Core-Shell Fe/FeS Nanoparticles with Controlled Shell Thickness for Enhanced Trichloroethylene Removal.

Zero-valent iron nanoparticles (nZVI) treated by reduced sulfur compounds (i.e., sulfidated nZVI, S-nZVI) have attracted increased attention as promising materials for environmental remediation. While the preparation of S-nZVI and its reactions with various groundwater contaminants such as trichloroethylene (TCE) were already a subject of several studies, nanoparticle synthesis procedures investigated so far were suited mainly for laboratory-scale preparation with only a limited possibility of easy and cost-effective large-scale production and FeS shell property control. This study presents a novel approach for synthesizing S-nZVI using commercially available nZVI particles that are treated with sodium sulfide in a concentrated slurry. This leads to S-nZVI particles that do not contain hazardous boron residues and can be easily prepared off-site. The resulting S-nZVI exhibits a core-shell structure where zero-valent iron is the dominant phase in the core, while the shell contains mostly amorphous iron sulfides. The average FeS shell thickness can be controlled by the applied sulfide concentration. Up to a 12-fold increase in the TCE removal and a 7-fold increase in the electron efficiency were observed upon amending nZVI with sulfide. Although the FeS shell thickness correlated with surface-area-normalized TCE removal rates, sulfidation negatively impacted the particle surface area, resulting in an optimal FeS shell thickness of approximately 7.3 nm. This corresponded to a particle S/Fe mass ratio of 0.0195. At all sulfide doses, the TCE degradation products were only fully dechlorinated hydrocarbons. Moreover, a nearly 100% chlorine balance was found at the end of the experiments, further confirming complete TCE degradation and the absence of chlorinated transformation products. The newly synthesized S-nZVI particles thus represent a promising remedial agent applicable at sites contaminated with TCE.

Inhibition and stimulation of two perchloroethene degrading bacterial cultures by nano- and micro-scaled zero-valent iron particles.

The pollutant perchloroethene (PCE) can often be found at urban contaminated sites. Thus in-situ clean-up methods, like remediation using zero valent iron (ZVI) or bacterial dechlorination, are preferred. During the remediation with ZVI particles anaerobic corrosion occurs as an unwanted, particle consuming side reaction with water. However, in this reaction H2 is formed, which is usually scarce during anaerobic microbial dechlorination. Dehalococcoides needs H2 for cell growth using it as an electron donor to dechlorinate chlorinated hydrocarbons. Combining application of ZVI with bacterial dechlorination can turn ZVI in a H2 donor leading to a more controllable bacterial dechlorination, a smaller amount of ZVI suspension and decreased remediation costs. In this study nano- and micro scaled ZVI particles (nZVI, mZVI) were combined in microcosms with two dechlorinating bacterial cultures. The two cultures showed different dechlorination behaviors with ethene and cis-DCE as final products. Phospholipid fatty acids (PLFA) associated with Dehalococcoides (18:1w7, 18:1w7c, 10:Me16:0) and Geobacteriaceae (16,1w7c; 15:0; 16:0) have been found in both bacterial cultures, slight differences in their abundance could explain the different dechlorinating behaviors. The combination of both bacterial cultures with mZVI led to a stimulated dechlorination process leading to about two times higher kobs for PCE dechlorination (0.01-0.05 h-1). In the otherwise cis-DCE accumulating culture complete dechlorination to ethene was achieved. While addition of nZVI inhibited both cultures. Combined with nZVI the completely dechlorinating culture produced lower amounts of dechlorinated products (3.2 µmol) as compared to the single biotic treatment (5.1 µmol). Combining the incompletely dechlorinating culture with nZVI significantly reduced the kobs,PCE (single: 8 × 10-3 ± 3 × 10-4 h-1; combination: 5 × 10-3 ± 2 × 10-4 h-1). H2 produced by nZVI and mZVI was utilized by both bacterial cultures. The particle size, resulting specific surface areas, agglomeration tendencies and reactivity appears to be crucial for the effect on microbial cells.

Differentiation between physical and chemical effects of oil presence in freshly spiked soil during rhizoremediation trial.

