煤矸石中氧化铝溶出的实验研究

煤矸石是主要的煤系固废,其中氧化铝的含量占到25%左右,又是一种可以利用的资源.本实验以山西潞安煤矿的煤矸石为原料,采用正交试验的方法,研究了盐酸作为酸浸介质浸取煤矸石中氧化铝.主要影响因素为煅烧温度、酸量、固液比及酸浸时间,最佳工艺条件为:煅烧温度为650℃,酸量为225mL(按照煤矸石中氧化铝和盐酸反应的摩尔比为1:6计)、固液比为1:3、酸浸时间为3 h,单因素重复试验结果和正交实验的结果相符,在最佳条件下,氧化铝的溶出实验验证结果表明,三氧化二铝溶出率为71.49%.本研究对实现煤矸石的资源化综合利用具有重要的意义.     

用钛白废酸和副产锌泥制备活性氧化锌

以次硫酸氢钠甲醛副产锌泥和钛白废酸为原料,经高剪切乳化、酸浸、锌粉置换、除杂、碱锌合成等工艺制得碱式碳酸锌,再经过滤、洗涤、干燥、煅烧制备活性氧化锌。考察了浸取工艺液固比(硫酸与副产锌泥的质量比)和硫酸质量分数对锌浸出率的影响,以及煅烧温度和时间对活性氧化锌质量的影响。实验结果表明,锌泥酸浸工艺的最佳液固比4,硫酸质量分数30%,在此工艺条件下,锌浸出率达95%。活性氧化锌的最佳煅烧温度为600℃,煅烧时间为240 min,在此条件下测定产品质量,氧化锌质量分数大于96%,比表面积大于50 m2/g,堆积密度小于0.35 g/mL。     

煤矸石中的铝、铁在高浓度盐酸中的浸出行为

考察了煤矸石中Al2O3和Fe2O3在不同浓度盐酸中的浸出行为,着重探讨了Al2O3和Fe2O3在高浓度盐酸中的溶出规律。通过与文献中AlCl3和FeCl3在不同浓度盐酸中的溶解度数据对照,发现煤矸石中Al2O3的溶出率受AlCl3溶解度的影响显著,而Fe2O3的溶出则基本不受FeCl3溶解度影响。进一步的研究结果表明,在高浓度盐酸中,煤矸石中Al2O3的溶出率显著降低,高浓度的盐酸不影响Fe2O3的溶出。当煤矸石的煅烧温度为700℃、酸浸温度为33℃时,酸浸固液比为1∶1(g/mL),利用37%的高浓度盐酸酸浸,Fe2O3和Al2O3的溶出率分别为48.7%和7.3%,可实现煤矸石中铁铝的有效分离。     

煤矸石热活化性能研究

系统地研究了徐州夹河煤矸石在不同煅烧温度下的物理、化学变化及活性成分的溶出规律.采用扫描电子显微镜(SEM)、差热分析(DTA)、X射线衍射(XRD)等测试方法研究了热活化前后煤矸石的矿物组成、SiO2及Al2O3溶出率和微观结构,并采用水泥强度的测试方法对热活化煤矸石的活性进行宏观表征.结果表明,煅烧能有效去除有机挥发物和碳.破坏煤矸石中的硅氧键、铝氧键,形成无定形物质和玻璃相,从而提高煤矸石的活性.徐州夹河煤矸石的最佳热活化工艺条件是煅烧650℃、保温2 h.经此条件热活化后,SiO2和Al2O3的最高溶出率分别是76.32%、91.48%,添加50%(质量分数)的热活化煤矸石到水泥中,其强度比同掺量原样煤矸石的水泥强度提高了230%.     

