Photoinduced toxicity of retene to Daphnia magna under enhanced UV-B radiation

The effects of UV radiation on the acute toxicity of retene (7-isopropyl-1-methylphenanthrene) to Daphnia magna Straus were studied. Dehydroabietic acid (DHAA) from which retene is formed in the vicinity of pulp and paper industry was also studied. Pyrene, anthracene, and phenanthrene were used as model PAH compounds. The time taken for immobilization (ET50) was monitored under biologically effective UV-B dose rates of 240, 365, 565, and 650 mW m(-2) (UV-A and visible light also present). Median effective concentrations (EC50) were determined after a 15-min UV exposure (565 mW m(-2)) followed by 24 h in the dark. Retene (10-320 microg l(-1)) was not acutely toxic in the dark. The induction of phototoxicity was in agreement with the absorption properties of the compounds (absorption peak of retene at around 300 nm). Photoinduced toxicity followed an order pyrene > anthracene > retene. Phenanthrene and DHAA were not acutely phototoxic. Accumulation of the compound in Daphnia before UV exposure was essential. Some changes in the absorption spectra of the compounds were seen after a 5-h UV irradiation (565 mW m(-2)), but none of the irradiated compounds were acutely toxic without further UV exposure. Therefore, the enhanced acute toxicity was primarily due to internal photosensitization reactions rather than photomodification. The dissolved fraction of 25% pulp and paper mill effluent reduced phototoxicity by attenuating UV radiation. The phototoxicity of retene was a function of both the exposure concentration and the UV-B dose rate, but relatively high UV-B dose rates and concentrations were needed for the acute photoinduced toxicity.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

Effects of NO2 and SO2 on selective catalytic reduction of nitrogen oxides by ammonia

The selective catalytic reduction (SCR) characteristics of NO and NO(2) over V(2)O(5)-WO(3)-MnO(2)/TiO(2) catalyst using ammonia as a reducing agent have been determined in a fixed-bed reactor at 200-400 degrees C. The presence of NO(2) enhances the SCR activity at lower temperatures and the optimum ratio of NO(2)/NO(x) is found to be 0.5. During the SCR reactions, there are some side reactions occurred such as ammonia oxidation and N(2)O formation. At higher temperatures, the selective catalytic oxidation of ammonia and the nitrous oxide formation compete with the SCR reactions. The denitrification (DeNO(x)) conversion decreases at lower temperatures but it increases at higher temperatures with increasing SO(2) concentration. The presence of SO(2) in the feeds inhibits N(2)O formation.     

Application of CALINE4 to roadside NO/NO2 transformations

The CALINE4 roadway dispersion model has been applied to concentrations of NO_x and NO₂ measured near Gandy Boulevard in Tampa, FL (USA) during May 2002. A NO_x emission factor of 0.86 gr mi⁻¹ was estimated by treating NO+NO₂ (NO_x) as a conserved species and minimizing the differences between measured and calculated NO_x concentrations. This emission factor was then used to calculate NO₂ concentrations using the NO/NO₂ transformation reactions built into CALINE4. A comparison of measured and calculated NO₂ concentrations indicates that for ambient O₃ concentrations less than 40 ppb the model under-predicts the chemical transformation of NO. The enhanced transformation of NO may be due to reactions of NO with oxidants such as peroxy radicals that are present either in the atmosphere or in vehicle exhaust.     

The importance of liquid water concentration in the atmospheric oxidation of SO2

The concentration of condensed water available for aqueous chemical reactions is viewed as a fundamental parameter of the heterogeneous conversion of gaseous SO₂ to particulate sulfate. New results from a series of dispersed-phase experiments in a cloud chamber, in which the magnitude of this parameter was allowed to vary widely, demonstrate that the heterogeneous SO₂ conversion rate in hazes is generally limited by the small concentration of condensed water. This limitation precludes the heterogeneous oxidation pathway from being important in the atmosphere during haze episodes except under extreme conditions of high humidities and aerosol loadings. In clouds, on the other hand, the liquid water concentrations are relatively large, permitting chemically related factors, such as pH-dependent equilibria and oxidant abundances, to limit the SO₂ conversion rate.     

