Biochemical evolution III: Polymerization on organophilic silica-rich surfaces, crystal–chemical modeling, formation of first cells, and geological clues

Catalysis at organophilic silica-rich surfaces of zeolites and feldspars might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and other geological sources. Crystal–chemical modeling yielded packings for amino acids neatly encapsulated in 10-ring channels of the molecular sieve silicalite-ZSM-5-(mutinaite). Calculation of binding and activation energies for catalytic assembly into polymers is progressing for a chemical composition with one catalytic Al–OH site per 25 neutral Si tetrahedral sites. Internal channel intersections and external terminations provide special stereochemical features suitable for complex organic species. Polymer migration along nano/micrometer channels of ancient weathered feldspars, plus exploitation of phosphorus and various transition metals in entrapped apatite and other microminerals, might have generated complexes of replicating catalytic biomolecules, leading to primitive cellular organisms. The first cell wall might have been an internal mineral surface, from which the cell developed a protective biological cap emerging into a nutrient-rich “soup.” Ultimately, the biological cap might have expanded into a complete cell wall, allowing mobility and colonization of energy-rich challenging environments. Electron microscopy of honeycomb channels inside weathered feldspars of the Shap granite (northwest England) has revealed modern bacteria, perhaps indicative of Archean ones. All known early rocks were metamorphosed too highly during geologic time to permit simple survival of large-pore zeolites, honeycombed feldspar, and encapsulated species. Possible microscopic clues to the proposed mineral adsorbents/catalysts are discussed for planning of systematic study of black cherts from weakly metamorphosed Archaean sediments.

Dinâmica do fósforo no solo em função da adição de ácidos orgânicos de baixa massa molar

A baixa eficiência da adubação fosfatada em solos altamente intemperizados é devido, entre outros fatores, à adsorção do fósforo (P) à superfície das argilas silicatadas do tipo 1:1 e, principalmente, dos (hidr)óxidos de Fe e de Al. Manejos do solo que induzem a solubilização de formas de P indisponíveis para as plantas têm sido intensamente estudados nos últimos anos. Uma tentativa de aumentar a concentração de P disponível na solução do solo para sua absorção pelas plantas é a mobilização de P por ânions de ácidos orgânicos de baixa massa molar (AOBMM). Ânions derivados de AOBMM exsudados pelas raízes de plantas ou excretados por microrganismos são associados com algumas condições de rizosfera como deficiência de P e fitotoxidez de Al e interagem com o solo de forma a aumentar a biodisponibilidade de P. Dependendo dos atributos do solo, do grau de dissociação, das propriedades e do número de grupos carboxílicos dos ânions orgânicos, o P pode ser mobilizado do solo principalmente devido à dissolução complexométrica de minerais e à adsorção competitiva dos grupos funcionais carboxílicos e fosfato nos sítios de superfície coloidais. A capacidade dos ânions citrato, malato e oxalato em mobilizar P de amostras de um Neossolo Quartzarênico típico (RQ) e de um Latossolo Vermelho ácrico (LVwf) foi avaliada por meio de um estudo de lixiviação de ânions em colunas. Devido a não detecção de P nos efluentes das colunas com LVwf, foi realizado outro estudo em colunas, no qual somente citrato foi lixiviado, mas num volume maior, e as alterações das formas de P nas amostras desse solo induzidas pela lixiviação de citrato foram identificadas por espectroscopia de absorção de raios-X na borda K do fósforo (X-ray absorption near edge structure -XANES - spectroscopy). A capacidade dos ânions de AOBMM em solubilizar P foi mais dependente do teor de P disponível e de outros atributos do solo que do número de grupos funcionais carboxílicos dos ânions orgânicos. Somente o oxalato mobilizou P do RQ, enquanto todos os ânions de AOBMM foram capazes de mobilizar P do LVwf. Quando baixos volumes de solução contendo ânions de AOBMM foram lixiviados no solo, além do aumento do pH, a mobilização de P foi acompanhada pela mobilização de Al no RQ (pH água = 5), e pela mobilização de Ca no LVwf (pH água = 5.6), o que indica solubilização de P pela complexação de Al, Ca, ou Fe, de fosfatos insolúveis, ou pela inibição da precipitação de P com esses metais. Ao lixiviar um volume maior de citrato no LVwf, o P também não foi detectado nos efluentes das colunas, mas houve lixiviação intensa de Al e Fe, bem como mudanças nas proporções de formas de P no solo caracterizadas pelos espectros XANES. Embora tenhamos encontrado indícios da ação dos principais mecanismos de solubilização de P (dissolução complexométrica de minerais e troca de ligantes entre grupos funcionais carboxílicos e P adsorvido ao solo), os ânions de AOBMM mostraram pouco potencial de efetivamente aumentar a biodisponibilidade de P.

