Characterization of black volcanites from the Limay river basin, Patagonia, Argentina, using energy dispersive X-ray fluorescence spectrometry: an aid to infer human group mobility

The investigation of hunter-gatherers archaeological sites in the Limay river basin, Patagonia, Argentina, raised questions concerning the lithic technology. The chemical characterization of artifacts, rocks and possible sources of provenances could help to elucidate the hunter-gatherer mobility. In three archaeological sites—Rincón Chico 2 (RCh2/87; ¹⁴C 710 ± 60 BP), Cueva Traful I (CTI; ¹⁴C 9430 ± 230 BP) and Casa de Piedra de Ortega (CPO; ¹⁴C 2840 ± 80 BP), tools and debitage or discarded flakes made in black volcanic rock have been found. Nearby an extensive rock outcrop of black volcanite, Paso Limay quarry (CPL), with similar characteristics was located. Samples coming from these four sites were analyzed by energy dispersive X-ray fluorescence spectrometry. This characterization allowed the geochemical classification of the lithic material and to correlate the samples with the suspected source after a previous statistical analysis. The majority of the samples were classified as dacites and rhyolites. Only samples coming from CPO site, the closest place to CPL were made exclusively with the quarry rocks. A set of five samples from RCh2/87 and two samples from CTI appear to have same chemical composition as CPL in spite of this site is placed in the opposite bank of the Limay river suggesting that hunter-gatherers could accede to the quarry, eventually. Finally, only a set of five samples coming from RCh2/87 and CTI do not group with the quarry. This fact evidences the existence of secondary sources of supply. The information of this research allowed inferring ancient human mobility patterns in the region.     

Environmetric modeling of emission sources for dry and wet precipitation from an urban area

Monitoring data from chemical analysis of rainwater and aerosol samples collected in an urban area have been interpreted by the use of environmetric approaches. An attempt was done to compare the data set structures of both type of precipitation and to estimate the contribution of different anthropogenic and naturally occurring emission sources to the total mass of the wet and dry precipitation. It was found that three latent factors explaining over 80% of the total variance of the set are responsible for the rainwater set structure-'sea spray', 'soil dust', and 'anthropogenic'. Only two were the latent factors explaining the dominant part of the variance in the case of aerosol samples-'anthropogenic' and 'natural'. It is shown that the anthropogenic influence for aerosol samples is more complex that that of rainwater samples and represents interaction between typical anthropogenic sources and natural emitters. Additionally, a source apportioning using multiple regression on absolute principal component scores is performed in order to obtain qualitative information about the impact of the different identified emission sources on the urban environment.     

Determination of elemental composition of atmospheric aerosol in the urban area of Islamabad, Pakistan

Summary This study provides useful information about the level and chemical composition of particulate matter and about the possible sources of the aerosol pollutant in Islamabad, the capital of Pakistan. Atmospheric aerosol samples were collected during winter (January and February) 1995, from two locations of Islamabad, namely of Sector F-7 and Sector I-9. Twenty-four elements were detected by using thermal neutron activation analysis (NAA) and atomic absorption spectrometry (AAS). The concentration of total suspended particulates (TSP) in the area around the industrial sector (I-9) was found to be more than twice higher (297 μg/m³) than in the Sector F-7 (133 μg/m³). The enrichment factor analysis revealed Zn, As, Br, Sb, I and Pb, originated mainly from anthropogenic sources. The elemental ratio analysis indicated that both Sectors I-9 and F-7 are under the influence of coal burning processes whereas transportation is responsible for the toxic pollutants Pb and Br. The present results were discussed and compared with those of the literature. The results may also serve as base line level as this work employed samples collected in 1995 and many of the air environmental change factors occurred after the sampling year.     

Prediction and measurement of pollutant emissions in CNG fired internal combustion engine

In the present study, the detailed reaction mechanisms were developed and Chemkin 4.1.1 was implemented to predict the formation of pollutant species in compressed natural gas (CNG) fired internal combustion (IC) engine. The proposed mechanisms were developed by coupling the EXGAS (an automatic mechanism generation tool for alkane oxidation) mechanisms with the Leed's NOx mechanism (version 2.0). The simulation results of each proposed mechanism were validated by the experimental measurements for profiles of temperature, pressure and pollutant species (CO, NOx). The rate of production analysis of each mechanism identified the important reactions in each mechanism which contributed to the formation of pollutant species. In spite of some discrepancies, the experimental measurements indicate that Mechanism-IV (consisting of 208 reactions and 78 species) showed closer agreement for each of the predicted profiles of temperature, pressure and pollutant species (CO, NOx).     

