Kinetics and Equilibrium Sorption Studies of 4-Nitrophenol on pyrolyzed and activated oil shale residue

Sorption of the organic pollutant 4-nitrophenol (4-NP) by pyrolyzed and activated Jordanian oil-shale was studied. Pyrolyzed oil shale was prepared using a fluidized bed reactor at 520 °C in the presence of nitrogen. Physical activation was carried out by treating the pyrolyzed oil shale with CO₂ at 830 °C, while chemical activation was achieved by using KOH and ZnCl₂ as impregnating agents. Batch kinetics and isotherm studies were conducted to evaluate the sorption process. Effects of contact time, initial sorbate concentration, sorbent concentration, temperature, pH and inorganic salts (NaCl and KCl) on the sorption process by the different sorbents were considered. Chemically activated oil shale, pretreated with ZnCl₂, gave the highest uptake of 4-NP. The isotherm experimental data fit reasonably well to Langmuir, Freundlich and Redlich-Paterson models. Three kinetic models, namely the Morris-Weber, Lagergren, and Pseudo-Second-Order model (PSOM), were applied to represent the experimental results for both pyrolyzed and ZnCl₂-oil shale sorbents.     

Chemical and Isotopic Characteristics of the Kuroko‐Forming Volcanism

The Miocene northeast Honshu magmatic arc, Japan, formed at a terrestrial continental margin via a stage of spreading in a back‐arc basin (23–17 Ma) followed by multiple stages of submarine rifting (19–13 Ma). The Kuroko deposits formed during this period, with most forming during the youngest rifting stage. The mode of magma eruption changed from submarine basalt lava flows during back‐arc basin spreading to submarine bimodal basalt lava flows and abundant rhyolitic effusive rocks during the rifting stage. The basalts produced during the stage of back‐arc basin spreading are geochemically similar to mid‐ocean ridge basalt, with a depleted Sr–Nd mantle source, whereas those produced during the rifting stage possess arc signatures with an enriched mantle source. The Nb/Zr ratios of the volcanic rocks show an increase over time, indicating a temporal increase in the fertility of the source. The Nb/Zr ratios are similar in basalts and rhyolites from a given rift zone, whereas the Nd isotopic compositions of the rhyolites are less radiogenic than those of the basalts. These data suggest that the rhyolites were derived from a basaltic magma via crystal fractionation and crustal assimilation. The rhyolites associated with the Kuroko deposits are aphyric and have higher concentrations of incompatible elements than do post‐Kuroko quartz‐phyric rhyolites. These observations suggest that the aphyric rhyolite magma was derived from a relatively deep magma chamber with strong fractional crystallization. Almost all of the Kuroko deposits formed in close temporal relation to the aphyric rhyolite indicating a genetic link between the Kuroko deposits and highly differentiated rhyolitic magma.     

Investigations and assessment of the landslide hazards of Fengdu county in the reservoir region of the Three Gorges project on the Yangtze River

The spatial database of landslides in Fengdu County of the reservoir region of the Three Gorges project (TGP) on the Yangtze River was compiled from a variety of different sources including field investigations on landslides, existing catalogues and archives on landslides, reports of meteorological events and human engineering activities that triggered slope failures. The major factors that are found to have affected the slope stabilities are outlined, and an assessment and zonation of landslide hazards of the region is made using an integrated information model, which is divided into destructive, disastrous, likely disastrous and essentially non-disastrous areas from the assessment of landslide hazards. The destructive and disastrous areas are respectively 1.9 and 13.8% of the total region, mostly being nearby townships, highways along the south bank of the Yangtze River and residential quarters along two flanks of the Yangtze River and its distributaries, that will impose direct impact to highway transportation and residential lives, and may effect to some degree the navigation of the Yangtze River, reservoir banks, and building of cities and towns.     

Picophytoplankton and bacterioplankton in the Mississippi River plume and its adjacent waters

Picoplankton abundance and distribution in the Mississippi River plume and its adjacent waters were studied during two cruises in April (high discharge) and October (low discharge) 2000 using flow cytometry. Concentrations of photosynthetic picoplankton,Synechococcus and picoeukaryotes were low in the turbid plume water but high in the coastal waters—i.e., the green waters resulting from mixing of river and oceanic waters. In this region, three types ofSynechococcus, characterized by their phycoerythrin chromophore composition, were found:Synechococcus cells with a low phycourobilin to phycoerythrobilin ratio (PUB:PEB) occurred throughout the region and dominated the totalSymechococcus abundance during both seasons; high PUB:PEB cells, which are the dominant strains in the open or blue ocean, occurred only at the outer shelf stations; and PEB-onlySynechococcus were abundant in most of the surveyed area during april, but were not observed during October.Prochlorococcus cyanobacteria only occurred at the oceanic stations, but extended farther inshore in October compared to April. This was a consequence of the reduced discharge and plume size during October. Picophytoplankton were a less important component of total phytoplankton biomass in the turbid river water and more important in the oligotrophic Gulf water. Seasonally, the contribution of picophytoplankton to total phytoplankton biomass in the surveyed area was higher during low discharge in October than during high discharge in April, even though the spring 2000 river discharge was unusually low and might not present a typical high discharge scenario. The abundance of heterotrophic bacteria was weakly correlated to chlorophylla (chla) concentration, but better correlated to picophytoplankton biomass. A higher proportion of High DNA bacteria occurred in the river-impacted regions during both seasons, with the ratio of High DNA bacteria to Low DNA bacteria significantly higher in April.     

