4(86) /2015

Hazards of hand skin of furniture industry workers
Joanna Kurpiewska   s. 5
Contact skin diseases, which occur among the workers in the furniture industry, are most often caused by harmful chemical and mechanical factors at the workplace.
To collect data to suggest a suitable prevention of contact dermatoses, 50 employees at different workplaces in furniture industry were surveyed.
Among the respondents, the largest group were carpenters (46%) and upholsterers (10%). The most frequently performed activities include cutting boards, veneering, grinding, painting, staining, gluing, assembling and upholstering.
Exposure of hands and applied individual and skin protection were recognized. Employees involved in painting or staining elements, making up components and preparing and replenishing adhesives were exposed to chemicals. Symptoms
of cutaneous lesions such as roughness, dryness, cracking skin, thickening of skin, fl aking, redness, rash, were observed. In 42% of cases, these changes are permanent. Personal protective equipment is used by 74.5% of the respondents.
Employees do not use skin protection measures and about 80.4% of the respondents declared that they did not know this type of preparations.
In some companies care creams are incorrectly offered as protective preparations
Three-stage program prevents hand dermatoses by using appropriately selected skin protecting measures, mild detergents for washing hands and skin regenerating preparations after work.

1,4-Dichlorobenzene. Documentation of proposed values of occupational exposure limits (OELs)
Katarzyna Konieczko, Sławomir Czerczak s. 13
1,4-Dichlorobenzene is a solid crystalline substance, colorless or white, with camphorlike odour. It sublimes at room temperature. It is used as insecticide (mainly in the mothballs), as a fumigant and as a component of indoor deodorants and air-fresheners used in dumpsters. 1,4-Dichlorobenzene is used in the synthesis of polyphenylene sulfi de, 1,2,4-trichlorobenzene, 2,5-dichloroaniline and dyes. It is also used in pharmaceutical industry.
1,4-Dichlorobenzene is absorbed into the body mainly by inhalation. It has low acute toxicity. Chronic effects in humans include irritation to eyes
and mucous membranes of the upper respiratory tract, impaired lung function parameters, impaired kidney and liver function.
In prolonged and chronic animal studies changes were observed mainly in a liver. In male rats changes were also observed in kidneys. After chronic exposure to 1,4-dichlorobenzene, changes due to irritation were observed in epithelium of the nasal cavity.
1,4-Dichlorobenzene has no signifi cant genotoxic potential. Most in vitro and in vivo mutagenicity studies were negative.
1,4-Dichlorobenzene was carcinogenic to animals.
Liver tumors were observed in the male and female mice after oral administration of 1,4-dichlorobenzene and after inhalation. The mechanism of liver tumor in mice after administration of 1,4-dichlorobenzene by ingestion or inhalation is not exactly clear but studies indicate the threshold nature of this effect. Adenocarcinomas of the renal tubule were observed in male rats after oral administration of 1,4-dichlorobenzene. Specifi c genotoxic mechanism,
irrelevant for humans, is responsible for kidney tumors in male rats exposed to 1,4-dichlorobenzene.
1,4-Dichlorobenzene is not embryotoxic, teratogenic or fetotoxic. There was no impact on reproductive functions of animals in the two-generation study in
rats exposed to 1,4-dichlorobenzene by ingestion or by inhalation.
A critical effect for exposure to 1,4-dichlorobenzene is hepatotoxic activity. Oral administration of 1,4-dichlorobenzene (in capsules) in dogs for 52
weeks caused changes in liver and NOAEL value obtained from this study was 10 mg/kg/day.
On the basis of this NOAEL value, after taking into account uncertainty factors, the MAC (TWA) value of 12 mg/m³ and STEL of 36 mg/m³ (3 times NDS)
were recommended.
There is no quantitative experimental data on skin absorption of 1,4-dichlorobenzene, but on the basis of modeling data the “Skin” notation was added because absorption of substances through the skin can be as important as inhalation. It is recommended to label the substance with symbol “I” (irritant).

