Photostabilizers for azadirachtin-A (a neem-based pesticide)

Photostability of azadirachtin-A (a neem based pesticide) has been studied without and with adding stabilizers such as ter. butyl-p-cresol, 8-hydroxy quinoline and ter. butyl hydroquinone as thin film on glass surface and on leaf surface under sunlight and UV light. Half-life of azadirachtin has been found to be 48 min and 3.98 days as thin film under UV light and sunlight and 2.47 days on leaf surface, respectively. 8-Hydroxy quinoline and ter. butyl hydroquinone have been found effective in controlling degradation of azadirachtin under both sunlight and UV light with half-life of 44.42 and 35.90 days under sunlight, and 55.80 and 48.50 h under UV light, respectively. Whereas ter. butyl-p-cresol has been found effective A only under sunlight. Significant decreases in antifeedant and insect growth regulatory activity against third instar larvae of Spodopterra litura has been observed with azadirachtin when exposed to sunlight and UV light. However, by the addition of above stabilizers, the biological activity of azadirachtin-A has been retained even after 24 h of irradiation under UV light and up to 30 days of exposure to sunlight.     

水中四环素类化合物在不同光源下的光降解

研究了模拟太阳光和实际室外太阳光下四环素类化合物在水溶液中的光降解。结果表明,四环素类化合物(TCs)在模拟太阳光照射下均能发生直接光降解,且其降解速率随pH不同变化很大。四环素(TC)、土霉素(OTC)、金霉素(CTC)和多西环素(DTC)的光降解速率随溶液pH升高明显加快,而米诺环素(MTC)在水中的光降解速率随溶液pH升高略有下降。天然水体pH范围内,模拟太阳光照下四环素类化合物表观光降解速率常数在0.004～0.026 min-1范围内,降解半衰期在26～136 min范围内。在室外实际太阳光照下,四环素类化合物光降解反应速率与太阳光强成正比例关系。晴朗无云天气下,四环素类化合物降解半衰期在春冬季节较长、夏季节较短;四环素在东江实际水体中表观光降解速率很快,在冬季晴天天气下,其平均半衰期仅为8.2 min。     

Bioclimate and city planning – open space planning

The planning and using of open spaces in urban areas very much depend on the shading of the surrounding building structures. This article presents a method for the investigation of the sunlight and the bioclimatic conditions in dependence on the surrounding buildings. It is illustrated for typical courtyards in Berlin, Germany, as one type of open spaces. The programme HelioDat determines the shading of any spot of an open space. It gives the possible duration of direct sunlight for the selected spot for each day of the year. The sunlight conditions in the courtyards differ from one another a lot in dependence on their size the tallness of the surrounding buildings. The calculation of the PMV on the basis of the results of the programme HelioDat determine the bioclimatic situation in the discussed courtyards. Although the results of HelioDat are only one input among the weather conditions and the personal characteristics of the test-person, the bioclimatic conditions correlate very much with the sunlight conditions. In a projected building structure, the sunlight conditions vary a lot between the present situation and the two architectural alternatives. Since the bioclimatic situation is correlated to the sunlight conditions, this example demonstrates the importance for the investigation of the sunlight conditions and the bioclimate already during the planning process of buildings.     

Photocatalytic Treatment of RDX Wastewater with Nano-Sized Titanium Dioxide (5 pp)

