Radiolysis of aqueous 4-nitrophenol solution with Al2O3 or TiO2 nanoparticles

Aqueous 4-nitrophenol solutions containing TiO₂ or Al₂O₃ nanoparticles were irradiated with electron beam. 4-nitrophenol was decomposed by the ionizing radiation process in the absence of the nanoparticles. The addition of TiO₂ or Al₂O₃ (2 g l⁻¹) before irradiation improved the removal of 4-nitrophenol, total organic carbon (TOC) but also nitrogen (TN). To identify the origin of the loss (catalysis or simply adsorption), TiO₂ or Al₂O₃ nanoparticles were added after irradiation. Experiments show that the effect of the presence of TiO₂ or Al₂O₃ during irradiation is just due to adsorption.     

Nitrogen trace gas emissions from a riparian ecosystem in southern Appalachia

In this paper, we present two years of seasonal nitric oxide (NO), ammonia (NH₃), and nitrous oxide (N₂O) trace gas fluxes measured in a recovering riparian zone with cattle excluded and adjacent riparian zone grazed by cattle. In the recovering riparian zone, average NO, NH₃, and N₂O fluxes were 5.8, 2.0, and 76.7 ng N m⁻² s⁻¹ (1.83, 0.63, and 24.19 kg N ha⁻¹ y⁻¹), respectively. Fluxes in the grazed riparian zone were larger, especially for NO and NH₃, measuring 9.1, 4.3, and 77.6 ng N m⁻² s⁻¹ (2.87, 1.35, and 24.50 kg N ha⁻¹ y⁻¹) for NO, NH₃, and N₂O, respectively. On average, N₂O accounted for greater than 85% of total trace gas flux in both the recovering and grazed riparian zones, though N₂O fluxes were highly variable temporally. In the recovering riparian zone, variability in seasonal average fluxes was explained by variability in soil nitrogen (N) concentrations. Nitric oxide flux was positively correlated with soil ammonium (NH₄⁺) concentration, while N₂O flux was positively correlated with soil nitrate (NO₃⁻) concentration. Ammonia flux was positively correlated with the ratio of NH₄⁺ to NO₃⁻. In the grazed riparian zone, average NH₃ and N₂O fluxes were not correlated with soil temperature, N concentrations, or moisture. This was likely due to high variability in soil microsite conditions related to cattle effects such as compaction and N input. Nitric oxide flux in the grazed riparian zone was positively correlated with soil temperature and NO₃⁻ concentration. Restoration appeared to significantly affect NO flux, which increased ≈600% during the first year following restoration and decreased during the second year to levels encountered at the onset of restoration. By comparing the ratio of total trace gas flux to soil N concentration, we show that the restored riparian zone is likely more efficient than the grazed riparian zone at diverting upper-soil N from the receiving stream to the atmosphere. This is likely due to the recovery of microbiological communities following changes in soil physical characteristics.     

Phenol nitration upon oxidation of nitrite by Mn(III,IV) (hydr)oxides

An interesting aspect of the chemistry of nitrite is the possibility for this compound to interact with other environmental factors and many oxidising species, which results in the oxidation of nitrite to nitrogen dioxide. This is a potentially interesting process that can lead to the formation of nitroaromatic compounds in the environment. In previous papers we have shown that nitrite can interact with dissolved Fe(III) and nitrate under irradiation, Fenton and heterogeneous photo-Fenton reagents, and semiconductor oxides such as TiO2, alpha-Fe2O3, and beta-FeOOH under irradiation. This paper reports on the interaction between nitrite/nitrous acid and the Mn(III,IV) (hydr)oxides beta-MnO2 and gamma-MnOOH, both in neutral solution under irradiation and in acidic conditions in the dark. beta-MnO2 and gamma-MnOOH originate from the oxidation of Mn(II) and play a key role in the redox cycling of manganese in the environment. These Mn(III,IV) (hydr)oxides show some photocatalytic activity, and they can act as thermal oxidants at acidic pH. The photoinduced oxidation of nitrite and the thermal oxidation of nitrous acid by Mn(III,IV) (hydr)oxides yield nitrogen dioxide and lead to the formation of nitrophenols in the presence of phenol. These processes can take place at the water-sediment or water-colloid interface in natural waters and on the surface of atmospheric particulate. Furthermore, the phenol/gamma-MnOOH/HNO2 system in dark acidic solution is an interesting model due to the formation of phenoxyl radical upon phenol monoelectronic oxidation by gamma-MnOOH. The kinetics of nitrophenol generation under such conditions indicates that phenol nitration is unlikely to take place upon reaction between phenoxyl and *NO2 and suggests a solution to a literature debate on the subject.     

