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PRINCIPLES AND METHODS OF ASSESSING THE WORKING ENVIRONMENT

NUMBER 1 (99) 2019




  • But-2-enal. Determination in workplace air
    Anna Jeżewska, Agnieszka Woźnica, p. 5-17
  • Chlorobenzene. Determination in workplace air
    Anna Jeżewska, Agnieszka Woźnica, p. 19-27
  • Ethylenediamine. Determination in workplace air with high performance liquid chromatography – spectrophotometric technique
    Marek Zieliński, Ewa Twardowska, Marzena Bonczarowska, p. 29-43
  • Hexachlorobenzene. Determination in workplace air
    Joanna Kowalska, p. 45-59
  • Hydrazine. Determination in workplace air with high performance liquid chromatography
    Marzena Bonczarowska, Patryk Piątek, Sławomir Brzeźnicki, p. 61-76
  • Pentachlorophenol. Determination in workplace air by means of high performance liquid chromatography
    Sławomir Brzeźnicki, Marzena Bonczarowska, p. 77-91
  • Pentane-1-ol and its isomers. Determination in workplace air with GC with Flame Ionization Detector (GC-FID)
    Marek Zieliński, Ewa Twardowska, Małgorzata Kucharska, p. 93-106
  • The activity of the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment in 2018 and the work plan in 2019
    Danuta Koradecka, Jolanta Skowroń, p. 107-126
  • But-2-enal. Determination in workplace air
    Anna Jeżewska, Agnieszka Woźnica

    But-2-enal (crotonaldehyde) is a colourless liquid with an unpleasant suffocating odour. But-2-enal occurs naturally in food. It is mainly used for the production of sorbic acid, a food preservative. But-2-enal is a very toxic, highly irritating and allergenic substance – it is suspected of causing genetic defects. The aim of the study was to develop a method for determination of but-2-enal, which will enable determination of concentrations of this substance in the workplace air in the range from 1/10 to 2 MAC values. The tests were performed using a liquid chromatograph (HPLC) with a diode array detector (DAD), equipped with an Ultra C18 column (250 × 4.6 mm; 5 μm). The method consists in retaining the but-2-enal on a silica gel coated with 2,4-dinitrophenylhydrazine. The sample is extracted with acetonitrile and analyzed by HPLC. Validation of the method was carried out in accordance with the requirements of the European standard EN482. The measuring range of the method is from 0.1 to 2 mg/m3 for a 12 l sample of air. The following validation parameters were obtained: limit of detection: 1.26 ng/ml (0.21 μg/m3), limit of quantification: 3.77 ng/ml (0.63 μg/m3), the overall accuracy of the method: 5.08%, expanded uncertainty: 22%. The developed analytical method enables selective determination of but-2-enal in workplace air at concentrations ranging from 0.1 mg/m3, i.e. from 1/10 of the MAC value in the presence of co-occurring substances. The method is characterized by good precision and accuracy and meets the requirements of the European standard PN-EN 482 for procedures for determination of chemical agents. The developed method of determining but-2-enal has been recorded as an analytical procedure (see Appendix). This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering.



    Chlorobenzene. Determination in workplace air
    Anna Jeżewska, Agnieszka Woźnica

    Chlorobenzene is a colorless, flammable liquid that has an almond-like odor. It is used in industry as a solvent: resins, paints and fats, raw material for the production of plastics, as well as for the production of phenol, aniline and nitrobenzene. Occupational exposure to chlorobenzene vapors can occur through inhalation, absorption through the skin or ingestion. Harmful if inhaled, it causes skin irritation. Long-term exposure affects the central nervous system. The study aimed to amend Standard No. PN-Z-04022-03:2001 withdrawn from the Polish set of standards, and tovalidate the method for determining concentrations of chlorobenzene in workplace air in the range from 1/10 to 2 MAC values, in accordance with the requirements of Standard No. PN-EN 482. The study was performed using a gas chromatograph (GC) with a flame ionization detector (FID) equipped with a capillary column HP-5 (30 m × 0.32 mm, 0.25 μm). This method is based on the adsorption of chlorobenzene vapors on activated charcoal, desorption with carbon disulfide, and analyzed by GC-FID. Application of HP-5 column allows selective determination of chlorobenzene in the presence of carbon disulfide, aniline, phenol and nitrobenzene. The measurement range was 2.3–46 mg/m3 for a 15-L air sample. Limit of detection: 6.75 ng/ml and limit of quantification: 20.25 ng/ml. The analytical method described in this paper enables selective determination of chlorobenzene in workplace atmosphere in the presence of other solvents at concentrations from 2.3 mg/m3 (1/10 MAC value). The method is characterized by good precision and accuracy and it meets the criteria for the performance of procedures for measuring chemical agents, listed in Standard No. EN 482. The method may be used for assessing occupational exposure to chlorobenzene and the associated risk to workers’ health. The developed method of determining chlorobenzene has been recorded as an analytical procedure (see Appendix). This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering.



