[Determination of phenyl(2-naphthyl)amine concentrations in the working environment air using HPLC-FLD technique]. / Oznaczanie stezen fenylo(2-naftylo)aminy w powietrzu srodowiska pracy technika HPLC-FLD.

BACKGROUND: Phenyl(2-naphthyl)amine (FNA) is a flammable solid with a characteristic odor. FNA is used, among others, in the production of paints and dyes, and as an antioxidant in rubber processing, lubricant for automobile engines, in brake fluids, oils, etc. In the European Union, FNA is classified as a category 2 carcinogen. In Poland, the value of the maximum admissible concentration (MAC) for FNA is 0.02 mg/m3. The aim of this study was to develop a new method for the determination of FNA, which will allow for the determination of this substance in the working environment within the concentration range of 0.1-2 of MAC value. MATERIAL AND METHODS: The method is based on the retention of FNA on a cellulose filter, recovery of the substance with methanol and analysis of the solution thus obtained using a high-performance liquid chromatograph with a fluorescence detector. RESULTS: The developed method enables the determination of FNA in the concentration range 2-40 µg/m3. The limit of detection (LOD) is 0.23 ng/l and the limit of quantification (LOQ) is 0.69 ng/l. CONCLUSIONS: The method complies with the requirements of the European Standard PN-EN 482 and can be used to determine FNA concentrations in the workplaces air. Med Pr. 2022;73(1):25-31.

[A new method for the determination of naphatylamines in workplace air for occupational exposure assessment]. / Nowa metoda oznaczania naftyloamin w powietrzu do oceny narazenia zawodowego.

BACKGROUND: Naphthylamine (NA), i.e., 1-naphthylamine (1-NA) and 2-naphthylamine (2-NA) and its salts (2-naphthylamine hydrochloride and 2-naphthylamine acetate) are colorless crystalline solids. They have been used, among others, in the production of paints and dyes. In the European Union, 1-NA is classified as a toxic substance, and 2-NA and its salts as carcinogenic category 1A. The aim of this study was to develop a new method for the determination of NA, which will enable the determination of 1-NA and 2-NA and its salts in the working environment, in the concentration range of 0.3-6 µg/m3. MATERIAL AND METHODS: The method consists in passing the test air containing the substances to be determined through a glass fiber filter impregnated with sulphuric acid(VI). After recovery with water and sodium hydroxide solution followed by extraction into a solid on Oasis HLB columns, the solutions in methanol are analyzed using a high-performance liquid chromatograph with a fluorescence detector and Ultra C18 column. RESULTS: The method developed allows determining 1-NA and 2-NA and its salts in the concentration range of 0.3-6 µg/m3. The limit of detection for 1-NA is 81 pg/ml and for 2-NA - 80.6 pg/ml. CONCLUSIONS: The method is characterized by good precision and accuracy; it meets the requirements of European Standard PN-EN 482 and can be used by occupational hygiene laboratories to measure the level of 1-NA and 2-NA and its salts in workplace air to assess workers' exposure to these substances. Med Pr. 2021;72(2):145-54.

[Determination of 1-chloro-2,3-epoxypropane in order to assess the working environment]. / Oznaczanie 1-chloro-2,3-epoksypropanu dla potrzeb oceny srodowiska pracy.

BACKGROUND: 1-Chloro-2,3-epoxypropane, known as epichlorohydrin (ECH), is a colorless liquid used in the production of epoxy resins, synthetic glycerine, elastomers, glycidyl ethers, surfactants, polyamide-epichlorohydrin resins and others. Epichlorohydrin may cause cancer. The aim of this study was to develop a new method for determining concentrations of ECH in workplace air in the range of 1/10-2 values of the maximum admissible concentration (MAC). MATERIAL AND METHODS: The paper presents a method for the determination of ECH in workplace air using a gas chromatograph coupled with a mass spectrometer (GC-MS). The developed method is based on the adsorption of ECH on an activated charcoal, extraction with acetone, and a chromatographic analysis of the resulting solution. RESULTS: The method developed makes it possible to determine ECH in the concentration range of 0.1-2 mg/m3, i.e., 1/10-2 values of MAC established in Poland. The limit of detection (LOD) is 0.24 µg/m3 and the limit of quantification (LOQ) is 0.71 µg/m3. CONCLUSIONS: The method is characterized by good precision and accuracy; it meets the requirements of the European standard PN-EN 482, and can be used by occupational hygiene laboratories to measure concentrations of ECH in workplace air, with a view to assessing workers' exposure to this substance. Med Pr. 2020;71(6):715-23.

