Biomass of mesozooplankton in the western part of the Black Sea in summer 1991 during the NATO Programme Hydroblack

The "Hydroblack91" dataset is based on samples collected in the summer of 1991 and covers part of North-Western in front of Romanian coast and Western Black Sea (Bulgarian coasts) (between 43°30' - 42°10' N latitude and 28°40'- 31°45' E longitude). Mesozooplankton sampling was undertaken at 20 stations. The whole dataset is composed of 72 samples with data of zooplankton species composition, abundance and biomass. Samples were collected in discrete layers 0-10, 0-20, 0-50, 10-25, 25-50, 50-100 and from bottom up to the surface at depths depending on water column stratification and the thermocline depth. Zooplankton samples were collected with vertical closing Juday net,diameter - 36cm, mesh size 150 µm. Tows were performed from surface down to bottom meters depths in discrete layers. Samples were preserved by a 4% formaldehyde sea water buffered solution. Sampling volume was estimated by multiplying the mouth area with the wire length. Mesozooplankton abundance: The collected materia was analysed using the method of Domov (1959). Samples were brought to volume of 25-30 ml depending upon zooplankton density and mixed intensively until all organisms were distributed randomly in the sample volume. After that 5 ml of sample was taken and poured in the counting chamber which is a rectangle form for taxomomic identification and count. Large (> 1 mm body length) and not abundant species were calculated in whole sample. Counting and measuring of organisms were made in the Dimov chamber under the stereomicroscope to the lowest taxon possible. Taxonomic identification was done at the Institute of Oceanology by Asen Konsulov using the relevant taxonomic literature (Mordukhay-Boltovskoy, F.D. (Ed.). 1968, 1969,1972). The biomass was estimated as wet weight by Petipa, 1959 (based on species specific wet weight). Wet weight values were transformed to dry weight using the equation DW=0.16*WW as suggested by Vinogradov & Shushkina, 1987. Taxon-specific abundance: The collected material was analysed using the method of Domov (1959). Samples were brought to volume of 25-30 ml depending upon zooplankton density and mixed intensively until all organisms were distributed randomly in the sample volume. After that 5 ml of sample was taken and poured in the counting chamber which is a rectangle form for taxomomic identification and count. Copepods and Cladoceras were identified and enumerated; the other mesozooplankters were identified and enumerated at higher taxonomic level (commonly named as mesozooplankton groups). Large (> 1 mm body length) and not abundant species were calculated in whole sample. Counting and measuring of organisms were made in the Dimov chamber under the stereomicroscope to the lowest taxon possible. Taxonomic identification was done at the Institute of Oceanology by Asen Konsulov using the relevant taxonomic literature (Mordukhay-Boltovskoy, F.D. (Ed.). 1968, 1969,1972). The biomass was estimated as wet weight by Petipa, 1959 ussing standard average weight of each species in mg/m3. WW were converted to DW by equation DW=0.16*WW (Vinogradov ME, Sushkina EA, 1987).

Abundance of mesozooplankton in the north-eastern Black Sea during SESRU01 cruise in April 2008

The SESRU01_mesozooplankton dataset contains data collected in April 2008 at 19 stations located between 37°E and 39.5°E and between 42.4°N and 44.5°N in the north-eastern Black Sea. Samples were collected with a Juday net (mesh size 180 ?m, mouth area 0.1 m**2). Integrated samples were taken from the lower boundary of the oxic zone to the surface, stratified samples were taken according to CTD-profiles: samples were taken from the following depth strata: 1) the upper mixed layer (UML); 2) the layer of high temperature gradients (from the upper boundary of thermocline to the depth of 8 deg C temperature); 3) cold Intermediate layer (CIL) - the layer with the T< 8 deg C; 4) from the depth of sigma theta = 15.8 (oxycline) to the lower boundary of CIL; 5) from the depth of sigma theta = 16.2 to the depth of sigma theta = 15.8. Samples were analysed for zooplankton species and stage composition and abundance. Juday net: Vertical tows of a closing Juday net, with mouth area 0.1 m**2, mesh size 180µm. Samples were taken from different layers. Towing speed: 1m/s. Samples were preserved by a 4% formaldehyde sea water buffered solution. Sampling volume was estimated by multiplying the mouth area by the wire length. The entire sample or an aliquot (1/2 to1/4) was analyzed under the binocular microscope. Mesozooplankton species and stages were identified and enumerated; meroplankton were identified and enumerated at higher taxonomic level. Taxonomic identification was done at Shirshov Institute of Oceanology using the relevant taxonomic literature (Rose, 1933, Brodsky, 1950, and Internet resources).

