Lanthanide complexes of 2-hydroxynicotinic acid: synthesis, luminescence properties and the crystal structures of [Ln(HnicO)(2)(mu-HnicO)(H2O)] center dot nH(2)O (Ln = Tb, Eu)

New lanthanide complexes of 2-hydroxynicotinic acid (H(2)nicO) [Ln(HnicO)(2)(mu-HnicO)(H2O)] (.) nH(2)O (Ln = Eu, Gd, Tb, Er, Tm) were prepared. The crystal structures of the [Tb(HnicO)(2)(g-HnicO)(H2O)] (.) 1.75H(2)O(1) and [Eu(HniCO)(2)(mu-HnicO)(H2O)] (.) 1.25H(2)O (2) complexes were determined by X-ray diffraction. The 2-hydroxynicotinate ligand coordinates through O,O-chelation to the lanthanide(III) ions as shown by X-ray diffraction and the infrared, Raman and NMR spectroscopy results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes. Lifetimes of 0.592 +/- 0.007 and 0.113 +/- 0.002 ms were determined for the Eu3+ and Tb3+ emitting states D-5(0) and D-5(4), respectively. A value around 30% was found for the D-5(0) quantum efficiency. The energy transfer mechanisms between the lanthanide ions and the ligands are discussed and compared with those observed in similar complexes involving the 3-hydroxypicolinate ligand based on the luminescence of the respective Gd3+-based complexes. (C) 2003 Published by Elsevier Ltd.

Impact of increasing resolution and a warmer climate on extreme weather from NH extra-tropical cyclones

The effect of a warmer climate on the properties of extra-tropical cyclones is investigated using simulations of the ECHAM5 global climate model at resolutions of T213 (60 km) and T319 (40 km). Two periods representative of the end of the 20th and 21st centuries are investigated using the IPCC A1B scenario. The focus of the paper is on precipitation for the NH summer and winter seasons, however results from vorticity and winds are also presented. Similar number of events are identified at both resolutions. There are, however, a greater number of extreme precipitation events in the higher reso- lution run. The difference between maximum intensity distributions are shown to be statistically significant using a Kolmogorov-Smirnov test. A Generalised Pareto Distribution is used to analyse changes in extreme precipitation and wind events. In both resolutions, there is an increase in the number of ex- treme precipitation events in a warmer climate for all seasons, together with a reduction in return period. This is not associated with any increased verti- cal velocity, or with any increase in wind intensity in the winter and spring. However, there is an increase in wind extremes in the summer and autumn associated with tropical cyclones migrating into the extra-tropics.

The predictability of extratropical storm tracks and the sensitivity of their prediction to the observing system

A new method for assessing forecast skill and predictability that involves the identification and tracking of extratropical cyclones has been developed and implemented to obtain detailed information about the prediction of cyclones that cannot be obtained from more conventional analysis methodologies. The cyclones were identified and tracked along the forecast trajectories, and statistics were generated to determine the rate at which the position and intensity of the forecasted storms diverge from the analyzed tracks as a function of forecast lead time. The results show a higher level of skill in predicting the position of extratropical cyclones than the intensity. They also show that there is potential to improve the skill in predicting the position by 1 - 1.5 days and the intensity by 2 - 3 days, via improvements to the forecast model. Further analysis shows that forecasted storms move at a slower speed than analyzed storms on average and that there is a larger error in the predicted amplitudes of intense storms than the weaker storms. The results also show that some storms can be predicted up to 3 days before they are identified as an 850-hPa vorticity center in the analyses. In general, the results show a higher level of skill in the Northern Hemisphere (NH) than the Southern Hemisphere (SH); however, the rapid growth of NH winter storms is not very well predicted. The impact that observations of different types have on the prediction of the extratropical cyclones has also been explored, using forecasts integrated from analyses that were constructed from reduced observing systems. A terrestrial, satellite, and surface-based system were investigated and the results showed that the predictive skill of the terrestrial system was superior to the satellite system in the NH. Further analysis showed that the satellite system was not very good at predicting the growth of the storms. In the SH the terrestrial system has significantly less skill than the satellite system, highlighting the dominance of satellite observations in this hemisphere. The surface system has very poor predictive skill in both hemispheres.

