Brines Across the Solar System

This study examines siderite (FeCO₃) reactivity in MgCl₂ and MgSO₄ brines with varying salt concentrations (0.01M, 1M, and 3M) at both acidic (pH ∼ 2 and pH ≤ 2) and near-neutral (pH ∼ 7) conditions. We measured aqueous Fe concentrations through time to determine dissolution rates and characterized the solid reaction products with scanning electron microscopy, electron dispersive X-ray spectroscopy, and Raman spectroscopy. Iron-based siderite dissolution rates at pH 2 were equivalent in the 0.01M and 1M MgSO₄ brines and slower in 3M MgSO₄; rates in the MgCl₂ brines slow systematically with increasing brine concentration for equivalent initial pH values. Fe-based dissolution rates could not be determined in the neutral pH experiments due to precipitation of iron (hydr)oxide phases. After 1 day in acidic brines, abundant etch pits were observed; however, in the neutral experiments, siderite was identified with Raman spectroscopy even after 1 yr of dissolution along with a range of iron (hydr)oxide phases. Scanning electron microscopy imaging of the neutral experiment products found Mg-sulfate brines produced a chaotic surface texture. Therefore, micron-scale textural observations could be used to discriminate between alteration in chloride and sulfate brines. Initial iron release rates were similar in dilute brines, but decreased by less than an order of magnitude in the two highest-concentration pH 2 brine experiments; therefore, siderite-bearing assemblages exposed to acidic fluids, regardless of salinity, would likely dissolve completely over geologically short periods of time, thus erasing siderite and likely other carbonate minerals from the geologic record.

Recent work has sought to constrain the composition and makeup of the dwarf planet Ceres's mantle, which has a relatively low density, between 2400 and 2800 kg m⁻³, as inferred by observations by the Dawn mission. Explanations for this low density have ranged from a high fraction of porosity-filled brines to a high fraction of organic matter. We present a series of numerical thermodynamic models that yield the mineralogy and fluid composition in the mantle as a function of Ceres's thermal evolution. We find that the resulting phase assemblage could have changed drastically since the formation of Ceres, as volatile-bearing minerals such as serpentine and carbonates would partially destabilize and release their volatiles as temperatures in the mantle reach their maximum about 3 Gyr after Ceres's formation. These volatiles consist mainly of aqueous fluids containing Na⁺ and HS⁻ throughout the metamorphic evolution of Ceres and, in addition, high concentrations of CO₂ at high temperatures relatively recently. The predicted present-day phase assemblage in the mantle, consisting of partially devolatilized minerals and 13–30 vol% fluid-filled porosity, is consistent with the mantle densities inferred from Dawn. The metamorphic fluids generated in Ceres's mantle may have replenished an ocean at the base of the crust and may even be the source of the Na₂CO₃ and NaHCO₃ mineral deposits observed at Ceres's surface.

The formation and stability of brines on the surface of present-day Mars remains an important question to resolve the astrobiological potential of the red planet. Although modeling and experimental work have constrained the processes controlling the stability of single-salt brines exhibiting low freezing temperatures, such as calcium perchlorate, the Martian regolith is far more complex because multiple salts coexist in various concentrations, leading to brines whose behavior remains untested. Here we modeled the stability of complex brines of compositions determined from the Phoenix lander's Wet Chemistry Laboratory. We find that such brines would form in equilibrium with sodium and magnesium perchlorates, chlorides, and calcium chlorate, but never calcium perchlorate, which has been widely considered as the most likely to produce brines on Mars. Furthermore, we find that only chlorate-rich brines can potentially remain liquid, for small periods of time, at temperatures compatible with those measured by the Phoenix lander. Therefore, liquid brines remain overly unstable under present-day Martian conditions and are unlikely to contribute to surface geomorphological activity, such as recurring slope lineae. In these conditions, of cold and salty brines, the present-day Martian surface remains highly unhabitable.

Hygroscopic salts within the Martian regolith may actively participate in the near-surface water cycle by exchanging water vapor via solid-state salt hydration and deliquescence. To elucidate this process, experimental work has constrained the phase diagram of Mars-relevant salts and the stability of the resultant brines. However, salt interactions with a Mars-like regolith, which itself can exchange water vapor with the atmosphere via adsorption, has not yet been well explored. Here, to better understand water exchange with a salty Mars-like regolith and, particularly, the potential to form brines, we have conducted a series of experiments using JSC Mars-1 regolith simulant mixed with calcium perchlorate in a Mars simulation chamber at a temperature <5°C and a relative humidity <20%. During the experiments, we measured the sample mass, as well as the temperature and relative humidity of the sample and the chamber. We found that the water uptake of a salty Mars-like regolith is about twice as fast as that of a salt-free regolith. Furthermore, we found evidence to suggest that deliquescence occurred; however, not all the salt within the sample may have entered solution. The amount of water in solution was small and did not lead to regolith darkening. Our results suggest that, under the tested experimental conditions, salt deliquescence and regolith adsorption can occur simultaneously.

