Photocatalytic degradation of humic acid in saline waters part 2. Effects of various photocatalytic materials

The present study explores for the first time, the effectiveness of photocatalytic oxidation of. humic acid (HA) in the increasingly important highly saline water. TiO2 (Degussa P25), TiO2 (Anatase), TiO2 (Rutile), TiO2 (Mesoporous) and ZnO dispersions were used as catalysts employing a medium pressure mercury lamp. The effect of platinum loading on P25 and zinc oxide was also investigated. The zinc oxide with 0.3% platinum loading was the most efficient catalyst. The preferred medium for the degradation of HA using ZnO is alkaline, whereas for TiO2 it is acidic. In addition, a comparative study of HA decomposition in artificial seawater (ASW) and natural seawater (NSW) is reported, and the surface areas and band gaps of the catalysts employed were also determined. A spectrophotometric method was used to estimate the extent of degradation of HA. (C) 2003 Elsevier Science B.V. All rights reserved.

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO2 (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 g l(-1); whiled the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure. oxygen, an optimal flow rate was observed at 300 nil min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 ( +/-0.6) kJ mol(-1). (C) 2003 Elsevier Science Ltd. All rights reserved.

The role of atmosphere feedbacks during ENSO in the CMIP3 models. Part III: the shortwave flux feedback

Previous studies using coupled general circulation models (GCMs) suggest that the atmosphere model plays a dominant role in the modeled El Nin ̃ o–Southern Oscillation (ENSO), and that intermodel differences in the thermodynamical damping of sea surface temperatures (SSTs) are a dominant contributor to the ENSO amplitude diversity. This study presents a detailed analysis of the shortwave flux feedback (aSW) in 12 Coupled Model Intercomparison Project phase 3 (CMIP3) simulations, motivated by findings that aSW is the primary contributor to model thermodynamical damping errors. A ‘‘feedback decomposition method,’’ developed to elucidate the aSW biases, shows that all models un- derestimate the dynamical atmospheric response to SSTs in the eastern equatorial Pacific, leading to un- derestimated aSW values. Biases in the cloud response to dynamics and the shortwave interception by clouds also contribute to errors in aSW. Changes in the aSW feedback between the coupled and corresponding atmosphere-only simulations are related to changes in the mean dynamics. A large nonlinearity is found in the observed and modeled SW flux feedback, hidden when linearly cal- culating aSW. In the observations, two physical mechanisms are proposed to explain this nonlinearity: 1) a weaker subsidence response to cold SST anomalies than the ascent response to warm SST anomalies and 2) a nonlinear high-level cloud cover response to SST. The shortwave flux feedback nonlinearity tends to be underestimated by the models, linked to an underestimated nonlinearity in the dynamical response to SST. The process-based methodology presented in this study may help to correct model ENSO atmospheric biases, ultimately leading to an improved simulation of ENSO in GCMs.

Accurate analysis of noble gas concentrations in small water samples and its application to fluid inclusions in stalagmites

The concentrations of dissolved noble gases in water are widely used as a climate proxy to determine noble gas temperatures (NGTs); i.e., the temperature of the water when gas exchange last occurred. In this paper we make a step forward to apply this principle to fluid inclusions in stalagmites in order to reconstruct the cave temperature prevailing at the time when the inclusion was formed. We present an analytical protocol that allows us accurately to determine noble gas concentrations and isotope ratios in stalagmites, and which includes a precise manometrical determination of the mass of water liberated from fluid inclusions. Most important for NGT determination is to reduce the amount of noble gases liberated from air inclusions, as they mask the temperature-dependent noble gas signal from the water inclusions. We demonstrate that offline pre-crushing in air to subsequently extract noble gases and water from the samples by heating is appropriate to separate gases released from air and water inclusions. Although a large fraction of recent samples analysed by this technique yields NGTs close to present-day cave temperatures, the interpretation of measured noble gas concentrations in terms of NGTs is not yet feasible using the available least squares fitting models. This is because the noble gas concentrations in stalagmites are not only composed of the two components air and air saturated water (ASW), which these models are able to account for. The observed enrichments in heavy noble gases are interpreted as being due to adsorption during sample preparation in air, whereas the excess in He and Ne is interpreted as an additional noble gas component that is bound in voids in the crystallographic structure of the calcite crystals. As a consequence of our study's findings, NGTs will have to be determined in the future using the concentrations of Ar, Kr and Xe only. This needs to be achieved by further optimizing the sample preparation to minimize atmospheric contamination and to further reduce the amount of noble gases released from air inclusions.

