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Surfactant production accompanying the modified Fenton oxidation of hydrocarbons in soil.

A hydrocarbon-contaminated soil was treated in laboratory slurry reactors using two types of modified Fenton (MF) chemistry. Liquid hydrogen peroxide (HP) with Fe(3+) was compared with a calcium peroxide (CaO(2))-based oxidant (Cool-Oxtrade mark). Bioslurry treatment served as a control. During oxidation, samples of slurry filtrate were tested to quantify hydrocarbon concentrations and bulk surfactant concentrations, using the critical micelle dilution method. The results showed that both oxidants resulted in the temporary accumulation of surfactants to maximum levels of four times the critical micelle concentration, but that surfactants were completely removed by the end of treatment. Removal of surfactants was complete within 2h for liquid HP treatment versus 2 days for the CaO(2)-based oxidant. For both MF oxidants, hydrocarbon concentrations in filtrate were 3-4 orders of magnitude greater than in the biological control. Both MF oxidants also showed enhanced removal of the high molecular weight fractions of the petroleum hydrocarbons relative to biological treatment, though this effect was considerably greater with the CaO(2)-based oxidant. The chemical treatments did not considerably reduce numbers of culturable hydrocarbon-degrading microorganisms relative to the bioreactor, suggesting that chemical and biological oxidation may have occurred simultaneously in the slurry.

Bioreactors↗

Mechanochemical approach to remove phenanthrene from a contaminated soil.

Soil samples collected from a cultivated soil of Southern Italy after artificial contamination with phenanthrene (PHE) were ground in a ball mill and compared with spiked (via acetone) sample as control. The mechanochemical treatment was also applied to a simple binary system birnessite (delta-MnO(2))-PHE and to soil added with birnessite to evaluate the oxide role in removing the contaminant. Different extraction methods, such as Soxhlet, sonication, and desorption from resin beads were adopted to estimate the residual PHE analysed with HPLC. X-ray diffraction and TG-DTA analyses were performed to quantify mineralogical phases in soil and their possible modifications after grinding. The results showed that the grinding was more efficient in removal of PHE when the pollutant was in solid phase ( approximately 50% of removal) than when it was spiked via acetone in the same soil ( approximately 20% of removal). Addition of birnessite to soil did not change significantly the removal of PHE through time. Independently of the extraction methods used, the PHE recovered after the mechanochemical treatment in the presence of solid PHE was always lower, suggesting a higher efficiency of such a treatment in degrading PHE or forming bound residues in its original or transformed form. X-ray powder diffraction of milled solid PHE showed that order-disorder phase transition occurred in solid phenanthrene as consequence of the mechanochemical treatment. X-ray diffractometry and TG-DTA analyses were crucial in evidencing that interaction between PHE and birnessite occurred.

Bacteria↗

Kinetics of photocatalytic VOCs abatement in a standardized reactor.

A standardized micro-pilot scale continuous flow apparatus has been built up, using two types of differential photoreactors, and equipped with a refined control of the working conditions in order to study the photocatalytic degradation as a way to abate VOCs in air. Kinetic measurements have been carried out on trichloroethylene (TCE), methanol and benzene as model pollutants. The absence of diffusional limitation and of reaction product effect on the kinetics have both been demonstrated under our working conditions. The influences of concentration, light flux and temperature on the initial degradation rate have been studied. A simple Langmuir-Hinshelwood kinetic model has been verified for TCE and methanol, whereas benzene degradation was more complex and did not follow this simple mechanism. The determined experimental data aim at being useful in the scaling-up of photocatalytic reactors.

Air Pollutants↗

Effects of oxygen, catalyst and PVC on the formation of PCDDs, PCDFs and dioxin-like PCBs in pyrolysis products of automobile residues.

