Chemical recycling of glass fibre reinforced composites using subcritical water

A hydrolysis process is applied to degrade an unsaturated polyester resin based on DCPD (dicyclopentadiene) and crosslinked with styrene, as the matrix of a composite material reinforced with long glass fibres. Subcritical conditions of water (200 °C < temperature < 374 °C and pressure < 221bars) were chosen regarding the involved chemistry for the case of simple esters. Several experiments were realised to measure the effects of the process parameters on the efficiency of hydrolysis, on the quality of the recovered fibres and finally on the nature of the recovered organic products. A washing of the fibres is necessary and appears to be an important step of the process realised in batch conditions. The identification of the recovered organic products indicates that monomers of the resin are obtained but also that secondary reactions occur during the hydrolysis process.     

Recycling of carbon fibre reinforced composites using water in subcritical conditions

In this paper, a method of chemical recycling of thermosetting epoxy composite was discussed. Water was used to be reaction medium and the decomposition of carbon fibre reinforced epoxy composites was studied. Experiments were devised in order to identify the significant process parameters that affect fibre reinforced composite recovery potential including temperature, time, catalyst, feedstock, and pressure. Experiments were performed in a batch-type reactor without stirring. Under the condition that the temperature was 260 °C and the ratio of resin and water was 1:5 g/mL, the decomposition rate could reach 100 wt.% and the carbon fibres were obtained. The results from the Scanning Electron Microscopy (SEM) and Atomic Force Microscope (AFM) measurements showed that the fibres were clean and no cracks or defects were found. The average tensile strength of the reclaimed fibres was about 98.2% than that of the virgin fibres.     

Off-line coupling of subcritical water extraction with subcritical water chromatography via a sorbent trap and thermal desorption

In this study, the off-line coupling of subcritical water extraction (SBWE) with subcritical water chromatography (SBWC) was achieved using a sorbent trap and thermal desorption. The sorbent trap was employed to collect the extracted analytes during subcritical water extraction. After the extraction, the trap was connected to the subcritical water chromatography system, and thermal desorption of the trapped analytes was performed before the SBWC run. The thermally desorbed analytes were then introduced into the subcritical water separation column and detected by a UV detector. Anilines and phenols were extracted from sand and analyzed using this off-line coupling technique. Subcritical water extraction of flavones from orange peel followed by subcritical water chromatographic separation was also investigated. The effects of water volume and extraction temperature on flavone recovery were determined. Because a sorbent trap was used to collect the extracted analytes, the sensitivity of this technique was greatly enhanced as compared to that of subcritical water extraction with solvent trapping. Since no organic solvent-water extractions were necessary prior to analysis, this technique eliminated any use of organic solvents in both extraction and chromatography processes.     

Enhanced paraquat removal from contaminated water using cell-immobilized biochar

Clean Technologies and Environmental Policy - The efficient performance of cell-immobilized biochar in removing paraquat (PQ) from contaminated water is described in this work. Pseudomonas putida...     

Retention behavior of phenols, anilines, and alkylbenzenes in liquid chromatographic separations using subcritical water as the mobile phase

The unique characteristic of subcritical water is its widely tunable physical properties. For example, the polarity (measured by dielectric constant) of water is significantly decreased by raising water temperature. At temperatures of 200-250 °C (under moderate pressure to keep water in the liquid state), the polarity of pure water is similar to that of pure methanol or acetonitrile at ambient conditions. Therefore, pure subcritical water may be able to serve as the mobile phase for reversed-phase separations. To investigate the retention behavior in subcritical water separation, the retention factors of BTEX (benzene, toluene, ethylbenzene, and m-xylene), phenol, aniline, and their derivatives have been determined using subcritical water, methanol/water, and acetonitrile/water systems. Subcritical water separations were also performed using alumina, silica-bonded C18, and poly(styrene-divinylbenzene) columns to study the influence of the stationary phase on analyte retention under subcritical water conditions.     

