A MEMS Light Modulator Based on Diffractive Nanohole Gratings

We present the design, fabrication, and testing of a microelectromechanical systems (MEMS) light modulator based on pixels patterned with periodic nanohole arrays. Flexure-suspended silicon pixels are patterned with a two dimensional array of 150 nm diameter nanoholes using nanoimprint lithography. A top glass plate assembled above the pixel array is used to provide a counter electrode for electrostatic actuation. The nanohole pattern is designed so that normally-incident light is coupled into an in-plane grating resonance, resulting in an optical stop-band at a desired wavelength. When the pixel is switched into contact with the top plate, the pixel becomes highly reflective. A 3:1 contrast ratio at the resonant wavelength is demonstrated for gratings patterned on bulk Si substrates. The switching time is 0.08 ms and the switching voltage is less than 15V.

Development and characterization of fluorescent pH sensors based on porous silica and hydrogel support matrices

The hydrogen ion activity (pH) is a very important parameter in environment monitoring, biomedical research and other applications. Optical pH sensors have several advantages over traditional potentiometric pH measurement, such as high sensitivity, no need of constant calibration, easy for miniaturization and possibility for remote sensing. Several pH indicators has been successfully immobilized in three different solid porous materials to use as pH sensing probes. The fluorescent pH indicator fluorescein-5-isothiocyanate (FITC) was covalently bound onto the internal surface of porous silica (pore size ~10 nm) and retained its pH sensitivity. The excited state pK* a of FITC in porous silica (5.58) was slightly smaller than in solution (5.68) due to the free silanol groups (Si-OH) on the silica surface. The pH sensitive range for this probe is pH 4.5 - 7.0 with an error less than 0.1 pH units. The probe response was reproducible and stable for at least four month, stored in DI water, but exhibit a long equilibrium of up to 100 minutes. Sol-gel based pH sensors were developed with immobilization of two fluorescent pH indicators fluorescein-5-(and-6)-sulfonic acid, trisodium salt (FS) and 8-hydroxypyrene- 1,3,6-trisulfonic acid (HPTS) through physical entrapment. Prior to immobilization, the indicators were ion-paired with a common surfactant hexadecyltrimethylammonium bromide (CTAB) in order to prevent leaching. The sol-gel films were synthesized through the hydrolysis of two different precursors, ethyltriethoxysilane (ETEOS) and 3- glycidoxypropyltrimethoxysilane (GPTMS) and deposited on a quartz slide through spin coating. The pK a of the indicators immobilized in sol-gel films was much smaller than in solutions due to silanol groups on the inner surface of the sol-gel films and ammonium groups from the surrounding surfactants. Unlike in solution, the apparent pK a of the indicators in sol-gel films increased with increasing ionic strength. The equilibrium time for these sensors was within 5 minutes (with film thickness of ~470 nm). Polyethylene glycol (PEG) hydrogel was of interest for optical pH sensor development because it is highly proton permeable, transparent and easy to synthesize. pH indicators can be immobilized in hydrogel through physical entrapment and copolymerization. FS and HPTS ion-pairs were physically entrapped in hydrogel matrix synthesized via free radical initiation. For covalent immobilization, three indicators, 6,8-dihydroxypyrene-1,3- disulfonic acid (DHPDS), 2,7-dihydroxynaphthalene-3,6-disulfonic acid (DHNDS) and cresol red were first reacted with methacrylic anhydride (MA) to form methacryloylanalogs for copolymerization. These hydrogels were synthesized in aqueous solution with a redox initiation system. The thickness of the hydrogel film is controlled as ~ 0.5 cm and the porosity can be adjusted with the percentage of polyethylene glycol in the precursor solutions. The pK a of the indicators immobilized in the hydrogel both physically and covalently were higher than in solution due to the medium effect. The sensors are stable and reproducible with a short equilibrium time (less than 4 minutes). In addition, the color change of cresol red immobilized hydrogel is vivid from yellow (acidic condition) to purple (basic condition). Due to covalently binding, cresol red was not leaching out from the hydrogel, making it a good candidate of reusable "pH paper".