Chemometrical investigation of the presence and distribution of organochlorine and polyaromatic compounds in sediments of the Ebro River Basin

A multivariate statistical data analysis, using principal component analysis, of historical data from 1996 to 2003 concerning the concentration of different polycyclic aromatic hydrocarbons and organochlorine compounds in sediment samples from different sampling sites of the Ebro River Basin was performed under the UE funded project AQUATERRA. Three major contamination sources were identified and their composition and distribution profiles were resolved. The first contamination profile was mostly loaded by polycyclic aromatic hydrocarbons, the second contamination profile was loaded by some organochlorine compounds and the third contamination profile was more specifically loaded by naphthalene. Samples from the different geographical regions of the Ebro River Basin were grouped according to the contamination described by these three major profiles.     

Neutron activation analysis on sediments from Victoria Land,Antarctica: multi-elemental characterization of potential atmospheric dust sources

The elemental composition of 40 samples of mineral sediments collected in Victoria Land, Antarctica, in correspondence of ice-free sites, is presented. Concentration of 36 elements was determined by instrumental neutron activation analysis, INAA. The selection of 6 standard reference materials and the development of a specific analytical procedure allowed to reduce measurements uncertainties and to verify the reproducibility of the results. The decision to analyze sediment samples from Victoria Land ice-free areas is related to recent investigations regarding mineral dust content in the TALos Dome ICE core (159°11′E; 72°49′S, East Antarctica, Victoria Land), in which a coarse local fraction of dust was recognized. The characterization of Antarctic potential source areas of atmospheric mineral dust is the first step to identify the active sources of dust for the Talos Dome area and to reconstruct the atmospheric pathways followed by air masses in this region during different climatic periods. Principal components analysis was used to identify elements and samples correlations; attention was paid specially to rare earth elements (REE) and incompatible/compatible elements (ICE) in respect to iron, which proved to be the most discriminating elemental groups. The analysis of REE and ICE concentration profiles supported evidences of chemical weathering in ice-free areas of Victoria Land, whereas cold and dry climate conditions of the Talos Dome area and in general of East Antarctica.     

Use of radiofrequency power to enable glow discharge optical emission spectroscopy ultrafast elemental mapping of combinatorial libraries with nonconductive components: nitrogen-based materials

Combinatorial chemistry and high-throughput techniques are an efficient way of exploring optimal values of elemental composition. Optimal composition can result in high performance in a sequence of material synthesis and characterization. Materials combinatorial libraries are typically encountered in the form of a thin film composition gradient which is produced by simultaneous material deposition on a substrate from two or more sources that are spatially separated and chemically different. Fast spatially resolved techniques are needed to characterize structure, composition, and relevant properties of these combinatorial screening samples. In this work, the capability of a glow discharge optical emission spectroscopy (GD-OES) elemental mapping system is extended to nitrogen-based combinatorial libraries with nonconductive components through the use of pulsed radiofrequency power. The effects of operating parameters of the glow discharge and detection system on the achievable spatial resolution were investigated as it is the first time that an rf source is coupled to a setup featuring a push-broom hyperspectral imaging system and a restrictive anode tube GD source. Spatial-resolution optimized conditions were then used to characterize an aluminum nitride/chromium nitride thin-film composition spread. Qualitative elemental maps could be obtained within 16.8 s, orders of magnitude faster than typical techniques. The use of certified reference materials allowed quantitative elemental analysis maps to be extracted from the emission intensity images. Moreover, the quantitative procedure allowed correcting for the inherent emission intensity inhomogeneity in GD-OES. The results are compared to quantitative depth profiles obtained with a commercial GD-OES instrument.     

Absolute modelling of urban aerosol elemental composition by factor analysis

Data on the elemental composition of urban aerosols from a Danish city are treated by R-mode factor analysis to identify and quantify contributions from different sources. The analysis produced a 6-factor solution. If it is assumed that all sources contributing to the total suspended particulates were determined, absolute calculations of emission profiles and source contributions are possible.     

