Endeavors on the development of efficient and sustainable supported metal catalysts for chemical synthesis on solid–liquid interfaces

Supported metal catalysts, particularly for precious metals, have gained increasing attention in green synthetic chemistry. They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue, as well as reusability of the high-cost catalysts. Although great effort has been spent, the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable r...     

Microbial quality and physical–chemical characteristics of thermal springs

Microbial quality and physical–chemical properties of recreational spas were surveyed to investigate the health aspect of the spas’ water. A total of 195 samples were collected from pools and springs of the spas in five sites from Ardebil Province of Iran. The effects of an independent factor defined as ‘condition’ and its component sub-factors (i.e., sampling point, location, and sampling date) on microbial quality and physical–chemical properties of the spas were studied by applying path analysis. The influence of physical–chemical properties on microbial quality was also considered. The percentage of samples exceeding the ISIRI (Swimming pool water microbiological specifications (vol 9412), Institute of Standards and Industrial Research of Iran, Tehran, 2007) limits for Staphylococcus (spp.) was up to 55.8 in the springs and 87.8 in the pools, 58.1 and 99.2 for HPC, 90.7 and 97.8 for total coliform and fecal coliform, and 9.3 and 34.4 for Pseudomonas aeruginosa, respectively. There were significant differences between the pools and springs for both physical–chemical properties and microbial quality. From the path analysis, sampling point was the most effective sub-factor of ‘condition’ on both the physical–chemical properties and microbial quality. Among the physical–chemical properties, water color had the most enhancing or additive influence on microbial pollution, while EC indicated a reducing or subtractive effect.     

Statistical interpolation model for the description of ground pollution due to the TCDD produced in the 1976 chemical accident at seveso in the heavily contaminated zone “A”;

The influence of NTA on chromium genetic activity was studied in the D7 strain of Saccharomyces cerevisiae. At low dose (subgenotoxic) of sodium chromate (CrVI) (5mM), NTA increased the point mutation while at higher dose (25 mM) of chromate in the presence of NTA a decrease of point reverse mutation was observed. Probably NTA affected either the uptake of Cr(VI) favouring the intracellular reduction to Cr(III), or the recombinational repair of DNA breaks induced by chromate oxiding activity.

An increase of point (reverse) mutation was obtained in the experiments with NTA and chromium chloride, suggesting the hypothesis that NTA might interact with Cr(III) forming NTA‐Cr(III) complexes able to permeate cellular membranes and bind to DNA. In addition NTA genetic inactivity was confirmed.     

Quality of groundwater contaminated by leachates from seven Polish landfills – chemical and ecotoxicological classifications

The article presents the results of screening research on acute toxicity of groundwater contaminated by leachates to the bacterium Vibrio fischeri (ToxAlert 100® test) and crustacean Daphnia magna (Daphtoxkit F? magna test according to PN-EN ISO 6341), as well as on chronic toxicity to D. magna (test according to ISO 10706). The groundwater samples were taken from seven large city landfills in the Pomeranian province (Poland), which were open before 1990 and designed without proper attention to being leak-tight. Due to the lack of either European or Polish classification of ecotoxicological qualities of surface and underground waters, an attempt was made to evaluate the ecotoxicological quality of the examined waters on the basis of the Helsinki Committee's recommendations for industrial effluents, the classification of sediment according to Krebs (Krebs F. The pT-value as a classification index in aquatic toxicology. GIT Edition Umweltanalytik-Umweltschutz 1988;1:57–63) and the classification system of toxicity levels for natural waters and sewers, recently proposed by Persoone et al. (Persoone G, Marsalek B, Blinova, I, Törökne A, Zarina D, Manusadzianas L, Nalecz-Jawecki G, Tofan L, Stepanova N, Tothova L, Kolar B. A practical and user-friendly toxicity classification system with microbiotests for natural waters and wastewaters. Environ. Toxicol. 2003;18 (6):395-402).     

Trends of chemical speciation profiles of anthropogenic volatile organic compounds emissions in China, 2005–2020

