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The production of activated carbons (ACs) from rapeseed cake and raspberry seed cake using slow pyrolysis followed by physical activation of the obtained solid residues is the topic of this study. The effect of activation temperature (850, 900 and 950 °C), activation time (30, 60, 90 and 120 min) and agent (steam and CO₂) on the textural characteristics of the ACs is investigated by N₂ adsorption. In general, higher activation temperatures and longer activation times increase the BET specific surface area and the porosity of the ACs, regardless of the activation agent or raw material. Steam is more reactive than CO₂ in terms of pore development, especially in the case of raspberry seed cake. The performance of the ACs in liquid adsorption is evaluated by batch phenol adsorption tests. Experimental data are best fitted by the Freundlich isotherm model. Based on total yield, textural characteristics and phenol adsorption, steam activation at 900 °C for 90 min and CO₂ activation at 900 °C for 120 min are found as the best activation conditions. Raspberry seed cake turns out to be a better raw material than rapeseed cake. Moreover, AC from raspberry seed cake produced by steam activation at 900 °C for 90 min performs as well as commercial AC (Norit GAC 1240) in phenol adsorption. The adsorption kinetics of the selected ACs are best fitted by the pseudo-second-order model.

Ectomycorrhizal fungi are thought to have a key role in mobilizing organic nitrogen that is trapped in soil organic matter (SOM). However, the extent to which ectomycorrhizal fungi decompose SOM and the mechanism by which they do so remain unclear, considering that they have lost many genes encoding lignocellulose-degrading enzymes that are present in their saprotrophic ancestors. Spectroscopic analyses and transcriptome profiling were used to examine the mechanisms by which five species of ectomycorrhizal fungi, representing at least four origins of symbiosis, decompose SOM extracted from forest soils. In the presence of glucose and when acquiring nitrogen, all species converted the organic matter in the SOM extract using oxidative mechanisms. The transcriptome expressed during oxidative decomposition has diverged over evolutionary time. Each species expressed a different set of transcripts encoding proteins associated with oxidation of lignocellulose by saprotrophic fungi. The decomposition 'toolbox' has diverged through differences in the regulation of orthologous genes, the formation of new genes by gene duplications, and the recruitment of genes from diverse but functionally similar enzyme families. The capacity to oxidize SOM appears to be common among ectomycorrhizal fungi. We propose that the ancestral decay mechanisms used primarily to obtain carbon have been adapted in symbiosis to scavenge nutrients instead., (© 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.)

In temperate and boreal forest ecosystems, nitrogen (N) limitation of tree metabolism is alleviated by ectomycorrhizal (ECM) fungi. As forest soils age, the primary source of N in soil switches from inorganic (NH4 (+) and NO3 (-)) to organic (mostly proteins). It has been hypothesized that ECM fungi adapt to the most common N source in their environment, which implies that fungi growing in older forests would have greater protein degradation abilities. Moreover, recent results for a model ECM fungal species suggest that organic N uptake requires a glucose supply. To test the generality of these hypotheses, we screened 55 strains of 13 Suillus species with different ecological preferences for their in vitro protein degradation abilities. Suillus species preferentially occurring in mature forests, where soil contains more organic matter, had significantly higher protease activity than those from young forests with low-organic-matter soils or species indifferent to forest age. Within species, the protease activities of ecotypes from soils with high or low soil organic N content did not differ significantly, suggesting resource partitioning between mineral and organic soil layers. The secreted protease mixtures were strongly dominated by aspartic peptidases. Glucose addition had variable effects on secreted protease activity; in some species, it triggered activity, but in others, activity was repressed at high concentrations. Collectively, our results indicate that protease activity, a key ectomycorrhizal functional trait, is positively related to environmental N source availability but is also influenced by additional factors, such as carbon availability., (Copyright © 2016, American Society for Microbiology. All Rights Reserved.)

TiO2 get positively charged upon UV-irradiation and repel the cationic pollutants away from the surface. Hybridization of AC onto TiO2 (ACT) tends catalyst surface negatively charged besides providing highly favorable adsorptions sites for cationic pollutants. The photodegradation of benzalkonium chloride (BKC), a quaternary ammonium surfactant and a pharmaceutical, is investigated with ACT. The surface charge of the catalyst in surfactant and non-surfactant aqueous dispersion under UV-irradiation is investigated and explained. The anomalous increase in COD values at the beginning of BKC-photodegradation is explained. The intermediate products formed are identified in both solution and solid phase. Trace amount of dodecane remained adsorbed on the catalyst surface after 1h UV-irradiation, but complete mineralization of BKC is achieved with 2h UV-irradiation. We propose that BKC photodegradation starts by central fission of benzyl CN bond followed by dealkylation, and demethylation steps., (Copyright © 2015 Elsevier B.V. All rights reserved.)

