Pollen, plant macrofossil and charcoal records for palaeovegetation reconstruction in the Mediterranean-Black Sea Corridor since the Last Glacial Maximum

New reconstructions of changing vegetation patterns in the Mediterranean-Black Sea Corridor since the Last Glacial Maximum are being produced by an improved biomisation scheme that uses both pollen and plant macrofossil data, in conjunction. Changes in fire regimes over the same interval will also be reconstructed using both microscopic and macroscopic charcoal remains. These reconstructions will allow a diagnosis of the interactions between climate, fire and vegetation on millennial timescales, and will also help to clarify the role of coastline and other geomorphic changes, salinity and impacts of human activities in this region. These new data sets are being produced as a result of collaboration between the Palynology Working Group (WG-2) within the IGCP-521 project and the international Palaeovegetation Mapping Project (BIOME 6000). The main objective of this paper is to present the goals of this cooperation, methodology, including limitations and planned improvements, and to show the initial results of some applications.

Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): an overview of the REPARTEE experiment and its conclusions

The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types.

Progress in observing and modelling the urban boundary layer

The urban boundary layer (UBL) is the part of the atmosphere in which most of the planet’s population now lives, and is one of the most complex and least understood microclimates. Given potential climate change impacts and the requirement to develop cities sustainably, the need for sound modelling and observational tools becomes pressing. This review paper considers progress made in studies of the UBL in terms of a conceptual framework spanning microscale to mesoscale determinants of UBL structure and evolution. Considerable progress in observing and modelling the urban surface energy balance has been made. The urban roughness sub-layer is an important region requiring attention as assumptions about atmospheric turbulence break down in this layer and it may dominate coupling of the surface to the UBL due to its considerable depth. The upper 90% of the UBL (mixed and residual layers) remains under-researched but new remote sensing methods and high resolution modelling tools now permit rapid progress. Surface heterogeneity dominates from neighbourhood to regional scales and should be more strongly considered in future studies. Specific research priorities include humidity within the UBL, high-rise urban canopies and the development of long-term, spatially extensive measurement networks coupled strongly to model development.

Inverse modeling of the 14C bomb pulse in stalagmites to constrain the dynamics of soil carbon cycling at selected European cave sites

The decomposition of soil organic matter (SOM) is temperature dependent, but its response to a future warmer climate remains equivocal. Enhanced rates of decomposition of SOM under increased global temperatures might cause higher CO2 emissions to the atmosphere, and could therefore constitute a strong positive feedback. The magnitude of this feedback however remains poorly understood, primarily because of the difficulty in quantifying the temperature sensitivity of stored, recalcitrant carbon that comprises the bulk (>90%) of SOM in most soils. In this study we investigated the effects of climatic conditions on soil carbon dynamics using the attenuation of the 14C ‘bomb’ pulse as recorded in selected modern European speleothems. These new data were combined with published results to further examine soil carbon dynamics, and to explore the sensitivity of labile and recalcitrant organic matter decomposition to different climatic conditions. Temporal changes in 14C activity inferred from each speleothem was modelled using a three pool soil carbon inverse model (applying a Monte Carlo method) to constrain soil carbon turnover rates at each site. Speleothems from sites that are characterised by semi-arid conditions, sparse vegetation, thin soil cover and high mean annual air temperatures (MAATs), exhibit weak attenuation of atmospheric 14C ‘bomb’ peak (a low damping effect, D in the range: 55–77%) and low modelled mean respired carbon ages (MRCA), indicating that decomposition is dominated by young, recently fixed soil carbon. By contrast, humid and high MAAT sites that are characterised by a thick soil cover and dense, well developed vegetation, display the highest damping effect (D = c. 90%), and the highest MRCA values (in the range from 350 ± 126 years to 571 ± 128 years). This suggests that carbon incorporated into these stalagmites originates predominantly from decomposition of old, recalcitrant organic matter. SOM turnover rates cannot be ascribed to a single climate variable, e.g. (MAAT) but instead reflect a complex interplay of climate (e.g. MAAT and moisture budget) and vegetation development.

