煤质炭制备条件的优化及对酚类吸附性能与吸附动力学

KOH为活化剂,正交实验方法优化了煤质炭的制备条件。对2种酚类有机物苯酚、氯苯酚进行了静态吸附,观察了温度、时间、初始浓度及投加量对吸附性能的影响,优化了吸附条件。实验数据与Langmuir、Freundlich和Temkin吸附等温线进行了拟合,并对准一级、准二级动力学模型和内扩散模型拟合。结果表明,优化得煤质炭制备条件为:碱碳质量比3∶1,浸泡时间12 h,活化时间80 min,活化温度800℃。在温度为25℃,投加量为0.05 g时,苯酚的平衡时间为60 min,初始浓度为200 mg/L时的吸附量为58.89 mg/g;氯苯酚的吸附平衡时间为90 min,初始浓度为300 mg/L时的吸附量为84.32 mg/g。煤质炭对苯酚的吸附过程与Langmuir吸附等温线,氯苯酚的吸附过程与Temkin吸附等温线拟合得较好。二级动力学模型能够较好地描述这2个吸附过程,且颗粒内扩散不是唯一的速率控制步骤。     

东京根霉对重金属Cr3+、Mn2+和Zn2+的吸附研究

利用固定化发酵中产生的废菌体--东京根霉(Rhizopus tonkinesis)去除废水中Cr3 、Mn2 和Zn2 ,研究了预处理、pH、温度、金属离子初始浓度、吸附时间等条件对吸附量的影响.结果表明,用NaOH浸泡4～6 h、在pH=5～6,温度25～35℃时吸附效果最好,用Langmuir、Freundlich和Temkin方程对其吸附等温线进行拟合,相关性都比较好;用不同的吸附动力学方程描述东京根霉吸附金属离子的最优和最次模型分别为Elovich方程和一级扩散方程,双常数方程和抛物线扩散方程拟合介于前二者之间.     

聚甲亚胺酰胺树脂对水中Cu~(2+)的吸附

制备了聚甲亚胺酰胺树脂,对其进行傅里叶变换红外光谱分析。采用批处理方法实验了pH、铜离子初始浓度、吸附时间、吸附剂用量对吸附量的影响,研究了等温吸附模型和吸附动力学模型。优化后的吸附条件为:在铜离子溶液体积50 mL、初始浓度为300 mg/L、pH为6.0时,吸附剂投放量50 mg、吸附时间60 min,此时吸附量达到269.1 mg/g,去除率达89.7%。25℃时在研究浓度范围内,铜离子吸附过程用Langmuir等温线模型和Freundlich等温线模型描述均可;与准一级动力学方程、Elovich方程及内扩散方程相比,准二级动力学方程能更好地描述其吸附动力学过程。     

核桃壳对模拟废水中Cu~(2+)的吸附性能研究

采用核桃壳作为吸附剂,对模拟废水中的Cu2+进行吸附去除,考察了吸附剂粒径、水样初始pH、吸附剂用量、Cu2+初始浓度、吸附时间等因素对Cu2+吸附效果的影响,确定最佳吸附参数,并进行了吸附动力学和吸附等温线分析。结果表明:最佳吸附参数为核桃壳吸附剂粒径1.25~1.60mm、水样初始pH 5.0、吸附剂用量2.5g,Cu2+初始质量浓度20mg/L、吸附时间360min,在此条件下100mL水样在200r/min、25℃条件下吸附的Cu2+去除率达70%以上,吸附量约为0.702mg/g;本实验过程采用伪二级动力学方程的拟合更好,R2均在0.9以上,Cu2+吸附速率与其浓度的二次方成正比;Langmuir方程可以较好地描述核桃壳吸附剂对Cu2+的吸附过程,此吸附过程是单分子层的吸附。     

东京根霉对重金属Cr^3＋、Mn^2＋和Zn^2＋的吸附研究

利用固定化发酵中产生的废菌体——东京根霉（Rhizopustonkinesis）去除废水中Cr^3＋、Mn^2＋和Zn^2＋,研究了预处理、pH、温度、金属离子初始浓度、吸附时间等条件对吸附量的影响。结果表明，用NaOH浸泡4—6h、在pH=5—6，温度25-35℃时吸附效果最好，用Langmuir、Freundlich和Temkin方程对其吸附等温线进行拟合，相关性都比较好；用不同的吸附动力学方程描述东京根霉吸附金属离子的最优和最次模型分别为Elovich方程和一级扩散方程，双常数方程和抛物线扩散方程拟合介于前二者之间。     

