环糊精改性蛭石对水中Cr(Ⅵ)的吸附

以环糊精为改性剂,环氧氯丙烷为交联剂对蛭石进行改性,合成具有特殊结构的环糊精改性蛭石基吸附材料(CDMV)。采用FTIR、SEM、XRD对环糊精改性蛭石进行了表征,结果表明,蛭石表面性能得到改进。通过实验研究得到CDMV的最佳合成工艺:反应温度60℃,100 m L质量浓度7%NaOH;MEPI∶Mβ-CD摩尔比6∶1;第1阶段和第2阶段反应时间分别是6 h和5 h。同时对CDMV吸附Cr(Ⅵ)的等温吸附行为和吸附动力学进行了研究,结果表明,25℃下,1.00 g CDMV对Cr(Ⅵ)的吸附量达到最大为0.973 mg/g;Langmuir等温线(R2=0.9985)和Freundlich等温线(R2=0.9585)均能很好地描述改性蛭石对Cr(Ⅵ)的吸附规律,且其对Cr(Ⅵ)的吸附符合准二级动力学方程(R20.99)。     

改性蛭石结合鸟粪石沉淀法回收垃圾渗滤液中氨氮的实验研究

研究了使用氯化镁改性蛭石,利用磷酸铵镁沉淀的原理,在垃圾渗滤液中按比例加入PO43-,处理垃圾渗滤液中氨氮的同时,在蛭石上生成磷酸铵镁沉淀,以便于磷酸铵镁沉淀的回收利用。结果表明,筛取蛭石粒径为60～80目,配制浓度20%的氯化镁溶液浸泡改性蛭石20 min,取25 g改性蛭石,100 mL垃圾渗滤液调节pH为9,按n(NH4+)∶n(PO34-)=1∶1.2的比例加入PO43-离子,垃圾渗滤液中氨氮去除率为85.06%,实验并对磷酸铵镁沉淀进行了结构成分分析,为垃圾渗滤液中氨氮的处理及磷酸铵镁沉淀的回收提供了一种新的方法。     

藻类生长期对改性蛭石絮凝除藻的影响

以水华微囊藻为研究对象,采用壳聚糖改性蛭石,研究了藻类不同生长期的除藻效果及其影响机制,结果表明平均藻细胞去除率为:对数期稳定期衰亡期迟缓期衰亡后期,衰亡后期EOM含量是对数期的4.6倍,藻细胞去除率仅为30%左右,是对数期的1/3。其原因与不同生长期Zeta电位和胞外分泌物(EOM)的变化有关,衰亡后期的电负性显著增强,且EOM含量也显著增大。过量的EOM会增大改性蛭石的投加量,当达到相同去除率时,未移除EOM藻液的投加量是移除EOM藻液的3倍。EOM对絮凝除藻具有低促高抑的作用,低浓度(DOC10 m L)时EOM可发挥吸附架桥作用,利于絮凝;高浓度(DOC30 m L)时EOM的电负性发挥主导作用,抑制絮凝。     

温度对改性矿物吸附剂脱除气态汞影响

以蛭石、丝光沸石、膨润土及经改性后各物质为吸附剂，N2气氛下，在固定床实验台上进行了对烟气中单质汞脱除的实验研究，主要考察了温度的改变对改性矿物吸附剂脱除气态汞的影响。研究结果显示，膨润土、蛭石对汞的吸附基本不受温度的影响；未改性的吸附剂对汞的吸附能力均比较差；温度的提高有利于改性吸附剂对单质汞的脱除，说明改性后的吸附剂的脱汞过程以化学吸附为主；真正起作用的活性组分CeO2占据了丝光沸石的大部分表面积和空隙；丝光沸石经CuO改性前后吸附能力几乎未发生变化。     

微波辅助（NH4）2S2O8改性竹炭对Cu2+的吸附性能

以竹炭为原料,采用(NH4)2S2O8作为改性药剂,通过微波辅助加热的方法对竹炭进行改性;运用Boehm滴定、扫描电镜(SEM)、电子能谱(EDAX)和傅里叶红外光谱(FTIR)对改性竹炭进行表征;考察了pH、时间、温度和离子强度等对改性竹炭吸附Cu2+的影响。结果表明,微波辅助(NH4)2S2O8改性使得竹炭表面的酚羟基、内酯基、羧基等酸性含氧官能团的数量有所增加;改性竹炭对Cu2+吸附更符合Langmuir等温方程,吸附为自发的吸热过程;吸附动力学符合准二级动力学方程;溶液离子强度增大不利于其对Cu2+的吸附。     

氧化-负载铁组合工艺改性活性炭及其对Cr(Ⅵ)的去除

通过氧化-负载铁组合工艺对活性炭进行改性,对比了不同氧化剂(硝酸/磷酸)对改性效果的影响,利用Boehm、FT-IR、BET、XRD对改性活性炭(ACNF/ACPF)进行了表征,并对改性活性炭吸附水中痕量Cr(Ⅵ)的性能进行了研究。结果显示:硝酸与磷酸氧化均可显著增加活性炭表面酸性官能团数量,提高表面亲水性;改性后活性炭比表面积、孔体积和平均孔径均减小;负载的铁主要以铁(氢)氧化物形式存在于活性炭表面(ACPF)和介孔(ACNF)中;在Cr(Ⅵ)初始浓度0.5 mg/L,p H值3.0,活性炭投加量100 mg/L时,吸附12 h达到平衡,ACNF对Cr(Ⅵ)的去除率达到97.82%,出水Cr(Ⅵ)剩余浓度降至0.05 mg/L以下,满足《生活饮用水卫生标准》(GB5749-2006)要求,改性可显著提高对Cr(Ⅵ)的吸附容量。     

