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- The verification methods for the extraction of thoracic fraction sulfuric acid(VI) and validation the ion chromatography method
MAŁGORZATA SZEWCZYŃSKA
- Ethyl silicate Documentation of proposed values of occupational exposure limits (OELs)
ANNA KILANOWICZ, MAŁGORZATA SKRZYPIŃSKA-GAWRYSIAK
- Iron oxides – calculated on Fe. Documentation of proposed values of occupational exposure limits (OELs)
ELŻBIETA BRUCHAJZER, BARBARA FRYDRYCH, JADWIGA SZYMAŃSKA
- Exposure to the electromagnetic field in the work space during the use of transmitting devices of radiocommunication systems. The method of in situ measurements of the electromagnetic field – specific requirements
PAWEŁ BIEŃKOWSKI , HALINA ANIOŁCZYK, JOLANTA KARPOWICZ , JAROSŁAW KIELISZEK s. 89
- 1,2-Dimethoxyethane Determination in working air with gas chromatography-mass spectrometer
MAŁGORZATA KUCHARSKA , WIKTOR WESOŁOWSKI
- 2-Ethylhexan-1-ol Determination in working air
ANNA JEŻEWSKA
- 2,2’-Oxydiethanol Determination in workplace air
ANNA JEŻEWSKA
- 1,2-Propanediol Determination in working air with gas chromatography with mass spectrometer
WIKTOR WESOŁOWSKI, MAŁGORZATA KUCHARSKA
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The verification methods for the extraction of thoracic fraction sulfuric acid(VI) and validation the ion chromatography method
MAŁGORZATA SZEWCZYŃSKA
Sulfuic acid is widely used in many industries, which is associated with the exposure of a large group of employees to this harmful substance. In 2012, a new value of occupational exposure limit for sulfuric acid as the thoracic fraction was introduced in Poland. Due to this change, the method enabling determination of sulfuric acid in the thoracic fraction has been established in accordance with the requirements of the Standard No. EN 481. The practical use of this method indicated the necessity of modificating the procedure for sulfuric acid extraction from methylcellulose filters.
The aim of this study was to modify the extraction method of sulfuric acid(VI) and to validate the ion chromatography method.
The determination of sulfuric acid(VI) with ion chromatography with conductivity detection was applied in this study. The study used an analytical column IonPac® Dionex AS22 (4 × 250 mm) with
a precolumn Dionex IonPac AG22 (4 × 50mm) and a mixture of carbonate and bicarbonate, as a carrier phase of an isocratic flow rate 1.2 ml/min. The proposed conditions for the chromatographic separation of ions enabled the determination of sulfuric acid (VI) in the presence of fluoride ions, acetate, chloride, bromide, nitrate, nitrite and phosphate. Parallel Particle Impactors (PPI) with mixed cellulose filter dedicated for thoracic fraction was used for sampling.
The determination method was achieved at 2.125 µg/m3 for 480 m3 of air and extraction of MCE filter with water (10 ml). The detection limit calculated on the basis of the signal-to-noise ratio was 1.9 ng, and the limit of quantification was 5.7 ng. The uncertainty of the overall method is 11% and 23% of expanded uncertainty. PPI sampler dedicated to collect thoracic fractions has been tested in real conditions in factories producing and processing sulfuric acid.
The method of vacuum filtration for sulfates extraction from filters MCE, which was published in The Principles and “Methods of Assessing the Working Environment” (PiMOŚP), was modified. The use of a mechanical shaking MCE filter with ultrapure water Milli-Q for 30 min enabled to receive approximately 100% recovery of sulfuric acid from the filter analyzed while avoiding the leaching of interferents. The results confirmed the presence of sulfuric acid(VI) in the thoracic fraction of aerosol tested at concentrations ranging from 0.03 to 1.47 MAC value.
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Ethyl silicate Documentation of proposed values of occupational exposure limits (OELs)
ANNA KILANOWICZ, MAŁGORZATA SKRZYPIŃSKA-GAWRYSIAK
Ethyl silicate is a colorless liquid with a slightly perceptible odor. This compound finds numerous applications in many industrial branches, e.g., paint and lacquer, chemical (in chemical coatings which has a contact with food), pharmaceutical, semiconductor and in nanotechnology. It is also used as an agent to harden natural stone, terracotta, artificial marble, frescoes and clay and in production of waterproof and acidproof mortar and cements.
According to the State Sanitary Inspection data, in Poland in 2007, 2010 and 2013, there were no workers exposed to ethyl silicate at levels exceeding maximum allowable concentration (MAC) of 80 mg/m3.
