Chlorophenylmethane. Documentation of suggested occupational exposure limits (OELs)   Anna Kilanowicz,  Andrzej Sapota s. 7 Propano-1,3-sulton. Documentation of suggested occupational exposure limits (OELs)   Jadwiga Szymańska, Barbara Frydrych s. 40 Hydroquinone. Determination in workplace air Anna Jeżewska, Agnieszka Woźnica   s. 58   Fluoride. Determining fluorides in the inhalable and respirable aerosol fraction  in the working environment with  ion chromatography Małgorzata Szewczyńska,  Emilia Pągowska, Małgorzata Pośniak, Krystyna Pyrzyńska   s. 72 Methanol. Chromatographic determination in workplace air Anna Jeżewska,   Agnieszka Woźnica   s. 90 Respirable crystalline silica: quartz i cristobalite.Determinantion in workplace air with infrared spectrometry (FT-IR), direct on filters Aleksandra Maciejewska, Małgorzata Król   s. 104

Chlorophenylmethane.  Documentation of suggested occupational exposure  limits (OELs)
ANNA KILANOWICZ, ANDRZEJ SAPOTA s. 7

Chlorophenylmethane, commonly known as, benzyl chloride is a colorless liquid with a characteristic acrid and pungent odor. It is a synthetic product obtained due to the reaction between gas chloride and toluene in the presence of light acting as a catalyst (radical addition reaction). There is multi-tonne production of benzyl chloride.  In 1995 benzyl chloride was produced in 16 countries. No information about the Polish production of this compound is available.  The 2010 records do not mention workers employed at workstations with benzyl chloride concentrations exceeding the binding maximum admissible concentration (MAC) of 3 mg/m³. Benzyl chloride is used, inter alia, in the manufacture of butylbenzyl phthalate flexibilizers and benzyl-cellulose. This compound is a semi-product used in the production of triphenylmethane dyes and tanning agents. It is also used in the production of benzyl alcohol and its derivatives used in the pharmaceutical, chemical, perfume and food industries. Occupational exposure to benzyl chloride may occur during its production and use. Benzyl chloride is absorbed from the lungs and gastrointestinal tract. In the body, it couples with glutathione, undergoes hydrolytic dechlorination and further oxidation to benzene car-boxylic acid. The produced metabolites are excreted mainly with urine (about 76% of a given dose) during  72 h after exposure. Regarding its acute toxic effect, this compound can be classified into the group of substances toxic after inhalation exposure and harmful after swallowing. It exerts an irritating effect on mucous membranes of the upper respiratory tract,  eyes (risk of serious damage) and skin.  Experiments on guinea pigs have also revealed allergenic effects of the compound. The major effects of occupational exposure to benzyl chloride in high concentrations are manifested by eye irritation demonstrated by burning sensation and profuse lacrimation with concomitant pain. Frequent cases of conjunctivitis have also been noted. In humans, the irritating effect of benzyl chloride on the upper respiratory tract is manifested by the inflammation of mucous membranes. In studies carried out in a group of volunteers, the threshold concentrations inducing irritation of eyes and nose were determined at the level of 41 and 180 mg/m³, respectively.  Benzyl chloride concentrations generating eye irritation not tolerable by volunteers was set at the level of 410 mg/m3. Epidemiological studies performed in workers involved in the production of α-chlorinated toluene and benzoyl chloride revealed excess mortality due to lung cancer in this occupational group. A combined exposure to a number of chemical compounds, including trichlorophenylmethane regarded as a carcino-gen, was involved in this process. Therefore, it is not possible to establish the relationship between exposure to benzyl chloride and increased lung cancer risk in humans despite the fact that the carcinogenic effect of benzyl chloride has been evidenced in animal experimental studies. Inhalation exposure of experimental animals to benzyl chloride in concentrations higher than 800  mg/m³ for at least half an hour increased