Substitution refers to the process of substituting a user's "dirty" urine with "clean" urine from another person or an animal, or with synthetic urine. Earlier substitution methods included collecting a "clean" person's or a pet's urine in a container and then dispensing it into the collection cup discreetly. However, the freshness of the urine became a problem. Further, it was difficult to constantly stash a volume of this urine in preparation for random testing. Recently, synthetic urine kits with long shelf life have become available. A typical kit consists of a pouch of liquid or lyophilized synthetic urine with temperature indicator, disposable heating pad, a strap to hold the pouch, and tubing with clamp to deliver the synthetic urine.

To prevent detection under observed collection, one company even markets a prosthetic delivery device shaped like a penis (named the Whizzinator™), which comes in five different colors that match the color of one's skin.

A modification of the substitution process is subjecting the "dirty" urine sample to a purification procedure to remove drug molecules. Products such as Zip N Flip™ and Bake-n-shake™ are kits with a zip-lock bag containing a resinous material like activated charcoal. The urine sample from the collection cup is poured into the bag and swished. The cleansed urine is then poured back into the cup. Such action, of course, can be performed only with unobserved collection.

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