Characterisation of early Archaean chemical sediments by trace element signatures

Rare earth element (REE) plus yttrium (Y) patterns of modem seawater have characteristic features that can be used as chemical fingerprints. Reliable proxies for marine REE + Y chemistry have been demonstrated from a large geological time span, including Archaean banded iron formation (BIF), stromatolitic limestone, Phanerozoic reef carbonate and Holocene microbialite. Here we present new REE + Y data for two distinct suites of early Archaean (ca. 3.7-3.8 Ga) metamorphosed rocks from southern West Greenland, whose interrelationships, if any, have been much debated in recent literature. The first suite comprises mangetite-quartz BIF, magnetite-carbonate BIF and banded magnetite-rich quartz rock, mostly from the Isua Greenstone Belt (IGB). The REE + Y patterns, particularly diagnostic anomalies (Ce/Ce*, Pr/Pr*), are closely related to those of published seawater proxies. The second suite includes banded quartz-pyroxene-amphibole +/- garnet rocks with minor magnetite from the so-called Akilia Association enclaves (in early Archaean granitoid gneisses) of the coastal region, some 150 km southwest of the IGB. Rocks of this type from one much publicised and highly debated locality (the island of Akilia) have been identified by some workers [Nature 384 (1996) 55; Geochim. Cosmochim. Acta 61 (1997) 2475] as BIF-facies, and their C-13-depleted signature in trace graphite interpreted as a proxy for earliest life on Earth. However, REE + Y patterns of the Akilia Association suite (except for one probably genuine magnetite-rich BIF from Ugpik) are inconsistent with a seawater origin. We agree with published geological and geochemical (including REE) work [Science 296 (2002) 1448] that most of the analysed Akilia rocks are not chemical sediments, and that C-isotopes in such rocks therefore cannot be used as biological proxies. Application of the REE + Y discriminant for the above two rock suites has been facilitated in this study by the use of MC-ICP technique which yields a more complete and precise REE + Y spectrum than was available in many previous studies. (C) 2004 Elsevier B.V. All rights reserved.

Iron isotope and chemical compositions of sediments and basalts drilled seaward of the Mariana Trench

The purpose of this work is to study the mobility and budget of Fe isotopes in the oceanic crust and in particular during low-temperature interaction of seawater with oceanic basalt. We carried out this investigation using samples from Ocean Drilling Program (ODP) Site 801C drilled during Leg 129 and Leg 185 in Jurassic Pacific oceanic crust seaward of the Mariana Trench. The site comprises approximately 450 m of sediment overlying a section of 500 m of basalt, which includes intercalated pelagic and chemical sediments in the upper basaltic units and two low-temperature (10-30°C) ocherous Si-Fe hydrothermal deposits. Fe was chemically separated from 70 selected samples, and 57Fe/54Fe ratios were measured by MC-ICP-MS Isoprobe. The isotopic ratios were measured relative to an internal standard solution and are reported relative to the international Fe-standard IRMM-14. Based on duplicate measurements of natural samples, an external precision of 0.2? (2 sigma) has been obtained. The results indicate that the deep-sea sediment section has a restricted range of d57Fe, which is close to the igneous rock value. In contrast, large variations are observed in the basaltic section with positive d57Fe values (up to 2.05?) for highly altered basalts and negative values (down to ?2.49?) for the associated alteration products and hydrothermal deposits. Secondary Fe-minerals, such as Fe-oxyhydroxides or Fe-bearing clays (celadonite and saponite), have highly variable d57Fe values that have been interpreted as resulting from the partial oxidation of Fe(2+) leached during basalt alteration and precipitated as Fe(3+)-rich minerals. In contrast, altered basalts at Site 801C, which are depleted in Fe (up to 80%), display an increase in d57Fe values relative to fresh values, which suggest a preferential leaching of light iron during alteration. The apparent fractionation factor between dissolved Fe(2+) and Fe remaining in the mineral is from 0.5? to 1.3? and may be consistent with a kinetic isotope fractionation where light Fe is stripped from the minerals. Alternatively, the formation of secondary clays minerals, such as celadonite during basalt alteration may incorporate preferentially the heavy Fe isotopes, resulting in the loss of light Fe isotopes in the fluids. Because microbial processes within the oceanic crust are of potential importance in controlling rates of chemical reactions, Fe redox state and Fe-isotope fractionation, we evaluated the possible effect of this deep biosphere on Fe-isotope signatures. The Fe-isotope systematics presented in this study suggest that, even though iron behavior during seafloor weathering may be mediated by microbes, such as iron-oxidizers, d57Fe variations of more than 4? may also be explained by abiotic processes. Further laboratory experiments are now required to distinguish between various processes of Fe-isotope fractionation during seafloor weathering.