Background, Aim and Scope The polynitramines, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are important military explosives and regulated toxic hazardous compounds. Production, testing and use of the compounds has resulted in numerous acres of contaminated soils and groundwater near many munitions facilities. Economical and efficient methods for treatment of wastewater and cleanup of soils or groundwater containing RDX and HMX are needed. This study focuses on the photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (nano-TiO2) under simulated sunlight, whose intensity and wavelength are similar to that of the real sunlight in Xi'an at noon. The objective is to determine the potential for RDX destruction with nano-TiO2 in aqueous solution. Materials and Methods: An activated carbon fiber (ACF) cloth-loaded with nano-TiO2 was put into the RDX containing solution, and the concentration of RDX was measured (by HPLC–UV) at regular time intervals under simulated sunlight. Results: The RDX degradation percentage of the photocatalytic process is higher than that of Fenton oxidation before 80 min, equivalent after 80 min, and it reaches 95% or above after 120 min. The nano-TiO2 catalyst can be used repeatedly. Discussion: The photocatalytic degradation kinetics of RDX under simulated sunlight can be described by a first-order reaction kinetics equation. The possible degradation mechanism of RDX was presented and the degradation performance was compared with that of biological method. Conclusions: It was demonstrated that the degradation of RDX wastewater is very effective with nano-TiO2 as the photocatalytic catalyst under simulated sunlight. The efficiency of the nano-TiO2 catalyst for RDX degradation under simulated sunlight is nearly identical to that of Fenton oxidation. Recommendations and Perspectives: To date, a number of catalysts show poor absorption and utilization of sunlight, and still need ultraviolet light irradiation during wastewater degradation. The nano-TiO2 used in the described experiments features very good degradation of RDX under simulated sunlight, and the manufacturing costs are rather low (around 10 Euro/m2). Moreover, the degradation efficiency is higher compared to that of the biological method. This method exhibits great potential for practical applications owing to its easiness and low cost. If it can be applied extensively, the efficiency of wastewater treatment will be enhanced greatly.     

Solar activated ozonation of phenol and malic acid

The effect that sunlight has on the degradation rate of two model organic compounds, phenol and malic acid, by ozone is studied. The effect seems to be due to both direct light absorption (300-320 nm photons) by ozone, which produces the pollutant degradation, and light absorption by reaction intermediates. The presence of such a light notably improves the reactivity of ozone toward the organic species, leading to a faster and complete mineralization even at large initial total organic carbon values. The use of artificial sunlight (Xe lamp) is also explored. Finally, the simultaneous presence of sunlight and other ozone degradation catalyst like transition metal ions is studied, showing the beneficial effect of such a combination.     

Effects of riboflavin on the phototransformation of benzo[a]pyrene

Riboflavin (Vitamin B2) is a natural dye-sensitizer habitually present in natural waters. Effects of riboflavin as photosensitizer on the transformation of benzo[a]pyrene (BaP) (10 microM) in the aqueous-organic solvent (water/acetonitrile/methanol 50/40/10) were investigated in this study. The photolysis half life of BaP in solution containing 50 microM riboflavin was 5 min, compared to 98 min in the absence of riboflavin. The rate of phototransformation of BaP increased as the concentration of riboflavin was raised from 10 microM to 100 microM under both natural sunlight and UVA irradiation. The half life of BaP in the presence of 50 microM riboflavin was 10.6 min and 43.1 min when exposed to visible range of natural sunlight and UVA irradiation respectively. Riboflavin decomposes under natural sunlight. Lumichrome, a principal photoproduct of riboflavin, was shown to photosensitize BaP under natural sunlight after photolysis of riboflavin. Our study indicated that other photoproducts from riboflavin, such as lumiflavin, were also involved in the phototransformation of BaP under sunlight when riboflavin diminished. The major photoproducts in the photolysis of BaP were identified as 1,6-benzo[a]pyrene-dione, 3,6-benzo[a]pyrene-dione, 6,12-benzo[a]pyrene-dione by using high performance liquid chromatography (HPLC). All these products were detected in the samples which were irradiated under different light sources and in the presence or absence of riboflavin. The possible phototransformation mechanism was discussed.     

Investigation and modeling of solar UV-induced chlorine decay in disinfection contact basins at full-scale wastewater treatment plants

Residual chlorine loss due to UV sunlight in the chlorine disinfection contact basins (DCBs) was investigated at two full-scale wastewater treatment plants (WWTPs). Chlorine decay due to solar UV-induced photochemical reaction was found to be significant and had diurnal and seasonal variations. The total chlorine loss due to sunlight ranged from 19 to 26% of the total chlorine chemical use at the two plants studied. Covering chlorine contact basins led to more stable chlorine demand regardless of the diurnal and seasonal sunlight intensity. Therefore, covering chlorine contact basins offers more stable, or accurate, chlorine dosage and effluent residual control and requires less effort by plant operators. A mathematical model was developed to calculate the amount of UV-induced chlorine decay. The model developed can be used to estimate the UV-induced chlorine decay rate and total chlorine loss due to sunlight at WWTPs with various basin configurations, flowrates, chlorine dosages, and geographical locations. The model results allow the capital cost of covering needs to be assessed against the chlorine chemical cost savings.     