Prediction of nutrient digestibility and energy concentrations in fresh grass using nutrient composition

Improved nutrient utilization efficiency is strongly related to enhanced economic performance and reduced environmental footprint of dairy farms. Pasture-based systems are widely used for dairy production in certain areas of the world, but prediction equations of fresh grass nutritive value (nutrient digestibility and energy concentrations) are limited. Equations to predict digestible energy (DE) and metabolizable energy (ME) used for grazing cattle have been either developed with cattle fed conserved forage and concentrate diets or sheep fed previously frozen grass, and the majority of them require measurements less commonly available to producers, such as nutrient digestibility. The aim of the present study was therefore to develop prediction equations more suitable to grazing cattle for nutrient digestibility and energy concentrations, which are routinely available at farm level by using grass nutrient contents as predictors. A study with 33 nonpregnant, nonlactating cows fed solely fresh-cut grass at maintenance energy level for 50 wk was carried out over 3 consecutive grazing seasons. Freshly harvested grass of 3 cuts (primary growth and first and second regrowth), 9 fertilizer input levels, and contrasting stage of maturity (3 to 9 wk after harvest) was used, thus ensuring a wide representation of nutritional quality. As a result, a large variation existed in digestibility of dry matter (0.642-0.900) and digestible organic matter in dry matter (0.636-0.851) and in concentrations of DE (11.8-16.7 MJ/kg of dry matter) and ME (9.0-14.1 MJ/kg of dry matter). Nutrient digestibilities and DE and ME concentrations were negatively related to grass neutral detergent fiber (NDF) and acid detergent fiber (ADF) contents but positively related to nitrogen (N), gross energy, and ether extract (EE) contents. For each predicted variable (nutrient digestibilities or energy concentrations), different combinations of predictors (grass chemical composition) were found to be significant and increase the explained variation. For example, relatively higher R(2) values were found for prediction of N digestibility using N and EE as predictors; gross-energy digestibility using EE, NDF, ADF, and ash; NDF, ADF, and organic matter digestibilities using N, water-soluble carbohydrates, EE, and NDF; digestible organic matter in dry matter using water-soluble carbohydrates, EE, NDF, and ADF; DE concentration using gross energy, EE, NDF, ADF, and ash; and ME concentration using N, EE, ADF, and ash. Equations presented may allow a relatively quick and easy prediction of grass quality and, hence, better grazing utilization on commercial and research farms, where nutrient composition falls within the range assessed in the current study.

Designing a sampling scheme to reveal correlations between weeds and soil properties at multiple spatial scales

Weeds tend to aggregate in patches within fields and there is evidence that this is partly owing to variation in soil properties. Because the processes driving soil heterogeneity operate at different scales, the strength of the relationships between soil properties and weed density would also be expected to be scale-dependent. Quantifying these effects of scale on weed patch dynamics is essential to guide the design of discrete sampling protocols for mapping weed distribution. We have developed a general method that uses novel within-field nested sampling and residual maximum likelihood (REML) estimation to explore scale-dependent relationships between weeds and soil properties. We have validated the method using a case study of Alopecurus myosuroides in winter wheat. Using REML, we partitioned the variance and covariance into scale-specific components and estimated the correlations between the weed counts and soil properties at each scale. We used variograms to quantify the spatial structure in the data and to map variables by kriging. Our methodology successfully captured the effect of scale on a number of edaphic drivers of weed patchiness. The overall Pearson correlations between A. myosuroides and soil organic matter and clay content were weak and masked the stronger correlations at >50 m. Knowing how the variance was partitioned across the spatial scales we optimized the sampling design to focus sampling effort at those scales that contributed most to the total variance. The methods have the potential to guide patch spraying of weeds by identifying areas of the field that are vulnerable to weed establishment.

Environmental controls on the distribution and diversity of lentic Chironomidae (Insecta: Diptera) across an altitudinal gradient in tropical South America