Electrochemical EDTA recycling after soil washing of Pb, Zn and Cd contaminated soil

Recycling of chelant decreases the cost of EDTA-based soil washing. Current methods, however, are not effective when the spent soil washing solution contains more than one contaminating metal. In this study, we applied electrochemical treatment of the washing solution obtained after EDTA extraction of Pb, Zn and Cd contaminated soil. A sacrificial Al anode and stainless steel cathode in a conventional electrolytic cell at pH 10 efficiently removed Pb from the solution. The method efficiency, specific electricity and Al consumption were significantly higher for solutions with a higher initial metal concentration. Partial replacement of NaCl with KNO₃ as an electrolyte (aggressive Cl⁻ are required to prevent passivisation of the Al anode) prevented EDTA degradation during the electrolysis. The addition of FeCl₃ to the acidified washing solution prior to electrolysis improved Zn removal. Using the novel method 98, 73 and 66% of Pb, Zn and Cd, respectively, were removed, while 88% of EDTA was preserved in the treated washing solution. The recycled EDTA retained 86, 84 and 85% of Pb, Zn and Cd extraction potential from contaminated soil, respectively.     

Integrated treatment of PAH contaminated soil by soil washing, ozonation and biological treatment

The aim of the study was to optimise three different treatment methods and to find out if the integration of soil washing, ozonation and biological treatment could be a feasible method for the remediation of aged oil contaminated with PAHs. Three different ozone doses and soil washing were studied in different pHs in order to assess their effect to the degradation and enhancement of biodegradability of PAH in the soil and water phase. Main target of the study was to find out a method with which the PAH concentrations could be decreased below the Finnish guideline level for total PAHs. In this case, the initial concentration of PAHs was 1200 mg kg(-1) and therefore almost 85% degradation of PAHs was required. Any of the methods studied was not able to reach this target level alone, but by several combinations of the methods studied achieved 90% reduction of PAHs. The consumption of ozone was 5-10 times lower in the integrated treatments of soil washing, ozonation and biological treatment than without prewashing.     

Bioremediation of endosulfan contaminated soil and water -- optimization of operating conditions in laboratory scale reactors

A mixed bacterial culture consisted of Staphylococcus sp., Bacillus circulans-I and -II has been enriched from contaminated soil collected from the vicinity of an endosulfan processing industry. The degradation of endosulfan by mixed bacterial culture was studied in aerobic and facultative anaerobic conditions via batch experiments with an initial endosulfan concentration of 50mg/L. After 3 weeks of incubation, mixed bacterial culture was able to degrade 71.58+/-0.2% and 75.88+/-0.2% of endosulfan in aerobic and facultative anaerobic conditions, respectively. The addition of external carbon (dextrose) increased the endosulfan degradation in both the conditions. The optimal dextrose concentration and inoculum size was estimated as 1g/L and 75mg/L, respectively. The pH of the system has significant effect on endosulfan degradation. The degradation of alpha endosulfan was more compared to beta endosulfan in all the experiments. Endosulfan biodegradation in soil was evaluated by miniature and bench scale soil reactors. The soils used for the biodegradation experiments were identified as clayey soil (CL, lean clay with sand), red soil (GM, silty gravel with sand), sandy soil (SM, silty sand with gravel) and composted soil (PT, peat) as per ASTM (American society for testing and materials) standards. Endosulfan degradation efficiency in miniature soil reactors were in the order of sandy soil followed by red soil, composted soil and clayey soil in both aerobic and anaerobic conditions. In bench scale soil reactors, endosulfan degradation was observed more in the bottom layers. After 4 weeks, maximum endosulfan degradation efficiency of 95.48+/-0.17% was observed in red soil reactor where as in composted soil-I (moisture 38+/-1%) and composted soil-II (moisture 45+/-1%) it was 96.03+/-0.23% and 94.84+/-0.19%, respectively. The high moisture content in compost soil reactor-II increased the endosulfan concentration in the leachate. Known intermediate metabolites of endosulfan were absent in all the above degradation studies.     

Feasibility of analyzing fine particulate matter in air using solid-phase extraction membranes and dynamic subcritical water extraction

We have evaluated the feasibility of using Empore solid-phase extraction (SPE) membranes as an alternative to conventional techniques for sampling fine airborne particulate matter (PM), including nanoparticles, utilizing a scanning mobility particle sizer (SMPS) and a condensation particle counter to evaluate their efficiency for trapping fine particles in the 10-800 nm size range. The results demonstrate that the membranes can efficiently trap these particles and can then be conveniently packed into an extraction cell and extracted under matrix solid-phase dispersion (MSPD) conditions. The potential utility of sampling PM using Empore membranes followed by dynamic subcritical water extraction (DSWE) for fast, efficient, class-selective extraction of polycyclic aromatic hydrocarbons (PAHs) associated with the particles, prior to changing the solvent and analysis by GC/MS, was then explored. The performance of the method was tested using National Institute of Standards and Technology (NIST)-certified "urban dust" reference material (SRM 1649a) and real samples collected at a site in central Rome with heavy road traffic. The method appears to provide comparable extraction efficiency to that of conventional techniques and with using GC/MS, detection limits ranged in the few picograms per cubic meter level. Sampling PM by Empore membranes may reduce the risks of losses of semivolatile compounds, while allowing relatively high sampling flow rates and safe sample storage. Moreover, the combination of MSPD with DSWE permits specific fractions of the PM components to be eluted, thereby generating clean extracts and reducing both analysis time and sample manipulation.     

