Interactions of ozone with organic surface films in the presence of simulated sunlight: impact on wettability of aerosols.

Heterogeneous reactions between organic films, taken as proxies for atmospheric aerosols, with ozone in presence of simulated sunlight and the photosensitizer 4-carboxybenzophenone (4-CB) were observed to alter surface properties as monitored by contact angle during the reaction. Attenuated total reflectance Fourier transform infrared spectroscopy (FTIR-ATR) was used in addition for product identification. Two types of model surfaces were systematically studied: 4-CB/4-phenoxyphenol and 4-CB/catechol. Solid organic films made of 4-CB/catechol were observed to become hydrophilic by simultaneous exposure to ozone and simulated sunlight, whereas organic films made of 4-CB/4-phenoxyphenol become hydrophobic under the same conditions. These changes in contact angle indicate that photo-induced aging processes involving ozone (such as oligomerisation) not necessarily favour increased hygroscopicity of organic aerosols in the atmosphere. The ratio between hydrophobic and hydrophilic functional groups should reflect the chemical property of organic films with respect to wettability phenomena. Contact angles and surface tensions of the exposed organic film made of 4-CB/4-phenoxyphenol were found to correspond to the hydrophobic/hydrophilic ratios obtained from the FTIR-ATR spectra.

Photodegradation study of decabromodiphenyl ether by UV spectrophotometry and a hybrid hard- and soft-modelling approach.

This work presents an exploratory study of the photochemical degradation process of decabromodiphenyl ether (decaBDE) and gives an interpretation of the kinetic pathway, species and effects of the key factors involved in the degradation process. Use of lowly brominated diphenyl ethers (PBDE) has been banned by the EU and there seems to be evidence of the photolytic degradation of highly brominated PBDEs into lowly brominated congeners. Hence, the importance of knowing the photodegradation process of decaBDE. The photodegradation was investigated under UV light by UV-spectrophotometric monitoring. A novel hybrid data analysis approach, based on the combination of hard- and soft-spectrophotometric multivariate curve resolution, was applied to elucidate the mechanism of the degradation process, to resolve kinetic profiles and pure spectra of the photodegradation products and to evaluate the rate constants. The photodegradation process could be described with a kinetic model based on three consecutive first-order reactions and a decrease of the degradation process was observed as solvent polarity increased. Complementary identification of photodegradation products by gas chromatography coupled to mass spectrometry using negative chemical ionization (GC-NCI-MS) is attempted. This work presents a novel attempt of describing in a comprehensive way the photochemical degradation process of decaBDE, with all successive steps and related rate constants. This study proves also the potential of the proposed hybrid data analysis methodology as a general strategy to interpret the evolution of these photochemical reactions.

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution.

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.

Photochemical degradation of six polybrominated diphenyl ether congeners under ultraviolet irradiation in hexane.

The photodegradation of six individual PBDE congeners (BDE-28, 47, 99, 100, 153, 183) in hexane was investigated under UV light in the sunlight region, employing a mercury lamp filtered with Pyrex glass. All photodegradation reactions followed the pseudo-first-order kinetics, with the half-lives ranging from 0.26h for BDE-183 to 6.46h for BDE-100. The photochemical reaction rates of PBDEs decreased with decreasing number of bromine substituents in the molecule, also in some cases were influenced by the PBDE substitution pattern. Principal photoproducts detected were less brominated PBDEs, and no PBDE-solvent adducts were found. Consecutive reductive debromination was confirmed as the main mechanism for the photodegradation of PBDEs in hexane. In general, debromination firstly occurred on the more substituted rings, when the numbers of bromine atoms on the two phenyl rings were unequal. For less brominated PBDEs, the photoreactivity of bromines at various positions of phenyl rings decreased in the order: ortho>para; while for higher brominated PBDEs, the difference became not significant.

Deposition versus photochemical removal of PBDEs from Lake Superior air.

Analysis of a sediment core collected from Siskiwit Lake, located on a remote island in Lake Superior, provides evidence that polybrominated diphenyl ethers (PBDEs) are removed effectively from the atmosphere via deposition processes during long-range transport. A mass balance model based on photochemical rate constants and data from atmospheric samples was created to understand the relative importance of various photochemical and deposition processes in removing PBDEs from the atmosphere. Photolysis rate constants were derived from UV absorption spectra of 25 PBDEs recorded in isooctane over the range of 280-350 nm at 298 K. Photolysis decays measured for BDE-3 and -7 in the gas phase were substantial compared to a well-defined chemical actinometer, indicating that their photolysis quantum yields are significant. Dibenzofuran production was observed when PBDE congeners containing ortho-bromines were photolyzed in helium. From estimates of removal rates of PBDEs from the lower troposphere, we find that wet and dry deposition accountfor >95% of the removal of BDE-209, while photolysis accounts for -90% of the removal of gas-phase congeners such as BDE-47. These results help explain the deposition patterns of PBDEs found in lake and river sediments and have important implications concerning the inclusion of photolysis as a fate process in multimedia models.