2-Ethylhexan-1-ol. Documentation of proposed values of occupational exposure limits (OELs)
Katarzyna Konieczko, Sławomir Czerczak s. 61
2-Ethylhexan-1-ol is a colorless liquid with sweet taste and light, fl oral, rose-like odour. This aliphatic alcohol is an important intermediate
for synthesis of low-volatile esters, e.g., di(2-ethylhexyl) phthalate (DEHP), used as plasticizers mainly as PVC softeners. 2-Ethylhexan-1-ol is
also used as a solvent, an additive to diesel fuels and lubricating oils, in laundries for dry cleaning, in the production of nitrocellulose, paper
and rubber, in the textile and food industry.
2-Ethylhexan-1-ol is emitted to the environment from plastics, mainly from building materials and floor coverings, but also from other equipment,
e.g., computer cases. This substance is considered as one of socalled sick building syndrome (SBS)causes.
In the working environment, 2-ethylhexan-1-ol is absorbed into the body mainly by inhalation. Animal studies indicate also the possibility of dermal absorption but to a much less extent than by inhalation. There are no reports on acute human poisoning due to low acute toxicity of this substance.
According to results of human acute studies on chemosensory effects after inhalation exposure, sensory irritation occurs at much lower concentrations than it was considered on the basis of animal studies. “Moderate” (LMS scale)
irritation of eyes and nose was detected in human volunteers after 4-h inhalation of 2-ethylhexanol at the constant concentration of 57.6 mg/m³.
Exposure to sinusoidally variable concentrations over 4 h (mean concentration was also 57.6 mg/m³) caused the increase of concentration of the
substance P, which is a neuropeptide indicating nasal chemosensory irritation, in nasal lavage, decrease of nasal fl ow and increase of eye blinks.
All of the mentioned parameters indicate the irritation properties of 2-ethylhexan-1-ol. Clinical effects of acute exposure of animals are
apathy, incoordination, ataxia, depression of central nervous system and breathing difficulties. In mice, decrease of respiratory rate of 50%
was observed at concentration 238 mg/m³ of 2-ethylhexanol (RD50). Critical organs in subacute or long-term exposure are liver and kidney.
2-Ethylhexan-1-ol is rapidly eliminated from the body as metabolites, mainly in the urine. There were no carcinogenicity, mutagenicity and
reprotoxicity observed in animals. The result of inhalation experiment with human volunteers showed that the critical effect of 2-ethylhexanol is irritation. The Scientific Committee on Occupational Exposure Limits
(SCOEL) proposed much smaller occupational exposure limit (OEL) than occupational exposure limits in particular countries. SCOEL established
concentration of 8.1 mg/m³ (1.5 ppm) for NOAEC and 5.42 mg/m3 (1 ppm) for OEL.
On the based of 4-h inhalation experiment on human volunteers the 2-ethylhexanol
concentration of 57.6 mg/m³ was established as LOAEC. On the basis of this LOAEC value, after taking into account uncertainty factors, the
MAC (TWA) value of 4.8 mg/m³ was established. The value of 5.4 mg/m³proposed by SCOEL was recommended as MAC (TWA). To protect workers from peak exposure to 2-ethylhexane-1-ol, STEL value of 10.8 mg/m³ (2 x MAC) was recommended. Due to irritation properties of 2-ethyhexan-1-ol it was recommended to label the substance with symbol “I”.

