Singlet molecular oxygen—mediated photooxidation of monochloro and mononitrophenols. A kinetic study

A kinetic and mechanistic study on the aerobic dye sensitized photooxidation of the mono—nitro and chlorophenols was carried out. A singlet molecular oxygen mechanism operates in the photooxidation. Solvent and substituent effects, suggest the intermediacy of a complex with partial charge transfer character, as has been postulated for other phenols.

Chemical (reactive) and physical interactions of the substrates with singlet molecular oxygen were discriminated. Quantum yields for photooxidation (higher for the chlorophenols) range from 3 × 10^‐2 to 2 × 10^‐3, as measured by substrate or oxygen consumption. These values indicate the viability of a singlet molecular oxygen photooxidation as a way for the degradation of nitro and chlorophenol environmental contaminants.     

Sensitized photooxygenation of mononitrophenols in micellar media

The singlet molecular oxygen‐mediated photooxidation of simple nitrophenols was studied in micellar (CTAB) alkaline solutions.

A different behaviour for the values of the overall rate constant (K_t ) and the reactive rate constant (K_t ) in the interaction nitrophenol‐singlet molecular oxygen was observed as a function of surfactant concentration. The former decreases as [CTAB] increases, from values of 1–3 × 10⁹ M^–1 s^–1 in the absence of surfactant to values at least one order of magnitude lower at [CTAB] ～0.1 M. Parallel, k_t remains practically unaffected, in values of the order of 10⁶ — 10⁷ M^–l s^–1, depending on the particular nitrophenol, within the same [CTAB] range. The quantum yield of nitrophenols photooxidation reaches a maximum at [CTAB] ～0.1 M.

The results are discussed in terms of a combination of causes, the polarity of the nitrophenolic microenvironment being the driving effect. The implication of the results on environmental decontamination are also analyzed.     

The influence of some biological antioxid ants on the light emission from the oxytetracycline oxidation reaction

The effect of the Superoxide radical (O₂ ^–)‐, hydroxyl radical (HO')‐inhibitors, singlet oxygen (¹O₂)‐quenchers and catalase on the light emission during autoxidation reaction of oxytetracycline was measured. The influence of the ¹O₂‐quenchers was investigated quantitatively and the rate constants were established.     

Acute nitrate poisoning in two cattle

Abstract

The rate and product composition during photooxidation of aromatic hydrocarbons (toluene, o‐, m‐, p‐xylene and cumene) dissolved in n‐hexane and spread as a liquid film on water is reported. The photo degradability of these chemicals is 10–20%. The products identified are oxygenated aromatic compounds. It is observed that the absorption bands of the compounds under investigation depend upon the partial pressure of dissolved oxygen and these bands extend up to 290 nm. The new absorption band around 290 nm is probably due to broadening of ¹L_b bands which is responsible for direct photolysis.

stream. We have been especially interested in investigating the rate of disappearance and distribution of main oxidation products in two phases. Besides that an attempt has been made to throw some light on the reaction mechanism.     

Quantification of singlet oxygen and hydroxyl radicals upon UV irradiation of surface water

We measured the formation rate and the steady-state concentration of hydroxyl radicals and of singlet oxygen upon irradiation of lake water. There is controversy about the importance of singlet oxygen in the environmental photochemistry, but here we show that the steady-state concentration of ¹O₂ under irradiation can be higher by about two orders of magnitude compared to the hydroxyl radical. The higher occurrence of singlet oxygen in surface waters is mainly due to a higher rate of formation, because the transformation rate constants of ¹O₂ (collision with the solvent) and of ^·OH (reaction with dissolved compounds) are comparable.     

Rose Bengal‐sensitized photooxygenation of chlorohydroxyaromatic contaminants in water: A kinetic study

A kinetic study of the RB‐sensitized photooxygenation of a series of chlorohydroxyaromatic (ClArOH) water contaminants (phenolic and dihydroxybenzene derivatives) has been carried out. In addition, an exhaustive study on the possible interactions of RB electronically excited triplet and singlet states with ClArOH was also developed. The determination of relative rates of oxygen uptake upon sensitized irradiation, employing auxiliar selective quenchers of oxygen active species, indicate the contribution of both singlet molecular oxygen (ca. 71%) and Superoxide ion (ca. 26%) as the reactive pathways for ClArOH degradation. The substitution by chlorine atoms in position meta greatly decrease the photooxygenation rate of the phenolic derivatives. For the dihydroxybenzene series, increase in nuclear chlorination parallels a decrease in the photodegradation rate.