Processes involved in uptake and release of nitrogen dioxide from soil and building stones into the atmosphere

Atmospheric NO₂ was taken up by samples of various soils and building stones. The NO₂ uptake rate constants were highest in soil samples taken during the summer months. However, the NO₂ uptake rate constants of the soils and building stones were not significantly correlated with any of the following variables: moisture, pH, ammonium, nitrite, or nitrate. NO₂ uptake by soil and stone was not abolished by autoclaving indicating a chemical uptake process. NO₂ uptake by acidic and air-dry soils and stones resulted in nearly stoichiometric reduction of NO₂ to NO. This reduction was enhanced by the addition of ferrous iron and was further enhanced by incubation under 1 ppmv SO₂. The results suggest that NO₂ reduction may be coupled to oxidation of ferrous to ferric iron which may be reduced again by atmospheric SO₂ thus regenerating the ferrous iron content of the soil or stone. Conversion of NO₂ to NO was not observed in neutral or/and moist soils and stones. NO₂ was also taken up by purified and sterilized quartz sand moistend with water. This uptake was enhanced by addition of humic material but not by addition of bacteria which both had been extracted from genuine soil. Under most conditions, only uptake but no release of NO₂ was observed. However, NO₂ was released in air-dry soils that were heated to 45–65°C, or in ammonium-fertilized soil or stone that was drying up at room temperature. Under the latter conditions mimicking field practice, the NO₂ release reached rates that were similar to the NO release rates.     

Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

On the effect of pH in aromatic photonitration upon nitrate photolysis

This paper studies the pH effect on the photonitration of catechol, 1-naphthol, naphthalene, and benzene. The pH trend is influenced by the generation of HNO(2) and peroxynitrous acid (HOONO) upon nitrate photolysis. HNO(2) can be involved in a direct and an indirect nitration process. Direct nitration follows the pH distribution of HNO(2) (flexus around 3). Indirect nitration, possibly involving nitrosation+oxidation, would be highest around pH3. HOONO can be involved in electrophilic nitration, where the initial formation rate of the nitroderivatives is proportional to [H(+)], or take part in nitration directly, in which case a less important pH effect in photonitration is observed. The relative importance of the various nitration pathways for each substrate determines the resulting pH effect in photonitration upon nitrate photolysis.     

The reaction of nitrogen dioxide with lung surface components: The reaction with cholesterol

The reaction of nitrogen dioxide (NO₂) with cholesterol was investigated. NO₂ reacted with the hydroxyl group in cholesterol to produce cholesteryl nitrite. In this reaction, other minor products were observed. Cholesteryl nitrate, however, was not detected as was reported by other workers. Water accelerates and oxygen retards this reaction.     

Model reactor for photocatalytic degradation of persistent chemicals in ponds and waste water

A laboratory scale flow-through model reactor for the degradation of persistent chemicals using titanium dioxide (TiO₂) as photocatalyst immobilized on glass beads is presented. In the test system with a volume of 18 L contaminated water is pumped to the upper part of the floating reactor and flows over the coated beads which are exposed to UV-radiation. The degradation of two dyes of different persistance was investigated. Primary degradation of methylene blue did not fit a first order kinetic due to coincident adsorption onto the photocatalyst and direct photolysis, resulting in a half-life of 6 h. A filtrate of a green algae suspension accelerated the colour removal. In contrast, reactive red 2 was degraded only by photocatalysis; neither adsorption nor direct photolysis led to a colour removal. The course of primary degradation followed a first order kinetic with a half-life of 18 h and a rate constant of 0.04 h⁻¹. Analysis of the degradation products indicated mineralization by detection of NO₂⁻ and NO₃⁻, accompanied by a decrease of pH and an increase of conductivity. A successful adaptation of the model reactor (scale 1:10) to dimensions required for surface waters and waste water treatment plants would be a costefficient and environmentally sustainable application of photocatalysis for the treatment of industrially polluted water and could be of relevance for third world contries, particularly those favoured by high solar radiation.     

