膨胀石墨对U(Ⅵ)的吸附特性

高温加热可膨胀石墨制得膨胀石墨,用于去除溶液中的U(Ⅵ)。通过静态吸附实验,研究了初始p H、吸附剂投加量、U(Ⅵ)初始浓度、温度以及吸附时间对膨胀石墨吸附U(Ⅵ)效果的影响。实验结果表明,膨胀石墨吸附U(Ⅵ)的最佳p H为6.5,在温度为30℃,投加量为2.0 g/L,U(Ⅵ)初始质量浓度为10 mg/L时,对U(Ⅵ)的去除率达到98.08%,反应在4 h达到平衡。Langmuir等温吸附模型和准二级动力学模型较好地拟合了吸附过程,30℃时饱和吸附量为27.03 mg/g;热力学分析表明,膨胀石墨对U(Ⅵ)的吸附是自发的放热反应。比表面积测试、扫描电镜、X射线能谱与傅里叶红外光谱分析结果表明,膨胀石墨对U(Ⅵ)的吸附以物理吸附为主,表面官能团起辅助作用。解吸实验证明,膨胀石墨是可重复利用的吸附剂。     

5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六羟肟酸甲氧基杯[6]芳烃对铀(Ⅵ)的萃取

以上沿羧基化的杯[6]芳烃羟肟衍生物-5,11,17,23,29,35-六羧基-37,38,39,40,41,42-六羟肟酸甲氧基杯[6]芳烃(HHMHC)为萃取剂,利用HHMHC萃取U(Ⅵ),探讨U(Ⅵ)溶液初始p H值、萃取剂浓度、温度、萃取时间、初始U(Ⅵ)浓度等因素对HHMHC萃取U(Ⅵ)的影响。实验结果表明,在萃取剂浓度为2×10-4mol/L,U(Ⅵ)初始浓度为2.1×10-5mol/L,温度为25℃时,HHMHC萃取U(Ⅵ)的最佳p H值为6.0,萃取平衡时间为30 min,且最佳萃取分配比大于10。用准二级动力学模型(R20.99)和Freundlich等温模型(R20.999)均可较好地拟合其萃取过程,通过计算萃取过程的热力学参数焓变(ΔH0)小于0,表明此萃取反应是一个放热反应。以0.1 mol/L的HCl溶液作为反萃取液,初次反萃取率达96%,证明HHMHC具有一定的重复利用价值。     

改性废弃皮革对U(Ⅵ)的动态吸附

以改性废弃皮革为吸附剂对U(Ⅵ)进行动态吸附实验,采用直径3 cm、高50 cm的玻璃吸附柱,在填料高度为3、4和5 cm,U(Ⅵ)溶液进水流速为0.85、1.7和2.55 m L·min~(-1),初始U(Ⅵ)浓度为6、12和18 mg·L~(-1)的条件下,考察了各因素对U(Ⅵ)吸附穿透曲线的影响。动态实验表明:柱高的降低、流速的增大和U(Ⅵ)浓度的增加均会使穿透时间提前;动态吸附穿透曲线能很好地符合Thomas模型的条件(R2 0.95),同时吸附量的预测值与实际测试值较为接近。使用穿透时间(ta)与填料高度(h)的关系式ta=220h-433(R2=0.998),在仅改变流速和初始U(Ⅵ)浓度时,穿透时间预测值与实际测试值相差较小,表明BDST模型能确定固定床的动态吸附周期。     

烟秸杆生物碳对铬(Ⅵ)废水的吸附动力学和热力学

以农业废弃物烟秸杆为原料,以KH2PO4为活化剂,制备了烟秸杆生物碳(简称TSC500),通过静态吸附实验研究了TSC500对含Cr(Ⅵ)废水的吸附性能。采用比表面积分析仪对TSC500进行了测试,实验考察了p H值、吸附剂用量、吸附时间、Cr(Ⅵ)初始浓度和温度对Cr(Ⅵ)吸附的影响,深入研究了TSC500对Cr(Ⅵ)的吸附行为。结果表明,在p H=3、温度313 K条件下,0.2 g TSC500吸附100 mg/L Cr(Ⅵ),去除率和吸附容量分别达到91.32%和45.66 mg/g,Langmuir和Freundlich比Temkin等温模型更好地拟合吸附实验数据;准一级和准二级动力学模型均能较好地描述该吸附行为,相关系数高达0.99;计算得到热力学参数ΔGθ、ΔHθ和ΔSθ值表明该吸附过程为自发吸热过程。     

发酵麸皮对酸性含铬废水中Cr(Ⅵ)的吸附与解吸研究

以发酵行业产生的发酵麸皮废弃物为生物吸附剂处理酸性含铬废水中的Cr(Ⅵ),研究了pH、吸附时间、Cr(Ⅵ)初始浓度、发酵麸皮投加量对Cr(Ⅵ)吸附效果的影响,确定发酵麸皮吸附去除Cr(Ⅵ)的适宜条件。分别以NaOH、HCl、NaCl为解吸剂处理吸附饱和的发酵麸皮,利用正交实验研究解吸剂种类、解吸时间、解吸剂浓度、发酵麸皮投加量等因素对Cr(Ⅵ)解吸效果的影响。结果表明,在强酸条件下发酵麸皮对Cr(Ⅵ)的吸附效果最好,发酵麸皮吸附Cr(Ⅵ)的适宜条件为pH=1,吸附时间90min,Cr(Ⅵ)初始质量浓度20mg/L,发酵麸皮投加量0.35g。发酵麸皮解吸Cr(Ⅵ)的正交实验结果表明,最佳解吸条件为以0.20mol/L NaOH为解吸剂,发酵麸皮投加量0.50g,解吸时间60min。各因素对Cr(Ⅵ)解吸效果的影响程度排序为解吸剂种类解吸时间解吸剂摩尔浓度发酵麸皮投加量。吸附饱和后的发酵麸皮可以通过解吸再生,但再生第4次已经失去了重复利用的价值。     

