Technical and environmental long-term properties of industrial residues--summary of field and laboratory investigations

In Sweden, use of industrial residues is still hindered by concern for their long-term properties. A three-year research project was therefore initiated aiming to (1) identify the crucial processes of ageing related to the usefulness of residues in roads; (2) investigate the consequences of these processes for technical and environmental properties of the residues, and (3) propose a method for accelerated ageing to predict the long-term properties. This paper gives an overview of the project methodology, a summary of the test results and references to papers where further details are given.The project, running through 2006-2008, compared naturally aged samples of two residues used as sub-bases in existing asphalt paved roads with samples of fresh residues from producers’ piles. Steel slag of electric arc furnace (EAF) type and municipal solid waste incinerator (MSWI) bottom ash were chosen. The samples were thoroughly characterised in order to identify which ageing processes had been crucial.The results showed that:

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Bottom ash from the pavement edge was more aged than bottom ash from the road centre. However, no difference in pH was found, instead the differences were caused by differences in water exposure.

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Steel slag from the pavement edge showed traces of carbonation and leaching processes, whereas slag from the road centre was identical to fresh slag.

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Water exposure to the subbase materials after ten years in an asphalt paved road was calculated to less than 0.1-0.5 litres per kg.

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Ageing reactions in steel slag and MSWI bottom ash, ready for use, were too small to be verified by laboratory measurement of deformation properties under loaded conditions.

An accelerated ageing test for steel slag was set up to achieve the carbonation (decrease in pH) and leaching that was observed in the pavement edge material.An accelerated ageing test for bottom ash was set up to achieve the pozzolan reactions that were observed in SEM analyses of in situ specimens.It is recommended to use uncrushed particles when properties of aged material are studied, in order to preserve the original particle surfaces.     

Preparation and Characterization of Polyaniline and Ag/ Polyaniline Composite Nanoporous Particles and Their Antimicrobial Activities

Polyaniline (PANI) and Ag/PANI nanoporous composite were prepared by an oxidative polymerization method. The oxidation process of PANI nanoparticles was occurred using (NH₄)₂S₂O₈ while the oxidation process of Ag/PANI nanoporous composite was occurred using AgNO₃ under the effect of artificial radiation. The structural, morphological, and optical properties of the PANI and Ag/PANI nanoporous structures were studied using different characterization tools. The results confirm the formation of polycrystalline nanoporous PANI and spherical nanoporous composite of Ag/PANI particles. Antibacterial activity tests against gram-positive bacteria, Bacillus subtilis and Staphylococcus aureus, and gram-negative bacteria, Escherichia coli, and Salmonella species were carried out using different concentrations of PANI nanoparticles and Ag/PANI nanoporous composites. PANI has not antibacterial effect against all studied pathogens. In contrast, Ag/PANI nanoporous composites possessed antibacterial activity that is identified by the zone of inhibition. The inhibition zones of bacteria are in order; Salmonella species?>?S. aureus?>?B. subtilis?>?E. coli. The inhibition zones of all bacteria increased with increasing concentrations of Ag/PANI nanoporous composites from 200 to 400 ppm then decreased with further increasing of the dose concentrations to 600 ppm. Finally, a simplified mechanism based on the electrostatic attraction is presented to describe the antimicrobial activity of Ag/PANI nanoporous composite.     

Effect of Varying Filler Concentration on Zinc Oxide Nanoparticle Embedded Chitosan Films as Potential Food Packaging Material

Prevailing scenario of non-biodegradable food packaging materials worldwide was the motivation for this research. More than half of the packaging materials used today are non-biodegradable and lack one or the other feature that keeps it from being an ideal food packaging material. Based on the current need of food grade packaging materials, the present study illustrates the amelioration of the properties of biodegradable chitosan films with the incorporation of zinc oxide (ZnO) nanoparticles in varying concentration. The ZnO nanoparticles (ZnONPs) used as fillers in the chitosan films were synthesized by supersaturation method. They were characterized using UV–visible spectrophotometry, X-ray diffraction and field emission scanning electron microscopy (FE-SEM). The particles were observed to be around 100–200 nm in size. The chitosan films with varying concentration of ZnONPs were synthesized and characterized using Fourier transform infrared spectroscopy and FE-SEM. The films were studied for their thermal stability, water vapor transmission rate (WVTR) and mechanical properties. The thermal stability, as determined by Thermo Gravimetric Analysis and Differential Scanning Calorimetry increased slightly with increasing percentage of embedded ZnONPs while a substantial decrease in WVTR was observed. Mechanical properties also showed improvements with 77% increment in tensile modulus and 67% increment in tensile strength. The antimicrobial activity of the films was also studied on gram positive bacterium Bacillus subtilis (B. subtilis) and gram negative bacterium Escherichia coli (E. coli) by serial dilution method. A twofold and 1.5-fold increment in the antimicrobial activity was observed for B. subtilis and E. coli, respectively, with increased ZnONPs concentration in the films from 0(w/w) to 2%(w/w). Films thus prepared can prove to be of immense potential in the near future for antimicrobial food packaging applications.     

