Is Ozone a Reliable Proxy for Molecular Oxygen? II. The impact of N$_2$O on the O$_2$-O$_3$ relationship for Earth-like atmospheres

Jo\~ao M. Mendon\c{c}a; Lars A. Buchhave; Luisa M. Lara; Thea Kozakis

Is Ozone a Reliable Proxy for Molecular Oxygen? II. The impact of N$_2$O on the O$_2$-O$_3$ relationship for Earth-like atmospheres

T0 review · reviewed 2026-08-07 · deepseek-v4-flash

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Pith's one-line read The paper finds that the O2-O3 relationship on Earth-like planets is strongly controlled by nitrous oxide abundance, so ozone cannot serve as a reliable oxygen proxy without measuring N2O as well.

desk verdict Systematic N2O parameter sweep shows the O2-O3 proxy is host-star dependent and N2O-sensitive, but the cool-host/low-O2 smog reversal is a model prediction that would benefit from a network comparison. read the letter →

arxiv 2505.23279 v2 pith:EEN4TMG2 submitted 2025-05-29 astro-ph.EP

Thea Kozakis , João M. Mendonça , Lars A. Buchhave , Luisa M. Lara This is my paper

classification astro-ph.EP

keywords astrobiologyterrestrialplanets:atmospheresozoneproxynitrousoxidemolecularoxygenphotochemistryMdwarfhoststarssmogmechanism

verification ladder T0 review T1 audit T2 compute T3 formal

The pith

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

The reading

Molecular oxygen paired with a reducing gas is the classic disequilibrium biosignature, but O2 is often hard to detect, so ozone, its photochemical product, has been proposed as a proxy. This paper argues that the proxy is not safe without knowing the atmosphere's nitrous oxide level. Using coupled climate-photochemistry models of Earth-like planets around G0V through M5V stars, with O2 from 0.01 to 150% of present atmospheric level (PAL) and N2O at 10%, 100%, or 1000% of modern abundance, the authors find that the O2-O3 relationship shifts strongly with N2O: hot-star, high-O2 cases lose ozone to the NOx catalytic cycle, while cool-star, low-O2 cases gain ozone from smog production. The result matters because it changes how much harmful ultraviolet reaches the surface and how deep the 9.6 micron ozone emission feature appears, and it implies that a separate measurement of N2O is needed before O3 can be used to estimate O2.

What carries the argument

The argument is carried by the competition between two ozone pathways fed by N2O: the NOx catalytic cycle that destroys stratospheric O3 and the smog mechanism that produces tropospheric O3 from NO2 photolysis. The NOx-limited versus NOx-saturated regimes, adapted from Logan et al. (1981), decide which pathway wins as N2O and O2 vary, and the host star's ultraviolet spectrum sets how much N2O is converted into NOx versus destroyed by photolysis.

What would settle it

Rerun the same model grid with the methyl-containing smog pathways that Grenfell et al. (2013) included; if tropospheric O3 at 0.1% PAL O2 with 1000% PAL N2O around an M5V host changes by more than the paper's quoted enhancement factors, the NOx-regime explanation is incomplete.

Watch

Extended reading notes

Core claim

The paper establishes that nitrous oxide is a controlling variable in the already nonlinear O2-O3 relationship. In models with 1000% PAL N2O and O2 above roughly 1% PAL, planets around every host except M5V lose a significant fraction of their ozone to faster NOx catalytic cycles, with the K2V-hosted planet at 100% PAL O2 retaining only 47% of its modern-N2O ozone column. At the lowest O2 modeled, 0.1% PAL, the Chapman mechanism is starved of O2 and the smog mechanism takes over, so all hosts gain ozone when N2O is high. The M5V host is the most extreme case because its low ultraviolet flux never pushes the atmosphere into the NOx-saturated regime where excess NOx locks up HOx and suppresses smog; around M5V, extra N2O increases ozone starting at 10% PAL O2. These ozone changes translate into large swings in surface UVC flux, up to a 15 billion-fold increase for the G0V host at 100% PAL O2, and they alter the 9.6 micron O3 emission feature primarily through abundance changes rather than temperature-profile changes.

Load-bearing premise

The conclusions rest on the photochemical network being complete enough that the omitted methyl-containing smog pathways, such as CH3O2 reactions, would not materially change ozone production in high-N2O, low-O2 atmospheres.

