KOH活化花生壳生物质炭对亚甲基蓝吸附性能研究

以花生壳生物质炭(P-BC)为原料,KOH为活化剂,采用化学活化法制得活化生物质炭(K-BC),通过考察对亚甲基蓝的吸附性能,研究了花生壳生物质炭的最佳活化条件,并利用N2吸附-脱附实验、SEM等对最佳活化条件下的生物质炭进行表征。结果表明,K-BC活化的最佳条件为碱炭比为1.5∶1,活化温度为800℃,活化时间为90 min,此时K-BC的比表面积达到597.93 m2/g,总孔容达到0.76 cm3/g。并考察了亚甲基蓝初始浓度、pH等对K-BC吸附亚甲基蓝的影响,随着初始浓度的增加,吸附平衡时间显著延长,亚甲基蓝去除率显著降低;当pH=6时,K-BC对亚甲基蓝的吸附量最大;K-BC对亚甲基蓝的吸附动力学曲线符合伪二阶动力学模型,吸附平衡时K-BC对亚甲基蓝的吸附能力为80~149.95 mg/g。     

微波活化中孔酸性生物质炭对亚甲基蓝的吸附行为与机理

以甘蔗渣为原料,采用微波辅助磷酸活化法制备了同时富含中孔结构和含氧酸官能团的生物质炭,以氮气吸附、红外光谱FT-IR等技术对炭样品表面物化性质进行了表征,通过静态实验法测定了生物质炭对水中亚甲基蓝的吸附特性,分析了溶液pH、初始浓度、温度对吸附的影响,研究了不同pH下蔗渣生物质炭对亚甲基蓝的吸附行为,并从热力学及动力学角度探讨了生物质炭对亚甲基蓝的吸附机理。结果表明,不同制备参数下生物质炭的得率均大于39.2%,但表面物化性质因参数变化有较大差异。在浸渍比1∶1,烘干时间10 h,活化功率900 W,活化时间22 min的条件下,制得的生物质炭的比表面积为1 021 m2/g,亚甲基蓝值超过国家一级品标准1.70倍,表面富含微中孔结构和羟基、羰基、羧基等酸性官能团,中孔约占总孔的40%。静态吸附实验表明,溶液初始浓度对吸附有较大的影响,吸附量随初始浓度的增加,pH的升高及温度的上升而增大,Freundlich方程、Redlich-Peterson方程与Temkin方程能较好地描述等温吸附行为;吸附动力学结果表明,数据符合Elovich方程,吸附行为更倾向于化学吸附;热力学研究表明,吸附吉布斯自由能(ΔG0)0,吸附标准焓变(ΔH0)70 kJ/mol,说明该吸附为自发的吸热反应,且化学反应在吸附过程中发挥了重要作用。     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性

以甘蔗渣为原料,采用微波辅助H3PO4活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征,并通过静态实验法,探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明,H3PO4活化制备蔗渣生物质炭的适宜条件为浸渍比1：1,烘干时间10h,活化功率900W,活化时间22min,在此条件下制得的生物质炭得率为39．2％,碘值为817mg／g,亚甲基蓝值为229mg／g,为国家一级品标准的1．7倍。红外光谱分析表明,炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明,Freundlich方程与Redlich—Peterson方程能较好地描述等温吸附行为,表现为优惠吸附。热力学研究表明,吸附吉布斯自由能（△G0）〈0,说明吸附反应是自发过程,而吸附标准焓变（△H0）〉70KJ／mol,表明亚甲基蓝在制备炭样上的吸附是吸热反应,升温有利于吸附,且化学反应在吸附过程中发挥了重要作用。     

磷酸微波活化多孔生物质炭对亚甲基蓝的吸附特性简

以甘蔗渣为原料,采用微波辅助H₃PO₄活化法制备富含含氧酸官能团的中孔生物质炭。通过扫描电子显微镜SEM、傅立叶变换红外光谱FT-IR等技术对生物质炭物理化学性质进行表征,并通过静态实验法,探讨炭样对亚甲基蓝的吸附行为及热力学性质。结果表明,H₃PO₄活化制备蔗渣生物质炭的适宜条件为浸渍比1：1,烘干时间10 h,活化功率900 W,活化时间22 min,在此条件下制得的生物质炭得率为39.2%,碘值为817 mg/g,亚甲基蓝值为229 mg/g,为国家一级品标准的1.7倍。红外光谱分析表明,炭样表面以羟基、羰基、羧基等酸性官能团为主。静态吸附实验表明,Freundlich方程与Redlich-Peterson方程能较好地描述等温吸附行为,表现为优惠吸附。热力学研究表明,吸附吉布斯自由能（ΔG⁰）<0,说明吸附反应是自发过程,而吸附标准焓变（ΔH⁰）>70 KJ/mol,表明亚甲基蓝在制备炭样上的吸附是吸热反应,升温有利于吸附,且化学反应在吸附过程中发挥了重要作用。     