The effect of shoulder variation on IMRT and SmartArc for Head and Neck Cancer

Purpose: First, to determine an average and maximum displacement of the shoulder relative to isocenter over the course of treatment. Second, to establish the dosimetric effect of shoulder displacements relative to correct isocenter alignment on the dose delivered to the target and the surrounding structures for head and neck cancer patients. Method and Materials: The frequency of shoulder shifts of various magnitudes relative to isocenter was assessed for 4 patients using image registration software. The location of the center of the right and left humeral head relative to isocenter (usually C2) was found daily from CT on rails scans, and was compared to the location of the humeral heads relative to isocenter on the initial simulation CT. Three Baseline head and neck IMRT and SmartArc plans were generated in Pinnacle based on simulation CTs. The CT datasets (external contour and boney structures) were then modified to represent shifts of the shoulder (relative to isocenter) between 3 mm and 15 mm in the SI, AP, and LR directions. The initial plans were recalculated on the image sets with shifted shoulders. Results: On average, shoulder variation was 2-5 mm in each direction, although displacements of over 1 cm in the inferior and posterior directions occurred. Shoulder shifts induced perturbations in the dose distribution, although generally only for large shifts. Most substantially, large, superior shifts resulted in coverage loss by the 95% isodose line for targets in the lower neck. Inferior shifts elevated the dose to the brachial plexus by 0.6-4.1 Gy. SmartArc plans showed similar loss of target coverage as IMRT plans. Conclusions: The position of the shoulder can have an impact on target coverage and critical structure dose. Shoulder position may need to be considered for setup of head and neck patients depending on target location.

Hyalotekite, (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2)(Si,B)(2)O28F, a Tectosilicate Related to Scapolite: New Structure Refinement, Phase Transitions and a Short-Range Ordered 3B Superstructure

Hyalotekite, a framework silicate of composition (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2) (Si,B)(2)O28F, is found in relatively high-temperature(greater than or equal to 500 degrees C) Mn skarns at Langban, Sweden, and peralkaline pegmatites at Dara-i-Pioz, Tajikistan. A new paragenesis at Dara-i-Pioz is pegmatite consisting of the Ba borosilicates leucosphenite and tienshanite, as well as caesium kupletskite, aegirine, pyrochlore, microcline and quartz. Hyalotekite has been partially replaced by barylite and danburite. This hyalotekite contains 1.29-1.78 wt.% Y2O3, equivalent to 0.172-0.238 Y pfu or 8-11% Y on the Ca site; its Pb/(Pb+Ba) ratio ranges 0.36-0.44. Electron microprobe F contents of Langban and Dara-i-Pioz hyalotekite range 1.04-1.45 wt.%, consistent with full occupancy of the F site. A new refinement of the structure factor data used in the original structural determination of a Langban hyalotekite resulted in a structural formula, (Pb1.96Ba1.86K0.18)Ca-2(B1.76Be0.24)(Si1.56B0.44)Si8O28F, consistent with chemical data and all cations with positive-definite thermal parameters, although with a slight excess of positive charge (+57.14 as opposed to the ideal +57.00). An unusual feature of the hyalotekite framework is that 4 of 28 oxygens are non-bridging; by merging these 4 oxygens into two, the framework topology of scapolite is obtained. The triclinic symmetry of hyalotekite observed at room temperature is obtained from a hypothetical tetragonal parent structure via a sequence of displacive phase transitions. Some of these transitions are associated with cation ordering, either Pb-Ba ordering in the large cation sites, or B-Be and Si-B ordering on tetrahedral sites. Others are largely displacive but affect the coordination of the large cations (Pb, Ba, K, Ca). High-resolution electron microscopy suggests that the undulatory extinction characteristic of hyalotekite is due to a fine mosaic microstructure. This suggests that at least one of these transitions occurs in nature during cooling, and that it is first order with a large volume change. A diffuse superstructure observed by electron diffraction implies the existence of a further stage of short-range cation ordering which probably involves both (Pb,K)-Ba and (BeSi,BB)-BSi.

