多孔方沸石球的除氟及再生机理

利用鄂尔多斯盆地白垩系的方沸石岩样,通过提纯和改性等处理制成多孔方沸石球,用于处理含氟水。用过的方沸石球经再生处理也用于处理含氟水。实验结果表明,多孔方沸石球和再生方沸石球都有明显的除氟效果。对于100mL浓度5.00 mg/L的含氟水,多孔方沸石球较佳的水处理工艺条件为:用量3.0 g,搅拌后静置48 h。对于浓度3.00 mg/L的含氟水,一次水处理就能将F-浓度降到国家标准以内,除氟效率达60%。对于浓度5.00 mg/L的含氟水,2次水处理可以将F-浓度降到国家标准以内,除氟效率达80%。多孔方沸石球对氟离子的吸附符合Langmuir等温式,吸附速度符合斑厄姆公式。再生方沸石球对氟离子的吸附也符合Langmuir等温式,吸附速度也符合斑厄姆公式。多孔方沸石球和再生方沸石球的饱和吸附量相当,这说明用过的方沸石球经再生处理后活性基本恢复,可循环用于含氟水的处理。     

悬挂铁改性活性炭的美人蕉浮床除氟效果试验

设计制作了悬挂氯化铁改性颗粒椰壳活性炭(以下简称铁改性活性炭)的美人蕉(Canna indica)浮床,利用自制聚氯乙烯(PVC)水槽,研究了该浮床在不同水力停留时间(HRT)下对3.0、5.0mg/L含氟水的处理效果,并与未悬挂铁改性活性炭的美人蕉浮床进行除氟效果对比。结果表明,未悬挂铁改性活性炭的美人蕉浮床对3.0mg/L含氟水的氟去除率最高仅为9.4%。悬挂铁改性活性炭的美人蕉浮床在较长HRT(4.5d)下对3.0mg/L含氟水具有较好去除效果,水槽出水氟质量浓度最低可降至0.8mg/L,达到《地表水环境质量标准》(GB 3838—2002)Ⅲ类标准(≤1.0mg/L),氟去除率最高可达77.5%。由于受铁改性活性炭对氟离子吸附容量的影响,悬挂铁改性活性炭的美人蕉浮床在较短HRT(1.8d)下对5.0mg/L含氟水处理效果不理想,水槽出水氟质量浓度最低仅降至1.9mg/L,未达到GB 3838—2002Ⅴ类标准(≤1.5mg/L),氟离子去除率最高为58.0%。     

锆负载型树脂用于含氟废水深度处理的研究

本文研制了一种以火力发电厂废树脂为载体的锆负载型氟离子吸附剂 ,并在评价了该树脂对氟离子的吸附性能之后探讨了该树脂用于火力发电厂含氟废水深度处理的可能性。研究结果表明 ,锆的最佳负载的最佳浓度为0 .5mol/L ,该负载树脂的最佳吸附pH为 3.0— 4 .0 ,用填充柱进行的动态实验结果表明 ,pH =3时的吸附容量显著高于 pH=4时的值。利用该树脂对火力发电厂模拟含氟废水进行了双柱串联吸附工艺处理 ,当柱流量为 35mL/min(SV10 )、第二柱穿透时 ,第一柱的吸附容量为 10 2 2 8mg/L湿树脂 ;用 0 .1mol/L的NaOH溶液进行再生 ,柱流量选择为 35mL/min(SV10 )时 ,脱附率在 95 %以上。     

改性粘土除氟剂处理高氟地下水研究

利用自行制备的改性粘土除氟剂处理含氟量较高的配水,研究了改性粘土的优化制备条件和不同因素对其除氟效果的影响,并进行地下水原水除氟验证,最后考察了改性粘土除氟剂的再生性能.结果表明,将0.3 mol/L的Al2(SO4)3和2%(质量分数)的NaOH按1:3(质量比)混合制成改性溶液.再将改性溶液与粘土按1.0:3.0(质量比)混合后,在400℃下煅烧2 h所制得的除氟剂除氟效果最好,最高氟吸附容量可达0.216 8 mg/g;地下水出水氟质量浓度为0.807 mg/L,低于<生活饮用水卫生标准>(GB5749--2006)限值(1 mg/L);制得的改性粘土除氟剂对氟具有较好的吸附重复性,可实现多次再生.     

复合分子筛去除水中氟化物的研究

通过使用复合分子筛对模拟含氟水进行静态吸附实验,研究了复合分子筛对水中氟化物的吸附性能,并分析了吸附过程中温度、pH值和停留时间等因素对分子筛除氟效率的影响。结果表明,用80 g粒径0.9 mm的分子筛处理150 mL浓度为5 mg/L的模拟含氟水,分子筛的除氟效率达到90%以上,而同样条件下天然沸石和改性涂铁沸石的去除率分别为23.35%和80.69%。分子筛的除氟效率随着温度呈现先上升后下降的趋势,50℃时去除效率达到最高,为92.7%;在弱酸性条件下的去除率比碱性条件要高,在pH=4时去除率最大,为91.8%;停留时间初始阶段与去除率保持正相关,在45 min后反应达到平衡。分子筛的吸附速率符合二级动力学方程dqe/dt=k(qe-qt)2,吸附等温线符合Langmuir方程。     

