Enhanced degradation of benzo[a]pyrene by Mycobacterium sp. in conjunction with green alga

Previous work in this laboratory has confirmed that the bacteria Mycobacterium sp. strain RJGII.135 and Sphingomonas yanoikuyae strain B1 and the green alga Selanastrum capricornutum strain UTEX 1648 degrade benzo[a]pyrene (BaP) to various BaP intermediates. S. capricornutum was first grown with BaP for 4 days. The organic extract of this media was then introduced into separate cultures of strain RJGII.135 and strain B1; separate cultures were grown with BaP for comparison. Cultures grown with BaP and those grown with the algal/BaP extract showed similar mineralization patterns. The quantity of total metabolites formed was greater in bacterial cultures grown with the algal/BaP extract than those grown with BaP alone. For strain RJGII.135, only 27% of the original BaP remained in cultures grown with the algal/BaP extract; 59% remained in cultures grown with BaP. For strain B1, only 6% of the original BaP remained in cultures grown with the algal/BaP extract; 38% remained in cultures grown with BaP. These results indicate that strategies utilizing organisms together may be necessary in being able to degrade large, recalcitrant polycyclic aromatic hydrocarbons (PAHs) such as BaP.     

Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.     

Environmental fate of chlorothalonil in a Costa Rican banana plantation

The environmental fate of chlorothalonil (CHT) and its metabolites were studied under field-variable conditions in a commercial banana plantation in Costa Rica. Weather conditions were representative of a tropical environment and the fungicide applications were typical of those in banana production. The test plots were treated with Bravo 720 at 1.2 l ha(-1) of formulated product. Field persistence of CHT in soil and on banana leaves was measured during five consecutive months and after three aerial applications of the fungicide. Residues were analyzed in soil, sediment, water, banana leaves and drift cards by gas and liquid chromatography coupled to mass spectrometry. In soil and on the surface of banana leaves, CHT dissipated rapidly with half-lives of 2.2 and 3.9 d, respectively. Soil residues persisted and were detected 85 d after application. The main metabolite found in soil, 4-hydroxy-chlorothalonil, accounted for approximately 65% of residues detected and was measured up to 6d after application.     

Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Seasonal variations of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïda, copepoda). Part 1: PCBs and PAHs

Hydrophobic organic contaminants (HOC) (i.e. PAHs and PCBs) were measured in the water column and in Eurytemora affinis samples from the Seine Estuary collected from November 2002 to February 2005. Results showed seasonal variations of both total PCB and PAH levels in the suspended particulate matter (SPM) and in the copepods with maximum levels during winter times. PAH and PCB concentrations in the SPM ranged from 499 to 5819ngg(-1) and from 58 to 463ngg(-1), respectively. Phenanthrene, pyrene and benzo[b+j+k]fluoranthene (B[b+j+k]F) were the predominant PAH compounds in the water column, while CB 101, 118, 153 and 138 were the most abundant PCB congeners. PCBs and PAHs bioaccumulated by E. affinis (EA) varied between 383 and 1785ngg(-1) and 165-3866ngg(-1). CB101, 153, 138 and B[b+j+k] were, respectively, the major compounds of PCB and PAH fingerprints in EA. Thereby, the copepods could reach high accumulation factor (ACF) (91000 for PCBs and 17000 for PAHs). The principal component analyses of contaminant concentrations and environmental parameter datasets distinguished two groups of copepods. The winter time cluster, with high percentage of adult copepods, which bioaccumulated the highest PCB and PAH body-burdens, and the second cluster with juveniles showing the lowest HOC concentrations. Thus, PAH and PCB concentrations in EA exhibited significant correlations with the percentage of adults making up the samples.     

Reliable evidences that the removal mechanism of hexavalent chromium by natural biomaterials is adsorption-coupled reduction

For the last few decades, over 200 papers have been published in the Cr(VI) biosorption research field. Most early studies have claimed that Cr(VI) was removed from aqueous phase through an anionic adsorption, but this approach has been lost old original position. It has been newly explained that these findings were misinterpreted due to errors in measuring the concentrations of different chromium species in the aqueous phase, insufficient contact time required for equilibrium and the lack of information about the oxidation state of the chromium bound to biomaterials. Although 'adsorption-coupled reduction' is now widely accepted as the mechanism of Cr(VI) biosorption by natural biomaterials, a number of researchers still believe that Cr(VI) is removed by anionic adsorption onto the biomaterials. Therefore, the objective of this study was to show reliable evidences that the removal mechanism of Cr(VI) by natural biomaterials is 'adsorption-coupled reduction'. Sixteen natural biomaterials were used to study the Cr(VI) biosorption. Not only Cr(VI) but also total Cr in the aqueous phase were analyzed. X-ray photoelectron spectroscope was also used to verify the oxidation state of the chromium bound to the biomaterials. Finally, the removal behavior of Cr(VI) by each biomaterial was described by a kinetic model based on a redox reaction.     

