Facile in situ copper(ii) mediated C–S bond activation transforming dithiocarbimate to carbamate and thiocarbamate generating Cu(ii) and Cu(i) complexes

Facile in situ Cu(II) mediated transformation of p-tolylsulfonyldithiocarbimate in conjunction with polypyridyl or phosphine ligands into corresponding carbamate and thiocarbamate led to the formation of new copper complexes with varying nuclearities and geometries, via C-S bond activation of the ligand within identical reaction systems.

In situ preservation of wetland heritage: hydrological and chemical change in the burial environment of the Somerset Levels, UK.

In Situ preservation is a core strategy for the conservation and management of waterlogged remains at wetland sites. Inorganic and organic remains can, however, quickly become degraded, or lost entirely, as a result of chemical or hydrological changes. Monitoring is therefore crucial in identifying baseline data for a site, the extent of spatial and or temporal variability, and in evaluating the potential impacts of these variables on current and future In Situ preservation potential. Since August 2009, monthly monitoring has taken place at the internationally important Iron Age site of Glastonbury Lake Village in the Somerset Levels, UK. A spatial, stratigraphic, and analytical approach to the analysis of sediment horizons and monitoring of groundwater chemistry, redox potential, water table depth and soil moisture (using TDR) was used to characterize the site. Significant spatial and temporal variability has been identified, with results from water-table monitoring and some initial chemical analysis from Glastonbury presented here. It appears that during dry periods parts of this site are at risk from desiccation. Analysis of the chemical data, in addition to integrating the results from the other parameters, is ongoing, with the aim of clarifying the risk to the entire site.

Integration of Space and In Situ Observations to Study Global Climate Change

The currently available model-based global data sets of atmospheric circulation are a by-product of the daily requirement of producing initial conditions for numerical weather prediction (NWP) models. These data sets have been quite useful for studying fundamental dynamical and physical processes, and for describing the nature of the general circulation of the atmosphere. However, due to limitations in the early data assimilation systems and inconsistencies caused by numerous model changes, the available model-based global data sets may not be suitable for studying global climate change. A comprehensive analysis of global observations based on a four-dimensional data assimilation system with a realistic physical model should be undertaken to integrate space and in situ observations to produce internally consistent, homogeneous, multivariate data sets for the earth's climate system. The concept is equally applicable for producing data sets for the atmosphere, the oceans, and the biosphere, and such data sets will be quite useful for studying global climate change.

Comprehensive ground-based and in situ observations of substorm expansion phase onset

In this paper, we present comprehensive ground-based and space-based in situ geosynchronous observations of a substorm expansion phase onset on 1 October 2005. The Double Star TC-2 and GOES-12 spacecraft were both located within the substorm current wedge during the substorm expansion phase onset, which occurred over the Canadian sector. We find that an onset of ULF waves in space was observed after onset on the ground by extending the AWESOME timing algorithm into space. Furthermore, a population of low-energy field-aligned electrons was detected by the TC-2 PEACE instrument contemporaneous with the ULF waves in space. These electrons appear to be associated with an enhancement of field-aligned Poynting flux into the ionosphere which is large enough to power visible auroral displays. The observations are most consistent with a near-Earth initiation of substorm expansion phase onset, such as the Near-Geosynchronous Onset (NGO) substorm scenario. A lack of data from further downtail, however, means other mechanisms cannot be ruled out.

