Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS⁻) was added at 40 to 250 μM h⁻¹ to 5 g L⁻¹ goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m⁻²) at pH 7.5. Dissolved Hg initially decreased from 10³ or 10⁴ nM (depending on initial conditions) to 10⁻¹ nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS_(s)) formed, based on identification using Hg L_III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS_(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g⁻¹) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS_(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.     

The kinematics of the ionized gas in the Circinus galaxy

The TAURUS-2 Fabry–Perot interferometer, mounted on the 3.9-m Anglo-Australian Telescope, has been used to observe the Circinus galaxy. We have mapped the intensity and velocity distribution of the ionized hydrogen in the galaxy using the Balmer series Hα spectral line.
The semiresolved core (observed with a seeing disc of 30 pc) appears amorphous in shape, which is commonly observed in Seyfert 2 galaxies. Its peak coincides with the core position measured in the radio continuum, suggesting that ionized gas surrounds a non-thermal source.
A circumnuclear ring or spiral of radius 220 pc and a rotational velocity of 350 km s⁻¹ (assuming circular motions) surrounds the core. The inclination angle of this feature, i =40°±10°, is less than that of the previously observed radio continuum disc. The velocity channel maps obtained for the Hα ring show that the kinematics resemble those of a rotating ring and the intensity displays a complex structure indicative of several, unresolved, H II regions. We believe the ring to represent a circumnuclear starburst.
Our Hα data also show the presence of the previously detected [O III ] ionization cone to the north-west of the core, measuring more than 400 pc in length. We suggest that the ionization cone lies in a different plane from that of the starburst ring and is directed away from us. Several kinematic components of the core are derived and we calculate an outflow velocity in excess of 150–200 km s⁻¹ for gas above the core of Circinus. We also present evidence for inflowing ionized gas at the centre of Circinus.
The correlation of the Hα and radio continuum features is discussed, as well as the possible presence of a starburst-driven superwind in the Circinus galaxy.     

Geochemistry of high-grade eclogites and metarodingites from the Central Alps

Analyses for major, minor, and trace element contents of metamorphosed, variably rodingitized mafic rocks demonstrate substantial removal of Na and as much as three-fold gains in Ca as a consequence of rodingitization. Modest declines in Si and Fe can be explained in terms of dilution effects. Losses in K and Ba do not correlate with Ca% and may have been caused by an alteration process not related to the rodingitization. The Ca-metasomatism was not accompanied by a gain in Sr. The relative contents of Ti, Zr, Hf, Y, Co, Sc, and heavy REE show no readily detectable changes, despite the rodingitization (±other alteration) and subsequent metamorphisms, namely, eclogite facies (T800° C, P 20kbar) followed by amphibolite facies, sillimanite zone. Protoliths were tholeiitic basalt or diabase, and gabbro, with trace element contents indicative of a spreading center origin. Trace element and REE patterns indicate low-pressure fractionation of this magma, with plagioclase stable. This petrogenesis is consistent with prior conclusions on the shallow crustal origin of the protolith of the eclogite-metarodingite-garnet lherzolite suite in the Cima Lunga-Adula nappe, Central Alps. Based on their bulk chemical composition, the mafic rocks in this suite could be the equivalent of Mesozoic ophiolitic rocks in the more external parts of the Alps.     

Metal binding capacity of selected maine surface waters

Concentrations of Ca, Cd, Cu, Fe, and Pb and binding capacities for Cd, Cu, and Pb were determined for water samples collected from 12 lakes in southwestern Maine using atomic absorption and ion-selective electrodes, respectively. Surface waters in this area are soft and characterized by low pH. Some lakes were highly colored with refractory organics, whereas others had very low organic carbon concentrations. Both Cu and Pb concentrations were positively correlated with organic carbon content. Copper and Pb binding capacities were significantly correlated with organic carbon content, whereas Cd binding capacity was positively correlated with pH, but not with organic carbon. Surface water binding capacity for Pb was greater than that for Cu or Cd. More than 99% of the Ca from all waters studied was removed onto cationic exchange resins. Less than 1% of the total Cu existed as cationic species in highly humic waters, whereas as much as 65% existed as cationic species in less huic waters. Conversely, more than 99% of the Cd present in humic waters existed as cationic species, whereas as little as 50% existed as cationic species in less humic, more alkaline waters. These correlative studies indicate that binding by organic carbon is important for both Cu and Pb in this area and must be considered in models of trace metal speciation. However, Cd binding in the same waters is not correlated with organic carbon, which does not need to be considered in speciation models for Cd.     

