Geochemical composition of surface snow, ice and debris from glaciers in Norway, Nepal and New Zealand

Alpine glacier samples were collected in four contrasting regions to measure supraglacial dust and debris geochemical composition. A total of 70 surface glacier ice, snow and debris samples were collected in 2009 and 2010 in Svalbard, Norway, Nepal and New Zealand. Trace elemental abundances in snow and ice samples were measured via inductively coupled plasma mass spectrometry (ICP-MS). Supraglacial debris mineral, bulk oxide and trace element composition were determined via X-ray diffraction (XRD) and X-ray fluorescence spectroscopy (XRF). A total of 45 elements and 10 oxide compound abundances are reported. The uniform data collection procedure, analytical measurement methods and geochemical comparison techniques are used to evaluate supraglacial dust and debris composition variability in the contrasting glacier study regions. Elemental abundances revealed sea salt aerosol and metal enrichment in Svalbard, low levels of crustal dust and marine influences to southern Norway, high crustal dust and anthropogenic enrichment in the Khumbu Himalayas, and sulfur and metals attributed to quiescent degassing and volcanic activity in northern New Zealand. Rare earth element and Al/Ti elemental ratios demonstrated distinct provenance of particulates in each study region. Ca/S elemental ratio data showed seasonal denudation in Svalbard and Norway. Ablation season atmospheric particulate transport trajectories were mapped in each of the study regions and suggest provenance pathways. The in situ data presented provides first order glacier surface geochemical variability as measured from four diverse alpine glacier regions. This geochemical surface glacier data is relevant to glaciologic ablation rate understanding as well as satellite atmospheric and land-surface mapping techniques currently in development.

Documentation, profile descriptions and analytical results of loes profiles from Bavaria, southern Germany

This study investigates the landscape evolution and soil development in the loess area near Regensburg between approximately 6000-2000 yr BP (radiocarbon years), Eastern Bavaria. The focus is on the question how man and climate influenced landscape evolution and what their relative significance was. The theoretical background concerning the factors that controlled prehistoric soil erosion in Middle Europe is summarized with respect to rainfall intensity and distribution, pedogenesis, Pleistocene relief, and prehistoric farming. Colluvial deposits , flood loams, and soils were studied at ten different and representative sites that served as archives of their respective palaeoenvironments. Geomorphological, sedimentological, and pedological methods were applied. According to the findings presented here, there was a high asynchronity of landscape evolution in the investigation area, which was due to prehistoric land-use patterns. Prehistoric land use and settlement caused highly difIerenciated phases of morphodynamic activity and stability in time and space. These are documented at the single catenas ofeach site. In general, Pleistocene relief was substantially lowered. At the same time smaller landforms such as dells and minor asymmetric valleys filled up and strongly transformed. However, there were short phases at many sites, forming short lived linear erosion features ('Runsen'), resulting from exceptional rainfalls. These forms are results of single events without showing regional trends. Generally, the onset of the sedimentation of colluvial deposits took place much earlier (usually 3500 yr BP (radiocarbon) and younger) than the formation of flood loams. Thus, the deposition of flood loams in the Kleine Laaber river valley started mainly as a consequence of iron age farming only at around 2500 yr BP (radiocarbon). A cascade system explains the different ages of colluvial deposits and flood loams: as a result of prehistoric land use, dells and other minor Pleistocene landforms were filled with colluvial sediments. After the filling of these primary sediment traps , eroded material was transported into flood plains, thus forming flood loams. But at the moment we cannot quantify the extent ofprehistoric soil erosion in the investigation area. The three factors that controlled the prehistoric Iandscapc evolution in the Ioess area near Regensburg are as follows: 1. The transformation from a natural to a prehistoric cultural landscape was the most important factor: A landscape with stable relief was changed into a highly morphodynamic one with soil erosion as the dominant process of this change. 2. The sediment traps of the pre-anthropogenic relief determined where the material originated from soil erosion was deposited: either sedimentation took place on the slopes or the filled sediment traps of the slopes rendered flood loam formation possible. Climatic influence of any importance can only be documented as the result of land use in connection with singular and/or statistic events of heavy rainfalls. Without human impact, no significant change in the Holocene landscape would have been possible.

