Development and testing of a prototype indicator-based tool for identification of potential problem areas for marine litter in Europe's seas.

We demonstrate a prototype multi-metric indicator-based assessment tool (i.e. Marine Litter Assessment Tool - MALT) for mapping and identification of 'problem areas' and 'non-problem areas' regarding the occurrence of marine litter in Europe's seas. The study is based on a European-wide data set consisting of three marine litter indicators: (1) litter at the seafloor, (2) beach litter and (3) floating micro-litter. This publicly available data allowed litter status to be determined in 1,957,081 km2 (19.1 %) of the total area of Europe's seas (10,243,474 km2). Of the area assessed, 25.8 % (505,030 km2) was found to be 'non-problem areas' whilst 'problem areas' accounted for 74.2 % (1,452,051 km2). This indicates that marine litter is a large-scale problem in Europe's seas.

Are European Blue Economy ambitions in conflict with European environmental visions?

We report the outcomes of a comprehensive study of the potential consequences of the implementation of the EU Maritime Spatial Planning Directive (MSPD) in Danish waters. The analyses are anchored in a framework developed in support of data-driven Ecosystem-Based Maritime Spatial Planning. The data for the models include not only human stressors but also information on the distribution of ecosystem components ranging from planktonic communities over benthic communities to fish, seabirds and marine mammals. We have established a baseline, based on state-of-the-art data sets, with respect to combined effects upon ecosystem components. Future scenarios for the developments in human stressors were estimated for 2030 and 2050 based on information on existing policies, strategies and plans and were compared to the baseline. In addition, we developed a scenario for implementation of the Marine Strategy Framework Directive (MSFD), i.e. working towards meeting the objectives of Good Environmental Status. Our results indicate that (1) combined human stressors will possibly increase in 2030 and 2050 compared to the baseline, (2) increased combined human stressors are likely to lead to a worsening of the environmental and ecological status sensu the Marine Strategy Framework Directive and the Water Framework Directive (WFD), and (3) the MSPD implementation process appears to conflict with the MSFD and WFD objectives. Accordingly, we are sceptical of claims of an untapped potential for Blue Growth in Danish marine waters.

Mixing apples and oranges: Assessing ecological status and its confidence from multiple and diverse indicators.

Ecosystem responses to increasing human pressures are complex and diverse, affecting organisms across all trophic levels. This has prompted the development of methods that integrate information across many indicators for environmental management. Legislative frameworks such as the European Water Framework Directive (WFD), specifically prescribe that integrated assessme nt (IA) of ecological status must consider indicators representing various biological and supporting quality elements. We present a general approach for an IA system based on a piece-wise linear transformation of indicator distributions to a standardized scale, allowing for integrating information from multiple and diverse indicators through a policy-dependent aggregation scheme. Uncertainties associated with monitoring data used for calculating indicators and their propagation throughout the integration scheme allow for confidence assessment at all levels of the hierarchical integration. Specific pressures leading to ecological impact can be identified through the most impaired indicators in the hierarchical and transparent aggregation scheme. The IA and its confidence are facilitated though the development of an online tool that accesses information from monitoring databases and presents the outcome at all levels of the assessment, ensuring consistency and transparency in the calculations for all potential stakeholders. We demonstrate the versality and applicability of the approach using indicators and aggregation principles from the Swedish national guidelines for assessing ecological status of rivers, lakes and coastal waters according to the WFD. Although the approach and the tool were developed specifically for the WFD ecological status assessment in Sweden, the generality of the approach implies that it can easily be adapted to the WFD assessment methods of other countries as well as other policies, where an integrated assessment is required.

Combined effects of human pressures on Europe's marine ecosystems.

Marine ecosystems are under high demand for human use, giving concerns about how pressures from human activities may affect their structure, function, and status. In Europe, recent developments in mapping of marine habitats and human activities now enable a coherent spatial evaluation of potential combined effects of human activities. Results indicate that combined effects from multiple human pressures are spread to 96% of the European marine area, and more specifically that combined effects from physical disturbance are spread to 86% of the coastal area and 46% of the shelf area. We compare our approach with corresponding assessments at other spatial scales and validate our results with European-scale status assessments for coastal waters. Uncertainties and development points are identified. Still, the results suggest that Europe's seas are widely disturbed, indicating potential discrepancy between ambitions for Blue Growth and the objective of achieving good environmental status within the Marine Strategy Framework Directive.

