高效液相色谱-等离子体质谱技术在溴元素形态分析中的应用

溴是一种在自然水体中都含有的元素,通常以B r-的形式存在。目前最常用的水净化方式就是向水中通入臭氧以杀灭细菌;而臭氧分解的副产物即为B r-转换成的B rO3-,这是一种公认的致癌物质。本实验室曾使用阴离子交换高效液相色谱(HPLC)与等离子体质谱(ICP-MS)联用分析B rO3-和B r-,方法虽能有效地将这两种溴形态分离,但分析每个样品需8 m in。本文试图建立新的方法缩短分析时间,并验证该方法应用于实际水样分析时测定其他含溴化合物的能力。1实验部分1.1高效液相色谱分析条件表1列出了等度淋洗和梯度淋洗两种模式下HPLC的分析条件,完成形态的分离。等度淋洗和梯度淋洗在分析中显示出不同     

Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions

This study explores garnet coronas around hedenbergite, which were formed by the reaction plagioclase + hedenbergite→garnet + quartz, to derive information about diffusion paths that allowed for material redistribution during reaction progress. Whereas quartz forms disconnected single grains along the garnet/hedenbergite boundaries, garnet forms ～20‐μm‐wide continuous polycrystalline rims along former plagioclase/hedenbergite phase boundaries. Individual garnet crystals are separated by low‐angle grain boundaries, which commonly form a direct link between the reaction interfaces of the plagioclase|garnet|hedenbergite succession. Compositional variations in garnet involve: (i) an overall asymmetric compositional zoning in Ca, Fe²⁺, Fe³⁺ and Al across the garnet layer; and (ii) micron‐scale compositional variations in the near‐grain boundary regions and along plagioclase/garnet phase boundaries. These compositional variations formed during garnet rim growth. Thereby, transfer of the chemical components occurred by a combination of fast‐path diffusion along grain boundaries within the garnet rim, slow diffusion through the interior of the garnet grains, and by fast diffusion along the garnet/plagioclase and the garnet/hedenbergite phase boundaries. Numerical simulation indicates that diffusion of Ca, Al and Fe²⁺ occurred about three to four, four and six to seven orders of magnitude faster along the grain boundaries than through the interior of the garnet grains. Fast‐path diffusion along grain boundaries contributed substantially to the bulk material transfer across the growing garnet rim. Despite the contribution of fast‐path diffusion, bulk diffusion through the garnet rim was too slow to allow for chemical equilibration of the phases involved in garnet rim formation even on a micrometre scale. Based on published garnet volume diffusion data the growth interval of a 20‐μm‐wide garnet rim is estimated at ～10³–10⁴ years at the inferred reaction conditions of 760 ± 50 °C at 7.6 kbar. Using the same parameterization of the growth law, 100‐μm‐ and 1‐mm‐thick garnet rims would grow within 10⁵–10⁶ and 10⁶–10⁷ years respectively.     

Gouging abrasion test for rock abrasiveness testing

Wear parts of many mineral processing and mining equipment are often subjected to high stress loads applied at high speeds and at varying angles of incidence, where the prevalent mode of wear is high-stress gouging/sliding impact abrasion. Examples include crusher liners, wear liners in hoppers and chutes, picks on roadheaders, discs on tunnel boring machines and ground engaging tools. Abrasion under these conditions is characterised by a high material removal rate and thus has a direct bearing on wear rates and service life of the equipment concerned. However, at present there appears to be no method for rock abrasiveness assessment under these conditions. This paper describes a new Gouging Abrasion method and apparatus for testing abrasivity of rocks under high-stress gouging/sliding impact wear. A Gouging Abrasion Index (Gi) is introduced, which can be used for prediction and assessment of component life expectancy and efficiency of mineral processing and materials handling equipment. Experimental data from Gouging Abrasion testing of numerous Australian rock types are presented. It is suggested that the results of Gi testing can be used for wear rate predictions for a variety of mineral processing and materials handling equipment working under high-stress gouging/sliding impact abrasion conditions.     

