Element determination in environmental samples using Z-GFAAS with variable magnetic field

Electrothermal atomic absorption spectrometry methods with Zeeman effect background correction (Z-GFAAS) for determination of As, Sb, Se, Ag, Cd, Pb, Cu, Fe, Zn, Cr, and Ni in water and sludge samples were developed. The measurements using Z-GFAAS and variable magnetic field at the three-field dynamic mode permit the sensitivity adaptation for higher analytical concentrations. Calibration ranges were expanded over two orders of magnitude within one measurement run by the applying three-field dynamic mode of this correction system. There are presented calibration data, furnace programs, modifiers, and microwave digestion programs of the obviously monitored elements in the environmental samples. Very low detection limits (3σ criterion) were obtained. Quality assurance was checked by the suitable CRM. The study brings simultaneous determination of the samples with different element concentration range and different sample matrixes, as an important application information for an analyst working in the area of the eco-analytical research.     

Land degradation assessment by geo-spatially modeling different soil erodibility equations in a semi-arid catchment

Land degradation by soil erosion is one of the most serious problems and environmental issues in many ecosystems of arid and semi-arid regions. Especially, the disturbed areas have greater soil detachability and transportability capacity. Evaluation of land degradation in terms of soil erodibility, by using geostatistical modeling, is vital to protect and reclaim susceptible areas. Soil erodibility, described as the ability of soils to resist erosion, can be measured either directly under natural or simulated rainfall conditions, or indirectly estimated by empirical regression models. This study compares three empirical equations used to determine the soil erodibility factor of revised universal soil loss equation prediction technology based on their geospatial performances in the semi-arid catchment of the Saraykoy II Irrigation Dam located in Cankiri, Turkey. A total of 311 geo-referenced soil samples were collected with irregular intervals from the top soil layer (0-10?cm). Geostatistical analysis was performed with the point values of each equation to determine its spatial pattern. Results showed that equations that used soil organic matter in combination with the soil particle size better agreed with the variations in land use and topography of the catchment than the one using only the particle size distribution. It is recommended that the equations which dynamically integrate soil intrinsic properties with land use, topography, and its influences on the local microclimates, could be successfully used to geospatially determine sites highly susceptible to water erosion, and therefore, to select the agricultural and bio-engineering control measures needed.     

The development of probabilistic models to estimate accident risk (due to runway overrun and landing undershoot) applicable to the design and construction of runway safety areas

The risks of landing overrun (LDOR – LanDing OverRun), Take-off Overrun (TOOR – Take-Off OverRun) and landing undershoot (LDUS – LanDing UnderShoot) are dependent on multiple factors related to operating conditions. These include wind, runway surface conditions, landing or take-off distances required, the presence of obstacles, runway distance available, the existence and dimensions of runway safety areas.In this paper we propose risk models for runway overrun and landing undershoot, using a probabilistic approach. These models are supported by historical data on accidents in the area around the runway and will enable us to determine if the risk level is acceptable or whether action must be taken to mitigate such risks at a given airport. Furthermore, these models permit comparison of the results of different risk mitigation actions in terms of operational risk and safety.The principal advantage of this method is the high quality results obtained for a limited investment in terms of time, computing power and data. As such the method is extremely practical and easy to apply in aerodrome planning, development and operation.     

Acute and reproductive toxicity of nano-sized metal oxides (ZnO and TiO₂) to earthworms (Eisenia fetida)

An increase in nanomaterial applications will likely lead to an increased probability of environmental exposures, raising concerns regarding the safety of these materials. Recent studies have indicated that manufactured nanomaterials, such as metal oxides, have the potential to be harmful to aquatic and terrestrial organisms. The majority of nano-metal oxide research addressing potential toxicological issues has been focused in aquatic environments with very little terrestrial data. This study characterized the acute and reproductive toxicity of zinc oxide (ZnO) and titanium dioxide (TiO(2)) to earthworms (Eisenia fetida) in a terrestrial system. Following a 14 d exposure, nano-sized ZnO on filter paper was acutely toxic to E. fetida, while nano-sized TiO(2) did not exhibit acute toxicity. In contrast, neither nano-sized ZnO nor TiO(2) exhibited acute toxicity to earthworms in sand. Both nano-sized ZnO and TiO(2), following a 4 week exposure, caused reproductive effects in earthworms in artificial soil. Overall, nano-sized ZnO exhibited greater toxicity than nano-sized TiO(2) in Eisenia fetida.     