Nematode abundance in cold seep sediments of the Darwin mud volcano

During the JC-10 cruise (2007), we sampled the Darwin mud volcano (MV) for meiofaunal community and trophic structure in relation of pore-water geochemistry along a 10 m transect from a seep site on the rim of the crater towards the MV slope. Sediment samples were retrieved by the ROV Isis using push cores. On board and after the pore water extraction, the top 10 cm of the cores were sliced into 1 cm sections and fixed them in 4% formaldehyde for meiofaunal community analysis. In the home laboratory, the formaldehyde-fixed samples were washed over a 32 µm mesh sieve and extracted the meiofauna from the sediment by Ludox centrifugation (Heip et al. 1985). Meiofauna was then sorted, enumerated and identified at coarse taxonomic level. From each slice, ca. 100 nematodes were identified to genus level. Afterwards, abundance of Nematoda were depth integrated over the top 5 cm to gain individual abundances per 10 cm**2. Overall, total nematode biomass in the top 5 cm of the seep sediment core was ~10x higher than that in the core taken 1100 m away. Nematode genus composition varied little among cores and was mainly dominated by Sabatieria.

Abundance of mesozooplankton during the long-tern mesozooplankton analysis in Sevastopol Bay from 1976 to 2003

The present dataset includes results of analysis of 227 zooplankton samples taken in and off the Sevastopol Bay in the Black Sea in 1976, 1979-1980, 1989-1990, 1995-1996 and 2002-2003. Exact coordinates for stations 1, 4, 5 and 6 are unknown and were calculated using Google-earth program. Data on Ctenophora Mnemiopsis leidyi and Beroe ovata are not included. Juday net: Vertical tows of a Juday net, with mouth area 0.1 m**2, mesh size 150µm. Tows were performed at layers. Towing speed: about 0.5 m/s. Samples were preserved by a 4% formaldehyde sea water buffered solution. Sampling volume was estimated by multiplying the mouth area with the wire length. The collected material was analysed using the method of portions (Yashnov, 1939). Samples were brought to volume of 50 - 100 ml depending upon zooplankton density and mixed intensively until all organisms were distributed randomly in the sample volume. After that 1 ml of sample was taken by calibrated Stempel-pipette. This operation was produced twice. If divergence between two examined subsamples was more than 30% one more subsample was examined. Large (> 1 mm body length) and not abundant species were calculated in 1/2, 1/4, 1/8, 1/16 or 1/32 part of sample. Counting and measuring of organisms were made in the Bogorov chamber under the stereomicroscope to the lowest taxon possible. Number of organisms per sample was calculated as simple average of two subsamples meanings multiplied on subsample volume. Total abundance of mesozooplankton was calculated as sum of taxon-specific abundances and total abundance of Copepods was calculated as sum of copepods taxon-specific abundances.

Abundance of mesozooplankton from the S-IT4 cruise in the Western Mediterranean Sea in March and April 2008

The "SESAME_IT4_ZooAbundance_0-50-100m_SZN" dataset contains data of mesozooplankton species composition and abundance (ind./m**3) from samples collected in the Western Mediterranean in the early spring of 2008 (20 March-5 April) during the SESAME-WP2 cruise IT4. Samples were collected by vertical tows with a closing WP2 net (56 cm diameter, 200 µm mesh size) in the following depth layers: 100-200 m, 50-100 m, 0-50 m. Sampling was always performed in light hours. A flowmeter was applied to the mouth of the net, however, due to its malfunctioning, the volume of filtered seawater was calculated by multiplying the the area by the height of the sampled layer from winch readings. After collection, each sample was split in two halves (1/2) after careful mixing with graduated beakers. Half sample was immediately fixed and preserved in a formaldehyde-seawater solution (4% final concentration) for species composition and abundance. The other half sample was kept fresh for biomass measurements (data already submitted to SESAME database in different files). Here, only the zooplankton abundance of samples in the upper layers 0-50 m and 50-100 m are presented. The abundance data of the samples in the layer 50-100 m will be submitted later in a separate file. The volume of filtered seawater was estimated by multiplying the the area by the height of the sampled layer from winch readings. Identification and counts of specimens were performed on aliquots (1/20-1/5) of the fixed sample or on the total sample (half of the original sample) by using a graduate large-bore pipette. Copepods were identified to the species level and separated into females, males and juveniles (copepodites). All other taxa were identified at the species level when possible, or at higher taxonomic levels. Taxonomic identification was done according to the most relevant and updated taxonomic literature. Total mesozooplankton abundance was computed as sum of all specific abundances determined as explained above.

