Liquid matrix deposition on conductive hydrophobic surfaces for tuning and quantitation in UV-MALDI mass spectrometry

With its highly fluctuating ion production matrix-assisted laser desorption/ionization (MALDI) poses many practical challenges for its application in mass spectrometry. Instrument tuning and quantitative ion abundance measurements using ion signal alone depend on a stable ion beam. Liquid MALDI matrices have been shown to be a promising alternative to the commonly used solid matrices. Their application in areas where a stable ion current is essential has been discussed but only limited data have been provided to demonstrate their practical use and advantages in the formation of stable MALDI ion beams. In this article we present experimental data showing high MALDI ion beam stability over more than two orders of magnitude at high analytical sensitivity (low femtomole amount prepared) for quantitative peptide abundance measurements and instrument tuning in a MALDI Q-TOF mass spectrometer. Samples were deposited on an inexpensive conductive hydrophobic surface and shrunk to droplets <10 nL in size. By using a sample droplet <10 nL it was possible to acquire data from a single irradiated spot for roughly 10,000 shots with little variation in ion signal intensity at a laser repetition rate of 5-20 Hz.

Seasonal variations of the physical and optical characteristics of Saharan Dust: results from the Dust outflow and Deposition to the Ocean (DODO) experiment

North African dust is important for climate through its direct radiative effect on solar and terrestrial radiation and its role in the biogeochemical system. The Dust Outflow and Deposition to the Ocean project (DODO) aimed to characterize the physical and optical properties of airborne North African dust in two seasons and to use these observations to constrain model simulations, with the ultimate aim of being able to quantify the deposition of iron to the North Atlantic Ocean. The in situ properties of dust from airborne campaigns measured during February and August 2006, based at Dakar, Senegal, are presented here. Average values of the single scattering albedo (0.99, 0.98), mass specific extinction (0.85 m^2 g^-1 , 1.14 m^2 g^-1 ), asymmetry parameter (0.68, 0.68), and refractive index (1.53--0.0005i,1.53--0.0014i) for the accumulation mode were found to differ by varying degrees between the dry and wet season, respectively. It is hypothesized that these differences are due to different source regions and transport processes which also differ between the DODO campaigns. Elemental ratios of Ca/Al were found to differ between the dry and wet season (1.1 and 0.5, respectively). Differences in vertical profiles are found between seasons and between land and ocean locations and reflect the different dynamics of the seasons. Using measurements of the coarse mode size distribution and illustrative Mie calculations, the optical properties are found to be very sensitive to the presence and amount of coarse mode of mineral dust, and the importance of accurate measurements of the coarse mode of dust is highlighted.

Quantifying uncertainty in critical loads: (B) acidity mass balance critical loads on a sensitive site

This paper reports an uncertainty analysis of critical loads for acid deposition for a site in southern England, using the Steady State Mass Balance Model. The uncertainty bounds, distribution type and correlation structure for each of the 18 input parameters was considered explicitly, and overall uncertainty estimated by Monte Carlo methods. Estimates of deposition uncertainty were made from measured data and an atmospheric dispersion model, and hence the uncertainty in exceedance could also be calculated. The uncertainties of the calculated critical loads were generally much lower than those of the input parameters due to a "compensation of errors" mechanism - coefficients of variation ranged from 13% for CLmaxN to 37% for CL(A). With 1990 deposition, the probability that the critical load was exceeded was > 0.99; to reduce this probability to 0.50, a 63% reduction in deposition is required; to 0.05, an 82% reduction. With 1997 deposition, which was lower than that in 1990, exceedance probabilities declined and uncertainties in exceedance narrowed as deposition uncertainty had less effect. The parameters contributing most to the uncertainty in critical loads were weathering rates, base cation uptake rates, and choice of critical chemical value, indicating possible research priorities. However, the different critical load parameters were to some extent sensitive to different input parameters. The application of such probabilistic results to environmental regulation is discussed.

