用H2O2/Fe3+处理高浓度含甲醛废水的研究

研究采用H₂O₂/Fe³⁺催化氧化处理高浓度含甲醛废水,探讨了双氧水和催化剂投加量、反应pH及反应温度等操作条件对处理效果的影响,并通过酸溶解回用失活催化剂。结果表明,较优的操作条件为：H₂O₂/COD（质量比）=2.2～2.6,Fe³⁺/H₂O₂（摩尔比）=0.048～0.058,反应pH 1.80～2.68,反应温度50℃,反应时间40 min;在上述操作条件下,甲醛去除率达到99%以上,COD去除率达到85%以上。失活的催化剂可通过稀酸溶解后循环使用,其效果与三价铁盐作催化剂的基本相同。采用H₂O₂/Fe³⁺处理含甲醛废水具有比采用H₂O₂/Fe³⁺较优的效果。     

光助Ce-Fe/Al2O3催化H2O2降解阳离子红GTL模拟废水

利用Ce-Fe/Al₂O₃为催化剂的非均相光Fenton体系降解阳离子红GTL模拟废水，考察了H₂O₂浓度、催化剂用量、初始pH值及不同工艺过程对降解效果的影响，通过紫外-可见漫反射光谱、红外光谱、XPS手段研究铁在反应中的价态变化。结果表明，在11 W低压汞灯照射下，非均相光Fenton体系能够有效地降解结构稳定的阳离子红GTL，在pH 6，反应温度20℃，时间90 min，Ce-Fe/Al₂O₃ 2 g/L，H₂O₂浓度340 mg/L，含50 mg/L阳离子红GTL模拟废水TOC去除率为92.40%；光Fenton反应中Fe(Ⅲ)转化为Fe(Ⅱ)。     

O3/H2O2降解阿特拉津影响因素研究

采用O3/H2O2氧化去除水中内分泌干扰物阿特拉津,考察了反应条件及水质对去除的影响,并对反应机制进行了初步探讨。阿特拉津初始浓度2 mg/L,投量为7.5 mg/L的O₃单独氧化去除率为27.2%;相同O₃投量下,控制H₂O₂/O₃摩尔比为0.75,5 min阿特拉津的去除率最高可达96.5%;pH 值为7.5～8.5,温度在25～40℃的范围内,都维持了较高的去除率,表明H₂O₂/O₃体系对阿特拉津的去除效果良好,降解速度快,反应条件温和。0.5 mg/L的腐殖酸,对阿特拉津的去除影响不大,腐殖酸浓度为1、2和5 mg/L时,平均去除率分别为63.4%、50.7%和30.2%;碳酸氢钠的浓度为50和200 mg/L时,去除率分别为88.1%和73.8%,说明水质对阿特拉津的去除影响较大。叔丁醇的浓度为5和20 mg/L时,阿特拉津的去除率分别降低到44.7%和27.5%,去除率随自由基抑制剂叔丁醇增加而降低,说明H₂O₂/O₃降解阿特拉津主要为该体系产生的羟基自由基的贡献。     

Fe/活性炭多相类Fenton法湿式氧化罗丹明B废水的研究

采用自制的Fe/活性炭（Fe/AC）为催化剂,H₂O₂为氧化剂,组成多相类Fenton试剂催化降解罗丹明B染料废水。实验结果表明,在催化剂加入量为0.8 g/L,H₂O₂体积分数为0.3%,废水pH值为13,反应时间为30 min的条件下,质量浓度为200 mg/L的罗丹明B染料废水的脱色率达100%。反应动力学研究表明,罗丹明B脱色反应近似为一级反应,30℃时反应速率常数为0.02675 min^-1,表观活化能为69.47 kJ/mol。     

CuCoOx/TiO2催化氧化NO性能研究

采用浸渍法制备了CuCoOx/TiO₂催化剂,考察了焙烧温度、反应温度、氧含量、NO浓度和空间速度对催化剂催化氧化NO性能的影响,并考察了催化剂的抗硫抗水性能。XRD、TPR和BET分析表明,350℃焙烧的催化剂具有CuCo₂O₄尖晶石结构,比表面积大,对NO的氧化效果好。在空速为5 000 h^-1,NO进口浓度500 mg/m³,含氧量10%的条件下,反应温度300℃时NO转化率可达79.5%,250℃时NO转化率接近50%。该催化剂具有良好的单独抗SO₂、抗H₂O毒化性能,H₂O和SO₂同时存在时很快失活。该催化剂可用于不同时含H₂O和SO₂的含NO气体催化氧化后再吸收处理。     