Low water activity limits the habitability of aqueous environments, and salts present on Mars are known to reduce water activity. As environmental brines are not pure solutions of a single salt, predicting their water activity is difficult without direct measurement. Martian brines are likely complex and dominated by ions including sulfates and perchlorates, unlike typical terrestrial aqueous environments dominated by sodium chloride. We used the Pitzer model to predict the water activity of multicomponent brines and tested against laboratory-produced brines, including for the first time perchlorate salts that are known to exist on Mars. Our calculations match measurements of single-salt solutions and predict the water activity of multicomponent brines with an accuracy dependent on the quality of thermodynamic data available for a given ion combination. We tested the hypothesis that some salts will dominate the water activity, and therefore habitability, of multicomponent brines. Some salts, such as sodium and magnesium sulfates, did not strongly modulate the water activity of the solution, whereas others such as magnesium chloride and some perchlorates did. Applied to the history of Mars, the data suggest that sulfates and sodium chloride present in Noachian and early Hesperian environments would not have limited habitability. Perchlorates produced photochemically later in the Amazonian could impose a water activity limit at high concentrations that is not significantly changed by other salts. Overall we found that magnesium and calcium chlorides mixed with perchlorates can reach the lowest water activity values and therefore the lowest habitability of the brines tested.

Although previous studies have shown that the near-surface environmental conditions on Mars may permit salt deliquescence and therefore brine production, there is significant uncertainty in the kinetics of the process. Indeed, experimental studies have shown that deliquescence is either very rapid or too slow to be relevant to Mars. To resolve this uncertainty, we performed laboratory experiments to investigate the growth rate of Mars-relevant calcium perchlorate brines over a range of temperatures (184–273 K) and water vapor pressures (0.2–220 Pa). We show that the brine growth is faster at higher water vapor pressures and lower temperatures and for smaller particles. From our data, we determined a temperature-dependent net uptake coefficient for gas phase water molecules colliding with a perchlorate brine surface in the range of 3.8 × 10⁻⁴ at 185 K to 4.2 × 10⁻⁶ at 273 K. These values suggest that deliquescence on Mars is likely to be slow even when conditions thermodynamically permit a brine to form. We find that along the Curiosity rover traverse at Gale Crater, the near-surface conditions would only allow particles <1 μm to fully deliquesce over a typical sol. At the higher-latitude Phoenix landing site, deliquescence may be 30% faster due to the higher water vapor pressures, but still, only micron-scale salt grains or coatings would be expected to deliquesce during a typical sol. These results suggest that brines formed via deliquescence on the surface of Mars are likely only present on small scales that may not be readily detected using conductivity or imaging techniques.

Phyllosilicates on Mars record a complex history of aqueous activity, including at Gale crater and Meridiani Planum, where stratigraphic differences in clay mineralogy have been recorded in outcrops that also contain calcium sulfate minerals. Thus, characterizing associations between phyllosilicates and calcium sulfates may provide constraints that are useful for constraining the geochemical environments that formed these outcrops. Previous studies have documented calcium sulfate precipitation as a result of clay–salt–atmospheric H₂O interactions, but the compositions of brines throughout Mars' history would have depended on the volume of water available on the Martian surface. Variations in brine composition influence the type and extent of reactions between the brines and the minerals that they come in contact with. To better understand how clay–brine interactions affected near-surface mineral assemblages on Mars, we performed two sets of experiments. The first set of experiments examined the effect of differing total brine concentrations and the second set explored variations in Na⁺ and SO₄²⁻ concentrations independently. The results of this study show that gypsum readily forms due to cation exchange between montmorillonite and Na₂SO₄ brines of any concentration, but only near-saturated MgSO₄ brines produced gypsum, and these also produced higher quantities of epsomite. Additionally, we found that the amount of gypsum produced from clay–Na₂SO₄ brine reactions is more strongly influenced by SO₄²⁻ than Na⁺ or Cl⁻ concentrations. Understanding how rapidly gypsum forms as a product of clay–brine interactions, as well as the influence of SO₄²⁻ on cation exchange, will aid interpretations of sediments and environments that are observed on Mars.

On Mars, liquid water may form in regolith when perchlorate salts absorb water vapor and dissolve into brine, or when ice-salt mixtures reach their melting temperature and thaw. Brines created in this way can chemically react with minerals, alter the mechanical properties of regolith, mobilize salts in the soil, and potentially create habitable environments. Although Martian brines would exist in contact with regolith, few studies have investigated how regolith alters the formation and stability of brines at Mars-relevant conditions. To fill this gap, we studied magnesium perchlorate brine in a Martian regolith simulant at salt concentrations up to 5.8 wt.%. We measured the water mass fraction and water activity between 3 and 98% relative humidity at 25 °C using the isopiestic method, and monitored salt and ice crystallization between −150 °C and 20 °C with differential scanning calorimetry. Results show that regolith inhibits salt and ice crystallization, allowing water to form and persist at much colder and drier conditions than pure brine. Remarkably, in several samples, neither salt nor ice crystallized at any conditions. These results suggest that brines could exist in regolith for longer periods of the Martian year than previously thought, and could persist indefinitely under certain conditions. By retaining water, inhibiting salt and ice crystallization, and maintaining habitable water activity, briny regolith may be a more favorable environment for life than pure brine alone. These findings indicate the critical importance of brine–regolith interactions for understanding the properties, evolution, and potential habitability of Mars's surface.

