Geochemical assessement of actinide isolation in a German salt repository environment

A significant criterion in evaluating disposal strategies for high-level nuclear waste is the assessment of the isolation capacity for the most radiotoxic radionuclides, the actinides. Important processes pertinent to potential mobilization from the waste forms, retention in secondary phases and migration of actinides in the geochemical environment of the near field of disposal locations are summarized. Criteria are formulated for assessing engineered barrier performance as a geochemical barrier for actinide long-term retention.     

The impact of incorrectly estimating factor productivity in agriculture on the environment and human health

 This paper explores the implications of a misspecification of the production function on the use of factor inputs in the context of the adoption of an alternative production practice (a technological innovation) designed to mitigate the impact of agricultural production on human health and the environment. It is demonstrated that if the level of the use of some inputs is considered rather than their consumptive use (i.e., the actual amount used by a plant), the productivity of the input is inaccurately measured. It is also demonstrated that an aggregate production function approach can lead to overestimation of the value of the marginal product of an input due to the frequently implicit assumptions that the output supply, output demand, and fertilizer demand are infinitely price elastic. The implications of the results are important for determining the optimal use of inputs such as fertilizer and pesticides which have known adverse impacts on the environment and human health. Received: 22 November 1996 · Accepted: 4 May 1998     

Assessing Cryptic Invasion State: Fine-Scale Genetic Analysis of Ciona savignyi Population in Putative Native Habitat of the Korean Coast

The solitary ascidian, Ciona savignyi (Ascidiacea, Enterogona) is a notorious marine invader still expanding its habitat range worldwide. This species is considered native to the North West Pacific, but its indigeneity in Korean coastal waters has been questioned because of outdated taxonomic records and its inhabitation of oceanographically marginal areas. To clarify their cryptic invasion state, 247 individual C. savignyi samples were collected from 12 harbors and marinas on the Korean coast, and a 744 bp region of mitochondrial DNA (mtDNA) cytochrome c oxidase subunit I gene was sequenced and analyzed. Our analyses of population genetic structure and demographic history provided considerable pieces of evidence supporting their long-term establishment on the Korean coasts: differentiated population genetic structure, sequentially arrayed star-shape haplotype network, neutrality test results of past population expansions, and post-glacial colonization pattern of demography. Consequently, we concluded that C. savignyi populations on the Korean Coast are indigenous rather than exotic. These results could be used as reference data for further phylogeo graphic and demographic studies of problematic Ciona species, and to clarify and resolve similar cryptic invasion states of the other Korean coastal marine organisms. This study is the first to resolve the cryptic in vasion state of Korean marine organisms using genetic analysis.

     

Reactions of aqueous iron-DFOB (desferrioxamine B) complexes with flavin mononucleotide in the absence of strong iron(II) chelators

The mechanisms controlling microbial uptake of Fe^III-siderophore complexes and subsequent release of the metal for cellular use have been extensively studied in recent years. Reduction of the Fe^III center is believed to be necessary to labilize the coordinated Fe and facilitate exchange with cellular ligands. Previous studies report reduction of Fe^III-DFOB by various reducing agents in solutions containing Fe^II-chelating colorimetric agents for monitoring reaction progress, but the importance of these findings is unclear because the colorimetric agents themselves stabilize and enhance the reactions being monitored. This study examines the reduction of Fe^III complexes with DFOB (desferrioxamine B), a trihydroxamate siderophore, by the fully reduced hydroquinone form of flavin mononucleotide (FMN_HQ) in the absence of strong Fe^II-chelating agents, and Fe redox cycling in solutions containing DFOB and oxidized and reduced FMN species. Experimental results demonstrate that the rate and extent of Fe^III-DFOB reduction is strongly dependent on pH and FMN_HQ concentration. At pH ? 5, incomplete Fe^III reduction is observed due to two processes that re-oxidize Fe^II, namely, the autodecomposition of Fe^II-DFOB complexes (Fe^II oxidation is coupled with reduction of a protonated hydroxamate moiety) and reaction of Fe^II-DFOB complexes with the fully oxidized flavin mononucleotide product (FMN_OX). Chemical speciation-dependent kinetic models for the forward reduction process and both reverse Fe^II oxidation processes are developed, and coupling kinetic models for all three Fe redox processes leads to successful predictions of steady-state Fe^II concentrations observed over a range of pH conditions in the presence of excess FMN_HQ and FMN_OX. The observed redox reactions are also in agreement with thermodynamic constraints imposed by the combination of Fe^III/Fe^II and FMN_OX/FMN_HQ redox couples. Quantitative comparison between kinetic trends and changing Fe speciation reveals that FMN species react predominantly with diprotonated Fe^III-DFOB and Fe^II-DFOB complexes, where protonation of one hydroxamate group opens up two Fe coordination positions. This finding suggests that ternary complex formation (FMN-Fe-DFOB) facilitates inner-sphere electron transfer reactions between the flavin and Fe center.     

