Ocean-atmosphere trace gas exchange

The oceans contribute significantly to the global emissions of a number of atmospherically important volatile gases, notably those containing sulfur, nitrogen and halogens. Such gases play critical roles not only in global biogeochemical cycling but also in a wide range of atmospheric processes including marine aerosol formation and modification, tropospheric ozone formation and destruction, photooxidant cycling and stratospheric ozone loss. A number of marine emissions are greenhouse gases, others influence the Earth's radiative budget indirectly through aerosol formation and/or by modifying oxidant levels and thus changing the atmospheric lifetime of gases such as methane. In this article we review current literature concerning the physical, chemical and biological controls on the sea-air emissions of a wide range of gases including dimethyl sulphide (DMS), halocarbons, nitrogen-containing gases including ammonia (NH3), amines (including dimethylamine, DMA, and diethylamine, DEA), alkyl nitrates (RONO2) and nitrous oxide (N2O), non-methane hydrocarbons (NMHC) including isoprene and oxygenated (O)VOCs, methane (CH4) and carbon monoxide (CO). Where possible we review the current global emission budgets of these gases as well as known mechanisms for their formation and loss in the surface ocean.

Low molecular weight halocarbons in the Humber and Rhine estuaries determined using a new purge-and-trap gas chromatographic method

A number of chlorinated and brominated low molecular weight hydrocarbons (halocarbons) have been measured in and adjacent to the North Sea estuaries of the Humber and the Rhine. The measurements have been carried out using a newly constructed purge-and-trap sample work-up system coupled to megabore gas chromatography with electron capture detection. The results show that whereas the Humber is a pronounced source of the anthropogenic halocarbons carbon tetrachloride and perchloroethylene, the input from the Rhine into the North Sea of these compounds is more modest. Some halocarbons normally considered as mainly or even exclusively of natural origin are released from the two investigated estuaries into the North Sea. A distinct patch of high concentrations of the naturally produced compound bromoform was observed in the southwestern North Sea. The results have also been used to examine some of the halocarbons for common sources.

Immunofluorescence detection and localization of B[a]P and TCDD in earthworm tissues

An immunohistochemical method using antibodies against polycyclic aromatic hydrocarbons (PAHs) and dioxins was developed on frozen tissue sections of the earthworm Eisenia andrei exposed to environmentally relevant concentrations of benzo[a]pyrene (B[a]P) (0.1, 10, 50 ppm) and 2,3,7,8-tetrachlorodibenzo-para-dioxin (TCDD) (0.01, 0.1, 2 ppb) in spiked standard soils. The concentrations of B[a]P and TCDD in E. andrei exposed to the same conditions were also measured using analytical chemical procedures. The results demonstrated that tissues of worms exposed to even minimal amount of B[a]P and TCDD reacted positively and specifically to anti-PAHs and -dioxins antibody. Immunofluorescence revealed a much more intense staining for the gut compared to the body wall; moreover, positively immunoreactive amoeboid coelomocytes were also observed, i.e. cells in which we have previously demonstrated the occurrence of genotoxic damage. The double immunolabelling with antibodies against B[a]P/TCDD and the lysosomal enzyme cathepsin D demonstrated the lysosomal accumulation of the organic xenobiotic compounds, in particular in the cells of the chloragogenous tissue as well as in coelomocytes, involved into detoxification and protection of animals against toxic chemicals. The method described is timesaving, not expensive and easily applicable.

