石英砂滤料表面润湿改性

采用硅烷偶联剂、钛酸酯偶联剂和铝酸酯偶联剂对石英砂进行表面改性,以制备亲油疏水性滤料。研究得出,钛酸酯偶联剂改性石英砂的最佳工艺条件为:偶联剂用量15%,反应温度90℃,搅拌时间15 min;硅烷偶联剂和铝酸酯偶联剂改性石英砂的最佳工艺条件均为:偶联剂用量15%,反应温度110℃,搅拌时间15 min。水对钛酸酯偶联剂改性石英砂滤料的润湿重量由改性前的1.5589 g降低到0.0282 g,水对硅烷偶联剂改性石英砂滤料的润湿重量降低到0.0607 g,水对铝酸酯改性石英砂滤料的润湿重量降低到0.2664 g。静态吸附实验表明,硅烷偶联剂、钛酸酯偶联剂和铝酸酯偶联剂改性石英砂滤料对油的吸附容量分别增加了33.67%、42.87%和22.30%。XPS和FT-IR分析表明,偶联剂均以化学键的方式包覆在石英砂滤料表面,结合稳定。     

改性木屑对海上溢油的吸附

为提高吸油倍率降低吸水倍率,对天然松木屑进行了改性,得到了一种新的除油吸附剂。对该吸附剂的吸油吸水性能进行测定,并确定最佳条件。结果显示:改性木屑吸油效果提升显著,在纯原油中吸油倍率是天然松木屑的2.50倍;吸水倍率降低了80%;漂浮性能好;吸附2 min就能达到吸附平衡,吸附速率是原始松木屑和活性炭的15倍;粒径对改性木屑吸水吸油性能基本无影响;低温和中性条件有利于油的吸附。     

石墨烯复合改性海绵的制备及其吸油性能

将三聚氰胺海绵(MF)浸入氧化石墨烯(GO)悬浮液,经微波溶剂热还原反应后,用聚二甲基硅氧烷(PDMS)进一步修饰,得到超疏水亲油的石墨烯复合改性吸油海绵(rGO-PDMS-MF)。优化了GO和PDMS改性试剂的浓度,通过扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FTIR)及接触角(CA)测定仪对海绵结构和性质进行了表征,测试了海绵的饱和吸油性能、重复使用性能及油水分离性能。结果表明:GO悬浮液和PDMS溶液最适浓度分别为2.0g·L~(-1)和1.0%(质量分数);所得海绵的接触角达151.5°,饱和吸油能力达45～110g·g~(-1),可通过吸附-挤压方式重复使用10次以上;rGO-PDMS-MF海绵对油水体系具有良好的选择性,与泵装置结合后可以连续有效地将油从水面分离,再生使用后仍保持较高的浮油回收速率和较强的疏水性能。     

氯碱废渣盐泥的干法表面改性与填充性能研究

为了提高盐泥粉体与有机体系的相容性,采用4种偶联剂对盐泥进行干法表面改性,考察了不同改性剂种类、用量及改性时间对改性盐泥在液体石蜡中分散性的影响,并利用傅立叶红外光谱（FTIR）研究了改性机理。结果表明每种改性剂都有一个较佳用量,钛酸酯NDZ-105、 NDZ-311和NDZ-401型的较佳液固比分别为1∶20、1∶10和1∶10,硅烷偶联剂KH-570型的较佳液固比为1∶20;而在这4种偶联剂中,NDZ-105型改性效果最好,在其较佳液固比（1∶20）下,使得改性盐泥在液体石蜡中的浊度达到1 100 NTU以上,其与有机物的亲和性得到很好的改善,其合适改性时间为球磨20 min。通过对改性与未改性盐泥的红外光谱、热重与差示扫描量热分析表明改性剂与盐泥表面发生了化学吸附。通过工业填充,得到了改性盐泥填充的聚氨酯产品,其性能达到填充CaCO₃粉体的聚氨酯性能。     

氧化石墨烯修饰MoS2-PAN吸附膜对铜离子吸附性能的影响

通过氧化石墨烯(GO)对硫化钼(MoS₂)-聚丙烯腈(PAN)进行改性处理,采用相转化法成功制备了对水溶液中Cu²⁺进行吸附的GO-MoS₂-PAN改性吸附膜。通过扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)及接触角测试对该吸附剂材料进行了表征。探究了不同GO固含量对GO-MoS₂-PAN改性吸附膜的孔隙率、纯水通量以及接触角的影响。在pH为5、Cu²⁺质量浓度为100 mg·L^-1的溶液中,GO固含量为0.03%的改性吸附膜对Cu²⁺的最大平衡吸附量达到224.28 mg·g^-1,且其脱附率为84%。结果表明,改性吸附膜对溶液中Cu²⁺的吸附动力学符合准二级动力学模型,等温吸附过程符合Freundlich等温吸附模型,热力学分析结果表明该吸附过程为自发吸热过程。     

