Title 5/38 Hybrid (Most pharmacists, probably you too):
It's both. Standard for annual leave is 6 h per 80 hours at 3 years plus a 10 hour one pay period so it adds to 160 h/year and 8 h per 80 hours at 15 years (so if you work 60 hours a pay period, your hours are multiplied by 0.75) and caps at 240 h in a calendar year (as in, you cannot carry over more than 240 to the next calendar year). Promotions to GS-14 and higher may come with a bump to the next level 8 hours as an incentive for supervision (the way that works is that you get whatever the next level as comp time). If you did a year of residency, that tends to count toward the seniority accumulation. There are provisions for accumulating leave in OT situations but they are rather rare.
Sick leave is always 4 hours per 80 hours and is separate than the annual leave where it does not cap.
Titles 10 and 42 (~3%):
8 hours per two weeks irrespective of actual hours (no prorating for partial weeks or super overtime). Cap is 720 hours. HOWEVER, leave must be contiguous (so, if you want two weeks off continuously starting on the Monday, you have to take off the Saturday and Sunday as well for 96 hours and not just Monday through Friday each week).
Title 5 SES (7 pharmacists currently):
8 hours per two weeks irrespective of actual hours (no prorating for partial weeks or super overtime). Cap is 720 hours. Does not have the contiguous penalty that Title 10 and Tile 42 have. Instead, leave has to be countersigned by the ADUSH or DASH(IT) of your organization which means that you have to submit your leave a fiscal quarter in advance. Also, you can be ordered to take leave against your will in this mode.