Adenine oxidation by pyrite-generated hydroxyl radicals

Cellular exposure to particulate matter with concomitant formation of reactive oxygen species (ROS) and oxidization of biomolecules may lead to negative health outcomes. Evaluating the particle-induced formation of ROS and the oxidation products from reaction of ROS with biomolecules is useful for gaining a mechanistic understanding of particle-induced oxidative stress. Aqueous suspensions of pyrite particles have been shown to form hydroxyl radicals and degrade nucleic acids. Reactions between pyrite-induced hydroxyl radicals and nucleic acid bases, however, remain to be determined. Here, we compared the oxidation of adenine by Fenton-generated (i.e., ferrous iron and hydrogen peroxide) hydroxyl radicals to adenine oxidation by hydroxyl radicals generated in pyrite aqueous suspensions. Results show that adenine oxidizes in the presence of pyrite (without the addition of hydrogen peroxide) and that the rate of oxidation is dependent on the pyrite loading. Adenine oxidation was prevented by addition of either catalase or ethanol to the pyrite/adenine suspensions, which implies that hydrogen peroxide and hydroxyl radicals are causing the adenine oxidation. The adenine oxidation products, 8-oxoadenine and 2-hydroxyadenine, were the same whether hydroxyl radicals were generated by Fenton or pyrite-initiated reactions. Although nucleic acid bases are unlikely to be directly exposed to pyrite particles, the formation of ROS in the vicinity of cells may lead to oxidative stress.     

Deterministic vs. probabilistic earthquake hazards and risks

Both probabilistic and deterministic methods have a role in seismic hazard and risk analyses performed for decision-making purposes. These two methods can complement one another to provide additional insights to the seismic hazard or risk problem. One method will have priority over the other, depending on how quantitative are the decisions to be made, depending on the seismic environment, and depending on the scope of the project (single site or a region). In many applications a recursive analysis, where deterministic interpretations are triggered by probabilistic results and vice versa, will give the greatest insight and allow the most informed decisions to be made.     

Geomorphic context of channel locational probabilities along the Lower Mississippi River, USA

Channel change is an important aspect of geomorphological evolution and habitat dynamics in large alluvial rivers. Planimetric maps of channel locations were used to investigate spatio-temporal alluvial channel changes in a geomorphic context along the Lower Mississippi River (LMR). Analyses were conducted with the aid of a time-weighted locational probability map. The locational probability map was constructed in ArcGIS and covered a period of 205 years. An examination of the pixel data from the probability maps indicates a high occurrence of low probability pixels along the Lower Mississippi River, which is in accordance with the dynamism of alluvial rivers. The northern section of the Lower Mississippi River (Columbus, KY to Memphis, TN) has been much more stable than the southern river segments (Helena, AR to Natchez, MS). Areas of high channel probability (channel stability) were often associated with alluvial channel confinement from a combination of flood-plain deposits, geologic structures and large stable islands. Low channel probability locations were found along sections exhibiting the following geomorphic characteristics: changes in meander amplitude, meander neck and chute cutoffs, meander extensional processes and islands lost in channel migrational processes. The results provide a strong foundation for understanding channel change on the Lower Mississippi River and serves as a valuable instrument for future management and restoration schemes.     

Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10⁻¹¹ mol Fe(II) m⁻² g⁻¹), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)_aq and bacterially-generated Fe(II)_aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.     

Tidally phased emergence events in a strongly tidal estuary

Acoustic backscatter from an active sonar system over a range of six frequencies between 265 kHz and 3 MHz in the tidally dominated Damariscotta River estuary, Maine, United States, revealed that the major emergence event of the night commenced on the first tidal deceleration after dark (3.5–4 h after local slack), irrespective of flow direction. Emergence traps identified the mysid shrimp,Neomysis americana, as the dominant migrator. Water-column-integrated, acoustically estimated biovolume at our 10-m deep study location increased by a factor of about 6 during these large events, entirely dominating the holoplanktonic contribution and likely being a major component in benthic-pelagic coupling. Application of the same algorithm used to locate this nighttime emergence revealed a parallel but considerably smaller daytime emergence event near the same phase of the tide. Daytime trap samples failed to recover the organisms responsible, but transmissometry rejected the alternative hypothesis that we observed resuspension events. We suspect, but have yet only weak evidence, that animals emerging in daylight are copepods rather than mysids.     