Static subcritical water extraction combined with anion exchange disk sorption for determining chlorinated acid herbicides in soil

Static subcritical water extraction (SbWE) was coupled with collection on a strong anion exchange (SAX) disk for the determination of chlorinated acid herbicides and their esters in soil. With 100-150 degrees C water, esters were hydrolyzed into their acid form, and the herbicide acids extracted by subcritical water were trapped onto/into a SAX disk as the extraction cell was cooled. The trapped solutes were then derivatized for gas chromatographic (GC) analysis by placing the disk into a GC autosampler vial containing 1 mL of N,O-bis(trimethylsilyl)trifluoroacetamide derivatizing reagent. With the static SbWE/SAX disk extraction, nearly quantitative recoveries (typically over 80%) were obtained at 100 degrees C for 30 min in the extraction of herbicide acids and esters spiked on several different soils covering a range of organic content from 0.3 to 12%. Good agreements were reached between this method and EPA method 8151 for aged spiked soils. Detection limits of the static SbWE/SAX disk extraction were from 0.05 to 0.5 ppm and from 0.01 to 0.5 ppm using GC/electron capture detector and GC/mass spectrometry, respectively. The method is fast and simple and uses a small amount of organic solvent.     

Efficiency modeling of solidification/stabilization of multi-metal contaminated industrial soil using cement and additives

In a laboratory study, formulations of 15% (w/w) of ordinary Portland cement (OPC), calcium aluminate cement (CAC) and pozzolanic cement (PC) and additives: plasticizers cementol delta ekstra (PCDE) and cementol antikorodin (PCA), polypropylene fibers (PPF), polyoxyethylene-sorbitan monooleate (Tween 80) and aqueous acrylic polymer dispersion (Akrimal) were used for solidification/stabilization (S/S) of soils from an industrial brownfield contaminated with up to 157, 32,175, 44,074, 7614, 253 and 7085 mg kg⁻¹ of Cd, Pb, Zn, Cu, Ni and As, respectively. Soils formed solid monoliths with all cementitious formulations tested, with a maximum mechanical strength of 12 N mm⁻² achieved after S/S with CAC + PCA. To assess the S/S efficiency of the used formulations for multi-element contaminated soils, we propose an empirical model in which data on equilibrium leaching of toxic elements into deionized water and TCLP (toxicity characteristic leaching procedure) solution and the mass transfer of elements from soil monoliths were weighed against the relative potential hazard of the particular toxic element. Based on the model calculation, the most efficient S/S formulation was CAC + Akrimal, which reduced soil leachability of Cd, Pb, Zn, Cu, Ni and As into deionized water below the limit of quantification and into TCLP solution by up to 55, 185, 8750, 214, 4.7 and 1.2-times, respectively; and the mass transfer of elements from soil monoliths by up to 740, 746, 104,000, 4.7, 343 and 181-times, respectively.     

Immobilization of copper in contaminated sandy soils using calcium water treatment residue

Chemical remediation has attracted increasing attention for heavy metal contaminated soils because of its relatively low cost and high efficiency. In this study laboratory incubation and column leaching experiments were conducted to understand the mechanisms of copper (Cu) immobilization by calcium water treatment residue (Ca-WTR) and to estimate the optimal rate for remediating Cu-contaminated soils. The results showed that Ca-WTR amendment significantly raised soil pH and decreased water soluble and exchangeable Cu by 62-90% in the contaminated soils. Most of the bioavailable Cu was converted into more stable Cu fractions, i.e. oxides-bound and residual Cu. The cumulative amount of Cu in the leachate after 10 leaching events was reduced by 80% and 73%, respectively for the two tested soils at the Ca-WTR rate of 20 g kg(-1) for Alfisol and 100 g kg(-1) for Spodosol. These results indicate that Ca-WTR is effective in raising soil pH and converting labile Cu to more stable forms in the contaminated soils. A pH value of 6.5 was found to be critical for lowering Cu availability in the soils. Based on this criterion and pH response curve to Ca-WTR application, the optimal rates of Ca-WTR can be estimated for different Cu-contaminated soils.     

