载Ca磁性碳纳米管对水中腐殖酸的去除

采用化学共沉淀一步法以钙盐和铁盐对多壁碳纳米管(MWCNTs)改性以制备具有去除水中微污染物腐殖酸的磁性碳纳米管复合材料。X射线能谱分析表明改性MWCNTs上载有Ca和Fe元素。通过振动样品磁强计测得该复合材料具有较强磁性。改性后的MWCNTs 30 min对水中腐殖酸的去除率由改性前的63.89%提高到90.27%。研究了改性MWCNTs投加量、腐殖酸初始浓度、吸附时间、振荡速度、pH及温度对水中腐殖酸去除的影响。结果表明,腐殖酸去除率随着载Ca磁性MWCNTs投加量增大而提高。吸附量随着腐殖酸初始浓度的增大而增加,但去除率却减小。吸附初期腐殖酸去除速率快,0.5 g·L~(-1)的载Ca磁性多壁碳纳米管在腐殖酸初始浓度为20 mg·L~(-1)时,5 h达到吸附平衡,平衡吸附量为39.41mg·g~(-1)。腐殖酸去除率随着振荡速度的增大而增大,在225 r·min~(-1)时达最大,随后随着振荡速度的增大而缓慢下降。在弱酸性下,腐殖酸去除率较高,当pH为5时,腐殖酸去除率达到92.24%;当pH5时,酸性加强,腐殖酸去除率下降;当pH5时,腐殖酸去除率随pH增大呈下降趋势。腐殖酸去除率随着温度的升高而降低。     

海泡石改性及在酱油废水处理中的应用研究

通过正交实验对海泡石改性条件及在酱油废水处理中的应用进行了实验研究。结果表明,酸度是海泡石改性的主要影响因素,海泡石在酸度4%,温度120℃,时间12 h下改性,对酱油废水的脱色效果较好;当酱油废水浓度为1 033 mg/L,改性海泡石投加量为3 g(液固比70∶1),pH5,反应时间90 min,改性海泡石对废水COD和色度的去除率分别达到59.6%和76.4%。     

包覆型纳米零价铁的制备及其去除水中的活性艳蓝

采用流变相法,以FeSO4.7H2O∶KBH4=1∶2(摩尔比)为固相介质,0.06 g/mL CMC(羧甲基纤维素)水溶液为液相介质,固液比1∶2,反应2 h制备出包覆型纳米零价铁;采用XRD、TEM等手段对合成的纳米零价铁进行表征。探讨不同反应条件对包覆型纳米铁去除活性艳蓝的影响。实验结果表明,初始活性艳蓝(浓度100 mg/L)pH为5,包覆型纳米铁的投加量为6 g/L,反应时间为30 min时,活性艳蓝的去除率可达96%。通过研究机理,其吸附过程符合二级吸附动力学,降解过程符合一级反应动力学。     

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。     

骨炭对Pb(Ⅱ)的吸附特性

通过间歇实验研究了骨炭对重金属Pb(Ⅱ)的吸附特性。探讨了固液比、pH、离子强度、反应时间、温度及初始浓度等因素的影响。实验结果表明,pH与固液比显著影响去除率,温度与离子强度的影响较小。当温度为20℃,pH=2.5,Pb(Ⅱ)的初始浓度为200 mg/L,固液比为1 g/L时,最大去除率近100%。动力学实验结果表明,骨炭对Pb(Ⅱ)的吸附为快速反应,在30 min内可达到平衡,准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。骨炭对Pb(Ⅱ)的吸附机制主要为表面络合反应与分解置换-沉淀反应。     

