Synthesis and antibacterial evaluation of ureides of Baylis-Hillman derivatives

The synthesis of several 1-(2-cyano-3-aryl-allyl)-3-aryl-urea(thiourea) constructed from the reaction between allyl amines generated from Baylis-Hillman acetates and substituted isocyanates and isothiocyanates has been described. Further their cyclization in the presence of a base led to the formation of 5-arylmethyl-4-imino-3-aryl-3,4-dihydro-1H-pyrimidin-2-ones. All compounds were tested for their antibacterial activity. Few of the compounds showed superior activity or were equipotent to the standard antibacterial agents.

Age modeling of young non-varved lake sediments: methods and limits. Examples from two lakes in Central Chile

High-resolution and highly precise age models for recent lake sediments (last 100–150 years) are essential for quantitative paleoclimate research. These are particularly important for sedimentological and geochemical proxies, where transfer functions cannot be established and calibration must be based upon the relation of sedimentary records to instrumental data. High-precision dating for the calibration period is most critical as it determines directly the quality of the calibration statistics. Here, as an example, we compare radionuclide age models obtained on two high-elevation glacial lakes in the Central Chilean Andes (Laguna Negra: 33°38′S/70°08′W, 2,680 m a.s.l. and Laguna El Ocho: 34°02′S/70°19′W, 3,250 m a.s.l.). We show the different numerical models that produce accurate age-depth chronologies based on 210Pb profiles, and we explain how to obtain reduced age-error bars at the bottom part of the profiles, i.e., typically around the end of the 19th century. In order to constrain the age models, we propose a method with five steps: (i) sampling at irregularly-spaced intervals for 226Ra, 210Pb and 137Cs depending on the stratigraphy and microfacies, (ii) a systematic comparison of numerical models for the calculation of 210Pb-based age models: constant flux constant sedimentation (CFCS), constant initial concentration (CIC), constant rate of supply (CRS) and sediment isotope tomography (SIT), (iii) numerical constraining of the CRS and SIT models with the 137Cs chronomarker of AD 1964 and, (iv) step-wise cross-validation with independent diagnostic environmental stratigraphic markers of known age (e.g., volcanic ash layer, historical flood and earthquakes). In both examples, we also use airborne pollutants such as spheroidal carbonaceous particles (reflecting the history of fossil fuel emissions), excess atmospheric Cu deposition (reflecting the production history of a large local Cu mine), and turbidites related to historical earthquakes. Our results show that the SIT model constrained with the 137Cs AD 1964 peak performs best over the entire chronological profile (last 100–150 years) and yields the smallest standard deviations for the sediment ages. Such precision is critical for the calibration statistics, and ultimately, for the quality of the quantitative paleoclimate reconstruction. The systematic comparison of CRS and SIT models also helps to validate the robustness of the chronologies in different sections of the profile. Although surprisingly poorly known and under-explored in paleolimnological research, the SIT model has a great potential in paleoclimatological reconstructions based on lake sediments

Validation of water vapour profiles (version 13) retrieved by the IMK / IAA scientific retrieval processor based on full resolution spectra measured by MIPAS on board Envisat

Vertical profiles of stratospheric water vapour measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) with the full resolution mode between September 2002 and March 2004 and retrieved with the IMK/IAA scientific retrieval processor were compared to a number of independent measurements in order to estimate the bias and to validate the existing precision estimates of the MIPAS data. The estimated precision for MIPAS is 5 to 10% in the stratosphere, depending on altitude, latitude, and season. The independent instruments were: the Halogen Occultation Experiment (HALOE), the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), the Improved Limb Atmospheric Spectrometer-II (ILAS-II), the Polar Ozone and Aerosol Measurement (POAM III) instrument, the Middle Atmospheric Water Vapour Radiometer (MIAWARA), the Michelson Interferometer for Passive Atmospheric Sounding, balloon-borne version (MIPAS-B), the Airborne Microwave Stratospheric Observing System (AMSOS), the Fluorescent Stratospheric Hygrometer for Balloon (FLASH-B), the NOAA frostpoint hygrometer, and the Fast In Situ Hygrometer (FISH). For the in-situ measurements and the ground based, air- and balloon borne remote sensing instruments, the measurements are restricted to central and northern Europe. The comparisons to satellite-borne instruments are predominantly at mid- to high latitudes on both hemispheres. In the stratosphere there is no clear indication of a bias in MIPAS data, because the independent measurements in some cases are drier and in some cases are moister than the MIPAS measurements. Compared to the infrared measurements of MIPAS, measurements in the ultraviolet and visible have a tendency to be high, whereas microwave measurements have a tendency to be low. The results of χ2-based precision validation are somewhat controversial among the comparison estimates. However, for comparison instruments whose error budget also includes errors due to uncertainties in spectrally interfering species and where good coincidences were found, the χ2 values found are in the expected range or even below. This suggests that there is no evidence of systematically underestimated MIPAS random errors.

