Optical absorption and mössbauer spectra of purple and green yoderite,a kyanite-related mineral

Mössbauer and polarized optical absorption spectra of the kyanite-related mineral yoderite were recorded. Mössbauer spectra of the purple (PY) and green yoderite (GY) from Mautia Hill, Tanzania, show that the bulk of the iron is Fe³⁺ in both varieties, with Fe²⁺/(Fe²⁺+Fe³⁺) ratios near 0.05. Combining this result with new microprobe data for PY and with literature data for GY gives the crystallochemical formulae: $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.95}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{0}}{\text{.01}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.34}}}^{{\text{3 + }}} {\text{Mn}}_{{\text{0}}{\text{.07}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.57}}} )_{5.97}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.98}}} {\text{P}}_{{\text{0}}{\text{.03}}} ){\text{O}}_{{\text{18}}{\text{.02}}} ({\text{OH)}}_{{\text{1}}{\text{.98}}} ] \hfill \\ \end{gathered}$$ and PY and $$\begin{gathered} ({\text{Mg}}_{{\text{1}}{\text{.98}}} {\text{Fe}}_{{\text{0}}{\text{.02}}}^{{\text{2 + }}} {\text{Mn}}_{{\text{< 0}}{\text{.001}}}^{{\text{2 + }}} {\text{Fe}}_{{\text{0}}{\text{.45}}}^{{\text{3 + }}} {\text{Ti}}_{{\text{0}}{\text{.01}}} {\text{Al}}_{{\text{3}}{\text{.56}}} )_{6.02}^{[5,6]} \hfill \\ {\text{Al}}_{{\text{2}}{\text{.00}}}^{{\text{[5]}}} [({\text{Si}}_{{\text{3}}{\text{.91}}} {\text{O}}_{{\text{17}}{\text{.73}}} {\text{(OH)}}_{{\text{2}}{\text{.27}}} ] \hfill \\ \end{gathered}$$ for GY. The Mössbauer spectra at room temperature contain one main doublet with isomer shifts and quadrupole splittings of 0.36 (PY), 0.38 (GY) and 1.00 (PY), 0.92 (GY) mm s^?1, respectively. These values correspond to Fe³⁺ in six or five-fold coordination. The doublet components have anomalously large half widths indicating either accomodation of Fe³⁺ in more than one position (e.g., octahedraA1 and five coordinatedA2) or the yet unresolved superstructure. Besides strong absorption in the ultraviolet (UV) starting from about 25,000 cm^?1, the polarized optical absorption spectra are dominated by strong bands around 16,500 and 21,000 cm^?1 (PY) and a medium strong band at around 13,800 cm^?1 (GY). Position and polarization of these bands, in combination with the UV absorption, explain the colour and pleochroism of the two varieties. The bands in question are assigned to homonuclear metal-to-metal charge transfer transitions: Mn²⁺(A1) Mn³⁺(A1′) ? Mn³⁺(A1) Mn²⁺(A1′) and Mn²⁺(A1) Mn³⁺(A2 ? Mn³⁺(A1) Mn²⁺(A2) in PY and Fe²⁺(A1) Fe³⁺(A1′) ? Fe³⁺(A1) Fe²⁺(A1′) in GY. The evidence for homonuclear Mn²⁺ Mn³⁺ charge transfer (CTF) is not quite clear and needs further study. Heteronuclear FeTi CTF does not contribute to the spectra. In PY, additional weak bands were resolved at energies around 17,700, 18,700, 21,000, and 21,900 cm^?1 and assigned to Mn³⁺ in two positions. Weak bands around 10,000 cm^?1 in both varieties are assigned to Fe²⁺ spin-alloweddd-transitions. Very weak and sharp bands, around 15,400, 16,400, 21,300, 22,100, 23,800, and 25,000 cm^?1 are identified in GY and assigned to Fe³⁺ spin-forbiddendd-transitions.     

Mixed-function oxygenases as biological monitors around petroleum hydrocarbon development sites: Potential for induction by diesel and other drilling mud base oils containing reduced levels of polycyclic aromatic hydrocarbons

The use of oil-based drilling muds has been discouraged in hydrocarbon exploration and production in the marine environment but these muds are presently being used to a considerable degree in the United Kingdom and Norwegian sectors of the North Sea. Field studies in the North Sea have demonstrated only localized impacts around individual drilling sites,^1,2 even including those sites where ‘toxic’ diesel oils were employed as base fluids in drilling muds. Yet the question of disposal of cuttings contaminated with oil from drilling muds remains somewhat controversial. The induction of mixed-function oxygenases (MFO) has been validated on a number of occasions in the field as a sensitive index of low level hydrocarbon exposure (reviewed by Payne),³ including sites in the North Sea where diesel-based muds were used.⁴ The present study demonstrates that any potential for induction by hydrocarbon contaminated cuttings will probably be reduced by substitution of low-aromatic base oils for diesel in drilling mud formulations.     