End-of-life vehicles are dismantled to recover reusable parts and then sent to a shredding facility for steel material recovery. The residue generated from the shredding process, so-called automobile shredder residue, is now being mostly disposed in landfill, however landfill will be prohibited in the near future. More recycling and energy recovery must be made by the regulation. The most appropriate method is the thermal treatment that will produce various forms of fuels and less volume of vitrified residue. In this research, an automobile shredder residue was simulated with considering the residue from a shredding factory based on the new vehicle and thermally treated by pyrolysis or gasification to observe the yields of gas, oil and char. In the temperature range of 400-800 degrees C, the yields of gas, oil, and char were 38.7-45.8%, 12.3-18.2%, and 36.0-49.0%, respectively. The optimum pyrolyzing temperature for more oil production was around 600 degrees C. Emission characteristics of the byproducts, PCDDs, PCDFs and dioxin-like PCBs were studied at the temperature of 600 degrees C. The analysis on the concentration and distribution of the isomers in various forms of the products were completed with and without oxygen, PVC, and catalytic metals, in order to observe how the existence of oxygen, PVC, and catalytic metals affect the formation of PCDDs, PCDFs, and dioxin-like PCBs from pyrolysis or gasification process. Without PVC, no PCDDs, PCDFs and dioxin-like PCBs were found in any products. PCDFs were predominant in any conditions. Catalyst and oxygen were found to affect to form more PCDDs, PCDFs, and dioxin-like PCBs. Effects of catalyst and oxygen on the byproduct formation seemed to be similar in oil and gas while that was different in char.

Automobiles↗

Study on the pyrolysis of polyethylene in the presence of iron and copper chlorides.

Pyrolysis experiments were conducted to elucidate the effects of metal chlorides on the thermal degradation of low-density polyethylene on a continuous pyrolysis temperature range of 600 degrees C to 1100 degrees C. The present work focusses on the ratio of aromatics generated on increasing the pyrolysis temperature in the presence of metal salts, iron(II), iron(III) and copper(II) chlorides. It was observed that beside alpha,omega-dienes, alpha-olefins and n-alkanes which are usually observed during the thermal decomposition of polyethylene, the level of aromatics noticeably increases with the addition of metal salts. At high temperatures, the formation of these aromatics took place in such a way that they become the major products when polyethylene is pyrolyzed in presence of FeCl(3) and CuCl(2). Quantification of the effect of metal salts has been tempted comparing the variation of the ratio of aromatics with pyrolysis temperatures. Mechanisms responsible for the formation of these aromatics in presence of metal salts have been tentatively investigated. They are proposed to result from cyclization/dehydrogenation reactions similar to those observed during the thermal decomposition of polyethylene, but with an increased efficiency due to the metal salts.

Chlorides↗

Cleaner co-combustion of lignite-biomass-waste blends by utilising inhibiting compounds of toxic emissions.

In this paper, the co-combustion behaviour of coal with wastes and biomass and the related toxic gaseous emissions were investigated. The objective of this work is to add on towards a cleaner co-combustion of lignite-waste-biomass blends by utilizing compounds that could inhibit the formation of toxic pollutants. A series of co-combustion tests was performed in a pilot scale incinerator, and the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were measured. The co-combustion behaviour of lignite with olive kernels, MDF and sawdust was studied and the ability of additives such as urea, almond shells and municipal sewage sludge to reduce the PCDD/F emissions was examined. All blends were proven good fuels and reproducible combustion conditions were achieved. The addition of inhibitors prior to combustion showed in some cases, relatively high PCDD/F emissions reduction. Among the inhibitors tested, urea seems to achieve a reduction of PCDD/F emissions for all fuel blends, while an unstable behaviour was observed for the others.

Air Pollutants↗

Environmental release and mass flux partitioning of PCDD/Fs during normal and transient operation of full scale waste to energy plants.

The paper reports on global release and mass partitioning in the flux of residues of PCDD/Fs, evaluated with dedicated field campaigns at a municipal solid waste incineration plant during normal and transient operation. Results are compared with those obtained in other installations equipped with furnaces, energy recovery options and flue gas treatment technologies representative of most of the European incineration plants currently in operation. Levels of the pollutants of interest were determined in all the solid, liquid and gaseous residues produced by every single facility, and the results analysed in terms of the effects arising from the fed waste and the configuration of the plant. PCDD/Fs total release between 1.5 and 45 microg I-TEQ per ton of burned waste was evaluated, with lower values resulting from the adoption of catalytic conversion process for flue gas treatment. Most of the mass flux emitted is associated with solid residues deriving from activated carbon PCCD/F dry removal options, with significant contributions also from fly ash produced by particulate removal devices located immediately downstream the boiler and from scrubber blowdowns treatment sludge. During transient operating conditions the dioxin total release may increase by 50% with comparison to steady-state functioning.