Photoinduced transformation processes of 2,4-dichlorophenol and 2,6-dichlorophenol on nitrate irradiation

2,4-Dichlorophenol (2,4-DCP) and 2,6-dichlorophenol (2,6-DCP) undergo oxidation, nitrosation and nitration in the presence of nitrate under UV irradiation. Nitration is favoured under acidic conditions, most likely because HNO(2) is formed on nitrate photolysis. The most likely photonitration pathway is the reaction between radiation-excited dichlorophenols (DCP*) and HNO(2). HNO(2) is also able to nitrate DCP in the dark with elevated yields. Irradiation also causes DCP direct photolysis, which is more efficient for the dichlorophenolate anions. The photolysis of the dichlorophenols and that of the dichlorophenolates also produce different intermediates, by dechlorination in the former and ring contraction in the latter case.     

Essential and non-essential element concentrations in two sleeper shark species collected in arctic waters

A number of elements/metals have increased in arctic biota and are of concern due to their potential toxicity. Most studies on elements in the Arctic have focused on marine mammals and seabirds, but concentrations in the Greenland shark (Somniosus microcephalus) and Pacific sleeper shark (Somniosus pacificus), the only two shark species known to regularly inhabit arctic waters, have never been reported. To address this data gap, concentrations and patterns of 25 elements were analyzed in liver of Greenland sharks collected about Cumberland Sound (n=24) and Pacific sleeper sharks collected about Prince William Sound (n=14). Several non-essential elements differed between species/locations, which could suggest geographical exposure differences or ecological (e.g., diet) differences between the species. Certain essential elements also differed between the two sleeper sharks, which may indicate different physiological requirements between these closely related shark species, although information on such relationships are lacking for sharks and fish.     

Chemically catalyzed uptake of 2,4,6-trinitrotoluene by Vetiveria zizanioides

The efficiency of vetiver grass (Vetiveria zizanioides) in removing 2,4,6-trinitrotoluene (TNT) from aqueous media was explored in the presence of a common agrochemical, urea, used as a chaotropic agent. Chaotropic agents disrupt water structure, increasing solubilization of hydrophobic compounds (TNT), thus, enhancing plant TNT uptake. The primary objectives of this study were to: (i) characterize TNT absorption by vetiver in hydroponic media, and (ii) determine the effect of urea on chemically catalyzing TNT uptake by vetiver grass in hydroponic media. Results showed that vetiver exhibited a high TNT uptake capacity (1.026 mgg(-1)), but kinetics were slow. Uptake was considerably enhanced in the presence of urea, which significantly (p<0.001) increased the 2nd-order reaction rate constant over that of the untreated (no urea) control. Three major TNT metabolites were detected in the roots, but not in the shoot, namely 1,3,5-trinitrobenzene, 4-amino 2,6-dinitrotoluene, and 2-amino 4,6-dinitrotoluene, indicating TNT degradation by vetiver grass.     

In situ studies on the distribution patterns and dynamics of microcystins in a biomanipulation fish--bighead carp (Aristichthys nobilis)

The distribution and dynamics of microcystins in various organs of the phytoplanktivorous bighead carp were studied monthly in Lake Taihu, which is dominated by toxic cyanobacteria. There was a good agreement between LC-MS and HPLC-UV determinations. Average recoveries of spiked fish samples were 63% for MC-RR and 71% for MC-LR. The highest MC contents in intestine, liver, kidney and spleen were 85.67, 2.83, 1.70 and 1.57 microg g-1 DW, respectively. MCs were much higher in mid-gut walls (1.22 microg g-1 DW) than in hind- and fore-gut walls (0.31 and 0.18 microg g-1 DW, respectively), suggesting the importance of mid-gut wall as major site for MC absorption. A cysteine conjugate of MC-LR was detected frequently in kidney. Among the muscle samples analyzed, 25% were above the provisional tolerable daily intake level by WHO. Bighead is strongly resistant to microcystins and can be used as biomanipulation fish to counteract cyanotoxin contamination in eutrophic waters.