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.     

Release of ultraviolet-absorbing compounds by the red-tide dinoflagellateLingulodinium polyedra

We tested the hypothesis that ultraviolet-absorbing compounds known as mycosporine-like amino acids (MAAs) are not only synthesized but also excreted by marine phytoplankton. An experiment was performed with cultures of the marine dinoflagellateLingulodinium polyedra (previously known asGonyaulax polyedra) exposed to visible (photosynthetically available, PAR, 400 to 700 nm) and ultraviolet (UV, 290 to 400 nm) radiation. Absorption properties of both particulate and dissolved organic matter pools (POM and DOM, respectively) showed maxima in ultraviolet absorption at 360 nm. Chromatographic analysis confirmed the presence of MAAs in both pools. Release of organic matter byL. polyedra, as measured spectrophotometrically by changes in UV absorption in the surrounding medium, showed a differential increase at 360 nm in cultures exposed to UV-B + PAR radiation. The changes in absorption in the DOM fraction were inversely proportional to intracellular UV absorption. Photodegradation experiments in which the DOM fraction was exposed to visible and UV-B radiation showed a decrease in absorption with dose. First-order photooxidation decay rates varied between – 0.005 and – 0.26 m² (mol quanta)^–1 and were also a function of the initial optical density (OD). These results indicate that UV-absorbing compounds synthesized by phytoplankton, such as certain dinoflagellates, may be a component of the DOM pool in surface waters of the ocean and contribute to the attenuation of UV radiation in the water column. Photooxidation consumes only 3 to 10% of the daily production of the DOM absorbing between 280 and 390 nm (including MAAs). This suggests that MAAs dissolved in seawater may contribute to the decrease of UV transmission through the water column on a time scale representative of phytoplankton growth (days) and bloom development (weeks).     

The evolution of pollution profile and health risk assessment for three groups SVOCs pollutants along with Beijiang River,China

Three important groups of semi-volatile organic compounds (SVOCs), polycyclic aromatic hydrocarbons (PAHs), organic chlorinated pesticides (OCPs) and phthalate esters (PAEs), were produced by various human activities and entered the water body. In this study, the pollution profiles of three species including 16 PAHs, 20 OCPs and 15 PAEs in water along the Beijiang River, China were investigated. The concentrations of Σ₁₆PAHs in the dissolved and particulate phases were obtained as 69–1.5 × 10² ng L^?1 and 2.3 × 10³–8.6 × 10⁴ ng g^?1, respectively. The levels of Σ₂₀OCPs were 23–66 ng L^?1 (dissolved phase) and 19–1.7 × 10³ ng g^?1 (particulate phase). Nevertheless, higher levels of PAEs were found both in the dissolved and particulate phases due to abuse use of plastic products. Furthermore, non-cancer and cancer risks caused by these SVOCs through the ingestion absorption and dermal absorption were also assessed. There was no non-cancer risk existed through two kinds of exposure of them at current levels, whereas certain cancer risk existed through dermal absorption of PAHs in the particulate phase in some sampling sites. The results will show scientific insights into the evaluation of the status of combined pollution in river basins, and the determination of strategies for incident control and pollutant remediation.     

Relationships between octan‐1‐ol/water partition coefficients,aqueous activity coefficients and reversed phase HPLC capacity factors of alkylbenzenes,chlorobenzenes, chloronaphthalenes and chlorobiphenyls

Linear relationships between logarithms of octan‐1‐ol/water partition coefficients (K_d,oct), aqueous activity coefficients (y_aq) and extrapolated RP HPLC capacity factors (k‘_w) are found for four types of aromatic hydrocarbons (alkylbenzenes and poly‐chlorinated benzenes, ‐naphthalenes and ‐biphenyls).

Both log K,_d,oct and logk‘_w increase with the increasing number of chlorine or methyl‐ene substituents. These increases of log K,_d,oct and log k‘_w are proportional and almost independent of the parent compound. In addition, these increases are linear to increases of logy_aq. The slopes of logk‘_w‐logy_aq and log K,_d,oct‐logv_aq relationships deviate significantly from 1.0. This suggests that the activity coefficients of the test compounds in both octan‐1‐ol and in the stationary phase of the RP column increase after substitution of aromatic compounds with methylene or chlorine.     

