Impact of ozone on the growth of birch (Betula pendula) saplings

Saplings of one half-sib family of birch, Betula pendula, were exposed to three levels of ozone in open-top chambers (OTCs) during two growing seasons 1997-1998. The ozone treatments were non-filtered air (NF, accumulated daylight AOT40 over the two growing seasons of 3.0 l l-1 h), non-filtered air with extra ozone (NF+, accumulated daylight AOT40 of 27.3 l l-1 h) and non-filtered air with additional extra ozone (NF++, accumulated daylight AOT40 of 120 l l-1 h). The birch saplings, including the roots, were harvested after the first and second growing seasons. After the first growing season, the NF++ treatment reduced the total wood biomass by 22%, relative to the NF treatment. There was no further reduction of the total wood biomass in the NF++ treatment after the second growing season. The root biomass was reduced by 30% after the first growing season. The shoot/root ratio, as well as the proportional biomass of leaves, were increased by ozone during both years. The ozone impact on the relative growth rate was estimated to -2% per 10 l l-1 h daylight AOT40 per growing season.     

粉煤灰沸石负载Ce^3＋／TiO2光催化降解水中的菲和荧蒽

以钛酸四丁酯为前驱体,粉煤灰合成沸石为载体,采用溶胶-凝胶方法,在低温条件下制备了稀土铈掺杂的TiO2光催化剂。利用SEM—EDS、XRD、FTIR对催化剂进行了分析和表征。以高压汞灯为灯源,对多环芳烃菲、荧蒽的降解进行了研究。实验考查了稀土铈掺杂质量分数、催化剂用量、溶液pH、目标物初始质量浓度等因素对光催化降解的影响,研究了其光降解动力学。结果表明,当稀土铈含量为0．5％,催化剂用量为3g／L,pH偏碱性时,催化效果最佳。光催化反应符合Langmuir—Hinshelwood动力学规律,菲、荧蒽的降解过程符合一级反应动力学,反应速率常数分别为0．0126min^-1,0．0099min^-1。     

粉煤灰沸石负载Ce3+/TiO2光催化降解水中的菲和荧蒽

以钛酸四丁酯为前驱体,粉煤灰合成沸石为载体,采用溶胶-凝胶方法,在低温条件下制备了稀土铈掺杂的TiO₂光催化剂。利用SEM-EDS、XRD、FTIR对催化剂进行了分析和表征。以高压汞灯为灯源,对多环芳烃菲、荧蒽的降解进行了研究。实验考查了稀土铈掺杂质量分数、催化剂用量、溶液pH、目标物初始质量浓度等因素对光催化降解的影响,研究了其光降解动力学。结果表明,当稀土铈含量为0.5%,催化剂用量为3 g/L,pH偏碱性时,催化效果最佳。光催化反应符合Langmuir-Hinshelwood 动力学规律,菲、荧蒽的降解过程符合一级反应动力学,反应速率常数分别为0.0126 min^-1,0.0099 min^-1。     

Dechlorination and destruction of PCDD,PCDF and PCB on selected fly ash from municipal waste incineration

The potential of fly ash to dechlorinate and destroy PCDD, PCDF and PCB was tested under oxygen deficient conditions in the laboratory. Specifically, two types of fly ash were compared, originating either from a fluidized bed incinerator using Ca(OH)₂ spray (FA1), or a stoker incinerator without Ca(OH)₂ impact (FA2).

Results from the present study indicate that on FA2 type fly ash, the degradation processes of OCDD, OCDF and D₁₀CB occurred primarily via dechlorination/hydrogenation up to temperature settings of 340 °C. In contrast, FA1 type fly ash was found to effect both dechlorination and destruction of these compounds already at temperature settings of 260 °C.

The dechlorination velocity of PCDD and PCDF did not differ significantly. However, the first dechlorination step of OCDF in the 1,9-position occurred faster compared to the first dechlorination step of OCDD.

The isomer pattern resulting from the dechlorination processes was quite similar on both FA1 and FA2, indicating that differences in alkalinity or elemental composition of the two types of fly ashes do not have a significant influence on the position of dechlorination. PCDD and PCDF dechlorination of the 2,3,7,8-positions was not favoured over dechlorination of the 1,4,6,9-positions on either type of fly ash. In contrast, dechlorination of PCB occurred predominantly on the toxicological relevant 3- and 4-positions.

The dechlorination/destruction processes were completed on both types of fly ash at 380 °C within one hour, which correlates well with results obtained from actual plant operation practices.     

