Competitive Scavenging Research Articles

Photolysis of chlorite by solar light: An overlooked mitigation pathway for chlorite and micropollutants

Chlorite (ClO2−) is an undesirable toxic byproduct commonly produced in the chlorine dioxide and ultraviolet/chlorine dioxide oxidation processes. Various methods have been developed to remove ClO2− but require additional chemicals or energy input. In this study, an overlooked mitigation pathway of ClO2− by solar light photolysis with a bonus for simultaneous removal of micropollutant co-present was reported. ClO2− could be efficiently decomposed to chloride (Cl−) and chlorate by simulated solar light (SSL) at water-relevant pHs with Cl− yield up to 65% at neutral pH. Multiple reactive species including hydroxyl radical (•OH), ozone (O3), chloride radical (Cl•), and chlorine oxide radical (ClO•) were generated in the SSL/ClO2− system with the steady-state concentrations following the order of O3 (≈ 0.8 μΜ) > ClO• (≈ 4.4 × 10−6 μΜ)> •OH (≈ 1.1 × 10−7 μΜ)> Cl• (≈ 6.8 × 10−8 μΜ) at neutral pH under investigated condition. Bezafibrate (BZF) as well as the selected six other micropollutants was efficiently degraded by the SSL/ClO2− system with pseudofirst-order rate constants ranging from 0.057 to 0.21 min−1 at pH 7.0, while most of them were negligibly degraded by SSL or ClO2− treatment alone. Kinetic modeling of BZF degradation by SSL/ClO2− at pHs 6.0 – 8.0 suggested that •OH contributed the most, followed by Cl•, O3, and ClO•. The presence of water background components (i.e., humic acid, bicarbonate, and chloride) exhibited negative effects on BZF degradation by the SSL/ClO2− system, mainly due to their competitive scavenging of reactive species therein. The mitigation of ClO2− and BZF under photolysis by natural solar light or in realistic waters was also confirmed. This study discovered an overlooked natural mitigation pathway for ClO2− and micropollutants, which has significant implications for understanding their fate in natural environments.

FeS-mediated mobilization and immobilization of Cr(III) in oxic aquatic systems

Reduction of soluble Cr(VI) into insoluble Cr(III) by iron sulfide (FeS) minerals under anoxic conditions has been widely observed in natural and engineered systems. Yet, information has been lacking on the FeS-mediated oxidation and remobilization potential of Cr(III) under varying environmental conditions. The objective of this study was to investigate FeS-mediated redox transformation of Cr(III) to Cr(VI) and the associated mobilization and immobilization when Cr(III)-FeS systems are exposed to atmospheric conditions. The results showed that FeS nanoparticles facilitated rapid and strong Fenton-like reactions during the early-stage oxygenation of FeS, resulting in rapid production of hydroxyl radicals (•OH). Consequently, Cr(III) was rapidly oxidized into Cr(VI). Yet, as the reactions proceeded, the oxidative potential was counteracted by competitive scavenging of •OH by Fe(II) and S(-II) from FeS and the reduction reactions by these electron donors. At equilibrium, all Cr(VI) was reduced back to Cr(III) at an FeS-Cr(III) molar ratio of 10:1, while a small fraction of Cr(VI) persisted in solid products of Cr(OH)3(s) at an FeS-Cr(III) molar ratio of 1:1. Acidic conditions favored the generation of Cr(VI) and the equilibrium concentration of Cr(VI) in oxic FeS NPs systems at pH 5.0 was 1.7 times higher than at pH 9.0. Overall, the FeS-induced Fenton-like reactions and the oxidation of Cr(III) were favored in the early stage, but quenched in the later stage and outcompeted by the reduction of Cr(VI) if sufficient FeS was available. The findings provide new insights into the hydrochemical processes that can affect the speciation, toxicity, and mobility of Cr in aquatic systems containing FeS and Cr.

