Polycyclic aromatic hydrocarbons and their molecular diagnostic ratios in urban atmospheric respirable particulate matter

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) in Santiago de Chile city were evaluated to study particulate PAHs profiles during cold and spring weather periods. Urban atmospheric particulate matter PM10 was collected using High Volume PM10 samplers. Fifteen samples of 24 h during austral winter and 20 samples of 24 h during spring, 2000 were collected at two sampling sites (North–East and Central areas of the city) whose characteristics were representative of the prevailing conditions. Seventeen PAHs were quantified and total PAHs concentration ranged from 1.39 to 59.98 ng m⁻³, with a seasonal variation (winter vs. spring ratio) from 0.5 to 12.6 ng m⁻³. Molecular diagnostic ratios were used to characterize and identify PAHs emission sources such as combustion and biogenic emissions. Results showed that the major sources of respirable organic aerosol PM10 in Santiago are mobile and stationary ones.     

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.     

The Ordovician Sierras Pampeanas–Puna basin connection: Basement thinning and basin formation in the Proto-Andean back-arc

The Ordovician Sierras Pampeanas, located in a continental back-arc position at the Proto-Andean margin of southwest Gondwana, experienced substantial mantle heat transfer during the Ordovician Famatina orogeny, converting Neoproterozoic and Early Cambrian metasediments to migmatites and granites. The high-grade metamorphic basement underwent intense extensional shearing during the Early and Middle Ordovician. Contemporaneously, up to 7000 m marine sediments were deposited in extensional back-arc basins covering the pre-Ordovician basement. Extensional Ordovician tectonics were more effective in mid- and lower crustal migmatites than in higher levels of the crust. At a depth of about 13 km the separating boundary between low-strain solid upper and high-strain lower migmatitic crust evolved to an intra-crustal detachment. The detachment zone varies in thickness but does not exceed about 500 m. The formation of anatectic melt at the metamorphic peak, and the resulting drop in shear strength, initiated extensional tectonics which continued along localized ductile shear zones until the migmatitic crust cooled to amphibolite facies P–T conditions. P–T–d–t data in combination with field evidence suggest significant (ca. 52%) crustal thinning below the detachment corresponding to a thinning factor of 2.1. Ductile thinning of the upper crust is estimated to be less than that of the lower crust and might range between 25% and 44%, constituting total crustal thinning factors of 1.7–2.0. While the migmatites experienced retrograde decompression during the Ordovician, rocks along and above the detachment show isobaric cooling. This suggests that the magnitude of upper crustal extension controls the amount of space created for sediments deposited at the surface. Upper crustal extension and thinning is compensated by newly deposited sediments, maintaining constant pressure at detachment level. Thinning of the migmatitic lower crust is compensated by elevation of the crust–mantle boundary. The degree of mechanical coupling between migmatitic lower and solid upper crust across the detachment zone is the main factor controlling upper crustal extension, basin formation, and sediment thickness in the back-arc basin. The initiation of crustal extension in the back-arc, however, crucially depends on the presence of anatectic melt in the middle and lower crust. Consumption of melt and cooling of the lower crust correlate with decreasing deposition rates in the sedimentary basins and decreasing rates of crustal extension.     

Evaluation of a Quality Control Monitor Material for the Routine Electron Probe Microanalysis of Kimberlite Exploration Garnets

Election probe microanalysis of indicator minerals is extensively used in the exploration for kimberlite deposits, the evaluation of specific kimberlite occurrences for their diamond bearing potential and to classify grains into different chemical and lithological mantle associations. Kimberlite exploration programmes can involve several tens of thousands of indicator mineral analyses. Procedures for monitoring data quality and consistency of analyses across large data sets are commonly absent. Suitable monitor minerals should be used to verify the data quality of kimberlite exploration and evaluation data sets. This material should have a suitable composition, be homogenous, be available in sufficient quantities and have a similar appearance to the unknown samples. Garnet P1, a megacryst garnet from the Premier kimberlite, was found to have a suitable composition as a monitor for kimberlite garnet analyses. Data were collected on the monitor material at regular intervals during routine analyses, over an extended period, both as a fixed grain mounted on the sample holder and as separate grains set within batches of routine samples. The data were evaluated to assess the quality and consistency in the analyses of large data sets over time. The monitor material was also analysed at independent laboratories using their routine analytical set-up and calibration procedures for comparative purposes. Values are given for the mean ± 2s range, which can serve as guide values for acceptable analyses for all elements.     

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).     

