钠基膨润土插层改性的微结构与吸附机理

以钠基膨润土为原料,采用十六烷基三甲基溴化铵(CTMAB)、十二烷基硫酸钠(SDS)、聚合羟基铁离子作为插层改性剂,制备出多种有机、无机、复合插层改性膨润土。运用X射线荧光光谱、扫描电镜、X射线衍射及红外光谱分析等手段研究了各插层改性膨润土的微结构变化及对苯酚和4-氯苯酚的吸附行为。结果表明:不同改性剂的插层改性效果不同,CTMAB效果最好;2种复合插层改性膨润土的层间结构有着明显的差异,CTMAB-Fe复合插层土中聚合羟基铁离子分布于有机相之外,SDS-Fe复合插层土中聚合羟基铁离子镶嵌于SDS单分子层中;各插层改性土之间吸附量的大小关系与层间距的大小关系基本一致;CTMAB插层改性膨润土对苯酚和4-氯苯酚的吸附均符合Langmuir等温方程,吸附过程均为优惠吸附。     

PDMDAAC改性膨润土对石油类污染物脱附行为的研究

石油类污染是水体环境主要的污染源之一,并且石油是不可再生资源,用吸附法处理含有石油类污染的废水有较好的处理效果.膨润土是一种优良的吸附剂,对其进行改性能提高其吸附石油类污染物的性能.改性膨润土在在含油废水处理方面得到广泛的应用,但其对石油类污染物脱附行为的研究还较少.本实验考察了搅拌时间、搅拌速度、pH、温度和盐度的变化对饱和吸附含油废水的聚二甲基二烯丙基氯化铵(PDMDAAC)改性膨润土脱附行为的影响,并通过正交实验优化了最佳脱附条件:搅拌时间为25 min,搅拌速度为200 r/min,pH为3,温度为35℃,在此条件下,脱附率可达92.05%.在最佳脱附条件下使其再生,并和原土进行了比较,通过脱附动力学研究了其脱附的过程.结果表明,饱和吸附含油废水的PDMDAAC改性膨润土在最优条件下,脱附率可达92.05%,可以用来回收石油;再生得到的改性膨润土用于处理含油废水,去除率在82.84%左右,可以重复使用来处理含油废水;准二级脱附动力学能较好地描述脱附过程.旨在探索改性膨润土的吸附及脱附的规律, 为膨润土用于含油废水处理奠定基础.     

铁镍改性膨润土对废水中有机污染物的吸附性能研究

以钠基膨润土为原料,制备了铁镍无机改性土和铁镍有机复合改性土,并应用于造纸废水的处理,探讨了改性土用量、废水pH值、搅拌时间等因素对COD去除率的影响,通过正交实验对实验条件进行了优化.结果表明:铁镍有机复合改性土和铁镍元机改性土对废水的处理效果明显好于原土;膨润土的用量、废水的pH对COD的去除率影响较大;对于铁镍无机改性土,吸附剂用量为12g/L,溶液pH=2,吸附时间为10 min时,对废水中COD的去除率为54.06%;对于铁镍有机复合改性土,吸附剂用量为14g/L,溶液pH=3,吸附时间为20 min时,对废水中COD的去除率为70.10%.     

铁镍改性膨润土对废水中有机污染物的吸附性能研究

以钠基膨润土为原料,制备了铁镍无机改性土和铁镍有机复合改性土,并应用于造纸废水的处理,探讨了改性土用量、废水pH值、搅拌时间等因素对COD去除率的影响,通过正交实验对实验条件进行了优化.结果表明：铁镍有机复合改性土和铁镍元机改性土对废水的处理效果明显好于原土;膨润土的用量、废水的pH对COD的去除率影响较大;对于铁镍无机改性土,吸附剂用量为12g/L,溶液pH=2,吸附时间为10 min时,对废水中COD的去除率为54.06%;对于铁镍有机复合改性土,吸附剂用量为14g/L,溶液pH=3,吸附时间为20 min时,对废水中COD的去除率为70.10%.     

有机膨润土的制备及其在6-硝废水处理中的应用

以CTMAB为改性剂制备有机膨润土,并用改性后的膨润土吸附6-硝废水.膨润土改性条件为:液固体积(mL)质量(g)比6∶1,pH值为1,反应温度为60℃,反应时间为1 h进行酸活化;将上述酸活化的膨润土按膨润土阳离子交换容量的100%加人CTMAB,反应时间为80 min得到有机膨润土;6-硝废水吸附条件为:取上述有机...     