棉秆基活性炭的制备及其对2,4-二硝基苯酚的吸附

以棉秆为原料,以KOH为活化剂,制备了高比表面棉秆基生物质活性炭。分析了制得的活性炭的元素组成、表面官能团、吸附能力等物化性能,探讨了浸渍比,活化温度,活化时间等工艺参数对制备活性炭得率、表面官能团、碘值、亚甲基蓝值等性能的影响,并通过静态吸附实验比较了不同条件下制备活性炭对2,4-二硝基苯酚的吸附性能,探讨了典型炭样品对2,4-二硝基苯酚的等温吸附特性。结果表明,KOH活化棉秆基生物质活性炭的表面物化性质随浸渍比、活化温度等工艺参数变化而变化,活化适宜条件为浸渍比1：3、活化温度800℃、活化时间90 min,在此条件下制得的炭样的碘值为1 251 mg/g,亚甲基蓝吸附值为478 mg/g,分别是国家一级品标准的1.25倍与3.54倍;对2,4-二硝基苯酚的Langmuir最大吸附量为747 mg/g,与Freundlich模型相比,Langmuir模型能较好地描述2,4-二硝基苯酚在炭样上的吸附行为,表明制备活性炭样品表面吸附位的能量分布较为均一。     

NaOH活化栗苞生物质炭对亚甲基蓝的吸附性能

以栗苞炭化料(C-BC)为原料,以NaOH为活化剂制备栗苞活化生物质炭(Na-BC),研究其对水中亚甲基蓝的吸附行为。选取炭碱比、活化温度和活化时间为影响因素,通过正交试验确定了最佳活化工艺,即炭碱比为1∶4,活化温度为800℃,活化时间为30 min,此时Na-BC的最大吸附量为609.38 mg·g~(-1)。对最优条件下制备的生物质炭进行SEM、BET等表征,比表面积达1 563.78 m~2·g~(-1),总孔容达1.452 cm~3·g~(-1)。吸附实验结果显示,吸附反应能较好用Langmuir模型和准二级动力学方程模型进行模拟,Na-BC对亚甲基蓝的吸附为自发吸热反应。通过热法与碱法再生处理饱和吸附生物质炭,再生后的Na-BC对亚甲基蓝具有较好的吸附能力。     

木镁基碳质吸附剂的制备及其性能

用木镁聚合物(PML)制备碳质吸附剂,探讨了影响产物吸附性能的主要制备因素。结果表明,当活化温度为400℃,磷料比为2∶1和活化时间为2.5 h时,木镁基碳质吸附剂(MLCA)的吸附性能较好,其亚甲基蓝吸附值为142.5 mg/g,碘吸附值为946.43 mg/g。红外光谱分析表明,经过高温处理后,产物保持了PML的基本结构特征,而其比表面积由0.07 m2/g增大至642.38 m2/g。MLCA对染料亚甲基蓝的吸附过程符合Langmuir吸附等温式。     

微波蔗渣中孔生物质炭对水中对氯苯酚的吸附特性

通过微波快速热解活化技术制备并探究了中孔蔗渣生物质炭对水中对氯苯酚的吸附性能、影响因素及等温吸附行为与动力学特性。结果表明,微波活化蔗渣炭富含微中孔结构,主要分布在2~5 nm,对水中对氯苯酚的吸附值高达165 mg·g-1,5 min内完成饱和吸附量的75%,表明中孔蔗渣炭是去除对氯苯酚的良好吸附材料。值得注意的是,蔗渣中孔炭对对氯苯酚吸附性能与效率均高于以微孔为主的市售炭粉与炭纤维,说明介孔结构的存在可缩短被吸附物质到达吸附活性点的路径,增大多孔炭对水中有机物的捕捉机率,增强多孔炭对水中对氯苯酚的吸附效率。降低溶液p H和温度有利于中孔蔗渣炭对水中对氯苯酚的吸附,吸附行为符合弗兰德里希和雷德利克·彼得森模型,表明吸附呈多分子层的指数分布。     

硫酸活化市政污泥对亚甲基蓝的吸附

采用市政剩余污泥作为原料,以硫酸作为活化剂制备吸附剂,并将其应用到含亚甲基蓝废水处理中。系统地研究了溶液初始pH值、亚甲基蓝初始浓度和吸附时间等因素对硫酸活化市政污泥吸附性能的影响。研究结果表明,在吸附剂投加量2 g/L,pH7.5,温度293 K条件下,硫酸活化市政污泥对亚甲基蓝的最大吸附量为38.4794 mg/g。吸附动力学和热力学研究结果表明,吸附剂对亚甲基蓝的吸附过程可用准二级动力学模型(R2=0.9910)、Freundlich吸附等温式(R2=0.9935)来描述。颗粒内扩散速率也是其吸附反应限制因素,但不是惟一限制因素。该研究表明,硫酸活化剩余污泥可以作为含亚甲基蓝染料废水的处理材料。     

生物质基炭膜的制备及其对Pb(Ⅱ)的吸附

以生物质二层牛皮为原料,在控制热分解条件下制备了生物质基炭膜。利用TG/DTG、XRD、FT-IR、SEM、TEM和低温N_2吸附-脱附等方法对在不同炭化温度下(550~950℃)制备的生物质基炭膜形貌特征、孔隙结构及其表面化学性质进行了表征。考察了炭化温度、反应时间、溶液pH、加入量等因素对炭膜吸附溶液中铅离子的影响。表征结果表明:随着炭化温度的升高,生物质基炭膜碳微晶趋于石墨化发展,总孔容积持续增大,孔隙结构变得更加发达。实验结果表明:随炭化温度升高,生物质基炭膜对铅离子的吸附效果明显变好;在初始铅离子质量浓度为50 mg·L~(-1)、溶液pH为5.5、吸附剂加入量为1.5 g·L~(-1)、吸附时间为6 h的条件下,950℃下所制炭膜对铅离子有较好去除效果,去除率可达99.9%,吸附容量为32.76 mg·g~(-1)。     

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.     

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.     

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.     

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 and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.