Four climate cycles of recurring deep and surface water destabilizations on the Iberian margin

Centennial climate variability over the last ice age exhibits clear bipolar behavior. High-resolution analyses of marine sediment cores from the Iberian margin trace a number of associated changes simultaneously. Proxies of sea surface temperature and water mass distribution, as well as relative biomarker content, demonstrate that this typical north-south coupling was pervasive for the cold phases of climate during the past 420,000 years. Cold episodes after relatively warm and largely ice-free periods occurred when the predominance of deep water formation changed from northern to southern sources. These results reinforce the connection between rapid climate changes at Mediterranean latitudes and century-to-millennial variability in northern and southern polar regions.     

Foliar residue dynamics of azadirachtins following direct stem injection into white and green ash trees for control of emerald ash borer

BACKGROUND: Azadirachtins are natural insecticides derived from the neem tree. The emerald ash borer (EAB) is an exotic invasive insect pest that infests various ash tree species and has the potential for significant economic, aesthetic and ecological impacts throughout North America. The initial translocation and foliar residue dynamics of azadirachtins were examined following direct injection into white and green ash trees growing in urban scenarios as a potential control for EAB. RESULTS: Substantial concentrations of azadirachtins A and B [mean maxima > 0.98 mg kg^?1 fresh weight (f.w.)] were observed within 2 days of injecting a specifically designed formulation of azadirachtins. Foliar residues declined exponentially through time, with half‐life estimates ranging from 5.1 to 12.3 days. At the time of leaf senescence, foliar residue levels approximated 0.01 mg kg^?1 f.w., strongly mitigating the potential effects of non‐target biota in soil or aquatic compartments. CONCLUSION: The magnitude and duration of exposures observed in this field study were considered to be above the thresholds required for biological effectiveness against both larval and adult life stages of EAB. Results support the use of azadirachtins as an environmentally acceptable systemic insecticide for control of EAB and protection of high‐value ash trees in urban environments. Copyright © 2011 Society of Chemical Industry     

Polycyclic Aromatic Hydrocarbons in Soils from European High Mountain Areas

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in 70 soils distributed in mountain areas such as Montseny (300?C1,700 m), Pyrenees (1,500?C2,900 m), Alps (1,100?C2,500 m), and Tatras (1,400?C1,960 m). Average total PAH concentrations, excluding retene and perylene, were about 400 ng/g in the Pyrenees and 1,300?C1,600 ng/g in the other mountain ranges. No correlations between PAH concentrations and total organic carbon were observed. Retene was the major PAH in the Pyrenean soils of lower altitude. No altitudinal dependence was found between soil PAH concentrations and elevation for the whole dataset. However, in the Tatra soils a statistically significant correlation with altitude was observed involving higher concentrations at higher altitude. This correlation was due to the statistically significant altitudinal dependence of the more volatile PAHs. Another observed altitudinal trend concerned the benz[a]anthracene/(benz[a]anthracene + chrysene + triphenylene) and the benzo[a]pyrene/(benzo[a]pyrene + benzo[e]pyrene) ratios that exhibited a decrease in the more chemically labile compounds, benz[a]anthracene and benzo[a]pyrene, respectively, in the soils located at higher altitude. This observation is consistent with the expected higher photooxidation at higher mountain altitude.     

Direct determination of paclobutrazol residues in pear samples by liquid chromatography-electrospray tandem mass spectrometry

A rapid and sensitive liquid chromatography/electrospray ionization/tandem mass spectrometry (LC-ESI-MS-MS) method has been developed for the determination of the plant growth regulator paclobutrazol in pear samples. Extraction was performed with methanol by using a high-speed blender Ultra-Turrax, and 10 microL of pear extract was directly injected in the LC-ESI-MS-MS system without any previous sample treatment. The highest sensitivity of the method was achieved under MS-MS conditions obtaining a limit of detection of 0.7 microg/kg and a quantification limit of 5 microg/kg, with a run time of only 5.5 min. Recoveries for paclobutrazol from spiked pear samples at 0.005, 0.05, and 0.5 mg/kg were around 82-102% with relative standard deviations between 2 and 7%. The method was applied to real treated and untreated samples of pears, using quality control samples as a evaluation of the method reliability. Two MS-MS transitions were selected, one for quantification (294 > 70) and the other for confirmation of the analyte (296 > 70). All the experiments were performed in compliance with good laboratory practices.     

