Chemical composition of manganese micronodules from expedition VA-05/1 in the Pacific Ocean

A radioisotope energy-dispersive X-ray (EDX) system has been used on board the German research vessel "Valdivia" during an exploration expedition in the northern equatorial Pacific in 1973. The instrumentation used consisted of an X-ray detection system incorporating a 30 mm2 effective-area Si (Li) detector with a measured energy resolution of 195 eV for Mn K alpha X-rays, standard nuclear electronics, a 1024-channel analyser and a data read-out unit. The X-ray spectra in the manganese-nodule samples were excited by a 30-mCi 238Pu source. The six elements Mn, Fe, Co, Ni, Cu and Zn were analysed on board. Precision values for the analyses were less than 3% for Mn, Fe, Ni, Cu and Zn and about 5% for Co. A total amount of 350 analyses was carried out during a one-month cruise. Average contents of 190 analysed whole manganese-nodule samples from all the sampling sites of the covered area were 23.3% Mn, 6.7% Fe, 0.23% Co, 1.16% Ni, 0.94% Cu and 0.10% Zn. The average content of the base metals expressed as the sum of the Co, Ni, Cu and Zn contents was 2.48%. A linear relationship between Mn and Ni in all analysed samples, including whole manganese-nodule samples, zones of manganese nodules and manganese crusts, was observed. The Mn/Ni ratio calculated by regression analysis was 23.0. Zonal variations of the chemical contents of the six elements in the manganese nodules were found. A size classification of the manganese nodules has been suggested. Geochemical correlations of Cu and Ni versus Mn/Fe in the investigated samples are given.

Mineral and chemical compositions of a ferromanganese nodule from Station DM41-3911-76

Processes of authigenic manganese ore formation in sediments of the North Equatorial Pacific are considered on the basis of a study of the surface layer (<2 mm) of a ferromanganese nodule and four micronodule size fractions from associated surface sediment (0-7 cm). Inhomogeneity of nodule composition is shown. Mn/Fe ratio is maximal in samples from lateral sectors of the nodule at the water-sediment interface. Compositional differences of nodules are related to preferential accumulation of trace elements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenic component trapped during nodule growth (Ga, Rb, Ba, and Cs). Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by minimal Mn/Fe values. A compositional comparison of manganese micronodules and surface layers of the nodule demonstrates that micronodule material was subjected to more intense reworking during diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe, but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are the least mobile elements during diagenesis. Differences in chemical composition of the micronodules and nodules are related not only to additional input of Mn in the process of diagenesis, but also to transformation of iron oxyhydroxides after removal of Mn from the close association with Fe formed in suspended matter during sedimentation.

(Figure 2, page 940) K-T boundary enrichment for cerium and iridium chemical composition of layers inside the ZETES-3D manganese nodule in the Pacific Ocean

Hydrogenous manganese nodules form on the ocean floor by slow authigenic precipitation (1-6 mm/Ma) of the oxyhydroxides of manganese and iron that continuously scavenge trace elements from the marine environment. Consequently, these nodules represent independent marine deposits useful for the study of the chemical signatures of the paleomarine environments. The results presented are a continuation of a study of the Zetes-3D nodule from the Pacific Ocean. It is a large (24x17x10 cm) hydrogenous nodule whose slow growth rate of 1.3 mm/Ma was detremined using 10Be techniques. A positive cerium anomaly is observed throughout the nodule and its Ir content indicates a sharp spike at 54-62 Ma in fair agreement with the K-T event.