Basalts of unusual composition from the Chyulu Hills,Kenya

Five Ne-normative basalts are unusually rich in Cr, to a lesser degree in Co, and have very high La/Lu ratios and high contents of several excluded trace elements resembling kimberlites in these and other aspects. They seem to represent mantle-derived magmas, only slightly modified by shallow level crystal/liquid fractionation. Cr was apparently excluded from the crystalline phases in equilibrium with these magmas in the upper mantle.The Chyulu rocks differ in several respects from other Gregory Rift basalts, but closely resemble those from Jan Mayen Island near the Mid-Atlantic ridge. The generation of these unusual basalts is therefore not related simply to mantle composition or tectonic setting, but may reflect unusually high-T (1450°C), low-P (15–29 kbars) environments in the zones of last effective equilibration of these magmas with mantle rocks.     

Structure energies of the alkali feldspars

Structural energetics of the alkali feldspars have been studied using a “lattice” or structure energy model. Electrostatic energies, U _e,for 20 well-refined, non-intergrown alkali feldspars were calculated using Bertaut's (1952) summation procedure and average about ?13,400 kcal/mol; the repulsive energies of the alkali site in each structure (～15 kcal/mol) were calculated using repulsive parameters for K-O and Na-O interactions estimated from bulk modulus data for NaF and KF and the exponential form of the repulsive potential. Using a procedure in which the position of the alkali cation was varied while the oxygen cage was kept fixed, structure energy gradients for the alkali sites of high albite and a hypersolvus Ab₄₂Or₅₈ structure were computed. In both cases, a broad structure energy well, elongated approximately parallel to c and subparallel to the observed split Na positions, was found. In both structures there is a single energy minimum corresponding closely with the observed single alkali positions. Comparison of U _e values for the alkali feldspars with different K/Na ratios shows that intermediate compositions are predicted to be less “stable” than either endmember and that the potassic end-member is predicted to be less “stable” than the sodic one, assuming that all other factors contributiong to the free energies of each phase are approximately the same. Comparison of U _e values for the high albite and low sanidine structures with different Al/Si distributions and a fixed tetrahedral framework indicates that the ordered charge distributions are 63.0 and 54.8 kcal/mol, respectively, more “stable” than the disordered distributions. Smaller, more realistic energy differences were obtained by using U _evalues averaged from four separate calculations with a +3 charge on a different T site in each and with +4 charges on the other T sites. If, in addition, the charges on cations and oxygen are reduced to half their nominal formal charges, in agreement with Pauling's electroneutrality principle and the results of recent molecular orbital calculations on silicates, the predicted electrostatic energy differences are reduced to 3.6 and 1.6 kcal/mol, respectively. These calculations also indicate that the T₁O site in the high albite structure energetically favors Al and that the Al/Si distribution determines the Na position within the alkali site.     

Atmospheric effects in the remote sensing of phytoplankton pigments

We investigate the accuracy with which relevant atmospheric parameters must be estimated to derive phytoplankton pigment concentrations (chlorophyll a plus phaeophytin a ) of a given accuracy from measurements of the ocean's apparent spectral radiance at satellite altitudes. The analysis is limited to an instrument having the characteristics of the Coastal Zone Color Scanner scheduled to orbit the Earth on NIMBUS-G. A phytoplankton pigment algorithm is developed which relates the pigment concentration (C) to the three ratios of upwelling radiance just beneath the sea surface which can be formed from the wavelengths () 440, 520 and 550 nm. The pigment algorithm explains from 94 to 98% of the variance in log₁₀ C over three orders of magnitude in pigment concentration. This is combined with solutions to the radiative transfer equation to simulate the ocean's apparent spectral radiance at satellite altitudes as a function of C and the optical properties of the aerosol, the optical depth of which is assumed to be proportioned to ^-n . A specific atmospheric correction algorithm, based on the assumption that the ocean is totally absorbing at 670 nm, is then applied to the simulated spectral radiance, from which the pigment concentration is derived. Comparison between the true and derived values of C show that: (1) n is considerably more important than the actual aerosol optical thickness; (2) for C 0299-1 0.2 g l^-1 acceptable concentrations can be determined as long as n is not overestimated; (3) as C increases, the accuracy with which n must be estimated, for a given relative accuracy in C, also increases; and (4) for C greater than about 0.5 g 1^-1, the radiance at 440 nm becomes essentially useless in determining C. The computations also suggest that if separate pigment algorithms are used for C 1gl^-1 and C 1 gl^-1, accuracies considerably better than ±± in log C can be obtained for C 1 g l^-1 with only a coarse estimate of n, while for C 10 gl^-1, this accuracy can be achieved only with very good estimates of n.Contribution No. 387 from the NOAA/ERL Pacific Environmental Laboratory.On leave from Department of Physics, University of Miami, Coral Gables, Florida.