Kinetic analysis of constructed systems for the recovery of contaminated areas by acid mine drainage

INTRODUCTION: Flowing of the acid mine drainage may contaminate the adjacent water bodies causing substantial changes in the aquatic ecosystem. This aspect is the most relevant problem in the southern of Santa Catarina once the contaminated areas are inserted in the watershed of the Araranguá, Urussanga, and Tubar?o rivers, increasing the need for recovery studies. These areas are between Criciúma, I?ara, Urussanga, Siderópolis, Lauro Müller, Orleans, and Alfredo Wagner towns where a conservation unit exist called the Environmental Preservation Area of Baleia Franca. Aiming to compare the kinetics of the ash derived from burning coal and to neutralize acid mine drainage, different neutralizer, limestone, fly, and bottom ash, was mounted on a pilot scale experiment. DISCUSSION: The transport parameters showed the same order of infiltration and dispersion: fly ash < bottom ash < limestone. The order of measured alkalinity was: limestone < fly ash < bottom ash, with pH values of 9.34, 12.07, and 12.25, respectively. The limestone kinetics of acidic drainage neutralization was first order with reaction rate constant k?=?0.0963 min(-1), bottom ash was 3/4 with k?=?0.0723 mol(1/4) L(-1/4) min(-1), and the fly ash had higher order kinetics, 4/3, with reaction rate constant k?=?27.122 L(1/3) mol(-1/3) min(-1). However, by mathematical modeling, it was found that due to a combination of transport and kinetics, only limestone treatment reached a pH above 6 within 5 years, corresponding to the ideal as planned.     

Kinetics of quinoline degradation by O3/UV in aqueous phase

The kinetics of quinoline degradation by O3/UV in aqueous phase was studied in this paper. It was found that the stoichiometric factor for the number of ozone molecule consumed by per quinoline molecule was 1. The second-order rate constants at 15 degrees C for the direct reaction of quinoline with ozone and that for the reaction of quinoline with *OH were determined to be 51.0 and 7.24 x 10(9) M(-1)s(-1), respectively. In O3/UV reaction system, *OH was the more important oxidant to degrade quinoline than ozone. For a comparison, in O3 reaction system, the relative importance of the two oxidants depended on the pH value greatly. To make the degradation of quinoline more practical, improvement of the concentration of *OH is more feasible.     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Polycyclic aromatic hydrocarbons (PAHs) concentrations and related carcinogenic potencies in soil at a semi-arid region of India

A study of polycyclic aromatic hydrocarbons in surface soil was conducted at selected locations in Agra (semi-arid region of India) for a span of one year in order to ascertain the contamination levels. The concentrations of PAH were measured at four locations in the city of Agra, which covers industrial, residential, roadside and agricultural areas. The samples were extracted with hexane by ultrasonic agitation. The extracts were then fractioned on a silica-gel column and the aromatic fraction was subjected to HPLC. The average concentration of total PAH in all samples was 12.1 microg g(-1) and the range was from 3.1 microg g(-1) to 28.5 microg g(-1). The maximum concentrations of PAHs were found to be in winter season. The concentration of PAH decreased in the order chrysene > benzo(b)fluoranthene > fluoranthene. Factor analysis suggests that the mixed signature of all the sources are intermediate between vehicular and combustion activities.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzo-furans in solid residues from wood combustion by HRGC/HRMS

PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.     

Chemical and physical characterization of emissions from birch wood combustion in a wood stove

The purpose of this study was to characterize the emissions of a large number of chemical compounds emitted from birch wood combustion in a wood stove. Birch wood is widely used as fuel in Swedish household appliances. The fuel load was held constant during six experiments.Particles <2.5 μm in diameter were collected and the size distribution of the particles was measured. The results were compared to the size distribution in road traffic emissions. It could be seen that the number distribution differed between the sources. In traffic exhaust, the number of particles maximized at 20 nm, while the number distribution from wood burning ranged from 20 to 300 nm. The ratio K/Ca on particles was found to be significantly different in wood burning compared to road dust, range 30–330 for the former and 0.8±0.15 for the latter. The source profile of common elements emitted from wood burning differed from that found on particles at a street-level site or in long-distance transported particles.The ratio toluene/benzene in this study was found to be in the range 0.2–0.7, which is much lower than the ratio 3.6±0.5 in traffic exhaust emissions.Formaldehyde and acetone were the most abundant compounds among the volatile ketones and aldehydes. The emission factor varied between 180–710 mg/kg wood for formaldehyde and 5–1300 mg/kg wood for acetone. Of the organic acids analyzed (3,4,5)-trimethoxy benzoic acid was the most abundant compound. Of the PAHs reported, fluorene, phenanthrene, anthracene, fluoranthene and pyrene contribute to more than 70% of the mass of PAH. Of the elements analyzed, K and Si were the most abundant elements, having emission factors of 27 and 9 mg/kg wood, respectively.Although fluoranthene has a toxic equivalence factor of 5% of benzo(a)pyrene (B(a)P), it can be seen that the toxic potency of fluoranthene in wood burning emissions is of the same size as B(a)P. This indicates that the relative carcinogenic potency contribution of fluoranthene in wood smoke would be about 40% of B(a)P.     