Quantitative structure-property relationships for direct photolysis of polybrominated diphenyl ethers.

Using semiempirical quantum chemical descriptors, by partial least squares (PLS) regression, quantitative structure-property relationships (QSPRs) were established for direct photolysis quantum yields (Phi) and rate constants (k) of polybrominated diphenyl ether congeners dissolved in water/methanol and methanol solutions, respectively, and irradiated by artificial ultraviolet A light. Q(cum)(2), a parameter indicating robustness and predictive abilities of PLS models, for the significant QSPR models is larger than 0.702. The gap of frontier molecular orbital energies (E(LUMO)-E(HOMO)) and the most positive Mulliken atomic charges on a hydrogen atom (q(H+)) are two main molecular structural factors governing the logPhi values. logPhi increases with increasing E(LUMO)-E(HOMO) and q(H+) values. logk is mainly related to bromination degree and pattern which can be characterized by molecular weight (Mw), average molecular polarizability (alpha), and average Mulliken atomic charges on bromine atoms (q(Br)). logk increases with bromination degree (Mw, alpha) and q(Br).

Ah receptor agonists in UV-exposed toluene solutions of decabromodiphenyl ether (decaBDE) and in soils contaminated with polybrominated diphenyl ethers (PBDEs).

GOAL, SCOPE AND BACKGROUND: The use of polybrominated diphenyl ethers (PBDEs) as flame retardants increases the risk for emissions of other brominated compounds, such as polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). The large homology in structure of PBDD/Fs and mechanism of toxic action, i.e. the capacity to activate the Ah receptor (AhR) pathway, compared to their well-studied chlorinated analogues, justifies a raised concern to study the environmental levels and fate of these compounds. Decabromodiphenyl ether (decaBDE) is the most widely used PBDE today. Studies on photolytic debromination of decaBDE in organic solvents have shown debromination of decaBDE, as well as formation of PBDFs. However, little is known about the transformation mechanisms and there are only scarce data on photoproducts and PBDE transformation in environmentally relevant matrices. In this study, mechanism-specific dioxin bioassays were used to study photolytic formation of AhR agonists in toluene solutions of decaBDE. In addition, the influence of irradiation time and UV-light wavelength on the formation was studied. PBDE congener patterns and presence of PBDD/Fs were analysed. Further, AhR agonists were analysed in agricultural soils contaminated with PBDEs. Soils were also exposed to UV-light to study changes in AhR agonist levels. METHODS: Toluene solutions of decaBDE were irradiated using three different spectra of UV-light, simulating UV-A (320-400 nm), UV-AB (280-400 nm), and UV-ABC (250-400 nm). Additionally, decaBDE solutions were exposed to narrow wavelength intervals (10 nm bandwidth) with the central wavelengths 280, 290, 300, 310, 320, 330, 340, 350, 360 nm. AhR agonists in decaBDE solutions were analysed with two different bioassays, the chick embryo liver-cell assay for dioxins (Celcad) and the dioxin responsive, chemically activated luciferase expression assay (DR-Calux). Also, the decaBDE solutions were analysed with LRGC-LRMS to obtain PBDE congener patterns for breakdown of decaBDE, and with HRGC-HRMS, for presence of PBDD/Fs. Four soils were exposed to UV-AB light, under both dry and moist conditions. Levels of AhR agonists in soil extract fractions, before and after UV-exposure, were analysed with the DR-Calux. RESULTS AND DISCUSSION: Significant levels of photoproducts able to activate the AhR pathway, up to 31 ng bio-TEQ/ml, were formed in UV-exposed decaBDE solutions. The transformation yield of decaBDE into AhR agonists was estimated to be at the 0.1%-level, on a molar basis. The net formation was highly dependent on wavelength, with the sample irradiated at 330 nm showing the highest level of dioxin-like activity. No activity was detected in controls. PBDE analysis confirmed decaBDE degradation and a clear time-dependent pattern for debromination of PBDE congeners. AhR agonist effect in the recalcitrant fractions of the soils corresponded to the levels of chemically derived TEQs, based only on chlorinated dioxin-like compounds in an earlier study. It was concluded that no significant levels of other AhR agonists, e.g. PBDFs, were accumulated in the soil. UV-light caused changes in AhR-mediated activity in the more polar and less persistent fractions of the soils, but it is not known which compounds are responsible for this. RECOMMENDATIONS AND PERSPECTIVES: The laboratory experiments in this study show that high levels of AhR agonists can be formed as photoproducts of decaBDE and it is important to elucidate if and under which conditions this might occur in nature. However, soil analysis indicates that photoproducts of PBDE do not contribute to the accumulated levels of persistent dioxin-like compounds in agricultural soil. Still, more data is needed to fully estimate the environmental importance of PBDE photolysis and occurrence of its photoproducts in other environmental compartments. Analysis with dioxin bioassays enabled us to gather information about photoproducts formed from decaBDE even though the exact identities of these compounds were not known. CONCLUSION: Bioassays are valuable for studying environmental transformation processes like this, where chemical analysis and subsequent toxicological evaluation requires available standard compounds and information on toxicological potency. The use of bioassays allows a rapid evaluation of toxicological relevance.