Investigação de aquífero fraturado para entendimento de fluxo e transporte de contaminantes clorados: estudo de caso em Valinhos, SP

Casos de contaminação de aquíferos fraturados são bastante complexos, tendo em vista a heterogeneidade das redes de fraturas, e no geral, sua investigação demanda a utilização de técnicas pouco usuais, como por exemplo o imageamento acústico e a perfilagem de velocidade de fluxo de água. Na área de estudo, localizada em Valinhos/SP, o uso inadequado de solventes organoclorados no passado ocasionou a contaminação do aquífero raso em duas áreas, e o aparecimento de concentrações no aquifero profundo levaram a condução do atual trabalho, que teve como principal objetivo a elaboração de um modelo conceitual de fluxo de água e transporte de contaminantes no aquífero cristalino. Previamente à investigação do aquífero fraturado, foi realizada uma análise de trabalhos existentes, incluindo a interpretação de lineamentos, levantamentos geológicos além de perfilagens geofísicas de superfície. Em cada área investigada, foi realizada a perfuração de um poço profundo e aplicadas as técnicas de perfilagens de raios gama, cáliper, flowmeter, imageamento acústico, além da filmagem do poço e realização de ensaios hidráulicos nos dois pontos perfurados. Para caracterização química do aquífero fraturado, foram realizadas coletas de água subterrânea em intervalos selecionados com a utilização de obturadores pneumáticos. As cargas hidráulicas medidas durante a amostragem também auxiliaram no entendimento da direção do fluxo de água. O aquífero cristalino é formado por rochas gnáissicas e se encontra bastante fraturado e intemperizado, principalmente na porção superficial da rocha (até aproximadamente 65,0 m) onde as maiores velocidades de fluxo de água também foram observadas. A rocha sã possui uma menor densidade de fraturas e predominância de minerais mais claros. As fraturas de baixo a médio angulo de mergulho (Grupo 1) são as mais frequentes em ambas as perfurações e possuem direção principal N-S a NE-SW. São observadas, no geral, exercendo grande influência sobre o fluxo de água, principalmente na porção alterada do gnaisse. Fraturas com ângulo elevado de mergulho, classificadas como Grupo 2 (paralelas à foliação) e Grupo 3 (direção NW à W), são também observadas ao longo de toda a perfuração estabelecendo a conexão hidráulica entre as fraturas do Grupo 1. Em menor proporção, são ainda verificadas fraturas com ângulos de mergulho >40 ° pertencente aos Grupos 4 (NE-SW), 5 (E-W), 6 (NW-SE) e 7 (E-W). O fluxo de água subterrânea se mostrou descendente na porção superior da rocha alterada e ascendente na porção mais profunda, possivelmente direcionando a água subterrânea para a região de transição da rocha mais alterada para a rocha sã (entre 61 a 65 m de profundidade). Apesar do fluxo ascendente em profundidade, o bombeamento de poços tubulares existentes no entorno ao longo dos anos, favoreceu a migração dos contaminantes para porções mais profundas. Os contaminantes observados no poço tubular P6 possuem maior semelhança com os contaminantes observados na Área 2, e ambos estão localizados entre lineamentos NW-SE, indicando uma possível influência dos lineamentos no controle sobre o fluxo de água. No entanto, para entendimento do transporte dos contaminantes em área, é necessário um adensamento da rede de monitoramento, levando em consideração a heterogeneidade do meio e as incertezas relacionadas à extrapolação dos dados para áreas não investigadas.

