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240℃，氧气分压3.0MPa，催化剂用量30g/L，此时废水的COD法除率达到90％以上。     

催化臭氧氧化降解糖蜜酒精废水的研究

以SnO2为催化剂,研究糖蜜酒精废水在臭氧条件下的氧化降解反应,为糖蜜酒精废水的治理提供一种新的处理方法.研究表明,SnO2加速了臭氧氧化反应,使糖蜜酒精废水的氧化降解加快.影响糖蜜酒精废水氧化降解的主要因素有臭氧流量、废水的初始pH和催化剂用量等.加大臭氧流量及增加催化剂用量,均有利于糖蜜酒精废水的降解.适宜的反应条件是:糖蜜酒精废水的稀释倍数为10倍,臭氧流量为130 mg/h,催化剂用量为2.500 g/L,废水的初始pH为4.25,温度为30 ℃.在该条件下反应60 min,废水的脱色率为60.2%,COD去除率为44.5%.动力学分析表明,单独臭氧氧化降解糖蜜酒精废水和SnO2催化臭氧氧化降解糖蜜酒精废水均为拟一级反应.     

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。     

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、γ-Al2O3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／γ-Al2O3（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10g／L为佳；在300℃下反应30min或在280℃下反应60min,处理水可达到污水综合排放标准GB9878—1996的三级标准。     

H2O2处理酸性大红GR染料废水的研究

通过对废水pH值、H2O2用量、催化剂用量、反应时间、反应温度等工艺条件的考察,确定了H2O2催化氧化处理酸性大红染料废水的最佳工艺条件pH 4、H2O2用量6 mL/L、催化剂用量3 g/L、反应时间100 min、反应温度70℃.在该条件下,COD和色度的去除率分别为76.7%和99.4%;通过反应前后的紫外-可见光光谱分析表明,H2O2催化氧化处理酸性大红GR染料废水有比较好的效果,为该工艺处理酸性大红GR染料废水提供了科学依据.     

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.     

H2O2处理酸性大红GR染料废水的研究

通过对废水pH值、H2O2用量、催化剂用量、反应时间、反应温度等工艺条件的考察，确定了H2O2催化氧化处理酸性大红染料废水的最佳工艺条件：pH4、H2O2用量6mL／L、催化剂用量3g／L、反应时间100min、反应温度70℃。在该条件下，c0D和色度的去除率分别为76．7％和99．4％；通过反应前后的紫外一可见光光谱分析表明，H2O2催化氧化处理酸性大红GR染料废水有比较好的效果，为该工艺处理酸性大红GR染料废水提供了科学依据。     

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.     

光催化氧化处理有机废水

介绍了光催化氧化法的原理,对光催化氧化法处理有机废水的可行性进行了试验,探讨了ＣＯＤ随反应时间的变化规律及催化剂用量,温度、浓度的影响。试验表明,光催化氧化可降解象洗涤剂这样难降解的有机物,反应１２０ｍｉｎＣＯＤ去除率可达５０％以上。     

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.