SHRIMP zircon dating and Sm/Nd isotopic investigations of Neoproterozoic granitoids, Eastern Desert, Egypt

There is an increasing evidence for the involvement of pre-Neoproterozoic zircons in the Arabian–Nubian Shield, a Neoproterozoic crustal tract that is generally regarded to be juvenile. The source and significance of these xenocrystic zircons are not clear. In an effort to better understand this problem, older and younger granitoids from the Egyptian basement complex were analyzed for chemical composition, SHRIMP U–Pb zircon ages, and Sm–Nd isotopic compositions. Geochemically, the older granitoids are metaluminous and exhibit characteristics of I-type granites and most likely formed in a convergent margin (arc) tectonic environment. On the other hand, the younger granites are peraluminous and exhibit the characteristics of A-type granites; these are post-collisional granites. The U–Pb SHRIMP dating of zircons revealed the ages of magmatic crystallization as well as the presence of slightly older, presumably inherited zircon grains. The age determined for the older granodiorite is 652.5 ± 2.6 Ma, whereas the younger granitoids are 595–605 Ma. Xenocrystic zircons are found in most of the younger granitoid samples; the xenocrystic grains are all Neoproterozoic, but fall into three age ranges that correspond to the ages of other Eastern Desert igneous rocks, viz. 710–690, 675–650 and 635–610 Ma. The analyzed granitoids have (+3.8 to +6.5) and crystallization ages, which confirm previous indications that the Arabian–Nubian Shield is juvenile Neoproterozoic crust. These results nevertheless indicate that older Neoproterozoic crust contributed to the formation of especially the younger granite magmas.     

Extensional tectonic origin of gneissosity and related structures of the Feiran–Solaf metamorphic belt, Sinai, Egypt

The Feiran–Solaf metamorphic belt consists of low-P high-T amphibolite facies, partly migmatized gneisses, schists, amphibolites and minor calc-silicate rocks of metasedimentary origin. There are also thick concordant synkinematic sheets of diorite, tonalite and granodiorite orthogneiss and foliated granite and pegmatite dykelets. The gneissosity (or schistosity) is referred to as S₁, and is almost everywhere parallel to lithological layering, S₀. This parallelism is not due to transposition. The gneissosity formed during an extensional tectonic event (termed D1), before folding of S₀. S₁ formed by coaxial pure shear flattening strain (Z normal to S₀, i.e. vertical; with X and Y both extensional and lying in S₁). This strain also produced chocolate tablet boudinage of some layers and S₁-concordant sills and veins. S₁ has a strong stretching lineation L₁ with rodding characteristics. Within-plane plastic anisotropy (lower ductility along Y compared to along X) resulted in L₁-parallel extensional ductile shears and melt filled cracks. Continued shortening of these veins, and back-rotation of foliations on the shears produced intrafolial F₁ folds with hinges parallel to the stretching lineation. F₁ fold asymmetry variations do not support previous models involving macroscopic F₁ folds or syn-gneissosity compressional tectonics. The sedimentary protoliths of the Feiran–Solaf gneisses were probably deposited in a pre-800 Ma actively extending intracratonic rift characterizing an early stage of the break-up of Rodinia.     

Paleomagnetism and Detrital Zircon Geochronology of the Upper Vindhyan Sequence, Son Valley and Rajasthan, India: A ca. 1000 Ma Closure age for the Purana Basins?

The utility of paleomagnetic data gleaned from the Bhander and Rewa Groups of the “Purana-aged” Vindhyanchal Basin has been hampered by the poor age control associated with these units. Ages assigned to the Upper Vindhyan sequence range from Cambrian to the Mesoproterozoic and are derived from a variety of sources, including ⁸⁷Sr/⁸⁶Sr and δ ¹³C correlations with the global curves and Ediacara-like fossil finds in the Lakheri–Bhander limestone. New analyses of the available paleomagnetic data collected from this study and previous work on the 1073 Ma Majhgawan kimberlite, as well as detrital zircon geochronology of the Upper Bhander sandstone and sandstones from the Marwar SuperGroup suggest that the Upper Vindhyan sequence may be up to 500 Ma older than is commonly thought. Paleomagnetic analysis generated from the Bhander and Rewa Groups yields a paleomagnetic pole at 44°N, 214.0°E (A95 = 4.3°). This paleomagnetic pole closely resembles the VGP from the well-dated Majhgawan intrusion (36.8°N, 212.5°E, α₉₅ = 15.3°).Detrital zircon analysis of the Upper Bhander sandstone identifies a youngest age population at 1020 Ma. A comparison between the previously correlated Upper Bhander sandstone and the Marwar sandstone detrital suites shows virtually no similarities in the youngest detrital suite sampled. The main 840–920 Ma peak is absent in the Upper Bhander. This supports our assertion that the Upper Bhander is older than the 750–771 Ma Malani sequence, and is likely close to the age of the 1073 Ma Majhgawan kimberlite on the basis of the paleomagnetic similarities. By setting the age of the Upper Vindhyan at 1000–1070 Ma, several intriguing possibilities arise. The Bhander–Rewa paleomagnetic pole allows for a reconstruction of India at 1000–1070 Ma that overlaps with the 1073 ± 13.7 Majhgawan kimberlite VGP. Comparisons between the composite Upper Vindhyan pole (43.9°N, 210.2°E, α₉₅ = 12.2°) and the Australian 1071 ± 8 Ma Bangamall Basin sills and the 1070 Ma Alcurra dykes suggest that Australia and India were not adjacent at this time period.     

