Sulfur biogeochemical cycling and novel Fe-S mineralization pathways in a tidally re-flooded wetland

Sulfur biogeochemical cycling and associated Fe-S mineralization processes exert a major influence over acidity dynamics, electron flow and contaminant mobility in wetlands, benthic sediments and groundwater systems. While S biogeochemical cycling has been studied intensively in many environmental settings, relatively little direct information exists on S cycling in formerly drained wetlands that have been remediated via tidal re-flooding. This study focuses on a tidal wetland that was drained in the 1970s (causing severe soil and water acidification), and subsequently remediated by controlled re-flooding in 2002. We examine reduction rates and Fe-S mineralization at the tidal fringe, 7 years after the commencement of re-flooding. The initial drainage of the wetland examined here caused in-situ pyrite (FeS₂) oxidation, resulting in the drained soil layers being highly acidic and rich in -bearing Fe(III) minerals, including jarosite (KFe₃(SO₄)₂(OH)₆). Tidal re-flooding has neutralized much of the previous acidity, with the pore-water pH now mostly spanning pH 5-7. The fastest rates of in-situ reduction (up to ∼300 nmol cm⁻³ day⁻¹) occur within the inter-tidal zone in the near-surface soil layers (to ∼60 cm below ground surface). The reduction rates correlate with pore-water dissolved organic C concentrations, thereby suggesting that electron donor supply was the predominant rate determining factor. Elemental S was a major short-term product of reduction, comprising up to 69% of reduced inorganic S in the near-surface soil layers. This enrichment in elemental S can be partly attributed to interactions between biogenic H₂S and jarosite - a process that also contributed to enrichment in pore-water Fe²⁺ (up to 55 mM) and (up to 50 mM). The iron sulfide thiospinel, greigite (Fe₃S₄), was abundant in near-surface soil layers within the inter- to sub-tidal zone where tidal water level fluctuations created oscillatory redox conditions. There was evidence for relatively rapid pyrite re-formation within the re-flooded soil layers. However, the results indicate that pyrite re-formation has occurred mainly in the lower formerly drained soil layers, whereas the accumulation of elemental S and greigite has been confined towards the soil surface. The discovery that pyrite formation was spatially decoupled from that of elemental S and greigite challenges the concept that greigite is an essential precursor required for sedimentary pyrite formation. In fact, the results suggest that greigite and pyrite may represent distinct end-points of divergent Fe-S mineralization pathways. Overall, this study highlights novel aspects of Fe-S mineralization within tidal wetlands that have been drained and re-flooded, in contrast to normal, undisturbed tidal wetlands. As such, the long-term biogeochemical trajectory of drained and acidified wetlands that are remediated by tidal re-flooding cannot be predicted from the well-studied behaviour of normal tidal wetlands.     

Surface complexation modeling for predicting solid phase arsenic concentrations in the sediments of the Mississippi River Valley alluvial aquifer, Arkansas, USA

The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6 m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6 m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory.     

Metamorphic differentiation at Einasleigh,Northern Queensland

Biotite‐muscovite‐garnet gneisses at Einasleigh contain quartz‐feldspar veins composed of the same minerals as found in the enclosing rock. The vein‐gneiss boundaries are commonly irregular and on a microscopic scale, gradational.

Certain amphibolite layers contain quartz‐feldspar veins composed of the same minerals as found in the amphibolite. Hornblende‐rich extraction zones surround these veins, and material balance calculations show that all or nearly all of the vein‐forming matter was locally derived. Variation in the abundance of hornblende and plagioclase in the amphibolite as a function of distance from a quartz‐feldspar vein can be expressed by error‐function curves, thus suggesting that the mineral‐segregation process was diffusion‐controlled. During the mineral rearrangement, the Na and Ca contents of plagioclase have evidently remained unchanged, but the vein hornblende has become slightly richer in Fe+3, Mg, and Ca, and poorer in Si and Al relative to hornblende in the adjacent amphibolite.

A certain biotite‐plagioclase rock forms layers and boudins in the gneisses and contains pegmatite veins composed of the same minerals as found in the host rock. The plagioclase in these veins is more sodic than that in the host rock while the biotite contains slightly more Ti and Fe+² and less Si and Mg than the biotite of the enclosing rock.

The data indicate that significant portions of the vein‐forming matter at Einasleigh were locally derived. The chemistry of some minerals has changed slightly during the segregation process, resulting possibly from different diffusion rates for the different mineral‐forming constituents.     

Late Cenozoic paleovalley fill sequence from the Southern Liverpool Plains,New South Wales—implications for groundwater resource evaluation