Nano Aerosol Chamber for In-Vitro Toxicity (NACIVT) studies.

Abstract Inhalation of ambient air particles or engineered nanoparticles (NP) handled as powders, dispersions or sprays in industrial processes and contained in consumer products pose a potential and largely unknown risk for incidental exposure. For efficient, economical and ethically sound evaluation of health hazards by inhaled nanomaterials, animal-free and realistic in vitro test systems are desirable. The new Nano Aerosol Chamber for in-vitro Toxicity studies (NACIVT) has been developed and fully characterized regarding its performance. NACIVT features a computer-controlled temperature and humidity conditioning, preventing cellular stress during exposure and allowing long-term exposures. Airborne NP are deposited out of a continuous air stream simultaneously on up to 24 cell cultures on Transwell® inserts, allowing high-throughput screening. In NACIVT, polystyrene as well as silver particles were deposited uniformly and efficiently on all 24 Transwell® inserts. Particle-cell interaction studies confirmed that deposited particles reach the cell surface and can be taken up by cells. As demonstrated in control experiments, there was no evidence for any adverse effects on human bronchial epithelial cells (BEAS-2B) due to the exposure treatment in NACIVT. The new, fully integrated and transportable deposition chamber NACIVT provides a promising tool for reliable, acute and sub-acute dose-response studies of (nano)particles in air-exposed tissues cultured at the air-liquid interface.

Intercomparison of C-14 Analysis of Carbonaceous Aerosols: Exercise 2009

Radiocarbon analysis of the carbonaceous aerosol allows an apportionment of fossil and non-fossil sources of airborne particulate matter (PM). A chemical separation of total carbon (TC) into its subfractions organic carbon (OC) and elemental carbon (EC) refines this powerful technique, as OC and EC originate from different sources and undergo different processes in the atmosphere. Although C-14 analysis of TC, EC, and OC has recently gained increasing attention, interlaboratory quality assurance measures have largely been missing, especially for the isolation of EC and OC. In this work, we present results from an intercomparison of 9 laboratories for C-14 analysis of carbonaceous aerosol samples on quartz fiber filters. Two ambient PM samples and 1 reference material (RM 8785) were provided with representative filter blanks. All laboratories performed C-14 determinations of TC and a subset of isolated EC and OC for isotopic measurement. In general, C-14 measurements of TC and OC agreed acceptably well between the laboratories, i.e. for TC within 0.015-0.025 (FC)-C-14 for the ambient filters and within 0.041 (FC)-C-14 for RM 8785. Due to inhomogeneous filter loading, RM 8785 demonstrated only limited applicability as a reference material for C-14 analysis of carbonaceous aerosols. C-14 analysis of EC revealed a large deviation between the laboratories of 28-79 as a consequence of different separation techniques. This result indicates a need for further discussion on optimal methods of EC isolation for C-14 analysis and a second stage of this intercomparison.

Atmospheric CO₂ response to volcanic eruptions: The role of ENSO, season, and variability