Determination of Propane-1,3-sultone in Workplace Air for Occupational Exposure Assessment.

Propane-1,3-sultone (PS) is an alkylating substance used in the production of polymers, fungicides, insecticides, dyes, and detergents. It is absorbed into the human body by inhalation, digestion, and through the skin; it is also a possible carcinogen. Occupational exposure to this substance may occur on industrial or laboratory contact. In Poland, the maximum allowable concentration (MAC) for PS in workplace air is 7 µg/m3. The paper presents a method for determination of PS in workplace air using a gas chromatograph coupled with a mass spectrometer (GC-MS). Air containing PS is passed through a glass tube containing a glass fiber filter and two layers of silica gel. The substance is washed with acetonitrile and the solution obtained analysed using GC-MS. The measuring range for an air sample of 360 L is 0.7 ÷ 14 µg/m3. The limit of detection (LOD) is 13 ng/m3, limit of quantification (LOQ) is 40 ng/m3.

Determination of Triglycidyl Isocyanurate in Workplace Air.

Triglycidyl isocyanurate (TGIC) is a white solid in powder or granular form. TGIC does not occur naturally in the environment. It is intentionally manufactured and used as a crosslinking agent or hardener to produce polyester powder coatings. TGIC may cause genetic defects. This article presents the method of TGIC determination in workplace air using high-performance liquid chromatography (HPLC) with a diode-array detector (DAD). The method is based on the collection of TGIC present in the air on a polypropylene filter, extraction with acetonitrile, and chromatographic analysis of the solution obtained in this way. The determination was carried out in the reverse-phase system (mobile phase: acetonitrile: water) using an Ultra C18 column. The measurement range is 2 to 40 µg/m3 for a 720 liters air sample. Limit of detection (LOD) is 23 ng/m3 and limit of quantification (LOQ): 70 ng/m3. The method can be used for assessing occupational exposure to TGIC and associated risk to workers' health.

[Optimization of the method for the determination of diethyl sulfate at workplaces]. / Optymalizacja metody oznaczania siarczanu dietylu na stanowiskach pracy.

BACKGROUND: Diethyl sulfate (DES) is a substance classified to the group of carcinogens. The value of maximum admissible concentration for this substance in workplace air is not specified in Poland. Due to the use of DES in domestic companies there is a need to develop a sensitive method for the determination of diethyl sulfate in the work environment. MATERIAL AND METHODS: Studies were performed using gas chromatography (GC) technique. An Agilent Technologies chromatograph, series 7890A, with a mass selective detector (5975C, Agilent Technologies, USA) was used in the experiment. Separation was performed on a capillary column with Rtx-5MS (30 m × 0.25 mm × 0.25 µm) (Restek, USA). The possibility of using sorbent tubes filled with activated carbon (100 mg/50 mg), silica gel (100 mg/50 mg) and Porapak Q (150 mg/75 mg) for absorption of diethyl sulphate was investigated. RESULTS: The method of sampling air containing diethyl sulfate was developed. Among the sorbents to absorb DES Porapak Q was chosen. Determination of the adsorbed vapor includes desorption of DES, using dichloromethane/methanol mixture (95:5, v/v) and chromatographic analysis of so obtained solution. Method is linear (r = 0.999) within the investigated working range of 0.27- -5.42 µg/ml, which is an equivalent to air concentrations 0.0075-0.15 mg/m3 for a 36 l air sample. CONCLUSIONS: The analytical method described in this paper allows for selective determination of diethyl sulfate in the workplace air in the presence of dimethyl sulfate, ethanol, dichloromethane, triethylamine, 2-(diethylamino)ethanol, and triethylenetetramine. The method meets the criteria for performing procedures aimed at measuring chemical agents, listed in EN 482. Med Pr 2018;69(3):291-300.