Radiogenic Hf isotopic composition of continental eolian dust in Pacific Ocean sediments

The inorganic silicate fraction extracted from bulk pelagic sediments from the North Pacific Ocean is eolian dust. It monitors the composition of continental crust exposed to erosion in Asia. 176Lu/177Hf ratios of modern dust are subchondritic between 0.011 and 0.016 but slightly elevated with respect to immature sediments. Modern dust samples display a large range in Hf isotopic composition (IC), -4.70 < epsilon-Hf < +16.45, which encompasses that observed for the time series of DSDP cores 885/886 and piston core LL44-GPC3 extending back to the late Cretaceous. Hafnium and neodymium isotopic results are consistent with a dominantly binary mixture of dust contributed from island arc volcanic material and dust from central Asia. The Hf-Nd isotopic correlation for all modern dust samples, epsilon-Hf= =0.78 epsilon-Nd = +5.66 (n =22, R**2 =0.79), is flatter than those reported so far for terrestrial reservoirs. Moreover, the variability in epsilon-Hf of Asian dust exceeds that predicted on the basis of corresponding epsilon-Nd values (34.76 epsilon-Hf < +2.5; -10.96< epsilon-Nd <-10.1). This is attributed to: (1) the fixing of an important unradiogenic fraction of Hf in zircons, balanced by radiogenic Hf that is mobile in the erosional cycle, (2) the elevated Lu/Hf ratio in chemical sediments which, given time, results in a Hf signature that is radiogenic compared with Hf expected from its corresponding Nd isotopic components, and (3) the possibility that diagenetic resetting of marine sediments may incorporate a significant radiogenic Hf component into diagenetically grown minerals such as illite. Together, these processes may explain the variability and more radiogenic character of Hf isotopes when compared to the Nd isotopic signatures of Asian dust. The Hf-Nd isotope time series of eolian dust are consistent with the results of modern dust except two samples that have extremely radiogenic Hf for their Nd (epsilon-Hf =+8.6 and +10.3, epsilon-Nd =39.5 and 39.8). These data may point to a source contribution of dust unresolved by Nd and Pb isotopes. The Hf IC of eolian dust input to the oceans may be more variable and more radiogenic than previously anticipated. The Hf signature of Pacific seawater, however, has varied little over the past 20 Myr, especially across the drastic increase of eolian dust flux from Asia around 3.5 Ma. Therefore, continental contributions to seawater Hf appear to be riverine rather than eolian. Current predictions regarding the relative proportions of source components to seawater Hf must account for the presence of a variable and radiogenic continental component. Data on the IC and flux of river-dissolved Hf to the oceans are urgently required to better estimate contributions to seawater Hf. This then would permit the use of Hf isotopes as a monitor of past changes in erosion.