This study estimates the detailed chemical profiles of China＇s anthropogenic volatile organic com- pounds （VOCs） emissions for the period of 2005-2020. The chemical profiles of VOCs for seven activity sectors are calculated, based on which the Photochemical Ozone Creation Potential （POCP） of VOCs for these sectors is evaluated. At the national level, the VOCs species emitted in 2005 include alkanes, alkenes and alkynes, aromatic compounds, alcohols, ketones, aldehydes, esters, ethers and halocarbons, accounting for 26.4wt.%, 29.2wt.%, 21.3 wt.%, 4.7 wt.%, 5.4 wt.%, 1.7 wt.%, 2.1 wt.%, 0.7 wt. % and 2.2wt.% of total emissions, respectively. And during 2005-2020, their mass proportions would respec- tively grow or decrease by - 34.7%, -48.6%, 108.5%, 6.9%, -32.7%, 7.3%, 65.3%, 100.5%, and 55.4%. This change would bring about a 13% reduction of POCP for national VOCs emissions in the future. Thus, although the national VOCs emissions are expected to increase by 33% over the whole period, its ozone formation potential is estimated to rise only by 14%. Large discrepancies are found in VOCs speciation emissions among provinces. Compared to western provinces, the eastern provinces with a more developed economy would emit unsaturated hydrocarbons and benzene with lower mix ratios, and aromatic compounds except benzene, oxidized hydrocar- bons and halocarbons with higher mix ratios. Such differences lead to lower POCP of VOCs emitted in eastern provinces, and higher POCP of VOCs emitted in western provinces. However, due to the large VOCs emissions from Chinese eastern region, the ozone forma- tion potential of VOCs emission in eastern provinces would be much higher than those in western provinces by about 156%-235%.     

Basis for a national strategy for integrated coastal zone management—in Portugal

This paper includes the proposals made in the report “Basis for a National Strategy for Coastal Zone Management” prepared for the Portuguese Ministry of Environment, Territorial Planning and Regional Development. The final version of that report was presented in June 2006. This paper describes a theme framework followed by a discussion of concepts. Nine Primary Principles, eight Principal Objectives, and 37 Strategic Options for an Integrated Coastal Zone Management are then presented. These Strategic Options are set hierarchically according to their sequential priority, identifying the dominant types of Associated Measures. The analysis of these arrives at a set of Structural Measures, which interlink and aggregate various actions and propose a new method of integrated management for the coastal zone, which includes the “Legal Basis of Coastal Zone”; the Organization System; the Action Plan and Monitoring.     

Up to 95 % reduction of chemical oxygen demand of slaughterhouse effluents using Fenton and photo-Fenton oxidation

Meat industries produce effluents containing high concentrations of organic and inorganic compounds, which must be removed before being discharged or reused. Advanced oxidation processes using Fenton reaction coupled with UV, solar radiation, and electrochemical oxidation are promising methods. Here, we treated the effluent from an anaerobic digester using: (a) the photoelectro-Fenton process, using a system with a Ti-RuO₂ anode and a carbon felt cathode, (b) the solar photo-Fenton process, using a batch reactor and a compound parabolic collector, and (c) a combination of Fenton and solar photo-Fenton processes. The effluent had an initial chemical oxygen demand (COD) of 1159 mgL^?1, and we obtained high removal efficiencies of COD, up to 95 %, using the combination of Fenton and solar photo-Fenton processes.     

Does defoliation induce chemical and morphological defenses in the leaves of silver birch seedlings under changing climate?

Summary.  We examined the effects of defoliation con-currently with elevated temperature and CO₂ on some chemical and morphological characteristics in the leaves of silver birch seedlings (Betula pendula). We also analyzed the consequent changes in the palatability of leaves for adult blue alder leaf beetles (Agelastica alni). Under the different climatic treatments, the seedlings were subjected to three fertilizer treatments (0 kg, 130 kg and 270 kg N ha⁻¹) and defoliation treatments (0%, 25% and 50% of the total leaf area). In each climatic treatment, fertilization increased the nitrogen content in the leaves, but decreased total concentrations of soluble phenolics, detected by high-performance liquid chromatography (HPLC), and insoluble condensed tannins. Defoliation, both independently and in combination with elevated temperature and CO₂, decreased the concentrations of the phenolics. Compared to the intact controls, the leaves of the defoliated seedlings were smaller and tougher. Under elevated temperature, the beetles consumed a smaller amount of the leaves of plants subjected to the high fertilization, while under ambient climatic conditions, fertilization increased the feeding. The total leaf consumption was higher under the ambient climatic conditions than under elevated temperature, elevated CO₂ or the combination of elevated temperature and CO₂.     

Within-plant allocation of a chemical defense in Secale cereale. Is concentration the appropriate currency of allocation?

