Comparative studies of fungal degradation of single or mixed bioaccessible reactive azo dyes

A screening using several fungi (Phanerochaete chrysosporium, Pleurotus ostreatus, Trametes versicolor and Aureobasidium pullulans) was performed on the degradation of syringol derivatives of azo dyes possessing either carboxylic or sulphonic groups, under optimized conditions previously established by us. T. versicolor showed the best biodegradation performance and its potential was confirmed by the degradation of differently substituted fungal bioaccessible dyes. Enzymatic assays (lignin peroxidase, manganese peroxidase, laccase, proteases and glyoxal oxidase) and GC-MS analysis were performed upon the assay obtained using the most degraded dye. The identification of hydroxylated metabolites allowed us to propose a possible metabolic pathway. Biodegradation assays using mixtures of these bioaccessible dyes were performed to evaluate the possibility of a fungal wastewater treatment for textile industries.     

PCB congener selective biodegradation by the white rot fungus Pleurotus ostreatus in contaminated soil

Six strains of white rot fungi were tested for their biodegradation ability of low chlorinated polychlorinated biphenyl (PCB) commercial mixture (Delor 103) in real soil system. Phanerochaete chrysosporium and Trametes versicolor did not show any ability to degrade PCBs in soil. On the contrary, four strains of Pleurotus ostreatus were able to remove about 40% of Delor 103 in two months. All P. ostreatus strains decomposed PCBs selectively with the preference for congeners with chlorine atoms in ortho > meta > para position. Degradation efficiency decreased with increasing number of chlorination.     

Coupling of 2,4,6-trinitrotoluene (TNT) metabolites onto humic monomers by a new laccase from Trametes modesta

During degradation of trinitrotoluene (TNT) by Trametes modesta, addition of humic monomers prevented the accumulation of all major stable TNT metabolites (aminodinitrotoluenes [AMDNT]) by at least 92% in the presence of 200 mM ferulic acid and guaiacol. Acute toxicity tests with individual TNT metabolites and in T. modesta cultures supplemented with 200 microM TNT demonstrated that the TNT biodegradation process lead to less toxic metabolites. Toxicity decreased in the order TNT>4-HADNT (4-hydroxylaminodinitrotoluene)>2-HADNT>2,6-DNT (2,6-dinitrotoluene)>2',2',6,6-azoxytetranitrotoluene>4-AMDNT>2-AMDNT>2,4-diamninonitrotoluene (2,4-DAMNT) while 2,4-DNT and 2,6-DAMNT were the least toxic. Ferulic acid is the best candidate for immobilization TNT biodegradation metabolites since it prevented the accumulation of AMDNTs in cultures during TNT biodegradation and its products were less toxic. All humic monomers were very effective in immobilizing 2-HADNT [100%], 4-HADNT [100%] and 2,2,6,6-azoxytetranitrotoluene [100%]. Two distinct laccase isoenzymes (LTM1 and LTM2) potentially involved in immobilization of TNT degradation products were purified to electrophoretic homogeneity. LTM1 and LTM2 have molecular weights of 77.6 and 52.5 kDa, are 18% and 24% glycosylated, have pI values of 3.6 and 4.2, respectively. Both enzymes oxidized all the typical laccase substrates tested. LTM1 showed highest kinetic constants (K(m)=0.03 microM; K(cat)=8.8 4x 10(7)s(-1)) with syringaldazine as substrate.     

Laccase activity in soils: considerations for the measurement of enzyme activity

Laccases (benzenediol: oxygen oxidoreductases, EC 1.10.3.2) are copper-containing enzymes that catalyze the oxidative conversion of a variety of chemicals, such as mono-, oligo-, and polyphenols and aromatic amines. Laccases have been proposed to participate in the transformation of organic matter and xenobiotics as well as microbial interactions. Several laccase assays have been proposed and used in soils. Here, we show that the optimal pH conditions for the laccase substrates 2,2'-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS, pH 3-5), 2,6-dimethoxyphenol (4-5.5), L-3,4-dihydroxyphenylalanine (DOPA; 4-6), guaiacol (3.5-5), 4-methylcatechol (3.5-5), and syringaldazine (5.5-7.0) are similar between purified laccases from Trametes versicolor and Pyricularia sp. and soil extracts; the substrate affinities of purified enzymes (K(M)) and soil extracts were also similar. The laccase assays showed specificity overlap with tyrosinase and ligninolytic peroxidases when hydrogen peroxide is present. The ABTS oxidation assay is able to reliably detect the presence of 13.5 pg mL(-1) or 0.199×10(-12) mol mL(-1) of T. versicolor laccase, which is three times more sensitive than the 2,6-dimethoxyphenol-based assay and more than 40 times more sensitive than any of the other assays. The low molecular mass soil-derived compounds and the isolated fulvic and humic acids influence the laccase assays and should be removed from the soil extracts before measurements of the enzyme activity are performed.     