A late Neoproterozoic paleomagnetic pole for the Congo craton: Tectonic setting, paleomagnetism and geochronology of the Nola dike swarm (Central African Republic)

New structural, geochronological and paleomagnetic data were obtained on dolerite dikes of the Nola region (Central African Republic) at the northern border of the Congo craton. In this region, metavolcanic successions were thrust southward onto the craton during the Panafrican orogenic events. Our structural data reveal at least two structural klippes south of the present-day limits of the Panafrican nappe suggesting that it has once covered the whole Nola region, promoting the pervasive hydrothermal greenschist metamorphism observed in the underlying cratonic basement and also in the intrusive dolerite dikes. Paleomagnetic measurements revealed a stable dual-polarity low-inclination magnetization component in nine dikes (47 samples), carried by pyrrhotite and magnetite. This component corresponds to a paleopole at 304.8°E and 61.8°S (dp = 5.4, dm = 10.7) graded at Q = 6. Both metamorphism and magnetic resetting were dated by the ⁴⁰Ar/³⁹Ar method on amphibole grains separated from the dikes at 571 ± 6 Ma. The Nola pole is the first well-dated paleomagnetic pole for the Congo craton between 580 and 550 Ma. It marks a sudden change in direction of the Congo craton apparent polar wander path at the waning stages of the Panafrican orogenic events.     

The role of heterogeneous strain in the development and preservation of a polymetamorphic record in high-P granulites, western Canadian Shield

Mafic rocks in the Chipman domain of the Athabasca granulite terrane, western Canadian Shield, provide the first well‐documented record of two distinct high‐P granulite facies events in the same domain in this region. Textural relations and the results of petrological modelling (NCFMASHT system) of mafic granulites are interpreted in terms of a three‐stage tectonometamorphic history. Stage 1 involved development of the assemblage Grt + Cpx + Qtz ± Pl (M₁) from a primary Opx‐bearing igneous precursor at conditions of 1.3 GPa, 850–900 °C. Field and microstructural observations suggest that M₁ developed synchronously with an early S₁ gneissic fabric. Stage 2 is characterized by heterogeneous deformation (D₂) and synkinematic partial retrogression of the peak assemblage to an amphibole‐bearing assemblage (M₂). Stage 3 involved a third phase of deformation and a return to granulite facies conditions marked by the prograde breakdown of amphibole (Amph₂) to produce matrix garnet (Grt_3a) and the coronitic assemblage Cpx_3b + Opx_3b + Ilm_3b + Pl_3b (M_3b) at 1.0 GPa, 800–900 °C. M₁ and M_3b are correlated with 2.55 and 1.9 Ga metamorphic generations of zircon, respectively, which were dated in a separate study. Heterogeneous strain played a crucial role in both the development and preservation of these rare examples of multiple granulite facies events within single samples. Without this fortuitous set of circumstances, the apparent reaction history could have incorrectly led to an interpretation involving a single‐cycle high‐grade event. The detailed P–T–t–D history constructed for these rocks provides the best evidence to date that much of the east Lake Athabasca region experienced long‐term lower crustal residence from 2.55 to 1.9 Ga, and thus the region represents a rare window into the reactivation and ultimate stabilization processes of cratonic lithosphere.     