A comparison of recent reanalysis datasets using objective feature tracking: Storm tracks and tropical easterly waves

Data from four recent reanalysis projects [ECMWF, NCEP-NCAR, NCEP - Department of Energy ( DOE), NASA] have been diagnosed at the scale of synoptic weather systems using an objective feature tracking method. The tracking statistics indicate that, overall, the reanalyses correspond very well in the Northern Hemisphere (NH) lower troposphere, although differences for the spatial distribution of mean intensities show that the ECMWF reanalysis is systematically stronger in the main storm track regions but weaker around major orographic features. A direct comparison of the track ensembles indicates a number of systems with a broad range of intensities that compare well among the reanalyses. In addition, a number of small-scale weak systems are found that have no correspondence among the reanalyses or that only correspond upon relaxing the matching criteria, indicating possible differences in location and/or temporal coherence. These are distributed throughout the storm tracks, particularly in the regions known for small-scale activity, such as secondary development regions and the Mediterranean. For the Southern Hemisphere (SH), agreement is found to be generally less consistent in the lower troposphere with significant differences in both track density and mean intensity. The systems that correspond between the various reanalyses are considerably reduced and those that do not match span a broad range of storm intensities. Relaxing the matching criteria indicates that there is a larger degree of uncertainty in both the location of systems and their intensities compared with the NH. At upper-tropospheric levels, significant differences in the level of activity occur between the ECMWF reanalysis and the other reanalyses in both the NH and SH winters. This occurs due to a lack of coherence in the apparent propagation of the systems in ERA15 and appears most acute above 500 hPa. This is probably due to the use of optimal interpolation data assimilation in ERA15. Also shown are results based on using the same techniques to diagnose the tropical easterly wave activity. Results indicate that the wave activity is sensitive not only to the resolution and assimilation methods used but also to the model formulation.

The prediction of extratropical storm tracks by the ECMWF and NCEP ensemble prediction systems

The prediction of extratropical cyclones by the European Centre for Medium Range Weather Forecasts (ECMWF) and the National Centers for Environmental Prediction (NCEP) Ensemble Prediction Systems (EPS) has been investigated using an objective feature tracking methodology to identify and track the cyclones along the forecast trajectories. Overall the results show that the ECMWF EPS has a slightly higher level of skill than the NCEP EPS in the northern hemisphere (NH). However in the southern hemisphere (SH), NCEP has higher predictive skill than ECMWF for the intensity of the cyclones. The results from both EPS indicate a higher level of predictive skill for the position of extratropical cyclones than their intensity and show that there is a larger spread in intensity than position. Further analysis shows that the predicted propagation speed of cyclones is generally too slow for the ECMWF EPS and show a slight bias for the intensity of the cyclones to be overpredicted. This is also true for the NCEP EPS in the SH. For the NCEP EPS in the NH the intensity of the cyclones is underpredicted. There is small bias in both the EPS for the cyclones to be displaced towards the poles. For each ensemble forecast of each cyclone, the predictive skill of the ensemble member that best predicts the cyclones position and intensity was computed. The results are very encouraging showing that the predictive skill of the best ensemble member is significantly higher than that of the control forecast in terms of both the position and intensity of the cyclones. The prediction of cyclones before they are identified as 850 hPa vorticity centers in the analysis cycle was also considered. It is shown that an indication of extratropical cyclones can be given by at least 1 ensemble member 7 days before they are identified in the analysis. Further analysis of the ECMWF EPS shows that the ensemble mean has a higher level of skill than the control forecast, particularly for the intensity of the cyclones, 2 from day 3 of the forecast. There is a higher level of skill in the NH than the SH and the spread in the SH is correspondingly larger. The difference between the ensemble mean and spread is very small for the position of the cyclones, but the spread of the ensemble is smaller than the ensemble mean error for the intensity of the cyclones in both hemispheres. Results also show that the ECMWF control forecast has ½ to 1 day more skill than the perturbed members, for both the position and intensity of the cyclones, throughout the forecast.

Regional Differences in the Prediction of Extratropical Cyclones by the ECMWF Ensemble Prediction System

A regional study of the prediction of extratropical cyclones by the European Centre for Medium-Range Weather Forecasts (ECMWF) Ensemble Prediction System (EPS) has been performed. An objective feature-tracking method has been used to identify and track the cyclones along the forecast trajectories. Forecast error statistics have then been produced for the position, intensity, and propagation speed of the storms. In previous work, data limitations meant it was only possible to present the diagnostics for the entire Northern Hemisphere (NH) or Southern Hemisphere. A larger data sample has allowed the diagnostics to be computed separately for smaller regions around the globe and has made it possible to explore the regional differences in the prediction of storms by the EPS. Results show that in the NH there is a larger ensemble mean error in the position of storms over the Atlantic Ocean. Further analysis revealed that this is mainly due to errors in the prediction of storm propagation speed rather than in direction. Forecast storms propagate too slowly in all regions, but the bias is about 2 times as large in the NH Atlantic region. The results show that storm intensity is generally overpredicted over the ocean and underpredicted over the land and that the absolute error in intensity is larger over the ocean than over the land. In the NH, large errors occur in the prediction of the intensity of storms that originate as tropical cyclones but then move into the extratropics. The ensemble is underdispersive for the intensity of cyclones (i.e., the spread is smaller than the mean error) in all regions. The spatial patterns of the ensemble mean error and ensemble spread are very different for the intensity of cyclones. Spatial distributions of the ensemble mean error suggest that large errors occur during the growth phase of storm development, but this is not indicated by the spatial distributions of the ensemble spread. In the NH there are further differences. First, the large errors in the prediction of the intensity of cyclones that originate in the tropics are not indicated by the spread. Second, the ensemble mean error is larger over the Pacific Ocean than over the Atlantic, whereas the opposite is true for the spread. The use of a storm-tracking approach, to both weather forecasters and developers of forecast systems, is also discussed.