HPLC-MSn and GC-MS methods to study sunlight and UV-lamp degradations of 1-amino-5-naphthalene sulfonate

HPLC-DAD, HPLC-MS/MS, GC-MS and spectrophotometric methods are employed to investigate the degradation process of sodium 1-amino-5-naphthalene sulfonate (1A5NS) aqueous solutions, when exposed to sunlight and UV-lamp (254 nm) irradiations. Experimental results show that both sunlight and 254 nm UV-lamp irradiations destroy the chemical and give rise to major degradation products, characterised by the same m/z ratios. Degradation times are lower for sunlight irradiation, for which a t(1/2) value of 137.4 min has been evaluated, in comparison with the value of t(1/2) of 26.8 min, observed for UV-lamp irradiation. The degradation pathway and the structures of the degradation products are proposed.     

Comparison of photochemical behavior of various humic substances in water: I. Sunlight induced reactions of aquatic pollutants photosensitized by humic substances

Humic substances are shown to photosensitize transformations of several types of synthethic chemicals that do not photoreact when exposed to sunlight in distilled water. In most cases, photoproducts were the same in colored natural waters and in solutions of soil-derived humic substances, including those obtained commercially. Kinetic studies in sunlight indicated that the efficiencies of the reactions photosensitized by humic substances of various origins were the same within a factor of 2.     

Direct and indirect photolysis of two quinolinecarboxylic herbicides in aqueous systems

The photodegradation of two quinolinecarboxylic herbicides, 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and 3,7-dichloroquinoline-8-carboxylic acid (QCl), was studied in aqueous solution at different irradiation wavelengths. The effect of sunlight irradiation was investigated also in the presence of titanium dioxide (TiO₂). UV irradiation degraded rapidly QMe affording 7-chloro-3-methylquinoline (MeQ) through a decarboxylation reaction. The reaction rate was lower in the presence of dissolved organic carbon (DOC) because of the adsorption of the herbicide on the organic components. Instead, QCl was stable under both UV light and sunlight irradiation. The irradiation of QMe or QCl solutions with simulated sunlight in the presence of TiO₂ produced the complete mineralization of the two herbicides.     

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in aqueous solutions and in organic solvents

Aqueous solutions of selected polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were prepared using a generator column and exposed to UV (300 nm) light in the laboratory and to sunlight in an outdoor environment. In the laboratory, additional exposures were also carried out using 60% acetonitrile/water solutions. At 300 nm di- and tetra PCDDs had higher first-order photodegradation rate constants in 60% acetonitrile/water than in pure water. The solvent effect was reversed for PCDFs. These results may be a reflection of the higher polarity of PCDFs compared to PCDDs. In both the indoor and outdoor exposures photodegradation rates decreased with increasing concentrations of chlorination. However, OCDF exposed to 300 nm light in 60% acetonitrile/water and to sunlight in pure water photodegraded more rapidly than tetra CDF. Photolysis rates in sunlight were considerably slower (t(1/2) of 6.4-23 h) than photolysis rates at 300 nm in the laboratory (t(1/2) of 4.3-680 min), reflecting the lower intensity of sunlight in the 300 nm region of the UV/Vis spectrum. The extent of dechlorination of the PCDDs/PCDFs was less than 20% and reductive dechlorination does not appear to be a major process in the photodegradation of PCDDs/PCDFs in aqueous solutions.     

Natural sunlight NO(3)(-)/NO(2)(-)-induced photo-degradation of phenylurea herbicides in water

The nitrate-induced photodegradation of phenylureas in water was demonstrated to occur efficiently using natural sunlight irradiation. The kinetics of disappearance was found to be dependent on the inducer and substrate concentrations, the phenylurea structure and the origin and composition of the aqueous matrix including the presence of nitrite. The measured effects under sunlight were of the same order of those measured previously in the lab using our solar light simulated system. However, by-product distribution might differ substantially particularly considering the nitration pathway.     