An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate

In situ atomic force microscopy (AFM) has been used to compare the growth of pure calcite and the growth of calcite in the presence of sulfate ions from aqueous solutions at a constant value of supersaturation (S.I. = 0.89) with respect to calcite. The effect of sulfate ions on calcite growth rates is determined and a potential incorporation of sulfate ions is identified in the calcite during growth. Solutions supersaturated with respect to calcite with solution concentration ratio of one and a constant pH of 10.2, were prepared and sulfate was added as Na₂SO₄ aqueous solution. The solution composition was readjusted in order to keep the supersaturation and pH constant. PHREEQC was used to determine relevant solution concentrations. In situ AFM experiments of calcite growth were performed using a fluid cell and flowing solutions passed over a freshly cleaved calcite surface. Growth rates were determined from the closure of the rhombohedral etch pits induced by initial dissolution with pure water. The spreading rate of 2-dimensional nuclei was also measured. At low concentrations of sulfate (≤ 0.5 mM), no effect on the growth rate of the calcite was observed. At higher concentrations (2 to 3 mM) of sulfate, the growth rate increased, possibly because a higher concentration of calcium and carbonate was necessary to maintain the supersaturation constant. At much higher concentrations of additional sulfate (up to 60 mM) the growth rate of the calcite was substantially decreased, despite the fact that a further increase of calcium and carbonate was required. The morphology of 2-dimensional growth nuclei became increasingly elongated with increasing sulfate content. Measurements of step height showed that newly grown steps were approximately 1 Å higher when grown in high sulfate concentrations, compared to steps grown in sulfate-free solutions. At sulfate concentrations above 5 mM the growth mechanism changes from layer growth to surface roughening. These observations suggest that the new growth has incorporated sulfate into the calcite surface.     

History of crustal growth and recycling at the Pacific convergent margin of South America at latitudes 29°–36° S revealed by a U–Pb and Lu–Hf isotope study of detrital zircon from late Paleozoic accretionary systems

Detrital zircon provides a powerful archive of continental growth and recycling processes. We have tested this by a combined laser ablation ICP-MS U–Pb and Lu–Hf analysis of homogeneous growth domains in detrital zircon from late Paleozoic coastal accretionary systems in central Chile and the collisional Guarguaráz Complex in W Argentina. Because detritus from a large part of W Gondwana is present here, the data delineate the crustal evolution of southern South America at its Paleopacific margin, consistent with known data in the source regions.Zircon in the Guarguaráz Complex mainly displays an U–Pb age cluster at 0.93–1.46 Ga, similar to zircon in sediments of the adjacent allochthonous Cuyania Terrane. By contrast, zircon from the coastal accretionary systems shows a mixed provenance: Age clusters at 363–722 Ma are typical for zircon grown during the Braziliano, Pampean, Famatinian and post-Famatinian orogenic episodes east of Cuyania. An age spectrum at 1.00–1.39 Ga is interpreted as a mixture of zircon from Cuyania and several sources further east. Minor age clusters between 1.46 and 3.20 Ga suggest recycling of material from cratons within W Gondwana.The youngest age cluster (294–346 Ma) in the coastal accretionary prisms reflects a so far unknown local magmatic event, also represented by rhyolite and leucogranite pebbles. It sets time marks for the accretion history: Maximum depositional ages of most accreted metasediments are Middle to Upper Carboniferous. A change of the accretion mode occurred before 308 Ma, when also a concomitant retrowedge basin formed.Initial Hf-isotope compositions reveal at least three juvenile crust-forming periods in southern South America characterised by three major periods of juvenile magma production at 2.7–3.4 Ga, 1.9–2.3 Ga and 0.8–1.5 Ga. The ¹⁷⁶Hf/¹⁷⁷Hf of Mesoproterozoic zircon from the coastal accretionary systems is consistent with extensive crustal recycling and addition of some juvenile, mantle-derived magma, while that of zircon from the Guarguaráz Complex has a largely juvenile crustal signature. Zircon with Pampean, Famatinian and Braziliano ages (< 660 Ma) originated from recycled crust of variable age, which is, however, mainly Mesoproterozoic. By contrast, the Carboniferous magmatic event shows less variable and more radiogenic ¹⁷⁶Hf/¹⁷⁷Hf, pointing to a mean early Neoproterozoic crustal residence. This zircon is unlikely to have crystallized from melts of metasediments of the accretionary systems, but probably derived from a more juvenile crust in their backstop system.