Diethyl phthalate - inhalable fraction. Documentation of proposed values of occupational exposure limits (OELs)
Jadwiga Szymańska, Barbara Frydrych s. 15
Diethyl phthalate (DEP) is a colorless, oily liquid. It is obtained in the reaction of phthalic acid with ethanol in the presence of concentrated sulfuric
acid. Diethyl phthalate is used as a plasticizer in plastics, a solvent of cellulose acetate and nitrocellulose and a base of perfume in cosmetics and detergents. It is also used as a lubricant and a moisturizer in the production of packaging for food and pharmaceuticals. The exposure to diethyl phthalate occurs during its production and use. The exposure of the general population is associated with contact with products containing this compound (cosmetics,
toys) and the consumption of contaminated food or water.
According to GUS, in 2007, 2010 and 2011 there were no cases of exceedances of the existing norms for diethyl phthalate in workplace air (MACTWA 5 mg/m³, STEL 15 mg/m³). Available data from measurements taken in 5 provinces
reported two people who in 2010 were exposed to diethyl phthalate concentrations in the range of 0.1 - 0.5 of the MAC-TWA (NDS). According to
the Classifi cation of Activities (PKD) of the Polish Central Statistical Offi ce (GUS) these persons were employed in education sector (section 85).
The exposure of workers to diethyl phthalate at a concentration above 0.1 TWA values in these 5 provinces was not noticed in 2011. Skin irritation, sensitization, phototoxicity and photosensitization were not observed after
application of diethyl phthalate to the human.
According to results of epidemiological studies evaluating toxicity of various phthalates on environmental exposure to men, the effect of these compounds on a reduced number and motility of spermatozoa was pointed out. Diethyl phthalate is not classifi ed as harmful substance. After intragastric administration of
this compound to rats and mice, LD50 values were very high (5.600 ÷ 31.000 mg/kg). After dermal exposure, LD50 value in guinea pigs and rabbits
has been set at 22,400 mg/kg.
Intragastric administration of diethyl phthalate to rats at the doses 1000 - 1600 mg/kg/day and to mice at doses 3250 - 3750 mg/kg/day in shortterm
experiment (4 - 14-day) did not cause any effects. The administration of diethyl phthalate to rats at the dose 2000 mg/kg/day (for 1–3 weeks) caused the increase in the relative liver weight, the decrease of testosterone levels in serum and testis, the increase of catalase activity in liver and the induction of peroxisomes proliferation.
Repeated exposure of rats to diethyl phthalate(for 6 weeks at the dose 750 mg/kg/day and 16 weeks at the dose 150 mg/kg/day) resulted in the decrease of body weight and food consumption, and (in females) the increase in the relative weight of the liver, stomach and small intestine. Based on the results of chronic toxicity studies in rats, LOAEL value accepted as 5000 mg/kg/day causing in animals the decrease body weight.
After a 2-year application of diethyl phthalate on skin of rats at the doses of 320 - 1560 mg/kg/day skin irritation and keratosis of the epidermis were
observed. Repeated intragastric administration (for 2–7 days) of diethyl phthalate to male rats at the dose of 2000 mg/kg/day resulted in abnormal
reproductive capacity: changes in the Leydig cells and decrease of the testosterone concentration in serum and testes. The adverse reproductive
effects (reduced sperm count and motility) after 28 days of diethyl phthalate exposure at a dose of 500 mg/kg/day were also reported.
After 5 months of intragastric (in feed) administration of diethyl phthalate to rats at the doses of 0.57 - 2.85 mg/kg bw/day and to mice at doses of 1.25 - 6.25 mg/kg bw/day for 90 days, observed changes indicated the liver damage and metabolic disturbances of the glycogen, cholesterol and triglycerides.
In pregnant rats, diethyl phthalate caused the decrease of body weight and food consumption and the increase in resorption and fetal mortality (at a dose of 600 mg/kg/day), and disorders of the skeletal (vestigial ribs on the lumbar region after doses 500 - 3210 mg/kg/day).
Conclusive results were not obtained in the Ames test. Diethyl phthalate did not cause genotoxic effects (chromosome aberration and DNA repair test).
The results of two years of experiments on rats showed no carcinogenic potential of diethyl phthalate. The observations of mice showed
an increased risk of cancer of the liver and skin (after initiation by DMBA, and after promotion by giving the TPA).
EPA included diethyl phthalate in class D, and ACGIH in A4 as compounds not classifi ed as carcinogenic for humans.
Diethyl phthalate is rapidly absorbed from the gastrointestinal tract, but is also rapidly distribution and excreted from the body, it does not accumulate in tissues. Diethyl phthalate passes through the placental barrier. The main
metabolite of diethyl phthalate is monoethyl phthalate, mainly excreted in the urine. In humans, about 5% of the applied dose of diethyl phthalate is absorbed through the skin, while in rats about 35%. The data on the toxicity of diethyl phthalate for animals indicate hepatotoxic effect (histopathological and biochemical changes) that occurred after 5-month of oral exposure of rats at the dose of 1.425 mg/kg/day (LOAEL value).
This value was the basis for proposing the level of
maximum allowable concentration (MAC-TWA)
for diethyl phthalate - 3 mg/m3. There is no basis
to determine the value of the short-term exposure
limit (STEL) and the biological exposure index
(BEI). It is recommended to label this substance
as „Ft” (fetotoxicity).