Tropical explosive volcanism is one of the most important natural factors that significantly impact the climate system and the carbon cycle on annual to multi-decadal time scales. The three largest explosive eruptions in the last 50�years�Agung, El Chichón, and Pinatubo�occurred in spring/summer in conjunction with El Niño events and left distinct negative signals in the observational temperature and CO2 records. However, confounding factors such as seasonal variability and El Niño-Southern Oscillation (ENSO) may obscure the forcing-response relationship. We determine for the first time the extent to which initial conditions, i.e., season and phase of the ENSO, and internal variability influence the coupled climate and carbon cycle response to volcanic forcing and how this affects estimates of the terrestrial and oceanic carbon sinks. Ensemble simulations with the Earth System Model (Climate System Model 1.4-carbon) predict that the atmospheric CO2 response is �60 larger when a volcanic eruption occurs during El Niño and in winter than during La Niña conditions. Our simulations suggest that the Pinatubo eruption contributed 11�±�6 to the 25�Pg terrestrial carbon sink inferred over the decade 1990�1999 and �2�±�1 to the 22�Pg oceanic carbon sink. In contrast to recent claims, trends in the airborne fraction of anthropogenic carbon cannot be detected when accounting for the decadal-scale influence of explosive volcanism and related uncertainties. Our results highlight the importance of considering the role of natural variability in the carbon cycle for interpretation of observations and for data-model intercomparison.

Exposure to the Asp f 1 allergen in nonindustrial occupational environments

Sick Building Syndrome is a prevalent problem with patient complaints similar to typical allergy symptoms. Unlike most household allergens, the Asp f 1 allergen is conceivably ubiquitous in the work environment. This project examined levels of the Asp f 1 allergen in office and non-industrial occupational environments, and studied the bioaerosol and dust reservoirs of Aspergillus fumigatus responsible for those levels. ^ Culturable bioaerosols of total mesophilic fungi were sampled with Andersen N6 impactors. Aggressive airborne and bulk dust samples were concurrently collected and assayed for Asp f 1. Bulk dusts were selectively cultured for A. fumigatus. Samples were collected during both wet and dry climatological conditions to examine the possibility of Asp f 1 increases due to fungal growth blooms. ^ Only very low levels of Asp f 1 were detected in relatively few samples. Analysis of wet versus dry period samples showed no differences in Asp f 1 levels, although A. fumigatus counts from dusts did fluctuate significantly with exterior moisture events as did indoor prevalence of total colony forming units. These results indicate that even in the presence of elevated fungal concentrations, levels of Asp f 1 are extremely low. These levels do not correlate with climatological moisture events, despite distinct fungal blooms in the days immediately following those events. Non-industrial office buildings devoid of indoor air quality issues did not demonstrate significant levels or occurrence of Asp f 1 contamination in the geographical region of this study. ^

ICESat Measurements Reveal Complex Pattern of Elevation Changes on Siple Coast Ice Streams, Antarctica

We compare ICESat data (2003-2004) to airborne laser altimetry data (1997-98 and 1999-2000) to monitor surface changes over portions of Van der Veen (VdVIS), Whillans (WIS) and Kamb ice streams (KIS) in the Ross Embayment of the West Antarctic Ice Sheet. The spatial pattern of detected surface changes is generally consistent with earlier observations. However, important changes have occurred during the past decade. For example, areas on the VdVIS and WIS, where large thinning was detected by the airborne surveys, are now closer to being in balance. The upper trunk of KIS continues to build up with thickening rates reaching 0.4 m/year. Our results provide new evidence that the overall mass balance of the region is becoming more positive, but a significant spatial variability exists. They also demonstrate the potential of ICESat data for detecting spatial patterns of surface elevation change in Antarctica.

Thickness Changes on Whillans Ice Stream and Ice Stream C, West Antarctica, Derived from Laser Altimeter Measurements

Repeat airborne laser altimeter measurements are used to derive surface elevation changes on parts of Whillans Ice Stream and Ice Stream C, West Antarctica. Elevation changes are converted to estimates of ice equivalent thickness change using local accumulation rates, surface snow densities and vertical bedrock motions. The surveyed portions of two major tributaries of Whillans Ice Stream are found to be thinning almost uniformly at an average rate of similar to 1 m a(-1). Ice Stream C has a complicated elevation-change pattern, but is generally thickening. These results are used to estimate the contribution of each surveyed region to the current rate of global sea-level rise.

