Catalytic hydrolysis of gaseous HCN over Cu–Ni/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst: parameters and conditions

To decompose efficiently hydrogen cyanide (HCN) in exhaust gas, g-Al₂O₃-supported bimetallicbased Cu–Ni catalyst was prepared by incipient-wetness impregnation method. The effects of the calcination temperature, H₂O/HCN volume ratio, reaction temperature, and the presence of CO or O₂ on the HCN removal efficiency on the Cu–Ni/g-Al₂O₃ catalyst were investigated. To examine further the efficiency of HCN hydrolysis, degradation products were analyzed. The results indicate that the HCN removal efficiency increases and then decreases with increasing calcination temperature and H₂O/HCN volume ratio. On catalyst calcined at 400°C, the efficiency reaches a maximum close to 99% at 480 min at a H₂O/HCN volume ratio of 150. The HCN removal efficiency increases with increasing reaction temperature within the range of 100°C–500°C and reaches a maximum at 500°C. This trend may be attributed to the endothermicity of HCN hydrolysis; increasing the temperature favors HCN hydrolysis. However, the removal efficiencies increases very few at 500°C compared with that at 400°C. To conserve energy in industrial operations, 400°C is deemed as the optimal reaction temperature. The presence of CO facilitates HCN hydrolysis andincreases NH₃ production. O₂ substantially increases the HCN removal efficiency and NO _x production but decreases NH₃ production.

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Photodegradation of Ibuprofen,Cetirizine, and Naproxen by PAN-MWCNT/TiO<Subscript>2</Subscript>–NH<Subscript>2</Subscript> nanofiber membrane under UV light irradiation

Background

In this study, the photodegradation of three pharmaceuticals, namely Ibuprofen (IBP), Naproxen (NPX), and Cetirizine (CIZ) in aqueous media was investigated under UV irradiation. The photocatalyst used in this work consists of surface functionalized titanium dioxide (TiO₂–NH₂) nanoparticles grafted into Polyacrylonitrile (PAN)/multi-walled carbon nanotube composite nanofibers. Surface modification of the fabricated composite nanofibers was illustrated using XRD, FTIR, and SEM analyses.

Results

Sets of experiments were performed to study the effect of pharmaceuticals initial concentration (5–50 mg/L), solution pH (2–9), and irradiation time on the degradation efficiency. The results demonstrated that more than 99% degradation efficiency was obtained for IBP, CIZ, and NPX within 120, 40, and 25 min, respectively.

Conclusions

Comparatively, the photocatalytic degradation of pharmaceuticals using PAN-CNT/TiO₂–NH₂ composite nanofibers was much more efficient than with PAN/TiO₂–NH₂ composite nanofibers.

     

A revised calculation of the econometric factors α- and β for the Extended Exergy Accounting method

Extended Exergy Accounting (“EEA”) is a method to compute the space- and time integral of the primary exergy required to produce a good or a service: the extended exergy of a commodity measures its “embodied exergy”, including externalities (Labour, Capital and Environmental Costa). A crucial point of the method is the calculation of two econometric coefficients, commonly referred to as “α” and “β”,used to calculate the extended exergy equivalents of Labour and Capital respectively. In previous applications of the EEA method, these coefficients have been assigned approximate values estimated on the basis of global system considerations. In this paper, a novel procedure is described that leads to the calculation of “exact” values of both econometric coefficients, based on detailed exergy- and monetary balances of the Society to which the EEA is applied. It is shown that both α and β depend in a non-trivial way from the consumption patterns, the technological level and the life- and socio-economic standards of each Country. It is also shown that the values are substantially different for developed (OECD) and underdeveloped Countries, and representative samples of values are calculated and critically analysed. On the basis of these new model coefficients, the specific exergy equivalents of Labour (ee_L) and of Capital (ee_K) are calculated, and shown to differ from the values used in previous EEA calculations.     