To predict the response of aquatic ecosystems to future global climate change, data on the ecology and distribution of keystone groups in freshwater ecosystems are needed. In contrast to mid- and high-latitude zones, such data are scarce across tropical South America (Neotropics). We present the distribution and diversity of chironomid species using surface sediments of 59 lakes from the Andes to the Amazon (0.1–17°S and 64–78°W) within the Neotropics. We assess the spatial variation in community assemblages and identify the key variables influencing the distributional patterns. The relationships between environmental variables (pH, conductivity, depth, and sediment organic content), climatic data, and chironomid assemblages were assessed using multivariate statistics (detrended correspondence analysis and canonical correspondence analysis). Climatic parameters (temperature and precipitation) were most significant in describing the variance in chironomid assemblages. Temperature and precipitation are both predicted to change under future climate change scenarios in the tropical Andes. Our findings suggest taxa of Orthocladiinae, which show a preference to cold high-elevation oligotrophic lakes, will likely see range contraction under future anthropogenic-induced climate change. Taxa abundant in areas of high precipitation, such as Micropsectra and Phaenopsectra, will likely become restricted to the inner tropical Andes, as the outer tropical Andes become drier. The sensitivity of chironomids to climate parameters makes them important bio-indicators of regional climate change in the Neotropics. Furthermore, the distribution of chironomid taxa presented here is a vital first step toward providing urgently needed autecological data for interpreting fossil chironomid records of past ecological and climate change from the tropical Andes.

The impact of European legislative and technology measures to reduce air pollutants on air quality, human health and climate

European air quality legislation has reduced emissions of air pollutants across Europe since the 1970s, affecting air quality, human health and regional climate. We used a coupled composition-climate model to simulate the impacts of European air quality legislation and technology measures implemented between 1970 and 2010. We contrast simulations using two emission scenarios; one with actual emissions in 2010 and the other with emissions that would have occurred in 2010 in the absence of technological improvements and end-of-pipe treatment measures in the energy, industrial and road transport sectors. European emissions of sulphur dioxide, black carbon (BC) and organic carbon in 2010 are 53%, 59% and 32% lower respectively compared to emissions that would have occurred in 2010 in the absence of legislative and technology measures. These emission reductions decreased simulated European annual mean concentrations of fine particulate matter(PM2.5) by 35%, sulphate by 44%, BC by 56% and particulate organic matter by 23%. The reduction in PM2.5 concentrations is calculated to have prevented 80 000 (37 000–116 000, at 95% confidence intervals) premature deaths annually across the European Union, resulting in a perceived financial benefit to society of US$232 billion annually (1.4% of 2010 EU GDP). The reduction in aerosol concentrations due to legislative and technology measures caused a positive change in the aerosol radiative effect at the top of atmosphere, reduced atmospheric absorption and also increased the amount of solar radiation incident at the surface over Europe. We used an energy budget approximation to estimate that these changes in the radiative balance have increased European annual mean surface temperatures and precipitation by 0.45 ± 0.11 °C and by 13 ± 0.8 mm yr−1 respectively. Our results show that the implementation of European legislation and technological improvements to reduce the emission of air pollutants has improved air quality and human health over Europe, as well as having an unintended impact on the regional radiative balance and climate.

Hydralazine reduces leukocyte migration through different mechanisms in spontaneously hypertensive and normotensive rats

In addition to reducing blood pressure, hydralazine can reduce the production of inflammatory cytokines and reduce the expression of leukocyte adhesion molecules. Differences in leukocyte behavior and leukocyte adhesion molecule expression in spontaneously hypertensive rats (SHR) compared to normotensive rats have been reported. However, whether hydralazine can reduce leukocyte migration in vivo in hypertension and in normotension remains unknown. To address this question, male SHR and Wistar rats were treated for 15 days with hydralazine at a dose of similar to 3.5 mg/kg or similar to 14 mg/kg in their drinking water. The numbers of rollers and adherent and migrated cells were determined by direct vital microscopy, and blood pressure was assessed by tail plethysmography. In addition, following treatment with the higher dose, immunohistochemistry was used to measure the expression of intercellular adhesion molecule-1 (ICAM-1), P-selectin, and platelet-endothelial cell adhesion molecule-1 (PECAM-1) in endothelial cells, while flow cytometry was used to evaluate the expression of leukocyte CD18 and L-selectin. Hydralazine reduced leukocyte adherence and migration in SHR either at the higher, that reduced blood pressure levels, or lower dose, which did not reduce it. Reduced ICAM-1 expression might be involved in the reduced migration observed in SHR. In Wistar rats, only at the higher dose hydralazine reduced blood pressure levels and leukocyte migration. Reduced P-selectin expression might be involved. We therefore conclude that hydralazine reduces leukocyte migration by different mechanisms in SHR and Wistar rats, specifically by reducing ICAM-1 expression in the former and P-selectin expression in the latter. (c) 2008 Elsevier B.V. All rights reserved.