In situ burning of emulsions R&D in Norway

SINTEF Applied Chemistry has been working in the field of in situ burning since 1988, beginning with the first open water testing of the 3M fire proof boom which took place on Spitsbergen. In recent years, the focus of SINTEF's research activities in this area has been on the burning of emulsions. An experimental programme was initiated by NOFO in 1990 to study the in situ burning of water-in-oil (w/o) emulsions, as part of a wider NOFO programme ‘Oil spill contingency in Northern and Arctic waters’ (ONA). The research conducted under this programme has addressed many areas of in situ burning including:

• •• study of processes governing burning emulsions
• •• development of ignition techniques for emulsions
• •• effect of environmental conditions on burning
• •• burning crude oil and emulsions in broken ice
• •• uncontained burning of crude oil and emulsions.

     

Biodegradability and Thermal Properties of Novel Natural Rubber/Linear Low Density Polyethylene/Thermoplastic Starch Ternary Blends

This work aimed to prepare biodegradable thermoplastic elastomers based on NR/LLDPE/TPS ternary simple blends to achieve some exclusive properties, i.e., good biodegradability in terms of water absorption and weight loss after burial, together with reasonable mechanical and thermal properties. A comparative study on biodegradability and other related properties of NR/LLDPE binary and NR/LLDPE/TPS ternary blends was performed. It was found that increasing the TPS proportion decreased storage modulus and complex viscosity. In addition, the size of dispersed TPS domains in the NR/LLDPE co-continuous matrix increased with TPS proportion, while the mechanical properties in terms of 100% moduli, tensile strength, elongation at break, and hardness decreased. This might be attributed to decreased interfacial adhesion with increasing size of TPS domains. Furthermore, increasing the TPS loading in the blend reduced the temperatures for 5 or 50% mass loss (T₅ or T₅₀) and the degradation temperature (T _d ). However, the biodegradability improved, in terms of increased water absorption and weight loss after burial in soil, with the loading level of TPS.     

Overview of the Compensation and Liability Regimes Under the International Oil Pollution Compensation Fund (IOPC)

This paper focuses on the cost recovery issues arising through the operation of the International Oil Pollution Compensation Fund (IOPC) and administrative matters which arose following the Braer and Sea Empress oil tanker pollution incidents in the UK. Each of these oil spills brought very different problems.Any major oil spill will have prolonged economic and social consequences for the communities affected. Membership of the International Oil Pollution Compensation Fund (IOPC Fund) will do much to soften the impact as regards economic damage. However, the operation of the Fund brings difficulties which may not have been considered by the administration prior to the spill. Some of the difficulties are foreseeable.It covers details of the international compensation and liability regimes, it considers a number of administrative consequences and highlights seven lessons that have been learned in the UK in the light of recent experience. These lessons are:

• •Claims may not be paid quickly or in full.
• •Claimants will need advice and government involvement.
• •Action by the government may be needed to complement the IOPC Fund.
• •Governments have to balance their obligations as a member state with the needs of claimants.
• •It is better for claimants to keep matters out of court for as long as possible.
• •Administrative consequences will continue for a long time after the oil has been cleared from the shoreline.
• •Each major oil spill brings different cost recovery problems and will also bring demands ‘to learn the lessons’.

In much the same way as contingency plans are regularly tested, each state party to the regime would be wise, from time to time, to think through the likely scenarios so as to better prepare themselves in the light of experiences elsewhere. The United Kingdom has had rather more experience in recent years than it would have wished!     

