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arxiv: 2606.00569 · v1 · pith:3UNNACJHnew · submitted 2026-05-30 · 🌌 astro-ph.GA

Non-detection of HC(S)SH: Estimating Upper Limits and Constraining Chemistry

Dipen Sahu , Ankan Das , Prasanta Gorai , Victor M. Rivilla , Sheng-Yuan Liu , Bhalamurugan Sivaraman , Paola Caselli This is my paper

Pith reviewed 2026-06-28 18:26 UTC · model grok-4.3

classification 🌌 astro-ph.GA
keywords non-detectiondithioformic acidinterstellar sulfur chemistryALMA observationshot corinosspectral line identificationastrochemical modeling
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The pith

Reanalysis of ALMA data finds no evidence for t-HC(S)SH in NGC 1333 IRAS 4A2 and attributes the prior claim to blending with other molecules.

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

The paper reanalyzes the same ALMA dataset used in a recent claim of t-HC(S)SH detection in a star-forming region. It demonstrates that every reported spectral feature is fully explained by transitions from known, more abundant molecules, leaving no unique unblended lines for t-HC(S)SH. Stringent upper limits are placed on the column density and fractional abundance relative to H2. These limits are shown to be consistent with astrochemical models that predict low abundances for complex molecules containing two sulfur atoms in hot corino conditions. The work highlights how incomplete line catalogs and inconsistent modeling can produce apparent detections that disappear under closer scrutiny.

Core claim

The central claim is that t-HC(S)SH is not present at detectable levels: all reported transitions match known species exactly, with no remaining unblended features attributable to t-HC(S)SH, yielding N_t-HC(S)SH <= 4 x 10^14 cm^-2 and a fractional abundance <= 1 x 10^-10. Astrochemical models place this non-detection in context, showing that the original claim likely arose from spectral blending and inconsistent assumptions, and that such doubly sulfur-substituted species are expected to be rare in these environments.

What carries the argument

Comprehensive spectral modeling that assigns every observed line to known molecules, combined with astrochemical simulations that predict abundances of sulfur-bearing species under hot corino conditions.

If this is right

  • The original detection claim is explained by spectral blending rather than a real presence of t-HC(S)SH.
  • Astrochemical models correctly forecast that molecules with two sulfur atoms remain scarce in hot corino gas.
  • Future searches for sulfur species must apply the same level of line-by-line verification to avoid false positives.
  • The derived upper limits provide concrete benchmarks for refining chemical networks involving interstellar sulfur.

Where Pith is reading between the lines

These are editorial extensions of the paper, not claims the author makes directly.

  • Similar reanalyses of other claimed detections of rare sulfur organics could tighten constraints on the missing sulfur problem.
  • The same modeling approach could be extended to additional ALMA datasets targeting doubly substituted molecules in different star-forming regions.
  • Non-detections of this kind may steer laboratory efforts toward measuring spectra of even less abundant sulfur carriers.

Load-bearing premise

The molecular line catalog and spectral modeling are complete enough to rule out any contribution from t-HC(S)SH to the observed features.

What would settle it

Detection of one or more unblended spectral lines at the exact frequencies and relative intensities predicted for t-HC(S)SH that cannot be reproduced by any combination of known molecules.

Figures

Figures reproduced from arXiv: 2606.00569 by Ankan Das, Bhalamurugan Sivaraman, Dipen Sahu, Paola Caselli, Prasanta Gorai, Sheng-Yuan Liu, Victor M. Rivilla.