MnO2/Al2O3吸附草甘膦及微波紫外耦合降解再生工艺

以掺混煅烧法制备MnO2/Al2O3,并对草甘膦进行吸附,将吸附态草甘膦置于微波紫外耦合系统中进行降解和再生。研究并给出了MnO2/Al2O3的最佳制备条件、最佳吸附条件和微波紫外耦合降解再生的最佳工艺参数。MnO2/Al2O3最佳制备条件为MnO2质量分数15%,煅烧温度500℃,煅烧时间2 h。在常温下,MnO2/Al2O3对草甘膦的最大吸附量为75 mg/g。微波紫外耦合系统最佳工艺参数为功率500 W,时间25 min,空气量0.06 m3/h。在此操作条件下,MnO2/Al2O3的再生率达到85%,并且可以多次再生利用,草甘膦最终降解产物为二氧化碳、氮氧化物、磷酸和水,矿化率为65%。     

循环流化床灰制备聚合氯化铝铁絮凝剂

以煤矸石电厂循环流化床灰(CFB灰)为原料,采用酸浸、水解、聚合和熟化等工艺过程,制备聚合氯化铝铁(PAFC)絮凝剂产品。重点对制备PAFC絮凝剂的酸浸工艺参数进行研究,其最佳工艺条件为:盐酸浓度为20.2%、酸浸温度为110℃、酸浸时间为2 h、液固比为4∶1;Fe2O3浸出率为90.6%,Al2O3的浸出率为48.5%。同时采用实验得出的最优工艺参数进行了产品制备,并对产品进行了絮凝性能实验。结果表明,在相同条件下PAFC的絮凝效果明显好于聚合氯化铝(PAC),用CFB灰制备PAFC絮凝剂产品是可行的。     

电镀锌泥饼的酸浸条件对锌浸出率的影响

研究了含锌泥饼的浸出条件。试验结果表明，适宜的酸浸条件：浸取液终点pH值为5左右；液固化（3：1）－（4：1）；分段加酸时间为2h；搅拌速度为100－200r/min，在上述条件下用硫酸溶液进行常温浸取，锌浸出率可达98％，铁浸出率小于1％。     

粉煤灰制备混凝剂及其对黄河水的处理效果

以粉煤灰和铁泥为原料、加入一定量NaCl作助溶剂室温下制备粉煤灰混凝剂,考察酸灰比与酸浓度对Fe3+、Al3+溶出率及混凝剂对黄河水处理效果的影响。结果表明,Fe3+、Al3+的最佳溶出条件为酸灰比3 mL/g、HCl浓度4 mol/L,此时Fe3+溶出率为28.1%,浓度为11.81 g/L;Al3+溶出率为5.2%,浓度为1.86 g/L。粉煤灰混凝剂对黄河水的处理效果在投加量2.38 mL/L、沉降时间30 min、pH 6.2～7.5时最佳,对浊度、SS和CODMn平均去除率分别为89.7%、83.6%和62.3%,优于传统市售混凝剂PAC和FC,Fe3+、Al3+同时存在有利于各自优势的发挥从而提高混凝效果。     

固体超强酸SO24-/TiO2-SnO2/Ce4+光催化降解含酚废水

采用共沉淀-浸渍法制备了固体超强酸SO42-/TiO2-SnO2/Ce4+,并用XRD、SEM等方法对其结构进行了表征.以苯酚的光催化降解为反应模型,确定了最佳的工艺条件和催化剂再生方法.结果表明:在pH值为6,苯酚初始浓度为50mg/L,催化剂投加量4 g/L,光照距离12 cm,光照时间为150 min,降解率达67.73％,添加助催化剂H2O2后,反应60 min,苯酚降解率达到86.33％,催化剂的最佳再生方法是先用1 mol/L的硫酸浸渍24 h后,在450℃下焙烧6h.     

高铁脱硫渣制备高纯度硫酸亚铁及草酸亚铁的研究

以高铁脱硫渣为原料,采取酸浸、除杂和结晶等工艺制备出99%以上硫酸亚铁晶体。研究了酸浸过程中硫酸浓度、浸取温度、时间对铁浸出率的影响,分析了各个影响因素的规律性。结果表明：适宜的浸取条件为硫酸溶液质量分数为25%,在70℃下,不断搅拌浸取6 h。固液分离后调节硫酸亚铁溶液pH=1～2,在70℃下蒸发浓缩结晶,即可得到99%以上硫酸亚铁晶体。     

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.     

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.     

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.     

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.     

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.     

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.     