Photodegradation of the organophosphorus insecticide ‘Phorate’

The photolysis of Phorate(I) (0,0‐diethyl S‐ethyl thiomethyl phosphordithioate) has been studied as a thin film on a glass surface and in a solution of methanol‐water (60:40) by ultraviolet light (λ > 290 nm). The rate of disappearance of Phorate in the solution show first order Kinetics with a rate constant of 4.9 × 10^–5 S ^–1. The half‐life of (I) exposed on a glass surface is found to be 5 hours. The structure of the major photoproducts were characterised by ¹H NMR and mass spectroscopy.     

Soil organic matter chemistry. Part 1. Characterization of several humic preparations by proton and carbon‐13 nuclear magnetic resonance spectroscopy

Both laboratory and commercial preparations of humic substances (HSs) such as fulvic acids and humic acids along with HC1‐HF preparation of Manitoba peat soil organic matter were characterized using Fourier Transformation (FT) proton (¹H) and carbon‐13 (¹³C) nuclear magnetic resonance (NMR) spectroscopy. All the samples were dissolved in a solution of 0.4 N NaOD in D₂O. In the case of ‘H‐NMR spectroscopy, all the investigated humic samples displayed resonance absorption peaks in the region of 1–4 ppm indicating the likely presence of aliphatic protons in the preparations. However, with the exception of one fulvic acid preparation (extracted from Manitoba Carrol clay‐loam soil with 0.5 N NaOH), ¹H‐NMR spectra of all other samples provided evidence for strong aromatic character. The aliphatic and aromatic characteristics of such samples of HSs were further confirmed with the aid of ¹³C‐NMR spectra.     

Improvement of the photostability of selected substances in aqueous medium

The photodegradation of some pesticides in water has been investigated. The kinetics of the photochemical processes is discussed and the photolytic half‐life is calculated. The objective of this paper is to present some of the recent results on the kinetics and on the products of sunlight‐induced reactions of Parathion, Gardona, Diazinon, Atrazine and Phenmediphame at low concentrations in distilled water and fresh water. The quantum yield, measured at 263 nm for Phenmediphame in aerated water at 5 × 10^‐4 M and 30°C, was 1.4 × 10^‐2, and for Parathion, measured at 300 nm in aqueous solution at 3.42 M at pH 6.4 and 25 °C, was 1.5 × 10^‐3. The measured absorption spectra and the variable light intensity were used to estimate the environental phototransformation process and the persistence of these compounds in water.     

Photolytical property of L(+)-α-phenylglycine in aqueous solution

A wide range of pharmaceutical compounds have been identified in the environment, and their existence is a topic of growing concern, both for human and ecological health. The work described here has investigated the photolytic properties of L(+)-α-phenylglycine (L-α-PG-H) in aqueous solution as it can be degraded by photo-catalysis. In 266 nm laser flash photolysis of aqueous solution of L-α-PG-H saturated with nitrogen, two transient absorption bands are observed at 280–330 nm and 450–800 nm, respectively, due to L-α-PG-H radical cation and hydrated electrons (e_aq⁻). Then e_aq⁻ reacts with L-α-PG-H to form the L-α-PG-H radical anion. Decaying rate constants of e_aq⁻ observed at 720 nm is to be 8.9 × 10⁸ dm³ mol⁻¹ s⁻¹. The rate constant for oxidation of L-α-PG-H by SO₄ ⁻ is calculated as 4.5 × 10⁸ and 4.3 × 10⁸ s⁻¹ mol⁻¹ dm³, respectively. The dissociation constants (pKa) of L-α-PG-H is 3. Excited triplet of L-α-PG-H in solution is formed by laser flash photolysis. The quench rate constant of L-α-PG-H excited triplet (k _s) is determined to be 1.3 × 10⁷ dm³ mol⁻¹ s⁻¹ and k ₀ is equal to 1.7 × 10⁵ s⁻¹.     

A chemical mechanism for dry deposition—the role of biogenic hydrocarbon (Terpene) emissions in the dry deposition of O3, SO2 and NOx in forest areas

Terpenes react quite rapidly with ambient ozone and lead via ozonides to highly oxidizing radicals and consecutive products forming aerosols. In the presence of SO₂ sulphur containing compounds, mainly as sulphate, are formed. By means of gas chromatography/mass spectrometry and by comparison with known spectra the main products of the reaction of ß‐pinene (as a model compound) with ozone and sulphur dioxide could be identified.