(Table 3, page 280) Chemical composition of micronodules from a series of stations and sediment depths from Areas C, F, G and K in the Pacific Ocean from R/V Sonne Cruise SO06

Compositional data for coexisting manganese nodules, micronodules, sediments and pore waters from five areas in the equatorial and S.W. Pacific have been obtained. This represents the largest study of its type ever undertaken to establish the distribution of elements between the various phases within the sediment column. The composition of manganese nodules, micronodules and sediments (on a carbonate-free basis) shows marked differences between the equatorial high productivity zone and the low productivity region of the S.W. Pacific. In the case of the nodules, th is reflects an increased supply of transition elements (notably Ni, Cu and Zn) to the nodules as a result of the in situ dissolution of siliceous tests within the sediment column in the equatorial Pacific high productivity zone. Micronodules display similar, but somewhat different, compositions to those of the associated nodules in each area. Micronodule composition is therefore influenced by the same basic factors that control nodule composition, but is modified by dissolution of the micronodules in situ within the sediment column. Locally, as in the area immediately south of the Marquesas Fracture Zone, the micronodule population is contaminated by small, angular volcanic rock fragments; this leads to apparently anomalous micronodule compositions. Micronodules appear to be a transient feature in the sediment column, especially in the equatorial Pacific. Dissolution of micronodules in the sediment column therefore represents an important source of elements for the growth of manganese nodules in the equatorial Pacific. Sediment composition is markedly influenced by the carbonate content. On a carbonate-free basis, the sediments from the equatorial high productivity zone are quite distinct in composition from those in the S.W. Pacific. This reflects differences in the lithology of the sediments. In the Aitutaki Passage, the local influence of volcanoclastic material in sediment composition has been established. The major cations and anions in pore waters measured here show no major differences between equatorial and S.W. Pacific sediments. Silica is, however, higher in equatorial Pacific pore waters reflecting the dissolution of siliceous tests in these sediments.

(Supplement Table1) Abundances of major elements from KH93-3_DR10 at the Southwest Indian Ridge near the Rodriguez Triple Junction

Petrographic and geochemical analyses of basaltic rocks dredged from the first segment of the Southwest Indian Ridge near the Rodriguez Triple Junction have been completed in order to investigate water-rock interaction processes during mid-ocean ridge (MOR) hydrothermal alteration in the Indian Ocean. In the study area, we have successfully recovered a serial section of upper oceanic crust exposed along a steep rift valley wall which was uplifted and emplaced along a low angle normal fault. On the basis of microscopic observation, dredged samples are classified into three types: fresh lavas, low-temperature altered rocks, and high-temperature altered rocks. The fresh lavas have essentially the same chemical composition as typical N-MORB, although LILE and Nb are slightly enriched and depleted, respectively. Low temperature alteration brought about the enrichment of K2O, Rb, and U due to the presence of K-rich celadonite and U-adsorption onto Fe-oxyhydroxide and clay minerals. On the other hand, chloritization, albitization, and addition of base metals by high temperature hydrothermal alteration result in enrichments of MnO, MgO, Na2O, Cu, and Zn and depletions of CaO, K2O, Cr, Co, Ni, Rb, Sr, and Ba. In addition, U-enrichment is also observable in the high temperature altered rocks probably due to the decrease of uranite solubility in the reducing high-temperature hydrothermal solution. These petrological and geochemical features are comparable to those of the volcanic zone to transition zone rocks in the DSDP/ODP Hole 504B, indicating that our samples were recovered from the upper ~1000 m section of the oceanic crust. Only the alteration minerals related to off-axis alteration are absent in our samples dredged from near the spreading axis. The similarity of alteration between our samples from the Indian Ocean and the Hole 504B rocks from the Pacific Ocean suggests that MOR hydrothermal systems are probably similar across all world oceans.

(Table 2, Page 270) Average chemical composition of manganese nodules and crust collected at different localities the Pacific Ocean

Considerable regional variations in the chemical composition of manganese nodules from a wide range of the Pacific Ocean have been observed. These variations can be more exactly expressed in terms of inter-element relationships. In particular, Cu-Mn and Cu-Ni associations reveal that Cu content in pelagic nodules increases rapidly in proportion to those of Mn or Ni. In nodules from continental borderland and hemipelagic areas, even if Mn or Ni contents increase, that of Cu increases only slightly. It is suggested that the considerable chemical differences within individual nodules and between nodules from the same site, at a limited pelagic area where there is no marked change in depositional conditions of nodules, are due to the role of hydrolyzable trace elements in the formation of nodules.