Effect of heavy metals on the production of several laccase isoenzymes by Trametes versicolor and on their ability to decolourise dyes

The white-rot fungus Trametes versicolor growing in submerged culture on a basal medium, with barley bran as a carbon source, produced two laccase isoenzymes LacI and LacII. The addition of metal ions to the culture medium was performed to improve the total laccase activity and to determine the effect on the production of laccase isoenzymes. From all the tested metals, only Cu2+ increased laccase activity (up to 12-fold with respect to control cultures) and T. versicolor in presence of all metals produced the two isoenzymes in different proportion with ratios of activity (LacI/LacII) varying between 0.11 and 0.51. This factor played an important role in the decolourisation of the textile dye Indigo Carmine.     

Organochlorine contaminants in narwhal (Monodon monoceros) from the Canadian Arctic

Organochlorine pesticides (DDT, chlordane, polychlorinated camphenes (PCCs), dieldrin, hexachloroheclohexanes (SigmaHCH), mirex), polychlorinated biphenyl congeners (PCBs) and chlorobenzenes (SigmaCBz) were determined in blubber and liver of narwhal (Monodon monoceros) collected during 1982-1983 from Pond Inlet on northern Baffin Island in the Canadian Arctic. PCCs were the predominate organochlorines in narwhal blubber, ranging in concentration from 2990 to 13 200 ng g(-1) (wet wt) in males and from 1910 to 8390 ng g(-1) in females. PCCs consisted of two major components, an octachlorobornane and a nonachlorobornane with gas chromatographic retention times of 1.05 and 1.22, relative to 4,4'-DDE. SigmaPCB concentrations in blubber ranged from 2250 to 7290 ng g(-1) in males and from 894 to 5710 ng g(-1) in females. Seven PCB congeners (tetra-, penta- and hexachlorobiphenyls) accounted for 45% of total PCB (SigmaPCB) in narwhal blubber. Narwhal had 1.4- to 8.6-fold higher ratios of tetra- and pentachlorobiphenyls to PCB-153 (2,2',4,4',5,5'-hexachlorobiphenyl), lower 4,4'-DDE/SigmaDDT ratios and lower proportions of trans-nonachlor to total chlordane components than reported for odontocetes living in more contaminated environments. Mean SigmaPCB concentrations in narwhal were 6- to 15-fold lower than in dolphins from the Canadian east coast and belugas from the St Lawrence River estuary, respectively, while PCC levels were from 4- to about 2-fold lower, and SigmaHCH, dieldrin and SigmaCBz differed by <2-fold. The pattern of organochlorines in narwhal tissues suggests they are exposed to proportionally more volatile compounds, and may have less capacity to metabolize some of these compounds, relative to odontocetes living nearer sources of these contaminants.     

Biomimetic chemical degradation of polychlorobiphenyls below 100°C

PCBs were rapidly degraded by hydroxy radicals formed in the biomimetic degradation systems of superoxide, ferric chloride, and hydrogen peroxide at high concentrations below 100°C. The degradation rates of Kanechlor KC 300, KC 400, KC 500 and KC 600 were 95.4%, 89.1%, 59.9% and 47.9%, respectively. The generation of carbon dioxide gas was recognized and chloride ion showed 89.9 – 102.7% of the theoretical yield in the degradation of KC 300, KC 400 and KC 500.     

