Venus: Preliminary prediction of the mineral composition of surface rocks

A thermodynamical analysis of the multicomponent system SiTiAlFeMnMgCaNaKPCHO open with respect to CO₂, CO, H₂O was carried out. Hydration and carbonatization processes are proposed to be geochemical consequences of the hypothesis of quasi-equilibrium conditions between the troposphere and crustal surface rocks. The probable rock-forming hydrated mineral phases are represented by epidote, glaucophane, tremolite, phlogopite, and annite; the carbonatization results in existence of calcite and dolomite as rock-forming minerals of weathered alkaline lavas. The surface rocks are assumed to have high ferric/ferrous iron ratios. The wollastonite equilibrium is rejected as a buffering chemical reaction. Hydrated minerals could be stable at least up to 5-km depths and contribute about 0.1 × 10²⁴ g of H₂O whereas about (0.7–0.8) × 10²⁴ g of H₂O would be consumed in ferrous iron oxidation with concomitant hydrogen dissipation. The distribution of H₂O in the outer planetary shells is possibly a function of their temperatures.     

Stability of hydrous minerals on the martian surface

The presence of water-bearing minerals on Mars has long been discussed, but little or no data exist showing that minerals such as smectites and zeolites may be present on the surface in a hydrated state (i.e., that they could contain H₂O molecules in their interlayer or extra-framework sites, respectively). We have analyzed experimental thermodynamic and X-ray powder diffraction data for smectite and the most common terrestrial zeolite, clinoptilolite, to evaluate the state of hydration of these minerals under martian surface conditions. Thermodynamic data for clinoptilolite show that water molecules in its extra-framework sites are held very strongly, with enthalpies of dehydration for Ca-clinoptilolite up to three times greater than that for liquid water. Using these data, we calculated the Gibbs free energy of hydration of clinoptilolite and smectite as a function of temperature and pressure. The calculations demonstrate that these minerals would indeed be hydrated under the very low-P (H₂O) conditions existing on Mars, a reflection of their high affinities for H₂O. These calculations assuming the partial pressure of H₂O and the temperature range expected on Mars suggest that, if present on the surface, zeolites and Ca-smectites could also play a role in affecting the diurnal variations in martian atmospheric H₂O because their calculated water contents vary considerably over daily martian temperature ranges. The open crystal structure of clinoptilolite and existing hydration and kinetic data suggest that hydration/dehydration are not kinetically limited. Based on these calculations, it is possible that hydrated zeolites and clay minerals may explain some of the recent observations of significant amounts of hydrogen not attributable to water ice at martian mid-latitudes.     

Solar wind contribution to surficial lunar water: Laboratory investigations

Remote infrared spectroscopic measurements have recently re-opened the possibility that water is present on the surface of the Moon. Analyses of infrared absorption spectra obtained by three independent space instruments have identified water and hydroxyl (-OH) absorption bands at ∼3 μm within the lunar surface. These reports are surprising since there are many mechanisms that can remove water but no clear mechanism for replenishment. One hypothesis, based on the spatial distribution of the -OH signal, is that water is formed by the interaction of the solar wind with silicates and other oxides in the lunar basalt. To test this hypothesis, we have performed a series of laboratory simulations that examine the effect of proton irradiation on two minerals: anorthite and ilmenite. Bi-directional infrared reflection absorption spectra do not show any discernable enhancement of infrared absorption in the 3 μm spectral region following 1 or 100 keV proton irradiation at fluences between 10¹⁶ and 10¹⁸ ions cm⁻². In fact, the post-irradiation spectra are characterized by a decrease in the residual O-H band within both minerals. Similarly, secondary ion mass spectrometry shows a decrease rather than an increase of the water group ions following proton bombardment of ilmenite. The absence of significant formation of either -OH or H₂O is ascribed to the preferential depletion of oxygen by sputtering during proton irradiation, which is confirmed by post-irradiation surface analysis using X-ray photoelectron spectroscopy measurements. Our results provide no evidence to support the formation of H₂O in the lunar regolith via implantation of solar wind protons as a mechanism responsible for the significant O-H absorption in recent spacecraft data. We determine an upper limit for the production of surficial -OH on the lunar surface by solar wind irradiation to be 0.5% (absorption depth).     