Assessing the impact of biological control of Plutella xylostella through the application of Lotka–Volterra model

The Lotka–Volterra model was applied to the population densities of diamondback moth (DBM), Plutella xylostella (L.) and its exotic larval parasitoid Diadegma semiclausum (Hellen) data that was collected earlier by icipe's DBM biological control team. The collections were done for 15 months before the release and 36 months after release of the parasitoid in two areas; in Werugha, Coast Province of Kenya and Tharuni, Central Province of Kenya, respectively. For each area in pre- and post-release periods, we estimated Lotka–Volterra model parameters from the minimization of the loss function between the theoretical and experimental time-series datasets following the Nelder-Mead multidimensional method. The model estimated a reduction in the value of the steady state of DBM population from 4.86 to 2.17 in Werugha and from 6.11 to 3.76 and 3.45 (with and without exclusion of the time before D. semiclausum recovery) in Tharuni when transiting from the pre- and post-release periods, respectively. This change was a consequence of the newly introduced parasitoid, in the areas. The study presented a successful and detailed technique for non-linear model parameters restoration which was demonstrated by the correct mimicking of empirical datasets from the classical biological control with D. semiclausum, in different areas of Kenya. The applied model has measured the parasitoids impact on the DBM biological control through a quantitative estimate of the effectiveness of the newly introduced species D. semiclausum. These equations may therefore be used as tool for decision making in the implementation for such pests’ management system strategy.     

Evaluation of discrete host–parasitoid models for diamondback moth and Diadegma semiclausum field time population density series

The performance of discrete mathematical models to describe the population dynamics of diamondback moth (DBM) (Plutella xylostella L.) and its parasitoid Diadegma semiclausum was investigated. The parameter values for several well-known models (Nicholson–Bailey, Hassell and Varley, Beddington, Free and Lawton, May, Holling type 2, 3 and Getz and Mills functional responses) were estimated. The models were tested on 20 consecutive sets of time series data collected at 14 days interval for pest and parasitoid populations obtained from a highland cabbage growing area in eastern Kenya. Model parameters were estimated from minimized squared difference between the numerical solution of the model equations and the empirical data using Powell's method. Maximum calculated DBM growth rates varied between 0.02 and 0.07. The carrying capacity determined at 16.5 DBM/plant by the Beddington et al. model was within the range of field data. However, all the estimated parameter values relating to the parasitoid, including the instantaneous searching rate (0.07–0.28), per capita searching efficiency (0.20–0.27), search time (5.20–5.33), handling time (0.77–0.90), and parasitism aggregation index (0.33), were well outside the range encountered empirically. All models evaluated for DBM under Durbin–Watson criteria, except the May model, were not autocorrelated with respect to residuals. In contrast, the criteria applied to the parasitoid residuals showed strong autocorrelations. Thus, these models failed to estimate parasitoid dynamics. We conclude that the interactions of the DBM with its parasitoid cannot be explained by any of the models tested. Two factors may be associated with this failure. First, the parasitoid in this integrated biological control system may not be playing a major role in regulating DBM population. Second, and perhaps more likely, poor correlations reflect gross inadequacies in the theoretical assumptions that underlie the existing models.     

Consideration of fuzziness: Is it necessary in modelling fish habitat preference of Japanese medaka (Oryzias latipes)?

The present study aims to clarify the necessity and effectiveness of considering fuzziness in modelling fish habitat preference, and the advantages which would be achieved by considering it. For this purpose, genetic algorithm (GA) optimized habitat preference models under three different levels of fuzzification were compared with regard to prediction ability of the habitat use of Japanese medaka (Oryzias latipes) dwelling in agricultural canals in Japan. Field surveys were conducted in agricultural canals in Japan to establish a relationship between fish habitat preference and physical environments of water depth, current velocity, lateral cover ratio and percent vegetation coverage. The habitat preference models employed for testing the fuzzy-based approach were category model, fuzzy habitat preference model, and fuzzy habitat preference model with fuzzy inputs. All the models were developed at 50 different initial conditions. The effectiveness of the fuzzification in fish habitat modelling was assessed by comparing mean square error and standard deviation of the models, and fluctuation in habitat preference curves evaluated by each model. As a result, the effect of fuzzification appeared as smoother curves and was found to reduce fluctuation in habitat preference curves in proportion to the level of fuzzification. The smooth curves would be appropriate for expressing uncertainty in habitat preference of the fish, by which fuzzy habitat preference model with fuzzy input achieve the best prediction ability among the models. In conclusion, the present study revealed that there are two advantages of fuzzification: reducing fluctuations in habitat preference evaluation and improving prediction ability of the model. Therefore, the consideration of fuzziness would be appropriate for representing fish habitat preference under natural conditions.     