A feeding inhibition based prediction of the toxic effect of dissolved metal mixtures upon Echinogammarus marinus (Crustacea: Amphipoda) at field relevant concentrations across a latitudinal gradient

Risk assessment of metals in the environment is performed mainly with toxicity evaluations on single metals, which is largely inadequate since these substances occur in mixtures. The development of models predicting combined toxic effects on the basis of the concentration-response relationships of individual compounds has emerged as an answer. In the present study, metal effects on post-exposure anorexia (the concept of FdC(50)--concentration causing 50% of feeding inhibition--is implemented) in Echinogammarus marinus, a widely distributed gammarid amphipod, were assessed and compared with modelled ones obtained through the application of the concentration addition (CA) model, which represents a reasonable worst-case scenario for the risk assessment of metal mixtures. Data were validated using in situ experiments performed along a latitudinal gradient (Iceland, Scotland and Portugal) aiming at establishing a geographic profile of autochthonous population susceptibilities to metals. For all of the metals studied concentrations in the water column at exposure sites were in good agreement with feeding inhibition levels. Models gave low to relatively high percentage agreement between predictions and experimental data. Boreal populations demonstrated higher susceptibility to single metals, but not to mixture exposures. Meridional populations denoted lower susceptibilities with higher FdC(50).     

Characterization of PM10-bound polycyclic aromatic hydrocarbons in the ambient air of Spanish urban and rural areas

Urban areas constitute major pollution sources due to anthropogenic activities located in these areas. Among the legislated air pollutants, the particulate matter with an aerodynamic diameter less than or equal to 10 microns (PM10) and polycyclic aromatic hydrocarbons (PAH) are controlled under Directive 2008/50/EC and Directive 2004/107/EC, respectively due to their adverse health effects. A study was carried out at four urban and rural Spanish areas during the warm and cold seasons in 2008-2009 to quantify 19 PAH associated with the atmospheric PM10 by gas chromatography-mass spectrometry-mass spectrometry detection (GC-MS-MS) with the internal standard method. The particle-bound composition of the analysed PAH was 5 and 10 times greater in industrial and urban areas, respectively when compared to those measured in rural areas. The highest PAH concentrations during the cold period were possibly due to the additional contribution of domestic heating sources and meteorological conditions such as low temperature and solar irradiation. The use of molecular diagnostic ratios indicated that the possible, major PAH pollution sources in the most polluted areas were pyrogenic sources, mainly attributed to petroleum combustion sources (motor vehicle emissions and crude oil combustion). Petrogenic sources related to evaporative emissions also seemed to contribute in the most polluted area during the warm period. Those dates with high carcinogenic character according to the benzo(a)pyrene equivalent (BaP-eq) were also possibly attributed to petroleum combustion sources.     

Distribution and availability of trace elements in municipal solid waste composts

Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl(2)-DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.     

Nucella lapillus L. imposex levels after legislation prohibiting TBT antifoulants: temporal trends from 2003 to 2008 along the Portuguese coast

Nucella lapillus (dog whelk) imposex levels were assessed along the mainland Portuguese coast in 2006 and 2008 and were compared with available data from 2003 for the same area. Given that specimen size has been described as a factor inducing variation in some of the imposex assessment indices, and thus resulting in less reliable results, new monitoring and data analysis procedures are described and applied to study change of imposex levels from 2003 to 2008. A significant decline in imposex intensity was observed in the study area during the study period, and the Portuguese coast ecological status (under the terms defined by the OSPAR Commission) notably improved after 2003, confirming the effectiveness of the Regulation (EC) No. 782/2003 in reducing TBT pollution. Nevertheless, N. lapillus populations are still extensively affected by imposex, and fresh TBT inputs were detected in seawater throughout the coast in 2006. These recent inputs are attributed to vessels still carrying TBT antifoulants applied before 2003, as their presence in vessels was only forbidden in 2008. Considering that Regulation (EC) No. 782/2003 is an anticipation of the IMO global ban entered into force in September 2008, a worldwide-scale decrease in TBT pollution can be expected in the near future.