Underpotential deposition and anodic stripping voltammetry at mesoporous microelectrodes

Using the technique of liquid crystal templating a series of high surface area mesoporous platinum microelectrodes was fabricated. The underpotential deposition of metal ions at such electrodes was found to be similar to that at conventional platinum electrodes. The phenomena of underpotential deposition, in combination with the intrinsic properties of mesoporous microelectrodes (i.e. a high surface area and efficient mass transport) was exploited for the purpose of anodic stripping voltammetry. In particular the underpotential deposition of Ag+, Pb2+ and Cu2+ ions was investigated and it was found that mesoporous microelectrodes were able to quantify the concentration of ions in solution down to the ppb range. The overall behaviour of the mesoporous electrodes was found to be superior to that of conventional microelectrodes and the effects of interference by surfactants were minimal.

Using the significant dust deposition event on the glaciers of Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009 to develop a method for dating and "provenancing" of desert dust events recorded in snow pack

A significant desert dust deposition event occurred on Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009, where the deposited dust later appeared as a brown layer in the snow pack. An examination of dust transportation history and analysis of chemical and physical properties of the deposited dust were used to develop a new approach for high-resolution “provenancing” of dust deposition events recorded in snow pack using multiple independent techniques. A combination of SEVIRI red-green-blue composite imagery, MODIS atmospheric optical depth fields derived using the Deep Blue algorithm, air mass trajectories derived with HYSPLIT model and analysis of meteorological data enabled identification of dust source regions with high temporal (hours) and spatial (ca. 100 km) resolution. Dust, deposited on 5 May 2009, originated in the foothills of the Djebel Akhdar in eastern Libya where dust sources were activated by the intrusion of cold air from the Mediterranean Sea and Saharan low pressure system and transported to the Caucasus along the eastern Mediterranean coast, Syria and Turkey. Particles with an average diameter below 8 μm accounted for 90% of the measured particles in the sample with a mean of 3.58 μm, median 2.48 μm. The chemical signature of this long-travelled dust was significantly different from the locally-produced dust and close to that of soils collected in a palaeolake in the source region, in concentrations of hematite. Potential addition of dust from a secondary source in northern Mesopotamia introduced uncertainty in the “provenancing” of dust from this event. Nevertheless, the approach adopted here enables other dust horizons in the snowpack to be linked to specific dust transport events recorded in remote sensing and meteorological data archives.

Using the significant dust deposition event on the glaciers of Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009 to develop a method for dating and provenancing of desert dust events recorded in snow pack.

A significant desert dust deposition event occurred on Mt. Elbrus, Caucasus Mountains, Russia on 5 May 2009, where the deposited dust later appeared as a brown layer in the snow pack. An examination of dust transportation history and analysis of chemical and physical properties of the deposited dust were used to develop a new approach for high-resolution provenancing of dust deposition events recorded in snow pack using multiple independent techniques. A combination of SEVIRI red-green-blue composite imagery, MODIS atmospheric optical depth fields derived using the Deep Blue algorithm, air mass trajectories derived with HYSPLIT model and analysis of meteorological data enabled identification of dust source regions with high temporal (hours) and spatial (ca. 100 km) resolution. Dust, deposited on 5 May 2009, originated in the foothills of the Djebel Akhdar in eastern Libya where dust sources were activated by the intrusion of cold air from the Mediterranean Sea and Saharan low pressure system and transported to the Caucasus along the eastern Mediterranean coast, Syria and Turkey. Particles with an average diameter below 8 μm accounted for 90% of the measured particles in the sample with a mean of 3.58 μm, median 2.48 μm and the dominant mode of 0.60 μm. The chemical signature of this long-travelled dust was significantly different from the locally-produced dust and close to that of soils collected in a palaeolake in the source region, in concentrations of hematite and oxides of aluminium, manganese, and magnesium. Potential addition of dust from a secondary source in northern Mesopotamia introduced uncertainty in the provenancing of dust from this event. Nevertheless, the approach adopted here enables other dust horizons in the snowpack to be linked to specific dust transport events recorded in remote sensing and meteorological data archives.

