Source rates and ion recycling rates for Na and K in Mercury's atmosphere

The supply rates of Na and K to the atmosphere of Mercury by processes acting on the extreme surface—thermal vaporization, photon-stimulated desorption (PSD), and ion-sputtering—are limited by the rates at which atoms can be supplied to the extreme surface by diffusion from inside the regolith grains. Supply rates to the atmosphere are further regulated by ion retention and by gardening rates that supply new grains to the surface. We consider the limits on supply of sodium and potassium atoms to the atmosphere, and rates of photoion recycling to the surface. Thermal vaporization rates are severely limited by the ability of atoms to diffuse to the surface of the grain. Therefore, the diffusion-limited thermal vaporization rates on Mercury's surface are comparable to or less than the PSD rates. Ion sputtering is primarily due to highly ionized heavy ions, even though they represent a small fraction of the solar wind. We have shown that up to 60% of the Na photoions are deposited on the surface of Mercury. Ion recycling to the surface can have a long-term effect on the regolith abundance if an average recycling pattern persists such that more ions return to a particular area than are launched there. It is unknown whether the formation of latitude bands of >100% ion retention persist on average despite a rapidly changing magnetosphere. The total exospheric column of sodium observed at Mercury between 1997 to 2003 varied by a factor of 2-3 from perihelion to aphelion.     

Monte-Carlo simulation of Mercury's exosphere

Because of its proximity to the Sun and its small size, Mercury has not been able to retain its atmosphere and only a thin exosphere surrounds the planet. The exospheric pressure at the planetary surface is approximately 10⁻¹⁰ mbar, set by the Mariner 10 occultation experiment. The existence of gaseous species H, He, and O has been established by Mariner 10. In addition Na, K, and Ca have been observed by ground based instrumentation. Other elements are expected to be found in Mercury's exosphere since the total pressure of the known species is almost two orders of magnitude less than the exospheric pressure.It is intended to measure these exospheric particle densities in situ with an instrument on board of ESA's BepiColombo Mercury Planetary Orbiter (MPO) spacecraft. Since the expected exospheric densities are very small we developed a Monte-Carlo computer model to investigate if such a measurement is feasible along the MPO spacecraft orbit. We model energy and ejection angle distributions of the particles at the surface, with the emission process determining the actual distribution functions. Our model follows the trajectory of each particle by numerical integration until the particle hits Mercury's surface again or escapes from the calculation domain. Using a large set of these trajectories bulk parameters of the exospheric gas are derived, e.g., particle densities for various atomic and molecular species. Our study suggests that a mass spectrometric measurement is feasible and, at least at MPO's periherm, all species that are released from the surface will be observed.     

The variability of Mercury's exosphere by particle and radiation induced surface release processes