We present a hole injection layer processed from solution at room temperature for inverted organic solar cells. Bis(2,4-pentanedionato) molybdenum(VI) dioxide (MoO2(acac)2) is used as the precursor for MoOx. Small amounts of Nafion in the precursor solution allow it to form continuous films with good wetting onto the active layers. The hydrolysis of MoO2(acac)2 and the effects of adding Nafion to the precursor solution are studied by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The devices with solution-processed MoOx including Nafion exhibited comparable performance to the reference devices based on the commonly used hole injection layers such as poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) or evaporated MoO3. Inverted poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester devices with Nafion-modified MoOx maintain 80% of their initial power conversion efficiency upon exposure to ambient air for ∼5000 h, outperforming devices with PEDOT:PSS or with evaporated MoO3.

Short rotation coppice (SRC) of willow and poplar is proposed for economic valorization and concurrently as remediation strategy for metal contaminated land in northeast-Belgium. However, metal phytoextraction appears insufficient to effectuate rapid reduction of soil metal contents. To increase both biomass production and metal accumulation of SRC, two strategies are proposed: (i) in situ selection of the best performing clones and (ii) bioaugmentation of these clones with beneficial plant-associated bacteria. Based on field data, two experimental willow clones, a Salix viminalis and a Salix alba x alba clone, were selected. Compared to the best performing commercial clones, considerable increases in stem metal extraction were achieved (up to 74% for Cd and 91% for Zn). From the selected clones, plant-associated bacteria were isolated and identified. All strains were subsequently screened for their plant growth-promoting and metal uptake enhancing traits. Five strains were selected for a greenhouse inoculation experiment with the selected clones planted in Cd-Zn-Pb contaminated soil. Extraction potential tended to increase after inoculation of S. viminalis plants with a Rahnella sp. strain due to a significantly increased twig biomass. However, although bacterial strains showing beneficial traits in vitro were used for inoculation, increments in extraction potential were not always observed.

To examine the potential of Pseudomonas putida W619-TCE to improve phytoremediation of Ni-TCE co-contamination, the effects of inoculation of a Ni-resistant, TCE-degrading root endophyte on Ni-TCE phytotoxicity, Ni uptake and trichloroethylene (TCE) degradation of Ni-TCE-exposed poplar cuttings are evaluated. After inoculation with P. putida W619-TCE, root weight of non-exposed poplar cuttings significantly increased. Further, inoculation induced a mitigation of the Ni-TCE phytotoxicity, which was illustrated by a diminished exposure-induced increase in activity of antioxidative enzymes. Considering phytoremediation efficiency, inoculation with P. putida W619-TCE resulted in a 45% increased Ni uptake in roots as well as a slightly significant reduction in TCE concentration in leaves and TCE evapotranspiration to the atmosphere. These results indicate that endophytes equipped with the appropriate characteristics can assist their host plant to deal with co-contamination of toxic metals and organic contaminants during phytoremediation. Furthermore, as poplar is an excellent plant for biomass production as well as for phytoremediation, the obtained results can be exploited to produce biomass for energy and industrial feedstock applications in a highly productive manner on contaminated land that is not suited for normal agriculture. Exploiting this land for biomass production could contribute to diminish the conflict between food and bioenergy production.

This study aims to uncover the spatiotemporal involvement of glutathione (GSH) in two major mechanisms of cadmium (Cd)-induced detoxification (i.e. chelation and antioxidative defence). A kinetic study was conducted on hydroponically grown Arabidopsis thaliana (L. Heyhn) to gain insight into the early events after exposure to Cd. Cadmium detoxification was investigated at different levels, including gene transcripts, enzyme activities and metabolite content. Data indicate a time-dependent response both within roots and between plant organs. Early on in roots, GSH was preferentially allocated to phytochelatin (PC) synthesis destined for Cd chelation. This led to decreased GSH levels, without alternative pathways activated to complement GSH's antioxidative functions. After one day however, multiple antioxidative pathways increased including superoxide dismutase (SOD), ascorbate (AsA) and catalase (CAT) to ensure efficient neutralization of Cd-induced reactive oxygen species (ROS). As a consequence of Cd retention and detoxification in roots, a delayed response occurred in leaves. Together with high leaf thiol contents and possibly signalling responses from the roots, the leaves were protected, allowing them sufficient time to activate their defence mechanisms., (Copyright © 2014 Elsevier Masson SAS. All rights reserved.)