In-situ comparison of the NOy instruments flown in MOZAIC and SPURT

Two aircraft instruments for the measurement of total odd nitrogen (NOy) were compared side by side aboard a Learjet A35 in April 2003 during a campaign of the AFO2000 project SPURT (Spurengastransport in der Tropopausenregion). The instruments albeit employing the same measurement principle (gold converter and chemiluminescence) had different inlet configurations. The ECO-Physics instrument operated by ETH-Zürich in SPURT had the gold converter mounted outside the aircraft, whereas the instrument operated by FZ-Jülich in the European project MOZAIC III (Measurements of ozone, water vapour, carbon monoxide and nitrogen oxides aboard Airbus A340 in-service aircraft) employed a Rosemount probe with 80 cm of FEP-tubing connecting the inlet to the gold converter. The NOy concentrations during the flight ranged between 0.3 and 3 ppb. The two data sets were compared in a blind fashion and each team followed its normal operating procedures. On average, the measurements agreed within 7%, i.e. within the combined uncertainty of the two instruments. This puts an upper limit on potential losses of HNO3 in the Rosemount inlet of the MOZAIC instrument. Larger transient deviations were observed during periods after calibrations and when the aircraft entered the stratosphere. The time lag of the MOZAIC instrument observed in these instances is in accordance with the time constant of the MOZAIC inlet line determined in the laboratory for HNO3.

Seasonality and extent of extratropical TST derived from in-situ CO measurements during SPURT

We present airborne in-situ trace gas measurements which were performed on eight campaigns between November 2001 and July 2003 during the SPURT-project (SPURenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region). The measurements on a quasi regular basis allowed an overview of the seasonal variations of the trace gas distribution in the tropopause region over Europe from 35°-75°N to investigate the influence of transport and mixing across the extratropical tropopause on the lowermost stratosphere. From the correlation of CO and O3 irreversible mixing of tropospheric air into the lowermost stratosphere is identified. The CO distribution indicates that transport and subsequent mixing of tropospheric air across the extratropical tropopause predominantly affects a layer, which closely follows the shape of the local tropopause. In addition, the seasonal cycle of CO2 illustrates the strong coupling of that layer to the extratropical troposphere. Both, horizontal gradients of CO on isentropes as well as the CO-O3-distribution in the lowermost stratosphere reveal that the influence of quasi-horizontal transport and subsequent mixing weakens with distance from the local tropopause. The mixing layer extends to about 25 K in potential temperature above the local tropopause exhibiting only a weak seasonality. However, at large distances from the tropopause a significant influence of tropospheric air is still evident. The relation between N2O and CO2 indicates that a significant contribution of air originating from the tropical tropopause contributes to the background air in the extratropical lowermost stratosphere.

A methodology for in-situ and remote sensing of microphysical and radiative properties of contrails as they evolve into cirrus

Contrails and especially their evolution into cirrus-like clouds are thought to have very important effects on local and global radiation budgets, though are generally not well represented in global climate models. Lack of contrail parameterisations is due to the limited availability of in situ contrail measurements which are difficult to obtain. Here we present a methodology for successful sampling and interpretation of contrail microphysical and radiative data using both in situ and remote sensing instrumentation on board the FAAM BAe146 UK research aircraft as part of the COntrails Spreading Into Cirrus (COSIC) study.

The accuracy of SST retrievals from AATSR: An initial assessment through geophysical validation against in situ radiometers, buoys and other SST data sets

The Advanced Along-Track Scanning Radiometer (AATSR) was launched on Envisat in March 2002. The AATSR instrument is designed to retrieve precise and accurate global sea surface temperature (SST) that, combined with the large data set collected from its predecessors, ATSR and ATSR-2, will provide a long term record of SST data that is greater than 15 years. This record can be used for independent monitoring and detection of climate change. The AATSR validation programme has successfully completed its initial phase. The programme involves validation of the AATSR derived SST values using in situ radiometers, in situ buoys and global SST fields from other data sets. The results of the initial programme presented here will demonstrate that the AATSR instrument is currently close to meeting its scientific objectives of determining global SST to an accuracy of 0.3 K (one sigma). For night time data, the analysis gives a warm bias of between +0.04 K (0.28 K) for buoys to +0.06 K (0.20 K) for radiometers, with slightly higher errors observed for day time data, showing warm biases of between +0.02 (0.39 K) for buoys to +0.11 K (0.33 K) for radiometers. They show that the ATSR series of instruments continues to be the world leader in delivering accurate space-based observations of SST, which is a key climate parameter.