Springtime Nutrient and Phytoplankton Dynamics on Georges Bank

The dynamics of phytoplankton and nutrients before, during and after the winter-spring bloom on Georges Bank were studied on 6 monthly survey cruises from January to June 1999. We measured hydrography, phytoplankton cell densities, chlorophyll a, dissolved inorganic nutrients (NO3 + NO2, NH4, Si(OH)(4), PO4), dissolved organic nitrogen (DON) and phosphorus (DOP), particulate organic carbon (POC) and nitrogen (PON) and total particulate phosphorus (TPP). We present evidence that phytoplankton production may be significant year-round, and that the winter-spring bloom may have started in January. From January to April the phytoplankton was comprised almost exclusively of diatoms, reaching cell densities in March and April of ca. 450 cells ml(-1); chlorophyll a concentrations exceeded 10 mug l(-1) in April. Diatoms decreased to relatively low levels in May (< 50 x 10(3) cells l(-1)) and increased again in June (>300 x 10(3) cells l(-1)). Densities of dinoflagellates and nanoflagellates were low (< 10 x 10(3) cells l(-1)) from January to April, and increased in May and June to nearly 300 x 10(3) cells l(-1). Nitrate + nitrite concentrations in January were <3 muM in the shallow, central portion of the bank and decreased steadily each month. Silicate was also <3 muM over an even larger area of the central bank in January and declined to <1.5 muM over most of the Bank in April. The data suggest that silicate depletion, not DIN, contributed to the cessation of the diatom bloom. Regeneration of silicate occurred in May and June, presumably as a result of rising water temperatures in late spring which increased the dissolution rate of diatom frustules from the earlier diatom bloom. Dissolved organic nitrogen may have been utilized at the start of the winter-spring bloom; concentrations were ca, 14 muM in January, dropping to < 6 mug l(-1) in February, after which DON concentrations steadily rose to > 15 mug l(-1) in June. Overall micro-and nanoplankton biomass, measured as POC, PON and TPP, increased over the 6 mo period, as did nutritional quality of that biomass as indicated by declining C:N ratios. Our results suggest there may have been an increase in the heterotrophic component of the plankton in May and June which coincided with a second burst in diatom abundance. We discuss general features of planktonic production and nutrient dynamics with respect to year-round production on the Bank.

Size-Fractionated Nitrogen Uptake Measurements in the Equatorial Pacific and Confirmation of the Low Si-High-Nitrate Low-Chlorophyll Condition

The equatorial Pacific Ocean is the largest natural source of CO(2) to the atmosphere, and it significantly impacts the global carbon cycle. Much of the large flux of upwelled CO(2) to the atmosphere is due to incomplete use of the available nitrate (NO(3)) and low net productivity. This high-nutrient low-chlorophyll (HNLC) condition of the equatorial upwelling zone (EUZ) has been interpreted from modeling efforts to be due to low levels of silicate ( Si( OH) 4) that limit the new production of diatoms. These ideas were incorporated into an ecosystem model, CoSINE. This model predicted production by the larger phytoplankton and the picoplankton and effects on air-sea CO(2) fluxes in the Pacific Ocean. However, there were no size-fractionated rates available for verification. Here we report the first size-fractionated new and regenerated production rates (obtained with (15)N - NO(3) and (15)N - NH(4) incubations) for the EUZ with the objective of validating the conceptual basis and functioning of the CoSINE model. Specifically, the larger phytoplankton ( with cell diameters > 5 mu m) had greater rates of new production and higher f-ratios (i.e., the proportion of NO(3) to the sum of NO(3) and NH(4) uptake) than the picoplankton that had high rates of NH(4) uptake and low f-ratios. The way that the larger primary producers are regulated in the EUZ is discussed using a continuous chemostat approach. This combines control of Si(OH)(4) production by supply rate (bottom-up) and control of growth rate ( or dilution) by grazing ( top-down control).

Assessment of STR Typing Success Rate in Soft Tissues from Putrefied Bodies Based on a Quantitative Grading System for Putrefaction.

To date, there is no systematic investigation of the association of short tandem repeat (STR) typing success rate in soft tissues with different signs of putrefaction. Herein, putrefaction was rated using a newly developed 19-parameter system in soft tissues from a collective of 68 decaying bodies, and DNA yield was determined in 408 samples. DNA integrity was rated using a self-devised pentaplex PCR generating an "integrity score" (Si ). STR typing success rate was then assessed for selected cases. DNA yield and Si differed significantly between tissues with kidney on average exhibiting the highest Si values. Statistical analysis revealed that nine parameters were significantly and positively correlated with Si . The observed values for each of these nine parameters were summed up to generate a putrefaction score (Sp ) for each sample. Our results show that STR typing success rate can be predicted based on Sp before expensive multiplex STR profiling is performed.