Sediment contaminant surveillance in Milford Haven Waterway

Sediment contaminants were monitored in Milford Haven Waterway (MHW) since 1978 (hydrocarbons) and 1982 (metals), with the aim of providing surveillance of environmental quality in one of the UK’s busiest oil and gas ports. This aim is particularly important during and after large-scale investment in liquefied natural gas (LNG) facilities. However, methods inevitably have changed over the years, compounding the difficulties of coordinating sampling and analytical programmes. After a review by the MHW Environmental Surveillance Group (MHWESG), sediment hydrocarbon chemistry was investigated in detail in 2010. Natural Resources Wales (NRW) contributed their MHW data for 2007 and 2012, collected to assess the condition of the Special Area of Conservation (SAC) designated under the European Union Habitats Directive. Datasets during 2007-2012 have thus been more comparable. The results showed conclusively that a MHW-wide peak in concentrations of sediment polycyclic aromatic hydrocarbons (PAHs), metals and other contaminants occurred in late 2007. This was corroborated by independent annual monitoring at one centrally-located station with peaks in early 2008 and 2011. The spatial and temporal patterns of recovery from the 2007 peak, shown by MHW-wide surveys in 2010 and 2012, indicate several probable causes of contaminant trends, as follows: atmospheric deposition, catchment runoff, sediment resuspension from dredging, and construction of two LNG terminals and a power station. Adverse biological effects predictable in 2007 using international sediment quality guidelines, were independently tested by data from monitoring schemes of more than a decade duration in MHW (starfish, limpets), and in the wider SAC (grey seals). Although not proving cause and effect, many of these potential biological receptors showed a simultaneous negative response to the elevated 2007 contamination following intense dredging activity in 2006. Wetland bird counts were typically at a peak in the winter of 2005-2006 previous to peak dredging. In the following winter 2006-2007, shelduck in Pembroke River showed their lowest winter count, and spring 2007 was the largest ever drop in numbers of broods across MHW between successive breeding seasons. Wigeon counts in Pembroke River were again low in late 2012 after further dredging nearby. These results are strongly supported by PAH data reported previously from invertebrate bioaccumulation studies in MHW 2007-2010, themselves closely reflecting sediment

Biomonitoring of air pollutants by using lichens (Evernia prunastri) in areas between Kenitra and Mohammedia cities in Morocco.

In this study, Evernia prunastri, a lichen growing in its natural habitat in Morocco was analysed for the concentration of five heavy metals (Fe, Pb, Zn, Cu and Cr) from eleven sites between Kenitra and Mohammedia cities. The control site was Dar Essalam, an isolated area with low traffic density and dense vegetation. In the investigated areas, the concentration of heavy metals was correlated with vehicular traffic, industrial activity and urbanization. The total metal concentration was highest in Sidi Yahya, followed by Mohammedia and Bouznika. The coefficient of variation was higher for Pb and lower for Cu, Zn and Fe. The concentrations of most heavy metals in the thalli differed significantly between sites (p<0.01). Principal component analysis (PCA) revealed a significant correlation between heavy metal accumulation and atmospheric purity index. This study demonstrated also that the factors most strongly affecting the lichen flora were traffic density, the petroleum industry and paper factories in these areas. Overall, these results suggest that the index of atmospheric purity and assessment of heavy metals in lichen thalli are good indicators of the air quality at the studied sites.

Las infraestructuras de recarga y el despegue del vehículo eléctrico.

Este trabajo revisa la evolución y estado actual de la automoción eléctrica; analiza las ventajas ambientales, de eficiencia energética y de costes del motor eléctrico frente al de combustión interna; y presenta como limitaciones para el uso del vehículo eléctrico, el desarrollo actual de las baterías recargables y la lenta implantación de electrolineras. Con el objetivo de contribuir al desarrollo de una actividad económica respetuosa con el medio ambiente y basada en nuevas tecnologías, se proyecta, a partir de experiencias previas, una instalación de puntos de recarga para una ciudad de 50.000 habitantes con un parque de 100 vehículos eléctricos que dispone de dos plazas de recarga rápida (poste trifásico 400V CA), siete plazas de recarga lenta (postes monofásicos 230V CA) y de 50 módulos fotovoltaicos que producen diariamente la energía equivalente a la recarga lenta de un vehículo en los meses fríos y de dos en los meses cálidos.

