木质素降解酶及其调控机理研究的进展

近年来有关木质素降解微生物和木质素降解酶的产与调控机理的研究表明，腐霉和细菌在木质自然降解中起着重要作用，腐霉的降解作用发生在次级代谢阶段，而细菌发生在初级代谢阶段，影响木质素降解酶的产生酶活力高低的因素有碳氮的选择与限制；诱导物的添加；表面活性剂的使用；某些金属离子浓度水平的改变；菌丝的固定化，温度和摇床转速的变换等。     

Investigation of trace metal binding properties of lignin by diffusive gradients in thin films

The binding behavior of lignin for Pb, Cu, Co, Mn, Cd and Ni was studied using the diffusive gradients in thin films technique (DGT). Samplers with different structures of diffusive gel were used in the well-stirred systems containing known concentrations of metals along with (a) 10, 20 and 40 μM lignin and; (b) 0.64 and 6.47 μM Suwannee river fulvic acid + 40 μM lignin at an ionic strength of 0.01 M (NaNO₃) and pH = 7. Diffusion coefficients of lignin complexes in acrylamide gels were estimated and found to be less than 5% of the equivalent coefficients for the uncomplexed metal ions. These values were used to calculate concentrations of labile metals from DGT measurements in solutions, where lignin could discriminate metals in the order of Pb⁺² > Cu⁺² > Cd⁺² > Ni⁺² > Co⁺² > Mn⁺². Stability constants (Log K) were calculated using Visual MINTEQ II and WHAM V software. The K values were compared with the stability constants from titration of Pb and Cd with 10 μM lignin aqueous samples and with those of humic substances in natural waters. The constants obtained from measurement of complexing capacities might bias the real corresponding values unless two line regression analyses on titration data are considered. The DGT study of fractionation of metal species at varying ratios indicated that the proportion of organic complexes decreased with increasing ratios and gradually more metals were exchanged with inorganic phases. Speciation of Pb and Cd is affected by the concentrations of FA, Cd is dominantly bound with FA while Pb is evenly partitioned between the ligands. The comprehensive knowledge of metal-lignin complexes sheds some light on in situ operational speciation information that can be achieved by DGT.     

Molecular composition of recycled organic wastes,as determined by solid-state 13C NMR and elemental analyses

Using solid state ¹³C NMR data and elemental composition in a molecular mixing model, we estimated the molecular components of the organic matter in 16 recycled organic (RO) wastes representative of the major materials generated in the Sydney basin area. Close correspondence was found between the measured NMR signal intensities and those predicted by the model for all RO wastes except for poultry manure char. Molecular nature of the organic matter differed widely between the RO wastes. As a proportion of organic C, carbohydrate C ranged from 0.07 to 0.63, protein C from <0.01 to 0.66, lignin C from <0.01 to 0.31, aliphatic C from 0.09 to 0.73, carbonyl C from 0.02 to 0.23, and char C from 0 to 0.45. This method is considered preferable to techniques involving imprecise extraction methods for RO wastes. Molecular composition data has great potential as a predictor of RO waste soil carbon and nutrient outcomes.     

木质纤维素原料预处理技术研究近况

木质纤维素的结构导致其不易降解。通过酸处理、碱处理、液态高温水技术、爆破处理、湿式氧化、超临界CO2处理、生物降解等预处理手段，可使后续过程的效率大大提高。较为全面地对国内外木质纤维素原料预处理技术的研究近况做了总结，主要对国外学者的试验方法和现象分析进行了简要描述，并对萼合于我国的方法提出了自己的观点。     

Matrix based fertilizers reduce nitrogen and phosphorus leaching in three soils

We compared the efficacy of matrix based fertilizers (MBFs) formulated to reduce NO3-, NH4+, and total phosphorus (TP) leaching, with Osmocoate 14-14-14, a conventional commercial slow release fertilizer (SRF) and an unamended control in three different soil textures in a greenhouse column study. The MBFs covered a range of inorganic N and P in compounds that are relatively loosely bound (MBF 1) to more moderately bound (MBF 2) and more tightly bound compounds (MBF 3) mixed with Al(SO4)3H2O and/or Fe2(SO4)3 and with high ionic exchange compounds starch, chitosan and lignin. When N and P are released, the chemicals containing these nutrients in the MBF bind N and P to a Al(SO4)3H2O and/or Fe2(SO4)3 starch-chitosan-lignin matrix. One milligram (8000 spores) of Glomus intradices was added to all formulations to enhance nutrient uptake. In all three soil textures the SRF leachate contained a higher amount of NH4+, NO3- and TP than leachate from all other fertilizers. In all three soils there were no consistent differences in the amount of NH4+, NO3- and TP in the MBF leachates compared to the control leachate. Plants growing in soils receiving SRF had greater shoot, root and total biomass than all MBFs regardless of Al(SO4)3H2O or Fe2(SO4)3 additions. Arbuscular mycorrhizal infection in plant roots did not consistently differ among plants growing in soil receiving SRF, MBFs and control treatments. Although the MBFs resulted in less plant growth in this experiment they may be applied to soils growing plants in areas that are at high risk for nutrient leaching to surface waters.     