Measurement of non-methane hydrocarbons in Taipei city and their impact on ozone formation in relation to air quality

Air pollutants data from semi-continuous measurements at multiple sampling sites in Taipei metropolitan area of Taiwan was obtained by collecting air samples in canisters. The hydrocarbon composition was determined by using GC/MS and GC/FID. The air samples were pre-concentrated onto glass beads prior to separation by PLOT and DB-1 columns of GC. The method showed detection limit of <1 ppb and relative standard deviation in the range of 5-30% for different compounds. Aromatic hydrocarbons (toluene, benzene, etc.) and aliphatic hydrocarbons (ethylene, acetylene, propane, etc.) were correlated primarily to determine the source of emission. The estimated hydrocarbons were ranked according to their abundance and photochemical reactivity. The criteria pollutants, ozone and NO₂ were measured by UV-differential optical absorption spectroscopy (UV-DOAS), and were utilized to determine the relative importance of non-methane hydrocarbons (NMHC) and significant contribution of NO₂ in limiting ozone formation. The obtained results suggest that ozone formation in Taipei city is probably limited by the supply of non-methane hydrocarbons. The concentration profile of targeted pollutants was compared to other metropolitan areas to determine air quality and the pollutant sources.     

几种不同进口“铅矿”的表征及属性分析研究

通过5种申报为“铅矿”的进口含铅物料的分析,发现铅矿伪报的现象时有发生,这些物料从外观上、铅含量上很难确认其真实属性,实验通过分析样品的理化特征,比对研究和文献查找的方法,分析进口含铅物料来源,进而获得属性判定的方法。其方法主要包括以下5个步骤:(1 )观察样品的外观性状,包括形状、粒度、颜色、手感、气味、磁性等特征;(2)测试样品的理化性质,包括元素组成、物相组成、微观形貌以及酸碱性等其他可能必要的信息;(3)对比研究所属申报品名的样品特征,即对铅矿样品进行比对研究;(4) 比对查证文献资料等,根据获得的样品的相关检测数据和铅矿信息,查阅相关的文献资料,对样品可能产生的来源进行查证分析; (5)确立样品的来源,从而确认样品的属性。     

Quantitative analysis of biodiesel in blends of biodiesel and conventional diesel by comprehensive two-dimensional gas chromatography and multivariate curve resolution

In this paper, a method to determine the composition of blends of biodiesel with mineral diesel (BXX) by multivariate curve resolution with Alternating Least Squares (MRC-ALS) combined to comprehensive two-dimensional gas chromatography with Flame Ionization Detection (GC × GC-FID) is presented. Chromatographic profiles of BXX blends produced with biodiesels from different sources were used as input data. An initial evaluation carried out after multiway principal component analysis (MPCA) was used to reveal regions of the chromatograms were the signal was likely to be dependent on the concentration of biodiesel, regardless its vegetable source. After this preliminary step MCR-ALS modeling was carried out only using relevant parts of the chromatograms. The resulting procedure was able to predict accurately the concentration of biodiesel in the BXX samples regardless of its origin.     

Polybrominated diphenyl ethers (PBDEs) in marine sediment of Thermaikos Gulf,Greece

Polybrominated diphenyl ether (PBDE) concentrations were determined in marine sediment samples collected from 7 different locations around Thermaikos Gulf in north Greece. PBDEs were detected in all sampling sites and their average total concentration (ΣPBDEs) ranged from 0.26 to 4.92?ng?g^?1?d.w. Concentrations were an order of magnitude higher in locations outlining the inner part of the Gulf, which were also closer to industrial areas, sewage treatment plant discharges, the city's harbour and landfill area. These findings suggest pollution in the aquatic ecosystem from industrial and urban activities in the area. Congener profiles exhibit predominance of BDE-209, while concentrations of other PBDE congeners were usually lower, when compared to similar studies from other countries globally, indicating that Thermaikos Gulf is among the low-polluted areas. Statistical analysis showed significant differences among the higher polluted sampling stations. Statistically significant differences also existed between sampling stations with high and low PBDE concentrations. Correlations between congeners suggested local contamination sources; however, specific point sources of pollution were not established.     

Chemometrical Interpretation of Lake Waters after their Chemical Analysis by Using Aas,Flame Photometry and Titrimetric Techniques

This article reports the distribution of trace metals and major ions in lake waters of Sultansazl L < L , a reedfield near Kayseri, Turkey. The determination of elements such as Cr, Ni, Cu, Cd and Pb in lake water samples was performed by AAS after a preconcentration step using a column packed with Amberlite XAD-16 resin. Both flame- and graphite furnace-atomic absorption spectrometry was used to determine these metals in lake water samples. The concentrations of the metals bound to humic substances, and free metal ions were determined after their sorption-elution on the resin, separately. The column method optimized with sodium tetraborate reagent was used in determining the free metal ions. In the determinations of Ca²⁺ and Mg²⁺, K⁺ , and SO2-4 , Cl ^m and total hardness, flame atomic absorption spectrometry, flame photometry, and titrimetry were used, respectively. In order to evaluate the analytical data by multivariate statistical techniques which enable feature reduction and grouping of the pollutant sources in lake waters from their chemical composition, principal component analysis (PCA), cluster analysis (CA) and correlation analysis were used. As a consequence of multivariate statistical evaluation, main anthropogenic sources like traffic, industry and agricultural processes were drawn to be responsible from the pollution in the environment investigated.     