Highly toxic coplanar PCBs: occurrence, source, persistency and toxic implications to wildlife and humans

Isomer-specific determinations of PCB congeners in a wide variety of animal species such as fish, marine mammals (whale, dolphin and porpoise) and terrestrial mammals (dog, cat and human) revealed the environmental occurrence of highly toxic coplanar 3,3',4,4'-tetrachlorobiphenyl (T(4)CB), 3,3',4,4',5-pentachlorobiphenyl (P(5)CB) and 3,3',4,4',5,5'-hexachlorobiphenyl (H(6)CB) within a range of few pg g(-1) to several ten ng g(-1) in fat tissues (except fish) on a wet weight basis. Detection of these toxic residues in wild specimens collected from remote areas such as the North Pacific suggests the already widespread distribution of coplanar PCBs as in the case of general PCB pollution. The clear positive correlations between concentrations of total PCBs and each of the three coplanar PCBs obtained in all mammals analysed suggest that the sources of coplanar PCB contamination to the environment are mainly commercial PCB preparations. Comparison of the composition of three toxic coplanar PCBs in commercial PCB mixtures and in the various animals indicates the relative metabolisability of these congeners as follows: 3,3',4,4'-T4CB>3,3',4,4',5-P5CB>3,3',4,4',5,5'-H6CB. Moreover, marine mammals seem to have lower potency to metabolise the coplanar PCBs in comparison with terrestrial mammals. In human adipose tissues, the concentrations of coplanar PCBs were found to be much higher than 2,3,7,8-tetrachlorodibenzo-p-dioxin (T(4)CDD), 2,3,4,7,8-pentachlorodibenzofuran (P(5)CDF) and other toxic congeners. 'T(4)CDD-equivalent' analysis based on the enzyme induction potencies and the residues of these toxic chemicals indicates that 3,3',4,4',5-P(5)CB may impose a greater toxic threat than dioxins and furans to the humans and probably to wildlife also.     

Influence of a soil enzyme on iron-cyanide complex speciation and mineral adsorption

Cyanide is commonly found as ferrocyanide [Fe(II)(CN)(6)](-4) and in the more mobile form, ferricyanide [Fe(III)(CN)(6)](-3) in contaminated soils and sediments. Although soil minerals may influence ferrocyanide speciation, and thus mobility, the possible influence of soil enzymes has not been examined. In a series of experiments conducted under a range of soil-like conditions, laccase, a phenoloxidase enzyme derived from the fungi Trametes versicolor, was found to exert a large influence on iron-cyanide speciation and mobility. In the presence of laccase, up to 93% of ferrocyanide (36-362ppm) was oxidized to ferricyanide within 4h. No significant effect of pH (3.6 and 6.2) or initial ferrocyanide concentration on the extent or rate of oxidation was found and ferrocyanide oxidation did not occur in the absence of laccase. Relative to iron-cyanide-mineral systems without laccase, ferrocyanide adsorption to aluminum hydroxide and montmorillonite decreased in the presence of laccase and was similar to or somewhat greater than that of ferricyanide without laccase. Laccase-catalyzed conversion of ferrocyanide to ferricyanide was extensive though up to 33% of the enzyme was mineral-bound. These results demonstrate that soil enzymes can play a major role in ferrocyanide speciation and mobility. Biotic soil components must be considered as highly effective oxidation catalysts that may alter the mobility of metals and metal complexes in soil. Immobilized enzymes should also be considered for use in soil metal remediation efforts.     

Atrazine degradation by fungal co-culture enzyme extracts under different soil conditions

This investigation was undertaken to determine the atrazine degradation by fungal enzyme extracts (FEEs) in a clay-loam soil microcosm contaminated at field application rate (5 μg g^?1) and to study the influence of different soil microcosm conditions, including the effect of soil sterilization, water holding capacity, soil pH and type of FEEs used in atrazine degradation through a 2⁴ factorial experimental design. The Trametes maxima–Paecilomyces carneus co-culture extract contained more laccase activity and hydrogen peroxide (H₂O₂) content (laccase = 18956.0 U mg protein^?1, H₂O₂ = 6.2 mg L^?1) than the T. maxima monoculture extract (laccase = 12866.7 U mg protein^?1, H₂O₂ = 4.0 mg L^?1). Both extracts were able to degrade atrazine at 100%; however, the T. maxima monoculture extract (0.32 h) achieved a lower half-degradation time than its co-culture with P. carneus (1.2 h). The FEE type (p = 0.03) and soil pH (p = 0.01) significantly affected atrazine degradation. The best degradation rate was achieved by the T. maxima monoculture extract in an acid soil (pH = 4.86). This study demonstrated that both the monoculture extracts of the native strain T. maxima and its co-culture with P. carneus can efficiently and quickly degrade atrazine in clay-loam soils.     

