PRINCIPLES AND METHODS OF ASSESSING THE WORKING ENVIRONMENT

NUMBER 1 (87) 2016




  • Acrylamide Determination in workplace air
    Anna Jeżewska, p. 5
  • Triethylenetetramine Determination in workplace air
    Joanna Kowalska, p. 19
  • Phthalic anhydride Determination in workplace air
    Agnieszka Woźnica, p. 33
  • Cisplatin Determination in workplace air with high performance liquid chromatography
    MAŁGORZATA SZEWCZYŃSKA, MAŁGORZATA POŚNIAK, SYLWIA KRZEMIŃSKA , p. 47
  • N,N-Dimethylacetamide Determining in workplace air with GC/FID
    AGATA WZIĄTEK, DOMINIKA ADAMUS, SŁAWOMIR BRZEŹNICKI, p. 65
  • Dibutyl phthalate Determination in workplace air
    Agnieszka Woźnica, p. 79
  • Methotrexate Determination method in workplace air
    SŁAWOMIR BRZEŹNICKI, MARZENA BONCZAROWSKA, KAROLINA MIKOŁAJEWSKA, p. 93
  • 2-Methyl-4,6-dinitrophenol Determination in workplace air
    Anna Jeżewska, p. 109
  • Toluene diisocyanate Determination of toluene diisocyanate isomers with high performance liquid chromatography
    MARZENA BONCZAROWSKA, SŁAWOMIR BRZEŹNICKI, p. 123
  • The activity of the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment in 2015
    JOLANTA SKOWROŃ, p. 139
  • Acrylamide Determination in workplace air
    Anna Jeżewska

    Acrylamide is an odourless, white crystalline solid, highly soluble in polar solvents (e.g., water, ethanol). Acrylamide is a synthetic compound widely used in several industries but par-ticularly in the production of polyacrylamide. International Agency for Research on Cancer (IARC) classifi ed acrylamide as a probably carcinogenic to humans. The aim of this study was to develop a method for determining concentrations of acrylamide in workplace air in the range from 1/10 to 2 MAC values, in accordance with the requirements of Standard No. EN 482.
    The study was performed using an liquid chromatograph (Agilent Technologies series 1200) with a diode array detector (DAD) with an analytical wavelength of 195 nm and 208 nm. The determination was performed in the reversephase system (mobile phase: water: acetonitrile) using an Ultra C18 column (250 × 4.6 mm with dp = 5 μm).The method is based on passing air through a glass midget impinger with water. The aqueous solution was analyzed with HPLC-DAD after sampling.
    The procedure was validated according to Standard No. PN-EN 482. The measurement range was 0.007 ÷ 0.14 mg/m3 for a 120-L air sample. The linearity of the standard curve is characterized by the correlation coeffi cient. Correlation coeffi cient is r = 0.9999. The limit of detection (LOD) is 0.045 ng/ml (wavelength: 208 nm) and 0.026 ng/ml (wavelength: 195 nm), the relative total uncertainty of the method is 11,18%.
    A simple and cheap method was developed for determining concentrations of acrylamide in workplace air. The method can be used for determining concentrations of acrylamide in work-place air to assess occupational exposure to acrylamide in the working environment. The developed method of determining acrylamide has been recorded as an analytical procedure (see appendix)



    Triethylenetetramine Determination in workplace air
    Joanna Kowalska

    Triethylenetetramine (TETA) is a yellowish, slightly oily liquid very soluble in water. Triethylenetetramine is frequently used as a curing agents for epoxy resins, intermediary for auxiliary agents used in the paper industry, the
    textile industry and in glues or intermediate for asphalt emulsifi ers. The aim of this study was to develop and validate a sensitive method for determining concentrationsof TETA 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 method was based on passing the air which
    contains TETA through impringer fi lled with hydrochloric acid solution. TETA was determined indirectly by determining the product of its reaction with 1-naphtyhyl isothiocyanate (NIT). Studies were performed using high-performance liquid chromatography (HPLC) technique. An Agilent Technologies (Germany) chromatograph,
    series 1200, with a diode-array detector (DAD) was used in the experiment. An Ultra C18 column (250 × 4.6 mm, dp = 5 mm), with a precolumn (10 × 4.0 mm) was applied. The method is linear (r = 0.999) within the working range 0.6–12 μg/ml, which is equivalent to air concentrations from 0.1 to 2.0 mg/m3 for a 60-L air sample.
    The analytical method described in this paper makes it possible to selectively determine TETA in workplace air in the presence of other amines. The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. PN-EN 482. This method can be used for assessing occupational exposure to TETA and associated risk to workers’ health. The developed method of determining TETA has been recorded as an analytical procedure (see appendix).