Relative impacts of multiple human stressors in estuaries and coastal waters in the North Sea-Baltic Sea transition zone.

The objectives of this study are 1) to map the potential cumulative impacts of multiple human activities and stressors on the ecosystems in the transition zone between the North Sea and Baltic Sea, for Danish waters 2) to analyse differences in stressor contribution between the European Union's Marine Strategy Framework Directive (MSFD, off-shore waters) and Water Framework Directive (WFD, coastal waters), and 3) to assess the local relative importance of stressors for 14 areas along a land-sea gradient, from inner fjords or coastal areas to offshore waters. The mapping of cumulative impacts is anchored in 35 datasets describing a broad range of human stressors and 47 ecosystem components ranging from phytoplankton over benthic communities to fish, seabirds and marine mammals, which we combined by means of a widely used spatial human impact model. Ranking of the stressor impacts for the entire study area revealed that the top five stressors are: 'Nutrients', 'Climate anomalies', 'Non-indigenous species', 'Noise' and 'Contaminants'. The gradient studies showed that some stressors (e.g. 'Nutrients', 'Shipping' and 'Physical modification') have a relatively higher impact within the fjord/estuarine systems whilst others (e.g. 'Fisheries', 'Contaminants' and 'Noise') have relatively higher impact in the open waters. Beyond mapping of cumulative human impacts, we discuss how the maps can be used as an analytical tool to inform ecosystem-based management and marine spatial planning, using the MSFD and WFD as examples.

Long-term temporal and spatial trends in eutrophication status of the Baltic Sea.

Much of the Baltic Sea is currently classified as 'affected by eutrophication'. The causes for this are twofold. First, current levels of nutrient inputs (nitrogen and phosphorus) from human activities exceed the natural processing capacity with an accumulation of nutrients in the Baltic Sea over the last 50-100 years. Secondly, the Baltic Sea is naturally susceptible to nutrient enrichment due to a combination of long retention times and stratification restricting ventilation of deep waters. Here, based on a unique data set collated from research activities and long-term monitoring programs, we report on the temporal and spatial trends of eutrophication status for the open Baltic Sea over a 112-year period using the HELCOM Eutrophication Assessment Tool (HEAT 3.0). Further, we analyse variation in the confidence of the eutrophication status assessment based on a systematic quantitative approach using coefficients of variation in the observations. The classifications in our assessment indicate that the first signs of eutrophication emerged in the mid-1950s and the central parts of the Baltic Sea changed from being unaffected by eutrophication to being affected. We document improvements in eutrophication status that are direct consequences of long-term efforts to reduce the inputs of nutrients. The reductions in both nitrogen and phosphorus loads have led to large-scale alleviation of eutrophication and to a healthier Baltic Sea. Reduced confidence in our assessment is seen more recently due to reductions in the scope of monitoring programs. Our study sets a baseline for implementation of the ecosystem-based management strategies and policies currently in place including the EU Marine Strategy Framework Directives and the HELCOM Baltic Sea Action Plan.

Approaches for integrated assessment of ecological and eutrophication status of surface waters in Nordic Countries.

We review approaches and tools currently used in Nordic countries (Denmark, Finland, Norway and Sweden) for integrated assessment of 'ecological status' sensu the EU Water Framework Directive as well as assessment of 'eutrophication status' in coastal and marine waters. Integration principles for combining indicators within biological quality elements (BQEs) and combining BQEs into a final-integrated assessment are discussed. Specific focus has been put on combining different types of information into indices, since several methods are currently employed. As a consequence of the variety of methods used, comparisons across both BQEs and water categories (river, lakes and coastal waters) can be difficult. Based on our analyses, we conclude that some principles and methods for integration can be critical and that a harmonised approach should be developed. Further, we conclude that the integration principles applied within BQEs are critical and in need of harmonisation if we want a better understanding of potential transition in ecological status between surface water types, e.g. when riverine water enters a downstream lake or coastal water body.

Development and testing of a prototype tool for integrated assessment of chemical status in marine environments.