Fe-Mn nodules and host sediments from the Gulf of Finland

Distributions of major and trace elements in ferromanganese nodules, which are buried or exposed on the sea floor and in host sediments, were studied in ten concretion/sediment pairs by various physical and chemical methods. It was established that, in addition to Fe and Mn, a limited number of major and trace elements (P, Ca, Sr, Ba, Mo, Co, Zn, Ni, As, Pb, Sb, Tl, U, W, Y, and Ga) is accumulated with variable degree of intensity (relative to sediments) in the nodules. The maximal content of Mn in the nodules is 100 times higher than in the host sediments, whereas for all other elements listed above these ratios vary from more than one to 10-20. Manganese and, to a lesser extent, Ba and Sr are concentrated in the buried concretions. Other elements are primarily concentrated in concretions exposed on the sea floor. The occurrence mode of the concretions and compositional data on interstitial water suggest that metals in the concretions derive from seawater and suspended particulates, in addition to sediments. Burial of concretions in the sediment pile is accompanied by alteration of their composition, accumulation of Mn (relative to Fe), and loss of several associated metals.

Mineral and chemical compositions of hydrothermal ores and sediments from the Menez Gwen Hydrothermal Field, Mid-Atlantic Ridge

Mineralogy and geochemistry of sulfide-bearing rocks and ores discovered within the Menez Gwen Hydrothermal Field are studied. Samples were taken during Cruise 49 of R/V Akademik Mstislav Keldysh of the p.p. Shirshov Institute of Oceanology. Mineral composition of rocks and ores were studied by traditional methods of optical microscopy, scanning electron microscopy (CAMSCAN), and microprobe analysis (EPMA SX-50). Contents of trace elements were determined by laser ablation inductively coupled plasma - mass spectrometry (LA-ICP-MS). Zn-Cu ore comprises zonal sulfide chimney intergrowths. Numerous Se-rich copper ore fragments occur in volcanomictic layered gritstones and/or barite slabs. Mineral composition, zonality and association of trace elements in ore are typical of black smokers formed at the basalt base near the Azores Triple Junction in the MAR. Obtained results make it possible to reconstruct formation history of the Menez Gwen Hydrothermal Field into the high-temperature (Cu-Se association in ore clasts), medium-temperature (Zn-Cu-As association in ore), and recent (Ba-SiO2 association) stages.

Geochemical analysis of surface sediments along the Portuguese Margin

Twenty-nine surface samples from the Portuguese shelf, recovered offshore from the mouths of the Ave, Douro, Lis and Mira rivers, were analysed using ICP-OES for selected major and trace elements, after total dissolution. Organic carbon, carbonate content and grain size were also determined. Five evaluation tools have been applied in order to compare the three study areas and to evaluate sediment geochemistry and other sediment compositional variability in the acquired samples: (1) empirical methods based on comparison with standard reference criteria, e.g. the NOAA sediment quality guidelines, (2) normalisation ratios using a grain-size proxy element, (3) "Gradient Method", plotting contaminant vs. organic matter or Al, (4) definition of a regional geochemical baseline from a compiled database, and (5) enrichment factors. The evaluation of element and component associations indicates differences related both to the onshore drainage areas and to the environmental shelf setting. Despite the considerable variability in total metal contents indicated by our results, the sediment metal composition is largely of natural origin. Metal enrichments observed in the Mira area are associated with the drainage of mineralised areas rich in Cu, Pb, Zn, Fe and Mn. The near absence of human impact on shelf sediments, despite the vicinity to urban areas with high industrialisation levels, such as the Ave-Douro and Lis areas, is attributed to effective trapping in the estuaries and coastal zones, as well dilution with less contaminated sediments shelf sediments and removal with fine fractions due to grain-size sorting. The character of the contaminated sediments transported to these shelf areas is further influenced by grain-size sorting as well as by dilution with less contaminated marine sediments. The results obtained individually by the different methods complement each other and allow more specific interpretations.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.

