Chemical immobilisation of arsenic in contaminated soils using iron(II)sulphate—advantages and pitfalls

Chemical immobilisation of inorganic contaminants by increasing the sorption capacity of soils and/or promoting the formation of sparingly soluble precipitates may be a cost-effective approach to counteract groundwater pollution. This study focuses on the enhanced retention of arsenic in two contaminated soils by addition of solid iron(II)sulphate. Four lab-scale column experiments were performed under unsaturated conditions with subsoil material sampled at a former timber preservation site and a pigment production plant. Arsenic effluent concentrations indicated 89.9 to 99.8% immobilisation in the treated columns. Sequential extractions showed a shift in contaminant binding forms towards the iron(hydr)oxide and residual fractions. Possible immobilisation mechanisms are the precipitation of FeAs phases, the formation of inner sphere complexes, and/or the occlusion of arsenic in newly formed amorphous/crystalline iron oxides. Bromide breakthrough curves point to the fact that the addition of iron(II)sulphate only moderately affects soil hydraulic properties. In contrast to reduced emissions of arsenic, increased seepage water concentrations were observed for other trace elements (e.g., cobalt, nickel, zinc). Mass balances indicate that this effect is primarily related to the temporary pH-drop caused by the oxidation of ferrous iron. The results show that chemical immobilisation using iron(II)sulphate is a promising way to protect groundwater quality at sites contaminated with timber preservation and pigment production remnants. As a prerequisite, optimum amendment levels need to be established and practical/field tests should be accompanied by a monitoring for a broad range of relevant trace elements.     

Chemical Changes in Sediment Pore-Waters of an Acidic Mining Lake After Addition of Organic Substrate and Lime for Stimulating Lake Remediation

In the past five years, enclosures have beeninstalled in an acidic mining lake in Lusatia to investigate insitu remediation processes. They were treated with straw, withstraw and Carbokalk, or with Carbokalk alone, where Carbokalkis a by-product of the sugar industry (solid precipitate ofnon-sugars after lime clarification of extracted sugar beetjuice). Sediment samples were taken as cores to get informationabout the behaviour of organic and inorganic components insediment pore-water with depth. Vertical distributions of pH,soluble reactive phosphate, nitrate, ammonium, silica,aluminium, iron, manganese, calcium, magnesium, sodium,potassium, sulphate, and DOC were measured. The resultingprofiles, each consisting of 15 data points at differentdepths, were compared by cluster analysis. The similarities ofsediment cores from different treated enclosures relating toprofiles of chemical components were discussed. Increasedconcentrations of potassium and sulphate were found in pore-water after substrate treatment. The data imply dissolution ofpotassium iron sulphate hydroxide minerals (jarosite) after anincrease of pH caused by dissolution of lime and by sulphatereducing processes which were stimulated by organic substrateaddition.     

Structure and Properties of Cocoons and Silk Fibers Produced by Attacus atlas

Silk fibers in the three layers of Attacus atlas (A. atlas) cocoons have morphological structure and tensile properties similar to that of Bombyx mori silk. Attempts are being made to produce silk for commercial applications from cocoons of relatively unknown wild insects due to the unique properties of the fibers and as a source of income and employment. In this research, A. atlas cocoons were used to study the chemical composition, morphology, physical structure and tensile properties of the silk fibers in the cocoons and ability of the fibers to support the attachment and proliferation of mouse fibroblast cells. It was found that A. atlas cocoons consists of outer, intermediate and inner layer with average breaking tenacity of 4.1, 4.3 and 3.6 g/den, respectively similar to that of B. mori silk (4.3–5.2 g/den). The heavier cocoons, less restrictive rearing conditions and good properties of the fibers compared to B. mori silk makes A. atlas a potential alternative to common silks for commercial scale silk production. A. atlas fibers had about 80 % higher optical densities of cells and extensive growth of F-actin compared to B. mori silk fibers.     