    Phthalic anhydride Determination in workplace air
    Agnieszka Woźnica

    Phthalic anhydride is a crystalline solid. Phthalic anhydride is an important intermediate in the chemical industry. It is harmful, irritating and sensitizing.
    The aim of this study was to develop a new method for determining concentrations of phthal-ic anhydride in workplace air in the range from 1/10 to 2 MAC values, in accordance with the requirements of Standard No. EN 482. The study was performed using an liquid chromatograph (Agilent Technologies series 1200) with a diode array detector (DAD). The determination was performed in the reverse-phase system (mobile phase: acetonitrile: solution of phosphoric acid) using an Ultra C18 column (250 × 4.6 mm with dp = 5 μm) and with precolumn (10 × 4 mm). The method is based on passing air through a 3,4-dimethoxybenzylamine-coated glass fiber filter. Samples were extracted with acetonitrile/ammonia and analyzed with HPLC-DAD. The procedure was validated according to Standard No. EN 482. The measuring range was 0,1 ÷ 2 mg/m3, the limit of detection (LOD) was 9.91 ng/ml (0.000137 mg/m3 a 720-L air sample), the limit of quantification (LOQ) was 29.74 ng/ml (0.000413 mg/m3 a 720-L air sample), the overall accuracy of the method was 5.31% and the relative total uncertainty of the method was 11.63%. The analytical method described in this paper enables selective determination of phthalic an-hydride in workplace air in the presence of other compounds at concentrations from 0.1 mg/m³ (1/10 MAC value). The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. EN 482.
    The developed method of determining phthalic anhydride has been recorded as an analytical procedure (see Appendix).



    Cisplatin Determination in workplace air with high performance liquid chromatography
    MAŁGORZATA SZEWCZYŃSKA, MAŁGORZATA POŚNIAK, SYLWIA KRZEMIŃSKA

    Cytostatic drugs are a specific group of chemotherapy drugs whose toxicity for patients undergoing treatment is reasonably well understood. However, there is no data on the harmful effects of the impacts of these chemicals on exposed persons during preparation and application of anticancer drugs.
    The aim of this study was to develop a method for determining an inhalable aerosol fraction of cisplatin in workplace air at the level of 0.2 mg/m3, which is 1/10 of allowable concentration level of 2 ug/m3 proposed by the ACGIH.
    This method is based on sampling of inhalable fraction of cisplatin from the air on the filter glass fiber. After extracting with distilled water, derivative with sodium diethyldithiocarbamate (NaDDTC) was analyzed with high performance liquid chromatography with spectrophotometric detection. Analysis was performed on reverse phase (mobile phase – methanol: water) using an analytical column with modified silica gel column (18).
    On the basis of performed studies, measuring range of 0.03–10 mg/ml was determined which gave 0.18–62.5 ug /m3 when downloading 960 L of air and 0.25–83.3 ug/m3 when downloading 720 L of air. The resulting calibration curve was linear as demonstrated by the regression coefficient of 0.996. The overall precision of the study was 6.25% and expanded uncertainty of the method was 27.71.
    The results and validation parameters confirm the usefulness of newly developed method for determining cisplatin to determine concentrations of this substance in workplace air to evaluate occupational exposure in a wide concentration range of 0.03–10 ug/ml. The developed method of determining cisplatin in workplace air has been recorded as an analytical procedure for measuring range of 0.03–0.5 mg/ml which corresponds to 0.1–1.6 NDS value when downloading the 960 L of air and from 0.125–2 when downloading 720 L of air.