M.T. Arts and B.C. Wainman: Lipids in Freshwater Ecosystems

Water, Air, &; Soil Pollution -     

Stephen T. Holgate,Jonathan M. Samet,Hillel S. Koren and Robert L. Maynard (eds.), Air Pollution and Health

Water, Air, &; Soil Pollution -     

Analytical study of trichlorfon residues in Kaki fruit and cauliflower samples by liquid chromatography-electrospray tandem mass spectrometry

A detailed analytical study on trichlorfon residues in selected vegetables samples has been carried out, focused on the reliable quantification and confirmation of this compound, and on stability of residues under storage. As a consequence, a rapid and sensitive LC-ESI-MS/MS method has been developed for the determination of residues of this insecticide in kaki fruit (flesh and peel) and cauliflower samples. Extraction was performed with acetonitrile using a high-speed blender. After 4-fold dilution of the extract with water, 20 microL was directly injected in the LC-ESI-MS/MS system (triple quadrupole), using matrix-matched standards calibration for quantification. Under optimized MS/MS conditions, limit of detections between 0.006 and 0.013 mg/kg were reached, and a limit of quantification of 0.05 mg/kg was established, with a runtime of only 15 min. Recoveries from spiked blank samples at 0.05 and 0.5 mg/kg were in the range 83-101% with relative standard deviations lower than 10%. The method was applied to treated and untreated samples collected from field residues trials, using quality control samples analysis for the evaluation of the method. Despite the acquisition of two MS/MS transitions in selected reaction monitoring mode, the analysis of treated samples revealed the presence of a chromatographic peak close to the analyte that corresponded to a trichlorfon isobaric compound that shared the same MS/MS transitions. This unusual situation in LC-MS/MS-based procedures required the application of an efficient chromatographic separation to avoid this interference. All experiments have been made in compliance with the principles of Good Laboratory Practices (GLP) and following the European SANCO guidelines for pesticides residue analysis (PRA).     

Remote mountain lakes as indicators of diffuse acidic and organic pollution in the Iberian peninsula (AL:PE 2 studies)

In the framework of the AL:PE 2 project, studies on acidification and organic pollution in mountain lakes have been conducted in several ranges in the Iberian peninsula: Pyrenees (Northeastern Spain), Sierra de Gredos (Central Spain), Sierra Nevada (Southern Spain) and Serra da Estrela (Central Portugal). These studies focused on water and sediment chemistry and organisms (benthic diatoms, Zooplankton, aquatic macroinvertebrates, and fish) as indicators of acidification. Organic micropollutants (PAH, PCB, DDE, hexachlorobenzene and others) in lake sediments and fish have been studied as tracers of atmospheric pollution. The Iberian peninsula lakes do not show severe anthropogenic acidification. pH values are in the range of sensitive lakes, but the levels of acidic pollutants are low. The status of the organisms surveyed agreed with this diagnosis. Pyrenean lakes showed the highest fluxes of organic pollutants related to fossil fuel combustion., higher pollutioninduced versus natural acidity ratios, and modeled alkalinity and pH declines.     

Analytical study of azadirachtin and 3-tigloylazadirachtol residues in foliage and phloem of hardwood tree species by liquid chromatography-electrospray mass spectrometry

A rapid and sensitive LC-ESI-MS method has been developed and validated for the quantitation of azadirachtin and 3-tigloylazadirachtol in deciduous tree matrices. The method involves automated extraction and simultaneous cleanup using an accelerated solvent technique with the matrix dispersed in solid phase over a layer of primary-secondary amine silica. The limits of quantification were 0.02 mg/kg for all matrices with the exception of Norway maple foliage (0.05 mg/kg). Validation at three levels (0.02, 0.1, and 1 mg/kg), demonstrated satisfactory recoveries (71-103%) with relative standard deviation <20%. Two in-source fragment ions were used for confirmation at levels above 0.1 mg/kg. Over a period of several months, quality control analyses showed the technique to be robust and effective in tracking the fate of these natural botanical insecticides following systemic injection into various tree species for control of invasive insect pest species such as the emerald ash borer and Asian longhorned beetle.     

Abrupt temperature changes in the Western Mediterranean over the past 250,000 years

A continuous high-resolution Western Mediterranean sea surface temperature (SST) alkenone record spanning the past 250,000 years shows that abrupt changes were more common at warming than at cooling. During marine isotope stage (MIS) 6, SST oscillated following a stadial-interstadial pattern but at lower intensities and rates of change than in the Dansgaard/Oeschger events of MIS 3. Some of the most prominent events occurred over MISs 5 and 7, after prolonged warm periods of high stability. Climate during the whole period was predominantly maintained in interglacial-interstadial conditions, whereas the duration of stadials was much shorter.