Kinetics of biochemically driven metal precipitation in synthetic landfill leachate

This study investigates the effectiveness of using metal sulphide and carbonate precipitation mechanisms combined with a landfill‐derived mixed bacterial population. The study was conducted under controlled substrate conditions in anaerobic batch reactors. High chemical oxygen demand (COD):sulphate ratios, butyrate, propionate, and acetate were used anaerobically by bacteria for growth with associated sulphate reduction as well as sulphide and carbonate generation. Propionate and butyrate degradation occurred during sulphate reduction by sulphate‐reducing bacteria while acetate degradation was associated with methanogenesis by methanogenic bacteria. Using low COD, sulphate ratios showed limited acetate utilization, but sulphate reduction still occurred. Precipitation of Cd, Cu, Zn, Ni, and Fe sulphides occurred quickly and was completed in 15 to 30 days, while Ca, Mn, and Mg carbonates formed after 40 to 50 days and some soluble metal remained even after 120 days. The rate of metal precipitation was in the order of Cd>Cu>Zn>Ni>Fe>Mn>Mg>Ca. Bacterially mediated metal precipitation occurred slower than that recognized for chemical precipitation. These findings suggest that contaminant transport models based on chemical equilibrium metal behaviors may over‐predict metal removal by bio‐precipitation. © 2002 Wiley Periodicals, Inc.     

Formulation of a Photosensitized Polyethylene Film; Its Structure and Property Variation Under the Weathering Conditions of Tehran

To develop an environmentally degradable polymer material, a masterbatch pro-oxidant system was blended into low-density polyethylene. The polymer film samples were prepared by compression molding. The prepared films were placed under the natural environment of Tehran for weathering studies and accelerated conditions were also performed for UV aging in UV chamber. At different time intervals, the changes in chemical structure of photosensitized polyethylene samples were studied by FTIR and compared to that of the control polyethylene films. Also the mechanical properties of photosensitized polyethylene films were determined in comparison with the control films by measuring the tensile strength and elongation at break after exposure to the natural environment and UV radiation. Results showed that the overall rate of degradation process is clearly dependent on the polyethylene composition, test conditions (natural or accelerated), season of the year, and the duration of the weathering of the samples.     

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.     

Grafting of Wool with Alginate Biopolymer/Nano Ag as a Clean Antimicrobial and Antioxidant Agent: Characterization and Natural Dyeing Studies

There is a continuous search for green and sustainable materials and processes in textile dyeing and finishing. In the current study, wool yarns were grafted with Sodium Alginate-Silver nanoparticles (SA-Ag NPs) and consecutively dyed with Cochineal or Madder. The weight gain of the samples was measured to find the optimized SA-Ag NPs initial concentration, and Scanning Electron Microscopy (SEM) was used to study their surface morphology. The effects of the initial dye concentration, pH, temperature on the color strength of the dyed samples were investigated. It was found that the pretreatment enhanced the dye-ability, antimicrobial, and antioxidant characteristics of the samples noticeably. Under the same dyeing conditions, the fixation of dyes on the treated wool fibers was noticeably higher than that of the untreated wool fibers. The colorfastness characteristics of the treated samples dyed with Cochineal or Madder were slightly improved. The results clearly showed that the application of SA-Ag NPs on the wool samples could be considered as a green finishing process with promising antioxidant and antimicrobial activities. A very high level of antimicrobial efficiency (99%) was achieved after the pretreatment, which remained as high as 90% even after ten repeated washing cycles.

     

Report: anaerobic digestion of a sulphate-rich high-strength landfill leachate: the effect of differential dosing with FeCl3.

The effect of different dose concentrations of FeCl3 on the performance of a mesophilic anaerobic digester treating a highly alkaline, high-strength and sulphate-rich landfill leachate was tested. The results indicated that sulphate reduction was the predominant reaction and methanogenic processes were entirely inhibited in the reactor without FeCl3 addition. Adding FeCl3 into the reactor restored some methanogenic activity and also improved the rates of sulphate reduction. A combination of sulphate reduction and methanogenic activity resulted in up to 75% chemical oxygen demand (COD) removal and 85% sulphate removal. Sulphate reduction remained the principle mechanism by which COD removal took place with a methane yield of only between 0.14 and 0.18 m3 CH4 kg(-1) COD removed being achieved. The process was, however, stable and offered advantages for the further treatment or conveyance of the anaerobically treated leachate.     