Controls on the Basal Water Pressure in Subglacial Channels Near the Margin of the Greenland Ice Sheet

Assuming a channelized drainage system in steady state, we investigate the influence of enhanced surface melting on the water pressure in subglacial channels, compared to that of changes in conduit geometry, ice rheology and catchment variations. The analysis is carried out for a specific part of the western Greenland ice-sheet margin between 66 degrees N and 66 degrees 30' N using new high-resolution digital elevation models of the subglacial topography and the ice-sheet surface, based on an airborne ice-penetrating radar survey in 2003 and satellite repeat-track interferometric synthetic aperture radar analysis of European Remote-sensing Satellite 1 and 2 (ERS-1/-2) imagery, respectively. The water pressure is calculated up-glacier along a likely subglacial channel at distances of 1, 5 and 9 km from the outlet at the ice margin, using a modified version of Rothlisberger's equation. Our results show that for the margin of the western Greenland ice sheet, the water pressure in subglacial channels is not sensitive to realistic variations in catchment size and mean surface water input compared to small changes in conduit geometry and ice rheology.

​Indole is an essential herbivore-induced volatile priming signal in maize

Herbivore-induced volatile organic compounds prime non-attacked plant tissues to respond more strongly to subsequent attacks. However, the key volatiles that trigger this primed state remain largely unidentified. In maize, the release of the aromatic compound ​indole is herbivore-specific and occurs earlier than other induced responses. We therefore hypothesized that ​indole may be involved in airborne priming. Using ​indole-deficient mutants and synthetic indole dispensers, we show that herbivore-induced ​indole enhances the induction of defensive volatiles in neighbouring maize plants in a species-specific manner. Furthermore, the release of ​indole is essential for priming of mono- and homoterpenes in systemic leaves of attacked plants. ​Indole exposure markedly increases the herbivore-induced production of the stress hormones ​jasmonate-isoleucine conjugate and ​abscisic acid, which represents a likely mechanism for ​indole-dependent priming. These results demonstrate that ​indole functions as a rapid and potent aerial priming agent that prepares systemic tissues and neighbouring plants for incoming attacks.

Evaluation of aeolian dust records obtained from Polar Ice Cores

When an ice core sample is analysed for its aeolian dust content, it is melted and the particles detected are suspended in water. Consequently, dust measurement techniques employed in the ice core community differ from those used for in-situ studies of airborne dust. Methods commonly used to classify insolubles suspended in a liquid are either based on the particles’ interaction with light or on the detection of resistive pulses by means of Coulter counting. Data sets obtained with Coulter counters are widely accepted as references and other techniques are judged against their ability to reproduce these. Unfortunately, optically acquired ice core dust records were found to differ. By analyzing two sections of the NEEM dust record, two different evaluation procedures are discussed before a third protocol is proposed. It is found that relative changes in the archived dust load can be reproduced, while the simultaneous attainment of absolute concentrations or changes in the grain size frequency histograms in high resolution remains difficult.

Bathymetry of Lake Constance – a High-Resolution Survey in a Large, Deep Lake

Within the project “Tiefenschärfe – hochauflösende Vermes- sung Bodensee” a high-resolution seamless terrain model is created using airborne topobathymetric laserscanning and multibeam echosounder (MBES) techniques. The project visu- alizes the enormous wealth of features of underwater land- scapes of lakes. The combination of hydroacoustic (multibeam echosounder) and laser-optic (topobathymetric laserscan- ning) methods was used for the first time in a freshwater body of this size. Opportunities, limitations and restrictions of these high-resolution methods are presented.

Study of mineral dust entrainment in the planetary boundary layer by lidar depolarisation technique

Measurements on 27 June 2011 were performed over the Southern Iberian Peninsula at Granada EARLINET station, using active and passive remote sensing and airborne and surface in-situ data in order to study the entrainment processes between aerosols in the free troposphere and those in the planetary boundary layer (PBL). To this aim the temporal evolution of the lidar depolarisation, backscatter-related Angström exponent and potential temperature profiles were used in combination with the PBL contribution to the aerosol optical depth (AOD). Our results show that the mineral dust entrainment in the PBL was caused by the convective processes which ‘trapped’ the lofted mineral dust layer, distributing the mineral dust particles within the PBL. The temporal evolution of ground-based in-situ data evidenced the impact of this process at surface level. Finally, the amount of mineral dust in the atmospheric column available to be dispersed into the PBL was estimated by means of POLIPHON (Polarizing Lidar Photometer Networking). The dust mass concentration derived from POLIPHON was compared with the coarse-mode mass concentration retrieved with airborne in-situ measurements. Comparison shows differences below 50 µg/m³ (30% relative difference) indicating a relative good agreement between both techniques.