Butyl acetate (n-butyl) and its isomers – sec-butyl acetate and isobutyl acetates. Documentation of proposed values of occupational exposure limits (OELs)
MAŁGORZATA KUPCZEWSKA-DOBECKA s. 131
Butyl acetates, or acetic acid esters and a suitable butyl alcohol, are four compounds with identical molecular formulas which differ from each other
by sequence of bonding of atoms. These are n-butyl acetate with a straight carbon chain and its three isomers: isobutyl acetate, sec-butyl and
tert-butyl acetate.
The subjects of this documentation are n-butyl acetate and isomers: sec- and iso-, because they have similar physical and chemical properties, route of metabolism and critical effect. Isomer tert- was described in separate documentation.
n-Butyl, sec-butyl and isobutyl acetates are colorless, fl ammable liquids with a fruity odor. They are mainly used as organic solvents and as ingredients of solvent blends for resins, waxes, varnishes, perfumes, fats, inks, adhesives,
camphors and in the production of nitrocellulose lacquer.
The median lethal concentration for n-butyl acetate is in the range from 750 mg/m³/4h to 45 000 mg/m³/4h for rats and depends on the method of its generation. LD50 values after intragastric administration of n-butyl acetate
amounts to approx. 14 130 mg/kg for rat and 7100 mg/kg for mice. The minimum value of LD50 for isobutyl acetate is 4800 mg/kg. While in the case of sec-butyl acetate LD50 value is within the range of 3200 - 6400 mg/kg.
Acetates cause irritation to mucous membranes of the respiratory tract. For n-butyl acetate and isobutyl acetate RD50 values are 3470 mg/m³ and 3890 mg/m³, respectively.
n-Butyl acetate, sec-butyl acetate and isobutyl acetate are similar in structure, physicochemical properties and metabolic pathway. Most of the
quantitative data are available only for acetate of straight carbon chain. Hence, it is proposed to establish an equal limit value for these three
substances.
In humans, weak irritation of eye, nose, throat, esophagus were observed in the concentration of n-butyl acetate of 1000 mg/m³ at 5-min exposure.
n-Butyl acetate at a concentration of 1449 mg/m³ in most individuals exposed for 2 to 5 min caused irritation of eyes, nose and throat rated as sharp.
In volunteers exposed for 20 min for n-butyl acetate, the highest concentration at which no irritation to eyes, nose, throat, skin, respiratory system were observed was of 1050 mg/m³. Although in the same study, signifi cant differences
compared with the control group which include irritation to throat, diffi culties in breathing, sensing odor were observed at a concentration of 700 mg/m³ for 4 h. SCOEL and ACGIH proposed TWA of 240 mg/m³ and STEL at 720 mg/m³ for all isomers of butyl acetates. To calculate the MAC value for butyl acetates
The Expert Group adopted the study on volunteers as a starting point. Assuming that the concentration of 700 mg/m³ is the LOAEC value for irritation on the mucous membranes of the respiratory tract and the respective uncertainties, The Expert Group proposed MAC-NDS for n-butyl, sec-butyl and isobutyl acetate of
200 mg/m³. Due to the mild irritant of butyl acetates and the possibility of ceiling concentrations in workplace, The Expert Group proposed STEL of 3 times higher than the MAC-NDS of 600 mg/m³.
After discussion and voting, the Interdepartmental Commission for Maximum Admissible Concentration and Intensities for Agents Harmful to Health in the Working Environment at its 79th meeting adopted the MAC value of n-butyl
acetate and its isomers sec-butyl and isobutyl proposed by SCOEL of 240 mg/m³ and STEL value of 720 mg/m³.
n-Butyl acetates are slightly absorbed through the skin (1.6 ± 0.1 g/m2 · h), hence it is not recommended to label them as ”skin” (absorption of substances through the skin can be just as important as for inhalation). It is recommended
to label this substance as ”I” (irritant).

Procedure for measuring ultrasonic noise
Jan Radosz s. 169
The need to develop a new procedure for measuring ultrasonic noise was taken from the analysis results of current legislations to ultrasonic noise
in a working environment, methods of measuring noise, metrological requirements for measuring equipment, and identifi cation of factors affecting
the measurement result.
A new ultrasonic noise measurement procedure was developed on the basis of the results of research conducted in the Central Institute for Labour Protection - National Research Institute. The procedure includes requirements for measuring
equipment, periodic metrological control, test environment (temperature, humidity, static pressure) and a description of proceeding during
measurements.
The procedure also includes the use of correction for measuring results and the method of determination of measurement uncertainty in accordance with other acoustic ISO standards.

Hydrazine. Documentation of proposed values of occupational exposure limits (OELs)
Anna Jeżewska s. 191
Tetrahydrofuran (THF) is a colorless and highly flammable liquid with an ether-like odor. 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 THF vapors can occur through inhalation, absorption through the skin or ingestion.
The aim of this study was to amend PN-Z-04230-02:1993 withdrawn from Polish standards and validate method for determining concentrations
of THF in workplace air in the range from 1/10 to 2 MAC values, in accordance with the requirements of Standard PN-EN 482.
The study was performed using a gas chromatograph (GC) with a fl ame ionization
detector (FID) equipped with a capillary column HP-INNOWAX (60 m × 0.25 mm × 0.15 μm). This method is based on the adsorption of tetrahydrofuran vapors on activated charcoal, desorption with carbon disulfi de and GC-FID analysis. The average desorption effi ciency of THF from activated charcoal was 104%. The
use of HP-INNOWAX column enabled selective determination of THF in a presence of other solvents. The measurement range was 15 – 300 mg/m³ for a 5-L air sample. The limit of detection is 0.18 μg/ml and the limit of quantifi cation is 0.55 μg/ml.
The analytical method described in this paper enables selective determination of THF in workplace air in the presence of other solvents at concentrations from 15 mg/m³ (1/10 MAC value). The method is precise, accurate and it
meets the criteria for procedures for measuring chemical agents listed in EN 482. The method can be used for assessing occupational exposure to
THF and associated risk to workers’ health.
The developed method of determining THF has been recorded as an analytical procedure (see Appendix).