Desert dust deposition on Mt. Elbrus, Caucasus Mountains, Russia in 2009-2012 as recorded in snow and shallow ice core: high-resolution "provenancing", transport patterns, physical properties and soluble ionic composition

A record of dust deposition events between 2009 and 2012 on Mt. Elbrus, Caucasus Mountains derived from a snow pit and a shallow ice core is presented for the first time for this region. A combination of isotopic analysis, SEVIRI red-green-blue composite imagery, MODIS atmospheric optical depth fields derived using the Deep Blue algorithm, air mass trajectories derived using the HYSPLIT model and analysis of meteorological data enabled identification of dust source regions with high temporal (hours) and spatial (cf. 20–100 km) resolution. Seventeen dust deposition events were detected; fourteen occurred in March–June, one in February and two in October. Four events originated in the Sahara, predominantly in north-eastern Libya and eastern Algeria. Thirteen events originated in the Middle East, in the Syrian Desert and northern Mesopotamia, from a mixture of natural and anthropogenic sources. Dust transportation from Sahara was associated with vigorous Saharan depressions, strong surface winds in the source region and mid-tropospheric south-westerly flow with daily winds speeds of 20–30 m s−1 at 700 hPa level and, although these events were less frequent, they resulted in higher dust concentrations in snow. Dust transportation from the Middle East was associated with weaker depressions forming over the source region, high pressure centered over or extending towards the Caspian Sea and a weaker southerly or south-easterly flow towards the Caucasus Mountains with daily wind speeds of 12–18 m s−1 at 700 hPa level. Higher concentrations of nitrates and ammonium characterise dust from the Middle East deposited on Mt. Elbrus in 2009 indicating contribution of anthropogenic sources. The modal values of particle size distributions ranged between 1.98 μm and 4.16 μm. Most samples were characterised by modal values of 2.0–2.8 μm with an average of 2.6 μm and there was no significant difference between dust from the Sahara and the Middle East.

A Lagrangian model of air-mass photochemistry and mixing using a trajectory ensemble: the Cambridge Tropospheric Trajectory model of Chemistry And Transport (CiTTyCAT) version 4.2

A Lagrangian model of photochemistry and mixing is described (CiTTyCAT, stemming from the Cambridge Tropospheric Trajectory model of Chemistry And Transport), which is suitable for transport and chemistry studies throughout the troposphere. Over the last five years, the model has been developed in parallel at several different institutions and here those developments have been incorporated into one "community" model and documented for the first time. The key photochemical developments include a new scheme for biogenic volatile organic compounds and updated emissions schemes. The key physical development is to evolve composition following an ensemble of trajectories within neighbouring air-masses, including a simple scheme for mixing between them via an evolving "background profile", both within the boundary layer and free troposphere. The model runs along trajectories pre-calculated using winds and temperature from meteorological analyses. In addition, boundary layer height and precipitation rates, output from the analysis model, are interpolated to trajectory points and used as inputs to the mixing and wet deposition schemes. The model is most suitable in regimes when the effects of small-scale turbulent mixing are slow relative to advection by the resolved winds so that coherent air-masses form with distinct composition and strong gradients between them. Such air-masses can persist for many days while stretching, folding and thinning. Lagrangian models offer a useful framework for picking apart the processes of air-mass evolution over inter-continental distances, without being hindered by the numerical diffusion inherent to global Eulerian models. The model, including different box and trajectory modes, is described and some output for each of the modes is presented for evaluation. The model is available for download from a Subversion-controlled repository by contacting the corresponding authors.

Glacial-interglacial changes in dust deposition on the Chinese Loess Plateau

The Chinese Loess Plateau (CLP) contains an extensive record of aeolian deposition through multiple glacial–interglacial cycles. Independent chronologies based on pedostratigraphy, magnetic susceptibility, radiocarbon and luminescence dating were developed for 79 sites and used to estimate aeolian mass accumulation rates (MARs) for marine isotope stages 1–5. The regional median value of MAR for Stage 2 is 310 g/m2/yr compared to an estimate of 65 g/m2/yr for Stage 5. Estimated MARs from individual sites for Stage 2 are approximately 4.3 times greater than MARs for Stage 5 and 2.1 times greater than for Stage 1. MAR values at individual sites are consistently highest in the northwest and lowest in the southwest of the CLP during all marine isotope stages. MARs estimated on sections through loess terraces are consistently higher than MAR estimates at other sites, indicating that local recycling of loess material from exposed river valley deposits has been significant throughout the last 130 kyr. Although the spatial and temporal patterns in MAR are robust, there are uncertainties about the magnitude of these changes due to (a) lack of bulk density measurements and uncertainties in the chronologies for individual sites, (b) site and chronological biases in the sampling used to derive regional estimates, and (c) the unquantified nature of human impact on accumulation rates during the late Holocene. Nevertheless, the records from the CLP pose a number of challenges which could be addressed by numerical models of the palaeo-dust cycle.