Development of a modified flyash as a permeable reactive barrier media for a former manufactured gas plant site Northern Ireland

A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (

Microbial analysis of soil and groundwater from a gasworks site and comparison to a sequenced biological reactive barrier remediation process (SEREBAR)

Aims: To investigate the distribution of a polymicrobial community of biodegradative bacteria in (i) soil and groundwater at a former manufactured gas plant (FMGP) site and (ii) in a novel SEquential REactive BARrier (SEREBAR) bioremediation process designed to bioremediate the contaminated groundwater. Methods and Results: Culture-dependent and culture-independent analyses using denaturing gradient gel electrophoresis (DGGE) and polymerase chain reaction (PCR) for the detection of 16S ribosomal RNA gene and naphthalene dioxygenase (NDO) genes of free-living (planktonic groundwater) and attached (soil biofilm) samples from across the site and from the SEREBAR process was applied. Naphthalene arising from groundwater was effectively degraded early in the process and the microbiological analysis indicated a dominant role for Pseudomonas and Comamonas in its degradation. The microbial communities appeared highly complex and diverse across both the sites and in the SEREBAR process. An increased population of naphthalene degraders was associated with naphthalene removal. Conclusion: The distribution of micro-organisms in general and naphthalene degraders across the site was highly heterogeneous. Comparisons made between areas contaminated with polycyclic aromatic hydrocarbons (PAH) and those not contaminated, revealed differences in the microbial community profile. The likelihood of noncultured bacteria being dominant in mediating naphthalene removal was evident. Significance and Impact of the Study: This work further emphasizes the importance of both traditional and molecular-based tools in determining the microbial ecology of contaminated sites and highlights the role of noncultured bacteria in the process.

Electrochemical synthesis and characterization of conducting polyparaphenylene using room-temperature melt as the electrolyte

Freestanding polyparaphenylene films were obtained on polymerization of benzene at potential of 1.2 V versus Al wire on substrates like platinum/transparent conducting glass as an anode. The electrolyte used was chloroaluminate room-temperature melt, which was prepared by intimate mixing of a 1:2 ratio of cetyl pyridinium chloride and anhydrous aluminum chloride to yield a viscous liquid. This liquid was miscible in all proportions with benzene and other aromatic hydrocarbons in all proportions at room temperature. The polyparaphenylene films deposited on platinum anode exhibited a prominent cyclic voltammetric peak at 0.7 V versus Al wire as reference electrode in chloroaluminate medium. The impedance spectra gave low charge transfer resistance. The diffused reflectance electronic spectra of the film gave the peaks at 386 nm and 886 nm. The PPP films showed electronic conductivity around 3–4 × 104 S/cm by four probe method under nitrogen atmosphere. The polymer was also characterized by IR spectra, thermal studies, and SEM studies.

Performance of a Sequential Reactive Barrier for Bioremediation of Coal Tar Contaminated Groundwater

Following a thorough site investigation, a biological Sequential Reactive Barrier (SEREBAR), designed to remove Polycyclic Aromatic Hydrocarbons (PAHs) and BTEX compounds, was installed at a Former Manufactured Gas Plant (FMGP) site. The novel design of the barrier comprises, in series, an interceptor and six reactive chambers. The first four chambers (2 nonaerated-2 aerated) were filled with sand to encourage microbial colonization. Sorbant Granular Activated Carbon (GAC) was present in the final two chambers in order to remove any recalcitrant compounds. The SEREBAR has been in continuous operation for 2 years at different operational flow rates (ranging from 320 L/d to 4000 L/d, with corresponding residence times in each chamber of 19 days and 1.5 days, respectively). Under low flow rate conditions (320-520 L/d) the majority of contaminant removal (>93%) occurred biotically within the interceptor and the aerated chambers. Under high flow rates (1000-4000 L/d) and following the installation of a new interceptor to prevent passive aeration, the majority of contaminant removal (>80%) again occurred biotically within the aerated chambers. The sorption zone (GAC) proved to be an effective polishing step, removing any remaining contaminants to acceptable concentrations before discharge down-gradient of the SEREBAR (overall removals >95%).

