A Raman spectroscopic study on the structural disorder of monazite–(Ce)

This study addresses whether Raman spectra can be used to estimate the degree of accumulated radiation damage in monazite-(Ce) samples whose chemical composition was previously determined. Our results indicate that the degree of disorder in monazite–(Ce), as observed from increasing Raman band broadening, generally depends on both the structural state (i.e., radiation damage) and the chemical composition (i.e., incorporation of non-formula elements). The chemical effects were studied on synthetic orthophosphates grown using the Li-Mo flux method, and non radiation-damaged analogues of the naturally radiation-damaged monazite–(Ce) samples, produced by dry annealing. We found that the “chemical” Raman-band broadening of natural monazite–(Ce) can be predicted by the empirical formula, $$ {\hbox{FWHM}} {\hbox{[c}}{{\hbox{m}}^{ - {1}}}{]} = {3}{.95} + {26}{.66} \times {\hbox{(Th}} + {\hbox{U}} + {\hbox{Ca}} + {\hbox{Pb)}} {\hbox{[apfu]}} $$ where, FWHM = full width at half maximum of the main Raman band of monazite–(Ce) (i.e., the symmetric PO₄ stretching near 970?cm^?1), and (Th+U+Ca+Pb) = sum of the four elements in apfu (atoms per formula unit). Provided the chemical composition of a natural monazite–(Ce) is known, this “chemical band broadening” can be used to estimate the degree of structural radiation damage from the observed FWHM of the ν₁(PO₄) band of that particular sample using Raman spectroscopy. Our annealing studies on a wide range of monazite–(Ce) reference materials and other monazite–(Ce) samples confirmed that this mineral virtually never becomes highly radiation damaged. Potential advantages and the practical use of the proposed method in the Earth sciences are discussed.     

Fluid inclusion studies of the Abawso gold prospect,near the Ashanti Belt,Ghana

The major Ghanaian lode gold deposits are preferentially aligned along the western and eastern contacts of the Kumasi Basin with the Ashanti and Sefwi Belts, respectively. The investigated area of the Abawso small-scale concession, covering the workings of the old Ettadom mine, is situated 3 km west of the lithological contact of the Birimian metavolcanic rocks of the Akropong Belt in the east with the Birimian metasedimentary rocks of the Kumasi Basin in the west. The rocks of the Abawso concession represent a steeply NW-dipping limb of a SE-verging anticline with an axis plunging to the SW. Quartz veining occurs predominantly in the form of en échelon dilatational veins along NNE–SSW-striking shear zones of a few metres width and shows evidence of brittle and ductile deformation. Also stockwork-style quartz veining occurs in the vicinity of the main shaft of the old Ettadom mine. Hydrothermal alteration includes sericitisation, sulphidation and locally carbonatisation. The auriferous quartz veins mainly follow the trend of brittle to ductile deformed quartz veins; however, some occur in stockwork. Fluid inclusion studies reveal a large number of H₂O inclusions along intragranular trails in auriferous quartz vein samples, as well as an overall dominance of H₂O and H₂O-CO₂ inclusions over CO₂ inclusions. Textural observations and physico-chemical fluid inclusion properties indicate post-entrapment modifications for all quartz vein samples due to grain boundary migration recrystallisation. This process is interpreted to be responsible for the generation of the CO₂ inclusions from a H₂O-CO₂ parent fluid. In comparison with mineralisation at the Ashanti and Prestea deposits, which are characterised by CO₂±N₂ inclusions, the observed inclusion assemblage may be due to a shallower crustal level of mineralisation, or different degrees and styles of recrystallisation, or a less pronounced development of laminated quartz veins due to comparably restricted pressure fluctuations. Furthermore, the microthermometric observations allow the reconstruction of a possible retrograde P-T path, depicting near-isothermal decompression in the P-T range of the brittle/ductile transition.Editorial handling: E. Frimmel     

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.     

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.     

The study of metal contamination in urban topsoils of Mexico City using GIS

This research presents and discusses information concerning the spatial distribution of heavy metals (Pb, Cu, Zn, Ba, Co, Cr, Ni and V) in the urban environments of Mexico City using geographical information system and statistical analysis. Superficial soil samples (n = 146) were analyzed. The highest contamination indices were found in the north and center zone of the metropolitan area. In contrast, the surrounding rural fields show a lower impact grade. The higher concentrations of Pb, Cu, Zn and Ba were observed as being related to high vehicular traffic, nevertheless other elements such as Co, Cr, Ni and V do not show anthropogenic influence and their content can be attributed to the parental rock. The results are compared with previous surveys carried out in 2003 in order to evaluate temporal deposition trends. No changes were found on reported concentrations except for Cu and Zn, whose concentration has increased in later years. The results suggest that spatial distribution analysis and results in comparison with previous studies could be useful for the management and sustainable development of the metropolitan area of Mexico City.     

Hydrogeology and sustainable future groundwater abstraction from the Agua Verde aquifer in the Atacama Desert,northern Chile

The hyper-arid conditions prevailing in Agua Verde aquifer in northern Chile make this system the most important water source for nearby towns and mining industries. Due to the growing demand for water in this region, recharge is investigated along with the impact of intense pumping activity in this aquifer. A conceptual model of the hydrogeological system is developed and implemented into a two-dimensional groundwater-flow numerical model. To assess the impact of climate change and groundwater extraction, several scenarios are simulated considering variations in both aquifer recharge and withdrawals. The estimated average groundwater lateral recharge from Precordillera (pre-mountain range) is about 4,482 m³/day. The scenarios that consider an increase of water withdrawal show a non-sustainable groundwater consumption leading to an over-exploitation of the resource, because the outflows surpasses inflows, causing storage depletion. The greater the depletion, the larger the impact of recharge reduction caused by the considered future climate change. This result indicates that the combined effects of such factors may have a severe impact on groundwater availability as found in other groundwater-dependent regions located in arid environments. Furthermore, the scenarios that consider a reduction of the extraction flow rate show that it may be possible to partially alleviate the damage already caused to the aquifer by the continuous extractions since 1974, and it can partially counteract climate change impacts on future groundwater availability caused by a decrease in precipitation (and so in recharge), if the desalination plant in Taltal increases its capacity.     

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.     

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。