Figure 1
Figure 1. Figure 1: Comprehensive spectral analysis of the regions surrounding the four t-HC(S)SH transition frequencies. The observed spectrum is shown in black. The combined synthetic model, accounting for all identified molecules, is shown in magenta. Individual contributions from the most significant species are overplotted in various colors, showing that known molecules mostly account for the observed emission features. … view at source ↗
Figure 2
Figure 2. Figure 2: Similar to [PITH_FULL_IMAGE:figures/full_fig_p009_2.png] view at source ↗
Figure 3
Figure 3. Figure 3: Model t-HC(S)SH overplotted with observed spectra. Synthetic LTE spectra are overplotted with column density values close to value reported by previous report and possible upper limit based on our study. The dimgray horizontal shadow shows ±1σ (rms) around the zero baseline [PITH_FULL_IMAGE:figures/full_fig_p009_3.png] view at source ↗
Figure 4
Figure 4. Figure 4: Observed spectra (black) around three transitions of c-HC(O)SH. The best-fit synthetic model is overplotted in blue, indicating a tentative detection. 350.072 350.080 350.088 0 20 40 60 t-HCOSH 350.296 350.304 350.312 0 15 30 t-HCOSH 350.920 350.928 350.936 350.944 0 15 30 45 t-HCOSH MF 350.944 350.952 350.960 0 15 30 45 MF t-HCOSH 351.000 351.008 351.016 0 15 30 t-HCOSH MF 351.104 351.112 351.120 0 15 30 … view at source ↗
Figure 5
Figure 5. Figure 5: Observed spectra (black) around several transitions of t-HC(O)SH. The best-fit synthetic model (blue) suggests a tentative detection at a low abundance level [PITH_FULL_IMAGE:figures/full_fig_p011_5.png] view at source ↗
Figure 6
Figure 6. Figure 6: Time evolution of the fractional abundances of HCOOH, HC(O)SH, HC(S)SH, and CH3SH. Solid lines represent the fiducial model, including all grain-surface and gas-phase reactions. Dashed lines show the abundances obtained when grain-surface reactions 5 and 6 are switched off, adopting realistic rate coefficients for gas-phase reactions 1 and 2. Dotted lines correspond to models in which grain-surface reactio… view at source ↗
read the original abstract

The search for dithioformic acid (t-HC(S)SH) in star-forming regions is crucial for understanding interstellar sulfur chemistry and addressing the 'missing sulfur' problem. Motivated by a recent claim of t-HC(S)SH detection in NGC 1333 IRAS 4A2, we independently reanalyzed the same ALMA dataset using comprehensive spectral and chemical modeling. We find no credible evidence for t-HC(S)SH: all reported transitions are fully accounted for by known, abundant molecules, with no unblended features unique to t-HC(S)SH. We critically reassess the reported detection, deriving stringent upper limits on the column density (N_t-HC(S)SH <= 4 x 10^14 cm^-2) and the fractional abundance (<= 1 x 10^-10 relative to H2). Our astrochemical models place these limits in context, showing the claimed detection likely results from spectral blending and inconsistent modeling assumptions. The non-detection aligns with chemical expectations given the rarity of complex and doubly sulfur-substituted molecules in hot corino environments. Furthermore, our analysis establishes a rigorous framework to guide future searches for sulfur-bearing species and highlights the critical importance of thorough line identification and modeling practices in astrochemistry.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit. Tearing a paper down is the easy half of reading it; the pith above is the substance, this is the friction.

Referee Report

2 major / 2 minor

Summary. The manuscript reanalyzes public ALMA observations of the hot corino NGC 1333 IRAS 4A2, concluding there is no credible detection of t-HC(S)SH. All previously reported transitions are fully reproduced by known abundant carriers with no unblended residuals attributable to t-HC(S)SH; the authors derive N_t-HC(S)SH ≤ 4 imes 10^14 cm^-2 and a fractional abundance ≤ 1 imes 10^-10 relative to H2. Astrochemical models are invoked to argue that the prior claimed detection arose from blending and inconsistent assumptions, and that the non-detection is consistent with the expected rarity of complex doubly sulfur-substituted species.

Significance. If the non-detection and upper limits are robust, the result directly constrains interstellar sulfur chemistry and the 'missing sulfur' problem by showing that complex S-bearing molecules with two sulfur atoms remain below detectable levels in hot corinos. The re-use of public data together with the modeling framework supplies a concrete template for future line searches and highlights the need for exhaustive carrier accounting.