Air Pollutants↗

Destruction of PCDD/Fs by SCR from flue gases of municipal waste incinerator and metal smelting plant.

Partitioning of PCDD/F congeners between vapor/solid phases and removal and destruction efficiencies achieved with selective catalytic reduction (SCR) system for PCDD/Fs at an existing municipal waste incinerator (MWI) and metal smelting plant (MSP) in Taiwan are evaluated via stack sampling and analysis. The MWI investigated is equipped with electrostatic precipitators (EP, operating temperature: 230 degrees C), wet scrubbers (WS, operating temperature: 70 degrees C) and SCR (operating temperature: 220 degrees C) as major air pollution control devices (APCDs). PCDD/F concentration measured at stack gas of the MWI investigated is 0.728 ng-TEQ/Nm(3). The removal efficiency of WS+SCR system for PCDD/Fs reaches 93% in the MWI investigated. The MSP investigated is equipped with EP (operating temperature: 240 degrees C) and SCR (operating temperature: 290 degrees C) as APCDs. The flue gas sampling results also indicate that PCDD/F concentration treated with SCR is 1.35 ng-TEQ/Nm(3). The SCR system adopted in MSP can remove 52.3% PCDD/Fs from flue gases (SCR operating temperature: 290 degrees C, Gas flow rate: 660 kN m(3)/h). In addition, the distributions of PCDD/F congeners observed in the flue gases of the MWI and MSP investigated are significantly different. This study also indicates that the PCDD/F congeners measured in the flue gases of those two facilities are mostly distributed in vapor phase prior to the SCR system and shift to solid phase (vapor-phase PCDD/Fs are effectively decomposed) after being treated with catalyst. Besides, the results also indicate that with SCR highly chlorinated PCDD/F congeners can be transformed to lowly chlorinated PCDD/F congeners probably by dechlorination, while the removal efficiencies of vapor-phase PCDD/Fs increase with increasing chlorination.

Air Pollution↗

The effect of operating variables on chelant-assisted remediation of contaminated dredged sediment.

The paper shows the results from a number of lab-scale washing treatments using the four chelating agents EDTA, NTA, citric acid and [S,S]-EDDS aiming at the remediation of a real heavy metal-contaminated sediment. Investigation of the influence of chelant type and concentration as well as solution pH was the major focus of the work. The analysis of speciation of metals and chelating agents in solution was carried out through geochemical speciation modelling in order to identify the optimal conditions for the washing process as well as to evaluate the competition phenomena of metal-chelant complexes in solution. The major competing cations were found to be Ca above all and Mg under specific conditions. Among the investigated chelating agents, EDDS appeared to be less affected by competition by major cations while ensuring adequate heavy metal extraction efficiencies. For a 1:1 chelant/metal ratio, the following ranking was observed: EDDS>Cit>NTA>EDTA for As, EDDS>NTA congruent withEDTA>>Cit for Cu, EDDS congruent withEDTA congruent withNTA>Cit for Zn, EDTA>NTA>EDDS>Cit for Pb at pH 5 and EDTA congruent withEDDS congruent withNTA>>Cit for Pb at pH 8. For a 10:1 chelant/metal ratio geochemical modelling indicated that at the equilibrium the extracting solutions were dominated by the free form of the chelating agents, indicating the inability of such species to complex trace metals due the strong interactions existing between heavy metal ions and sediment constituents.

Arsenic↗

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone.

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.

Acetone↗

Multi-step leaching of Pb and Zn contaminated soils with EDTA.

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.

Chelating Agents↗

Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron.