Decomposition of 14C-fenitrothion under the influence of UV and sunlight under tropical and subtropical conditions

The decomposition of (14)C-fenitrothion on silica gel chromatoplates as well as in polar and non polar solvents under sunlight and ultraviolet light was investigated, Its stability to sunlight on leaf surfaces of bean plants and on different surfaces (such as glass, quartz and plastic) was also determined. The main photoproducts were identified as carboxyfenitrothion, fenitrooxon, carboxyfenitrooxon and 3-methyl-4-nitrophenol and a small amount 3-caboxy-4-nitrophenol and methyl parathion. The addition of carbaryl and deltamethrin insecticides slightly accelerated the photodecomposition of fenitrothion on silica gel plates and in solution.     

Photo-oxidation of biodegraded crude oil and toxicity of the photo-oxidized products

We investigated the physicochemical changes resulting from irradiation by sunlight of biodegraded crude oil. An Arabian light crude oil sample was first subjected to microbial degradation. n-Alkanes and aromatic compounds such as naphthalenes, fluorenes, dibenzothiophenes and phenanthrenes possessing short, alkyl side chain(s) were almost completely degraded, while the contents of the saturated and aromatic fractions were reduced by 70% and 40%, respectively. This biodegraded oil was then suspended in seawater and exposed to sunlight irradiation for several weeks. The most remarkable change caused by the irradiation was a substantial decline in the aromatic fraction with a concomitant increase in the resin and asphaltene fractions. A 13C-nuclear magnetic resonance (NMR) spectroscopic analysis showed that the aromaticity of the biodegraded oil was significantly lower in the irradiated sample. A field desorption-mass spectrometric (FD-MS) analysis showed that sunlight irradiation reduced the average molecular weight of the oil components and formed oxygenated compounds. Consistent with this observation is that the oxygen content in the oil increased as the irradiation was prolonged. The bioavailability of the biodegraded oil was increased by the photo-oxidation: the growth of seawater microbes was minimal when the non-irradiated biodegraded oil was used as the source of carbon and energy; however, growth was significant when irradiated biodegraded oil was used. The concentration of dissolved organic carbon (DOC) increased linearly during the sunlight irradiation of the biodegraded oil, and this increase was matched by an increase in ultraviolet-absorptive materials in the seawater. The photochemically formed, water-soluble fraction (WSF) showed acute toxicity against the halophilic crustacean, Artemia.     

The stability of butyltin compounds in a dredged heavily-contaminated sediment

A treatment process for marine sediment heavily contaminated with tributyltin (TBT) was designed that included dehydrating, sunlight drying and dumping processes. The time course in butyltin (BTs) compounds, TBT, dibutyltin (DBT) and monobutyltin concentrations were investigated in the sediment treated under various conditions (light (UV, sunlight and light exclusion), moisture (air-drying and water saturation) and wetting and drying cycles). Significant changes in all the BT compound concentrations with time were not found regardless of the sediment conditions for light and moisture. The results indicated the high stabilities of TBT and DBT in the sediments versus light and moisture condition changes, probably taking place in the treatment process. It is also estimated that the BTs in the sediment are resistant to photo-degradation and biochemical degradation and their half lives are relatively long. In contrast, the decreases in the TBT and DBT were observed during the wetting and drying cycle treatment for the water saturated sediment both during exposure to sunlight and under a dark condition. This result suggested the hypothesis that the TBT degradation could be accelerated by the high microbial activity induced by the moisture changing treatments.     

Leaching and persistence of ametryn and atrazine in red–yellow latosol

This study evaluated the mobility and persistence of atrazine and ametryn in red–yellow latosols using polyvinyl chloride columns with a diameter of 100 mm and a height of 15 cm. The assays simulated 60-mm rainfall events at 10-day intervals for 70 days. The persistence and leaching were evaluated for these two herbicides. The analytes obtained from the samples were quantified by gas chromatography using flame ionization detection. Compared with ametryn, atrazine showed a greater potential to reach depths below 15 cm over 30 days of simulated rain. Ametryn, however, showed greater persistence in soil at 70 days after application. The persistence of atrazine and ametryn in soil under sunlight was 10 and 144 days respectively. Atrazine was more susceptible to sunlight than ametryn because sunlight favored atrazine degradation in hydroxyatrazine. The results indicate that in red–yellow latosol, atrazine has a high leaching potential in short term, but that ametryn is more persistent and has a high leaching potential in long term.     