Outdoors sensitized solar irradiation experiments on different ClArOH mixtures leads to measurable levels of oxygen after a few minutes exposure. From the environmental point of view, and ruling out the possibility of direct‐irradiation photoreactions, sensitized photooxygenation appears as an alternative pathway for ClArOH degradation, in competence with other naturally‐occurring photoprocesses involving reactive transient species.     

Luminescence in the oxidation of isoproterenol by the superoxide anion radical in dimethyl sulfoxide

Chemiluminescence appearing during oxidation of isoproterenol using chemical system involving superoxide anion radical has been studied. Chemiluminescence and fluorescence spectra were measured. The chemiluminescence spectrum was measured with cut‐off filters and revealed bands with maximum at 440, 480, 550, 640 and 700 nm. The bands at 480, 640 and 700 nm were similar to those observed for singlet oxygen. The fluorescence spectrum exhibited maximum at 560 nm.

The inhibitory effect of several biologically important compounds known as O₂ ^?‐ HO^? and ¹O₂ scavengers on the light emission was studied.

The obtained results indicate that oxidation of isoproterenol by O₂ ^?‐ involves products in the electronically excited states. The data also seem to indicate the protective effect of isoproterenol on the deoxyribose degradation.     

Effect of chlorophenolic pesticides on the photochemistry of riboflavin

The possibility of riboflavin sensitized photo‐oxidation of polychlorinated pesticides was investigated. The dye proved to be an inefficient sensitizer for that purpose, when irradiated with visible light, in aereated aqueous solutions. A quenching of singlet and triplet excited states of the chromophore (depending on the concentrations of the quencher) is responsible for this failure in the photo‐degradation of the pesticides, which resulted easily oxidizable, via singlet oxygen mechanism, when proflavine was employed as a sensitizer. Parallel, and as a direct consequence, the rate of aerobic riboflavin photobleaching decreased drastically in the presence of the chlorophenols.

The implication of our results on the inhibition of riboflavin degradation by the presence of chlorinated phenolic pesticides in the environment, is discussed, from the point of view of a kinetic and mechanistic study.     

Low molecular-weight factor from Plesiastrea versipora (Scleractinia) that modifies release and glycerol metabolism of isolated symbiotic algae

When symbiotic dinoflagellate algae (Symbiodinium sp., isolated from the coral Plesiastrea versipora) were incubated with NaH¹⁴CO₃ in the light in seawater, they released 22.69±9.16 nmol carbon/10⁶ algae. Release of photosynthetically fixed carbon was stimulated more than six-fold for algae incubated in host-tissue homogenate (148.54±97.03 nmol C/10⁶ algae) and more than four-fold (102.00±49.16 nmol C/10⁶ algae) for algae incubated in a low molecular weight fraction (≤1 000 M _r ) prepared from host homogenate. Soluble released ¹⁴C-labelled products, as determined by chromatography and autoradiography, were the same when algae were incubated in either host homogenate or the low molecular weight fraction. After 4 h incubation in the light (300 mol photons m⁻² s⁻¹),␣intracellular␣glycerol increased in algae incubated with the low molecular weight fraction (an increase of 0.39 to␣0.67 nmol glycerol/10⁶ algae) compared with little or no increase in algae incubated in seawater (0 to 0.12 nmol glycerol/10⁶ algae). Partial inhibition of triglyceride synthesis (up to 51%) was also observed when algae were incubated in the low molecular weight fraction. All these effects are the same as those observed when algae were incubated in host homogenate. These data indicate that the “host release-factor” activity of P.␣versipora is a compound of low molecular weight. Received: 13 February 1997 / Accepted: 24 October 1997     

The influence of suspension density and temperature on the filtration rate of Hiatella arctica

The rate of filtering Phaeodactylum tricornutum and Isochrysis galbana was measured in Hiatella arctica (L.) by the indirect suspension depletion method monitored by optical density measurement. The filtration rate of H. arctica was found to be 1.412×10^–2 l/h/g wet weight at a temperature of 15°C when fed with P. tricornutum, at average cell concentrations up to 3.5×10⁶ cells/ml. The filtration rate dropped almost to zero when the concentration of P. tricornutum reached 11×10⁶ cells/ml. The filtration rate of I. galbana diminished at a much lower cell concentration of 1×10⁶ cells/ml, and almost ceased at 3 to 4×10⁶ cells/ml. In mixed cultures of I. galbana and P. tricornutum, the filtration rate ratio was 0.37 to 1.00, and this was believed to be due to a proportion of the smaller former cells passing through the ostia. However, when resuspended in sea water, I. galbana cells were taken at a rate slightly less than P. tricornutum. The medium in which the I. galbana cells had been grown was inhibitory to the filtering activity of H. arctica, since, when cells of either alga were resuspended in the medium, the filtration rate was considerably reduced. No inhibitory factor existed in either of the original nutrient media. Hence, the importance of using low cell concentrations and of eliminating any inhibitory metabolic products when measuring filtration rates of bivalves is stressed. H. arctica shows a typical activity temperature eurve for a boreo-arctic species, with a steady rise from 0°C to a maximum between 15° and 17°C, and a sharp fall in activity to about zero at 25°C. The rates of filtration of various species at temperatures approaching the optimum were compared after allowance was made for fall in filtration rate with increasing body weight. The results suggested that the Mytilacea had the highest filtration rates and that H. arctica possesses one of the lowest filtration rates recorded.     