敬告读者&#183;作者

根据《中国学术期刊综合评价数据库（CAJCED）》2007年6500余种统计刊源析出的350余万条中国期刊引文数据及CNKI“中国期刊网”中心网站2007年全年下载记录（3．1亿余篇次）的大样本数据统计分析得到的年度报告数据,本刊计量指标统计结果为：总被引频次1071、影响因子1．168、5年影响因子1．418、即年指标0．098、他引总引比0．96、被引期刊数396、被引半衰期6．2、2007年载文量82、基金论文比0．98、Web即年下载61．2、H指数（CN）15。     

δ<Superscript>13</Superscript>C and δ<Superscript>15</Superscript>N values in reef corals <Emphasis Type="Italic">Porites lutea</Emphasis> and <Emphasis Type="Italic">P. cylindrica</Emphasis> and in their epilithic and endolithic algae

In summer 1998, shallow water corals at Sesoko Island, Japan (26°38′N, 127°52′E) were damaged by bleaching. In August 2003, partially damaged colonies of the massive Porites lutea and the branching P. cylindrica were collected at depths of 1.0–2.5 m. The species composition of epilithic algal communities on dead skeletal surfaces of the colonies (‘red turfs’, ‘green turfs’, ‘red crusts’) and the endolithic algae (living in coral skeletons) growing close to and away from living coral polyps was determined. Carbon and nitrogen stable isotope values of organic matter (δ¹³C and δ¹⁵N) from all six of these biological entities were determined. There were no significant differences in the isotope composition of coral tissues of the two corals, with P. lutea having δ¹³C of −15.3 to −9.6‰ and δ¹⁵N of 4.7–6.1‰ and P. cylindrica having similar values. Polyps in both species living close to an interface with epilithic algae had similar isotope values to polyps distant from such an interface. Despite differences in the relative abundance of the algal species in red turfs and crusts, their δ¹³C and δ¹⁵N values were not significantly different from each other (−18.2 to −13.9, −20.6 to −16.2, 1.1–4.3, and 3.3 to 4.9‰, respectively). The green algal turf had significantly higher δ¹³C values (−14.9 to −9.3‰) than that of red turfs and crusts but similar δ¹⁵N (1.2–4.1‰) to the red algae. The data do not suggest that adjoining associations of epilithic algae and coral polyps exchange carbon- and nitrogen-containing metabolites to a significant extent. The endolithic algae in the coral skeletons had δ¹³C values of −14.8 to −12.3‰ and δ¹⁵N of 4.0–5.4‰. Thus they did not differ significantly from the coral polyps in their carbon and nitrogen isotope values. The similarity in carbon isotope values between the coral polyps and endolithic algae may be attributed to a common source of CO₂ for zooxanthellae and endolithic algae, namely, from respiration by the coral host. While it is difficult to fully interpret similarity in the nitrogen isotope composition of coral tissue and of green endolithic algae and the difference in δ¹⁵N between green epilithic and endolithic algae, the data are consistent with nitrogen-containing metabolites from the scleractinian coral serving as a significant source of nitrogen for the endolithic algae.     