Photodegradation of new amino acid derivatives suitable for chelating agents in pulp bleaching applications

The purpose of this study was to evaluate photodegradabilities of the following new low-nitrogen chelating agents: N-bis[(carboxymethoxy)ethyl]glycine (compound 1), N-bis[(1,2-dicarboxyethoxy)ethyl]glycine (compound 2) and N-bis[(1,2-dicarboxyethoxy)ethyl]aspartic acid (compound 3). At first photodegradation of these chelating agents as uncomplexed Na-compound 1–3 and Cu(II) complexes were tested, both in lake and distilled water, by exposing them to near-UV region radiation at the range of 315–400 nm. Uncomplexed Na-compounds 2 and 3 were selected to sunlight exposure experiments carried out in lake and distilled water. Compound 3 was also tested in sunlight as Cu and Ca complexes in both solutions. Photodegradation of Na₆-compound 3 in distilled water was studied by exposing it to radiation at the wavelength of 253.7 nm. Photodegradation products were analysed by means of GC-MS (gas chromatography with mass selective detector).

The results demonstrated that compound 1 was quite photostable even as Cu complex while compounds 2 and 3 were found to be photodegradable. Over 90% reduction of compound 3 was achieved during one week and 80% reduction of compound 2 in two weeks' time when they were added as Na salt to lake water and exposed to sunlight. Compound 3 as Cu complex degraded totally in the sunlight in less than one week. In the case of compound 3, the degradation rate decreased depending on the counter cation in the order Cu > Na  Ca. The study demonstrated that photodegradation of Na₆-compound 3 does not result in total mineralization of the compound. A photodegradation pathway for Na₆-compound 3 is proposed.     

Photodegradation of sulfonamide antibiotics in simulated and natural sunlight: Implications for their environmental fate

The photochemical fate of seven sulfonamides was investigated in matrices representative of natural water bodies under various light sources. Fundamental photolysis parameters such as molar absorption coefficient, quantum yield (QY) and first-order rate constants were determined. The photolysis decay rate was dependent on the protonation state of the molecule, pH of the water sample and dissolved organic matter. Natural organic matter was the most significant factor in the indirect photolysis of sulfonamides. Half-lives were in the range of minutes at 254 nm to days under natural sunlight. Under natural sunlight, all sulfonamides showed higher removal rates in natural waters implying that indirect photolysis is the predominant mechanism.     

Photodegradation of the antifouling compounds Irgarol 1051 and Diuron released from a commercial antifouling paint

The antifouling compound Irgarol 1051 and its degradation product M1 (also known as GS26575), along with another antifouling compound Diuron, have recently been found in Japanese coastal waters. This study was undertaken to find the origin of these chemicals and investigate their aquatic fate. Five glass plates, each coated with 1 g of antifouling paint containing Irgarol and Diuron, were submerged in 250 ml of five different test waters and the plates removed after several months. The aqueous solutions were divided into two groups: one exposed to natural sunlight, and the other kept in the dark as a control. Irgarol and Diuron were detected in all aqueous solutions, suggesting leaching from antifouling paints is the origin of these antifouling biocides found in Japanese coastal waters. Under sunlight conditions, Irgarol underwent a rapid degradation to produce M1, which remained even after Irgarol had disappeared from the system. These compounds were persistent in any aqueous solutions tested under dark conditions, indicating high stability to hydrolysis. Diuron and M1 were more persistent than Irgarol under sunlight irradiation. Since these compounds have high herbicidal activities, their ultimate impact on aquatic ecosystems is closely related to their aquatic fate.     

Phototransformation of herbicide metsulfuron methyl

Phototransformation of the herbicide metsulfuron methyl was investigated on glass surface under sunlight and ultraviolet (UV) light and compared with dark condition. The half-lives of metsulfuron methyl under UV light and sunlight were found to be 0.5 and 7.8 days respectively. Rate of phototransformation followed first order kinetics with significant correlation coefficient. The major photoproducts were identified as methyl-2-sulfonyl-amino-benzoate, 2-amino-6-methoxy-4-methyltriazine and saccharin (O-sulfobenzoimide). Various metabolites from this study were identified by high performance liquid chromatography (HPLC). Authentic samples required for HPLC comparison were prepared in laboratory and characterized on the basis of nuclear magnetic resonance (NMR) and infra red (IR) spectral data. These metabolites were also identified from metsulfuron methyl treated wheat field soil.