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PubMed2005

Dependence of mechanochemically induced decomposition of mono-chlorobiphenyl on the occurrence of radicals.

Mechanochemically induced dechlorination of mono-chlorobiphenyl (BP-Cl) on the surfaces of metal oxides was compared with that on metal hydroxides, using the three metals of Mg, Al, and La as examples. The metal oxides, such as gamma-alumina (gamma-Al2O3), magnesium oxide (MgO) and lanthanum oxide (La2O3) showed an efficient ability to dechlorinate the BP-Cl; however, BP-Cl remained in the ground samples when the hydroxides were used. From the product analysis using gas chromatography/mass spectrometry (GC/MS) and electron spin resonance (ESR) measurements, it was confirmed that the charge transfer from the O2- site on the surface of the oxide additives due to the intense grinding has plays a significant role in the decomposition of the chlorinated compound. Based on the observed dependence of the dechlorination on the radical occurrence, some practical methods were proposed to improve the destruction efficiency of the chlorinated organic compounds.

Aluminum Hydroxide↗

PubMed2005

Comparative toxicity of effluents processed by different treatments in V79 fibroblasts and the algae Selenastrum capricornutum.

The efficacy of ozonation and of photocatalysis processing in the treatment of pulp mill ECF (elementary chlorine free) bleaching and textile effluents was evaluated by determining total organic carbon reduction (TOC) and the toxicity. The chronic toxicity of the effluents was evaluated by the ability to inhibit the growth of algae Selenastrum capricornutum. Cultured hamster V79 fibroblasts were used to assess the cytotoxicity of effluents submitted to different detoxification processes. Two endpoints were measured in V79 cells: 3-(4,5-dimethylthiazole-2-yl)-2,5-biphenyl tetrazolium bromide (MTT) reduction and neutral red uptake (NRU). Both treatment processes were able to reduce the TOC, although ozonization was less effective for pulp mill ECF bleaching. The pulp mill ECF bleaching and textile effluents reduced the growth of S. capricornutum by 39% and 27%, respectively. However, at the highest concentration tested, the textile effluents treated by photochemical process for 60 min showed increased cytotoxicity in V79 cells compared to the untreated effluent when assessed by the NRU and MTT reduction assays (increases of 30% and 40%, respectively). Pulp mill ECF bleaching effluent treated by ozonization had a similar cytotoxicity to that of untreated effluent in the NRU assay. In contrast, the MTT reduction assay indicated that effluents treated with ozone were around 20% more cytotoxic than untreated effluents. These results show that cultured fibroblasts may be useful for studying cellular responses to pollutants and may be included in tests to monitor the efficiency of effluent detoxification processes.

Animals↗

PubMed2005

Anaerobic degradation of hexachlorocyclohexane isomers in liquid and soil slurry systems.

Gamma-hexachlorocyclohexane (gamma-HCH or lindane), one of the most commonly used insecticides, has been mainly used in agriculture. Organochloride compounds are known to be highly toxic and persistent, causing serious water and soil pollution. The objective of the present study is the evaluation of the anaerobic degradation of alpha-, beta-, gamma-, delta-HCH in liquid and slurry cultures. The slurry system with anaerobic sludge appears as an effective alternative in the detoxification of polluted soils with HCH, as total degradation of the four isomers was attained. While alpha- and gamma-HCH disappeared after 20-40d, the most recalcitrant isomers: beta- and delta-HCH were only degraded after 102d. Intermediate metabolites of HCH degradation as pentachlorocyclohexane (PCCH), tetrachlorocyclohexene (TCCH), tri-, di- and mono-chlorobenzenes were observed during degradation time.

Anaerobiosis↗

PubMed2005

Modeling EDTA enhanced electrokinetic remediation of lead contaminated soils.