Ocular chitosan films were prepared in order to prolong ocular delivery of cyclosporine A. The mucoadhesive films were prepared using the solvent casting evaporation method. A 2(4) full factorial design was used to evaluate the effect of 4 preparation parameters on the film thickness, swelling index and mechanical properties. Moreover, uniformity of content and in vitro drug release were investigated. Possible interactions between the film excipients were studied by FTIR analysis. In vitro experiments were performed in order to evaluate the cytotoxicity and anti-inflammatory activity of the chitosan films. Film thickness, water uptake, mechanical properties and in vitro release of cyclosporine A were dependent on film composition, especially on the amount of plasticizer. Lower drug release was measured from chitosan films containing a higher amount of plasticizer as glycerol decreased the swelling of chitosan films. FTIR spectra suggest a reorganization of hydrogen bonds between chitosan chains in the presence of glycerol and cyclodextrins. None of the film formulations showed significant cytotoxicity as compared to the negative control using human epithelial cells (HaCaT). Cyclosporine A dispersed in the various film formulations remained anti-inflammatorily active as significant suppression of interleukin-2 secretion in concanavalin A stimulated Jurkat T cells was measured., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Brewer's spent grain is a low cost residue generated by the brewing industry. Its chemical composition (high nitrogen content 4.35 wt.%, fibres, etc.) makes it very useful for the production of added value in situ nitrogenised activated carbon. The composition of brewer's spent grain revealed high amounts of cellulose (20.8 wt.%), hemicellulose (48.78 wt.%) and lignin (11.3 wt.%). The fat, ethanol extractives and ash accounted for 8.17 wt.%, 4.7 wt.% and 3.2 wt.%, respectively. Different activated carbons were produced in a lab-scale pyrolysis/activation reactor by applying several heat and steam activation profiles on brewer's spent grain. Activated carbon yields from 16.1 to 23.6 wt.% with high N-contents (> 2 wt.%) were obtained. The efficiency of the prepared activated carbons for phenol adsorption was studied as a function of different parameters: pH, contact time and carbon dosage relative to two commercial activated carbons. The equilibrium isotherms were described by the non-linear Langmuir and Freundlich models, and the kinetic results were fitted using the pseudo-first-order model and the pseudo-second-order model. The feasibility of an activated carbon production facility (onsite and offsite) that processes brewer's spent grain for different input feeds is evaluated based on a techno-economic model for estimating the net present value. Even though the model assumptions start from a rather pessimistic scenario, encouraging results for a profitable production of activated carbon using brewer's spent grain are obtained., (© The Author(s) 2014.)

The presence of explosives in soils and the interaction with drought stress and nutrient limitation are among the environmental factors that severely affect plant growth on military soils. In this study, we seek to isolate and identify the cultivable bacteria of a 2,4-dinitrotoluene (DNT) contaminated soil (DS) and an adjacent grassland soil (GS) of a military training area aiming to isolate new plant growth-promoting (PGP) and 2,4-DNT-degrading strains. Metabolic profiling revealed disturbances in Ecocarbon use in the bare DS; isolation of cultivable strains revealed a lower colony-forming-unit count and a less diverse community associated with DS in comparison with GS. New 2,4-DNT-tolerant strains were identified by selective enrichments, which were further characterized by auxanography for 2,4-DNT use, resistance to drought stress, cold, nutrient starvation and PGP features. By selecting multiple beneficial PGP and abiotic stress-resistant strains, efficient 2,4-DNT-degrading consortia were composed. After inoculation, consortium UHasselt Sofie 3 with seven members belonging to Burkholderia, Variovorax, Bacillus, Pseudomonas and Ralstonia species was capable to successfully enhance root length of Arabidopsis under 2,4-DNT stress. After 9 days, doubling of main root length was observed. Our results indicate that beneficial bacteria inhabiting a disturbed environment have the potential to improve plant growth and alleviate 2,4-DNT stress., (© 2014 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.)

The aim of the study is to increase the bioavailability of itraconazole (ITRA) using nanosized cocrystals prepared via wet milling of ITRA in combination with dicarboxylic acids. Wet milling was used in order to create a nanosuspension of ITRA in combination with dicarboxylic acids. After spray-drying and bead layering, solid state was characterized by MDSC, XRD, Raman and FT-IR. The release profiles and bioavailability of the nanococrystalline suspension, the spray-dried and bead layered formulation were evaluated. A monodisperse nanosuspension (549±51nm) of ITRA was developed using adipic acid and Tween®80. Solid state characterization indicated the formation of nanococrystals by hydrogen bounds between the triazole group of ITRA and the carboxyl group of adipic acid. A bioavailability study was performed in dogs. The faster drug release from the nanocrystal-based formulation was reflected in the in vivo results since Tmax of the formulations was obtained 3h after administration, while Tmax of the reference formulation was observed only 6h after administration. This fast release of ITRA was obtained by a dual concept: manufacturing of nanosized cocrystals of ITRA and adipic acid via wet milling. Formation of stable nanosized cocrystals via this approach seems a good alternative for amorphous systems to increase the solubility and obtain a fast drug release of BCS class II drugs., (Copyright © 2013 Elsevier B.V. All rights reserved.)

In this study, prilling was evaluated as a technique for the development of multiparticulate dosage forms using the fatty acids, stearic acid, and behenic acid as potential matrix formers to control the release of metoprolol tartrate (MPT), a highly water soluble drug. The in vitro drug release was dependent on the drug load, type of fatty acid, and pH of the dissolution medium. Higher drug loads resulted in faster release with behenic acid releasing drug over longer periods relative to stearic acid. The in vitro drug release was pH-dependent at low drug load with the release being slower at lower pH. Due to ionization of the fatty acid at pH 7.4, drug release was susceptible to the ionic strength at this pH value. Solid state characterization indicated that the crystalline state of the fatty acids was not affected by thermal processing via prilling, while the crystallinity of MPT was decreased. During storage, the amorphous MPT fraction recrystallized in the entire matrix. Drug release from behenic acid matrices was increased during storage at 40 °C; however, no polymorphism of behenic acid was detected. The bioavailability of MPT, after oral administration to dogs as prills containing 30% and 40% MPT using behenic acid as matrix former, was not significantly different from a commercial sustained release reference formulation, although the 40% MPT prills showed a burst release., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding., (Copyright © 2013 Elsevier B.V. All rights reserved.)