    N,N-Dimethylacetamide Determining in workplace air with GC/FID
    AGATA WZIĄTEK, DOMINIKA ADAMUS, SŁAWOMIR BRZEŹNICKI

    AGATA WZIĄTEK, DOMINIKA ADAMUS, SŁAWOMIR BRZEŹNICKI s.61 N,N-Dimethylacetamide (DMAC) is a colorless liquid with a characteristic amine odour.
    N,N-Dimethylacetamide mixes with polar and non-polar organic solvents and water. This substance is used in plastic and fibers industries as a solvent. N,N-Dimethylacetamide vapours and aerosols are absorbed through inhalation, gastrointestinal tract and skin. Inhalation of N,N-dimethylacetamide can cause cough or breathlessness. Vapours and solutions of N,N-dimethylacetamide can cause irritation and burns of skin. The aim of this study was to develop sensitive method for determining N,N-dimethylacetamide in workplace air in the range from 1/10 to 2 MAC value, in accordance with the requirements of Standard No. PN-EN 482. A 6890 Hewlett Packard gas chromatography equipped with a flame ionization detector (FID) and analytical column ZB-WAX 60 m × 0.32 mm × 0.5 µm was used.  The method is based on the adsorption of N,N-dimethylacetamide on silica gel, desorption with methanol and gas chromatographic analysis of the resulting solution. The measurement range was 1 ÷ 70 mg/m3 for 20-L air sample. Limit of quantification (LOQ) was 3.14 µg/ml. The method described as recipe of analysis (appendix) enables selective determination of N,N-dimethylacetamide. This method is precise, accurate and it meets the criteria listed in Standard No. PN-EN 482.



    Dibutyl phthalate Determination in workplace air
    Agnieszka Woźnica

    Dibutyl phthalate (DBP) is a colorless liquid with an ester-like odour. It is used in industry as a solvent for a variety of resins, plastics and elastomers, and as an adhesive for joining plastic parts. Occupational exposure to DBP can occur through inhalation or ingestion. The aim of this study was to validate method determining concentrations of DBP 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-INNOWAX (60 m × 0.25 mm, 0.15 µm).
    This method is based on sorption of dibutyl phthalate vapours on glass microfiber filter, desorption with ethanol and analysis with GC-FID. The average desorption efficiency of DBP from filter was 96%. Application of HP-INNOWAX column allows selective determination of DBP in a presence of other solvents. The measurement range was 0.5 ÷ 10 mg/m3 for a 720-L air sample. The limit of detection was 24.72 ng/ml
    and limit of quantification was 74.17 ng/ml.
    The analytical method described in this paper makes it possible to determine DBP in workplace air in the presence of other solvents at concentrations from 0.5 mg/m3 (1/10 MAC value). The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standrad No. EN 482. The method can be used for assessing occupational exposure to DBP and associated risk to workers’ health. The developed method of determining DBP has been recorded as an analytical procedure (see appendix)



    Methotrexate Determination method in workplace air
    SŁAWOMIR BRZEŹNICKI, MARZENA BONCZAROWSKA, KAROLINA MIKOŁAJEWSKA

