Combined effect of microwave and activated carbon on the remediation of polychlorinated biphenyl-contaminated soil

The application of microwave and activated carbon for the treatment of polychlorinated biphenyl (PCB) contaminated soil was explored in this study with a model compound of 2,4,5-trichlorobiphenyl (PCB29). PCB-contaminated soil was treated in a quartz reactor by microwave irradiation at 2450MHz with the addition of granular activated carbon (GAC). In this procedure, GAC acted as microwave absorbent for reaching high temperature and reductant for dechlorination. A sheltered type-K thermocouple was applied to record the temperature rising courses. It was shown that the addition of GAC could effectively promote the temperature rising courses. The determination of PCB residues in soil by gas chromatography (GC) revealed that rates of PCB removal were highly dependent on microwave power, soil moisture content, and the amount of GAC added. GC with mass spectrum (MS) detector and ion chromatography were employed for the analysis of degradation intermediates and chlorine ions, respectively. It was suggested that microwave irradiation with the assistance of activated carbon might be a potential technology for the remediation of PCB-contaminated soil.     

Investigation of polychlorinated biphenyl removal from contaminated soil using microwave-generated steam

A feasibility study of polychlorinated biphenyl (PCB) removal from contaminated soils using microwave-generated steam (MGS) was performed. Initial experimental results show that MGS effectively removed PCBs from contaminated soil with an overall removal efficiency of greater than 98% at a steam-to-soil mass ratio of 3:1. Removal efficiency was found to be dependent upon the amount of steam employed, expressed as a mass ratio of steam applied to soil mass. Evaporation was identified as a major mechanism in removing PCBs from the soil. Rapid expansion and evaporation of pore water by microwave dielectric heating accelerated evaporation rates of PCB molecules. Increased solubility of PCBs into the heated aqueous phase is also hypothesized. Together these effects increase mass-transfer rates, thus enhancing removal of PCBs from the soil.     

In Memoriam

ABSTRACT

A feasibility study of polychlorinated biphenyl (PCB) removal from contaminated soils using microwave-generated steam (MGS) was performed. Initial experimental results show that MGS effectively removed PCBs from contaminated soil with an overall removal efficiency of greater than 98% at a steam-to-soil mass ratio of 3:1. Removal efficiency was found to be dependent upon the amount of steam employed, expressed as a mass ratio of steam applied to soil mass. Evaporation was identified as a major mechanism in removing PCBs from the soil. Rapid expansion and evaporation of pore water by microwave dielectric heating accelerated evaporation rates of PCB molecules. Increased solubility of PCBs into the heated aqueous phase is also hypothesized. Together these effects increase mass-transfer rates, thus enhancing removal of PCBs from the soil.     

微波辐射回用活性炭对水中亚甲基蓝和Cd~(2+)去除效果的研究

考察了微波-活性炭联合处理技术对模拟染料废水中亚甲基蓝和Cd2+的去除效果。对于100 mL浓度为1 000 mg/L的亚甲基蓝溶液、活性炭用量为10 g时,新活性炭对亚甲基蓝的去除率为99.99%;采用700 W微波对吸附亚甲基蓝的活性炭辐射10 min进行再生并回用,经微波辐射再生10次后活性炭对亚甲基蓝的去除率为99.68%,未经微波作用反复使用10次的活性炭对亚甲基蓝的去除率为85.41%。结果表明:微波处理有效地减缓了活性炭吸附能力的下降速率,实现了活性炭再生和反复使用。在吸附过程中,Cd2+使活性炭对亚甲基蓝的吸附能力略有下降,而共存的亚甲基蓝则促进了活性炭对Cd2+的吸附,对新炭和再生后活性炭物理化学特性的表征证明了活性炭对亚甲基蓝的吸附为物理吸附,对Cd2+的吸附为化学吸附。     