Paleo-sea surface temperature calculations in the equatorial east Atlantic

We present two ~270 kyr paleo-sea surface temperature (SST) records from the Equatorial Divergence and the South Equatorial Current derived from Mg/Ca ratios in the planktic foraminifer Globigerinoides sacculifer. The present study suggests that the magnesium signature of G. sacculifer provides a seasonal SST estimate from the upper ~50 m of the water column generated during upwelling in austral low-latitude fall/winter. Common to both down-core records is a glacial-interglacial amplitude of ~3°-3.5°C for the last climatic changes and lower Holocene and glacial oxygen isotope stage 2 temperatures compared with interglacial stage 5.5 and glacial stage 6 temperatures, respectively. The comparison to published SST estimates from alkenones, oxygen isotopes, and foraminiferal transfer function from the same core material pinpoints discrepancies and conformities between methods.

Chemical composition of ferromanganese concretions and host bottom sediments from the Black Sea

Ferromanganese concretions spread out on the bottom of the shallow northwest part of the Black Sea are mainly represented by Fe and Mn nodules on shells and substituted worm tubes. Element composition of these formations was measured by methods of chemical, atomic absorbtion, neutron activation, and ICP-MS analyses. It was established that Fe and Mn contents and Mn/Fe ratio in the concretions varied considerably and which controlled occurrence of several associated metals and minor elements; some of them have not been studied in Black Sea concretions before.

Incorporation of Mg and Sr in calcite of cultured benthic foraminifera (Heterostegina depressa and Ammonia tepida) and seawater carbonate chemistry, 2010

We investigated the effect of the calcium concentration in seawater and thereby the calcite saturation state (omega) on the magnesium and strontium incorporation into benthic foraminiferal calcite under laboratory conditions. For this purpose individuals of the shallow-water species Heterostegina depressa (precipitating high-Mg calcite, symbiont-bearing) and Ammonia tepida (low-Mg calcite, symbiont-barren) were cultured in media under a range of [Ca2+], but similar Mg/Ca ratios. Trace element/Ca ratios of newly formed calcite were analysed with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) and normalized to the seawater elemental composition using the equation DTE=(TE/Cacalcite)/(TE/Caseawater). The culturing study shows that DMg of A. tepida significantly decreases with increasing omega at a gradient of -4.3x10-5 per omega unit. The DSr value of A. tepida does not change with omega, suggesting that fossil Sr/Ca in this species may be a potential tool to reconstruct past variations in seawater Sr/Ca. Conversely, DMg of H. depressa shows only a minor decrease with increasing omega, while DSr increases considerably with omega at a gradient of 0.009 per omega unit. The different responses to seawater chemistry of the two species may be explained by a difference in the calcification pathway that is, at the same time, responsible for the variation in the total Mg incorporation between the two species. Since the Mg/Ca ratio in H. depressa is 50-100 times higher than that of A. tepida, it is suggested that the latter exhibits a mechanism that decreases the Mg/Ca ratio of the calcification fluid, while the high-Mg calcite forming species may not have this physiological tool. If the dependency of Mg incorporation on seawater [Ca2+] is also valid for deep-sea benthic foraminifera typically used for paleostudies, the higher Ca concentrations in the past may potentially bias temperature reconstructions to a considerable degree. For instance, 25 Myr ago Mg/Ca ratios in A. tepida would have been 0.2 mmol/mol lower than today, due to the 1.5 times higher [Ca2+] of seawater, which in turn would lead to a temperature underestimation of more than 2 °C.