Chemical composition of ocean manganese nodules from the Pacific Ocean using different techniques

Mineralogical and chemical analyses performed on 67 ferromanganese nodules from widely varying locations and depths within the marine environment of the Pacific Ocean indicate that the minor element composition is controlled by the mineralogy and that the formation of the mineral phases is depth dependent. The pressure effect upon the thermodynamics or kinetics of mineral formation is suggested as the governing agent in the depth dependence of the mineralogy. The minor elements, Pb and Co, appear concentrated in the dMnO2 phase, whereas Cu and Ni are more or less excluded from this phase. In the manganites, Pb and Co are relatively low in concentration, whereas Cu and Ni are spread over a wide range of values. The oxidation of Pb and Co from divalent forms in sea water to higher states can explain their concentration in the dMnO2 phase.

Patterns of rare earth and other trace elements in Paleogene and Miocene clayey sediments from the Mondego platform (Central Portugal)

In the present study the origin of clay deposits occurring in an inland platform, in central Portugal, was investigated by their mineralogical and chemical composition. The clay deposits, exploited for ceramic industry are composed of silt-clay facies, the Monteira Member and the Arroça Member, which are assigned to the Coja Formation (Paleogene) and the Campelo Formation (Miocene), respectively. These clayey facies show almost compositional homogeneity, especially concerning texture. The mineralogical composition of the Monteira Member displays slightly higher content in smectite and interstratified clay minerals, which is supported by the chemical composition of samples analyzed. Both members present similar REE patterns, displaying an intense weathering record and little variation in the source area composition. Minor element geochemistry suggests low content in heavy minerals and transition metals. REE patterns and ratios of geochemical parameters support the dominant metasedimentary provenance, with a granite source contribution and also mature recycled sediments of continental origin. The study results’ suggest that the clays of these two members have the same source in terms of lithology and recycled sediments from the Hesperian massif. During the deposition of the Arroça Member, a major remobilization of the Monteira Member is suggested, explaining the geochemical similarity of both facies.

STRUCTURAL ANALYSIS OF RIBOSOME BINDING ELEMENTS OF THE 3´ UTR IN TWO POSITIVE-STRAND PLANT RNA VIRUSES

Turnip crinkle virus (TCV) and Pea enation mosaic virus (PEMV) are two positive (+)-strand RNA viruses that are used to investigate the regulation of translation and replication due to their small size and simple genomes. Both viruses contain cap-independent translation elements (CITEs) within their 3´ untranslated regions (UTRs) that fold into tRNA-shaped structures (TSS) according to nuclear magnetic resonance and small angle x-ray scattering analysis (TCV) and computational prediction (PEMV). Specifically, the TCV TSS can directly associate with ribosomes and participates in RNA-dependent RNA polymerase (RdRp) binding. The PEMV kissing-loop TSS (kl-TSS) can simultaneously bind to ribosomes and associate with the 5´ UTR of the viral genome. Mutational analysis and chemical structure probing methods provide great insight into the function and secondary structure of the two 3´ CITEs. However, lack of 3-D structural information has limited our understanding of their functional dynamics. Here, I report the folding dynamics for the TCV TSS using optical tweezers (OT), a single molecule technique. My study of the unfolding/folding pathways for the TCV TSS has provided an unexpected unfolding pathway, confirmed the presence of Ψ3 and hairpin elements, and suggested an interconnection between the hairpins and pseudoknots. In addition, this study has demonstrated the importance of the adjacent upstream adenylate-rich sequence for the formation of H4a/Ψ3 along with the contribution of magnesium to the stability of the TCV TSS. In my second project, I report on the structural analysis of the PEMV kl-TSS using NMR and SAXS. This study has re-confirmed the base-pair pattern for the PEMV kl-TSS and the proposed interaction of the PEMV kl-TSS with its interacting partner, hairpin 5H2. The molecular envelope of the kl-TSS built from SAXS analysis suggests the kl-TSS has two functional conformations, one of which has a different shape from the previously predicted tRNA-shaped form. Along with applying biophysical methods to study the structural folding dynamics of RNAs, I have also developed a technique that improves the production of large quantities of recombinant RNAs in vivo for NMR study. In this project, I report using the wild-type and mutant E.coli strains to produce cost-effective, site-specific labeled, recombinant RNAs. This technique was validated with four representative RNAs of different sizes and complexity to produce milligram amounts of RNAs. The benefit of using site-specific labeled RNAs made from E.coli was demonstrated with several NMR techniques.

