Photodegradation of the steroid hormones 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) in dilute aqueous solution

The photochemical transformation of natural estrogenic steroid 17beta-estradiol (E2) and the synthetic oral contraceptive 17alpha-ethinylestradiol (EE2) has been studied in dilute non buffered aqueous solution (pH 5.5-6.0) upon monochromatic (254 nm) and polychromatic (lambda>290 nm) irradiation. Upon irradiation at 254 nm, the quantum yields of E2 and EE2 photolysis were similar and evaluated to be 0.067+/-0.007 and 0.062+/-0.007, respectively. Upon polychromatic excitation, and by using phenol as chemical actinometer, the photolysis efficiencies have been determined to be 0.07+/-0.01 and 0.08+/-0.01 for E2 and EE2, respectively. For both estrogens, photodegradation by-products were identified with GC/MS and LC/MS. In a first step, a model compound--5,6,7,8-tetrahydro-2-naphthol (THN)--, which represents the photoactive phenolic group, was used to obtain basic photoproduct structural informations. Numerous primary and secondary products were observed, corresponding to hydroxylated phenolic- or quinone-type compounds.     

Quantum yield study of the photodegradation of hydrophobic dyes in the presence of acetone sensitizer.

The photodegradation of hydrophobic disperse dyes with different chromophores in the presence of acetone (ACE) was investigated. In this study, the photodecay of dyes was carried out in the Rayonet RPR-200 merry-go-round photoreactor, with 253.7 nm monochromatic ultraviolet (UV) lamps. A typical azo disperse dye (CI disperse yellow 7--DY7) and an anthraquinone disperse dye (CI disperse orange--DO11) were used as the probe compounds. The results demonstrate that the addition of acetone increases the solubility of hydrophobic disperse dyes and enhances the photosensitization reaction simultaneously. More than ten times of quantum yield enhancement is observed in the presence of ACE photosensitizer than in water alone. The photodegradation of DY7 and DO11 is dominated by photoreduction, which follows pseudo first-order decay, and the rate constants strongly depend on the solvent system (i.e., ACE/H2O ratios) and the initial pH levels. The decay quantum yields of dyes are normally observed with the increase of the ACE/H2O ratio. The optimum quantum yields of DY7 and DO11 were determined at 0.5 (v/v) and 0.25 (v/v), respectively, in alkaline conditions. A further increase in the ACE/H2O ratio reduces the quantum yields, possibly due to light attenuation by excess acetone.     

Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

Abiotic degradation of imazethapyr in aqueous solution

The photodegradation of imazethapyr [2-(4,5-dihydro-4-méthyl-4-(1-méthylethyl)-5-oxo-1H-imidazol-2-yl)-5-ethyl-3-pyridinecarboxylic acid] in aqueous solution in the presence of titranium dioxide (TiO2) and humic acids (HA) at different ratios of herbicide/TiO2 and herbicide/humic acids was studied at pH 7.0. Irradiation was carried out with polychromatic light using Heraeus apparatus equipped with xenon lamp to simulate sunlight having a spectral energy distribution similar to solar irradiation (>290 nm). The concentration of remaining herbicide was followed using a High Pressure Liquid Chromatograph (HPLC) equipped with UV detector at 230 nm. In pure aqueous solution imazethapyr degrades slowly and the photodegradation leads to the formation of two metabolites labelled A and B. The presence of TiO2 caused enhancement of the degradation rate. The presence of HA induced an increase of the photodegradation of the pesticide with respect to pure aqueous solution.     

Determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes in aqueous solution using a novel kinetic method

The determination of quantum yields for the photolysis of Fe(III)-hydroxo complexes is important for the quantitative investigation of hydroxyl radical (*OH) production, not only in a natural water body, but also in the photo-Fenton process. A novel kinetic method, using a *OH probe compound, was established for the determination of the quantum yields in this study. The method was based on measuring the pseudo-first-order rate constant of the photodecomposition of dimethylsulfoxide (DMSO) in which DMSO and its primary products scavenged the *OH at an identical rate. The preliminary experiments for the photodecomposition kinetics supported the suitability of DMSOs as a probe compound for determining quantum yields. The individual quantum yields for the photolysis of the monomeric Fe(III) complexes, in the wavelength range 240-380 nm, were determined by the photodecomposition kinetics of the hydroxyl radical (*OH) probe compound (DMSO). The determined values of the individual quantum yields were 0.046+/-0.00052 for Fe3+ (H2O)6 (hexaaquo ion) and 0.69+/-0.025 for Fe(OH)2+ (H2O)5 (hydroxypentaaquo ion) at 254 nm, and showed decreasing values with increasing wavelength, in the ranges of 240-380 nm. The quantum yields between 240 and 280 nm were newly reported in this study, and the values obtained between 280 and 380 nm were in good agreement with the literature values.     