Ethyl silicate is well absorbed via respiratory and alimentary tracts, but its absorption through the skin is rather poor. In workers exposed to ethyl silicate, irritating properties to eye and nasal mucosa have been observed. Data on chronic ethyl silicate effects in humans are not available in the literature.
In laboratory animals, ethyl silicate acute toxicity expressed in median lethal doses is relatively low. Ethyl silicate shows a mild irritating effect on rabbit’s eyes, it does not cause dermal irritation or allergic effects. There are no data on ethyl silicate chronic toxicity. Short-term and subchronic studies performed on mice and rats exposed to ethyl silicate through inhalation and after its administration in other ways showed except for necrotic lesions in the olfactory epithelium of nasal cavity (in mice), changes in the liver (in rats) and kidneys. The latter comprised interstitial inflammation and necrotic lesions in renal tubules. Short-term exposure of rats to high ethyl silicate concentrations induced its toxic effect also on lungs.
Ethyl silicate mutagenic effect has not been revealed in Ames tests. On the basis of few data, it has been proved that this compound did not cause reproductive and developmental toxicity. This compound has not been categorized by the International Agency for Research on Cancer (IARC) with respect to its potential carcinogenic risk.
The presented evidence shows that the major toxic effect of ethyl silicate at high concentrations (over 2000 mg/m3) is eye and nasal mucosa irritation in humans, whereas the nephrotoxic effect and damage to the olfactory epithelium of nasal cavity are observed in laboratory animals.
On the basis of the nephrotoxic effect of ethyl silicate, its maximum allowable concentration (MAC) was calculated. The results of two independent inhalation experiments in mice were used to determine NOAEL value. Inhalation exposure of mice to ethyl silicate at concentration of 430 mg/m3 (50 ppm) for 90 days or 2 and 4 weeks did not cause nephrotoxic effects. This compound at higher concentrations caused nephrotoxicity. Exposure to concentration of 760 mg/m3 (88 ppm) caused significant decrease in kidney weight, and after exposure to concentration of 865 mg/m3 (100 ppm) in 20% of animals interstitial inflammation of kidney tubules have been observed. The authors of the documentation proposed to adopt a concentration of 430 mg/m3 as NOAEC value of ethyl silicate for the nephrotoxic effects observed in mice. After adopting relevant uncertainty coefficients (total value, 8) the calculated MAC value for ethyl silicate is 54 mg/m3.
Taking into consideration the fact that in 2008 SCOEL proposed a concentration of 44 mg/m3 as 8-h TWA for ethyl silicate, which was based on the same effects (nephrotoxicity) and NOAEC value adopted from the same experiments, it was proposed to assume a concentration of 44 mg/m3 as MAC value of ethyl silicate. This substance is included in the directive establishing the IV list of indicative occupational exposure limit values without establishing a short-term STEL value.
The proposed MAC value for ethyl silicate should protect workers against systemic effect and potential irritating effect. There are no reasons for adopting STEL and BEI values for this compound.
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Iron oxides – calculated on Fe. Documentation of proposed values of occupational exposure limits (OELs)
ELŻBIETA BRUCHAJZER, BARBARA FRYDRYCH, JADWIGA SZYMAŃSKA
Iron (III) oxide, (Fe2O3, nr CAS 1309-37-1) in natural conditions occurs as iron ore. The most common (hematite) contains about 70% pure iron. Iron (III) oxide is used as a red dye in ceramics, glass and paper industries and as a raw material for abrasive metalworking (cutting).
Iron (II) oxide, (FeO, CAS 1345-25-1) occurs as a mineral wurtzite and is used as a black dye in cosmetics and as a component of tattoo ink.
Iron (II) iron (III) oxide (Fe3O4, CAS 1309-38-2; 1317-61-9) is a common mineral. It has strong magnetic properties (so called magnetite). It occurs in igneous rocks (gabbro, basalt). It is the richest and the best iron ore for industry.
Occupational exposure to iron oxides occurs in the mining and metallurgical industry in the production of iron, steel and its products. Welders, locksmiths, lathes and workers employed in milling ores and polishing silver are exposed to iron oxides.
According to data from the State Sanitary Inspection, in 2013, 389 people in Poland were exposed to iron oxide in concentrations exceeding the current NDS (5 mg/m3) and in 2014 – 172 people.
After single and multiple intratracheal and inhalation exposure of animals, transient intensification of oxidative stress and inflammatory reactions were reported.
Iron (III) oxide did not cause genotoxic and carcinogenic effects. In literature, there are no data on its effects on fertility, reproduction and pregnancy.