微波辐射回用活性炭对水中亚甲基蓝和Cd2＋去除效果的研究

考察了微波-活性炭联合处理技术对模拟染料废水中亚甲基蓝和Cd2＋的去除效果。对于100 mL浓度为1 000 mg/L的亚甲基蓝溶液、活性炭用量为10 g时,新活性炭对亚甲基蓝的去除率为99.99%;采用700 W微波对吸附亚甲基蓝的活性炭辐射10 min进行再生并回用,经微波辐射再生10次后活性炭对亚甲基蓝的去除率为99.68%,未经微波作用反复使用10次的活性炭对亚甲基蓝的去除率为85.41%。结果表明：微波处理有效地减缓了活性炭吸附能力的下降速率,实现了活性炭再生和反复使用。在吸附过程中,Cd2＋使活性炭对亚甲基蓝的吸附能力略有下降,而共存的亚甲基蓝则促进了活性炭对Cd2＋的吸附,对新炭和再生后活性炭物理化学特性的表征证明了活性炭对亚甲基蓝的吸附为物理吸附,对Cd2＋的吸附为化学吸附。     

微波修复氯丹污染土壤中氯丹降解的影响因素研究

对微波修复氯丹污染土壤进行研究,重点考察了含水率、微波辐射时间、碱浓度、活性炭添加量和土壤量对其中氯丹降解的影响。结果表明:(1)总体上,氯丹降解率随着含水率的增加而先增加后减少,随着微波辐射时间的延长而增加。当含水率为20%、微波辐射15min后,α-氯丹和γ-氯丹的降解率分别增加到65%和56%。(2)总体上,氯丹降解率随着微波辐射时间的延长而不断增加,7min后氯丹的降解过程基本趋于平衡。10mol/L氢氧化钠溶液存在条件下氯丹降解效果最好,15min时α-氯丹和γ-氯丹的降解率分别为94%和82%。(3)氢氧化钠溶液最佳摩尔浓度为10mol/L。(4)添加1.0g活性炭条件下,氯丹降解率随着微波辐射时间延长而迅速增加,15min时α-氯丹和γ-氯丹的降解率分别为98%和94%。(5)当土壤和活性炭的质量比固定为15∶1时,随着土壤量的增加,氯丹降解率明显增加。     

Microwave Process for Volatile Organic Compound Abatement

ABSTRACT

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.     

Microwave process for volatile organic compound abatement

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.     

微波辅助双氧水氧化降解水中磺胺二甲嘧啶

采用微波辐照技术辅助双氧水氧化降解水中磺胺二甲嘧啶（SM2）,研究了微波辅助双氧水氧化降解水中SM2的影响因素。结果表明,单纯使用微波辐照并不能显著降解SM2,而微波辐照可显著促进双氧水对SM2的氧化作用,提高SM2的降解率。在初始浓度为50 mg/L,微波功率为900 W,加入0.25 mL质量分数为30%的双氧水,pH值为4的条件下辐照6 min,SM2的降解率可达96.5%,COD去除率为72%。     

TiO2 photocatalytic degradation of PCBs in soil-water systems containing fluoro surfactant

Titanium dioxide-mediated photodegradation of Polychlorinated biphenyls (PCBs) in soil/aqueous systems with added fluorinated surfactant was investigated. PCBs can bind tightly to organic matter in the soil, especially in aged, contaminated soil. Experiments showed an effective PCB photocatalytic degradation in mixed systems of soil/clay with anionic fluorinated surfactant FC-143 and TiO2. The FC-143 surfactant is stable in this photochemical process. PCB degradation rates in samples followed the order: spiked clay > spiked soil > Hudson River bank soil. The results suggest that anionic fluorinated surfactant may form semimicelles and/or admicelles on the surface of positively charged TiO2. The hydrophobic surface of TiO2 can provide a nonpolar phase that acts as a partioning medium for hydrophobic PCBs. Therefore, PCBs in soil can be released to the semimicelle and/or admicelle on the TiO2 surface and are effectively photodegraded in a dispersion containing anionic fluorinated surfactant. The combination of surfactant extraction and photooxidation forms the basis for a novel two-stage process for the removal and destruction of PCBs from soil.     