The direct photolysis and photocatalytic degradation of alachlor at different TiO2 and UV sources

Direct photolysis and photocatalytic degradations of alachlor, a widely used herbicide, were studied using three different monochromatic UV lamps (254, 300 and 350 nm) and two TiO(2) sources. Both the direct photolysis and photocatalytic degradations of alachlor follow pseudo-first-order decay kinetics. TiO(2)-P25 was found to be an effective photocatalyst compared to TiO(2)-BDH. The direct photolysis of alachlor was dominant at 254 nm even if TiO(2) was present in the solution. Among the three UV wavelengths used, the highest photocatalysis quantum yield was obtained at 300 nm. The photocatalytic degradation rate of alachlor increased with the dosages of TiO(2), but an overdose of TiO(2) would retard the reaction due to light attenuation. Photocatalytic reactions were slightly enhanced in an alkaline medium, and the different proton sources causing various degrees of rate retardation were due to the presence of the corresponding counter anions. This effect was diminished at a later stage after the reaction intermediates were formed.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at lambda = 254 nm. The photolysis of (alpha + beta: 2 + 1) endosulfan, alpha-endosulfan and beta-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 x 10(-4) s(-1); 1 x 10(-4) s(-1); and 2 x 10(-5) s(-1), respectively, and the calculated quantum yields (phi) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

Kinetic studies of endosulfan photochemical degradations by ultraviolet light irradiation in aqueous medium

Kinetic studies of endosulfan photochemical degradation in controlled aqueous systems were carried out by ultraviolet light irradiation at λ = 254 nm. The photolysis of (α + β: 2 + 1) endosulfan, α-endosulfan and β-endosulfan were first-order kinetics. The observed rate constants obtained from linear least-squares analysis of the data were 1 × 10^?4 s^?1; 1 × 10^?4 s^?1; and 2 × 10^?5 s^?1, respectively, and the calculated quantum yields (φ) were 1, 1 and 1.6, respectively. Preliminary differential pulse polarographic (DPP) analysis allowed to observe the possible endosulfan photochemical degradation pathway. This degradation route involves the formation of the endosulfan diol, its transformation to endosulfan ether and finally the ether's complete degradation by observing the potential shifts.     

The use of PLS algorithms and quantum chemical parameters derived from PM3 hamiltonian in QSPR studies on direct photolysis quantum yields of substituted aromatic halides

The Partial Least-Squares (PLS) method was used to further study Quantitative Structure-Property Relationship (QSPR) for photohydrolysis quantum yields of selected aromatic halides. The cluster of substituted bromobenzenes and iodobenzenes was further grouped into two clusters, substituted bromobenzenes and substituted iodobenzenes, for which QSPRs were obtained, respectively. The QSPRs obtained by PLS are more significant than those obtained in previous studies. The studies showed that only when the compounds belonging to different groups are studies separately, inherent relationships between molecular properties and their structure characteristics can be revealed. It can be generally concluded that the photohydrolysis quantum yields of the substituted aromatic halides are dependent on the overall characters of the molecules, the characters of the carbon–halogen bonds to be broken in the photolysis, and the character of the halogen atoms to be replaced in the photolysis. Electronegativity has great relevance to the photohydrolysis processes of the compounds. Substituted aromatic halides with large average molecular polarizability and molecular weight values tend to have low photolysis quantum yields.     

Kinetics of photodegradation and ozonation of pentachlorophenol

The oxidation of 2,3,4,5,6-pentachlorophenol (PCP) has been carried out by a photodecomposition process using a polychromatic UV irradiation, and by an ozonation process. In the photodegradation process, the pH accelerated the decomposition rate and the approximate first-order rate constants were evaluated, with values between 0.16+/-0.005 min(-1) at pH=3 and 0.26+/-0.007 min(-1) at pH=9. A more rigorous kinetic study led to the determination of the quantum yields of the reaction, with values of 200+/-7x10(-3) mol/Eins for pH=3 and 22+/-1.1x10(-3) mol/Eins for pH=9. In the ozonation process, the rate constants for the reaction between ozone and PCP were determined by means of a competition kinetics, with values in the range from 0.67x10(5) to 314x10(5) l/mols. The specific rate constants for the un-dissociated and dissociated forms of PCP were also calculated. Finally, in both processes, the intermediate reaction products were identified, the most important being tetrachlorocatechol, tetrachlorohydroquinone and tetra-p-chlorobenzoquinone. Free chloride ion released, which was favored at high pHs, was also followed in both processes.     