Phytochemistry, In-vitro antioxidant, Microbicidal, Anti-ulcerogenic and Biosafety Potential of Emilia coccinea Aqueous Extract in Animal models.

Emilia coccinea enhances the treatment of several disease conditions include; vertigo management, ringworm, cough, gonorrhoea, ulcers, lice, measles, seizure, eye drop. This study investigates the phytochemistry, In-vitro antioxidant, anti-ulcerogenic, microbicidal and biosafety effect of aqueous extracts of E. coccinea using animal model. E. coccinea leaf was freshly obtained, shade dried, pulverized and prepared into aqueous extract. Standard procedure were used for the evaluation of the phytochemicals, in-vitro antioxidant and antimicrobial activities. Twenty five (25) Wistar rats were acclimitized and randomly selected into five groups (n=5) such as untreated group, 10 mg/kg cimetidine and graded doses (100, 200 and 400 mg/kg b.w.) of aqueous extract of E. coccinea to evaluate antiulcer and biosafety effects. Results from the qualitative and quantitative phytochemical screening showed the present of phenol (47.19 mg), saponins (84.64 mg), alkaloids (75.17 mg), cardiac glycosides (63.12 mg) and anthraquinone (48.79 mg). The antioxidant property showed a competitive scavenging effect against DPPH radical when compared with ascorbic acids. Microbial activities of the aqueous extract of E. coccinea at various concentration elicited inhibitory effect against Salmonella typhii, Escherichia coli, Helicobacter pyloris. The ulceration in rat stomach lining induced with 70% ethanol and pretreated with prophylactic measure of aqueous crude extract showed significant reduction in ulcer count, ulcer index with increased % inhibition of ulcer when compared with untreated and reference control. The haematological and histopathological study shows no significant difference in the aqueous crude extract with absent toxicity when comparisons with the control.

Titania-Catalyzed H2O2 Thermal Oxidation of Styrenes to Aldehydes.

We investigated the selective oxidation of styrenes to benzaldehydes by using a non-irradiated TiO2–H2O2 catalytic system. The oxidation promotes multi-step reactions from styrenes, including the cleavage of a C=C double bond and the addition of an oxygen atom selectively and stepwise to provide the corresponding benzaldehydes in good yields (up to 72%). These reaction processes were spectroscopically shown by fluorescent measurements under the presence of competitive scavengers. The absence of the signal from OH radicals indicates the participation of other oxidants such as hydroperoxy radicals (•OOH) and superoxide radicals (•O2−) into the selective oxidation from styrene to benzaldehyde.

Impact of iron coordination isomerism on pyoverdine recognition by the FpvA membrane transporter of Pseudomonas aeruginosa.

Pyoverdines, the primary siderophores of Pseudomonas bacteria, scavenge the iron essential to bacterial life in the outside medium and transport it back into the periplasm. Despite their relative simplicity, pyoverdines feature remarkably flexible recognition characteristics whose origins at the atomistic level remain only partially understood: the ability to bind other metals than ferric iron, the capacity of outer membrane transporters to recognize and internalize noncognate pyoverdines from other pseudomonads… One of the less examined factors behind this polymorphic recognition lies in the ability for pyoverdines to bind iron with two distinct chiralities, at the cost of a conformational switch. Herein, we use free energy simulations to study how the stereochemistry of the iron chelating groups influences the structure and dynamics of two common pyoverdines and impacts their recognition by the FpvA membrane transporter of P. aeruginosa. We show that conformational preferences for one metal binding chirality over the other, observed in solution depending on the nature of the pyoverdine, are canceled out by the FpvA transporter, which recognizes both chiralities equally well for both pyoverdines under study. However, FpvA discriminates between pyoverdines by altering the kinetics of stereoisomer interconversion. We present structural causes of this intriguing recognition mechanism and discuss its possible significance in the context of the competitive scavenging of iron.