不同种类金属离子改性椰壳活性炭吸附分离CO2/CH4的研究

分别用碱金属(K)、碱土金属(Ca、Mg)和重金属(Fe、Cu、Ag)对椰壳活性炭(AC)进行改性,对改性前后AC的理化性质及其对CO_2/CH_4的吸附分离效果进行了综合对比分析。结果表明,经金属离子改性后AC的比表面积、总孔体积和微孔体积下降,中孔体积变大;AC改性前后主要官能团基本相同,除Ag~+改性AC中出现了Ag的衍射峰外,其余的物相结构基本没有改变。经金属离子改性后,AC对CO_2的吸附量增大,这与负载的金属增加了AC的表面极性密切相关;而对CH_4的吸附则大体低于原AC。改性AC对CO_2/CH_4混合气的分离效果均优于原AC,其中以K~+改性效果最优。金属离子改性AC对CO_2吸附能力和对CO_2/CH_4混合气分离效果的优劣程度大体为:碱金属改性AC碱土金属改性AC重金属改性AC。     

3种改良剂对铅锌矿渣中重金属形态及植物富集的影响

以衡阳市某铅锌尾矿库的矿渣作为土壤基质,泥炭土、红壤、蛭石作为改良剂,夹竹桃作为受试植物,进行室外盆栽试验,考察了3种改良剂对夹竹桃生长、重金属(Pb、Zn)富集转移能力以及土壤基质中Pb、Zn形态的影响。结果表明:(1)在5%(质量分数,下同)～15%的添加量下,3种改良剂均显著(p0.05)提高夹竹桃的株高增量与生物量增量,根系形态指标值也均有所提高,总体改良效果为蛭石泥炭土红壤。(2)夹竹桃地下部分Pb、Zn含量高于地上部分,添加改良剂后地上部分与地下部分Pb、Zn含量降低,说明改良剂高效抑制了重金属在夹竹桃中的富集;红壤与蛭石可抑制夹竹桃体内Pb的转运,但泥炭土却对Pb的转运起促进作用;除蛭石15%处理外,其余所有处理均促进了Zn在夹竹桃体内的转运。(3)3种改良剂在不同添加量下均显著降低了矿渣中弱酸可提取态Pb、Zn的含量(p0.05),有效降低了重金属Pb、Zn在土壤基质中的活性。     

改良剂对重金属复合污染土壤的修复效果

为揭示不同改良剂及其联合施用对重金属复合污染土壤的修复效果,采用室内土壤培养实验和室外盆栽实验相结合,研究不同施用量(10和20 g·kg~(-1))的蛭石(A)、泥炭(B)和骨粉(C)以及两两组合施用下,改良剂对土壤重金属DT-PA有效态、植物(以空心菜为例)生物量、株高以及植物可食部重金属含量的影响。结果表明:不同处理条件下的土壤p H值的提升与空白对照相比变化不显著;单施2%泥炭对土壤重金属Cu、Zn的钝化效果优于其他处理组,相对空白对照组,在第42天2种金属有效态含量分别降低了57.65%和65.55%,而1%蛭石和1%骨粉的混合添加能有效降低土壤中有效态Cd含量,相对空白对照组在第42天有效态Cd含量降低了40.52%;3种改良剂单施和混施对空心菜均具有增产增收的显著效果,且混施改良剂对空心菜增产效果较好;各处理组中空心菜体内Cu、Zn和Cd含量均有显著的降低,其中2%泥炭、1%蛭石+1%泥炭和1%蛭石+1%骨粉处理组分别对空心菜体内Cu、Zn和Cd含量降低效果最好,相对空白对照组分别降低了75.39%、70.75%和75.42%。因此,在该污染类型土壤泥炭、蛭石+泥炭和蛭石+骨粉分别对空心菜吸收土壤中的Cu、Zn和Cd具有较好的阻控效果。     

DSB+CPB复合改性膨润土对磷酸盐的吸附

为研究两性-阳离子表面活性剂复合改性膨润土的吸附除磷性能及其机理,采用不同比例两性表面活性剂——十二烷基二甲基磺丙基甜菜碱(DSB)和阳离子表面活性剂溴代十六烷基吡啶(CPB)对膨润土进行了有机复合改性,制得DSB+CPB复合改性膨润土,利用X射线衍射分析(XRD)、傅里叶红外分析(FT-IR)、扫描电子显微镜(SEM)、接触角(CA)以及热重分析(TGA)等手段对膨润土土样进行了表征,并用吸附等温模型和动力学方程拟合其吸附过程,探讨了改性比例、pH和温度等因素对吸附的影响。结果表明:DSB改性能提高膨润土对磷酸盐的吸附能力,当加入CPB复合改性后,可进一步促进DSB改性膨润土对磷酸盐的吸附能力,且吸附能力均随改性比例的增大而增强;对于0.5 DSB和1.0 DSB的改性膨润土,其与CPB最佳复合比例均为DSB+1.5CPB,最大吸附量分别为原土的7.81倍和8.19倍;改性膨润土对磷酸盐的吸附均符合Langmuir等温模型和伪二级吸附动力学方程,其吸附能力随pH的升高而降低,且吸附为物理和化学吸附同时存在的自发吸热熵增过程。上述研究结果可为两性-阳离子表面活性剂复合改性膨润土吸附除磷提供参考。     

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.     

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.     

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.     

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.