贵金属催化剂活性组分分布对催化湿式氧化处理非达霉素提炼废水的影响

采用均匀型和蛋白型Ru/TiO_2催化剂为湿式氧化催化剂,应用于催化湿式氧化非达霉素提炼废水,以出水COD和TOC去除率作为指标来评价2种催化剂的催化活性差异;采用实验室连续评价装置对柱状颗粒催化剂在不同pH、不同废水流量和不同温度下处理非达霉素提炼废水进行了优化评价。结果表明:在265℃、pH=4.1、废水流量为10 mL·h~(-1)时,催化剂的催化活性最高,故确定此条件为该废水处理的最优条件;同时对比均匀型和蛋白型2种催化剂,蛋白型催化剂具有更高的催化效率;结合SEM及N_(2~-)物理吸附结果,推断蛋白型催化剂活性组分集中分布在催化剂颗粒的较浅层,有利于降低反应过程中的扩散阻力,提高贵金属活性组分的利用率,进而提高催化剂的催化活性。以上结果对开发高效湿式氧化催化剂,充分利用贵金属活性组分降低催化剂成本具有十分重要的意义。     

催化湿式氧化吡虫啉农药废水催化剂的研究

通过共沉淀法制备了用于湿式氧化吡虫啉农药废水的Cu/Mn复合氧化物催化剂,研究了沉淀剂种类、沉淀温度、焙烧温度和活性组分配比等因素等对Cu/Mn复合氧化物催化剂的活性及稳定性的影响,确定了最佳制备条件,利用BET比表面积测定和XRD对催化剂进行了表征.结果表明,优化条件制备的Cu/Mn复合氧化物催化剂催化湿式氧化处理吡虫啉农药废水时,具有较高的催化活性和稳定性.催化剂用量4 g/L,反应温度190℃,氧分压1.6 MPa,反应120 min,COD去除率为92.3%,活性组分溶出量较小.     

催化湿式氧化中负载型催化剂的稳定性与应用

催化剂在应用过程中必须具有良好的催化活性和稳定性.优化制备的CuO/γ-Al2O3催化剂用于处理高浓度难降解的乳化液废水时具有良好的催化活性,在200℃时反应2 h,TOC去除率为81.3%,比未加催化剂的湿式氧化提高了14.9%.该催化剂对分散兰废水具有更高的活性和稳定性:在220℃反应1.5 h后,COD和TOC去除率分别为68.8%和56.5%,比非催化氧化分别提高了18.7%和18.9%.     

催化湿式氧化法处理吡虫啉农药废水的优化工艺条件

采用催化湿式氧化技术在2 L高压反应釜中处理吡虫啉农药废水,分别以复合金属氧化物Cu/Mn、Cu/Ce、Ce/Mn及Ce/Ag为催化剂来考察对废水COD去除率的影响.发现Cu/Ce、Ce/Mn、Cu/Mn催化剂有较高的催化活性;Ce/Mn催化剂最稳定;Ce/Ag催化剂的Ag溶出量很大.选用性能良好的Ce/Mn催化剂,考察了反应温度、反应压力和废水的初始pH对催化湿式氧化效果的影响.结果表明,催化剂的加入可使COD去除率提高37%左右,同时处理后废水的BOD5/COD从0.19提高到0.65以上;当反应温度为150～230 ℃时,处理效率随温度升高明显增加;总压4.8 MPa、氧分压1.2～2.4 MPa时,适当增加氧分压亦能提高氧化效率;废水初始pH对氧化效果影响不大,但对催化剂的稳定性有影响.优化工艺条件最终为:催化剂为Ce/Mn;温度190 ℃;氧分压1.6 MPa;进水pH为6.21;反应时间120 min.     