Estudios de especiación de arsénico y acumulación de metales en muestras de interés medioambiental : Arsenic speciation and metal accumulation studies in environmental samples

Se ha estudiado la determinación de especies de arsénico y de contenidos totales de arsénico y metales pesados, específicamente cadmio, cromo, cobre, níquel, plomo y cinc, en muestras de interés medioambiental por su elevada capacidad acumuladora de metales, concretamente algas marinas comestibles y plantas terrestres procedentes de suelos contaminados por la actividad minera. La determinación de contenidos totales se ha llevado a cabo mediante espectrometría de emisión atómica con plasma de acoplamiento inductivo (ICP‐AES), así como por espectrometría de fluorescencia atómica con generación de hidruros (HG‐AFS), para bajos contenidos de arsénico. Las muestras fueron mineralizadas en medio ácido y calentamiento en horno de microondas. Los métodos fueron validados a través de su aplicación a materiales de referencia de matriz similar a la de las muestras, certificados en contenidos totales de los elementos seleccionados. Los resultados obtenidos mostraron su elevada capacidad de bioabsorción, especialmente en relación a los elevados contenidos de arsénico encontrados en algunas especies de algas pardas (Phaeophytas). En las plantas, se calcularon los factores de translocación, acumulación y biodisponibilidad de los elementos estudiados, permitiendo identificar a la especie Corrigiola telephiifolia como posible acumuladora de plomo e hiperacumuladora de arsénico. La determinación de especies de arsénico hidrosolubles en las muestras objeto de estudio, se llevó a cabo por cromatografía líquida de alta eficacia (HPLC) acoplado a ICP‐AES, HG‐ICP‐AES y HG‐AFS, incluyendo una etapa previa de foto‐oxidación. Los métodos desarrollados, mediante intercambio aniónico y catiónico, permitieron la diferenciación de hasta once especies de arsénico. Para el análisis de las muestras, fue necesaria la optimización de métodos de extracción, seleccionándose la extracción asistida por microondas (MAE) con agua desionizada. Asimismo, se realizaron estudios de estabilidad de arsénico total y de las especies hidrosolubles presentes en las algas, tanto sobre la muestra sólida como en sus extractos acuosos, evaluando las condiciones de almacenamiento adecuadas. En el caso de las plantas, la aplicación del diseño factorial de experimentos permitió optimizar el método de extracción y diferenciar entre las especies de arsénico presentes en forma de iones sencillos de mayor movilidad y el arsénico más fuertemente enlazado a componentes estructurales. Los resultados obtenidos permitieron identificar la presencia de arseniato (As(V)) y arsenito (As(III)) en las plantas, así como de ácido monometilarsónico (MMA) y óxido de trimetilarsina (TMAO) en algunas especies. En la mayoría de las algas se encontraron especies tóxicas, tanto mayoritarias (arseniato) como minoritarias (ácido dimetilarsínico (DMA)), así como hasta cuatro arsenoazúcares. Los resultados obtenidos y su estudio a través de la legislación vigente, mostraron la necesidad de desarrollar una reglamentación específica para el control de este tipo de alimentos. La determinación de especies de arsénico liposolubles en las muestras de algas se llevó a cabo mediante HPLC, en modo fase inversa, acoplado a espectrometría de masas con plasma de acoplamiento inductivo (ICP‐MS) y con ionización por electrospray (ESI‐MS), permitiendo la elucidación estructural de estos compuestos a través de la determinación de sus masas moleculares. Para ello, fue necesaria la puesta a punto de métodos extracción y purificación de los extractos. La metodología desarrollada permitió identificar hasta catorce especies de arsénico liposolubles en las algas, tres de ellas correspondientes a hidrocarburos que contienen arsénico, y once a arsenofosfolípidos, además de dos especies desconocidas. Las masas moleculares de las especies identificadas fueron confirmadas mediante cromatografía de gases acoplada a espectrometría de masas (GC‐MS) y espectrometría de masas de alta resolución (HR‐MS). ABSTRACT The determination of arsenic species and total arsenic and heavy metal contents (cadmium, chromium, cooper, nickel, lead and zinc) in environmental samples, with high metal accumulator capacity, has been studied. The samples studied were edible marine algae and terrestrial plants from soils polluted by mining activities. The determination of total element contents was performed by inductively coupled plasma atomic emission spectrometry (ICP‐AES), as well as by hydride generation atomic fluorescence spectrometry (HG‐AFS) for low arsenic contents. The samples studied were digested in an acidic medium by heating in a microwave oven. The digestion methods were validated against reference materials, with matrix similar to sample matrix and certified in total contents of the elements studied. The results showed the high biosorption capacity of the samples studied, especially regarding the high arsenic contents in some species of brown algae (Phaeophyta division). In terrestrial plants, the translocation, accumulation and bioavailability factors of the elements studied were calculated. Thus, the plant species Corrigiola telephiifolia was identified as possible lead accumulator and arsenic hyperaccumulator. The determination of water‐soluble arsenic species in the samples studied was carried out by high performance liquid chromatography (HPLC) coupled to ICP‐AES, HG‐ICP‐AES and HG‐AFS, including a prior photo‐oxidation step. The chromatographic methods developed, by anion and cation exchange, allowed us to differentiate up to eleven arsenic species. The sample analysis required the optimization of extraction methods, choosing the microwave assisted extraction (MAE) with deionized water. On the other hand, the stability of total arsenic and water‐soluble arsenic species in algae, both in the solid samples and in the water extracts, was studied, assessing the suitable storage conditions. In the case of plant samples, the application of a multivariate experimental design allowed us to optimize the extraction method and differentiate between the arsenic species present as simple ions of higher mobility and the arsenic more strongly bound to structural components. The presence of arsenite (As(III)) and arsenate (As(V)) was identified in plant samples, as well as monomethylarsonic acid (MMA) and trimethylarsine oxide (TMAO) in some cases. Regarding algae, toxic arsenic species were found in most of them, both As(V) and dimethylarsinic acid (DMA), as well as up to four arsenosugars. These results were discussed according to the current legislation, showing the need to develop specific regulations to control this kind of food products. The determination of lipid‐soluble arsenic species in alga samples was performed by reversed‐phase HPLC coupled to inductively coupled plasma and electrospray mass spectrometry (ICP‐MS and ESI‐MS), in order to establish the structure of these compounds by determining the corresponding molecular masses. For this purpose, it was necessary to develop an extraction method, as well as a clean‐up method of the extracts. The method developed permitted the identification of fourteen lipid‐soluble arsenic compounds in algae, corresponding to three arsenic‐hydrocarbons and eleven arsenosugarphospholipids, as well as two unknown compounds. Accurate mass measurements of the identified compounds were performed by gas chromatography coupled to mass spectrometry (GC‐MS) and high resolution mass spectrometry (HR‐MS).