Dioxin mass balance in a municipal waste incinerator

A dioxin mass balance in an Spanish municipal waste incinerator (MWI) is presented. Input and output inventories from two sampling collection episodes including the analysis of PCDD/PCDF in urban solid waste (USW), stack gas emissions, fly ash and slag are reported. In one collection the levels of USW were around 8 pg I-TEQ/g and non-thermal destruction was observed overall. In the other collection the levels of USW were higher (around 64 pg I-TEQ/g) and the dioxin balance revealed a thermal destruction. Analysis of the different waste materials (textile, organic, plastic, wood and paper) was performed separately and the textile samples presented the highest levels.     

Using Radiocarbon to Apportion Sources of Polycyclic Aromatic Hydrocarbons in Household Soot

To determine whether polycyclic aromatic hydrocarbons (PAHs) in household soot were derived from the combustion of scrap wood or creosote that was impregnated in the wood (or some combination of both), the molecular composition and radiocarbon ( 14 C) content of the total carbon and several PAHs in the soot was investigated. The 5730-year half-life of 14 C makes it an ideal marker for identifying creosote-derived PAHs ( 14 C-free) versus those derived from the combustion of wood (contemporary 14 C). The 14 C abundance of phenanthrene, fluoranthene, pyrene, and retene was determined by accelerator mass spectrometry after solvent extraction and purification by preparative capillary gas chromatography. The molecular analysis (presence of retene and 1,7-dimethylphenanthrene) and bulk 14 C content (contemporary) of the soot indicated that wood combustion was a strong source of carbon to the soot. The 14 C of retene in two soot samples was also contemporary, indicating that it was derived from the combustion of the scrap wood. These results are consistent with previous work that has suggested that retene is an excellent marker of wood combustion. However, the 14 C content of phenanthrene, fluoranthene, and pyrene in one soot sample was much lower and revealed that these compounds had a mixed creosote and wood source. Using an isotopic mass balance approach, we estimate that 40 to 70% of phenanthrene, fluoranthene, and pyrene were derived from the combustion of the scrap wood. The results of this study show that molecular marker and bulk 14 C analysis can be potentially misleading in apportioning sources of every PAH, and that molecular-level 14 C analysis of PAHs can be a powerful tool for environmental forensics.     

Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.     

Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Accelerated carbonation of wood combustion ash for CO<Subscript>2</Subscript> removal from gaseous streams and storage in solid form

In this work, ash generated by the combustion of wood in a central heating plant was used to remove and permanently store by accelerated carbonation CO₂ contained in a gas mixture simulating biogas. The process was studied as an alternative treatment to the ones currently available on the market for biogas upgrading. The process was investigated at laboratory scale by setting up a facility for directly contacting the wood ash and the synthetic biogas in a fixed bed reactor. The process was able to completely remove CO₂ during its initial phase. After about 30 h, CO₂ started to appear again in the outlet stream and its concentration rapidly increased. The specific CO₂ uptake achieved in solid carbonate form was of about 200 g/kg of dry wood ash. This value is an order of magnitude higher than the ones found for waste incineration bottom ash carrying out similar experiments. The difference was ascribed to the physicochemical properties of the ash, characterized by a fine particle size (d₅₀ <?0.2 mm) and high content of reactive phases with CO₂ (e.g., Ca hydroxides). The leaching behavior of the wood ash was examined before and after the accelerated carbonation process showing that the release of several elements was lower after the treatment; Ba leaching in particular decreased by over two orders of magnitude. However, the release of the critical elements for the management of this type of residues (especially Cr and sulfates) appeared not to be significantly affected, while V leaching increased.     