Ethnoarchaeology and Plio-Pleistocene sites: Some lessons from the Hadza

Exploration and analyses of early archaeological sites and their faunal assemblages have grown increasingly sophisticated since the sites were first proposed to be home bases where ancestral hunters brought meat to share with their mates and offspring. Debates about that proposition motivated quantitative attention to hunting, scavenging, butchery and transport of big game among modern Hadza and the faunal assemblage characteristics and archaeological sites they create. Findings prompted a hypothesis about competitive scavenging that might explain the character and ecological context of the early sites, a hypothesis since strengthened by consensus among archaeologists working at Olduvai that the sites are not home bases. Hadza carcass procurement rates calibrate estimates for ancestral populations without similar technology, underscoring the likelihood that other food resources were especially important in human evolution.

Temporally unpredictable supplementary feeding may benefit endangered scavengers

The monitoring of an experimental feeding station established in northern Spain allowed the evaluation of how this type of resource, predictable in space but not in time, was exploited by a guild of avian scavengers in relation to factors such as season, hour of disposal and presence of the dominant species. The presence of Egyptian Vultures Neophron percnopterus at carcasses was more likely during spring, and richness and diversity of avian scavengers was lower during the summer and when Griffon Vultures Gyps fulvus arrived earlier. The temporal unpredictability of the resource may favour exploitation by smaller and less competitive scavengers. New European regulations may present an opportunity to develop effective conservation measures to support functional scavenger assemblages.

Application of intensified Fenton oxidation to the treatment of sawmill wastewater

The application of the Fenton process for the treatment of sawmill wastewater has been investigated. The sawmill wastewater was characterized by a moderate COD load (≈3gL−1), high ecotoxicity (≈40toxicity units) and almost negligible BOD/COD ratio (5×10−3) due to the presence of different fungicides such as propiconazole and 3-iodo-2-propynyl butyl carbamate, being the wastewater classified as non-biodegradable. The effect of the key Fenton variables (temperature (50–120°C), catalyst concentration (25–100mgL−1 Fe3+), H2O2 dose (1 and 2 times the stoichiometric dose) and the mode of H2O2 addition) on COD reduction and mineralization was investigated in order to fulfill the allowable local limits for industrial wastewater discharge and achieve an efficient consumption of H2O2 in short reaction times (1h). Increasing the temperature clearly improved the oxidation rate and mineralization degree, achieving 60% COD reduction and 50% mineralization at 120°C after 1h with the stoichiometric H2O2 dose and 25mgL−1 Fe3+. The distribution of H2O2 in multiple additions throughout the reaction time was clearly beneficial avoiding competitive scavenging reactions and thus, achieving higher efficiencies of H2O2 consumption (XCOD≈80%). The main by-products were non-toxic short-chain organic acids (acetic, oxalic and formic). Thus, the application of the Fenton process allowed reaching the local limits for industrial wastewater discharge into local sewer system at a relatively low cost.

Puma spatial ecology in open habitats with aggregate prey

Solitary felids are commonly associated with structurally complex habitats, where their foraging success is attributed to stealth and remaining undetected by competitive scavengers. Research in North America suggests that pumas (Puma concolor), a wide-ranging species found throughout the Americas, conform to the general characteristics of solitary felids and avoid open grasslands with aggregating prey. Researchers hypothesize that pumas are limited to structurally complex habitats in North America because of pressures from other large, terrestrial competitors. We explored the spatial ecology of pumas in open habitat with aggregating prey in Chilean Patagonia, where pumas lack large, terrestrial competitors. We tracked 11 pumas over 30 months (intensive location data for 9 pumas with GPS collars for 9.33±5.66 months each) in an area where mixed steppe grasslands composed 53% of the study area and carried 98% of available prey biomass, to track resource use relative to availability, assess daily movements, quantify home ranges and calculate their density. As determined by location data and kill sites, Patagonia pumas were primarily associated with open habitats with high prey biomass, but at finer scales, preferentially selected for habitat with complex structure. On average, pumas traveled 13.42±2.50km per day. Estimated 95% fixed kernel home ranges averaged 98±31.8km2 for females and 211±138.8km2 for males, with high spatial overlap within and between the sexes. In a multivariate analysis, available prey biomass was the strongest predictor of variation in the size of an individual puma's home range. Finally, we determined a total puma density of 3.44pumas/100km2, a significantly smaller estimate than previously reported for Patagonia, but similar to densities reported for North America.

