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Number 4 (54) 2007

Carcinogenic and mutagenic agents in Polish and UE legal regulations
Jolanta Skowroń


The article presents Polish regulations for carcinogenic and mutagenic agents, the evaluation of carcinogenic/ mutagenic risks and prevention of workers’ health occupationally exposed to them. Information about occu-pational cancer, data collected on the exposure to carcinogenic or mutagenic hydrocarbons or substances derived from coal and statistical data is also presented. Moreover, some information about UE regulations in this area is given.

3-Amino-1,2,4-triazole – determination method
Anna Jeżewska


Determination of a worker’s exposure to airborne 3-amino-1,2,4-triazole is carried out by use of a paper filters (37 mm). Air samples are collected at a maximum flow rate of 180 litres/hour until a maximum collection volu-me of 360 litres is reached. The filters are analyzed by extracting with 1% methanol in water and analyzed by high performance liquid chromatography (HPLC) using an ultraviolet (UV) detector. A 15-cm × 4.6-mm i.d. Ultra 5 micron C18 column was used in this evaluation.
The determination limit of the method is 0.015 mg/m³.

Cyanamide – determination method
Anna Jeżewska


The method is based on the chemisorption of cyanamide on XAD-2 resin coated with 1-naphthylisothiocyanate. The cyanamide derivative formed was subsequently desorbed with acetonitrile and analysed by HPLC with UV detection.
The determination limit of the method is 0.09 mg/m³.

Allyl propyl disulfide – determination method
Anna Jeżewska


The method is based on the adsorption of allyl propyl disulfide vapours on active charcoal and desorption with 1 mL of solvent mixture (carbon disulfide, acetone). The obtained solution is analyzed by gas chromatographic (GC-FID).
The determination limit of the method is 1.2 mg/m³.

Hydrazine – determination method
Elżbieta Dobrzyńska


The method is based on the chemisorption of hydrazine on the glass fiber filter treated with sulphuric acid, extraction of hydrazine sulphate with the buffered EDTA disodium solution (pH 3.5), derivatization with benzaldehyde solution and determination of the obtained benzalazine by HPLC/UV.
The determination limit of the method is 0.005 mg/m³.

Metals and metalloids and theirs compounds – complemented determination metod
Ewa Gawęda


The method is based on stopping of selected metals and metalloids and theirs compounds on membrane filter, mineralization the sample with concentrated nitric acid or with nictric acid and hydrochloric acid, and prepara-tion solution to analysis in diluted nitric acid.
Antymony, arsenic, cadmium, copper, lead, nickel, selenium, silver, vanadium In the solution are determined by atomic absorption spektrometry with graphite tube. Aluminium, calcium chromium, iron, manganese, magnesium and zinc are determinated by flame atomic spectrophotometry.
The detection limits of determinated substances for presented method are: aluminium – 0.25 mg/m³ (total dust) and 0.12 mg/m³ (respirabile dust), arsnic – 0.0008 mg/m³, chromium – 0.05 mg/m³, cadmium – 0.0006 mg/m³, manganese – 0.030 mg/m³, copper – 0.008 mg/m³ (fumes) and 0.08 mg/m3 (dusts), nickel – 0.02 mg/m3, vanadium pentaoxide – 0.004 mg/m³, lead – 0.004 mg/m³, selenium – 0.008 mg/m3, silver – 0.004 mg/m³, zinc oxide – 0.4 mg/m³, magnesium oxide – 0.4 mg/m3 (fumes) and 1.0 mg/m³ (dusts), calcium oxide – 0.14 mg/m³, iron – 0.4 mg/m³.

4-Methyl-3-penten-2-one  – determination method
Anna Jeżewska  


Determination of a worker’s exposure to airborne 4-methyl-3-penten-2-one is made using ORBO-33 tube (100/50 mg sections). Samples are collected at a maximum flow rate of 12 litres/hour until a maximum collection  volume of 12 litres is reached. After sampling the ORBO-33 tube is desorbed in carbon disulfide/propan-2-ol (98:2). Analysis is conducted by gas chromatography using a flame ionisation detector (GC-FID).
The determination limit of the method is 2 mg/m³.

Morpholine – determination method
Joanna Kowalska


The determination method is based on the adsorption of morpholine vapours on sampling tubes containing 80/40 mg sections of XAD-2 resin coated with 1-naphtylisothiocyanate (NIT), desorption with 2 ml of ace-tonitryle and high performance liquid chromatographic (HPLC/UV) analysis of the resulting solution.
The determination limit of the method is 3.6 mg/m³.

o-Toluidine – determination method
Anna Jeżewska


The method is based on the adsorption of o-toluidine vapours on ORBO™ 655 and desorption with 1 ml of toluene. The obtained solution is analyzed by gas chromatographic (GC-FID).
The determination limit of the method is 0.3 mg/m³.

Ethanolamine. Documentation
Danuta Ligocka


Ethanolamine (MEA) is viscous liquid, strongly alkaline and can cause severe irritation. Because of its low va-pour pressure, ethanolamine should pose very little inhalation hazard at ordinary temperature. According to the study of Weeks et al (1960), NOAEL of 12.5 mg/m³ was established for irritating effect. The recommended 8-hour TWA was 3 mg/m³ and a STEL (15 mins) of 9 mg/m³ were recommended to prevent exposure to irritating levels. There are no data supporting BEI value. A „skin” notation and „I” – irritation notations were rec-ommended.