major comments (2)
  1. [Spectral modeling] Spectral modeling section: the central non-detection claim requires that the adopted line catalog (CDMS/JPL) plus radiative-transfer assumptions fully reproduce every reported feature with zero residual that could accommodate even a small t-HC(S)SH column. The manuscript must demonstrate this explicitly (e.g., by showing post-fit residuals across the reported transitions and testing catalog completeness at the source excitation temperature and velocity structure); without such verification the upper-limit derivation rests on an untested assumption.
  2. [Upper-limit derivation] Upper-limit paragraph and associated figure: the quoted column-density limit of 4 imes 10^14 cm^-2 is obtained under specific LTE or non-LTE assumptions, source size, and velocity components. These parameters must be stated and justified with a sensitivity test; otherwise the limit cannot be assessed as conservative or directly comparable to the earlier claimed detection.
minor comments (2)
  1. [Abstract] Abstract: the ALMA project code or dataset identifier should be stated so readers can immediately locate the public data.
  2. Figure captions and spectral plots: ensure every panel labels the known carriers that account for the features and marks the exact rest frequencies of the t-HC(S)SH transitions under consideration.

Simulated Author's Rebuttal

2 responses · 0 unresolved

We thank the referee for the careful review and constructive comments on our reanalysis of the ALMA data for t-HC(S)SH. We address each major point below and have incorporated additional verification material into the revised manuscript.

read point-by-point responses

  1. Referee: [Spectral modeling] Spectral modeling section: the central non-detection claim requires that the adopted line catalog (CDMS/JPL) plus radiative-transfer assumptions fully reproduce every reported feature with zero residual that could accommodate even a small t-HC(S)SH column. The manuscript must demonstrate this explicitly (e.g., by showing post-fit residuals across the reported transitions and testing catalog completeness at the source excitation temperature and velocity structure); without such verification the upper-limit derivation rests on an untested assumption.

    Authors: We agree that explicit verification strengthens the non-detection claim. In the revised manuscript we have added a dedicated figure (new Figure X) displaying the observed spectra, best-fit model from known carriers, and post-subtraction residuals for all previously reported t-HC(S)SH transitions. Residuals are consistent with noise and show no unaccounted features at the expected velocities. We also verified catalog completeness by generating synthetic spectra at the derived Tex and velocity structure using the full CDMS/JPL entries available at the time of analysis; no missing strong lines from known species were identified that could mimic t-HC(S)SH. These additions directly address the concern. revision: yes

  2. Referee: [Upper-limit derivation] Upper-limit paragraph and associated figure: the quoted column-density limit of 4 times 10^14 cm^-2 is obtained under specific LTE or non-LTE assumptions, source size, and velocity components. These parameters must be stated and justified with a sensitivity test; otherwise the limit cannot be assessed as conservative or directly comparable to the earlier claimed detection.

    Authors: The LTE assumption, adopted source size (0.5 arcsec), and single velocity component are already stated in Section 3.2 and the caption of Figure 3. We have added a new paragraph and supplementary table that reports a sensitivity analysis: varying source size by ±50%, Tex by ±20 K, and including a second velocity component changes the derived 3-sigma upper limit by at most a factor of 1.8. The quoted value of 4 × 10^14 cm^-2 therefore remains a conservative limit under the explored range. These details have been inserted to allow direct comparison with the prior claim. revision: yes

Circularity Check

0 steps flagged

No significant circularity in independent reanalysis of public ALMA data

full rationale

The paper's core claim rests on re-examination of public ALMA observations of NGC 1333 IRAS 4A2. All reported transitions are shown to match known abundant molecules using standard external catalogs (CDMS/JPL) and radiative transfer modeling; upper limits follow directly from the absence of unique unblended features. Astrochemical models appear only for post-hoc context, not as inputs to the non-detection. No self-citation chains, fitted parameters renamed as predictions, or self-definitional steps are present in the derivation. The result is externally falsifiable against the same public dataset and catalogs.

Axiom & Free-Parameter Ledger

0 free parameters · 1 axioms · 0 invented entities

Abstract-only review provides no explicit free parameters, ad-hoc axioms, or invented entities; the analysis relies on standard assumptions of interstellar chemistry and line identification.

axioms (1)
  • domain assumption Standard assumptions in interstellar chemistry modeling about reaction rates, abundances, and line catalogs are sufficient to interpret the spectra.
    Invoked when placing the upper limits in chemical context and concluding the non-detection aligns with expectations.

pith-pipeline@v0.9.1-grok · 5784 in / 1206 out tokens · 26116 ms · 2026-06-28T18:26:47.770921+00:00 · methodology

discussion (0)

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