ALBERT

Description: The combination of scanning electron microscope–cathodoluminescence (CL), fluid inclusion analysis and high-resolution electron probe microanalysis of Al, Ti, K and Fe in vein quartz has yielded results permitting a greater understanding of the complex mineralisation of the Central Oyu Tolgoi and Zesen Uul porphyry-style deposits, southern Mongolia. These data demonstrate the relationship between quartz precipitation, dissolution and ore deposition as the mineralising fluid chemistry changed through time. Four major quartz generations are identified in the A-type veins from the stockworks of both the Central Oyu Tolgoi (OTi to OTiv) and Zesen Uul deposits (ZUi to ZUiv). Despite differences in the associated alteration and mineralisation style, the observed CL textures and trace element signatures of the quartz generations are comparable between deposits. The OTi and ZUi stage formed both the primary network of A-type veins and pervasive silicification of the host rock. Using the Ti-in-quartz geothermometer, crystallisation temperatures for OTi and ZUi of between 598°C and 880°C are indicated. The main stage of sulphide mineralisation was accompanied by the dissolution of pre-existing quartz (OTi and ZUi) and precipitation of a weakly luminescent generation of quartz (OTii and ZUii) with a low Ti content, reflected in a calculated temperature drop from approximately 700°C to 340°C in Central Oyu Tolgoi and 445°C in Zesen Uul. OTii and ZUii stage quartzes show high and variable Al concentrations. The next stage of quartz in both deposits (OTiii and ZUiii) forms a fine network of veins in cracks formed in pre-existing quartz. OTiii and ZUiii quartz contain measurable fluid inclusions of moderate salinity (3–17.1 wt.% NaCl eq.), entrapped in the temperature range 256°C to 385°C. OTiii and ZUiii are not related to any sulphide mineralisation. The final OTiv and ZUiv stages are characterised by quartz–calcite micro-breccias that penetrate the A-type veins. Based on the calculated entrapment temperatures, the OTiv/ZUiv stage crystallised between 212°C and 335°C, and the quartz is characterised by elevated but variable Al and Fe contents. The CL and trace element signatures of the OTi to OTiii and ZUi to ZUiii stages of the two Mongolian porphyries show similar features to those observed in porphyry-style deposits from other regions. This suggests that a common sequence of quartz crystallisation occurs during the formation of early veins in many porphyry copper systems.

Description: Tropospheric ozone and particulate matter affect human health and cause vegetation stress, dysfunction and damages. In this study we investigate the effect of increasing urban vegetation i.e. tree species on atmospheric chemistry, a potential urban management strategy to counteract high levels of local pollutants such as ozone, OH and PM10 caused by e.g. traffic. We use an extended version of an atmospheric chemistry box model including detailed gas-phase chemistry, mixing layer height variation and secondary organic aerosol calculations based on observations for Berlin, Germany. It is shown to accurately simulate the observed ozone volume mixing ratios during the intensive measurement period in July 2014 (BAERLIN2014) if basic parameters such as nitrogen oxides, meteorological conditions, PM10 concentrations as well as volatile organic compounds (VOCs) are considered as 1 h resolved datasets. Based on this setup the effects of changing present day vegetation mixture by 24 different relevant tree species and of urban greening is tested to elucidate benefits and drawbacks in order to support future urban planning. While the present day vegetation causes boundary layer ozone to decline slightly at 35 °C, individual tree types alter the ozone production rate and concentration as well as the secondary organic aerosol mass in different ways. Our results suggest that trees intensively emitting isoprene such as black locust, European oak and poplar result in higher ozone and total PM10 concentrations than at present, while tree species emitting primarily monoterpenes such as beech, magnolia and wayfaring trees yield less of both. This is in line with the similar behaviour of OH concentration and new particle formation rates. Thus, for future urban planning including urban greening, consideration of the beneficial and harmful aspects of tree species need to ensure that citizens benefit from and are not being negatively affected by climate adaptation strategies.

Description: The Toba eruption that occurred some 74 ka ago in Sumatra, Indonesia, is among the largest volcanic events on Earth over the last 2 million years. Tephra from this eruption has been spread over vast areas in Asia, where it constitutes a major time marker close to the Marine Isotope Stage 4/5 boundary. As yet, no tephra associated with Toba has been identified in Greenland or Antarctic ice cores. Based on new accurate dating of Toba tephra and on accurately dated European stalagmites, the Toba event is known to occur between the onsets of Greenland interstadials (GI) 19 and 20. Furthermore, the existing linking of Greenland and Antarctic ice cores by gas records and by the bipolar seesaw hypothesis suggests that the Antarctic counterpart is situated between Antarctic Isotope Maxima (AIM) 19 and 20. In this work we suggest a direct synchronization of Greenland (NGRIP) and Antarctic (EDML) ice cores at the Toba eruption based on matching of a pattern of bipolar volcanic spikes. Annual layer counting between volcanic spikes in both cores allows for a unique match. We first demonstrate this bipolar matching technique at the already synchronized Laschamp geomagnetic excursion (41 ka BP) before we apply it to the suggested Toba interval. The Toba synchronization pattern covers some 2000 yr in GI-20 and AIM- 19/20 and includes nine acidity peaks that are recognized in both ice cores. The suggested bipolar Toba synchronization has decadal precision. It thus allows a determination of the exact phasing of inter-hemispheric climate in a time interval of poorly constrained ice core records, and it allows for a discussion of the climatic impact of the Toba eruption in a global perspective. The bipolar linking gives no support for a long-term global cooling caused by the Toba eruption as Antarctica experiences a major warming shortly after the event. Furthermore, our bipolar match provides a way to place palaeoenvironmental records other than ice cores into a precise climatic context.