Reduction of Mercury(II) by the Carbon Dioxide Radical Anion: A Theoretical and Experimental Investigation

The laser flash photolysis technique (λ(exc) = 266 nm) was used to investigate the mechanism of the HgCl(2) reduction mediated by CO(2)(·-) radicals in the temperature range 291.7-308.0 K. For this purpose, the CO(2)(·-) radicals were generated by scavenging of sulfate radicals by formic acid. The absorbance of the reduced radical of methyl viologen, a competitive scavenger of CO(2)(·-), was monitored at 390 nm. Moreover, theoretical calculations, including solvent effects, were also performed within the framework of the density functional theory for various chemical species of Hg(I) and Hg(II) to aid in the modeling of the reaction of reduction of HgCl(2) by CO(2)(·-).

Shark scavenging behavior in the presence of competition

Abstract The distribution of organisms within a community can often be determined by the degree of plasticity or degree of specialization of resource acquisition. Resource acquisition is often based on the morphology of an organism, behavior, or a combination of both. Performance tests of feeding can identify the possible interactions that allow one species to better exploit a prey item. Scavenging behaviors in the presence or absence of a competitor were investigated by quantifying prey selection in a trophic generalist, spiny dogfish Squalus acanthias, and a trophic specialist, smooth-hounds Mustelus canis, in order to determine if each shark scavenged according to its jaw morphology. The diet of dogfish consists of small fishes, squid, ctenophores, and bivalves; they are expected to be nonselective predators. Smooth-hounds primarily feed on crustaceans; therefore, they are predicted to select crabs over other prey types. Prey selection was quantified by ranking each prey item according to the order it was consumed. Dietary shifts were analyzed by comparing the percentage of each prey item selected during solitary versus competitive scavenging. When scavenging alone, dogfish prefer herring and squid, which are easily handled by the cutting dentition of dogfish. Dogfish shift their diet to include a greater number of prey types when scavenging with a competitor. Smooth-hounds scavenge on squid, herring, and shrimp when alone, but increase the number of crabs in the diet when scavenging competitively. Competition causes smooth-hounds to scavenge according to their jaw morphology and locomotor abilities, which enables them to feed on a specialized resource.

Semicontinuous Fenton oxidation of phenol in aqueous solution. A kinetic study

This work investigates the Fenton oxidation of phenol in a semicontinuous reactor where the overall amount of H 2O 2 is distributed as a continuous feed upon the reaction time. The experiments were carried out at 25 °C and atmospheric pressure, with 100 mg/L initial phenol concentration and iron dosages from 1 to 100 mg/L. H 2O 2 aqueous solution was continuously fed during 4 h reaction time up to an overall dose varying within the range of 500–5000 mg/L. The results in terms of evolution of phenol, H 2O 2 and intermediates, as well as TOC abatement were compared with those obtained in conventional batch operation. It was found that the oxidation rates for phenol and intermediates were lower when adding the H 2O 2 continuously. However, a higher abatement of TOC was reached at the end of the 4-h reaction time, in spite of a similar overall H 2O 2 consumption. This is the result of a more efficient OH generation throughout the semicontinuous process, favouring the reaction with the organic species and reducing the occurrence of competitive scavenging reactions involving Fe 2+, H 2O 2 and OH. Two kinetic models were proposed, one for describing the evolution of phenol, aromatics and H 2O 2 and the other for TOC. The influence of the operating conditions on the kinetic constants was also studied, looking for the optimal conditions in terms of both, environmental and economic points of view.

