MINDS. The Detection of ¹³CO₂ with JWST-MIRI Indicates Abundant CO₂ in a Protoplanetary Disk

The inner 10 au of protoplanetary disks are regions of active chemistry, with high temperatures and densities and with the snowlines of H₂O and CO₂ controlling the gas composition (e.g., Pontoppidan et al. 2014; Walsh et al. 2015; Bosman et al. 2022). The chemistry in this region is expected to impact the atmospheric compositions of any exoplanets, the bulk of which are expected to form in this region (Dawson & Johnson 2018; Öberg & Bergin 2021; Mollière et al. 2022), which is difficult to probe with the Atacama Large Millimeter/submillimeter Array (ALMA).

Of the several species that emit from the inner ∼10 au of disks, CO₂ is a particularly informative tracer of the physical and chemical conditions in this region. In the interstellar medium, ices are rich in CO₂ (abundances of 10⁻⁵ with respect to the total gas density; de Graauw et al. 1996; Gibb et al. 2004; Bergin et al. 2005; Pontoppidan et al. 2008; Boogert et al. 2015). However, the CO₂ abundance in disks, derived from both local thermodynamic equilibrium (LTE) slab models and full disk non-LTE modeling of Spitzer-InfraRed-Spectrograph (IRS) observations, is between 10⁻⁹ and 10⁻⁷ with respect to the total gas density, indicating reprocessing in the disk (Salyk et al. 2011; Pontoppidan & Blevins 2014; Bosman et al. 2017). Despite these lower disk abundances, Pontoppidan et al. (2010) found that CO₂ was the second most common molecule detected in disks (20 disks) after water (25 disks) in a sample of 73 protoplanetary disks observed with Spitzer-IRS. In those sources, the CO₂ Q branch at 14.9 μm was useful as a diagnostic of the gas temperature and abundance in their inner regions. Besides ice production, CO₂ is also formed in the gas phase at moderate temperatures (100–200 K) through the reaction of CO + OH → CO₂ + H. At higher temperatures, OH primarily reacts with H₂ to form H₂O. Thus, the CO₂/H₂O ratio is sensitive to the gas temperature.

Despite the usefulness of its typically bright Q branch, ¹²CO₂ is thought to be largely optically thick in the regions of the disk where it is emitting (Bosman et al. 2017). Therefore, optically thinner lines and isotopologues are more useful in determining the column density of CO₂, as well as the physical and chemical conditions in the disk. Moderate spectral resolution and high signal-to-noise observations are needed to detect the weaker optically thin lines and isotopologues, which was not possible with Spitzer. JWST-MIRI provides a new opportunity to study the Q branches of ¹²CO₂ and ¹³CO₂, and the ability to identify individual P- and R-branch lines for ¹²CO₂.

We present JWST-MIRI observations of one of the CO₂-bright sources identified in Spitzer observations: GW Lup (Pontoppidan et al. 2010; Salyk et al. 2011; Bosman et al. 2017). GW Lup (Sz 71) is an M1.5 star (T_eff = 3630 K, L_* = 0.33 L_⊙, M_* = 0.46 M_⊙) in the Lupus I cloud at a distance of 155 pc (Alcalá et al. 2017; Andrews et al. 2018). This target was observed as part of the DSHARP survey (Andrews et al. 2018), which found a very narrow ring of continuum emission at a radius of 85 au in addition to a centrally peaked continuum (Dullemond et al. 2018). We redetect C₂H₂ and strong ¹²CO₂ emission in this disk (Pontoppidan et al. 2010; Salyk et al. 2011; Banzatti et al. 2020) and additionally detect ¹³CO₂, H₂O, HCN, and OH for the first time in this source. We fit the 13.6–16.3 μm wavelength range of the MIRI spectrum with LTE slab models to constrain the column density and temperature for each species. We discuss our findings, in particular the detection of ¹³CO₂, which is the first such detection in a protoplanetary disk, and the column density ratio of CO₂ to H₂O, which provides new insight into the inner disk structure.

