Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 °C to 25 °C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars.Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl₂·4H₂O, FeCl₂·6H₂O, FeSO₄·H₂O, FeSO₄·7H₂O, FeCO₃, and Fe(OH)₃] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO₄, Fe-HCO₃, H-Fe-Cl, and H-Fe-SO₄.We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO₃), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification.What began as a dilute Mg-Fe-HCO₃ dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO₄-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O₂(g)], but later caused oxidation of iron [high O₂(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses.     

Sulfur-isotope distribution and contamination related to the Balya Pb–Zn Mine in Turkey

Sulfur-isotope (³⁴S) values and weight (%) of acid-volatile sulfur (AVS), chrome-reducible sulfide (CRS), elemental sulfur (ES), and acid-soluble sulfates were determined in Balya Mine ore rock, mine wastes, and Kocacay River and Lake Manyas sediments. Estimation of isotopic fractionation (³⁴S) between product sulfate and initial CRS (pyrite) was used to evaluate the progress of sulfide oxidation in the mine-waste area. Water- and acid-soluble sulfate produced from different mine-waste samples, such as metallurgical waste (MW) and waste rock (WR), in laboratory experiments also shows distinct ³⁴S values and allows identification of the acid-mine-drainage sources in the mine-waste area. Average ³⁴S_SO4values are –1.43 for MW (n=4) and +2.06 for WR (n=8). Short (24 hr) and long (60 days) term leach experiments were considered using alternating wet/dry conditions to simulate sulfate-production capacity and metal-discharge characteristics for MW and WR piles. Release of heavy metals follows the order of Pb²⁺ >Mn²⁺ >Zn²⁺ >Cu²⁺ for these pile samples. Values of ³⁴S_SO4 for river water that was collected after 3–4 h of heavy rainfall are close to values of ³⁴S_SO4 for water-soluble sulfates from mine-waste piles used in laboratory leach experiments.This revised version was published in February 2005 with corrections to the placement of the figures.     

Groundwater occurrence in cold environments: examples from Nunavik,Canada

Water availability and management issues related to the supply of drinking water in northern communities are problematic in Canada. While rivers and lakes are abundant, they are vulnerable to contamination and may become dry in winter due to freezing. Groundwater can often provide a more secure and sustainable water source, however its availability is limited in northern Canada due to the presence of permafrost. Moreover, the exploitation of northern aquifers poses a dual challenge of identifying not only permafrost-free areas, but also permeable areas which will allow groundwater recharge and exploitation. Suitable aquifers are not as common in northern Canada since the shallow subsurface is mostly composed of low-permeability crystalline rocks or unconsolidated sediments of glacial origin that are highly heterogeneous. In order to investigate groundwater occurrence and associated geological contexts in Nunavik (northern Quebec, Canada), along with exploring how these resources will evolve in response to climate change, field and compilation work were conducted in the surroundings of the four villages of Salluit, Kuujjuaq, Umiujaq and Whapmagoostui-Kuujjuarapik. These villages are located in different permafrost zones, ranging from continuous to discontinuous, as well as in different geological environments. It was found that despite the ubiquitous presence of permafrost, unfrozen aquifers could be identified, which suggests that groundwater may be available as a source of drinking water for small communities. Expected climate change, with predicted permafrost thawing and increases in temperature and precipitation, should enhance groundwater availability and may contribute to a more secure source of drinking water for northern communities.     

Septarian concretions: internal cracking caused by synsedimentary earthquakes

Septarian concretions are abundant in many Phanerozoic marine and marginal‐marine shales and mudstones. They range from a few centimetres to several metres in size and are spherical or ellipsoidal in morphology. In general, formation by localized calcite or siderite cementation in argillaceous sediments began under less than a few metres of burial. Septarian cracks vary widely in shape and configuration: included are networks of wide, vertically, radially and sometimes concentrically oriented, lenticular shrinkage cracks; and narrower, parallel‐sided, straight to irregular tension cracks locally accompanied by brecciation, and plumose and en échelon sigmoidal cracks indicative of shear stresses. Crack types are intergradational; many concretions exhibit multiple cracking events. Enclosed macrofossils and isopachous fibrous calcite cement that lines earlier formed cracks are commonly broken and displaced. In some cases, cracks contain injected lime mud and silt. These features, taken together, testify that cracking involved a spectrum of responses in concretion interiors, from loss of shear strength, dewatering and shrinkage to brittle failure, demonstrating variations in, and contrasts between, the rheological properties of the matrix and enclosed objects. Localization to interiors and outward tapering of lenticular cracks make a case for fracture partitioning and indicate that interiors were softer than exteriors at the time of shrinkage. Parallel‐sided cracks point to greater stiffness, and evolving crack shape in multiply cracked concretions shows that rigidity increased with time. Crack orientations indicate highly variable tensile and shear stress directions within individual concretions. Rupture, brecciation, displacement of fragments, loss of shear strength, liquefaction and injection of unconsolidated granular sediment suggest that deformation events were rapid, if not virtually instantaneous. Previous explanations for the internal cracking, such as gas generation, spontaneous chemical dehydration or localized overpressuring due to compaction, seem either untenable or fail to account for the spectrum of observed features. However, syndepositional earthquake‐induced shaking of cementing bodies of varying rigidity at shallow burial depths seems to be a plausible source for the requisite short‐lived, variable to anisotropic, high‐stress regime inside the concretions. Septarian concretions may thus preserve a signature of basin seismicity as it relates to their cementation history.     