On Zn-polluted soils, populations of the ectomycorrhizal basidiomycete Suillus bovinus exhibit an elevated Zn tolerance when compared to populations on non-polluted sites. To elucidate the mechanism of Zn tolerance, the time-course of Zn uptake was studied in isolates with contrasting Zn tolerance. Unidirectional fluxes and subcellular compartmentation of Zn were investigated through radiotracer flux analyses. Fluorescence imaging was used to support the subcellular Zn compartmentation. After 2 h of exposure to 200 μM Zn, significantly more Zn was accumulated in Zn-sensitive isolates compared to tolerant isolates, despite similar short-term uptake kinetics and similar extracellular Zn sequestration in cell walls. In Zn-sensitive isolates twice as much Zn accumulated in the cytoplasm and 12 times more Zn in the vacuole. (65)Zn efflux analyses revealed a considerably faster Zn export in the Zn-tolerant isolate. The adaptive Zn tolerance in S. bovinus is therefore achieved by a preferential removal of Zn out of the cytoplasm, back into the apoplast, instead of the usual transfer of Zn into the vacuole. Zn exclusion in the fungal symbiont eventually contributes to a lower Zn influx in host plants.

Slow and fast pyrolysis of sludge and sludge/disposal filter cake (FC) mix are performed to investigate the liquid and solid products for their use as value added products. The obtained slow pyrolysis liquid products separate in an oil, a water rich fraction and a valuable crystalline solid 5,5-dimethyl hydantoin. During fast pyrolysis, mainly an oil fraction is formed. Aliphatic acids and amides present in the water rich fractions can be considered as value added products and could be purified. The oil fractions have properties which make them promising as fuel (25-35 MJ/kg, 14-20 wt% water content, 0.2-0.6 O/C value), but upgrading is necessary. Sludge/FC oils have a lower calorific value, due to evaporation of alcohols present in FC. ICP-AES analyses reveal that almost none of the metals present in sludge or sludge/FC are transferred towards the liquid fractions. The metals are enriched in the solid fractions., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Copper and zinc removal from water (pH = 5.0) using adsorbents produced from slow and fast pyrolysis of industrial sludge and industrial sludge mixed with a disposal filter cake (FC), post treated with HCl, is investigated in comparison with a commercial adsorbent F400. The results show that a pseudo-second order kinetics model is followed. The Langmuir-Freundlich isotherm model is found to fit the data best. The capacity for heavy metal removal of studied adsorbents is generally better than that of commercial F400. The dominant heavy metal removal mechanism is cation exchange. Higher heavy metal removal capacity is associated with fast pyrolysis adsorbents and sludge/FC derived adsorbents, due to enhanced cation exchange. Improvement of Zn(2+) removal via 1 N HCl post-treatment is only effective when exchangeable cations of the adsorbent are substituted with H(+) ions, which boost the cation exchange capacity. Increase of temperature also enhances metal removal capacity. Fast pyrolysis sludge-based adsorbents can be reused after several adsorption-desorption cycles., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The aim was to evaluate near-infrared spectroscopy for the in-line determination of the drug concentration, the polymer-drug solid-state behaviour and molecular interactions during hot-melt extrusion. Kollidon® SR was extruded with varying metoprolol tartrate (MPT) concentrations (20%, 30% and 40%) and monitored using NIR spectroscopy. A PLS model allowed drug concentration determination. The correlation between predicted and real MPT concentrations was good (R(2)=0.97). The predictive performance of the model was evaluated by the root mean square error of prediction, which was 1.54%. Kollidon® SR with 40% MPT was extruded at 105°C and 135°C to evaluate NIR spectroscopy for in-line polymer-drug solid-state characterisation. NIR spectra indicated the presence of amorphous MPT and hydrogen bonds between drug and polymer in the extrudates. More amorphous MPT and interactions could be found in the extrudates produced at 135°C than at 105°C. Raman spectroscopy, DSC and ATR FT-IR were used to confirm the NIR observations. Due to the instability of the formulation, only in-line Raman spectroscopy was an adequate confirmation tool. NIR spectroscopy is a potential PAT-tool for the in-line determination of API concentration and for the polymer-drug solid-state behaviour monitoring during pharmaceutical hot-melt extrusion., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Background: Urinary kidney injury molecule 1 is a recently discovered early biomarker for renal damage that has been proven to be correlated to urinary cadmium in rats. However, so far the association between urinary cadmium and kidney injury molecule 1 in humans after long-term, low-dose cadmium exposure has not been studied., Methods: We collected urine and blood samples from 153 non-smoking men and women aged 60+, living in an area with moderate cadmium pollution from a non-ferrous metal plant for a significant period. Urinary cadmium and urinary kidney injury molecule 1 as well as other renal biomarkers (alpha1-microglobulin, beta2-microglobulin, blood urea nitrogen, urinary proteins and microalbumin) were assessed., Results: Both before (r = 0.20; p = 0.01) and after (partial r = 0.32; p < 0.0001) adjustment for creatinine, age, sex, past smoking, socio-economic status and body mass index, urinary kidney injury molecule 1 correlated with urinary cadmium concentrations. No significant association was found between the other studied renal biomarkers and urinary cadmium., Conclusions: We showed that urinary kidney injury molecule 1 levels are positively correlated with urinary cadmium concentration in an elderly population after long-term, low-dose exposure to cadmium, while other classical markers do not show an association. Therefore, urinary kidney injury molecule 1 might be considered as a biomarker for early-stage metal-induced kidney injury by cadmium.

