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.     

Loss of carbofuran from rice paddy water: chemical and physical factors.

The loss of carbofuran was studied from rice paddy water treated with a granular formulation of the insecticide, and from ponds filled with drainage from the paddy. The average half-life (t 1/2) for carbofuran loss was 57 hr. Controlled experiments indicated that pH was the predominating factor governing carbofuran loss from water in the environment studied. The loss due to hydrolysis was over 700 times more rapid at pH (t 1/2 = 1.2 hr.) than at pH (t 1/2 = 864 hr.) in buffered deionized water. The average pH of the rice paddy was 8, but diurnal fluctuations of 7 to 9.5 are common in similar environments. Impurities in the water, sunlight, and temperature influence the rate of carbofuran loss but not nearly so much as pH. There was no evidence for significant loss due to evaporation or oxidation. The results have important implications for the duration of the insecticide's activity and the effect on fish within or downstream from treated paddies.     

Evaluation of the toxicity of marine sediments and dredge spoils with the Microtox bioassay

The Microtox^R bioassay was used to evaluate the toxicity of sediment and dredge spoil elutriates from several potentially-contaminated sites in Mobile and Pascagoula Bays. Elutriates were prepared using either local seawater or distilled deionized water (osmotically adjusted with NaCl prior to testing), and Microtox^R assays were performed with the elutriates and three reference toxicants. There were marked differences in the toxicity of several elutriates and reference toxicants in the two different waters, with the seawater generally resulting in the same or lesser toxicity than the osmotically-adjusted distilled deionized water.     

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.     

Evaluation of photolysis and hydrolysis of atrazine and its first degradation products in the presence of humic acids

Relative importance of hydrolysis and photolysis of atrazine and its degradation products in aqueous solutions with dissolved humic acids (HA) has been assessed under exposure to sunlight and under UV irradiation. Quantum yield for direct photolysis of atrazine at 254 nm was 0.037 mol photon(-1), the reaction order was 0.8. Atrazine, desethylatrazine and desisopropylatrazine converted to their 2-hydroxy analogs with rate constants 0.02-0.08 min(-1) in clear solutions, while addition of HA (300 mg L(-1)) caused a 10-fold increase in rate constants. Hydroxyatrazine was not degraded. No evidence of photo-Fenton reaction was found. Under exposure to solar light, atrazine, desethylatrazine and desisopropylatrazine were converted to 2-hydroxy analogs only at pH 2 because of acid hydrolysis and possible contribution of photolysis. At lower HA concentration, only their light-shielding effect was noticed, while at higher concentrations, HA-catalysed hydrolysis prevailed. Hydroxyatrazine concentration diminished at all pH values in solutions without HA exposed to sunlight.     

Dissipation of the herbicide clopyralid in an allophanic soil: laboratory and field studies

Soil dissipation of the herbicide clopyralid (3,6-dichloropicolinic acid) was measured in laboratory incubations and in field plots under different management regimes. In laboratory studies, soil was spiked with commercial grade liquid formulation of clopyralid (Versatill, 300 g a.i. L(-1) soluble concentrate) @ 0.8 microg a.i. g(-1) dry soil and the soil water content was maintained at 60% of water holding capacity of the soil. Treatments included incubation at 10 degrees C, 20 degrees C, 30 degrees C, day/night cycles (25/15 degrees C) and sterilized soil (20 degrees C). Furthermore, a field study was conducted at the Waikato Research Orchard near Hamilton, New Zealand starting in November 2000 to measure dissipation rates of clopyralid under differing agricultural situations. The management regimes were: permanent pasture, permanent pasture shielded from direct sunlight, bare ground, and bare ground shielded from direct sunlight. Clopyralid was sprayed in dilute solution @ 600 g a.i. ha(-1) on to field plots. Herbicide residue concentrations in soil samples taken at regular intervals after application were determined by gas chromatograph with electron capture detector. The laboratory experiments showed that dissipation rate of clopyralid was markedly faster in non-sterilized soil (20 degrees C), with a half-life (t1/2) of 7.3 d, than in sterilized soil (20 degrees C) with t1/2 of 57.8 d, demonstrating the importance of micro-organisms in the breakdown process. Higher temperatures led to more rapid dissipation of clopyralid (t1/2, 4.1 d at 30 degrees C vs 46.2 d at 10 degrees C). Dissipation was also faster in the day/night (25/15 degrees C) treatment (t1/2, 5.4 d), which could be partly due to activation of soil microbes by temperature fluctuations. In the field experiment, decomposition of clopyralid was much slower in the shaded plots under pasture (t1/2, 71.5 d) and bare ground (t1/2, 23.9 d) than in the unshaded pasture (t1/2, 5.0 d) and bare ground plots (t1/2, 12.9 d). These studies suggest that environmental factors such as temperature, soil water content, shading, and different management practices would have considerable influence on rate of clopyralid dissipation.     