Bioremediation of phenols and polycyclic aromatic hydrocarbons in creosote contaminated soil using ex-situ landtreatment.

Soil from a former creosoting plant containing phenols and polycyclic aromatic hydrocarbons, was remediated using an ex-situ landtreatment process. Total 16 USEPA priority PAH and total phenol were reduced from 290 mg/kg and 40 mg/kg to < 200 mg/kg and 2 mg/kg, respectively. The bioremediation process involved soil mixing, aeration, and slow release fertilizer addition. The indigenous populations of PAH and phenol utilizing populations of microorganisms were shown to increase during the treatment process, indicating that biostimulation was effective. The most extensive degradation was apparent with the 2- and 3-ring PAH, with decreases of 97% and 82%, respectively. The higher molecular weight 3- and 4-ring PAH were degraded at slower rates, with reductions of 45% and 51%, respectively. Six-ring PAH were degraded the least with average reductions of < 35%. The residual concentrations of PAH and total phenol obtained in the study allowed the treated soil to be disposed of as low level contaminated landfill.     

Solubility of triazine pesticides in pure and modified subcritical water

Solubility measurements in pure and modified water serve as a basis for optimizing the subcritical water extraction of target analytes such as food contaminants. The solvent strength of the water is affected by both the system's temperature and the amount and type of cosolvent modifier that is added to the water, which causes a reduction in the dielectric constant of water. In the present work, the solubilities of the triazine pesticides atrazine, cyanazine, and simazine were measured in pure and modified water at temperatures ranging from 50 to 125 degrees C and at a pressure of 50 atm. The solubility data were obtained using a static solubility apparatus with on-line liquid chromatographic (LC) detection. By increasing the temperature of the water, the solubilities of the triazine pesticides increased approximately 3-fold in pure water for each 25 degrees C temperature increment. Cyanazine was 5 times more soluble than atrazine and an order of magnitude more soluble than simazine at 100 degrees C. The solubility of atrazine was also measured in ambient and hot water modified with ethanol and urea. At 100 degrees C, the solubility of atrazine is doubled when the water is modified with urea, and is increased over an order of magnitude when ethanol is used as modifier. The data, therefore, indicate that adding a cosolvent to water in addition to increasing the system temperature increases the solubilities of triazine pesticides in subcritical water. It was further determined that the solutes do not thermally degrade or hydrolyze at the temperatures reported in this study.     

Synthesis of erbium hydroxide microflowers and nanostructures in subcritical water

The effects of temperature, pressure, pH, residence time and reactant concentrations, as well as the presence or absence of CO(2), on the size and morphology of erbium hydroxide particles synthesized in a hydrothermal batch reactor and a diamond-anvil cell (DAC) reactor have been investigated. Several new erbium-based microstructures and nanostructures were obtained that encompass different phases and shapes, including crystalline microflowers, hexagonal microlayers, microsticks and microspheres made from nanoparticles, as well as nanofibers, nanorods and nanolayers. The Er(2)OCO(3)(OH)(2) microflowers are pure, structurally uniform, and mostly free from dislocations. Their crystallinity, morphology, optical properties and structural features have been examined and compared with those of the other phases by field-emission scanning electron microscopy (SEM), x-ray diffraction (XRD), and energy-dispersive x-ray (EDX) analysis, and by Raman, infrared, UV-visible and fluorescence spectroscopy.     

Electrokinetic remediation of wood preservative contaminated soil containing copper, chromium, and arsenic

As a result of wood treatment, and the recent banning of the copper, chromium, and arsenic (CCA) treated wood for residential use many CCA treatment facilities have been abandoned or being closed. Soil contamination resulting from CCA is common at these sites. In this study, the feasibility of electrokinetic technique to remove CCA from contaminated soil was investigated. To better understand the ionic mobility within the soil and to detect the generation and advancement of acid front, sampling ports were provided along the longitudinal axis of a test cell. To determine the effect of varying current, three tests were performed at different current densities of 5.9, 2.9, and 1.5mA/cm(2) for a period of 15 days. The initial concentrations of copper, chromium, and arsenic in the soil were 4800, 3100, and 5200mg/kg, respectively. Dilute nitric acid was used as an amendment to neutralize the hydroxyl ions produced at the cathode. Experiments resulted in removal efficiencies as high as 65% for copper, 72% for chromium, and 77% for arsenic. The results also indicated that the advancement of acid front favored desorption of metals from the soil and the metals were mobilized either as free cations or metal complexes. Chromium that was in its +6 valence state was transported as anion prior to its reduction. However, once the chromium was reduced to chromium(III) its transport direction reversed with transport being favored towards the cathode.     