Geologia e geoquimica do complexo cambaizinho, sao gabriel - RS

Mapeamentos geológicos feitos pelo autor na região do Arroio Cambaizinho - são Gabriel/RS, resultaram na definição do Complexo Cambaizinho, representado pelas seqüências meta-sedimentar e máfica-ultramáfica, intimamente associadas ao longo de toda a extensão da associação supracrustal. A seqüência meta-se dimentar é constitu1da por gnaisses quartzo-feldspáticos dominan tes, anfibolitos bandados e quartzitos subordinados, derivados de sedimentos areno-pelítico-carbonatados estruturados, de forma ritmica em ambiente subaquoso. Niveis composicionais de ocorrência restrita contendo estaurolita, definem o grau metamórfico (médio) para esta região. Intercalações de serpentinitos, xistos magnesianos variados e anfibolitos a granulação fina, na forma de camadas e/ou lentes interestratificadas nos meta-sedimentos indicam suas derivações a partir de derrames e/ou intrusões , ígneas de pequena profundidade de composição básica-ultrabásica. Este juntamente com níveis de sedimentos qu1micos intercalados e corpos de gabros, constituem a seqüência máfica-ultramáfica. O complexo, representa o segmento norte de um cintu rão supracrustal polideformado de forma geométrica aproximadamente linear, com orientação NNE, que se extende desde a localidade de Passo do Ivo, situado mais a sul, até a região objeto deste trabalho. Quatro fases de deformação dúcteis foram das para a área, estando as duas primeiras (Dl e D2) identifica associadas xx aos eventos metamórficos regionais Ml e M2. O metamorfismo mais antigo (Ml), assinalado por paragêneses diagnósticas em metapelitos alcançou o fácies anfibolito (zona da estaurolita), estando representado em outras litologias pela ocorrência de olivina metamórfica em paragênese com tremolita e/ou talco (meta-serpentinitos) e hornblenda mais oligoclásio/andesina em meta-básicas. O M2, mais jovem, atingiu o fácies xistos verdes, cujas assembléias mineralógicas se associam à foliação S2, de distribuição ir regular ao longo do cinturão. As condições fisicas de Ml foram de média P/T, similares às do metamorfismo Dalradiano. Intrusões graniticas na forma de lâminas (corpos ta bulares) durante a segunda fase de deformação D2, datados pelo mé todo Rb/Sr em 661 :: 29 Ma e agrupados sob a denominação de Granatóides Sanga do Jobim, fornecem idades mínimas para o complexo. Os vários grupos composiciconais da seqüência máfic~ -ultramáfica, individualizados com base em critérios petrográf~ cos e conteúdo de elementos maiores correspondem a: serpentinitos e olivina-talco ultramafitos (cumulados komatilticos); xis tos magnesianos à talco e clorita e anfibólio xistos (komatiitos); clorita-hornblenda xistos (basaltos komatiiticos), litos e metagabros (basaltos e gabros tolelticos). anfibo Estes vários tipos litológicos foram originados através de diferentes graus de fusão parcial do manto como indicado pelo hiato composicional de MgO (11 à 17%) e os diferentes padrões de ETR existentes entre os anfibolitos/metagabros (toleitos) e os serpentinitos/xistos magnesianos (komatiltos).As variações composicionais no interior de cada grupo, foram controladas pelo fracionamento (acumulação ou extração) de olivina e pouco ortopiroxênio (serpentinitos e olivina-talco ultramafitos)clinopiroxênios (clorita e anfibólios xistos, clorita hornblenda xistos), clinopiroxênio e plagioclásio (anfibolitos e metagabros). As abundâncias e os padrões de ERTL (elementos terras raras leves) enriquecidos, juntamente com os baixos valores das razões A1203/Ti02 e CaO/Ti02 das amostras de xistos magnesiinos das camadas A e B sugerem derivações deste material a partir de baixas percentagens de fusão de um manto enriquecido em mentos incompatíveis. As anomalias negativas de Ce e Eu na ele maio ria das rochas da seqüência máfica-ultramáfica indicam que protólitos ígneossofreram alterações em ambiente submarino.

Caracterização petrográfica das zonas de alteração hidrotermais no alvo Arex, do depósito polimetálico de Aripuanã, MT

The Roosevelt-Domain Aripuanã that by Filho et al 2004 is characterized by a metavolcanic sedimentary sequence, containing acidic to interemediary metavolcanic rocks and clastic and chemical sediments, deformed and metamorphosed at low grade, with U-Pb age of 1.743 +- 4 Ma, (by Granito Zé do Torno), and circumscribed bodies of granites late to post-orogenic (Aripuanã)...

Geochemistry of late Archaean stromatolites from Zimbabwe: evidence for microbial life in restricted epicontinental seas