Simulating metals and mine discharges in river basins using a new integrated catchment model for metals: pollution impacts and restoration strategies in the Aries-Mures river system in Transylvania, Romania

The INtegrated CAtchment (INCA) model has been developed to simulate the impact of mine discharges on river systems. The model accounts for the key kinetic chemical processes operating as well as the dilution, mixing and redistribution of pollutants in rivers downstream of mine discharges or acid rock drainage sites. The model is dynamic and simulates the day-to-day behaviour of hydrology and eight metals (cadmium, mercury, copper, zinc, lead, arsenic, manganese and chromium) as well as cyanide and ammonia. The model is semi-distributed and can simulate catchments, sub-catchment and in-stream river behaviour. The model has been applied to the Roia Montan Mine in Transylvania, Romania, and used to assess the impacts of old mine adits on the local catchments as well as on the downstream Aries and Mures river system. The question of mine restoration is investigated and a set of clean-up scenarios investigated. It is shown that the planned restoration will generate a much improved water quality from the mine and also alleviate the metal pollution of the river system.

Potential impacts of climate change on water quality and ecology in six UK rivers

A modelling study has been undertaken to assess the likely impacts of climate change on water quality across the UK. A range of climate change scenarios have been used to generate future precipitation, evaporation and temperature time series at a range of catchments across the UK. These time series have then been used to drive the Integrated Catchment (INCA) suite of flow, water quality and ecological models to simulate flow, nitrate, ammonia, total and soluble reactive phosphorus, sediments, macrophytes and epiphytes in the Rivers Tamar, Lugg, Tame, Kennet, Tweed and Lambourn. A wide range of responses have been obtained with impacts varying depending on river character, catchment location, flow regime, type of scenario and the time into the future. Essentially upland reaches of river will respond differently to lowland reaches of river, and the responses will vary depending on the water quality parameter of interest.

A new set of orthogonal patterns in weather and climate: Optimally interpolated patterns.

A new spectral-based approach is presented to find orthogonal patterns from gridded weather/climate data. The method is based on optimizing the interpolation error variance. The optimally interpolated patterns (OIP) are then given by the eigenvectors of the interpolation error covariance matrix, obtained using the cross-spectral matrix. The formulation of the approach is presented, and the application to low-dimension stochastic toy models and to various reanalyses datasets is performed. In particular, it is found that the lowest-frequency patterns correspond to largest eigenvalues, that is, variances, of the interpolation error matrix. The approach has been applied to the Northern Hemispheric (NH) and tropical sea level pressure (SLP) and to the Indian Ocean sea surface temperature (SST). Two main OIP patterns are found for the NH SLP representing respectively the North Atlantic Oscillation and the North Pacific pattern. The leading tropical SLP OIP represents the Southern Oscillation. For the Indian Ocean SST, the leading OIP pattern shows a tripole-like structure having one sign over the eastern and north- and southwestern parts and an opposite sign in the remaining parts of the basin. The pattern is also found to have a high lagged correlation with the Niño-3 index with 6-months lag.

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.

Life cycle of the QBO-modulated 11-year solar cycle signals in the Northern Hemispheric winter

This paper provides some insights on the quasi-biennial oscillation (QBO) modulated 11-year solar cycle (11-yr SC) signals in Northern Hemisphere (NH) winter temperature and zonal wind. Daily ERA-40 Reanalysis and ECMWF Operational data for the period of 1958-2006 were used to examine the seasonal evolution of the QBO-solar cycle relationship at various pressure levels up to the stratopause. The results show that the solar signals in the NH winter extratropics are indeed QBO-phase dependent, moving poleward and downward as winter progresses with a faster descent rate under westerly QBO than under easterly QBO. In the stratosphere, the signals are highly significant in late January to early March and have a life span of 30-50 days. Under westerly QBO, the stratospheric solar signals clearly lead and connect to those in the troposphere in late March and early April where they have a life span of 10 days. As the structure changes considerably from the upper stratosphere to the lower troposphere, the exact month when the maximum solar signals occur depends largely on the altitude chosen. For the low-latitude stratosphere, our analysis supports a vertical double-peaked structure of positive signature of the 11-yr SC in temperature, and demonstrates that this structure is further modulated by the QBO. These solar signals have a longer life span (3-4 months) in comparison to those in the extratropics. The solar signals in the lower stratosphere are stronger in early winter but weaker in late winter, while the reverse holds in the upper stratosphere.