Assessment of pilot-scale acid washing of soil contaminated with As, Zn and Ni using the BCR three-step sequential extraction

This study performed pilot-scale washing of soil contaminated with both oxyanion and cations as a recalcitrant remediation case due to their different chemical behavior. The soil contaminated with As, Zn and Ni, partially recalcitrant due to their strong binding properties, was obtained near a closed iron/serpentine mining area. This study monitored the variation of chemical speciation of As, Zn and Ni for acid solutions and particle size fraction using the BCR sequential extraction and evaluated the optimal condition of physical separation of highly contaminated fine particles for enhanced washing. H(2)SO(4) and H(3)PO(4), including competitive oxyanions, enhanced removal of As with the simultaneous extraction of Zn and Ni. Less nickel from the residual fraction in coarse particles was extracted than As and Zn due to the recalcitrant serpentine. Fe/Mn oxide, organic/sulfides and residual fractions in fine particles were enriched with contaminants due to the high surface areas and recalcitrant minerals. The chemical extraction of As was also restricted in the fine particles, whereas the chemical extraction of Zn and Ni was determined by the residual form of various particle size fractions. Further extraction was limited in the exchangeable and residual fractions and retained a gradual extraction from Fe/Mn oxide and organic/sulfides fractions, which indicated an instant detachment from the easily bound fraction. Correspondingly, extraction from the acid-attackable fraction was related to the exchangeable Fe/Mn oxide and organic/sulfides fractions. Due to the limitation of chemical extraction, the physical separation of fine particles could enhance the effectiveness of acid washing. In addition, the chemical properties of the soil were affected by strong acid washing. The treated soil then needed to be regenerated.     

Early events in 2,4,6-trinitrotoluene (TNT) degradation by porphyrins: binding of TNT to porphyrin by hydrophobic and hydrogen bonds

The interaction of meso-tri(4-sulfonatophenyl)mono(4-carboxyphenyl) porphyrin (C1TPP) with 2,4,6-trinitrotoluene (TNT) has been explored by UV-vis and fluorescence spectroscopy. The influence of temperature on the interaction has also been studied. C1TPP binds to TNT at pH 7.0 at room temperature via 1.94 kcal/mole hydrogen bonds with absorbance loss at 412-413 nm and the appearance of a new peak at 422-424 nm. The hydrogen binding of TNT to C1TPP was confirmed by the dissolution of the complex upon the addition of urea. Increasing the temperature results in the appearance of a new absorbance peak at 540 nm and absorbance loss at 515 nm with activation energy of 29.7 kcal/mole in the range of the hydrophobic bond energy. This suggests the hydrophobic bonding of TNT with the pyrrole nitrogens in the porphyrin. Increasing the concentration of the TNT in the solution quenches the fluorescence of the porphyrin following the Stern-Volmer equation. The association constants calculated from absorbance and fluorescence are expectedly similar.     

Technological prospecting: Patent mapping of bioremediation of soil contaminated with agrochemicals using fungi

The purpose of this study was to investigate the development of biotechnologies related to the bioremediation of soil contaminated by agrochemicals using fungi through technological prospecting with patent mapping and analysis of scientific products. Due to the high complexity of biotechnologies involving microorganisms, it is observed that the state of the art is still in development, with several technological advantages already elucidated and important challenges to be overcome. Patent mapping revealed that the number of granted or pending patents showed a positive trend. In this context, a high number of patent documents were observed that describe processes and methods aimed at the preparation and application of fungi in soil bioremediation, as well as biotechnologies that use consortia of different strains of fungi or fungi and bacteria and advanced approaches involving genetic engineering. In short, it was found that inventions related to the investigated biotechnology have been protected mainly in China, the USA, Japan, and the European Union, with emphasis on the technological impact of patents in India. Finally, the findings indicated that soil bioremediation with the use of fungi presents a potential for development due to a series of technological and environmental aspects.