    Methotrexate (MTX) is solid at room temperature. It is a yellowish-orange, crystalline powder with a slight odor characteristic of aromatic compounds. Methotrexate is an antineoplastic drug commonly used in the treatment of malignant diseases. Occupational exposure to methotrexate may occur during its production, preparation and application of methotrexate on oncology wards.  In terms of exposure by inhalation, methotrexate can irritate the eyes and mucous membranes of the nose. Other adverse effects of methotrexate include chill and fever, sweating, arthralgia, myalgia, decreased resistance to infection, septicemia, upper respiratory infection, osteoporosis, hypogammaglobulinemia, cystitis, dysuria, vaginal discharge, diabetes and death.  Exposure to methotrexate may also cause  myelosuppression, hepatotoxicity and impaired fertility. Due to the growing  use of methotrexate, number of persons occupationally  exposed  to its harmful effect may reach in Poland several thousand.
    The aim of this study was to develop and validate a sensitive method for determining methotrexate 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 tandem mass detection (HPLC-MS/MS). All chromatographic analyses were performed with Supelcosil LC 18 150 × 3 mm
    analytical column, which was eluted with amixture of methanol and water with 0.1% of formic acid.
    This method is based on the collection of methotrexate on a glass fiber filter, extraction with mixture of methanol and water with
    formic acid (0.1%), and chromatographic analysis of the resulting solution with HPLC-MS/MS technique. The average extraction efficiency of methotrexate from filters was 90%. This method
    is linear (r = 0.999) within the investigated working range of 0.00007–0.0028 mg/m3 for
    a 720-L air sample. Limit of detection (LOD) and limit of quantification (LOQ) were 0.0013 and 0.0044 μg/ml, respectively.
    The analytical method described in this paper, thanks to the use of HPLC MS/MS technique, makes it possible to selectively determine methotrexate in workplace air in the presence of other compounds at concentrations from 0.00007 mg/m3. This method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. EN 482: 2006.
    This method can be used for assessing occupational exposure to methotrexate and associated risk to workers’ health. The developed method of determining methotrexate has been recorded as an analytical procedure (see appendix).



    2-Methyl-4,6-dinitrophenol Determination in workplace air
    Anna Jeżewska

    2-Methyl-4,6-dinitrophenol (DNOC) is a yellow crystalline solid. It has insecticidal, fungicidal and herbicidal properties. Nowadays, DNOC is used as a polymerization inhibitor and as an intermediate in the chemical industry. It is extremely toxic to humans.
    The aim of this study was to develop a new method for determining DNOC concentrations in workplace air in the range from 1/10 to 2 MAC values in accordance with the requirements of Standard No. EN 482.
    The study was performed using a liquid chromatograph (Agilent Technologies series 1200) with a diode array detector (DAD). The determination was performed in the reverse-phase system (mobile phase: methanol: solution of acetic acid) using an Ultra C18 column (250 × 4.6 mm with dp = 5 μm).
    The method was based on passing air through a silica gel tube. Samples were desorbed with methanol and analyzed with HPLC-DAD. The procedure was validated according to Standard No. EN 482. The measuring range was 0.005 ÷ 0,1 mg/m3, the limit of detection (LOD) was 1.55 ng/ml, the limit of quantification (LOQ) was 4.66 ng/ml, the overall accuracy of the method was 5.24% and the relative total uncertainty of the method was 11.5%.
    The analytical method described in this paper makes it possible to selectively determine DNOC in workplace air in the presence of phenols and cresols at concentrations from 0.005 mg/m³ (1/10 MAC value). The method is precise, accurate and it meets the criteria for proce-dures for measuring chemical agents listed in Standard No. EN 482.
    The developed method of determining DNOC has been recorded as an analytical procedure (see appendix).



    Toluene diisocyanate Determination of toluene diisocyanate isomers with high performance liquid chromatography
    MARZENA BONCZAROWSKA, SŁAWOMIR BRZEŹNICKI

    Toluene-2,4 and 2,6-diisocyanate (2,4-TDI; 2,6-TDI) are colorless to pale yellow liquids with a sharp acrid odor. 2,4-TDI and 2,6-TDI are two commonly used isomers of toluenediisocyanate (TDI). TDI mixture is most often used in manufacturing polyurethane plastics and widely used in different kinds of industry like furniture, car, chemical, shipbuilding and construction industry. Occupational exposure to TDI vapors can cause severe irritant effects on mucous membranes, the respiratory tract, the eyes, and an acute attack of an asthma-like syndrome.
    The aim of this study was to develop and validate a sensitive method for determining 2,4 and 2,6-TDI concentrations in workplace air in the range from 1/40 to 2 MAC values, in accordance with the requirements of Standard No. PN-EN 482.
    The study was performed using a liquid chromatograph equipped with spectrofluorimetric detector (FLD). All chromatographic analysis were performed with Supelcosil LC-RP-Amide 150 × 3 mm analytical column, which was eluted with a mixture of acetonitrile:dimethylsulfoxide (9: 1).
    The method is based on the collection of TDI on glass fiber filter coated with 1 (2-pyridyl) piperazine solution, extraction of formed derivatives with a mixture of acetonitrile:dimethylsulfoxide and chromatographic determination of resulted solu-tion with HPLC technique. The average extraction efficiency of TDI from filters was 103% (2,4-TDI and 108% (2,6-TDI). The method is linear (r = 0.999) within the investigated working range 0.028–2.8 μg/ml, which is equivalent to air concentrations from 0.00014 to 0.014 mg/m3 for a 200-L air sample. The limit of quantification (LOQ) of 2,4-TDI and 2,6-TDI was 0.0006 and 0.0003 μg/ml, respectively.
    The analytical method described in the form of Analytical Procedure (see appendix), makes it possible to selectively determine 2,4-TDI and 2,6-TDI in workplace air in the presence of other compounds. 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 2,4-TDI and 2,6-TDI and associated risk to workers’ health.



