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.

Use of fused airborne scanning laser altimetry and digital map data for urban flood modelling

Flood modelling of urban areas is still at an early stage, partly because until recently topographic data of sufficiently high resolution and accuracy have been lacking in urban areas. However, Digital Surface Models (DSMs) generated from airborne scanning laser altimetry (LiDAR) having sub-metre spatial resolution have now become available, and these are able to represent the complexities of urban topography. The paper describes the development of a LiDAR post-processor for urban flood modelling based on the fusion of LiDAR and digital map data. The map data are used in conjunction with LiDAR data to identify different object types in urban areas, though pattern recognition techniques are also employed. Post-processing produces a Digital Terrain Model (DTM) for use as model bathymetry, and also a friction parameter map for use in estimating spatially-distributed friction coefficients. In vegetated areas, friction is estimated from LiDAR-derived vegetation height, and (unlike most vegetation removal software) the method copes with short vegetation less than ~1m high, which may occupy a substantial fraction of even an urban floodplain. The DTM and friction parameter map may also be used to help to generate an unstructured mesh of a vegetated urban floodplain for use by a 2D finite element model. The mesh is decomposed to reflect floodplain features having different frictional properties to their surroundings, including urban features such as buildings and roads as well as taller vegetation features such as trees and hedges. This allows a more accurate estimation of local friction. The method produces a substantial node density due to the small dimensions of many urban features.

Using airborne laser altimetry to improve river flood extents delineated from SAR data

Flood extent maps derived from SAR images are a useful source of data for validating hydraulic models of river flood flow. The accuracy of such maps is reduced by a number of factors, including changes in returns from the water surface caused by different meteorological conditions and the presence of emergent vegetation. The paper describes how improved accuracy can be achieved by modifying an existing flood extent delineation algorithm to use airborne laser altimetry (LiDAR) as well as SAR data. The LiDAR data provide an additional constraint that waterline (land-water boundary) heights should vary smoothly along the flooded reach. The method was tested on a SAR image of a flood for which contemporaneous aerial photography existed, together with LiDAR data of the un-flooded reach. Waterline heights of the SAR flood extent conditioned on both SAR and LiDAR data matched the corresponding heights from the aerial photo waterline significantly more closely than those from the SAR flood extent conditioned only on SAR data.

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.

Seasonality of modern pollen and sediment deposition in an estuarine context: the Severn Estuary Levels, southwest England

Recent sedimentological and palynological research on subfossil Holocene banded sediments from the Severn Estuary Levels suggested seasonality of deposition, registered by variations in mineral grain-size and pollen assemblages between different parts of the bands. Here we provide data that strengthen this interpretation from sampling of modern sediments and pollen deposition on an active mudflat and saltmarsh on the margin of the Severn Estuary, and comparison with a vegetation survey and contemporary records of climate, river and tidal regimes. The results of grain-size analysis indicate deposition of comparatively coarse-grained silts during the relatively cool and windy conditions of winter and comparatively fine-grained sediments during relatively warm and calm summer months. Pollen analysis demonstrates the significance of long-term storage of pollen grains and fern spores in the estuarine waterbody, superimposed on which seasonal variations in pollen inputs from local and regional vegetation remain detectable. Copyright (C) 2007 John Wiley & Sons, Ltd.

Laser granulometry of Holocene estuarine silts: effects of hydrogen peroxide treatment

The Holocene estuarine silts of the Severn Estuary Levels (southwest Britain) are representative of their kind in northwest Europe. They contain two broad types of plant material: particles codeposited with mineral grains from the estuarine water body, and extraneous debris (stems of indigenous prior plants; post depositional root matter) which is difficult to remove completely by physical means. Treatment with hydrogen peroxide before laser granulometry removes all plant material regardless of kind, drastically reduces values for the mean grain size and median size relative to untreated samples, but has little effect on the mode, except for a restricted group of bimodal-platykurtic, medium-coarse silts. It is concluded that, in the case of sediments of the general kind examined, no advantages acrue from the treatment of samples with hydrogen peroxide prior to analysis. Although a discrete rather than continuous variable, values of the mode obtained from untreated sediments are suggested to be acceptable for most purposes where a measure of central tendency is required.