Effects of UV-A LED light irradiation on growth of cultured RAW 264.7 cells

The aim of this study was to examine the effects of ultraviolet A (UV-A) irradiation-induced damage on cultured macrophage RAW 264.7 cells and determine which components produced these manifestations. RAW 264.7 cells were irradiated with 365 nm UV-A using a light-emitting diode (LED). Cell viability and damage were determined using a calcein-AM and propidium iodide dual-staining assay and lactate dehydrogenase leakage, respectively. Intracellular reactive oxygen species (ROS) were measured by H₂DCF-DA. The components of ROS in each medium were measured using an electron paramagnetic resonance (EPR) spectrometer in the presence of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and 2,2,5,5-tetramethyl-3-pyrroline-3-carboxamide (TPC). While UV-A irradiation for 2 min significantly suppressed cell growth, LDH leakage did not occur. Addition of N-acetyl cysteine restored inhibition of cell proliferation, and reduced intracellular ROS levels. The EPR signal in the presence of TPC increased with time but was decreased by sodium azide. In addition, a typical EPR spectrum was obtained in the presence of DMPO, indicating the presence of a hydroxyradical. The spectrum was diminished by L-histidine. Data suggest that ROS generated in cells or culture medium by UV-A irradiation is predominantly singlet oxygen, and this singlet oxygen suppressed cell proliferation.     

The acidobasic and complexation properties of Humic acids

Complexation of Humic Acids (HA) of different origin, like Fluka, and especially those extracted from bohemian brown coal, with cadmium(II) and lead(II) was studied at pH 5.0 using differential pulse anodic stripping voltammetry. Conditions close to those present in the environment were chosen with 3‐ 10^‐4 moll^‐4 for HAs and 2. 10^‐8‐l . 10^‐5 moll^‐1 for Cd(II) and Pb(II). Stability constants evaluation was done assuming the electrode process is diffusion controlled and the complexes are labile. Obtained log K values were in the range 4.49–5.25 for Cd(II) and as expected the higher log K values 6.05–6.60 were found for Pb(II). There was no significant difference between complexation properties of HA extracted from bohemian brown coal and that of Fluka. The results obtained are in good agreement with the literature and those obtained by ISE in our laboratory.     

Photodegradation of atrazine and ametryn with visible light using water soluble porphyrins as sensitizers

The photodegradation of the herbicides atrazine and ametryn with visible light in aerated neutral aqueous solutions and 5, 10, 15, 20-tetrakis (2,6-dichloro-3-sulfophenyl) porphyrin or 5, 10, 15, 20-tetrakis (4-sulfophenyl) porphyrin as sensitizers are reported for the first time. Our findings show that the degradation percentage reached 30% for atrazine and 63% for ametryn. The final photoproducts were characterized as dealkylated s-triazines. Photolysis of the pesticides in the presence of a singlet oxygen quencher showed only a minor contribution of this type of mechanism, while a bimolecular quenching reaction between the triplet state of the sensitizer and the pesticides is excluded by flash photolysis studies. It is proposed that the mechanism may involve the formation of a superoxide radical anion from the triplet state of the sensitizer and molecular oxygen, followed by a radical decomposition pathway. Selected article from 1st International Meeting on Photochemistry, Photocatalysis and Environmental Applications, Agadir, 2006, organised by Prof. Dr. Ait Ichou, University Ibn Zohr, Agadir, Morocco     