    The activity of the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment in 2015
    JOLANTA SKOWROŃ

    In 2015, the Commission met at four sessions, in which 10 documentations for recommended exposure limits of chemical substances were discussed. Moreover, the Commission discussed: draft text of the MAI (NDN) for electromagnetic fields in the context of the implementation of the Directive 2013/35/EU of the European Parliament and of the Council of 26 June 2013 on the minimum health and safety requirements regarding the exposure of workers to the risks arising from physical agents (electromagnetic fields) (20th individual Directive within the meaning of Article 16(1) of Directive 89/391/EEC) and repealing Directive 2004/40/EC (OJ L 179, 29.6.2013, p. 1) and a proposal to amend provisions regarding the dust listed in section B of Annex 1 to the Regulation of the Minister of Labour and Social Policy of 6 June 2014.
    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: 3,3’-dimethoxybenzidine (CAS: 119-90-4, Carc. 1B), ethyl carbamate (CAS: 51-79-6, Carc. 1B) changing MAC values for 8 chemicals: chromium(VI) compounds (as Cr(VI), 1,4-dichlorobenzene (CAS: 106-46-7), 2-ethylhexane-1-ol (CAS: 104-76-7), diethyl phthalate (CAS: 84-66-2), n-butyl acetate (CAS: 123-86-4), sec-butyl acetate (CAS: 105-46-4), isobutyl acetate (CAS: 110-19-0) and lithium hydrogen (CAS: 7580-67-8) introduction in Annex 1 in Part A of the list „Chemicals” the dust agreed at the 80th meeting of the Interdepartmental Commission for MAC and MAI on 23 September 2015. For wood dust, the Commission adopted a simplified recording, leaving only dust oak and beech, whose carcinogenic effects are proven epidemiologically, until new research findings in this area are published and a new document is developed: (a) the wood dusts –  the inhalable fraction NDS (TWA): 4 mg/m3; (b) wood dusts of beech and oak – the inhalable fraction NDS (TWA): 2 mg/m3 removal of „Comments” currently listed in Annex 1 for the list in Part B.
    Occupational Exposure Limits for 1,2-dimethoxyethane (NDS (TWA): 10 mg/m3 NDSCh (STEL): not determined) and propane-1,2-diol (propylene glycol - inhalable fraction and vapours; NDS (TWA): 100 mg/m3 NDSCh (STEL): not determined ) proposed by the Group of Experts of Chemical Agents were adopted by the Interdepartmental Commission for MACs and MAIs at 81st meeting on 12 November 2015, but will be applied to the regulation of the minister responsible for labour affairs after developing methods for the determination of their concentrations in the working environment in 2016. Four issues of the Principles and Methods of Assessing the Working Environment were published in 2015. The following were published: 11 documentation of occupational exposure limit, 8 methods of determining chemical concentrations in the working environment, 5 articles, procedure for measuring ultrasonic noise, report on the activities of the Interdepartmental Commission for MAC and MAI in 2014 and indexes of documentations, methods and articles published in 2000–2015. Three sessions of the Commission are planned for 2016. MAC values for 13 chemicals substances will be discussed at those meetings. The Commission and the Group of Experts will continue working on adapting the Polish list of occupational exposure limit values to the draft Directive setting fourth list of indicative occupational exposure limit values, on proposals for binding values and on work being done at SCOEL.



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