Results from regional vibroseis profiling: Appalachian ultra-deep core hole site study

Summary. In 1985, 180 km of regional vibroseis profiles were acquired in the Carolinas and Georgia, southeastern United States, as part of the Appalachian Ultra-Deep Core Hole (ADCOH) Site Study. The data quality is excellent, with large-amplitude reflections from faults and crystalline rocks, lower Palaeozoic shelf strata and from within autochthonous Grenville basement. The profiles image the subsurface more clearly than other available data and allow the possibility of alternative interpretations of important elements of the tectonic framework of the southern Appalachians.
The major points in the interpretation are: 1) The Blue Ridge master decollement is at a depth of 2-3 km beneath the Blue Ridge. This thrust increases in dip just NW of the Brevard fault zone. 2) The Brevard fault zone appears to splay from the master decollement at 6 km (2.2 s) near Westminster, S.C., and defines the base of the crystalline Inner Piedmont allochthon. 3) Below the Blue Ridge thrust sheet are images of duplex and imbricate structures ("duplex tuning wedges") connected by other thrust faults that duplicate shelf strata to a thickness of 4–5 km. 4) Subhorizontal reflections from depths of 6 to 9 km may be from relatively undisturbed lower Palaeozoic strata as suggested by others. 5) Eocambrian-Cambrian(?) rift basins in the Grenville basement are also imaged.
The ADCOH data were originally recorded with 14–56 Hz bandwidth and 8 s length, but an extended Vibroseis correlation was used to produce 17 s data length revealing reflections from within the upper crust. Below 8 s, reflections from within the Grenville basement become weak, but are observable as late as 13 s; however, these Moho (?) reflections are generally short segments.     

A comfortable night out? Alcohol, drunkenness and inclusive town centres

The Licensing Act (2003) was enacted in England and Wales against the backdrop of media concern about 'binge Britain' and violent town centres avoided by 'social drinkers'. This paper responds to these concerns by asking how to create more inclusive urban centres at night. Findings from focus groups found it was not alcohol consumption or a reluctance to partake in urban life that was detracting residents. Using the notion of 'comfort', the paper instead reveals a strong desire for varied late-night experiences ranging from quiet local venues, to active streets and live venues.     

Are fossil groups a challenge of the cold dark matter paradigm?

We study six groups and clusters of galaxies suggested in the literature to be 'fossil' systems (i.e. to have luminous diffuse X-ray emission and a magnitude gap of at least 2 mag R between the first and the second ranked member within half of the virial radius), each having good quality X-ray data and Sloan Digital Sky Survey (SDSS) spectroscopic or photometric coverage out to the virial radius. The poor cluster AWM 4 is clearly established as a fossil system, and we confirm the fossil nature of four other systems (RX J1331.5+1108, RX J1340.6+4018, RX J1256.0+2556 and RX J1416.4+2315), while the cluster RX J1552.2+2013 is disqualified as fossil system. For all systems, we present the luminosity functions within 0.5 and 1 virial radius that are consistent, within the uncertainties, with the universal luminosity function of clusters. For the five bona fide fossil systems, having a mass range  2 × 10¹³–3 × 10¹⁴ M_⊙  , we compute accurate cumulative substructure distribution functions (CSDFs) and compare them with the CSDFs of observed and simulated groups/clusters available in the literature. We demonstrate that the CSDFs of fossil systems are consistent with those of normal observed clusters and do not lack any substructure with respect to simulated galaxy systems in the cosmological Λ cold dark matter (ΛCDM) framework. In particular, this holds for the archetype fossil group RX J1340.6+4018 as well, contrary to earlier claims.