超声波有机改性凹凸棒土的苯酚吸附性能研究

采用超声波技术,对凹凸棒土进行有机改性,提高凹凸棒土的苯酚吸附能力,比较了不同的阳离子表面活性剂的改性效果,并且通过正交实验得出了超声波改性的最优化工艺条件为:十八烷基三甲基氯化铵的添加比例为35mmol/100g,超声波处理时间10min,屏极电流0·5A。在此条件下,苯酚去除率可达酸处理凹凸棒土的80倍以上,是搅拌有机改性的1.5倍。     

有机改性凹凸棒土的制备表征及其对4-氯苯酚的吸附

利用十六烷基三甲基溴化铵（HDTMA）对凹凸棒土进行有机改性，并通过SEM、XRD、FT—IR、表面积及孔径分析对改性前后的凹凸棒土进行结构表征，结果表明，利用HDTMA对凹凸棒土改性仅是表面的负载修饰，并未改变凹凸棒土的内部结构；改性凹土对4-氯苯酚的吸附实验表明，吸附速率很快，30min即达到吸附平衡，吸附符合准二级动力学方程，吸附等温线符合H型吸附等温方程，在pH为中性的环境下有利于吸附。     

以凹凸棒土为载体的非均相Fenton催化剂处理苯酚废水研究

采用浸渍法制备载铁凹凸棒土,并用其作为非均相Fenton催化剂处理模拟苯酚废水,研究该体系中各影响因素对模拟苯酚废水处理效果的影响,确定适宜反应条件,并对载铁凹凸棒土进行简单造粒研究。结果表明,载铁凹凸棒土与原凹凸棒土相比吸附能力有所增强,是一种良好的非均相Fenton催化剂。对于50 mL质量浓度为500 mg/L的模拟苯酚废水,适宜的非均相Fenton反应条件为载铁凹凸棒土14g/L、H_2O_2 1.0mL,在此条件下反应2.5h后苯酚及总有机碳(TOC)的去除率分别在98%、56%以上,非均相Fenton反应在一定程度上拓宽了Fenton反应的pH范围。将载铁凹凸棒土手工制成2~3mm颗粒,重复使用8次仍具有较高的活性,铁溶量低,具有良好的稳定性和回收性。     

烷基胍有机改性凹凸棒土研究

利用十六烷基胍盐对凹凸棒土进行有机改性,通过红外(IR)、X-射线衍射仪(XRD)、电镜(SEM)、差热(TG)、比表面积测定(BET)等分析手段对改性前后凹凸棒土进行了表征。结果表明,有机改性剂以静电吸附形式存在于凹凸棒土表面。十六烷基胍盐改性降低了凹凸棒土的空隙度和表面积。改性凹凸棒土对甲基橙模拟废水的脱色率显著提高,由改性前的3%左右提高到98%。     

改性凹凸棒土负载纳米铁的制备及性能

以200目的天然凹凸棒土为原料,先对原土进行酸活化与微波改性,再以改性凹凸棒土为载体,采用液相还原法由Fe Cl3·6H2O和Na BH4制备改性凹凸棒土负载纳米铁。通过正交实验、扫描电镜(SEM)、能谱仪(EDS)及红外光谱(IR)对负载前后的凹凸棒土进行表征分析确定其最佳条件。并通过稳定性实验和去除实验对改性凹凸棒土负载纳米铁的性能分析。结果表明:改性凹凸棒土负载纳米铁的最佳条件是铁土比为2.5∶1,酸浓度为3 mol·L~(-1),微波时间为6 min,微波功率为600 W,改性时间为24 h。改性凹凸棒土负载纳米铁在常规水处理环境中能稳定存在。对水中的Cr(Ⅵ)有良好的去除效果,去除率可达97.67%。     

改性凹凸棒粘土脱硫剂脱除SO2

采用单因素法,在传统搅拌混合下,研究了煅烧温度、煅烧时间、酸碱浸渍等对改性凹凸棒粘土脱硫剂穿透硫容与最大硫容的影响.然后在超声波混合作用下,采用正交实验确定了超声时间、超声温度以及活性组分(CaO)、促进剂(V2O5)的复配比例.结果表明:(1)甘肃临泽凹凸棒粘土富Al、Mg、Fe,且其比表面积较大.(2)改性凹凸棒粘土脱硫剂最佳制备条件:煅烧温度300℃;煅烧时间2.0 h;酸碱浸渍最佳pH9～10;混合采用超声波,超声时间30 min;超声温度40℃;CaO质量分数30%;V2O5质量分数5%.采用在最佳条件下制备的改性凹凸棒粘土脱硫剂进行脱除SO2实验,其最大硫容为38.16%.(3)改性凹凸棒粘土脱除SO2的性能比工业Fe2O3脱硫剂强.(4)X射线衍射分析表明,改性凹凸棒粘土脱硫剂脱除SO2后,将SO2转变为SO2-4,从而达到完全脱除SO2的目的,这与红外光谱分析的结果一致.     

偶联剂改性凹凸棒土处理含汞(Ⅱ)废水的研究

利用一种含氮硅烷偶联剂γ-氨丙基三乙氧基硅烷改性凹凸棒土,对凹凸棒土改性前后的表面性质进行了分析,并通过静态吸附实验研究了材料对水中汞离子的吸附性能.研究结果表明,酸活化增加了凹凸棒土吸附材料的孔道直径,使吸附速度加快,30 min即达到吸附平衡.通过硅烷偶联剂对凹凸棒土的改性,在材料表面引入了大量氨基,提高了材料对汞...     

有机改性成都粘土预处理垃圾渗滤液

以成都粘土为原料,十六烷基三甲基溴化铵(HDTMA)为改性剂制备有机改性土,并将其应用于垃圾渗滤液的预处理。采用单因素静态吸附实验,以粘土对垃圾渗滤液COD和氨氮的去除率作为考查指标,初步探究有机改性土预处理垃圾渗滤液的适宜条件;并对有机改性粘土及原土进行性能表征,初步分析其吸附机理。研究结果表明,有机土的处理效果明显优于原土,处理效果上比原土提高了1.6~2.3倍;有机土预处理垃圾渗滤液适宜条件为:投加量120 g/L、搅拌速度200 r/min、搅拌时间50 min、pH=7、静置时间为6 h。     

固定化改性蒙脱土对苯酚吸附性能的研究

利用十六烷基三甲基溴化铵对天然蒙脱土进行改性,并用聚乙烯醇对改性蒙脱土进行固定化处理,然后进行柱状吸附和振荡条件的吸附试验。研究结果表明,HDTMA改性蒙脱土固定化后能有效吸附苯酚,不同环境条件对苯酚的柱状吸附能力产生不同的影响。在pH4~8的范围内,固定化改性蒙脱土对苯酚的吸附效果无显著性差异,pH在10以上,其吸附能力明显下降;温度对吸附效果影响不大;进水苯酚浓度越高,改性蒙脱土对苯酚的吸附量越大,但出水苯酚浓度也高;苯酚的流速越小,吸附容量越高,吸附效果越好。     

磷酸改性凹凸棒粘土对Pb^2＋的吸附研究

研究了不同浓度磷酸改性凹凸棒粘土的比表面积、孔结构性质以及其对水中Pb（Ⅱ）的吸附.结果表明,凹凸棒粘土磷酸改性后比表面积明显增大,具有明显的中孔分布;9 mol/L磷酸改性处理的凹凸棒粘土吸附能力最佳,在改性凹凸棒粘土加入量为20～30 g/L,水样pH=5条件下,废水中Pb（Ⅱ）的被吸附率接近99%.     

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.     

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.     

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.     

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.     

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.     

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.