Application of chemometric methods to the investigation of main microcontaminant sources of endocrine disruptors in coastal and harbour waters and sediments

Identification, resolution and distribution of main microcontaminant sources of endocrine disruptors in Spanish harbours, coastal waters and sediments are investigated using chemometric methods. We investigated eighteen different endocrine disruptor chemical compounds, including non-ionic surfactants, their degradation products and linear alkylbenzene sulfonates, found in a total number of 74 samples (35 water samples and 39 sediment samples) over a period of 16 months from March 1999 to July 2000, and in 32 different geographical sites along the Spanish Mediterranean Coast (e.g. Barcelona, Tarragona, Almeria Harbour, Malaga and the Bay of Cadiz). Main environmental contamination sources of these endocrine disruptor compounds were investigated and interpreted according to their chemical composition and according to their resolved geographical distribution profiles.An erratum to this article can be found at     

SnS_2纳米材料的水热合成及光催化性质(英文)

在不同的表面活性剂和硫源的条件下,采用水热法制备了多种形貌的SnS2纳米材料,详细讨论了反应条件对其形貌和性质的影响,并采用X射线衍射(XRD)、扫描电镜(SEM)、和BET比表面积法对制备的样品的物相、形貌和组成进行了表征,通过光催化降解罗丹明B研究了所得样品的光催化性能。结果表明:表面活性剂和硫源对产物的结构和形貌起到了重要的作用。当Sn4+与表面活性剂的物质量的比为1∶1时,样品均为纯的六方相SnS2。采用柠檬酸三钠为表面活性剂、硫脲为硫源时制得的SnS2纳米片具有最大的比表面积,同时表现出了最优的光催化性能。     

SnS2纳米材料的水热合成及光催化性质

在不同的表面活性剂和硫源的条件下,采用水热法制备了多种形貌的SnS₂纳米材料,详细讨论了反应条件对其形貌和性质的影响,并采用X射线衍射(XRD)、扫描电镜(SEM)、和BET比表面积法对制备的样品的物相、形貌和组成进行了表征,通过光催化降解罗丹明B研究了所得样品的光催化性能。结果表明：表面活性剂和硫源对产物的结构和形貌起到了重要的作用。当Sn⁴⁺与表面活性剂的物质量的比为1：1时,样品均为纯的六方相SnS₂。采用柠檬酸三钠为表面活性剂、硫脲为硫源时制得的SnS₂纳米片具有最大的比表面积,同时表现出了最优的光催化性能。     

Effect of PCBM Concentration on Photoluminescence Properties of Composite MEH‐PPV/PCBM Nanoparticles Investigated by a Franck–Condon Analysis of Single‐Particle Emission Spectra

The emission of composite conjugated polymer (MEH‐PPV)/fullerene (PCBM) nanoparticles is investigated by single particle spectroscopy (SPS), and changes in vibronic structure with nanoparticle composition are evaluated by means of a detailed Franck–Condon analysis. Consistent with previous reports we find that the emission spectra can be modeled as the superposition of two types of emitters, one with aggregate character and one with molecular character. Major findings from the fitting of the SPS data to a Franck–Condon model are that 1) the occurrence of each of the two types of emitters changes with nanoparticle composition to the point that no aggregate emitters are detected (at 50 wt % PCBM), 2) at the highest PCBM doping levels (75 wt % PCBM) aggregate emitters reappear due to nanoscale phase separation in the composite nanoparticles, 3) the molecular emitters show small Huang–Rhys factors that increase with PCBM doping, indicative of extensive delocalization and exciton migration that is reduced by the disorder introduced in the polymer material by PCBM doping and 4) the aggregate emitters show large Huang–Rhys factors, indicative of the localized nature of these energy trap sites, with a broad distribution of values of these Huang–Rhys factors. The latter observation suggests a broad heterogeneous distribution of aggregate morphologies in blended conducting polymer materials, which can be attributed to variations in polymer chain folding and stacking at the aggregate sites. The reported results obtained by the SPS approach show how blending conjugated polymers with fullerenes at various doping levels induces changes in interchain interactions and aggregate site density even at length scales below a few tens of nanometers that affect conjugated polymer material properties, an observation that has gone unnoticed in bulk studies of blended conjugated polymer films.     

