Occupational Hygiene in the Oil Gas Industry Day

Oxygenates - Alcohols or Ethers: Alcohols Methanol (Me. OH) Ethanol (Et. OH) Isopropyl alcohol

Gasoline Blends Around the World • North America E 85 (85% Ethanol, 15% gasoline)

Environmental Concerns • Air • Water – Groundwater, drinking water, surface water, runoff water,

CONCAWE Report 4/12 (2012) 5. © 2013 Petroch Services Pty Ltd BP Version J

Australia - Gasoline Grades with Ethanol • E 10 commenced Sept 2007 contains 10%

End of Section 9 Oxygenates 7. © 2013 Petroch Services Pty Ltd BP Version

Occupational Hygiene in the Oil & Gas Industry Day 2 – Section 10 ALKYL

Alkyl Lead Blending Facilities 9. © 2013 Petroch Services Pty Ltd BP Version J

Tetraethyl Lead (TEL) • Discovered by Midgley, went on sale 1923 Ohio USA •

Alkyl Lead compounds/ Tank cleaning • Alkyl Lead compounds, – Tetraethyl lead (TEL) –

Tank repair Rust on tank floor. Leaded sludge may be under floor or in

Alky Lead – Groups at Risk • Product Blending – Aviation gasoline still uses

Lead-in-Air Test Kit • Air sample captured in Iodine solution, chemical reaction, colourmetric analysis

End of Section 10 Alkyl Lead 15. © 2013 Petroch Services Pty Ltd BP

Occupational Hygiene in the Oil & Gas Industry Day 2 – Section 11 CONTROL

Laboratories • Work practices • Fume Hoods • Potential Chemical exposure 17. © 2013

Control Laboratories Octane Rating Engine ‘Knock engine’ Research Octane Test Engine Various blends are

Testing the face velocity of a fume hood 19. © 2013 Petroch Services Pty

Lab wash area 20. © 2013 Petroch Services Pty Ltd BP Version J 11002–

Lab fume hood ? – Poor Design 21. © 2013 Petroch Services Pty Ltd

Terminal Laboratory – Poor work practices 22. © 2013 Petroch Services Pty Ltd BP

Field ‘Lab’ & Testing 23. © 2013 Petroch Services Pty Ltd BP Version J

End of Section 11 Control Laboratories 24. © 2013 Petroch Services Pty Ltd BP

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Oxygenates - Alcohols or Ethers: Alcohols Methanol (Me. OH) Ethanol (Et. OH) Isopropyl alcohol (IPA) n-butanol (Bu. OH) Gasoline grade t-butanol (GTBA) 2. © 2013 Petroch Services Pty Ltd Ethers Methyl tert-butyl ether (MTBE) Tertiary amyl methyl ether (TAME) Tertiary hexyl methyl ether (THEME) Ethyl tertiary butyl ether (ETBE) Tertiary amyl ether (TAEE) Diisopropyl ether (DIPE) BP Version J 11002– Occupational Hygiene in the Oil & Gas Industry

Gasoline Blends Around the World • North America E 85 (85% Ethanol, 15% gasoline) – MTBE (11 – 15%vol. ) • South America (some are 100% ethanol) • Typical gasoline blends E 10 (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 3. © 2013 Petroch Services Pty Ltd BP Version J 11002– 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. ’ 4. © 2013 Petroch Services Pty Ltd BP Version J 11002– Occupational Hygiene in the Oil & Gas Industry

Australia - Gasoline Grades with Ethanol • E 10 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) 6. © 2013 Petroch Services Pty Ltd BP Version J 11002– Occupational Hygiene in the Oil & Gas Industry

Occupational Hygiene in the Oil & Gas Industry Day 2 – Section 10 ALKYL LEAD Tetraethyl Lead & Tetramethyl Lead 8. © 2013 Petroch Services Pty Ltd BP Version J 11002– 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) 10. © 2013 Petroch Services Pty Ltd BP Version J 11002– 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 Du. Pont, Ethyl Corporation, and Associated Octel Limited, now Innospec 11. © 2013 Petroch Services Pty Ltd BP Version J 11002– 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. 12. © 2013 Petroch Services Pty Ltd BP Version J 11002– 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 13. © 2013 Petroch Services Pty Ltd BP Version J 11002– 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) 14. © 2013 Petroch Services Pty Ltd BP Version J 11002– 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 [n. C 7 Octane = 0, i. C 8 Octane = 100, add TEL for blends above 100 Octane] 18. © 2013 Petroch Services Pty Ltd BP Version J 11002– Occupational Hygiene in the Oil & Gas Industry