We report the development and application of a prototype tool for integrated assessment of chemical status in aquatic environments based on substance- and matrix-specific environmental assessment criteria (thresholds). The Chemical Status Assessment Tool (CHASE) integrates data on hazardous substances in water, sediments and biota as well as bio-effect indicators and is based on a substance- or bio-effect-specific calculation of a 'contamination ratio' being the ratio between an observed concentration and a threshold value. Values <1.0 indicate areas potentially 'unaffected', while values >1.0 indicate areas potentially 'affected'. These ratios are combined within matrices, i.e. for water, sediment and biota and for biological effects. The overall assessment used a 'one out, all out principle' with regard to each matrix. The CHASE tool was tested in the Baltic Sea and the North Sea in 376 assessment units. In the former, the chemical status was >1.0 in practically all areas indicating that all areas assessed were potentially affected. The North Sea included areas classified as unaffected or affected. The CHASE tool can in combination with temporal trend assessments of individual substances be advantageous for use in remedial action plans and, in particular, for the science-based evaluation of the status and for determining which specific substances are responsible for a status as potentially affected.

Effect of reaction mechanism on precursor exposure time in atomic layer deposition of silicon oxide and silicon nitride.

Atomic layer deposition (ALD) of highly conformal, silicon-based dielectric thin films has become necessary because of the continuing decrease in feature size in microelectronic devices. The ALD of oxides and nitrides is usually thought to be mechanistically similar, but plasma-enhanced ALD of silicon nitride is found to be problematic, while that of silicon oxide is straightforward. To find why, the ALD of silicon nitride and silicon oxide dielectric films was studied by applying ab initio methods to theoretical models for proposed surface reaction mechanisms. The thermodynamic energies for the elimination of functional groups from different silicon precursors reacting with simple model molecules were calculated using density functional theory (DFT), explaining the lower reactivity of precursors toward the deposition of silicon nitride relative to silicon oxide seen in experiments, but not explaining the trends between precursors. Using more realistic cluster models of amine and hydroxyl covered surfaces, the structures and energies were calculated of reaction pathways for chemisorption of different silicon precursors via functional group elimination, with more success. DFT calculations identified the initial physisorption step as crucial toward deposition and this step was thus used to predict the ALD reactivity of a range of amino-silane precursors, yielding good agreement with experiment. The retention of hydrogen within silicon nitride films but not in silicon oxide observed in FTIR spectra was accounted for by the theoretical calculations and helped verify the application of the model.

Nitrogen inputs from agriculture: towards better assessments of eutrophication status in marine waters.

Nutrient enrichment of coastal marine waters caused by losses of nitrate (NO(3)(-)) from agriculture is an increasing global problem. In the European Union, the Nitrates Directive (ND) of 1991 was meant to be a cornerstone in reducing eutrophication effects in coastal waters downstream from intensively farmed catchments. Although reductions in losses of nitrate have been attained, very few Member States have yet been able to reduce eutrophication effects caused by inputs of NO(3)(-) from agriculture. We report trends in concentrations of NO(3)(-) and chlorophyll-a (Chl-a) in Danish coastal and open marine waters during the period from 1996 to 2011 together with an assessment of eutrophication status based on multiple indicators (e.g. nutrient concentrations, Chl-a, submerged aquatic vegetation and benthic macroinvertebrates). Despite decreasing concentrations of both NO(3)(-)and Chl-a, Danish coastal waters are not yet to be classified as 'unaffected by eutrophication'. In order to improve future pan-European evaluations of the effectiveness of the ND, we argue for the added value of including indicators and assessment principles from other European Directives, i.e. the Water Framework Directive and the Marine Strategy Framework Directive.

Density functional theory predictions of the composition of atomic layer deposition-grown ternary oxides.

The surface reactivity of various metal precursors with different alkoxide, amide, and alkyl ligands during the atomic layer deposition (ALD) of ternary oxides was determined using simplified theoretical models. Quantum chemical estimations of the Brønsted reactivity of a metal complex precursor at a hydroxylated surface are made using a gas-phase hydrolysis model. The geometry optimized structures and energies for a large suite of 17 metal precursors (including cations of Mg, Ca, Sr, Sc, Y, La, Ti, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, and Ga) with five different anionic ligands (conjugate bases of tert-butanol, tetramethyl heptanedione, dimethyl amine, isopropyl amidine, and methane) and the corresponding hydrolyzed complexes are calculated using density functional theory (DFT) methods. The theoretically computed energies are used to determine the energetics of the model reactions. These DFT models of hydrolysis are used to successfully explain the reactivity and resulting stoichiometry in terms of metal cation ratios seen experimentally for a variety of ALD-grown ternary oxide systems.