Comparative study of immobilized Trametes versicolor laccase on nanoparticles and kaolinite

Laccase from Trametes versicolor was immobilized on nanoparticles and kaolinite by physical adsorption or chemical covalence in which the supporters were activated by cross-linked with glutaraldehyde. Thermal and pH stabilities of immobilized laccase on these different supporters were compared. The degradation efficiencies of these immobilized laccases on oxidation of benzo[a]pyrene (BaP) were also compared. The results showed that the immobilized laccases on nanoparticles were more stable in resisting pH and thermal changes. After 48h oxidation, laccase immobilized on kaolinite using the covalent coupling method showed a higher efficiency of oxidation with the BaP residue of 23% in the presence of 1mM HBT and with BaP residue of 37% in 1mM ABTS as the mediator. The results also exhibited a significant inhibition by 1% surfactant Tween 80. According to the HPLC analysis, the oxidation products including 1,6-benzo[a]pyrene quinone, 3,6-benzo[a]pyrene quinone and 6,12-benzo[a]pyrene quinone were identified.     

Congener-specific analysis of non-dioxin-like polychlorinated biphenyls in blood collected from 127 elderly residents in Nakagawa Town, Fukuoka Prefecture, Japan

We conducted congener-specific analysis of non-dioxin-like polychlorinated biphenyls (non-dioxin-like PCBs) in blood collected in February 2004 from 127 elderly residents living in Nakagawa Town, Fukuoka Prefecture, Japan. The present study is one of the few studies in which 56 non-dioxin-like PCBs congeners were measured in human blood. Of the 127 elderly residents, 51 were men (mean: 68.1 years) and 76 were women (mean: 68.1 years). Among 197 non-dioxin-like PCB congeners, 56 were identified in the blood of elderly residents. The arithmetic mean total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women in Nakagawa Town were 419 (median: 378) and 363 (median: 323)ngg(-1)lipid, respectively, and the concentrations were in the range of 172-1102 and 119-1226ngg(-1)lipid, respectively, indicating that the total concentrations in elderly men are significantly higher than those in elderly women. The contamination of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture was found to have decreased compared to past levels. The ratios of hexachlorinated biphenyls (hexaCBs) to the total concentrations of 56 non-dioxin-like PCBs congeners in the blood of elderly men and women were 44.6% and 45.6%, respectively, which was particularly high compared with those of other congeners. 2,2',4,4',5,5'-HexaCB (#153) among hexaCBs congeners, the most abundant congener in the blood of elderly men and women, contributed approximately 23.0% and 23.5% to the total concentrations of 56 non-dioxin-like PCBs congeners, respectively. Furthermore, 2,2',3,4,4',5'-hexaCB (#138), 2,3,3',4',5,6-hexaCB (#163)/2,3,3',4',5',6-hexaCB (#164), 2,2',3,4,4',5,5'-heptaCB (#180), and 2,2',3,4,4',5,6'-heptaCB (#182)/2,2',3,4',5,5',6-heptaCB (#187) also showed high ratios to the total concentrations of 56 non-dioxin-like PCBs congeners detected in the blood of elderly men and women. A statistical examination of the relationship between the total concentrations of 56 non-dioxin-like PCBs congeners in blood and the age of elderly residents who were over 60 years indicated statistically significant correlations between the total concentrations of these PCBs congeners and the age of elderly women. However, similar correlations were not observed in elderly men. The results of the present study have indicated the current levels of non-dioxin-like PCBs in the blood of elderly men and women in Fukuoka Prefecture, Japan and can be used as baseline data for those over age 60.     

The significance of PCBs in the atmosphere of the southern hemisphere

Air monitoring stations were set up at 2 sites in the southern hemisphere--Moody Brook, Falkland Island (51 degrees 25' S, 57 degrees 56' W) and Halley, Research Station, Antarctica (75 degrees 35' S, 26 degrees 30' W). PCBs were monitored at the stations throughout 1999. Highest concentrations were observed when temperatures were greater. In general, concentrations were greater at Moody Brook than at Halley, although the difference in concentrations between sites was less for more chlorinated congeners. Air concentrations at both sites were compared with samples collected nearby over-water. Over water air concentrations were found to be greater than over land air concentrations. Concentrations were also compared with literature data for air concentrations at a remote site in the Canadian Arctic. Atmospheric concentrations of tri-chlorinated biphenyls were found to be approximately double those reported for Ellesmere Island in the Canadian Arctic, whilst concentrations in samples from Antarctica were very similar to those found in the high Arctic. Most other PCBs were a factor of 2-4 greater in the Canadian Arctic.     