Puesta a punto de métodos de análisis de combustibles basados en la espectrometría atómica

El presente proyecto tiene como objeto la puesta a punto de métodos de análisis de combustibles basados en la espectrometría atómica, centrándose en un equipo de absorción atómica que, como su nombre indica, funciona bajo el principio de la absorción atómica y un equipo ICP que trabaja por plasma acoplado inductivamente y que se rige bajo el principio espectrométrico de la emisión atómica. La finalidad de la puesta a punto de ambos métodos es llevar un control de calidad periódico sobre los combustibles. Se pondrán a punto dos métodos normalizados de ensayos, uno bajo la norma UNE EN 16135 para la determinación del contenido de manganeso en gasolinas; otro bajo la norma EN 16576 para determinar el contenido de manganeso y de hierro en gasóleos de automoción. La puesta a punto de ambos métodos tiene un procedimiento asociado que se puede resumir en cuatro pasos: lectura de la norma, creación del método en el software informático con el que trabaja el equipo, calibración del mismo y realización del estudio de exactitud del método. Abstract The aim of this project is to tune up analytical methods based on the principle of the atomic spectrometry, focusing on testing equipment which works under the principle of atomic absorption and Inductively Coupled Plasma (ICP) equipment governed under the principle of atomic emission. The purpose of tuning up both methods is to perform a quality control on fuels. Two different standard methods will be developed: One under the standard UNE EN 16135 for measuring the content of manganese in gasolines; the other one under the standard EN 16576 for the determination of manganese and iron content in middle distillate fuels. Tune up of both methods procedure can be summarized in four steps: Reading the standard, creation of the method on the computer software associated to the equipment, calibration of the equipment and completion of accuracy study.

