漆酶对活性艳蓝染料废水脱色

用白腐真菌漆酶对活性艳蓝X-BR和活性艳蓝K-NR 2种活性染料进行脱色实验。研究了pH、温度、染料浓度和酶活力对脱色率的影响。结果表明,漆酶脱色的适宜条件为:反应温度45℃,pH 6～7,适宜染料浓度为50 mg/L,酶浓度5 U/mL,反应1 h两种染料脱色率可达到75%;通过正交实验确定2种染料的最佳脱色组合分别为:反应温度55℃、pH7、活性艳蓝X-BR浓度50 mg/L、酶浓度5 U/mL和反应温度55℃、pH 6、活性艳蓝K-NR浓度50 mg/L、酶浓度5 U/mL。在所得最优条件下反应1 h,活性艳蓝X-BR和活性艳蓝K-NR的脱色率分别为74.2%和78.6%;反应2 h,脱色率分别为78%和79.5%。     

灵芝漆酶对直接蓝86的催化脱色性能

利用灵芝菌Ganoderma lucidum U-281漆酶对直接蓝86进行酶促氧化脱色,并对其降解机理进行了探讨。结果表明,染料-漆酶共反应体系在20～50℃及pH小于5.0范围内,直接蓝86均可脱色50%以上;漆酶对直接蓝86具有宽泛的浓度适应性,对300 mg/L的该染料仍具有耐受性。最优脱色工艺参数为温度40℃、pH 5.0、染料初始浓度200 mg/L、漆酶用量1 U/mL。在优化条件下,直接蓝863 h的脱色率达到54.54%,48 h脱色率达到91.54%。紫外-可见吸收光谱分析表明,漆酶的酶促氧化导致染料的分子结构产生了变化,是造成直接蓝86脱色的主要发生机制。     

漆酶/HBT介质系统对靛蓝染料及废水脱色的初步研究

以云芝(Trametes versicolor)1126发酵所得漆酶粗酶液与1-羟基苯并三唑(HBT)组成的漆酶/HBT介质系统对靛蓝染料进行脱色实验,分别考察了温度、转速、pH和HBT与漆酶的加入量等条件对靛蓝染料脱色的影响.最终确定的优化脱色条件为:温度60℃,转速200r/min, pH4.5, 100mL靛蓝染料"溶液"中粗酶液和HBT溶液分别加入2mL.以上述脱色条件对靛蓝印染废水进行脱色实验,反应80min,脱色率可达90.1%.     

漆酶对活性黑KN-B和直接大红染料的脱色性能

利用白腐真菌漆酶对活性黑KN-B和直接大红2种偶氮染料进行脱色实验。考察反应时间、加酶量、pH值、染料浓度、温度对脱色率的影响,研究了ABTS介体以及金属离子存在下的脱色效果,并分析了漆酶脱色的动力学性能以及其对偶氮染料的降解规律。结果表明,活性黑KN-B和直接大红脱色适宜条件为：反应时间为30 min,加酶量8 U/mL,pH=7,染料浓度分别为50 mg/L和80 mg/L,温度40~45℃。ABTS介体对酶促偶氮染料脱色没有明显促进作用。Fe²⁺对漆酶脱色有较强的抑制作用;Cu²⁺对漆酶催化活性黑KN-B促进作用较大,对直接大红影响较小。漆酶对2种染料的脱色反应符合米氏方程,其催化活性黑KN-B和直接大红染料的K_m值分别为114.81 mg/L,317.5 mg/L,v_max值分别为6.57 mg/（L·min）和26.0 mg/（L·min）。     

Ganoderma sp. SYBC L48漆酶酶学性质及其对酸性红1的脱色性能

对灵芝菌Ganoderma sp. SYBC L48漆酶进行了纯化和酶学性质分析,并利用该漆酶对偶氮染料酸性红1进行脱色处理;考察了脱色体系中各因素对脱色效率的影响;采用小麦种子和水稻种子对酶处理后的染料进行了毒性测试。结果表明,以ABTS为底物时,该酶的最适pH为2.5,最适温度为60 ℃,在pH 5~9和20~60 ℃具有良好的稳定性,Co2+、Cr3+和Fe3+离子对酶活性有较强的抑制作用。在染料浓度100 mg·L-1,酶浓度0.5 U·mL-1,介体HOBT浓度0.25 mmol·L-1,pH为4,50 ℃的条件下反应30 min后,该漆酶对酸性红1的脱色率可达90.3%;1 mmol·L-1的Cr3+、Cu2+、Al3+和Ni2+存在下,漆酶仍能催化酸性红1脱色;脱色后染料的植物毒性下降。上述结果表明该漆酶在纺织废水处理中具有一定的应用前景。     

