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     

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.     

Intriguing climatic shifts in a 90 kyr old lake record from northern Russia

A 22 m long sediment core from Lake Yamozero on the Timan Ridge in northern Russia has provided evidence of intriguing climatic shifts during the last glacial cycle. An overall shallowing of the lake is reflected in the lower part of the cores, where pollen indicates a transition from glacial steppe vegetation to interstadial shrub-tundra. These beds are capped by a well-defined layer of compact clay deposited in relatively deep water, where pollen shows surrounding spruce forests and warmer-than-present summer temperatures. The most conservative interpretation is that this unit represents the last interglacial period. However, a series of Optical Stimulated Luminescence (OSL) dates suggests that it corresponds with the Early Weichselian Odderade interstadial (MIS 5a). This would imply that the Odderade interstadial was just as warm as a normal interglacial in this continental part of northern Europe. If correct, then pollen analysis, as a correlation tool, is less straightforward and the definition of an interglacial is more complex than previously thought. We discuss the validity and possible systematic errors of the OSL dates on which this age model is based, but conclude they really indicate a MIS 5a age for the warm period. Above the clay is an unconformity, most likely reflecting a period of subaerial exposure implying dry conditions. Deposition of silt under fluctuating cold climates in the Middle Weichselian continued until a second gap in the record at c . 40 kyr BP. The lake basin started to fill up again around 18 kyr BP.     

New evidence of the Littorina transgressions in the Kattegat: Optically Stimulated Luminescence dating of a beach ridge system on Anholt, Denmark

Recent geomorphological and sedimentological investigation of the raised beach ridge plain on Anholt in the Kattegat Sea, Denmark, has demonstrated how these deposits, when combined with Optically Stimulated Luminescence (OSL) dating, can provide information about past changes in relative sea level. The southwest–northeast trending plain is divided into three topographic levels, one of which has been surveyed using Ground-Penetrating Radar (GPR). Samples retrieved from the survey line indicate that the initial part of the beach ridge plain formed about 7700 years ago in response to a mid-Holocene Littorina transgression. The raised marine deposits document a subsequent rise in relative sea level of about 9 m, and OSL dates indicate that this transgression took place about 6650 years ago. The flooding of the Kattegat Sea 7700 years ago might possibly be related to a rapid global sea-level rise peaking around 7500 years ago.     

Three-dimensional discontinuous deformation analysis (3-D DDA) using a new contact resolution algorithm

This paper presents a new contact calculating algorithm for contacts between two polyhedra with planar boundaries in the three-dimensional discontinuous deformation analysis (3-D DDA). In this algorithm, all six type contacts in 3-D (vertex-to-face, vertex-to-edge, vertex-to-vertex, face-to-face, edge-to-edge, and edge-to-face) are simply transformed into the form of point-to-face contacts. The presented algorithm is a simple and efficient method and it can be easily coded into a computer program. In this paper, formulations of normal contact, shear contact and frictional force submatrices based on the new method are derived and the algorithm has been programmed in VC⁺⁺. Examples are provided to demonstrate the new contact rule between two blocks.     

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.     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.