Electrokinetic extraction has been tested for lead removal from Algerian contaminated soils. For this purpose, a chelating reagent (EDTA, 0.1M) has been injected into the catholyte. This procedure is expected to enhance the process by desorption of the contaminant and formation of new mobile species negatively charged. A mathematical model based on Nernst-Planck theory has also been developed to predict the evolution of lead distribution across the soil as a function of time. The results of several experiments carried out on various duration (10, 20 and 40 days) have shown the importance on treatment efficiency of pollution age and contaminant speciation as determined by sequential chemical extraction.

Adsorption↗

PubMed2005

Dynamic purification of coal ash by a gas-solid fluidized bed.

Fluidized bed filtration classified as granular bed filtration is a solution for removing particles from flue gas. Fine particles are captured by colliding with bed material. Binary mixtures including fines exist in the fluidized bed; the situation becomes more complex because the fines increases with time as particles enter continuously. Coal ash was put into the inlet gas of a gas-solid fluidized bed with silica sand and the variations in concentration with time was monitored, to elucidate the dynamic purification of fines by bed material and the interaction therewith. Water was injected into the inlet gas also to study the influence of water content on the removal of particles. Experimental results showed that the particle concentration rapidly increased with time until equilibrium was achieved. The outlet concentrations exceeded the inlet concentration (such that the removal efficiency was negative) at operating time between 26 and 30 min, yielding an efficiency as low as -35%. The removal efficiency increased with the relative humidity from 30% to 70%. The maximum cumulative collection ratios of particles (by mass) were 20%, 22% and 27% at humidities of 30%, 50% and 70%, declining to 7%, 13%, and 19% at the end.

Adsorption↗

PubMed2005

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils.

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof.

Biodegradation, Environmental↗

PubMed2005

Enhancement of lead uptake by alfalfa (Medicago sativa) using EDTA and a plant growth promoter.

Phytoremediation is a novel cleanup technology for the removal of contaminants from polluted waters and soils. In phytoremediation, the plant uptake capability and the availability of the pollutant in the media are important. Here we show the results of a study on the combined effects of ethylenediaminetetraacetic acid (EDTA) and the phytohormone indole-3-acetic acid (IAA) on Pb uptake by Medicago sativa (alfalfa). Plants were grown in hydroponics media containing a nutrient solution amended with Pb at 0.2mM and different combinations of EDTA, and IAA. After 10d of treatment, the Pb content in plant tissues was quantified using an Inductively Coupled Plasma Optical Emission Spectrometer (ICP/OES). The results showed that the combination of 100 microM IAA/0.2 mM EDTA increased the Pb accumulation in leaves by about 2800% and by about 600%, as compared to Pb content in leaves of plants exposed to Pb alone and those cultivated with Pb/EDTA, respectively. These results indicate that non-metal hyperaccumulator plants could increase their hyperaccumulating potential without genetic manipulation.

Biodegradation, Environmental↗

PubMed2005

Electrokinetic remediation of a Cu-Zn contaminated red soil by controlling the voltage and conditioning catholyte pH.

Electrokinetics is an innovative technique for treating heavy metals contaminated soil, especially low pH soils such as the Chinese red soil (Udic Ferrisols). In this paper, a Cu-Zn contaminated red soil is treated by electrokinetics. When the Cu-Zn contaminated red soil was treated without control of catholyte pH during the electrokinetic treatment, the soil pH in the soil sections near cathode after the experiment was high above 6, which resulted in accumulation of large amounts of Cu and Zn in the soil sections with such high pH values. Compared to soil Cu, soil Zn was more efficiently removed from the soil by a controlled electrokinetic method. Application of lactic acid as catholyte pH conditioning solution caused an efficient removal of Cu and Zn from the soil. Increasing the electrolyte strength (salt concentration) of the conditioning solution further increased Cu removal, but did not cause a significant improvement for soil Zn. Soil Cu and Zn fractions after the electrokinetic treatments were analyzed using sequential extraction method, which indicated that Cu and Zn precipitation in the soil section closest to the cathode in the treatments without catholyte pH control limited their removal from the soil column. When the catholyte pH was controlled by lactic acid and CaCl(2), the soil Cu and Zn removal percentage after 554 h running reached 63% and 65%, respectively. Moreover, both the residual soil Cu and Zn concentrations were lower than 100 mg kg(-1), which is adequate and meets the requirement of the Chinese soil environmental quality standards.

