Biofuels production – priority trent of research   Jolanta Skowroń, Wojciech Golimowski   s. 6 Principles of occupational risk management related to exposure to nano-objects, their agglomerates and aggregates (NOAA)   Elżbieta Jankowska s. 18 2,3-Butanedione. Documentation of proposed values of occupational exposure  limits (OELs)   Andrzej Starek   s. 38 2-Methylpentane-2,4-diol – vapours, inhable fraction. Documentation of proposed values of occupational  exposure limits (OELs)   Renata Soćko, Małgorzata Kupczewska-Dobecka   s. 62 Ethyl acrylate. Determination in workplace air with GC-FID   Marzena Bonczarowska, Agata Wziątek, Sławomir Brzeźnicki     s. 90 Dichlorobenzene. Determination in workplace air with GC-FID Agata Wziątek, Katarzyna Janoszka, Sławomir Brzeźnicki   s. 106 tert-Butyl ethyl eter. Determination in workplace air with gas chromatography-mass spectrometry   Wiktor Wesołowski, Małgorzata Kucharska   s. 124

Biofuels production – priority trent of research  
Jolanta Skowroń, Wojciech Golimowski   s. 6
Under the Act of biofuels and biocomponents of August 25, 2006, liquid biofuels
include gas oil which contains over 7% of biocomponents. The law allows their production by agricultural producers which creates a risk of exposure of farmers to various chemicals. Research on the production of second
generation biofuels from inedible biomass (cellulose, lignocellulose or fats from the secondary market) and organic waste materials in biochemical or thermochemical processes are conducted around the world.
The use of second-generation biofuels are environmentally-friendly operation, as it reduces greenhouse gas emissions, particularly carbon dioxide from combustion engines, by 80-85% compared with conventional fuels.
The number of workers exposed to biofuels both during their production and use
in the near future will increase, but little is known about the dangers of second-generation biofuels. This article discusses the risks posed by biofuels on employees during the production and the use, and results of the research
on emissions and toxicity of biofuels.

Principles of occupational risk management related to exposure to nano-objects, their agglomerates and aggregates (NOAA)
ELŻBIETA JANKOWSKA s. 17
The article presents principles of occupational risk management and practical advice on their implementation in accordance with the recommendations proposed in the technical specifi cations ISO/TS 12901-1:2012 Nanotechnologies – Occupational risk management applied to engineered nanomaterials – Part 1. Principles and approaches and ISO/TS 12901-2:2014 Nanotechnologies – Occupational risk management applied to engineered nanomaterials – Part 2. Use of the control banding approach. Because there are no commonly accepted
methods to assess the occupational risksassociated with exposure to NOAA, based
on the measurement data determined  in the real conditions of exposure, and
reference values (limits) for each NOAA inthe working environment method based
on determining hazard category (HB) andestimating the level of exposure (EB)
presented in ISO/TS 12901-2 can be used in the process of occupational risk management related to exposure to NOAA.

2,3-Butanedione. Documentation of proposed values of occupational exposure  limits (OELs)  
Andrzej Starek   s. 38
2,3-Butanedione (diacetyl) is a greenish-yellow liquid with a characteristic buttery odour.
Diacetyl is used as an artifi cial fl avouring substance in processed food, e.g., microwave popcorn, confectionery, dairy products and beverages. Exposure to this compound occurs in chemical and food manufacturing industries. The concentrations of diacetyl atthe workplace air range from several to several
hundred mg/m3. In Poland, the averageair concentration of diacetyl at the confectionarymanufacture was 51 mg/m3.
A single and repeated exposures to diacetyllead to irritation to the eyes, respiratory tractand skin. Persons professionally exposed to
this compound had respiratory tract disorderswith spirometric changes indicating
obstruction and restriction of the small airways.Moreover, diacetyl is consider as etiologicfactor of bronchiolitis obliterans.
The basis for calculating the maximum admissibleconcentration (MAC) of diacetyl
were the results of epidemiologic studies which indicated that both obstructive andrestrictive changes in respiratory systemexpressed in a lowered forced expiratoryvolume in fi rst second (FEV1) did not occurin workers at the cumulative exposure levelof 2.33 mg/m3 · years. This concentrationwas considered as NOAEC value. Uncertaintyfactors with joint value of 4 were used to
calculate MAC at level of 0.05 mg/m3. STEL value for diacetyl at level of 0.1 mg/m3 wascalculated on the basis of MAC value.
The Interdepartmental Commission for MaximumAdmissible Concentrations and Intensitiesfor Agents Harmful to Health in the Working Environment at its 77th meeting adopted the MAC value of diacetyl proposed
by SCOEL (project of the directions 4. Doc. 1893/14) of 0.07 mg/m3 and STEL value of 0.36 mg/m3. It is recommended to label this substance as I (irritant).