Study of transportation and distribution of PCBs using an ecologically simulated growth chamber

This study was designed to investigate the transportation, distribution, and bioaccumulation of PCBs in various environmental media and compartments using an ecologically simulated growth chamber. Spatial and temporal trends of PCBs in the growth chamber were discussed. The release of PCB congeners in soil was affected by the amount of rainfall with the transporting direction moving away from PCBs contaminated point. Two pathways of PCBs accumulation in plants were the uptake of roots and the deposition on shoots/leaves. There were 29 PCB congeners been found in the lalang grass. Higher concentrations of lower chlorinated PCBs were identified than higher chlorinated PCBs because of relatively higher vapor pressure for lower chlorinated congeners. After 10months of monitoring, PCBs were detected in water samples which were contributed by the release of PCBs from leached soil. Analysis of sediment showed that the percentages of low- and mid-chlorinated biphenyls were decreased 1% and 13%, respectively compared to the increase (14%) of high-chlorinated biphenyls. The increase of high-chlorinated PCBs was possibly caused by their low hydrophilicity which had resulted higher adsorption rate in sediment. All of five species of fish had been found significant amount of PCBs accumulation ( summation operatorPCBs: 21.7-102.1 microg/g-lipid). The concentrations of PCBs in fish were varied significantly among species. The range of bioaccumulation factors (BAFs) among different species of fish could be as much as 5 times depending on the consumption habits of fish. The mass balance of PCBs distribution in the growth chamber was also discussed.     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

微波促进含Cr(VI)-H2O2体系降解甲基橙溶液的研究

研究了微波辐射下Cr(VI)－H₂O₂催化降解甲基橙溶液的行为，探索了微波功率、微波辐射时间、pH值、H₂O₂浓度、Cr(VI)等对甲基橙溶液脱色率和COD去除率的影响。研究结果表明，Cr(VI)-H₂O₂能形成类Fenton体系；微波辐射可提高H₂O₂产生羟基自由基(·OH)的效率。1000 mg/L的甲基橙溶液，在Cr(VI)浓度为10.0 mmol/L、pH值为2.5、H₂O₂浓度为20.0 mmol/L、微波功率为700W下加热2 min，甲基橙溶液的脱色率为99.2%，COD去除率为82.8%。     

Solvent extraction and tandem dechlorination for decontamination of soil

The United States Environmental Protection Agency (US EPA) guidelines allow removal of polychlorinated biphenyls (PCBs) from soils via solvent extraction. This option holds promise for removal of other recalcitrant organic contaminants as well. A study was undertaken to evaluate the effectiveness of solvent extraction with two tandem degradation techniques. The degradation techniques were chemical dehalogenation with immobilized reagents and gamma-ray irradiation. The integrated approach was evaluated with contaminated soils from wood treatment and electric power substation sites. Evaluations were carried out on a bench scale in the laboratory and on a semi-pilot scale at a contaminated site. Binary solvent mixture of alkanes and alcohols yielded the highest extraction efficiencies. Extraction efficiencies in excess of 90% were obtained for PCBs, polychlorinated dibenzo-p-dioxins (PCDDs) and polynuclear aromatic hydrocarbons (PAHs). Extracted PCBs were rapidly degraded through chemical dehalogenation or with high doses of the gamma-ray irradiation. The residual organics in the solvent mixture were removed with activated carbon, and the solvent was recycled for subsequent soil extractions. Contaminants adsorbed on the activated carbon were destroyed with a counter flow oxidation process.     