The effect of two surfaces (amorphous silica and silica sand) on the reduction of chromium(VI) by zero-valent iron (Fe(0)) was investigated using batch reactors. The amendment of both surfaces significantly increased the rate and extent of Cr(VI) removal. The rate enhancement by amended surfaces is presumed to result from scavenging of Fe(0)-Cr(VI) reaction products by the provided surfaces, which minimized surface deactivation of Fe(0). The rate enhancing effect was greater for silica compared to sand, and the difference is attributed to silica's higher surface area, greater affinity for reaction products and pH buffering effect. For a given mass of Fe(0), the reactivity and longevity of Fe(0) to treat Cr(VI) increased with increasing dose of silica. Elemental analyses of the reacted iron and silica revealed that chromium removed from the solution was associated with both surfaces, with its mass distribution being approximately 1:1 per mass of iron and silica. The overall result suggests reductive precipitation was a predominant Cr(VI) removal pathway, which involves initial reduction of Cr(VI) to Cr(III), followed by formation of Cr(III)/Fe(III) hydroxides precipitates.

Adsorption↗

Improving petroleum contaminated land remediation decision-making through the MCA weighting process.

Internationally petroleum contamination is widespread, posing serious environmental risks including surface and groundwater contamination, thus remediation is essential. The implementation of remediation options is becoming more complex with the increasing influence of stakeholders on the outcome of decision-making processes. Acceptance of remediation schemes during implementation can be increased by involving stakeholders and the public in the decision-making stage. In petroleum remediation involving multiple stakeholders, Multicriteria Analysis has been employed due to its ability to incorporate the preferences of each stakeholder through weighting. The research focused on investigating ways to improve the weighting process. The study demonstrated the utility of SWING, and determined which type of participant and how many participants to include in the decision process, through the application of ELECTRE III and Weighted Summation. It was recommended that a mixture of stakeholders, the public and experts be involved. The total number of participants will be limited by the choice of participatory and weighting methods. The careful selection of participants, as well as the choice of participatory and weighting methods, can minimize the subjectivity involved in MCA weighting, thereby lending decisions in petroleum remediation greater legitimacy.

Adult↗

Arsenic release from iron rich mineral processing waste: Influence of pH and redox potential.

This paper presents the effect of pH and redox potential on the potential mobility of arsenic (As) from a contaminated mineral processing waste. The selected waste contained about 0.47 g kg(-1) of As and 66.2 g kg(-1) of iron (Fe). The characteristic of the waste was identified by acid digestion, X-ray diffraction and sequential extraction procedures. Less than 2% of the total As was acid extractable with the remaining 98% associated with Fe-oxyhydroxides and oxides. Batch leaching tests at different pH conditions showed a strong pH dependence on arsenic and iron leaching. Arsenic leaching followed a "V" shaped profiles with significant leaching in the acidic and alkaline pH region. Acid extractable phases dissolved at acidic pH, while desorption of arsenic due to increase in pH resulted in high arsenic concentration at alkaline pH. Under aerobic conditions and pH 7, As solubility was low, probably due to its precipitation on Fe-oxyhydroxides. Maximum As solubilization occurred at pH 11 (3.59 mg l(-1)). Similarity in the As and Fe leaching profiles suggested that the release of As was related to the dissolution of Fe in the low pH region. In general, redox potential did not play a significant role in arsenic or iron solubilization. It was thus concluded that for this solid waste, desorption was the predominant mechanism in arsenic leaching. A simple thermodynamic model based on arsenic and iron redox reactions was developed to identify the more sensitive redox couple.

Arsenicals↗

Evolution of heavy metal speciation during the aerobic composting process of sewage sludge.

The contents of heavy metals and their bioavailability to the soil-plant system were the major limitation to the application of sewage sludge compost in soil. This study was conducted to determine the evolution of heavy metal speciation in the course of an aerobic composting, and investigate the influence of changes of composting process parameters including pH, temperature and organic matter (OM) content on distribution of heavy metal speciation in composted sludge. The sequential extraction procedure developed by Tessier et al. was used in sludge compost to determine the heavy metal speciation. Results showed that, during composting, (1) the contents of the residue fraction for Pb, Zn and Cd were decreased but those for Ni and Cr were increased; the Cu residue fraction was almost constant; (2) the contents of the total mobile fractions (including fractions 1-4) for Zn and Pb were significantly increased, but the increase of those for Cu and Ni were not so remarkable; (3) there were significant degrees of correlation between heavy metal fractions and changes of some selected parameters (for example, pH, composting temperature, and OM content). Only the content of the total mobile fractions for Cu could be predictable from its total content. For the prediction of the total mobile fractions of Zn, Ni, Cd and Cr, the R(2) value was significantly increased by the inclusion of other variables such as pH, temperature and OM content.

