溴化十六烷基吡啶改性沸石对水中甲基橙的吸附

采用溴化十六烷基吡啶(CPB)对天然沸石进行改性制备得到了CPB改性沸石,通过批量吸附实验考察了CPB改性沸石对水中阴离子染料甲基橙的去除作用。结果表明,天然沸石对水中甲基橙的吸附能力很差,而CPB改性沸石则可以有效吸附去除水中的甲基橙。CPB改性沸石对水中甲基橙的吸附能力随CPB负载量的增加而增加,CPB负载量最大的改性沸石对水中甲基橙的吸附能力最强。双分子层CPB改性沸石对水中甲基橙的去除率随吸附剂投加量的增加而增加,而CPB改性沸石对水中甲基橙的单位吸附量则随吸附剂投加量的增加而降低。双分子层CPB改性沸石对水中甲基橙的吸附平衡数据可以采用Langmuir等温吸附模型加以描述。根据Langmuir模型计算得到的CPB负载量为341 mmol/(kg沸石)的双分子层CPB改性沸石对水中甲基橙的最大吸附容量为63.7 mg/g(303 K和pH 7)。准二级动力学模型适合用于描述双分子层CPB改性沸石对水中甲基橙的吸附动力学过程。pH和反应温度对双分子层CPB改性沸石吸附水中甲基橙的影响较小。以上结果说明,双分子层CPB改性沸石适合作为一种吸附剂用于去除废水中的甲基橙。     

壳聚糖-沸石杂化膜的制备及其对甲基橙的吸附

采用物理共混法制备了壳聚糖-沸石杂化膜,用扫描电镜(SEM)和热重分析仪(TGA)对其进行表征,并系统地研究了壳聚糖-沸石杂化膜对甲基橙的吸附行为。结果表明,最佳质量配比为(沸石/壳聚糖)为1∶20;pH值对吸附的影响最为关键,在实验浓度的范围内对甲基橙溶液最大吸附量为974.05 mg/g。杂化膜对甲基橙的等温吸附行为符合Lang-muir模型,吸附动力学模式符合准二级动力学方程,考虑以化学吸附行为为主。杂化膜有良好的再生能力。     

沸石对降雨径流中氨氮的吸附特性

城市面源污染是重要水体污染源之一,降雨发生时,雨水径流会携带累积在路面、屋面的含有机物、氮磷、重金属等污染物质进入水体,其中氮磷是造成水体富营养化的重要因素。针对这一情况,采用不同种类沸石,对雨水径流中的氮磷进行了吸附研究,着重考察了沸石对氨氮的吸附动力学,吸附等温线特征,并考察了p H、共存阳离子以及COD对吸附能力的影响。结果表明,Na型改性沸石吸附性能优于其他2种,饱和吸附量达到9.09 mg/g,沸石的吸附过程符合准二级动力学模型。Mg2+、Ca2+对Na型改性沸石的影响较大,Na型改性沸石吸附氨氮的适宜p H为5~8。本研究为探索用物化方法来处理雨水提供了依据,Na型改性沸石可以作为吸附雨水中氨氮的优选吸附剂。     

阳离子表面活性剂改性油茶果壳对水溶液中甲基橙的吸附

以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对油茶果壳进行改性,制备CTAB-油茶果壳(CTABCOS)吸附材料,并采用批实验法对其对水溶液中甲基橙的吸附去除进行了研究。考察了溶液p H、吸附剂用量和离子强度等对水溶液中甲基橙的吸附影响,并研究了体系的吸附动力学和吸附热力学特征。结果表明,向100 m L浓度为50 mg/L的甲基橙溶液中加入0.40 g CTAB-COS,在最佳实验条件下,CTAB-COS对甲基橙的去除率可达96.66%。溶液离子强度增大,甲基橙去除率降低。CTAB-COS对甲基橙的吸附行为符合拟二级动力学模型,吸附等温线可用Langmuir模型进行较好拟合,在20℃时最大吸附量为18.31 mg/g。吸附热力学结果表明,吸附过程为可自发进行的放热过程。再生性实验结果表明,再生6次后,CTAB-COS对甲基橙的吸附去除率仍可达到80%。该改性油茶果壳可应用于阴离子型染料废水的吸附法处理。     

十六烷基三甲基溴化铵改性沸石对腐殖酸的吸附性能研究

以十六烷基三甲基溴化铵(CTAB)为改性剂,制备了CTAB改性沸石,并用于对腐殖酸的吸附性能研究。考察了pH、吸附时间及腐殖酸初始浓度对CTAB改性沸石吸附腐殖酸的影响,采用吸附等温方程和反应动力学方程进行拟合分析,并利用扫描电子显微镜(SEM)、X射线光电子能谱仪(XPS)、傅立叶转换红外光谱分析仪(FTIR)对沸石改性前后进行结构表征。结果表明,在温度为25℃、转速为200r/min的条件下,选择pH为7.0、腐殖酸初始质量浓度为10mg/L、吸附时间为180min,此时CTAB改性沸石对腐殖酸的平衡吸附容量为0.16mg/g。相比Freundlich吸附等温方程(R2=0.967),CTAB改性沸石对腐殖酸的吸附更符合Langmuir吸附等温方程(R2=0.998),吸附机制为单分子层吸附。准一级反应动力学方程和准二级反应动力学方程均可以描述CTAB改性沸石对腐殖酸的吸附(R2=0.978)。吸附实验后的CTAB改性沸石上出现了甲基、亚甲基、羟基与羰基伸缩振动吸收峰,说明沸石已负载了CTAB,且腐殖酸已被CTAB改性沸石吸附。     