Editorial extensions

If this is right

A separate measurement of N2O is required before O3 can be interpreted as a proxy for O2, since the same O3 abundance can correspond to very different O2 levels depending on N2O and host star.
Around hotter stars at high O2, elevated N2O can deplete ozone enough to raise surface UVC flux by a factor of 15 billion, with direct consequences for surface habitability.
Around M5V hosts and at very low O2, elevated N2O increases ozone through the smog mechanism and improves ultraviolet shielding, the opposite of the hot-host trend.
The 9.6 micron O3 emission feature responds to N2O mainly through changes in O3 abundance, so feature depth alone cannot be read as an O2 abundance without N2O context.
The high-N2O model cases (3 ppm) fall within the plausible range of N2O mixing ratios for terrestrial planets, so the predicted O3 variations are not restricted to extreme atmospheres.

Reading between the lines

Editorial extensions of the paper, not claims the author makes directly.

Editorial inference: because the N2O spectral feature overlaps the CH4 feature in the mid-infrared, separating the two gases will be a practical bottleneck for the O3-plus-N2O interpretation strategy this paper proposes.
Editorial inference: the same mechanism suggests that Proterozoic-like planets with high N2O and around 10% PAL O2 orbiting Sun-like stars may have had substantially different ozone shielding than modern-Earth scaling would predict, affecting estimates of surface UV environments.
Editorial inference: the model grid could be extended to joint retrieval of N2O and O3 from emission spectra; the covariance between the two retrievals would directly test whether the claimed degeneracy is observable.

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Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, and a circularity audit.

Desk Editor's Note

read the letter

Quick take: this is a solid follow-up to Kozakis et al. 2022. It does something genuinely new—maps N2O abundance against the O2-O3 relationship across G0V-M5V hosts and O2 levels from 0.01-150% PAL—and the central qualitative result, that N2O modulates O3 in a regime-dependent way, is well supported by the model output. The writing is clear, the figures carry the argument, and the limitations are stated rather than hidden.

The main result that matters: at modern-ish O2 levels, high N2O depletes O3 for hotter hosts via NOx catalysis (K2V retaining only 47% of modern-N2O O3), while for cool hosts and low O2, high N2O increases O3 through smog production. That reversal is the paper's most novel claim, and it is also the softest spot. The network (Atmos modern Earth template, 233 reactions) omits methyl-peroxy smog pathways such as CH3O2 + NO. The authors acknowledge this in Sect. 5.1 and cite Grenfell et al. (2013) for the classical CO-based mechanism being the common route. That citation is reasonable, but it does not quantify how much the missing branch matters specifically in the low-O2, high-N2O, M5V corner where the predicted O3 enhancement is largest. If the omitted branch contributes significantly at elevated NOx, the magnitude of the enhancement—and the O2 threshold where the sign flips—could shift. I would not call this a fatal flaw: the NOx-limited/NOx-saturated regime logic is chemically reasonable, and the qualitative pattern is consistent with earlier studies. But it is a genuine caveat on the headline result, and a single Atmos run with the extended network would settle it.

Other soft spots are minor: fixed N2O mixing ratios rather than surface fluxes partially sidestep the host-star-dependent relationship between flux and mixing ratio (Sect. 5.2 does discuss this), and there is no uncertainty quantification on the photochemistry. Neither undermines the parameter-space mapping.

Bottom line: this is a careful, reproducible-in-principle study with public codes and clearly described inputs. It is a useful contribution to the biosignature-proxy literature and directly relevant to mid-IR mission planning (LIFE). It deserves a serious referee. I'd send it to review, with a request that the authors either run a network comparison or soften the strength of the M5V/low-O2 claim.

Referee Report

0 major / 0 minor

Summary. This manuscript is the second paper in a series investigating whether ozone (O3) can serve as a reliable proxy for molecular oxygen (O2) in Earth-like exoplanet atmospheres. The authors use the publicly available 1D coupled climate-photochemistry code Atmos to simulate atmospheres around G0V, Sun, K2V, K5V, and M5V host stars, varying O2 from 0.01-150% of present atmospheric level (PAL) and N2O at 10%, 100%, and 1000% of the modern Earth value. They find that the O2-O3 relationship is sensitive to N2O abundance, but the effect is highly nonlinear and depends on both the host star and the O2 level. For hot hosts and O2 levels near modern Earth, high N2O depletes O3 via the NOx catalytic cycle, with K2V retaining as little as 47% of the modern-N2O O3 column at 100% PAL O2. For cool hosts (especially M5V) and low O2 levels, high N2O increases O3 via the tropospheric smog mechanism, with the M5V-hosted planet showing enhanced O3 already at 10% PAL O2 and all hosts showing enhancement at 0.1% PAL O2. The authors further quantify the resulting changes in surface UV (especially UVC) fluxes and in the strength of the 9.6 micron O3 emission feature, concluding that a separate measurement of N2O is needed before O3 can be used to infer O2 abundance.