Study on the photocatalytic degradation of glyphosate by TiO(2) photocatalyst

In this paper, the photocatalytic degradation of glyphosate selected as the deputy of organic pollutant in aqueous solution with TiO(2) powder as a photocatalyst has been studied. The effects of various parameters, such as the amount of the photocatalyst, illumination time, initial pH value, electron acceptors, metal ions, and anions on the photocatalytic degradation of glyphosate were investigated. From the studies, the best condition for the effect of the parameters on the photocatalytic degradation of glyphosate was obtained. The results show that the optimum amount of the photocatalyst used is 6.0 g l(-1) for the photocatalytic reactions. The photodegradation efficiency of glyphosate increases with the increase of the illumination time. With the addition of Fe(3+), Cu(2+), H(2)O(2), K(2)S(2)O(8) or KBrO(3), the photocatalytic degradation of glyphosate is accelerated. However, with the addition of Na(+), K(+), Mg(2+), Ca(2+), Zn(2+), Co(2+) and Ni(2+), or with the addition of trace amounts of Cl(-), Br(-), SO(4)(2-), there are no obvious effects on the reactions. Acidic or alkaline mediums are favorable for the photocatalytic degradation of glyphosate. The possible roles of the additives on the reactions and the possible mechanisms of effect were discussed.     

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method.

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.     

Spatial distribution of atmospheric PAHs and PCNs along a north-south Atlantic transect

Ship-board air samples collected between The Netherlands and South Africa in January-February 2001 were analysed for polycyclic aromatic hydrocarbons (PAHs) and polychlorinated naphthalenes (PCNs). The highest PAH concentrations occurred in the European samples, and in samples close to West Africa and South Africa. Consistently low PAH concentrations were measured in the southern hemisphere open ocean samples (190-680 pg/m3). The highest PCN concentrations occurred in the European samples, but high values were also detected off the West African coast, and in the sample taken closest to South Africa. Data are presented for diurnal cycles taken in the remote South Atlantic. The day:night ratios of phenanthrene, 1-methylphenanthrene and fluoranthene were typically approximately 1.5-2.5:1. The mechanism(s) causing this observation is/are not understood at present, but dynamic environmental process(es) is/are implicated.     

Fe(3+)- and Cu(2+)-reduction by phenol derivatives associated with Azure B degradation in Fenton-like reactions

Several phenol derivatives were evaluated regarding their capacities for Fe(3+) and Cu(2+) reduction. Selected compounds were assayed in Fenton-like reactions to degrade Azure B. 3,4-Dihydroxyphenylacetic, 2,5-dihydroxyterephtalic, gallic, chromotropic and 3-hydroxyanthranilic acids were the most efficient reducers of both metallic ions. The reaction system composed of 3-hydroxyanthranilic acid/Fe(3+)/H(2)O(2) was able to degrade Azure B at higher levels than the conventional Fenton reaction (87% and 75% of decolorization after 20min reaction, respectively). Gallic and syringic acids, catechol and vanillin induced Azure B degradations at lower levels as compared with conventional Fenton reaction. Azure B was not degraded in the presence of 10% (v/v) methanol or ethanol, which are OH radical scavengers, confirming the participation of this radical in the degradation reactions. Iron-containing reactions consumed substantially more H(2)O(2) than reactions containing copper. In iron-containing reactions, even the systems that caused a limited degradation of the dye consumed high concentrations of H(2)O(2). On the other hand, the reactions containing Fe(3+), H(2)O(2) and 3-hydroxyanthranilic acid or 3,4-dihydroxyphenylacetic acid were the most efficient on degradation of Azure B and also presented the highest H(2)O(2) consumption. These results indicate that H(2)O(2) consumption occurs even when the dye is not extensively degraded, suggesting that part of the generated OH radicals reacts with the own phenol derivative instead of Azure B.     

Replacement of H2O2 by O2 in Fenton and photo-Fenton reactions

The consumption of oxygen during the degradation of aniline by Fenton and photo-Fenton reactions is studied. The effect that parameters like aniline, Fe(II) and H2O2 initial concentration, pH, temperature and O2 flow rate have on the ratio O2 consumed/H2O2 consumed is examined. The determination of those combinations of experimental conditions for which an effective partial replacement of H2O2 by O2 as electron acceptor takes place is investigated. The results show that this replacement takes place in a variable extent, but the presence of H2O2 is necessary along the reaction, and the maximum consumption of O2 only takes place when the ratio amount of aniline mineralized vs. initial aniline concentration is minimal.     

Photodestruction of Acid Orange 7 (AO7) in aqueous solutions by UV/H2O2: influence of operational parameters

The photodestruction of Acid Orange 7 (AO7), an anionic acidic dye, was studied in the UV/H2O2 process. H2O2 and UV light have a negligible effect when they were used on their own. Removal efficiency of AO7 was sensitive to the operational parameters such as initial H2O2 concentration, initial AO7 concentration, pH and different light sources. The photodestruction of AO7 was inhibited by addition of EtOH as an electron scavenger. The semi-logarithmic graphs of the concentration of AO7 versus time (t<30 min) were linear, suggesting pseudo-first order reactions (k(optimum)=0.105 min(-1)). A simple kinetic model is proposed which is in agreement with experimental results.     