Polychlorinated biphenyls (PCBs) in sediments in Hong Kong: a congener-specific approach to the study of coplanar PCBs in aquatic ecosystems

Patterns of contamination by polychlorinated biphenyls (PCBs) were investigated in fourteen samples of coastal sediments from Hong Kong. Congener-specific analyses revealed nine sediment samples from Junk Bay to contain PCBs at concentrations ranging from 31 to 2200 ng g(-1) dry weight, concentrations generally increasing with distance north in the Bay. By contrast, five sediments from the Tolo area to the north-east of Hong Kong exhibited total PCB levels of only 6.6 to 45 ng g(-) dry weight. The patterns of relative abundance of PCB congeners in the northern Junk Bay sediments suggested the existence of ongoing source(s) of PCBs in this area; biphenyls of lower chlorination were present at high concentration in these samples. Three coplanar PCBs (3', 4, 4'-tetrachlorobiphenyl; 3,3',4,4',5-pentachlorobiphenyl; and 3,3',4,4',5,5'-hexachlorobiphenyl) were found to be present in Junk Bay sediments; these are highly toxic and are cause for concern in aquatic environments. The abundance of the three coplanar PCBs in the sediments studied was similar to that in commercial PCB mixtures, suggesting that these congeners are not enriched over other PCBs by the sediments of coastal ecosystems. It is concluded that the preferential enrichment of coplanar PCBs occurs in the biosphere, rather than in sediments.     

Dechlorination comparison of mono-substituted PCBs with Mg/Pd in different solvent systems

It is widely recognized that polychlorinated biphenyls (PCBs) are a dangerous environmental pollutant. Even though the use and production of PCBs have been restricted, heavy industrial use has made them a wide-spread environmental issue today. Dehalogenation using zero-valent metals has been a promising avenue of research for the remediation of chlorinated compounds and other contaminants that are present in the environment. However, zero-valent metals by themselves have shown little capability of dechlorinating polychlorinated biphenyls (PCBs). Mechanically alloying the metal with a catalyst, such as palladium, creates a bimetallic system capable of dechlorinating PCBs very rapidly to biphenyl. This study primarily aims to evaluate the effects of solvent specificity on the kinetics of mono-substituted PCBs, in an attempt to determine the mechanism of degradation. Rate constants and final byproducts were determined for the contaminant systems in both water and methanol, and significant differences in the relative rates of reaction were observed between the two solvents.     

Concentrations and possible sources of polychlorinated biphenyls in the surface water of the Yangtze River Delta, China

In this study, polychlorinated biphenyls (PCBs) pollution in the surface water of the Yangtze River Delta (YRD) was investigated. A total of 26 samples were collected from water bodies in three cities within the YRD during the dry season from October to November of 2009. The total PCBs (dissolved plus particulate) ranged from 1.23 to 16.6 ng L(-1) and were dominated by tri-, tetra-, and penta-chlorinated biphenyls. The mean PCBs in the Beijing-Hangzhou Grand Canal and the Yangtze River were 8.84 and 3.36 ng L(-1), respectively. A t-test showed that there were no significant differences in the concentration of samples from the metropolitan area and the development zone. According to the Chinese national environmental quality standards for surface water (GB 3838-2002), the concentrations of PCBs observed in this study do not pose a hazard to aquatic or human health. Overall, this study described the PCB concentration and homolog distribution patterns in one of the most rapidly developing areas in China, and the results can be used as reference levels for future PCB monitoring programs.     