Microbial community, biomarker concentrations and their isotopic signature in sediment of Gullfaks and Tommeliten methane seeps in the Northern North Sea

Gullfaks is one of the four major Norwegian oil and gas fields, located in the northeastern edge of the North Sea Plateau. Tommeliten lies in the greater Ekofisk area in the central North Sea. During the cruises HE 208 and AL 267 several seep locations of the North Sea were visited. At the Heincke seep at Gullfaks, sediments were sampled in May 2004 (HE 208) using a video-guided multiple corer system (MUC; Octopus, Kiel). The samples were recovered from an area densely covered with bacterial mats where gas ebullition was observed. The coarse sands limited MUC penetration depth to maximal 30 centimeters and the highly permeable sands did not allow for a high-resolution, vertical subsampling because of pore water loss. The gas flare mapping and videographic observation at Tommeliten indicated an area of gas emission with a few small patches of bacterial mats with diameters <50 cm from most of which a single stream of gas bubbles emerged. The patches were spaced apart by 10-100 m. Sampling of sediments covered by bacterial mats was only possible with 3 small push cores (3.8 cm diameter) mounted to ROV Cherokee. These cores were sampled in 3 cm intervals. Lipid biomarker extraction from 10 -17 g wet sediment was carried out as described in detail elsewhere (Elvert et al., 2003; doi:10.1080/01490450303894). Briefly, defined concentrations of cholestane, nonadecanol and nonadecanolic acid with known delta 13C-values were added to the sediments prior to extraction as internal standards for the hydrocarbon, alcohol and fatty acid fraction, respectively. Total lipid extracts were obtained from the sediment by ultrasonification with organic solvents of decreasing polarity. Esterified fatty acids (FAs) were cleaved from the glycerol head group by saponification with methanolic KOH solution. From this mixture, the neutral fraction was extracted with hexane. After subsequent acidification, FAs were extracted with hexane. For analysis, FAs were methylated using BF3 in methanol yielding fatty acid methyl esters (FAMES). The fixation for total cell counts and CARD-FISH were performed on-board directly after sampling. For both methods, sediments were fixed in formaldehyde solution. After two hours, aliquots for CARD-FISH staining were washed with 1* PBS (10mmol/l sodium phosphate solution, 130mmol/l NaCl, adjusted to a pH of 7.2) and finally stored in a 1:1 PBS:ethanol solution at -20°C until further processing. Samples for total cell counts were stored in formalin at 4°C until analysis. For sandy samples, the total cell count/CARD-FISH protocol was optimized to separate sand particles from the cells. Cells were dislodged from sediment grains and brought into solution with the supernatant by sonicating each sample onice for 2 minutes at 50W. This procedure was repeated four times and supernatants were combined. The sediment samples were brought to a final dilution of 1:2000 to 1:4000 and filtered onto 0.2µm GTTP filters (Millipore, Eschbonn, Germany).

Nematode abundance in cold seep sediments of the Nordic Margins (Nyregga, Styregga, Haakon Mosby Mud Volcano)

Cold-seep environments and their associated symbiont-bearing mega faunal communities create islands of primary production for macro-and meiofauna in the otherwise monotonous and nutrient-poor deep-sea environment. To examine the spatial variation and distribution patterns of metazoan meiobenthos in different seepage-related habitats, samples were collected in two regions off Norway: several pockmarks associated with the Storegga Slide including the Nyegga pockmark area, and the active, methane-venting Haakon Mosby Mud Volcano west of the Barents Sea during the Vicking cruise aboard the RV ''PourquoiPas?'' in May-June 2006. Meiofaunal samples at control sites were sampled with a multiple corer, while the other sites were sampled with push cores operated by the ROV Victor6000.The meiofaunal samples were fixed in 4% buffered formaldehyde and washed over a 32 mm-mesh sieve. Metazoan meiofauna were extracted by density gradient centrifugation. All material was fixed with 4% buffered formalin and stained with Rose Bengal. The metazoan meiofauna was sorted out, enumerated and identified down to major taxa under the stereomicroscope. Afterwards, abundances of Nematodes were depth integrated over the top 5 cm to gain individual abundances per 10 cm**2.

