磁性CoFe_2O_4/MgAl-LDH去除水中的磷酸盐

采用共沉淀法制备了磁性复合材料Co Fe2O4/Mg Al-LDH,通过静态吸附实验研究了Co Fe2O4/Mg Al-LDH对磷酸盐的吸附性能,考察了吸附剂投加量、溶液p H值、吸附时间、温度、共存离子等因素对磷酸盐去除效果的影响。结果表明,在实验条件下,Co Fe2O4/Mg Al-LDH对磷酸盐的吸附量随溶液p H值的增大而逐渐降低,吸附的最佳p H值为1.5。磁性Co Fe2O4/Mg Al-LDH对磷酸盐的吸附动力学符合准二级动力学模型,吸附等温线符合Langmiur等温吸附模型,理论最大吸附容量为105.37 mg/g。吸附热力学参数表明,Co Fe2O4/Mg Al-LDH对磷酸盐的吸附是自发、吸热的过程。     

改性木屑吸附除亚甲基蓝性能

为提高对亚甲基蓝的去除效果,采用热解+Na OH浸泡方法制备了改性木屑,用SEM研究了改性对木屑表面结构的影响,并以该改性木屑为吸附剂,进行了从水溶液中吸附亚甲基蓝的性能研究。研究结果显示,改性木屑表面光滑,并出现多发熔孔。常温下,改性木屑对亚甲基蓝的吸附等温线符合Langmuir方程,最大吸附量322.58 mg/g,是原始木屑的10倍,是活性炭的3倍,改性效果显著;对浓度为200 mg/L、p H值为7的亚甲基蓝溶液,改性木屑投加量为0.8 g/L时,去除率达到了99.01%,去除效果理想。吸附动力学符合伪二级速率方程。     

磁性花生壳基活性炭对亚甲基蓝的吸附特性

以花生壳为原料,在K2CO3和Fe3O4共活化条件下制备了磁性花生壳基活性炭(MPSAC)。通过扫描电子显微镜、氮气吸附脱附等温线、X射线衍射和振动样品磁强计等手段表征了材料的结构和性质,测定了其对亚甲基蓝的吸附特性,考察了初始pH、吸附时间、MPSAC投加量、亚甲基蓝初始浓度和温度对吸附的影响。结果表明:(1)初始pH对亚甲基蓝的吸附影响较小;吸附时间对亚甲基蓝的吸附效率有明显的影响,在120min时吸附达到平衡,吸附过程符合准二级动力学方程。(2)吸附平衡数据更好地符合Langmuir方程,在25、35、45℃下,MPSAC的理论饱和吸附量分别为617.28、617.28、666.67mg/g。(3)热力学参数吉布斯自由能变0J/mol、焓变0J/mol、熵变0J/(mol·K),说明MPSAC对亚甲基蓝的吸附属于熵变增加的自发吸热反应过程。     

城镇有机垃圾热解生物炭对水中亚甲基蓝的吸附

热解是一项极具前景的城镇垃圾资源化处理技术,对热解产物的合理利用有助于热解技术的推广应用。以1套垃圾分选、热解工程设备产生的生物炭为原料,研究生物炭对水中亚甲基蓝的吸附效果,分析吸附动力学和吸附等温线;通过红外光谱、比表面积、孔径及微观形貌的表征方法阐释其吸附机理,并进行经济性分析。结果表明,生物炭对亚甲基蓝的去除率随生物炭投加量的增加而增加,随亚甲基蓝溶液初始浓度的增加而降低,在pH为9时达到最高。生物炭对亚甲基蓝的吸附过程符合准二级动力学方程和Langmuir吸附等温线方程,为单分子层吸附,最大吸附量为35.7 mg·g~(-1)。生物炭具有较强的非均质性,其对亚甲基蓝的吸附主要发生在微孔中,且亚甲基蓝与生物炭表面的O—H、NH~(3+)、NH_2、C—O等基团发生了作用,说明亚甲基蓝在生物炭表面的吸附受生物炭孔结构和化学性质2个方面的影响。生物炭的制备过程可产生446～708元·t~(-1)的经济效益,作为废水处理的吸附剂具有较好的应用前景。     