Factors influencing temporal changes in chemical composition of biogenic deposits in the middle Tążyna River Valley (Kuyavian Lakeland, central Poland)

The present paper discusses the influence of geochemical properties on biogenic deposits in the Wilkostowo mire near Toruń, central Poland. The analysed core has allowed the documentation of environmental changes between the older part of the Atlantic Period and the present day (probably interrupted at the turn of the Meso- and Neoholocene). In order to reconstruct the main stages in the sedimentation of biogenic deposits, we have used stratigraphic variability of selected litho-geochemical elements (organic matter, calcium carbonate, biogenic and terrigenous silica, macro- and micro-elements: Na, K, Mg, Ca, Fe, Mn, Cu, Zn, Pb, Cr and Ni). The main litho-geochemical component is CaCO 3 ; its content ranges from 4.1 per cent to 92 per cent. The variability of CaCO 3 content reflects mainly changes in hydrolog- ical and geomorphological conditions within the catchment area. The effects of prehistoric anthropogenic activities in the catchment of the River Tążyna, e.g., the use of saline water for economic purposes, are recorded in a change from calcareous gyttja into detritus-calcareous gyttja sedimentation and an increased content of lithophilous elements (Na, K, Mg and Ni) in the sediments. Principal component analysis (PCA) has enabled the distinction the most important factors that affected the chemical composition of sediments at the Wilkostowo site, i.e., mechanical and chemical den- udation processes in the catchment, changes in redox conditions, bioaccumulation of selected elements and human activity. Sediments of the Wilkostowo mire are located in the direct vicinity of an archaeological site, where traces of intensive settlement dating back to the Neolithic have been documented. The settlement phase is recorded both in li- thology and geochemical properties of biogenic deposits which fill the reservoir formed at the bottom of the Parchania Canal Valley.

The use of wild fruits of Fragaria vesca L. in preparations with bioactive properties: chemical characterization, antioxidant, antibacterial and antibiofilm activities

Wild strawberry, Fragaria vesca L., belongs to Rosaceae family and is commonly found in roadsides and slopes [1]. The most consumed parts of this plant are its sweet small fruits, which constitute a source of vitamins and phenolic compounds, being also used in infusions due to their organoleptic properties and for the treatment of some intestinal disorders [2, 3]. In the present work, F. vesca fruits were evaluated for their nutritional value and further used in the preparation of infusions. The chemical composition of the fruits and corresponding infusions was determined in terms of soluble sugars, organic acids, tocopherols, folates (by HPLC coupled to different detectors), phenolic compounds (by HPLC-DAD/ESI-MS) and mineral elements (atomic absorption spectroscopy). Some of these bioactive compounds were correlated with antioxidant and antibacterial properties evaluated either in infusions as also in hydromethanolic extracts. Carbohydrates were the main macronutrients in the fruits, followed by fat and proteins. Regarding the fatty acids, polyunsaturated fatty acids showed higher prevalence, mainly due to the presence of D-linolenic (Cl8:3n3) and y-linolenic (Cl8:3n6) acids. Sucrose and citric acid were, respectively, the main sugar and organic acid found in the fruits and in its infusions. The microelement found in higher amounts in both samples was manganese, while potassium and calcium were the macroelements present in higher levels in the fruits and infusions, respectively. Both samples presented folates and tocopherols, being ytocopherol the main isoform detected in the fruits, while a-tocopherol was the only isoform quantified in the infusion. The hydromethanolic extract prepared from the fruits gave higher antioxidant and antibacterial activities, namely against Escherichia coli and Pseudomonas aeruginosa, than the infusion; it also showed capacity to inhibit the formation of bacterial biofilm. Both bioactivities are highly correlated with the presence of phenolic compounds, in which the major are ellagic acid derivatives (sanguiin hlO) followed by tlavan 3-ols ((+)catechin) and anthocyanin compounds (pelargonidin-3-glucoside). Although fruits of wild F. vesca are mainly consumed in fresh, this study also proves the potentiality of their infusions as a source of bioactive molecules and properties.