Triassic redbeds in the Malaguide Complex (Betic Cordillera — Spain): petrography, geochemistry and geodynamic implications

Sandstone petrography and mudstone mineralogy and geochemistry of Triassic mudstones and sandstones from continental redbeds of the Malaguide Complex (Betic Cordillera, southern Spain) provide useful information on provenance, palaeoclimate and geodynamics during the early stages of the Pangea break-up, and on their diagenetic evolution. The sandstones are quartzarenites to sub-litharenites, with minor lithic fragments and rare feldspars. The mudstone samples show a PAAS like elemental distribution. The samples likely record recycling processes from their metasedimentary basement rocks that significantly affected the weathering indices, and monitors cumulative effects, including a first cycle of weathering at the source rocks. Sandstone composition and chemical–mineralogical features of mudstones record a provenance derived from continental block and recycled orogen that were weathered under warm and episodically wet climate. Source areas were located towards the east of the present-day Malaguide outcrops, and were formed by fairly silicic rock types, made up mainly of Palaezoic metasedimentary rocks, similar to those of the Paleozoic underlying series, with subordinate contributions from magmatic–metamorphic sources, and a rare supply from mafic metavolcanic rocks. Clay-mineral distribution of mudstones is dominated by illite and illite/smectite mixed-layer that result from differences in provenance, weathering, and burial/temperature history. Illite crystallinity values, illitization of kaolinite, occurrence of typical authigenic minerals and apatite fission-track studies, coupled with a subsidence analysis of the whole Malaguide succession suggest burial depths of at least 4–6 km with temperatures of 140–160 °C, typical of the burial diagenetic stage, and confirm the Middle Miocene exhumation of the Betic Internal Domain tectonic stack topped by the Malaguide Complex.

Inflation-Targeting, Flexible Exchange Rates and Macroeconomic Performance since the Great Recession. CEPS Working Document No. 394, March 2014

Has inflation targeting (IT) conferred benefits in terms of economic growth on countries that followed this particular monetary policy strategy during the crisis period 2007-12? This paper answers this question in the affirmative. Countries with an IT monetary regime with flexible exchange rates weathered the crisis much better than countries with other monetary regimes, predominantly countries with fixed exchange rates. Part of this difference in growth performance reflects differences in export performance during the initial years of the crisis, which in turn can be explained by real exchange rate depreciations. However, IT seems also to confer other benefits on the countries above and beyond the effects from currency depreciation.

Catchment characteristics and soil and water chemistry of the San Francisco basin and subbasins, Ecuador

In this study, the Mean Transit Time and Mixing Model Analysis methods are combined to unravel the runoff generation process of the San Francisco River basin (73.5 km**2) situated on the Amazonian side of the Cordillera Real in the southernmost Andes of Ecuador. The montane basin is covered with cloud forest, sub-páramo, pasture and ferns. Nested sampling was applied for the collection of streamwater samples and discharge measurements in the main tributaries and outlet of the basin, and for the collection of soil and rock water samples. Weekly to biweekly water grab samples were taken at all stations in the period April 2007-November 2008. Hydrometric data, Mean Transit Time and Mixing Model Analysis allowed preliminary evaluation of the processes controlling the runoff in the San Francisco River basin. Results suggest that flow during dry conditions mainly consists of lateral flow through the C-horizon and cracks in the top weathered bedrock layer, and that all subcatchments have an important contribution of this deep water to runoff, no matter whether pristine or deforested. During normal to low precipitation intensities, when antecedent soil moisture conditions favour water infiltration, vertical flow paths to deeper soil horizons with subsequent lateral subsurface flow contribute most to streamflow. Under wet conditions in forested catchments, streamflow is controlled by near surface lateral flow through the organic horizon. Exceptionally, saturation excess overland flow occurs. By absence of the litter layer in pasture, streamflow under wet conditions originates from the A horizon, and overland flow.

Chemical and mineral compositions of sediments from ODP Site 127-797

In order to reconstruct past variations in the aeolian dust (Kosa) contribution to the Japan Sea, and to establish a direct link between terrestrial and marine climatic records, we have applied statistical procedures to distinguish and quantify detrital subcomponents within the detrital fraction of the late Quaternary hemipelagic sediments in the Japan Sea. Q-mode factor analysis with varimax and oblique rotation of the factors followed by multiple-regression analysis between mineral composition and factor loadings was conducted using six ''detrital'' elements. Four detrital subcomponents were defined, which are attributed to Kosa derived from ''typical'' loess, Kosa from ''weathered'' loess, and fine and coarse arc-derived detritus, respectively, based on comparisons with the chemical and mineral compositions of probable source materials. Using these detrital subcomponents, the variation in Kosa fraction was reconstructed for the last 200 ky. The results reveal millennial-scale as well as glacial-interglacial scale variations in Kosa contribution. Especially, millennial-scale variability of Kosa contribution suggests the presence of high frequency variation in summer monsoon precipitation in the central to east Asia during the last 200 ky.