Do common ravens (Corvus corax) rely on human or conspecific gaze cues to detect hidden food?

The ability of non-human animals to use experimenter-given cues in object-choice tasks has recently gained interest. In such experiments, the location of hidden food is indicated by an experimenter, e.g. by gazing, pointing or touching. Whereas dogs apparently outperform all other species so far tested, apes and monkeys have problems in using such cues. Since only mammalian species have been tested, information is lacking about the evolutionary origin of these abilities. We here present the first data on object-choice tasks conducted with an avian species, the common raven. Ravens are highly competitive scavengers, possessing sophisticated cognitive skills in protecting their food caches and pilfering others' caches. We conducted three experiments, exploring (i) which kind of cues ravens use for choosing a certain object, (ii) whether ravens use humans' gaze for detecting hidden food and (iii) whether ravens would find hidden food in the presence of an informed conspecific who potentially provides gaze cues. Our results indicate that ravens reliably respond to humans' touching of an object, but they hardly use point and gaze cues for their choices. Likewise, they do not perform above chance level in the presence of an informed conspecific. These findings mirror those obtained for primates and suggest that, although ravens may be aware of the gaze direction of humans and conspecifics, they apparently do not rely on this information to detect hidden food.

Competitive Scavenging of Trace Metals by HFO and HMO during Redox-driven Early Diagenesis of Ferromanganese Nodules (11 pp)

Dedicated to Prof. Dr. Ulrich Forstner on his 65th birthday Surface complexation models (SCM) alone have yet less successfully reproduced sorption isotherms of hydrous manganese oxides (HMO). This is in part due to the fact that the HMO structure may vary with pH, and also because microbially formed natural HMO has an oxidation number O/Mn 〈 2, i.e. is of non-stoichiometrical composition. The former effect has often led to severe artefacts, such as an under-prediction of metal sequestration at low pH, and non-comparable pK and pHZPC values in literature. The latter effect is of particular importance for environments of varying redox conditions like sediments. We propose therefore a new sorption model comprising of amphoteric site SCM, ion exchange due to permanent charge compensation, and solid solution formation, in order to comply at least in part with the redox complexity of HMO phases of stable birnessite- and buserite-type structures. The model is run by a new Gibbs energy minimization code which is shown to be particularly suitable for such a sorption continuum approach. Initial calibration of the model was performed by experimental literature data on simple laboratory systems. Thus parameterised, we simulated on the basis of available field data the effect of redox-driven dissolution of a ferromanganese nodule on the partitioning of metals between the interacting HMO, HFO, and marine water phases. Our scenario model suggests that significant fraction of Mn and other metals, probably 50% or more, may be recycled to water column from the surface of the ferromanganese nodule upon gradual development of the bottom water stagnation, except of Zn for which a by far stronger net retention was found. Our model, even if only a first approximation, clearly shows that stagnation in the marine bottom water, once occurring, can drastically change primary element proxy records in ferromanganese nodules, smoothing out any anomalous patterns in the most recent record.

Arsenite causes DNA damage in keratinocytes via generation of hydroxyl radicals.

