Rapid photo-oxidation of Mn(II) mediated by humic substances

The oxidation of Mn(II) by O₂ to Mn(III) or Mn(IV) is thermodynamically favored under the pH and pO₂ conditions present in most near surface waters, but the kinetics of this reaction are extremely slow. This work investigated whether reactive oxygen species, produced through illumination of humic substances, could oxidize Mn at an environmentally relavent rate. The simulated sunlight illumination of a solution containing 200 μM Mn(II) and 5 mg/L Aldrich humic acid buffered at pH 8.1 produced ∼19 μM of oxidized Mn (MnO_x where x is between one and two) after 45 minutes. The major oxidants reponsible for this reaction appear to be photoproduced superoxide radical anion, O₂⁻, and singlet molecular oxygen, ¹O₂. The dependencies of MnO_x formation on Mn(II), humic acid, and H⁺ concentration were characterized. A kinetic model based largely on published rate constants was established and fit to the experimental data. As expected, analysis of the model indicates that the key reaction rate controlling MnO_x production is the rate of decomposition of a MnO₂⁺ complex formed from the reaction of Mn(II) with O₂⁻. This rate is strongly dependent on the Mn(II) complexing ligands in solution. The MnO_x production in the seawater sample taken from Bodega Bay, USA and spiked with 200 μM Mn(II) was well reproduced by the model. Extrapolations from the model imply that Mn photo-oxidation should be a significant reaction in typical surface seawaters. Calculated rates, 5.8 to 55 pM h⁻¹, are comparable to reported rates of biological Mn oxidation, 0.07 to 89 pM h⁻¹. Four fresh water samples that were spiked with 200 μM Mn(II) also showed significant MnO_x production. Based on these results, it appears that Mn photo-oxidation could constitute a significant, and apparently unrecognized geochemical pathway in natural waters.     

Abundance and distribution of PGE and Au in the island-arc mantle: implications for sub-arc metasomatism

Ultramafic xenoliths from a veined mantle wedge beneath the Kamchatka arc have non-chondritic, fractionated chondrite-normalized platinum-group element (PGE) patterns. Depleted (e.g., low bulk-rock Al₂O₃ and CaO contents) mantle harzburgites show clear enrichment in the Pd group relative to the Ir group PGEs and, in most samples, Pt relative to Rh and Pd. These PGE signatures most likely reflect multi-stage melting which selectively concentrates Pt in Pt–Fe alloys while strongly depleting the sub-arc mantle wedge in incompatible elements. Elevated gold concentrations and enrichment of strongly incompatible enrichment (e.g., Ba and Th) in some harzburgites suggest a late-stage metasomatism by slab-derived, saline hydrous fluids. Positive Pt, Pd, and Au anomalies coupled with Ir depletions in heavily metasomatized pyroxenite xenoliths probably reflect the relative mobility of the Pd and Ir groups (especially Os) during sub-arc metasomatism which is consistent with Os systematics in arc mantle nodules. Positive correlations between Pt, Pd, and Au and various incompatible elements (Hf, U, Ta, and Sr) also suggest that both slab-derived hydrous fluids and siliceous melts were involved in the sub-arc mantle metasomatism beneath the Kamchatka arc.     

Crustal structure beneath Spain from deep seismic sounding experiments

Major tectonic units of Spain have been investigated by deep seismic sounding experiments since 1974 to determine crustal structures and to delineate their differences. These areas are the central part of the Hercynian Meseta, and the Alpine chains: the Betic Cordillera in the south, including the Balearic promontory and the Alboran Sea, and the Pyrenees in the north.The main features of the crust and the upper mantle along a NNE-SSW cross-section from the Pyrenees to the Alboran Sea are described.The crust under the Meseta is typical of Hercynian areas found elsewhere in Europe, with an average thickness of 31 km, whereas the two Alpine regions are characterized by very large lateral inhomogeneities, such as rapid thickening of the crust to 50 and 40 km under the Pyrenees and the Betics, respectively. The deep-reaching E-W-trending North Pyrenean fault has a throw of 10–15 km at the base of the crust. A P_n velocity of 8.1 km s^?1 is found under the entire Iberian Peninsula.In the Alboran Sea, strongly varying thicknesses of sediments, shallow variable depths to the Moho (～ 13 km under the Alboran ridge), and strong variations of P_n velocity between 7.5 and 8.2 km s^?1 have been found.     

Spatial and temporal structure of the Denmark Strait Overflow revealed by acoustic observations

In spite of the fundamental role the Atlantic Meridional Overturning Circulation (AMOC) plays for global climate stability, no direct current measurement of the Denmark Strait Overflow, which is the densest part of the AMOC, has been available until recently that resolve the cross-stream structure at the sill for long periods. Since 1999, an array of bottom-mounted acoustic instruments measuring current velocity and bottom-to-surface acoustic travel times was deployed at the sill. Here, the optimization of the array configuration based on a numerical overflow model is discussed. The simulation proves that more than 80% of the dense water transport variability is captured by two to three acoustic current profilers (ADCPs). The results are compared with time series from ADCPs and Inverted Echo Sounders deployed from 1999 to 2003, confirming that the dense overflow plume can be reliably measured by bottom-mounted instruments and that the overflow is largely geostrophically balanced at the sill.     