铁炭复配修复地下水中NO3^--N的条件研究

采用了铁炭复配修复地下水中NO3^--N,探讨了实验条件对修复效果的影响。结果表明,在pH值近中性条件（初始pH 6.42）下,反应时间为1 h时NO3^--N修复率达到60.85%;Fe/C=1∶1时介质最佳用量分别为45 g;Fe/C=1/1.5时修复率为72.80%;反应速率在高振荡强度下大于低振荡强度;氧化铜的催化效果最好,可使修复率提高7.5个百分点。铁炭复配介质修复地下水中NO3^--N是有效可行的,修复率随反应时间的增加而提高,在Fe/C=1∶1时修复率与介质用量呈正相关,无限减小Fe/C比并不能无限提高修复率,振荡强度对修复具有显著影响,低振荡强度下的修复过程较高强度存在滞后现象,并非所有金属氧化物催化剂对铁炭修复NO3--N均有促进作用。     

铁炭复配修复地下水中NO_3~--N的条件研究

采用了铁炭复配修复地下水中NO3--N,探讨了实验条件对修复效果的影响。结果表明,在pH值近中性条件(初始pH 6.42)下,反应时间为1 h时NO3--N修复率达到60.85%;Fe/C=1∶1时介质最佳用量分别为4~5 g;Fe/C=1/1.5时修复率为72.80%;反应速率在高振荡强度下大于低振荡强度;氧化铜的催化效果最好,可使修复率提高7.5个百分点。铁炭复配介质修复地下水中NO3--N是有效可行的,修复率随反应时间的增加而提高,在Fe/C=1∶1时修复率与介质用量呈正相关,无限减小Fe/C比并不能无限提高修复率,振荡强度对修复具有显著影响,低振荡强度下的修复过程较高强度存在滞后现象,并非所有金属氧化物催化剂对铁炭修复NO3--N均有促进作用。     

油泥制备除油吸附剂

以油泥为原料,采用ZnCl_2活化法制备吸附剂,吸附处理水中的油类物质。研究了制备油泥吸附剂过程中活化剂ZnCl_2溶液浓度、固液体积比、活化温度、活化时间对吸附剂性能的影响,并对吸附剂比表面积和孔隙分布进行了分析。确定了技术经济性最佳的制备条件为ZnCl_2溶液浓度5.0 mol·L~(-1),固液体积比1∶1.5,活化时间2.0 h,活化温度450℃,吸附剂BET比表面积为316.088 2 m~2·g~(-1),对水中油类污染物质去除率为94.61%。     

接触氧化过滤去除地表水中的氨氮

接触氧化过滤工艺普遍用于去除地下水中的氨氮,在去除地表水中氨氮的应用较少。为了对此工艺去除地表水中的氨氮进行研究,以附有铁锰氧化物的石英砂为滤料填充滤柱,测试了滤柱对地表水中的铁、锰和氨氮的去除效果,并重点分析了影响氨氮去除的主要因素。结果表明:当滤速为8 m·h-1,进水铁、锰、氨氮浓度分别为0.6、1.1和1.8 mg·L~(-1)时,滤柱对3种污染物的去除率分别为83.3%,95.3%和80.6%,3种污染物的出水浓度均达标。此外,升高进水温度、提高进水碱度可增大氨氮的去除率。当温度由8℃增大到14℃时,氨氮去除率提高了近一倍。进水投加NaOH(浓度为4mg·L~(-1))时,氨氮的平均去除率比不投加NaOH时高23.1%。     

改性蔗渣焚烧灰去除糖蜜酒精废液中硫酸根

以改性蔗渣灰(MBA)为吸附剂,通过单因素实验,等温吸附模型拟合实验和正交实验,探讨了MBA去除糖蜜酒精废液的高浓度硫酸根离子的实验条件。结果表明,当MBA粒径60目,投加量为3 g·(25 m L)~(-1),反应温度45℃,pH为4.2,反应时间50 min时,溶液中的硫酸盐去除效果最优。等温吸附模型拟合结果表明,Langmuir模型更适合拟合该过程,MBA去除硫酸根离的反应为单分子层吸附。正交实验次优反应条件可以确定为:废液浓度为稀释15倍,MBA投加量3.0 g·(25 m L)~(-1),MBA粒径80目,反应时间1 h,反应温度为35℃。经验证,硫酸根离子的去除率达到88.86%。     

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.     

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.     

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 in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

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.