The moving gardens: Reef fishes grazing, cleaning, and following green turtles in SW Atlantic

Reef fishes may associate with marine turtles and graze on their shells, or clean their head, neck and flippers. on a reef flat at Fernando de Noronha Archipelago, SW Atlantic, we recorded green turtles (Chelonia mydas) grazed, cleaned and followed by reef fishes. The green turtle seeks specific sites on the reef and pose there for the grazers and/or cleaners. Fishes recorded associated to green turtles included omnivorous and herbivorous reef species such as the dam-selfish Abudefduf saxatilis and the surgeonfishes Acanthurus chirurgus and A. coeruleus. The turtle is followed by the wrasse Thalassoma noronhanum only while engaged in foraging bouts on benthic algae. Following behaviour is a previously unrecorded feeding association between turtles and fishes.

Plankton-feeding aggregation and occasional cleaning by adult butterflyfish, Chaetodon striatus (Chaetodontidae), in Southwestern Atlantic

Butterflyfishes of the genus Chaetodon (Chaetodontidae) are mostly bottom-feeders, and juveniles of some Pacific species are known to clean other fish, Herein we report on occasional cleaning by adult individuals of the Western Atlantic butterflyfish Chaetodon striatus, during their plankton-feeding aggregation, Four species of reef fish solicited cleaning to the butterflyfish amidst the aggregation.

Produção de lacases pelo fungo filamentoso de origem marinha Peniophora sp. CBMAI 1063 em biorreator de bancada

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Shear force and torsion in reinforced concrete beam elements: theoretical analysis based on Brazilian Standard Code ABNT NBR 6118:2007

Reinforced concrete beam elements are submitted to applicable loads along their life cycle that cause shear and torsion. These elements may be subject to only shear, pure torsion or both, torsion and shear combined. The Brazilian Standard Code ABNT NBR 6118:2007 [1] fixes conditions to calculate the transverse reinforcement area in beam reinforced concrete elements, using two design models, based on the strut and tie analogy model, first studied by Mörsch [2]. The strut angle θ (theta) can be considered constant and equal to 45º (Model I), or varying between 30º and 45º (Model II). In the case of transversal ties (stirrups), the variation of angle α (alpha) is between 45º and 90º. When the equilibrium torsion is required, a resistant model based on space truss with hollow section is considered. The space truss admits an inclination angle θ between 30º and 45º, in accordance with beam elements subjected to shear. This paper presents a theoretical study of models I and II for combined shear and torsion, in which ranges the geometry and intensity of action in reinforced concrete beams, aimed to verify the consumption of transverse reinforcement in accordance with the calculation model adopted As the strut angle on model II ranges from 30º to 45º, transverse reinforcement area (Asw) decreases, and total reinforcement area, which includes longitudinal torsion reinforcement (Asℓ), increases. It appears that, when considering model II with strut angle above 40º, under shear only, transverse reinforcement area increases 22% compared to values obtained using model I.

Bond strength of adhesives to dentin contaminated with smoker's saliva.