Assessment of soil particle redistribution on two contrasting cultivated hillslopes

The particle size distributions of surface soils from two cultivated silty fields (Moorfield and Railway South) in Herefordshire, UK, were assessed by sampling on 20-m grids across the fields. Moorfield (8 ha) had a uniform landscape sloping mainly in a North-South direction while Railway South (12 ha) had complex undulating landscape characteristics. Samples from 3 surficial layers were also taken at 3 landscape positions at Moorfield to investigate recent (within-season) soil particle redistribution. Size fractions were determined using chemical dispersion, wet sieving (to separate the sand fractions) and laser gramilometry (for the finer fractions). The distribution of various fractions and the relationships between elevation and the various fractions suggest preferential detachment and movement of coarse to very coarse silt fractions (16-63 mu m), which were found mostly at downslope or depositional areas. Upper slope samples had higher clay to fine silt (< 16 mu m) contents than bottom slope samples. The upslope-downslope patterns of size fractions, particularly on uniformly sloping areas, of the 2 fields were similar and their deposited sediments were dominated by coarse silt fractions. Samples from 3 landscape positions at Moorfield became coarser from the less eroded summit, through the eroding side-slope to the bottom-slope depositional area. Within each of these landscape positions the top 0-2.5 cm layers were more enriched in coarse silt fractions than the bottom layers. The spatial patterns of soil particle size distributions in the 2 fields may be a result of sediment detachment and deposition caused by water erosion and tillage operations. (c) 2005 Elsevier B.V. All rights reserved.

Seasonal deposition of Holocene banded sediments in the Severn Estuary Levels (southwest Britain): palynological and sedimentological evidence

Banded sediments outcrop widely in the intertidal zone of the Severn Estuary and have been suggested, on the basis of textural analysis, to have formed in response to seasonal variations in sea temperature and windiness (Holocene, 14 (2004) 536). Here palynological and sedimentological analyses of banded sediments of mid-Holocene date from Gold Cliff, on the Welsh side of the Severn Estuary, are combined to test and further develop the hypothesis of seasonal deposition. Pollen percentage and concentration data are presented from a short sequence of bands to establish whether textural variations in the bands coincide with variations in pollen content reflecting seasonal flowering patterns. It is shown that fine-grained band parts contain higher total pollen concentrations, and a higher proportion of pollen from late spring- to summer-flowering plants, than coarse-grained band parts. Pollen in the coarser deposits appears primarily to reflect deposition from the buffering `reservoir' of suspended pollen in the estuarine water-body and from rivers, when there is little pollen in the air in winter, while the finer sediments contain pollen deposited from the atmosphere during the flowering season, superimposed on these `background' sources. The potential of such deposits for refining chronologies and identifying seasonality of coastal processes is noted, and the results of charcoal particle analysis of the bands presented as an example of how they have the potential to shed light on seasonal and annual patterns of human activity. (C) 2004 Elsevier Ltd. All rights reserved.

The use of earth observation techniques to improve catchment-scale pollution predictions

Remote sensing can potentially provide information useful in improving pollution transport modelling in agricultural catchments. Realisation of this potential will depend on the availability of the raw data, development of information extraction techniques, and the impact of the assimilation of the derived information into models. High spatial resolution hyperspectral imagery of a farm near Hereford, UK is analysed. A technique is described to automatically identify the soil and vegetation endmembers within a field, enabling vegetation fractional cover estimation. The aerially-acquired laser altimetry is used to produce digital elevation models of the site. At the subfield scale the hypothesis that higher resolution topography will make a substantial difference to contaminant transport is tested using the AGricultural Non-Point Source (AGNPS) model. Slope aspect and direction information are extracted from the topography at different resolutions to study the effects on soil erosion, deposition, runoff and nutrient losses. Field-scale models are often used to model drainage water, nitrate and runoff/sediment loss, but the demanding input data requirements make scaling up to catchment level difficult. By determining the input range of spatial variables gathered from EO data, and comparing the response of models to the range of variation measured, the critical model inputs can be identified. Response surfaces to variation in these inputs constrain uncertainty in model predictions and are presented. Although optical earth observation analysis can provide fractional vegetation cover, cloud cover and semi-random weather patterns can hinder data acquisition in Northern Europe. A Spring and Autumn cloud cover analysis is carried out over seven UK sites close to agricultural districts, using historic satellite image metadata, climate modelling and historic ground weather observations. Results are assessed in terms of probability of acquisition probability and implications for future earth observation missions. (C) 2003 Elsevier Ltd. All rights reserved.

