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When I was there, there was no way to purchase at border.
Also, not even a tiny bit of English spoken by guards so brush up on your Spanish. Our friends from Chile drove their car and had no difficulty. There are two different protocols depending on which country you are entering.
The immigration people at Iquique didn't want anything to do with the reciprocity fee so I didn't pay.
For Argentina you must pay the fee online before embarking on plane, bus or boat and need to show the receipt before you embark. The pass over the Andes can close at any time of year due to bad weather, so leave at least a couple of days between crossing by land and a flight.