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.     

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.     

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.     

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.     

Using ALSM to map sinkholes in the urbanized covered karst of Pinellas County,Florida—1, methodological considerations

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.     

Hydrochemical characteristics and the effects of irrigation on groundwater quality in Harran Plain,GAP Project,Turkey

Improper design, faulty planning, mismanagement and incorrect operation of irrigation schemes are the principle reasons for the deterioration of groundwater quality in a large number of countries, in particular in semi-arid and arid regions. The aim of this study is to determine the dimensions of groundwater quality after surface irrigation was begun in the semi-arid Harran Plain. Physical and chemical parameters of the groundwater including pH, temperature, electrical conductivity (EC), sodium, potassium, calcium, magnesium, chloride, bicarbonate, sulphate, nitrate, nitrite, ammonium, total phosphorus, total organic carbon and turbidity were determined monthly during the 2006 water year. The quality of the groundwater in the study area was assessed hydrochemically in order to determine its suitability for human consumption and agricultural purposes. In the general plain, the EC values measured were considerably above the guide level of 650 μS/cm, while nitrate in particular was found in almost all groundwater samples to be significantly above the maximum admissible concentration of 50 mg/l for the quality of water intended for human consumption as per the international and national standards. Total hardness reveals that a majority of the groundwater samples fall in the very hard water category. Interpretation of analytical data shows that Ca–HCO₃ and Ca–SO₄ are the dominant hydrochemical facies in the study area.     

Delineation of groundwater protection zones by the backward particle tracking method: theoretical background and GIS-based stochastic analysis

The backward particle tracking method, an effective and powerful tool that can be used to delineate groundwater protection zones, is presented. The theoretical background and insights on the applicability of this method are provided. Moreover, the present work enriches the backward particle tracking method with an uncertainty analysis concerning the porosity values, applying a Monte Carlo (MC) approach, coupled with the use of geographical information systems (GIS). As an application example, a wellfield in the Komotini area, Greece, is investigated. The present study may serve as a potential guideline for wellfield delineation, particularly in areas like Greece where lack of data related to the hydrogeological system is often a problem.     

Multivariate analysis of heavy metal contents of sediments from Gumusler creek, Nigde, Turkey

In this study, heavy metal contents of samples from Gumusler creek in Turkey were studied and the metal contamination characteristics were investigated. In this respect, considering the pollutant sites in the area, systematic sediment samples were collected in a zone starting from the manifestation part of the water to the entrance of the Karasu creek in Gumusler town. Samples were taken from lower section of the river bed at 30 stations along Gumusler creek, 13 km in length and their heavy metal contents were analyzed with XRF Spectrometer. Correlation coefficients, element coefitic coefficient correlation, dendogram hierarchical cluster, model summary and Annova analysis statistical methods were applied to data. Strong positive correlations were determined for some elements which are believed to have possibly the same origin. In addition, mineralizations in the area are thought to cause variation in metal contents. Results of chemical analysis show that soil limit values and clark values were exceeded. The heavy metal accumulation in the creek is believed to be derived from non-operated Sb-Hg-W and Fe quarries.