the secretion of mucus in the respiratory tract. In rats exposed to this compound at a concentration of 3300 mg/m³ for 8h  and at concentrations below 1100 mg/m³ for 7.5h  hemorrhagic foci  in the lungs and pneumothorax, respectively, were observed. In Swiss male mice, the concentration of benzyl chloride responsible for a 50% decrease (RD50) in the respiratory rate is 88 mg/m³. Rats and hamsters exposed to benzyl chloride at a concentration of 539 mg/m³ for 4 weeks developed airway irritation symptoms (nose irritation, sneezing). The adverse effects of benzyl chloride on the respiratory tract were not confirmed by a long-term (27 weeks) inhalation exposure of guinea pigs  at concentrations up to 148 mg/m³.In exposed animals, only slight changes in relative and absolute masses of the internal organs, such as heart, spleen, liver and kidneys have been noted. The results of in vitro and in vivo studies revealed mutagenic and clas-togenic effects. Carcinogenicity of benzyl chlo-ride has been investigated in mice and rats after dermal, subcutaneous and intragastric administration. In dermally exposed  mice, skin cancer  cases  were found, whereas there were no cancer cases in the control group. The rats showed sarcoma in the place of benzyl chloride application. Intragastric administration of the compound in both animal species caused papilla-mas, forestomach cancers in both genders of mice,  thyroid C-cells  cancer in rat females and forestomach cancer in rat males. The experts of the International Agency for Research on Can-cer (IARC) have recognized  evidence for car-cinogenicity of α-chlorinated toluene (includ-ing benzyl chloride) and benzoyl chloride in humans as insufficient.  There is sufficient evidence of  carcinogenicity of benzyl chloride in laboratory animals. It has been generally agreed that combined exposure to α-chlo-rinated toluene and benzoyl chloride is proba-bly carcinogenic to humans (group 2A). In the European Union, benzyl chloride is classified as category 1B –  an agent suspected of being carcinogenic to humans, however, this classification is based on the results of animal studies. There are no literature data on the developmental toxicity of benzyl chloride and its effects on human reproduction, whereas animal studies yielded controversial results on the potential embryotoxic effect of the compound. Irritating effects on the eyes and mucous membranes of the respiratory tract have been recognized as the critical effects of benzyl chloride. The results of two experiments have been adopted as the basis for determining the MAC value for benzyl chloride. In the first experiment, the compound concentration of 88 mg/m³ responsible for a 50% decrease in the respiratory rate (RD50) of Swiss mice was considered. The mean value of the coefficient determining the MAC value on the RD50 value is  1/30, therefore, the calculated MAC value is about 3 mg/m³. In the other experiment, the results of a 104-day investigation of  rats exposed intragastrically   to   doses   of   0,  15  or  30  mg/kg body mass/day/3 days/week/104 days were the basis for  determining  the  MAC  value. A  dose  of 15 mg/kg body mass/day was adopted as the value of no-observed adverse effect level (NOAEL). This value was then used to calculate the equivalent air concentration of the compound for humans. After using coefficients of uncertainty, the concentration of 3 mg/m3 as the MAC value for benzyl chloride has been proposed. As benzyl chloride demonstrates an irritating effect on the skin and respiratory tract, the value of short-term exposure level (STEL)  has also been established. It was proposed to adopt the concentration of 9 mg/m³ as the maximum admissible STEL. The standard has been labeled “Sk” indicating dermal absorption of the substance in view of the DL50 value after dermal administration of a dose of 1000 mg/kg body mass, “I” (substance of irritating effect), “A” (substance of allergenic effect)  and “Carc.1B” as a carcinogenic compound, category 1B.

Propane-1,3-sultone. Documentation of suggested occupational exposure  limits (OELs)    
JADWIGA SZYMAŃSKA,  BARBARA FRYDRYCH s. 40

