Possible chemical structures and biological precursors of different vitrinites in coal measure in Northwest China

Chemical structure of Jurassic vitrinites isolated from the coals in basins in NW China have been checked using solid state ¹³C NMR and flash pyrolysis-GC/MS. Study shows some Jurassic collodetrinites are rich in aliphatic products in pyrolysates, consisting with the high amount of methylene carbon in ¹³C NMR spectra. In contrast, pyrolysates of Jurassic collotelinites are rich in phenols and alkylbenzenes. Also one Pennsylvanian and one Permian vitrinite selected from the Ordos basin, NW China have been checked for comparison. The proportion of aliphatics is low in pyrolysates, and aliphatic carbon peak in ¹³C NMR spectrum of Permian vitrinite is mostly composed of gas-prone carbons compared with collodetrinites in those Jurassic basins. But both pyrolysis and ¹³C NMR data shows the Pennsylvanian vitrinite is not only gas-prone but also oil-prone. Relatively high proportion of long chain aliphatic structure of some Jurassic vitrinite in Junggar, Turpan-Hami basins may be due to the contribution of liptodetrinites, which may be included during the formation of vitrinites. And it seems that suberinite is the most possible precursor of long chain aliphatics in the structure of Jurassic collodetrinite.     

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.     

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.     

Three‐dimensional simulation of tsunami run‐up around conical island

At the circular Babi Island in the Flores tsunami (1992) and pear shaped island in the Okushiri event (1993), unexpectedly large tsunami run‐up heights in the lee of conic islands were observed. The flume and basin physical model studies were conducted in the Coastal Hydraulic Laboratory, Engineering Research and Development Center, U.S. Army Corps of Engineers to provide a better understanding of the physical phenomena and verify numerical models used in predicting tsunami wave run‐up on beaches, islands, and vertical walls. Reasonably accurate comparison of run‐up height of solitary waves on a circular island has been obtained between laboratory experimental results and two‐dimensional computation model results. In this study we apply three‐dimensional RANS model to simulate wave run‐up on conical island. In the run‐up computation we obtain that 3D calculations are in very good comparison with laboratory and 2D numerical results. A close examination of the three‐dimensional velocity distribution around conical island to compare with depth‐integrated model is performed. It is shown that the velocity distribution along the vertical coordinate is not uniform: and velocity field is weaker in the bottom layer and higher on the sea surface. The maximum difference (about 40%) appears at the time when solitary wave reached the circular island.     

Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Rare Earth Deposits of North America