Products and mechanisms of the gas-phase reactions of OH radicals and O3 with 2-methyl-3-buten-2-ol

Products of the gas-phase reactions of OH radicals (in the presence of NO) and O₃ with the biogenic organic compound 2-methyl-3-buten-2-ol have been investigated using gas chromatography with flame ionization detection (GC-FID), combined gas chromatography–mass spectrometry (GC-MS), gas chromatography with Fourier transform infrared detection (GC-FTIR), in situ FT-IR spectroscopy and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS/MS). Formaldehyde, 2-hydroxy-2-methylpropanal and acetone were identified from both the OH radical and O₃ reactions, glycolaldehyde and organic nitrate (s) were also observed from the OH radical reaction, and the OH radical formation yield from the O₃ reaction was measured. The formaldehyde, 2-hydroxy-2-methylpropanal, glycolaldehyde, acetone and organic nitrate yields from the OH radical reaction were 0.29±0.03, 0.19±0.07, 0.61±0.09, 0.58±0.04 and 0.05±0.02, respectively, and the formaldehyde, 2-hydroxy-2-methylpropanal and OH radical formation yields from the O₃ reaction were 0.29±0.03, 0.30±0.06 (0.47 from FT-IR measurements) and 0.19 (uncertain to a factor of 1.5), respectively. Acetone was also observed from the O₃ reaction, but appeared to be formed from secondary reactions. Reaction mechanisms are presented and discussed.     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.     

The redox combustion of carbon monoxide for recovering pure carbon dioxide by using molten (Na+,K+)2(CO32-,SO42-) mixtures

Large-scale combustion systems, such as thermal power plants, emit large amounts of carbon dioxide, which can increase global warming. A molten salt redox combustion system was proposed to recover pure carbon dioxide exhausted from the combustion of fossil fuels. This system is composed of two successive processes by using reactions occurring in a molten salt. The molten salt is the mixture of the molten alkali metal sulfates and carbonates. The sulfate ions oxidize the fuels in first processes, being changed to reductive species such as sulfide ions. In this process, carbon dioxide and water are exclusively exhausted. The reductive species of sulfur compounds are oxidized to regenerate the sulfate ions by air in the second process. In this study, these above two processes were tried by using molten [(Na(+))(0.5),(K(+))(0.5)](2)[(CO(3)(2-))(0.9),(SO(4)(2-))(0.1)] alternatively. The oxidation of carbon monoxide as fuel by sulfate ions and the regeneration of sulfate ions by air were investigated in the temperature range of 700-950 degrees C, respectively. These reactions were exothermic. The rate of the regeneration of the sulfate ions was extremely high. During the oxidation of carbon monoxide, the reaction was first order in carbon monoxide with an activation energy of 101 kJ mol(-1). The optimum condition to recover pure carbon dioxide on practical operation was discussed.     

Photoassisted bleaching of dyes utilizing TiO2 and visible light

Titanium dioxide was shown to be generally effective as a catalyst for photobleaching many structural classes of organic dyes in aqueous solution, using visible light. However, results from study of 15 dyes indicate that photobleaching rates differ significantly from families of dyes with different functionalities, and are dependent on the light source and crystalline form of TiO2 used. Sorption characteristic on the TiO2 surface and the aqueous solubility of the dyes also play an important role in the photobleaching rate. Kinetic analysis indicates that the dye photobleaching rates can usually be approximated as pseudo-first-order kinetics. In addition to the generally proposed photocatalytic oxidation mechanism for TiO2 reactions, we observed evidence for two kinds of electron transfer mechanisms that are "photosensitized reduction" and "photosensitized oxidation". Natural sunlight was effectively used to photobleach some of the dyes.     