Summary. The among-leaves allocation of DIBOA, a hydroxamic acid associated with plant resistance, in the shoot of rye (Secale cereale) was evaluated over the vegetative development of the plant. The appropriateness of using the concentration of secondary metabolites, DIBOA in this case, as the parameter to evaluate defense allocation in plants is discussed. Both biological and statistical arguments are put forward to suggest that allocation of chemical defenses should refer to absolute content and not to concentration. Results showed that leaf age was significantly linked to leaf concentration of DIBOA, young leaves having higher concentrations. In contrast, leaf content of DIBOA, our proposed currency of allocation, was not significantly higher in younger leaves. Furthermore, a regression analysis showed that the DIBOA content of leaves was better explained by the leaf relative biomass (proportion of shoot biomass) than by leaf biomass itself. It is suggested that, rather than leaf age, leaf relative biomass is the major factor determining DIBOA allocation in rye shoots. It is proposed that studies addressing within-plant defense allocation should use chemical defense content as the currency, emphasizing the major factors driving this process and its underlying mechanisms. Likewise, it is proposed that studies aiming at characterizing optimal patterns of plant defense should use chemical defense concentration as the currency, and be accompanied by evaluations of the actual resistance against herbivores of the plant parts analyzed, together with the effect on plant fitness. Received 19 February 1999; accepted 28 April 1999.     

Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

The relation between chemical structure and mutagenic activity of some polycyclic aromatic sulfur heterocycles (s‐pah)

Results of Hückel Molecular Orbital (HMO) calculations strongly suggest identical metabolic activation routes for the mutagen benzo[2,3]phenanthro[4,5‐bcd]thiophene and its homocyclic parent, benzo[a]pyrene.     

Chemical communication in green and golden bell frogs: do tadpoles respond to chemical cues from dead conspecifics?

Captive bred animals often lack the ability of predator recognition and predation is one of the strongest causes of failure of breed and release projects. Several tadpole and fish species respond defensively to chemical cues from injured or dead conspecifics, often referred to as alarm pheromones. In natural conditions and in species that school, the association of chemical cues from predators to alarm pheromones released by attacked conspecifics may lead to the learning of the predator-related danger without experiencing an attack. In the laboratory, this chemical communication can also be used in associative learning techniques to teach naïve tadpoles to avoid specific predators and improve survivorship of released animals. In our experimental trials, tadpoles of the threatened green and golden bell frog (Litoria aurea) did not avoid or decrease their activity when exposed to solutions of conspecific macerate, suggesting that the chemicals released into the water by dead/injured conspecifics do not function as an alarm pheromone. This non-avoidance of dead conspecific chemicals may explain why green and golden bell frog tadpoles have seemingly not developed any avoidance behaviour to the presence of introduced mosquito fish, and may render attempts to teach naïve tadpoles to avoid this novel predator more difficult.     

Niche complementarity for nitrogen: an explanation for the biodiversity and ecosystem functioning relationship?

The relationship between plant diversity and productivity has largely been attributed to niche complementarity, assuming that plant species are complementary in their resource use. In this context, we conducted an 15N field study in three different grasslands, testing complementarity nitrogen (N) uptake patterns in terms of space, time, and chemical form as well as N strategies such as soil N use, symbiotic N fixation, or internal N recycling for different plant species. The relative contribution of different spatial, temporal, and chemical soil N pools to total soil N uptake of plants varied significantly among the investigated plant species, within and across functional groups. This suggests that plants occupy distinct niches with respect to their relative N uptake. However, when the absolute N uptake from the different soil N pools was analyzed, no spatial, temporal, or chemical variability was detected, but plants, and in particular functional groups, differed significantly with respect to their total soil N uptake irrespective of treatment. Consequently, our data suggest that absolute N exploitation on the ecosystem level is determined by species or functional group identity and thus by community composition rather than by complementary biodiversity effects. Across functional groups, total N uptake from the soil was negatively correlated with leaf N concentrations, suggesting that these functional groups follow different N use strategies to meet their N demands. While our findings give no evidence for a biodiversity effect on the quantitative exploitation of different soil N pools, there is evidence for different and complementary N strategies and thus a potentially beneficial effect of functional group diversity on ecosystem functioning.     

Ecological and evolutionary mechanisms for low seed: ovule ratios: need for a pluralistic approach?

Central to the ecology and evolution of a broad range of plants is understanding why they routinely have submaximal reproduction manifested as low seed : ovule and fruit : flower ratios. We know much less about the processes responsible for low seed : ovule ratios than we do for fruit : flower ratios. Current hypotheses for low seed : ovule ratios are largely drawn from those for fruit : flower ratios, including proximate (ecological) causes of pollen limitation, resource limitation, and pollen quality, as well as the ultimate (evolutionary) hypothesis of "bet hedging" on stochastic pollination. Yet, such mechanisms operating on fruit : flower ratios at the whole-plant level may not best explain low seed : ovule ratios at the individual-flower level. We tested each of these proximate and ultimate causes for low seed : ovule ratios using the specialized pollination mutualism between senita cacti (Pachycereus schottii) and senita moths (Upiga virescens). Seed : ovule ratios were consistently low (approximately 0.61). Such excess ovule production by senita likely has a strong genetic component given the significant differences among plants in ovule number and the consistency in ovule production by plants within and among flowering seasons. Excess ovule production and low seed : ovule ratios could not be explained by pollen limitation, resource limitation, pollen quality, or bet hedging. Nevertheless, phenotypic selection analyses did show significant selection gradients for increased ovule number, suggesting that other evolutionary processes may be responsible for excess ovule production and low seed : ovule ratios. In contrast, low fruit : flower ratios at the whole-plant level were explained by an apparent equilibrium between pollen and resource limitation. Thus, mechanisms responsible for low fruit : flower ratios at the whole-plant level are not necessarily in accord with those of low seed : ovule ratios at the individual-flower level. This suggests that we may need to adopt a more pluralistic approach to seed : ovule ratios and consider alternative hypotheses, including a greater array of proximate and ultimate causes. Initial results of this study suggest that floral allometry, selection on correlated floral traits, stigma clogging with pollen grains, and style clogging with pollen tubes may provide promising avenues for understanding low seed : ovule ratios.     