The abundance and isotopic composition of water in eucrites

Volatile elements play a key role in the dynamics of planetary evolution. Extensive work has been carried out to determine the abundance, distribution, and source(s) of volatiles in planetary bodies such as the Earth, Moon, and Mars. A recent study showed that the water in apatite from eucrites has similar hydrogen isotopic compositions compared to water in terrestrial rocks and carbonaceous chondrites, suggesting that water accreted very early in the inner solar system given the ancient crystallization ages (~4.5 Ga) of eucrites. Here, the measurements of water (reported as equivalent H₂O abundances) and the hydrogen isotopic composition (δD) of apatite from five basaltic eucrites and one cumulate eucrite are reported. Apatite H₂O abundances range from ~30 to ~3500 ppm and are associated with a weighted average δD value of ?34 ± 67‰. No systematic variations or correlations are observed in H₂O abundance or δD value with eucrite geochemical trend or metamorphic grade. These results extend the range of previously published hydrogen isotope data for eucrites and confirm the striking homogeneity in the H‐isotopic composition of water in eucrites, which is consistent with a common source for water in the inner solar system.     

Solar-wind interactions: Nature and composition of lunar atmosphere

The solar wind interacts directly with the lunar surface material resulting in an essentially complete absorption of the corpuscles producing no upstream bowshock but a cavity downstream from the Moon. The main source of most neutral species of the atmosphere, except probably⁴⁰Ar, is the solar-wind interaction products. The other sources which appear to be minor contributors to the atmosphere are the interaction products of cosmic rays, planetary degassing, effects of meteorite impacts and radioactive decays. Most of the hydrogen atoms derived from the solar-wind protons contribute to the atmosphere as hydrogen molecules rather than atoms. Only on the basis of the solar-wind protons, alpha particles and ions of oxygen and carbon, the atmospheric species concentration (cm^–3) near the lunar surface at 300K are as follows: H₂ 3.3 to 9.9 × 10³; He 2.4 to 4.7 × 10³; H 3.7; OH 0.25; H₂O 0.24; and O₂, O, CO, CO₂ and CH₄ in concentrations smaller than H₂. Whatever the source, the OH and H₂O concentrations in the atmosphere are about the same. The calculated concentrations are in good agreement with the observations by the Apollo 17 lunar surface mass spectrometer and the Apollo 17 orbital UV spectrometer. At the time of sample collection from the Moon, the hydrogen content in the trapped gas layer of the lunar surface material was partly as hydrogen atoms and partly as hydrogen molecules, but at the time of sample analysis hydrogen was mostly in molecular form. The H₂O content at the time of sample analysis was only a few parts per million by weight.Paper presented at the Conference on Interactions of the Interplanetary Plasma with the Modern and Ancient Moon, sponsored by the Lunar Science Institute, Houston, Texas and held at the Lake Geneva Campus of George Williams College, Wisconsin, between September 30 and October 4, 1974.     

Interstellar water and interstellar ice

There are two ways that water ice can form in the interstellar medium: H₂O molecules can form in the gas phase and then freeze out onto dust grain surfaces, or O and OH can be converted at the surfaces of grains to form H₂O, which is then retained. Bergin et al. (1998) have recently shown that shocks passing through interstellar clouds sufficiently frequently can make the first method effective. However, we present results from a similar chemical model which indicate that this requires significant optical shielding because of the high ionization fraction in regions exposedto a high UV flux. We deduce, therefore, that grain surface reactions probably represent the main source of H₂O ice on lines of sight with visual extinction up to about 6 magnitudes to an embedded source or 12 magnitudes to a background object. This revised version was published online in July 2006 with corrections to the Cover Date.     

