西江流域环境河水地球化学研究

River is a major component of the global surface water and CO2 cycles. The chemistry of river waters reveals the nature of weathering on a basin-wide scale and helps us understand the exogenic cycles of elements in the continent-river-ocean system. In particular, geochemical investigation of large river gives important information on the biogeochemical cycles of the elements, chemical weathering rates, physical erosion rates and CO2 consumption during the weathering of the rocks within the drainage basin. Its importance has led to a number of detailed geochemical studies on some of the world's large and medium-size river systems. Flowing in the south of China, the Xijiang River is the second largest river in the China with respect to its discharge, after the Yangtze River. Its headwaters drain the YunGui Plateau, where altitude is approximately 2000 meters. Geologically, the carbonate rocks are widely spread in the river drainage basin, which covers an area of about 0.17xl06 km2, i.e., 39% of the whole drainage basin. This study focuses on the chemistry of the Xijiang river system and constitutes the first geochemical investigation into major and trace elements concentrations for both suspended and dissolved loads of this river and its main tributaries, and Sr isotopic composition of the dissolved load is also investigated, in order to determine both chemical weathering and mechanical erosion rates. As compared with the other large rivers of the world, the Xijiang River is characterized by higher major element concentration. The dissolved major cations average 1.17, 0.33, 0.15, and 0.04 mmol I"1 for Ca, Mg, Na, and K, respectively. The total cation concentrations (TZ+) in these rivers vary between 2.2 and 4.4 meq I'1. The high concentration of Ca and Mg, high (Ca+Mg)/(Na+K) ratio (7.9), enormous alkalinity and low dissolved SiO2/HCO3 ratio (0.05) in river waters reveal the importance of carbonate weathering and relatively weak silicate weathering over the river drainage basin. The major elements in river water, such as the alkalis and alkaline-earths, are of different origins: from rain water, silicate weathering, carbonate and evaporite weathering. A mixing model based on mass budget equation is used in this study, which allows the proportions of each element derived from the different source to be calculated. The carbonate weathering is the main source of these elements in the Xijiang drainage basin. The contribution of rainwater, especially for Na, reaches to approximately 50% in some tributaries. Dissolved elemental concentration of the river waters are corrected for rain inputs (mainly oceanic salts), the elemental concentrations derived from the different rock weathering are calculated. As a consequence, silicate, carbonate and total rock weathering rates, together with the consumption rates of atmospheric CO2 by weathering of each of these lithologies have been estimated. They provide specific chemical erosion rates varying between 5.1~17.8 t/km2/yr for silicate, 95.5~157.2 t/km2/yr for carbonate, and 100.6-169.1 t/km2/yr for total rock, respectively. CO2 consumptions by silicate and carbonate weathering approach 13><109and 270.5x10 mol/yr. Mechanical denudation rates deduced from the multi-year average of suspended load concentrations range from 92-874 t/km2/yr. The high denudation rates are mainly attributable to high relief and heavy rainfall, and acid rain is very frequent in the drainage basin, may exceed 50% and the pH value of rainwater may be <4.0, result from SO2 pollution in the atmosphere, results in the dissolution of carbonates and aluminosilicates and hence accelerates the chemical erosion rate. The compositions of minerals and elements of suspended particulate matter are also investigated. The most soluble elements (e.g. Ca, Na, Sr, Mg) are strongly depleted in the suspended phase with respect to upper continent crust, which reflects the high intensity of rock weathering in the drainage basin. Some elements (e.g. Pb, Cu, Co, Cr) show positive anomalies, Pb/Th ratios in suspended matter approach 7 times (Liu Jiang) to 10 times (Nanpan Jiang) the crustal value. The enrichment of these elements in suspended matter reflects the intensity both of anthropogenic pollution and adsorption processes onto particles. The contents of the soluble fraction of rare earth elements (REE) in the river are low, and REE mainly reside in particulate phase. In dissolved phase, the PAAS-normalized distribution patterns show significant HREE enrichment with (La/Yb) SN=0.26~0.94 and Ce depletion with (Ce/Ce*) SN=0.31-0.98, and the most pronounced negative Ce anomalies occur in rivers of high pH. In the suspended phase, the rivers have LREE-enriched patterns relative to PAAS, with (La/Yb) SN=1 -00-1 .40. The results suggest that pH is a major factor controlling both the absolute abundances of REE in solution and the fractionation of REE of dissolved phase. Ce depletion in river waters with high pH values results probably from both preferential removal of Ce onto Fe-Mn oxide coating of particles and CeC^ sedimentation. This process is known to occur in the marine environment and may also occur in high pH rivers. Positive correlations are also observed between La/Yb ratio and DOC, HCO3", PO4", suggesting that colloids and (or) adsorption processes play an important role in the control of these elements.