Geoquímica multielementar de sedimentos de corrente no Estado de São Paulo: abordagem através da análise estatística multivariada

Este trabalho apresenta resultados geoquímicos multielementares de sedimentos de corrente no estado de São Paulo, obtidos através do projeto institucional do Serviço Geológico do Brasil denominado \"Levantamento Geoquímico de Baixa Densidade no Brasil\". Dados analíticos de 1422 amostras de sedimento de corrente obtidos por ICP-MS (Inductively Coupled Plasma Mass Spectrometry), para 32 elementos químicos (Al, Ba, Be, Ca, Ce, Co, Cr, Cs, Cu, Fe, Ga, Hf, K, La, Mg, Mn, Mo, Nb, Ni, P, Pb, Rb, Sc, Sn, Sr, Th, Ti, U, V, Y, Zn e Zr), foram processadas e abordadas através da análise estatística uni e multivariada. Os resultados do tratamento dos dados através de técnicas estatísticas univariadas forneceram os valores de background geoquímico (teor de fundo) dos 32 elementos para todo estado de São Paulo. A análise georreferenciada das distribuições geoquímicas unielementares evidenciaram a compartimentação geológica da área. As duas principais províncias geológicas do estado de São Paulo, Bacia do Paraná e Complexo Cristalino, se destacam claramente na maioria das distribuições geoquímicas. Unidades geológicas de maior expressão, como a Formação Serra Geral e o Grupo Bauru também foram claramente destacadas. Outras feições geoquímicas indicaram possíveis áreas contaminadas e unidades geológicas não cartografadas. Os resultados da aplicação de métodos estatísticos multivariados aos dados geoquímicos com 24 variáveis (Al, Ba, Ce, Co, Cr, Cs, Cu, Fe, Ga, La, Mn, Nb, Ni, Pb, Rb, Sc, Sr, Th, Ti, U, V, Y, Zn e Zr) permitiram definir as principais assinaturas e associações geoquímicas existentes em todo estado de São Paulo e correlacioná-las aos principais domínios litológicos. A análise de agrupamentos em modo Q forneceu oito grupos de amostras geoquimicamente correlacionáveis, que georreferenciadas reproduziram os principais compartimentos geológicos do estado: Complexo Cristalino, Grupos Itararé e Passa Dois, Formação Serra Geral e Grupos Bauru e Caiuá. A análise discriminante multigrupos comprovou, estatisticamente, a classificação dos grupos formados pela análise de agrupamentos e forneceu as principais variáveis discriminantes: Fe, Co, Sc, V e Cu. A análise de componentes principais, abordada em conjunto com a análise fatorial pelo método de rotação varimax, forneceram os principais fatores multivariados e suas respectivas associações elementares. O georreferenciamento dos valores de escores fatoriais multivariados delimitaram as áreas onde as associações elementares ocorrem e forneceram mapas multivariados para todo o estado. Por fim, conclui-se que os métodos estatísticos aplicados são indispensáveis no tratamento, apresentação e interpretação de dados geoquímicos. Ademais, com base em uma visão integrada dos resultados obtidos, este trabalho recomenda: (1) a execução dos levantamentos geoquímicos de baixa densidade em todo país em caráter de prioridade, pois são altamente eficazes na definição de backgrounds regionais e delimitação de províncias geoquímicas com interesse metalogenético e ambiental; (2) a execução do mapeamento geológico contínuo em escala adequada (maiores que 1:100.000) em áreas que apontam para possíveis existências de unidades não cartografadas nos mapas geológicos atuais.