Aerosol properties, in-canopy gradients, turbulent fluxes and VOC concentrations at a pristine forest site in Amazonia

Aerosol physical and chemical properties were measured in a forest site in central Amazonia (Cuieiras reservation, 2.61S; 60.21W) during the dry season of 2004 (Aug-Oct). Aerosol light scattering and absorption, mass concentration, elemental composition and size distributions were measured at three tower levels (Ground: 2 m; Canopy: 28 m, and Top: 40 m). For the first time, simultaneous eddy covariance fluxes of fine mode particles and volatile organic compounds (VOC) were measured above the Amazonian forest canopy. Aerosol fluxes were measured by eddy covariance using a Condensation Particle Counter (CPC) and a sonic anemometer. VOC fluxes were measured by disjunct eddy covariance using a Proton Transfer Reaction Mass Spectrometer (PTR-MS). At nighttime, a strong vertical gradient of phosphorus and potassium in the aerosol coarse mode was observed, with higher concentrations at Ground level. This suggests a source of primary biogenic particles below the canopy. Equivalent black carbon measurements indicate the presence of light-absorbing aerosols from biogenic origin. Aerosol number size distributions typically consisted of superimposed Aitken (76 nm) and accumulation modes (144 nm), without clear events of new particle formation. Isoprene and monoterpene fluxes reached respectively 7.4 and 0.82 mg m(-2) s(-1) around noon. An average fine particle flux of 0.05 +/- 0.10 10(6) m(-2) s(-1) was calculated, denoting an equilibrium between emission and deposition fluxes of fine mode particles at daytime. No significant correlations were found between VOC and fine mode aerosol concentrations or fluxes. (C) 2009 Elsevier Ltd. All rights reserved.

Square wave adsorptive cathodic stripping voltarnmetry automated by sequential injection analysis - Potentialities and limitations exemplified by the determination of methyl parathion in water samples

This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L-1 Britton-Robinson buffer (pH 10) in 0.25 mol L-1 NaNO3. The homogenized mixture is injected at a flow rate of 10 mu Ls(-1) toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from -0.3 to -1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mgL(-1), with detection and quantification limits of 2 and 7 mu gL(-1), respectively. The sampling throughput is 25 h(-1) if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h(-1) if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered. (C) 2007 Elsevier B.V. All rights reserved.

Electrocombustion of humic acid and removal of algae from aqueous solutions

This paper reports experiments involving the electrochemical combustion of humic acid (HA) and removal of algae from pond water. An electrochemical flow reactor with a boron-doped diamond film anode was used and constant current experiments were conducted in batch recirculation mode. The mass transfer characteristics of the electrochemical device were determined by voltammetric experiments in the potential region of water stability, followed by a controlled current experiment in the potential region of oxygen evolution. The average mass transfer coefficient was 5.2 x 10(-5) m s(-1). The pond water was then processed to remove HA and algae in the conditions in which the reaction combustion occurred under mass transfer control. To this end, the mass transfer coefficient was used to estimate the initial limiting current density applied in the electrolytic experiments. As expected, all the parameters analyzed here-solution absorbance at 270 nm, total phenol concentration and total organic carbon concentration-decayed according to first-order kinetics. Since the diamond film anode successfully incinerated organic matter, the electrochemical system proved to be predictable and programmable.

Local Structure and Photochromic Response in Ormosils Containing Dodecatungstophosphoric Acid

