Superoxide-mediated reduction of organically complexed iron(III): Impact of pH and competing cations (Ca)

The mechanism and kinetics of superoxide-mediated reduction of a variety of organic iron(III) complexes has been investigated over the pH range 7-9. Our experimental results show that the rate of iron(II) formation is a function of pH, ligand type and ligand concentration with the measured rate varying between 0.44 ± 0.07 and 39.25 ± 1.77 pM s⁻¹ in the systems investigated. Additionally, our results show that the presence of competing cations such as Ca²⁺ have a significant impact on iron(II) formation if the organic ligand is strongly complexed by Ca²⁺. Formation of iron(II) occurs by either (or, in some instances, both) reaction of superoxide with inorganic iron(III) after its dissociation from the complex (dissociative reduction) or by direct reaction of superoxide with the complex (non-dissociative reduction). In the presence of weak ligands, dissociative reduction (DR) dominates; however non-dissociative reduction (NDR) becomes important in the presence of either strongly binding ligands or high concentrations of weakly binding ligands. The major factors contributing to the pH dependence of the iron(II) formation rate are the complexation kinetics of inorganic iron(III) (which controls the DR contribution) and the reduction kinetics of the iron(III) complex (which controls the NDR contribution). The relative NDR contribution increases with increasing superoxide and ligand concentration and decreasing pH for all ligands examined. Since iron(II) formation occurring via NDR results in a significantly larger increase in the proportion of iron in free aquated form than does DR, this non-dissociative pathway of superoxide-mediated iron(III) reduction is particularly effective in increasing the lability of iron in aquatic systems.     

Quaternary depositional patterns and sea-level fluctuations, northeastern North Carolina

A detailed record of late Quaternary sea-level oscillations is preserved within the upper 45 m of deposits along an eight km transect across Croatan Sound, a drowned tributary of the Roanoke/Albemarle drainage system, northeastern North Carolina. Drill-hole and seismic data reveal nine relatively complete sequences filling an antecedent valley comprised of discontinuous middle and early Pleistocene deposits. On interfluves, lithologically similar marine deposits of different sequences occur stacked in vertical succession and separated by ravinement surfaces. Within the paleo-drainage, marine deposits are separated by fluvial and/or estuarine sediments deposited during periods of lowered sea level. Foraminiferal and molluscan fossil assemblages indicate that marine facies were deposited in a shallow-marine embayment with open connection to shelf waters. Each sequence modifies or truncates portions of the preceding sequence or sequences. Sequence boundaries are the product of a combination of fluvial, estuarine, and marine erosional processes. Stratigraphic and age analyses constrain the ages of sequences to late Marine Isotope Stage (MIS) 6 and younger (∼ 140 ka to present), indicating multiple sea-level oscillations during this interval. Elevations of highstand deposits associated with late MIS 5 and MIS 3 imply that sea level was either similar to present during those times, or that the region may have been influenced by glacio-isostatic uplift and subsidence.     

Paleoproterozoic gold deposits in the Bald Hill and Coyote areas, Western Tanami, Western Australia