Influence of arsanilic acid,Cu<Superscript>2+</Superscript>, PO<Subscript>4</Subscript><Superscript>3–</Superscript> and their interaction on anaerobic digestion of pig manure

Arsanilic acid (ASA), copper ion (Cu²⁺) and phosphate (PO₄ ^3–) are widely used as feed additives for pigs. Most of these three supplemented feed additives were excreted in feces and urine. Anaerobic digestion is often used for the management of pig manure. However, the interaction of ASAwith Cu²⁺ or PO₄ ^3– on anaerobic digestion is still not clear. In this study, the influence of ASA, Cu²⁺, PO₄ ^3– and their interaction on anaerobic digestion of pig manure and the possible mechanisms were investigated. The initial concentrations of ASA, Cu²⁺ and PO₄ ^3– were 0.46 mM, 2 mM and 2 mM in the anaerobic digester, respectively. The methanogenesis was severely inhibited in the assays with only ASA addition, only Cu²⁺ addition and ASA + PO₄ ^3– addition with the inhibition index of 97.8%, 46.6% and 82.6%, respectively, but the methanogenesis inhibition in the assay with ASA + Cu²⁺ addition was mitigated with the inhibition index of 39.4%. PO₄ ^3– had no obvious impacts on the degradation of ASA. However, Cu²⁺ addition inhibited the degradation of ASA, and mitigated the methanogenesis inhibition. The existence of ASA would inhibit methanogenesis and generate more toxic inorganic arsenic compounds during anaerobic digestion, implying the limitation of anaerobic digestion for ASA- contaminated animal manure. However, the co-existence of ASA and Cu²⁺ could mitigate the inhibition. These results could provide useful information for the management of anaerobic digestion of pig manure containing ASA and Cu²⁺.

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Covering α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> protection layer on the surface of p-Si micropillar array for enhanced photoelectrochemical performance

The spontaneous oxidation process of pristine silicon (Si) limits its application as photocatalyst or electrode in aqueous solution or moist air. Covering a protection layer on Si surface is an effective approach to overcome this disadvantage. In this paper, α-Fe₂O₃ is demonstrated to be an excellent alternative as a protection material. α-Fe₂O₃ layer was deposited around each p-type Si micropillar (SiMP) in well-ordered array by chemical bath deposition method. The diameter of SiMP was 5 mm and the thickness of α-Fe₂O₃ layer was about 20 nm. The photoeletrochemical stability of SiMP/α-Fe₂O₃ was proved by 10 circles cyclic voltammetry testing. Compared with SiMP, its optical absorption and photocurrent density improved 2 times and 4 times, respectively, and its onset potential for hydrogen evolution moved positively about 0.4 V. These improved performances could be ascribed to the enhanced photogenerated-charge-separation efficiency deriving from built-in electric field at the interface between Si and α-Fe₂O₃. The above results show an effective strategy to utilize Si material as photocatalyst or electrode in aqueous solution or moist air.

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Heterologous expression of <Emphasis Type="Italic">LamA</Emphasis> gene encoded endo-β-1,3-glucanase and CO<Subscript>2</Subscript> fixation by bioengineered <Emphasis Type="Italic">Synechococcus</Emphasis> sp. PCC 7002

The gene for the catalytic domain of thermostable endo-β-1,3-glucanase (laminarinase) LamA was cloned from Thermotoga maritima MSB8 and heterologously expressed in a bioengineered Synechococcus sp. PCC 7002. The mutant strain was cultured in a photobioreactor to assess biomass yield, recombinant laminarinase activity, and CO₂ uptake. The maximum enzyme activity was observed at a pH of 8.0 and a temperature of 70°C. At a CO₂ concentration of 5%, we obtained a maximum specific growth rate of 0.083 h^–1, a biomass productivity of 0.42 g?L^–1?d^–1, a biomass concentration of 3.697 g?L^–1, and a specific enzyme activity of the mutant strain of 4.325 U?mg^–1 dry mass. All parameters decreased as CO₂ concentration increased from 5% to 10% and further to 15% CO₂, except enzyme activity, which increased from 5% to 10% CO₂. However, the mutant culture still grew at 15% CO₂ concentration, as reflected by the biomass productivity (0.26 g?L^–1?d^–1), biomass concentration (2.416 g?L^–1), and specific enzyme activity (3.247 U?mg^–1 dry mass).