Comparison of three ornamental plants for phytoextraction potential of chromium removal from tannery sludge

Based on pre-experimentation, three ornamental plants, Mirabilis jalapa, Impatiens Balsamin (I. Balsamin) and Tagetes erecta L., were selected as target plants to study the phytoextraction of chromium (Cr) in tannery sludge irrigated with four treatments according to Cr concentration gradient [Control (CK); 20.50 × 10³ mg kg^?1 (T1); 51.25 × 10³ mg kg^?1 (T2); 102.50 × 10³ mg kg^?1 (T3)]. Results of pot experiments showed that the biomass of Mirabilis jalapa and Tagetes erecta L. had no significant differences among the four treatments, while I. Balsamin showed a decline trend in the biomass with the increase of Cr concentration, probably due to some extent to the poisoning effect of Cr under treatment T2 or T3. Mirabilis jalapa accumulated Cr concentration, with 408.97, 124.97, 630.16 and 57.30 mg kg^?1 in its roots, stems, leaves and inflorescence, respectively. The translocation factor and the bioaccumulation coefficient of Mirabilis jalapa are each greater than 1, indicating that Mirabilis jalapa has the strong ability to tolerate and enrich Cr by biological processes. Comparing accumulation properties of the three ornamental plants, in the amount and allocation, Mirabilis jalapa showed the highest phytoextraction efficiency and could grow well at the high Cr concentration. Our experiments suggest that Mirabilis jalapa is the expected flower species for Cr removal from tannery sludge.     

Physical Properties and Processes that Influence the Clean Up of Oil Spills in the Marine Environment

Based on a study carried out by the Versuchsanstalt für Wasserbau und Schiffbau, Berlin – VWS for the German Environmental Agency, this report represents an attempt to summarize the knowledge in the Federal Republic of Germany and world-wide concerning the control of hazards from discharged oil and other liquid chemicals after casualties on and in the hydrosphere. Because of technical reasons, control measures can be classified into passive and active types; this classification has been adopted for this report in the following order:

• •Part 1: Passive mechanisms: Booms and barriers.
• •Part 2: Active mechanisms: Recovery devices.
• •Part 3: Other means: Dispersion.
• •Part 4: Control of sinking and/or sunken chemicals.

Part 1 not only evaluates the behaviour of liquid chemicals on water, but also considers the physical fundamentals underlying the functioning of booms and barriers. Some widely used definitions and relations (such as the relationship between the blocking of liquid chemicals and boom draught or efficiency) will be refined. The discussion of the physical fundamentals is presented in the broadest sense and concludes with practical advice on the deployment of booms.Part 2 attempts to standardize recovery devices based on the application of fundamental physical principles. Four classes were identified and have been used to classify pick-up devices. Once again basic physical fundamentals have been presented in a way that facilitates deductions on application possibilities. The evaluation showed that practically only those methods that utilize adhesion and “hole-in-the-water” principles can be operated with sufficient efficiency which, in turn, reflects the world-wide state-of-the-art in equipment development. Special attention has been paid to hybrid systems which utilize both passive and active methodologies.In Part 3, the basics of dispersion of oil and other floating liquid chemicals are considered. It can be shown that mechanical dispersion has the same effect as its chemical counterpart. This relationship recognizes the necessity for applying a mechanical agitator for using dispersants effectively. This strategy calls into question the efficiency of chemical dispersion.Part 4 deals with the behaviour and control options for sinking and/or sunken liquid chemicals. Contrary to the general opinion that liquid chemicals which have disappeared from the surface cannot be controlled, it has been found that, under certain conditions, even these chemicals can be “herded” and recovered. It will be shown that practically the same techniques can be applied to submerged chemicals as has been used for the recovery of floating hazardous substances.     

Magnetic Cr(VI) Ion Imprinted Polymer for the Fast Selective Adsorption of Cr(VI) from Aqueous Solution

In this study, a novel magnetic Cr(VI) ion imprinted polymer (Cr(VI)-MIIP) was successfully synthesized and used as a selective sorbent for the adsorption of Cr(VI) ions from aqueous solution. It can be synthesized through the combination of an imprinting polymer and magnetic nanoparticles. The high selectivity achieved using MIIP is due to the specific recognition cavities for Cr(VI) ions created in Cr(VI)-MIIP. Also, the magnetic properties that could be obtained using magnetic nanoparticles, helps to separate adsorbent with an external magnetic field without either additional centrifugation or filtration procedures. The magnetic Fe₃O₄ nanoparticles (MNPs) were synthesized using an improved co-precipitation method and modified with tetraethylorthosilicate (TEOS) before imprinting. The magnetic Cr(VI) ion imprinted polymer was prepared through precipitation copolymerization of 4-vinylpyridine as the complexing monomer, 2-hydroxyethyl methacrylate as a co-monomer, the Cr⁶⁺ anion as a template, and ethylene glycol dimethacrylate (EGDMA) as a cross-linker in the presence of modified magnetite nanoparticles. This novel synthesized sorbent was characterized using different techniques. Batch adsorption experiments were performed to evaluate the adsorption conditions, selectivity, and reusability. The results showed that the maximum adsorption capacity was 39.3 mg g^?1, which was observed at pH 3 and at 25?°C. The equilibrium time was 20 min, and the amount of adsorbent which gave the maximum adsorption capacity was 1.7 g L^?1. Isotherm studies showed that the adsorption equilibrium data were fitted well with the Langmuir adsorption isotherm model and the theoretical maximum adsorption capacity was 44.86 mg g^?1. The selectivity studies indicated that the synthesized sorbent had a high single selectivity sorption for the Cr(VI) ions in the presence of competing ions. Thermodynamic studies revealed that the adsorption process was exothermic (\(\Delta H\)?<?0) and spontaneous (\(\Delta G\)?<?0). In addition, the spent MIIP can be regenerated up to five cycles without a significant decrease in adsorption capacity.     