A dendrochemical study of Pinus sylvestris from Siljansfors Experimental Forest, central Sweden

Inductively coupled plasma mass spectrometry (ICP-MS) was used to investigate changes in trace element concentration in two high resolution sequences of tree rings from central Sweden. Individual annual growth increments from 18002002 to 1930-2002 were sampled from two Scots pine (Pinus sylvestris) trees from the Siljansfors Experimental Forest. The aims of the study were: to test the viability of conventional solution induction ICP-MS as a technique for investigating the multi-elemental chemistry of long tree ring sequences at annual resolution, and, to test this specifically with a view to detecting changes in elemental concentrations of Swedish tree rings contemporary with the major (and relatively proximal) Icelandic eruption of Askja (1875). It was found that despite a time consuming sample preparation process, it was possible to use conventional ICP-MS for multi-elemental analysis of a long sequence of tree rings at annual resolution. Although promising data were produced, no truly conclusive concentration anomaly could be detected in the sequence to indicate the impact of the Askja eruption on environmental chemistry. Overall findings underlined the complexity of the tree/environment interaction and the cautious approach to data interpretation essential for any dendrochemical study. (c) 2006 Elsevier Ltd. All rights reserved.

Glyphosate e adubação foliar com manganês na cultura da soja transgênica

Com base na hipótese de que a soja transgênica tolerante ao glyphosate necessitaria da adição complementar de manganês devido a alterações na absorção e no metabolismo do elemento pelas plantas, objetivou-se estudar a interação da soja transgênica pulverizada com glyphosate e a adubação foliar com manganês. Foi desenvolvido experimento em campo, no ano agrícola 2007/2008, na Fazenda de Ensino, Pesquisa e Produção da UNESP, campus de Jaboticabal, SP. O delineamento experimental foi o de blocos ao acaso, no esquema fatorial 4 x 4, com quatro repetições. Foram avaliados quatro manejos de plantas daninhas [glyphosate (p.c. Roundup Ready) a 0,72 e 1,20 kg ha-1 de equivalente ácido, fluazifop-p-butyl + fomesafen (p.c. Fusiflex) a 0,25 + 0,25 kg ha-1 e testemunha capinada, sem herbicida] e quatro doses (0, 42, 84 e 126 g ha-1) de manganês em aplicação foliar na soja. Os tratamentos estudados não alteraram significativamente a produtividade de grãos, os teores de manganês no solo, a altura e a matéria seca das plantas de soja. Apenas a mistura fluazifop-p-butyl mais fomesafen ocasionou injúrias visuais nas plantas, porém os sintomas ficaram restritos às folhas que interceptaram o jato de pulverização. Para massa de 100 grãos, os herbicidas estudados não diferiram da testemunha; no entanto, as plantas tratadas com 0,72 kg ha-1 de glyphosate apresentaram menor massa de grãos. A aplicação de manganês não influenciou os teores do elemento nas plantas tratadas com glyphosate e naquelas sem herbicida. Portanto, o glyphosate não prejudicou a absorção ou o metabolismo do manganês pela planta, e o crescimento e desenvolvimento das plantas tratadas foram estatisticamente similares aos das não tratadas com herbicidas.

