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.     

Mineral inclusions and geochemical characteristics of microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, Canada

A mineral inclusion, carbon isotope, nitrogen content, nitrogen aggregation state and morphological study of 576 microdiamonds from the DO27, A154, A21, A418, DO18, DD17 and Ranch Lake kimberlites at Lac de Gras, Slave Craton, was conducted. Mineral inclusion data show the diamonds are largely eclogitic (64%), followed by peridotitic (25%) and ultradeep (11%). The paragenetic abundances are similar to macrodiamonds from the DO27 kimberlite (Davies, R.M., Griffin, W.L., O'Reilly, S.Y., 1999. Diamonds from the deep: pipe DO27, Slave craton, Canada. In: Gurney, J.J., Gurney, J.L., Pascoe, M.D., Richardson, S.H. (Eds.), The J. B. Dawson Vol., Proc. 7th Internat. Kimberlite Conf., Red Roof Designs, Cape Town, pp. 148–155) but differ to diamonds from nearby kimberlites at Ekati (e.g., Lithos (2004); Tappert, R., Stachel, T., Harris, J.W., Brey, G.P., 2004. Mineral Inclusions in Diamonds from the Panda Kimberlite, S. P., Canada. 8th International Kimberlite Conference, extended abstracts) and Snap Lake to the south (Dokl. Earth Sci. 380 (7) (2001) 806), that are dominated by peridotitic stones.

Eclogitic diamonds with variable inclusion compositions and temperatures of formation (1040–1300 °C) crystallised at variable lithospheric depths sometimes in changing chemical environments. A large range to very ¹³C-depleted C-isotope compositions (δ¹³C=−35.8‰ to −2.2‰) and an NMORB bulk composition, calculated from trace elements in garnet and clinopyroxene inclusions, are consistent with an origin from subducted oceanic crust and sediments. Carbon isotopes in the peridotitic diamonds have mantle compositions (δ¹³C mode −4.0‰). Mineral inclusion compositions are largely harzburgitic. Variable temperatures of formation (garnet T_Ni=800–1300 °C) suggest the peridotitic diamonds originate from the shallow ultra-depleted and deeper less depleted layers of the central Slave lithosphere. Carbon isotopes (δ¹³C av.=−5.1‰) and mineral inclusions in the ultradeep diamonds suggest they formed in peridotitic mantle (670 km). The diamonds may have been entrained in a plume and subcreted to the base of the central Slave lithosphere.

Poorly aggregated nitrogen (IaA without platelets) in a large number of eclogitic (67%) and peridotitic (32%) diamonds, with similar nitrogen contents, indicates the diamonds were stored in the mantle at low temperatures (1060–<1100 °C) following crystallisation in the Archean. Type IaA diamonds have largely cubo-octahedral growth forms, and Type II and Type IaAB diamonds, with higher nitrogen aggregation states, mostly have octahedral morphologies. However, no correlation between these groups and their mineral inclusion compositions, C-isotopes, and N-contents rules out the possibility of unique source origins and suggests eclogitic and peridotitic diamonds experienced variable mantle thermal states. Variation in mineral inclusion chemistries in single diamonds, possible overgrowths of ¹³C-depleted eclogitic diamond on diamonds with peridotitic and ultradeep inclusions, and Type I ultradeep diamond with low N-aggregation is consistent with diamond growth over time in changing chemical environments.     

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.     

Hydrogeochemical prospecting for porphyry copper deposits in the tropical-marine climate of Puerto Rico

A hydrogeochemical survey utilizing waters from streams and springs was conducted in the area of two known porphyry copper deposits in the tropical-marine climate of westcentral Puerto Rico. The most important pathfinder for regional hydrogeochemical surveys is sulfate which reflects the associated pyrite mineralization. Because of increased mobility due to intense chemical weathering and the low pH environment, dissolved copper can also be used as a pathfinder for regional surveys and has the advantage of distinguishing barren pyrite from pyrite associated with copper mineralization. For follow-up surveys, the most important pathfinders are copper, sulfate, pH, zinc, and fluoride. High concentrations of dissolved copper and moderate concentrations of sulfate is a diagnostic indication of nearby sources of copper minerals.An understanding of the geochemical processes taking place in the streambeds and the weathering environment, such as the precipitation of secondary copper minerals, contributes to the interpretation of the geochemical data and the selection of the most favorable areas for further exploration.     

Metasomatism and sulfide mobility in lithospheric mantle beneath eastern Australia: Implications for mantle Re–Os chronology

Spinel lherzolite xenoliths from Tertiary basaltic host magmas at Allyn River, eastern Australia reveal two distinct petrographic and geochemical types. One group is distinguished by xenoliths with undeformed, equilibrated microstructures and interstitial melt patches; The second group shows deformation and contains abundant fluid inclusions but no melt patches. Trace-element signatures of clinopyroxene in these xenoliths provide evidence for metasomatism by a silicate agent with hydrous component and by a carbonate-rich agent respectively.

