The effects of global climate change on the cycling and processes of persistent organic pollutants (POPs) in the North Sea

The fate and cycling of two selected legacy persistent organic pollutants (POPs), PCB 153 and gamma-HCH, in the North Sea in the 21st century have been modelled with combined hydrodynamic and fate and transport ocean models
(HAMSOM and FANTOM, respectively). To investigate the impact of climate variability on POPs in the North Sea in the 21st century, future scenario model runs for three 10-year periods to the year 2100 using plausible levels of both in
situ concentrations and atmospheric, river and open boundary inputs are performed. This slice mode under a moderate scenario (A1B) is sufficient to provide a basis for further analysis. For the HAMSOM and atmospheric forcing, results of the IPCC A1B (SRES) 21st century scenario are utilized, where surface forcing is provided by the REMO downscaling of the ECHAM5 global atmospheric model, and open boundary conditions are provided by the MPIOM global ocean model.
Dry gas deposition and volatilization of gamma-HCH increase in the future relative to the present by up to 20% (in the spring and summer months for deposition and in summer for volatilization). In the water column, total mass of
gamma-HCH and PCB 153 remain fairly steady in all three runs. In sediment,
gamma-HCH increases in the future runs, relative to the present, while PCB 153 in sediment decreases exponentially in all three runs, but even faster in the future, due to the increased number of storms, increased duration of gale wind conditions and increased water and air temperatures, all of which are the result of climate change. Annual net sinks exceed sources at the ends of all periods.
Overall, the model results indicate that the climate change scenarios considered here generally have a negligible influence on the simulated fate and transport of the two POPs in the North Sea, although the increased number and magnitude of storms in the 21st century will result in POP resuspension and ensuing revolatilization events. Trends in emissions from primary and secondary sources will remain the key driver of levels of these contaminants over time.

Air-Sea Exchange of Legacy POPs in the North Sea Based on Results of Fate and Transport, and Shelf-Sea Hydrodynamic Ocean Models

The air-sea exchange of two legacy persistent organic pollutants (POPs), γ-HCH and PCB 153, in the North Sea, is presented and discussed using results of regional fate and transport and shelf-sea hydrodynamic ocean models for the period 1996–2005. Air-sea exchange occurs through gas exchange (deposition and volatilization), wet deposition and dry deposition. Atmospheric concentrations are interpolated into the model domain from results of the EMEP MSC-East multi-compartmental model (Gusev et al, 2009). The North Sea is net depositional for γ-HCH, and is dominated by gas deposition with notable seasonal variability and a downward trend over the 10 year period. Volatilization rates of γ-HCH are generally a factor of 2–3 less than gas deposition in winter, spring and summer but greater in autumn when the North Sea is net volatilizational. A downward trend in fugacity ratios is found, since gas deposition is decreasing faster than volatilization. The North Sea is net volatilizational for PCB 153, with highest rates of volatilization to deposition found in the areas surrounding polluted British and continental river sources. Large quantities of PCB 153 entering through rivers lead to very high local rates of volatilization.

Investigating the promotional effect of methanol on the low temperature SCR reaction on Ag/Al2O3

Methanol has been shown to promote the hydrocarbon selective catalytic reduction of NO with octane and toluene over 2wt% Ag/AlO catalyst for the first time. In order to understand its role in the reaction fast transient kinetic methods and in situ DRIFTS analysis have been used. The catalytic activity tests showed that the addition of methanol to the HC-SCR reaction results in a significant improvement in the low temperature activity of a Ag/AlO catalyst, despite the fact that methanol on its own is not reactive for the HC-SCR reaction. This promotional effect of methanol is dependent on the concentration of added methanol and is not necessarily associated with a higher concentration of reductant in the SCR feed. The fast transient kinetic analysis has shown that at each temperature the addition of methanol enhances the conversions of both NO and octane and the production of N with high selectivity in comparison with those observed with n-octane or toluene alone. This phenomenon is similar to the effect of H which may be associated with the release of hydrogen and ammonia during the transient switches at 250 and 300°C. Together with the fast transient experiments, the DRIFTS results showed that NCO species are formed when introducing methanol to the n-octane-SCR feed while CN species are removed/consumed from the surfaces of the Ag catalyst. These NCO species formed by adding methanol may play a vital role in promoting the catalytic activity of NO reduction and methanol itself can be an in situ source for hydrogen formation, which subsequently enhances the SCR reaction. © 2014 Elsevier B.V.

Effect of isomalt consumption on faecal microflora and colonic metabolism in healthy volunteers

Due to its low digestibility in the small intestine, a major fraction of the polyol isomalt reaches the colon. However, little is known about effects on the intestinal microflora. During two 4-week periods in a double-blind, placebo-controlled, cross-over design, nineteen healthy volunteers consumed a controlled basal diet enriched with either 30 g isomalt or 30 g sucrose daily. Stools were collected at the end of each test phase and various microbiological and luminal markers were analysed. Fermentation characteristics of isomalt were also investigated in vitro. Microbiological analyses of faecal samples indicated a shift of the gut flora towards an increase of bifidobacteria following consumption of the isomalt diet compared with the sucrose diet (P

An understanding and implications of the coverage of surface free sites in heterogeneous catalysis

The crucial roles of the coverage of surface free sites in determining catalytic activity trend are quantitatively addressed with the help of density functional theory and microkinetics. First, by analyzing activity trends of NO oxidation catalyzed by Ru, Rh, Pd, Os, Ir, and Pt surfaces with full kinetic considerations, we identify that the activity trend is in general determined by the competition between the reaction barrier and the coverage of surface free sites. Second, since the dissociation of many important molecules, such as the dissociation of N(2), O(2), and CO, follows the same Bronsted-Evans-Polanyi relationship, the coverage of surface free sites is usually a decisive term that affects the overall activity. Third, an equation is derived for the coverage of surface free sites and it is found that the coverage of surface free sites contains not only all the key thermodynamic parameters but also all the kinetic properties in the catalytic system. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3140202]