Oxygen dependent sulfide detoxification in the lugwormArenicola marina

The lugwormArenicola marina L. oxidizes entering sulfide to thiosulfate. After 8 h of normoxic incubations with sulfide concentrations of 0.2 to 1.0 mmoll^-1 thiosulfate in the coelomic fluid amounted up to about 4 mmoll^-1 whereas sulfite concentrations were 100-fold lower and no accumulation of sulfate in the coelomic fluid was found. The sulfide oxidation was highly oxygen dependent. An increase of oxygen partial pressure ( ) in the medium was followed by enhanced thiosulfate production and by a decrease of sulfide concentration in the coelomic fluid. Under normoxia, the sulfide oxidation rate was sufficient to compensate the influx of sulfide into the coelomic fluid when the sulfide concentration in the medium was below 0.33 mmoll^-1. When external sulfide was raised beyond this level, sulfide up to 5 moll^-1 in the coelomic fluid appeared. Succinate in the body wall tissue was low as long as no sulfide appeared in the coelomic fluid, indicating the maintenance of an aerobic metabolism. The oxidation of sulfide to thiosulfate was localized in the mitochondria of the body wall tissue. The oxygen consumption of mitochondria was stimulated by the addition of sulfide. The mitochondrial sulfide oxidation rate depended on the amount of mitochondrial protein and followed a Michaelis-Menten kinetic. An apparentK _m of 0.68±0.29 moll^-1 and aV _max of 41.9±22.3 nmol min^-1 mg^-1 protein was calculated. Sulfide was stoichiometrically oxidized to thiosulfate with 1 mol sulfide consuming 1 mol oxygen. Sulfide oxidation was not inhibited by sulfide concentrations as high as 100 moll^-1. At low concentrations of cyanide or azide, when respiration without sulfide was already inhibited, sulfide oxidation could still be stimulated, tentatively indicating the existence of an alternative terminal oxidase. Specimens examined in the present study were collected near St. Pol de Leon, France, from 1989 to 1992.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part IV†: Incorporation of inorganic chlorine into organic matter and thermochemical aromatizations

The pyrolysis and chlorination of petroleum coke in a NaCl‐KCl melt results in the production of CCl₄ and C₆Cl₆. Polychlorinated dibenzo‐p‐dioxins (PCDDs) are produced from the air oxidation and chlorination of coal using HCl or Cl₂. Smoking of tobacco containing ³⁶Cl^e provides CH₃ ³⁶Cl.

At 350°C, the rateof aromatization of 1,3‐cyclohexadiene is negligible as compared to that of 1,4‐cyclohexadiene. The aromatization of the latter diene proceeds through the molecular elimination of hydrogen; while that of 1,3‐cyclohexadiene expecially at higher pressure (10–90 Torr) and at 362–421 °C involves free radical chain mechanism.     

Responses of hemolymph osmolality and tissue water of Penaeus chinensis Osbeck juveniles subjected to sudden change in salinity

Hemolymph osmolality and tissue water of laboratory-reared Penaeus chinensis Osbeck juveniles (0.83 to 1.86 g) were investigated, after they had been transferred individually from 10, 20, 30 and 40 ppt to 10, 20, 30 and 40 ppt for 0.25, 0.5, 1, 2, 5 and 10 d, respectively. Hemolymph osmolality and tissue water of shrimp were stablilized within 5 d after they had been subjected to a sudden change in salinity from each salinity level. Hemolymph osmolality had a positively linear relationship with medium osmolality. Tissue water decreased with increased medium osmolality, and decreased with increased hemolymph osmolality. The mean (SD) isosmotic point was 703 (8) mOsm kg^–1 which is equivalent to 24.2 (1.0) ppt. P. chinensis juveniles exhibited hyperosmotic regulation in salinities below isosmotic value, and hypoosmotic regulation in those above. The shrimp originally adapted to high salinity levels (30 and 40 ppt) showed less fluctuation of tissue water than those adapted to low salinity levels (10 and 20 ppt) when they were subjected to a sudden change in salinity.     

Growth and competition of the marine diatoms Phaeodactylum tricornutum and Thalassiosira pseudonana. I. Nutrient effects

Two marine diatoms, Phaeodactylum tricornutum (Bohlin) and Thalassiosira pseudonana (Hasle and Heimdal), were grown both separately and together in batch cultures on a mixture of waste water and seawater enriched with different components of f medium. At 17°C, the maximum division rates of the two species were statistically indistinguishable. The waste water-seawater mixture used proved to have insufficient Si, relative to N and P, for the growth of T. pseudonana, which requires approximately 5x10^-14 g-at Si cell^-1 to divide at a maximum rate. P. tricornutum, on the other hand, although capable of taking up nearly 9x10^-15 g-at Si cell^-1, could sustain maximum rates of division with 4.3x10^-18 g-at Si cell^-1 or less. No allelopathic interaction between the two species could be detected. We conclude that P. tricornutum enjoys a considerable competitive advantage over T. pseudonana in a waste water-seawater-based mariculture system that is not supplemented with Si. Although Si proved necessary for T. pseudonana to complete more successfully with the other diatom, the presence of excess amounts of Si is not necessarily sufficient for the maintenance of T. pseudonana in mixed continuous culture with P. tricornutum: other factors, such as light-related or photoperiod-related growth response, are believed to determine the ultimate outcome of competition between these algae in light-limited continuous culture.Contribution No. 3999, from the Woods Hole Oceanographic Institution.Communicated by M.R. Tripp, Newark     

