Abstract: In this study we investigate the model uncertainties involved in predicting long-term permeable reactive barrier (PRB) remediation efficiency based on a lab-scale column experiment under accelerated flow conditions. A PRB consisting of 20% iron and 80% sand was simulated in a laboratory-scale column and contaminated groundwater was pumped into the column for approximately 1 year at an average groundwater velocity of 3.7E – 1 m d(-1). Dissolved contaminants (PCE. TCE, cis-DCE, trans-DCE and VC) and inorganic (Ca2+, Fe2+, TIC and pH) concentrations were measured in groundwater sampled at different times and at eight different distances along the column. These measurements were used to calibrate a multi-component reactive transport model, which subsequently provided predictions of long-term PRB efficiency under reduced flow conditions (i.e., groundwater velocity of 1.4E -3 m d(-1)), representative of a field site of interest in this study. Iron reactive surface reduction due to mineral precipitation and iron dissolution was simulated using four different models. All models were able to reasonably well reproduce the column experiment measurements, whereas the extrapolated long-term efficiency under different flow rates was significantly different between the different models. These results highlight significant model uncertainties associated with extrapolating long-term PRB performance based on lab-scale column experiments. These uncertainties should be accounted for at the PRB design phase, and may be reduced by independent experiments and field observations aimed at a better understanding of reactive surface deactivation mechanisms in iron PRBs. (C) 2012 Elsevier B.V. All rights reserved.

Abstract: Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs. (C) 2010 Elsevier B.V. All rights reserved.

Abstract: Eight silicate glasses were prepared by directly fusing and stirring 50-100 g each of basalt, andesite, komatiite, peridotite, rhyolite, and quartz-diorite. These are referred to as MPI-DING glasses and were made for the purpose of providing reference materials for geochemical, in-situ microanalytical work. Results from various analytical techniques indicate that individual glass fragments are well homogenised with respect to major and trace elements at the mu m to mm scale. Heterogeneities due to quench crystallisation of olivine have been observed in small and limited areas of the two komatiitic glasses. In order to obtain concentration values for as many elements as possible, the glasses were analysed by a variety of bulk and microanalytical methods in a number of laboratories. From the analytical data, preliminary reference values for more than sixty elements were calculated. The analytical uncertainties of most elements are estimated to be between 1% and 10%.

Abstract: The intensity distributions of the coherent and partially coherent x-rays passed through a poly-capillary lens have been computed at the focal plane. The computations showed that at the appropriate experimental conditions the interference phenomenon does affect the intensity distribution. In the case of the coherent input radiation with the photon energy of 0.1 keV, the interference fringes were observed, while the non-coherent x-ray radiation produced no interference-like intensity distributions.

Abstract: The sensitivity and applicability of the synchrotron radiation induced X-ray microfluorescence (mu-SRXRF) spectrometer at the Hamburg synchrotron laboratory Hasylab for the determination of the distribution of trace concentrations of rare-earth elements (REE) in fossilized bone are discussed and critically compared to those of other trace analytical methods such as instrumental neutron activation analysis (INAA) and LAMP-ICPMS (laser ablation microprobe inductively-coupled plasma mass spectrometry). Measurements were carried out on two bone samples from contrasting terrestrial depositional environments at Olduvai Gorge (Tanzania). Results indicate that the microdistribution of the REE in these biological materials is not homogeneous and that the relative abundance of these elements can provide information on the palaeoenvironment during the fossilization process. The heterogeneous distribution of the REE can be determined in a quantitative and completely non-destructive manner provided the concentrations of individual REE are above 10 mu g/g.

Abstract: A polynomial approach is applied for a number of data from the Posener-tables to calculate the values of the intensity distribution function of atomic absorption lines – H(a, 0.726a) – at the tabulated damping-parameter values with an error not worse than 0.044 %. For the resultant H(a, 0.726a) data, the ninth and sixth order polynomials can be fitted according to the damping parameter range of 0-2, and 2-10, respectively, which results in a minimal error of approximation. The derived functions are simply applicable to the calculation of any H(a, 0.726a) value belonging to a damping-parameter of any arbitrarily selected spectral line, implying the influence of Doppler- and Lorentz-broadening. The overall error of the described method is lower than 0.4 %.

