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.     

Pyrite oxidation inhibition by a cross-linked lipid coating

The effect of a diacetylene-containing phospholipid on the oxidation of pyrite, FeS₂, was investigated. Earlier work reported by our research group showed that the adsorption of l,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine on pyrite suppressed the extent of its oxidation by about 75% over a specific time period. Results presented here show that the pre-exposure to UV radiation of this lipid after sorption onto pyrite results in a 90% suppression. Attenuated total reflection (ATR) Fourier transform infra-red spectroscopy (FTIR) suggests that the UV irradiation of the lipid does not result in degradation of the adsorbed layer. It is believed that the UV exposure results in the cross-linking and polymerization of the adsorbed phospholipid into a relatively impermeable barrier that separates the pyrite from the aqueous phase. The results of this study might have implications for the protection of pyrite from oxidation in the environment.     

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park,Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad™ AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site IC analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad™ AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns.     

S-wave spectral analysis of the 1995 Kozani-Grevena (NW Greece) aftershock sequence

S-wave spectral analysis is applied to 174 strong motion accelerationrecords to obtain the source parameters of 27 aftershocks(3.1 M_L 4.3) of the May 13, 1995, M_w 6.6,Kozani-Grevena (NW Greece) earthquake. The data are derived from atemporary network, of three-component digital accelerographs, deployedwithin the strongly affected area some days after the mainshock occurrence.Site effects were evident in the strong motion records at 3 out of the 4stations used, and a correction was applied to account for theoverestimation of seismic moment due to amplification of thelow-frequency part of the spectrum. The data from this analysis arecomplimented with previously obtained source parameters for earthquakesin Greece, in order to study the applicability of the empirical scalingrelations used so far, towards smaller magnitudes. In general, a goodcorrelation was observed in most cases, validating the use of empiricalrelations that are applicable to the Aegean area. Empirical relations aredetermined between seismic moment and seismic slip, as well as, betweenseismic moment and stress drop, applicable to small magnitude earthquakes(M_L < 4.3). Stress drop values were found to be relatively small,ranging from 2 to 41 bars, indicative of inter-plate environments. Thevalues of f_c and of f_max were found in good agreement withrelations based on observations from larger worldwide earthquakes.     

Surface fault traces,fault plane solution and spatial distribution of the aftershocks of the September 13, 1986 earthquake of Kalamata (Southern Greece)

A shallow earthquake ofM _S=6.2 occurred in the southern part of the Peloponnesus, 12 km north of the port of the city of Kalamata, which caused considerable damage. The fault plane solution of the main shock, geological data and field observations, as well as the distribution of foci of aftershocks, indicate that the seismic fault is a listric normal one trending NNE-SSW and dipping to WNW. The surface ruptures caused by the earthquake coincide with the trace of a neotectonic fault, which is located 2–3 km east of the city of Kalamata and which is related to the formation of Messiniakos gulf during the Pliocene-Quaternary tectonics. Field observations indicate that the earthquake is due to the reactivation of the same fault.A three-days aftershock study in the area, with portable seismographs, recorded many aftershocks of which 39 withM _S1.7 were very well located. The distribution of aftershocks forms two clusters, one near the epicenter of the main shock in the northern part of the seismogenic volume, and the other near the epicenter of the largest aftershock (M _S=5.4) in the southern part of this volume. The central part of the area lacks aftershocks, which probably indicates that this is the part of the fault which slipped smoothly during the earthquake.     

Probabilities of occurrence of large earthquakes in the Aegean and surrounding area during the period 1986–2006

Repeat times of large shocks are obtained for 17 seismic fracture zones of the Aegean and surrounding area, from times of historic and present century earthquakes. The mean standard deviation of the repeat times is approximately 50% of any one observation.A probabilistic approach is then used to forecast the likelihood of large future earthquakes in each fracture zone, using as input the time of the last large shock, the average repeat time and its standard deviation. Shallow and intermediate depth earthquakes are examined separately. The calculated probabilities are high for the entire Hellenic arc, both for shallow and intermediate depth seismicity, for the area of Leucas island (Ionian), of Lesbos island (Aegean), for Patraikos-west Corinthiakos Gulfs, for Evoikos Gulf as well as for southern Bulgaria.The probability estimates based on the most recent large earthquakes, involve a number of basic physical assumptions and we would think that they provide a semi-stochastic approach to the problem of earthquake prediction in Greece.     

Seismic faults in the Aegean area

Reliable fault plane solutions of shallow earthquakes and information on surface fault traces in combination with other seismic, geomorphological and geological information have been used to determine the orientation and other properties of the seismic faults in the Aegean and surrounding area.Thrust faults having an about NW-SE strike occur in the outer seismic zone along western Albania-westernmost part of mainland of Greece-Ionian Sea-south of Crete-south of Rhodes.The inner part of the area is dominated by strike-slip and normal faulting. Strike-slip with an about NE-SW slip direction occurs in the inner part of the Hellenic arc along the line Peloponnesus-Cyclades-Dodecanese-southwest Turkey as well as along a zone which is associated with the northern Aegean trough and the northwesternmost part of Anatolia. All other regions in the inner part of the area are characterized by normal faulting. The slip direction of the normal faults has an about SW-NE direction in Crete (N38°E) and an about E-W direction (N81°E) in a zone which trends N-S in eastern Albania and its extension to western mainland of Greece. In all other regions (central Greece-southern Yugoslavia and Bulgaria, western Turkey) the slip of the normal faults has an about N-S direction.     

The effect of adsorbed lipid on pyrite oxidation under biotic conditions

The chemolithoautotrophic bacterium, Acidithiobacillus ferrooxidans, commonly occurs in acid mine drainage (AMD) environments where it is responsible for catalyzing the oxidation of pyrite and concomitant development of acidic conditions. This investigation reports on the growth of this bacterial species on the pyrite surface and in the aqueous phase at a pH close to 2 as well as the role of adsorbed lipid in preventing pyrite dissolution. Both acid washed pyrite and acid-washed pyrite coated with lipids were used as substrates in the studies. The choice of lipid, 1,2-bis(10,12-tricosadiynoyl)-sn-Glycero-3-Phosphocholine lipid (23:2 Diyne PC), a phosphocholine lipid, was based on earlier work that showed that this lipid inhibits the abiotic oxidation rate of pyrite. Atomic force microscopy showed that under the experimental conditions used in this study, the lipid formed ~4–20 nm layers on the mineral surface. Surface-bound lipid greatly suppresses the oxidation process catalyzed by A. ferrooxidans. This suppression continued for the duration of the experiments (25 days maximum). Analysis of the bacterial population on the pyrite surface and in solution over the course of the experiments suggested that the pyrite oxidation was dependent in large part on the fraction of bacteria bound to the pyrite surface.     

Pyrite surface interaction with selected organic aqueous species under anoxic conditions

The interaction between low-molecular weight organic compounds and pyrite under anoxic conditions has been studied using a combination of electrophoresis and batch sorption experiments. The results suggest that acetate, carbamide, ethylamine, formamide, purine, D-ribose, and adenine, as well as the amino acids alanine, cysteine and glycine, interact within the electrophoretic shearplane of the pyrite surface. The observed surface interaction between the negatively charged surface of pyrite and the organic aqueous species takes place regardless of the formal charge of the aqueous species of interest. This indicates that the interaction of organic molecules with pyrite surfaces under anoxic conditions is dictated by interactions with specific surface sites (thiol or iron surface sites) rather than electrostatic forces. Dissolved metals typically enhance the interaction of the organics species. This enhancement is either due to an alteration in the distribution of thiol and iron groups on the pyrite surface or by the formation of ternary surface complexes.