Significant gold deposits in the western Tanami region of Western Australia include deposits in the Bald Hill and Coyote areas. The ca. 1,864 Ma Bald Hill sequence of turbiditic and mafic volcanic rocks hosts the Kookaburra and Sandpiper deposits and a number of smaller prospects. The ca. 1,835 Ma turbiditic Killi Killi Formation hosts the Coyote deposit and several nearby prospects. The Kookaburra deposit forms as a saddle reef within a syncline, and the Sandpiper deposit is localized within graphitic metasedimentary rocks along a limb of an anticline. Gold in these deposits is hosted by anastomosing quartz–(–pyrite–arsenopyrite) veins within quartz–sericite schist with disseminated arsenopyrite, pyrite, and marcasite (after pyrrhotite). Based on relative timing relationships with structural elements, the auriferous veins are interpreted to have been emplaced before or during the ca. 1,835–1,825 Ma Tanami Orogeny (regional D₁). Gold deposition is thought to have been caused by pressure drops associated with saddle reef formation (Kookaburra) and chemical reactions with graphitic rocks (Sandpiper). The Coyote deposit, the largest in the western Tanami region, consists of a number of ore lenses localized along the limbs of the Coyote Anticline, which formed during the Tanami Orogeny. The largest lenses are associated with the Gonzalez Fault, which is located along the steeply dipping southern limb of this fold. Gold was introduced at ca. 1,790 Ma into dilatant zones that formed in local perturbations along this fault during later reactivation (regional D₅) towards the end of a period of granite emplacement. Gold is associated with quartz–chlorite–pyrite–(arsenopyrite–galena–sphalerite) veins with narrow (<?5 mm) chloritic selvages. A quartz–muscovite–biotite–K–feldspar–(tourmaline–actinolite–arsenopyrite) assemblage, which is interpreted to relate to granite emplacement, overprints the regional greenschist facies metamorphic assemblage. The mineralogical similarity between this overprinting assemblage and the vein assemblage suggests that the auriferous veins at the Coyote deposit are associated with the granite-related metamorphic–metasomatic assemblage. Gold deposition is thought to have been caused by pressure drops within dilatant zones.     

Biomediation of calcrete at the gold anomaly of the Barns prospect,Gawler Craton,South Australia

Anomalously high Au concentrations (2.5 to 50 ppb) in regolith carbonate accumulations, such as calcrete and calcareous sands in aeolian sand dunes overlying Au mineralisation of the Gawler Craton, South Australia, show a marked covariance of Au with K, Mg and most notably Ca. This relationship appears to be linked to the authigenic formation of smectites and carbonates within the aeolian dunes in the region. However, little is known about the processes involved in the formation of carbonates under semi-arid and arid conditions. In this study the geochemical properties of aeolian dunes along several depth profiles of 2 to 4 m are investigated in order to assess the relationship between Au mobility and calcrete formation. In the profiles a strongly systematic relationship between Au and the increasing Ca–Mg contents at depth highlights the close association between the enrichment of Au in the calcrete and the underlying hydrothermal mineralisation. Intense calcrete formation and concurrent Au enrichment also occurs in the vicinity of roots penetrating the dune. Thin section petrography and cathodoluminescence show that most of the calcrete in the regolith profiles is micritic; some sparic crystallites have also been identified. To demonstrate the presence of microbial processes that may mediate the formation of calcrete, samples from a depth profile in the dune were taken under sterile conditions. After amendment with urea and incubation of up to 24 h, up to 18 mg/l of NH₄⁺ were detected in near surface samples. At depth of 2.3 m 1 mg/l NH₄⁺ were detected compared to a control that contained below 0.05 mg/l NH₄⁺. These results suggest that the genesis of calcrete and pedogenic carbonate in the area may be partly biologically mediated via processes such as the metabolic breakdown of urea by resident microbiota which generates a pH and pCO₂ environment conducive to the precipitation of carbonate. In the process of urea breakdown organic Au complexes such as Au-amino acid complexes may become destabilised in solution and Au may be co-precipitated, resulting in the fine, non-particulate distribution of Au throughout the micritic calcrete carbonate. In conclusion, this study suggests a coupled mechanism of biologically mediated and inorganic mechanisms that lead to the formation of Au-in-calcrete anomalies.     

A method for generating uniform size-segregated pyrite particle fractions

Background  

Standardized sample preparation techniques allow comparison of pyrite dissolution experiments under diverse conditions. Our objective was to assess dry and wet sieving preparation methodologies, and to develop a reproducible technique that yields uniformly size-distributed material within a limited size range of interest.     