Abstract: It is well known that airborne particulate matter (APM) has an impact on our cultural heritage. A limited number of articles have been published on the sequential application of elemental and molecular techniques to estimate the degradation potential of APM in environments of cultural heritage importance, and most of these were concerned with indoor environments. The Alhambra monument (Granada, Spain) represents one of the grandest and finest examples of Islamic art and architecture from the Middle Ages. As part of an air quality investigation, two sets of APM were collected at the Hall of the Ambassadors and characterised to determine its potential degradation profile. These were analysed by means of micro-Raman spectroscopy (MRS) and electron probe microanalysis with X-ray detection (EPXMA). The Raman data indicated the presence of various mixed salts of acidic and/or hygroscopic nature, such as sodium and ammonium nitrates and sulfates, especially in the finer fraction. Automated EPXMA estimated this fraction to be as high as 50%. Apart from the potential chemical attack, the soiling due to carbonaceous matter deposition is a real concern. Soot was identified by MRS and EPXMA in all size fractions, reaching values of up to 55%, and was often intertwined with soluble inorganic salts. Ongoing degradation of the pigments is implicated by the presence of brightly coloured particles. MRS and molar abundance ternary diagrams elicited the chemical structure of individual APM so that the degradation potential could be established.

Abstract: Here we show that mineral dust retrieved from an ice core in the central West Antarctic sector, spanning the last five decades, provides evidence that northerly air mass incursions into Antarctica, tracked by dust microparticles, have slightly declined. This result contrasts with dust in ice core records reported in West/coastal Antarctica, which show significant increases to the present day. We attribute that difference, in part, to changes in the regional climate regime triggered by the ozone depletion and its consequences for the polar vortex intensity. The vortex maintains the Antarctic central region relatively isolated from mid-latitude air mass incursions with implications to the intensification of the Westerlies and to a persistent positive phase of the Southern Annular Mode. We also show that variability of the diameter of insoluble microparticles in central West Antarctica can be modeled by linear/quadratic functions of both cyclone depth (energy) and wind intensity around Antarctica.

Abstract: The risk profile of Cr and Pb in urban road deposited sediment Exponential urbanisation and industrial growth occur on a global scale and result in an ecological burden, of which one important part is pollution. It is well known that the extent of air pollution has escalated over the past two decades in several parts of the world, despite mitigating measures and legislation. Current research points to the fact that air pollution in urban and industrial areas is substantially different from that found in rural areas. Road dust (RD) contributes up to 35% of airborne particulate matter due to resuspension thereof, and poses a health concern due to carcinogenic and toxic components potentially present in the micron-sized fractions. Although literature does report on the concentrations of trace, toxic metals and metalloids present in RD (Hooker and Nathanail 2006), the molecular make-up of particulates generated due to the resuspension of the RD is not well documented. In vitro and animal toxicological studies have confirmed that the chemical composition of inhaled particles plays a major role in its toxic, genotoxic and carcinogenic mechanisms, but the component-specific toxic effects are still not understood. Transition metals binding to air particle matter can result in reactive oxygen species in the human body (particularly in the lungs), and this is a significant risk, especially for vulnerable population groups like elderly people, children and terminally ill patients. The characterisation of the molecular composition of the fine fraction is evidently of importance for public health. During an earlier study, road dust from an inner-city environment in the UK was collected and partially characterised (Barrett e.a. 2010). These same-size fractions were analysed for their elemental concentrations, using X-ray Fluorescence Spectrometry (XRFS) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). In addition, single-particle analysis was performed on the different fractions by means of Computer Controlled Electron Probe X-ray Micro Analysis (CC-EPXMA) and their molecular structure probed by studying elemental associations. These findings were correlated with Micro Raman Spectroscopy (MRS) results. It was found that the fine fraction (<38 μm) had the highest Pb (238 ppm) and Cr (171 ppm) concentrations. The CC-EPXMA data showed >50% association of Cr-rich particles with Pb and the MRS data showed that the Cr was mostly present as lead chromate and therefore in the Cr(VI) oxidation state. Concentrations of both Pb and Cr decreased substantially (279 (<38 mm) 13 ppm (<1mm); 171 (<38 mm) 91 ppm (<1mm) respectively) in the larger fractions. Apart from rather alarmingly high concentrations of oxidative stressors (Cu, Fe, Mn), the carcinogenic and toxic potential of the inhalable fraction is evident. Preliminary bioaccessibility data indicated that both Cr and Pb are readily