Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.     

Production and Certification of Synthetic Selenium Isotopic Reference Materials

Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with ⁷⁶Se, ⁷⁸Se, ⁸⁰Se and ⁸²Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding ⁷⁸Se/⁷⁶Se isotope mixtures and ⁸²Se/⁷⁶Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ^82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

Down‐slope facies variability within deep‐water channel systems: Insights from the Upper Cretaceous Cerro Toro Formation,southern Patagonia

In southern Patagonia, outcrops of the Upper Cretaceous Cerro Toro Formation preserve a >150 km long deep‐water axial channel belt in the Magallanes–Austral Basin, providing a unique opportunity to investigate longitudinal variations in the depositional characteristics of a deep‐water channel system. This study documents sedimentological, stratigraphical and geochronological data from the Cerro Toro Formation in the Argentine sector of the basin. New results are integrated with previous work from the Chilean basin sector to conduct a basin‐scale comparison of the timing of deposition, provenance and lithofacies proportions. The Cerro Toro channel belt includes a nearly 1000 m thick section characterized by high‐density turbidites and mass‐wasting deposits. Two ash beds from the base of the section yield U–Pb zircon ages of 90·4 ± 2 Ma and 88·0 ± 3 Ma, indicating similar initiation ages as documented in the Chilean sector. The U–Pb detrital zircon age spectra from samples in the study area reveal similar provenance trends to samples from the Chilean basin sector, with peak age populations at 310 to 260 Ma, 160 to 135 Ma and 110 to 82 Ma. The maximum depositional age of the channel belt in the Argentine sector is 87·8 ± 1·5 Ma and all new geochronology data corroborate an 86 to 80 Ma depositional age for the main Cerro Toro channel belt. Statistical analyses of 7370 beds from nearly 8000 m of new and previously published stratigraphic sections along the entire outcrop belt suggest progressive variations in the down‐system proportion of lithofacies. In the up‐slope region, lithofacies representing mass wasting processes (for example, debris‐flow and mass‐transport deposits) account for ca 29% of the stratigraphic thickness, as opposed to 5% in the down‐slope region of the channel belt, where turbidity current deposits are more prevalent. The proportion of beds >1 m thick also decreases systematically down slope, particularly for conglomeratic turbidite deposits. This work highlights that: (i) the proportion of thick beds and distribution of lithofacies are key down‐system changes in the stratigraphic fill of this deep‐water channel belt; (ii) detrital zircon trends suggest a relatively well‐mixed longitudinal depositional system; and (iii) geochronology of the main Cerro Toro outcrop belt supports but does not necessitate the model of a single, roughly age‐equivalent, channel system. This study has implications for understanding the downslope variability in depositional processes, stratigraphic architecture and reservoir quality of submarine channel systems.     

投喂四种饵料对曼氏无针乌贼(Sepiella maindroni)繁殖性能的影响

以双齿围沙蚕、泥鳅、黄鲫、福寿螺4种不同饵料强化培育胴长(6.50±0.20)cm的曼氏无针乌贼,用曼氏无针乌贼肝脏和卵巢的氨基酸与脂肪酸变化、亲体产卵量、卵径、卵子孵化率及其幼体成活率等指标来评价4种饵料对其繁殖性能的影响.结果表明,黄鲫组曼氏无针乌贼肝脏与卵巢中∑EAA、∑SEAA、∑EAA+SEAA、∑NEAA、∑AA含量在第一次卵巢成熟与第二次卵巢成熟时均显著高于其它投喂组(P＜0.05).黄鲫组乌贼肝脏DHA/EPA在第一次卵巢成熟时显著高于其它投喂组,在第二次卵巢成熟时DHA、DHA/EPA、∑n3PUFA、∑n6PUFA、∑n3/n6PUFA都显著高于其它投喂组(P＜0.05);该组乌贼第一次卵巢成熟卵巢DHA、∑n3PUFA、∑n6PUFA、∑n3/n6PUFA及在第二次卵巢成熟时卵巢DHA、DHA/EPA、∑n3PUFA、∑n3/n6PUFA均显著高于其它投喂组(P＜0.05),该组第二次卵巢成熟时∑n6PUFA百分含量与沙蚕组无显著差异(P＞0.05).产卵量多少顺序为黄鲫组＞沙蚕组＞泥鳅组＞福寿螺组(P＜0.05);孵化率高低顺序为黄鲫组＞福寿螺组＞泥鳅组＞沙蚕组(P＜0.05);所产卵子平均直径大小顺序为黄鲫组＞泥鳅组＞沙蚕组＞福寿螺组(P＜0.05);幼体成活率高低顺序为黄鲫组＞泥鳅组＞沙蚕组、福寿螺组(P＜0.05).各指标吻合程度高.     