Plutonic inclusions and olivines in high-K volcanics from Ulreung island,Korea

Summary Major and trace element data are presented for four alkali gabbroic inclusions, two monzonitic inclusions, and nine syenitic inclusions from Ulreung island, Korea. Analytical results are also given for the mineral constituents. Although the major element chemistry suggests that the plutonic inclusions are comagmatic with the associated volcanic rocks, the trace element data demonstrate that they do not represent a simple liquid line of descent. In addition, the mineralogical data indicate that they are not likely to represent cumulates on the floor of the magma chamber from which the observed volcanic rocks have been derived. Titanbiotite crystallization preceded kaersutite crystallization in the plutonic rocks but that order was inverse in the volcanic rocks. The trachytic-phonolitic rocks contain Fe-rich olivine phenocrysts, whereas the plutonic inclusions do not. These discrepancies can be accounted for by the assumption that the investigated plutonic rocks represent some cumulus parts of intrusive bodies solidified at shallower depth than the magma reservoir beneath the island. Petrographic features of the gabbroic inclusions are suggestive that olivine was probably in a reaction relationship with liquid to form titanbiotite. Comparison with petrological data of the volcanic rocks also implies that olivine was in a reaction relationship with an intermediate alkalic magma in both the intruded magmas at shallow depth and in the magma chamber at great depth. This is the cause of the olivine compositional gap in the high-K volcanic suite. Titanbiotite is a major reaction product.

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Plutonische Einschlüsse und Olivine in Kalium-reichen Vulkaniten von Ulreung Island, Korea

Zusammenfassung Haupt- und Spurenelementdaten von vier alkalischen gabbroiden, zwei monzonitische Haupt- und Spurenelementdaten von vier alkalischen gabbroiden, zwei monzonitische und neun syenitischen Einschlüssen von Ulreung Island, Korea, sowie analytische Daten der Mineralkomponenten werden vorgelegt. Obwohl der Hauptelementchemismus andeutet, daß die plutonischen Intrusionen und die vergesellschafteten vulkanischen Gesteine comagmatisch sind, zeigen die Spurenelementdaten, daß diese nicht eine einfache Magmenlinie darstellen. Außerdem zeigen die mineralogischen Daten an, daß die Gesteine wahrscheinlich keine Kumulate vom Boden der Magmenkammer sind, von welcher die beobachteten vulkanischen Gesteine herstammen. In den plutonischen Gesteinen kristallisierte Titan-Biotit früher als der Kaersutit. In den vulkanischen Gesteinen ist diese Reihenfolge jedoch umgekehrt. Die trachitischen/phonolitischen Gesteine enthalten im Gegensatz zu den plutonischen Einschlüssen Fe-reiche Olivin-Phenokrysten. Diese Unterschiede können durch die Annahme erklärt werden, daß die untersuchten plutonischen Gesteine bestimmte Kumulate eines intrusiven Körpers sind, der in geringerer Tiefe als das Magmenreservoir unterhalb der Inseln erstarrte. Petrographische Kennzeichen von gabbroischen Einschlüssen deuten darauf hin, daß der Olivin wahrscheinlich mit der Schmelze reagiert hat und Titan-Biotit bildete. Ein Vergleich der petrographischen Daten der vulkanischen Gesteine Vergleich der petrographischen Daten der vulkanischen Gesteine läßt ebenfalls den Schluß zu, daß Olivin mit einem intermediären alkalischen Magma in beiden, dem intrudierten Magma in geringer Tiefe und der Magmakammer in großer Tiefe, reagierte. Dies ist der Grund für die Lücke in der Olivinzusammensetzung in der Kalium-reichen vulkanischen Suite. Titan-Biotit ist ein Hauptreaktionsprodukt.

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With 9 Figures     

Temporal variability in summertime bottom hypoxia in shallow areas of Mobile Bay,Alabama

This paper addresses temporal variability in bottom hypoxia in broad shallow areas of Mobile Bay, Alabama. Time-series data collected in the summer of 2004 from one station (mean depth of 4 m) exhibit bottom dissolved oxygen (DO) variations associated with various time scales of hours to days. Despite a large velocity shear, stratification was strong enough to suppress vertical mixing most of the time. Bottom DO was closely related to the vertical salinity gradient (ΔS). Hypoxia seldom occurred when ΔS (over 2.5 m) was <2 psu and occurred almost all the time when ΔS was >8 psu in the absence of extreme events like hurricanes. Oxygen balance between vertical mixing and total oxygen demand was considered for bottom water from which oxygen demand and diffusive oxygen flux were estimated. The estimated decay rates at 20°C ranging between 0.175–0.322 d⁻¹ and the corresponding oxygen consumption as large as 7.4 g O₂ m⁻² d⁻¹ fall at the upper limit of previously reported ranges. The diffusive oxygen flux and the corresponding vertical diffusivity estimated for well mixed conditions range between 8.6–9.5 g O₂ m⁻² d⁻¹ and 2.6–2.9 m² d⁻¹, respectively. Mobile Bay hypoxia is likely to be associated with a large oxygen demand, supported by both water column and sediment oxygen demands, so that oxygen supply from surface water during destratification events would be quickly exhausted to return to hypoxic conditions within a few hours to days after destratification events are terminated.     

A novel approach to estimate iron distribution within different pore domains of structured media

The Fe content of soils and aquifer solids is usually quantified using different extraction solutions performed with homogenized samples in a well-mixed batch experiment. For structured media where preferential flow prevails over the matrix flow, however, the Fe content determined from homogenized samples may not well represent the Fe available for biogeochemical reactions. In this study ammonium oxalate extraction was performed on a core of intact saprolite where physical structure was preserved. An unsaturated flow setup was modified with the intent of allowing the extraction under two pore tensions, 15 and 0 cm of water, although a malfunctioning vacuum regulator made this more difficult than anticipated. Approximately 85% of the oxalate-extractable Fe was contained within the finer pore domain (matrix potential larger than 15 cm). Less than 15.5% of the extracted Fe mass (an upper bound) was present in domains of pore tension less than15 cm. To the extent that Fe(III) oxides play an important role in contaminant biogeochemistry and solute transport, their distribution in structured subsurface media is critical to the understanding of these processes.