Biodegradation of aromatic compounds by white rot and ectomycorrhizal fungal species and the accumulation of chlorinated benzoic acid in ectomycorrhizal pine seedlings

The capability of different white rot (WR, Heterobasidion annosum, Phanerochaete chrysosporium, Trametes versicolor) and ectomycorrhizal (ECM, Paxillus involutus, Suillus bovinus) fungal species to degrade different aromatic compounds and the absorption of 3-chlorobenzoic acid (3-CBA) by ECM pine seedlings was examined. The effect of aromatic compounds on the fungal biomass development varied considerably and depended on (a) the compound, (b) the external concentration, and (c) the fungal species. The highest effect on the fungal biomass development was observed for 3-CBA. Generally the tolerance of WR fungi against aromatic compounds was higher than that of the biotrophic fungal species. The capability of different fungi to degrade aromatic substances varied between the species but not generally between biotrophic and saprotrophic fungi. The highest degradation capability for aromatic compounds was detected for T. versicolor and H. annosum, whereas for Phanerochaete chrysosporium and the ECM fungi lower degradation rates were found. However, Paxillus involutus and S. bovinus showed comparable degradation rates at low concentrations of benzoic acid and 4-hydroxybenzoic acid. In contrast to liquid cultures, where no biodegradation of 3-CBA by S. bovinus was observed, mycorrhizal pines inoculated with S. bovinus showed a low capability to remove 3-CBA from soil substrates. Additional X-ray microanalytical investigations showed, that 3-CBA supplied to mycorrhizal plants was accumulated in the root cell cytoplasm and is translocated across the endodermis to the shoot of mycorrhizal pine seedlings.     

Reduction of serum thyroxine concentrations by methylsulfonyl metabolites of tetra-, penta- and hexachlorinated biphenyls in male Sprague-Dawley rats

Male Sprague-Dawley rats received four consecutive intraperitoneal doses of nine methylsulfonyl (MeSO2) metabolites of tetra-, penta- and hexachlorinated biphenyls (tetra-, penta- and hexaCBs) to determine their effects on thyroid hormone levels. Nine MeSO2 metabolites, major MeSO2-PCBs detected in human milk, liver and adipose tissue, were 3-MeSO2-2,2',4',5-tetraCB (3-MeSO2-CB49), 3-MeSO2-2,3',4',5-tetraCB (3-MeSO2-CB70), 3-MeSO2-2,2',3',4',5-pentaCB (3-MeSO2-CB87), 3-MeSO2-2,2',4',5,5'-pentaCB (3-MeSO2-CB101), 4-MeSO2-2,2',4',5,5'-pentaCB (4-MeSO2-CB101), 3-MeSO2-2,2',3',4',5,6-hexaCB (3-MeSO2-CB132), 3-MeSO2-2,2',3',4',5,5'-hexaCB (3-MeSO2-CB141), 3-MeSO2-2,2',4',5,5',6-hexaCB (3-MeSO2-CB149) and 4-MeSO2-2,2',4',5,5',6-hexaCB (4-MeSO2-CB149). All nine MeSO2 metabolites (20 micromol/kg once daily for four days) reduced serum total thyroxine levels (16-44%) at a much lower dose than phenobarbital (431 micromol/kg once daily for four days) on days 2, 3, 4 and 7 after the last dosage. Total triiodothyronine level was reduced 37% by treatments with 3-MeSO2-CB49 and 3-MeSO2-CB149 at day 7, but increased 35% and 38% by 3-MeSO2-CB70 and 4-MeSO2-CB101 at days 3 and 4, respectively. The reductions in thyroxine levels led to an increase in thyroid-stimulating hormone levels by 3-MeSO2-CB49, 3-MeSO2-CB87, 3-MeSO2-CB101, 3-MeSO2-CB132, 3-MeSO2-CB141, 3-MeSO2-CB149 and 4-MeSO2-CB149. A 30% increase in thyroid weight was produced by 3-MeSO2-CB101 and 3-MeSO2-CB141 treatments. Total cytochrome P450 content and the activity of 7-pentoxyrosorufin O-dealkylase were increased by all seven 3-MeSO2-PCBs. 3-MeSO2-CB49, 3-MeSO2-CB87, 3-MeSO2-CB101 and 3-MeSO2-CB132 also increased the activity of 7-ethoxyresorufin O-dealkylase. Thus, it is likely that all nine tested MeSO2 metabolites could influence thyroid hormone metabolism. The results show that tested 3- and 4-MeSO2 metabolites of tetra-, penta- and hexaCBs reduce thyroid hormone levels in rats, suggesting that the metabolites may act as endocrine-disrupters.     

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.