Arsenic is an environmental and occupational toxin. Dermatologic toxicities due to arsenic exposure are well-documented and include basal cell and squamous cell carcinomas. However, the mechanism of arsenic-induced skin cancer is not well-understood. Recent studies indicate that arsenic exposure results in the generation of reactive oxygen species (ROS) and oxidative stress. Here, we examined the chemical nature of the specific ROS, studied the interrelationship among these species, and identified the specific species that is responsible for the subsequent DNA damage in a spontaneously immortalized keratinocyte cell line. We detected the formation of O(2)(*)(-) and H(2)O(2) in keratinocytes incubated with arsenite [As(III)] but not with arsenate. As(III)-induced DNA damage was detected in a concentration-dependent manner and evident at low micromolar concentrations. Catalase, an H(2)O(2) scavenger, eliminated H(2)O(2) and reduced the As(III)-mediated DNA damage. Superoxide dismutase, by enhancing the production of H(2)O(2) and (*)OH, significantly increased the As(III)-mediated DNA damage. Sodium formate, a competitive scavenger for (*)OH, and deferoxamine, a metal chelator, both reduced the DNA damage. These results suggest that exposure to arsenite generates O(2)(*)(-) and H(2)O(2), and (*)OH, derived from H(2)O(2), is responsible, at least in part, for the observed DNA damage. These findings demonstrate arsenic-induced formation of specific ROS and provide the direct evidence of (*)OH-mediated DNA damage in keratinocytes, which may play an important role in the mechanism for arsenic-induced skin carcinogenicity.

8‐Hydroxy‐1,3,6‐pyrene trisulfonic acid (pyranine) bleaching by 2,2′‐azobis(2‐amidinopropane) derived peroxyl radicals

Abstract8‐Hydroxy‐1,3,6‐pyrene trisulfonic acid, trisodium salt (pyranine), readily reacts with peroxyl radicals generated in the aerobic pyrolysis of 2,2′‐azobis(2‐amidinopropane) (AAPH). The process can be followed by monitoring the decrease in pyranine absorbance (460 nm) or fluorescence (excitation: 460 nm; emission: 510 nm). The reaction follows a nearly zero‐order kinetics in pyranine (0.25–30 μM range), suggesting a very efficient trapping of peroxyl radicals. In agreement with this, the process is order one in AAPH. The bleaching process is totally prevented by Trolox (μM range), and partially prevented by Trp (mM range). The protection afforded by Trp is very little dependent upon the pyranine concentration. This result indicates that the main protective pathway is not a competitive scavenging of the peroxyl radicals. The data suggest protection due to repair of the initially produced pyranyl radicals. These radicals are also very efficient in the destruction of C‐phycocyanin bilin groups. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 525–531, 2003

Rare earth elements in the water column of Lake Vanda, McMurdo Dry Valleys, Antarctica

We present data on the composition of water from Lake Vanda, Antarctica. Vanda and other lakes in the McMurdo Dry Valleys of Antarctica are characterized by closed basins, permanent ice covers, and deep saline waters. The meromictic lakes provide model systems for the study of trace metal cycling owing to their pristine nature and the relative simplicity of their biogeochemical systems. Lake Vanda, in the Wright Valley, is supplied by a single input, the Onyx River, and has no output. Water input to the lake is balanced by sublimation of the nearly permanent ice cap that is broken only near the shoreline during the austral summer. The water column is characterized by an inverse thermal stratification of anoxic warm hypersaline water underlying cold oxic freshwater.Water collected under trace-element clean conditions was analyzed for its dissolved and total rare earth element (REE) concentrations by inductively coupled plasma mass spectrometry. Depth profiles are characterized by low dissolved REE concentrations (La, Ce, <15 pM) in surface waters that increase slightly (La, 70 pM; Ce, 20 pM) with increasing depth to ∼55 m, the limit of the fresh oxic waters. Below this depth, a sharp increase in the concentrations of strictly trivalent REE (e.g., La, 5 nM) is observed, and a submaximum in redox sensitive Ce (2.6 nM) is found at 60- to 62-m depth. At a slightly deeper depth, a sharper Ce maximum is observed with concentrations exceeding 11 nM at a 67-m depth, immediately above the anoxic zone. The aquatic concentrations of REE reported here are ∼50-fold higher than previously reported for marine oxic/anoxic boundaries and are, to our knowledge, the highest ever observed at natural oxic/anoxic interfaces. REE maxima occur within stable and warm saline waters. All REE concentrations decrease sharply in the sulfidic bottom waters. The redox-cline in Lake Vanda is dominated by diffusional processes and vertical transport of dissolved species driven by concentration gradients. Furthermore, because the ultraoligotrophic nature of the lake limits the potential for organic phases to act as metal carriers, metal oxide coatings and sulfide phases appear to largely govern the distribution of trace elements. We discuss REE cycling in relation to the roles of redox reactions and competitive scavenging onto Mn- and Fe-oxides coatings on clay sized particles in the upper oxic water column and their release by reductive dissolution near the anoxic/oxic interface.