2.1. Observations and Data Reduction

GW Lup was observed with the Mid-InfraRed Instrument (MIRI; Rieke et al. 2015; Wells et al. 2015; Wright et al. 2015, Wright et al. 2023, I. Argyriou et al. 2023, in preparation) in the Medium Resolution Spectroscopy (MRS) mode on 2022 August 8. These observations are part of the MIRI mid-INfrared Disk Survey (MINDS) JWST Guaranteed Time Observations Program (PID: 1282, PI: T. Henning). Target acquisition was used so that a point-source fringe flat could be used in the data reduction. A four-point dither was performed in the positive direction. The total exposure time was 1 hr. All the JWST data used in this paper can be found in MAST doi:10.17909/aez2-za93.

The MIRI MRS observations were processed through all three reduction stages (Bushouse et al. 2022) using Pipeline version 1.8.4. The reference files were generated from the observation of the reference A-type star HD 163466. Additional details on the reference files used can be found in Gasman et al. (2023). A single dedicated point-source fringe flat and dedicated spectrophotometric calibration were used in the reduction process. We skip the outlier rejection step in Spec3, as this produces spurious results due to the undersampling of the point-spread function (PSF), causing undersampling artifacts (e.g., short-period oscillations at the beginning and end of each subband) in the extracted spectrum. Undersampling of the PSF and its artifacts will be discussed in an upcoming paper (D. R. Law et al. 2023, in preparation). Finally, the centroid of the PSF was found manually prior to the extraction of the spectra in each subband, which included aperture correction, with an aperture size of 2.5λ/D. The correction factors are the same as those presented in I. Argyriou et al. (2023, in preparation), which include the contribution of the PSF wings to the estimated background determined from an annulus around the source. The background emission from this annulus is subtracted and its value ranges from ∼0.001 Jy in Channel 1 to ∼0.1 Jy around 22 μm. The continuum emission is not extended in the 2D images; therefore, the disk is not resolved.

The final GW Lup spectrum through Channel 4A is presented in Figure 1. At longer wavelengths the flux calibration becomes increasingly uncertain, due to the low flux level at these wavelengths in the reference star used for calibration; therefore, we only show through Channel 4A. The ν₂ = 1–0 ¹²CO₂ Q branch is the most prominent, but a large number of weaker lines are detected as well. A spurious, single-pixel spike at 18.8 μm has been removed. Below 7.5 μm, the Spitzer low-resolution spectrum of GW Lup has a ∼20% higher flux. However, above 7.5 μm, the flux of the JWST-MIRI spectrum is ∼15% higher than the Spitzer-IRS high- and low-resolution spectra of this target, but the overall shape is very similar (see Figure 5 in the Appendix). These offsets may be due to calibration issues and/or variability in this system. This will be investigated in a future work. In this work, we use the MIRI continuum-subtracted spectrum for analysis.

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2.2. Slab Modeling Procedure

The best-fit model is presented in Figure 2 together with the continuum-subtracted spectrum in the 13.6–16.3 μm range. The best-fit model parameters are given in Table 1. The χ² maps show that at low column densities (below ∼10¹⁷–10¹⁸ cm⁻², depending on the molecule, see Figure 7), in the optically thin regime, the column density and emitting radius are completely degenerate (e.g., Salyk et al. 2011). In the optically thick regime, the emitting radius can more accurately be determined, although there is still a degeneracy between temperature and column density. Typical uncertainties can be read from the χ² maps where the degeneracies are also evident. The degeneracy between our three free parameters is reduced by fitting a combination of optically thick and thin lines. For optically thin emission, the total number of molecules ${{ \mathcal N }}_{\mathrm{tot}}$ = π N R² is well determined and is included in Table 1. In GW Lup, we find that the emission of all species is optically thick, or at least on the border between optically thick and optically thin; therefore, the number of molecules should be taken as a lower limit.

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Table 1. Best-fit Model Parameters

Species	N	T	R	${{ \mathcal N }}_{{tot}}$ a
	(cm−2)	(K)	(au)	(mol.)
H2O	3.2 × 1018	625	0.15	5 × 1043
HCN	4.6 × 1017	875	0.06	1.2 × 1042
C2H2	4.6 × 1017	500	0.05	9.3 × 1041
12CO2	2.2 × 1018	400	0.11	1.7 × 1043
13CO2	1 × 1017	325	0.11	9.3 × 1041
OH	1 × 1018	1075	0.06	2.6 × 1042

Note.