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Covering behaviour in <Emphasis Type="Italic">Paracentrotus</Emphasis><Emphasis Type="Italic">lividus</Emphasis>: is light important?

"Covering" or "heaping" behaviour is common to a number of regular echinoids living in a variety of different habitats. Many theories have been proposed to explain this behaviour, among which are several that link covering to light, including ultraviolet (UV) light. However, previous investigations of this light theory have been largely qualitative. In the present study, we used a systematic laboratory protocol to examine quantitatively the covering behaviour of the shallow water echinoid, Paracentrotus lividus, under four different light regimes: white light (400-700 nm), UV-A+B (315-400 nm), UV-A (320-400 nm), and darkness. These experiments demonstrated that light, in particular UV light, influences the covering behaviour of P. lividus. Under the UV regimes, significantly more individuals were found to display covering behaviour, and individuals spent more time at the base of aquaria, farthest from the light source. Moreover, covering items were retained for the longest period of time under the UV-A+B regime. We propose that protection against the harmful effects of UV radiation may be one of the functions of covering behaviour in P. lividus.     

Tissue,ontogenic and sex-related differences in δ<Superscript>13</Superscript>C and δ<Superscript>15</Superscript>N values of the oceanic squid <Emphasis Type="Italic">Todarodes filippovae</Emphasis> (Cephalopoda: Ommastrephidae)

Stable isotopes are increasingly used in the study of trophic interactions of many aquatic animals and most recently cephalopods. To evaluate the application of the method to squids, it is important to assess isotopic differences among and within consumer tissues that may confound the resolution of ecological relationships. Inter- and intra-tissue isotopic variation was examined in 55 individuals of the oceanic squid Todarodes filippovae that were collected at the beginning of April 2000 in the southwestern Indian Ocean (between 44°S, 76°E, and Saint Paul and Amsterdam islands, 38°S, 78°E). Delipidated soft tissues (mantle, arm, buccal mass, gill and reproductive organs) showed small δ¹³C and δ¹⁵N differences, which were probably tissue-specific. A lower carbon value was observed in the digestive gland as a consequence of incomplete lipid removal. Hard tissues, such as beaks and gladii, had lower ¹⁵N values than soft tissues, which can be explained by the presence of chitin, a ¹⁵N-depleted molecule. Females (n = 38) and males (n = 17) had identical δ¹³C values, but females showed higher δ¹⁵N values than males. The difference was size-related rather than sex-related, however, as females were generally larger than males. A comparison of similar-sized females and males produced identical nitrogen values. These data suggest dietary shifts from lower to higher trophic levels during growth, because δ¹⁵N values of large T. filippovae were much higher than that of small specimens. As expected, nitrogen values of lower beaks and gladii of large squids increased from the oldest to the most recently formed region, reflecting the progressive growth of chitinized tissues in parallel with dietary changes. Sequential sampling along the growth increments of squid beaks and gladii can likely be used to produce a chronological record of dietary information throughout an individual’s history.     

Zur Beständigkeit von Aluminiumchloridlösungen mit tridekameren Kationen (Al<Subscript><Emphasis Type="Bold">13</Emphasis></Subscript>)

Background, aim, and scopeThe focus of popular interest on the subject of acid rain has been on the effects, which it has on aquatic ecosystems. Aluminium toxicity and the bioavailability depend on the species of aluminium present. The cationic aluminium species are important for the phytotoxocity and for the precipitation of aluminium containing precipitate.Materials and methodsSpeciation diagrams of aqueous aluminium chloride solutions with tridecameric cations (Al₁₃) at room temperature as function of concentration (1·10^–1–1·10^–5 mol·l^–1 Al) and aging time (9 month) have been obtained from a kinetic method; these Ferron method offers a simple and inexpensive alternative for identification and quantification of aluminium cations.ResultsThe Al₁₃-cation stability decrease with decreasing concentration and increasing aging time.DiscussionPolynuclear aluminium species can be formed in nature by the dissolution of Al-containing minerals, as a consequence of surface water acidification, followed by neutralization process. The question of the occurrence of the tridecameric polycation (Al₁₃) in natural soil solutions and stream waters is of considerable interest.ConclusionsThe results are important on the occurrence of the Al₁₃ in natural waters, for the precipitation of aluminium species by acidification and for the aluminium phytotoxicity.Recommendations and perspectivesThis research suggests strongly that Al₁₃ should be negligible in natural soil and surface waters. The toxicity of Al₁₃ to plants and aquatic organism in natural conditions may be considered to be very low.     