Pesticide by-products in the Rhône delta (Southern France). The case of 4-chloro-2-methylphenol and of its nitroderivative

A field monitoring campaign for pesticides and their transformation intermediates was carried out in the Rh?ne delta (Southern France). It was evidenced the following transformation sequence: MCPA-->4-chloro-2-methylphenol (CMP)-->4-chloro-2-methyl-6-nitrophenol (CMNP). Interestingly CMP disappeared about as quickly as MCPA, while CMNP was environmentally more persistent than the parent molecules. This is very relevant to the environmental risk associated with the occurrence of these compounds, because the nitration of chlorophenols reduces their acute toxicity but the nitroderivatives could have more marked long-term effects, associated with their genotoxicity. Irradiation experiments suggested that the photonitration of CMP into CMNP involves nitrogen dioxide, generated from the photolysis of nitrate and from the photooxidation of nitrite by ()OH. The photochemistry of Fe(III) species could also play a significant role, but its contribution is still difficult to be quantified. Another important intermediate of CMP transformation is methylnitrophenol (MNP), produced via a dechlorination/nitration pathway, with ortho-cresol as the most likely reaction intermediate.     

Preparation of agricultural residue anion exchangers and its nitrate maximum adsorption capacity

Anion exchangers were prepared from different agricultural residues (AR) after reaction with epichlorohydrin and dimethylamine in the presence of pyridine and N,N-dimethylformamide (EDM method). Agricultural residues anion exchangers (AR-AE) produced by the EDM method were inexpensive and showed almost the same NO₃⁻ removal capacities as Amberlite IRA-900. AR-AE produced from AR with higher hemicelluloses, lignin, ash and extractive contents resulted in the lower yields. Sugarcane bagasse with the highest -cellulose contents of 51.2% had the highest yield (225%) and lowest preparation cost. The highest maximum adsorption capacity (Q_max) for nitrate was obtained from rice hull (1.21 mmol g⁻¹) and pine bark natural exchangers (1.06 mmol g⁻¹). No correlation was found between Q_max and -cellulose content in the original AR. AR-AE produced from different AR demonstrated comparable Q_max due to the removal of non-active compounds such as extractives, lignin and hemicelluloses from AR during the preparation process. Similar preparation from pure cellulose and pure alkaline lignin demonstrated that the EDM method could not produce anion exchangers from pure lignin due to its solubilization after the reaction with epichlorohydrin.     

Intermediate distributions and primary yields of phenolic products in nitrobenzene degradation by Fenton's reagent

Nitrobenzene thermal degradation was investigated using the Fenton reagent in different experimental conditions. Reaction products were analyzed by HPLC, GC-MS, LC-MS and IC. The products obtained at different nitrobenzene conversion degrees show that degradation mainly involves successive hydroxylation steps of the aromatic ring and its subsequent opening followed by oxidation of corresponding aliphatic compounds. Our results show as primary reaction products: 4-nitrophenol, 3-nitrophenol, 2-nitrophenol, phenol and 1,3-dinitrobenzene, indicating that both hydroxylation and nitration reactions are involved. The formation of phenolic products can be explained by postulating an initial step of HO() addition to nitrobenzene ring. The mechanisms of primary reaction pathways are discussed and a detailed kinetic analysis to obtain the true primary yields of phenolic products is proposed. The relative yields observed for nitrophenol isomers do not follow the expected orientation according to deactivating characteristics of the nitro group but significantly depend on Fe(+2), Fe(+3), H(2)O(2) and O(2) concentrations. The understanding of the effect of reaction conditions on the relative product distribution benefits the application of Fenton and Fenton-like systems to waste water treatment.     

The gas phase addition of NOx to olefins

The addition of N₂O₅ to 1-hexene in synthetic air results in 1,2-hexanedioldinitrate and 2-hexanon-1-ol-nitrate as the main products and some -hydroxy-1-ol-nitrate. In the reaction with cyclohexene, cis/trans-1,2-cyclohexanediol-dinitrate and cyclohexene-1-on-2-ol-nitrate have been detected. The addition of NO₃ to isoprene produces 4-nitrato-3-methylbutenal-2. The reaction of NO₃ with methylenecyclohexane and sabinene in air results in 1-(methylnitrate) cyclohexane-1-ol and both epimers of 1-(methylnitrate)-4-(isopropyl) cyclo-hexene-4-ol, respectively. The main products of the addition of NO₃ to - and β-pinene were probably rearranged compounds of the limonene type: -pinene produces 1-(methyl)-2-(nitrato)-4-(2-propane-2-ol)-cyclohex-1-ene and β-pinene produces 1-(methylnitrate)-4-(2-propane-2-ol)cyclohex-1-ene. Other rearrangements give rise to a variety of nitrates and ketonitrates of structures as yet unknown in the - and β-pinene systems.

