Homer Bhullar
Vice President, Investor Relations and Finance at Valero Energy
Thanks, Joe. For the third quarter of 2021, net income attributable to Valero stockholders was $463 million or $1.13 per share compared to a net loss of $464 million or $1.14 per share for the third quarter of 2020. Third quarter 2021 adjusted net income attributable to Valero stockholders was $500 million or $1.22 per share compared to an adjusted net loss of $472 million or $1.16 per share for the third quarter of 2020.
For reconciliations to adjusted amounts, please refer to the financial tables that accompany the earnings release. The refining segment reported $835 million of operating income for the third quarter of 2021 compared to a $629 million operating loss for the third quarter of 2020. Third quarter 2021 adjusted operating income for the refining segment was $853 million compared to an adjusted operating loss of $575 million for the third quarter of 2020.
Refining throughput volumes in the third quarter of 2021 averaged 2.9 million barrels per day, which was 338,000 barrels per day higher than the third quarter of 2020. Throughput capacity utilization 91% in the third quarter of 2021 compared to 80% in the third quarter of 2020. Refining cash operating expenses of $4.53 per barrel were $0.27 per barrel higher than the third quarter of 2020, primarily due to higher natural gas prices. The renewable diesel segment operating income was $108 million for the third quarter of 2021 compared to $184 million for the third quarter of 2020.
Renewable diesel sales volumes averaged 671,000 gallons per day in the third quarter of 2021, which was 199,000 gallons per day lower than the third quarter of 2020. The lower operating income and sales volumes in the third quarter of 2021 are primarily attributed to plant downtime due to Hurricane Ida. The ethanol segment reported a $44 million operating loss for the third quarter of '21 compared to $22 million of operating income for the third quarter of 2020.
Excluding the adjustments shown in the accompanying earnings release tables, third quarter 2021 adjusted operating income was $4 million compared to $36 million for the third quarter of 2020. Ethanol production volumes averaged 3.6 million gallons per day in the third quarter of 2021, which was 175,000 gallons per day lower than the third quarter of 2020. For the third quarter of 2021, G&A expenses were $195 million and net interest expense was $152 million.
Depreciation and amortization expense was $641 million and income tax expense was $65 million for the third quarter of 2021. The effective tax rate was 11%, which reflects the benefit from the portion of DGD's net income that is not taxable to us. Net cash provided by operating activities was $1.4 billion in the third quarter of 2021. Excluding the favorable impact from the change in working capital of $379 million and our joint venture partner's 50% share of Diamond Green Diesel's net cash provided by operating activities, excluding changes in DGD's working capital, adjusted net cash provided by operating activities was $1 billion.
With regard to investing activities, we made $585 million of total capital investments in the third quarter of 2021, of which $191 million was for sustaining the business, including costs for turnarounds, catalysts and regulatory compliance and $394 million was for growing the business. Excluding capital investments attributable to our partner's 50% share of Diamond Green Diesel and those related to other variable interest entities, capital investments attributable to Valero were $392 million in the third quarter of 2021. Moving to financing activities.
We returned $400 million to our stockholders in the third quarter of 2021 through our dividend, resulting in a payout ratio of 40% of adjusted net cash provided by operating activities for the quarter. With respect to our balance sheet at quarter end, total debt and finance lease obligations were $14.2 billion, and cash equivalents were $3.5 billion. And as Joe mentioned earlier, we redeemed the entire outstanding principal amount of our $575 million Floating Rate Senior Notes due in 2023 in the third quarter.
The debt-to-capitalization ratio, net of cash and cash equivalents was 37%. And at the end of September, we had $5.2 billion of available liquidity, excluding cash. Turning to guidance. We still expect capital investments attributable to Valero for 2021 to be approximately $2 billion, which includes expenditures for turnarounds, catalysts and joint venture investments. About 60% of our capital investments is allocated to sustaining the business and 40% to growth.
And over 60% of our growth capital in 2021 is allocated to expanding our renewable diesel business. For modeling our fourth quarter operations, we expect refining throughput volumes to fall within the following ranges: Gulf Coast at 1.67 million to 1.72 million barrels per day; Mid-Continent at 455,000 to 475,000 barrels per day; West Coast at 230,000 to 250,000 barrels per day; and North Atlantic at 435,000 to 455,000 barrels per day. We expect refining cash operating expenses in the fourth quarter to be approximately $4.70 per barrel.
With respect to the renewable diesel segment, we expect sales volumes to average one million gallons per day in 2021. Operating expenses in 2021 should be $0.50 per gallon, which includes $0.15 per gallon for noncash costs such as depreciation and amortization. Our ethanol segment is expected to produce 4.2 million gallons per day in the fourth quarter. Operating expenses should average $0.43 per gallon, which includes $0.05 per gallon for noncash costs such as depreciation and amortization. For the fourth quarter, net interest expense should be about $150 million and total depreciation and amortization expense should be approximately $600 million. For 2021, we still expect G&A expenses, excluding corporate depreciation, to be approximately $850 million.
That concludes our opening remarks. [Operator Instructions]