Significance. If the results hold, this is a useful contribution to the exoplanet biosignature literature. It extends the authors' earlier O2-O3 study (Kozakis et al. 2022) by adding a second biologically relevant gas, N2O, and demonstrates that the O3 proxy requires additional atmospheric context. The paper is systematic: it uses a public, well-documented photochemistry code; a transparent parameter grid in both O2 and N2O; and it reports quantitative outputs for O3 columns, surface UV fluxes, and the 9.6 micron feature. The central qualitative claim—that the sign of the N2O effect on O3 reverses between hot hosts at high O2 (depletion) and cool hosts or low O2 (enhancement via smog)—is physically plausible and consistent with known photochemistry. The paper also makes a concrete, actionable recommendation for future observations: measure N2O (or at least treat it as a free parameter) when using O3 as an O2 proxy. These strengths support publication.

Circularity Check

0 steps flagged · score 0.0 of 10

No circularity: the O2-O3-N2O results are forward photochemistry/climate simulations with no fitted target quantity; the Kozakis et al. (2022) baseline is an independent prior calculation rather than a load-bearing self-citation.

full rationale

The paper's central claim — that changing N2O alters O3 column depths differently by host star and O2 level, with smog production dominating at cool hosts and low O2 — is the direct output of the public Atmos climate/photochemistry code. O2 and N2O mixing ratios are specified inputs (Table 1); O3, NOx, HOx, surface UV fluxes, and 9.6 micron features are computed, not fitted. No parameter is adjusted to reproduce a target O3 abundance, and no equation defines O3 in terms of the N2O input in a way that would make the result true by construction. The many references to Kozakis et al. (2022) provide the modern-N2O comparison models and the O2-only relationships; those are prior, published forward simulations with the same code, and the present paper's new content is the delta introduced by the 10% and 1000% PAL N2O runs. This is a self-citation used as a baseline, not as an unverified premise that forces the conclusion. The acknowledged omission of CH3O2-type methyl smog pathways (Sect. 5.1) is a chemical-network completeness concern about the magnitude and robustness of the low-O2/cool-host reversal, not a circularity: the reversal is an emergent model result, and the classical CO-based smog chain cited to Grenfell et al. (2013) is external comparative support, not the paper's own input. Accordingly no circular step can be quoted, and the appropriate score is 0.

Assumptions & free parameters 2 free parameters · 4 assumptions · 0 invented entities

The central claim rests mainly on the choice of N2O and O2 input grids and on the adequacy of the public Atmos and PICASO models. The fixed N2O mixing ratios are hand-chosen parameter-space points, not fitted values, so they are listed as free parameters. The chemical network and 1D climate assumptions are domain assumptions; no new entities are invented.

free parameters (2)

N2O mixing ratio = 10%, 100%, 1000% PAL (3e-8, 3e-7, 3e-6)
Chosen by hand to map the parameter space, not derived from a surface flux model or observations.
O2 mixing ratio grid = 0.01-150% PAL (2.1e-5 to 0.315)
Chosen by hand from 0.01 to 150% PAL, with limits justified by stability and combustibility.

assumptions (4)

domain assumption The Atmos photochemistry network with 233 reactions and the modern Earth template adequately represents O3 chemistry for the simulated atmospheres.
Invoked throughout; the paper notes in Sect. 5.1 that Grenfell et al. used a more complex network with CH3O2 pathways, which are omitted here.
domain assumption N2O can be treated as a fixed mixing ratio boundary condition rather than a flux-balanced species.
Stated in Methods (Sect. 3.1) and flagged in Sect. 5.2 as a simplification because surface flux to mixing ratio is nonlinear.
domain assumption The 1D climate and photochemistry coupling converges to a representative steady state for each parameter combination.
The short-stepping method and convergence criteria are described in Sect. 3.1, but single-column models cannot capture 3D transport or cloud feedbacks.
domain assumption Stellar spectra from Rugheimer et al. (2015) and MUSCLES are representative for the assigned spectral types.
Used as inputs in Sect. 3.2; UV variability of real stars, especially M dwarfs, is large.