Calcium Chloride↗

PubMed2005

Influence of ozonation on extractability of Pb and Zn from contaminated soils.

The effect of soil ozonation on Pb and Zn extraction with EDTA, bioavailability (Ruby's Physiologically Based Extraction Test, PBET) and mobility (Toxicity Characteristic Leaching Procedure, TCLP) of Pb was studied on contaminated soils taken from 7 different locations in the Mezica Valley, Slovenia. EDTA extraction (40 mmol kg(-1)) removed from 27.4+/-1.5% to 64.8+/-1.5% of Pb, and from 1.9+/-0.2% to 22.4+/-2.0% of Zn from tested soils, and significantly reduced soil Pb bioavailability (PBET) and mobility (TCLP). Pretreatment of tested soils with ozone before EDTA extraction enhanced EDTA extractability of Pb for 11.0 to 28.9%, but had no effect on the extractability of Zn. In most of the soils, ozonation had no statistically significant effect on bioavailability and mobility of Pb, residual after EDTA extraction. Using linear regression analysis we found a significant increase (p<0.01) in EDTA extractability of Pb after soil ozonation in soils with a higher initial Pb content. EDTA extractability of Pb after soil ozonation was also significantly higher for soils with a lower Pb extractability when treated with EDTA alone. We found no correlation between soil organic matter content and the percentage of the Pb fraction bound to soil organic matter (where from 25.6+/-1.3% to 73.2+/-0.6% of Pb reside in tested soils) and Pb extractability with EDTA after soil ozonation.

Biological Availability↗

PubMed2005

The passivation of pyrrhotite by surface coating.

The potential of triethylenetetramine (TETA) to inhibit the oxidation of three pyrrhotites, Garson, McCreedy and Po-97 has been studied systematically and confirmed by comparing the release of Fe and SO4(2-) from samples with and without coating treatment. Each sample, original or coated by TETA, was exposed to oxygen, 1 x 10(-3) M FeCl3, and Acidithiobacillus ferrooxidans, respectively, for specific oxidation periods. Both abiotic and biotic oxidation of samples treated by this passivating agent has been reduced significantly in this study. Under the aerobic condition, lower concentrations of ferric, total Fe or SO4(2-) were obtained from the coated samples than those from the uncoated samples. In the presence of 1 x 10(-3) M FeCl3 at 30 degrees C, TETA was able to reduce oxidation rates of Garson, McCreedy and Po-97 by 83%, 79%, and 81% (based on Fe release), respectively. A higher pH, lower Eh, and lower concentrations of total Fe and SO4(2-) were also observed in the biotic oxidation of coated Garson by Acidithiobacillus ferrooxidans. The protection of pyrrhotite surface from oxidant attack by TETA barrier and the alkaline property of this coating agent can be used to interpret the inhibition of oxidation.

Acidithiobacillus↗

PubMed2005

Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber.

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).

Adsorption↗

PubMed2005

Enhanced chemical oxidation of aromatic hydrocarbons in soil systems.

Fenton's destruction of benzene, toluene, ethylbenzene, and xylene (BTEX) was investigated in soil slurry batch reactors. The purpose of the investigation was to quantify the enhancement of oxidation rates and efficiency by varying process conditions such as iron catalyst (Fe(II) or Fe(III); 2, 5, and 10mM), hydrogen peroxide (H2O2; 30, 150, 300 mM), and metal chelating agents (l-ascorbic acid, gallic acid, or N-(2-hydroxyethyl)iminodiacetic acid). Rapid contaminant mass destruction (97% after 3h) occurred in the presence of 300 mM H2O2 and 10 mM Fe(III). An enhanced removal rate (>90% removal after 15 min and 95% removal after 3h) was also observed by combining Fe(III), N-(2-hydroxyethyl)iminodiacetic acid and 300 mM H2O2. The observed BTEX mass removal rate constants (3.6-7.8 x 10(-4)s(-1)) were compared to the estimated rate constants (4.1-10.1 x 10(-3)s(-1)). The influence of non-specific oxidants loss (by reaction with iron hydroxides and soil organic matter) was also explored.