Loss of carbofuran from rice paddy water: Chemical and physical factors

Abstract

The loss of carbofuran was studied from rice paddy water treated with a granular formulation of the insecticide, and from ponds filled with drainage from the paddy. The average half‐life (t_1/2) for carbofuran loss was 57 hr. Controlled experiments indicated that pH was the predominating factor governing carbofuran loss from water in the environment studied. The loss due to hydrolysis was over 700 times more rapid at pH 10 (t_1/2 = 1.2 hr.) than at pH 7 (t_1/2 = 864 hr.) in buffered deionized water. The average pH of the rice paddy was 8, but diurnal fluctuations of 7 to 9.5 are common in similar environments. Impurities in the water, sunlight, and temperature influence the rate of carbofuran loss but not nearly so much as pH. There was no evidence for significant loss due to evaporation or oxidation. The results have important implications for the duration of the insecticide's activity and the effect on fish within or downstream from treated paddies.     

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.     

Transformation and Ecotoxicity of Carbamic Pesticides in Water (5 pp)

Background N-methylcarbamate insecticides are widely used chemicals for crop protection. This study examines the hydrolytic and photolytic cleavage of benfuracarb, carbosulfan and carbofuran under natural conditions. Their toxicity and that of the corresponding main degradation products toward aquatic organisms were evaluated. Methods Suspensions of benfuracarb, carbosulfan and carbofuran in water were exposed to sunlight, with one set of dark controls, for 6 days, and analyzed by 1H-NMR and HPLC. Acute toxicity tests were performed on Brachionus calyciflorus, Daphnia magna, and Thamnocefalus platyurus. Chronic tests were performed on Pseudokirchneriella subcapitata, and Ceriodaphnia dubia. Results and Discussion Under sunlight irradiation, benfuracarb and carbosulfan gave off carbofuran and carbofuran-phenol, while only carbofuran was detected in the dark experiments. The latter was degraded to phenol by exposure to sunlight. Effects of pH, humic acid and KNO3 were evaluated by kinetics on dilute solutions in the dark and by UV irradiation, which evidenced the lability of the pesticide at pH 9. All three pesticides and phenol exhibited acute and higher chronic toxicity towards the aquatic organisms tested. Conclusion Investigation on the hydrolysis and photolysis of benfuracarb and carbosulfan under natural conditions provides evidence concerning the selective decay to carbofuran and/or phenol. Carbofuran is found to be more persistent and toxic. Recommendations and Outlook The decay of benfuracarb and carbosulfan to carbofuran and the relative stability of this latter pesticide account for many papers that report the detection of carbofuran in water, fruits and vegetables.     

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.     

Effect of short-term sunlight irradiation on absorbance spectra of chromophoric organic matter dissolved in coastal and riverine water

Samples of riverine and coastal, filtered (filter pore size 0.2 μm) water were exposed to short-term sunlight irradiation which reduced their absorbance in the UV and visible regions. Absorbance losses in coastal chromophoric dissolved organic matter (CDOM) were up to 10-fold smaller than those in riverine CDOM. Accompanying changes of absorbance spectra shapes (increased slope parameter) were, probably, a result of decrease of the mean molecular size of light absorbing organic matter. The potential of coastal CDOM to photodegradation was smaller and was exhausted during the course of a day-long experiment. A distinctive feature of spectral changes after sunlight exposure was a maximum absorbance decrease which appeared at 300 nm in riverine and at 280 nm in coastal water. That selective absorbance loss has been ascribed in both cases to the disappearance of chromophores of terrestrial origin which, in coastal water, had a lower mean molecular size (due to flocculation and/or prior photodegradation) but, nevertheless, retained their molecular properties.     

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.     

Photolysis of spinosyns in seawater, stream water and various aqueous solutions

Spinosad, a reduced-risk insecticide, contains primarily two active compounds, spinosyns A and D that are fermentation products of bacterium Saccharopolyspora spinosa. It is currently used to control fruit flies in Hawaii, USA. In this study, we investigated photodegradation of spinosyns A and D, respectively, in seawater, stream, tap and distilled-deionized waters under various light sources. Photodegradation of the two chemicals was also studied in various aqueous solutions prepared with phosphate buffer at different pH or chemical sensitizers. Two major photolytic products from spinosyn A were detected as spinosyn B and hydroxylated spinosyn A. Spinosyn D was similarly hydroxylated and N-demethylated. Spinosyns A and D were photodegraded rapidly under sunlight in Hawaii, USA. The half-life of spinosyns A and D in stream water was 1.1 and 1.0 h, respectively, and was a half of that in distilled-deionized water, 2.2 and 2.0 h, respectively. Photodegradation of spinosyns A and D followed an order of increasing rate constants in distilled-deionized, seawater, stream and tap water under 300 nm artificial light, and was enhanced approximately 8- and 17-fold, respectively, in acetone-sensitized solution as compared to in distilled-deionized water. Photolysis rates of spinosyns A and D in isopropanol- or humic acid-fortified water did not differ much as compared with those accordingly in distilled-deionized water. Spinosyns A and D photodegraded slower in acidic aqueous solution than in basic aqueous solution.     

Photodegradation of ethylenediaminetetraacetic acid (EDTA) and ethylenediamine disuccinic acid (EDDS) within natural UV radiation range.