We report comprehensive trace element and Sr-isotope data for microbial carbonates from the Archaean Mushandike limestone, Masvingo Greenstone Belt, Zimbabwe. The stromatolites have very coherent REE + Y patterns and share the essential shale-normalised characteristics of other Archaean marine precipitates (positive La and Gd anomalies, absence of a negative Cc anomaly and a strongly superchondritic Y/Ho ratio). Mixing models constrain the maximum amount of shale contamination to 0.25-1% and calculated detritus-free carbonate REE + Y systematics require precipitation from seawater. In terms of light-REE over heavy-REE depletion, however, the studied samples are very different from all other known Archaean marine precipitates. In shale-normalised plots, the Mushandike samples yield a negative slope. A very restricted, regional input source of the dissolved load is indicated because normalisation with locally occurring tonalite gneiss REE + Y data yields a pattern closely resembling typical shale-normalised Archaean marine chemical sediments. The disappearance of a negative Eu anomaly when patterns are normalised with local tonalite gneiss strengthens this interpretation. Sr-isotope ratios are strongly correlated with trace element contents and ratios, which explains the modest scatter in Sr-isotope ratios as representing (minor) clastic contamination. Importantly, even the least contaminated samples have very radiogenic initial Sr-87/Sr-86 ratios (0.7184) implying Sr input from an ancient high Rb/Sr source, such as the early Archaean gneisses of south-central Zimbabwe. A local ancient (3.5-3.8 Ga) source is also indicated by previously published Pb-isotope datasets for the Mushandike stromatolites. This is entirely compatible with the occurrence of 3.7-3.8 Ga zircons in quartzites and metapelites from comparably old greenstone belts within less than 150 km of the studied locality. Comparison of the Pb-isotope ratios of the Mushandike stromatolites with 2.7 and 2.6 Ga old stromatolites from the neighbouring, Belingwe Greenstone Belt demonstrates differences in initial isotope composition that relate to the extent of exchange with the open ocean. The development of numerous basins on old continental crust, with water masses variably restricted from the open ocean. suggests a lack of strong vertical topography on this late Archaean craton. (C) 2004 Elsevier B.V. All rights reserved.

An assessment of chemical contaminants in the marine sediments of southwest Puerto Rico

This report summarizes the results of a characterization of chemical contaminants in the sediments in southwest Puerto Rico. The report is part of a project to integrate various analytical specialties to assess linkages between chemical contaminants and the condition of coral reefs. In this phase of the project, over 120 chemical contaminants were analyzed in sediments collected, including a number of organic (e.g., hydrocarbons), inorganic (e.g., metals), and biological (bacterial) compounds/analytes. The report also provides a preliminary analysis of the association between sediment contaminants and coral species richness. Overall, the levels of chemical contaminants in the study area between Guanica Bay and the town of La Parguera were fairly low. At most of the sites sampled, particularly adjacent to the town of La Parguera, concentrations of organic and inorganic contaminants were below the median values from NOAA’s National Status and Trends Program, which monitors the Nation’s coastal and estuarine waters for chemical contaminants. Elevated levels of a number of contaminant classes were seen at the two sites sampled within Guanica Bay. An initial analysis of modeled PAH (hydrocarbon) data and coral species richness (reef building species) indicated a strong negative correlation between the presence of PAHs in the sediments and coral species richness. Additional work is needed to assess possible reasons for this observed pattern. (PDF contains 126 pages).

Magnitude and extent of chemical contamination and toxicity in sediments of Biscayne Bay and vicinity

The toxicity of sediments in Biscayne Bay and many adjoining tributaries was determined as part of a bioeffects assessments program managed by NOAA’s National Status and Trends Program. The objectives of the survey were to determine: (1) the incidence and degree of toxicity of sediments throughout the study area; (2) the spatial patterns (or gradients) in chemical contamination and toxicity, if any, throughout the study area; (3) the spatial extent of chemical contamination and toxicity; and (4) the statistical relationships between measures of toxicity and concentrations of chemicals in the sediments. The survey was designed to characterize sediment quality throughout the greater Biscayne Bay area. Surficial sediment samples were collected during 1995 and 1996 from 226 randomly-chosen locations throughout nine major regions. Laboratory toxicity tests were performed as indicators of potential ecotoxicological effects in sediments. A battery of tests was performed to generate information from different phases (components) of the sediments. Tests were selected to represent a range in toxicological endpoints from acute to chronic sublethal responses. Toxicological tests were conducted to measure: reduced survival of adult amphipods exposed to solid-phase sediments; impaired fertilization success and abnormal morphological development in gametes and embryos, respectively, of sea urchins exposed to pore waters; reduced metabolic activity of a marine bioluminescent bacteria exposed to organic solvent extracts; induction of a cytochrome P-450 reporter gene system in exposures to solvent extracts; and reduced reproductive success in marine copepods exposed to solid-phase sediments. Contamination and toxicity were most severe in several peripheral canals and tributaries, including the lower Miami River, adjoining the main axis of the bay. In the open basins of the bay, chemical concentrations and toxicity generally were higher in areas north of the Rickenbacker Causeway than south of it. Sediments from the main basins of the bay generally were less toxic than those from the adjoining tributaries and canals. The different toxicity tests, however, indicated differences in severity, incidence, spatial patterns, and spatial extent in toxicity. The most sensitive test among those performed on all samples, a bioassay of normal morphological development of sea urchin embryos, indicated toxicity was pervasive throughout the entire study area. The least sensitive test, an acute bioassay performed with a benthic amphipod, indicated toxicity was restricted to a very small percentage of the area. Both the degree and spatial extent of chemical contamination and toxicity in this study area were similar to or less severe than those observed in many other areas in the U.S. The spatial extent of toxicity in all four tests performed throughout the bay were comparable to the “national averages” calculated by NOAA from previous surveys conducted in a similar manner. Several trace metals occurred in concentrations in excess of those expected in reference sediments. Mixtures of substances, including pesticides, petroleum constituents, trace metals, and ammonia, were associated statistically with the measures of toxicity. Substances most elevated in concentration relative to numerical guidelines and associated with toxicity included polychlorinated biphenyls, DDT pesticides, polynuclear aromatic hydrocarbons, hexachloro cyclohexanes, lead, and mercury. These (and other) substances occurred in concentrations greater than effects-based guidelines in the samples that were most toxic in one or more of the tests. (PDF contains 180 pages)