The Liverpool Plains in northern New South Wales contain some of the best agricultural land in Australia and are underlain by extensive smectite clay-dominated soils sourced from weathering the alkali basalts of the Liverpool Ranges. It had been thought that a relatively simple geological model explained the underlying Cenozoic sequence with salt-rich clays of the Narrabri Formation overlying sands and gravel aquifers comprising the Gunnedah Formation. Extensive groundwater modelling based upon this simple conceptualisation has been used in management plans proposed by the mining and agricultural industries. A 31.5 m core has been recovered using minimally disturbed triple-tube coring methods at Cattle Lane (Latitude –31.52° S, Longitude 150.47° E) to resolve uncertainty concerning the aquitard status of the upper layer. Recovered core has been examined and tested to determine grainsize, cation-exchange capacity, X-ray diffraction, X-ray fluorescence and microscopic examination of granular components. These measurements complement surface and borehole geophysical techniques, hydrogeological data and hydrochemical analysis of water samples recovered from a series of specially constructed piezometers adjacent to the cored hole. The sequence overlies a Late Cretaceous channel cut into Permian bedrock at 91 m depth with sands and clays below 31.5 m considered to represent various alluvial fill events mostly occurring since the Early Pliocene. Erosion of Late Eocene alkali basalts on the Liverpool Ranges, with the formation of smectite clays, pedogenic carbonates and with the addition of quartz from both eolian sources and locally derived from adjacent Triassic sandstone hills, provides the great majority of the sediment recovered from the cores. Late Pleistocene (114 ka) to Holocene ages were determined for the core from three optically stimulated luminescence (OSL) measurements on fine sands (13, 23 and 29 m BG). Detailed examination has failed to detect any evidence of a boundary between Narrabri and Gunnedah formations revealing rather a gradual change in dominance of clays and silts over sands and gravels embedded in a clay-rich matrix. This result challenges the conceptualisation used to conduct groundwater modelling on the Liverpool Plains.     

Role of a rheophyte in bench development on a sand‐bed river in southeast Australia

Casuarina cunninghamiana Miq. is an important rheophytic tree in New South Wales, Australia because it is fast growing and can tolerate flood disturbance. Widden Brook is an active sand‐bed stream that has widened substantially since initial European settlement in the early 1800s and is characterized by high flood variability and multi‐decadal periods of alternating high and low flood frequency, called flood‐ and drought‐dominated regimes. Channel contraction by bench formation is currently occurring. Conversion of coarse‐grained point bars to benches is an important process of channel contraction. When point bars grow to a height where suspended sediment is first deposited to thicknesses of at least 50 mm by sub‐bankfull floods, rapid establishment of C. cunninghamiana occurs. As the trees grow they partially block bankside flows, thereby locally reducing flow velocity and inducing further deposition on the benches. Such synergistic relationships between bar height and inundation, fine‐grained sediment deposition, tree establishment and the development of a bankside low current velocity zone are fundamental for bench development. Size‐class frequency data demonstrate that C. cunninghamiana on the benches consists of pure even‐aged stands with most trees clustering near the average diameter. Two benches have similar size class frequency distributions but a third has significantly smaller trees. Recruitment on benches is episodic, may occur in areas open to grazing and is dependent on favourable conditions that allow tree survival. These favourable conditions include high seed availability, low levels of competition, deposition of fine sediments and adequate moisture for tree growth. Although C. cunninghamiana germinates on bars, seedlings are eliminated by prolonged inundation or flood scour and do not reach maturity. Recurring catastrophic floods or a sequence of large floods in rapid succession episodically destroy benches by substantial channel widening and initiate a new phase of bar and bench development. A conceptual model of the conversion of point bars to benches by thick mud deposition and C. cunninghamiana recruitment has been developed for sand‐bed streams draining similar sandstone catchments. Copyright © 2009 John Wiley & Sons, Ltd.     

Numbers,types, and compositions of an unbiased collection of cosmic spherules

Abstract— Micrometeorites collected from the bottom of the South Pole water well (SPWW) may represent a complete, well‐preserved sample of the cosmic dust that accreted on Earth from 1100–1500 A.D. We classified 1588 cosmic spherules in the size range 50–800 μm. The collection has 41% barred olivine spherules, 17% glass spheres, 12% cryptocrystalline spherules, 11% porphyritic olivine spherules, 12% relicgrain‐bearing spherules, 3% scoriaceous spherules, 2% I‐type spherules, 1% Ca‐AI‐Ti‐rich (CAT) spherules, and 1% G‐type spherules. We also found bubbly glass spherules, spherules with glass caps, and ones with sulfide coatings—particles that are absent from other collections. A classification sequence of the stony spherules (scoriaceous, relic‐grain‐bearing, porphyritic, barred olivine, cryptocrystalline, glass, and CAT) is consistent with progressive heating and evaporation of Fe from chondritic materials. The modern‐day accretion rate and size distribution measured at the SPWW can account for the stony spherules present in deep‐sea collection through preferential dissolution of glass and small stony spherules. However, weathering alone cannot account for the high accretion rate of I‐type spherules determined for two deep‐sea collections. The SPWW collection provides data to constrain models of atmospheric‐entry heating and to assess the effects of terrestrial weathering.     

Harmonic analysis of tides and tidal currents in South San Francisco Bay,California

Water level observations from tide stations and current observations from current-meter moorings in South San Francisco Bay (South Bay), California have been harmonically analysed. At each tide station, 13 harmonic constituents have been computed by a least-squares regression without inference. Tides in South Bay are typically mixed; there is a phase lag of approximately 1 h and an amplification of 1·5 from north to south for a mean semi-diurnal tide. Because most of the current-meter records are between 14 and 29 days, only the five most important harmonics have been solved for east-west and north-south velocity components. The eccentricity of tidal-current ellipse is generally very small, which indicates that the tidal current in South Bay is strongly bidirectional. The analyses further show that the principal direction and the magnitude of tidal current are well correlated with the basin bathymetry. Patterns of Eulerian residual circulation deduced from the current-meter data show an anticlockwise gyre to the west and a clockwise gyre to the east of the main channel in the summer months due to the prevailing westerly wind. Opposite trends have been observed during winter when the wind was variable.