催化湿式氧化农药废水及催化剂的研究

通过浸渍法制备了4种氧化物为主活性组分的负载固定型催化剂，用于过氧化氢催化湿式氧化（CWHPO）处理有机农药废水。用实验确定了催化湿式氧化的条件，不同催化剂处理效果的比较表明，四元组合MnO2-CuO-CeO2-CoO催化剂性能较好，当反应在常温常压下，维持pH=7～9，反应时间为40min时，COD的去除率大于80％，色度去除率大于90％。     

催化湿式氧化处理高含硫废水的研究

利用催化湿式氧化法对一高含硫废水的处理效果进行了系统的研究。筛选出适合处理该种废水的WH型合金催化剂 ,并在此催化剂上考察了反应温度、压力、空速以及气水比 (体积 )等工艺条件对废水处理效果的影响 ,同时考察了废水在催化湿式氧化反应处理前后可生化性的变化。在 2 6 5℃、7.0MPa、空速 =1.0h- 1 、气 H2 O(体积 ) =2 0 0条件下 ,废水COD去除率可达到 77.1%。经过催化湿式氧化处理后 ,废水的BOD5 CODCr值显著提高 ,其值由 0 .0 16提高至 0 .6 4 ,可生化性良好     

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%.     

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%.     

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。     

催化湿式氧化处理高含硫废水的研究

利用催化湿式氧化法对一高含硫废水的处理效果进行了系统的研究。筛选出适合处理该种废水的WH型合金催化剂，并在此催化剂上考察了反应温度、压力、空速以及气水比(体积)等工艺条件对废水处理效果的影响，同时考察了废水在催化湿式氧化反应处理前后可生化性的变化。在265℃、7．0MPa、空速＝1．0h^-1、气／H2O(体积)＝200条件下，废水COD去除率可达到77．1％。经过催化湿式氧化处理后，废水的BOD5／CODcr值显著提高，其值由0．016提高至0．64,可生化性良好。     

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。     

陶瓷-活性炭球为载体的CWAO催化剂

以陶瓷-活性炭球为载体制备载Ru催化剂,用于催化湿式氧化(CWAO)法处理酚醛树脂废水,考察了陶瓷-活性炭球载体、Ru负载量和陶瓷球宏孔孔径等对催化剂的催化活性和稳定性的影响。实验结果表明,催化剂催化活性的顺序为:Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>无催化剂。在200℃,氧气分压为1.5 MPa等条件下,催化湿式氧化酚醛树脂废水,3%Ru/KC-120催化剂表现良好的催化活性与稳定性,在120 min内,COD和苯酚去除率分别达到91%和96%。     

湿式双氧水氧化处理染料中间体H-酸钠盐溶液的研究

在0.5 L压力反应器内,对染料中间体H-酸钠盐溶液进行湿式双氧水氧化(WPO)及湿式双氧水催化氧化(CWPO)降解处理.分别考察反应时间、双氧水用量、温度、进水pH值和催化剂等对反应过程与对象污染物降解的影响规律.结果表明,WPO能在温和的条件下降解难于生物降解的有机物,在温度为110℃、压力为0.5 MPa、双氧水用量为理论需用量、进水pH=5的条件下,处理含10 g/L H-酸钠盐的H-酸盐溶液的COD和色度去除率分别为62.0%和98.7%;采用非均相Cu/Ni复合催化剂,在同样操作条件下,CWPO对同一废水的COD和色度去除率分别可达到92.0%和99.9%.表明催化剂的存在大大提高了WPO的氧化效果.     

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.     

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.