改性木屑对水中苯胺的动态吸附

采用β-环糊精对木屑改性用于吸附苯胺,通过固定床实验考察了吸附床高度(10~30 mm)、进水流速(2.7~8.1 m L·min-1)和苯胺初始浓度(50~200 mg·L-1)对穿透曲线的影响,同时使用BDST模型对吸附穿透曲线进行拟合。结果表明,改性木屑可以有效吸附苯胺,随着高度的增加,穿透时间延长,固定床对苯胺的去除率增大;随着苯胺进水流速和初始浓度的增加,穿透时间缩短,固定床对苯胺的去除率降低;BDST模型对穿透曲线的拟合效果较好(Ct/C0=0.7,R2=0.999 0),随着运行时间的增加,固定床的吸附速率常数(Ka)变小,对苯胺的吸附量(N0)增大;当改变流速时,运用该模型能较准确的预测吸附固定床的操作时间。     

麦草对水中苯胺的动态吸附研究

通过对苯胺初始浓度、流速、初始pH值和吸附床高度对穿透曲线的影响进行探讨，采用BDST模型和Thomas模型对动态实验数据进行线性拟合分析，研究了麦草对水中苯胺的动态吸附性能。结果表明：麦草能够有效地去除水中的苯胺，随着吸附床高度增加，穿透时间延长；而随着苯胺初始浓度、流速和pH值的增大，穿透时间急剧缩短。BDST模型能够准确地预测新的操作条件下的穿透时间，误差均〈5％；Thomas模型能够很好地描述麦草对苯胺的动态吸附动力学，由Thomas模型获得的麦草吸附柱对苯胺的动态吸附量与实验值相符。对吸附饱和后的麦草可用0．6mol／L盐酸进行解吸。     

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。     

粉状褐煤对水中草甘膦的动态吸附

采集内蒙霍林河煤矿褐煤样品,加工成粒径0.38~0.83 mm作为吸附剂,对模拟草甘膦废水进行动态吸附实验。考察了吸附柱高(3、5和10 cm)、草甘膦初始浓度(0.5%、0.75%和1.0%)、流速(1、2和3 m L/min)、pH(9、11和13)和离子强度(IS,0.001、0.01和0.1 mol/L)对草甘膦的吸附穿透曲线和传质区长度的影响。实验结果表明,降低柱高、增大初始浓度、提高流速、增加离子强度均会使穿透时间提前,pH变化对穿透时间影响很小;柱高、初始浓度、流速、IS和pH引起的传质区长度的平均变化率绝对值分别为0.675、6.300、1.625、47.727和0.263,可见,与柱高、初始浓度和流速相比,IS对传质区长度的影响较大,pH影响较小。低浓度条件下,吸附穿透曲线的实验数据符合BDST模型拟合条件(R20.99),在仅改变柱高或流速时,穿透时间理论值与实测值的最大误差均为5.71%,运用该模型能够准确地预测褐煤吸附柱的操作时间。     

涂铁多孔陶瓷对水中亚甲基蓝的动态吸附

研究了涂铁多孔陶瓷填料柱对水中亚甲基蓝（MB）的动态吸附性能。探讨了填料高度、MB初始质量浓度和流速对穿透曲线的影响；分别用BDST模型、Thomas模型和线性回归对动态吸附实验数据拟合，获得了相关参数，并研究了填料的再生性能。结果表明，涂铁多孔陶瓷（IOCPC）能有效去除水中MB，填料层升高，穿透曲线上的穿透点向右移动，穿透时间延长；而随流速、MB初始质量浓度的增大，穿透曲线上的穿透点向左移动，穿透时间缩短。用BDST模型能准确预测穿透时间，误差＜5%；用Thomas模型可较好地描述了MB浓度为10和50 mg/L、初速为2 mL/min时IOCPC对MB的吸附动力学，相关系数分别为0.99和0.93，平衡吸附容量分别为0.078和0.13 mg/g。对吸附饱和后的涂铁多孔陶瓷可用pH=3的硝酸再生，重复使用3次穿透曲线上的穿透点基本不变。     

聚甲醛单宁酸树脂对水体中苯胺的动态吸附研究

以单宁酸为原料,甲醛为交联剂制备了聚甲醛单宁酸树脂(PFTR),利用扫描电子显微镜和氮吸附仪对其表面孔径进行了表征和分析,并对模拟废水中的苯胺浓度进行了动态吸附性能研究,采用Thomas、Yoon-Nelson和BDST 3种模型对实验数据进行拟合分析,探讨PFTR对苯胺的吸附性能和原理。结果表明,PFTR表面含有丰富的孔状结构,能有效吸附水体中的苯胺。当PFTR用量为0.1g,吸附柱填充高度为1cm,流速为0.1cm/min,苯胺初始质量浓度为1 000~2 500mg/L时,其穿透时间随苯胺初始浓度的增大而提前。Thomas模型可较好地估算饱和吸附量,Yoon-Nelson和BDST模型能预测穿透时间。     

