Adsorption of (Poly)vanadate onto Ferrihydrite and Hematite: An <i>In Situ</i> ATR–FTIR Study
Bibliographic record
Abstract
Vanadium (V) geochemistry offers insight into Earth’s global biogeochemical cycles over geologic time. Additionally, increasing anthropogenic release of this redox-sensitive metal has led to elevated V concentrations in soils, sediments, and waters. Although Fe (oxyhydr)oxides are important sinks for aqueous V in soils and sediments, our understanding of adsorption mechanisms is currently limited to mononuclear species (i.e., HxVO4(3–x)–). Here, we use in situ attenuated total reflectance–Fourier transform infrared spectroscopy to examine the sorption mechanisms for (poly)vanadate attenuation by ferrihydrite and hematite from pH 3 to 6. Adsorption isotherms illustrate the low affinity of polyvanadate species for ferrihydrite surfaces compared to that for hematite. Mononuclear V species (i.e., [HxVO4](3–x)– and VO2+) were present at all experimental conditions. At low surface loadings and pH values of 5 and 6, H2VO4– adsorption onto ferrihydrite and hematite surfaces results in the formation of inner-sphere complexes. At [V]T above 250 μM, adsorbed polynuclear V species in this study include H2V2O72– and V4O124–, whereas, HV10O286–, H3V10O285–, and NaHV10O284– are the predominant adsorbed species at pH values of 3 and 4 and elevated [V]T’s. Surface polymers were identified on hematite at all experimental pH values, whereas polymeric adsorption onto ferrihydrite was limited to pH values of 3 and 4. Results also suggest that hematite is a more suitable substrate for polymer complexation than ferrihydrite. Our results demonstrate the pH- and concentration-dependent removal of (poly)vanadate species by Fe(III) (oxyhydr)oxides, which has implications for understanding V mobility, behavior, and fate in the environment.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".