[A new method for determination of toluene-2,4-diamine and toluene-2,6-diamine in workplace air]. / Nowa metoda oznaczania tolueno-2,4-diaminy i tolueno-2,6-diaminy w powietrzu na stanowisku pracy.

BACKGROUND: Toluenediamines are harmful substances. Toluene-2,4-diamine has been assigned to Carcinogen 1B hazard class, pursuant to Regulation (European Community - EC) No. 1272/2008 of the European Parliament and of the Council, and toluene- 2,6-diamine to Mutagen 2 hazard class. The main routes of exposure to toluene-2,4-diamine and toluene-2,6-diamine are via the respiratory tract and the skin. Toluene-2,4-diamine and toluene-2,6-diamine occur in the work environment in Poland. The aim of this study was to develop and validate a method for the determination of toluene-2,4-diamine and toluene-2,6-diamine that allows the simultaneous determination of their concentrations in the workplace air by personal sampling. MATERIAL AND METHODS: Determination of toluene-2,4-diamine and toluene-2,6-diamine derivatives in acetonitrile were carried out by means of liquid chromatography with a diode assay detector. The method involves passing amine-containing air through sulfuric acidtreated glass fiber filter, washing out the substance settled on the filter, using water and solution of sodium hydroxide, followed by the extraction with toluene, reaction with 3,5-dinitobenzoyl chloride, replacement of dissolvent with acetonitrile and analysis of obtained solution. RESULTS: The method developed in this study enables the researcher to determine the content of toluene-2,4-diamine and toluene-2,6-diamine in the presence of other hazardous substances. In the specified measuring range (2.88-57.6 µg/ml) calibration curves are linear. Under the optimized conditions of determination, the limit of detection (LOD) values achieved: 51.36 ng/ml for toluene-2,4-diamine and 52.93 ng/ml for toluene-2,6-diamine. CONCLUSIONS: This method makes it possible to determine the concentration of toluene-2,4-diamine and toluene-2,6-diamine in the workplace air within the specified measuring range of 0.004-0.08 mg/m3 (for air sample volume of 720 l). Med Pr 2017;68(4):497-505.

[Method for determining 1,2:3,4-Diepoxybutane in workplace air]. / Metoda oznaczania 1,2:3,4-Diepoksybutanu w powietrzu na stanowiskach pracy.

BACKGROUND: 1,2:3,4-Diepoxybutane (DEB) is a substance classified to a group of carcinogens. The maximum admissible concentration (MAC) value for this substance in workplace air is not specified in Poland. Due to the fact that DEB has been used in domestic companies there is a need to develop a sensitive method for determining 1,2:3,4-diepoxybutane in the work environment. MATERIAL AND METHODS: The studies were performed using gas chromatography (GC) technique. An Agilent Technologies chromatograph, series 7890A, with a mass selective detector (5975C, Agilent Technologies, USA) was employed in the experiment. Separation was performed on a capillary column with Rtx-5MS (30 m × 0.25 mm × 0.25 µm) (Restek, USA). RESULTS: The developed method consists in passing the known volume of air through sorbent tube filled with activated carbon, desorpting the DEB vapor with dichloromethane/methanol mixture (95:5, v/v) and analyzing the obtained solution. The method is linear (r = 0.999) within the investigated working range of 0.09-2.06 µg/ml, which is equivalent to air concentrations of 5-114 µg/m3 for a 18 l air sample; limit of detection (LOD) - 9.89 ng/ml and limit of quantification (LOQ) - 29.67 ng/ml. CONCLUSIONS: The described analytical method enables selective determination of 1,2:3,4-diepoxybutane in the workplace air in the presence of 1,3-butadiene, 1,2-epoxypropane, toluene, styrene and 1,2-epoxy-3-phenoxypropane. The method is characterized by good precision and accuracy and meets the criteria for measurement of chemical agents, listed in PN-EN 482:2012. Med Pr 2016;67(5):645-652.

[Studies on an efficient method for determining 3,3'-dimethylbenzidine in the workplace air]. / Badania nad skuteczna metoda oznaczania 3,3'-dimetylobenzydyny w powietrzu na stanowiskach pracy.