The probably particle-borne addition of NO₂ to -pinene, β-pinene and camphene in air produces 2-nitrolimonene, 7-nitrolimonene and nitrocamphene as the main reaction products.     

Modelling photochemical reactions in atmospheric water droplets: An assessment of the importance of surface processes

The relative importance of surface versus bulk processes was computed in spherical water drops, based on the model photochemical reaction yielding phenol from benzene via the ^•OH radicals, formed on UV photolysis of nitrate. The coadsorption of benzene and nitrate at the droplet surface was taken into account by means of the Wagner–Onsager–Samaras interaction model. The results indicate that the surface accumulation of benzene and the coadsorption of benzene and nitrate, which substantially increase the value of the concentration product of the model species at the droplet surface compared to the bulk, would cause surface processes to play a very significant role, in particular in small drops (1 μm radius, as can be found in haze and mist). Under such circumstances, over 15% of phenol photoformation would take place in just 0.1% of the drop volume. Similar results are expected in the case of benzene hydroxylation and nitration on nitrite photolysis.     

Characteristics of roadside air pollution in Korean metropolitan city (Daegu) over last 5 to 6 years: temporal variations, standard exceedances, and dependence on meteorological conditions

The present study performed a roadside data analysis to provide baseline data for exploring associations between environmental exposure to four gaseous pollutants and health effects on residents living near roadways. The yearly roadside concentrations of CO and SO₂ showed a well-defined decreasing trend, whereas those of NO₂ and O₃ exhibited the reverse trend. In most cases, the diurnal trends of the roadside concentrations were well-defined for all seasons, plus the daytime concentrations were higher than the nighttime concentrations. In contrast to the other target pollutants, the daytime O₃ concentrations observed at the roadside sites were lower than those observed at the residential site, likely due to high-levels of fresh NO from traffic emissions that rapidly react with O₃, thereby reducing the O₃ roadside level. The Sunday roadside concentrations of CO, NO₂, and SO₂ were similar to or somewhat lower than the weekday concentrations. Conversely, for O_3, the Sunday roadside concentrations were similar to or somewhat higher than the weekday concentrations. The higher O₃ concentrations on Sunday may be due to the reduced titration from a decrease in NO_x emissions under VOC-limited conditions (low VOC/NO_x conditions). The monthly averages of O₃ concentrations exhibited the reverse seasonal variation to the other target compounds, with peak O₃ concentrations between April and June, and the second peak between August and October. It is also suggested that for O₃, the 8-h standard is more stringent than the 1-h standard, while for NO₂ and SO₂, the 1-h standard is more stringent than the 24-h standard. The multiple regression equations obtained from the relationship between the concentrations and five meteorological parameters indicated that the number and type of meteorological variables in the equations varied according to the pollutant, monitoring station, or season.     

Assessing the transformation kinetics of 2- and 4-nitrophenol in the atmospheric aqueous phase. Implications for the distribution of both nitroisomers in the atmosphere

Different transformation processes for nitrophenols in the atmospheric aqueous phase were considered to assess their relative importance, and their ability to account for the higher occurrence of 4-nitrophenol (4NP) compared to 2-nitrophenol (2NP) in the atmosphere. The importance of the different processes was in the order ^?OH > ^?NO₃ > direct photolysis > nitration to 2,4-dinitrophenol. 2NP is more reactive than 4NP with the hydroxyl radical, but the difference is low. Accordingly, such a process could account for the higher atmospheric occurrence of 4NP only if the observed atmospheric nitrophenols were what was left of an almost complete degradation by ^?OH. This would imply the unlikely scenario that the known nitrophenol sources to the atmosphere were only a limited fraction of the actual ones. A more likely, tentative possibility would be connected with the higher occurrence of 4NP on particles. If the reactivity order of nitrophenols in the atmospheric compartments was water droplets > gas phase > particles, particulate matter could act as a reservoir of 4NP. 2NP would undergo degradation in gas phase or solution at a higher rate than 4NP on particles, which could decrease the atmospheric levels of 2NP below those of 4NP.     