^a As the best-fit model parameters reported here are either totally in the optically thick regime or on the border between optically thick and thin, the total molecule number should be taken as a lower limit.

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3.1.  ¹²CO₂ and ¹³CO₂

Our best-fitting ¹²CO₂ model has N = 2.2 × 10¹⁸ cm⁻², a temperature of 400 K, and an emitting radius of 0.11 au. ¹²CO₂ is well constrained to a temperature below ∼700 K, with the shape of the main Q branch being particularly constraining for the temperature. Using similar models and a similar technique on Spitzer-IRS data, Salyk et al. (2011) fit the fundamental ¹²CO₂ Q branch at 14.9 μm and find a temperature of 750 K, a column density of 1.6 × 10¹⁵ cm⁻², and an emitting radius of 1.01 au. While this optically thin model from Salyk et al. (2011) reproduces the main 14.9 μm Q branch, it does not reproduce the ¹²CO₂ hot-band Q branches at 13.9 and 16.2 μm (10⁰0–01¹0) as well as the optically thick model does (Figure 3). An example of the effect of changing the temperature by ± 100 K and column density by ± 0.5 dex on the ¹²CO₂ model is shown in the Appendix in Figure 10.

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For ¹³CO₂, models from both the optically thick and optically thin regimes reproduce the feature well. With respect to ¹²CO₂, the standard ¹²CO₂/¹³CO₂ abundance ratio of 68 from the local interstellar medium (Wilson & Rood 1994; Milam et al. 2005) is within the allowable range. The ¹³CO₂ temperature is lower than that of ¹²CO₂, with the best-fit temperature of 325 K. This indicates that the optically thinner ¹³CO₂ is tracing deeper layers into the disk or larger radii (e.g., in a thin annulus farther out than the ¹²CO₂, but with the same emitting area). The combination of ¹³CO₂ and the P(23) line of ¹²CO₂, reproduces the feature at 15.42 μm.

3.2. H₂O

3.3. Other Species

As CO₂ and H₂O are two of the main oxygen carriers in protoplanetary disks, the relative abundances of these species is informative. While H₂O emission is present in the MIRI MRS spectrum of GW Lup, it is relatively weak compared to CO₂ with an ${N}_{{\mathrm{CO}}_{2}}$/${N}_{{{\rm{H}}}_{2}{\rm{O}}}$ ratio of ∼0.7. It should be stressed that column density ratios should not be equated with abundance ratios since the emission of different molecules (or even of different bands of the same molecule) may originate from different regions or layers of the disk (Bruderer et al. 2015; Woitke et al. 2018). Moreover, the emission seen at mid-infrared wavelengths only probes the upper layers of the disk above the τ_mid−IR = 1 contour where the dust continuum becomes optically thick. To infer local abundances and their ratios, retrieval methods such as used in Mandell et al. (2012) or full forward thermochemical models using a physical structure tailored to the GW Lup disk are needed. Such models are beyond the scope of this paper. However, given the relatively small difference in emitting radii between CO₂ and H₂O, it is still informative to put the column density ratio into perspective.

The large T Tauri Spitzer sample of Salyk et al. (2011) find a median ${N}_{{\mathrm{CO}}_{2}}$/${N}_{{{\rm{H}}}_{2}{\rm{O}}}$ ratio of 5 × 10⁻⁴. However, the column density ratios from Salyk et al. (2011) are largely derived from the low column density and high temperature (optically thin) regime that we exclude using the weaker hot-band ¹²CO₂ Q branches at 13.9 and 16.2 μm. If the best-fitting radii found for H₂O and CO₂ of 0.15 and 0.11 au, respectively, correspond to the actual emitting radius (i.e., not coming from a thin annulus at larger radii with the same emitting area), then we note that these radii are smaller than the estimated midplane snowline of H₂O, which is at ∼0.3–0.4 au for the stellar mass of GW Lup (Mulders et al. 2015). At high temperatures greater than ∼250 K, OH will react with H₂ to form H₂O (Glassgold et al. 2009). Why, then, is CO₂ so abundant relative to H₂O at these temperatures and locations in this disk? We present three scenarios.