Abundance,distribution, and feeding patterns of juvenile coho salmon (Oncorhynchus kisutch) in the Juan de Fuca Eddy

The Juan de Fuca Eddy is a seasonal, counter-clockwise gyre off the mouth of the Strait of Juan de Fuca between Washington, USA and British Columbia, Canada that may provide favorable feeding habitat for juvenile coho salmon (Oncorhynchus kisutch) during their early marine existence. In late September 2002, physical and biological sampling was conducted along two transects of the eddy region. Surface rope trawling was conducted to capture juvenile salmon and other nekton, along with bongo and neuston net tows to examine potential mesozooplanktonic salmon prey. Presence of the Juan de Fuca Eddy was confirmed with vertical water profiles. In addition, nutrient and chlorophyll a concentrations collected from 3-m depth were within the range observed in previous studies within the eddy region. In the mesozooplankton community, euphausiids, chaetognaths, and decapod megalopae were common. In the diet of juvenile coho salmon, euphausiids and decapod megalopae were dominant by percent number, and larval and juvenile fish were dominant by percent weight. Feeding intensity (percent body weight) based on stomach contents was variable, but not significantly different among stations. To compare the Juan de Fuca Eddy region with an upwelling area, we sampled along a transect off La Push (LP), Washington, USA which is south of the eddy. The eddy region was found to be less productive than the LP transect. Nutrients were lower, chlorophyll a concentrations were higher, and zooplankton abundance was generally higher along the LP transect than in the eddy region. In addition, more juvenile coho salmon were captured from the LP transect than the eddy region. Prey items in stomachs of salmon from the LP transect were heterogeneous compared to those from the eddy region. Feeding intensity along the LP transect was slightly lower and more variable than in the eddy region, and differences in feeding intensity among LP stations were significant. In addition, feeding intensities among stations nested within regions were significantly different.     

Integrating spectral and non-spectral data to improve urban settlement mapping in a large Latin-American city

ABSTRACT

Information on urban settlements is crucial for sustainability planning and management. While remote sensing has been used to derive such information, its applicability can be compromised due to the complexity in the urban environment. In this study, we developed a remote sensing method to map land cover types in a large Latin-American city, which is well known for its mushrooming unplanned and informal settlements. After carefully considering the landscape complexity there, we designed a data fusion method combining multispectral imagery and non-spectral data for urban and land mapping. Specifically, we acquired a cloud-free Landsat-8 image and two non-spectral datasets, i.e., digital elevation models and road networks. Then, we implemented a set of experiments with different inputs to evaluate their merits in thematic mapping through a supervised protocol. We found that the map generated with the multispectral data alone had an overall accuracy of 73.3% but combining multispectral imagery and non-spectral data yielded a land cover map with 90.7% overall accuracy. Interestingly, the thermal infrared information helped substantially improve both the overall and categorical accuracies, particularly for the two urban classes. The two types of non-spectral data were critical in resolving several spectrally confused categories, thus considerably increasing the mapping accuracy. However, the panchromatic band with higher spatial resolution and its derived textural measurement only generated a marginal accuracy improvement. The novelties of our work are with the successful separation between the two major types of urban settlements in a complex environment using a carefully designed data fusion approach and the insight into the relative merits of the thermal infrared information and non-spectral data in helping resolve the issue of class ambiguity. These findings should be valuable in deriving accurate urban settlement information which can further advance the research on socio-ecological dynamics and urban sustainability.