Cadmium Distribution in a Timberline Forest in the Hengduan Mountains in the Eastern Tibetan Plateau

In order to study the regional distribution, characterization, and possible source of Cadmium in the eastern Tibetan Plateau, samples of leaves, xylem, twigs, bark, and roots of timberline forest trees (fir or spruce) and soils at depths from 0 to 40 cm were collected in eight sites in Hengduan Mountains. According to Cd contents, organs and tissues were divided into three groups: the highest-level organ (roots: 0.237 mg · kg^?1), the high-level organ/tissue (bark: 0.183 mg · kg^?1 and twigs: 0.159 mg · kg^?1), and the low-level organ/tissue (xylem: 0.054 mg · kg^?1and leaves: 0.048 mg · kg^?1). Cd contents in Transect A were a little higher than Transect B. Sites near pollutant sources and high-levels are more sensitive to Cd pollution and accumulated more Cd, while Cd contents in sites far away from pollutant sources and low-level organ/tissue were relatively low. It is suggested that the eastern Tibetan Plateau has already been polluted by the influence of general circulation to some extent. Nevertheless, low Cd contents in some sites prove that high mountains may barricade Cd pollutants from monsoon.     

Usefulness of nuclear and atomic-based analysis techniques in air pollution studies in Nigeria

Three nuclear and atomic-based techniques for elemental analysis of air-particulate samples are discussed in terms of their usefulness in an environmental monitoring and impact assessment programme, supported by the European Economic Community, in Nigeria. Instrumental neutron activation analysis (INAA) and proton induced X-ray emission (PIXE) analysis are compared with respect to the number of elements detected and the detection limits obtained for air-particulate matrices. The latter is used in conjunction with Rutherford backscattering spectrometry (RBS) in order to correct for variations in matrix composition. A scanning electron microprobe (SEM) with analytical facilities is also employed mainly for characterization of the air-particulates through measurement of particle size and morphology. The value of carrying out statistical analysis for differentiating between collection sites or sources of pollution is emphasised. Reference to results obtained from the analysis of air-particulates collected during the Harmattan season at Kano and Ife, separated by about 1000 km place the problem in context and serve to illustrate the requirements.     

Multiphase chemistry of orographic clouds: observations at subalpine mountain sites

Summary Observations out of two cloud events at elevated sites in the Black Forest/Germany and in the Vosges Mtn./France, are presented. The cloud-water, the particulate matter, and the gas-phase have been characterized chemically. Besides main ions, both inorganic and organic, the data sets include 17 trace elements. The air masses pollutant loadings indicated strong anthropogenic influence. The dominant cloud-water solutes were ammonium, nitrate and sulfate, as well as acidity. The latter was even more important than ammonium to counterbalance the strong acid anions in cloud-water collected at the Vosges Mtn. site. Acidity reached up to pH 2.8 in that case, whereas at the Black Forest site pH of cloud-water samples was between 4.9 and 4.0. Organic acids contributed a substantial part to cloud-water acidity at the Vosges Mtn. site, 11% by average. The fractions of the trace species incorporated into cloud-water, have been estimated based on cloud-water and aerosol loadings and differences have been identified. In particular, in one cloud a different behaviour of nitrate and sulfate was indicated in such a way, that a smaller fraction of sulfate was incorporated. The interstitial aerosol was enriched in carbon when compared to pre-cloud and after-cloud situations. Most of the elements specified, in particular those, which are thought to be dominated by crustal sources, were incorporated into the cloud-water to a higher extent, when compared to carbon. An increase of the free acid content of particulate matter (on a mass per volume of sampled air basis) was observed in both after-cloud situations when compared to the respective pre-cloud situations. No information is available, however, about the relative significance of transport from the source regions to the sites and source strength on one hand, and microphysical and chemical processes in the multiphase system on the other hand, which both may have contributed to changes in aerosol composition. When collecting cloud-water simultaneously with a pair of identical collectors beneath and above a conifer canopy, a higher liquid water content was found above the canopy, whereas higher concentrations of most of the solvents were found in cloud-water beneath the canopy.