Computational parameter estimation for a maize crop

During a whole growing season, the evolution of the displacement height, d, and roughness length, z ₀, of a maize crop has been estimated by a measurement programme. The results have been used to check different types of existing models to calculate these parameters from canopy characteristics only; a simple geometric model and two matching models have been investigated. A geometric model is based on geometric features of the surface only. After a simple modification, the geometric model gives good results for the displacement height as well as for the roughness length.A matching model, based on gradient-diffusion theory, yields good results for the displacement height. The roughness parameter, however, is overestimated by 17%. By a simple modification, the model results could be improved considerably.A matching model, based on a second-order closure procedure, yields excellent results for the displacement height and good results for the roughness length. But it appears that, when applying this model, the plant density index and plant area density distribution as a function of height must be well known.     

UNCLOS and the marine scientist

The deliberations at UNCLOS have been watched with great interest by individual marine scientists and by those who have attended as observers on behalf of scientific groups. Most of all these scientists have been apprehensive that their ability (freedom) to carry out research would be significantly limited by many of the provisions of the ICNT. In fact, one author goes as far as to state that progress has been made, largely at the expense of the marine research scientist¹.     

Geochemistry and origin of albite gneisses,northeastern Adirondack Mountains,New York

Albite gneisses containing up to 8.7 percent Na₂O and as little as 0.1% K₂O comprise a significant part of the Proterozoic Lyon Mountain Gneiss in the Ausable Forks Quadrangle of the northeastern Adirondacks, New York State. Two distinct types of albite gneisses are present. One is a trondhjemitic leucogneiss (LAG) consisting principally of albite (Ab95–Ab98) and quartz with minor magnetite and, locally, minor amounts of amphibole or acmiterich pyroxene. LAG probably originated by metamorphism of a rhyolitie or rhyodacitic ash-flow tuff with A-type geochemical affinities, following post-depositional analcitization in a saline or saline-alkaline environment. The other type is a mafic albite gneiss (MAG) containing albite and pyroxene along with 0–45 percent quartz, minor amphibole, and titanite. MAG locally displays pinstripe banding and contains albite (Ab98) megacrysts up to 5 cm across. Its precursor may have been a sediment composed of diagenetic analcite or albite, dolomite, and quartz. Both types of albite gneiss are interlayered with granitic gneisses (LMG) of variable composition derived from less altered tuffs. A potassium-rich (up to 9.7% K₂O) microcline gneiss facies may have had a protolith rich in diagenetic K feldspar. We propose that the albite gneisses and associated granitic gneisses are the granulite-facies metamorphic equivalent of a bimodal, dominantly felsic, volcanic suite with minor intercalated sediments, probably including evaporites. The volcanics were erupted in an anorogenic setting, such as an incipient or failed intracontinental rift. Deposition took place in a closed-basin, playa lake environment, where diagenetic alteration resulted in redistribution of the alkalis and strong oxidation.     

Measurement of Kodaikanal White-Light Images – II. Rotation Comparison and Merging with Mount Wilson Data

Sunspot umbral positions and areas were measured for 82 years (1906–1987) of daily, full-disk photoheliogram observations at the Kodaikanal station of the Indian Institute of Astrophysics. The measurement technique and reduction procedures used were nearly identical to those used earlier for the reduction of Mount Wilson daily full-disk photoheliograms, covering an overlapping interval of 69 years. In this paper we compare the differential rotation of the Sun from the analysis of the Kodaikanal data with the Mount Wilson results. In addition, we analyze the data set formed by combining the data from the two sites for differential rotation. While doing this, it has become apparent to us that small, subtle optical effects at both sites produce systematic errors that have an influence on rotation (and other) results from these data. These optical effects are analyzed here, and corrections are made to the positional data of the sunspots from both sites. A data set containing the combined positional data of sunspots from both sites, corrected for these optical aberrations, has been constructed. Results for both sunspot groups and individual sunspots are presented. It is pointed out that optical aberrations similar to those found in the Kodaikanal data may also exist in the Greenwich photoheliograph data, because these two sets of solar images were made with similar telescopes.     

