The effects of interspecific fungal interactions between Trametes versicolor and Phanerochaete chrysosporium on laccase activity and enzymatic oxidation of polycyclic aromatic hydrocarbons （PAHs） were investigated. A deadlock between the two mycelia rather than replacement of one fungus by another was observed on an agar medium. The laccase activity in crude enzyme extracts from interaction zones reached a maximum after a 5-day incubation, which was significantly higher than that from regions of T. versicolor or P. chrysosporium alone. The enhanced induction of laccase activity lasted longer in half nutrition than in normal nutrition. A higher potential to oxidize benzo[a]pyrene by a crude enzyme preparation extracted from the interaction zones was demonstrated. After a 48 hr incubation period, the oxidation of benzo[a]pyrene by crude enzyme extracts from interaction zones reached 26.2%, while only 9.5% of benzo[a]pyrene was oxidized by crude extracts from T. versicolor. The oxidation was promoted by the co-oxidant 2,2＇-azinobis-3- ethylbenzthiazoline-6-sulphonate diammonium salt （ABTS）. These findings indicate that the application of co-culturing of white-rot fungi in bioremediation is a potential ameliorating technique for the restoration of PAH-contaminated soil.
A series of calcined carbonate layered double hydroxides （CLDHs） with various metal compositions and different M^2＋/M^3＋ ratios were prepared as adsorbents for perchlorate. Adsorption isotherms fit Langmuir model well, and the adsorption amount followed the order of MgA1-CLDHs 1〉 MgFeCLDHs 〉〉 ZnA1-CLDHs. The isotherms of MgA1-CLDHs and MgFe-CLDHs displayed a two-step shape at low and high concentration ranges and increased with an increase in the M^2＋/M^3＋ ratio from 2 to 4. The two-step isotherm was not observed for ZnA1-CLDHs, and the adsorption was minimally affected by the M^2＋/M^3＋ ratio. The LDHs, CLDHs and the reconstructed samples were characterized by X-ray diffraction, SEM, FT-IR and Raman spectra to delineate the analysis of perchlorate adsorption mechanisms. The perchlorate adsorption of MgA1-CLDHs and MgFe-CLDHs was dominated by the structural memory effect and the hydrogen bonds between the free hydroxyl groups on the reconstructed-LDHs and the oxygen atoms of the perchlorates. For ZnAI-CLDHs, the perchlorate adsorption was controlled by the structural memory effect only, as the hydroxyl groups on the hydroxide layers preferred to form strong hydrogen bonds with carbonate over perchlorate, which locked the intercalated perchlorate into a more confined nano-interlayer. Several distinct binding mechanisms of perchlorate by CLDHs with unique M^2＋ ions were proposed.
Biosorption and biodegradation of phenanthrene and pyrene by live and heat-killed Phanerochaete chrysosporium are investigated to elucidate the bio-dissipation mechanisms of polycyclic aromatic hydrocarbons(PAHs) in aqueous solution and its regulating factors.The effects of nutrient conditions(carbon source and nitrogen source concentrations),the co-existing Cu 2+,and repeated-batch feed of PAHs on the biosorption and biodegradation are systematically studied.The removal of PAHs by dead bodies of P.chrysosporium is attributed to biosorption only,and the respective partition coefficients of phenanthrene and pyrene are 4040 and 17500 L/kg.Both biosorption and biodegradation contribute to the dissipation of PAHs by live P.chrysosporium in water.After a 3-d incubation,the removal percentage via biosorption are 19.71% and 52.21% for phenanthrene and pyrene,respectively.With the increase of the incubation time(3 40 d),biodegradation gradually increases from 20.40% to 60.62% for phenanthrene,and from 15.55% to 49.21% for pyrene.Correspondingly,the stored-PAHs in the fungal bodies decrease.Under the carbon-rich and nitrogen-limit nutrient conditions,the removal efficiency and biodegradation of phenanthrene and pyrene are significantly promoted,i.e.99.55% and 92.77% for phenanthrene,and 99.47% and 83.97% for pyrene after a 60-d incubation.This phenomenon is ascribed to enhanced-biosorption due to the increase of fungal biomass under carbon-rich condition,and to stimulated-biodegradation under nitrogen-limit condition.For the repeated-batch feed of phenanthrene,the pollutant is continuously removed by live P.chrysosporium,and the contribution of biodegradation is enhanced with the repeated cycles.After 3 cycles,the biodegradation percentage is up to 90% with each cycle of a 6-d incubation.