Review of disposal technologies for chromated copper arsenate (CCA) treated wood waste, with detailed analyses of thermochemical conversion processes

Several alternative methods for the disposal of chromated copper arsenate (CCA) treated wood waste have been studied in the literature, and these methods are reviewed and compared in this paper. Alternative disposal methods include: recycling and recovery, chemical extraction, bioremediation, electrodialytic remediation and thermal destruction. Thermochemical conversion processes are evaluated in detail based on experiments with model compounds as well as experimental and modelling work with CCA treated wood. The latter category includes: determination of the percentage of arsenic volatilised during thermal conversion of CCA treated wood, identification of the mechanisms responsible for arsenic release, modelling of high temperature equilibrium chemistry involved when CCA treated wood is burned, overview of options available for arsenic capture, characterisation of ash resulting from (co-)combustion of CCA treated wood, concerns about polychlorinated dibenzo-p-dioxins/furans (PCDD/F) formation. Finally, the most appropriate thermochemical disposal technology is identified on short term (co-incineration) and on long term (low-temperature pyrolysis or high-temperature gasification).     

臭氧氧化法处理焦化废水生化出水的反应动力学

对臭氧氧化去除焦化废水生化出水COD的反应动力学及其影响因素进行了实验研究,结果表明,在臭氧投加量为8．50mg／min,反应温度为20＇E和初始pH为10．61条件下,对COD的降解符合表观一级反应动力学模型,其相关系数R。=0．9991,表观反应速率常数k。。=1．01×10^-3s-1。该条件下,臭氧氧化对COD的降解主要来源于高活性羟基自由基的强氧化作用。在不同的臭氧投加量（4．25～12．75mg／min）、不同的反应温度（10～40℃）和不同的初始pH（3．76～12．53）下,COD的降解也同样遵循一级反应动力学规律。随着臭氧投加量的增大,COD降解的表观反应速率常数从（0．554×10^-3）s-1增加到（1．06×10＆-3）s-1;随着反应温度的升高,表观反应速率常数从（0．427×10^-3）s-1增加到（1．40×10-3）s-1,温度越高反应速率提高的幅度却越小;在初始pH3．76～10．61范围内,表观反应速率常数从（0．218×10^-3）s-1增加到（1．01×10^-3）s-1,在初始pH为12．53时表观反应速率常数下降到（0．857×10^-3）s-1。     

Air-surface exchange of mercury with soils amended with ash materials

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing -10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing -10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, -0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, -20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O3 concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m2 day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m2 day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m2 day and for soil with pads constructed of ash ranged from -50 to 90 ng/m2 day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Kinetics of endosulfan sorption on to wood charcoal

Abstract

A part of the research work conducted to evaluate the efficiency of a locally available low cost wood charcoal in removing endosulfan, an organochlorine insecticide, has been presented here in this paper. In the batch experiments conducted at 1 mg/I initial concentration of endosulfan, it was found that wood charcoal could remove endosulfan from water up to 95%. Kinetic profiles were developed for various conditions and they followed second order kinetic reactions. Adsorption equilibrium time was determined by two different approaches namely rough estimate and 2% slope criteria. The equilibrium time was found to be 5 hrs. Forward, reverse, and overall reaction rate constants were determined by approximating the kinetic data to the first order reversible kinetic model. Rate constants increased with increasing initial concentration of endosulfan. Rate limiting process was determined by using kinetics data and further confirmed by the multiple interruption test. Pore and film diffusion coefficients were determined from the half time equations. Film diffusion appeared to be the rate limiting which was further supported by the multiple interruption test.     

Decomposition of gas-phase trichloroethene by the UV/TiO2 process in the presence of ozone.

The decomposition of gas-phase trichloroethene (TCE) in air streams by direct photolysis, the UV/TiO2 and UV/O3 processes was studied. The experiments were carried out under various UV light intensities and wavelengths, ozone dosages, and initial concentrations of TCE to investigate and compare the removal efficiency of the pollutant. For UV/TiO2 process, the individual contribution to the decomposition of TCE by direct photolysis and hydroxyl radicals destruction was differentiated to discuss the quantum efficiency with 254 and 365 nm UV lamps. The removal of gaseous TCE was found to reduce by UV/TiO2 process in the presence of ozone possibly because of the ozone molecules could scavenge hydroxyl radicals produced from the excitation of TiO2 by UV radiation to inhibit the decomposition of TCE. A photoreactor design equation for the decomposition of gaseous TCE by the UV/TiO2 process in air streams was developed by combining the continuity equation of the pollutant and the surface catalysis reaction rate expression. By the proposed design scheme, the temporal distribution of TCE at various operation conditions by the UV/TiO2 process can be well modeled.