微气泡曝气 O3/ H2O2处理 RO 浓水的效能及影响因素简

采用O₃/H₂O₂高级氧化工艺处理炼油厂反渗透（RO）浓水,用溶气泵加压溶气并产生微气泡强化传质,确定装置运行条件,考察气体中臭氧浓度、H₂O₂/O₃初始摩尔比、pH和温度对O₃/H₂O₂处理RO浓水效果的影响,并对RO浓水处理效能进行研究。结果表明,随着气体中臭氧浓度的增加,COD的去除率基本呈线性增加;加入适当量H₂O₂能提高臭氧氧化RO浓水的效果,H₂O₂/O₃初始摩尔比在0~0.8范围内,COD的去除率先增加后下降,H₂O₂/O₃初始摩尔比为0.5时COD去除率最大;pH从6.84增加到9.01,COD去除率逐渐增大,pH为10.03时COD去除率反而降低;在14~28℃范围内,温度低时,升高温度COD去除率增加较大,温度较高时,升高温度对COD去除率的影响较小。为考察该工艺的稳定性,在H₂O₂/O₃初始摩尔比为0.5、溶液pH为8~9、臭氧浓度为80~100 mg/L、温度为10~28℃条件下,对COD为90~140 mg/L的RO浓水氧化处理4~10 h,出水COD维持在39.9~49.9 mg/L,达到《城镇污水处理厂污染物排放标准（GB 18918-2002）》中的一级A标准;去除1 g COD消耗O₃ 1.4~3.3 g,消耗O₃与H₂O₂的总氧量为2.2~4.4 g。     

Fenton氧化破解污水处理厂污泥

研究了Fenton氧化反应的影响因素pH值、H₂O₂/Fe²⁺投加比、反应温度和反应时间对污泥破解效果的影响,并以污泥上清液中蛋白质、糖类、SCOD及污泥TSS、VSS的变化来表征污泥破解的程度。结果表明,最佳破解条件为：pH=5,最佳H₂O₂/Fe²⁺投加比为24：1,反应温度为70℃,反应时间为90 min,在该条件下,SCOD、溶解性蛋白质和多糖分别由88.76、19.70和14.95 mg/L增加到3 714.64、2 039.90和289.70 mg/L;TSS及VSS分别由34.60 g/L、19.76 g/L降为26.60 g/L、14.22 g/L,去除率分别为23.12%和 28.14%。Fenton氧化破解污泥,能够有效促进污泥絮体分解,有利于进行后续的厌氧消化处理。     

UV-Fenton光催化氧化处理高浓度邻苯二甲酸二辛酯生产废水

采用UV-Fenton技术光催化氧化高浓度邻苯二甲酸二辛酯（DOP）生产废水，确定最佳操作条件为：初始pH=3.8，H₂O₂浓度为9.99 g/L，H₂O₂/Fe²⁺摩尔比为20∶1，光照反应60 min。此条件下的废水COD去除率为89.1%，出水COD值在570 mg/L左右。经正交试验确定影响处理效果各因素的重要性顺序为：H₂O₂浓度＞H₂O₂/Fe²⁺摩尔比＞光照反应时间＞pH。UV的加入与单独的Fenton体系存在正相关的协同作用。废水降解的表观过程符合一级反应动力学模式。     

微波促进含Cr(VI)-H2O2体系降解甲基橙溶液的研究

研究了微波辐射下Cr(VI)－H₂O₂催化降解甲基橙溶液的行为，探索了微波功率、微波辐射时间、pH值、H₂O₂浓度、Cr(VI)等对甲基橙溶液脱色率和COD去除率的影响。研究结果表明，Cr(VI)-H₂O₂能形成类Fenton体系；微波辐射可提高H₂O₂产生羟基自由基(·OH)的效率。1000 mg/L的甲基橙溶液，在Cr(VI)浓度为10.0 mmol/L、pH值为2.5、H₂O₂浓度为20.0 mmol/L、微波功率为700W下加热2 min，甲基橙溶液的脱色率为99.2%，COD去除率为82.8%。     

不同高级氧化法对水中低浓度药物甲硝唑降解过程的比较

采用UV、H₂O₂、UV/H₂O₂、Fenton、UV/Fenton和UV/TiO₂方法,对水中低浓度的药物甲硝唑进行降解。通过HPLC和UV-Vis光谱得到的甲硝唑去除率。详细讨论了Fe²⁺、TiO₂和H₂O₂的初始浓度以及溶液的初始pH值对降解效率的影响。结果表明,UV/Fenton和UV/TiO₂ 2种系统对水中低浓度甲硝唑均有很好的去除效果,但前者的光催化效率更高。在甲硝唑浓度=6 μmol/L,H₂O₂和Fe²⁺的初始浓度分别为0.5 mg/L和2.94 μmol/L,pH=4的条件下,UV/Fenton方法对甲硝唑水溶液光催化的最佳效率为95.8%。     

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.