Description: Snow in the environment acts as a host to rich chemistry and provides a matrix for physical exchange of contaminants within the ecosystem. The goal of this review is to summarise the current state of knowledge of physical processes and chemical reactivity in surface snow with relevance to polar regions. It focuses on a description of impurities in distinct compartments present in surface snow, such as snow crystals, grain boundaries, crystal surfaces, and liquid parts. It emphasises the microscopic description of the ice surface and its link with the environment. Distinct differences between the disordered air–ice interface, often termed quasi-liquid layer, and a liquid phase are highlighted. The reactivity in these different compartments of surface snow is discussed using many experimental studies, simulations, and selected snow models from the molecular to the macro-scale. Although new experimental techniques have extended our knowledge of the surface properties of ice and their impact on some single reactions and processes, others occurring on, at or within snow grains remain unquantified. The presence of liquid or liquid-like compartments either due to the formation of brine or disorder at surfaces of snow crystals below the freezing point may strongly modify reaction rates. Therefore, future experiments should include a detailed characterisation of the surface properties of the ice matrices. A further point that remains largely unresolved is the distribution of impurities between the different domains of the condensed phase inside the snowpack, i.e. in the bulk solid, in liquid at the surface or trapped in confined pockets within or between grains, or at the surface. While surface-sensitive laboratory techniques may in the future help to resolve this point for equilibrium conditions, additional uncertainty for the environmental snowpack may be caused by the highly dynamic nature of the snowpack due to the fast metamorphism occurring under certain environmental conditions. Due to these gaps in knowledge the first snow chemistry models have attempted to reproduce certain processes like the long-term incorporation of volatile compounds in snow and firn or the release of reactive species from the snowpack. Although so far none of the models offers a coupled approach of physical and chemical processes or a detailed representation of the different compartments, they have successfully been used to reproduce some field experiments. A fully coupled snow chemistry and physics model remains to be developed.

Description: The evaluation and intercomparison of air quality models is key to reducing model errors and uncertainty. The projects AQMEII3 and EURODELTA-Trends, in the framework of the Task Force on Hemispheric Transport of Air Pollutants and the Task Force on Measurements and Modelling, respectively (both task forces under the UNECE Convention on the Long Range Transport of Air Pollution, LTRAP), have brought together various regional air quality models to analyze their performance in terms of air concentrations and wet deposition, as well as to address other specific objectives. This paper jointly examines the results from both project communities by intercomparing and evaluating the deposition estimates of reduced and oxidized nitrogen (N) and sulfur (S) in Europe simulated by 14 air quality model systems for the year 2010. An accurate estimate of deposition is key to an accurate simulation of atmospheric concentrations. In addition, deposition fluxes are increasingly being used to estimate ecological impacts. It is therefore important to know by how much model results differ and how well they agree with observed values, at least when comparison with observations is possible, such as in the case of wet deposition. This study reveals a large variability between the wet deposition estimates of the models, with some performing acceptably (according to previously defined criteria) and others underestimating wet deposition rates. For dry deposition, there are also considerable differences between the model estimates. An ensemble of the models with the best performance for N wet deposition was made and used to explore the implications of N deposition in the conservation of protected European habitats. Exceedances of empirical critical loads were calculated for the most common habitats at a resolution of 100 × 100m2 within the Natura 2000 network, and the habitats with the largest areas showing exceedances are determined. Moreover, simulations with reduced emissions in selected source areas indicated a fairly linear relationship between reductions in emissions and changes in the deposition rates of N and S. An approximate 20% reduction in N and S deposition in Europe is found when emissions at a global scale are reduced by the same amount. European emissions are by far the main contributor to deposition in Europe, whereas the reduction in deposition due to a decrease in emissions in North America is very small and confined to the western part of the domain. Reductions in European emissions led to substantial decreases in the protected habitat areas with critical load exceedances (halving the exceeded area for certain habitats), whereas no change was found, on average, when reducing North American emissions in terms of average values per habitat.