    Ethylenediamine. Determination in workplace air with high performance liquid chromatography – spectrophotometric technique
    Marek Zieliński, Ewa Twardowska, Marzena Bonczarowska

    Ethylenediamine (EDA) is a colorless, viscous liquid with ammonia-like odor. It is used as an intermediate in manufacturing chelating agents (EDTA), fungicide, poliamide and formaldehyde-urea resins, surfactants, corrosion inhibitors, emulsifying agents and stabilizer of rubber products. EDA may cause irritation of the upper respiratory tract, eye and skin. Occupational exposure to EDA may lead to allergic reactions and asthma. EDA is not classified as carcinogenic to humans. The aim of this study was to develop and validate a sensitive method for determining hydrazine concentrations in workplace air in the range from 1/10 to 2 MAC values, in accordance with the requirements of Standard No. PN-EN 482. The study was performed using a liquid chromatograph with spectrophotometric detection. All chromatographic analyses were performed with a Supelcosil LC-18 (150 × 3 mm, 5 μm) analytical column, which was eluted with a mixture of acetonitrile and water (6:4 v/v). The method is based on the collection of EDA on silica gel impregnated with sulfuric acid, extraction with a mixture of acetonitrile and water (62:38 v/v), derivatization of extracted compound with 9-fluorenylmethyl chloroformate and chromatographic determination of the resulting solution with HPLC. The method is linear (r = 0.9994) within the investigated working range 0.1–2 μg/ml (2–40 mg/m3 for a 10-L air sample). The calculated limit of detection (LOD) and limit of quantification (LOQ) were 0.04 μg/ml and 0.13 μg/ml, respectively. The average extraction efficiency of EDA from silica gel was 86% and samples stored in a refrigerator are stable for 10 days. The analytical method described in this paper enables determination of EDA in workplace air. The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. PN-EN 482. The method can be used for assessing occupational exposure to EDA and associated risk to workers’ health. The developed method of determining EDA has been recorded as an analytical procedure (see Appendix). This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering.



    Hexachlorobenzene. Determination in workplace air
    Joanna Kowalska

    The aim of this study was to develop and validate a method for determining of inhalable fraction of hexachlorobenzene in workplace air. The determination method is based on the adsorption of hexachlorobenzene on a polypropylene filter, extraction with hexane and an analysis of the resulting solution with gas chromatography with electron capture detection (GC-ECD). A capillary column with HP-5 (30 m × 0.32 mm, i.d. × 0.25 μm film thickness) was used. The method is linear within the working range from 0.018 μg/ml to 0.375 μg/ml, which is equivalent to air concentrations from 0.0003 to 0.006 mg/m3 for a 120-L air sample. The analytical method described in this paper enables selective determination of analytes in workplace air in the presence of coexisting substances. The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. EN 482. This method can be used for assessing occupational exposure to hexachlorobenzene and the associated risk to workers’ health. The developed method of determining hexachlorobenzene has been recorded as an analytical procedure (see appendix). This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering.



    Hydrazine. Determination in workplace air with high performance liquid chromatography
    Marzena Bonczarowska, Patryk Piątek, Sławomir Brzeźnicki