Upper limits of water contents in olivine and orthopyroxene of equilibrated chondrites and several achondrites

Hydroxyl defects in nominally anhydrous minerals (NAMs) were potential carriers of water in the early Solar System and might have contributed to the accretion of terrestrial water. To better understand this, we have conducted a nanoscale secondary ion mass spectrometry survey of water contents in olivine and orthopyroxene from a set of equilibrated ordinary chondrites of the L and LL groups (Baszkówka, Bensour, Kheneg Ljouâd, and Tuxtuac) and several ultramafic achondrites (Zakłodzie, Dhofar 125, Northwest Africa [NWA] 4969, NWA 6693, and NWA 7317). For calibration, we used terrestrial olivine and orthopyroxene with H₂O contents determined by Fourier transform infrared. Our 99.7% (~3SD) detection limits are 3.6–5.4 ppmw H₂O for olivine and 7.7–10.9 ppmw H₂O for orthopyroxene. None of the meteoritic samples studied consistently shows water contents above the detection limits. A few exceptions slightly above the detection limits are suspected of terrestrial contamination by ferric oxyhydroxides. If the meteorite samples investigated accreted in the presence of small amounts of water ice, the upper limits of water contents provided by our survey suggest that the retention of hydrogen during thermal metamorphism and differentiation was ineffective. We suggest that loss occurred through combinations of low internal pressures, high permeability along grain boundaries, and speciation of hydrogen into reduced compounds such as H₂ and methane, which are less soluble in NAMs than in water.     

Simulating OH/H2O formation by solar wind at the lunar surface

We simulate the OH/H₂O production from the action of keV protons on the lunar regolith using a vacuum chamber and a mass analyzer to examine the molecular products released from olivine and SiO₂ powders during their irradiation by deuterium ions. The measured mass spectra, showing the OD/D₂O signature, confirm the possibility of OH/H₂O formation on the lunar surface by solar-wind hydrogen.     

The H2O and CO2 adsorption properties of phyllosilicate-poor palagonitic dust and smectites under martian environmental conditions

The recent detection of up to ∼10 wt% water-equivalent H heterogeneously distributed in the upper meter of the equatorial regions of the martian surface and the presence of the 3-μm hydrations feature across the entire planet raises the question whether martian surficial dust can account for this water-equivalent H. We have investigated the H₂O and CO₂ adsorption properties of palagonitic dust (<5 μm size fraction of phyllosilicate-poor palagonitic tephra HWMK919) as a martian dust analog and two smectites under simulated martian equatorial surface conditions. Our results show that the palagonitic dust, which contains hydrated and hydroxylated volcanic glass of basaltic composition, accommodates significantly more H₂O under comparable humidity and temperature conditions than do the smectites nontronite and montmorillonite.     

Hydrous Silicates and Water on Venus

We used thermochemical equilibrium calculations to predict stabilities of pure rock-forming hydrous silicates on Venus' surface as a function of elevation, atmospheric H₂O and SO₂concentrations, and oxygen fugacity (f_O2). About 50 different hydrous silicates were included in our calculations. We find that many of these are unstable on Venus's surface because of the low atmospheric H₂O content of 30–45 parts per million by volume (ppmv) and the high surface temperatures (660 K on Maxwell Montes to 740 K in the plains). Hydrous Fe²⁺-bearing silicates are unstable due to oxidation to magnetite and/or hematite at the f_O2of the near-surface atmosphere. Ca-bearing hydrous silicates are unstable because of sulfatization to anhydrite. Some Fe-free micas (e.g., eastonite, eastonite–phlogopite micas), and some alkali amphiboles might be stable on Venus' surface, especially in the lower temperature highlands. We discuss hydrous mineral formation in the interior and on the surface of Venus. We review the literature on mica and amphibole thermal decomposition and find that dehydration of phlogopitic micas and fibrous amphiboles produces (metastable) dehydroxylated anhydrides that decompose to more stable minerals at temperatures hundreds of degrees higher than the onset of dehydroxylation. These observations raise the possibility that anhydrides formed from hydrous silicates, which may have been present during a wetter period in Venus' history, may persist somewhere on Venus' present surface. We discuss experiments that could be used on future spacecraft missions to detect hydroxyl in rocks and hydrous silicates on Venus. Finally, we review estimates of the amount of water and OH (hydroxyl) in the Earth's mantle. Based on this review, we suggest that even if no hydrous silicates are stable on Venus, significant amounts of water are plausibly present in surface rocks as OH in nominally anhydrous minerals.     