血粉对废水中镉离子的高效去除效应

以屠宰场废弃动物血液为原料,经高温干燥、粉碎为血粉,以此血粉为吸附剂,研究血粉添加量、溶液初始浓度、吸附温度、溶液pH、吸附时间对废水中Cd2+吸附量与去除率的影响。结果表明,在25℃、pH=5时,4 g血粉对初始浓度为20mg·L~(-1)的镉离子溶液(100 m L)振荡吸附2 h后,溶液中剩余镉离子浓度为0.1 mg·L~(-1),Cd2+的去除率为99.38%,达到污水综合排放标准(GB 8978-1996)中镉排放限值0.1 mg·L~(-1);血粉对镉离子的吸附反应符合Langmuir等温吸附方程,可决系数为0.999 7,Cd2+的理论饱和吸附量为10.24 mg·g-1。为了使剩余Cd2+浓度达到更低(电镀废水排放标准),在吸附工艺上设计出2步吸附法,即第1次吸附后的混合液进行过滤,再将滤液加1 g血粉进行第2次吸附。结果表明,2步吸附法大大降低了溶液中剩余Cd2+离子浓度,即经过第1步、第2步吸附后,溶液中剩余Cd2+离子浓度降至0.006 mg·L~(-1),达到或低于电镀污染物排放标准(GB 21900-2008)对Cd2+的排放限值(0.05 mg·L~(-1))。这是常规吸附剂活性炭、石英砂、高岭土等所不能达到的技术指标,为废水去除Cd2+提供了一种可能的新技术。     

高比表面积活性炭的制备及对Cr(Ⅵ)吸附的研究

以椰树壳为原料,运用水蒸汽和二氧化碳复合物理活化法在4 h内制备了2 162.84 m2/g的高比表面积活性炭,其孔径分布范围为1.1~2.5 nm。应用此吸附剂考察了溶液pH、吸附剂用量、接触时间和初始浓度对Cr(VI)离子吸附效果的影响,并讨论了固定吸附床中不同溶液流量对Cr(VI)去除效果的影响。结果表明:在温度为298 K、溶液pH为1.96、吸附剂用量为0.10 g、铬离子初始浓度为100 mg/L与接触时间为70 min的条件下,活性炭对铬离子具有较高的吸附容量,去除率高达99.32%;铬离子在吸附床中的穿透曲线具有陡峭的传质锋面,但随着铬离子溶液流量的增大脱除果率降低。     

粉煤灰对模拟河流中DMP的动态吸附

针对污染物泄露导致的河流污染问题,以邻苯二甲酸二甲酯(DMP)为研究对象,以粉煤灰作为吸附剂、有机玻璃反应槽作为反应装置,向其持续注入初始浓度相同的DMP溶液,将其所得实验数据拟合Logistic穿透模型,研究模拟河流条件下,粉煤灰对DMP的动态吸附规律;同时,分析了水流速度、DMP初始浓度及吸附剂投加方式3种因素对粉煤灰去除DMP性能的影响。结果表明:Logistic穿透模型能较好地拟合河流中粉煤灰动态吸附DMP的过程;提高溶液的进水流速,污染物更容易穿透吸附剂表面,单位时间内的最大吸附量由17.81μg·g~(-1)增加至27.78μg·g~(-1),最大去除率由35.63%升高至55.57%,穿透时间提前;随着DMP溶液初始浓度的增加,粉煤灰与DMP分子之间的浓度差增大,相同时间内与粉煤灰接触的DMP污染物增多,达到饱和的时间由131 min缩短至119 min,穿透曲线上的穿透点左移,粉煤灰的吸附性能提高;将粉煤灰全部平铺在槽体底部时,吸附质能够充分地与其接触,传质阻力减小,吸附速率常数由0.003 9提高至0.004 7,粉煤灰的吸附率升高。该研究可为河流突发性污染的应急处理提供一定理论依据。     

磁性活性炭处理含铜废水

利用自制磁性活性炭对水中Cu(Ⅱ)的去除进行静态吸附研究,考察了吸附时间、Cu(Ⅱ)初始浓度以及磁性活性炭投加量对铜离子去除率的影响。结果表明,磁性活性炭投加量为3 g/L时,对铜离子的去除率达92.6%;磁性活性炭对铜离子的吸附在最初的20 min是一个快速吸附,去除率达到总去除率的90%以上;随着Cu(Ⅱ)初始浓度的增大,Cu(Ⅱ)的去除率逐渐减小,磁性活性炭吸附铜离子可用Langmuir吸附等温式和Freundlich方程描述;利用磁铁对溶液中磁性活性炭进行回收,回收率达到87%。     

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.