Aerobiosis↗

Phytoremediation: novel approaches to cleaning up polluted soils.

Environmental pollution with metals and xenobiotics is a global problem, and the development of phytoremediation technologies for the plant-based clean-up of contaminated soils is therefore of significant interest. Phytoremediation technologies are currently available for only a small subset of pollution problems, such as arsenic. Arsenic removal employs naturally selected hyperaccumulator ferns, which accumulate very high concentrations of arsenic specifically in above-ground tissues. Elegant two-gene transgenic approaches have been designed for the development of mercury or arsenic phytoremediation technologies. In a plant that naturally hyperaccumulates zinc in leaves, approximately ten key metal homeostasis genes are expressed at very high levels. This outlines the extent of change in gene activities needed in the engineering of transgenic plants for soil clean-up. Further analysis and discovery of genes for phytoremediation will benefit from the recent development of segregating populations for a genetic analysis of naturally selected metal hyperaccumulation in plants, and from comprehensive ionomics data--multi-element concentration profiles from a large number of Arabidopsis mutants.

Arabidopsis↗

Using the stress response to monitor process control: pathways to more effective bioremediation.

Environmental contamination with a variety of pollutants has prompted the development of effective bioremediation strategies. But how can these processes be best monitored and controlled? One avenue under investigation is the development of stress response systems as tools for effective and general process control. Although the microbial stress response has been the subject of intensive laboratory investigation, the environmental reflection of the laboratory response to specific stresses has been little explored. However, it is only within an environmental context, in which microorganisms are constantly exposed to multiple changing environmental stresses, that there will be full understanding of microbial adaptive resiliency. Knowledge of the stress response in the environment will facilitate the control of bioremediation and other processes mediated by complex microbial communities.

Adaptation, Physiological↗

Modulation of flyash-induced genotoxicity in Vicia faba by vermicomposting.

Cytogenetic effects of pre- and postvermicomposted flyash samples were evaluated on the root meristem cells of Vicia faba. Seedlings of V. faba were directly sown in flyash and cow dung-soil mixtures (20%, 40%, 60%, and 80%) and the lateral roots grown in these test mixtures were sampled at 5 days. Negative control was run parallel in cow dung-soil (CS) mixture alone. One set of flyash-cow dung-soil (FCS) mixture was subjected to vermicomposting by introducing Eisenia foetida species of earthworms for 30 days and the cytogenetic effects were reinvestigated through V. faba root meristems. Chemical analysis carried out prior to vermicomposting revealed high concentrations of heavy metals such as Cr, Cu, Pb, Zn, and Ni in FCS samples. CS samples also showed the presence of these metals. Cytogenetic examinations of root meristems exposed to the FCS mixtures showed significant inhibition of mitotic index (MI), induction of chromosome aberrations (CA), and a significantly increased frequency of mitotic aberrations (MA). The increase of the aberrations was dependent on the flyash concentrations. Roots grown in CS samples also showed chromosomal and MAs; however, the percentage was lower than that observed with FCS and also statistically nonsignificant. Cytogenetic analysis of vermicomposted samples of FCS revealed a 15-45% decline in the aberration frequencies whereas chemical analysis showed a 10-50% decline in the metal concentrations, viz. Cr, Cu, Pb, Zn, and Ni, which indicates E. foetida a potential accumulator of heavy metals and the decline in metal concentrations may be the cause of the decrease in aberration frequencies. The present study indicates the genotoxicity potential of flyash and also the feasibility of vermicomposting for cleanup of metal-contaminated soil to mitigate the toxicity/genotoxicity.

Animals↗