Determination of trace elemental species in periostracum of Cypraea shells

n this work, three Cypraea species (C. talpa, C. tigris and C. zebra) were exhaustively studied. The shells have been separated in the structural layers. The mineralogy, ultra- and micro-structure of each layer were analyzed by Confocal Laser Scanning Microscopy (CLSM), Scanning Electron Microscopy (SEM), X-Ray Diffractometry (XRD) and Raman Spectroscopy (RS). The presence of biologically relevant trace metals (Mn, Co, Fe, Zn, Cr, etc.) has been investigated using Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) as detection tool. A new method has been developed and optimized to extract and analyze the soluble organic matrix (SOM) of the shell. Although the molecular nature of the SOM is not really known, it contains at least large protein fraction, if not only consists of proteins. The extracted matrices were compared between layers and species using Size Exclusion High Performance Liquid Chromatography coupled with Ultra Violet Spectrometry (SE-HPLC-UV), Gel electrophoresis (GE) and protein quantification tests. For the first time to our knowledge the association of trace elements to the protein in the SOM of the shell was studied using hyphenated on line as well as combined off line techniques and validated through inter-comparison tests between the different methods applied. Interesting correlations between the trace element concentration, the microstructure and the protein content were directly and indirectly detected. The metals Cu, Ni, Co and Zn have shown to bind to the SOM extracted from C. talpa, C. tigris and C. zebra shells. Within the conclusions of this work it was demonstrated that these protein-metal-complexes (or metal containing proteins) change from one layer to the other and are different between the three snails analyzed. In addition, the complexes are clearly related only to certain protein fractions of the SOM, and not to the whole SOM observed. These fractions and show not to be very metal-specific (i.e. some of these fractions bind two or three different metals).

Charakterisierung von plasmafunktionalisierten Oberflächen mittels ToF-SIMS und multivariaten Analysemethoden

Die grundlegenden Prinzipien und Möglichkeiten der Oberflächencharakterisierung mittels ToF-SIMS (Flugzeit-Sekundärionen Massenspektrometrie) werden an ausgewählten Beispielen aus einem aktuell laufenden und vom BMBF geförderten Verbundforschungsprojekt (Fkz: 03N8022A) zum Thema Nanofunktionalisierung von Grenzflächen vorgestellt. Ein Schwerpunkt innerhalb des Projekts stellen die nichtgeschlossenen Schichtsysteme dar, die entweder über Domänenstrukturen oder einer definierten Einzelfunktionalisierung neuartige funktionelle Oberflächen bereitstellen. Mithilfe der sehr oberflächensensitiven ToF-SIMS Methode sowie der Möglichkeit einer graphischen Darstellung lateraler Molekülionenverteilungen auf funktionalisierten Oberflächen können Informationen über Struktur und Belegungsdichte der Funktionsschicht gewonnen werden. Die Kombination des ToF-SIMS Experimentes und eines multivariaten Algorithmus (partial least squares, PLS) liefert eine interessante Möglichkeit zur quantitativen und simultanen Bestimmung von Oberflächeneigenschaften (Element- und molekulare Konzentrationen sowie Kontaktwinkelwerte). Da das ToF-SIMS Spektrum einer plasmafunktionalisierten Oberfläche im Allgemeinen eine Vielzahl unterschiedlicher Fragmentsignale enthält, lässt eine einfache eindimensionale Korrelation (z.B. CF3 - Fragmentintensität ßà CF3-Konzentration) den größten Teil der im Spektrum prinzipiell enthaltenen Information unberücksichtigt. Aufgrund der großen Anzahl von atomaren und molekularen Signalen, die repräsentativ für die chemische Struktur der analysierten Oberflächen sind, ist es sinnvoll, diese Fülle von Informationen zur Quantifizierung der Oberflächeneigenschaften (Elementkonzentrationen, Kontaktwinkel etc.) zu verwenden. Zusätzlich ermöglicht diese Methode eine quantitative Bestimmung der Oberflächeneigenschaften auf nur µm-großen Bereichen. Das ist vorteilhaft für Untersuchungen chemisch strukturierter Oberflächen, da die Größe der Strukturierung für viele Anwendungen in einem Bereich von mehreren µm liegt. Anhand eines Beispieles aus dem biologisch-medizinischen Fachgebiet, soll der erfolgreiche Einsatz multivariater Modelle aufgezeigt werden. In diesem Experiment wurden menschlichen Bindegewebs- (Fibroblasten) und Pankreaszellen auf plasmafunktionalisiserten Oberflächen kultiviert, um die Beeinflussung der Funktionalisierung auf das Zellwachstum zu untersuchen. Die plasmabehandelten Oberflächen wurden durch die Verwendung von TEM-Gittern mit µm-großen Öffnungen chemisch strukturiert und das Wachstumsverhalten der Zellen beobachtet. Jedem dieser µm-großen Bereiche können mithilfe der multivariaten Modelle quantitative Größen zugeordnet werden (Konzentrationen und Kontaktwinkelwerte), die zur Interpretation des Wachstumsverhaltens der Zellen beitragen.