Phytoextraction of lead-contaminated soil using vetivergrass (<Emphasis Type="Italic">Vetiveria zizanioides</Emphasis> L.), cogongrass (<Emphasis Type="Italic">Imperata cylindrica</Emphasis> L.) and carabaograss (<Emphasis Type="Italic">Paspalum conjugatum</Emphasis> L.)

Background, Aims and Scope The global problem concerning contamination of the environment as a consequence of human activities is increasing. Most of the environmental contaminants are chemical by-products and heavy metals such as lead (Pb). Lead released into the environment makes its way into the air, soil and water. Lead contributes to a variety of health effects such as decline in mental, cognitive and physical health of the individual. An alternative way of reducing Pb concentration from the soil is through phytoremediation. Phytoremediation is an alternative method that uses plants to clean up a contaminated area. The objectives of this study were: (1) to determine the survival rate and vegetative characteristics of three grass species such as vetivergrass, cogongrass and carabaograss grown in soils with different Pb levels; and (2) to determine and compare the ability of the three grass species as potential phytoremediators in terms of Pb accumulation by plants. Methods The three test plants: vetivergrass (Vetiveria zizanioides L.); cogongrass (Imperata cylindrica L.); and carabaograss (Paspalum conjugatum L.) were grown in individual plastic bags containing soils with 75 mg kg⁻¹ (37.5 kg ha⁻¹) and 150 mg kg⁻¹ (75 kg ha⁻¹) of Pb, respectively. The Pb contents of the test plants and the soil were analyzed before and after experimental treatments using an atomic absorption spectrophotometer. This study was laid out following a 3 × 2 factorial experiment in a completely randomized design. Results On the vegetative characteristics of the test plants, vetivergrass registered the highest whole plant dry matter weight (33.85–39.39 Mg ha⁻¹). Carabaograss had the lowest herbage mass production of 4.12 Mg ha⁻¹ and 5.72 Mg ha⁻¹ from soils added with 75 and 150 mg Pb kg⁻¹, respectively. Vetivergrass also had the highest percent plant survival which meant it best tolerated the Pb contamination in soils. Vetivergrass registered the highest rate of Pb absorption (10.16 ± 2.81 mg kg⁻¹). This was followed by cogongrass (2.34 ± 0.52 mg kg⁻¹) and carabaograss with a mean Pb level of 0.49 ± 0.56 mg kg⁻¹. Levels of Pb among the three grasses (shoots + roots) did not vary significantly with the amount of Pb added (75 and 150 mg kg⁻¹) to the soil. Discussion Vetivergrass yielded the highest biomass; it also has the greatest amount of Pb absorbed (roots + shoots). This can be attributed to the highly extensive root system of vetivergrass with the presence of an enormous amount of root hairs. Extensive root system denotes more contact to nutrients in soils, therefore more likelihood of nutrient absorption and Pb uptake. The efficiency of plants as phytoremediators could be correlated with the plants’ total biomass. This implies that the higher the biomass, the greater the Pb uptake. Plants characteristically exhibit remarkable capacity to absorb what they need and exclude what they do not need. Some plants utilize exclusion mechanisms, where there is a reduced uptake by the roots or a restricted transport of the metals from root to shoots. Combination of high metal accumulation and high biomass production results in the most metal removal from the soil. Conclusions The present study indicated that vetivergrass possessed many beneficial characteristics to uptake Pb from contaminated soil. It was the most tolerant and could grow in soil contaminated with high Pb concentration. Cogongrass and carabaograss are also potential phytoremediators since they can absorb small amount of Pb in soils, although cogongrass is more tolerant to Pb-contaminated soil compared with carabaograss. The important implication of our findings is that vetivergrass can be used for phytoextraction on sites contaminated with high levels of heavy metals; particularly Pb. Recommendations and Perspectives High levels of Pb in localized areas are still a concern especially in urban areas with high levels of traffic, near Pb smelters, battery plants, or industrial facilities that burn fuel ending up in water and soils. The grasses used in the study, and particularly vetivergrass, can be used to phytoremediate urban soil with various contaminations by planting these grasses in lawns and public parks. ESS-Submission Editor: Dr. Willie Peijnenburg (wjgm.peijnenburg@rivm.nl)