Influence of Glutaraldehyde Crosslinking and Alkaline Post-treatment on the Properties of Chitosan-Based Films

Depending on the modifications proposed, chitosan films present different characteristics, for instance correlated to hydrophilicity, chemical and mechanical properties. The aim of this study was to evaluate the influence of glutaraldehyde crosslinking and an alkaline post-treatment with NaOH on the characteristics of chitosan based films. Films were obtained by casting and characterized by thickness, swelling degree, mechanical and thermal properties and chemical structure. The water vapor permeability (WVP) was also evaluated for food packaging application. It was observed that crosslinking and NaOH post-treatment have great influence on the chitosan films characteristics. Crosslinking reduced the swelling degree of films and increased its fragility, whereas NaOH treatment also reduces the swelling degree and changes mechanical properties, acting in the same way as a crosslinker. The WVP analyses showed that the basic treatment could substitute the glutaraldehyde crosslinking for film water stability, without greatly compromising the barrier properties of chitosan based films.     

A study of the corrosion products of mild steel in high ionic strength brines

The corrosion layer on steel surfaces that formed after exposure to waste isolation pilot plant (WIPP) brines under anoxic conditions was characterized for chemical composition, thickness and phase composition. The chemical composition of the corrosion layer was determined both by X-ray photoelectron spectroscopy (XPS) and by chemical analysis of acid solutions used to remove the corrosion layer. Atomic force microscopic (AFM) images indicated that the brine-corroded surface layer shows extensive granulation along the contours of the steel surface that is characteristic of sharp polishing marks. The corrosion layer seemed to be porous and could be dissolved and detached in dilute hydrochloric acid. The corrosion layer appears to be composed of iron oxides with some ionic substitutions from the brines. The 77 K M?ssbauer spectrum recorded for iron powder leached under similar conditions indicated the corrosion layer was comprised principally of green rust.     

An Overview on the Mechanical Behaviour of Biodegradable Agricultural Films

The mechanical behavior of various types of biodegradable materials depends, mainly, on their chemical composition and the application conditions. Various additives are added into the bioblends to improve their properties, which sometimes even reach the levels of the conventional plastics. It is well known that the environmental conditions during production, storage, and usage of these materials influence their mechanical properties. Ageing during the useful lifetime also causes great losses in the elongation. In the present paper, the overall mechanical behavior of biodegradable films, which may be considered suitable for agricultural applications, but also of partially biodegradable films, is reviewed and analyzed. Selected critical mechanical properties of films before their exposure to biodegradation are investigated and compared against those of conventional agricultural films.     

The Effect of Natural Tree Gum and Environmental Condition on the Degradation of a Typical Automotive Clear Coat

In this work the effects of natural gum and its simulated compound (Arabic gum) on an acrylic based clear coat applied on different basecoats were studied. The experiments were conducted at various aging processes to simulate the real outdoor conditions by the aid of different analytical techniques including optical microscopy, scanning electron microscopy, ATR-FTIR spectroscopy, DMTA and micro hardness measurements, by which the chemical and mechanical responses of the system were investigated. Results showed that, Arabic and natural gums, due to their sticky nature in the slurry state, can strongly attach to the clear coat surface and perform a significant stress during the drying process. It was shown that, this stress was responsible for the surface cracks produced by gums, indicating a physical degradation mechanism. However, it was revealed that, biological materials could also affect the clear coat chemically. In addition, different surface cracks produced by gums on the clear coat applied on silver and black basecoats were observed and attributed to their surface chemistry and mechanical properties differences. It was shown that different amounts of aluminum flakes existed in the basecoat layers of silver and black system can effectively influence the curing degree of the clear coats applied on the se systems. This leads to different cross-linking density, toughness and surface chemistries. Therefore, different interactions of clear coats and gums, as well as stress distribution and relaxation behaviors of these two systems were found effective in such degradations. Comparison of the mechanical properties and visual effects of gums on clear coats indicated a more severe degradation under the post aging, due to the greater effect of UV light.     