Studies of ultracompact H ii regions — II. High-resolution radio continuum and methanol maser survey

High spatial resolution radio continuum and 6.67-GHz methanol spectral line data are presented for methanol masers previously detected by Walsh et al. (1997). Methanol maser and/or radio continuum emission is found in 364 cases towards IRAS -selected regions. For those sources with methanol maser emission, relative positions have been obtained to an accuracy of typically 0.05 arcsec, with absolute positions accurate to around 1 arcsec. Maps of selected sources are provided. The intensity of the maser emission does not seem to depend on the presence of a continuum source. The coincidence of water and methanol maser positions in some regions suggests there is overlap in the requirements for methanol and water maser emission to be observable. However, there is a striking difference between the general proximity of methanol and water masers to both cometary and irregularly shaped ultracompact (UC) H  ii regions, indicating that, in other cases, there must be differing environments conducive to stimulating their emission. We show that the methanol maser is most likely present before an observable UC H  ii region is formed around a massive star and is quickly destroyed as the UC H  ii region evolves. There are 36 out of 97 maser sites that are linearly extended. The hypothesis that the maser emission is found in a circumstellar disc is not inconsistent with these 36 maser sites, but is unlikely. It cannot, however, account for all other maser sites. An alternative model which uses shocks to create the masing spots can more readily reproduce the maser spot distributions.     

Controls on Fe reduction and mineral formation by a subsurface bacterium

The reductive dissolution of FeIII (hydr)oxides by dissimilatory iron-reducing bacteria (DIRB) could have a large impact on sediment genesis and Fe transport. If DIRB are able to reduce FeIII in minerals of high structural order to carry out anaerobic respiration, their range could encompass virtually every O₂-free environment containing FeIII and adequate conditions for cell growth. Previous studies have established that Shewanella putrefaciens CN32, a known DIRB, will reduce crystalline Fe oxides when initially grown at high densities in a nutrient-rich broth, conditions that poorly model the environments where CN32 is found. By contrast, we grew CN32 by batch culture solely in a minimal growth medium. The stringent conditions imposed by the growth method better represent the conditions that cells are likely to encounter in their natural habitat. Furthermore, the expression of reductases necessary to carry out dissimilatory Fe reduction depends on the method of growth. It was found that under anaerobic conditions CN32 reduced hydrous ferric oxide (HFO), a poorly crystalline FeIII mineral, and did not reduce suspensions containing 4 mM FeIII in the form of poorly ordered nanometer-sized goethite (α-FeOOH), well-ordered micron-sized goethite, or nanometer-sized hematite (α-Fe₂O₃) crystallites. Transmission electron microscopy (TEM) showed that all minerals but the micron-sized goethite attached extensively to the bacteria and appeared to penetrate the outer cellular membrane. In the treatment with HFO, new FeII and FeIII minerals formed during reduction of HFO-Fe in culture medium containing 4.0 mmol/L P_i (soluble inorganic P), as observed by TEM with energy-dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The minerals included magnetite (Fe₃O₄), goethite, green rust, and vivianite [Fe₃(PO₄)₂ · 8H₂O]. Vivianite appeared to be the stable end product and the mean coherence length was influenced by the rate of FeIII reduction. When P_i was 0.4 mol/L under otherwise identical conditions, goethite was the only mineral observed to form, and less Fe²⁺ was produced overall. Hence, the ability of DIRB to reduce Fe (hydr)oxides may be limited when the bacteria are grown under nutrient-limited conditions, and the minerals that result depend on the vigor of FeIII reduction.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

Turbulence Statistics Above And Within Two Amazon Rain Forest Canopies

The turbulence structure in two Amazon rain forestswas characterised for a range of above-canopystability conditions, and the results compared withprevious studies in other forest canopies and recenttheory for the generation of turbulent eddies justabove forest canopies. Three-dimensional wind speedand temperature fluctuation data were collectedsimultaneously at up to five levels inside and abovetwo canopies of 30–40 m tall forests, during threeseparate periods. We analysed hourly statistics, jointprobability distributions, length scales, spatialcorrelations and coherence, as well as power spectraof vertical and horizontal wind speed.The daytime results show a sharp attenuation ofturbulence in the top third of the canopies, resultingin very little movement, and almost Gaussianprobability distributions of wind speeds, in the lowercanopy. This contrasts with strongly skewed andkurtotic distributions in the upper canopy. At night,attenuation was even stronger and skewness vanishedeven in the upper canopy. Power spectral peaks in thelower canopy are shifted to lower frequencies relativeto the upper canopy, and spatial correlations andcoherences were low throughout the canopy. Integrallength scales of vertical wind speed at the top of thecanopy were small, about 0.15 h compared to avalue of 0.28 h expected from the shear lengthscale at the canopy top, based on the hypothesis that theupper canopy air behaves as a plane mixing layer. Allthis suggests that, although exchange is not totallyinhibited, tropical rain forest canopies differ from other forests in that rapid, coherentdownward sweeps do not penetrate into the lowercanopy, and that length scales are suppressed. This isassociated with a persistent inversion of stability inthat region compared to above-canopy conditions. Theinversion is likely to be maintained by strong heatabsorption in the leaves concentrated near thecanopy top, with the generally weak turbulence beingunable to destroy the temperature gradients over thelarge canopy depth.