Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.     

Quantification of river water infiltration in shallow aquifers using acesulfame and anthropogenic gadolinium

This study has investigated the use of the artificial sweetener acesulfame and the magnetic resonance imaging contrast agent gadolinium as quantitative tracers for river water infiltration into shallow groundwater. The influence of a river on alluvial groundwater in a subalpine catchment in western Europe has been assessed using the ‘classical’ hydrochemical tracer chloride and the trace contaminants acesulfame and anthropogenic gadolinium. Mixing ratios for riverine bank filtrate with ambient groundwater and the uncertainties associated with the temporal and spatial tracer variability were calculated using acesulfame and gadolinium and compared with those obtained using chloride. The temporal variability of tracer concentrations in river water of gadolinium (standard deviation SD: 63%) and acesulfame (SD: 71%) both exceeded that of chloride (SD: 27%), and this was identified as the main source of uncertainty in the mixing analysis. Similar spatial distributions were detected in the groundwater for chloride and gadolinium, but not for acesulfame. Mixing analyses using acesulfame resulted in calculated mixing ratios that differed from those obtained using gadolinium and chloride by up to 83% and 92%, respectively. At the investigated site, which had oxic conditions and moderate temperatures, acesulfame was found to be a less reliable tracer than either gadolinium or chloride, probably because of natural attenuation and input from other sources. There was no statistically significant difference between the mixing ratios obtained using chloride or gadolinium, the mixing ratios obtained using gadolinium were 40–50% lower than those obtained using chloride. This is mainly due to a bias of the mean gadolinium concentration in river water towards higher values. In view of the uncertainties of the two tracers, neither could be preferred over the other for the quantification of bank filtrate in groundwater. At this specific site gadolinium was able to reliably identify river water infiltration and was a more precise tracer than chloride at low mixing ratios (<20%), because of the exclusive occurrence of gadolinium in river water and its high dynamic range. Copyright © 2015 John Wiley & Sons, Ltd.     

川西地区台阵环境噪声瑞利波相速度层析成像

2006年中国地震局地质研究所地震动力学国家重点实验室在川西地区(26°N~32°N,100°E~105°E)布设了由297台宽频带数字地震仪组成的流动观测台阵.利用该密集台阵29°N以北156个台站2007年1~12月份的地震环境噪声记录和互相关技术,我们得到了所有台站对的面波经验格林函数和瑞利波相速度频散曲线,并进一步反演得到了观测台阵下方2~35 s周期的瑞利波相速度分布图像．本文结果表明,观测台阵覆盖的川滇地块、松潘-甘孜地块和四川盆地的地壳速度结构存在显著差异,具体表现为：(1)短周期（2~8 s）相速度分布与地表构造特征相吻合,作为川滇地块、松潘-甘孜地块和四川盆地之间的边界断裂,龙门山断裂带和鲜水河断裂带对上述三个地块上地壳的速度结构具有明显的控制作用,四川盆地前陆低速特征表明相应区域存在较厚的（约10 km）沉积盖层;(2)中周期（12~18 s）相速度分布表明,川滇地块和松潘-甘孜地块中上地壳速度结构存在明显的不均匀横向变化,并形成了尺度不同且高、低速相间的分块结构,而四川盆地中地壳整体上已经表现出相对高速;(3)长周期（25~35 s）相速度分布表明,松潘-甘孜地块,特别是川滇地块中下地壳表现为广泛的明显低速异常,意味着它们的中下地壳相对软弱,而四川盆地的中下地壳呈现整体性的相对高速,意味着四川盆地具有相对坚硬的中下地壳,并且以汶川地震的震中为界,龙门山断裂带的地壳结构显示了北段为高速异常,南段为低速异常的分段特征．     

Reprint of: Diagenetic controls on evolution of porosity and permeability in lower Tertiary Wilcox sandstones from shallow to ultradeep (200–6700 m) burial,Gulf of Mexico Basin,U.S.A.