Petroleum contamination and its remediation via plant-based solutions have got increasing attention by environmental scientists and engineers. In the current study, the physiological and growth responses of two diesel-tolerant plant species (tolerance limit: 1500-2000 mg/kg), Italian ryegrass (Lolium multiflorum) and Birdsfoot trefoil (Lotus corniculatus), have been investigated in vegetable oil- and diesel oil-amended soils. A long-term (147-day) greenhouse pot experiment was conducted to differentiate the main focus of the study: physical and chemical effects of oil (vegetable and diesel) in freshly spiked soils via evaluating the plant performance and hydrocarbon degradation. Moreover, plant performance was evaluated in terms of seed germination, plant shoot biomass, physiological parameters, and root biomass. Addition of both diesel oil and vegetable oil in freshly spiked soils showed deleterious effects on seedling emergence, root/shoot biomass, and chlorophyll content of grass and legume plants. Italian ryegrass showed more sensitivity in terms of germination rate to both vegetable and diesel oil as compared to non-contaminated soils while Birdsfoot trefoil reduced the germination rate only in diesel oil-impacted soils. The results of the current study suggest that both physical and chemical effects of oil pose negative effects of plant growth and root development. This observation may explain the phenomenon of reduced plant growth in aged/weathered contaminated soils during rhizoremediation experiments.

Microbe and plant assisted-remediation of organic xenobiotics and its enhancement by genetically modified organisms and recombinant technology: A review.

Environmental problems such as the deterioration of groundwater quality, soil degradation and various threats to human, animal and ecosystem health are closely related to the presence of high concentrations of organic xenobiotics in the environment. Employing appropriate technologies to remediate contaminated soils is crucial due to the site-specificity of most remediation methods. The limitations of conventional remediation technologies include poor environmental compatibility, high cost of implementation and poor public acceptability. This raises the call to employ biological methods for remediation. Bioremediation and microbe-assisted bioremediation (phytoremediation) offer many ecological and cost-associated benefits. The overall efficiency and performance of bio- and phytoremediation approaches can be enhanced by genetically modified microbes and plants. Moreover, phytoremediation can also be stimulated by suitable plant-microbe partnerships, i.e. plant-endophytic or plant-rhizospheric associations. Synergistic interactions between recombinant bacteria and genetically modified plants can further enhance the restoration of environments impacted by organic pollutants. Nevertheless, releasing genetically modified microbes and plants into the environment does pose potential risks. These can be minimized by adopting environmental biotechnological techniques and guidelines provided by environmental protection agencies and other regulatory frameworks. The current contribution provides a comprehensive overview on enhanced bioremediation and phytoremediation approaches using transgenic plants and microbes. It also sheds light on the mitigation of associated environmental risks.

Impact of sorption processes on PCE concentrations in organohalide-respiring aquifer sediment samples.

The evaluation of groundwater contaminant e.g. tetrachloroethene (PCE) degradation processes requires complete quantification of and pathway analysis of the groundwater contaminant under investigation. For example the reduction of PCE concentrations in the groundwater by unknown dissolution and/or sorption processes will impede interpretation of the fate and behaviour of such contaminants. In the present study PCE dissolution and sorption processes during anaerobic microbial degradation of chlorinated ethenes were investigated. For this purpose, microcosms were prepared using sediment samples from a PCE-contaminated aquifer, which in previous studies had demonstrated anaerobic organohalide respiration of PCE. Solid/water distribution coefficients (kd) of PCE were determined and validated by loss-on-ignition (LOI) and PCE sorption experiments. The determined kd magnitudes indicated methodological congruency, yielding values for sediment samples within a range of 1.15±0.02 to 5.93±0.34L·kg-1. The microcosm experiment showed lower PCE concentrations than expected, based on spiked PCE and observed anaerobic microbial degradation processes. Nevertheless the amount of PCE spike added was completely recovered albeit in the form of lower chlorinated metabolites. A delay due to dissolution processes was not responsible for this phenomenon. Sorption to sediments could only partially explain the reduction of PCE in the water phase. Accordingly, the results point to reversible sorption processes of PCE, possibly onto bacterial cell compartments and/or exopolymeric substances.

Isotopic effects of PCE induced by organohalide-respiring bacteria.

Reductive dechlorination performed by organohalide-respiring bacteria (OHRB) enables the complete detoxification of certain emerging groundwater pollutants such as perchloroethene (PCE). Environmental samples from a contaminated site incubated in a lab-scale microcosm (MC) study enable documentation of such reductive dechlorination processes. As compound-specific isotope analysis is used to monitor PCE degradation processes, nucleic acid analysis-like 16S-rDNA analysis-can be used to determine the key OHRB that are present. This study applied both methods to laboratory MCs prepared from environmental samples to investigate OHRB-specific isotope enrichment at PCE dechlorination. This method linkage can enhance the understanding of isotope enrichment patterns of distinct OHRB, which further contribute to more accurate evaluation, characterisation and prospection of natural attenuation processes. Results identified three known OHRB genera (Dehalogenimonas, Desulfuromonas, Geobacter) in diverse abundance within MCs. One species of Dehalogenimonas was potentially involved in complete reductive dechlorination of PCE to ethene. Furthermore, the isotopic effects of PCE degradation were clustered and two isotope enrichment factors (ε) (- 11.6‰, - 1.7‰) were obtained. Notably, ε values were independent of degradation rates and kinetics, but did reflect the genera of the dechlorinating OHRB.