Reaction of terpenes with NO₃‐radicals, which build up in the atmosphere at night‐time, leads to the formation of organic nitrates that form aerosols. The kinetics as well as the products of the reaction between NO₃‐radicals and ß‐pinene have been studied by FTIR and MS.     

Comparative Toxicities of Polar and Non-Polar Organic Fractions From Sediments Affected By the Exxon Valdez Oil Spill in Prince William Sound,Alaska

Abstract

Standardized tests were applied to aromatic and polar fractions of sediment extracts to determine whether polar constituents or oxidative degradation products contributed significantly to the toxicity of sediments oiled by the Exxon Valdez spill. Intertidal sediment and pore-water samples were collected in September 1990 from two heavily oiled sites and an unoiled site in Prince William Sound (PWS). Methylene chloride extracts from these samples were fractionated by liquid chromatography into aliphatic, aromatic and polar fractions, and the aromatic and polar fractions were tested for toxicity using the Microtox^R test, bivalve larval mortality and development (Mytilus); several measures of genotoxicity in Mytilus, including SOS Chromotest^R, anaphase aberrations and sister chromatid exchange; and survival, anaphase aberrations and teratogenicity in coho salmon (Onchorhynchus kisutch). Microtox^R and SOS Chromotest^R protocols were applied in a screening mode to all samples, whereas other tests were applied only to selected fractions from two sites. Samples from Bay of Isles (oiled) were consistently more toxic (usually only 2 to 5-fold) than the Mooselips Bay (unoiled) samples, which gave very low responses in all tests. for both sites, however, responses to polar and aromatic fractions were about the same in most tests, suggesting that while the overall toxicity of the oil was low in these samples, at least part of that toxicity was derived from polar constituents. Compared to the parent hydrocarbons, polar oxidation products partition preferentially into pore-water and are more rapidly diluted and dispersed in the water column. These results suggest that polar oxidation products of petroleum hydrocarbons pose little risk to marine organisms, except possibly for infauna continuously exposed to pore-water in heavily oiled sediments. Independent surveys showed that sediment toxicity in PWS declined during 1989–1991 to near background levels, in accord with previous understanding of oil weathering and toxicity.     

Environmentally significant photochemistry of chlorinated benzenes and their derivatives in aquatic systems†

The pollution of soil and aquatic environments by chlorinated aromatic pollutants (CAPs) such as polychlorobenzenes (PCBzs), polychlorophenols (PCPs), polychloro‐diphenyl ethers (PCDPEs), phenoxyacetic acids, etc., creates growing public anxiety. Phototransformation is an important process for pollutants in aquatic systems. This article extensively reviews the environmentally significant solution phase photochemistry of PCBzs as well as other CAPs derived therefrom. The paper includes photochemical fate of these CAPs at wavelengths >285 nm on the one hand and their photolysis in solution in aquatic systems on the other. In this article, photolytic reductive dechlorination and isomerization of PCBzs are reviewed together with the photoformation of several products including polychlorobiphenyls (PCBs) from PCBzs. Recently developed phenomena of photoincorporation of PCBzs into humic model monomers is also described. This review also describes the environmental photochemistry of chlorobenzene derivatives, namely, α‐substituted p‐chlorotoluenes of the general structure p‐ClC₆H₄CH₂‐X (X = H, Cl, CN, COOH and OH), di‐through pentachlorophenols, PCDPEs (having Cl_1–5 contents) with and without o‐OH substituents, and 2,4‐di‐ and 2,4,5‐trichlorophenoxyacetic acid (2,4‐D and 2,4,5‐T, respectively) as well as their esters and some formulations.     

Fungicidal activity and molecular modeling of fusarubin analogues from Fusarium oxysporum

Abstract

Fusarubin analogues of Fusarium oxysporum f. sp. ciceris were investigated for antifungal activity in vitro against five soil borne phytopathogenic fungi. 3-O-Methyl-8-O-methyl-fusarubin was inhibitory towards S. sclerotiorum (EC₅₀ 0.33?mmol L^?1) and Sclerotium rolfsii (EC₅₀ 0.38?mmol L^?1). A structure–antifungal activity relationship of fusarubin analogues was established from their activity performance. Possible mechanism of action of these compounds was studied using molecular docking and simulations against three target enzymes which revealed receptor ligand binding affinity. Docking of 3-O-methyl-8-O-methyl-fusarubin into the succinate dehydrogenase site revealed formation of salt bridge, hydrogen bond, π–anion, π–alkyl, and Van der Waals interactions.     

Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

Photodegradation of pesticides .1. Photolysis rates and half‐life of acylanilides and their major metabolites in water

The photolysis in water solution of three fungicides (Metalaxyl, Benalaxyl, and Furalaxyl) was studied under artificial light. At λ = 254 Benalaxyl and Furalaxyl underwent fast degradation with rearrangement reactions less complex than those of Metalaxyl. Under A = 254–290 the photolysis was very fast and Benalaxyl and Furalaxyl show a common behaviour. This was found to be a kinetic consecutive process leading, at first, to N‐2,6‐xylyl‐D,L‐alaninate (II), which was degraded to 2,6‐dimethylaniline (IV). This amine gives unknown products. Metalaxyl underwent a parallel/consecutive photodegradtion to give (II) and N‐(methoxyacetyl)‐2,6‐dimethylaniline (VI). While (II) was easily converted to (IV) as earlier, (VI) was more stable to photolysis. Under λ > 290 all the fungicides shown very slow degradation with pseudo first order rate constants. The photoproducts were degraded faster than the parent compounds by factors from 13 to 1800. The presence of photosensitizer in water (humic acids or acetone) resulted in total decomposition of fungicides and of their photoproducts.     

Photodegradation of fungicide triadimefon and pesticide pirimicarb in aqueous TIO2 suspension

Two agrochemicals composed of nitrogen‐containing heterocyclic ring, triadimefon and pirimicarb, were degraded photocatalytically. The disappearance and TOC elimination rates of triadimefon were close to those of pirimicarb, whereas the photolysis of triadimefon was 4 times slower than that of pirimicarb. For triadimefon its aromatic moiety degraded quickly and Cl^‐ was released immediately, while triazole moiety degraded slowly. The formation rates of NH⁺ ₄ and NO₃ ^‐ by the degradation of triazole moiety were influenced by the rest of the molecule. The difference between disappearance and TOC elimination rates of both triadimefon and pirimicarb were far larger than those of aromatic compounds.     

Uptake and elimination kinetics of triphenyltin hydroxide by two fish species

The uptake from water and the elimination of carbon‐14 radiolabelled triphenyltin hydroxide ([¹⁴C]TPTH) was studied in two fish species: guppy (Poecilia reticulata) and rainbow trout larvae (Salmo gairdneri). During all the experiments no steady state in fish was found. TPTH was rapidly taken up, while elimination was very slow. Uptake and elimination rate constants (k ₁ and k ₂, respectively), and a bioconcentration factor were estimated, assuming first order kinetics.

During eight days of exposure of guppy to TPTH an uptake rate constant k ₁ of 70±7L/kg.d and an elimination rate constant k ₂ of 0.005 ±0.029d ^‐1 was found. This resulted in a biconcentration factor of at least 2.1 × 10³L/kg (wet weight). Comparable results were obtained during a 30 days exposure experiment with guppy: k ₁ was 41±2L/kg.d, k ₂ 0.014 + 0.002d^‐1, and the bioconcentration factor was estimated to be 2.9 × 10³ L/kg (wet weight).

Four days exposure of rainbow trout larvae resulted in a it, of 22+ 2 L/kg.d, and a k ₂ of 0.031 ±0.007d^‐1. Using these k, and k ₂ values it was estimated that the biconcentration factor exceeds 650 L/kg (wet weight).     

Microbiological degradation of polycyclic aromatic hydrocarbons: Anthracene,benzo(K)fluoranthene,dibenzothiophene, benzo(H) quinoline and 2‐nitronaphthalene

Biodegradation experiments of various polycyclic aromatic hydrocarbons were studied with mixed bacteria culture under aerobic conditions. An easy‐to‐handle clean‐up procedure was developed for PAH and their metabolites simultaneously as well as a gc‐ms‐method to identify and quantify these compounds.

Anthracene and dibenzothiophene are completely degradable in an aqeous system, whereas biodegradation of benzo(k)fluoranthene and benzo(h)quinoline is possible only in an oil‐in‐water‐system with dodecane as cosubstrate. No degradation of nitronaphthalene was observed in aqueous systems. New metabolites are 2,3‐dihydroxybenzothiophene, hydroxybenzothiophenecarbonic acid and benzothiophenequinone for dibenzothiophene and hydroxyfluoranthenic acid for benzo(k)flouranthene. Whereas the former metabolites are degradable under the experimental conditions, the latter accumulates during the degradation experiment.