• 1.  
  Temperature structure. The temperature structure of the disk, which is largely controlled by the stellar luminosity, has a large impact on the inner disk CO₂ and H₂O abundances and on their molecular emission (e.g., Walsh et al. 2015; Woitke et al. 2018; Anderson et al. 2021). Models and observations have shown that the inner disks around low-mass stars are richer in carbon-bearing species in the disk atmosphere than those around higher-mass stars (e.g., Pascucci et al. 2013; Walsh et al. 2015). GW Lup, with a stellar mass of 0.46 M_⊙, may be a borderline case where the C/O in the infrared emitting region is moderately high, but not so high that C₂H₂ is booming. Additionally, it is clear that H₂O is not so abundant in the upper layers that self-shielding is taking place, since ¹³CO₂ is detected, indicating a deep layer of CO₂. Bosman et al. (2022) show that this occurs if the vertical H₂O column density remains low enough that water self-shielding is suppressed, producing more OH which is needed for additional CO₂ formation. There is always some small amount of H₂O in the disk atmosphere that is being dissociated by UV photons from the star, decreasing the water abundance. This may be contributing to the relatively weak H₂O emission as some OH emission is detected. In the cooler disks around M-type stars, some of the oxygen may also be driven into the unobservable O₂ rather than H₂O, making the atmosphere appear to be carbon rich even though the C/O ratio is solar (Walsh et al. 2015). The moderately low luminosity of GW Lup may contribute to the the higher ${N}_{{\mathrm{CO}}_{2}}$/${N}_{{{\rm{H}}}_{2}{\rm{O}}}$ determined here; however, GW Lup is not so low-mass that this is likely the sole explanation. Future observations of additional targets, will help to demonstrate the impact of temperature structure on the derived column densities.
• 2.  
  Pebble drift. If dust grains coated in CO₂-rich ices are drifting inward from the outer disk without any traps halting the drift, the inner disk will be enriched in oxygen (Banzatti et al. 2020). However, if ice enrichment is taking place both CO₂ and H₂O should be enriched at a ratio of 0.2–0.3 (Boogert et al. 2015), but only if the ices are transported vertically and there is no chemical reset. There may still be additional H₂O and CO₂ hidden below the dust τ_15μm = 1 line. Bosman et al. (2017) compare the flux of the ¹³CO₂ Q-branch at 15.42 μm to the neighboring ¹²CO₂ P(25) line at 15.45 μm, and show that this ratio is sensitive to enhancements of CO₂ at its snowline. In GW Lup, the P(25) line is stronger than the P(23) line, indicative of a contribution from the 11¹0–10⁰0 hot-band Q branch of ¹²CO₂ that is only present at high temperatures/column densities and was not seen in the models of Bosman et al. (2017). Therefore, the P(25) line is not a good representative of an individual P-branch line at these J levels. Instead, the P(27) line at 15.48 μm can be used. From the best-fit models, the peak of the ¹³CO₂ Q-branch is at 6.5 mJy, compared to 4.7 mJy for the P(27) line. In the modeling setup of Bosman et al. (2017), this ¹³CO₂/P(27) line ratio of 1.4 points to a low outer (10⁻⁸ with respect to the total gas density) and high inner (10⁻⁶) disk CO₂ abundance. While this is intriguing, further modeling efforts, such as the full 2D physical-chemical models used by Bosman et al. (2017), are needed to realistically compare the inner and outer disk CO₂ distribution for GW Lup specifically.
• 3.  
  Inner cavity and/or dust trap. If there is an inner gas and dust cavity in the disk that extends to between the H₂O and CO₂ snowlines (estimated at ∼0.4 and >1 au, respectively), the H₂O will be suppressed but the CO₂ will still be abundant in the gas phase. The models of T Tauri disks from Walsh et al. (2015) and Anderson et al. (2021) show that the column densities of H₂O dominate over those of CO₂ in the inner 1 au. A cavity or gap may be present in GW Lup, which would remove abundant H₂O and result in the relatively strong CO₂ lines and relatively weak H₂O lines observed in the GW Lup disk. In this case, the H₂O will only be present in the uppermost layers of the disk atmosphere or at the heated edge of the cavity/gap where the icy grains are warm enough to sublimate water ice and/or where any free volatile oxygen is driven into H₂O. Anderson et al. (2021) find that the H₂O flux decreases substantially if an inner gas cavity is present, while the CO₂ flux is less affected due to having more contribution from emission at larger radii, although as they note, the fluxes may not accurately reflect the column densities and abundances. If there is a dust trap between the snowlines, either created by the same mechanism opening the cavity or by other means, water ice-rich grains could be trapped beyond the H₂O snowline, keeping H₂O from sublimating but allowing for the sublimation and enrichment of CO₂. Such a small cavity cannot be seen in the ALMA data, even with the high resolution of the DSHARP data. A small cavity in the dust could be traced in the dust continuum with near-infrared interferometry, whereas a gas cavity could be traced using high-spectral-resolution spectroscopy, for instance, of the CO rovibrational lines at 4.7 μm (e.g., Brown et al. 2013; Banzatti et al. 2022). None of these data exist yet for the GW Lup disk.

