1. 1. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Occupational Hygiene in the Oil & Gas Industry Day 2 – Section 9 Oxygenates

2. 2. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Oxygenates - Alcohols or Ethers: Alcohols Methanol (MeOH) Ethanol (EtOH) Isopropyl alcohol (IPA) n-butanol (BuOH) Gasoline grade t-butanol (GTBA) Ethers Methyl tert-butyl ether (MTBE) Tertiary amyl methyl ether (TAME) Tertiary hexyl methyl ether (THEME) Ethyl tertiary butyl ether (ETBE) Tertiary amyl ethyl ether (TAEE) Diisopropyl ether (DIPE)

3. 3. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Gasoline Blends Around the World North America E85 (85% Ethanol, 15% gasoline) –MTBE (11 – 15%vol.) South America (some are 100% ethanol) Typical gasoline blends E10 (10% Ethanol, 90% gasoline) Gasoline Ether Oxygenates (GEO) used in 30 European countries – refer CONCAWE report 4/12 EU Directive 98/70/EC: Up to Maximum 15%vol. Ether Oxygenates in gasolines

4. 4. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Environmental Concerns Air Water – Groundwater, drinking water, surface water, runoff water, precipitation (rain/snow) However CONCAWE Report 4/12 concluded: ‘Gasoline Ether Oxygenates (GEO) not detected at concentrations that give rise to taste or odour concerns or to ecological or human health impacts.’

5. 5. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry CONCAWE Report 4/12 (2012 )

6. 6. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Australia - Gasoline Grades with Ethanol E10 commenced Sept 2007 contains 10% Ethanol 90% unleaded gasoline, <1% of Australian Gasoline market (2008) Shell V Power (100 RON) contains 5% Ethanol Oxygenates usually blended at refinery, however for low sales volumes may be blended at terminal. IH Monitoring issues when sampling on charcoal tubes (desorption solvent - consult lab)

7. 7. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry End of Section 9 Oxygenates

8. 8. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Occupational Hygiene in the Oil & Gas Industry Day 2 – Section 10 ALKYL LEAD Tetraethyl Lead & Tetramethyl Lead

9. 9. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Alkyl Lead Blending Facilities

10. 10. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Tetraethyl Lead (TEL) Discovered by Midgley, went on sale 1923 Ohio USA Widely used around the world from 1930’s until 1990’s. Still used in motor gasoline in several countries Still used in some aviation gasolines Major octane improver for gasolines ‘TEL-B’ comprises :TEL 61.4%, Ethylene Dibromide 35.7%, Dyes & Kero (balance)

11. 11. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Alkyl Lead compounds/ Tank cleaning Alkyl Lead compounds, –Tetraethyl lead (TEL) –Tetramethyl lead (TML) Used since 1923 in refining operations as a motor gasoline and aviation gasoline additive. TEL and TML are extremely toxic. –Adverse effects can occur as a result of inhalation or skin absorption Main suppliers were DuPont, Ethyl Corporation, and Associated Octel Limited, now Innospec

12. 12. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Tank repair Rust on tank floor. Leaded sludge may be under floor or in tank support legs Alkyl Lead sludge is very toxic.

13. 13. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Alky Lead – Groups at Risk Product Blending –Aviation gasoline still uses TEL Knock test laboratory employees –Used to make calibration blends Tank Inspection/repair/cleaners –Old leaded gasoline tanks, lead sludge Maintenance personnel –Handling alkyl lead contaminated equipment

14. 14. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Lead-in-Air Test Kit Air sample captured in Iodine solution, chemical reaction, colourmetric analysis Limited use – toxic chemicals (cyanide solutions)

15. 15. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry End of Section 10 Alkyl Lead

16. 16. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Occupational Hygiene in the Oil & Gas Industry Day 2 – Section 11 CONTROL LABORATORIES

17. 17. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Laboratories Work practices Fume Hoods Potential Chemical exposure

18. 18. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Control Laboratories Octane Rating Engine ‘Knock engine’ Research Octane Test Engine Various blends are made up at specific octane numbers [nC7 Octane = 0, iC8 Octane = 100, add TEL for blends above 100 Octane]

19. 19. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Testing the face velocity of a fume hood

20. 20. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Lab wash area

21. 21. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Lab fume hood ? – Poor Design

22. 22. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Terminal Laboratory – Poor work practices

23. 23. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry Field ‘Lab’ & Testing

24. 24. © 2013 Petroch Services Pty Ltd BP Version J11002– Occupational Hygiene in the Oil & Gas Industry End of Section 11 Control Laboratories