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Cite this review

Pith. "Pith review of Is Ozone a Reliable Proxy for Molecular Oxygen? II. The impact of N$_2$O on the O$_2$-O$_3$ relationship for Earth-like atmospheres." pith.science (2026). https://pith.science/paper/EEN4TMG2

@misc{pith2026250523279,
  author       = {Pith},
  title        = {Pith review of: Is Ozone a Reliable Proxy for Molecular Oxygen? II. The impact of N$_2$O on the O$_2$-O$_3$ relationship for Earth-like atmospheres},
  year         = {2026},
  howpublished = {\url{https://pith.science/paper/EEN4TMG2}},
  note         = {Machine review of arXiv:2505.23279}
}

abstract

Molecular oxygen (O2) will be an important molecule in the search for biosignatures in terrestrial planetary atmospheres in the coming decades. In particular, O2 combined with a reducing gas is thought to be strong evidence for disequilibrium caused by surface life. However, there are circumstances where it would be very difficult or impossible to detect O2, in which cases it has been suggested that ozone (O3), the photochemical product of O2, could be used instead. Unfortunately, the O2-O3 relationship is highly nonlinear and dependent on the host star, as shown in detail in the first paper in this series. We explore the O2-O3 relationship around G0V-M5V host stars, using climate/photochemistry modeling to simulate atmospheres while varying abundances of O2 and nitrous oxide (N2O). N2O is of particular importance to the O2-O3 relationship not just because it is produced biologically, but because it is the primary source of nitrogen oxides (NOx), which fuel the NOx catalytic cycle which destroys O3, and the smog mechanism that produces O3. We vary the O2 mixing ratio from 0.01-150% present atmospheric level (PAL), and N2O abundances of 10% and 1000% PAL. We find that varying N2O impacts the O2-O3 relationship differently depending strongly on both the host star and the amount of atmospheric O2. Planets orbiting hotter hosts with strong UV fluxes efficiently convert N2O into NOx, often depleting a significant amount of O3 via faster NOx catalytic cycles. However, for cooler hosts and low O2 levels we find that increasing N2O can lead to an increase of overall O3 due to the smog mechanism producing O3 in the lower atmosphere. Variations in O3 result in significant changes in the amount of harmful UV reaching the surfaces of the model planets as well as the strength of the 9.6 $\mu$m O3 emission spectral feature, demonstrating potential impacts on habitability and future observations.

Figures

Figures reproduced from arXiv: 2505.23279 by the authors.

**Figure 1.** Impact of HO2 and OH in the NOx-limited and NOx-saturated regimes on modern Earth, adapted from Logan et al. (1981). In the NOx-limited regime (white background), increasing NOx allows for a more efficient smog mechanism, with the resulting increase in O3 causing a corresponding rise in HOx . In the NOx-saturated regime (gray background), the abundance of NOx rises to the point where smog O3 production is suppresse… view at source ↗

**Figure 2.** UV stellar spectra of the host stars in this study (top) and corresponding absorption cross sections of relevant gaseous species (bottom). The two plots cover the same wavelength range in order to facilitate comparisons. Cross sections for NO2 and N2O are cut off at shorter wavelengths, due to the dominance of absorption from CO2 and other atmospheric species. The climate model (Kasting & Ackerman 1986; Kopparapu… view at source ↗

**Figure 3.** Total O3 abundances for models with high N2O (left) and low N2O (right) normalized to models with modern levels of N2O from Kozakis et al. (2022). Overall, the high N2O models impacted the O2-O3 relationship more than the low N2O models, with the results being highly dependent on the stellar host and the amount of O2. High N2O models with hotter stars experience significant O3 depletion due to faster NOx catalytic c… view at source ↗

Figures from the paper (4 more)

**Figure 4.** Figure 4: O2-O3 relationship with high, low, and modern N2O models for planets around the Sun and M5V hosts. Vertical dashed lines indicate O2 levels of 100%, 10%, 1%, and 0.1% PAL. The phenomena causing maximum O3 production for the planet around the Sun to occur at O2 values l…

**Figure 5.** Figure 5: NO and HO2 profiles at 100 and 0.1% PAL O2 for planets around the Sun and M5V hosts. Plots containing NO profiles indicate the NOxsaturated regime by a gray background, while the NOx-limited regime has a white background. When NO profiles enter the NOx-saturated regim…

**Figure 6.** Figure 6: UVC surface fluxes for planets around all hosts from Kozakis et al. (2022) with modern N2O (top) and with high and low N2O abundances from this study with O2 levels of 100% (second row), 10%, (third row), and 0.1% (bottom) PAL. The first panel in the top row indicates …

**Figure 7.** Figure 7: 9.6 µm O3 feature for models from Kozakis et al. (2022) (left) and normalized models from varying N2O (right) from simulated planetary emission spectra. Changes in the O3 feature for this study depended primarily on changes in O3 abundance – rather than on changes in t…

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Reviewed August 7, 2026 · model on record in the stance chip above.

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