Visible luminescence spectroscopy of free-base and zinc phthalocyanines isolated in cryogenic matrices.

The absorption, emission and excitation spectra of ZnPc and H(2)Pc trapped in Ne, N(2), Ar, Kr and Xe matrices have been recorded in the region of the Q states. A comparison of the matrix fluorescence spectra with Raman spectra recorded in KBr pellets reveals very strong similarities. This is entirely consistent with the selection rules and points to the occurrence of only fundamental vibrational transitions in the emission spectra. Based on this behaviour, the vibronic modes in emission have been assigned using results obtained recently on the ground state with large basis-set DFT calculations [Murray et al. PCCP, 12, 10406 (2010)]. Furthermore, the very strong mirror symmetry between excitation and emission has allowed these assignments to be extended to the excitation (absorption) bands. While this approach works well for ZnPc, coupling between the band origin of the S(2)(Q(Y)) state and vibrationally excited levels of S(1)(Q(X)), limits the range of its application in H(2)Pc. The Q(X)/Q(Y) state coupling is analysed from data obtained from site-selective excitation spectra, revealing pronounced matrix and site effects. From this analysis, the splitting of the Q(X) and Q(Y) states has been determined more accurately than in any previous attempts.

Efficacy of a cognitive stimulation therapy programme for people with dementia.

OBJECTIVES: Cognitive stimulation therapy (CST) has been shown to produce improvements in cognition and quality of life which compare favourably with trials of cholinesterase inhibitors. The aim of the present study was to evaluate the efficacy of CST, replicating the methods of Spector et al in the British Journal of Psychiatry in 2003 in a smaller sample using a control group engaged in routine activities. METHODS: Eligible participants (mild to moderate dementia; MMSE range 10-23) were randomised to CST group or control conditions. Pre- and post-intervention testing was undertaken by assessors who were blind to condition. Measures included MMSE, CDR (sum of boxes), ADAS-cog, RAID (anxiety), abbreviated GDS (depression), QoL-AD, and the CAPE Behaviour Rating Scale (BRS). Analysis was by non-parametric statistics. Occupational therapists facilitated two sessions per week for seven weeks in two long-term care facilities and the same programme was run by the activity co-ordinator in a nursing home unit. RESULTS: Fourteen CST and 13 control participants completed the study. Between group difference scores analysis showed that the CST group improved compared to controls on MMSE (Mann-Whitney U = 32, p = 0.013) and on the QoL-AD which just fell short of significant (U=51.5, p = 0.055). Qualitatively, therapists noted that CST participants demonstrated good interaction and enthusiasm in the group environment, with continuity and carryover between sessions. CONCLUSIONS: Even though the sample sizes are small the current study is consistent with the Spector et al's findings in 2003 of beneficial effects in people with dementia following CST. The programme is recommended as an intervention for people with mild to moderate dementia.

Infra-red and Raman spectroscopy of free-base and zinc phthalocyanines isolated in matrices.

The infrared absorption spectra of matrix-isolated zinc phthalocyanine (ZnPc) and free-base phthalocyanine (H(2)Pc) have been recorded in the region from 400 to 4000 cm(-1) in solid N(2), Ar, Kr and Xe. Raman spectra have been recorded in doped KBr pellets. The isotopomers HDPc and D(2)Pc have been synthesised in an attempt to resolve the conflicting assignments that currently exist in the literature for the N-H bending modes in H(2)Pc spectra. A complete correlation between the vibrational modes of the three free-base isotopomers and ZnPc has been achieved. Comparison of the IR and Raman spectroscopic results, obtained with isotopic substitution and with predictions from large basis set ab initio calculations, allows identification of the in-plane (IP) and out-of-plane (OP) N-H bending modes. The largest IP isotope shift is observed in the IR at 1046 cm(-1) and at 1026 cm(-1) in Raman spectra while the largest effect in the OP bending modes is at 764 cm(-1). OP bending modes are too weak to be observed in the experimental Raman data. The antisymmetric N-H stretching mode is observed at approximately 3310 cm(-1) in low temperature solids slightly blue shifted from, but entirely consistent with the literature KBr data. With the exception of the N-H stretches, the recorded H/D isotope shifts in all the N-H vibrations are complex, with the IP bending modes exhibiting small nu(H)/nu(D) ratios (the largest value is 1.089) while one of the observed OP modes has a ratio < 1. DFT results reveal that the small ratios arise in particular from strong coupling of the N-H IP bending modes with IP stretching modes of C-N bonds. The unexpected finding of a nu(H)/nu(D) ratio smaller than one was analysed theoretically by examining the evolution of the frequencies of the free base by increasing the mass from H to D in a continuous manner. A consequence of this frequency increase in the heavier isotopomer is that the direction of the N-D OP bend is reversed from the N-H OP bend.