Two hybrid materials based on dodecatungstophosphoric acid (HPW) dispersed in ormosils modified with 3-aminopropiltrietoxysilane (APTS) or with N-(3-(trimethoxysilyl)-propyl)-ethylene-diamine (TSPEN) show reversible photochromic response induced by irradiation in the 200-390 nm UV range. A set of solid-state nuclear magnetic resonance (NMR) techniques was used to analyze the structural properties of the main components of these hybrids (the HPW polyanion, the inorganic matrix, and the organic functionalities). For the ormosils, the use of (29)Si NMR, {(1)H}-(29)Si cross-polarization, and {(1)H}-(29)Si HETCOR revealed a homogeneous distribution of silicon species Q ``, T(2), and T(3) for the APTS hybrid, contrasting with the separation of T(3) species in the TSPEN hybrid. The combination of (31)P NMR, {(1)H}-(31)P cross-polarization and (31)P-{(1)H} spin-echo double resonance (SEDOR) revealed the dispersion of the HPW ions in the ormosil, occupying sites with a high number of close protons (>50). Differences in the molecular dynamics at room temperature, inferred from SEDOR experiments, indicate a state of restricted mobility of the HPW ion and the surrounding molecular groups in the TSPEN hybrid. This behavior is consistent with the presence of more amino groups in the TSPEN, acting as chelating groups to the HPW ion. This hybrid, with the strong chelate interaction of the diamine group, shows the most intense photochromic response, in agreement with the charge transfer models proposed to explain the photochromic effect. Electronic reflectance spectroscopy in irradiated samples revealed the presence of one-electron and two-electron reduced polyanions. The one-electron reduced species could be detected also by (31)P NMR spectroscopy immediately after UV irradiation.

Synthesis, spectroscopic characterization and X-ray structures of five-coordinate diorganotin(IV) complexes containing 5-hydroxypyrazoline derivatives as ligands

Four new diorganotin(IV) complexes have been prepared from R(2)SnCl(2) (R = Me, Ph) with the ligands 5-hydroxy-3-metyl-5-phenyl-1-(S-benzildithiocarbazate)-pyrazoline (H(2)L(1)) and 5-hydroxy-3-methyl-5-phenyl-1-(2-thiophenecarboxylic)-pyrazoline (H(2)L(2)). The complexes were characterized by elemental analysis, IR. (1)H (13)C, (119)Sn NMR and Mossbauer spectroscopes The complexes [Me(2)SnL(1)], [Ph(2)SnL(1)] and [Me(2)SnL(2)] were also studied by single crystal X-ray diffraction and the results showed that the Sn(IV) central atom of the complexes adopts a distorted trigonal bipyramidal (TBP) geometry with the N atom of the ONX-tridentate (X = O and S) ligand and two organic groups occupying equatorial sites. The C-Sn-C angles for [Me(2)Sn(L(1))] and [Ph(2)Sn(L(1))] were calculated using a correlation between (119)Sn Mossbauer and X-ray crystallographic data based on the point-charge model Theoretical calculations were performed with the B3LYP density functional employing 3-21G(*) and DZVP all electron basis sets showing good agreement with experimental findings General and Sn(IV) specific IR harmonic frequency scale factors for both basis sets were obtained from comparison with selected experimental frequencies (C) 2010 Elsevier B V All rights reserved

Coumarins and phenolic fingerprints of oak and Brazilian woods extracted by sugarcane spirit

A total of 25 sugarcane spirit extracts of six different Brazilian woods and oak, commonly used by cooperage industries for aging cachaca, were analyzed for the presence of 14 phenolic compounds (ellagic acid, gallic acid, vanillin, syringaldehyde, synapaldehyde, coniferaldehyde, vanillic acid, syringic acid, quercetin, trans-resveratrol, catechin, epicatechin, eugenol, and myricetin) and two coumarins (scopoletin and coumarin) by HPLC-DAD-fluorescence and HPLC-ESI-MS(n). Furthermore, an HPLC-DAD chromatographic fingerprint was build-up using chemometric analysis based on the chromatographic elution profiles of the extracts monitored at 280 nm. Major components identified and quantified in Brazilian wood extracts were coumarin, ellagic acid, and catechin, whereas oak extracts shown a major contribution of catechin, vanillic acid, and syringaldehyde. The main difference observed among oak and Brazilian woods remains in the concentration of coumarin, catechin, syringaldehyde, and coniferaldehyde. The chemometric analysis of the quantitative profile of the 14 phenolic compounds and two coumarins in the wood extracts provides a differentiation between the Brazilian wood and oak extracts. The chromatographic fingerprint treated by multivariate analysis revealed significant differences among Brazilian woods themselves and oak, clearly defining six groups of wood extracts: (i) oak extracts, (ii) jatoba extracts, (iii) cabreuva-parda extracts, (iv) amendoim extracts, (v) canela-sassafras extracts and (vi) pequi extracts.