2-Metylopentano-2,4-diol – pary, frakcja wdychalna Dokumentacja proponowanych dopuszczalnych wielkości narażenia zawodowego
RENATA SOĆKO, MAŁGORZATA KUPCZEWSKA-DOBECKA s. 62
2-Methylpentane-2,4-diol (hexylene glycol) is a liquid used as a chemical intermediate, selective solvent and industrial cleaning/washing
agent and disinfectant. It irritates eyes and skin. 2-Methylpentane-2,4-diol has a relatively low acute toxicity. The clinical effects observed in animals acutely intoxicated were predominately of central nervous system depression and included decreased activity, muscle incoordination and fl accidity,
palpebral closure, piloerection, narcosis and anaesthesia. Hepatotoxic and nephrotoxic effects manifested by swelling of intrahepatic
bile ducts and proximal renal tubular extension were described during the administration of the substance with feed. 2-Methylpentane-2,4-diol does not induce gene mutations.
Fetotoxicity is observed at maternally toxic dose levels. Systemic effect and local irritation of eyes were adopted as critical effects of 2-methylpentane-2,4-diol. Exposure at 240 mg/m3 in air for 15 minutes produced a slight odor and a few volunteer subjects noticed eye irritation. At 400 mg/m3 for 5 minutes, the odor was plainly detectable, and slight nasal and respiratory discomfortwas noted by some of the subjects. MAC value of 50 mg/m3 as the average value obtained from studies in human volunteers
and experimental animals was established.
2-Methylpentane-2,4-diol is a rapidly acting substance – in volunteers effects such as irritation of nose and breathing diffi - culties were observed after only 5 minutes of exposure. It is proposed to determine the STEL of 100 mg/m3. It is recommend-ed to label the substance with symbol
„I” (irritant).

Ethyl acrylate. Determination in workplace air with GC-FID
MARZENA BONCZAROWSKA, AGATA WZIĄTEK, SŁAWOMIR BRZEŹNICKI s. 15
Ethyl acrylate is a colorless liquid with a sour, pungent odor. It is widely used in chemical, textile, leather, paper and pharmaceutical industries
in manufacturing synthetic fibers, synthetic rubber, paints, lacquers and pharmaceuticals.
Occupational exposure to ethyl acrylate can cause irritation of eyes, skin and respiratory system. International Agency for Research on Cancer (IARC) classified ethyl acrylate as a compounds possibly carcinogenic to humans (Group 2B).The method is based on the adsorption of ethyl acrylate on charcoal, desorption with a mixture of carbon disulfide and methanol (95: 5) and gas
chromatographic analysis of the resulting solution.
Extraction efficiency of ethyl acrylate from charcoal was 102.2%. Samples of ethyl acrylate can be stored in a refrigerator for up to 20 days.
The use of a ZB-WAX 60 m × 0.32 mm × 0.5 μm capillary column enabled selective determination of ethyl acrylate in a mixture of other compounds.
This method is linear (r = 0.999) within the investigated working range 0.01 - 0.4 μg/ml, which is equivalent to air concentrations from 1 to 40 mg/m3 for a 10-L air sample. The limit of quantification (LOQ) is 0.85 μg/ml.
The analytical method described in this paper enables selective determination of ethyl acrylate in workplace air in the presence of other compounds
at concentrations from 0.01 mg/m3 (1/20 MAC value). The method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in EN 482: 2006. The method can be used for assessing occupational exposure to ethyl acrylate and associated risk to workers’ health. The developed method of determining ethyl acrylate has been recorded as an analytical procedure (see Appendix).

