超细粉煤灰-氟石膏在道路修补工程中的综合利用研究

针对我国现有水泥混凝土路面的破坏问题,研究开发了以工业废料--超细粉煤灰和氟石膏为主要组分的水泥基道路修补材料,利用氟石膏与超细粉煤灰在水泥水化过程中的相互激发作用,通过试验优选出超细粉煤灰-氟石膏高性能道路修补材料,并应用于道路修补混凝土的配制,同时测试了其力学性能及部分长期性能,试验表明其性能优良,在此基础上对其水化硬化机理作了初步的探讨.     

粉煤灰资源化特性及路面工程应用技术研究

对粉煤灰的各项技术参数进行了试验研究,揭示出粉煤灰的不同成分和形貌对其资源化特性的影响规律,初步完成了消除不利于粉煤灰资源化的有害成分炭的优化实验工作,进行了脱炭粉煤灰混凝土配合比等试验研究,并在路面修复工程中予以应有,结果表明,经脱炭处理的粉煤灰应用于混凝土工程可以明显改善混凝土的工作性能,实际道路运营和技术性能符合路面工程的要求,具有重大的经济效益和环境效益。     

石灰-石膏-粉煤灰水泥浆体的水化机理研究

通过增钙法对粉煤灰水泥浆体的凝结时间、水化放热和力学性能的测定,以及采用差示热重分析、扫描电镜、X射线衍射,研究了在有石灰、石膏时不同掺量粉煤灰水泥浆体的水化机理。结果表明：早期水化性能弱,后期持久。随粉煤灰掺量增加,浆体的凝结时间延长,水化热减少,高掺超过40%时龄期强度下降明显;早期水化产物主要为：大量的水化硅酸钙凝胶(C-S-H）,未水化的硅酸钙（C₃S、 C₂S）,少量的钙矾石（AFt、 AFm）和氢氧化钙Ca(OH)₂,后期在石灰石膏的活性效应和填充效应的激发下,水化产物主要为：Ca(OH)₂、AFm。Ca(OH)₂与AFm及少量的C-S-H填充在水泥孔隙中且相互交联,改善了粉煤灰水泥浆体强度。     

磷石膏基胶结材固结磷尾矿性能及浸出特征

以磷石膏基材料代替水泥作为磷尾矿充填胶结材,研究了磷尾矿固结浆体和硬化体性能、浸出液污染特性和固结机理。结果表明,在同样条件下,磷石膏基材料固结磷尾矿浆体比水泥泌水量要小、浆体流动性能更优;磷石膏基材料胶结磷尾矿硬化体除3 d抗压强度略低外,其他龄期的强度是水泥的1.21~1.95倍。3 d之后,磷石膏基材料和水泥胶结尾矿硬化体浸出液总磷含量基本相近,但pH明显远低于水泥,总磷也低于污水综合排放标准限值,对环境危害低。硬化体SEM和XRD分析发现,磷石膏基材料水化生成的水化硅酸钙凝胶、针状钙矾石晶体和磷尾矿中白云石、含磷矿物生成的透钙磷石等,是整个磷尾矿固结硬化体具有较高强度、较低总磷含量和pH值主要原因。该研究表明,磷石膏基材料固化磷尾矿比水泥更有应用前景。     

粉煤灰黑液胶凝材料的研究

研究了改性黑液作粉煤灰的激发剂,并与石灰、磷石膏一起制成一种新型的胶凝材料,讨论了粉煤灰、石灰、磷石膏及黑液的用量对胶凝材料性能的影响,并通过正交试验与模糊数学分析求出了最佳工艺参数。试验结果表明,该种新材料的抗压强度能达≥20MPa,耐水性良好,且工艺简单、成本低。     

赤泥掺加硅灰用于道路基层材料的试验研究

选用洛阳某铝业尾矿库赤泥为试验材料,添加不同量的水泥、粉煤灰和硅灰,采用单因素正交试验,分析赤泥固化体的无侧限抗压强度、微观形貌及其浸出液的pH、含氟量,得出赤泥道路基层材料的最佳配合比:水泥掺量10%(质量分数,下同),粉煤灰掺量10%,硅灰掺量15%。该配合比在工程上不仅能满足道路基层技术要求,通过掺加硅灰还减小了水泥掺量,使赤泥固化体浸出液的碱性和含氟量降低。     

粉煤灰聚苯乙烯新型保温建筑材料的制备及其机理分析

以石灰、石膏作为粉煤灰活性激发剂,用废弃聚苯乙烯颗粒(EPS)作为保温成分,通过优化配比,研制新型节能环保墙体砌块材料,分析了砌块材料的水化机理。XRD（X射线衍射）、TGA-DTA（热重-差热分析）和SEM（扫描电子显微镜）分析证实：当粉煤灰掺量为20%~25%、EPS为2.5%时,保温砌块材料的施工及保温性良好,耐久与耐候性能优良。     

Plackett-Burman设计和响应曲面法优化除磷陶粒的制备

为制备得到除磷效果较强的功能型陶粒,采用Plackett-Burman和响应曲面法对陶粒原料配比进行优化研究。采用Plackett-Burman实验设计筛选出具有显著除磷效应的4种原料——粉煤灰、水泥、石膏和氢氧化钠。以Box-Behnken Design响应面法建立数学回归模型,确定了最佳原料配比为:粉煤灰60.0 g、水泥15.0 g、氨基材料2.0 g、生石灰15.0 g、石膏3.0 g、氢氧化钠15.0 g,制得的陶粒磷去除率可达93.04%,颗粒强度为118.3 N。通过显著性检验和响应曲面等高线图分析,粉煤灰和氢氧化钠是显著影响陶粒磷去除率的主要原料,且粉煤灰与石膏、粉煤灰与氢氧化钠对陶粒的磷去除率有显著的交互影响,显著性p值分别为0.010 8和0.029 5。     

β-半水磷石膏低温制备及固化铅污染土壤性能研究

惰性材料、化学物质和工业废渣掺入磷石膏,低温制备改性β-半水磷石膏(MHG),并对其煅烧温度、抗压强度、凝结时间及固化铅污染土壤的效果进行研究。结果表明,磷石膏、矿渣、粉煤灰和生石灰按91∶4∶3∶2(质量比)制备的MHG性能最好,抗压强度达到6.47MPa,相对于β-半水磷石膏抗压强度提高了24.18%,凝结时间延长7～23min。MHG固化铅污染土壤,养护3d的铅浸出质量浓度为0.015～0.028mg/L,相对于水泥铅浸出质量浓度降低了43.90%～57.14%。     

高铝粉煤灰提取氧化铝后硅钙渣用作水泥混合材

为了使高铝粉煤灰提取氧化铝后所产生的硅钙渣被大量的用作水泥混合材,通过水泥强度、水化放热和干缩性实验研究了原状硅钙渣和脱碱硅钙渣对水泥强度和稳定性的影响。结果表明,当硅钙渣掺量达30%时,硅钙渣水泥强度仍可满足P·C 32.5水泥要求。且随硅钙渣掺入量的增加,水泥早期水化放热速率增加的同时水泥累计水化放热量和干缩率还会显著降低。与原状硅钙渣相比,在同等掺量的情况下,脱碱硅钙渣更有利于保持水泥强度,降低其水化热和改善干缩性。     

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.