Ascorbic Acid↗

PubMed2005

Synergic effect of calcium oxide and iron (III) oxide on the dechlorination of hexachlorobenzene.

Dechlorination of hexachlorobenzene (HCB) was achieved by a mixture of commercial CaO and alpha-Fe2O3 (CaO/alpha-Fe2O3) in closed systems at temperatures of 300 degrees C and 350 degrees C, which exhibited a synergic effect compared to CaO or alpha-Fe2O3 alone, and the dechlorination efficiency was dramatically enhanced. When CaO and alpha-Fe2O3 coexisted, HCB was dechlorinated by about 98% after 0.5 h reaction at 300 degrees C. All TeCB-, TrCB-, and DCB-isomers were detected, showing the presence of more than one dechlorination pathway. The pathway to form 1,2,4-TrCB must be a major pathway because the greatest amount of 1,2,4-TrCB was detected. There existed discrepancy of the material balance between the starting and dechlorinated materials. It implies that besides dechlorination other decomposition processes may be present. The mechanism of synergic effect of calcium and iron oxides was investigated.

Calcium Compounds↗

PubMed2005

Appropriate combination of physico-chemical methods (coagulation/flocculation and ozonation) for the efficient treatment of landfill leachates.

An integrated technique consisted of ozonation and coagulation/flocculation processes was studied, aiming to provide an efficient method for the treatment of stabilized/biologically pre-treated leachates, in order to reduce the organic pollutants' content to concentration values lower than the corresponding limits, imposed by the legislation. Leachates were collected from a municipal landfill site; samples containing around 1000 mg l(-1) COD and BOD(5)/COD ratio about 0.17 were treated by using two different processes or combinations between them, i.e. ozonation, coagulation-flocculation, ozonation followed by coagulation/flocculation and coagulation/flocculation followed by ozonation. The application of single ozonation resulted to the efficient removal of color and organic loading, due to the respective oxidation, induced by ozonation; however, COD values lower than 200 mg l(-1) could be only achieved after prolonged reaction times and for high ozone production rates. The coagulation of leachate samples was studied by the addition of ferric chloride or poly-aluminum chloride agents at various dosages. Maximum COD removal rates (up to 72%) were achieved by the addition of 7 mM Fe, or of 11 mM Al respectively. However, final COD values higher than 200 mg l(-1) were obtained indicating the requirement of an additional treatment step. Pre-ozonation followed by coagulation/flocculation was not found to be an efficient treatment approach for this aim, but coagulation/flocculation followed by ozonation, was proved to be an efficient process for the reduction of COD to lower than 180 mg l(-1).

Chemistry, Physical↗

PubMed2005

Phosphorus release from ash, dried sludge and sludge residue from supercritical water oxidation by acid or base.

Leaching of ash and dried sewage sludge were investigated and compared with the leaching results of sludge residue from supercritical water oxidation (SCWO). This article focuses on how the composition of ash and sludge residues influences the extraction of phosphate and heavy metals and if different treatment temperatures of the sludge effect the leachability. Results showed that acid leaching gave a higher release of phosphate than alkaline leaching for all ash and sludge residue samples. Also, alkaline leaching dissolved phosphate with a lower metal contamination than acid leaching. Furthermore, it was found that iron had a low release at both alkaline and acid leaching from ash and from SCWO residue. The difference in composition of ash and sludge residue samples had no significant influence on release of phosphate at high concentrations of acid. Phosphate release from ash, dried sludge at 300 degrees C and SCWO residue showed similar results at 1M acid leaching. However, it seems to be easier to release phosphate from the SCWO residue than from the ash at low acid concentrations. SCWO residue showed higher release than the other ashes at 0.5M HCl. Results for alkaline leaching showed higher release from ash at 1M NaOH than from SCWO residue or from dried sludge at 300 degrees C. The leaching of phosphate from dried sludge seems to be temperature dependent, as the dried sludge treated at higher temperature showed less release of phosphate. It was found that the pre-treatment of the ash may be important for better release of phosphate.