Rare earth elements (REE) have been mined in North America since 1885, when placer monazite was produced in the southeast USA. Since the 1960s, however, most North American REE have come from a carbonatite deposit at Mountain Pass, California, and most of the world’s REE came from this source between 1965 and 1995. After 1998, Mountain Pass REE sales declined substantially due to competition from China and to environmental constraints. REE are presently not mined at Mountain Pass, and shipments were made from stockpiles in recent years. Chevron Mining, however, restarted extraction of selected REE at Mountain Pass in 2007. In 1987, Mountain Pass reserves were calculated at 29 Mt of ore with 8.9% rare earth oxide based on a 5% cut‐off grade. Current reserves are in excess of 20 Mt at similar grade. The ore mineral is bastnasite, and the ore has high light REE/heavy REE (LREE/HREE). The carbonatite is a moderately dipping, tabular 1.4‐Ga intrusive body associated with ultrapotassic alkaline plutons of similar age. The chemistry and ultrapotassic alkaline association of the Mountain Pass deposit suggest a different source than that of most other carbonatites. Elsewhere in the western USA, carbonatites have been proposed as possible REE sources. Large but low‐grade LREE resources are in carbonatite in Colorado and Wyoming. Carbonatite complexes in Canada contain only minor REE resources. Other types of hard‐rock REE deposits in the USA include small iron‐REE deposits in Missouri and New York, and vein deposits in Idaho. Phosphorite and fluorite deposits in the USA also contain minor REE resources. The most recently discovered REE deposit in North America is the Hoidas Lake vein deposit, Saskatchewan, a small but incompletely evaluated resource. Neogene North American placer monazite resources, both marine and continental, are small or in environmentally sensitive areas, and thus unlikely to be mined. Paleoplacer deposits also contain minor resources. Possible future uranium mining of Precambrian conglomerates in the Elliott Lake–Blind River district, Canada, could yield by‐product HREE and Y. REE deposits occur in peralkaline syenitic and granitic rocks in several places in North America. These deposits are typically enriched in HREE, Y, and Zr. Some also have associated Be, Nb, and Ta. The largest such deposits are at Thor Lake and Strange Lake in Canada. A eudialyte syenite deposit at Pajarito Mountain in New Mexico is also probably large, but of lower grade. Similar deposits occur at Kipawa Lake and Lackner Lake in Canada. Future uses of some REE commodities are expected to increase, and growth is likely for REE in new technologies. World reserves, however, are probably sufficient to meet international demand for most REE commodities well into the 21st century. Recent experience shows that Chinese producers are capable of large amounts of REE production, keeping prices low. Most refined REE prices are now at approximately 50% of the 1980s price levels, but there has been recent upward price movement for some REE compounds following Chinese restriction of exports. Because of its grade, size, and relatively simple metallurgy, the Mountain Pass deposit remains North America’s best source of LREE. The future of REE production at Mountain Pass is mostly dependent on REE price levels and on domestic REE marketing potential. The development of new REE deposits in North America is unlikely in the near future. Undeveloped deposits with the most potential are probably large, low‐grade deposits in peralkaline igneous rocks. Competition with established Chinese HREE and Y sources and a developing Australian deposit will be a factor.     

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for ²⁰⁶pb/²³⁸U and 0.7392 ± 0.0003 for ²⁰⁷pb/²³⁵U. Its ²⁰⁶pb/²³⁸U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ～ 840 μg g^?1 U (Th/U ～ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 10¹⁸ g^?1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.     

Unequal Competition Among Chains of Supercenters: Kmart,Target, and Wal‐Mart

The three largest discount chains, Kmart, Target, and Wal‐Mart, have adopted the supercenter format for expansion. This article examines the locations of and the competition among these supercenters. Wal‐Mart has the greatest number of supercenters and is driving the expansion of the supercenter format. Both Kmart and Target have clustered their supercenters in a small number of metropolitan markets. In contrast to Wal‐Mart and Kmart, Target has focused on a middle‐class rather than a blue‐collar clientele. Now Kmart is struggling following a declaration of bankruptcy. Wal‐Mart has largely defeated its supercenter competitors and now is confronting the major grocery chains for grocery sales.     

Tests on low‐ductility RC frames under high‐ and low‐frequency excitations

The response of low‐ductility reinforced concrete (RC) frames, designed typically for a non‐seismic region, subjected to two frequencies of base excitations is studied. Five half‐scaled, two‐bay, two‐storey, RC frames, each approximately 5 m wide by 3.3 m high, were subjected to both horizontal and/or vertical base excitations with a frequency of 40 Hz as well as a lower frequency of about 4 Hz (close to the fundamental frequency) using a shake table. The imposed acceleration amplitude ranged from 0.2 to 1.2g. The test results showed that the response characteristics of the structures differed under high‐ and low‐frequency excitations. The frames were able to sustain high‐frequency excitations without damage but were inadequate for low‐frequency excitations, even though the frames exhibited some ductility. Linear‐elastic time‐history analysis can predict reasonably well the structural response under high‐frequency excitations. As the frames were not designed for seismic loads, the reinforcement detailing may not have been adequate, based on the crack pattern observed. The effect of vertical excitation can cause significant additional forces in the columns and moment reversals in the beams. The ‘strong‐column, weak‐beam’ approach for lateral load RC frame design is supported by experimental observations. Copyright © 2001 John Wiley & Sons, Ltd.