Abundance and biomass of phytoplankton in the western part of the Black Sea during Parshin cruise BSRP in September and October 2005

The dataset is composed of 61 samples from 15 stations. The phytoplankton samples were collected by 5l Niskin bottles attached to the CTD system. The sampling depths were selected according to the CTD profile and the in situ fluorometer readings: surface, temperature, salinity and fluorescence gradients and 1 m above the bottom. At some stations phytoplankton net samples (20 µm mesh-size) were collected to assist species biodiversity examination. The samples (1l sea water) were preserved in 4% buffered to pH 8-8.2 with disodiumtetraborate formaldehyde solution and stored in plastic containers. On board at each station few live samples were qualitatively examined under microscope for preliminary analysis of taxonomic composition and dominant species. Taxon-specific phytoplankton abundance were concentrated down to 50 cm**3 by slow decantation after storage for 20 days in a cool and dark place. The species identification was done under light microscope OLIMPUS-BS41 connected to a video-interactive image analysis system at magnification of the ocular 10X and objective - 40X. A Sedgwick-Rafter camera (1ml) was used for counting. 400 specimen were counted for each sample, while rare and large species were checked in the whole sample (Manual of phytoplankton, 2005). Species identification was mainly after Carmelo T. (1997) and Fukuyo, Y. (2000). The cell biovolume of the taxon-specific phytoplankton biomass was determined based on morpho-metric measurement of phytoplankton units and the corresponding geometric shapes as described in detail in (Edier, 1979).

Abundance of mesozooplankton from the S-IT3 cruise in the Sicily Channel in March 2008

The "SESAME_IT3_ZooAbundance_0-50-100m_SZN" dataset contains data of mesozooplankton species composition and abundance (ind. m-3) from samples collected in the Sicily Channel in the early spring of 2008 (17,18 March) during the SESAME-WP2 cruise IT3. Samples were collected by vertical tows with a closing WP2 net (56 cm diameter, 200 µm mesh size) in the following depth layers: 100-200 m, 50-100 m, 0-50 m. Sampling was always performed in light hours with the exception of station S-IT3-03 where zooplankton were collected in dark hours. A flowmeter was applied to the mouth of the net, however, due to its malfunctioning, the volume of filtered seawater was calculated by multiplying the the area by the height of the sampled layer from winch readings. After collection, each sample was split in two halves (1/2) after careful mixing with graduated beakers. Half sample was immediately fixed and preserved in a formaldehyde-seawater solution (4% final concentration) for species composition and abundance. The other half sample was kept fresh for biomass measurements (data already submitted to SESAME database in different files).Here, only the zooplankton abundance of samples in the upper layers 0-50 m and 50-100 m are presented. The abundance data of the samples in the layer 50-100 m will be submitted later in a separate file. The volume of filtered seawater was estimated by multiplying the the area by the height of the sampled layer from winch readings. Identification and counts of specimens were performed on aliquots (1/20-1/5) of the fixed sample or on the total sample (half of the original sample) by using a graduate large-bore pipette. Copepods were identified to the species level and separated into females, males and juveniles (copepodites). All other taxa were identified at the species level when possible, or at higher taxonomic levels. Taxonomic identification was done according to the most relevant and updated taxonomic literature. Total mesozooplankton abundance was computed as sum of all specific abundances determined as explained above.

Abundance and biomass of phytoplankton in the western part of the Black Sea during the R/V Akademik cruise Ak082001 in August 2001

