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I've just bought a 2002 Chevy Suburban with the Flex-Fuel 5.3 liter engine (code Z). Does this engine have an aluminum or cast iron block? How about the heads?
 

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Your engine should be the 5.3 L59 aluminum

GM does make an aluminum block variant of the 5.3 that has been used in GM's truck lineup with models like the SSR.
The 5.3 Generation III engines came in the following variants: LM4, L59 (aluminum) LM7 (cast iron) and were used in:

L59 (flexible-fuel, allowing E85) applications:

Chevrolet Silverado 1500-2500/GMC Sierra 1500-2500
Chevrolet Suburban/GMC Yukon XL
Chevrolet Tahoe/GMC Yukon

LM4 (all-aluminum) applications:

Chevrolet TrailBlazer EXT
GMC Envoy XL
2004 Chevrolet SSR

LM7 (iron block, low-emmissions) applications:

Cadillac Escalade
Chevrolet Avalanche
Chevrolet Express/GMC Savana
Chevrolet Silverado 1500-2500/GMC Sierra 1500-2500
Chevrolet Suburban/GMC Yukon XL
Chevrolet Tahoe/GMC Yukon

For 2007 GM offered the following 5.3 engines:
5.3L FlexFuel V-8 (LMG), E85-capable with iron block and Active Fuel Management; 315 hp and 338 lb.-ft. of torque.
5.3L FlexFuel V-8 (LC9), E85-capable with aluminum block and Active Fuel Management; 315 hp and 338 lb.-ft. of torque.
5.3L V-8 (LH6), with aluminum block and Active Fuel Management; 315 hp and 338 lb.-ft. of torque.
5.3L V-8 (LY5), with iron block and Active Fuel Management; 315 hp and 338 lb.-ft. of torque.
 
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