Acids↗

PubMed2005

Mineralization of Reactive Black 5 in aqueous solution by basic oxygen furnace slag in the presence of hydrogen peroxide.

Basic oxygen furnace slag (BOF slag) is a solid waste arisen from the steel making process. FeO is one of the major components of BOF slag. The FeO-containing property of BOF slag makes it possible to catalyze the Fenton reaction. Reactive Black 5 (RB5) dye is chosen as the target compound in this study. This study has investigated the catalytic performance of BOF slag on the Fenton reaction to decompose RB5 in aqueous solution. A first-order kinetic model with respect to TOC was adopted to explain the mineralization of RB5 by the H(2)O(2)/BOF slag process. The experimental results in this study suggested that dosage with 1.49 x 10(-4)M min(-1) H(2)O(2) and 12.5 g l(-1) BOF slag in the solution at pH 2 provided the optimal operation conditions for the mineralization of RB5 yielding a 51.2% treatment efficiency at 100 min reaction time, and complete decoloration can be achieved within 30 min reaction time. The H(2)O(2)/Fe(2+) ratio was then determined to be 6.06:1.

Hydrogen Peroxide↗

PubMed2005

The role of SBR mixed liquor volume exchange ratio in aerobic granulation.

Four sequencing batch reactors (SBR) were operated at different volume exchange ratios of 20-80%. Results showed that a rapid aerobic granulation could be achieved in SBR run at high volume exchange ratios, and the characteristics of mature aerobic granules in terms of mean size, SVI, granule fraction, EPS and calcium content were all closely related to the volume exchange ratio applied to SBR. To interpret the role of volume exchange ratio in aerobic granulation, a concept of minimum settling velocity of bioparticles was proposed, which is the function of both settling time and volume exchange ratio. It was further demonstrated that the effect of volume exchange ratio on aerobic granulation in SBR would be realized through selecting the minimum settling velocity of bioparticles. In fact, the minimum settling velocity would serve as a major selection pressure exerted on bioparticles. It appeared from this study that the production of EPS was stimulated significantly by high volume exchange ratio, which was associated with marketable accumulation of calcium ion in aerobic granulation. It is expected that this study may offer insights into the mechanism of aerobic granulation.

Aerobiosis↗

PubMed2005

Studies on removal of metal ions and sulphate reduction using rice husk and Desulfotomaculum nigrificans with reference to remediation of acid mine drainage.

The utility of rice husk as an adsorbent for metal ions such as iron, zinc and copper from acid mine water was assessed. The adsorption isotherms exhibited Langmuirian behavior and were endothermic in nature. The free energy values for adsorption of the chosen metal ions onto rice husk were found to be highly negative attesting to favorable interaction. Over 99% Fe(3+), 98% of Fe(2+) and Zn(2+) and 95% Cu(2+) uptake was achieved from acid mine water, with a concomitant increase in the pH value by two units using rice husk. The remediation studies carried out on acid mine water and simulated acid mine water pretreated with rice husk indicated successful growth of Desulfotomaculum nigrificans (D. nigrificans). The amount of sulphate bioreduction in acid mine water at an initial pH of 5.3 was enhanced by D. nigrificans from 21% to 40% in the presence of rice husk filtrate supplemented with carbon and nitrogen. In simulated acid mine water with fortified husk filtrate, the sulphate reduction was even more extensive, with an enhancement to 73%. Concurrently, almost 90% Fe(2+), 89% Zn(2+) and 75% Cu(2+) bioremoval was attained from simulated acid mine water. Metal adsorption by rice husk was confirmed in desorption experiments in which almost complete removal of metal ions from the rice husk was achieved after two elutions using 1M HCl. The possible mechanisms of metal ion adsorption onto rice husk and sulphate reduction using D. nigrificans are discussed.

Adsorption↗