    Anhydrous hydrazine in room temperature is colorless fuming oily liquid with ammonia-like odor. It is used in various industries for electrolytic plating of metals on glass and plastics, as a chemical intermediate for the synthesis of pesticides, insecticides, medicines and days. It is used also as water treatment agent in energy industry (corrosion inhibitor), rocket propellant and as explosives material. Long term exposure to hydrazine may cause to skin irritation and allergic reactions. Diluted aqueous solutions of hydrazine may be irritating for skin, eye and respiratory tract. Epidemiologic studies shows that chronic exposure to hydrazine may cause cancer. In European Union hydrazine is classified as a carcinogenic substance (cat. 1B). Experts from International Agency for Research on Cancer (IARC) have classified hydrazine as a compound probably carcinogenic to humans (Group 2A). Due to decreasing of MAC value for hydrazine in Poland it was necessary to develop and validate a sensitive method for determining hydrazine concentrations in the workplace air in the range from 1/10 to 2 MAC values, in accordance with the requirements of Standard No. PN-EN 482. The study was performed using a liquid chromatograph with spectrophotometric detection. All chromatographic analysis were performed with Discovery LC-18 150 × 2,1 mm analytical column, which was eluted with mixture of acetonitrile and water (6:4 v/v). The method is based on the collection of hydrazine on glass fiber filter impregnated with sulfuric acid, extraction with mixture of sodium dihydrogen phosphate and EDTA, derivatization of extracted compound with benzaldehyde and chromatographic determination of resulted solution with HPLC technique. The method is linear (r = 0.9989) within the investigated working range 0.15–3.5 μg/ml (0.00125–0.029 mg/m3 for a 240-L air sample). Calculated limit of detection (LOD) and limit of quantification (LOQ) were 0.0007 μg/ml and 0.0023 μg/ml, respectively. The average extraction efficiency of hydrazine from filters was 97% and samples stored in refrigerator are stable for 14 days. The analytical method described in this paper enables determination of hydrazine in workplace air. The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. PN-EN 482. The method can be used for assessing occupational exposure to hydrazine and associated risk to workers’ health. The developed method of determining hydrazine has been recorded as an analytical procedure (see appendix). This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering.



    Pentachlorophenol. Determination in workplace air by means of high performance liquid chromatography
    Sławomir Brzeźnicki, Marzena Bonczarowska

    Pentachlorophenol (PCF) in room temperature is a crystalline solid with phenol-like odor. It is soluble in most organic solvents (diethyl ether, acetone, carbon tetrachloride, methanol). It is slightly soluble in water. Pentachlorophenol is used as a fungicide, insecticide and as non-selective herbicide (defoliant) in cotton crops. It is also used as antimicrobial agent in leather, paper and textile industry. It has been widely used as wood preservative in wood and construction industry. Occupational exposure to pentachlorophenol may cause irritation of mucous membranes of the eyes and the upper respiratory tract and skin lesions. It may also lead to changes in the central nervous system like headache, insomnia, vertigo and depression. Acute poisoning may cause pulmonary edema, cardio-respiratory disorder and even death. Pentachlorophenol is also suspected to be carcinogenic to humans. The aim of this study was to develop and validate a sensitive method for determining pentachlorophenol concentrations in workplace air in the range from 1/10 to 2 MAC values, in accordance with the requirements of Standard No. PN-EN 482. The study was performed using a liquid chromatograph with spectrophotometric detection. All chromatographic analysis were performed with Zorbax SB-CN 250 × 4.6 mm analytical column, which was eluted with mixture of 0.1% phosphoric acid in acetonitrile and 0.1% phosphoric acid in water (6:4 v/v). The method is based on the collection of pentachlorophenol on XAD 7 resin preceded by a glass fiber filter, extraction with methanol and chromatographic determination of resulted solution with HPLC technique. The method is linear (r = 0.9997) within the investigated working range 0.625–12.5 μg/ml (0.05–1.0 mg/m3 for a 25-L air sample). The calculated limit of detection (LOD) and limit of quantification (LOQ) were 0.014 μg/ml and 0.048 μg/ml, respectively. The average extraction efficiency of pentachlorophenol from filter and XAD 7 amounted to 95% and samples stored in refrigerator are stable for 14 days. The analytical method described in this paper enables determination of pentachlorophenol in workplace air. The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. PN-EN 482. The method can be used for assessing occupational exposure to pentachlorophenol and associated risk to workers’ health. The developed method of determining pentachlorophenol has been recorded as an analytical procedure (see Appendix). This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering.



    Pentane-1-ol and its isomers. Determination in workplace air with GC with Flame Ionization Detector (GC-FID)
    Marek Zieliński, Ewa Twardowska, Małgorzata Kucharska