粉末状和颗粒状有机膨润土对克百威的吸附

用十六烷基三甲基溴化铵(CTMAB)和十二烷基苯磺酸钠(SDBS)制得粉末状CTMAB阳离子有机膨润土(简称CTMAB-膨润土)和CTMAB-SDBS阴阳离子有机膨润土(简称CTMAB-SDBS-膨润土),并利用聚乙烯醇(PVA)包埋固定化技术将2种粉末状有机膨润土制成颗粒状有机膨润土,研究了粉末状与颗粒状有机膨润土对水中克百威的吸附性能.结果表明:粉末状CTMAB-膨润土和CTMAB-SDBS-膨润土对克百威的吸附效果较好,最终去除率分别为90.9％和92.5％,颗粒状CTMAB-膨润土和CTMAB-SDBS-膨润土对克百威的最终去除率分别为55.5％和60.3％;有机膨润土对克百威的吸附等温线符合Freundlich方程;颗粒状有机膨润土吸附克百威最多可重复利用6次.     

有机膨润土吸附苯胺的性能及其在水处理中的应用

分别用氯化十六烷基吡啶(CPC)和溴化十六烷基三甲铵(CTMAB)改性的有机膨润土吸附处理水中的苯胺,研究了两种有机膨润土吸附处理苯胺的性能及适宜条件.结果表明,有机膨润土对苯胺的去除率比原土增大了十几倍,CTMAB-膨润土、CPC-膨润土及原土的饱和吸附容量分别为130mg/g、87.5mg/g及37.5mg/g.     

微波强化有机改性膨润土对磷的吸附特性研究

利用十六烷基三甲基溴化铵(CTMAB)在微波辐射条件下对浙江临安膨润土进行改性,制得有机改性膨润土,利用其含磷模拟废水进行处理,考察了不同的工艺条件如有机改性剂用量、微波辐射强度、辐照时间、吸附时间、改性膨润土投加量、pH值对废水中磷去除效果的影响。结果表明:在有机改性剂用量为3 mmol/g,微波辐照强度为96 W/g,微波辐照时间8 min为最佳制备条件。改性膨润土用量为12 mg/L,反应时间为15 min,溶液pH为7及常温条件下,改性膨润土对浓度为50 mg/L的含磷废水去除率达到97.3%,吸附符合Freundlich吸附等温方程。     

改性膨润土助凝消除水体中全氟辛烷磺酸盐

以十六烷基三甲基溴化铵(CTMAB)微波改性膨润土(CTMAB-膨润土)作为助凝剂,采用聚合氯化铝(PAC)联用CTMAB-膨润土进行强化混凝实验,对水体中全氟辛烷磺酸盐(PFOS)的消除进行研究。结果表明:经微波改性后,CTMAB进入到膨润土层间,增大了膨润土层间距;PAC的最佳投加量为15mg/L;强化混凝最佳pH为6~7;PFOS去除率随原水浊度的增大而增大;在同等条件下CTMAB-膨润土对PFOS去除率整体优于粉末活性炭。     

阴/阳离子有机膨润土制备及其对苯酚吸附性能的实验研究

采用十六烷基三甲基溴化铵(CTMAB)和十二烷基硫酸钠(SDS)对辽宁黑山钙基膨润土进行不同工艺的阴/阳离子有机膨润土制备,并探讨其对被苯酚污染的地下水的吸附机理及其影响因素,为阴/阳离子有机膨润土在污染地下水修复新技术--渗透反应格栅(PRB)中应用的可行性提供必要的技术参数.研究结果表明,制备阴/阳离子有机膨润土的最佳工艺是加入3.0%(质量分数)的Na2CO3钠化,以120CTMAB/15SDS的投加量对其进行阴/阳离子有机改性;阴/阳离子有机膨润土对水中有机物具有协同去除效应;阴/阳离子有机膨润土Na-ACOMMT对苯酚吸附的最佳条件是投加60 g/L、80～100目的Na-ACOMMT,在温度20℃、pH为6～8、振荡转速200 r/min的条件下振荡30 min,此时苯酚的去除率高达78.74%,且吸附等温线符合Langmuir和Freundlich方程;Na-ACOMMT可通过多次吸附(累积吸附量为0.045 9 mg/g)达到降低成本的目的.但是Na-ACOMMT吸附被苯酚污染的地下水时,可能会有微量阴/阳离子表面活性剂的解吸.     

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.     

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.     

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.     

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.     

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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)