Determination of carbon isotope enrichment factors of cis-dichloroethene after precursor amendment.

RATIONALE: Bacterial reductive dechlorination of the groundwater contaminant tetrachloroethene (PCE) involves the formation of lower chlorinated metabolites. Metabolites can be instantaneously formed and consumed in this sequential process; quantification and validation of their isotopic effects conventionally rely on separate laboratory microcosm studies. Here, we present an evaluation method enabling the determination of the carbon isotope enrichment factor (ε) for the intermediate cis-dichloroethene (cis-DCE) by a single laboratory microcosm study initially amending the precursor PCE only. METHODS: Environmental samples harboring organohalide-respiring bacteria were incubated under anaerobic conditions and then successively and repeatedly amended with PCE and cis-DCE in two separate laboratory microcosm studies. Reductive dechlorination was monitored by analyzing liquid samples using Purge-and-Trap gas chromatography isotope ratio mass spectrometry GC/MS-C/IRMS. The prerequisites of the presented evaluation method are mass and δ-value balancing. The evaluation method was validated by agglomerative hierarchical classification of Rayleigh plot data points. RESULTS: The sample-sensitive range of εcis-DCE extended from -10.6 ± 0.2‰ to -26.8 ± 0.6‰ (R2 ≥98%). The maximum standard deviations of εcis-DCE were ±1.8‰ for single microcosms, ±1.8‰ for replicates and ±1.0‰ for the compiled replicate data of PCE and cis-DCE amendments. A linear regression of the εcis-DCE for replicates obtained by each amendment study showed a slope of 95% (5 of the 7 data points are within a 95% confidence interval), demonstrating factor congruency and the practicability of the evaluation method. CONCLUSIONS: We found metabolite degradation and formation to be sequential but also stepwise during bacterial reductive dechlorination. The stepwise phases of the degradation of the intermediate eliminate the impact of instantaneous precursor degradation. These stepwise sections were used to determine εcis-DCE -values. Our results showed the validity of εcis-DCE -values over a wide range at initial precursor degradation (PCE). The presented evaluation method could substantially decrease lab costs for microcosm studies designed for εcis-DCE determinations. Moreover, the results indicated that the evaluation method can be applied to other PCE-metabolites.

The relative abundance and seasonal distribution correspond with the sources of polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of Chenab River, Pakistan.

Chenab River is one of the most important rivers of Punjab Province (Pakistan) that receives huge input of industrial effluents and municipal sewage from major cities in the Central Punjab, Pakistan. The current study was designed to evaluate the concentration levels and associated ecological risks of USEPA priority polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of Chenab River. Sampling was performed from eight (n = 24) sampling stations of Chenab River and its tributaries. We observed a relatively high abundance of ∑16PAHs during the summer season (i.e. 554 ng g(-1)) versus that in the winter season (i.e. 361 ng g(-1)), with an overall abundance of two-, five- and six-ring PAH congeners. Results also revealed that the nitrate and phosphate contents in the sediments were closely associated with low molecular weight (LMW) and high molecular weight (HMW) PAHs, respectively. Source apportionment results showed that the combustion of fossil fuels appears to be the key source of PAHs in the study area. The risk quotient (RQ) values indicated that seven PAH congeners (i.e. phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)pyrene, chrysene and benzo(a)anthracene) could pose serious threats to the aquatic life of the riverine ecosystem in Pakistan.

Transpiration and metabolisation of TCE by willow plants - a pot experiment.