竹粉含量对竹浆造纸白泥/聚氯乙烯复合材料性能的影响

以竹粉、竹浆造纸白泥和聚氯乙烯为原料,采用铝酸酯偶联剂对竹粉和竹浆造纸白泥进行改性处理,通过热压成型技术制备竹浆造纸白泥/聚氯乙烯复合材料,研究竹粉含量对复合材料密度、力学性能、尺寸稳定性和阻燃性能的影响,并通过XRD、扫描电镜和红外光谱对竹浆造纸白泥进行表征。结果表明:偶联剂与竹浆造纸白泥产生了化学作用;竹粉含量在一定范围内时,对复合材料的力学性能具有一定的增强效果,但其尺寸稳定性能和阻燃性能随竹粉含量的增加而下降;当竹粉含量为10%时,复合材料的密度为1.03 g·cm~(-3),拉伸强度为4.84 MPa,拉伸断裂伸长率为2.84%,弯曲强度11.83 MPa,弯曲模量为8 883.33 MPa,24 h TS为1.65%,24 h WA为5.16%,氧指数为38.6%,其综合性能较优,其中氧指数达到国家建筑材料阻燃等级B1级的要求。     

棕刚玉渣的硬脂酸湿法改性

以棕刚玉渣、硬脂酸为原料,在乙醇体系中进行机械力化学改性研究。分别研究了球磨过程中球料比、球磨时间、转速、硬脂酸用量、浆料浓度等参数对实验样品亲油化度、活化指数的影响。在最佳工艺基础上进行了正交实验,实验结果表明,适宜条件为硬脂酸用量3.5%,球料比4∶1,球磨时间30 min,球磨转速450 r/min,浆料浓度25%时,实验样品的亲油化度和活化指数分别达到46.8%和100%,且完全疏水。     

氧化石墨烯-FeCl3改性沸石联合生物预处理对氨氮的强化处理研究

以氧化石墨烯(GO)和FeCl_3·6H_2O为改性剂,制备GO-FeCl_3改性沸石,与生物预处理技术结合,对含(2.98±0.38)mg/L氨氮的微污染水进行强化处理,探讨了GO-FeCl_3改性沸石表面的挂膜性能以及GO-FeCl_3改性沸石的表面特性,并对GO-FeCl_3改性沸石、FeCl_3改性石英砂(IOCS)和普通石英砂(RQS)3种滤料联合生物预处理的强化处理效果进行了比较分析。结果表明:(1)与RQS和IOCS比较,GO-FeCl_3改性沸石表面生物量最高(17.26μg/cm~3);(2)GO-FeCl_3改性沸石联合生物预处理,对氨氮的去除率最高(95.60%),出水中悬浮物粒径最小(由进水的458.70nm下降至1.49nm),生物安全性最高;(3)GO-FeCl_3改性沸石比表面积最大,表面结构更加复杂且多孔,表面含有羟基、羧基等官能团,且煅烧过程形成的Fe_3O_4和α-FeOOH与GO结合,具有一定的可见光催化作用,因而强化处理效果最好。     

改性锰砂滤料处理高铁锰煤矿矿井水

采用KMnO4溶液浸渍法制备了新型改性锰砂滤料,研究了滤料表面性能和过滤处理高铁锰矿井水的效果。结果表明,锰砂滤料除铁锰性能优于石英砂、陶粒以及瓷砂,采用KMnO4溶液浸渍能够提高锰砂滤料的过滤性能,最优的浸渍浓度为5%。5%KMnO4改性锰砂滤料过滤处理高铁锰矿井水的最佳工艺参数为：过滤周期24 h,反冲洗强度3.2 L/（s.m2）,反冲洗时间5 min;通过比表面积测试分析和SEM表征分析发现,KMnO4溶液浸渍能够提高锰砂滤料比表面积,并在锰砂滤料表面形成了氧化膜,从而提高除铁除锰效果,而且浸渍液浓度越高,这种作用越明显。     

改性火山岩滤料去除矿井水中铁锰离子影响因素研究

以改性火山岩滤料作为除铁除锰的滤料,通过对模拟矿井水的过滤试验,研究了滤速、pH值、滤层厚度及铁锰离子浓度对其除铁除锰效率的影响。结果表明：改性火山岩滤料能实现模拟矿井水中Mn²⁺的100%去除,效果明显优于未改性火山岩;最为合理的过滤滤速为7～8 m/h;除铁除锰的过程主要发生在滤层厚度为90 cm的上部滤层中;随着铁锰浓度的升高,改性火山岩滤料除铁的效率变化很小,除锰效率呈快速、线性降低;中性或偏碱性的环境有利于改性火山岩滤料充分发挥高效吸附去除能力。     

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.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

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.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

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.     

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.     

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.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

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.