Isotopic composition of carbonates from the Logachev Hydrothermal Field, MAR 14°45'N

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45' N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a d44/40Ca_HydEnd of -0.95+/-0.07 per mil relative to seawater (SW) and a 87Sr/86Sr isotope ratio of 0.7034(4). We demonstrate that d44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a d44/40Ca of -1.17+/-0.04 per mil (SW) for the host-rocks in the reaction zone and -1.45+/-0.05 per mil (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed d44/40Ca for Bulk Earth of -0.92+/-0.18 per mil (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta 61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta 62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about D44/40Ca = -0.5 per mil relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average d44/40Ca of -1.54+/-0.08 per mil (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.

Sedimentology and geochemistry of ODP Site 184-1144

We analyzed sediment from Ocean Drilling Program (ODP) Site 1144 in the northern South China Sea to examine the weathering response of SE Asia to the strengthening of the East Asian Monsoon (EAM) since 14 ka. Our high-resolution record highlights the decoupling between continental chemical weathering, physical erosion and summer monsoon intensity. Mass accumulation rates, Ti/Ca, K/Rb, hematite/goethite and 87Sr/86Sr show sharp excursions from 11 to 8 ka, peaking at 10 ka. Clay minerals show a shorter-lived response with a higher kaolinite/(illite + chlorite) ratio at 10.7-9.5 ka. However, not all proxies show a clear response to environmental changes. Magnetic susceptibility rises sharply between 12 and 11 ka. Grain-size becomes finer from 14 to 10 ka and then coarsens until ~7 ka, but is probably controlled by bottom current flow and sealevel. Sr and Nd isotopes show that material is dominantly eroded from Taiwan with a lesser flux from Luzon, while clay mineralogy suggests that the primary sources during the Early Holocene were reworked via the shelf in the Taiwan Strait, rather than directly from Taiwan. Erosion was enhanced during monsoon strengthening and caused reworking of chemically weathered Pleistocene sediment largely from the now flooded Taiwan Strait, which was transgressed by ~8 ka, cutting off supply to the deep-water slope. None of the proxies shows an erosional response lasting until ~6 ka, when speleothem oxygen isotope records indicate the start of monsoon weakening. Although more weathered sediments were deposited from 11 to 8 ka when the monsoon was strong these are reworked and represent more weathering during the last glacial maximum (LGM) when the summer monsoon was weaker but the shelves were exposed.

Geochemistry of marine sediments of the world's major subduction zones

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world's major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them. Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, epsilon-Hf = 1.55 * epsiolon-Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (epsilon-Hf = 1.36 * epsilonNd + 2.89; Vervoort et al., 1999, doi:10.1016/S0012-821X(99)00047-3) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array. In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.

(Table 19, page 199) Minor constituents of one of the San Clemente iron concretions and its metallic core

The chemical and mineralogical composition of pelagic sediments from the East Pacific Ocean has been determined with the aim of defining the ultimate sources and the mechanisms of formation of the solid phases. The distribution of elements between sea-water, the pore solution and the various solid components of the sediments permits interpretations of the variations in time and space of the gross chemical composition of pelagic clays. For example, manganese, present in sea-water in a divalent form, is apparently oxidized at the sediment-water interface to tetravalent species which subsequently become a part of the group of ferromanganese oxide minerals which are found in the marine environment. It is suggested the rate of manganese accumulation in sediments is some function of the length of time the sediment surface is in contact with sea-water. The contribution of chemical species from the different geospheres is considered. The quantitative importance of pelagic clays in the major sedimentary cycle is studied on the basis of the distribution of the weathered igneous rock products between continental and pelagic deposits and sea-water. These analyses of a wide variety of pelagic clays allow a reformulation of the geochemical balance and it is concluded that pelagic clays account for approximately 13 per cent of the total mass of sediments produced over geologic time.