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.     

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.     

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.     

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。     

Cognate clinopyroxene from Paleogene mantle xenolith-bearing basanite lavas (East Serbia, SE Europe): the role of dissolution of mantle orthopyroxene

The study focuses on clinopyroxene from mantle xenolith-bearing East Serbian basanites and suggests that dissolution of mantle orthopyroxene played an important role in at least some stages of the crystallization of these alkaline magmas. Five compositional types of clinopyroxene are distinguished, some of them having different textural forms: megacrysts (Type-A), green/colourless-cored phenocrysts (Type-B), overgrowths and sieve-textured cores (Type-C), rims and matrix clinopyroxene (Type-D), and clinopyroxene from the reaction rims around orthopyroxene xenocrysts (Type-E). Type-A is high-Al diopside that probably crystallized at near-liquidus conditions either directly from the host basanite or from compositionally similar magmas in previous magmatic episodes. Type-B cores show high ^VIAl/^IVAl≥1 and low Mg# of mostly <75 and are interpreted as typical xenocrysts. Type-C, D and E are interpreted as typical cognate clinopyroxene. Type-D has Mg#<78, Al₂O₃?=?6–13?wt.%, TiO₂?=?1.5–4.5?wt.%, and Na₂O?=?0.4–0.8?wt.% and compositionally similar clinopyroxene is calculated by MELTS as a phase in equilibrium with the last 30?% of melt starting from the average host lava composition. Type-C has Mg#?=?72–89, Al₂O₃?=?4.5–9.5?wt.%, TiO₂?=?1–2.5?wt.%, Na₂O?=?0.35–1?wt.% and Cr₂O₃?=?0.1–1.5?wt.%. This clinopyroxene has some compositional similarities to Type-E occurring exclusively around mantle orthopyroxene. Cr/Al vs Al/Ti and Cr/Al vs Na/Ti plots revealed that Type-C clinopyroxene can crystallize from a mixture of the host basanite magma and 2–20?wt.% mantle orthopyroxene. Sieve-textured Type-C crystals show characteristics of experimentally produced skeletal clinopyroxene formed by orthopyroxene dissolution suggesting that crystallization of Type-C was both texturally and compositionally controlled by orthopyroxene breakdown. According to FeO/MgO^cpx/melt modelling the first clinopyroxene precipitating from the host basanite was Type-A (T?~?1250?°C, p?~?1.5?GPa). Dissolution of orthopyroxene produced decreasing FeO/MgO^melt and crystallization of Type-E and sieve-textured Type-C clinopyroxene (0.3–0.8?GPa and 1200–1050?°C). The melt composition gradually shifted towards higher FeO/MgO^melt ratios precipitating more evolved Type-C and Type-D approaching near-solidus conditions (<0.3?GPa; ~950?°C).     

Dauphiné twinning and texture memory in polycrystalline quartz. Part 3: texture memory during phase transformation

Samples of quartz-bearing rocks were heated above the α (trigonal)–β (hexagonal) phase transformation of quartz (625–950°C) to explore changes in preferred orientation patterns. Textures were measured both in situ and ex situ with neutron, synchrotron X-ray and electron backscatter diffraction. The trigonal–hexagonal phase transformation does not change the orientation of c- and a-axes, but positive and negative rhombs become equal in the hexagonal β-phase. In naturally deformed quartzites measured by neutron diffraction a perfect texture memory was observed, i.e. crystals returned to the same trigonal orientation they started from, with no evidence of twin boundaries. Samples measured by electron back-scattered diffraction on surfaces show considerable twinning and memory loss after the phase transformation. In experimentally deformed quartz rocks, where twinning was induced mechanically before heating, the orientation memory is lost. A mechanical model can explain the memory loss but so far it does not account for the persistence of the memory in quartzites. Stresses imposed by neighboring grains remain a likely cause of texture memory in this mineral with a very high elastic anisotropy. If stresses are imposed experimentally the internal stresses are released during the phase transformation and the material returns to its original state prior to deformation. Similarly, on surfaces there are no tractions and thus texture memory is partially lost.     

A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions

Diffusion of Al in synthetic forsterite was studied at atmospheric pressure from 1100 to 1500 °C in air along [100] with activities of SiO₂, MgO and Al₂O₃ (a_SiO2, a_MgO and a_Al2O3) buffered. At low a_SiO2, the buffer was forsterite + spinel + periclase (fo + sp + per) at all temperatures, while at high a_SiO2 and subsolidus conditions a variety of three-phase assemblages containing forsterite and two other phases from spinel, cordierite, protoenstatite or sapphirine were used at 1100–1350 °C. Experiments at high a_SiO2 and 1400 °C used forsterite + protoenstatite + melt (fo + en + melt), and at 1500 °C, fo + melt. The resulting diffusion profiles were analysed by LA–ICP–MS in scanning mode. Diffusion profiles in the high a_SiO2 experiments were generally several hundred microns in length, but diffusion at low a_SiO2 was three orders of magnitude slower than in high a_SiO2 experiments carried out at the same temperature, producing short profiles only a few microns in length and close to the spatial resolution of the analytical method. Interface concentrations of Al in the forsterite, obtained by extrapolating the diffusion profiles to the crystal/buffer interface, were only a fraction of those expected at equilibrium, and varied among the differing buffer assemblages according to (a_Al2O3)^1/2 and (a_SiO2)^3/4, pointing to the substitution of Al in forsterite by an octahedral-site, vacancy-coupled (OSVC) component with the stoichiometry Al _4/3 ³⁺ vac_2/3SiO₄, whereas the main substitution expected from previous equilibrium studies would be the coupled substitution of 2 Al for Mg + Si, giving the stoichiometry MgAl₂O₄. It is proposed that this latter substitution is not seen on the length scales of the present experiments because it requires replacement of Si by Al on tetrahedral sites, and is accordingly rate-limited by the slow diffusivity of Si. Instead, diffusion of Al by the OSVC mechanism is relatively fast, and at high a_SiO2, even faster than Fe–Mg interdiffusion.