Time scale of an early to mid-Paleozoic orogenic cycle of the long-lived Central Asian Orogenic Belt, Inner Mongolia of China: Implications for continental growth

We present a detailed, new time scale for an orogenic cycle (oceanic accretion–subduction–collision) that provides significant insights into Paleozoic continental growth processes in the southeastern segment of the long-lived Central Asian Orogenic Belt (CAOB). The most prominent tectonic feature in Inner Mongolia is the association of paired orogens. A southern orogen forms a typical arc-trench complex, in which a supra-subduction zone ophiolite records successive phases during its life cycle: birth (ca. 497–477 Ma), when the ocean floor of the ophiolite was formed; (2) youth (ca. 473–470 Ma), characterized by mantle wedge magmatism; (3) shortly after maturity (ca. 461–450 Ma), high-Mg adakite and adakite were produced by slab melting and subsequent interaction of the melt with the mantle wedge; (4) death, caused by subduction of a ridge crest (ca. 451–434 Ma) and by ridge collision with the ophiolite (ca. 428–423 Ma). The evolution of the magmatic arc exhibits three major coherent phases: arc volcanism (ca. 488–444 Ma); adakite plutonism (ca. 448–438 Ma) and collision (ca. 419–415 Ma) of the arc with a passive continental margin. The northern orogen, a product of ridge-trench interaction, evolved progressively from coeval generation of near-trench plutons (ca. 498–461 Ma) and juvenile arc crust (ca. 484–469 Ma), to ridge subduction (ca. 440–434 Ma), microcontinent accretion (ca. 430–420 Ma), and finally to forearc formation. The paired orogens followed a consistent progression from ocean floor subduction/arc formation (ca. 500–438 Ma), ridge subduction (ca. 451–434 Ma) to microcontinent accretion/collision (ca. 430–415 Ma); ridge subduction records the turning point that transformed oceanic lithosphere into continental crust. The recognition of this orogenic cycle followed by Permian–early Triassic terminal collision of the CAOB provides compelling evidence for episodic continental growth.     

Denitrification coupled to pyrite oxidation and changes in groundwater quality in a shallow sandy aquifer

This study focuses on denitrification in a sandy aquifer using geochemical analyses of both sediment and groundwater, combined with groundwater age dating (³H/³He). The study sites are located underneath cultivated fields and an adjacent forested area at Oostrum, The Netherlands. Shallow groundwater in the region has high nitrate concentrations (up to 8 mM) due to intense fertilizer application. Nitrate removal from the groundwater below cultivated fields correlates with sulfate production, and the release of dissolved Fe²⁺ and pyrite-associated trace metals (e.g. As, Ni, Co and Zn). These results, and the presence of pyrite in the sediment matrix within the nitrate removal zone, indicate that denitrification coupled to pyrite oxidation is a major process in the aquifer. Significant nitrate loss coupled to sulfate production is further confirmed by comparing historical estimates of regional sulfate and nitrate loadings to age-dated groundwater sulfate and nitrate concentrations, for the period 1950-2000. However, the observed increases in sulfate concentration are about 50% lower than would be expected from complete oxidation of pyrite to sulfate, possibly due to the accumulation of intermediate oxidation state sulfur compounds, such as elemental sulfur. Pollutant concentrations (NO₃, Cl, As, Co and Ni) measured in the groundwater beneath the agricultural areas in 1996 and 2006 show systematic decreases most likely due to declining fertilizer use.     

The Zn abundance and isotopic composition of diatom frustules,a proxy for Zn availability in ocean surface seawater

We have developed cleaning methods for extracting diatomopal from bulk marine sediment samples, for measurement of both zinc (Zn) abundance and isotope composition. This cleaning technique was then applied to a set of Holocene core-top samples from the Southern Ocean. The measured δ⁶⁶Zn (reported relative to the JMC_Lyon standard) and Zn/Si ratios from the Southern Ocean diatom_opal samples range from 0.7 to 1.5‰, and from 14 to 0.9 μmol/mol, respectively. The Zn abundance and isotope composition data show a clear correlation with opal burial rates and other oceanographic parameters. In common with previous work, we interpret the systematic changes in the Zn/Si ratio to be linked to the variability in the concentrations of bioavailable Zn in the ambient surface seawater where the diatom opal is formed. This variability is likely to be primarily controlled by the degree to which Zn is taken up into phytoplankton biomass. The observed systematic pattern in the δ⁶⁶Zn compositions of the diatom_opal core-top samples is, similarly, likely to reflect changes in the δ⁶⁶Zn composition of the ambient Zn in the surface waters above the core-top sites, which is progressively driven towards isotopically heavier values by preferential incorporation of the lighter isotopes into phytoplankton organic material. Thus, the systematic relationship between Zn isotopes and abundance observed in the core-top diatom_opal samples suggests a potential tool for investigating the biogeochemical cycling of Zn in the past surface ocean for down-core diatom_opal material. In this respect, it may be possible to test hypotheses that attribute variations in atmospheric CO₂ on glacial–interglacial timescales to the degree to which trace metals limited primary productivity in HNLC zones.