Physical separation,mechanical enrichment and recycling-oriented characterization of spent NiMH batteries

Nickel–metal hydride (NiMH) batteries contain high amount of industrial metals, especially iron, nickel, cobalt and rare earth elements. Although the battery waste is a considerable secondary source for metal and chemical industries, a recycling process requires a suitable pretreatment method before proceeding with recovery step to reclaim all valuable elements. In this study, AA- and AAA-type spent NiMH batteries were ground and then sieved for size measurement and classification. Chemical composition of the ground battery black mass and sorted six different size fractions were determined by an analytical technique. Crystal structures of the samples were analyzed by X-ray diffraction. Results show that after mechanical treatment, almost 87 wt% of the spent NiMH batteries are suitable for further recycling steps. Size classification by sieving enriched the iron content of the samples in the coarse fraction which is bigger than 0.25 mm. On the other hand, the amounts of nickel and rare earth elements increased by decreasing sample size, and concentrated in the finer fractions. Anode and cathode active materials that are hydrogen storage alloy and nickel hydroxide were mainly collected in finer size fraction of the battery black mass.     

Processing of copper converter slag for metal reclamation. Part I: Extraction and recovery of copper and cobalt.

Clean processing of copper converter slag to reclaim cobalt and copper could be a challenge. An innovative and environmentally sound approach for recovering valuable metals from such a slag has been developed in the present study. Curing the slag with strong sulphuric acid, without re-smelting or roasting as practiced currently in the industry, render it accessible to leaching, and more than 95% of cobalt and up to 90% of copper was extracted together with iron by water leaching, leaving silica behind in a residue. The copper in the leach liquor was recovered by cementation with iron and the dissolved iron crystallized as ferrous sulphate monohydrate. The cobalt in the mother-liquor rich in iron was recovered by either cementation or sulphide precipitation. Operation variables in the new process were also investigated and optimized.     

Dual Function of Cellulose Triacetate–Graft–Polymethacrylic Acid Films for Dyes Removal and for High-Dose Radiation Dosimetry

Graft copolymerization of methacrylic acid (MAc) onto cellulose triacetate (CTA) films was conducted by gamma rays. The grafting conditions were optimized. The structure of grafted CTA films was characterized by Fourier transform infra red–attenuated total reflection, scanning electron microscopy, thermal gravimetric analysis, CHNS/O microanalyzer and, surface area and porosity analyzer. The grafted CTA films were exploited in adsorption of ethyl violet (EV) and phenol red (PR) dyes. The adsorption capacity of the grafted CTA films was investigated at various variables. The adsorption isotherms and kinetic study were examined. Further, the dyed grafted CTA films were used in measurements of high dose radiation. The results indicate that the useful dose range extents up to 440 and 300 kGy for EV and PR, respectively. The effects of relative humidity during irradiation, shelf-life, pre- and post-irradiation storage in dark and indirect daylight conditions on dosimeters performance were investigated.     

Investigation of the Structure and Properties of Silk Fibers Produced by Actias lunas

This paper reports the structure and properties of silk fibers produced by Actias lunas in comparison to Bombyx mori and the common wild silks. Considerable efforts are being made to find new sources for natural silk and also to develop regenerated protein fibers to supplement the limited amounts of B. mori and wild silks available in the market. In addition, it has been found that non-traditional silks have unique properties and utilizing uncommon wild silks can provide income and employment to indigenous people where the wild silks are found. Actias lunas belongs to the Saturniidae family of silk producing insects. However, the structure and properties of silk produced by A. lunas have not been studied. This research showed that the silk fibers produced by the luna moth had morphological and physical structure similar to that of the common wild silks but tensile properties similar to that of B. mori silk. A. lunas silk fibers are composed of higher amounts of hydrophobic amino acids and had much less glycine than B. mori and common wild silks. With a fineness of 2 denier, breaking tenacity of 4.3?g/den and breaking elongation of 10.9?%, the tensile properties of A. lunas silk fibers were similar to that of B. mori and much better than that of the common wild silks that are coarser and have lower breaking tenacity. A. lunas fibers show good potential to be useful for applications currently using B. mori silk.     