Insights into the Staggered Nature of Hydrogenation Reactivity over the 4d Transition Metals

Hydrogenation reactions at transition metal surfaces comprise a key set of reactions in heterogeneous catalysis. In this paper, density functional theory methods are employed to take an in-depth look at this fundamental reaction type. The energetics of hydrogenation of atomic C, N, and O have been studied in some detail over low index Zr, Nb, Mo, Tc, Ru, Rh, and Pd surfaces. Detailed bonding analysis has also been employed to track carefully the chemical changes taking place during reaction. A number of interesting horizontal and vertical trends have been uncovered relating to reactant valency and metal d-band filling. A general correlation has also been found between the reaction barriers and the reaction potential energies. Moreover, when each reaction is considered independently, correlation has been found to improve with decreasing reactant valency. Bonding analysis has pointed to this being related to the relative position of the transition state along the reaction coordinate and has shown that as reactant valency decreases, the transition states become progressively later.

Microbial Ecology and Geo-electrical Responses across a Groundwater Plume

We have used geophysics, microbiology, and geochemistry to link large-scale (30+ m) geophysical self-potential (SP) responses at a groundwater contaminant plume with its chemistry and microbial ecology of groundwater and soil from in and around it. We have found that microbially mediated transformation of ammonia to nitrite, nitrate, and nitrogen gas was likely to have promoted a well-defined electrochemical gradient at the edge of the plume, which dominated the SP response. Phylogenetic analysis demonstrated that the plume fringe or anode of the geobattery was dominated by electrogens and biodegradative microorganisms including Proteobacteria alongside Geobacteraceae, Desulfobulbaceae, and Nitrosomonadaceae. The uncultivated candidate phylum OD1 dominated uncontaminated areas of the site. We defined the redox boundary at the plume edge using the calculated and observed electric SP geophysical measurements. Conductive soils and waste acted as an electronic conductor, which was dominated by abiotic iron cycling processes that sequester electrons generated at the plume fringe. We have suggested that such geoelectric phenomena can act as indicators of natural attenuation processes that control groundwater plumes. Further work is required to monitor electron transfer across the geoelectric dipole to fully define this phenomenon as a geobattery. This approach can be used as a novel way of monitoring microbial activity around the degradation of contaminated groundwater plumes or to monitor in situ bioelectric systems designed to manage groundwater plumes.

Enchytraeid worms retard polycyclic aromatic hydrocarbon degradation in a coniferous forest soil

In this study the fate of naphthalene, fluorene and pyrene were investigated in the presence and absence of enchytraeid worms. Microcosms were used, which enabled the full fate of ¹⁴C-labelled PAHs to be followed. Between 60 and 70% of naphthalene was either mineralised or volatilised, whereas over 90% of the fluorene and pyrene was retained within the soil. Mineralisation and volatilisation of naphthalene was lower in the presence of enchytraeid worms. The hypothesis that microbial mineralisation of naphthalene was limited by enchytraeids because they reduce nutrient availability, and hence limit microbial carbon turnover in these nutrient poor soils, was tested. Ammonia concentrations increased and phosphorus concentrations decreased in all microcosms over the 56 d experimental period. The soil nutrient chemistry was only altered slightly by enchytraeid worms, and did not appear to be the cause of retardation of naphthalene mineralisation. The results suggest that microbial availability and volatilisation of naphthalene is altered as it passes through enchytraeid worms due to organic material encapsulation. © 2004 Elsevier Ltd. All rights reserved.

Degradation of the polycyclic aromatic hydrocarbon (PAH) fluorene is retarded in a Scots pine ectomycorrhizosphere

Polycyclic aromatic hydrocarbons (PAHs) are an important class of persistent organic pollutants (POPs) in the environment and accumulate in forest soils. These soils are often dominated by ectomycorrhizal (EcM) roots, but little is known about how EcM fungi degrade PAHs, or the overall effect of field colonized EcM roots on the fate of PAHs. The ability of eight EcM fungi to degrade PAHs in liquid culture spiked with ¹⁴C labelled PAHs was investigated. Microcosms were used to determine the impact of naturally colonized mycorrhizal pine seedlings on PAH mineralization and volatilization. Only two EcM fungi (Thelephora terrestris and Laccaria laccata) degraded at least one PAH and none were able to mineralize the PAHs in pure culture. Where degradation occurred, the compounds were only mono-oxygenated. EcM pine seedlings did not alter naphthalene mineralization or volatilization but retarded fluorene mineralization by 35% compared with unplanted, ectomycorrhizosphere soil inoculated, microcosms. The EcM fungi possessed limited PAH degrading abilities, which may explain why EcM dominated microcosms retarded fluorene mineralization. This observation is considered in relation to the 'Gadgil-effect', where retarded litter decomposition has been observed in the presence of EcM roots. © New Phytologist (2004).

Influence of trace substances on methanation catalysts used in dynamic biogas upgrading

The aim of this work was to study the possible deactivation effects of biogas trace ammonia concentrations on methanation catalysts. It was found that small amounts of ammonia led to a slight decrease in the catalyst activity. A decrease in the catalyst deactivation by carbon formation was also observed, with ammonia absorbed on the active catalyst sites. This was via a suppression of the carbon formation and deposition on the catalyst, since it requires a higher number of active sites than for the methanation of carbon oxides. From the paper findings, no special pretreatment for ammonia removal from the biogas fed to a methanation process is required.