Dichlorobenzene Determination in workplace air with GC-FID
AGATA WZIĄTEK,  KATARZYNA JANOSZKA, SŁAWOMIR BRZEŹNICKI s. 106
1,2-Dichlorobenzene is a colorless liquid with a characteristic pleasant odor. 1,4-dichlorobenzene is a colorless or white crystalline solid with a
distinctive aromatic odor. Both compounds are used as intermediate in chemical synthesis and as insecticides or (1,4-DCB) space odorant. Occupational
exposure to dichlorobenzene isomers can lead to irritation of eyes, skin and respiratory system. International Agency for Research on
Cancer (IARC) classified 1,4-DCB as a compound possibly carcinogenic to humans (Group 2B). There is no evidence of mutagenic activity
of 1,4-DCB, but it demonstrate teratogenic activity
and negative impact on reproduction.The method is based on the adsorption of dichlorobenzene isomers on charcoal, desorption with carbon
disulfide and gas chromatographic analysis of the resulting solution. Extraction efficiency of dichlorobenzene isomers from charcoal was 100.4%
(1,2-DCB) and 100.9% (1,4-DCB). Samples of dichlorobenzene can be stored in a refrigerator for up to 30 days. The use of a ZB-1 50 m x 0.25 mm x
0.5 μm capillary column enabled selective determination of both isomers in a mixture of other compounds. This method is linear (r = 0.999) within the investigated working range of 0.06 – 1.8 mg/ml (1,2-DCB) and 0.01 – 0.3 mg/ml
(1,4-DCB). Limit of quantification for 1,2-DCB and 1,4-DCB was 1.6 and 0.5 μg/ml, respectively.
The analytical method described in this paper enables selective determination of 1,2-DCB and 1,4-DCB in workplace air in the presence of other
compounds at concentrations of 6 – 180 mg/m3 (1,2-DCB) and 1 – 30 mg/m3 (1,4-DCB), (1/15 –2 MAC value). This method is precise, accurate and it meets the criteria for procedures for measuring chemical agents listed in PN-EN 482.
This method can be used for assessing occupational exposure to DMA and associated risk to workers’ health. The developed method of
determining dichlorobenzene isomers has been recorded as an analytical procedure (see Appendix).

tert-Butyl ethyl eter Determination in workplace air with gas chromatography-mass spectrometry
WIKTOR WESOŁOWSKI, MAŁGORZATA KUCHARSKA s. 124
tert-Butyl ethyl ether (ETBE) is colorless flammable liquid with characteristic strong gasoline like odor. It is used in petrochemical industry as a gasoline additive for enhance the octane number and are thought to improve combustion efficiency. Main route of exposure to ETBE is an inhalation route. There is a limited data on adverse effect of ETBE in humans. Among group of volunteers exposed to ETBE via inhalation route, irritation of eyes, upper inhalation tract, and slightly changes in pulmonary function have been noticed. American Conference of Governmental Industrial Hygienists (ACGIH) classified ethyl
acrylate to group of compounds not classifiable as human carcinogens (Group A4).
The method is based on the adsorption of ETBE on charcoal, desorption with dichloromethane and gas chromatographic analysis of the resulting
solution. Extraction efficiency of ETBE from charcoal amounted to 98%. Samples of ETBE can be stored in refrigerator up to 30 days. Application of
a HP PONA 50 m x 20 mm x 0,5 μm capillary column enabled selective determination of ETBE in a mixture of dichloromethane, toluene, tert-
-buthyl methyl ether and other compounds.
Method is linear (r = 0,999) within the investigated working range 0.05 - 2,0 mg/ml, which is equivalent to air concentrations from 5 to 200 mg/m3 for
a 10 L air sample. Limit of quantification (LOQ) is 9,1 μg/ml.
Analytical method described in this paper enables selective determination of ETBE in workplace atmosphere in presence of other compounds at concentrations from 0.05 mg/m3 (1/20 MAC value). The method is characterized
by good precision and accuracy and meets the criteria for the performance of procedures for the measurement of chemical agents, listed in EN
482:2006. The method may be used for the assessment of occupational exposure to ETBE and the associated risk to workers’ health. The developed method of determining ETBE has been recorded as an analytical procedure (see
Appendix).