Luminescence spectroscopy of matrix-isolated atomic manganese: site size and orbital occupancy dependence of crystal field splitting.

Narrow linewidth emission features observed in the near-UV following y (6)P state excitation of atomic manganese isolated in the solid rare gases are assigned to b (4)D and a (4)P states. These states arise from the 3d(5)4s(2) electronic configuration, identical to that of the (6)S ground state, and the origin of the narrow linewidths. Two thermally stable sites, labeled blue and red on the basis of their position in absorption spectra, are occupied by atomic Mn in Ar and Kr while a single site is present in Xe. The red site produces a single, narrow line emission for the b (4)D state at 329 nm. In contrast, a lineshape analysis of the complex blue site b (4)D state emission between 331 and 332 nm reveals the occurrence of three zero phonon lines (ZPLs). Millisecond emission decay curves recorded for these features are found to be complex, requiring double and triple exponential fit functions. The origins of the complex decays and multiple ZPLs are shown to arise from weak crystal field splitting (CFS) of the J=7/2 spin-orbit level of the b (4)D state of atomic Mn isolated in the blue site of the solid rare gases. Fields of cubic symmetry are capable of inducing splitting for J>3/2 so atoms isolated in both single vacancy and tetravacancy sites in the fcc lattices of the solid rare gases are prone to this effect. b (4)D state emission is also produced following y (6)P excitation for Mn atoms occupying the red sites in Ar and Kr. However, Mn atoms isolated in the larger tetravacancy sites have small matrix shifts and do not exhibit any CFS. The magnitudes of the weak CF splittings are shown to depend on both the excited state electronic configurations 3d(5)4s(2) b (4)D and 3d(6)4s(1) a (4)D states and the size of the matrix site occupied by atomic Mn.

A simple method for confidence rating of eutrophication status classifications.

We report the development of a methodology for assessing confidence in ecological status classifications. The method presented here can be considered as a secondary assessment, supporting the primary assessment of eutrophication or ecological status. The confidence assessment is based on scoring the quality of the indicators on which the primary assessment is made. This represents a first step towards linking status classification with information regarding their accuracy and precision. Applied to an existing data set used for assessment of eutrophication status of the Baltic Sea (including the Kattegat and Danish Straits) we demonstrate that confidence in the assessment is Good or High in 149 out of 189 areas assessed (79%). Contrary to our expectations, assessments of the open parts of the Baltic Sea have a higher confidence than assessments of coastal waters. We also find that in open waters of the Baltic Sea, some biological indicators have a higher confidence than indicators representing physical-chemical conditions. In coastal waters, phytoplankton, submerged aquatic vegetation and indicators of physical-chemical conditions have a higher confidence than indicators of the quality of benthic invertebrate communities. Our analyses also show that the perceived weaknesses of eutrophication assessments are due more to Low confidence in reference conditions and acceptable deviations, rather than in the monitoring data.

Amplified emission of phthalocyanine isolated in cryogenic matrices.

Laser induced fluorescence spectroscopy of free-base (H(2)Pc) and zinc (ZnPc) phthalocyanines trapped in rare gas and nitrogen matrices reveals a quite unexpected phenomenon with a moderate increase in the laser intensity. In all matrices except Xe, a huge increase occurs in the intensity of an emission band near 755 nm when pumping the S(1) <-- S(0) transition. The band involves a vibrational mode of the ground state, located at 1550 and 1525 cm(-1) for H(2)Pc and ZnPc, respectively. Many of the characteristics of amplified emission (AE) are exhibited by this vibronic transition. Excitation scans recorded for the AE band yield greatly enhanced site selectivity compared to what is obtained in normal fluorescence excitation scans.