Photochemical transformations of tetrabromobisphenol A and related phenols in water

A method was developed for studies of the phototransformation at UV irradiation of aqueous solutions of tetrabromobisphenol A (TBBPA), tribromobisphenol A (TriBBPA), tetrachlorobisphenol A (TCBPA), 2,4-dichlorophenol at various pHs as well as 2-chlorophenol, 2-bromophenol, 3,4-dichlorophenol and bisphenol A at pH 11. The absorbance spectra of the compounds and the emission spectra of the light-source were determined and used to calculate disappearance quantum yields of the photochemical reactions that were taking place. No major differences between the disappearance quantum yields of TBBPA and TCBPA were observed at pH 10, while the disappearance quantum yield of TriBBPA was approximately two times higher. The rate of decomposition of TBBPA was six times higher at pH 8 than at pH 6. Identification of the degradation products of TBBPA and TriBBPA, by GC-MS analysis and by comparison to synthesised reference compounds, indicated that TBBPA and TriBBPA decompose via different mechanisms. Three isopropylphenol derivatives; 4-isopropyl-2,6-dibromophenol, 4-isopropylene-2,6-dibromophenol and 4-(2-hydroxyisopropyl)-2,6-dibromophenol, were identified as major degradation products of TBBPA while the major degradation product of TriBBPA was tentatively identified as 2-(2,4-cyclopentadienyl)-2-(3,5-dibromo-4-hydroxyphenyl)propane.     

Diffusivity measurement of heavy ions in Wyoming montmorillonite gels by X-ray computed tomography

Medical X-ray computed tomography (CT) was applied to the measurement of the diffusion coefficients of heavy ions in an artificial barrier material for the disposal of nuclear wastes. Cs(+), Sr(2+), I(-), and Br(-) are the heavy ions measured and the barrier used is the water-rich gel of Wyoming montmorillonite (86.5-100 wt.% H(2)O). X-ray CT yields an inevitable artifact (beam-hardening) in the obtained images. Before the diffusion experiments, the polychromatic primary X-ray spectrum of the CT scanner was measured by a CdZnTe detector, and the effects of the artifact were examined for an aqueous CsCl solution sample. The results show that the beam-hardening artifact derived from the polychromatic photon energy distribution can be suppressed by applying a special image reconstruction method assuming the chemical composition of samples. The transient one-dimensional diffusion of heavy ions in a plastic container filled with the gel was imaged nondestructively by the X-ray CT scanner with an in-plane resolution of 0.31 mm and slice thickness of 2 mm. The results show that diffusivities decrease with increasing clay weight fraction. The degree of the diffusivity decrease was high for cations (Cs(+) and Sr(2+)) and low for anions (I(-) and Br(-)). The quantitative decomposition of the contribution of the geometrical tortuosity and of the sorption to the diffusivity was performed by subtracting the diffusivity of nonsorbing I(-) from the measured diffusivities. The results show that the contribution of the sorption is large for Cs(+), Sr(2+) and small for Br(-). Because X-ray CT allows nondestructive and quick measurements of diffusivities, the technique would be useful particularly for measuring the diffusive migration of harmful radioactive elements.     

Determination of wavelength-averaged,near UV quantum yields for environmental chemicals

The present study describes a procedure for determination of an average quantum yield for the wavelength range of 310 to 410 nm. Solutions of the pollutant in sealed Pyrex tubes are irradiated in a Rayonet photoreactor fitted with fluorescent lamps emitting maximally at 355 nm. The integrated spectral overlap and the photolysis half-life for both the chemical actinometer and the pollutant are determined and from these data the quantum yield is calculated. The method has been evaluated by measuring quantum yields for organophosphorus, chlorinated hydrocarbon, and dinitroaniline pesticides and $\text{p}$-nitroanisole/pyridine mixtures. Corrected quantum yields are obtained on simultaneous irradiation of the trifluralin actinometer.     

Photochemical transformation of azoxystrobin in aqueous solutions

The photochemical behaviour of azoxystrobin fungicide (AZX) in water was studied under laboratory conditions. Photodegradation was initiated using a solar simulator (xenon arc lamp) or a jacketed Pyrex reaction cell equipped with a 125 W, high-pressure mercury lamp. HPLC/MS analysis (APCI and ESI in positive and negative modes) was used to identify AZX photoproducts. The calculated polychromatic quantum efficiencies (phi) of AZX at pH 4.5, 7 and 9 were 5.42 x 10(-3), 3.47 x 10(-3) and 3.06 x 10(-3) (degraded molecules per absorbed photon), respectively. The relatively narrow range of values indicates the stability of AZX with respect to photodegradation in the studied pH range. Results from the HPLC/MS analysis suggest that the phototransformation of AZX proceeds via multiple, parallel reaction pathways including: (1) photo-isomerization (E-->Z), (2) photo-hydrolysis of the methyl ester and of the nitrile group, (3) cleavage of the acrylate double bond, (4) photohydrolytic ether cleavage between the aromatic ring giving phenol, and (5) oxidative cleavage of the acrylate double bond.     