As more sources are observed with JWST-MIRI, these scenarios can be explored further. For instance, looking for trends of the CO₂ versus H₂O as a function of stellar luminosity and outer disk dust radius will be very informative in distinguishing between the importance of temperature structure versus pebble drift, as was done with Spitzer data. In the meantime, GW Lup can be put into context with other sources based on the Spitzer fluxes. Banzatti et al. (2020) (re)determined molecular line fluxes for H₂O, HCN, C₂H₂, and CO₂ for the Spitzer sample. While GW Lup has a relatively high Q-branch CO2 flux and relatively low 17 μm H2O flux compared to other disks, it is not a complete outlier (converted to line luminosities for comparison; Figure 4). Several disks in the Spitzer survey analyzed by Pontoppidan et al. (2010), Salyk et al. (2011), and Banzatti et al. (2020) also show high CO₂ fluxes and low water fluxes, including DN Tau, IM Lup, MY Lup, and CX Tau (Figure 4). With the sensitivity and resolution of MIRI, there are likely to be other disks that will show ¹³CO₂ emission, which will allow us to derive strong constraints on the CO₂ column density and ${N}_{{\mathrm{CO}}_{2}}$/${N}_{{{\rm{H}}}_{2}{\rm{O}}}$ ratio in these disks.

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• 1.  
  We identify ¹²CO₂, ¹³CO₂, H₂O, HCN, C₂H₂, and OH in the JWST-MIRI spectrum of GW Lup. Using LTE slab models, we reproduce the 13.6–16.3 μm spectrum. H₂O, HCN, ¹³CO₂, and OH are detected for the first time in this disk, as the features had line/continuum ratios that were too low to be detectable at the spectral resolution of Spitzer-IRS.
• 2.  
  The gas-phase ¹³CO₂ detection is the first in a protoplanetary disk. This detection points to a high CO₂ abundance deep into the disk, with a ¹²CO₂ column density of 2.2 × 10¹⁸ cm⁻², temperature of 400 K, and an emitting radius of 0.11 au. For ¹³CO₂, the best-fit model has a column density of 1 × 10¹⁷ cm⁻², temperature of 325 K, and an emitting radius of 0.11 au.
• 3.  
  The column density ratio of CO₂ to H₂O, derived from LTE slab models (${N}_{{\mathrm{CO}}_{2}}$/${N}_{{{\rm{H}}}_{2}{\rm{O}}}\sim$0.7) that fit simultaneously the ¹²CO₂ hot bands, is over 2 orders of magnitude higher than what has previously been found in typical T Tauri disks. This may indicate an inner cavity with a radius in between the H₂O and CO₂ midplane snowlines and/or an overall lower disk temperature.
• 4.  
  While GW Lup has a high CO₂ flux relative to H₂O, as seen with Spitzer, it is not completely an outlier, suggesting that other disks, such as those around MY Lup, IM Lup, DN Tau, and CX Tau are good candidates for the detection of ¹³CO₂.

Taken together, this study demonstrates that JWST-MIRI MRS has the ability to provide new and unique constraints on inner disk physical and chemical structures.

We thank the referee for thoughtful, constructive comments that improved the manuscript. The following National and International Funding Agencies funded and supported the MIRI development: NASA; ESA; Belgian Science Policy Office (BELSPO); Centre Nationale dEtudes Spatiales (CNES); Danish National Space Centre; Deutsches Zentrum fur Luft-und Raumfahrt (DLR); Enterprise Ireland; Ministerio De Economía y Competividad; Netherlands Research School for Astronomy (NOVA); Netherlands Organisation for Scientific Research (NWO); Science and Technology Facilities Council; Swiss Space Office; Swedish National Space Agency; and UK Space Agency.