电增强载铝活性炭纤维吸附氟离子性能

以载铝活性炭纤维毡为电极,在电场作用条件下对模拟含氟水进行静态吸附实验。结果表明,该载铝活性炭纤维毡正极化可以强化吸附除氟效果,吸附动力学数据很好地符合Lagergren二级速率方程,加电场时二级反应速率常数为4.50 g/(mg·h);其对高浓度含氟饮用水也有较高去除率,Freundlich吸附等温方程能很好地描述吸附平衡数据。加电场情况下,该载铝炭毡对氟离子的最大吸附量为16.584 mg/g,去除氟离子的最佳pH范围是5.5~8.9。共存阴离子Cl-、SO2-4和NO-3对炭毡吸附除氟没有抑制作用,但CO2-3的存在会导致除氟吸附量显著下降。     

平板炭气凝胶电极电吸附除氟

采用自制的炭气凝胶平板电极进行模拟水样中氟的电吸附去除研究,通过单因子实验优化了该电吸附技术的操作参数和适用的溶液条件,并研究了反接电极法的再生效果。研究结果表明,自制的炭气凝胶平板由纳米颗粒组成三维网络结构,比表面积为670.90 m2/g,具有良好的充放电可逆性和迅速形成表面双电层的特点。静态电吸附除氟效果最佳的条件为:水样氟离子浓度6 mg/L,pH 7.0,极板间距4 cm,电压1.6 V;共存物质硝酸根、腐殖酸、碳酸根和碳酸氢根等对氟离子的电吸附具有一定的促进作用。吸附氟离子后的炭气凝胶材料的比表面、孔体积、电容值有所减小。对于吸附氟离子后的炭气凝胶平板电极,采用反接电极法取得较好再生效果的条件为:流动状态、电压1.6 V、极板间距4 cm。再生后的炭气凝胶电极与原始炭气凝胶相比,依然具有良好的充放电可逆性。     

锆负载树脂用于含氟废水深度处理的研究

本文研制了一种以火力发电厂废树脂为载体的锆负载型氟离子吸附剂，并在评价了该树脂以氟离子的吸附性能之后探讨了该树脂用于火力发电厂含氟废水深度处理的可能性。研究结果表明，锆的最佳负载的最佳浓度为0．5mol／L，该负载树的最佳吸附pH为3．0－4．0，用填充柱进行的实验结果表明，pH＝3的吸附容量显著高于pH＝4时的值。利用该树脂对火力发电厂模拟含氟废水进行了双柱串联吸附工艺处理，当柱流量为35mL／min（SV10）、第二穿透时，第一柱的吸附容量为10228mg／L显著脂；用0．1mol／L的NaOH溶液进行再生，柱流量选择为35mL/min（SV10）时，脱附率在95％以上。     

煅烧的水滑石同时去除水体中砷和氟

为探讨水滑石类材料对水体中氟、砷离子的同时去除效果,采用共沉淀法合成(Mg∶Al=2∶1)纳米类水滑石(LDHs),用傅立叶转换红外光谱、电子扫描透射电镜、X射线晶体衍射等手段对合成的材料进行了表征,并研究纳米材料在不同初始浓度、pH、吸附时间、阴离子干扰条件下其同时除砷氟性能。结果表明,煅烧后的水滑石(LDOs)对砷最大吸附量为51.02 mg/g,对氟最大吸附量为36.63 mg/g。吸附动力学实验表明,煅烧水滑石对砷的吸附在前6 h内基本完成,对氟的吸附在前10 h内基本完成。砷氟共存溶液保持pH=4~10及pH=6~8时,水滑石分别对砷、氟保持良好的吸附效率。对比不同阴离子对水滑石共除砷氟效率的影响,水滑石除砷速率受到阴离子影响力大小为:HPO2-4CO2-3NO-3Cl-SO2-4;水滑石除氟速率受到阴离子影响力大小为:CO2-3HPO2-4SO2-4Cl-NO-3。材料再生循环利用4次后,对砷和氟的吸附效率均能达到90%以上。实验结果表明,所合成的水滑石是一种优秀的能共除砷氟的吸附剂。     

固定化啤酒废酵母对Cr(VI)的吸附

用2%海藻酸钠与1%明胶混合作为包埋剂固定啤酒废酵母,研究固定化啤酒废酵母对Cr(Ⅳ)的吸附特性.结果表明,固定化啤酒废酵母吸附Cr(Ⅵ)受吸附时间、起始pH、固定化菌体浓度、cr(Ⅵ)起始浓度及共存离子等因素的影响.确定固定化啤酒废酵母对Cr(Ⅵ)最佳吸附条件为:pH 2,Cr(Ⅵ)起始浓度100 mg/L,固定化菌体浓度2 g/L,吸附90 min.此条件下Cr(Ⅵ)的吸附率可达96.8%.Pd2+等并存离子可抑制固定化啤酒废酵母对Cr(Ⅵ)的吸附.用1 mol/L盐酸洗脱固定化啤酒废酵母所吸附的Cr(Ⅵ)3 h,解吸率为93.6%.     

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.