A modified dithionite reduction method for the quantification of iron-bound organic carbon in marine sediments

Iron-bound organic carbon (Fe-OC) plays a significant role in the global marine carbon cycle, facilitating the long-term accumulation and storage of organic carbon. However, the conventional method for quantifying Fe-OC, known as the citrate-bicarbonate-dithionite (CBD) method, has limitations in terms of its efficiency in extracting both Fe-OC and iron (Fe). Another CBD method, commonly used for Fe speciation analysis in paleoenvironmental reconstructions, has shown efficient and selective extraction of Fe oxides; however, its effectiveness in extracting Fe-OC remains uncertain. To evaluate the efficiency of the two CBD methods, synthetic samples spiked with organic acid/environmental organic matter‑iron (hydr)oxide coprecipitates and a marine sediment sample were subjected to extraction. The CBD approach for Fe speciation analysis at pH 4.8 on spiked samples demonstrated higher efficiency compared to the conventional CBD method, but not for samples of marine sediment. This result suggests that the synthetic Fe-OC in the spiked samples did not accurately represent the realistic state of Fe-OC in marine sediments. We found that the pH of the leaching solution during the CBD extraction significantly influenced the efficiency of the Fe-OC and Fe extraction. Our tests at pH 4.8, 5.5, 6.0, 6.5, and 7.0 revealed that lower pH enhanced the extraction of Fe, but hindered the release of Fe-OC. Our study revealed that the new CBD (pH 6.5) method resulted in approximately 30% higher yields of Fe-OC and Fe compared to the conventional CBD method, despite of significant variability in the Fe-OC data. The modified CBD (pH 6.5) method uses lower concentration of extraction reagent and reaction temperature, both of which is considered beneficial. Therefore, we suggest that the new CBD method (pH 6.5) is at least of similar efficiency as the conventional method, and can be employed alongside the established method to facilitate the evaluation of the role of Fe-OC in the marine carbon cycle.