PCBM or [6,6]-phenyl-C(61)-butyric acid methyl ester is nowadays still one of the most successful electron acceptors for plastic bulk heterojunction (BHJ) photovoltaic devices. In this study, a set of complementary techniques, i.e. solid-state NMR, XRD and DSC, is proposed as a fast and sensitive tool to screen the morphology of PCBM specimens with different preparation histories. Based on proton NMR relaxation decay time values, an interval can be derived that situates the average crystal dimensions and which can further be refined on the basis of XRD patterns and DSC thermograms., (Copyright © 2011 John Wiley & Sons, Ltd.)

The aim was to investigate if engineered endophytes that are capable of degrading organic contaminants, and deal with or ideally improve uptake and translocation of toxic metals, can improve phytoremediation of mixed organic-metal pollution. As a model system, yellow lupine was inoculated with the endophyte Burkholderia cepacia VM1468 possessing (a) the pTOM-Bu61 plasmid, coding for constitutive toluene/TCE degradation, and (b) the chromosomally inserted ncc-nre Ni resistance/sequestration system. As controls, plants were inoculated with B. vietnamiensis BU61 (pTOM-Bu61) and B. cepacia BU72 (containing the ncc-nre Ni resistance/sequestration system). Plants were exposed to mixes of toluene and Ni. Only inoculation with B. cepacia VM1468 resulted in decreased Ni and toluene phytotoxicity, as measured by a protective effect on plant growth and decreased activities of enzymes involved in antioxidative defence (catalase, guaiacol peroxidase, superoxide dismutase) in the roots. Besides, plants inoculated with B. cepacia VM1468 and B. vietnamiensis BU61 released less toluene through the leaves than non-inoculated plants and those inoculated with B. cepacia BU72. Ni-uptake in roots was slightly increased for B. cepacia BU72 inoculated plants. These results indicate that engineered endophytes have the potential to assist their host plant to deal with co-contamination of toxic metals and organic contaminants during phytoremediation.

Phytoremediation, more precisely phytoextraction, has been placed forward as an environmental friendly remediation technique, that can gradually reduce increased soil metal concentrations, in particular the bioavailable fractions. The aim of this study was to investigate the possibilities of growing willows and poplars under short rotation coppice (SRC) on an acid, poor, sandy metal contaminated soil, to combine in this way soil remediation by phytoextraction on one hand, and production of biomass for energy purposes on the other. Above ground biomass productivities were low for poplars to moderate for willows, which was not surprising, taking into account the soil conditions that are not very favorable for growth of these trees. Calculated phytoextraction efficiency was much longer for poplars than these for willows. We calculated that for phytoextraction in this particular case it would take at least 36 years to reach the legal threshold values for cadmium, but in combination with production of feedstock for bioenergy processes, this type of land use can offer an alternative income for local farmers. Based on the data of the first growing cycle, for this particular case, SRC of willows should be recommended.

The disposal problem associated with phytoextraction of farmland polluted with heavy metals by means of willow requires a biomass conversion technique which meets both ecological and economical needs. Combustion and gasification of willow require special and costly flue gas treatment to avoid re-emission of the metals in the atmosphere, whereas flash pyrolysis mainly results in the production of (almost) metal free bio-oil with a relatively high water content. Flash co-pyrolysis of biomass and waste of biopolymers synergistically improves the characteristics of the pyrolysis process: e.g. reduction of the water content of the bio-oil, more bio-oil and less char production and an increase of the HHV of the oil. This research paper investigates the economic consequences of the synergistic effects of flash co-pyrolysis of 1:1 w/w ratio blends of willow and different biopolymer waste streams via cost-benefit analysis and Monte Carlo simulations taking into account uncertainties. In all cases economic opportunities of flash co-pyrolysis of biomass with biopolymer waste are improved compared to flash pyrolysis of pure willow. Of all the biopolymers under investigation, polyhydroxybutyrate (PHB) is the most promising, followed by Eastar, Biopearls, potato starch, polylactic acid (PLA), corn starch and Solanyl in order of decreasing profits. Taking into account uncertainties, flash co-pyrolysis is expected to be cheaper than composting biopolymer waste streams, except for corn starch. If uncertainty increases, composting also becomes more interesting than flash co-pyrolysis for waste of Solanyl. If the investment expenditure is 15% higher in practice than estimated, the preference for flash co-pyrolysis compared to composting biopolymer waste becomes less clear. Only when the system of green current certificates is dismissed, composting clearly is a much cheaper processing technique for disposing of biopolymer waste., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The TCE-degrading poplar endophyte Pseudomonas putida W619-TCE was inoculated in poplar cuttings, exposed to 0, 200 and 400 mg l(-1) TCE, that were grown in two different experimental setups. During a short-term experiment, plants were grown hydroponically in half strength Hoagland nutrient solution and exposed to TCE for 3 days. Inoculation with P. putida W619-TCE promoted plant growth, reduced TCE phytotoxicity and reduced the amount of TCE present in the leaves. During a mid-term experiment, plants were grown in potting soil and exposed to TCE for 3 weeks. Here, inoculation with P. putida W619-TCE had a less pronounced positive effect on plant growth and TCE phytotoxicity, but resulted in strongly reduced amounts of TCE in leaves and roots of plants exposed to 400 mg l(-1) TCE, accompanied by a lowered evapotranspiration of TCE. Dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA), which are known intermediates of TCE degradation, were not detected., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