Chemical composition of Lake George (New York) iron-manganese nodules and underlying sediment

Lake George, New York, is the site of a new discovery of iron-manganese nodules. These nodules occur at a water depth between 21 and 36 m along a stretch of lake extending for about 5 mi north and south of the Narrows, a constricted island-dotted area which separates the north and south Lake George basins. Nodules occur on or within the uppermost 5 cm of a varved glacial clay. Some areas are solidly floored with a carpet of nodules in areas where active currents keep the nodules exposed. The nodules form around nuclei which consist of clay and less commonly of spore capsules, detrital particles, or bark. By their shape we recognize three types of nodules: spherical, discoidal, and lumps. On X-ray examination all nodules show small goethite peaks; in one nodule the manganese mineral birnessite was identified. Manganese and part of the iron appears to be in X-ray amorphous ferromanganese compounds. The Lake George nodules are enriched in iron with respect to marine nodules but are lower in manganese. They have a higher trace element concentration than nodules from other known freshwater lake occurrences, but a lower concentration than marine nodules.

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.

Composition of sediments, rocks, and ores from the Northern and Equatorial Indian Ocean

The monograph has been written on the base of data obtained from samples and materials collected during the 19-th cruise of RV ''Akademik Vernadsky'' to the Northern and Equatorial Indian Ocean. Geological features of the region (stratigraphy, tectonic structure, lithology, distribution of ore-forming components in bottom sediments, petrography of igneous rocks, etc.) are under consideration. Regularities of trace element concentration in Fe-Mn nodules, nodule distribution in bottom sediments, and engineering-geological properties of sediments within the nodule fields have been studied. Much attention is paid to ocean crust rocks. The wide range of ore mineralization (magnetite, chromite, chalcopyrite, pyrite, pentlandite, and other minerals) has been ascertained.

Chemical profiles in sediment and basalt at DSDP Hole 74-525A

Forty sediment and four basement basalt samples from DSDP Hole 525A, Leg 74, as well as nine basalt samples from southern and offshore Brazil, were subjected to instrumental neutron activation analysis. Thirty-two major, minor, and trace elements were determined. The downcore element concentration profiles and regression analyses show that the rare earth elements (REE) are present in significant amounts in both the carbonate and noncarbonate phases in sediments; Sr is concentrated in the carbonate phase, and most of the other elements determined exist mainly in the noncarbonate phase. The calculated partition coefficients of the REE between the carbonate phase and the free ion concentrations in seawater are high and increase with decreasing REE ionic radii from 3.9 x 10**6 for La to 15 x 10**6 for Lu. Calculations show that the lanthanide concentrations in South Atlantic seawater have not been changed significantly over the past 70 Ma. The Ce anomaly observed in the carbonate phase is a redox indicator of ancient seawater. Study of the Ce anomaly reveals that seawater was anoxic over the Walvis Ridge during the late Campanian. As the gap between South America and West Africa widened and the Walvis Ridge subsided from late Campanian to late Paleocene times, the water circulation of the South Atlantic improved and achieved oxidation conditions about 54 Ma that are similar to present seawater redox conditions in the world oceans. The chemical compositions of the basement rocks correspond to alkalic basalts, not mid-ocean ridge basalts (MORBs). The results add more evidence to support the hypothesis that the Walvis Ridge was formed by a series of volcanos moving over a "hot spot" near the Mid-Atlantic Ridge. From the chemical composition and REE pattern, one 112 Ma old basalt on the Brazilian continental shelf has been identified as an early stage MORB. To date, this is the oldest oceanic tholeiite recovered from the South Atlantic. This direct evidence indicates that the continental split between South America and Africa commenced > 112 Ma.