Propane-1,3-sultone is a white crystalline solid or a colorless liquid. It is very soluble in water and readily soluble in ketones, esters and aromatic hydrocarbons. It is not known to occur naturally; it is obtained by dehydration of γ-hydroxy-propanosulfonic acid. Propane-1,3-sultone is used in the production of dyes, resins, accelerators, fungicides and insecticides. A person involved in the production of the substance or using deter-gents, corrosion inhibitors and other products manufactured from this substance can be occupationally exposed to propane-1,3-sultone.The primary routes of potential human exposure to propane-1,3-sultone are ingestion, inhalation and dermal contact. Propane-1,3-sultone very strongly irritates mucous membranes and skin, and is classified as a substance that can cause changes in the nature of sensitisation. The main symptoms of acute toxicity have been observed in animals ex-posed to apathy, bloody diarrhoea, tremors, haemorrhagic pulmonary oedema, cerebral oedema.  There are no data in the literature on acute or chronic actions of propane-1,3-sultone in humans. In the available literature, there is information that this compound causes cancer in exposed workers. Results of standard experiments indicate that propane-1,3-sultone has mutagenic and genotoxic activity. Propane-1,3-sultone shows a strong car-cinogenic activity in the laboratory animals exposed by various routes. The main tumors observed in animals were related to the brain, mammary gland and cancer at the injection site after subcutaneous administration. For a concentration of 0.0074 mg/m³, the calculated risk of developing cerebral glioma is 10-3. Experts of the International Agency for Research on Cancer (IARC) have classified propane-1,3-sultone to Group 2B, i.e., factors possibly carcinogenic to humans. At its meeting on March 26, 2014, the Interdepartmental Commission for Maximum Admissible Concentrations and Intensities for Agents Harmful to Health in the Working Environment accepted a concentration of 0.007 mg/m³ for the value of  MAC for propane-1,3-sultone at risk 10-3. Notations Carc. Cat. 1B and Skin is recommended.

Hydroquinone  Determination in workplace air  
ANNA JEŻEWSKA, AGNIESZKA WOŹNICA   s. 58

This method describes how to measure hydro-quinone (HQ) in workplace air using HPLC with a diode array detector (DAD). Hydroquinone present in a measured volume of air is collected onto a sulfuric acid-treated silica gel tube. Samples are desorbed with acetonitrile. The determination was carried out in the reverse-phase system (mobile phase: acetonitrile: water) using an Ultra C18 column. The measurement range was 0.1 – 2 mg x m-3 for a 20-L air sample. Limit of detection (LOD): 0.35 µg x m-3 and limit of quantification (LOQ): 1.04 µg x m-3. The developed method of determining hydroquinone has been recorded as an analytical procedure, which is available in the Appendix.

Fluoride Determining fluorides in the inhalable and respirable aerosol fraction in the working environment with ion chromatography  
MAŁGORZATA SZEWCZYŃSKA,  EMILIA PĄGOWSKA, MAŁGORZATA POŚNIAK, KRYSTYNA PYRZYŃSKA s. 72

A new procedure for the determination of fluorides in aerosol fractions in the workplace air has been elaborated. The method is based on a collection of respirable and inhalation fractions of fluorides on methylcellulose filter and polyurethane foam using the IOM – type sampler, extraction of fluorides with deionized water and analysis by ion chromatography. The working range of the method is 0,005 – 5 mg/m³ for 20 l air sample. The procedure of the method is available in the Appendix.

Methanol. Chromatographic determination in workplace air  
ANNA JEŻEWSKA,  AGNIESZKA WOŹNICA s. 90

This article presents a method for analysing methanol with gas chromatography with flame ionization detection (GC-FID). This method is based on adsorbing methanol vapors on active charcoal and desorbing the solvent mixture (carbon disulfide, N,N-dimethylformamide). The obtained solution is analysed with gas chromatography. The working range is 10 to 200 mg/m³ for a 5-L air sample. The developed method of determining methanol has been recorded as an analytical procedure, which is available in the Appendix.

Respirable crystalline silica: quartz i cristobalite. Determinantion in workplace air with infrared  spectrometry (FT-IR), direct on filters  
ALEKSANDRA MACIEJEWSKA, MAŁGORZATA KRÓL   s. 104

A new procedure has been developed for the assay of respirable quartz and cristobalite with infrared spectrometry. Method is based on filtering the sample air through a filter of polyvinyl chloride (PVC), and direct determination of quartz and cristobalite in the dust deposited on the filter. The method enables the determination of the concentration of quartz in the range from 0,01 mg/m³to 0,7 mg/m³ and cristobalite in the range of 0,03 mg/m³ to 0,7 mg/m³ (in both cases, these values relate to air samples volume of 700 l). The developed method of determining quartz and cristobalite has been recorded as an analytical procedure, which is available in the Appendix.