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Some advice:
Learn the regs so that when there is an argument about what should be done, you can point to the bit of the frame work that says what must be and what should be done.
Try to leave emotion at the clock station when dealing with these issues.
Not all of it is cut and dried. Risk analysis is an imprecise tool and many people will come up with different answers for the same analysis.
You will have as much trouble changing employee behaviour as you will management. You will often be no ones friend (just like a union rep). Don't take that personally, it is part of the role and can help you to be objective if it doesn't get to you.
Learn as much as you can about safety in general and in your work place in particular. You will be looked to for information and if you can provided it, you will be seen as valuable.
The WA work cover site is a good start, but there are a few holes in it.
Workcover SA's site was very useful for me 5 years ago
Be consultative and consultative. Using decrees to implement OH&S policies means you will have to police them pretty much for ever, having people chose to do the right thing is harder in the short term but best in the long term.
Good luck and have fun, you will learn a lot about how people work
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Good on ya Andy.
There's too many people out there these days who are great at whinging about safety, but not prepared to do anything about it themselves.