Silicate‐oxide mineral chemistry of mafic–ultramafic rocks as an indicator of the roots of an island arc: The Chilas Complex,Kohistan (Pakistan)

The Chilas Complex is a major lower crustal component of the Cretaceous Kohistan island arc and one of the largest exposed slices of arc magma chamber in the world. Covering more than 8000 km², it reaches a current tectonic width of around 40 km. It was emplaced at 85 Ma during rifting of the arc soon after the collision of the arc with the Karakoram plate. Over 85% of the Complex comprises homogeneous, olivine‐free gabbronorite and subordinate orthopyroxene–quartz diorite association (MGNA), which contains bodies of up to 30 km² of ultramafic–mafic–anorthositic association (UMAA) rocks. Primary cumulate textures, igneous layering, and sedimentary structures are well preserved in layered parts of the UMAA in spite of pervasive granulite facies metamorphism. Mineral analyses show that the UMAA is characterized by more magnesian and more aluminous pyroxene and more calcic plagioclase than those in the MGNA. High modal abundances of orthopyroxene, magnetite and ilmenite (in MGNA), general Mg–Fe–Al spatial variations, and an MFA plot of whole‐rock analyses suggest a calc‐alkaline origin for the Complex. Projection of the pyroxene compositions on the Wo–En–Fs face is akin to those of pyroxenes from island arcs gabbros. The presence of highly calcic plagioclase and hornblende in UMAA is indicative of hydrous parental arc magma. The complex may be a product of two‐stage partial melting of a rising mantle diaper. The MGNA rocks represent the earlier phase melting, whereas the UMAA magma resulted from the melting of the same source depleted by the extraction of the earlier melt phase. Some of the massive peridotites in the UMAA may either be cumulates or represent metasomatized and remobilized upper mantle. The Chilas Complex shows similarities with many other (supra)subduction‐related mafic–ultramafic complexes worldwide.     

Sensitivity of the surface temperature to changes in total solar irradiance calculated with the WRF model

The temperature sensitivity of the WRF model to changes in Total Solar Irradiance (TSI). The simulations were performed for a region centered over the North Atlantic Ocean, including portions of Eastern North America, Western Europe and Northwest Africa. Four simulations were run with different TSI values. Also, a fifth simulation was performed in which we varied the initial atmospheric conditions, in order to compare the effect on the temperature of both, changes in the TSI and initial atmospheric conditions. Comparing temperature monthly averages we found that changes in TSI and in the initial conditions have a measurable impact on temperature in the region of study. The sensitivity of the model using non-dimensional parameters was also estimated. The numerical experiments show some features that might allow to distinguish between the effects on the temperature due to changes in TSI from those caused by initial conditions. However, TSI changes are of the same order of magnitude than those of disturbances in the initial conditions. We also found that the mean monthly values of temperature over the full grid, did not present significant variations due to changes of either initial conditions or TSI.     

Enhancing the Two-Step Floating Catchment Area Model for Community Food Access Mapping: Case of the Supplemental Nutrition Assistance Program

In this article, a Gaussian-based two-step floating catchment area (2SFCA) model is applied to evaluate the geographical accessibility to Supplemental Nutrition Assistance Program (SNAP)-authorized retailers. First, the proposed method considers the interaction between the food supply (in terms of categorized benefit redemptions) and demand (in terms of benefit-receiving households). Second, the model is used to visualize food access patterns at the level of refined administrative units (i.e., census block groups). The developed food access metric was compared to the U.S. Department of Agriculture (USDA) Food Access Research Atlas, justifying the validity of this new method for small area estimation. The following are important observations: (1) the choice of catchment size had a considerable impact on the accessibility measure in urban areas (or when small statistical units are used); (2) the 2SFCA measurement had a higher level of correspondence with that of the USDA Atlas at a smaller catchment size for identifying low food access units; and (3) there was no significant inequality regarding SNAP accessibility with respect to different socioeconomic deprivation variables. This new method can better assist the SNAP administration with store authorization on a refined geographic scale. Key Words: food access, inequality, scale, Supplemental Nutrition Assistance Program (SNAP), two-step floating catchment area (2SFCA).     

Simultaneous Determination of Fluorine,Chlorine, Bromine and Iodine in Six Geochemical Reference Materials Using Pyrohydrolysis,Ion Chromatography and Inductively Coupled Plasma‐Mass Spectrometry

Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO‐2, GS‐N, JG‐1, JR‐1, JB‐1b, JB‐2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma‐mass spectrometry for Br and I. The detection limits in solutions were 100 μg l^?1 for both F and Cl and 10 ng l^?1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg^?1 for F and Cl and 2 μg kg^?1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg^?1 for F and Cl, 100 μg kg^?1 for Br and 25 μg kg^?1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.     

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.