A Headspace needle-trap method for the analysis of volatile organic compounds in whole blood

Needle trap devices (NTDs) are a relatively new and promising tool for headspace (HS) analysis. In this study, a dynamic HS sampling procedure is evaluated for the determination of volatile organic compounds (VOCs) in whole blood samples. A full factorial design was used to evaluate the influence of the number of cycles and incubation time and it is demonstrated that the controlling factor in the process is the number of cycles. A mathematical model can be used to determine the most appropriate number of cycles required to adsorb a prefixed amount of VOCs present in the HS phase whenever quantitative adsorption is reached in each cycle. Matrix effect is of great importance when complex biological samples, such as blood, are analyzed. The evaluation of the salting out effect showed a significant improvement in the volatilization of VOCs to the HS in this type of matrices. Moreover, a 1:4 (blood:water) dilution is required to obtain quantitative recoveries of the target analytes when external calibration is used. The method developed gives detection limits in the 0.020–0.080 μg L−1 range (0.1–0.4 μg L−1 range for undiluted blood samples) with appropriate repeatability values (RSD < 15% at high level and <23% at LOQ level). Figure of merits of the method can be improved by using a smaller phase ratio (i.e., an increase in the blood volume and a decrease in the HS volume), which lead to lower detection limits, better repeatability values and greater sensibility. Twenty-eight blood samples have been evaluated with the proposed method and the results agree with those indicated in other studies. Benzene was the only target compound that gave significant differences between blood levels detected in volunteer non-smokers and smokers

Modelling nitrogen and phosphorus loads in a Mediterranean river catchment (La Tordera, NE Spain)

Human activities have resulted in increased nutrient levels in many rivers all over Europe. Sustainable management of river basins demands an assessment of the causes and consequences of human alteration of nutrient flows, together with an evaluation of management options. In the context of an integrated and interdisciplinary environmental assessment (IEA) of nutrient flows, we present and discuss the application of the nutrient emission model MONERIS (MOdelling Nutrient Emissions into River Systems) to the Catalan river basin, La Tordera (north-east Spain), for the period 1996–2002. After a successful calibration and verification process (Nash-Sutcliffe efficiencies E=0.85 for phosphorus and E=0.86 for nitrogen), the application of the model MONERIS proved to be useful in estimating nutrient loads. Crucial for model calibration, in-stream retention was estimated to be about 50 % of nutrient emissions on an annual basis. Through this process, we identified the importance of point sources for phosphorus emissions (about 94% for 1996–2002), and diffuse sources, especially inputs via groundwater, for nitrogen emissions (about 31% for 1996–2002). Despite hurdles related to model structure, observed loads, and input data encountered during the modelling process, MONERIS provided a good representation of the major interannual and spatial patterns in nutrient emissions. An analysis of the model uncertainty and sensitivity to input data indicates that the model MONERIS, even in data-starved Mediterranean catchments, may be profitably used by water managers for evaluating quantitative nutrient emission scenarios for the purpose of managing river basins. As an example of scenario modelling, an analysis of the changes in nutrient emissions through two different future scenarios allowed the identification of a set of relevant measures to reduce nutrient loads.

The age of the"Grande Coupure" mammal turnover: New constraints from the Eocene Oligocene record of the Eastern Ebro Basin (NE Spain.)

The Grande Coupure represents a major terrestrial faunal turnover recorded in Eurasia associated with the overall climate shift at the Eocene-Oligocene transition. During this event, a large number of European Eocene endemic mammals became extinct and new Asian immigrants appeared. The absolute age of the Grande Coupure, however, has remained controversial for decades. The Late Eocene-Oligocene continental record of the Eastern Ebro Basin (NE Spain) constitutes a unique opportunity to build a robust magnetostratigraphy- based chronostratigraphy which can contribute with independent age constraints for this important turnover. This study presents new magnetostratigraphic data of a 495-m-thick section (Moià-Santpedor) that ranges from 36.1 Ma to 33.3 Ma. The integration of the new results with previous litho- bio- and magnetostratigraphic records of the Ebro Basin yields accurate ages for the immediately pre- and post-Grand Coupure mammal fossil assemblages found in the study area, bracketing the Grande Coupure to an age embracing the Eocene-Oligocene transition, with a maximum allowable lag of 0.5 Myr with respect to this boundary. The shift to drier conditions that accompanied the global cooling at the Eocene-Oligocene transition probably determined the sedimentary trends in the Eastern Ebro Basin. The occurrence and expansion of an amalgamated-channel sandstone unit is interpreted as the forced response of the fluvial fan system to the transient retraction of the central-basin lake systems. The new results from the Ebro Basin allow us to revisit correlations for the controversial Eocene-Oligocene record of the Hampshire Basin (Isle of Wight, UK), and their implications for the calibration of the Mammal Palaeogene reference levels MP18 to MP21.

Looking beneath Dalí's paint: non-destructive canvas analysis

A new analytical method was developed to non-destructively determine pH and degree of polymerisation (DP) of cellulose in fibres in 19th 20th century painting canvases, and to identify the fibre type: cotton, linen, hemp, ramie or jute. The method is based on NIR spectroscopy and multivariate data analysis, while for calibration and validation a reference collection of 199 historical canvas samples was used. The reference collection was analysed destructively using microscopy and chemical analytical methods. Partial least squares regression was used to build quantitative methods to determine pH and DP, and linear discriminant analysis was used to determine the fibre type. To interpret the obtained chemical information, an expert assessment panel developed a categorisation system to discriminate between canvases that may not be fit to withstand excessive mechanical stress, e.g. transportation. The limiting DP for this category was found to be 600. With the new method and categorisation system, canvases of 12 Dalí paintings from the Fundació Gala-Salvador Dalí (Figueres, Spain) were non-destructively analysed for pH, DP and fibre type, and their fitness determined, which informs conservation recommendations. The study demonstrates that collection-wide canvas condition surveys can be performed efficiently and non-destructively, which could significantly improve collection management.