The aim of this work was to investigate if engineered endophytes can improve phytoremediation of co-contaminations by organic pollutants and toxic metals. As a model system, yellow lupine was inoculated with the endophyte Burkholderia cepacia VM1468 possessing (a) the pTOM-Bu61 plasmid, coding for constitutive trichloroethylene (TCE) degradation, and (b) the ncc-nre Ni resistance/sequestration system. Plants were exposed to Ni and TCE and (a) Ni and TCE phytotoxicity, (b) TCE degradation and evapotranspiration, and (c) Ni concentrations in the roots and shoots were determined. Inoculation with B. cepacia VM1468 resulted in decreased Ni and TCE phytotoxicity, as measured by 30% increased root biomass and up to 50% decreased activities of enzymes involved in anti-oxidative defence in the roots. In addition, TCE evapotranspiration showed a decreasing trend and a 5 times higher Ni uptake was observed after inoculation., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

Phytoremediation of volatile organic contaminants often proves not ideal because plants and their rhizosphere microbes only partially degrade these compounds. Consequently, plants undergo evapotranspiration that contaminates the ambient air and, thus, undermines the merits of phytoremediation. Under laboratory conditions, endophytic bacteria equipped with the appropriate degradation pathways can improve in planta degradation of volatile organic contaminants. However, several obstacles must be overcome before engineered endophytes will be successful in field-scale phytoremediation projects. Here we report the first in situ inoculation of poplar trees, growing on a TCE-contaminated site, with the TCE-degrading strain Pseudomonas putida W619-TCE. In situ bioaugmentation with strain W619-TCE reduced TCE evapotranspiration by 90% under field conditions. This encouraging result was achieved after the establishment and enrichment of P. putida W619-TCE as a poplar root endophyte and by further horizontal gene transfer of TCE metabolic activity to members of the poplar's endogenous endophytic population. Since P. putida W619-TCE was engineered via horizontal gene transfer, its deliberate release is not restricted under European genetically modified organisms (GMO) regulations.

Background, Aim, and Scope: Along transects under a mixed woodland of English Oak (Quercus robur) and Common Ash (Fraxinus excelsior) growing on a trichloroethylene (TCE)-contaminated groundwater plume, sharp decreases in TCE concentrations were observed, while transects outside the planted area did not show this remarkable decrease. This suggested a possibly active role of the trees and their associated bacteria in the remediation process. Therefore, the cultivable bacterial communities associated with both tree species growing on this TCE-contaminated groundwater plume were investigated in order to assess the possibilities and practical aspects of using these common native tree species and their associated bacteria for phytoremediation. In this study, only the cultivable bacteria were characterized because the final aim was to isolate TCE-degrading, heavy metal resistant bacteria that might be used as traceable inocula to enhance bioremediation., Materials and Methods: Cultivable bacteria isolated from bulk soil, rhizosphere, root, stem, and leaf were genotypically characterized by amplified rDNA restriction analysis (ARDRA) of their 16S rRNA gene and identified by 16S rRNA gene sequencing. Bacteria that displayed distinct ARDRA patterns were screened for heavy metal resistance, as well as TCE tolerance and degradation, as preparation for possible future in situ inoculation experiments. Furthermore, in situ evapotranspiration measurements were performed to investigate if the degradation capacity of the associated bacteria is enough to prevent TCE evapotranspiration to the air., Results and Discussion: Between both tree species, the associated populations of cultivable bacteria clearly differed in composition. In English Oak, more species-specific, most likely obligate endophytes were found. The majority of the isolated bacteria showed increased tolerance to TCE, and TCE degradation capacity was observed in some of the strains. However, in situ evapotranspiration measurements revealed that a significant amount of TCE and its metabolites was evaporating through the leaves to the atmosphere., Conclusions and Perspectives: The characterization of the isolates obtained in this study shows that the bacterial community associated with Oak and Ash on a TCE-contaminated site, was strongly enriched with TCE-tolerant strains. However, this was not sufficient to degrade all TCE before it reaches the leaves. A possible strategy to overcome this evapotranspiration to the atmosphere is to enrich the plant-associated TCE-degrading bacteria by in situ inoculation with endophytic strains capable of degrading TCE.