催化湿式氧化法处理糖蜜酒精废液的研究

以非贵金属Cu、Fe、Mn和Ce为主要活性成分和TiO2、-γA l2O3为载体,制备了10种用于催化湿式氧化法处理糖蜜酒精废液的催化剂。考察了载体、焙烧温度、成分配比对催化剂催化活性与稳定性的影响,研究了氧气分压、催化剂投加量、反应温度和反应时间对催化湿式氧化过程的影响规律。结果表明:(1)Fe-Mn/-γA l2O3(3∶1∶1)催化剂是催化湿式氧化法处理糖蜜酒精废液的可选催化剂;(2)适宜的氧气供应量为理论需氧量的3.4~4.6倍,催化剂的投加量以10 g/L为佳;在300℃下反应30 m in或在280℃下反应60 m in,处理水可达到污水综合排放标准GB9878-1996的三级标准。     

用于CWPO处理渗滤液的Cu/AC催化剂的制备及性能

采用浸渍法制备Cu负载型活性炭催化剂,运用该催化剂催化湿式氧化(CWPO)处理转运站垃圾渗滤液,以出水COD去除率为指标检测催化剂活性和稳定性。实验考察焙烧温度、焙烧时间、浸渍浓度3个因素对催化活性的影响,并对催化剂进行XRD和BET表征。结果表明:当焙烧温度为400℃,焙烧时间2 h,浸渍浓度0.4 mol·L~(-1)时,催化效率最高,渗滤液COD去除率为89.9%。紫外光谱和三维荧光光谱的结果表明,用所制备的Cu负载型活性炭催化湿式氧化垃圾渗滤液,可以较好地除去垃圾渗滤液中的难降解有机物。催化剂的重复利用实验表明该催化剂稳定性良好。     

催化湿式过氧化法处理蒽醌-2-磺酸钠废水

以过渡金属Cu为主活性组分,通过加入第2活性组分Mn和稀土元素Ce,研制出适用于催化湿式过氧化法(CWPO)处理含高浓度蒽醌-2-磺酸钠有机废水的复合催化剂。考察了活性组分配比对催化剂的催化活性和稳定性的影响,并利用SEM和XRD表征手段,研究了掺杂Ce对催化剂表面微观结构的影响。结果表明,当Cu、Mn和Ce的质量比为-时,催化剂的催化性能最佳,在100 min内,废水COD的去除率能达到95.3%;掺杂Ce能有效提高活性组分在催化剂表面的分散程度从而改善催化剂的催化活性,并能有效抑制Cu的溶出。通过LC-MS分析该催化剂催化氧化蒽醌-2-磺酸钠降解过程中的代谢产物,推断出了催化氧化降解蒽醌-2-磺酸钠的途径。     

稀土系列催化剂对焦化废水的催化湿式氧化

以稀土元素Ce制得催化剂系列 ,在高温、高压条件下对焦化废水进行催化湿式氧化研究 ,考察载体、焙烧温度、活性组分的配比对催化剂的催化活性的影响 ,以及反应温度、氧气分压、反应时间和催化剂用量对氧化过程的影响 ,设计正交实验确定最佳的工艺参数 :反应温度为 2 40℃、氧气分压 3 .0MPa ,催化剂用量 30g/L ,此时废水的COD去除率达到90 %以上     

催化湿式氧化技术处理山梨酸生产废水的研究

采用催化湿式氧化技术处理生产山梨酸过程中产生的高浓度有机废水,对催化剂组分进行优选.对反应温度、O2分压(Po2)和废水pH等工艺条件进行考察.实验结果表明:采用自制CuO-Cr2O3-La2O3/TiO2为复合催化剂处理该有机废水时表现出较好的催化活性;在190℃、Po2=2.1 MPa、pH=6.1、COD=10 030.0 mg/L时,反应90 min的COD去除率达到98.3%,而在相同条件下未加催化剂的湿式氧化的COD去除率只有60.1%.     

用于催化降解烷基苯磺酸钠的Cu-C催化剂的制备及性能分析

Cu-C是一种优化制备的负载型催化剂,实验中以其催化湿式氧化处理高浓度LAS废水。本实验用浸渍法和附着沉淀法制备该催化剂,并考察了反应时间、反应温度、溶液浓度、催化剂的投加量以及不同的制备方法等对催化剂性能的影响,以水样COD和LAS的去除率来评价催化剂的活性。实验结果表明,该方法制备的催化剂具有很好的处理高浓度LAS废水的能力;当反应温度为50℃,反应时间为120 min,催化剂的投加量为2 g时,催化剂的催化效果最好,COD去除率为79.76%,LAS去除率为88.28%。并且,当活性炭与催化剂的振荡吸附时间超过20 min时,活性炭的吸附对废水中LAS的去除基本上无影响。     

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.