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。     

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.     

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.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.