Biodegradation of LDPE/Modified Starch Blends Sterilized with Gamma Radiation

Blends of LDPE/modified starch were prepared, sterilized by gamma radiation and investigated with respect to their microbial degradation by a mixture of fungal strains in liquid medium after 90 days, was analyzed by carbon dioxide (CO₂) production (Sturm test). Biodegradation of blends was evaluated by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction; mechanical testing, scanning electron microscopy (SEM). The biodegradation of LDPE/modified starch blends was attributed to microbiological attack, with alterations in the chemical structure of the blend with an increase in the carbonyl and vinyl indices and the appearance of new crystalline symmetry generating a crystalline domain not existing before in the blend and decrease in the mechanical properties.     

Contribution of Pendant Ester Group Hydrolysis to the Erosion of Acrylic Polymers in Binders Aimed at Organotin-Free Antifouling Paints

Specific polymeric material applications as bioactive molecules delivery systems involve a strictly controlled degradation of polymer matrixes. One possibility to obtain a zero-order kinetic for small molecules release consists in a simple hydrolysis of ester groups contained in the macromolecular structure. The chemical degradation can lead to the continuous surface erosion of the formulated resins without loss of their mechanical properties and to a permanent activity of the delivery systems. Hydrolysis is a very well-known reaction in the case of organic molecules containing ester groups. The mechanism seems to be more complicated when ester groups are located in macromolecular structures. With the aim of antifouling applications, acrylic acid polymers bearing lateral ester groups of different chemical structures (hydrophilic, hydrophobic, hydrolyzable) have been prepared, characterized, and immersed in water, at pH 8, and their hydrolysis has been studied. Experimental data display two parameters, at least, which must be taken into account: the reactivity of the ester groups toward hydrolysis and the hydrophilic/hydrophobic balance of the polymer. The susceptibility of the acrylic polymers to hydrolysis has been compared to the erosion characteristics of the corresponding films. The results confirm that hydrolysis is necessary to obtain a regular degradation of the films without loss of mechanical properties. A relationship has been observed between the characteristics of hydrolysis and erosion for each studied polymer.     

A lysimeter experimental study and numerical characterisation of the leaching of incinerator bottom ash waste

Incinerator bottom ash (IBA) is a residual produced from incinerating municipal solid waste. In the past, IBA presented a big waste disposal problem; however, various recycling approaches have been adopted in recent years to mitigate this problem, as well as to provide a useful alternative to using primary aggregate resources. The use of IBA as an alternative to conventional aggregates in different civil engineering construction applications helps to conserve premium grade aggregate supplies; however, when IBA is in contact with water in the field, as a consequence of precipitation events or changes in water table, elements, such as salts and heavy metals, may be released to the soil and ground water. In this work, IBA waste was mixed with limestone aggregate to produce a blend with acceptable mechanical properties and minimum environmental risks for use as road foundation. The study focused on evaluating potential environmental impacts of some constituents, including sulphate, chloride, sodium, copper, zinc and lead in IBA blends using a lysimeter as a large scale leaching tool. Moreover, a specific scenario simulating field conditions was adopted in the lysimeter to assess the potential impact of changing conditions, such as IBA content in the blend, liquid to solid ratio (L/S) and pH value, on long-term release of heavy metals and salts. Then, numerical modelling was used to predict the release of the aforementioned constituents from IBA based on initial measurement of intrinsic material properties and the kinetic desorption process concept. Experimental results showed that zinc and lead were released in very low concentrations but sodium and sulphate were in high concentrations. The control limestone only blend also demonstrated low release concentrations of constituents in comparison to IBA blends, where constituent concentrations increased with increase in IBA content. Experimental results were compared with numerical results obtained using a non-equilibrium desorption model. Good agreement was found between the two sets of data.     

Stabilization/solidification of waste ferrous sulphate from titanium dioxide production by fluidized bed combustion product

A treatment procedure to allow the disposal of waste ferrous sulphate was developed. This waste contains sulphuric acid and originates from titanium dioxide production. The process is based on simultaneous neutralization and stabilization/solidification (S/S) of the waste by means of fluidized bed combustion product (FBC-P). The prepared stabilized waste specimens have a solid matrix and their batch leachates display practically neutral pH and also satisfactory conductivity values. The leachate composition is notable in its absence of toxic metals and even iron.