Reservoir quality is a critical risk factor in deep to ultradeep reservoirs at depths >4.5 km. Analysis of Paleogene Wilcox sandstones on the upper Texas Gulf Coast provides insight into the evolution of reservoir quality during shallow to ultradeep burial diagenesis. Reduction of porosity and permeability with burial in Wilcox sandstones was evaluated using subsurface samples from 200 to 6700 m, at temperatures of 25–230 °C. Diagenesis and petrophysical properties were interpreted from petrographic data and core analyses. Wilcox sandstones are mostly lithic arkoses and feldspathic litharenites having an average composition of Q₅₉F₂₂R₁₉. Provenance did not change significantly during Wilcox deposition in this area, nor does average sandstone composition vary among lower, middle, and upper Wilcox sandstones. However, composition does vary with sequence-stratigraphic position; lowstand slope-fan deposits contain more rock fragments than do deposits from highstand or transgressive systems tracts. Given observations from this onshore dataset, Wilcox sandstones deposited in deepwater environments in the Gulf of Mexico are likely to contain more rock fragments than their linked highstand equivalents.     

Assessing regression‐based statistical approaches for downscaling precipitation over North America

This paper assesses linear regression‐based methods in downscaling daily precipitation from the general circulation model (GCM) scale to a regional climate model (RCM) scale (45‐ and 15‐km grids) and down to a station scale across North America. Traditional downscaling experiments (linking reanalysis/dynamical model predictors to station precipitation) as well as nontraditional experiments such as predicting dynamic model precipitation from larger‐scale dynamic model predictors or downscaling dynamic model precipitation from predictors at the same scale are conducted. The latter experiments were performed to address predictability limit and scale issues. The results showed that the downscaling of daily precipitation occurrence was rarely successful at all scales, although results did constantly improve with the increased resolution of climate models. The explained variances for downscaled precipitation amounts at the station scales were low, and they became progressively better when using predictors from a higher‐resolution climate model, thus showing a clear advantage in using predictors from RCMs driven by reanalysis at its boundaries, instead of directly using reanalysis data. The low percentage of explained variances resulted in considerable underestimation of daily precipitation mean and standard deviation. Although downscaling GCM precipitation from GCM predictors (or RCM precipitation from RCM predictors) cannot really be considered downscaling, as there is no change in scale, the exercise yields interesting information as to the limit in predictive ability at the station scale. This was especially clear at the GCM scale, where the inability of downscaling GCM precipitation from GCM predictors demonstrates that GCM precipitation‐generating processes are largely at the subgrid scale (especially so for convective events), thus indicating that downscaling precipitation at the station scale from GCM scale is unlikely to be successful. Although results became better at the RCM scale, the results indicate that, overall, regression‐based approaches did not perform well in downscaling precipitation over North America. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of the REE in Geological Reference Materials DTS-1 (Dunite) and PCC-1 (Peridotite) by Ultrasonic and Microconcentric Desolvating Nebulisation ICP-MS

Inductively coupled plasma-mass spectrometry is well suited for the precise, accurate and rapid determination of rare earth elements in most geological samples. However, determination of rare earth elements in certain mantle-derived materials, without applying preconcentration techniques, remains problematical due to low natural concentrations (generally < 1 ng g⁻¹). Consequently, USGS reference materials DTS-1 (a dunite) and PCC-1 (a partially serpentinized harzburgite) have only suggested rather than recommended values for the rare earth elements in reference material compilations. We compared results obtained using two ICP-MS instruments: a U-5000AT ultrasonic nebuliser coupled to a PQ2+ quadrupole ICP-MS and an ELEMENT sector field ICP-MS equipped with a MCN-6000 microconcentric desolvating nebuliser, with the suggested literature values for these two reference materials. Precision and accuracy of analytical methods employed by both instruments were demonstrated by excellent relative standard deviations (< 2%) and inter-laboratory agreement (< 5%) for numerous analyses of BHVO-1 and BIR-1, which are well established with rare earth elements contents at the μg g⁻¹ level. Repeat analyses of DTS-1 and PCC-1 at each laboratory indicate that each method is generally precise to better than 5% at sub-g g⁻¹ levels. Furthermore, values from both instruments generally agree to within 10%. Our DTS-1 and PCC-1 values agree reasonably well with selected data reported in the literature (except for Ce and Sm in DTS-1) but exhibit poorer agreement with reported compilation values. With the demonstrated level of precision and accuracy, we contend that these new values for DTS-1 and PCC-1, generated by two different instruments, are the best estimates of the true whole-rock composition of these samples reported to date.     