海带对镉的吸附动力学与热力学研究

采用批量平衡法研究了海带对镉的吸附的动力学与热力学,并采用Lagrange假一级动力学方程、假二级动力学方程、Langmuir等温线方程、Freundlich等温线方程以及Dubimim-Radushkevich等温线方程对实验数据进行了拟合.结果表明,在4种温度下海带对镉的吸附率均随吸附反应时间增加而增大,在60 min时达到最大,此后基本保持不变,随着温度由20℃升高至50℃,其最大吸附率呈下降趋势,由90.2%降至77.5%;海带对镉的吸附动力学符合Lagrange假二级动力学方程;海带对镉的吸附热力学符合Langmuir等温线方程和Dubimim-Radushkevich等温线方程,表明吸附主要发生在海带表面的活性区位,属于单分子层吸附,其吸附平均活化自由能E为11.4 kJ/mol,表明该吸附过程为化学吸附,在4种温度下吉布斯自由能变化量△AG°均为负值,吸附焓变△H°也为负值,表明海带对镉的吸附为放热反应,能自发进行.     

胺化木质素对水中Cu（Ⅱ）、Cd（Ⅱ）的吸附

以胺化木质素作吸附剂对水中Cu2＋、Cd2＋的去除进行了研究，主要考察了吸附时间、溶液pH值、温度和金属离子初始浓度对吸附去除率的影响，并研究了其吸附等温线和动力学。结果表明，胺化木质素能有效去除水溶液中的Cu2＋、Cd2＋，且对Cd2＋的吸附能力大于Cu2＋吸附动力学符合准二级动力学方程，吸附等温线均可以很好地用Langmuir方程描述。     

牛粪生物炭对Cd~(2+)的吸附影响因素及特性

为了考察以牛粪为原料制备的生物炭对水溶液中Cd2+的吸附效果,进行了吸附影响因素、吸附等温线和动力学研究。结果表明,当热解温度为700℃、投加量为20 g/L、溶液初始pH为5、水溶液Cd2+初始浓度为10 mg/L、吸附平衡时间为60 min和溶液温度为25℃时,对Cd2+的吸附效果最佳,Cd2+去除率可达99%以上。提高溶液温度有利于吸附。降低生物炭热解温度和投加量对吸附效果影响不大。Langmuir方程能更好地拟合生物炭对Cd2+的吸附等温过程,吸附过程符合准二级动力学方程。牛粪生物炭是性能优良、价格经济的水溶液中Cd2+的吸附剂。     

香菇下脚料对水体中十二烷基苯磺酸钠的吸附

香菇下脚料经甲醛/硫酸混合溶液处理后制备成吸附剂。研究了吸附剂对SDBS的吸附性能,考察了溶液pH值、吸附剂粒径、初始浓度、吸附时间、浓度和温度的影响。结果表明,吸附适宜条件的为:pH 4.0,吸附时间60 min,吸附过程可以很好地用准二级动力学方程描述,吸附等温线用Langmuir方程的拟合效果优于Freundlich和Tempkin方程。在热力学研究中,ΔG0<0,ΔH0>0,ΔS0>0,表明此吸附过程是自发、吸热和熵增加的过程。     

大孔树脂吸附去除水中的2,4,6-三硝基甲苯

研究了2种大孔树脂XAD-4和NDA-804对水中的TNT的吸附行为。2种树脂对TNT的吸附等温线表明,温度的升高有利于吸附,在35℃条件下XAD-4树脂与NDA-804树脂对TNT的最高平衡吸附量分别达82.86 mg/g和94.26mg/g。采用Langmuir方程和Freundlich方程用于吸附等温线的解释,结果表明,吸附等温线更加符合Langmuir模型,相关系数均大于0.99。TNT在2种树脂上的吸附符合准二级动力学方程,TNT初始浓度越低,达到吸附平衡所需时间越短,在1 h内可达到吸附平衡。采用NDA-804处理对TNT废水,废水中TNT浓度由103.58 mg/L降至0.4 mg/L,去除率达99.6%,吸附后的树脂采用pH=2的乙醇和盐酸的混合液脱附可再生,高浓度再生溶液经蒸馏可回收TNT,实现了废水治理与资源化。     

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.     

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.     

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.