BACKGROUND: 3,3'-Dimethylbenzidene (DMB) is a substance classified into the group of carcinogens. The value of maximum admissible concentration for this substance in the workplace air is not specified in Poland. Bearing in mind that DMB is used in domestic companies there is a need to develop a sensitive method for determining 3,3'-dimethylbenzidine in the work environment. MATERIAL AND METHODS: The method consists in passing DMB-containing air through sulfuric acid-treated glass fiber filters, washing out the substance settled on the filter, using water and solution of sodium hydroxide, liquid-liquid extraction with toluene, replacing dissolvent with acetonitrile and analyzing the obtained solution. Studies were performed using high-performance liquid chromatography (HPLC) technique. An Agilent Technologies chromatograph, series 1200, with a diode-array detector (DAD) and a fluorescence detector (FLD) was used in the experiment. In the test, an Ultra C18 column of dimensions: 250×4.6 mm, particle diameter (dp) = 5 µm (Restek) was applied. RESULTS: The method is linear (r = 0.999) within the investigated working range of concentration 1.08-21.6 µg/ml, which is equivalent to air concentrations 2-40 µg/m3 for a 540 l air sample. The limit of detection (LOD) of quantification determination is 5.4 ng/ml and the limit of quantification (LOQ) - 16.19 ng/ml. CONCLUSIONS: The analytical method described in this paper allows for selective determination of 3,3'-dimethylbenzidine in the workplace air in the presence of 1,4-phenylenediamine, benzidine, aniline, 3,3'-dimethoxybenzidine, 2-nitrotoluene, 3,3'-dichlorobenzidine and azobenzene. The method is characterized by good precision and good accuracy, it also meets the criteria for procedures involving the measurement of chemical agents, listed in EN 482:2012.

[Occupational exposure to airborne chemical substances in paintings conservators]. / Narazenie konserwatorów malarstwa na substancje chemiczne wystepujace w powietrzu srodowiska pracy.

BACKGROUND: This paper presents the results of the quantitative study of the airborne chemical substances detected in the conservator's work environment. MATERIAL AND METHODS: The quantitative tests were carried out in 6 museum easel paintings conservation studios. The air test samples were taken at various stages of restoration works, such as cleaning, doubling, impregnation, varnishing, retouching, just to name a few. The chemical substances in the sampled air were measured by the GC-FID (gas chromatography with flame ionization detector) test method. RESULTS: The study results demonstrated that concentrations of airborne substances, e.g., toluene, 1,4-dioxane, turpentine and white spirit in the work environment of paintings conservators exceeded the values allowed by hygiene standards. It was found that exposure levels to the same chemical agents, released during similar activities, varied for different paintings conservation studios. It is likely that this discrepancy resulted from the indoor air exchange system for a given studio (e.g. type of ventilation and its efficiency), the size of the object under maintenance, and also from the methodology and protection used by individual employees. CONCLUSIONS: The levels of organic solvent vapors, present in the workplace air in the course of painting conservation, were found to be well above the occupational exposure limits, thus posing a threat to the worker's health.

New approaches to extraction techniques in determination of 4,4'-methylenebis(2-chloroaniline) in air and water solutions.

Extraction techniques for 4,4'-methylenebis(2-chloroaniline) (MOCA) in air samples and water solutions were developed and compared. Classic techniques for air sampling of MOCA were enhanced by incorporating a derivatization step (3,5-dinitrobenzoyl chloride solution in toluene), thus increasing the limit of detection and limit of quantification. Sampling of MOCA from water solution was performed using novel nanoporous polymeric (polypyrrole and polythiophene) fiber coatings and solid phase microextraction. Samples were analyzed by high-performance liquid chromatography coupled with a UV detector. Using the modified method for air sampling of MOCA, we found that the limit of detection was 7.90 ng m(-3) and the limit of quantification was 23.8 ng m(-3). In contrast, the limit of detection for MOCA in water samples was 11.26 ng mL(-1) (polypyrrole) and 84.62 ng mL(-1) (polythiophene) and the limit of quantification for MOCA was from 33.78 (polypyrrole) and 253.86 ng mL(-1) (polythiophene). Correlation coefficients were 0.9997 for air and 0.8790-0.9852 for water samples, respectively. The techniques presented provide alternative methods for the determination of MOCA in air samples and in water solutions that are more sensitive, quicker and less expensive than previously established procedures.