The dataset is composed of 41 samples from 10 stations. The phytoplankton samples were collected by 5l Niskin bottles attached to the CTD system. The sampling depths were selected according to the CTD profile and the in situ fluorometer readings: surface, temperature, salinity and fluorescence gradients and 1 m above the bottom. At some stations phytoplankton net samples (20 µm mesh-size) were collected to assist species biodiversity examination. The samples (1l sea water) were preserved in 4% buffered to pH 8-8.2 with disodiumtetraborate formaldehyde solution and stored in plastic containers. On board at each station few live samples were qualitatively examined under microscope for preliminary analysis of taxonomic composition and dominant species. The taxon-specific phytoplankton abundance samples were concentrated down to 50 cm**3 by slow decantation after storage for 20 days in a cool and dark place. The species identification was done under light microscope OLIMPUS-BS41 connected to a video-interactive image analysis system at magnification of the ocular 10X and objective - 40X. A Sedgwick-Rafter camera (1ml) was used for counting. 400 specimen were counted for each sample, while rare and large species were checked in the whole sample (Manual of phytoplankton, 2005). Species identification was mainly after Carmelo T. (1997) and Fukuyo, Y. (2000). Total phytoplankton abundance was calculated as sum of taxon-specific abundances. Total phytoplankton biomass was calculated as sum of taxon-specific biomasses. The cell biovolume was determined based on morpho-metric measurement of phytoplankton units and the corresponding geometric shapes as described in detail in (Edier, 1979).

MARECHIARA-phytoplankton long-term time-series (1984-2006) at the fixed coastal station in the Gulf of Naples, Southern Tyrrhenian Sea

The "MARECHIARA-phytoplankton" dataset contains phytoplankton data collected in the ongoing time-series at Stn MC ( 40°48.5' N, 14°15' E) in the Gulf of Naples. This dataset spans over the period 1984-2006 and contains data of phytoplankton species composition and abundance. Phytoplankton sampling was regularly conducted from January 1984 till July 1991 and in 1995-2006. Sampling was interrupted from August 1991 till January 1995. The sampling frequency was fortnightly till 1991 and weekly since 1995. Phytoplankton samples were collected at 0.5 m depth using Niskin bottles and immediately fixed with formaldehyde (0.8-1.6% final concentration) for species identification and counts.

Inmovilización de TiO2 sobre polímeros transparentes en el UV-A para la eliminación fotocatalítica de tricloroetileno en aire