腐殖酸修饰凹凸棒对U(VI)的吸附性能及机理

采用腐殖酸(HA)修饰凹凸棒(ATP)制备得到腐殖酸/凹凸棒(HA/ATP),用于去除废水中的U(VI)。通过静态吸附实验,研究了溶液初始p H、投加量、吸附时间和初始浓度对吸附的影响,并用扫描电镜(SEM),X射线能谱图(EDS),傅里叶红外光谱仪(FITR)分析吸附机理。实验结果表明,去除率随时间的增大而增大,在120 min内可以达到平衡;吸附剂投加量越大,溶液p H=6左右时越有利于U(VI)的去除;HA/ATP能多次重复使用,且经过5次吸附解吸后对U(VI)的去除率仍能达到96%。吸附过程均符合Langmuir和Frendlich等温方程。较之准一级动力学,准二级动力学模型能更好地拟合实验数据。SEM-EDS、FITR分析结果表明,U(VI)被成功地吸附到了HA/ATP的表面,吸附机理为络合作用。     

腐殖酸修饰凹凸棒对U(Ⅵ)的吸附性能及机理

采用腐殖酸(HA)修饰凹凸棒(ATP)制备得到腐殖酸/凹凸棒(HA/ATP),用于去除废水中的U(Ⅵ).通过静态吸附实验,研究了溶液初始pH、投加量、吸附时间和初始浓度对吸附的影响,并用扫描电镜(SEM),X射线能谱图(EDS),傅里叶红外光谱仪(FITR)分析吸附机理.实验结果表明,去除率随时间的增大而增大,在120 min内可以达到平衡;吸附剂投加量越大,溶液pH =6左右时越有利于U(Ⅵ)的去除;HA/ATP能多次重复使用,且经过5次吸附解吸后对U(Ⅵ)的去除率仍能达到96％.吸附过程均符合Langmuir和Frendlich等温方程.较之准一级动力学,准二级动力学模型能更好地拟合实验数据.SEM-EDS、FITR分析结果表明,U(Ⅵ)被成功地吸附到了HA/ATP的表面,吸附机理为络合作用.     

粉煤灰对Cr(Ⅵ)的吸附特性

通过间歇实验研究了粉煤灰对重金属Cr(Ⅵ)的吸附特性。探讨了固液比、pH、反应时间、温度、离子强度和初始浓度等因素的影响。实验结果表明,固液比、pH、温度与离子强度都对去除率有较大影响。当温度为20℃、pH=1、Cr(Ⅵ)的初始浓度为10 mg/L,固液比为100 g/L时,去除率达到50.13%。动力学实验结果表明,粉煤灰对Cr(Ⅵ)的吸附为快速反应,在180 min内可达到平衡,伪二级动力学模型可较好地拟合实验结果。等温吸附实验结果表明,Freundlich模型与Langmuir模型均可较好地拟合等温吸附实验结果。低温有助于粉煤灰对Cr(Ⅵ)的吸附。     

CoFe_2O_4/MgAl-LDO吸附水中的Cr(Ⅵ)

采用水热法、共沉淀法合成Co Fe2O4/Mg Al-LDH,于高温下焙烧4 h后,制备出同时具有高吸附性能和磁分离性能的镁铝复合氧化物(Co Fe2O4/Mg Al-LDO),研究其对水中Cr(Ⅵ)的吸附效果。采用X射线衍射(XRD)、红外光谱(FTIR)等技术对吸附剂进行表征。通过序批实验考察了焙烧温度、溶液初始p H值、吸附时间、温度等因素对Co Fe2O4/Mg AlLDO吸附Cr(Ⅵ)的影响。结果表明,当焙烧温度在450~550℃之间、溶液初始p H=2~6时,吸附剂对Cr(Ⅵ)均具有较好的吸附效果,且吸附反应在90 min内达到平衡。Co Fe2O4/Mg Al-LDO吸附Cr(Ⅵ)过程符合准二级动力学和Langmuir等温吸附模型,当温度为318 K时,理论饱和吸附容量为98.04 mg/g。热力学研究结果表明,该吸附过程为自发的、吸热反应过程。     

溶液化学环境对给水厂废弃铁铝泥吸附草甘膦的影响

考察了给水厂废弃铁铝泥(ferric and alum water treatment residuals,FARs)对有机磷农药草甘膦的吸附特征,探究了溶液初始p H、阳离子种类及其离子强度、磷酸盐和小分子有机酸浓度等对FARs吸附草甘膦的影响。研究结果表明:FARs对草甘膦的吸附较符合伪二级动力学模型(R2=0.942),Freundlich方程能较好地描述FARs对草甘膦的等温吸附过程(R2=0.994),其草甘膦吸附容量KF值达10.35,是已报道铝泥的2倍。溶液化学环境对FARs吸附草甘膦影响较大,随着溶液p H的增加,FARs对草甘膦的吸附量显著降低。与K+相比,Ca2+的存在能显著提高草甘膦的吸附量。此外,溶液中小分子有机酸(苹果酸和柠檬酸)对FARs吸附草甘膦存在明显的抑制作用,且抑制作用随着有机酸浓度的升高而增强。解吸实验结果进一步表明FARs吸附的草甘膦能稳定存在,不易被溶液中的磷酸盐所取代。     

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.     

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.