Melt patches in the undeformed xenoliths contain secondary minerals including clinopyroxene, olivine, feldspar, Mg- and Ca-rich carbonate, apatite, ilmenite and spinel. They are interpreted to represent volatile-rich melt captured shortly prior to entrainment in the host basalt. Sulfide globules, now recrystallised to discrete sulfide phases but inferred to be molten at lithospheric mantle T and P, are closely associated with the melt patches. The close association between sulfide and highly mobile, volatile-bearing fluid has important implications for the mobility of Re and Os, the use of their isotopes in dating mantle events, and the possible effect of volatile-bearing metasomatic agents on their composition.     

Considerations on the European Standard EN 14157 Test Methods: Abrasion Resistance of Natural Stones Used for Flooring in Buildings

In Europe, the Wide Wheel abrasion (WWA) test and the B?hme abrasion (BA) test are among the most widely used standard test methods for determining abrasion resistance of natural stones, the former being the reference test method in EN 14157 Standard. However, it is stated in the Annex-A (Informative) of EN 14157 Standard that very limited data are available to provide correlations between these two test methods. To be able to fill this gap, in this study, 25 different natural stones belonging to sedimentary, metamorphic and igneous groups were tested for their abrasion resistance as well as physico-mechanical properties. Also, for a better interpretation of abrasion resistance characteristics of the tested stone materials, relationships between abrasion resistance and physico-mechanical properties were statistically examined. A statistically significant linear correlation (R ² = 0.85; P value = 0.000) was established between the WWA test and the BA test, which could be used in practice for converting the measured abrasion resistance values from one testing method to another. It was also found that the correlation between these two test methods improved significantly (R ² = 0.93; P value = 0.001) when relatively high-porosity stone materials (porosity ≥1%) were separately evaluated. Both methods of abrasion resistance employed in the present study showed statistically significant linear correlations with uniaxial compressive strength and Brazilian tensile strength, the former proving to be a more influencing parameter on resistance to abrasion. Also, from the point view of representing actual abrasion mechanism of stone materials in practice, the necessity of simulating multi-directional foot traffic in abrasion testing methods was discussed. In this respect, the reference test method in the EN 14157 Standard was criticized for not fully meeting this requirement. It was also pointed out that the reference method could have some drawbacks when applied to coarse-grained granitic rocks having cleavable minerals such as plagioclase and orthoclase feldspars.     

离子色谱法测定水样中S~(2-)、SO_3~(2-)、SO_4~(2-)、S_2O_3~(2-)

该种方法利用离子色谱仪的电导检测器与电化学检测器串联 ,十几分钟即可连续完成水中S2 - 、SO2 - 3 、SO2 - 4、S2 O2 - 3 的测定 ,方法具有快速、高效、方便、灵敏、选择性好等特点。方法的检出限分别为 :S2 - 12 5 μg/L ;SO2 - 3 2 2 4 μg/L ;SO2 - 45 0 μg/L ;S2 O2 - 35 0 μg/L。相对标准偏差在 1 5 %～ 6 9%之间 ,能够满足水中S2 - 、SO2 - 3 、SO2 - 4、S2 O2 - 3四种阴离子分析测试的需要。     

Environmental controls on clay mineralogy of an Early Jurassic mudrock (Blue Lias Formation,southern England)

We present a dataset including clay mineralogy, gamma-ray spectrometry, organic matter content and magnetic susceptibility of the Hettangian to lowest Sinemurian successions of Dorset and Somerset, southern UK (Blue Lias Formation, Bristol Channel and Wessex basins). In both areas, the clay assemblages comprise predominantly detrital illite, kaolinite and illite/smectite mixed layers. Clays probably originated from the erosion of the Hercynian massifs, the relative proportions of kaolinite and illite being modulated by arid-humid climatic fluctuations. The organic matter (OM) content (types II to IV) ranges up to 12% in both areas. A clear stratigraphical trend in clay mineral assemblages is apparent in Somerset, whereas in Dorset sharp contrasts between adjacent horizons and a greater dilution by carbonate mask the long-term evolution. Correlations between both areas based on similar vertical trends in clay mineral abundance support the suggestion of a hiatus within the angulata Zone of the Dorset succession. As expected, the kaolinite/illite ratio correlates with the Th/K ratio deduced from gamma-ray spectrometry. However, significant departures from the correlation occur in OM-rich intervals, suggesting that Th may be partly adsorbed on to OM particles. Surprisingly, high magnetic susceptibility correlates with abundant kaolinite, not with Fe-rich clays, indicating either that kaolinite is accompanied by a soil-inherited magnetisable phase (possibly iron oxide) or that illite-rich rocks are more strongly diluted by carbonate than are kaolinite-rich strata.