The purpose of this study was to determine the effects of contamination with smoker's and non-smoker's saliva on the bond strength of resin composite to superficial dentin using different adhesive systems. The interfacial structure between the resin and dentin was evaluated for each treatment using environmental scanning electron microscopy (ESEM). Freshly extracted human molars were ground with 600-grit SiC paper to expose the superficial dentin. Adhesives [One-Up-Bond-F-Plus (OUFP) and Adper-Prompt-L-Pop (APLP)] and resin composite (TPHSpectrum) were bonded to the dentin (n = 8/group, 180 total specimens) under five surface conditions: control (adhesive applied following manufacturers' instructions); saliva, then 5-s air dry, then adhesive; adhesive, saliva, 5-s air dry; adhesive, saliva, 5-s water rinse, 5-s air dry (ASW group); and adhesive, saliva, 5-s water rinse, 5-s air dry, reapply adhesive (ASWA group). After storage in water at 37 degrees C for 24 h, the specimens were debonded under tension at a speed of 0.5 mm/min. ESEM photomicrographs of the dentin/adhesive interfaces were taken. Mean bond strength ranged from 8.1 to 24.1 MPa. Fisher's protected least significant difference (P = 0.05) intervals for critical adhesive, saliva, and surface condition differences were 1.3, 1.3, and 2.1 MPa, respectively. There were no significant differences in bond strength to dentin between contamination by smoker's and nonsmoker's saliva, but bond strengths were significantly different between adhesive systems, with OUFP twice as strong as APLP under almost all conditions. After adhesive application and contamination with either smoker's or nonsmoker's saliva followed by washing and reapplication of the adhesive (ASWA group), the bond strength of both adhesive systems was the same as that of the control group.

Signals underlying the induction and expression of long-term, injury-related plasticity in sensory neurons of Aplysia

An important goal in the study of long-term memory is to understand the signals that induce and maintain the underlying neural alterations. In Aplysia, long-term sensitization of defensive reflexes has been examined in depth as a simple model of memory. Extensive studies of sensory neurons (SNs) in Aplysia have led to a cellular and molecular model of long-term memory that has greatly influenced memory research. According to this model, induction of long-term memory in Aplysia depends upon serotonin (5-HT) release and subsequent activation of the cAMP-PKA pathway in SNs. The evidence supporting this model mainly came from studies of long-term synaptic facilitation (LTF) using dissociated (and therefore axotomized) cells growing in culture. However, studies in more intact preparations have produced complex and discrepant results. Because these SNs function as nociceptors, and display similar alterations (long-term hyperexcitability [LTH], LTF, and growth) in models of memory and nerve injury, this study examined the roles of 5-HT and the cAMP-PKA pathway in the induction and expression of long-term, injury-related LTH and LTF in Aplysia SNs. ^ The results presented here suggest that 5-HT is not a primary signal for inducing LTH (and perhaps LTF) in Aplysia SNs. Prolonged treatment with 5-HT failed to induce LTH of Aplysia SNs in either ganglia or dissociated-cell preparations. Treatment with a 5-HT antagonist, methiothepin, during noxious nerve stimulation failed to reduce 24 hr LTH. Furthermore, while 5-HT can induce LTF of SN synapses, this LTF appears to be an indirect effect of 5-HT on other cells. When neural activity was suppressed by elevating divalent cations or by using tetrodotoxin (TTX), 5-HT failed to induce LTF. Unlike LTF, LTH of the SNs could not be produced, even when 5-HT treatment occurred in normal artificial sea water (ASW), suggesting that LTH and LTF are likely to depend on different signals for induction. However, methiothepin reduced the later expression of LTH induced by nerve stimulation, suggesting that 5-HT contributes to the maintenance of LTH in Aplysia SNs.n of somata from the ganglion (which axotomizes SNs) or crushing peripheral n. ^ In summary, this study found that 5-HT and the cAMP-PKA pathway are not involved in the induction of long-term, injury-related LTH of Aplysia SNs, but persistent release of 5-HT and persistent PKA activity contribute to the maintenance of LTH induced by injury. (Abstract shortened by UMI.)^

Nutrients and oxygen concentrations measured in water samples from the North Atlantic during the James Cook cruise JC087 in March 2013