Effect of La3+ on the activities of antioxidant enzymes in wheat seedlings under lead stress in solution culture

In order to improve the plant ability to resist lead stress, effect of 0.05 mg/l La(NO₃)₃ on the activities of catalase (CAT), superoxide dismutase (SOD), the level of malondialdehyde (MDA) in wheat seedlings under lead stress was studied. The effect of La³⁺ on plant growth, chlorophyll content in wheat seedlings after adding 0, 50, 100 mg/l Pb(NO₃)₃ to the nutrient solution for 12 days was observed. The plants were grown in nutrient solution in a strictly controlled climate growth room. Effects of La³⁺ (with La treatment) compared with check groups was evidently observed. The activities of SOD and CAT in root were enhanced 0.45–1.69 times and 33.20–77.77% respectively and MDA content was reduced 11.05–27.49% in root after treatments from the second day till the end of the experiment. The activities of SOD and CAT was found to be increased slightly (P<0.05) and MDA content decreased in shoot and root of wheat seedlings by La³⁺ under lead stress within five days after treatments compared with Pb1 and Pb2 groups. It was assumed that antioxidant enzymes was found to be increased by La(NO₃)₃, the antioxidant potential of the wheat seedlings to resist lead stress enhanced. It is suggested that La³⁺ could be used to resist lead stress at the beginning under stress while the stress was not so serious.     

Heterogeneous photocatalytic decomposition of benzene on lanthanum-doped TiO2 film at ambient temperature

Lanthanum-doped anatase TiO₂ thin films on glass prepared via a sol–gel process have been shown to have much higher photocatalytic activity for the degradation of gaseous benzene than pure anatase TiO₂ thin film. The photodecomposition of benzene on both types of TiO₂ films follows the first-order kinetics while the CO₂ and CO formation followed the zero-order kinetics. GC/MS identification of the intermediates produced during the photodegradation of benzene revealed that doping lanthanum into TiO₂ thin film favors a cleavage of benzene ring. An optimal lanthanum amount with respect to photocatalytic activity was about 2.5 wt% (La₂O₃/TiO₂).     

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.     

Azo-dyes photocatalytic degradation in aqueous suspension of TiO2 under solar irradiation

The photodegradation of two common and very stable azo-dyes, i.e. methyl-orange (C₁₄H₁₄N₃SO₃Na) and orange II (C₁₆H₁₁N₂SO₄Na), is reported. The photocatalytic oxidation was carried out in aqueous suspensions of polycrystalline TiO₂ irradiated by sunlight. Compound parabolic collectors, installed at the “Plataforma Solar de Almería” (PSA, Spain) were used as the photoreactors and two identical reacting systems allowed to perform photoreactivity runs for the two dyes at the same time and under the same irradiation conditions. The disappearance of colour and substrates together with the abatement of total organic carbon content was monitored. The main sulfonate-containing intermediates were found to be in lower number in respect to those obtained under artificial irradiation. In particular there were no more evidence of the presence of hydroxylated transients. The dependence of dye photooxidation rate on: (i) substrate concentration; (ii) catalyst amount; and (iii) initial pH was investigated. The influence of the presence of strong oxidant species (H₂O₂, S₂O₈²⁻) and some ions (Cl⁻, SO₄²⁻) on the process was also studied.     

Determination and distribution characteristics of degradation products of nonylphenol polyethoxylates in the rivers of Taiwan

Concentrations of degradation products of nonylphenol polyethoxylates (NPEOs) were analyzed in river water samples in order to determine the distribution characteristic of these alkylphenolic compounds in 18 major rivers of Taiwan. The degradation products of NPEOs were detected in all river samples, with the dicarboxylates alkylphenolic degradation products (CAPEC) being detected most frequently and at the highest concentrations. Concentrations of NP and NP1EO in rivers ranged from n.d. to 5.1 μg l⁻¹ and n.d. to 0.5 μg l⁻¹, respectively. The total concentrations of shortened carboxylates (i.e., NP1EC + NP2EC + NP3EC) and dicarboxylates alkylphenolic degradation products (CAP1EC + CAP2EC) ranged from n.d. to 63.6 μg l⁻¹ and n.d. to 94.6 μg l⁻¹, respectively. Concentrations of NP2EC, NP3EC and all CAPEC residues were determined semi-quantitatively by comparing with the internal standard. Significantly higher concentrations of CAPEC residues were detected in the river waters as compared to those of NP, NP1EO and NPEC degradation products and the average proportions of these compounds in the samples of the rivers were as follows: NP + NP1EO was 5 ± 2.5%, total NPEC was 25 ± 12%, and total CAPEC was 70 ± 12%. The high concentration ratios of CAPEC/NPEC illustrate that aerobic biodegradation plays a main route in the fate of NPEO in the rivers of Taiwan.