Mercury's close orbit around the Sun, its weak intrinsic magnetic field and the absence of an atmosphere (P_surface<1×10⁻⁸ Pa) results in a strong direct exposure of the surface to energetic ions, electrons and UV radiation. Thermal processes and particle-surface-collisions dominate the surface interaction processes leading to surface chemistry and physics, including the formation of an exosphere (N?10¹⁴ cm⁻²) in which gravity is the dominant force affecting the trajectories of exospheric atoms. NASA's Mariner 10 spacecraft observed the existence of H, He, and O in Mercury's exosphere. In addition, the volatile components Na, K, and Ca have been observed by ground based instrumentation in the exosphere. We study the efficiency of several particle surface release processes by calculating stopping cross-sections, sputter yields and exospheric source rates. Our study indicates surface sputter yields for Na between values of about 0.27 and 0.35 in an energy range from 500 eV up to 2 keV if Na⁺ ions are the sputter agents, and about 0.037 and 0.082 at an energy range between 500 eV up to 2 keV when H⁺ are the sputter agents and a surface binding energy of about 2 eV to 2.65 eV. The sputter yields for Ca are about 0.032 to 0.06 and for K atoms between 0.054 to 0.1 in the same energy range. We found a sputter yield for O atoms between 0.025 and 0.04 for a particle energy range between 500 eV up to 2 keV protons. By taking the average solar wind proton surface flux at the open magnetic field line area of about 4×10⁸ cm⁻² s⁻¹ calculated by Massetti et al. (2003, Icarus, in press) the resulting average sputtering flux for O is about 0.8-1.0×10⁷ cm⁻² s⁻¹ and for Na approximately 1.3-1.6×10⁵ cm⁻² s⁻¹ depending on the assumed Na binding energies, regolith content, sputtering agents and solar activity. By using lunar regolith values for K we obtain a sputtering flux of about 1.0-1.4×10⁴ cm⁻² s⁻¹. By taking an average open magnetic field line area of about 2.8×10¹⁶ cm² modelled by Massetti et al. (2003, Icarus, in press) we derive an average surface sputter rate for Na of about 4.2×10²¹ s⁻¹ and for O of about 2.5×10²³ s⁻¹. The particle sputter rate for K atoms is about 3.0×10²⁰ s⁻¹ assuming lunar regolith composition for K. The sputter rates depend on the particle content in the regolith and the open magnetic field line area on Mercury's surface. Further, the surface layer could be depleted in alkali. A UV model has been developed to yield the surface UV irradiance at any time and latitude over a Mercury year. Seasonal and diurnal variations are calculated, and Photon Stimulated Desorption (PSD) fluxes along Mercury's orbit are evaluated. A solar UV hotspot is created towards perihelion, with significant average PSD particle release rates and Na fluxes of about 3.0×10⁶ cm⁻² s⁻¹. The average source rates for Na particles released by PSD are about 1×10²⁴ s⁻¹. By using the laboratory obtained data of Madey et al. (1998, J. Geophys. Res. 103, 5873-5887) for the calculation of the PSD flux of K atoms we get fluxes in the order of about 10⁴ cm⁻² s⁻¹ along Mercury's orbit. However, these values may be to high since they are based on idealized smooth surface conditions in the laboratory and do not include the roughness and porosity of Mercury's regolith. Further, the lack of an ionosphere and Mercury's small, temporally and spatially highly variable magnetosphere can result in a large and rapid increase of exospheric particles, especially Na in Mercury's exosphere. Our study suggests that the average total source rates for the exosphere from solar particle and radiation induced surface processes during quiet solar conditions may be of the same order as particles produced by micrometeoroid vaporization. We also discuss the capability of in situ measurements of Mercury's highly variable particle environment by the proposed NPA-SERENA instrument package on board ESA's BepiColombo Mercury Planetary Orbiter (MPO).     

Mercury speciation in surface and deep waters of the Mediterranean Sea

Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32 ± 0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33 ± 0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg⁰, represents a considerable proportion of THg (average 20%, 0.23 ± 0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67 ± 2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68 ± 0.43 pM and 0.29 ± 0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.     

Factors influencing the oxidation,reduction, methylation and demethylation of mercury species in coastal waters

The objective of this study was to examine the redox reactions and other transformations of mercury (Hg) species in surface waters, and the factors determining the rates of these reactions. For the redox studies completed at the Chesapeake Biological Laboratory (CBL), two isotopes (¹⁹⁹Hg^II and ²⁰²Hg⁰) were added into different types of filtered water (fresh to seawater) to examine the oxidation and reduction reactions. Further studies of both the redox reactions and methylation/demethylation reactions of Hg were conducted with unfiltered water on board research vessels during cruises in May and July 2005 on the Chesapeake Bay and shelf. While CH₃¹⁹⁹Hg^II was added to allow the examination of demethylation, ²⁰¹Hg^II was used to examine both reduction and methylation, and ²⁰²Hg⁰ was used to examine oxidation. Overall, the results showed that both Hg oxidation and reduction were simultaneously occurring and were photochemically mediated in the waters investigated. In contrast to the previously assumed “unreactive” nature of Hg⁰, the studies found that the magnitude of the rate constant for Hg⁰ oxidation was greater than that for reduction, indicating its importance in estuarine and coastal waters. In addition, both experiments at CBL and on board ship showed that Hg^II reduction was similar in magnitude, suggesting that biotic processes were relatively unimportant. While no measurable methylation occurred during the incubation period during the on board studies, concentration of CH₃¹⁹⁹Hg^II decreased over the time during the experiments. It appeared that the demethylation processes were not dominantly photochemically driven, but could be microbially mediated. Further studies are needed in order to help better understand Hg redox and transformations in natural water systems.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