A mucoadhesive combination of a maize starch (Amioca, mainly consisting of amylopectine) and a cross-linked acrylic acid-based polymer (Carbopol 974P) was spray-dried with metoprolol tartrate (used as model molecule) in order to develop a powder suitable for nasal drug delivery via a one-step manufacturing process. The bioavailability of metoprolol tartrate after nasal administration of this powder to rabbits was compared with powders manufactured via other procedures: (a) freeze-drying of a dispersion prepared using the co-spray-dried powder, (b) freeze-drying of a dispersion prepared using a physical mixture of drug and mucoadhesive polymers. After co-processing via spray-drying a low bioavailability (BA 10.8+/-2.3%) was obtained, whereas manufacturing procedures based on freeze-drying yielded a higher BA: 37.9+/-12.8% using the co-processed powder and 73.6+/-24.9% using the physical mixture. The higher bioavailability was due to the deprotonation of poly(acrylic acid) during neutralisation of the dispersion prior to freeze-drying. This induced repulsion of the ionised carboxyl groups and a lower interaction between poly(acrylic acid) and starch, creating a less compact matrix upon hydration of the polymer and allowing an easier escape of metoprolol tartrate from the matrix. This study showed that co-processing of a mucoadhesive Amioca/Carbopol 974P formulation with metoprolol tartrate via co-spray-drying did not provide any added value towards the bioavailability of the drug after nasal administration of the mucoadhesive powder.

A mucoadhesive spray-dried starch/poly(acrylic acid) powder underwent different heat treatments in order to induce cross-linking between the functional groups of starch (Amioca) and poly(acrylic acid) (Carbopol 974P). After heat treatment the water-absorbing capacity, viscosity and elasticity of the mucoadhesive powder increased. NMR analysis in combination with FT-IR indicated that heat treatment induced a low degree of cross-linking between the polymers. Nasal administration of Amioca/Carbopol 974P powders without heat treatment resulted in an absolute bioavailability in rabbits of 8.2+/-3.0% for insulin. Due to the difference in water-absorbing capacity (which opened the tight junctions of the nasal mucosa), elasticity and plasticity (which reduced mucociliairy clearance and prolonged residence time) heat treatment at 120 degrees C improved the bioavailability: 26.4+/-21.9, 36.5+/-11.0 and 19.3+/-17.3% after heat treatment during 30 min, 1 h and 4 h, respectively. Heat treatment at 60 degrees C was less efficient. This study demonstrated that the nasal insulin absorption improved via heat treatment of the Amioca/Carbopol 974P powder (prior to the addition of insulin). The bioavailability-enhancing effect of a 1 h heat treatment at 120 degrees C was confirmed using the same polymer matrix in combination with different drugs (salmon calcitonin, human growth hormone and metoprolol tartrate).

Soil metal pollution can trigger evolutionary adaptation in soil-borne organisms. An in vitro screening test showed cadmium adaptation in populations of Suillus luteus (L.: Fr.) Roussel, an ectomycorrhizal fungus of pine trees. Cadmium stress was subsequently investigated in Scots pine (Pinus sylvestris L.) seedlings inoculated with a Cd-tolerant S. luteus, isolated from a heavy metal contaminated site, and compared to plants inoculated with a Cd-sensitive isolate from a non-polluted area. A dose-response experiment with mycorrhizal pines showed better plant protection by a Cd-adapted fungus: more fungal biomass and a higher nutrient uptake at high Cd exposure. In addition, less Cd was transferred to aboveground plant parts. Because of the key role of the ectomycorrhizal symbiosis for tree fitness, the evolution of Cd tolerance in an ectomycorrhizal partner such as S. luteus can be of major importance for the establishment of pine forests on Cd-contaminated soils.

Thermal extraction-GC-MS (TE-GC-MS) is a relatively new analytical technique which demonstrates a large potential for the analysis of various solid matrices. This technique provides a rapid quantitative and simultaneous determination of a wide range of volatile and semi-volatile organic compounds without laborious sample preparation or any chemical pre-treatment. Its amenability to automation and coupling with on-line detection methods makes TE-GC-MS a promising technique, not only in laboratory analysis, but also for in situ emission monitoring. However, the number of studies dedicated to the application of TE-GC-MS to fly ashes, which are an unavoidable by-product of any thermal industrial process and also the sink of many environmental pollutants, is limited. The ability of TE-GC-MS to analyse a wide range of trace semi-volatile dioxin surrogate compounds in fly ash samples is investigated as an alternative to the well-established solvent extraction-GC-MS analysis (SE-GC-MS). Reproducibility, the effect of TE temperature, time, flow, and the influence of the analysed matrix are studied. Dedicated experiments demonstrate that the conversion (dechlorination and in situ formation) of target analytes and the decomposition of the fly ash matrix can take place at elevated TE temperatures and during prolonged TE times. Moreover, these effects are matrix-specific and vary from sample to sample. After optimizing the TE parameters, two fly ash samples of different origins are analysed and more than 50 individual analytes representing different classes of aromatic compounds are quantified and compared with those available from the SE-GC-MS analysis.

