Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.     

Application of Generalized Likelihood Uncertainty Estimation (GLUE) at different temporal scales to reduce the uncertainty level in modelled river flows

ABSTRACT

In this study, the distributed catchment-scale model, DiCaSM, was applied on five catchments across the UK. Given its importance, river flow was selected to study the uncertainty in streamflow prediction using the Generalized Likelihood Uncertainty Estimation (GLUE) methodology at different timescales (daily, monthly, seasonal and annual). The uncertainty analysis showed that the observed river flows were within the predicted bounds/envelope of 5% and 95% percentiles. These predicted river flow bounds contained most of the observed river flows, as expressed by the high containment ratio, CR. In addition to CR, other uncertainty indices – bandwidth B, relative bandwidth RB, degrees of asymmetry S and T, deviation amplitude D, relative deviation amplitude RD and the R factor – also indicated that the predicted river flows have acceptable uncertainty levels. The results show lower uncertainty in predicted river flows when increasing the timescale from daily to monthly to seasonal, with the lowest uncertainty associated with annual flows.     

Evaluation of Simultaneous Analyte Leaching/Vapour Phase Introduction for Direct Osmium Isotope Ratio Measurements in Solid Samples by Double-Focusing Sector Field ICP-MS

The analytical performance of a method for Os isotope ratio measurement by double‐focusing, sector field ICP‐MS (ICP‐SFMS) was evaluated. The method is based on several optimised, concurrent processes: Os extraction from samples in hot concentrated nitric acid; separation of Os from the digest solution by the formation of volatile osmium tetroxide accelerated by continuous hydrogen peroxide addition; transport of analyte vapour by an oxygen flow into the ICP; and isotopic determination by ICP‐SFMS. Due to the very efficient utilisation of analyte (approaching 0.5‰), Os isotope ratio measurement could be performed at low pg levels. Combined with an ability to process sample sizes up to 2 g (up to 50 g if the organic matrix of biological or botanical samples is eliminated by ashing), materials with Os concentrations in the low, or even sub pg g^?1 range could be determined by this method. Given that two complete digestion/distillation systems were available for interchangeable use, throughputs of up to fifteen samples per 8 hour shift could be achieved. The method precision, evaluated as the long‐term reproducibility of ¹⁸⁷ Os/¹⁸⁸Os ratio measurements in a commercial Os reference sample containing 0.5 ng Os, was 0.16% relative standard deviation (RSD, 1s). The method has been applied to perform replicate ¹⁸⁷ Os/¹⁸⁸ Os ratio measurements on a suite of fifty reference materials of various origins and matrix compositions, with Os concentrations varying from < 0.1 pg g^?1 to > 100 ng g^?1, yielding an average precision of 3% RSD. Though none of the materials tested are certified for Os content or Os isotope composition, comparison of the obtained data with published Os isotope information for similar sample types revealed close agreement between the two. The method can also be used for the simultaneous, semi‐quantitative determination of Os concentrations.     

Survey of estrogenic and androgenic disruption in Swedish coastal waters by the analysis of bile fluid from perch and biomarkers in the three-spined stickleback

The potential for endocrine disruption close to sewage treatment plant and pulp mill effluent discharge points along the Swedish Baltic Sea coast was explored using a dual survey strategy employing two stationary fish species. The levels of vitellogenin and spiggin as biomarkers of endocrine disruption were determined in juvenile three-spined sticklebacks (Gasterosteus aculeatus L.) together with the sex ratios and the presence of intersex. As an indication of exposure, estrogenic and androgenic substances were analysed by GC–MS in bile from perch (Perca fluviatilis L.). Spiggin and vitellogenin levels in juvenile three-spined sticklebacks were generally low, and, for most sampling sites no deviation in gonad type ratios were observed. No remarkable levels of natural or synthetic estrogens or androgens were observed in bile fluid from perch, while bisphenol A and 4-nonylphenol were detected in perch from both reference sites and exposed sites. Taken together, the results did not indicate estrogenic or androgenic disruption in the investigated waters.     