Data on chronic toxicity of iron oxides for humans exposed in working environment are limited. In epidemiological studies, all information presented in the documentation comes from observations of people exposed to the combined effects of iron oxides and other factors. It is not stated whether occupational exposure was related to the specific iron oxide and to what concentrations workers were exposed.
The most commonly encountered toxic effect in the occupational exposure of iron ore miners and iron welders and welders was minor lung fibrosis lesions and iron-silicon dust (as seen in the RTG study). Siderose is the occupational disease of miners and iron ore metallurgists. Moreover, cases of lung cancer have been reported in miners, steel workers and welders, but they were caused by total exposure to other compounds, including radioactive radon, carcinogenic chromium, manganese, nickel, other oxides (SiO2, ZnO, CO, NO, NO2, MgO) as well as exhaust gases from diesel engines. According to IARC, iron (III) oxide belongs to group 3 (cannot be classified as carcinogenic to humans).
Iron (III) oxides can accumulate in a lung tissue, this process may be responsible for the occurrence of fibrosis sites, particularly in higher parts of external lung parts. These effects were visible in the X-ray examination only. Pneumoconiosis (siderosis) caused by exposure to iron oxides is usually asymptomatic (lack of clinical symptoms and changes in lung function parameters).
The basis for the proposed MAC-TWA value for inhalable iron oxide fraction was NOAEL of 10 mg Fe/m3. People exposed for more than 10 years to iron (III) oxide had no pulmonary changes. After application of an uncertainty factor of 2 (for differences in personal sensitivity in humans), the MAC-TWA value for the iron oxide fraction was proposed at 5 mg/m3 (calculated as Fe). The same observations on humans were the basis for calculating the MAC-TWA value for respirable fraction of iron (III) oxide. On 12% of workers exposed to respirable fraction at mean concentrations of 10 ÷ 15 mg/m3, changes in pulmonary X-ray were observed. The value of 10 mg/m3 was assumed as LOAEL. After applying the appropriate uncertainty coefficients, the MAC-TWA value for the iron oxide respirable fraction was proposed at 2.5 mg/m3.
The authors propose to leave the short-term value (STEL) of 10 mg/m3 for inhaled fraction for iron oxides and to introduce STEL value of 5 mg/m3 for respirable fraction. It is recommended to label the substances with "I" - irritant substance.
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Exposure to the electromagnetic field in the work space during the use of transmitting devices of radiocommunication systems. The method of in situ measurements of the electromagnetic field – specific requirements
PAWEŁ BIEŃKOWSKI , HALINA ANIOŁCZYK, JOLANTA KARPOWICZ , JAROSŁAW KIELISZEK
Labour law sets out the obligation to identify and evaluate electromagnetic hazards in the vicinity of radiocommunication equipment and installations emitting an electromagnetic field (EM-field). Following the regulation of the Ministry of Labour, which established provisions regarding health and safety regarding the EM-field, the "broadcasting tele- and radiocommunication systems” and “mobile phone base stations” have been mentioned among the typi-cal sources of an EM-field (Regulation ...., OJ 2016 item 950, amended by item 2284, Annex 1, items
4 and 5). Radiocommunication devices also include “mobile and cordless phones and wireless short distance devices (Regulation...., OJ 2016 item 950, amended by item 2284, Annex 1, item 3), which are devices in common use that do not require a radio-communication permit, and so are not the subject of this article.
Today, radiocommunication devices and systems are among the most common sources of the EM-field, and while emissions the EM-field of protective zones exists in the vicinity of antennas and some other elements of such systems. The radiocommunication systems are usually operation-free, though they re-quire adjusting and maintenance so workspaces may be identified in their vicinity. The conditions of the workers’ exposure to the EM-field while using radio-communication systems must undergo periodic in-spections made according to the recommended and validated methods, in order to identify electromag-netic hazards and to take appropriate protective measures (Regulation..., Journal of Laws 2011, item 166; Regulation..., OJ 2016 item 950, amended by item 2284). The methods of measuring the EM-field to the extent necessary to meet these requirements are currently not standardised. Therefore, the aim of the work presented in this article was to develop a recommended method for measuring the parameters of the EM-field in-situ in the workspace, while using radiocommunication devices.
The recommended measurement method is based on a detailed investigation of the characteristics of ex-posure to the EM-field surrounding typical radio-communication devices and systems operated in
Poland in the vicinity of systems of antennas and transmitters of mobile phone base stations, broad-casting transmitters of radio and low power televi-sion and radio-television broadcasting centres. The work is based on the own results of measurements, as well as published literature and reports from
inspection measurements of the EM-field.
