Homer Bhullar
Vice President-Investor Relations & Finance at Valero Energy
Thanks, Joe. For the fourth quarter of 2022, net income attributable to Valero stockholders was $3.1 billion or $8.15 per share compared to $1 billion or $2.46 per share for the fourth quarter of 2021. Fourth quarter 2022 adjusted net income attributable to Valero stockholders was $3.2 billion or $8.45 per share compared to $988 million or $2.41 per share for the fourth quarter of 2021.
For 2022, net income attributable to Valero stockholders was $11.5 billion or $29.04 per share compared to $930 million or $2.27 per share in 2021. 2022 adjusted net income attributable to Valero stockholders was $11.6 billion or $29.16 per share compared to $1.2 billion or $2.81 per share in 2021. For reconciliations to adjusted amounts, please refer to the earnings release and the accompanying financial tables.
The Refining segment reported $4.3 billion of operating income for the fourth quarter of 2022 compared to $1.3 billion for the fourth quarter of 2021. Adjusted operating income for the fourth quarter of 2022 was $4.4 billion compared to $1.1 billion for the fourth quarter of 2021. Refining throughput volumes in the fourth quarter of 2022 averaged 3 million barrels per day. Throughput capacity utilization was 97% in the fourth quarter of 2022. Refining cash operating expenses of $5 per barrel in the fourth quarter of 2022 were $0.14 per barrel higher than the fourth quarter of 2021, primarily attributed to higher natural gas prices.
Renewable Diesel segment operating income was $261 million for the fourth quarter of 2022 compared to $150 million for the fourth quarter of 2021. Renewable Diesel sales volumes averaged 2.4 million gallons per day in the fourth quarter of 2022, which was 851,000 gallons per day higher than the fourth quarter of 2021. The higher sales volumes were due to the impact of additional volumes from the DGD St. Charles plant expansion and the fourth quarter 2022 start-up of the DGD Port Arthur plant.
The Ethanol segment reported $7 million of operating income for the fourth quarter of 2022 compared to $474 million for the fourth quarter of 2021. Adjusted operating income for the fourth quarter of 2022 was $69 million compared to $475 million for the fourth quarter of 2021. Ethanol production volumes averaged 4.1 million gallons per day in the fourth quarter of 2022. The higher operating income in the fourth quarter of 2021 was primarily attributed to multiyear high ethanol prices due to strong demand and low inventories.
For the fourth quarter of 2022, G&A expenses were $282 million and net interest expense was $137 million. G&A expenses were $934 million in 2022. Depreciation and amortization expense was $633 million and income tax expense was $1 billion for the fourth quarter of 2022. The annual effective tax rate was 22% for 2022. Net cash provided by operating activities was $4.1 billion in the fourth quarter of 2022 and $12.6 billion for the full year. Excluding the unfavorable change in working capital of $9 million in the fourth quarter and $1.6 billion in 2022 and the other joint venture member share of DGD's net cash provided by operating activities, excluding changes in DGD's working capital -- adjusted net cash provided by operating activities was $4 billion for the fourth quarter and $13.8 billion for the full year.
Regarding investing activities, we made $640 million of capital investments in the fourth quarter of 2022, of which $349 million was for sustaining the business, including costs for turnarounds, catalysts and regulatory compliance and $291 million was for growing the business. Excluding capital investments attributable to the other joint venture members share of DGD and those related to other variable interest entities, capital investments attributable to Valero were $538 million in the fourth quarter of 2022 and $2.3 billion for the year, which is higher than our annual guidance primarily due to project spend timing on the Port Arthur Coker project and the accelerated completion of the DGD Port Arthur plant.
Moving to financing activities. We returned $2.2 billion to our stockholders in the fourth quarter of 2022 and $6.1 billion in the year, resulting in a 2022 payout ratio of 45% of adjusted net cash provided by operating activities through dividends and stock buybacks. With respect to our balance sheet, we completed additional debt reduction transactions in the fourth quarter that reduced Valero's debt by $442 million through opportunistic open market repurchases.
As Joe noted earlier, this reduction, combined with a series of debt reduction and refinancing transactions since the second half of 2021, have collectively reduced Valero's debt by over $4 billion. We ended the year with $9.2 billion of total debt, $2.4 billion of finance lease obligations and $4.9 billion of cash and cash equivalents. The debt-to-capitalization ratio, net of cash and cash equivalents was approximately 21%, down from the pandemic high of 40% at the end of March 2021, which was largely the result of the debt incurred during the height of the COVID-19 pandemic. And we ended the year well capitalized with $5.4 billion of available liquidity, excluding cash.
Turning to guidance. We expect capital investments attributable to Valero for 2023 to be approximately $2 billion, which includes expenditures for turnarounds, catalysts and joint venture investments. About $1.5 billion of that is allocated to sustaining the business and $500 million to growth. For modeling our first quarter operations, we expect refining throughput volumes to fall within the following ranges: Gulf Coast at 1.59 million to 1.64 million barrels per day; Mid-Continent at 415,000 to 435,000 barrels per day; West Coast at 245,000 to 265,000 barrels per day; and North Atlantic at 415,000 to 435,000 barrels per day.
We expect refining cash operating expenses in the first quarter to be approximately $4.95 per barrel. With respect to the Renewable Diesel segment, we expect sales volumes to be approximately 1.2 billion gallons in 2023. Operating expenses in 2023 should be $0.49 per gallon, which includes $0.19 per gallon for noncash costs such as depreciation and amortization. Our Ethanol segment is expected to produce 4 million gallons per day in the first quarter. Operating expenses should average $0.51 per gallon, which includes $0.05 per gallon for noncash costs such as depreciation and amortization.
For the first quarter, net interest expense should be about $130 million and total depreciation and amortization expense should be approximately $655 million. For 2023, we expect G&A expenses, excluding corporate depreciation, to be approximately $925 million. That concludes our opening remarks.
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