The formation mechanism of Europa's large chaos terrain (>∼100 km diameter) and associated lenticulae (<∼10 km diameter) has been debated since their observations by the Galileo spacecraft. Their geomorphology and distribution suggest there may be reservoirs of saline liquid water 1–3 km beneath the surface—the "shallow water" model—generated by injection of ocean water or melting of the ice shell. Recent investigations on the evolution of small shallow-water bodies (≤10³ km³) suggests that salts with a small effect on melting point (MgSO₄) can extend the lifetime of saline bodies by ∼5% compared to freshwater reservoirs. However, sodium chloride, identified as a potential oceanic salt, has a significantly stronger impact on the freezing point, suggesting a further extension of liquid lifetimes. Moreover, the substantial volumes of liquid water (∼10⁴ km³) beneath large chaos could be melted in situ rather than injected through a fracture, implying a distinct chemistry and formation environment. Here, we use numerical models to explore how the chemistry and disparate origins of shallow water control its evolution and lifetime. For small, injected sills, we find that NaCl can extend their liquid lifetime to ∼140 kyr—up to a ∼60% increase over freshwater sills. Saline melt lenses will last at least 175 kyr but, in contrast to sills, may persist as a stable layer of brine beneath the surface for over 500 kyr. Our results provide further support for the presence of liquid water at shallow depths within Europa's ice shell today.

The Chemistry and Mineralogy X-ray diffraction (XRD) instrument aboard the Curiosity rover consistently identifies amorphous material at Gale Crater, which is compositionally variable, but often includes elevated sulfur and iron, suggesting that amorphous ferric sulfate (AFS) may be present. Understanding how desiccating ferric sulfate brines affect the spectra of Martian material analogs is necessary for interpreting complex/realistic reaction assemblages. Visible and near-infrared reflectance (VNIR), mid-infrared attenuated total reflectance (MIR, FTIR-ATR), and Raman spectra, along with XRD data are presented for basaltic glass, hematite, gypsum, nontronite, and magnesite, each at three grain sizes (<25, 25–63, and 63–180 μm), mixed with ferric sulfate (+/−NaCl), deliquesced, then rapidly desiccated in 11% relative humidity or via vacuum. All desiccated products are partially or completely XRD amorphous; crystalline phases include starting materials and trace precipitates, leaving the bulk of the ferric sulfate in the amorphous fraction. Due to considerable spectral masking, AFS detectability is highly dependent on spectroscopic technique and minerals present. This has strong implications for remote and in situ observations of Martian samples that include an amorphous component. AFS is only identifiable in VNIR spectra for magnesite, nontronite, and gypsum samples; hematite and basaltic glass samples appear similar to pure materials. Sulfate features dominate Raman spectra for nontronite and basaltic glass samples; the analog material dominates Raman spectra of hematite and gypsum samples. MIR data are least affected by masking, but basaltic glass is almost undetectable in MIR spectra of those mixtures. NaCl produces similar FTIR-ATR and Raman features, regardless of analog material.

Several icy moons and dwarf planets appear to have hosted subsurface liquid water. Liquid water intruding upwards into the icy outer shells of these worlds freezes, forming ice and (from ocean solutes) non-ice solids. Here, we model concentrated aqueous solutions below 273 K to simulate the compositional evolution of freezing spherical intrusions. Starting solutions are based on five previously reported compositional end members for Europa's ocean. For moderate-pH end members dominated by chloride, sulfate, and/or carbonate, the solids formed include Ca-, Mg-, and Na-sulfates and -carbonates, as well as Na- and K-chlorides. For silica-rich, high-pH end members, abundant amorphous silica forms with, potentially, similarly abundant NaOH and KOH. We further develop a new numerical model to compute the spatial distribution of the formed solids and residual brine as freezing progresses. If non-ice solids settle to the bottom, their deposits tend to have stacked hourglass shapes, widening each time the crystallization temperature of a new solid is reached. We discuss the applicability of this model to vertical fractures and global freezing of a subsurface ocean. These results inform (i) how compositional heterogeneities may affect the thermophysical properties of ice shells, which in turn influence convective and cryovolcanic transport, (ii) the compatibility of brine pockets with physicochemical conditions suitable for microbial life, and (iii) possible measurements of compositional heterogeneities within ice shells by spacecraft such as NASA's Europa Clipper and ESA's JUICE missions. The methodology developed here is applicable to other ice-covered ocean worlds.