Oceanography of Glacier Bay,Alaska: Implications for biological patterns in a glacial fjord estuary

Alaska, U.S.A, is one of the few remaining locations in the world that has fjords that contain temperate idewater glaciers. Studying such estuarine systems provides vital information on how deglaciation affects oceanographic onditions of fjords and surrounding coastal waters. The oceanographic system of Glacier Bay, Alaska, is of particular interest ue to the rapid deglaciation of the Bay and the resulting changes in the estuarine environment, the relatively high oncentrations of marine mammals, seabirds, fishes, and invertebrates, and the Bay’s status as a national park, where ommercial fisheries are being phased out. We describe the first comprehensive broad-scale analysis of physical and iological oceanographic conditions within Glacier Bay based on CTD measurements at 24 stations from 1993 to 2002. easonal patterns of near-surface salinity, temperature, stratification, turbidity, and euphotic depth suggest that freshwater nput was highest in summer, emphasizing the critical role of glacier and snowmelt to this system. Strong and persistent tratification of surface waters driven by freshwater input occurred from spring through fall. After accounting for seasonal nd spatial variation, several of the external physical factors (i.e., air temperature, precipitation, day length) explained a large mount of variation in the physical properties of the surface waters. Spatial patterns of phytoplankton biomass varied hroughout the year and were related to stratification levels, euphotic depth, and day length. We observed hydrographic atterns indicative of strong competing forces influencing water column stability within Glacier Bay: high levels of freshwater ischarge promoted stratification in the upper fjord, while strong tidal currents over the Bay’s shallow entrance sill enhanced ertical mixing. Where these two processes met in the central deep basins there were optimal conditions of intermediate tratification, higher light levels, and potential nutrient renewal. These conditions were associated with high and sustained hlorophylla levels observed from spring through fall in these zones of the Bay and provide a framework for understanding he abundance patterns of higher trophic levels within this estuarine system.     

Spatial and temporal variability of mesozooplankton and tintinnid ciliates in a seasonally hypersaline estuary

The zooplankton community of Mission Bay, San Diego, California, was monitored over two years, to study spatial and temporal patterns and the response of zooplankton species composition to environmental variation. Data were collected every two weeks from six stations and included hydrographic parameters, dissolved nutrient concentrations, and phytoplankton and zooplankton species composition. Hydrography varied seasonally, along a spatial gradient from the mouth to the back of the bay, and between the two years around the influence of rainfall. Spatially, Mission Bay could be divided into three regions during this study based on hydrography and zooplankton species composition. Zooplankton species composition followed a predictable seasonal progression, with different groups of species being characteristic to particular times of the year. Variability in zooplankton species composition was also evident between years, as certain species were more common in one or the other year of the study. Spatial patterns were more consistent than temporal ones, and related to distance from the mouth of the bay during much of the year and distance from freshwater inlets during the relatively short rainy season. Multivariate analysis revealed that variation in zooplankton species composition was best related to measured abiotic factors (temperature, salinity, rainfall, and tidal velocity).     

Mechanical shredding of water hyacinth (<Emphasis Type="Italic">Eichhornia crassipes</Emphasis>): Effects on water quality in the Sacramento-San Joaquin River Delta,California

Management actions to control invasive aquatic species can have significant ecosystem-scale effects. We evaluated the water chemistry and nutrient effects of mechanical shredding to control water hyacinth (Eichhornia crassipes) in an agricultural slough and a tidal wetland on the Sacramento-San Joaquin River Delta, California. Shredding was conducted with two types of shredder boats in fall of 2003 and another boat in spring of 2004. Shredding measurably affected water quality, but specific effects varied as a function of shredding site and season. Significant increases were observed for total Kjeldahl nitrogen and total phosphorus for all experiments. Dissolved oxygen effects varied by site, decreasing after shredding at the agricultural slough but increasing at the tidal wetland. The increase in dissolved oxygen likely resulted from tidal incursions from the adjacent river. A year-long time series of dissolved oxygen data indicated a negative relationship between hyacinth abundance and dissolved oxygen concentrations. Hyacinth contained similar tissue concentrations of mercury to underlying sediments, suggesting that plant harvesting could aid mercury remediation efforts. Simple mass calculations indicated that Delta-wide shredding operations could cause between 0.1% and 9.6% increases in the overall abundance of carbon, nitrogen, and phosphorus in the Delta water column. Results suggest that local effects of management actions to control invasive aquatic plants will vary widely as a function of site-specific hydrology, but that estuary-wide effects would be limited.