Nitrogen isotopic composition and chemical composition of altered oceanic crust from ODP Legs 129 and 185

Knowledge of the subduction input flux of nitrogen (N) in altered oceanic crust (AOC) is critical in any attempt to mass-balance N across arc-trench systems on a global or individual-margin basis. We have employed sealed-tube, carrier-gas-based methods to examine the N concentrations and isotopic compositions of AOC. Analyses of 53 AOC samples recovered on DSDP/ODP legs from the North and South Pacific, the North Atlantic, and the Antarctic oceans (with larger numbers of samples from Site 801 outboard of the Mariana trench and Site 1149 outboard of the Izu trench), and 14 composites for the AOC sections at Site 801, give N concentrations of 1.3 to 18.2 ppm and d15N_air of -11.6? to +8.3?, indicating significant N enrichment probably during the early stages of hydrothermal alteration of the oceanic basalts. The N-d15N modeling for samples from Sites 801 and 1149 (n=39) shows that the secondary N may come from (1) the sedimentary N in the intercalated sediments and possibly overlying sediments via fluid-sediment/rock interaction, and (2) degassed mantle N2 in seawater via alteration-related abiotic reduction processes. For all Site 801 samples, weak correlation of N and K2O contents indicates that the siting of N in potassic alteration phases strongly depends on N availability and is possibly influenced by highly heterogeneous temperature and redox conditions during hydrothermal alteration. The upper 470-m AOC recovered by ODP Legs 129 and 185 delivers approximately 800 kg/km N annually into the Mariana margin. If the remaining less-altered oceanic crust (assuming 6.5 km, mostly dikes and gabbros) has MORB-like N of 1.5 ppm, the entire oceanic crust transfers 5100 kg/km N annually into that trench. This N input flux is twice as large as the annual N input of 2500 kg/km in seafloor sediments subducting into the same margin, demonstrating that the N input in oceanic crust, and its isotopic consequences, must be considered in any assessment of convergent margin N flux.

Sediment geochemistry of ODP Holes 206-1256B and 206-1256C

We measured the chemical composition of 100 samples from the 250-m sediment sequence retrieved from Ocean Drilling Program Site 1256 in the Guatemala Basin using a newly developed microwave-assisted acid digestion protocol followed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) analysis. We compared these data gathered onshore to the results from the flux fusion prepared samples analyzed by shipboard ICP-AES during the leg and published in the Leg 206 Initial Reports volume, as well as to 35 randomly selected samples that were prepared by flux fusion at Boston University and analyzed by ICP-AES. Comparison of the newly developed acid digestion protocol to shore-based flux fusion demonstrates that the microwave-assisted acid technique yields a complete digestion, and because this procedure includes boric acid, it is safe for use with HF acid as boric acid neutralizes excess HF. The precision for nearly all elements in shore-based acid digestions is better than 3% of the measured values, including for elements such as Ni, Cr, and V, which are typically difficult to measure in biogenic-rich sediments. The shore-based flux fusions, while better than shipboard reported precision values (as expected), has precision better than 3% of their respective measured values for all major elements (Si, Al, Ti, Fe, Mn, Ca, Mg, Na, and K) and several trace elements (Ba and Sr). Results for P, Cr, Ni, V, Sc, and Zr are better than 5% of their measured values. Not only does the newly developed acid digestion provide better analytical results than the typical flux fusion method, the shore-based acid procedure also exhibits downhole lithologic and chemical characteristics similar to the shipboard flux fusion prepared results. These results confirm that the current shipboard methods are adequate for first-order geochemical interpretations and that the microwave-assisted acid digestion holds great potential to be the primary technique of preparing sediments on future Integrated Ocean Drilling Program expeditions.