Response of Earth's atmosphere to increases in solar flux and implications for loss of water from Venus

A one-dimensional radiative-convective model is used to compute temperature and water vapor profiles as functions of solar flux for an Earth-like atmosphere. The troposphere is assumed to be fully saturated, with a moist adiabatic lapse rate, and changes in cloudiness are neglected. Predicted surface temperatures increase monotonically from ?1 to 111°C as the solar flux increased from 0.81 to 1.45 times its present value. Surface temperatures corresponding to high solar fluxes may be underestimated, however, owing to neglect of H₂O continuum absorption outside of the 8- to 12-μm window region. These results imply that the surface temperature of a primitive water-rich Venus should have been at least 80–100°C and may have been much higher. The existence of liquid water at the surface depends on poorly known aspects of H₂O continuum absorption and on uncertainties concerning relative humidity and cloudiness. In any case, water vapor should have been a major atmospheric constituent at all altitudes, leading to the rapid hydrodynamic escape of hydrogen. The oxygen left behind by this process was presumably consumed by reactions with reduced minerals in the crust. Both the loss of oxygen and the presently observed enrichment of the deuterium-to-hydrogen ratio are most easily explained if oceans of liquid water were initially present.     

Search for sulfates on the surface of Ceres

The formation of hydrated salts is an expected consequence of aqueous alteration of Main Belt objects, particularly for large, volatile‐rich protoplanets like Ceres. Sulfates, present on water‐bearing planetary bodies (e.g., Earth, Mars, and carbonaceous chondrite parent bodies) across the inner solar system, may contribute to Ceres’ UV and IR spectral signature along with phyllosilicates and carbonates. We investigate the presence and stability of hydrated sulfates under Ceres’ cryogenic, low‐pressure environment and the consequent spectral effects, using UV–Vis–IR reflectance spectroscopy. H₂O loss begins instantaneously with vacuum exposure, measured by the attenuation of spectral water absorption bands, and a phase transition from crystalline to amorphous is observed for MgSO₄·6H₂O by X‐ray powder diffraction. Long‐term (>40 h), continuous exposure of MgSO₄·nH₂O (n = 0, 6, 7) to low pressure (10^?3–10^?6 Torr) causes material decomposition and strong UV absorption below 0.5 μm. Our measurements suggest that MgSO₄·6H₂O grains (45–83 μm) dehydrate to 2% of the original 1.9 μm water band area over ~0.3 Ma at 200 K on Ceres and after ~42 Ma for 147 K. These rates, inferred from an Avrami dehydration model, preclude MgSO₄·6H₂O as a component of Ceres’ surface, although anhydrous and minimally hydrated sulfates may be present. A comparison between Ceres emissivity spectra and laboratory reflectance measurements over the infrared range (5–17 μm) suggests sulfates cannot be excluded from Ceres’ mineralogy.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

The circumstellar envelope of VX Sgr

By use of the data for VLBI observation of SiO masrs, and MERLIN observation of H₂O and OH masers of VX Sgr, we found that the SiO, H₂O, OH 1665/7, OH 1612 masers occur on a few separated shells, and the order of magnitude of the radii of their corresponding shells is 10¹⁴, 10¹⁵, 10¹⁶ cm, respectively. The field of the expanding velocity of the shells is obtained. It is important to note ice-layer covers on the surface of dust and grain for outlayer envelopes.     

The evolution of an impact-generated atmosphere

Shock wave and thermodynamic data for rock-forming and volatile-bearing minerals are used to determine minimum impact velocities (v_cr) and minimum impact pressures (p_cr) required to form a primary H₂O atmosphere during planetary accretion from chondritelike planetesimals. The escape of initially released water from an accreting planet is controlled by the dehydration efficiency. Since different planetary surface porosities will result from formation of a regolith, v_cr and p_cr can vary from 1.5 to 5.8 km/sec and from 90 to 600 kbar, respectively, for target porosities between 0 and ～45%. On the basis of experimental data, hydration rates for forsterite and enstatite are derived. For a global regolith layer on the Earth's surface, the maximum hydration rate equals 6 × 10¹⁰ g H₂O sec^?1 during accretion of the Earth. Attenuation of impact-induced shock pressure is modeled to the extent that the amount of released water as a function of projectile radius, impact velocity, weight fraction of water in the target, target porosity, and dehydration efficiency can be estimated. The two primary processes considered are the impact release of water bound in hydrous minerals (e.g., serpentine) and the subsequent reincorporation of free water by hydration of forsterite and enstatite. These processes are described in terms of model calculations for the accretion of the Earth. Parameters which lead to a primary atmosphere/hydrosphere are: an accretion time of ? 1.6 × 10⁸years, the use of an accretion model defined by Weidenschilling (1974, 1976), a mean planetesimal radius of 0.5 km, a hydration rate of 6 × 10¹⁰ g H₂O sec^?1 inferred from a mean porosity of ～ 10% for the upper 1 km of the accreting Earth, and values for the dehydration efficiency, DE, of 0.55 and 0.07 for the maximum and minimum pressure decay model, respectively. Conditions which prohibit the formation of a primary atmosphere include an accretion time much longer than 1.6 × 10⁸ years, a hydration rate for forsterite and enstatite well in excess of 6 × 10¹⁰ g H₂O sec^?1, and a dehydration efficiency DE < 0.07. We conclude that the concept of dehydration efficiency is of dominant importance in determining the degree to which an accreting planet acquires an atmosphere during its formation.     