Performance of pile-restrained flexible floating breakwaters

The overall performance of pile-restrained flexible floating breakwaters is investigated under the action of linear monochromatic incident waves in the frequency domain. The aforementioned floating breakwaters undergo only vertical structural deflections along their length and are held in place by means of vertical piles. The total number of degrees of freedom equals the six conventional body modes, when the breakwater moves as a rigid body, plus the extra bending modes. These bending modes are introduced to represent the structural deflections of the floating breakwater and are described by the Bernoulli–Euler flexible beam equation. The number of bending modes introduced is determined through an appropriate iterative procedure. The hydrostatic coefficients corresponding to the bending modes are also derived. The numerical analysis of the flexible floating breakwaters is based on a three-dimensional hydrodynamic formulation of the floating body. A parametric study is carried out for a wide range of structural stiffness parameters and wave headings, to investigate their effect on the performance of flexible floating breakwaters. Moreover, this performance is compared with that of the corresponding pile-restrained rigid floating breakwater. Results indicated that the degree of structural stiffness and the wave heading strongly affect the performance of flexible floating breakwaters. The existence of an “optimum” value of structural stiffness is demonstrated for the entire wave frequency range.     

Connection between ozone concentration and atmosphere circulation at peak Moussala

Connection between ozone concentration and atmosphere circulation is investigated based on measurements at BEO station, peak Moussala (2,925 m a.s.l.), for the period 09 August 2006 to 29 January 2008. Ozone concentration data are collected with UV-analyzer “Environnement O₃ 42” and meteo data with weather station “Vaisala”. There are measurements of ⁷Be. Data from NOAA HYSPLIT model for particle trajectories are also used. Eight wind directions and three ranges of wind velocities are employed in the analysis. A comparison of ozone concentrations in upward and downward air transport according to HYSPLIT model is made. The number of cases with ozone concentration above 63 ppb has been counted. Mann–Whitney nonparametric test is employed as a basic statistical method. Correlation between atmosphere pressure and tropospheric ozone content is made. The same is done for ⁷Be and ozone. The main conclusion is that there is not any local or regional pollution effect detectable at peak Moussala, but most of the ozone measured is due to emissions of hydrocarbons and NO _x over a larger region. There could be some regional sources of ozone building substances in southwest direction from peak Moussala. Air transported from the north quarter has higher ozone concentrations compared to the south quarter. In vertical direction, upward transport of air masses shows higher values of ozone concentration. Higher wind velocity is associated with low ozone concentrations at peak Moussala. The annual course of ozone concentration has summer maximum and winter minimum. There is right connection between air pressure and ozone concentration. The same is valid for the correlation between ⁷Be and ozone. Diurnal ozone course shows daytime maximum in winter and nighttime maximum in summer.     

Empirical seismic vulnerability assessment of Icelandic buildings affected by the 2000 sequence of earthquakes

In June 2000, two Mw6.5 earthquakes occurred within a 4-day interval in the largest agricultural region of Iceland causing substantial damage and no loss of life. The distance between the earthquake epicentres and the fault rupture was approximately 15 km. Nearly 5000 low-rise residential buildings were affected, some of which were located between the faults and exposed to strong ground motion from both events. The post-earthquakes damage and repair costs for every residential building in the epicentral region were assessed for insurance purposes. The database is detailed and complete for the whole region and represents one of the best quality post-earthquake vulnerability datasets used for seismic loss estimation. Nonetheless, the construction of vulnerability curves from this database is hampered by the fact that the loss values represent the cumulative damage from two sequential earthquakes in some areas, and single earthquakes in others. A novel methodology based on beta regression is proposed here in order to define the geographical limits on areas where buildings sustained cumulative damage and predict the seismic losses for future sequence of events in each area. The results show that the average building loss in areas affected by a single event is below 10% of the building replacement value, whilst this increases to an average of 25% in areas affected by the two earthquakes. The proposed methodology can be used to empirically assess the vulnerability in other areas which experienced sequence of events such as Emilia-Romagna (Italy) in 2012.