磷石膏预分解的热分析研究

采用热分析的方法对磷石膏在不同掺碳量、不同气氛条件下的热反应过程进行了研究,针对近年来提出的利用水泥新型干法技术实现磷石膏预分解制硫酸联产水泥的设想,研究了磷石膏的热分解过程对预热分解炉的适应性。结果表明,在碳与磷石膏的混合体系中,碳仅能在一定程度上促进磷石膏分解,其完全分解温度接近1 300℃。而在较强还原气氛中,磷石膏+碳系统生成硫化钙,在约1 260℃时才完全分解。因此新型干法水泥工艺分解磷石膏制酸联产水泥新工艺在实际过程中将受限于硫酸盐及硫化物熔点较低与硫酸钙分解温度较高这对矛盾而不宜直接采用。     

CuMnO_x/γ-Al_2O_3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu-Mn复合氧化物催化剂和加入不同稀土含量的Cu-Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加人稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T_(99)(催化处理效率达到99%时的温度)比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

CuMnOx／γ-Al2O3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu—Mn复合氧化物催化剂和加入不同稀土含量的Cu—Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加入稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T99（催化处理效率达到99％时的温度）比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

活性组分稀土氧化物对甲苯催化燃烧性能的影响

以活性组分氧化铜、氧化锰为基础,加入活性组分稀土氧化物,研究对甲苯催化燃烧性能影响。研究结果表明,在所选稀土氧化物中,加入氧化铈时甲苯的起燃温度和完全燃烧温度最低;在一定的负载量下,Cu∶Mn∶Ce摩尔比为1∶2∶0.7时,制备的Cu Mn Ce/Zr O2整体催化剂甲苯完全燃烧温度最低;催化剂合理的焙烧温度为500℃,此时甲苯的起燃温度约200℃,完全燃烧温度为220℃;催化剂合理的焙烧时间为3 h。     

CuMnOx/γ-Al2O3及稀土助剂对VOCs催化燃烧性能的影响

利用浸渍法制备了Cu-Mn复合氧化物催化剂和加入不同稀土含量的Cu-Mn复合氧化物催化剂,通过实验优选出加入稀土催化剂中稀土含量的最优配比,以气相色谱为检测手段,考察了加入稀土和不加稀土催化剂的催化燃烧性能,结果表明,加入稀土的催化剂T₉₉（催化处理效率达到99%时的温度）比不加稀土的催化剂降低30～40℃,具有更好的低温活性,且对多种VOCs均能降低反应温度。     

温度对污泥与底泥烧结陶粒性能的影响

研究了温度对污泥与底泥烧结制备陶粒的主要性能(抗压强度、吸水率、比表面积和密度)的影响,并结合电镜扫描(SEM)和热重红外(TG-FTIR)分析对温度影响陶粒的膨胀特性和孔隙结构的机理进行分析。研究发现,随着烧结温度的升高,陶粒比表面积和吸水率降低,而抗压强度和表观密度有所提高。SEM分析表明,温度对烧结体内部形态影响显著:800℃时烧结体呈现出松散堆积状态,1 000℃时陶粒开始产生液相,1 050℃时烧结体出现大量液相,并且陶粒中有非常丰富的气孔。TG-FTIR分析表明,有机物所发生的分解产气反应只能起到轻质化的作用,并不能使陶粒膨胀;1 000℃以上发生产气反应的主要是铁的化合物和固定碳,污泥中有机物形态存在的碳有利于将碳元素保留到陶粒高温烧结阶段,这一过程使得铁的化合物得以与碳元素发生产气反应,对陶粒多孔结构起到重要作用。     

N_2O直接分解催化剂的研究进展

本文详细综述了用于Ｎ２Ｏ直接分解催化剂的研究进展情况。Ｎ２Ｏ分解催化剂大致可以分作以下几类，即：（１）稀土氧化物及相关氧化物；（２）复合金属氧化物；（３）沸石催化剂；（４）水滑石热分解产物催化剂。前两类催化剂注重探讨催化分解Ｎ２Ｏ的机理；而后两类催化剂主要研究催化分解Ｎ２Ｏ的活性。     

脱水污泥热调质的特性

热调质方法是污泥深度脱水的有效办法之一。研究结果表明,污泥热调质过程中反应温度和反应时间对污泥热调质效果影响较大,搅拌速度影响较小。当反应温度从160℃升至180℃,反应时间从30 min增至60 min时,污泥溶液中挥发性悬浮固体(VSS)急剧溶解,释放出细胞里的结合水,表明污泥细胞破壁的温度条件为160～180℃,时间条件为45～60 min。热调质后污泥的比阻变化较大。随着反应温度的不断提高,比阻不断减小,污泥的脱水性能越来越好。实验确定了污泥热调质的最佳反应条件为:反应温度180℃,反应时间60 min,搅拌转速30 r/min。在此条件下,压滤后泥饼含水率约50%,滤液中COD浓度可达19 000 mg/L,有利于后续污泥的消化。     

水热条件下碳酰肼分解二噁英的研究

研究了保温温度为245、260℃水热条件下使用碳酰肼分解垃圾焚烧飞灰中二噁英的分解效果.结果表明,在高温水热条件下使用碳酰肼作为添加剂有利于二噁英的分解;在245、260℃下保温1 h,二噁英的分解率分别达到80%和90%以上,但二噁英毒性当量因2,3,7,8-TCDD的再生成减小很少,甚至增大;同时,在水热条件下,垃圾焚烧飞灰中的重金属取得了良好的稳定效果.     

LaxCe1-xMnO/γ-Al2O3催化剂的制备及其催化燃烧甲苯的性能

为了研究镧、铈2种稀土元素共掺金属氧化物催化剂对甲苯的去除效果,采用等体积浸渍法制备了LaxCe1-xMnO/γ-Al2O3稀土改性催化剂。考察了活性组分负载量、焙烧温度对催化剂催化活性的影响,确定了催化剂的最佳制备工艺。同时对镧、铈两种稀土元素不同原子配比对催化活性的影响进行研究。实验结果表明,LaxCe1-xMnO负载量为12%,催化剂的焙烧温度为450℃,La、Ce物质的量比为4∶1,制得的催化剂催化活性最强,催化效率最高,在6 000 h-1空速下,反应温度为320℃时即可将甲苯气体完全燃烧。运用BET、XRD、SEM、XRF等方法对催化剂的结构进行表征,结果表明,催化剂表面活性组分具有高分散性,氧化物颗粒粒径均一且分散均匀。稀土共掺催化剂与单一稀土改性催化剂相比,活性组分易于负载在载体表面,负载效果有着显著的提高。     

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.