El gran desarrollo industrial y demográfico de las últimas décadas ha dado lugar a un consumo crecientemente insostenible de energía y materias primas, que influye negativamente en el ambiente por la gran cantidad de contaminantes generados. Entre las emisiones tienen gran importancia los compuestos orgánicos volátiles (COV), y entre ellos los compuestos halogenados como el tricloroetileno, debido a su elevada toxicidad y resistencia a la degradación. Las tecnologías generalmente empleadas para la degradación de estos compuestos presentan inconvenientes derivados de la generación de productos tóxicos intermedios o su elevado coste. Dentro de los procesos avanzados de oxidación (Advanced Oxidation Processes AOP), la fotocatálisis resulta una técnica atractiva e innovadora de interés creciente en su aplicación para la eliminación de multitud de compuestos orgánicos e inorgánicos, y se ha revelado como una tecnología efectiva en la eliminación de compuestos orgánicos volátiles clorados como el tricloroetileno. Además, al poder aprovechar la luz solar como fuente de radiación UV permite una reducción significativa de costes energéticos y de operación. Los semiconductores más adecuados para su empleo como fotocatalizadores con aprovechamiento de la luz solar son aquellos que tienen una banda de energía comparable a la de los fotones de luz visible o, en su defecto, de luz ultravioleta A (Eg < 3,5 eV), siendo el más empleado el dióxido de titanio (TiO2). El objetivo principal de este trabajo es el estudio de polímeros orgánicos comerciales como soporte para el TiO2 en fotocatálisis heterogénea y su ensayo para la eliminación de tricloroetileno en aire. Para ello, se han evaluado sus propiedades ópticas y su resistencia a la fotodegradación, y se ha optimizado la fijación del fotocatalizador para conseguir un recubrimiento homogéneo, duradero y con elevada actividad fotocatalítica en diversas condiciones de operación. Los materiales plásticos ensayados fueron el polietileno (PE), copolímero de etil vinil acetato con distintos aditivos (EVA, EVA-H y EVA-SH), polipropileno (PP), polimetil (metacrilato) fabricado en colada y extrusión (PMMA-C y PMMA-E), policarbonato compacto y celular (PC-C y PC-Ce), polivinilo rígido y flexible (PVC-R y PVC-F), poliestireno (PS) y poliésteres (PET y PETG). En base a sus propiedades ópticas se seleccionaron el PP, PS, PMMA-C, EVA-SH y PVC-R, los cuales mostraron un valor de transmitancia superior al 80% en el entorno de la región estudiada (λ=365nm). Para la síntesis del fotocatalizador se empleó la tecnología sol-gel y la impregnación multicapa de los polímeros seleccionados por el método de dip-coating con secado intermedio a temperaturas moderadas. Con el fin de evaluar el envejecimiento de los polímeros bajo la radiación UV, y el efecto sobre éste del recubrimiento fotoactivo, se realizó un estudio en una cámara de exposición a la luz solar durante 150 días, evaluándose la resistencia química y la resistencia mecánica. Los resultados de espectroscopía infrarroja y del test de tracción tras el envejecimiento revelaron una mayor resistencia del PMMA y una degradación mayor en el PS, PVC-R y EVA SH, con una apreciable pérdida del recubrimiento en todos los polímeros. Los fotocatalizadores preparados sobre soportes sin tratamiento y con tres capas de óxido de titanio mostraron mejores resultados de actividad con PMMA-C, PET y PS, con buenos resultados de mineralización. Para conseguir una mayor y mejor fijación de la película al soporte se realizaron tratamientos químicos abrasivos con H2SO4 y NaOH y tratamientos de funcionalización superficial por tecnología de plasma a presión atmosférica (APP) y a baja presión (LPP). Con los tratamientos de plasma se consiguió una excelente mojabilidad de los soportes, que dio lugar a una distribución uniforme y más abundante del fotocatalizador, mientras que con los tratamientos químicos no se obtuvo una mejora significativa. Asimismo, se prepararon fotocatalizadores con una capa previa de dióxido de silicio con la intervención de surfactantes (PDDA-SiO2-3TiO2 y SiO2FC-3TiO2), consiguiéndose buenas propiedades de la película en todos los casos. Los mejores resultados de actividad con tratamiento LPP y tres capas de TiO2 se lograron con PMMA-C (91% de conversión a 30 ppm de TCE y caudal 200 ml·min-1) mejorando significativamente también la actividad fotocatalítica en PVC-R y PS. Sin embargo, el material más activo de todos los ensayados fue el PMMA-C con el recubrimiento SiO2FC-3TiO2, logrando el mejor grado de mineralización, del 45%, y una velocidad de 1,89 x 10-6 mol· m-2 · s-1, que dio lugar a la eliminación del 100 % del tricloroetileno en las condiciones anteriormente descritas. A modo comparativo se realizaron ensayos de actividad con otro contaminante orgánico tipo, el formaldehído, cuya degradación fotocatalítica fue también excelente (100% de conversión y 80% de mineralización con 24 ppm de HCHO en un caudal de aire seco de 200 ml·min-1). Los buenos resultados de actividad obtenidos confirman las enormes posibilidades que ofrecen los polímeros transparentes en el UV-A como soportes del dióxido de titanio para la eliminación fotocatalítica de contaminantes en aire. ABSTRACT The great industrial and demographic development of recent decades has led to an unsustainable increase of energy and raw materials consumption that negatively affects the environment due to the large amount of waste and pollutants generated. Between emissions generated organic compounds (VOCs), specially the halogenated ones such as trichloroethylene, are particularly important due to its high toxicity and resistance to degradation. The technologies generally used for the degradation of these compounds have serious inconveniences due to the generation of toxic intermediates turn creating the problem of disposal besides the high cost. Among the advanced oxidation processes (AOP), photocatalysis is an attractive and innovative technique with growing interest in its application for the removal of many organic and inorganic compounds, and has emerged as an effective technology in eliminating chlorinated organic compounds such as trichloroethylene. In addition, as it allows the use of sunlight as a source of UV radiation there is a significant reduction of energy costs and operation. Semiconductors suitable to be used as photocatalyst activated by sunlight are those having an energy band comparable to that of the visible or UV-A light (Eg <3,5 eV), being titanium dioxide (TiO2), the most widely used. The main objective of this study is the test of commercial organic polymers as supports for TiO2 to be applied in heterogeneous photocatalysis and its assay for removing trichloroethylene in air. To accomplish that, its optical properties and resistance to photooxidation have been evaluated, and different operating conditions have been tested in order to optimize the fixation of the photocatalyst to obtain a homogeneous coating, with durable and high photocatalytic activity. The plastic materials tested were: polyethylene (PE), ethyl vinyl acetace copolymers with different additives (EVA, EVA-H and EVA -SH), polypropylene (PP), poly methyl (methacrylate) manufactured by sheet moulding and extrusion (PMMA-C and PMMA-E), compact and cellular polycarbonates (PC-C PC-Ce), rigid and flexible polyvinyl chloride (PVC-R and PVC-F), polystyrene (PS) and polyesters (PET and PETG). On the basis of their optical properties PP, PS, PMMA-C, EVA-SH and PVC-R were selected, as they showed a transmittance value greater than 80% in the range of the studied region (λ = 365nm). For the synthesis of the photocatalyst sol-gel technology was employed with multilayers impregnation of the polymers selected by dip-coating, with intermediate TiO2 drying at moderate temperatures. To evaluate the polymers aging due to UV radiation, and the effect of photoactive coating thereon, a study in an sunlight exposure chamber for 150 days was performed, evaluating the chemical resistance and the mechanical strength. The results of infrared spectroscopy and tensile stress test after aging showed the PMMA is the most resistant sample, but a greater degradation in PS, PVC-R and EVA SH, with a visible loss of the coating in all the polymers tested. The photocatalysts prepared on the untreated substrates with three layers of TiO2 showed better activity results when PMMA-C, PET and PS where used. To achieve greater and better fixation of the film to the support, chemical abrasive treatments, with H2SO4 and NaOH, as well as surface functionalization treatments with atmospheric pressure plasma (APP) and low pressure plasma (LPP) technologies were performed. The plasma treatment showed the best results, with an excellent wettability of the substrates that lead to a better and uniform distribution of the photocatalyst compared to the chemical treatments tested, in which no significant improvement was obtained. Also photocatalysts were prepared with the a silicon dioxide previous layer with the help of surfactants (SiO2- 3TiO2 PDDA-and-3TiO2 SiO2FC), obtaining good properties of the film in all cases. The best activity results for LPP-treated samples with three layers of TiO2 were achieved with PMMA-C (91% conversion, in conditions of 30 ppm of TCE and 200 ml·min-1 air flow rate), with a significant improvement of the photocatalytic activity in PVC-R and PS samples too. However, among all the materials assayed, PMMA-C with SiO2FC-3TiO2 coating was the most active one, achieving the highest mineralization grade (45%) and a reaction rate of 1,89 x 10-6 mol· m-2 · s-1, with total trichloroethylene elimination in the same conditions. As a comparative assay, an activity test was also performed with another typical organic contaminant, formaldehyde, also with good results (100% conversion with 24 ppm of HCHO and 200 ml·min-1 gas flow rate). The good activity results obtained in this study confirm the great potential of organic polymers which are transparent in the UV-A as supports for titanium dioxide for photocatalytic removal of air organic pollutants.