Quantitative structure-property relationships on photodegradation of polybrominated diphenyl ethers.

By partial least squares (PLS) regression, quantitative structure-property relationship (QSPR) models were developed for photodegradation rates (k(p)) and quantum yields (Phi) of polybrominated diphenyl ethers (PBDEs) in methanol/water (8:2), and photodegradation rates in pure methanol by UV light in the sunlight region, respectively. Quantum chemical descriptors computed by PM3 Hamiltonian were used as predictor variables. The cross-validated Q(cum)(2) values for three optimal QSPR models of PBDEs are above 0.90 (remarkably higher 0.50), indicating good predictive abilities for logk(p) and logPhi values of PBDEs. The QSPR results show that logk(p) values of PBDEs in methanol/water (8:2) and in pure methanol are governed by different molecular structural descriptors, respectively, which implies that photodegradation rates of PBDEs are affected by the characteristics of solution in which it takes place.

Decomposition of aqueous diphenyloxide by ozonolysis and by combined gamma-ray-ozone processing.

Diphenyloxide (DPO) is one of many, rather toxic pollutants produced by combustion of fossil fuels, which are emitted to the atmosphere with flue gases and brought to ground water by rain and snow. Its decomposition is investigated by ozonolysis at room temperature and the major products like phenol, resorcinol, hydroquinone, dihydroxy-benzoic acid as well as the total yield of aldehydes and carboxylic acids were determined as a function of applied ozone concentration. In addition, the DPO-degradation was studied by a combined action of gamma-ray under continuous bubbling of a known ozone concentration. In this case the formation of the same products is observed, but their yields differ from the above ones. Based on the synergistic action of ozone and gamma-ray the DPO-radiolysis is rather efficient, leading to an initial-G-value of 11.3. Some probable reaction mechanisms are presented for explanation of the degradation process.

Study of the mode of action of some nitrodiphenyl ethers.

Nitrosoderivatives of the nitrodiphenyl ether herbicides (nitrofen, bifenox) have been studied. UV irradiation in different organic solvents gives degradation products. In buffered aqueous media, in the presence of chloroplasts and spin traps such as DMPO, hydroxy and peroxy radicals have been characterized. In organic media and in the presence of spin traps such as DMPO, PBN, 4-POBN, solvent radicals (.CHCl2, .CCl3, .CH2 [symbol: see text]) have been formed. Nitro-derivatives have been studied under UV irradiation and in the presence of tetramethylethylene (TME), alkenylhydroxylamines are formed which autoxidize in nitroxide radicals. The formation of the stable nitroxide radical occurs in the dark process after continuous irradiation. The intensity of the signal decreases strongly when a new irradiation is applied. Radical species, with analogous ESR spectral characteristics are formed on reaction with nitrodiphenyl ethers and fatty acids. The reactivity of these herbicides in micellar media (SDS, Brij 35, and CTAB) has been investigated. The kinetics of formation of the ESR signal corresponding to the photoreduction of the nitrodiphenyl ether in the presence of TME behave differently in a micellar environment as compared to solution. The intensity of the formation of the nitroxide increases under irradiation and decreases in the dark; the rotational correlation time tau c has been determined for each type of micelle. Synthetic nitrosodiphenyl ether made by the reduction of nitrodiphenyl ether using hydrogen gas and PtO2 as a catalyst gives the corresponding amine, which is oxidized with meta-chloroperbenzoic acid (m.CPBA). The nitrosodiphenyl ether in the presence of soja azolectin liposome containing a fluorescent probe has been analysed.(ABSTRACT TRUNCATED AT 250 WORDS)