Fenton法制备污泥基活性炭及其性能表征

污泥基活性炭孔隙率低下是污泥资源化利用的主要制约因素,而Fenton法预处理污泥,可有效改善活性炭性质。通过考察H2O2投加量、H2O2/Fe2+、活化pH以及炭化条件等参数,确定了最佳污泥基活性炭制备条件:H2O2投加量为5%(质量分数),H2O2/Fe2+为5∶1(质量比),活化pH为3,活化时间为2.0h,污泥含固率为1.0%(质量分数),炭化温度为600℃,炭化时间为2.0h,炭化升温速率为10℃/min。此时,得到的污泥基活性炭吸附碘值为340mg/g,比表面积为353.563m2/g,孔容积为0.238cm3/g,微孔容积为0.095cm3/g。该活性炭对阳离子和阴离子染料(亚甲基蓝和甲基橙)具有良好的吸附性能,结果表明,对亚甲基蓝和甲基橙的吸附更符合Langmuir方程,且其饱和吸附量分别为71.53、57.73mg/g。对吸附动力学的拟合结果表明,该吸附更符合二级动力学方程。     

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。     

松树锯末对亚甲基蓝（MB）的吸附研究

采用松树锯末以及改性松树锯末对模拟废水中的亚甲基蓝进行吸附实验研究。研究结果表明，当亚甲基蓝的初始浓度为50 mg/L、pH为6、锯末投加量为1 g/L时，改性前后的锯末对亚甲基蓝的吸附量最大，分别为29.9 mg/g和60.6 mg/g。同时，对改性前后的锯末做了吸附等温线拟合及动力学研究。结果表明，吸附等温线均能很好地符合Langmuir吸附模式，吸附过程符合拟二级动力学方程。     

复合型生物炭对废水中亚甲基蓝的吸附作用

以木屑、二氧化硅为原料,采用慢速热解法制备了木屑生物炭(BC)和木屑-二氧化硅复合型生物炭(CBC),并对其物理化学性质进行表征,同时研究其吸附水中亚甲基蓝的吸附等温方程、动力学过程和影响因素。结果表明,和BC相比,CBC的比表面积、孔体积和平均孔径分别增加了2.85、7.00、1.21倍。CBC和BC对亚甲基蓝的吸附符合Langmuir吸附等温方程,其最大吸附量分别为26.60、5.37mg/g,CBC对亚甲基蓝的吸附能力更强。CBC和BC对亚甲基蓝的吸附动力学过程遵循准二级动力学方程。此外,和BC相比,CBC对亚甲基蓝的吸附效果受pH和离子强度影响较小。     

亚甲基蓝在污泥活性炭上的吸附

以剩余污泥为原料,氯化锌为活化剂制备污泥活性炭。研究了初始pH值、吸附温度及离子强度对污泥活性炭吸附亚甲基蓝效果的影响。采用高分辨电子扫描电镜(SEM)和氮吸脱附曲线对污泥活性炭进行了表征。结果表明,随着pH值的升高,吸附量增大,碱性条件下最好。在15～55℃的范围内,亚甲基蓝的吸附量先增加后降低,温度为35℃时吸附量达到最大值。加入氯化钠后的污泥活性炭的吸附能力变弱,但随着离子强度的增大,变弱的强度减少。污泥活性炭以中孔为主和污泥活性炭具有不规则结构,预示着污泥活性炭较高的吸附能力。污泥活性炭对亚甲基蓝的吸附符合Lang-muir等温吸附方程。污泥壳活性炭对亚甲基蓝的吸附符合二级反应动力学方程反应特征。     

胺化麻黄废渣生物吸附剂对水中阳离子染料的吸附

以麻黄废渣为原料,采用环氧氯丙烷和二乙烯三胺对其进行化学改性,得到麻黄废渣的改性产物。将其应用到中性红和亚甲基蓝2种染料模拟废水的吸附实验,并研究了p H值、吸附剂用量、吸附时间等因素对吸附的影响。结果表明,在p H值为5.5,吸附温度为25℃的条件下,用4 g/L的胺化麻黄废渣生物吸附剂吸附初始浓度为1 000 mg/L的中性红溶液0.5 h,去除率为99.89%;用10 g/L的胺化麻黄废渣生物吸附剂吸附初始浓度为500 mg/L的亚甲基蓝溶液1 h,去除率为99.38%。改性吸附剂对中性红和亚甲基蓝的吸附可以用准二级动力学方程描述,吸附等温线符合Langmuir和Freundlich模型,根据Langmuir方程,25℃时胺化麻黄废渣生物吸附剂对中性红和亚甲基蓝的最大吸附量分别为362.3 mg/g和152.7 mg/g。实验结果显示,胺化麻黄废渣生物吸附剂是一种吸附性能优异的吸附剂,用于处理染料废水有较好的应用前景。     

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.