From stellar to planetary composition: Galactic chemical evolution of Mg/Si mineralogical ratio

Aims. The main goal of this work is to study element ratios that are important for the formation of planets of different masses. Methods. We study potential correlations between the existence of planetary companions and the relative elemental abundances of their host stars. We use a large sample of FGK-type dwarf stars for which precise Mg, Si, and Fe abundances have been derived using HARPS high-resolution and high-quality data. Results. A first analysis of the data suggests that low-mass planet host stars show higher [Mg/Si] ratios, while giant planet hosts present [Mg/Si] that is lower than field stars. However, we found that the [Mg/Si] ratio significantly depends on metallicity through Galactic chemical evolution. After removing the Galactic evolution trend only the difference in the [Mg/Si] elemental ratio between low-mass planet hosts and non-hosts was present in a significant way. These results suggest that low-mass planets are more prevalent around stars with high [Mg/Si]. Conclusions. Our results demonstrate the importance of Galactic chemical evolution and indicate that it may play an important role in the planetary internal structure and composition. The results also show that abundance ratios may be a very relevant issue for our understanding of planet formation and evolution.

Geochemistry on sediments in Lake Biwa

Thirty sediment cores (30-40 cm in length), 47 Ekman dredge sediments, and Mn concretions were collected from Lake Biwa. The concentrations of 36 elements in the samples were determined by instrumental neutron activation, X-ray fluorescence, atomic absorption, and colorimetric analyses. The elements determined included Mn, P, As, Sb, Fe, Ni, Co, Zn, Cu, Pb, Hg, Cr, Ti, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Hf, La, Ce, Sm, Eu, Yb, Lu, U, Th, Au, Ta, Nd, Br and N. Based on statistical considerations and calculation of the concentration factors of the elements, the features of the elemental distribution in Lake Biwa sediment were determined. The main results are summarized as follows : (1) Concentrations of Mn and As were very high in the uppermost oxidized layer of the offshore sediment and Mn concretions. This resulted from the dissolution-deposition cycles of these elements within the sedimentary column and the bottom water. The fixation of As at the sediment surface is mainly attributed to the adsorption of arsenate onto Mn (II) -rich hydrous Mn (IV) oxide. (2) There were high concentrations of Zn, Cu, Pb and Hg in the recent sediments. Although the source of these elements is attributed to human activities, the individual distributions of Zn and Cu in the sediment may result from the deposition of metal-rich planktonic debris and subsequent degradation of the debris. (3) The orders of increasing concentrations of alkali metals and lanthanides in the sediment from the central region compared with the nearshore pediment were identical to the orders of increasing atomic numbers from Na to Cs and from La to Lu, respectively.

Effects of increased CO2 concentration on nutrient limited coastal summer plankton depend on temperature

Increasing seawater temperature and CO2 concentrations both are expected to increase coastal phytoplankton biomass and carbon to nutrient ratios in nutrient limited seasonally stratified summer conditions. This is because temperature enhances phytoplankton growth while grazing is suggested to be reduced during such bottom-up controlled situations. In addition, enhanced CO2 concentrations potentially favor phytoplankton species, that otherwise depend on costly carbon concentrating mechanisms (CCM). The trophic consequences for consumers under such conditions, however, remain little understood. We set out to experimentally explore the combined effects of increasing temperature and CO2 concentration for phytoplankton biomass and stoichiometry and the consequences for trophic transfer (here for copepods) on a natural nutrient limited Baltic Sea summer plankton community. The results show, that warming effects were translated to the next trophic level by switching the system from a bottom-up controlled to a mainly top-down controlled one. This was reflected in significantly down-grazed phytoplankton and increased zooplankton abundance in the warm temperature treatment (22.5°C). Additionally, at low temperature (16.5°C) rising CO2 concentrations significantly increased phytoplankton biomass. The latter effect however, was due to direct negative impact of CO2 on copepod nauplii which released phytoplankton from grazing in the cold but not in the warm treatments. Our results suggest that future seawater warming has the potential to switch trophic relations between phytoplankton and their grazers under nutrient limited conditions with the consequence of potentially disguising CO2 effects on coastal phytoplankton biomass.

Geochemistry on manganese nodules from Loch Fyne, Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10-15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180-200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5-8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments. The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn. The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice. Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.

(Table 1) Water column biogenic silica concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition (d30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer d30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the d30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the d30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.