E.v.D. acknowledges support from the ERC grant 101019751 MOLDISK and the Danish National Research Foundation through the Center of Excellence "InterCat" (DNRF150). B.T. is a Laureate of the Paris Region fellowship program (which is supported by the Ile-de-France Region) and has received funding under the Marie Sklodowska-Curie grant agreement No. 945298. D.G. would like to thank the Research Foundation Flanders for co-financing the present research (grant No. V435622N). T.H. and K.S. acknowledge support from the ERC Advanced Grant Origins 83 24 28. I.K., A.M.A., and E.v.D. acknowledge support from grant TOP-1614.001.751 from the Dutch Research Council (NWO). I.K. and J.K. acknowledge funding from H2020-MSCA-ITN-2019, grant No. 860470 (CHAMELEON). G.B. thanks the Deutsche Forschungsgemeinschaft (DFG) - grant 138 325594231, FOR 2634/2. O.A. and V.C. acknowledge funding from the Belgian F.R.S.-FNRS. I.A. and D.G. thank the European Space Agency (ESA) and the Belgian Federal Science Policy Office (BELSPO) for their support in the framework of the PRODEX Programme. D.B. has been funded by Spanish MCIN/AEI/10.13039/501100011033 grants PID2019-107061GB-C61 and No. MDM-2017-0737. A.C.G. has been supported by PRIN-INAF MAIN-STREAM 2017 and from PRIN-INAF 2019 (STRADE). T.P.R. acknowledges support from ERC grant 743029 EASY. D.R.L. acknowledges support from Science Foundation Ireland (grant No. 21/PATH-S/9339). L.C. acknowledges support by grant PIB2021-127718NB-I00, from the Spanish Ministry of Science and Innovation/State Agency of Research MCIN/AEI/10.13039/501100011033.

The comparison between the MIRI MRS data and the Spitzer-IRS data for GW Lup is shown in Figure 5. A spurious, single-pixel spike at 18.8 μm has been removed from the MIRI spectrum, as in Figure 1.

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The continuum is determined using a cubic spline interpolation (scipy.interpolate.interp1d) between selected regions with minimal line emission in the spectrum (Figure 6). Because the molecular emission is so rich in this wavelength region, the continuum points are selected to lie between emission features, which we confirm with our best-fit models (bottom panel). Due to the high signal-to-noise of the data and the fact that molecular features are not expected to produce an underlying continuum level at the column densities determined for this source, regions of low emission can be taken as the continuum level.

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The reduced χ² maps for H₂O, HCN, C₂H₂, ¹²CO₂, ¹³CO₂, and OH are shown in Figure 7. The reduced χ² is determined using the following formula:

$$\begin{eqnarray}&&{\chi }^{2}=\displaystyle \frac{1}{N}\displaystyle \sum _{i=1}^{N}\displaystyle \frac{{({F}_{\mathrm{obs},i}-{F}_{\mathrm{mod},i})}^{2}}{{\sigma }^{2}},\end{eqnarray} \tag{ C1 }$$

where N is the number of resolution elements in the spectral windows that the fit is done over and σ is the standard deviation in a region with minimal line emission from 15.90 to 15.94 μm (Figure 8). As the emitting radius is just a scaling factor, the degrees of freedom is only 2 for the column density and temperature. The contours in the reduced χ² shown in Figure 7 are the 1σ, 2σ, and 3σ levels determined as ${\chi }_{\min }^{2}$ + 2.3, ${\chi }_{\min }^{2}$ + 6.2, and ${\chi }_{\min }^{2}$ + 11.8, respectively (see Press et al. 1992 and Table 1 and Equation (6) of Avni 1976). Any contribution from other species in this line-rich region of the spectrum increases the overall χ² value, although the spectral windows are selected to minimize this contribution. The procedure is iterative, as described in Section 2.2, to reduce the influence of overlapping molecular features on the best-fit parameters for a given species. The best-fit models are shown in Figure 9, along with the final noise level of 0.44 mJy. Figure 10 shows the effects of changing temperature and column density on the CO₂ model as an example.

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