偶氮染料脱色菌Lysinibacillus sp. FS1的脱色性能

从佛山某工业园印染废水处理厂曝气池中,经梯度驯化筛选出一株对多种染料具有较强脱色能力的菌株FS1,通过16S rDNA基因序列分析初步鉴定为Lysinibacillus sp.,研究了该菌株在不同营养条件(氮源、碳源、碳源浓度),不同培养条件(pH、温度、供氧条件),不同染料(甲基橙、亚甲基蓝、中性红、酸性红B)和染料浓度下的脱色性能。结果表明,该菌株的最佳脱色条件:温度30~40℃,pH 7~9,氯化铵1 g/L, 葡萄糖2 g/L的厌氧条件下培养脱色效果最好,10 h时对酸性红B脱色率可达98.73%左右,且脱色过程符合一级反应动力学方程:-ln(At/A0)=0.0588t-0.0448。该菌株可降解多种染料,脱色率均随污染强度的升高先增大后减小,对高浓度染料和混合染料也表现出很好的脱色效果,是一株高效广谱的染料降解菌,具有处理印染废水的开发应用价值。     

固定化青霉X5对孔雀石绿的脱色研究

采用植物载体玉米芯对青霉X5进行固定化.利用正交实验,确定了固定化最优操作条件为:菌量0.4 g/L,载体大小为1/2×π×12×1 cm3,载体个数为10,摇床转速为100 r/min.同时考察了各种因素如温度、pH、碳源浓度和盐浓度等对染料脱色的影响,结果表明,在温度为30℃、pH 4.0、碳源浓度为10 g/L条件下,以100 r/min的摇速培养,脱色效果最佳,脱色率达96.1%.重复脱色实验表明,固定化青霉X5经过4次重复利用后,固定化细胞的结构仍良好,脱色率仍在90%以上.脱色平衡时间为360 min.     

应用漆酶SUKALacc脱色处理纺织染料

印染废水中含有大量的剩余染料,对生态环境构成了巨大威胁.漆酶能够氧化多种纺织染料使其脱色,在印染废水处理领域具有潜在的应用性.为了开发基于酶技术的印染废水处理工艺,利用商业化的漆酶制剂SUKALaccTM对5种常见纺织染料的脱色能力进行了测试,结果显示,SUKALaccTM对于这些测试的染料均具有脱色效果,脱色效率为14.85%~85.97%;此外,还考察了酶制剂浓度、染料浓度、温度和pH等因素对脱色效率的影响,确定了最优的反应条件;利用斜生栅藻 (Scenedesmus obliquus) 和大型溞 (Daphnia magna) 分别对酶处理后的染料毒性进行了测试,结果表明,酶制剂处理后的染料毒性减弱.这些实验结果为漆酶制剂实际应用于印染废水处理奠定了坚实基础.     

类Fenton反应对偶氮染料橙黄Ⅱ的脱色研究

以橙黄Ⅱ染料溶液为研究对象,通过正交实验确定了Fe-NTA/H2O2构成的类Fenton反应中各影响因子的最佳操作条件为:[H2O2]=20 mmol/L,[Fe-NTA]=2.5 mmol/L,pH=3.同时考察了反应时间、溶液pH值、H2O2浓度、Fe-NTA浓度对脱色效率的影响.实验表明脱色反应在30 min内基本完成,类Fenton试剂能在较宽的pH范围内保持较好的脱色效果,而且在pH=6时,类Fenton试剂比传统Fenton试剂的脱色效率提高约75%.增加双氧水浓度可以提高橙黄Ⅱ溶液脱色率,但超过20 mmol/L后效果提高不明显.在0.5～2.5 mmol/L的范围内,Fe-NTA浓度对脱色效果的影响不显著.     

漆酶-介体系统对多种不同结构染料的脱色效果

为研究漆酶在染料废水处理方面的潜力,选用毕赤酵母表达的担子菌Moniliophthora roreri来源的漆酶Mrl2,与小分子介体(1-羟基苯并三唑、藜芦醇、对香豆酸、N-羟基邻苯二甲酰亚胺) 协同,用于对5类不同结构和类型的染料(偶氮类、三苯甲烷类、蒽醌类、靛蓝类、吩噻嗪类)的脱色效果研究。结果表明：在小分子介体1-羟基苯并三唑(HOBT)的帮助下,漆酶对属于偶氮类、三苯甲烷类、蒽醌类、靛蓝类的9种染料脱色率均能达到95%以上;对结构更复杂的杂环吩噻嗪类染料天青I的脱色效率均较低,在最佳介体对香豆酸辅助下可达40%的脱色率。进一步对天青I染料脱色体系优化发现,在pH为6.0、对香豆酸浓度为2 mmol·L⁻¹、漆酶浓度为125 U·L⁻¹时,Mrl2对天青I的脱色率可达到81%。以上结果表明该重组漆酶在染料废水处理和环境保护等方面具有较好的应用价值和前景。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.