Trends in the frequency of synoptic types in central-southern Chile in the period 1961–2012 using the Jenkinson and Collison synoptic classification

Atmospheric circulation patterns in southern Chile (42° 30′ S) were studied in order to determine and analyse the most characteristic synoptic types and their recent trends, as well as to gain an understanding of how they are associated with low-frequency variability patterns. According to the Jenkinson and Collison (J&C) classification method, a 16-point grid of sea-level pressure data was employed. The findings reveal that some synoptic types show statistically significant trends with a 95% confidence level, positively for anticyclonic westerly hybrids (AW) and advective types for third and fourth quadrant wind flows (W, NW, and N) and negatively for SW and cyclonic hybrids (CS and CSW). A model has been constructed of the linear regression of some weather types with teleconnections that most affect Chile: the undetermined types (U), AW were associated with El Niño or the warm phase of the Pacific Decadal Oscillation (PDO), whereas the cyclonic northerly and cyclonic northeasterly types (CN and CNE) were associated with La Niña or cool phase of the PDO. The weather types associated with Antarctic Oscillation (AAO) in its positive phase are anticyclonic northerly and northeasterly and northerly advection types, while in its negative phase are cyclonic southwesterly and advection types.     

The effect of chemical composition and oxygen fugacity on the electrical conductivity of dry and hydrous garnet at high temperatures and pressures

The in situ electrical conductivity of hydrous garnet samples (Py₂₀Alm₇₆Grs₄–Py₇₃Alm₁₄Grs₁₃) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe₂O₃ + Fe₃O₄, Ni + NiO, Fe + Fe₃O₄, Fe + FeO, and Mo + MoO₂). Experimental results indicate that within a frequency range from 10⁻² to 10⁶ Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py₂₀Alm₇₆Grs₄, Py₃₀Alm₆₇Grs₃, Py₅₆Alm₄₃Grs₁, and Py₇₃Alm₁₄Grs₁₃) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py₇₃Alm₁₄Grs₁₃ garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm³/mol, respectively. The results show that small hopping polarons ( \textFe_\textMg ^· ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH ^· {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.     

Metasomatism and the crystallization of zircon megacrysts in Archaean peridotites from the Lewisian complex,NW Scotland

Zircon megacrysts are locally abundant in 1–40 cm-thick orthopyroxenite veins within peridotite host rocks in the Archaean Lewisian gneiss complex from NW Scotland. The veins formed by metasomatic interaction between the ultramafic host and Si-rich melts are derived from partial melting of the adjacent granulite-facies orthogneisses. The interaction produced abundant orthopyroxene and, within the thicker veins, phlogopite, pargasite and feldspathic bearing assemblages. Two generations of zircon are present with up to 1 cm megacrystic zircon and a later smaller equant population located around the megacryst margins. Patterns of zoning, rare earth element abundance and oxygen isotopic compositions indicate that the megacrysts crystallized from crustal melts, whereas the equant zircon represents new neocryst growth and partial replacement of the megacryst zircon within the ultramafic host. Both zircon types have U–Pb ages of ca. 2464 Ma, broadly contemporaneous with granulite-facies events in the adjacent gneisses. Zircon megacrysts locally form?>?10% of the assemblage and may be associated to zones of localized nucleation or physically concentrated during movement of the siliceous melts. Their unusual size is linked to the suppression of zircon nucleation and increased Zr solubility in the Si-undersaturated melts. The metasomatism between crustal melts and peridotite may represent an analog for processes in the mantle wedge above subducting slabs. As such, the crystallization of abundant zircon in ultramafic host rocks has implications for geochemistry of melts generated in the mantle and the widely reported depletion of high field strength elements in arc magmas.     

银额盆地哈日凹陷油气成藏条件及成藏模式

近年来,银额盆地哈日凹陷的油气勘探呈现出良好的态势,但对于哈日凹陷油气成藏条件相关研究甚少,已不能满足目前油气勘探开发的需求。本研究基于钻录井、地球物理、分析化验等资料,系统分析哈日凹陷油气成藏的烃源岩、储层、圈闭等条件,总结油气成藏条件配置关系,以期为哈日凹陷的后续油气勘探及地质研究提供依据。哈日凹陷主要发育三套烃源岩,其中银根组烃源岩有机质丰度极高,成熟度较低,有机质类型为Ⅰ-Ⅱ1型;巴二段烃源岩有机质丰度较高,成熟-高成熟,有机质类型为Ⅱ1-Ⅱ2型;巴一段烃源岩有机质丰度中等,成熟-高成熟,有机质类型为Ⅱ1-Ⅱ2型。储层类型为砂（砾）岩常规储层、碳酸质泥岩非常规储层和火山岩储层,且均属于特低孔超低渗储层,其中砂、砾岩储层和灰质泥岩储层物性最好,白云岩储层和火成岩储层次之,目前主力油藏主要集中在砂、砾岩储层和灰质泥岩储层这两种类型中。哈日凹陷主要发育两套岩性圈闭,即巴一段砂岩岩性圈闭和巴二段泥岩岩性圈闭,形成了源内（准）连续成藏模式和近源不连续成藏模式。