松果活性炭对有机染料的吸附

以松果为原料,利用ZnCl2活化法和FeCl3改性剂进行活性炭的制备和改性,测定了松果活性炭的比表面积,并研究其对甲基橙染料的吸附性能。结果表明:改性后的松果活性炭比表面积达到681 m2·g~(-1),并以中孔为主,有利于大分子有机染料的吸附;当松果活性炭的投加量为0.3 g·L~(-1)、吸附30 min、甲基橙初始浓度100 mg·L~(-1)、pH=7以及25℃温度条件下,吸附效果最佳,甲基橙去除率高达99.41%;Langmuir模型比Freundlich模型能更好地描述甲基橙染料的吸附行为,说明吸附以表面单层覆盖为主;吸附动力学符合Lagergren准二级动力学方程,R2大于0.999。可为松果的开发利用和制备低成本、高吸附性的吸附剂提供参考。     

NaCl改性沸石对氨氮吸附性能的研究

采用NaCl溶液对天然沸石进行改性,考察了NaCl浓度、温度及沸石用量对改性效果的影响。通过表面特征分析、吸附机制分析、吸附等温试验和吸附动力学试验,进一步比较了天然沸石和改性沸石对氨氮的吸附性能。结果表明,在NaCl溶液为6%(质量分数)、温度为303 K、天然沸石用量为15 g(以100 mL的NaCl溶液计)的优化条件下,改性沸石对氨氮的吸附效果最佳。扫描电子显微镜(SEM)和比表面积(BET)分析可知,沸石经改性后表面变粗糙,平均吸附孔径变小,比表面积变大。2种沸石对氨氮的吸附过程均可用Langmuir、Freundlich吸附等温方程较好地拟合,在温度为303 K时,改性沸石比天然沸石单分子层饱和吸附量增幅为34%以上。颗粒内扩散是沸石吸附氨氮的限制性因素,其吸附动力学较符合准二级反应动力学方程,拟合结果表明改性沸石具有更好的动力学性能,其吸附速率常数略大于天然沸石。     

热改性斜发沸石对富营养化水体的脱氮除磷效果

氮、磷是导致水体富营养化且又较难去除的一类物质。实验采用模拟的方法研究了天然沸石和不同温度改性沸石的脱氮除磷效果。结果表明,天然沸石对氮、磷静态吸附去除率分别达71%和91%。随着改性温度的升高,350℃改性沸石振荡吸附氮、磷效果最好,较之天然沸石提高了18%,改性温度继续上升则呈下降趋势。不同沸石对氮、磷的吸附特征可用一级动力学方程进行描述,其中350℃改性沸石对氮、磷的吸附特征在不同的固液比情况下均符合一级动力学方程。     

改性沸石对水中微量汞的吸附性能

为了更好的去除水体中微量汞,研究了采用二氧化锰和壳聚糖对天然斜发沸石进行改性,着重考察了pH、温度、离子强度、Hg~(2+)初始浓度和时间对改性前后沸石吸附Hg~(2+)的影响,并研究了其吸附机理。结果表明,改性沸石受pH、温度和离子强度影响较小,在pH、温度、离子强度和初始浓度为6、25℃、0.05 mol·L~(-1)和50μg·L~(-1)时,二氧化锰+壳聚糖改性沸石(ZCM)对Hg~(2+)的去除率高达99%,符合国家饮用水标准,并且二氧化锰+壳聚糖改性沸石(ZCM)具有更好的解吸再生性。3种沸石均较好的符合Langmuir等温吸附模型和假二级动力学模型,其中改性沸石对汞的吸附主要为离子交换和表面官能团的络合作用,二氧化锰+壳聚糖改性沸石(ZCM)和壳聚糖改性沸石(ZC)饱和吸附量由1.43 mg·g~(-1)提高到5和3.3 mg·g~(-1),吸附平衡时间由10 h减少至1和4 h,为治理汞微污染地表水提供一定的理论支持。     

天然及CaCl2改性沸石对四环素的吸附

通过静态吸附实验研究了水中四环素在天然和CaCl2改性沸石上的吸附行为及机制。实验表明,天然沸石对四环素具有吸附能力,CaCl2改性可以提高沸石对四环素的吸附能力。天然和改性沸石对四环素的吸附符合拟二级动力学模型,颗粒内扩散不是吸附过程的主要控制步骤。Freundlich和Dubinin-Radushkevich(D-R)等温吸附模型可以较好地描述实验所用2种沸石对四环素的吸附行为,D-R等温方程拟合结果显示吸附过程包含离子交换作用。通过对天然和改性沸石吸附四环素前后溶液中主要阳离子浓度变化分析证实了该吸附过程包含离子交换作用。实验研究了pH值变化对沸石吸附四环素的影响,当pH=3～5时,天然和改性沸石对四环素的吸附量均随pH值的增加而急剧下降,而pH=5～10时,天然和改性沸石对四环素的吸附量变化均不明显,推测可能是离子交换作用和化学沉淀吸附作用所致。另外,实验还初步探索了溶液离子强度对沸石吸附四环素的影响情况,随着溶液中Na+和Ca2+离子强度的增加,吸附量先急剧降低随后趋向平稳,进一步说明了沸石对四环素的吸附过程不是由单一机制控制的。     

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.