Effect of temperature and particle size on the thermal desorption of PCBs from contaminated soil

Thermal desorption is widely used for remediation of soil contaminated with volatiles, such as solvents and distillates. In this study, a soil contaminated with semivolatile polychlorinated biphenyls (PCBs) was sampled at an interim storage point for waste PCB transformers and heated to temperatures from 300 to 600 °C in a flow of nitrogen to investigate the effect of temperature and particle size on thermal desorption. Two size fractions were tested: coarse soil of 420–841 μm and fine soil with particles <250 μm. A PCB removal efficiency of 98.0 % was attained after 1 h of thermal treatment at 600 °C. The residual amount of PCBs in this soil decreased with rising thermal treatment temperature while the amount transferred to the gas phase increased up to 550 °C; at 600 °C, destruction of PCBs became more obvious. At low temperature, the thermally treated soil still had a similar PCB homologue distribution as raw soil, indicating thermal desorption as a main mechanism in removal. Dechlorination and decomposition increasingly occurred at high temperature, since shifts in average chlorination level were observed, from 3.34 in the raw soil to 2.75 in soil treated at 600 °C. Fine soil particles showed higher removal efficiency and destruction efficiency than coarse particles, suggesting that desorption from coarse particles is influenced by mass transfer.     

Degradation of 3,3′-iminobis-propanenitrile in aqueous solution by Fe0/GAC micro-electrolysis system

The degradation of 3,3′-iminobis-propanenitrile was investigated using the Fe⁰/GAC micro-electrolysis system. Effects of influent pH value, Fe⁰/GAC ratio and granular activated carbon (GAC) adsorption on the removal efficiency of the pollutant were studied in the Fe⁰/GAC micro-electrolysis system. The degradation of 3,3′-iminobis-propanenitrile was affected by influent pH, and a decrease of the influent pH values from 8.0 to 4.0 led to the increase of degradation efficiency. Granular activated carbon was added as cathode to form macroscopic galvanic cells between Fe⁰ and GAC and enhance the current efficiency of the Fe⁰/GAC micro-electrolysis system. The GAC could only adsorb the pollutant and provide buffer capacity for the Fe⁰/GAC micro-electrolysis system, and the macroscopic galvanic cells of the Fe⁰/GAC micro-electrolysis system played a leading role in degradation of 3,3′-iminobis-propanenitrile. With the analysis of the degradation products with GC–MS, possible reaction pathway for the degradation of 3,3′-iminobis-propanenitrile by the Fe⁰/GAC micro-electrolysis system was suggested.     

微波修复原油污染土壤的均匀设计实验

采用均匀设计实验方法,研究了微波修复原油污染土壤时原油去除率与微波能耗、含水率和含炭率等因素的关系,并应用MATLAB编程拟合出经验公式。结果分析表明:微波能耗在0～288 kJ范围内,污染土壤的原油去除率随微波能耗线性增加;在含水率为6%、含炭率为4%、微波能耗从0增加到288 kJ时,原油去除率从0%增加至92.3%;含炭率在0%～4%范围内原油去除率与含炭率成线性关系,在微波能耗为288 kJ、含水率为6%、含炭率从0%增加到4%时,原油去除率从12.3%增加至92.3%;原油去除率与含水率成二次曲线关系且开口向下,微波修复原油污染土壤的最佳含水率为6.6%。研究结果对微波修复原油污染土壤技术的优化提供了有价值的参考。     

Endocrine effects generated by photooxidation of coplanar biphenyls in water using titanium dioxide