Variability of competition at scales of 10<Superscript>1</Superscript>, 10<Superscript>3</Superscript>, 10<Superscript>5</Superscript>, and 10<Superscript>6</Superscript> m: encrusting arctic community patterns

Variability in interference competition was studied in benthic marine communities of the arctic and subarctic Atlantic intertidal and shallow subtidal zones. We sampled multiple square-metre quadrats at distances of 10¹, 10³, and 10⁵ m apart around the high polar island of Spitsbergen (Svalbard Archipelago). We also took some similar samples in Iceland and in the Faeroe Islands (10⁶ m apart from Spitsbergen samples). Encrusting fauna were present on high arctic intertidal rocks but we only found competitive interactions on subtidal substrata. On subarctic Icelandic and Faeroese shores, in contrast, spatial competition was common even in the intertidal zone. Analysis of variance of competition intensity data (numbers of interactions per area) revealed multiple factors to be significant influences explaining variability. Amongst the 10¹-, 10³-, and 10⁵-m spatial scales, only the largest emerged as a significant term. Whether intra- or interspecific competition dominated the types of interactions varied greatly between sites: 21–97% of competition was intraspecific. The proportion of competitive encounters resulting in a decided outcome (i.e. a win for one competitor and a loss for the other, rather than a tie or standoff between them) showed little variability at any scale. All the values of competition transitivity (how hierarchical a pecking order is) were very high compared to values reported in the literature from any other (polar or non-polar) locality. Variability in this measure was generally <10% across scales. We conclude from our data that great care must be taken in interpreting patterns of competition between similar taxa in large-scale space or time. Not only did most aspects of competition in our study communities vary significantly at the 10⁵-m scale but different aspects of competition varied at different scales and by hugely different amounts.Communicated by J.P. Thorpe, Port Erin     

TiO<Subscript><Emphasis Type="Bold">2</Emphasis></Subscript> nanoparticles – Relationship between dispersion preparation method and ecotoxicity in the algal growth test

PurposeLittle is known about the ecotoxicity of nanomaterials and there are no specific guidelines for sample preparation and testing. We set out to establish whether the method used to prepare TiO₂ dispersions had a significant impact on aquatic ecotoxicity. We also followed the formation of agglomerates during the incubation period.MethodsWe applied the algal growth inhibition test (OECD test guideline no. 201). Dispersions were prepared by stirring and/or ultrasonication for different durations, and by filtration according to an OECD procedure recommended for testing difficult substances.ResultsSamples stirred for 7?d were not toxic, but EC₂₀ values could be calculated for all the other treatments. Shorter treatments generated EC₂₀ values in the range 1–27?mg/L. Only the shortest treatment (1 min stirring, 1 min ultrasonication) produced an unusually high EC₂₀ value, indicating low toxicity. Development of agglomerate size and of toxicity depends on the nanoparticles. We found that ecotoxicity was predominantly caused by a fraction of nanoparticles and agglomerates obtained by passing dispersions through a 0.22-µm filter.ConclusionsWe propose a short treatment regime to generate the most relevant ecotoxicity data for TiO₂, for example stirring for 1?min followed by 3 min ultrasonication. Until more data concerning the ecotoxicity of different fractions are available, we recommend the testing of unfiltered dispersions rather than filtrates. Relating ecotoxicity to the total hydrodynamic surface of the nanomaterials rather than concentration does not seem to improve the accuracy of ecotoxicity assessments using the algal growth inhibition test.