The results are important for microbiological wastewater treatment, since knowledge of biodegradation processes is indespensable for the successful treatment of PAH‐containing wastewater.     

UV absorption by mycosporine-like amino acids in Phaeocystis antarctica Karsten induced by photosynthetically available radiation

Mycosporine-like amino acids (MAAs), which occur in diverse taxonomic groups, exhibit in vivo absorption maxima between 310 nm and 360 nm and may play a photoprotective role against ultraviolet (UV) exposure. Using cultures of colonial Phaeocystis antarctica, we examined the relationship between MAA concentration, in vivo UV absorption, photoprotective (carotenoid) and photosynthetic pigments, and photosynthetically available radiation (PAR, 350–700 nm). UV absorption was high; chlorophyll-specific absorption, a ^* _ph, at 330 nm ranged from 0.06 to 0.41 m²/mg chlorophyll a. Values of a ^* _ph (330) were 4–13 times greater than a ^* _ph (676). Mycosporine-glycine, shinorine, and mycosporine-glycine valine are responsible for the strong in vivo UV absorption. The sum of all MAAs increased with irradiance when normalized to chlorophyll a or carbon concentrations, whereas individual MAAs varied independently from each other. Mycosporine-glycine concentrations showed no statistically significant change over the range of light intensities, whereas mycosporine-glycine and shinorine concentrations increased at higher irradiances. The relative fluorescence yield for chlorophyll a was low in the UV region compared to the visible region, implying that absorbed UV radiation (<375 nm) is transferred inefficiently to chlorophyll a in the reaction center. Quantitative estimates of UV screening by MAAs are attributed to elevated MAA concentrations and increased diameter at high light. Received: 31 March 1999 / Accepted: 13 July 2000     

Biogeochemistry of aromatic hydrocarbons in the benthos of microcosms†

Investigations into the fate of petroleum compounds in the marine environment were carried out using experimental microcosms of two sizes and designs. Aromatic hydrocarbons or No. 2 fuel oil were spiked to the water of a 13 m³ continuous flow system and to a 2281 recycled flow system. The transport and alteration of this oil was traced in the sediment and benthic organisms (Glycera americana, Crepidula sp., and Nephtys incisa) of these microcosms. Measurable contamination was found in both sample types. The aromatic hydrocarbon distribution, including relative isomeric distribution (e.g., C₂‐phenanthrenes) was found to be different in sediment and in organisms from that which was originally introduced to the experimental microcosm. Differences in isomer distribution between Glycera and Crepidula were also detected. Based on the experimental data: molecular weight and specific isomeric form, biochemical processes, solubility, and particle adsorption/desorption influence the fate of petroleum compounds in benthic ecosystems.     

Bioavailability and metabolism of hexavalent chromium compounds †

Intratracheal instillation of ⁵¹CrCl₃ in anaesthetized rabbits resulted in partial absorption. In blood, the absorbed material was entirely confined to the plasma compartment. Only trace amounts were deposited in liver and kidney. By contrast, after similar application of Na, ⁵¹CrO₄ the bulk of blood radioactivity was present in red blood cells (RBC). Substantial deposition occurred in liver and kidneys. It is concluded that Cr(VI) may enter the body unreduced via the lung and is partially deposited in cells over a prolonged period of time.

Since chromium was accumulated in liver after administration of Cr(VI) we investigated the intracellular disposition of Cr(VI) in the isolated perfused liver. No significant sex differences in chromium distribution were observed. At the end of the experiments (1 h), 60% of the applied dose (312μg Cr/liver) was located in the cytosol, whilst 14% was in the mitochondria, 9% in the microsomal pellet and 2% was associated with the nuclei. Gel chromatography of the cytosolic compartment showed that the overwhelming part of chromium was eluted in fractions with an apparent molecular weight of 6,000 dalton. These fractions exhibited absorption maxima at 410nm and 548nm. It is concluded, that cytosolic reduction might be the main intracellular redox pathway for chromates. This view was confirmed by monitoring the reaction of Cr(VI) with GSH in vitro. GSH reduced Cr(VI) without further cofactors under formation of GSH‐chromium complexes, which possibly represent major intermediates in the metabolism of Cr(VI).