid chromatography (HPLC) with an ultraviolet detector. The method is based on the adsorption of acrylic acid in two (connected in a series) sorbent tubes containing Supelite DAX-8 resin. The adsorbed compound is eluted with a methanol: water (1:1) mixture. The resulting solutions are analysed with HPLC with ultraviolet (λ=210 nm) detection.
The working range of the analytical method is from 0.002 to 0.08 mg/ml (1 – 40 mg/m3 for a 20-L air sample). Limit of quantification: 0.02 µg/ml.
The developed method of determining acrylic acid has been recorded as an analytical proce-dure, which is available in the Appendix.
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Using gas chromatography with electron capture detection in analysing hexachlorocyclopentadiene in air samples
Joanna Kowalska
This article describes a fully validated methodology for analysing hexachlorocyclopentadiene with gas chromatography with electron capture detection (GC/ECD). Hexachlorocyclopentadiene can be determined in workplace air at the concentration range from 0.008 to 0.23 mg•m-3.The use of Rtx-5ms capillary column (30 m x 0.25 mm i.d. x 0.25 μm film thickness) makes it possible to de- termine HCCP. Samples of air for determining HCCP can be taken with a sorbent tube filled with Porapak T. Hexane was used for desorption of HCCP with an efficiency value of about 99%.
The developed method of determining hexachlorocyclopentadiene has been recorded as an analytical procedure, which is available in the Appendix.
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Amended method for determining hydrogen chloride in workplace air
Ewa Gawęda
This method is used for determining hydrogen chloride in workplace air. It is based on the adsorption of hydrogen chloride on a paper filter impregnated with sodium carbonate and extraction of the resulting salt. Silver nitrate is added to the resulting solution and the solution is completed with a 20% glycerol solution. The suspension of silver chloride in glycerol is determined with turbidimetry (wavelength – 400 nm). The determination limit of the method is approximately 0.5 mg/m3.
The developed method of determining hydrogen chloride has been recorded as an analytical procedure, which is available in the Appendix.
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Amended method for determining phosphorus pentoxide in workplace air
Ewa Gawęda
The method is used for determination of phosphorus pentoxide in the workplace air.
The method is based on the absorption of phosphorus pentoxide in water, hydrolysis to orthophosphoric acid, reaction with ammonium mo-
lybdate and ascorbic acid. The resulting blue complex compound is analysed by spectrophotometry in a visible region.
The determination limit of the method is approximately 0.1 mg/m3
The developed method of determining phosphorus pentoxide has been recorded as an analytical procedure, which is available in the Appendix.
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Amended method for determining phosphorus pentachloride in workplace air
Ewa Gawęda
The method is used for determining phosphorus pentachloride in workplace air. It is based on the absorption of phosphorus pentachloride in water, hydrolysis to orthophosphoric acid, reaction with ammonium molybdate and ascorbic acid. The resulting blue complex compound is analysed with spectrophotometry in the visible region.
The determination limit of the method is approximately 0.07 mg/m3
The developed method of determining phosphorus pentachloride has been recorded as an analytical procedure, which is 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 2012
Jolanta Skowroń
In 2012, the Commission met at three sessions, in which 13 documentations for recommended exposure limits of chemical substances were discussed. Moreover, the Commission discussed:
information on the results of environmen-tal measurements conducted by the State Sanitary Inspection (in 2010 and 2011) for the chemicals that were in the plan of work of the Interdepartmental Commission in 2012
comments on the SCOEL proposal of occupational exposure limits (OEL and STEL) for nitrogen dioxide (NO2) reported by KGHM Polish Copper SA and the Association of Employers of Poland Copper SCOEL transferred to the Contact Point
changes in the list of maximum admissible concentrations for chemicals and dusts (part A and B) in connection with the definition of the fraction of aerosols
verification of the MAC and STEL-ceiling value for acetaldehyde, acetic anhydride and chloro(phenyl)methane, because according to the rules adopted by the Commission, both of these values cannot be together
changes proposed by the Group of Experts on Microclimate in the regulation of Council of Ministers of 24 August 2004 on the list of work prohibited for young persons and their conditions of employment in some of types of work (Dziennik Ustaw 2004, No. 200 item. 2047, as amended in Dziennik Ustaw 2005, No. 136, item 1145, as amended in Dziennik Ustaw 2006, No. 107, item 724) in connection with replacing the WCI index for cold microclimate (air cooling power) with the tWC indicator (temperature of air cooling ) expressed in degrees Centigrade (°C) and describing the effect of skin cooling air flow.
The Commission suggested to the Minister of Labour and Social Policy the following changes in the list of MAC values:
– adding two new chemical substances to the list of MAC values: 3,4-dichloramine, phosphoryl trichoride
– changing MAC values for 10 chemicals: aniline, 1,1-dichloroethene, acetic acid, hydrogen peroxide, ethyl acetate, pyridine, mineral oil high refined (inhalable fraction), calcium oxide (respirable and inhalable fraction), nitroglycerin, calcium hydroxide (respirable and inhalable fraction). For 1,2-epoxypropane MAC value 9 mg/m3 was allowed until a position of SCOEL on comments made during the public consultation of OEL value 2.41 mg/m3 (1 ppm) by Contact Points will be known.
verifying the MAC and STEL-ceiling value for 3 chemicals: acetaldehyde, acetic anhydride, cholro (phenyl) methane
introducing in Appendix 1 in Part A of the list, changes for the 39 chemicals in the context of the definition of the fraction of aerosols
introducing in Appendix 1 in Part B of the list, changes for the 19 dusts in the context of the definition of the fraction of aerosols.
Under proposals of the Interdepartmental Com-mission for MACs and MAIs submitted to the Minister of Labour and Social Policy in 2011-2012 and subsequent regulations amended by the Minister (Dziennik Ustaw, 2005, No. 212, item 1769, Dziennik Ustaw, 2007, No. 161, item 1142; Dziennik Ustaw, 2009, No. 105, item 873, Dziennik Ustaw, 2010, No. 141, item 950; Dziennik Ustaw, 2011, No. 274, item 1621) began work on the text of a single regulation the Minister of Labour and Social Policy on the maximum admissible concentrations and intensities of harmful agents in the working environment. In addition, materials to the 8th edition of the Commission's brochure "Harmful agents in the workplace - the limit values" are prepared.
Four issues of the “Principles and Methods of Assessing the Working Environment” were published in 2012. Issue 1(71) contained 13 methods for assessing the working environment, 2 documentations and an article on assessing the impact of nanoparticles on the surface activity of the pulmonary surfactant. Issues 2(72) contained 5 documentations for recommended exposure limits and an article on preventing exposure to ultrasonic noise. Issues 3(73) contained 5 documentations along with analytical procedures, recommendations with respect to pre-employment and periodic medical examinations and contraindications to exposure. Issues 4(74) contained 3 docu-mentations, a method of measuring respirable fraction of crystalline silica and 3 articles: equip-ment and methods to measure ultrasonic noise, method of evaluating machines emitting nonlaser optical radiation and integrated testing strategy for toxicity testing of nanotechnology products.
Three sessions of the Commission are planned for 2013. MAC values for 15 chemical substances will be discussed at those meetings.
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