Clay mineralogy and multi-element chemistry of surface sediments on the Aiberian-Arctic Shelf

Clay mineral and bulk chemical (Si, Al, K, Mg, Sr, La, Ce, Nd) analyses of terrigenous surface sediments on the Siberian-Arctic shelf indicate that there are five regions with distinct, or endmember, sedimentary compositions. The formation of these geochemical endmembers is controlled by sediment provenance and grain size sorting. (1) The shale endmember (Al, K and REE rich sediment) is eroded from fine-grained marine sedimentary rocks of the Verkhoyansk Mountains and Kolyma-Omolon superterrain, and discharged to the shelf by the Lena, Yana, Indigirka and Kolyma Rivers. (2) The basalt endmember (Mg rich) originates from NE Siberia's Okhotsk-Chukotsk volcanic belt and Bering Strait inflow, and is prevalent in Chukchi Sea Sediments. Concentrations of the volcanically derived clay mineral smectite are elevated in Chukchi fine-fraction sediments, corroborating the conclusion that Chukchi sediments are volcanic in origin. (3) The mature sandstone endmember (Si rich) is found proximal to Wrangel Island and sections of the Chukchi Sea's Siberian coast and is derived from the sedimentary Chukotka terrain that comprises these landmasses. (4) The immature sandstone endmember (Sr rich) is abundant in the New Siberian Island region and reflects inputs from sedimentary rocks that comprise the islands. (5) The immature sandstone endmember is also prevalent in the western Laptev Sea, where it is eroded from sedimentary deposits blanketing the Siberian platform that are compositionally similar to those on the New Siberian Islands. Western Laptev can be distinguished from New Siberian Island region sediments by their comparatively elevated smectite concentrations and the presence of the basalt endmember, which indicate Siberian platform flood basalts are also a source of western Laptev sediments. In certain locations grain size sorting noticeably affects shelf sediment chemistry. (1) Erosion of fines by currents and sediment ice rafting contributes to the formation of the coarse-grained sandstone endmembers. (2) Bathymetrically controlled grain size sorting, in which fines preferentially accumulate offshore in deeper, less energetic water, helps distribute the fine-grained shale and basalt endmembers. An important implication of these results is that the observed sedimentary geochemical endmembers provide new markers of sediment provenance, which can be used to track sediment transport, ice-rafted debris dispersal or the movement of particle-reactive contaminants.

Hydrochemical and geothermic data on the Caribbean-Mexican region

Results of detailed geophysical, geological and gas- and hydrochemical research in the Caribbean-Mexican Basin and the Western Atlantic obtained during Cruise 4 of R/V Akademik Nikolaj Strakhov are published in the book. Distribution of the thermal field in different tectonic structures of the region is shown. Places of submarine hydrothermal vent discharge in tectonically active structures are described. They are confirmed by geothermal, geological and hydrochemical data. Based on lithofacies analysis of modern sediments installed their Specificity of different genetic types, facies and macrofacies of recent sediments in different geomorphological zones of the sea floor is shown. For description of hydrogeochemical situation of modern sedimentation and primary diagenesis the water column and interstitial sediment waters have been studied.

Geochemistry on the Kekesai composite intrusion

The late Carboniferous to Permian is a critical period for final amalgamation of the Central Asian Orogenic Belt (CAOB), which is characterized by voluminous igneous rocks, particularly granitoids. The Kekesai composite granitoid porphyry intrusion, situated in the Chinese western Tianshan (southwest part of CAOB) includes two intrusive phases, a monzogranite phase, intruded by a granodiorite phase. LA-ICPMS U-Pb zircon analyses suggest that the monzogranitic rocks formed at 305.5±1.1 Ma, with a wide age range of inherited zircons (358-488 Ma and 1208-1391 Ma), whereas the granodioritic rocks formed at 288.7±1.5 Ma. The monzogranitic and granodioritic phases have similar geochemical features and Sr-Nd-Hf isotopic compositions. They exhibit high and variable SiO2 (66-71 wt.%) and MgO (0.41-2.14 wt.%) contents with some arc-like geochemical characteristics (e.g., enrichment of large ion lithophile elements and negative anomalies of Nb, Ta and Ti) and relatively high initial 87Sr/86Sr ratios (ISr=0.7055-0.7059), low positive eNd(t) (+0.84 to +1.03) as well as a large variation in Hf isotopic compositions with eHf(t) between +3.43 to +14.8, implying both of them were derived from similar source materials. These geochemical characteristics suggest that they might be mainly derived from the partial melting of arc-derived Mesoproterozoic mafic lower crust with involvement of a mantle-derived component in variable proportions by mantle-derived magma underplating. The presence of late-Ordovician to earliest early Carboniferous inherited zircons and the Hf isotopic compositions in the monzogranitic sample, similar to that of the widespread juvenile arc rocks, indicates some crust contamination during magma emplacement. Our new data, combined with previous studies, imply that extensive post-collisional magmatism due to underplating of mantle-derived magma, could plausibly be explained by slab break-off regime.