A Full-Scale Porous Reactive Wall for Prevention of Acid Mine Drainage

The generation and release of acidic drainage containing high concentrations of dissolved metals from decommissioned mine wastes is an environmental problem of international scale. A potential solution to many acid drainage problems is the installation of permeable reactive walls into aquifers affected by drainage water derived from mine waste materials. A permeable reactive wall installed into an aquifer impacted by low-quality mine drainage waters was installed in August 1995 at the Nickel Rim mine site near Sudbury, Ontario. The reactive mixture, containing organic matter, was designed to promote bacterially mediated sulfate reduction and subsequent metal sulfide precipitation. The reactive wall is installed to an average depth of 12 feet (3.6 m) and is 49 feet (15 m) long perpendicular to ground water flow. The wall thickness (flow path length) is 13 feet (4 m). Initial results, collected nine months after installation, indicate that sulfate reduction and metal sulfide precipitation is occurring. Comparing water entering the wall to treated water exiting the wall, sulfate concentrations decrease from 2400 to 4600 mg/L to 200 to 3600 mg/L; Fe concentrations decrease from 250 to 1300 mg/L to 1.0 to 40 mg/L; pH increases from 5.8 to 7.0; and alkalinity (as CaCO₃) increases from 0 to 50 mg/L to 600 to 2000 mg/L. The reactive wall has effectively removed the capacity of the ground water to generate acidity on discharge to the surface. Calculations based on comparison to previously run laboratory column experiments indicate that the reactive wall has potential to remain effective for at least 15 years.     

Sedimentologic and stratigraphic constraints on emplacement of the Star Kimberlite, east–central Saskatchewan

Diamond-bearing kimberlites in the Fort à la Corne region, east–central Saskatchewan, consist primarily of extra-crater pyroclastic deposits which are interstratified with Lower Cretaceous (Albian and Cenomanian) marine, marginal marine and continental sediments. Approximately 70 individual kimberlite occurrences have been documented. The Star Kimberlite, occurring at the southeastern end of the main Fort à la Corne trend, has been identified as being of economic interest, and is characterized by an excellent drill core database. Integration of multi-disciplinary data-sets has helped to refine and resolve models for emplacement of the Star Kimberlite. Detailed core logging has provided the foundation for sedimentological and volcanological studies and for construction of a regionally consistent stratigraphic and architectural framework for the kimberlite complex. Micropaleontologic and biostratigraphic analysis of selected sedimentary rocks, and U–Pb perovskite geochronology on kimberlite samples have been integrated to define periods of kimberlite emplacement. Radiometric age determination and micropaleontologic evidence support the hypothesis that multiple kimberlite eruptive phases occurred at Star. The oldest kimberlite in the Star body erupted during deposition of the predominantly continental strata of the lower Mannville Group (Cantuar Formation). Kimberlites within the Cantuar Formation include terrestrial airfall deposits as well as fluvially transported kimberlitic sandstone and conglomerate. Successive eruptive events occurred contemporaneous with deposition of the marginal marine upper Mannville Group (Pense Formation). Kimberlites within the Pense Formation consist primarily of terrestrial airfall deposits. Fine- to medium-grained cross-stratified kimberlitic (olivine-dominated) sandstone in this interval reflects reworking of airfall deposits during a regional marine transgression. The location of the source feeder vents of the Cantuar and Pense kimberlite deposits has not been identified. The youngest and volumetrically most significant eruptive events associated with the Star Kimberlite occur within the predominantly marine Lower Colorado Group (Joli Fou and Viking Formations). Kimberlite beds, which occur at several horizons within these units, consist of subaerial and marine fall deposits, the latter commonly exhibiting evidence of wave-reworking. Black shale-encased resedimented kimberlite beds, likely deposited as subaqueous debris flows and turbidites, are particularly common in the Lower Colorado Group. During its multi-eruptive history, the Star Kimberlite body is interpreted to have evolved from a feeder vent and overlying positive-relief tephra ring, into a tephra cone. Initial early Joli Fou volcanism resulted in formation of a feeder vent (200 m diameter) and tephra ring. Subsequent eruptions, dominated by subaerial deposits, partly infilled the crater and constructed a tephra cone. A late Joli Fou eruption formed a small (70 m diameter) feeder pipe slightly offset to the NW of the early Joli Fou feeder vent. Deposits from this event further infilled the crater, and were deposited on top of early Joli Fou kimberlite (proximal to the vent) and sediments of the Joli Fou Formation (distal to the vent). The shape of the tephra cone was modified during multiple marine transgression and regression cycles coeval with deposition of the Lower Colorado Group, resulting in wave-reworked kimberlite sand along the fringes of the cone and kimberlitic event deposits (tempestites, turbidites, debris flows) in more distal settings.