Modelling stream and soil water nitrate dynamics during experimentally increased nitrogen deposition in a coniferous forest catchment at Gardsjon, Sweden

Increased atmospheric deposition of inorganic nitrogen (N) may lead to increased leaching of nitrate (NO3-) to surface waters. The mechanisms responsible for, and controls on, this leaching are matters of debate. An experimental N addition has been conducted at Gardsjon, Sweden to determine the magnitude and identify the mechanisms of N leaching from forested catchments within the EU funded project NITREX. The ability of INCA-N, a simple process-based model of catchment N dynamics, to simulate catchment-scale inorganic N dynamics in soil and stream water during the course of the experimental addition is evaluated. Simulations were performed for 1990-2002. Experimental N addition began in 1991. INCA-N was able to successfully reproduce stream and soil water dynamics before and during the experiment. While INCA-N did not correctly simulate the lag between the start of N addition and NO 2 3 breakthrough, the model was able to simulate the state change resulting from increased N deposition. Sensitivity analysis showed that model behaviour was controlled primarily by parameters related to hydrology and vegetation dynamics and secondarily by in-soil processes.

Record of natural and anthropogenic changes in reef environments (Barbados West Indies) using laser ablation ICP-MS and sclerochronology on coral cores

Coral growth rate can be affected by environmental parameters such as seawater temperature, depth, and light intensity. The natural reef environment is also disturbed by human influences such as anthropogenic pollutants, which in Barbados are released close to the reefs. Here we describe a relatively new method of assessing the history of pollution and explain how these effects have influenced the coral communities off the west coast of Barbados. We evaluate the relative impact of both anthropogenic pollutants and natural stresses. Sclerochronology documents framework and skeletal growth rate and records pollution history (recorded as reduced growth) for a suite of sampled Montastraea annularis coral cores. X-radiography shows annual growth band patterns of the corals extending back over several decades and indicates significantly lower growth rate in polluted sites. Results using laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the whole sample (aragonite, organic matter, trapped particulate matter, etc.), have shown contrasting concentrations of the trace elements (Cu, Sn, Zn, and Pb) between corals at different locations and within a single coral. Deepwater corals 7 km apart, record different levels of Pb and Sn, suggesting that a current transported the metal pollution in the water. In addition, the 1995 hurricanes are associated with anomalous values for Sn and Cu from most sites. These are believed to result from dispersion of nearshore polluted water. We compared the concentrations of trace elements in the coral growth of particular years to those in the relevant contemporaneous seawater. Mean values for the concentration factor in the coral, relative to the water, ranged from 10 for Cu and Ni to 2.4 and 0.7 for Cd and Zn, respectively. Although the uncertainties are large (60-80%), the coral record enabled us to demonstrate the possibility of calculating a history of seawater pollution for these elements from the 1940s to 1997. Our values were much higher than those obtained from analysis of carefully cleaned coral aragonite; they demonstrate the incorporation of more contamination including that from particulate material as well as dissolved metals.

Short-term effects of manipulated increase in acid deposition on soil, soil solution chemistry and fine roots in Scots pine (Pinus sylvestris) stand on a podzol

A manipulated increase in acid deposition (15 kg S ha(-1)), carried out for three months in a mature Scots pine (Pinus sylvestris) stand on a podzol, acidified the soil and raised dissolved Al at concentrations above the critical level of 5 mg l(-1) previously determined in a controlled experiment with Scots pine seedlings. The induced soil acidification reduced tree fine root density and biomass significantly in the top 15 cm of soil in the field. The results suggested that the reduction in fine root growth was a response not simply to high Al in solution but to the depletion of exchangeable Ca and Mg in the organic layer, K deficiency, the increase in NH4:NO3 ratio in solution and the high proton input to the soil by the acid manipulation. The results from this study could not justify the hypothesis of Al-induced root damage under field conditions, at least not in the short term. However, the study suggests that a short exposure to soil acidity may affect the fine root growth of mature Scots pine.