Based on the results of the study, it was shown that, besides the antennas, which create primary sources of EM-field (in some cases also transmitters and
elements of the antenna feeder), in the workspace in their vicinity there are also secondary sources of
EM-field: metal structures (ladders, handrails, fences, antennas supports, pipes and groundings) and re-ceiving or inactivated transmitting antennas exposed to the EM-field from active transmitting antennas. In the article, the worked out method is shown for measuring the EM-field in the work space in the vicinity of stationary transmitting radio-communication devices and systems, requiring a radiocommunication permit. The most important sources of uncertainty concerning EM-field meas-urements near these devices were also discussed.
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1,2-Dimethoxyethane Determination in working air with gas chromatography-mass spectrometer
MAŁGORZATA KUCHARSKA , WIKTOR WESOŁOWSKI
Under normal conditions, 1,2-dimethoxyethane (DME) is a colorless and transparent liquid with a faint odor of ether, very soluble in water, charac-terized by a high vapor pressure. It belongs to the group of alkyl ethers solvents, derivatives of eth-ylene glycol. 1,2-Dimethoxyethane is used as an ex-cipient in preparing and processing industrial chemicals, in the production of fluoric polymers and as a solvent and cleaning agent in the microe-lectronics and printing industries.
In the literature there are no data on the acute and chronic toxicity of 1,2-dimethoxyethane. However, long-term epidemiological studies on compounds of similar chemical structure suggest that human exposure to ethylene glycol alkyl ethers can ad-versely affect fertility and fetal development, and hematological parameters.
The aim of this study was to develop and validate a sensitive method for determining concentrations of 1,2-dimethoxyethane in workplace air in the range from 1/20 to 2 MAC values, in accordance with the requirements of Standard No. PN-EN 482+A1: 2016-1.
The study was performed using a gas chromato-graph (GC). A 7890B Agilent Technologies gas chromatograph with a 5977A mass spectrometry detector (MSD), HP PONA (50 m; 0,2 mm; 0,5 μm) capillary analytical column, auto sampler and Mass Hunter software was used for chromato-graphic separations.
The method is based on the adsorption of 1,2-di-methoxyethane on charcoal, desorption with di-chloromethane and GC/MSD analysis of the re-sulting solution. Extraction efficiency of 1,2-di-methoxyethane from charcoal was 96.4%. Samples of 1,2-dimethoxyethane can be stored in refrigera-tor for up to 28 days. The use of a HP-PONA capil-lary column enabled selective determination of 1,2-dimethoxyethane in a mixture of dichloromethane, toluene, carbon disulfide, ethylene and propylene glycol and other compounds.
The method is linear (r = 0.9999) within the inves-tigated working range from 5 to 200 μg/ml, which is equivalent to air concentrations from 0.5 to 20 mg/m3 for a 10-L air sample. The limit of quan-tification (LOQ) is 1,306 μg/ml.
The analytical method described in this paper ena-bles selective determination of 1,2-dimethoxye-thane in workplace atmosphere in presence of other compounds at concentrations from 0.5 to 20 mg/m3 (1/20 ÷ 2 MAC value). The method is precise, accurate and it meets the criteria for proce-dures for measuring chemical agents listed in Standard No. PN-EN 482+A1: 2016-1. The method can be used for assessing occupational exposure to 1,2-dimethoxyethane and associated risk to work-ers’ health.
The developed method of determining 1,2-di-methoxyethane has been recorded as an analytical procedure (see Appendix).
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2-Ethylhexan-1-ol Determination in working air
ANNA JEŻEWSKA
2-Ethylhexan-1-ol (2-EH) is a colorless liquid that is poorly soluble in water but soluble in most organic solvents. On an industrial scale, 2-Ethylhexanol is produced in the aldol condensation of n-butyralde-hyde. It is mainly used as an alcohol component in manufacturing ester plasticizers for soft poly(vinyl chloride) (PVC).
The aim of this study was to develop a method for determining concentrations of 2-ethylhexan-1-ol in workplace air in the range from 0.54 to 10.8 mg/m3, in accordance with the requirements of Standard No. EN 482.
The study was performed using a gas chromatograph (GC) with a flame ionization detector (FID) equipped with a capillary column Stabilwax (60 m × 0.32 mm, 0.5 µm).
The method is based on the adsorption of 2-ethylhexan-1-ol vapours on activated charcoal, desorption with dichloromethane and GC-FID analysis. The use of Stabilwax column enabled
selective determination of 2-ethylhexan-1-ol in the presence of other substances. The measurement range was from 0.013 to 0.26 mg/ml for a 24-L air sample. The limit of detection was 8.05 ng/ml and the limit of quantification was 24.14 ng/ml.