Conformation of coenzyme pyrroloquinoline quinone and role of Ca2+ in the catalytic mechanism of quinoprotein methanol dehydrogenase

The ab initio structures of 2,7,9-tricarboxypyrroloquinoline quinone (PQQ), semiquinone (PQQH), and dihydroquinone (PQQH2) have been determined and compared with ab initio structures of the (PQQ)Ca2+, (PQQH)Ca2+, and (PQQH2)Ca2+ complexes as well as the x-ray structure of (PQQ)Ca2+ bound at the active site of the methanol dehydrogenase (MDH) of methyltropic bacteria. Plausible mechanisms for the MDH oxidation of methanol involving the (PQQ)Ca2+ complex are explored via ab initio computations and discussed. Considering the reaction of methanol with PQQ in the absence of Ca2+, nucleophilic addition of methanol to the PQQ C-5 carbonyl followed by a retro-ene elimination is deemed unlikely due to large energy barrier. A much more favorable disposition of the methanol C-5 adduct to provide formaldehyde involves proton ionization of the intermediate followed by elimination of methoxide concerted with hydride transfer to the oxygen of the C-4 carbonyl. Much the same transition state is reached if one searches for the transition state beginning with Asp-303–CO2−general-base removal of the methanol proton of the (PQQ)Ca2+O(H)CH3 complex concerted with hydride transfer to the oxygen at C-4. For such a mechanism the role of the Ca2+ moiety would be to (i) contribute to the formation of the ES complex (ii) provide a modest decrease in the pKa of methanol substrate,; and (iii) polarize the oxygen at C-5.