Wastewater management for hazardous chemicals ‐ disposal of ammonium perchlorate wastes from propellant production for space vehicles

An attempt to depict the wastewater treatment system for the production of ammonium perchlorate, a component of solid propellant used in space vehicles, has been made. The waste‐water management system uses solar ponds and seawater dilution for the retention and disposal of the undesirable constituents of the wastewater. The details of the wastewater generation and its treatment are highlighted in this paper.     

Trace analysis of off-flavor/odor compounds in water using liquid-liquid microextraction coupled with gas chromatography—positive chemical ionization-tandem mass spectrometry

A rapid, inexpensive and laboratory friendly method was developed for analysis of off-flavor/odor compounds in fresh and salt water using gas chromatography with chemical ionization-tandem mass spectrometry. Off-flavor/odor compounds included geosmin, 2- methylisoborneol (MIB), 2-isobutyl-3-methyoxypyrazine (IBMP), and 2-isopropyl-3-methoxypyrazine (IPMP). Using this method, a single sample can be extracted within minutes using only 1 mL of organic solvent. The ion transitions for IPMP, IBMP, MIB, and geosmin were 153>121, 167>125, 152>95, and 165>109, respectively. The linearity of this method for analyzing MIB ranged from 4 to 200 ng·L^–1, and from 0.8 to 200 ng·L^–1 for the other analytes. Method recoveries ranged from 97% to 111% and percent relative standard deviations ranged from 3% to 9%, indicating that the method is accurate, precise, and reliable.     

Characterization of chemical species in universal sampler (PM2.5 and PM2.5–10) aerosols in suburban area of central Taiwan

Aerosol samples of particulate and chemical species for PM₁₀ (particulate matter with aerodynamic diameters less than 10 μm) collected by Universal sampler were studied from June to August 1998 in the suburban area of central Taiwan. The ratios of PM_2.5/PM_2.5–10 displayed that the fine particles (particle size < 2.5 μm) are prevailing in the suburban site. Ion Chromatography was used to analyze for the water‐soluble ions: sulphate and nitrate in the Universal samples. Also, the collected samples were analyzed by atomic absorption spectrophotometry for the elemental analysis of Ca, Fe, Pb, Cu and Cr. The results indicated that the crustal elements (Ca and Fe) and resuspended matters were dominated in the coarse particulate mode while the anthropogenic elements (Cr, Pb, Cu) and sulphate components are mainly in the fine particle fraction. The results also showed that the sulphate and nitrate make the largest portion of the chemical species collected by Universal sampler (PMio). The concentrations of heavy metals in THU are generally high, owing to the higher motor vehicle and industrial density nearby. The degree of pollution from this source differs from day to day, depending on the motor vehicle density.     

A ‘coastal-hazard GIS’ for Sri Lanka

Following the 2004 tsunami disaster in Sri Lanka, it was apparent that mapping the coast’s vulnerability was essential for future protection of the local populations. We therefore developed a prototype ‘Coastal-hazard GIS’ for Sri Lanka so as to provide an effective tool for decision makers to limit the impact of natural coastal hazards such as sea level rise, tsunamis, storm surges and coastal erosion, and thus protect the exposed assets (population, property, settlements, communications networks, etc.). The prototype was developed on a pilot site in Galle through building up homogeneous data on the land/sea interface from studies conducted on the exposure of the coastal populations, the aim being to enable an evaluation of the hazards combined with the vulnerability and thus an analysis of the risks. Coastal risk scenarios are developed so as to estimate the impacts and consequences of an event (tsunami, storm, etc.) on the assets, the principle behind this being that if, in general, the coastal hazard cannot be decreased, then a better knowledge of it through simulation should make it possible to limit the vulnerability and thus the risk. The Coastal-hazard GIS will also provide a planning tool in terms of locating new settlements, expanding urban areas, siting coastal protection works, etc.