This method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. EN 482. The method can be used for assessing occupational exposure to 2-ethylhexan-1-ol and associated risk to workers’ health.
The developed method of determining 2-ethyl- hexan-1-ol has been recorded as an analytical
procedure (see appendix).
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2,2’-Oxydiethanol Determination in workplace air
ANNA JEŻEWSKA
2,2’-Oxydiethanol (DEG) is a colorless and oily liquid.
2,2’-Oxydiethanol is a by-product of ethylene glycol production. 2,2’-Oxydiethanol is used in the production of unsaturated polyester resins, plasticizers, acrylate and methacrylate resins, and urethanes.
2,2’-Oxydiethanol is a mild irritant.
The aim of this study was to develop a method for determining concentrations of 2,2’-Oxydiethanol
(inhalable fraction) in workplace air in the range from 1/10 to 2 MAC values.
The study was performed using a gas chromatograph (GC) with a flame ionization detector (FID)
equipped with a capillary column Stabilwax (60 m × 0.32 mm, 0.5 μm).
This method is based on the adsorption of 2,2’-oxydiethanol on a polypropylene filter,
extraction with methanol and chromatographic analysis of the obtained solution. The masurement
range was from 1 to 20 mg/m3 for a 720-L air sample. Validation of the method was performed
in accordance with Standard No. EN 482.
The following validation parameters were determined: detection limit – 0.5 μg/ml, determination
limit – 1.5 μg/ml, the overall accuracy of the method – 5.25%, the relative total uncertainty of
the method – 11.5%.
This analytical method enables selective determination of 2,2’-Oxydiethanol in workplace air in the
presence of other alcohols at concentrations from 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 2,2’-oxydiethanol has been recorded as an analytical procedure
(see appendix).
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1,2-Propanediol Determination in working air with gas chromatography with mass spectrometer
WIKTOR WESOŁOWSKI, MAŁGORZATA KUCHARSKA
Propane-1,2-diol (propylene glycol, PG) is a color-less, strongly hygroscopic liquid used in the pro-duction of antifreeze fluids, polyester resins and detergents.
The main use of propane-1,2-diol is in the cosmetic industry as an ingredient of creams, toothpastes, mouthwashes and deodorant sticks. It is also used in medicine, pharmaceutics, food and cleaning products. Propane-1,2-diol is used as a hygroscopic agent in the plastics industry, textile products and in manufacturing cigarettes. Recently, it is used as the main component of fluids used in electronic cigarettes.
There are no reports in the literature on acute poi-soning with propylene glycol of people in occupa-tional exposure conditions. Clinical observations of people treated with propylene glycol applied as a drug solvent indicate a weak narcotic effect of the compound and mild irritation of the skin and con-junctives.
The aim of this study was to develop and validate a sensitive method for determining concentrations of propane-1,2-diol in workplace air in the range from 1/20 to 2 MAC values in accordance with the requirements of Standard No. PN-EN 482+A1:2016-1.
The study was performed using a gas chromatog-raphy (GC). A 6890N Agilent Technologies gas chromatograph with a 5973 mass spectrometry de-tector (MSD), HP-PONA (50 m; 0.2 mm; 0,5 μm) ca-pillary analytical column, autosampler and Chem-Station software were used for chromatographic separations.
The method is based on the adsorption of inhalable fraction and vapors of propane-1,2-diol on glass fi-ber filters and XAD-7 resin, desorption with ace-tonitrile and analysis of the resulting solution with gas chromatographic with mass detection (GC/MS). The extraction efficiency of propane-1,2--diol from filters and resin was 97.3%. Samples of propane-1,2-diol can be stored in refrigerator for up to 28 days. Application of a HP-PONA capillary column enabled selective determination of pro-pane-1,2-diol in a mixture of acetonitrile, dichloro-methane, toluene and other compounds.
The method is linear (r = 0.9992) within the work-ing range 10–500 μg/ml, which is equivalent to air concentrations range 4.4–222 mg/m3 for a 180-L air sample and 80-fold dilution. Limit of quantification (LOQ) is 1.303 μg/ml.
The analytical method described in this paper ena-bles selective determination of inhalable fraction and vapors of propane-1,2-diol in workplace air in presence of other compounds at concentrations from 4.4 to 222 mg/m3 (1/20–2 MAC value). The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in Standard No. PN-EN 482+A1:2016-1. The method can be used for assessing occupational exposure to propane-1,2-diol and associated risk to workers’ health.
The developed method of determining propane-1,2-diol has been recorded as analytical procedure (see appendix).
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