Potential of <Emphasis Type="Italic">pinhão</Emphasis> Coat as Constituents of Starch Based Films Using Modification Techniques

The potential of lignocellulosic fibers obtained by dry grinding of pinhão coat as fillers in starch filmogenic solutions for packaging applications was evaluated in this work. To improve the incorporation of this waste into the starch solutions different physical and chemical treatments were conducted. Thereafter, morphology, chemical structure, crystallinity and water absorption of the pinhão coat powders were determined. The composites were also characterized regarding their morphology, chemical structure, crystallinity, mechanical properties, water vapor permeability and hydrophilicity. Poor fiber/matrix adhesion and high water absorption of the fibers were evidenced. Consequently, water vapor permeability of composites was increased by incorporating the fibers. Moreover, mechanical properties were improved and the morphological results were used to support the water absorption differences among the powders. Regarding the food packaging applications, starch/pinhão coat composites appeared as promising materials to reach the requirements of respiring food products.     

Selective Lead(II) Adsorption and Flocculation Characteristics of the Grafted Sodium Alginate: A Comparative Study

Synthesis of sodium alginate-g-poly(acrylamide-co-N-methylacrylamide) [S-III], sodium alginate-g-poly(N-methylacrylamide-co-N,N-dimethylacrylamide) [S-II], sodium alginate-g-poly(acrylamide-co-N,N-dimethylacrylamide) [S-I]. Sodium alginate-g-poly(N,N-dimethylacrylamide) [SAG-g-PDMA] and sodium alginate-g-poly(acrylamide) [SAG-g-PAM] were prepared by solution polymerization technique using potassium peroxydisulfate as the initiator at 70?°C in water medium. The graft copolymers were characterized by FTIR and NMR (¹H and ¹³C) spectroscopy, SEM and XRD studies. All the five graft copolymers were used to remove Pb(II) ions from the aqueous solution and also in flocculation studies of kaolin clay (1.0 wt%), silica (1.0 wt%) and iron ore slime (0.25 wt%) suspensions. A comparative studies of all the five graft copolymers were also made in both the two cases. The Pb(II) ion removal capacity of all the graft copolymers follows the order S-III?>?SAG-g-PAM?>?S-II?>?SAG-g-PDMA?>?S-I. But the flocculation performance of the graft copolymers follows the order S-II?>?S-I?>?S-III?>?SAG-g-PDMA?>?SAG-g-PAM. S-III was also used for the competitive metal ion removal with Hg(II), Cd(II), Cu(II) and Zn(II). Pb(II) adsorption of S-III (the best Pb(II) ion adsorber) follows pseudo second order rate equation and Langmuir adsorption isotherm.     

Application of Ultraviolet Fluorescence Spectroscopy to Monitor Oil–Mineral Aggregate Formation

At an excitation wavelength of 320 nm, the ultraviolet fluorescence (UVF) spectra emitted by reference oils dispersed in seawater with mineral fines yielded two important results:

• (1)Resuspended negatively-buoyant oil–mineral aggregates (OMAs) exhibited maximum fluorescence at an emission wavelength of 450 nm and,
• (2)the hydrocarbons dispersed and/or dissolved in the seawater that remained after the aggregates had settled out exhibited maximum fluorescence at 355 nm.

Data from UVF analysis (450 nm emission) and microscopical observations of seven reference oils suggest that higher-viscosity oils are less likely to form aggregates with mineral fines. This decline in OMA formation with increased oil viscosity could be predicted from a decrease in the ratio of emission at 450–355 nm. The data suggest that direct UVF spectroscopy of dispersed/dissolved oil and OMAs in seawater can be used to predict and verify the extent of OMA formation.     