Incorporation of 32PO4 directly taken-up into acid-soluble phosphates of Artemia salina

A study of the direct uptake by Artemia salina of phosphate ion from the medium and its incorporation into acid-soluble organic phosphorous compounds over a range of exposure time from 2 to 30 min, using ³²PO₄ ion, indicated that the phosphate ion was directly taken up and was rapidly incorporated into the energy-rich compounds, such as adenosine triphosphate (ATP), guanosine triphosphate (GTP), and adenosine diphosphate (ADP), which were separated by ion-exchange chromatography using Dowex-1, X2. Even after an exposure of 2 min, the sum of the radioactivity of nucleotide-fractions was 37.4% of that of the whole acid-soluble extract. The most rapid incorporation of ³²P occurred into ATP, followed by GTP and ADP. The amount of ³²P incorporated into each fraction increased with increased exposure, giving straight lines when the radioactivity of each fraction was plotted against the exposure time on a logarithmic scale. Almost no difference, however, was observed in the distribution rate of ³²P into each fraction at 2, 5, 10 and 30 min. These results show that inorganic phosphate absorbed by A. salina is rapidly incorporated into the energy-rich nucleotides, and that a dynamic equilibrium is established among various acid-soluble phosphorous compounds even after very short periods of time.     

Effects of Cadmium on Nutrient Uptake and Translocation by Indian Mustard

Plants that hyperaccumulate metals are ideal subjects for studying the mechanisms of metal and mineral nutrient uptake in the plant kingdom. Indian Mustard (Brassica juncea) has been shown to accumulate moderate levels of Cd, Pb, Cr, Ni, Zn, and Cu. In this experiment, 10 levels of Cd concentration treatments were imposed by adding 10–190 mg Cd kg^–1 to the soils as cadmium nitrate [Cd(NO₃)₂]. The effect of Cd on phosphorus (P), potassium (K), calcium (Ca), magnesium (Mg), and the micronutrients iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn) in B. juncea was studied. Plant growth was affected negatively by Cd, root biomass decreased significantly at 170 mg Cd kg^–1 dry weight soils treatment. Cadmium accumulation both in shoots and roots increased with increasing soil Cd treatments. The highest concentration of Cd was up to 300 mg kg^–1 d.w. in the roots and 160 mg kg^–1 d.w. in the shoots. The nutrients mainly affected by Cd were P, K, Ca, Fe, and Zn in the roots, and P, K, Ca, and Cu in the shoots. K and P concentrations in roots increased significantly when Cd was added at 170 mg kg^–1, and this was almost the same level at which root growth was inhibited. Zn concentrations in roots decreased significantly when added Cd concentration was increased from 50 to 110 mg kg^–1, then remained constant with Cd treatments from 110 to 190 mg kg^–1. However, Zn concentrations in the shoots seemed less affected by Cd. It is possible that Zn uptake was affected by the Cd but not the translocation of Zn within the plant. Ca and Mg accumulation in roots and shoots showed similar trends. This result indicates that Ca and Mg uptake is a non-specific process.     

Cadmium uptake by a phytoplankton species in the presence of different inhibitors&

The uptake of cadmium by the Haptophyceae Hymenomonas elongata was studied as regards the energetic processes and Ca‐transport. For this purpose, experiments were carried out in the presence of an uncoupler of the phosphorylation : CCCP and of an inhibitor of calcium channels and also of Ca²⁺‐ATPase : verapamil. To reduce the number of assays, a factorial experimental design was used, in which all variables:— concentration of Cd in the medium—incubation time and—the presence of the inhibitor, are at two levels. In the absence of inhibitor, Cd uptake was found to vary as a function of metal concentration in the medium and of incubation time. CCCP significantly increased Cd uptake by H. elongata at sufficient incubation time. Therefore Cd uptake seemed linked to an energy‐dependent process, involving an ATPase. Verapamil immediately increased Cd uptake, implying an interaction between Cd and Ca.