Willows were grown in glass cylinders filled with compost above water-saturated quartz sand, to trace the fate of TCE in water and plant biomass. The experiment was repeated once with the same plants in two consecutive years. TCE was added in nominal concentrations of 0, 144, 288, and 721 mg l(-1). Unplanted cylinders were set-up and spiked with nominal concentrations of 721 mg l(-1) TCE in the second year. Additionally, (13)C-enriched TCE solution (δ(13)C = 110.3 ‰) was used. Periodically, TCE content and metabolites were analyzed in water and plant biomass. The presence of TCE-degrading microorganisms was monitored via the measurement of the isotopic ratio of carbon ((13)C/(12)C) in TCE, and the abundance of (13)C-labeled microbial PLFAs (phospholipid fatty acids). More than 98% of TCE was lost via evapotranspiration from the planted pots within one month after adding TCE. Transpiration accounted to 94 to 78% of the total evapotranspiration loss. Almost 1% of TCE was metabolized in the shoots, whereby trichloroacetic acid (TCAA) and dichloroacetic acid (DCAA) were dominant metabolites; less trichloroethanol (TCOH) and TCE accumulated in plant tissues. Microbial degradation was ruled out by δ(13)C measurements of water and PLFAs. TCE had no detected influence on plant stress status as determined by chlorophyll-fluorescence and gas exchange.

Electron efficiency of nZVI does not change with variation of environmental parameters.

Nanoscale zero-valent iron particles (nZVI) are already applied for in-situ dechlorination of halogenated organic contaminants in the field. We performed batch experiments whereby trichloroethene (TCE) was dehalogenated by nZVI under different environmental conditions that are relevant in practice. The tested conditions include different ionic strengths, addition of polyelectrolytes (carboxymethylcellulose and ligninsulphonate), lowered temperature, dissolved oxygen and different particle contents. Particle properties were determined by Mössbauer spectroscopy, XRD, TEM, SEM, AAS and laser obscuration time measurements. TCE dehalogenation and H2 evolution were decelerated by reduced ionic strength, addition of polyelectrolytes, temperature reduction, the presence of dissolved oxygen and reduced particle content. The partitioning of released electrons between reactions with the contaminant vs. with water (selectivity) was low, independent of the tested conditions. Basically out of hundred electrons that were released via nZVI oxidation only 3.1±1.4 were used for TCE dehalogenation. Even lower selectivities were observed at TCE concentrations below 3.5 mg l(-1), hence particle modifications and/or combination of nZVI with other remediation technologies seem to be necessary to reach target concentrations for remediation. Our results suggest that selectivity is particle intrinsic and not as much condition dependent, hence particle synthesis and potential particle modifications of nZVI particles may be more important for optimization of the pollutant degradation rate, than tested environmental conditions.

Effects of rapeseed oil on the rhizodegradation of polyaromatic hydrocarbons in contaminated soil.

Plants have the ability to promote degradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil by supporting PAH degrading microorganisms in the rhizosphere (rhizodegradation). The aim of this study was to evaluate if rapeseed oil increases rhizodegradation because various studies have shown that vegetable oils are able to act as extractants for PAHs in contaminated soils and therefore might increase bioavailability of PAHs for microbial degradation. In this study different leguminous and grass species were tested. The results suggested a significant impact of vegetable oil (1 and 3% w/w) on plant growth (decrease of plant height and biomass). The results of the pot experiment showed a decrease in the PAH content of the soil without amendment of rapeseed oil after six months. In soil amended with 1% and 3% of oil, there was no decrease in PAH content within this period. Although no enhancement of PAH degradation by plants could be measured in the bulk soil of the pot experiments, a rhizobox experiment showed a significant reduction of PAH content in the rhizosphere of alfalfa (Medicago sativa cv. Europe). Our investigations also showed significant differences in the degradation behaviour of the 16 individually analysed PAHs.

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste.

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ(13)C, δ(2)H and δ(18)O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration. We found significant differences in the δ(13)C-value of the dissolved inorganic carbon (δ(13)C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ(13)C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ(13)C-DIC of -20‰ to -25‰. The production of methane under anaerobic conditions caused an increase in δ(13)C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ(13)C-DIC of about -20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation-reduction status of MSW landfills. Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.

Design of top covers supporting aerobic in situ stabilization of old landfills--an experimental simulation in lysimeters.