Modeling the quantum yields of herbicide 2,4-D decay in UV/H2O2 process

The photodecay of herbicide 2,4-D in a hydrogen peroxide-aided photolysis process was studied and modeled. The decay rate of 2,4-D was known to be low in the natural environment, but rate improvement was achieved in an H2O2/UV system. The 2,4-D decay quantum yields under ultraviolet (UV) light at 253.7 nm increased from 4.86 x 10(-6) to 1.30 x 10(-4) as the ratio of [H2O2]/[2,4-D] increased from 0.05 to 12.5. Apparently, in the presence of UV light, the decay rate of 2,4-D could be greatly improved as the concentration of hydrogen peroxide increased. However, the efficiency of 2,4-D photodecay was retarded if the concentration of H2O2 was overdosed, because the excess hydrogen peroxide consumes the hydroxyl radicals (HO*) in the solution, resulting in a much weaker oxidant HO2*. The decay of 2,4-D was also pH dependent. A ranking of acid (highest), base (middle) and neutral (lowest) was observed owing to the property change of reactants and the shifting of dominant mechanisms among photolysis, photohydrolysis and chemical oxidation. Two mathematical models were proposed to predict the quantum yield for various [H2O2]/[2,4-D] ratios and initial pH levels, in which very good correlation was found for the ranges of regular application.     

Effect of herbicide and soil amendment on growth and photosynthetic responses in olive crops

Diuron [3-(3,4-dichlorophenyl)- = 1,1-dimethylurea] and simazine (6-chloro-N(2), N(4)-diethyl-1,3,5-triazine-2,4-diamine) are soil-applied herbicides used in olive crops. The objective of this study is to investigate the combined effect of these herbicides and the amendment of soil with an organic waste (OW) from the olive oil production industry on the growth and photosynthetic apparatus of adult olive trees and to compare the results with those obtained by Redondo-Gómez et al. for two-year-old trees. For this purpose, growth rate, gas exchange and chlorophyll fluorescence parameters were measured in 38-year-old olive trees, after one and two months of soil herbicide treatment and/or OW amendment. Soil co-application of OW and herbicide increases the quantum efficiency of Photosystem II (PSII) and the assimilation of CO(2) in olive trees, which led to a higher relative growth rate of the branches and leaves in length. Herbicide treatment reduced the photosynthetic efficiency in olive trees after two months of soil application, while this reduction is evident from week one in younger trees.     

Analysis of munitions constituents in groundwater using a field-portable GC-MS

The use of munitions constituents (MCs) at military installations can produce soil and groundwater contamination that requires periodic monitoring even after training or manufacturing activities have ceased. Traditional groundwater monitoring methods require large volumes of aqueous samples (e.g., 2-4 L) to be shipped under chain of custody, to fixed laboratories for analysis. The samples must also be packed on ice and shielded from light to minimize degradation that may occur during transport and storage. The laboratory’s turn-around time for sample analysis and reporting can be as long as 45 d. This process hinders the reporting of data to customers in a timely manner; yields data that are not necessarily representative of current site conditions owing to the lag time between sample collection and reporting; and incurs significant shipping costs for samples.The current work compares a field portable Gas Chromatograph-Mass Spectrometer (GC-MS) for analysis of MCs on-site with traditional laboratory-based analysis using High Performance Liquid Chromatography with UV absorption detection. The field method provides near real-time (within ∼1 h of sampling) concentrations of MCs in groundwater samples. Mass spectrometry provides reliable confirmation of MCs and a means to identify unknown compounds that are potential false positives for methods with UV and other non-selective detectors.     

First world-wide interlaboratory study on polybrominated diphenylethers (PBDEs)

The first world-wide interlaboratory study on PBDEs, organised between November 1999 and April 2000, involved five biological samples, two sediments and two standard solutions. These materials were sent to 26 participants in nine different countries. Results were returned from 18 laboratories. The results reported for BDE 47 were acceptable with a range of relative standard deviations (Rsd) of 17-40%. Results for the BDEs 99 (Rsd 25-77%), BDE 100 (Rsd 19-48%), 153 (Rsd 30-48%) and 154 (Rsd 25-43%) showed that a further improvement of these analyses is needed. The BDE 209 analysis is not under the control of the participating laboratories. The data reported for the biota samples were very variable and for the two sediments Rsd values of 48% and 78% were obtained. It is recommended that analysts pay more attention to the special requirements for the BDE 209 analysis such as avoiding exposure to intensive light and exposure for too long times to too high temperatures.