Set-up of a bottle sorting and recycling plant

An initial operation in Paris has made it possible to gauge the effectiveness of a selective pick-up of non-returnable bottles according to the following criteria: willingness of the people of Paris, the danger of breakage when collecting in special containers and the technical and economic aspects of the implementation of an industrial-scale sorting machine. In view of the positive results of this experiment, the following system has been installed:

• •• Containers have been placed on the public walkway, the drop of bottles being at the most 1 m.
• •• The bottles are transported to a plant with an annual capacity of 35,000 tons of glass or 20 million bottles.
• •• Following a first hand-sorting process, the bottles are washed and sorted in an automatic sorter.

Currently two sizes of each of three categories of wine bottles are recovered. Rejected bottles are sent to the scrap pile and shipped as cullett to glass factories to be melted down.This design constitute a complete system which enables us to recover not only glass but bottles which are intact and thus represent a higher level of energy savings.     

Kinetic Analysis of the Temperature Effect on Polyhydroxyalkanoate Production by <Emphasis Type="Italic">Haloferax mediterranei</Emphasis> in Synthetic Molasses Wastewater

Haloferax mediterranei is an extremely halophilic archaeon that is able to synthesize polyhydroxyalkanoate (PHA) in high salt environment with low sterility demand. In this study, a mathematical model was validated and calibrated for describing the kinetic behavior of H. mediterranei at 15, 20, 25, and 35 °C in synthetic molasses wastewater. Results showed that the production of PHA by H. mediterranei, ranging from 390 to 620 mg h^?1 L^?1, was strongly dependent on the temperature. The specific growth rate (µ _max), specific substrate utilization rate (q _max), and specific decay rate (k _d) of H. mediterranei increased with temperature following Arrhenius equation prediction. The estimated activation energy was 58.31, 25.59, and 22.38 kJ mol^?1 for the process of cell growth, substrate utilization, and cell decay of H. mediterranei, respectively. The high temperature triggered the increased PHA storage even without nitrogen limitation. Thus, working at high temperatures seems a good strategy for improving the PHA productivity of H. mediterranei.     

Accelerated Stability Testing of a Polyherbal Transdermal Patches Using Polyvinyl Alcohol and Hydroxypropyl Methylcellulose as a Controlling Polymer Layer

The present work was to evaluate the stability potential of (E)-4-(3,4-dimethoxyphenyl)but-3-en-l-ol (Compound D) in polyherbal transdermal patches. The polyherbal formulation composed of the rhizomes of Zingiber cassumunar and Curcuma longa, leaves and stems of Cymbopogon citratus, rind and leaves of Citrus hystrix fruit, and leaves of Acacia rugata and Tamarindus indica. Polyvinyl alcohol and hydroxypropyl methylcellulose were used as a matrix film, and glycerine was used as a plasticizer. Stability testing was established for 6 months under accelerated conditions as according to International Conference on Harmonisation guidelines. Mechanical properties, moisture uptake, swelling ratio, and in vitro studies were evaluated. New Zealand white rabbits were used as the animal model. Results obtained after 6 months showed that the polyherbal transdermal patches were stable, with a good mechanical properties and hydrophilicity. In vitro study kinetics for active Compound D fitted to the Higuchi model for both release and skin permeation. The transdermal patch containing polyherbal formulation was safe to apply on the skin without irritation. Thus, transdermal patches containing this polyherbal formulation had good stability potential, with no irritation on application.     

Green Synthesis of Silver Nanoparticles and Study of Their Antimicrobial Properties

One of the major disadvantages of polymers when used in food-contact applications is that they are very susceptible to microbial attack. On the other hand, silver nanoparticles have received increased attention as novel antimicrobial agents. Therefore, the introduction of silver nanoparticles into conventional polymers results in new materials with improved properties. In this investigation, colloidal silver nanoparticles using an environmentally friendly procedure were synthesized. An aqueous solution of AgNO₃ was used as a silver precursor with ‘green’ reducing agents either different types of honey, or β-d-glucose. In the first case, different pH values, as well as the addition of poly(ethylene glycol), PEG were studied, while in the latter, the effect of reduction time in the presence of PEG with various average molecular weights was examined. Properties of the nanoparticles were measured using X-Ray diffraction, UV–Vis and FTIR spectroscopy. Using honey it seems that spherical particles are produced with the smaller average particle size obtained at pH 8.5. Use of honey has the advantage of being a natural product, although its main drawback is that its composition varies and it cannot be predefined to result in reproducible results. Use of β-d-glucose results in stable silver nanoparticles with small average particle size after 24 h reduction. The addition of low molecular weight PEG seems to be beneficial in the production of stable nanoparticles. Finally, the antimicrobial activity of the nanoparticles produced was investigated at different concentrations on both Gram positive and negative bacteria, such as Bacillus cereus, Bacillus subtilis, Escherichia coli and Staphylococcus aureus.