Ferromanganese Nodules and their Associated Sediments from the Central Indian Ocean Basin: Rare Earth Element Geochemistry

Abstract The rare earth element (REE) distribution in nine deep-sea ferromanganese nodules and their associated siliceous sediments from the Central Indian Ocean Basin (CIOB) have been studied to elucidate the REE relationship among them. Total REE concentration varies from 398–928 ppm in the nodules and 137–235 ppm in the associated sediments, suggesting two- to four-fold enrichment in the nodules compared to associated sediments. REE of nodules and their associated sediments show a positive correlation, suggesting REE are supplied from a common source such as seawater. The positive correlation between REE of nodules and sediments from the CIOB is contrary to the competitive scavenging of REE between nodules and sediment in the equatorial Pacific Ocean. REEs in the nodules are carried by Fe, P, and Ti, whereas in the sediment they are carried by P and Mn phases. A similar REE fractionation pattern with middle REE enrichment over heavy and light REE in both the nodules and their associated sediment suggest fractionation is independent of REE abundance and their carrier phases.

Ferromanganese Nodules and their Associated Sediments from the Central Indian Ocean Basin: Rare Earth Element Geochemistry

The rare earth element (REE) distribution in nine deep-sea ferromanganese nodules and their associated siliceous sediments from the Central Indian Ocean Basin (CIOB) have been studied to elucidate the REE relationship among them. Total REE concentration varies from 398–928 ppm in the nodules and 137–235 ppm in the associated sediments, suggesting two- to four-fold enrichment in the nodules compared to associated sediments. REE of nodules and their associated sediments show a positive correlation, suggesting REE are supplied from a common source such as seawater. The positive correlation between REE of nodules and sediments from the CIOB is contrary to the competitive scavenging of REE between nodules and sediment in the equatorial Pacific Ocean. REEs in the nodules are carried by Fe, P, and Ti, whereas in the sediment they are carried by P and Mn phases. A similar REE fractionation pattern with middle REE enrichment over heavy and light REE in both the nodules and their associated sediment suggest fractionation is independent of REE abundance and their carrier phases.

Radiation Induced Catalytic Dechlorination of Hexachlorobenzene on Oxide Surfaces

Radiation induced catalytic dehalogenation of hexachlorobenzene (HCB) adsorbed to alumina (Al2O3), silica (SiO2), titania (TiO2), zirconia (ZrO2), and a commercially available zeolite has been studied using Cobalt-60 (60Co) as a radiation source. Solid-particulate samples were irradiated over a dose range of 0−58 kGy, and the chemical changes were monitored using Fourier transform infrared diffuse reflectance (FTIR-DR) and gas chromatography with electron capture detection (GC-ECD). The extent of HCB degradation on the metal oxides was found to increase dramatically in samples evacuated under vacuum, pointing to the competitive scavenging of conduction band electrons by surface adsorbed species, primarily oxygen. Coadsorbed water diminished HCB conversion on all oxides but to a greater degree on alumina. HCB degradation on metal oxides was found to be highly dependent upon the conduction band energy of the support material, thus confirming the occurrence of ultra-band-gap excitation and charge separation in irradiated oxides. Higher yields of dechlorination products were witnessed in alumina and silica samples. Zeolite, titania, and zirconia were also found to be inefficient in promoting radiation induced catalysis. The absence of oxidation products in the irradiated HCB/oxide samples suggests the inaccessibility of holes to undergo interfacial charge transfer with the organic substrate.