Analysis for micro-molar concentrations of nitrate and nitrite, nitrite, phosphate, silicate and ammonia was undertaken on a SEAL Analytical UK Ltd, AA3 segmented flow autoanalyser following methods described by Kirkwood (1996). Samples were drawn from Niskin bottles on the CTD into 15ml polycarbonate centrifuge tubes and kept refrigerated at approximately 4oC until analysis, which generally commenced within 30 minutes. Overall 23 runs with 597 samples were analysed. This is a total of 502 CTD samples, 69 underway samples and 26 from other sources. An artificial seawater matrix (ASW) of 40g/litre sodium chloride was used as the inter-sample wash and standard matrix. The nutrient free status of this solution was checked by running Ocean Scientific International (OSI) low nutrient seawater (LNS) on every run. A single set of mixed standards were made up by diluting 5mM solutions made from weighed dried salts in 1litre of ASW into plastic 250ml volumetric flasks that had been cleaned by washing in MilliQ water (MQ). Data processing was undertaken using SEAL Analytical UK Ltd proprietary software (AACE 6.07) and was performed within a few hours of the run being finished. The sample time was 60 seconds and the wash time was 30 seconds. The lines were washed daily with wash solutions specific for each chemistry, but comprised of MQ, MQ and SDS, MQ and Triton-X, or MQ and Brij-35. Three times during the cruise the phosphate and silicate channels were washed with a weak sodium hypochlorite solution.

Stratigraphic first occurrence of Emiliania huxleyi in sediments of the Chatham Rise (Table 2)

A quantitative analysis was carried out of planktonic diatoms (biogenic opal) and calcareous nannofossils (biogenic calcite) in late Quaternary sediments (MIS 1-6) from four cores along a N-S transect east of New Zealand from 39°50'S to 50°04'S across the E-W-trending submarine ridge, the Chatham Rise. This was done to trace movements of oceanic fronts and to improve calcareous nannofossil stratigraphy for the last 130 000 yr in the SW Pacific. Sites ODP 1123 and Q 858 are below present day subtropical surface waters north of Chatham Rise. Site DSDP 594 is below present-day mixed temperate-subantarctic surface water south of the rise, and site ODP 1120 is below subantarctic surface water. The more diverse and opportunistic planktonic diatoms provided marker species for subtropical surface waters (Alveus marina, Fragilariopsis doliolus, Rhizosolenia bergonii and Azpeitia nodulifer) and others for subantarctic surface waters (Nitzschia kerguelensis, Thalassiosira lentiginosa). Application of these tracers permits the following conclusions: (1) subtropical conditions persisted north of Chatham Rise throughout the past 130 000 yr, in spite of the cooling of surface waters during colder periods; (2) during warm times (MIS 5 and MIS 3, and in MIS 1), the sporadic occurrence of subtropical species south of Chatham Rise indicates occasional admixture of subtropical surface waters that far south; (3) subantarctic waters extended to the southern slopes of the Chatham Rise during MIS 5b, late MIS 5a to early MIS 4, during the warmer time intervals in early MIS 3, and during latest MIS 3 to early MIS 2; (4) subantarctic frontal conditions existed over southern Chatham Rise during early MIS 4 and late MIS 3 to early MIS 2; and (5) it is probable that during cooler times, MIS 6, MIS 5b, and in MIS 2, intensified particle transport from the Bounty Trough to the northern flank of Chatham Rise occurred by intensified boundary currents. The larger abundance fluctuations in both microfossil groups at the sites south of Chatham Rise than north of Chatham Rise reflect northward shifts of the Circumpolar Subantarctic Water (CSW) and a contemporaneous disappearance of Australasian Subantarctic Water (ASW), implying an elevated temperature gradient between the surface water masses north and south of the Chatham Rise at the times of such northward shifts of CSW. Calcareous nannofossils are less diverse than diatoms, and are less specialised. Some calcareous nannofossil species show abundance shifts at the same time at different latitudes. Two of these abundance shifts can be used for correlation between subtropical and subantarctic sediments in the SW Pacific: (1) reversal in the relative abundance of Calcidiscus leptoporus and Coccolithus pelagicus associated with the MIS 2/1 boundary; and (2) drop in abundance of Gephyrocapsa muellerae or medium-sized Gephyrocapsa at the MIS 4/3 boundary. An additional abundance shift seems to be restricted to subtropical to mixed temperate-subtropical-subantarctic surface waters: (3) increase in abundance of G. muellerae or medium-sized Gephyrocapsa at the beginning of MIS 2 below the Okareka tephra.

