Payments of PTO to employees are generally considered regular wages and would be included with taxable wages in box 1 of the W2. Taxes would be calculated the same as if the PTO amounts were regular wages.
Regarding fuel expenses paid to your employees, it depends under what type of plan or agreement you pay these to your employees;
1. If your employees submit their mileage to you and you reimburse them for the entire approved expense, there really is no need to report those amount on the W2. They are not taxable income to your employees. Please note, however, you can use box 14 to report any auto reimbursements or general information regarding wages, if you prefer.
2. If you pay your employees a set amount per month or don't require them to account for their mileage, then any amount you pay them would be considered taxable wages and should be included in box 1.
The IRS regulations on accountable and non accountable plans are quite extensive, but here is a link that has a good summary of the general rules: Accountable vs Non Accountable Auto Reimbursement Plans
Also, please note, you can use box 14 to report any auto reimbursements or general information regarding wages, if you prefer.
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