An assessment of chemical contaminants, toxicity and benthic infauna in sediments from the St. Thomas East End Reserves (STEER)

This report contains a chemical and biological characterization of sediments from the St. Thomas East End Reserves (STEER) in St. Thomas, U.S. Virgin Islands (USVI). The STEER Management Plan (published in 2011) identified chemical contaminants and habitat loss as high or very high threats and called for a characterization of chemical contaminants as well as an assessment of their effects on natural resources. The baseline information contained in this report on chemical contaminants, toxicity and benthic infaunal community composition can be used to assess current conditions, as well as the efficacy of future restoration activities. In this phase of the project, 185 chemical contaminants, including a number of organic (e.g., hydrocarbons and pesticides) and inorganic (e.g., metals) compounds, were analyzed from 24 sites in the STEER. Sediments were also analyzed using a series of toxicity bioassays, including amphipod mortality, sea urchin fertilization impairment, and the cytochrome P450 Human Reporter Gene System (HRGS), along with a characterization of the benthic infaunal community. Higher levels of chemical contaminants were found in Mangrove Lagoon and Benner Bay in the western portion of the study area than in the eastern area. The concentrations of polychlorinated biphenyls (PCBs), DDT (dichlorodiphenyltrichloroethane), chlordane, zinc, copper, lead and mercury were above a NOAA sediment quality guideline at one or more sites, indicating impacts may be present in more sensitive species or life stages in the benthic environment. Copper at one site in Benner Bay, however, was above a NOAA guideline indicating that effects on benthic organisms were likely. The antifoulant boat hull ingredient tributyltin, or TBT, was found at the third highest concentration in the history of NOAA’s National Status and Trends (NS&T) Program, which monitors the Nation’s coastal and estuarine waters for chemical contaminants and bioeffects. Unfortunately, there do not appear to be any established sediment quality guidelines for TBT. Results of the bioassays indicated significant sediment toxicity in Mangrove Lagoon and Benner Bay using multiple tests. The benthic infaunal communities in Mangrove Lagoon and Benner Bay appeared severely diminished.

Chemical forms of copper, zinc, lead and cadmium in sediments of the northern part of the Red Sea, Egypt

Total concentrations and chemical forms of heavy metals in sediment samples from the Gulf of Suez and the northern part of the Red Sea, collected during January 2003, were determined by atomic absorption spectrometry. Maximum concentrations of 49.56, 65.42, 33.52 and 3.52 µg/g were recorded for total Cu, Zn, Pb and Cd respectively at Adabiya location. These may reflect the high contribution of land-based activities in the northern part of the Gulf. Also, high percentages of heavy metals were found in the residual fraction (Cu=78.61, Zn=77.10 and Pb=66.80%) while a high percentage of Cd was found in the carbonate fraction (45.82%). However, few or negligible percentages were recorded in the exchangeable fractions (Cu=0.51, Zn=1.57 and Pb=1.74%). Concentration of Cd in the exchangeable fraction was too low to be detected.

Late cenozoic chemical weathering and environmental changes recorded in the Co Ngoin sediments, central Qinghai-Tibet Plateau

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