Isotope ratios of smectites, calcites and whole rocks from DSDP Legs 51 and 52, Atlantic Ocean

Delta180 and 87Sr/86Sr isotopic data from smectites, calcites, and whole rocks, together with published isotopic age determinations, alkali element concentration data and petrographic observations suggest a sequential model of ocean floor alteration. The early stage lasts about 3 m.y. and is characterized by palagonite and smectite formation, and solutions with a large basaltic component, increasing with temperature which varies from 15° to 80° C at DSDP site 418A. Most carbonates are deposited after this stage from solutions with a negligible basaltic Sr component and temperatures of 15° to 40° C. Water of seawater Sr and O isotopic composition is shown to percolate to at least 500 m into the basaltic basement. No evidence was found for continuing exchange of strontium or oxygen after 3 m.y.

Chemical composition of Late Cenozoic volcanic and volcaniclastic deposits from the western Woodlark Basin area, SW Pacific

Tephra fallout layers and volcaniclastic deposits, derived from volcanic sources around and on the Papuan Peninsula, form a substantial part of the Woodlark Basin marine sedimentary succession. Sampling by the Ocean Drilling Program Leg 180 in the western Woodlark Basin provides the opportunity to document the distribution of the volcanically-derived components as well as to evaluate their chronology, chemistry, and isotope compositions in order to gain information on the volcanic sources and original magmatic systems. Glass shards selected from 57 volcanogenic layers within the sampled Pliocene-Pleistocene sedimentary sequence show predominantly rhyolitic compositions, with subordinate basaltic andesites, basaltic trachy-andesites, andesites, trachy-andesites, dacites, and phonolites. It was possible to correlate only a few of the volcanogenic layers between sites using geochemical and age information apparently because of the formation of strongly compartmentalised sedimentary realms on this actively rifting margin. In many cases it was possible to correlate Leg 180 volcanic components with their eruption source areas based on chemical and isotope compositions. Likely sources for a considerable number of the volcanogenic deposits are Moresby and Dawson Strait volcanoes (D'Entrecasteaux Islands region) for high-K calc-alkaline glasses. The Dawson Strait volcanoes appear to represent the source for five peralkaline tephra layers. One basaltic andesitic volcaniclastic layer shows affinities to basaltic andesites from the Woodlark spreading tip and Cheshire Seamount. For other layers, a clear identification of the sources proved impossible, although their isotope and chemical signatures suggest similarities to south-west Pacific subduction volcanism, e.g. New Britain and Tonga- Kermadec island arcs. Volcanic islands in the Trobriand Arc (for example, Woodlark Island Amphlett Islands and/or Egum Atoll) are probable sources for several volcaniclastic layers with ages between 1.5 to 3 Ma. The Lusancay Islands can be excluded as a source for the volcanogenic layers found during Leg 180. Generally, the volcanogenic layers indicate much calc-alkaline rhyolitic volcanism in eastern Papua since 3.8 Ma. Starting at 135 ka, however, peralkaline tephra layers appear. This geochemical change in source characteristics might reflect the onset of a change in geotectonic regime, from crustal subduction to spreading, affecting the D'Entrecasteaux Islands region. Initial 143Nd/144Nd ratios as low as 0.5121 and 0.5127 for two of the tephra layers are interpreted as indicating that D'Entrecasteaux Islands volcanism younger than 2.9 Ma occasionally interacted with the Late Archean basement, possibly reflecting the mobilisation of the deep continental crust during active rift propagation.

Mineralogy and geochemistry of volcanic ash at Japan Trench from DSDP Legs 87 and 57

Volcanogenic sediments were obtained from Site 584, located on the midslope of the Japan Trench. Occurrences of volcanic ash in the diatomaceous mudstones increase within sediments dated 6-3 Ma. The frequency pattern and the sediment accumulation rate obtained at Site 584 are similar to those of Site 440 and to those of Sites 438 and 439, located on the upper slope basin. Explosive volcanism increased during the Pliocene and late Miocene in relation to the intrusion of Tertiary granites and uplift of the Tohoku Arc (northeastern Japan Arc). Hygromagmaphile element concentration shows that the glass does not belong to a unique series, and a comparison with Nankai Trough data distinguishes at least two different evolutionary lines.