Hydrogeochemistry of surface and spring waters in the surroundings of the CO2 injection site at Hontomín–Huermeces (Burgos, Spain)

In this paper the very first geochemical and isotopic data related to surface and spring waters and dissolved gases in the area of Hontomín–Huermeces (Burgos, Spain) are presented and discussed. Hontomín–Huermeces has been selected as a pilot site for the injection of pure (>99%) CO2. Injection and monitoring wells are planned to be drilled close to 6 oil wells completed in the 1980s for which detailed stratigraphical logs are available, indicating the presence of a confined saline aquifer at the depth of about 1500 m into which less than 100,000 tons of iquid CO2 will be injected, possibly starting in 2013. The chemical and features of the spring waters suggest that they are related to a shallow hydrogeological system as the concentration of the Total Dissolved Solids approaches 800 mg/L with a Ca2+(Mg2+)-HCO3− composition, similar to that of the surface waters. This is also supported by the oxygen and hydrogen isotopic ratios that have values lying between those of the Global and the Mediterranean Meteoric Water Lines. Some spring waters close to the oil wells are haracterized by relatively high concentrations of NO3− (up to 123 mg/L), unequivocally suggesting an anthropogenic source that adds to the main water–rock interaction processes. The latter can be referred to Ca-Mg-carbonate and, at a minor extent, Al-silicate dissolution, being the outcropping sedimentary rocks characterized by Palaeozoic to Quaternary rocks. Anomalous concentrations of Cl−, SO42−, As, B and Ba were measured in two springs discharging a few hundred meters from the oil wells and in the Rio Ubierna. These contents are significantly higher than those of the whole set of the studied waters and are possibly indicative of mixing processes, although at very low extent, between deep and shallow aquifers. No evidence of deep-seated gases interacting with the Hontomín–Huermeces waters was recognized in the chemistry of the disolved gases. This is likely due to the fact that they are mainly characterized by an atmospheric source as highlighted by the high contents of N2, O2 and Ar and by N2/Ar ratios that approach that of ASW (Air Saturated Water) and possibly masking any contribution related to a deep source. Nevertheless, significant concentrations (up to 63% by vol.) of isotopically negative CO2 (<−17.7‰ V-PDB) were found in some water samples, likely related to a biogenic source. The geochemical and isotopic data of this work are of particular importance when a monitoring program will be established to verify whether CO2 leakages, induced by the injection of this greenhouse gas, may be affecting the quality of the waters in the shallow hydrological circuits at Hontomín–Huermeces. In this respect, carbonate chemistry, the isotopic carbon of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) and selected trace elements can be considered as useful parameters to trace the migration of the injected CO2 into near-surface environments.

Gas discharges for continental Spain: geochemical and isotopic features

In this work the results of a geochemical and isotopic survey of 37 gas discharges was carried out in continental Spain are presented and discussed. On the basis of the gas chemical composition, four different areas can be distinguished, as follows: 1) Selva-Emborda (SE) region; 2) Guadalentin Valley (GV); 3) Campo de Calatrava (CC) and 3) the inner part of Spain (IS). The SE, GV and CC areas are characterized by CO2-rich gases, while IS has N2 as main gas compound. The CO2-rich gases can be distinguished at their turn on the basis on the helium and carbon isotopic composition. The SE and CC areas have a strong mantle signature (up to 3 Ra). Nevertheless, the carbon isotopic composition of CC is within the mantle range and that of SE is slightly more negative (down to -8‰ PDB). The GV gases have a lower mantle signature (61 Ra) with respect to SE and CC and more negative carbon isotopes (6-10‰ PDB). It is worth to mention that the SE, GV and CC areas are related to the youngest volcanic activity in continental Spain, for example the Garrotxa Volcanic Field in Catalonia records the latest event dated at 10,000 years, and the isotopic features, particularly those of helium, are suggesting the presence of magmatic bodies still cooling at depth. The N2-rich gases, i.e. those from the IS area, has an atmospheric origin, as highlighted by the N2/Ar ratio that ranges between those of air and ASW (Air Saturated Water). The isotopic composition of carbon is distinctly negative (down to -21‰ PDB) and that of helium is typically crustal (0.02-0.08 Ra), confirming that these gas discharges are related to a relatively shallow source.