Description: This study quantifies the present-day global and regional distributions (2010–2014) and trends (2000–2014) for five ozone metrics relevant for short-term and long-term human exposure. These metrics, calculated by the Tropospheric Ozone Assessment Report, are: 4th highest daily maximum 8-hour ozone (4MDA8); number of days with MDA8 〉 70 ppb (NDGT70), SOMO35 (annual Sum of Ozone Means Over 35 ppb) and two seasonally averaged metrics (3MMDA1; AVGMDA8). These metrics were explored at ozone monitoring sites worldwide, which were classified as urban or non-urban based on population and nighttime lights data. Present-day distributions of 4MDA8 and NDGT70, determined predominantly by peak values, are similar with highest levels in western North America, southern Europe and East Asia. For the other three metrics, distributions are similar with North–South gradients more prominent across Europe and Japan. Between 2000 and 2014, significant negative trends in 4MDA8 and NDGT70 occur at most US and some European sites. In contrast, significant positive trends are found at many sites in South Korea and Hong Kong, with mixed trends across Japan. The other three metrics have similar, negative trends for many non-urban North American and some European and Japanese sites, and positive trends across much of East Asia. Globally, metrics at many sites exhibit non-significant trends. At 59% of all sites there is a common direction and significance in the trend across all five metrics, whilst 4MDA8 and NDGT70 have a common trend at ~80% of all sites. Sensitivity analysis shows AVGMDA8 trends differ with averaging period (warm season or annual). Trends are unchanged at many sites when a 1995–2014 period is used; although fewer sites exhibit non-significant trends. Over the longer period 1970–2014, most Japanese sites exhibit positive 4MDA8/SOMO35 trends. Insufficient data exist to characterize ozone trends for the rest of Asia and other world regions.

Description: Measurement of reactive air pollutants and greenhouse gases underpin a huge variety of applications that span from academic research through to regulatory functions and services for individuals, governments, and businesses. Whilst the vast majority of these observations continue to use established analytical reference methods, miniaturization has led to a growth in the prominence of a generation of devices that are often described generically as “low-cost sensors” (LCSs). LCSs can in practice have other valuable features other than cost that differentiate them from previous technologies including being of smaller size, lower weight and having reduced power consumption. Different technologies falling within this class include passive electrochemical and metal oxide sensors that may have costs of only a few dollars each, through to more complex microelectromechanical devices that use the same analytical principles as reference instruments, but in smaller size and power packages. As a class of device, low-cost sensors encompass a very wide range of technologies and as a consequence they produce a wide range of quality of measurements. When selecting a LCS approach for a particular task, users need to ensure the specific sensor to be used will meet application’s data quality requirements. This report considers sensors that are designed for the measurement of atmospheric composition at ambient concentrations focusing on reactive gaseous air pollutants (CO, NOx, O3, SO2), particulate matter (PM) and greenhouse gases CO2 and CH4. It examines example applications where new scientific and technical insight may potentially be gained from using a network of sensors when compared to more sparsely located observations. Access to low-cost sensors appears to offer exciting new atmospheric applications, can support new services and potentially facilitates the inclusion of a new cohort of users. Based on the scientific literature available up to the end of 2017, it is clear however that some trade-offs arise when LCSs are used in place of existing reference methods. Smaller and/or lower cost devices tend to be less sensitive, less precise and less chemically-specific to the compound or variable of interest. This is balanced by a potential increase in the spatial density of measurements that can be achieved by a network of sensors. The current state of the art in terms of accuracy, reliability and reproducibility of a range of different sensors is described along with the key analytical principles and what has been learned so far about low-cost sensors from both laboratory studies and real-world tests. A summary of concepts is included on how sensors and reference instruments may be used together, as well as with modelling in a complementary way, to improve data quality and generate additional insight into pollution behaviour. The report provides some advice on key considerations when matching a project/study/application with an appropriate sensor monitoring strategy, and the wider application-specific requirements for calibration and data quality. The report contains a number of suggestions on future requirements for low-cost sensors aimed at manufacturers and users and for the broader atmospheric community. The report highlights that low-cost sensors are not currently a direct substitute for reference instruments, especially for mandatory purposes; they are however a complementary source of information on air quality, provided an appropriate sensor is used. It is important for prospective users to identify their specific application needs first, examine examples of studies or deployments that share similar characteristics, identify the likely limitations associated with using LCSs and then evaluate whether their selected LCS approach/technology would sufficiently meet the needs of the measurement objective.

Description: A series of various readily water-soluble carbamates were synthesized with good yields. These compounds are useful chemical tracers for assessing the cooling progress in a georeservoir during geothermal power plant operation. Acylation of primary amines was carried out as well as using a solution of sodium bicarbonate and without the presence of salt. Products were characterized by 1H-NMR and 13C-NMR. Purity was confirmed through elemental analysis.

Description: Open Access Publikationsfonds 2015

Description: A detailed electrochemical, photophysical and theoretical study is presented for various new thienyl and furyl derivatives of pyrene. Their optical properties are described based on UV-VIS absorption and both steady-state and time-resolved fluorescence spectroscopy. DFT and TDDFT calculations are also presented to support experimental data. The calculations results show that HOMO-LUMO orbitals are delocalized uniformly between aromatic core and aryl substituents. Good electrochemical stability of thienyl and furyl hybrids of pyrene confirm their potential application for light emitting electrochemical cells or spintronics mainly due to their beneficial optical and charge transport properties in electrochromic devices. In order to demonstrate this potential, an OLED device is presented. Synthesized compounds included in this OLED device both facilitate electron transport and act as a light emitting layer.