La lune mange-t-elle les couleurs?

The hydrogen radicals play an important role in the photochemistry of the troposphere of the Earth. The chemistry of OH, HO₂ and H₂O₂ is linked directly to the photodissociation of O₃ through the production of O(¹D). Gaseous H₂O₂ (hydrogen peroxide may be removed by heterogeneous reactions involving aerosols and liquid water. During the day and the night the solubility of ambient H₂O₂ in water is estimated and the oxidant capacity of H₂O₂ may explain the bleaching properties of the dew used in the past. This phenomenon may also explain some old maxims concerning the properties of the Moon's light to corrupt colors.     

Frost grain size metamorphism: Implications for remote sensing of planetary surfaces

An understanding of the rates of frost grain growth is essential to the goal of relating spectral data on surface mineralogy to the physical history of a planetary surface. Models of grain growth kinetics have been constructed for various frosts based on their individual thermodynamic properties and on the difference in binding energy between molecules on plane vs curved faces. A steady state situation can occur on planetary surfaces in which thermal elimination of small grains competes with their creation, usually by meteorite impact. We utilize predicted grain growth rates to explain telescopic spectral data on condensate surfaces throughout the solar system. On Pluto, predicted CH₄ ice grain growth rates are very high despite the low temperature, resulting in a multicentimeter optical path. This explains the strong CH₄ absorption band depths, which otherwise would require large amounts of CH₄ gas. On the Uranian and Saturnian satellites, extremely slow grain growth rates are predicted because of the low vapor pressure of H₂O at the existing average surface temperatures. This may explain evidence for fine grain size and peculiar microstructure. On Io, ordinary thermal exchange is more effective than sputtering in promoting grain growth because of the properties of SO₂. Over much of Io's disk, submicron size grains of SO₂ could plausibly reconfigure into a surface glaze on a timescale comparable to the resurfacing rate. This may explain the relatively strong SO₂ signature in Io's infrared absorption spectrum as opposed to its weaker manifestation in the visible spectrum. In spite of lower sputtering fluxes, sputtering plays a more important role in grain growth for Europa, Ganymede, and Callisto than on Io. This is a result of high rates of thermally activated grain growth and resurfacing on Io. The sequence of H₂O-ice absorption band depths (related to the mean grain size) is J₂(T) ～ J₃(T) > J₂(L) > J₃(L) ～ J₄(T) ～ J₄(L), where L = leading and T = trailing. This is to be expected if sputtering were dominant. The calculations show, however, that neither thermalized exchange fluxes nor sputtering exchange fluxes can produce the implied grain growth or the ordering by ice absorption band depths of the six satellite hemispheres. Only sputtering control by simple ejection of H₂O from the satellites, as the dominant cause of shorter mean lifetimes for smaller exposed grains, can satisfactorily explain the data. Some observations, which suggest that there are vertical grain size gradients, may result from a steady state balance between intense near surface production of fine frost by comminution, coupled with ongoing ubiquitous grain growth in the vertical column. In certain cases, e.g., Europa and Enceladus, the possibility exists that endogenic activity as well as comminution could affect grain size—at least locally. It is concluded that not only ice identification and mapping, but ice grain size mapping is an important experiment to be conducted on future missions.     

