Species-Specific Isotope Dilution-Based Calibration for Trace Element Speciation and Its Combined Uncertainty Evaluation: Determination of Tributyltin in Sediment by HPLC−ICPMS
Bibliographic record
Abstract
A method is described for the determination of tributyltin (TBT) in NRCC sediment CRM PACS-2 by isotope dilution (ID) analysis using HPLC-ICPMS. Reverse spike ID analysis was performed to determine the accurate concentration of a 117Sn-enriched TBT spike using a well-characterized natural abundance TBT standard. The accuracy of the latter is critical for obtaining reliable results. A unique approach, using hydride generation GC/MS, was developed to quantify the inorganic Sn and dibutyltin impurities in the natural abundance TBT standard. The true natural abundance TBT standard concentration was obtained following correction for these impurities. The total Sn concentration in the natural abundance TBT standard was determined by ID analysis using an enriched inorganic 117Sn following closed vessel mixed-acid digestion. Calibration of the enriched inorganic 117Sn standard was achieved by reverse ID analysis against a natural abundance inorganic tin standard prepared from the high-purity metal. An overall uncertainty associated with the present method was estimated, to which the uncertainties arising from measurement of the natural abundance TBT concentration, from the measurement of the isotope ratio in the spiked sample and in the reverse ID calibration solutions, and from estimation of the extraction efficiency were the main contributors. A concentration of 1.018 +/- 0.054 mg kg(-1) (expanded uncertainty, k = 2) as tin was obtained for TBT in PACS-2 using the present method, in excellent agreement with the certified value of 0.98 +/- 0.13 mg kg(-1) (95% confidence interval). A TBT concentration of 0.97 +/- 0.11 mg kg(-1) (expanded uncertainty, k = 2) as tin in PACS-2 was determined using the standard additions technique. Much smaller expanded uncertainty was obtained with ID, clearly demonstrating its superiority in providing more accurate and precise results over the method of additions. A detection limit (3sigma) of 0.02 mg kg(-1) for TBT, based on a 0.5-g subsample, was obtained.
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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) | 0.001 | 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".