Landfill aeration by means of low pressure air injection is a promising tool to reduce long term emissions from organic waste fractions through accelerated biological stabilization. Top covers that enhance methane oxidation could provide a simple and economic way to mitigate residual greenhouse gas emissions from in situ aerated landfills, and may replace off-gas extraction and treatment, particularly at smaller and older sites. In this respect the installation of a landfill cover system adjusted to the forced-aerated landfill body is of great significance. Investigations into large scale lysimeters (2 × 2 × 3m) under field conditions have been carried out using different top covers including compost materials and natural soils as a surrogate to gas extraction during active low pressure aeration. In the present study, the emission behaviour as well as the water balance performance of the lysimeters has been investigated, both prior to and during the first months of in situ aeration. Results reveal that mature sewage sludge compost (SSC) placed in one lysimeter exhibits in principle optimal ambient conditions for methanotrophic bacteria to enhance methane oxidation. Under laboratory conditions the mature compost mitigated CH(4) loadings up to 300 lCH(4)/m(2)d. In addition, the compost material provided high air permeability even at 100% water holding capacity (WHC). In contrast, the more cohesive, mineral soil cover was expected to cause a notably uniform distribution of the injected air within the waste layer. Laboratory results also revealed sufficient air permeability of the soil materials (TS-F and SS-Z) placed in lysimeter C. However, at higher compaction density SS-Z became impermeable at 100% WHC. Methane emissions from the reference lysimeter with the smaller substrate cover (12-52 g CH(4)/m(2)d) were significantly higher than fluxes from the other lysimeters (0-19 g CH(4)/m(2)d) during in situ aeration. Regarding water balance, lysimeters covered with compost and compost-sand mixture, showed the lowest leachate rate (18-26% of the precipitation) due to the high water holding capacity and more favourable plant growth conditions compared to the lysimeters with mineral, more cohesive, soil covers (27-45% of the precipitation). On the basis of these results, the authors suggest a layered top cover system using both compost material as well as mineral soil in order to support active low-pressure aeration. Conventional soil materials with lower permeability may be used on top of the landfill body for a more uniform aeration of the waste due to an increased resistance to vertical gas flow. A compost cover may be built on top of the soil cover underlain by a gas distribution layer to improve methane oxidation rates and minimise water infiltration. By planting vegetation with a high transpiration rate, the leachate amount emanating from the landfill could be further minimised. The suggested design may be particularly suitable in combination with intermittent in situ aeration, in the later stage of an aeration measure, or at very small sites and shallow deposits. The top cover system could further regulate water infiltration into the landfill and mitigate residual CH(4) emissions, even beyond the time of active aeration.

The inoculation method affects colonization and performance of bacterial inoculant strains in the phytoremediation of soil contaminated with diesel oil.

Plants in combination with microorganisms can remediate soils, which are contaminated with organic pollutants such as petroleum hydrocarbons. Inoculation of plants with degrading bacteria is one approach to improve remediation processes, but is often not successful due to the competition with resident microorganisms. It is therefore of high importance to address the persistence and colonization behavior of inoculant strains. The objective of this study was to determine whether the inoculation method (seed imbibement and soil inoculation) influences bacterial colonization, plant growth promotion and hydrocarbon degradation. Italian ryegrass was grown in non-sterilized soil polluted with diesel and inoculated with different alkane-degrading strains Pantoea sp. ITSI10, Pantoea sp. BTRH79 and Pseudomonas sp. MixRI75 individually as well as in combination. Inoculation generally had a beneficial effect on plant biomass production and hydrocarbon degradation, however, strains inoculated in soil performed better than applied by seed imbibement. Performance correlated with the colonization efficiency of the inoculated strains. The highest hydrocarbon degradation was observed in the treatment, in which all three strains were inoculated in combination into soil. Our study revealed that besides the degradation potential and competitive ability of inoculant strains the inoculation method plays an important role in determining the success of microbial inoculation.

Hydrocarbon degradation, plant colonization and gene expression of alkane degradation genes by endophytic Enterobacter ludwigii strains.

The genus Enterobacter comprises a range of beneficial plant-associated bacteria showing plant growth promotion. Enterobacter ludwigii belongs to the Enterobacter cloacae complex and has been reported to include human pathogens but also plant-associated strains with plant beneficial capacities. To assess the role of Enterobacter endophytes in hydrocarbon degradation, plant colonization, abundance and expression of CYP153 genes in different plant compartments, three plant species (Italian ryegrass, birdsfoot trefoil and alfalfa) were grown in sterile soil spiked with 1% diesel and inoculated with three endophytic E. ludwigii strains. Results showed that all strains were capable of hydrocarbon degradation and efficiently colonized the rhizosphere and plant interior. Two strains, ISI10-3 and BRI10-9, showed highest degradation rates of diesel fuel up to 68% and performed best in combination with Italian ryegrass and alfalfa. All strains expressed the CYP153 gene in all plant compartments, indicating an active role in degradation of diesel in association with plants.

Soil type affects plant colonization, activity and catabolic gene expression of inoculated bacterial strains during phytoremediation of diesel.