Antimony. Documentation
Marek Jakubowski

Antimony is a  silvery white brittle metal, most commonly found  in sulfides and sulfo salts. The predominant one is stibnite (Sb2S3). Antimony is a common constituent of metal alloys. The most important use of antimony metal  is as hardener  in lead storage batteries. Antimony trioxide is used in fire retardants  formulations for plastics, rubbers, textiles, paper, and paints; as an additive in glass and ceramic products; and as a catalyst in the chemical industry.
The intraperitoneal  LD50 for rats  was reported to be 100 mg/kg for the metal,  1000 mg/kg for the trisulfide, and 3250 mg/kg for the trioxide. Existing industrial toxicologic information indicates that antimony and its com-pounds irritate the upper respiratory tract. Several authors have remarked  on  pneumoconiosis-like X-ray pic-tures obtained from workers  with long-term occupational exposure to antimony. On examination  of antimony process workers  significant correlation between estimated  lung antimony  and period of employment was found.
Fisher 344 rats were exposed by inhalation to Sb203 dust of high purity at exposure levels of 0, 0.06, 0.51 and 4.5 mg/m³ for 12 months followed by a 12-month observation period. There were no Sb2O3 effects on clinical chemistry or hematology and only slight microscopic changes in the lungs.  There were no neoplasms among any of the groups and they were within the historical range for controls. The concentration of 4.5 Sb2O3 mg/m³  (3.92 mg Sb/m3) was adopted as the NOAEL value.
Using the total coefficient of uncertainty (equal to 8)  the calculated MAC value  for Sb is 0.5 mg/m³. There are no grounds for accepting STEL or BEI values for antimony.

Xylene (all isomers). Documentation
Danuta Ligocka


Xylene occurs in three isomeric forms: ortho, meta, and para. Commercial xylene is a mixture of the three iso-mers with m-xylene usually the principal component. There is no difference in the toxicity of the individual isomers. Liquid xylene is absorbed through intact human skin. However inhalation is the main way of occupa-tional exposure to xylene. The available data do not provide evidence for the carcinogenicity of xylenes in hu-mans. In experiment on mice RD50 for xylenes was about 10 000 mg/m³. In human volunteers exposed 4 h to 435 mg/m³ xylene impairment of performance on tests of memory and reaction time was observed (LOAEL). According to the above, the MAC-STEL of 100 mg/m³ and the skin (Sk) and irritation (I) notation is recommended. The measurement of total methylhippuric acids in urine collected at the end of shift is recommended. The BEI value is 1.4 g/g creatinine or 1 l of urine of density 1.024g/cm³.

Morpholine. Documentation
Edyta Reszka, Wojciech Wąsowicz


Morpholine is a colourless, oily, hygroscopic, volatile liquid with a characteristic amine odor. Morpholine has many derivatives including the production of insecticides and herbicides, in rubber industry, component ofwax-es and polishec etc., as a boiler chemical and as corrosion inhibitor. It is also used asa fungicide in fruit waxes.
Morpholine is well absorbed after orally and skin administration and inhalation. This substance can strongly irritates skin and mucous membranes of the eye and respiratory and digestive tract. In the investigated rodents, injected or inhaled morpholine was found at highest level in the kidney or in muscle, and this substance was excreted unchanged in urine. There is strong evidence tha morpholine can be nitrosated to the carcinogenic N-ni-trosomorpholine (NMOR) by rection outside or within the human body. Short-term animal studies shown hae-morrhage and diarrhoea in the digestive tract after morpholine oral administration and irritation, haemorrhage in respiratory tract after inhalation. Long-term animal studies have shown liver, kidney, and stomach nectrosis. There are no data on reproductive toxicity, embryotoxicity and teratogenicity.
No data are available on short- and long-term morpholine exposure in humans.
The recommend maximum exposure limit TLV (MAC) value were sustained at 36 mg/m³ and short-term expo-sure limit (STEL) at 72 mg/m3, on the basis of the Sprague-Dawley rats long-term inhalation study. The The Expert Goup also suggested additional notations: „Sk” (substance absorbed through the skin), „C” (corrosive subsatnce). Monitoring of ambient nitrous oxides is highly recommended, because of the potential for nitrosation of morpholine to form NMOR under some workplace conditions.

3a,4,7,7a-tetrahydro-4,7-metanoinden. Documentation
Krystyna Sitarek


3a,4,7,7a-Tetrahydro-4,7-metanoinden (DCPD) is a chemical intermediate used in the manufacturing of a wide range of organic chemicals. The odour of DCPD has been reported to be detectable at concentrations as low as 0.016 mg/m3. The LD50 value for DCPD is 353 mg/kg for rats orally exposed. Distribution studies using 14C-DCPD in mice, rats and dogs have shown that up to 85% of orally administered radioactivity appears in the urine or faeces within 24 hours. DCPD does not induce gene mutation in bacterial or yeast assays. Studies in animals have indicated there is no selective toxicity to the embryo or foetus or any teratogenic potential. No long-term or carcinogenicity studies have been reported. Repeated exposure of rats to DCPD vapour at concentrations of 106-399 mg/m³ produced kidney lesions in male rats and relative liver and kidney weights increased at high concentrations. The no observed adverse effect level (NOAEL) was 106 mg/m3. Given these data, the MAC value was calculated at 10 mg/m³.

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