Diagnostic studies of species concentrations in a capacitively coupled RF plasma containing CH4-H2-Ar

Three plasma diagnostic methods, tunable infrared diode laser absorption spectroscopy, optical emission spectroscopy and microwave interferometry have been used to monitor concentrations of transient and stable molecules, CH3, CH4, C2H2, C2H6, and of electrons in capacitively coupled CH4-H-2-Ar radiofrequency (RF) plasmas (f(RF) = 13.56 MHz, p = 100 Pa, phi (total)= 66 sccm) for various discharge power values (P = 10-100 W) and gas mixtures. The degree of dissociation of the methane precursor varied between 3% and 60%. The methyl radical concentration was found to be in the order of 10(12) molecules cm(-3) and the electron concentration in the order of loll cm(-3). The methyl radical concentration and the concentrations of the stable C-2 hydrocarbons, C2H2 and C2H6, produced in the plasma, increased with discharge power. The fragmentation rates of the methane precursor and conversion rates to the measured C-2 hydrocarbons were estimated in dependence on discharge power. Radial distributions of the electron and methyl radical concentrations, and of the gas temperature were measured for the first time simultaneously in the plasma region between the discharge electrodes. The measurements allow us to draw qualitative conclusions on the main chemical processes and the plasma chemical reaction paths.

Liquid clathrate formation in ionic liquid-aromatic mixtures

1-Alkyl-3-methylimidazolium containing ionic liquids with hexafluorophosphate, bis(trifyl)imide, tetrafluoroborate, and chloride anions form liquid clathrates when mixed with aromatic hydrocarbons; in the system 1,3-dimethylimidazolium hexafluorophosphate-benzene, the aromatic solute could be trapped in the solid state forming a crystalline 2: 1 inclusion compound.

Gas-phase photocatalytic oxidation of dichlorobutenes

Gas-phase photocatalysis of 1,4-dichlorobut-2-enes and 3,4-dichlorobut-1-ene (DCB) has been studied using TiO2 and 3%WO3/TiO2 supported on SiO2. DCB was found to oxidize efficiently over these catalysts; however, only low rates of CO2 formation were observed. With these chlorinated hydrocarbons, the catalysts were found to deactivate over time, probably via the formation of aldol condensation products of chloroacetaldehyde, which is the predominant intermediate observed. The variation in rate and selectivity of the oxidation reactions with O-2 concentration is reported and a mechanism is proposed. Using isotope ratio mass spectrometry, the initial step for the DCB removal has been shown not to be a carbon bond cleavage but is likely to be hydroxyl radical addition to the carbon-carbon double bond.

First-principles study of oxygenates on Co surfaces in Fischer-Tropsch synthesis

Extensive density function theory calculations are performed to study the mechanism of the formation of aldehyde and alcohol on Co surfaces in Fischer-Tropsch synthesis, a challenging issue in heterogeneous catalysis. Three possible pathways for the production of formaldehyde and methanol on flat and stepped Co(0001) surfaces are investigated: (i) CO + 4H -> CHO + 3H -> CH2O + 2H -> CH3O + H -> CH3OH; (ii) CO + 4H -> COH + 3H -> CHOH + 2H -> CH2OH + H -> CH3OH; and (iii) the coupling reactions of CH2 + O -> CH2O and CH3 + OH -> CH3OH. It is found that these pathways are generally favored at step sites, and the preferred mechanism is pathway (i) via CHO. Furthermore, the three traditional chain growth mechanisms in Fischer-Tropsch synthesis are semi quantitatively compared and discussed. Our results suggest that the two mechanisms involving oxygenate intermediates (the CO-insertion and hydroxycarbene mechanisms) are less important than the carbene mechanism in the production of long chain hydrocarbons. However, the CO-insertion mechanism may be responsible for the production of long-chain oxygenates.

Softened C-H modes of adsorbed methyl and their implications for dehydrogenation: An ab initio study

To investigate the softening of CH vibrational frequencies and their implications for dehydrogenation of adsorbed hydrocarbons, an issue of scientific and technological importance, density functional theory calculations have been performed on the chemisorption and dehydrogenation of CH3 on Cu(111) and Pt(111) surfaces. By comparing these results with those of Ni(111) we find that the CH bonds of the adsorbate, when close enough, interact with metal atoms of the surface. It is this interaction and its associated lengthening and weakening of CH bonds that is the physical origin of mode softening. We rule out the possibility of a relationship between the mere presence of mode softening and dehydrogenation. We do show, however, that there is a clear relationship between the extent to which a surface can induce mode softening and the activation energy to dehydrogenation. In addition, periodic trends concerning the extent of mode softening are reproduced. (C) 2001 American Institute of Physics.