A continuum of sudden stratospheric warmings

The k-means cluster technique is used to examine 43 yr of daily winter Northern Hemisphere (NH) polar stratospheric data from the 40-yr ECMWF Re-Analysis (ERA-40). The results show that the NH winter stratosphere exists in two natural well-separated states. In total, 10% of the analyzed days exhibit a warm disturbed state that is typical of sudden stratospheric warming events. The remaining 90% of the days are in a state typical of a colder undisturbed vortex. These states are determined objectively, with no preconceived notion of the groups. The two stratospheric states are described and compared with alternative indicators of the polar winter flow, such as the northern annular mode. It is shown that the zonally averaged zonal winds in the polar upper stratosphere at 7 hPa can best distinguish between the two states, using a threshold value of 4 m s−1, which is remarkably close to the standard WMO criterion for major warming events. The analysis also determines that there are no further divisions within the warm state, indicating that there is no well-designated threshold between major and minor warmings, nor between split and displaced vortex events. These different manifestations are simply members of a continuum of warming events.

Modelling impacts of pollution in river systems: a new dispersion model and a case study of mine discharges in the Abrud, Aries and Mures river system in Transylvania, Romania

A new model of dispersion has been developed to simulate the impact of pollutant discharges on river systems. The model accounts for the main dispersion processes operating in rivers as well as the dilution from incoming tributaries and first-order kinetic decay processes. The model is dynamic and simulates the hourly behaviour of river flow and pollutants along river systems. The model has been applied to the Aries and Mures River System in Romania and has been used to assess the impacts of potential dam releases from the Roia Montan Mine in Transylvania, Romania. The question of mine water release is investigated under a range of scenarios. The impacts on pollution levels downstream at key sites and at the border with Hungary are investigated.

Impacts of climate change scenarios on dissolved oxygen in the River Thames, UK

A water quality model is used to assess the impact of possible climate change on dissolved oxygen (DO) in the Thames. The Thames catchment is densely populated and, typically, many pressures are anthropogenic. However, that same population also relies on the river for potable water supply and as a disposal route for treated wastewater. Thus, future water quality will be highly dependent on future activity. Dynamic and stochastic modelling has been used to assess the likely impacts on DO dynamics along the river system and the probability distributions associated with future variability. The modelling predictions indicate that warmer river temperatures and drought act to reduce dissolved oxygen concentrations in lowland river systems

Cloud properties and their seasonal and diurnal variability from TOVS path-B

Eight years of cloud properties retrieved from Television Infrared Observation Satellite-N (TIROS-N) Observational Vertical Sounder (TOVS) observations aboard the NOAA polar orbiting satellites are presented. The relatively high spectral resolution of these instruments in the infrared allows especially reliable cirrus identification day and night. This dataset therefore provides complementary information to the International Satellite Cloud Climatology Project (ISCCP). According to this dataset, cirrus clouds cover about 27% of the earth and 45% of the Tropics, whereas ISCCP reports 19% and 25%, respectively. Both global datasets agree within 5% on the amount of single-layer low clouds, at 30%. From 1987 to 1995, global cloud amounts remained stable to within 2%. The seasonal cycle of cloud amount is in general stronger than its diurnal cycle and it is stronger than the one of effective cloud amount, the latter the relevant variable for radiative transfer. Maximum effective low cloud amount over ocean occurs in winter in SH subtropics in the early morning hours and in NH midlatitudes without diurnal cycle. Over land in winter the maximum is in the early afternoon, accompanied in the midlatitudes by thin cirrus. Over tropical land and in the other regions in summer, the maximum of mesoscale high opaque clouds occurs in the evening. Cirrus also increases during the afternoon and persists during night and early morning. The maximum of thin cirrus is in the early afternoon, then decreases slowly while cirrus and high opaque clouds increase. TOVS extends information of ISCCP during night, indicating that high cloudiness, increasing during the afternoon, persists longer during night in the Tropics and subtropics than in midlatitudes. A comparison of seasonal and diurnal cycle of high cloud amount between South America, Africa, and Indonesia during boreal winter has shown strong similarities between the two land regions, whereas the Indonesian islands show a seasonal and diurnal behavior strongly influenced by the surrounding ocean. Deeper precipitation systems over Africa than over South America do not seem to be directly reflected in the horizontal coverage and mesoscale effective emissivity of high clouds.