The oxidative photodegradation behaviors of selected three coplanar polychlorinated biphenyls (PCBs), (CB77, CB81, and CB169) using titanium dioxide (TiO(2)) in water were investigated. The main purposes were to clarify the structural relation between the original PCBs and the intermediates derived by TiO(2) oxidation and to evaluate the estrogenic and thyroid hormonal activity in the treated three coplanar PCBs during the oxidative reactions. Approximately 90% of the three coplanar PCBs decomposed within 180 min. Intermediates from the decomposition of the three coplanar PCBs, such as some hydroxylated-PCBs (OH-PCBs), carboxylic intermediates, phenolic intermediates, and other intermediates produced by the cleavage of a benzene ring were identified and quantified. In the degradation pathways, the produced amounts of OH-PCBs increased within 60 min of irradiation time. The estrogenic activity and thyroid hormonal activity of the intermediates from the three coplanar PCBs in water at 0, 60, 120, 180 and 240 min of irradiation time were assessed by using a yeast two-hybrid assay system for human estrogen receptor alpha (hERalpha) and human thyroid hormone receptor alpha (hTRalpha). The maximal estrogenic activities were induced by the solutions of decomposed PCBs with irradiation time at 60-120 min similar and slightly lower than those after the irradiation time. We found that the solutions occuring during the irradiation times of 60-120 min contained several 4-OH-PCBs substituted with OH and Cl at para- and para'-positions having estrogenic activity. The thyroid hormonal activity was not detected in the decomposed three coplanar PCBs solutions.     

Benzo[a]pyrene removal from soil by Phanerochaete chrysosporium grown on sugarcane bagasse and pine sawdust

The capacity of Phanerochaete chrysosporium grown on soil with added sugarcane baggase (BP) and pine sawdust (PS) to remove benzo(a)pyrene (BaP) was studied. A half factorial two-level experiment 2(4-1) was designed to determine the effect of: type of lignocellulosic material (BP and PS) for fungus growth, age of fungus (5 and 10d), amount of lignocellulosic material (10% and 15% w/w) and soil moisture content (water holding capacity of 45% and 56% w/w). Inoculum obtained at different ages showed that the capacity of P. chrysosporium to remove BaP depends on the lignocellulosic used and on inoculum age. Abiotic BaP removal was affected significantly (p<0.05) by inoculum age, type of lignocellulosic added and soil moisture content. The removal of BaP by lignocellulosic material was more effective by young inocula (71.97 mg BaP kg(-1) dry soil), with high percentage of added lignocellulosic (71.57 mg BaP kg(-1) dry soil) and at low soil moisture content (73.07 mg BaP kg(-1) dry soil). When fungus was grown on BP, maximum BaP removal rate was obtained at 5d of incubation (10.85 mg BaP d(-1)l(-1) and 50.12 mg BaP kg(-1) dry soil), while in PS maximum BaP removal was obtained at 10d of incubation (12.06 mg BaP d(-1)l(-1) and 39.94 mg BaP kg(-1) dry soil).     

Activated carbon amendment to sequester PAHs in contaminated soil: a lysimeter field trial

Activated carbon (AC) amendment is an innovative method for the in situ remediation of contaminated soils. A field-scale AC amendment of either 2% powder or granular AC (PAC and GAC) to a PAH contaminated soil was carried out in Norway. The PAH concentration in drainage water from the field plot was measured with a direct solvent extraction and by deploying polyoxymethylene (POM) passive samplers. In addition, POM samplers were dug directly in the AC amended and unamended soil in order to monitor the reduction in free aqueous PAH concentrations in the soil pore water. The total PAH concentration in the drainage water, measured by direct solvent extraction of the water, was reduced by 14% for the PAC amendment and by 59% for GAC, 12 months after amendment. Measurements carried out with POM showed a reduction of 93% for PAC and 56% for GAC. The free aqueous PAH concentration in soil pore water was reduced 93% and 76%, 17 and 28 months after PAC amendment, compared to 84% and 69% for GAC. PAC, in contrast to GAC, was more effective for reducing freely dissolved concentrations than total dissolved ones. This could tentatively be explained by leaching of microscopic AC particles from PAC. Secondary chemical effects of the AC amendment were monitored by considering concentration changes in dissolved organic carbon (DOC) and nutrients. DOC was bound by AC, while the concentrations of nutrients (NO(3), NO(2), NH(4), PO(4), P-total, K, Ca and Mg) were variable and likely affected by external environmental factors.