To better understand the interaction mechanisms of plant surfaces with polar organic compounds, sorption of 4-chlorophenol, 2,4- dichlorophenol, and 2,4,6-trichlorophenol by fruit cuticles （i.e., tomato, apple, and pepper）, and potato tuber periderm were investigated. The roles of cuticular components （waxes, cutin, cutan and sugar） on sorption of chlorophenols are quantitatively compared. Cutin and waxes govern the sorption capacity of bulk apple cuticle by hydrophobic interactions. Potato periderm with highest sugar content exhibits the lowest sorption capability for the chlorophenols. With the increase of hydrophobicity （i.e., Kow ） of sorbate, the relative contribution of lipophilic components （wax, cutin and cutan） on total sorption increases, however, the ratios of Koc to Kow decreases due to increasing ionization degree of sorbates.
Removal of polycyclic aromatic hydrocarbons （PAHs）, e.g., naphthalene, acenaphthene, phenanthrene and pyrene, from aqueous solution by raw and modified plant residues was investigated to develop low cost biosorbents for organic pollutant abatement. Bamboo wood, pine wood, pine needles and pine bark were selected as plant residues, and acid hydrolysis was used as an easily modification method. The raw and modified biosorbents were characterized by elemental analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The sorption isotherms of PAHs to raw biosorbents were apparently linear, and were dominated by a partitioning process. In comparison, the isotherms of the hydrolyzed biosorbents displayed nonlinearity, which was controlled by partitioning and the specific interaction mechanism. The sorpfion kinetic curves of PAHs to the raw and modified plant residues fit well with the pseudo second-order kinetics model. The sorption rates were faster for the raw biosorbents than the corresponding hydrolyzed biosorbents, which was attributed to the latter having more condensed domains （i.e., exposed aromatic core）. By the consumption of the amorphous cellulose component under acid hydrolysis, the sorption capability of the hydrolyzed biosorbents was notably enhanced, i.e., 6-18 fold for phenanthrene, 6-8 fold for naphthalene and pyrene and 5-8 fold for acenaphthene. The sorpfion coefficients （Kd） were negatively correlated with the polarity index [（O＋N）/C], and positively correlated with the aromaticity of the biosorbents. For a given biosorbent, a positive linear correlation between logKoc and logKow for different PAHs was observed. Interestingly, the linear plots of logKoc-logKow were parallel for different biosorbents. These observations suggest that the raw and modified plant residues have great potential as biosorbents to remove PAHs from wastewater.
Black carbons （e.g., charcoal） have a great impact on the transport of organic contaminants in soil and water because of its strong affinity and ubiquity in the environment. To further elucidate their interaction mechanism, sorption of polar （p-nitrotoluene, m-dinitrobenzene and nitrobenzene） and nonpolar （naphthalene） aromatic contaminants to burned straw ash charcoal under different de-ashed treatments were investigated. The sorption isotherms fitted well with Freundlich equation, and the Freundlich N values were all around 0.31-0.38, being independent of the sorbate properties and sorbent types. After sequential removal of ashes by acid treatments （HCl and HCl-HF）, both adsorption and partition were enhanced due to the enrichment of charcoal component. The separated contribution of adsorption and partition to total sorption were quantified. The effective carbon content in ash charcoal functioned as adsorption sites, partition phases, and hybrid regions with adsorption and partition were conceptualized and calculated. The hybrid regions increased obviously after de-ashed treatment. The linear relationships of Freundlich N values with the charring-temperature of charcoal or biochar （the charred byproduct in biomass pyrolysis） were observed based on the current study and the cited publications which included 15 different temperatures （100-850℃）, 10 kinds of precursors of charcoal/biochar, and 10 organic sorbates.
Wenhai Huang,Baoliang Chen Department of Environmental Science,Zhejiang University,Hangzhou 310028,China