The rate of photodegradation of two chelating agents, ethylenediaminetetraacetic acid (EDTA) and an isomeric mixture of ethylenediamine disuccinic acid (EDDS), was analysed in humic lake water and in distilled water using exposure to sunlight, and in the laboratory using lamps emitting UV radiation in the range 315-400 nm. Degradation was studied using Fe(III) complexes and sodium salts of chelates. Fe(III) complexes were illuminated at pH 3.1 and 6.5. The results demonstrated that the rate of photodegradation of Fe(III)-EDTA and Fe(III)-EDDS complexes seems to be pH dependent. In the laboratory experiments degradation occurred much faster when the original pH was 3.1 rather than 6.5. The photodegradation of the isomeric mixture of EDDS was markedly faster than the degradation of EDTA both in the laboratory and field experiments, and both in humic and distilled water. The results indicated that in natural waters photodegradation of EDDS is independent of initial speciation of EDDS, while degradation of EDTA is dependent on its existence as Fe(III)-EDTA species.     

Lethal effects on different marine organisms, associated with sediment�Cseawater acidification deriving from CO2 leakage

CO(2) leakages during carbon capture and storage in sub-seabed geological structures could produce potential impacts on the marine environment. To study lethal effects on marine organisms attributable to CO(2) seawater acidification, a bubbling CO(2) system was designed enabling a battery of different tests to be conducted, under laboratory conditions, employing various pH treatments (8.0, 7.5, 7.0, 6.5, 6.0, and 5.5). Assays were performed of three exposure routes (seawater, whole sediment, and sediment elutriate). Individuals of the clam (Ruditapes philippinarum) and early-life stages of the gilthead seabream, Sparus aurata, were exposed for 10?days and 72?h, respectively, to acidified clean seawater. S. aurata larvae were also exposed to acidified elutriate samples, and polychaete organisms of the specie Hediste diversicolor and clams R. philippinarum were also exposed for 10?days to estuarine whole sediment. In the fish larvae elutriate test, 100?% mortality was recorded at pH?6.0, after 48?h of exposure. Similar results were obtained in the clam sediment exposure test. In the other organisms, significant mortality (p?相似文献   

Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.     

In situ measurement of isoprene in the marine air and surface seawater from the western North Pacific

Isoprene (2-methyl-1,3-butadiene) was measured on board of R/V Mirai for eight air samples and 14 seawater samples collected in the western North Pacific during ACE-Asia campaign (from 18 to 26 May 2001). The measurements were conducted in situ using a cryo-focus/gas chromatography/mass spectrometry (Cryo/GC/MS). Concentrations of isoprene ranged from 7.2 to 110 parts-per-trillion (pptv) in the marine air, and ranged from below 12 to 94 pmol l⁻¹ in the seawater. Based on these results, sea-to-air fluxes of isoprene were calculated to be 184 and 300 nmol m⁻² day⁻¹ for two samples, and the upper limits of the fluxes were also calculated to be from 32 to 300 nmol m⁻² day⁻¹. Atmospheric isoprene concentrations cannot be explained only by the flux from the seawater. Thus, the concentrations of isoprene in the marine air in western North Pacific should be significantly affected by terrestrial vegetational emission and subsequent long-range atmospheric transport of isoprene.     

Photodechlorination of polychlorinated biphenyls in the presence of hydroquinone in aqueous alcoholic media

On exposure to sunlight or photolysis at λ >300nm, the dechlorination of a polychlorinated biphenyl mixture (Aroclor 1254) in the H donor alcohol 2-propanol under neutral conditions is enhanced by the presence of the photosensitizer hydroquinone. Dechlorination is strongly promoted by an increasingly aqueous solvent (1:1 water:alcohol) and by maintaining neutral conditions (pH 7.0 buffer) both in the presence and absence of sensitizer. Atmospheric oxygen (continuous aeration) retards the hydroquinone induced dechlorination less than the direct photolysis process.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

Hepatic monooxygenase (CYP1A and CYP3A) and UDPGT enzymatic activities as biomarkers for long-term carbofuran exposure in tench (Tinca tinca L)

The effect of a long-term exposure of tenchs to different concentrations (10 and 100 micro g/L) of the pesticide carbofuran has been evaluated. Microsomal hepatic cytochrome P450 subfamily 1A (CYP1A) and 3A (CYP3A) activities, as well as the phase II enzyme uridine diphospho-glucuronosyltransferase (UDPGT) activity were evaluated as adequate biomarkers of fish exposure to environmentally relevant concentrations of the pesticide carbofuran in freshwater ecosystems. A clear time-dependent inhibition of both CYP1A and UDPGT activities was observed in fish exposed to the highest dose of carbofuran with respect to controls, whereas in the case of CYP3A activity, values of exposed animals did not show a clear pattern of alteration during the experiment. The results of the present study demonstrated that hepatic CYP1A and UDPGT activities from tench could be considered as sensitive biomarkers for carbamate pesticides in polluted water, thus allowing future and ecologically relevant biomonitoring studies with this species.