    Amyl alcohol (pentan-1-ol) – C5H12O or C5H11OH – is an organic chemical compound from the group of saturated monohydric aliphatic alcohols. There are 8 known isomers of pentanol: pentan-1-ol (CAS:71-41-0), pentan-2-ol (CAS: 6032-29-7), pentan-3-ol (CAS: 584-02-1), 2-metylobutan-1-ol (CAS: 137-32-6), 3-metylobutan-1-ol (CAS: 123-51-3), 2-metylobutan-2-ol (CAS: 75-85-4), 3-metylobutan-2-ol (CAS: 598-75-4) i 2,2-dimetylopropan-1-ol (CAS: 75-84-3). All of them are commonly referred to as amyl alcohols. Pentanol isomers exhibit chemical properties characteristic of aliphatic alcohols, they are obtained by hydration of pentene isomers, hydrolysis of chloropentanes or by reaction of butene and carbon monoxide isomers. They are used as solvents for fats, resins and waxes. Pentan-1-ol is absorbed into the human body through the respiratory tract, skin, gastrointestinal tract. Symptoms of acute intoxication are usually tearing eyes, redness of the conjunctiva, irritation of the mucous membrane of the nose and throat. In higher concentrations it may cause headache, dizziness, nausea, vomiting, diarrhea, delirium, disturbances of consciousness, coma. Arrhythmia and respiratory disorders may cause redness and burning, as well as symptoms such as inhalation poisoning, eye contamination with liquid substance causes pain, burning of the eyes, redness of the conjunctiva, with the risk of long-lasting and permanent changes. Repeated skin contact with the liquid substance may cause its drying and inflammation. It is suggested that long-term exposure of the skin to the substance at high concentration may lead to changes in the nervous system. The aim of this study was to develop and validate a sensitive method of determining 8 pentan-1-ol isomers in the working environment in the range from 1/10 to 2 of the MAC values. The gas chromatography method with a flame ionization detector (GC-FID) was used to determine pentan-1-ol and its isomers. It was decided to develop a method that ensures the determination of at least 1/10 of the MAC values. Further considerations of the possibility of determining this substance in the air are based on previously developed analytical methods. The use of the HP-5 capillary column enables the selective determination of pentan-1-ol in the presence of carbon disulphide, methanol and other co-existing compounds. The detector’s response to the analyzed pentan-1-ol concentrations is linear (r2 = 0.9998) in the concentration range 10–2000 μg/ml, which corresponds to the range of 1–200 mg/m3(0.01–2 of the MAC values) for a 10-L air sample. The limit of quantification (LOQ) of this method is 0.026 μg/ml. The developed method is characterized by good precision and accuracy and meets the requirements of Standard No. PN-EN 482 for procedures regarding the determination of chemical agents. The developed method for determining pentan-1-ol has been recorded in the form of an analytical procedure (see Appendix).This article discusses the problems of occupational safety and health, which are covered by health sciences and environmental engineering.



    The activity of the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment in 2018 and the work plan in 2019
    Danuta Koradecka, Jolanta Skowroń

    In 2018 the Commission met at three sessions, during which 9 documentations for recommended exposure limits of chemical substances were discussed. Moreover the Commission discussed: a system for notifying entrepreneurs, employees and inspection bodies of proposals for new or verified binding values (for carcinogenic and mutagenic substances) or indicator values for harmful chemicals in the form of messages, rules for setting limit values for harmful to health chemicals in the working environment, a program to improve working conditions in copper mines of KGHM Polska Miedź SA. and the methodology for determining hygiene standards for active substances of cytostatics, taking into account the uncertainty factor „F”. The Commission suggested to the Minister of Family, Labour and Social Policy the following changes in the list of MAC values: adaptation of the Polish list of maximum admissible concentration (MAC-NDS) to Directive 2019/130/EC of 31/1/2019 amending Directive2004/37/EC on the protection of workers from the risks related to exposure to carcinogens or mutagens at work (these are: chloroethene, o-toluidine and 1,3-butadiene), adjusting the MAC value for trimethylamine to the value included in the draft directive setting the fifth list of indicative occupational exposure limits, introducing changes in the list of the maximum admissible concentration of chemicals and dust harmful to health for the substances mentioned, introducing the following substances into the list of maximum admissible concentrationsof chemical agents harmful to health: phenolphthalein (Carc. 1B), etoposide (Carc. 1B), fluorouracil (Muta. 1B, skin), 2-nitroanisole (Carc. 1B), N-nitrosodimethylamine (Carc. 1B). Four issues of the „Principles and Methods of Assessing the Working Environment” were published in 2018. The issues included: 11 documentations of occupational exposure limits,11 methods for the determination of chemical concentrations in the working environment, 4 articles, a report on the activities of the Interdepartmental Commission for MACs and MAIs in 2017 and the indexes of the documentations, methods and articles published in 2000-2018. Three sessions of the Commission are planned for 2019. MAC values for 10 chemical substances will be discussed at these meetings. The Commission and the Group of Experts will continue to work on adapting the Polish list of the maximum admissible concentrations to: proposals for binding values for carcinogenic or mutagenic substances, proposed concentration limit values developed by the Committee for Risk Assessment (RAC) and work carried out at SCOEL.



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