The removal of lignin and phenol from paper mill effluents by electrocoagulation

This study aims to investigate the treatment of paper mill effluents using electrocoagulation. Removal of lignin, phenol, chemical oxygen demand (COD) and biological oxygen demand (BOD) from paper mill effluents was investigated at various current intensities by using different electrodes (Al and Fe) and at various electrolysis times (1.0, 2.5, 5.0 and 7.5min). It was observed that the experiments carried out at 12V, an electrolysis time of 2min and a current intensity of 77.13mA were sufficient for the removal of these pollutants with each electrode. The removal capacities of the process using an Al electrode were 80% of lignin, 98% of phenol, 70% of BOD, and 75% of COD after 7.5min. Using an Fe electrode the removal capacities were 92%, 93%, 80% and 55%, respectively. In addition, it was found that removal of lignin, phenol, BOD and COD increased with increasing current intensity. In the experiments carried out at different current intensities, higher removal can be explained through a decrease in intra-resistance of solution and consequently an increase at the transfer speed of organic species to electrodes. It was also found that Al electrode performs higher efficiency than Fe electrode except for COD removal. However, the time required for removal of BOD was more than that of COD. The results suggest that electrocoagulation could be considered as an effective alternative to paper mill effluents treatment.     

Acute toxicity, biochemical and gene expression responses of the earthworm Eisenia fetida exposed to polycyclic musks

Phytoremediation is a novel and promising approach for the treatment of pollutants. This study did explore the potential of Aster amellus Linn. to decolorize a sulfonated azo dye Remazol Red (RR), a mixture of dyes and a textile effluent. Induction in the activities of lignin peroxidase, tyrosinase, veratryl alcohol oxidase and riboflavin reductase was observed during RR decolorization, suggesting their involvement in the metabolism of RR. UV-Visible absorption spectrum, HPLC and FTIR analysis confirmed the degradation of RR. Four metabolites after the degradation of the dye were identified as 2-[(3-diazenylphenyl) sulfonyl] ethanesulfonate, 4-amino-5-hydroxynaphthalene-2,7-disulfonate, naphthalene-2-sulfonate and 3-(1,3,5-triazin-2-ylamino)benzenesulfonate by using GC/MS. Textile effluent and mixture of dyes showed 47% and 62% decrease respectively in American Dye Manufacturers Institute value. BOD of textile effluent and mixture of dyes were reduced by 75% and 48% respectively, COD of industrial effluent and mixture of dyes was reduced by 60% and 75% and TOC was reduced by 54% and 69% respectively after the treatment by A. amellus for 60 h; this indicated that the plant can be used for cleaning textile effluents. Toxicity study revealed the phytotransformation of RR into non-toxic products.     

黄孢原毛平革菌所产木素过氧化物酶系对染料降解的研究

白腐真菌黄孢原毛平革菌所产生的胞外过氧化物酶系由两类同功酶木素过氧化物酶和锰过氧化物酶组成，木素过氧化物酶对所研究的染料都有解作用，锰过氧化物酶只对部分染料起作用。加入H2O2，胞外酶液可以降解多种酶性染料如卡布龙红、酸性大兰、弱酸黄和弱酸大红，它们的脱色速率依次下降，以卡布龙红为例研究了各种条件因素对其降解脱色的影响，最佳H2O2浓度是100μmol/L，最佳PH为4．0，温度越高，脱色越快，但高于50℃酶将明显失活，木素过氧化物酶活性越高脱色速率越快，高浓度染料对其脱色有抑制作用，最佳条件下，50mg/L浓度卡布龙红第一分钟的脱色率达70％。随着稀释倍数的增加，酶液的降解速率呈抛物线加速下降，表明酶液中的某些组分如元素离子的浓度也是一个重要影响因素。     

木质素过氧化物酶降解四环素机理的研究

为探究过氧化物酶对四环素类抗生素的降解机理,以白腐真菌Phanerochaete chrysosporium表达的木质素过氧化物酶(LiP)粗酶为研究对象,研究其产酶条件及其降解四环素(TC)的机理。结果表明:低浓度Mn2+可促进产酶,碳源、氮源限制是产酶的重要条件;降解反应进行10min后,H2O2消耗至阈值0.045mmol/L,LiP对TC的降解停止,其降解率达到82%;TC降解反应趋于平衡时,补加TC和H2O2后,LiP依然可以高效发挥作用,其二次降解率达到65%;LiP作用于不同初始浓度(10mg/L、25mg/L、50mg/L、100mg/L)TC,显示LiP对不同浓度TC均可有效降解,TC降解率分别为62%、80%、82%和90%;降解产物的抑菌性试验反映出降解产物较TC母体的抑菌性明显降低;LC/MS捕获到6种可能的降解产物E-TC、TP 461、E-TP 461、TP 477、TP 475和TP 445,并推测出LiP降解TC可能的降解途径。     

白腐菌处理造纸黑液工艺研究

研究了白腐菌变异前后对木质素降解效果及脱色率的影响，探索了水解酸化结合白腐菌挂膜工艺处理造纸黑液的可行性。