The combined use of plants and associated microorganisms has great potential for cleaning up soils contaminated with petroleum hydrocarbons. Apart from environmental conditions the physicochemical properties of the soil are the main factors influencing the survival and activity of an inoculated strain as well as the growth of plants. This study examined the effect of different soil types (sandy, loamy sand and loam) on the survival, gene abundance and catabolic gene expression of two inoculated strains (Pseudomonas sp. strain ITRI53 and Pantoea sp. strain BTRH79) in the rhizosphere and shoot interior of Italian ryegrass vegetated in diesel contaminated soils. High colonization, gene abundance and expression in loamy soils were observed. By contrast, low colonization, gene abundance and absence of gene expression in sandy soil were found. The highest levels of genes expression and hydrocarbon degradation were seen in loamy soil that had been inoculated with BTRH79 and were significantly higher compared to those in other soils. A positive correlation was observed between gene expression and hydrocarbon degradation indicating that catabolic gene expression is necessary for contaminant degradation. These results suggest that soil type influences the bacterial colonization and microbial activities and subsequently the efficiency of contaminant degradation.

Impact of different plants on the gas profile of a landfill cover.

Methane is an important greenhouse gas emitted from landfill sites and old waste dumps. Biological methane oxidation in landfill covers can help to reduce methane emissions. To determine the influence of different plant covers on this oxidation in a compost layer, we conducted a lysimeter study. We compared the effect of four different plant covers (grass, alfalfa+grass, miscanthus and black poplar) and of bare soil on the concentration of methane, carbon dioxide and oxygen in lysimeters filled with compost. Plants were essential for a sustainable reduction in methane concentrations, whereas in bare soil, methane oxidation declined already after 6 weeks. Enhanced microbial activity - expected in lysimeters with plants that were exposed to landfill gas - was supported by the increased temperature of the gas in the substrate and the higher methane oxidation potential. At the end of the first experimental year and from mid-April of the second experimental year, the methane concentration was most strongly reduced in the lysimeters containing alfalfa+grass, followed by poplar, miscanthus and grass. The observed differences probably reflect the different root morphology of the investigated plants, which influences oxygen transport to deeper compost layers and regulates the water content.

Is there a redox reaction between Cu(II) and gallic acid?

Interactions between transition metal ions and polyphenols can result in complexation, redox or polymerization, but the relative importance of these reactions is unclear. The present paper reports results from the reaction of gallic acid (GA) with Cu(II) using electron paramagnetic resonance (EPR) and UV/visible spectroscopy for various relative concentrations and pH values. Reduction of Cu(II) by GA does not occur under strongly acidic or strongly alkaline conditions. Di- or polymerization reactions between Cu(II) and carboxylate groups of GA dominate the results at acidic pH, whereas mononuclear complexes increase in importance at higher pH and GA concentrations. There was no evidence for any redox reaction between Cu(II) and GA and free radical formation from GA at high pH was shown to be the consequence of auto-oxidation, which was inhibited by Cu(II). Serious questions are thus raised about the existence of the frequently assumed redox reactions between Cu(II) and polyphenols.

Phylogenetic and functional diversity of alkane degrading bacteria associated with Italian ryegrass (Lolium multiflorum) and Birdsfoot trefoil (Lotus corniculatus) in a petroleum oil-contaminated environment.

Twenty-six different plant species were analyzed regarding their performance in soil contaminated with petroleum oil. Two well-performing species, Italian ryegrass (Lolium multiflorum var. Taurus), Birdsfoot trefoil (Lotus corniculatus var. Leo) and the combination of these two plants were selected to study the ecology of plant-associated, culturable alkane-degrading bacteria. Hydrocarbon degrading bacteria were isolated from the rhizosphere, root interior and shoot interior and subjected to the analysis of 16S rRNA gene, the 16S and 23S rRNA intergenic spacer region and alkane hydroxylase genes. Furthermore, we investigated whether alkane hydroxylase genes are plasmid located. Higher numbers of culturable, alkane-degrading bacteria were associated with Italian ryegrass, which were also characterized by a higher diversity, particularly in the plant interior. Only half of the isolated bacteria hosted known alkane hydroxylase genes (alkB and cytochrome P153-like). Degradation genes were found both on plasmids as well as in the chromosome. In regard to application of plants for rhizodegradation, where support of numerous degrading bacteria is essential for efficient break-down of pollutants, Italian ryegrass seems to be more appropriate than Birdsfoot trefoil.