PFS-MEX observation of ices in the residual south polar cap of Mars

The Mars Express spacecraft has a highly inclined orbit around Mars and so has been able to observe the south pole of Mars in illuminated conditions at the end of the southern summer (L_s=330). Spectra from the planetary Fourier spectrometer (PFS) short wavelength (SW) channel were recorded over the permanent ice cap to study its composition in terms of CO₂ ice and H₂O ice. Models are fitted to the observed data, which include a spatial mixture of soil (not covered by ice) and CO₂ frost (with a specific grain size and a small amount of included dust and H₂O ice). Two different kinds of spectra were observed: those over the permanent polar cap with almost pure CO₂ ice, negligible water ice, no soil fraction required, and bright; and those over mixed terrain (at the edge of the cap or near troughs) containing a significant soil spatial fraction, more water ice and smaller CO₂ grain size. The amount of water ice given by fits to scaled albedo models is less than 10 ppm by weight. When using multi-stream reflectance models with the appropriate lighting geometry, the water amount must be 2-5 times greater than the albedo fit (less than 50 ppm). At the periphery of the residual polar cap, we found a region almost completely covered by water frost, modeled as a mixture of micron-sized and sub-mm sized grains. Our result using a granular mixture of micron-sized grains of water ice and dust with the CO₂ grains is different from the modeling of OMEGA polar cap observations using molecular mixtures.     

Martian dust particles as condensation nuclei: A preliminary assessment of mineralogical factors

Condensation of frosts on Mars should depend not only on temperature and degree of vapor supersaturation but also on the nature of dust particles that would act as condensation nuclei. For a given particle size, the favorability of a condensate nucleator is determined by (1) degree of crystallographic misfit, or disregistry (δ), between substrate and condensate, (2) chemical-bond compatibility between substrate and condensate, and (3) abundance of substrate surface defects that would encourage assembly of condensate atoms or molecules. New data on ice-forming characteristics of candidate Martian materials, obtained by differential scanning calorimetry, confirmed previous evidence for systematic variations in ice-nucleation temperature, T_in, among geologic materials. By considering individual types of minerals separately, factors (2) and (3) can be held relatively constant and differences in nucleation effectiveness can be estimated by computation of (1). Both calorimetry data and cloud-chamber (literature) data indicate that T_in varies inversely with minimum absolute value of disregistry, /δ/. On Mars, H₂OIc might be an important form of water ice whereas H₂OIh is the common form on Earth. Phase H₂OIc offers the lowest overall /δ/ values for heterogeneous nucleation of other condensates, including H₂OIh, solid CO₂, and CO₂ hydrate, suggesting that the best overall mineral nuclei might be those that most effectively nucleate H₂OIc. Based on /δ/ values, good nucleators of H₂OIc should include nonexpandable clay minerals (e.g., kaolinite, chlorite), certain zeolites (e.g., clinoptilolite), goethite, and bassanite. Although goethite might preferentially nucleate H₂OIc, hematite should preferentially nucleate H₂OIh. Cryptocrystalline mineraloids (e.g., palagonite) should be generally poor nucleators and nucleating abilities of expandable clay minerals (e.g., nontronite, montmorillonite) should vary significantly with degree of c-axis expansion, as controlled by degree of interlayer hydration.     

Chemical effects of H2 formation excitation

The effects of the production on dust grain surfaces of molecular hydrogen in excited states have been investigated. On the assumption that all of the H₂ formed on the surface of grains has a sufficient level of excitation too vercome the energy barriers in the formation reactions for the important OH and CH⁺ radicals, we consider the likely abundances of excited H₂ (H₂ ^*), OH and CH⁺ in various situations. Two different models are employed; the first links the H₂ ^* abundance directly to that of H₂ using a steady-state approximation, whilst the second considers the time-dependence of H₂ ^*. The second model is applied to gas that has been subjected to a strong isothermal shock (specifically, the shock-induced collapse of a diffuse cloud), which results in an extreme (high density, high atomic hydrogen abundance) environment. In general, it is found that the presence of the excited H₂ has only marginal effects on the chemistry of interstellar clouds. However, in the isothermal shock model, the abundances of CH⁺ are significantly enhanced, but only on short timescales, whilst the effects on the OH abundances are smaller, but last longer. We conclude that other than in such exceptional environments there are no obvious chemical signatures of the formation of H₂ ^*. This revised version was published online in July 2006 with corrections to the Cover Date.