Mechanically induced self-propagating reactions: analysis of reactive substrates and degradation of aromatic sulfonic pollutants

Mechanochemical reactions have been identified as a valuable alternative to conventional methodologies for the degradation of toxic pollutants as well as for their abatement in contaminated matrices. This paper discusses the application of the mechanochemical technique to the degradation of sulfonic acids in a contaminated matrix. The degradation of the pollutant compound was carried out by taking advantage of combustive reactions on a suitable reactive system ignited under mechanical treatment conditions. Two systems have been investigated as possible reactive substrates. The first one was a Mg-SiO2 powder mixture while the second system was a Ca-SiO2 powder mixture. Milling trials performed under different mechanical processing conditions allowed one to characterise the reactivity of these chemical systems, which basically undergo a reduction/oxidation reaction involving the formation of MgO and Si phases when the Mg-SiO2 system is considered and CaO and Si phases when the Ca-SiO2 system is employed, respectively. The systematic change of the stoichiometric ratios Mg:SiO2 and Ca:SiO2 permitted to identify the minimum Mg or Ca content necessary for the ignition of the combustive reactions. The experimental runs performed with such systems have shown a greater effectiveness of the Mg-SiO2 because of less energy inputs required to ignite a combustion. For this reason the Mg-SiO2 has been considered as a reactive substrate in the following trials. Since the SiO2 amount in stoichiometric excess may be regarded as inert phase, it was substituted with a different phase consisting of the matrix contaminated by sulfonic acids. This aspect permitted to ignite a combustive reaction with the minimum possible content of Mg-SiO2 reacting mixture. The chemical analyses performed after the combustive reaction proved the complete removal of the sulfonic acid from the contaminated matrix.     

A comprehensive dynamic kinetic model for the UVC/H2O2 process: application to zinc bacitracin degradation in wastewater as a case study

Environmental Science and Pollution Research - A dynamic kinetic model is presented for the UVC/H2O2-driven process. The model comprises 103 reactions, including background species, such as...     

Simultaneous removal of NO and SO2 by high-temperature fluidized zero-valent iron processes

A new approach to simultaneously remove nitrogen monoxide (NO) and sulfur dioxide (SO2) by zero valent iron (ZVI) was investigated. Three different parameters, temperature, flux, and ZVI dosage, were tested in fluidized ZVI column studies containing 500 ppmv of NO and SO2, respectively. Under the ZVI dosage of 0.5 g at flux of 0.6 L/cm2 x min for temperature 573 K, there is neither NO nor SO2 reduction. For 623 K and 673 K, complete removal for NO and > 90% removal for SO2 were achieved. For temperatures of 723 K and 773 K, 100% removal was achieved for both NO and SO2. The amounts of NO or SO2 reduction (as milligrams of NO or SO2 per gram ZVI) increased as temperature increased, and linearities were observed with both correlation coefficients > 0.97. Compared with NO, SO2 had earlier breakthrough because of a slower diffusion rate and less reactivity but higher mass reduction because of a higher molecular weight for SO2 (64 g/mol for SO2 and 30 g/mol for NO). At same temperature, both NO and SO2 reductions (as milligrams of NO or SO2 per gram of ZVI) were constant regardless of either flux or ZVI dosage variation, but breakthrough time was affected by both flux and ZVI dosage. A parameter weight of ZVI/flux (W/F) was developed to represent these two parameters at the same time to assess the breakthrough time of NO and SO2. Higher breakthrough time was achieved for higher W/F value. Moreover, interestingly, longer breakthrough time and more NO and SO2 mass reduction were achieved for combined NO and SO2 than individual NO or SO2 treated by ZVI, and both oxidation and reduction reactions occurred instead of a reduction reaction only. Chemical reactions among ZVI/NO, ZVI/ SO2, and ZVI/NO/SO2 were also proposed and verified by X-ray diffraction analyses.     

以PEG为模板剂制备Bi2O2CO3及其可见光光催化性能

以聚乙二醇-6000（PEG-6000）为模板剂水热法制备碳酸氧铋（p-Bi2O2CO3）粉末,采用x射线衍射（XRD）、扫描电镜（SEM）、X射线光电子能谱（XPS）、透射电子显微镜（TEM）和紫外可见漫反射（DRS）对粉末进行了初步表征。在可见光（λ≥420nm）照射下,以罗丹明B（RbB）和水杨酸（SA）光催化降解实验为探针反应,实验结果表明,p-Bi2O2CO3具有较高的光催化活性,对RhB和SA有较好的降解效果。通过紫外-可见光谱（uV-Vis）、红外光谱（IR）和测定总有机碳（TOC）含量,光催化反应35h后RhB的矿化率为77％,同时对SA的降解率达到43％。同时,采用N,N-二乙基对苯二胺（DPD）分光光度法和对苯二甲酸荧光光度法分别测定了降解过程中H2O2和羟基自由基（·OH）的变化,表明p-Bi2O2CO3／Vis光催化降解机理涉及到·OH历程。