Assessment of mercury mobility and bioavailability by fractionation method in sediments from coastal zone inundated by the 26 December 2004 tsunami in Thailand

The 26 December 2004 tsunami covered significant portion of a coastal zone with a blanket of potentially contaminated sediments. In this report are presented results on mercury concentrations in sediments deposited by the tsunami in a coastal zone of Thailand. Since the total mercury concentrations are insufficient to assess mercury mobility and bioavailability in sediment, its fractionation was applied. Sediments were sampled within 50 days after the event and analyzed by sequential extraction method. The procedure of sequential extraction involved five subsequent stages performed with solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH, and aqua regia. The mean concentration of total mercury in sediments was 119 ± 50 ng g⁻¹ dry mass (range 66–230). The fractionation revealed that mercury is mainly bound to the least bioavailable sulphides 75 ± 6% (range 62–86), organomercury compounds 14 ± 7% (range 4–26), and humic matter 9 ± 7% (range 1–27). The lowest contributions bring fractions of water-soluble mercury 0.8 ± 1.0% (range 0.1–3.6) and acid soluble mercury 0.9 ± 0.5% (range 0.2–2.1). Although, the total mercury content is similar in a reference sample and in the tsunami sediments, the highly toxic organomercury fraction contribution is higher in the latter. The results were compared with chemical and sedimentological properties of the sediments but no significant correlations were obtained between them.     

From in-situ coal to fly ash: a study of coal mines and power plants from Indiana

This paper presents data on the properties of coal and fly ash from two coal mines and two power plants that burn single-source coal from two mines in Indiana. One mine is in the low-sulfur (<1%) Danville Coal Member of the Dugger Formation (Pennsylvanian) and the other mines the high-sulfur (>5%) Springfield Coal Member of the Petersburg Formation (Pennsylvanian). Both seams have comparable ash contents (11%). Coals sampled at the mines (both raw and washed fractions) were analyzed for proximate/ultimate/sulfur forms/heating value, major oxides, trace elements and petrographic composition. The properties of fly ash from these coals reflect the properties of the feed coal, as well as local combustion and post-combustion conditions. Sulfur and spinel content, and As, Pb and Zn concentrations of the fly ash are the parameters that most closely reflect the properties of the source coal.     

Modes of occurrence of mercury and other trace elements in coals from the warrior field, Black Warrior Basin, Northwestern Alabama

The mineralogic residence and abundance of trace metals is an important environmental issue. Data from the USGS coal quality database show that potentially toxic elements, including Hg, As, Mo, Se, Cu, and Tl are enriched in a subset of coal samples in the Black Warrior Basin of Alabama, USA. Although the coal as-mined typically is low in these elements, localized enrichments occur in high-pyrite coals and near faults. Microscopic analyses demonstrate that the residence of these elements is dominantly in a late-stage pyrite associated with structurally disrupted coal. Further, our data suggest addition of Hg to the coal matrix as well. The source of these trace elements was hydrothermal fluids driven into the Black Warrior Basin by Alleghanian age tectonism.     

Mercury in Eastern Kentucky coals: Geologic aspects and possible reduction strategies

Mercury emissions from US coal-fired power plants will be regulated by the US Environmental Protection Agency (USEPA) before the end of the decade. Because of this, the control of Hg in coal is important. Control is fundamentally based on the knowledge of the amounts of Hg in mined, beneficiated, and as-fired coal. Eastern Kentucky coals, on a reserve district level, have Hg contents similar to the USA average for coal at mines. Individual coals show greater variation at the bench scale, with Hg enrichment common in the top bench, often associated with enhanced levels of pyritic sulfur. Some of the variation between parts of eastern Kentucky is also based on the position relative to major faults. The Pine Mountain thrust fault appears to be responsible for elemental enrichment, including Hg, in coals on the footwall side of the thrust.Eastern Kentucky coals shipped to power plants in 1999, the year the USEPA requested coal quality information on coal deliveries, indicate that coals shipped from the region have 0.09 ppm Hg, compared to 0.10 ppm for all delivered coals in the USA. On an equal energy basis, and given equal concentrations of Hg, the high volatile bituminous coals from eastern Kentucky would emit less Hg than lower rank coals from other USA regions.