Surface complexation of U(VI) on goethite (α-FeOOH)

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.     

The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Redistriution of Major Elements in the Alteration of Some Basic Lavas during Burial Metamorphism

An Ordovician geanticlinal marine sequence is exposed in theCentral West of New South Wales, Australia. The sequence containingbasic lavas, labile sedimentary, and proclastic rocks, has undergoneextensive adjustment during regional burial metamorphism. Thebasic lavas have a patchy coloration due to the formation ofalternation minerals of the prehnite-pumpellyite facies whichapperar to have formed during the metamorphism. The hererogeneousappearance of the basic lavas reflects a pronouced chemicaland mineralogical departure from the original composition. Twodiverging trends result. One leads to the production of a Ca-enrichedlithology, the other, which by far dominates in area at eachouterop, leads to a ‘spilitic’ lithology. The alterationdomains in many cases cross–cut all primary textural featureand their chemical variation does not correspond to likely variationsin the original lava composition.     

An evaluation of temperature scales for silica diagenesis in diatomaceous sequences including a new approach based on the Miocene Monterey Formation,California

Geologic relations indicate that silica phases transformed in the Monterey Formation in two zones that persist over a narrow depth/temperature range and do not stratigraphically overlap. The wide and overlapping range of reported temperatures of these transformations is mainly a result of the many uncertainties inherent in the different methods used to estimate temperature and does not indicate that phases transform throughout these ranges. Our approach to a reliable temperature scale for silica diagenesis combines as empirical zonation of silica phases with temperature calibration from a sequence at maximum temperature and depth of burial.     

Land-based activities: what remains to be done

The Global Programme of Action for the Protection of the Marine Environment from Land-based Activities (GPA) represents an ambitious attempt to make the leap between the rhetoric of protecting and preserving the marine environment and action. With degradation of the marine environment from land based activities posing one of the most serious threats to the quality and productivity of the coastal and marine environment, the GPA can only be viewed as a milestone rather than a destination, as so much work remains to be done in this field.States supporting the GPA are entering the most challenging phase of the program, that of implementation. But the international community in taking on this challenge is not without a few signposts. The failure of the Montreal Guidelines to be implemented, provides States with many important lessons. This paper suggests that if the GPA is to have an impact on the complex problem of land-based activities then several tasks need to be grappled with. Substantial financial support needs to be generated, a proactive and cooperative secretariat established and the nexus between the GPA and United Nations Environment Programme Regional Seas Programme examined. The importance of people and training to the capacity building process needs to be recognised and a wider variety of stakeholders engaged in the follow up phase. Pivotal to the aforementioned is the need to generate political will to address the problem, without which the GPA will become yet another dusty volume on the bookshelf.     

Abundance versus rates of accumulation in fine-grained strata of the Miocene Santa Barbara Basin,California

Although best known as a deposit rich in silica and organic matter, the Miocene Monterey Formation actually had long-term rates of silica and organic Matter accumulation equal to or lower than values in the underlying and overlying detritus-rich formations in the Santa Barbara coastal area. The factor Mainly influencing the composition of the Monterey Formation in this area was the slow accumulation of terrigenous debris. In contrast, with greater than average silica abundance within the Monterey Formation probably resulted from rapid short-term silica accumulation (of hundreds to tens of thousands years duration) rather than from especially slow accumulation of diluting debris.     

Permeability development in vesiculating magmas: implications for fragmentation

 Fragmentation, or the "coming apart" of magma during a plinian eruption, remains one of the least understood processes in volcanology, although assumptions about the timing and mechanisms of fragmentation are key parameters in all existing eruption models. Despite evidence to the contrary, most models assume that fragmentation occurs at a critical vesicularity (volume percent vesicles) of 75–83%. We propose instead that the degree to which magma is fragmented is determined by factors controlling bubble coalescence: magma viscosity, temperature, bubble size distribution, bubble shapes, and time. Bubble coalescence in vesiculating magmas creates permeability which serves to connect the dispersed gas phase. When sufficiently developed, permeability allows subsequent exsolved and expanded gas to escape, thus preserving a sufficiently interconnected region of vesicular magma as a pumice clast, rather than fully fragmenting it to ash. For this reason pumice is likely to preserve information about (a) how permeability develops and (b) the critical permeability needed to insure clast preservation. We present measurements and calculations that constrain the conditions (vesicularity, bubble size distribution, time, pressure difference, viscosity) necessary for adequate permeability to develop. We suggest that magma fragments explosively to ash when and where, in a heterogeneously vesiculating magma, these conditions are not met. Both the development of permeability by bubble wall thinning and rupture and the loss of gas through a permeable network of bubbles require time, consistent with the observation that degree of fragmentation (i.e., amount of ash) increases with increasing eruption rate. Received: 5 July 1995 / Accepted: 27 December 1995     

Trace Element and Isotope Geochemistry of the Volcanic Rocks of Bequia, Grenadine Islands, Lesser Antilles Arc: a Study of Subduction Enrichment and Intra-crustal Contamination

Pliocene volcanics on the island of Bequia comprise two interbeddedsuites of basalts and andesites. The isotopically homogeneoussuite (IHS) has a limited range of Sr—Nd—Pb isotopes(⁸⁷Sr/⁸⁶Sr 0.7040–0.7046, ¹⁴³ Nd/¹⁴⁴ Nd 0.5130 and ²⁰⁶Pb/²⁰⁴Pb 19.36–19.51), and mantle-like ¹⁸O values (5.5in clinopyroxene). The isotopically diverse suite (IDS) is characterizedby much wider ranges of radiogenic isotopes (⁸⁷ Sr/⁸⁶Sr 0.7048–0.7077,¹⁴³ Nd/¹⁴⁴ Nd 0.5128–0.5123 and ²⁰⁶ Pb/²⁰⁴ Pb 19.7–20.2),in which all of the Sr and Pb ratios are higher and Nd ratiosare lower than those of the IHS. The IDS is also characterizedby high ¹⁸ O values, up to 7.6 in clinopyroxene. The Sr andPb isotope ratios are too high, and the Nd isotope ratios aretoo low in the IDS for any of these lavas to be derived fromunmodified depleted mantle. Both suites are petrologically very similar and their majorelement compositions and phenocryst contents suggest that theywere formed largely by fractional crystallization of a hydroustholeiitic melt at pressures <3 kbar. The isotopic ratiosand enrichments in large ion lithophile elements (LILE), andto some extent light rare earth elements (LREE), as comparedwith mid-ocean ridge basalts (MORB), of the IHS lavas suggestthat they were derived from a depleted mantle source which hadbeen re-enriched by the addition of 1–4% of a subductioncomponent. This component probably comprised a mixture of dehydrationfluids, and perhaps minor siliceous melts, released from subductingsediments and mafic crust. The extreme isotopic ranges, largeenrichments in incompatible elements, more fractionated LREEpatterns and higher ¹⁸ O values of the IDS lavas are interpretedas resulting from 10–55% assimilation—fractionalcrystallization of sediments, derived from the Guyana Shield,which are present in the arc crust, by IHS type melts. KEY WORDS: trace elements; radiogenic isotopes; arc lavas; Lesser Antilles ^*Corresponding author.