Thermogravimetric analysis (TGA) has been combined with evolved gas analysis (EGA) with the purpose of simulating the thermal behaviour of filter dust samples under inert (desorption) and de novo test oxidising conditions. Emphasis is on studying de novo formation of dioxins, surrogates and precursors arising from filter dust derived from thermal processes, such as municipal solid waste incineration and metallurgy. A new method is tested for sampling and analysing dioxin surrogates and precursors in the TGA effluent, which are collected on sampling tubes; the adsorbed compounds are eventually desorbed and quantified by TD-GC-MS. The major sources of error and losses are considered, including potential sorbent artefacts, possible breakthrough of volatiles through sampling tubes, or eventual losses of semi-volatiles due to their incomplete desorption or re-condensation inside the TG Analyser. The method is optimised and validated for di- to hexa-chlorinated benzenes in a range of 10-1000 ppb with average recovery exceeding 85%. The results are compared with data obtained in similar studies, performed by other research groups. As a result, the method provides the means for simulating de novo synthesis of dioxins in fly-ash and facilitates reliable and easy estimation of de novo activity, comparable with results of other studies, in combination with wide flexibility of testing conditions.

Contaminated soil particles and food are established routes of exposure. We investigated the relations between biomarkers of exposure to cadmium and lead, and the metal loading rates in house dust in the adult residents of an area with a soil cadmium concentration of > or = 3 mg/kg (n=268) and a reference area (n=205). We determined the metal concentrations in house dust allowed to settle for 3 months in Petri dishes placed in the participants' bedrooms. The continuously distributed vegetable index was the first principal component derived from the metal concentrations in six different vegetables. The biomarkers of exposure (blood cadmium 9.2 vs. 6.2 nmol/L; 24-h urinary cadmium 10.5 vs. 7.0 nmol; blood lead 0.31 vs. 0.24 micromol/L), the loading rates of cadmium and lead in house dust (0.29 vs. 0.12 and 7.52 vs. 3.62 ng/cm(2)/92 days), and the vegetable indexes (0.31 vs. -0.44 and 0.13 vs. -0.29 standardized units) were significantly higher in the contaminated area. A two-fold increase in the metal loading rate in house dust was associated with increases (P<0.001) in blood cadmium (+2.3%), 24-h urinary cadmium (+3.0%), and blood lead (+2.0%), independent of the vegetable index and other covariates. The estimated effect sizes on the biomarkers of internal exposure were three times greater for house dust than vegetables. In conclusion, in the adult population, house dust is potentially an important route of exposure to heavy metals in areas with contaminated soils, and should be incorporated in the assessment of health risks.

In order to reduce the health risks associated with historically enriched metal smelting sites in Flanders (Belgium), the capacities of a non-beringite cyclonic ash and commercial Na-silicates to fix metals and create conditions to restore vegetation cover were evaluated and compared to lime and H(3)PO(4). All tested amendments reduced Ca(NO(3))(2)-extractable soil metal concentrations and reduced metal uptake in Agrostis capillaris seedlings. Sodium released by Na-silicates was possibly toxic to bean plants while an isotopic dilution technique revealed that metals were only weakly sorbed by silicates (i.e. reversible sorption). Cyclonic ash appeared more efficient than lime in both reducing oxidative stress in beans and Zn, Cu and Pb uptake in grasses. The metal fixing mechanism for both amendments appeared similar (i.e. irreversible fixation at constant pH), in contrast to H(3)PO(4) where at least part of the immobilised Cd was irreversibly fixed across a range of pH.

Zn pollution has triggered evolution for adaptive Zn tolerance in populations of Suilloid ectomycorrhizal fungi. The objectives of this study were to determine differential physiological responses that are linked to the Zn tolerance trait and to obtain more insight in the general mechanism responsible for the differential growth in Zn-enriched medium. Therefore, we identified intrinsic growth rates and element profiles in Zn-sensitive and Zn-tolerant genotypes. Isolates from Zn-polluted and unpolluted sites were exposed in vitro to increasing Zn(2+) stress. The Zn concentration which inhibits growth by 50% (EC(50)) was determined, and element (Zn, Fe, Mn, Cu, Mg, Ca and P) profiles in the mycelia were analysed. The intraspecific variation in growth rate and nutrient content of the in vitro grown mycelia is great and was not reduced in Zn-tolerant populations. The Zn resistance was not correlated to the intrinsic mycelial growth rate of the isolates or to the concentrations of the elements analysed, except for Zn. At low external Zn, Zn-resistant genotypes had lower Zn concentrations than sensitive isolates. At high external Zn, the differential Zn accumulation pattern between resistant and sensitive isolates became very prominent. Zn-exclusion mechanisms are most likely involved in the naturally selected adaptive Zn resistance. Other mechanisms of Zn detoxification such as sequestration of Zn on cell wall compounds or intracellular chelation and/or compartmentation are probably active but cannot explain the differential Zn sensitivity of the isolates.