In situ and remote-sensing measurements of the mean microphysical and optical properties of industrial pollution aerosol during ADRIEX

We present a summary of the principal physical and optical properties of aerosol particles using the FAAM BAE-146 instrumented aircraft during ADRIEX between 27 August and 6 September 2004, augmented by sunphotometer, lidar and satellite retrievals. Observations of anthropogenic aerosol, principally from industrial sources, were concentrated over the northern Adriatic Sea and over the Po Valley close to the aerosol sources. An additional flight was also carried out over the Black Sea to compare east and west European pollution. Measurements show the single-scattering albedo of dry aerosol particles to vary considerably between 0.89 and 0.97 at a wavelength of 0.55 μm, with a campaign mean within the polluted lower free troposphere of 0.92. Although aerosol concentrations varied significantly from day to day and during individual days, the shape of the aerosol size distribution was relatively consistent through the experiment, with no detectable change observed over land and over sea. There is evidence to suggest that the pollution aerosol within the marine boundary layer was younger than that in the elevated layer. Trends in the aerosol volume distribution show consistency with multiple-site AERONET radiometric observations. The aerosol optical depths derived from aircraft measurements show a consistent bias to lower values than both the AERONET and lidar ground-based radiometric observations, differences which can be explained by local variations in the aerosol column loading and by some aircraft instrumental artefacts. Retrievals of the aerosol optical depth and fine-mode (<0.5 μm radius) fraction contribution to the optical depth using MODIS data from the Terra and Aqua satellites show a reasonable level of agreement with the AERONET and aircraft measurements.

18 Nov 2013 In situ detection of electrified aerosols in the upper troposphere and stratosphere

Electrified aerosols have been observed in the lower troposphere and in the mesosphere, but have never been detected in the stratosphere and upper troposphere. We present measurements of aerosols obtained during a balloon flight to an altitude of 24 km. The measurements were per- formed with an improved version of the Stratospheric and Tropospheric Aerosol Counter (STAC) aerosol counter dedi- cated to the search for charged aerosols. It is found that most of the aerosols are charged in the upper troposphere for altitudes below 10 km and in the stratosphere for altitudes above 20 km. Conversely, the aerosols seem to be uncharged between 10 km and 20 km. Model calculations are used to quantify the electrification of the aerosols with a stratospheric aerosol–ion model. The percentages of charged aerosols obtained with model calculations are in excellent agreement with the observations below 10 km and above 20 km. However, the model cannot reproduce the absence of electrification found in the lower stratosphere, as the processes leading to neutralisation in this altitude range are unknown. The presence of sporadic transient layers of electrified aerosol in the upper troposphere and in the stratosphere could have significant implications for sprite formation

In-situ spatio-temporal measurements of the detailed azimuthal substructure of the substorm current wedge

The substorm current wedge (SCW) is a fundamental component of geomagnetic substorms. Models tend to describe the SCW as a simple line current flowing into the ionosphere towards dawn and out of the ionosphere towards dusk, linked by a westward electrojet. We use multi-spacecraft observations from perigee passes of the Cluster 1 and 4 spacecraft during a substorm on 15 Jan 2010, in conjunction with ground-based observations, to examine the spatial structuring and temporal variability of the SCW. At this time, the spacecraft travelled east-west azimuthally above the auroral region. We show that the SCW has significant azimuthal sub-structure on scales of 100~km at altitudes of 4,000-7,000~km. We identify 26 individual current sheets in the Cluster 4 data and 34 individual current sheets in the Cluster 1 data, with Cluster 1 passing through the SCW 120-240~s after Cluster 4 at 1,300-2,000~km higher altitude. Both spacecraft observed large-scale regions of net upward and downward field-aligned current, consistent with the large-scale characteristics of the SCW, although sheets of oppositely directed currents were observed within both regions. We show that the majority of these current sheets were closely aligned to a north-south direction, in contrast to the expected east-west orientation of the pre-onset aurora. Comparing our results with observations of the field-aligned current associated with bursty bulk flows (BBFs) we conclude that significant questions remain for the explanation of SCW structuring by BBF driven ``wedgelets". Our results therefore represent constraints on future modelling and theoretical frameworks on the generation of the SCW.