226Ra behavior in the Pee Dee River-Winyah Bay estuary

Concentrations of dissolved²²⁶Ra in Winyah Bay, South Carolina, and in the adjacent Atlantic Ocean are augmented by the desorption of radium from sediments in the low-salinity area of the estuary and diffusion from bottom sediments. Desorption of²²⁶Ra is reflected by lower concentrations in suspended sediments from higher-salinity regions of the estuary. Bottom sediments from the high-salinity region have lower²²⁶Ra/²³⁰Th activity ratios than those from the low-salinity end.The shape of the dissolved²²⁶Ra vs. salinity profile is influenced by the river discharge. During average-discharge conditions, desorption of²²⁶Ra from suspended and bottom sediments increases the dissolved²²⁶Ra concentrations by a factor of 3.5 as the water passes through Winyah Bay. High river discharge produces an initial increase of dissolved²²⁶Ra by a factor of 2 to 3 and apparently reflects only desorption from suspended sediments. By driving the salt wedge down the estuary and reducing the zone of contact of salt water with bottom sediments, the high-flow conditions sharply reduce the flux of²²⁶Ra from bottom sediments.     

Consequences of change and variability in sea ice on marine ecosystem and biogeochemical processes during the 2007–2008 Canadian International Polar Year program

Change and variability in the timing and magnitude of sea ice geophysical and thermodynamic state have consequences on many aspects of the arctic marine system. The changes in both the geophysical and thermodynamic state, and in particular the timing of the development of these states, have consequences throughout the marine system. In this paper we review the ??consequences?? of change in sea ice state on primary productivity, marine mammal habitats, and sea ice as a medium for storage and transport of contaminants and carbon exchange across the ocean-sea-ice-atmosphere interface based upon results from the International Polar Year. Pertinent results include: 1) conditions along ice edges can bring deep nutrient-rich ??pacific?? waters into nutrient-poor surface waters along the arctic coast, affecting local food webs; 2) both sea ice thermodynamic and dynamic processes ultimately affect ringed seal/polar bear habitats by controlling the timing, location and amount of surface deformation required for ringed seal and polar bear preferred habitat 3) the ice edges bordering open waters of flaw leads are areas of high biological production and are observed to be important beluga habitat. 4) exchange of climate-active gases, including CO₂, is extremely active in sea ice environments, and the overall question of whether the Arctic Ocean is (or will be) a source or sink for CO₂ will be dependent on the balance of competing climate-change feedbacks.     

Remote sensing techniques for landslide studies and hazard zonation in Europe

An inventory is presented of researches concerning the use of remote sensing for landslide studies and hazard zonation as mainly carried out in the countries belonging to the European Community. An overview is given of the applicability of remote sensing in the following phases of landslide studies:

1. (1) Detection and classification of landslides. Special emphasis is given to the types of imagery required at different scales of analysis.

2. (2) Monitoring the activity of existing landslides using G.P.S., photogrammetrical techniques and radar interferometry.

3. (3) Analysis and prediction in space and time of slope failures. The different factors required in a landslide hazard study are evaluated, and the optimum remote sensing imagery for obtaining each of these factors is indicated.

Examples are given of research work carried out in these three phases from EC countries. Finally an evaluation is given of the aspects of uncertainty associated with the use of remote sensing data, and conclusions are given as to the incorporation of remote sensing techniques within the overall framework of techniques.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.