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     

珀金埃尔默公司分析科学部 《岩矿测试》2008,27(6):483-484

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  相似文献   

Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions   总被引：1，自引：0，他引：1  

L. M. KELLER  R. WIRTH  D. RHEDE  K. KUNZE  R. ABART 《Journal of Metamorphic Geology》2008,26(1):99-120

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.  相似文献   

Basement–cover relationships of the Kalak Nappe Complex, Arctic Norwegian Caledonides and constraints on Neoproterozoic terrane assembly in the North Atlantic region   总被引：1，自引：0，他引：1  

Christopher L. Kirkland  J. Stephen Daly  Martin J. Whitehouse 《Precambrian Research》2008,160(3-4):245-276

The Kalak Nappe Complex (KNC) has been regarded as Baltica passive margin metasediments telescoped eastwards onto the Baltic (Fennoscandian) Shield during the Caledonian Orogeny. Recent studies have questioned this interpretation, instead pointing to a Neoproterozoic exotic origin. In an effort to resolve this controversy we present a Sm–Nd and U–Th–Pb study of gnessic units, traditionally considered as the depositional basement, along with cover rock sediments and intrusives. Late Palaeoproterozoic gneisses now beneath the KNC were deposited after 1948 ± 33 Ma, before intrusion of the Tjukkfjellet Granite at 1796 ± 3 Ma, and were affected by later melting events at 1765 ± 9 and 1727 ± 9 Ma. These gneisses are interpreted as part of the Baltic Shield and underlie the KNC across a tectonic contact. An unconformity between psammites of the KNC and other paragneisses previously considered as its Precambrian basement is reinterpreted as a modified sedimentary contact between Neoproterozoic metasediments. These metasediments have statistically very similar detrital zircon populations with grains as young as 1034 ± 22, 1025 ± 32 and 1014 ± 14 Ma. The results indicate that the KNC sediments were deposited during the Neoproterozoic in basins along the Laurentian margin of eastern Rodinia and were not connected to Baltica via a depositional basement. Dating of the 851 ± 5 Ma Eidvågvatnet and 853 ± 4 Ma Nordneset granites shows that intrusive material associated with the Porsanger Orogeny (c. 850 Ma) affected a considerable region of the upper KNC terrane. Later Neoproterozoic events at 711 ± 6, 687 ± 12 and 617 ± 6 Ma are also recognised the latest of which may be an expression of rifting. Since early Neoproterozoic magmatism (c. 840–690 Ma) is unknown in Baltica, these results support an exotic origin for the KNC terranes.  相似文献   

SHRIMP zircon dating and Sm/Nd isotopic investigations of Neoproterozoic granitoids, Eastern Desert, Egypt   总被引：2，自引：0，他引：2  

Ewais M.M. Moussa  Robert J. Stern  William I. Manton  Kamal A. Ali 《Precambrian Research》2008,160(3-4):341-356

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.  相似文献   

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?     

S.J. Malone  J.G. Meert  D.M. Banerjee  M.K. Pandit  E. Tamrat  G.D. Kamenov  V.R. Pradhan  L.E. Sohl 《Precambrian Research》2008,164(3-4):137-159

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.  相似文献   

The role of heterogeneous strain in the development and preservation of a polymetamorphic record in high-P granulites, western Canadian Shield   总被引：1，自引：0，他引：1  

K. H. MAHAN  P. GONCALVES  R. FLOWERS  M. L. WILLIAMS  D. HOFFMAN-SETKA 《Journal of Metamorphic Geology》2008,26(6):669-694

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.  相似文献   

The effect of extracellular polymers (EPS) on the proton adsorption characteristics of the thermophile Bacillus licheniformis S-86     

Janette Tourney  Bryne T. Ngwenya  J.W. Fred Mosselmans  Laurence Tetley  Gregory L. Cowie 《Chemical Geology》2008,247(1-2):1-15

This study investigated proton adsorption to an extracellular polymeric substance (EPS) producing bacterial strain, Bacillus licheniformis S-86, in order to characterise and quantify the contribution made by EPS to cell surface reactivity. Potentiometric titrations were conducted using both untreated cells and cells from which the EPS layer had been extracted. Surface-complexation modelling indicated the presence of four different functional groups in both untreated and EPS-free cells. These sites are assigned to phosphodiester, (pK_a 3.3–3.4), carboxylic (pK_a 5.3–5.4), phosphoryl/ (pK_a 7.4–7.5) and hydroxyl/amine (pK_a 9.9–10.1) type groups. The pK_a values for the four groups were very similar for untreated and EPS-free cells, indicating no qualitative difference in composition, but site concentrations in the untreated cells were statistically found to be significantly higher than those in the EPS-free cells for the pK_a 3.3–3.4 and pK_a 9.9–10.1 sites. Infrared analysis provided supporting evidence that site 2 is carboxylic in nature but did not reveal any difference in IR absorption between the native and EPS-free cells. Dissolved organic carbon (DOC) analysis conducted during this study indicated that DOC release by cells is significant, and that the EPS layer is the major contributor.  相似文献   

Anoxic nitrification: Evidence from Humber Estuary sediments (UK)   总被引：3，自引：0，他引：3  

Rebecca Bartlett  Robert J.G. Mortimer  Katherine Morris 《Chemical Geology》2008,250(1-4):29-39

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.  相似文献   

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS   总被引：4，自引：0，他引：4  

Paul R. Craddock  Olivier J. Rouxel  Lary A. Ball  Wolfgang Bach   《Chemical Geology》2008,253(3-4):102-113

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.  相似文献   

Using ALSM to map sinkholes in the urbanized covered karst of Pinellas County,Florida—1, methodological considerations   总被引：1，自引：0，他引：1  

Larry D. Seale  Lee J. Florea  H. L. Vacher  Robert Brinkmann 《Environmental Geology》2008,54(5):995-1005

Comparison of a database of interpreted sinkholes made using airborne laser swath mapping (ALSM) with databases of sinkholes made from interpretation of aerial photographs reveals substantial disagreement. The discrepancies involve the location, number, areas, and circularity of interpreted sinkholes. Methodological factors that contribute to the discrepancies include blockage of ALSM laser returns in thick vegetation, multi-path reflections, and misrepresentation of the true extent of sinkholes. Comparison of two ALSM-derived databases made (1) independently from versus (2) in combination with earlier air photo analysis in undeveloped regions had the following result: one-fourth of the sinkholes interpreted by using the composite method were missed by the independent analysis, and one-third of the sinkholes that were interpreted from the independent analysis were not interpreted as sinkholes using the composite method. Subjective interpretation leads to a high level of uncertainty such that the results of the remote sensing studies are suspect, if not invalid.  相似文献