Fast Detection and Chemical Characterization of Gunshot Residues by CMV-GC-MS and LIBS

Gunshot residue (GSR) is the term used to describe the particles originating from different parts of the firearm and ammunition during the discharge. A fast and practical field tool to detect the presence of GSR can assist law enforcement in the accurate identification of subjects. A novel field sampling device is presented for the first time for the fast detection and quantitation of volatile organic compounds (VOCs). The capillary microextraction of volatiles (CMV) is a headspace sampling technique that provides fast results (< 2 min. sampling time) and is reported as a versatile and high-efficiency sampling tool. The CMV device can be coupled to a Gas Chromatography-Mass Spectrometry (GC-MS) instrument by installation of a thermal separation probe in the injection port of the GC. An analytical method using the CMV device was developed for the detection of 17 compounds commonly found in polluted environments. The acceptability of the CMV as a field sampling method for the detection of VOCs is demonstrated by following the criteria established by the Environmental Protection Agency (EPA) compendium method TO-17. The CMV device was used, for the first time, for the detection of VOCs on swabs from the hands of shooters, and non-shooters and spent cartridges from different types of ammunition (i.e., pistol, rifle, and shotgun). The proposed method consists in the headspace extraction of VOCs in smokeless powders present in the propellant of ammunition. The sensitivity of this method was demonstrated with method detection limits (MDLs) 4-26 ng for diphenylamine (DPA), nitroglycerine (NG), 2,4-dinitrotoluene (2,4-DNT), and ethyl centralite (EC). In addition, a fast method was developed for the detection of the inorganic components (i.e., Ba, Pb, and Sb) characteristic of GSR presence by Laser Induced Breakdown Spectroscopy (LIBS). Advantages of LIBS include fast analysis (~ 12 seconds per sample) and good sensitivity, with expected MDLs in the range of 0.1-20 ng for target elements. Statistical analysis of the results using both techniques was performed to determine any correlation between the variables analyzed. This work demonstrates that the information collected from the analysis of organic components has the potential to improve the detection of GSR.

Sexual selection in a tropical fruit fly : role of a plant derived chemical in mate choice

The specific mechanisms by which selective pressures affect individuals are often difficult to resolve. In tephritid fruit flies, males respond strongly and positively to certain plant derived chemicals. Sexual selection by female choice has been hypothesized as the mechanism driving this behaviour in certain species, as females preferentially mate with males that have fed on these chemicals. This hypothesis is, to date, based on studies of only very few species and its generality is largely untested. We tested the hypothesis on different spatial scales (small cage and seminatural field-cage) using the monophagous fruit fly, Bactrocera cacuminata. This species is known to respond to methyl eugenol (ME), a chemical found in many plant species and one upon which previous studies have focused. Contrary to expectation, no obvious female choice was apparent in selecting ME-fed males over unfed males as measured by the number of matings achieved over time, copulation duration, or time of copulation initiation. However, the number of matings achieved by ME-fed males was significantly greater than unfed males 16 and 32 days after exposure to ME in small cages (but not in a field-cage). This delayed advantage suggests that ME may not influence the pheromone system of B. cacuminata but may have other consequences, acting on some other fitness consequence (e.g., enhancement of physiology or survival) of male exposure to these chemicals. We discuss the ecological and evolutionary implications of our findings to explore alternate hypotheses to explain the patterns of response of dacine fruit flies to specific plant-derived chemicals.